EP1664860A1 - Durable optical element - Google Patents
Durable optical elementInfo
- Publication number
- EP1664860A1 EP1664860A1 EP04788684A EP04788684A EP1664860A1 EP 1664860 A1 EP1664860 A1 EP 1664860A1 EP 04788684 A EP04788684 A EP 04788684A EP 04788684 A EP04788684 A EP 04788684A EP 1664860 A1 EP1664860 A1 EP 1664860A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- optical film
- film according
- polymerized
- durable
- durable optical
- 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.)
- Withdrawn
Links
- 230000003287 optical effect Effects 0.000 title claims description 99
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- 239000010408 film Substances 0.000 claims description 149
- 239000000203 mixture Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 42
- 239000010415 colloidal nanoparticle Substances 0.000 claims description 31
- 230000002708 enhancing effect Effects 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003607 modifier Substances 0.000 claims description 17
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- -1 polyethylene naphthalate Polymers 0.000 claims description 13
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- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 7
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
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- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VSVDQVJQWXJJSS-UHFFFAOYSA-N [2,6-dibromo-4-[2-(3,5-dibromo-4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C(Br)=C(OC(=O)C=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OC(=O)C=C)C(Br)=C1 VSVDQVJQWXJJSS-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HZBGBOWFTGSNLM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl carbamate Chemical compound COCCOCCOCCOC(N)=O HZBGBOWFTGSNLM-UHFFFAOYSA-N 0.000 description 2
- JSOZORWBKQSQCJ-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C(C)=C JSOZORWBKQSQCJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- DYFMAHYLCRSUHA-UHFFFAOYSA-N ethenyl-tris(2-methylpropoxy)silane Chemical compound CC(C)CO[Si](OCC(C)C)(OCC(C)C)C=C DYFMAHYLCRSUHA-UHFFFAOYSA-N 0.000 description 1
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
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- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
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- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
- G02B6/0053—Prismatic sheet or layer; Brightness enhancement element, sheet or layer
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0231—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having microprismatic or micropyramidal shape
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0284—Diffusing elements; Afocal elements characterized by the use used in reflection
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
- G02B5/045—Prism arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates generally to durable optical elements. More particularly, the present invention relates to microstructured bearing articles such as, for example, a brightness enhancement film, an optical lighting film or a reflective element.
- Microstructure bearing articles such as, brightness enhancing films, optical turning films or reflective elements, are made in a variety of forms.
- One such form includes a series of alternating tips and grooves.
- One example of such a form is brightness enhancement film, which has a regular repeating pattern of symmetrical tips and grooves.
- Other examples include patterns in which the tips and grooves are not symmetrical and in which the size, orientation, or distance between the tips and grooves is not uniform.
- One drawback of current brightness enhancement films and optical lighting films, and the like, is that the tips of the microstructure are susceptible to mechanical damage.
- a durable optical film includes a polymerized optical film structure having a microstructured surface and a scratch contrast ratio value in a range of 1.0 to 1.15.
- a durable optical film includes a polymerized optical film structure having a microstructured surface including a plurality of rounded prism apexes extending along a first surface and a scratch contrast ratio value in a range of 1.0 to 1.65.
- a durable optical film includes a polymerized optical film structure having a microstructured surface including a plurality of surface modified colloidal nanoparticles of silica, zirconia, or mixtures thereof and a scratch contrast ratio value in a range of 1.0 to 1.65.
- FIG. 1 is a schematic view of an illustrative micro-structured article of the present invention in a bac lit liquid crystal display
- FIG. 2 is a perspective view of an illustrative polymerized structure bearing a micro-structured surface
- FIG. 3 is a cross-sectional view of an illustrative micro-structured article which has prism elements of varying height
- FIG. 4 is a cross-sectional view of an illustrative micro-structured article which has prism elements of varying height
- FIG. 5 is a cross-sectional view of an illustrative micro-structured article
- FIG. 1 is a schematic view of an illustrative micro-structured article of the present invention in a bac lit liquid crystal display
- FIG. 2 is a perspective view of an illustrative polymerized structure bearing a micro-structured surface
- FIG. 3 is a cross-sectional view of an illustrative micro-structured article which has prism elements of varying height
- FIG. 6 is a cross-sectional view of an illustrative micro-structured article in which the prism elements are of different heights and have their bases in different planes;
- FIG. 7 is a cross-sectional view of an illustrative micro-structured article;
- FIG. 8 is a cross-sectional view of an illustrative micro-structured article;
- FIG. 9 is a cross-sectional view of an illustrative micro-structured article;
- FIG. 10 is a schematic view of an illumination device including a turning film;
- FIG. 11 is a cross-sectional view of a turning film;
- FIG. 12 is a cross-sectional view of another turning film;
- FIG. 13 is a schematic flow diagram illustrating one scratch contrast ratio method; and FIG.
- FIG. 14 is a schematic diagram of an illustrative apparatus to determine scratch contrast ratio. While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. On the contrary, the mtention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
- Brightness enhancing films generally enhance on-axis luminance (referred herein as "brightness") of a lighting device.
- Brightness enhancing films can be light transmissible, microstructured films.
- the microstructured topography can be a plurality of prisms on the film surface such that the films can be used to redirect light through reflection and refraction.
- the microstructured optical film can increase brightness of an optical display by limiting light escaping from the display to within a pair of planes disposed at desired angles from a normal axis running through the optical display. As a result, light that would exit the display outside of the allowable range is reflected back into the display where a portion of it can be "recycled” and returned back to the microstructured film at an angle that allows it to escape from the display.
- the recycling is useful because it can reduce power consumption needed to provide a display with a desired level of brightness .
- Retro-reflective films generally are capable of returning a significant percentage of incident light at relatively high entrance angles regardless of the rotational orientation of the sheeting about an axis perpendicular to its major surface.
- Cube corner retro-reflective film can include a body portion typically having a substantially planar base surface and a structured surface comprising a plurality of cube corner elements opposite the base surface.
- Each cube corner element can include three mutually substantially perpendicular optical faces that typically intersect at a single reference point, or apex.
- the base of the cube corner element acts as an aperture through which light is transmitted into the cube corner element.
- polymer will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend by, for example, coextrusion or reaction, including transesterification. Both block and random copolymers are included, unless indicated otherwise.
- refractive index is defined herein as the absolute refractive index of a material which is understood to be the ratio of the speed of electromagnetic radiation in free space to the speed of the radiation in that material. The refractive index can be measured using known methods and is generally measured using an Abbe Refractometer in the visible light region.
- colloidal is defined herein to mean particles (primary particles or associated primary particles) with a diameter less than about 100 nm.
- associated particles refers to a grouping of two or more primary particles that are aggregated and/or agglomerated.
- aggregation as used herein is descriptive of a strong association between primary particles which may be chemically bound to one another. The breakdown of aggregates into smaller particles is difficult to achieve.
- agglomeration as used herein is descriptive of a weak association of primary particles which may be held together by charge or polarity and can be broken down into smaller entities.
- primary particle size is defined herein as the size of a non- associated single particle.
- sol is defined herein as a dispersion or suspension of colloidal particles in a liquid phase.
- surface modified colloidal nanoparticles refers to nanoparticles, each with a modified surface such that the nanoparticles provide a stable dispersion.
- stable dispersion is defined herein as a dispersion in which the colloidal nanoparticles do not agglomerate after standing for a period of time, such as about 24 hours, under ambient conditions - e.g. room temperature (about 20-22° C), atmospheric pressure, and no extreme electromagnetic forces.
- the temi "gain" is defined herein as a measure of the improvement in brightness of a display due to a brightness enhancing film, and is a property of the optical material, and also of the geometry of the brightness enhancing film. Typically, the viewing angle decreases as the gain increases. A high gain is desired for a brightness enhancing film because improved gain provides an effective increase in the brightness of the backlight display.
- the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
- each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviations found in their respective testing measurements.
- Durable microstructured articles such as, prismatic optical films, provide brightness enhancement functionality by refraction and total internal reflection (TIR) from the protruding prismatic structures. These structures are vulnerable to damage by compression or fracture, which accounts for some amount of yield loss.
- a cover sheet is, in many cases, placed above the top prism film to protect the prism surface from damage.
- Prism structure durability is an important attribute of a prism film, and therefore it is highly desirable to be able to accurately measure this quantity.
- the previous method for measuring prism "scratch-resistance" can detect differences between different prism films, but it is not sensitive enough to handle very slight scratches or compressions.
- the inventive method and apparatus presented here provides increased sensitivity, and its results correspond closely to the visibility of scratches on a backlight. The measurement method and analysis technique is described below and in the Example section.
- Durable microstructured articles can be fonned from a polymerizable composition.
- the polymerizable composition can be a substantially solvent-free radiation curable inorganic filled organic composite.
- the organic phase of the composition may consist of a reactive diluent, oligomer, crosslinldng monomer and optionally includes a photoinitiator.
- the organic component can have a refractive index of at least 1.50 for most product applications and exhibit significant durability in the cured form. Lower refractive index compositions, those less than 1.50, are generally easier to achieve based on the vast selection of commercially available materials in this refractive index region. Lower refractive index resins have usefulness in some applications those skilled in the art would recognize. High transmittance in the visible light spectrum can also be desired.
- the composition minimizes the effect of any induced scratch while optimizing the desired optical properties and maintaining a Tg (glass transition temperature) significantly high enough to avoid other brightness enhancement product failure modes such as those described in U.S. Patent No. 5,626,800.
- the polymerizable composition can also contain inorganic oxide particles whose size is chosen to avoid significant visible light scattering.
- the inorganic oxide particle selected can impart refractive index or scratch resistance increase or both. It may be desireable to use a mix of inorganic oxide particle types to optimize an optical or material property and to lower total composition cost.
- the total composition of inorganic oxide particles, organic monomers and oligomers preferably has a refractive index greater than 1.49 or greater than 1.56.
- the cured composite composition should meet any product properties of durability, high visible light transmittance, optical clarity, high index of refraction, environmental stability, and photo stability while possessing the uncured composition requirements of low viscosity, shelf stability (composition should not change chemically over time, particles should not settle or phase separate) and are energy curable in time scales preferably less than five minutes, and the composition is substantially solvent free.
- Compositions with high multi-functional monomer amounts and reactively functionalized inorganic oxide particles maintain the form of the original master as well as the existing brightness enhancement films available from 3M, Co.
- Durable articles can include a polymerized structure having a plurality of surface modified colloidal nanoparticles.
- the durable article can be an optical element or optical product constructed of a base layer and an optical layer.
- the base layer and optical layer can be formed from the same or different polymer material.
- the polymerized structure having a plurality of surface modified colloidal nanoparticles has the advantage that it can be formed in a solvent-less system.
- Surface modified colloidal nanoparticles can be present in the polymerized structure in an amount effective to enhance the durability and/or refractive index of the article or optical element.
- the surface modified colloidal nanoparticles described herein can have a variety of desirable attributes, including for example; nanoparticle compatibility with resin systems such that the nanoparticles form stable dispersions within the resin systems, surface modification can provide reactivity of the nanoparticle with the resin system making the composite more durable, properly surface modified nanoparticles added to resin systems provide a low impact on uncured composition viscosity.
- a combination of surface modifiers can be used to manipulate the uncured and cured properties of the composition.
- Appropriately surface modified nanoparticles can improve optical and physical properties of the optical element such as, for example, improve resin mechanical strength, minimize viscosity changes while increasing solid volume loading in the resin system and maintain optical clarity while increasing solid volume loading in the resin system.
- particularly solventless systems having nanoparticle loadings described herein have viscosities in a range from 1 to 1000 cps at 85 degrees
- the surface modified colloidal nanoparticles can be oxide particles having a particle size or associated particle size of greater than 1 nm and less than 100 nm. Their measurements can be based on transmission electron miscroscopy (TEM).
- the nanoparticles can include metal oxides such as, for example, alumina, tin oxides, antimony oxides, silica, zirconia, titania, mixtures thereof, or mixed oxides thereof.
- Surface modified colloidal nanoparticles can be substantially fully condensed or crystalline.
- Silica nanoparticles can have a particle size from 5 to 75 nm or 10 to 30 nm or 20 nm.
- Silica nanoparticles can be present in the durable article or optical element in an amount from 10 to 60 wt%, or 10 to 40 wt%.
- Silicas for use in the materials of the invention are commercially available from Nalco Chemical Co. (Naperville, 111.) under the product designation NALCO COLLOIDAL SILICAS.
- silicas include
- NALCO products 1040, 1042, 1050, 1060, 2327 and 2329 Suitable fumed silicas include for example, products sold under the tradename,AEROSIL series OX-50, -130, -150, and - 200 available from DeGussa AG, (Hanau, Germany), and CAB-O-SPERSE 2095, CAB- O-SPERSE A105, CAB-O-SLL M5 available from Cabot Corp. (Tuscola, HI.). Zirconia nanoparticles can have a particle size from 5 to 50 nm, or 5 to 15 nm, or 10 nm.
- Zirconia nanoparticles can be present in the durable article or optical element in an amount from 10 to 70 wt%, or 30 to 55 wt%.
- Zirconias for use in materials of the invention are commercially available from Nalco Chemical Co. (Naperville, 111.) under the product designation NALCO OOSSOO8. Titania, antimony oxides, alumina, tin oxides, and/or mixed metal oxide nanoparticles can have a particle size or associated particle size from 5 to 50 nm, or 5 to 15 nm, or 10 nm.
- Titania, antimony oxides, alumina, tin oxides, and/or mixed metal oxide nanoparticles can be present in the durable article or optical element in an amount from 10 to 70 wt%, or 30 to 50 wt%.
- Mixed metal oxide for use in materials of the invention are commercially available from Catalysts & Chemical Industries Corp., (Kawasaki, Japan) under the product designation Optolake 3.
- Surface-treating the nano-sized particles can provide a stable dispersion in the polymeric resin.
- the surface-treatment stabilizes the nanoparticles so that the particles will be well dispersed in the polymerizable resin and results in a substantially homogeneous composition.
- the nanoparticles can be modified over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or react with the polymerizable resin during curing.
- selection of a second surface modifer can provide rheology modification (i.e., to increase or decrease the viscosity) to allow for higher nanoparticle loadings with corresponding lower viscosity.
- the second surface modifier is different than a first surface modifier.
- the nanoparticles can be treated with a surface treatment agent.
- a surface treatment agent has a first end that will attach to the particle surface (covalently, ionically or through strong physisorption) and a second end that imparts compatibility of the particle with the resin and/or reacts with resin during curing.
- surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phospohonic acids, silanes and titanates.
- the preferred type of treatment agent is determined, in part, by the chemical nature of the metal oxide surface. Silanes are preferred for silica and other for siliceous fillers. Silanes and carboxylic acids are preferred for metal oxides such as zirconia.
- the surface modification can be done either subsequent to mixing with the monomers or after mixing.
- silanes it is preferred in the case of silanes to react the silanes with the particle or nanoparticle surface before incorporation into the resin.
- the required amount of surface modifier is dependant upon several factors such particle size, particle type, modifier molecular wt, and modifier type. In general it is preferred that approximately a monolayer of modifier is attached to the surface of the particle. The attachment procedure or reaction conditions required also depend on the surface modifier used. For silanes it is preferred to surface treat at elevated temperatures under acidic or basic conditions for from 1-24 hr approximately. Surface treatment agents such as carboxylic acids do not require elevated temperatures or extended time. Representative embodiments of surface treatment agents suitable for the durable compositions include compounds such as, for example, isooctyl trimethoxy-silane,
- the surface modification of the particles in the colloidal dispersion can be accomplished in a variety of ways.
- the process involves the mixture of an inorganic dispersion with surface modifying agents.
- a co-solvent can be added at this point, such as for example, l-methoxy-2-propanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide and l-methyl-2-pyrrolidinone.
- the co-solvent can enhance the solubility of the surface modifying agents as well as the surface modified particles.
- the mixture comprising the inorganic sol and surface modifying agents is subsequently reacted at room or an elevated temperature, with or without mixing, hi one method, the mixture can be reacted at about 85 degree C for about 24 hours, resulting in the surface modified sol.
- the surface treatment of the metal oxide can preferably involve the adsorption of acidic molecules to the particle surface.
- the surface modification of the heavy metal oxide preferably takes place at room temperature.
- the surface modification of ZrO2 with silanes can be accomplished under acidic conditions or basic conditions. In one case the silanes are heated under acid conditions for a suitable period of time. At which time the dispersion is combined with aqueous ammonia (or other base).
- This method allows removal of the acid counter ion from the ZrO2 surface as well as reaction with the silane.
- the particles are precipitated from the dispersion and separated from the liquid phase.
- the surface modified particles can then be incorporated into the curable resin in various methods.
- a solvent exchange procedure is utilized whereby the resin is added to the surface modified sol, followed by removal of the water and co-solvent (if used) via evaporation, thus leaving the particles dispersed in the polyerizable resin.
- the evaporation step can be accomplished for example, via distillation, rotary evaporation or oven drying.
- the surface modified particles can also be extracted into a water immiscible solvent followed by solvent exchange, if so desired.
- another method for incorporating the surface modified nanoparticles in the polymerizable resin involves the drying of the modified particles into a powder, followed by the addition of the resin material into which the particles are dispersed.
- the drying step in this method can be accomplished by conventional means suitable for the system, such as, for example, oven drying or spray drying.
- a combination of surface modifying agents can be useful, wherein at least one of the agents has a functional group co-polymerizable with a hardenable resin.
- the polymerizing group can be ethylenically unsaturated or a cyclic function subject to ring opening polymerization.
- An ethylenically unsaturated polymerizing group can be, for example, an acrylate or methacrylate, or vinyl group.
- a cyclic functional group subject to ring opening polymerization generally contains a heteroatom such as oxygen, sulfur or nitrogen, and preferably a 3-membered ring containing oxygen such as an epoxide.
- the optical layer or micro-structured layer can be formed from a wide variety of polymeric material including the partial listing of polymeric material described herein.
- This layer can be formed from high index of refraction materials, including monomers such as high index of refraction (meth) acrylate monomers, halogenated monomers, and other such high index of refraction monomers as are known in the art. See, for example, U.S. Pat. Nos. 4,568,445; 4,721,377; 4,812,032; and 5,424,339, all incorporated by reference herein.
- the thickness of this optical or micro-structured layer can be in the range of about 10 to about 200 microns.
- Suitable polymeric resins to form the optical or micro-structured layer include the u. v. -polymerized products of acrylate and/or methacrylate monomers.
- a suitable resin is the u. v.
- the polymerizable composition can be of flowable viscosity that is low enough that air bubbles do not become entrapped in the composition and that the full microstructure geometry is obtained.
- Reactive diluents are typically mono- or di- functional monomers such as SR-339, SR-256, SR-379, SR-395, SR-440, SR-506, CD- 611, SR-212, SR-230, SR-238, and SR-247 available from Sartomer Co., Exton, PA.
- Reactive diluents with refractive index greater than 1.50, like SR-339, may be preferred.
- Oligomeric materials, particularly those with high refractive index, are also useful.
- oligomeric material contributes bulk optical and durable properties to the cured composition.
- Typical useful oligomers and oligomeric blends include CN-120, CN-104, CN-115, CN-116, CN-117, CN-118, CN-119, CN-970A60, CN-972, CN-973A80, CN- 975 available from Sartomer Co., Exton, PA and Ebecryl 1608, 3200, 3201, 3302, 3605, 3700, 3701, 608, RDX-51027, 220, 9220, 4827, 4849, 6602, 6700-20T available from
- a multi-functional crosslinker can be used to achieve a durable, high crosslink density composite matrix.
- multifunctional monomers include SR-295, SR-444, SR-351, SR-399, SR-355, and SR-368 available from Sartomer Co., Exton, PA and PETA-K, PETIA and TMPTA-N available from Surface Specialties, Smyrna, GA.
- Multi-functional monomers can be used as crosslinking agents to increase the glass transition temperature of the polymer that results from the polymerizing of the polymerizable composition.
- the glass transition temperature can be measured by methods known in the art, such as Differential Scanning Calorimetry (DSC), modulated DSC, or Dynamic Mechanical Analysis.
- the polymeric composition can be crosslinked sufficiently to provide a glass transition temperature that is greater than 45° C.
- Monomer compositions can have a melting point that is below about 50° C.
- the monomer composition can be a liquid at room temperature.
- Monomer compositions can be polymerized by conventional free radical polymerization methods.
- initiators include, organic peroxides, azo compounds, quinines, nitro compounds, acyl halides, hydrazones, mercapto compounds, pyrylium compounds, imidazoles, chlorotriazines, benzoin, benzoin alkyl ethers, di-ketones, phenones, and the like.
- commercially available photoinitiators include, but not limited to, those available commercially from Ciba Geigy under the trade designations DARACUR 1173, DAROCUR 4265, LRGACURE 651, LRGACURE 1800, IRGACURE 369,
- Phosphine oxide derivatives include LUCIRJN TPO, which is 2,4,6-trimethylbenzoy diphenyl phosphine oxide, available from BASF, Charlotte, N.C.
- a photoinitiator can be used at a concentration of about 0.1 to 10 weight percent or about 0.1 to 5 weight percent.
- the polymerizable compositions described herein can also contain one or more other useful components that, as will be appreciated by those of skill in the art, can be useful in such a polymerizable composition.
- the polymerizable composition can include one or more surfactants, pigments, fillers, polymerization inhibitors, antioxidants, anti-static agents, and other possible ingredients.
- the polymerizable composition can be formed from a hard resin.
- hard resin means that the resulting polymer exhibits an elongation at break of less than 50 or 40 or 30 or 20 or 10 or 5 percent when evaluated according to the ASTM D-882-91 procedure.
- the hard resin polymer also can exhibit a tensile modulus of greater than 100 kpsi (6.89xl0 8 pascals) when evaluated according to the ASTM D-882-91 procedure.
- the optical layer can directly contact the base layer or be optically aligned to the base layer, and can be of a size, shape and thickness allowing the optical layer to direct or concentrate the flow of light.
- the optical layer can have a structured or micro- structured surface that can have any of a number of useful patterns as described below and shown in the FIGURES and EXAMPLES.
- the micro-structured surface can be a plurality of parallel longitudinal ridges extending along a length or width of the film. These ridges can be formed from a plurality of prism apexes. These apexes can be sharp, rounded or flattened or truncated.
- a useful microstructure is a regular prismatic pattern that can act as a totally internal reflecting film for use as a brightness enhancement film.
- Another useful microstructure is a corner-cube prismatic pattern that can act as a retro-reflecting film or element for use as reflecting film.
- Another useful microstructure is a prismatic pattern that can act as an optical element for use in an optical display.
- Another useful microstructure is a prismatic pattern that can act as an optical turning film or element for use in an optical display.
- the base layer can be of a nature and composition suitable for use in an optical product, i.e. a product designed to control the flow of light.
- any material can be used as a base material as long as the material is sufficiently optically clear and is structurally strong enough to be assembled into or used within a particular optical product.
- a base material can be chosen that has sufficient resistance to temperature and aging that performance of the optical product is not compromised over time.
- the particular chemical composition and thickness of the base material for any optical product can depend on the requirements of the particular optical product that is being constructed. That is, balancing the needs for strength, clarity, temperature resistance, surface energy, adherence to the optical layer, among others.
- Useful base materials include, for example, styrene-acrylonitrile, cellulose acetate butyrate, cellulose acetate propionate, cellulose triacetate, polyether sulfone, polymethyl methacrylate, polyurethane, polyester, polycarbonate, polyvinyl chloride, polystyrene, polyethylene naphthalate, copolymers or blends based on naphthalene dicarboxyhc acids, polycyclo-olefins, polyimides, and glass.
- the base material can contain mixtures or combinations of these materials.
- the base may be multi-layered or may contain a dispersed phase suspended or dispersed in a continuous phase.
- examples of preferred base materials include polyethylene terephthalate (PET) and polycarbonate.
- PET polyethylene terephthalate
- examples of useful PET films include photograde polyethylene terephthalate and MELL EXTM PET available from
- base materials can be optically active, and can act as polarizing materials.
- a number of bases, also referred to herein as films or substrates, are known in the optical product art to be useful as polarizing materials.
- Polarization of light through a film can be accomplished, for example, by the inclusion of dichroic polarizers in a film material that selectively absorbs passing light.
- Light polarization can also be achieved by including inorganic materials such as aligned mica chips or by a discontinuous phase dispersed within a continuous film, such as droplets of light modulating liquid crystals dispersed within a continuous film.
- a film can be prepared from microfine layers of different materials.
- the polarizing materials within the film can be aligned into a polarizing orientation, for example, by employing methods such as stretching the film, applying electric or magnetic fields, and coating techniques.
- polarizing films include those described in U.S. Pat. Nos. 5,825,543 and 5,783,120, each of which are incorporated herein by reference.
- the use of these polarizer films in combination with a brightness enhancement film has been described in U.S. Pat. No. 6,111,696, incorporated by reference herein.
- a second example of a polarizing film that can be used as a base are those films described in U.S. Pat. No. 5,882,774, also incorporated herein by reference.
- DBEF Dual Brightness Enhancement Film
- base materials are not exclusive, and as will be appreciated by those of skill in the art, other polarizing and non-polarizing films can also be useful as the base for the optical products of the invention. These base materials can be combined with any number of other films including, for example, polarizing films to form multilayer structures.
- additional base materials can include those films described in
- U.S. Pat. Nos. 5,612,820 and 5,486,949 can also depend on the above-described requirements of the optical product.
- Durable microstructure-bearing articles can be constructed in a variety of forms, including those having a series of alternating tips and grooves sufficient to produce a totally internal reflecting film.
- An example of such a film is a brightness enhancing film having a regular repeating pattern of symmetrical tips and grooves, while other examples have patterns in which the tips and grooves are not symmetrical.
- Examples of microstructure bearing articles useful as brightness enhancing films are described by U.S. Pat. Nos. 5,175,030 and 5,183,597, which are both incorporated herein by reference.
- a microstructure-bearing article can be prepared by a method including the steps of (a) preparing a polymerizable composition; (b) depositing the polymerizable composition onto a master negative microstructured molding surface in an amount barely sufficient to fill the cavities of the master; (c) filling the cavities by moving a bead of the polymerizable composition between a preformed base and the master, at least one of which is flexible; and (d) curing the composition.
- the master can be metallic, such as nickel, nickel-plated copper or brass, or can be a thermoplastic material that is stable under polymerization conditions and that preferably has a surface energy that permits clean removal of the polymerized material from the master.
- micro-structure topography can be similar to the molding process described in U.S. Patent No. 5,691,846 which is incorporated by reference herein.
- the micro-structure article according to the invention can be formed from a continuous process at any desired length such as, for example, 5, 10,
- the durable article can be used in applications needing durable micro- structured film including, for example, brightness enhancing films.
- the structure of these durable brightness enhancing films can include a wide variety of micro-structured films such as, for example, U.S. Patent No. 5,771,328, U.S. Patent No. 5,917,664, U.S. Patent
- a backlit liquid crystal display generally indicated at 10 in FIG. 1 includes a brightness enhancement film 11 of the present invention that can be positioned between a diffuser 12 and a liquid crystal display panel 14.
- the backlit liquid crystal display can also includes a light source 16 such as a fluorescent lamp, a light guide 18 for transporting light for reflection toward the liquid crystal display panel 14, and a white reflector 20 for reflecting light also toward the liquid crystal display panel.
- the brightness enhancement film 11 collimates light emitted from the light guide 18 thereby increasing the brightness of the liquid crystal display panel 14.
- the increased brightness enables a sharper image to be produced by the liquid crystal display panel and allows the power of the light source 16 to be reduced to produce a selected brightness.
- the brightness enhancement film 11 in the backlit liquid crystal display is useful in equipment such as computer displays (laptop displays and computer monitors), televisions, video recorders, mobile communication devices, handheld devices (i.e. cellphone, PDA), automobile and avionic instrument displays, and the like, represented by reference character 21. While FIG. 1 shows an edge lit system, it is understood that the lighting system could directly lighting the film 11 such as, for example, as used in transmissive LCD televisions.
- the brightness enhancement fihn 11 includes an array of prisms typified by prisms 22, 24, 26, and 28, as illustrated in FIG. 2. Each prism, for example, such as prism
- the prisms 22, 24, 26, and 28 can be formed on a body portion 34 that has a first surface 36 on which the prisms are formed and a second surface 38 that is substantially flat or planar and opposite the first surface.
- a linear array of regular right prisms can provide both optical performance and ease of manufacture.
- right prisms it is meant that the apex angle ⁇ is approximately 90°, but can also range from approximately 70° to 120° or from approximately 80° to 100°.
- the prism facets need not be identical, and the prisms may be tilted with respect to each other.
- FIGS. 3-9 illustrate representative embodiments of a construction for an optical element. It should be noted that these drawings are not to scale and that, in particular, the size of the structured surface is greatly exaggerated for illustrative purposes.
- the construction of the optical element can include combinations or two or more of the described embodiments below. Referring to FIG.
- the film 130 includes a first surface 132 and an opposing structured surface 134 which includes a plurality of substantially linearly extending prism elements 136.
- Each prism element 136 has a first side surface 138 and a second side surface 138', the top edges of which intersect to define the peak, or apex 142 of the prism element 136.
- the bottom edges of side surfaces 138, 138' of adjacent prism elements 136 intersect to form a linearly extending groove 144 between prism elements.
- the structured surface 134 of film 130 maybe described as having a plurality of alternating zones of prism elements having pealcs which are spaced at different distances from a common reference plane.
- the common reference plane may be arbitrarily selected.
- One convenient example of a common reference plane is the plane which contains first surface 132; another is the plane defined by the bottom of the lower most grooves of the structured surface, indicated by dashed line 139. In the embodiment illustrated in FIG.
- the shorter prism elements measure approximately 50 microns in width and approximately 25 microns in height, measured from dashed line 139, while the taller prism elements measure approximately 50 microns in width and approximately 26 microns in height.
- the width of the zone which includes the taller prism elements can measure between about 1 micron and 300 microns.
- the width of the zone which includes the shorter prism elements is not critical and can measures between 200 microns and 4000 microns. In any given embodiment the zone of shorter prism elements can be at least as wide as the zone of taller prism elements. It will be appreciated by one of ordinary skill in the art that the article depicted in FIG. 3 is merely exemplary and is not intended to limit the scope of the present invention.
- the height or width of the prism elements may be changed within practicable limits—it is practicable to machine precise prisms in ranges extending from about 1 micron to about 200 microns.
- the dihedral angles may be changed or the prism axis may be tilted to achieve a desired optical effect.
- the width of the first zone can be less than about 200 to 300 microns.
- variable height structured surface may also be implemented by varying the height of one or more prism elements along its linear extent to create alternating zones which include portions of prism elements having peaks disposed at varying heights above a common reference plane.
- FIG. 4 illustrates another embodiment of the optical element similar to FIG.
- the film 150 includes a structured surface 152 which has a zone of relatively shorter prism elements 154 separated by a zone including a single taller prism element 156.
- the taller prism element limits the physical proximity of a second sheet of film to structured surface 152, thereby reducing the likelihood of a visible wet-out condition. It has been dete ⁇ nined that the human eye is sensitive to changes in facet heights in light directing films and that relatively wide zones of taller prism elements will appear as visible lines on the surface of a film. While this does not materially affect the optical performance of the film, the lines may be undesirable in certain commercial circumstances.
- FIG. 5 is a representative example of another embodiment of an optical element in which the prism elements are approximately the same size but are arranged in a repeating stair step or ramp pattern.
- the film 160 depicted in FIG. 5 includes a first surface 162 and an opposing structured surface 164 including a plurality of substantially linear prism elements 166.
- Each prism element has opposing lateral faces 168, 168' which intersect at their upper edge to define the prism peaks 170.
- the dihedral angle defined by opposing lateral faces 168, 168' measures approximately 90 degrees.
- FIG. 6 illustrates a further embodiment of an optical element.
- the film 180 disclosed in FIG. 6 includes a first surface 182 and an opposing structured surface 184.
- FIG. 7 shows another embodiment of an optical element for providing a soft cutoff.
- FIG. 7 shows a brightness enhancement film, designated generally as 240, according to the invention.
- Brightness enhancement film 240 includes a substrate 242 and a structured surface material 244.
- Substrate 242 is can generally be a polyester material and structured surface material 244 can be an ultraviolet-cured acrylic or other polymeric material discussed herein.
- the exterior surface of substrate 242 is preferably flat, but could have structures as well.
- Structured surface material 244 has a plurality of prisms such as prisms 246, 248, and 250, formed thereon.
- Prisms 246, 248, and 250 have peaks 252, 254, and 256, respectively. All of peaks 252, 254, and 256 have peak or prism angles of preferably
- brightness enhancement film 240 increases the apparent on axis brightness of a backlight by reflecting and recycling some of the light and refracting the remainder like prior art brightness enhancement film, but with the prisms canted in alternating directions. The effect of canting the prisms is to increase the size of the output light cone.
- the brightness enhancement article 330 features a flexible, base layer 332 having a pair of opposed surfaces 334, 336, both of which are integrally formed with base layer 332.
- Surface 334 features a series of protruding light-diffusing elements 338. These elements may be in the form of "bumps" in the surface made of the same material as layer 332.
- Surface 336 features an array of linear prisms having blunted or rounded peaks 340 integrally formed with base layer 332.
- peaks are characterized by a chord width 342, cross-sectional pitch width 344, radius of curvature 346, and root angle 348 in which the chord width is equal to about 20-40% of the cross-sectional pitch width and the radius of curvature is equal to about 20-50% of the cross-sectional pitch width.
- the root angle ranges from about 70-110 degrees, or from about 85-95 degrees, with root angles of about 90 degrees being preferred.
- the placement of the prisms within the a ⁇ ay is selected to maximize the desired optical performance.
- Rounded prism apex brightness enhancement articles usually suffer from decreased gain. However, the addition of high refractive index surface modified colloidal nanoparticles can offset the lost gain from the rounded prism apex brightness enhancement articles.
- the brightness enhancement article 430 features a flexible, base layer 432 having a pair of opposed surfaces 434, 436, both of which are integrally formed with base layer 432.
- Surface 434 features a series of protruding light-diffusing elements 438. These elements may be in the form of "flat bumps" in the surface made of the same material as layer 432.
- Surface 436 features an array of linear prisms having flattened or planar peaks 440 integrally formed with base layer 432. These peaks are characterized by a flattened width 442 and cross-sectional pitch width 444, in which the flattened width can be equal to about 0-30% of the cross-sectional pitch width.
- TJJR frustrated total internal reflection
- the lightguide has a wedge shape, and light rays incident on a thick edge of the lightguide are totally internally reflected until achieving critical angle relative to the top and bottom surfaces of the lightguide. These sub-critical angle light rays are then extracted, or more succinctly refract from the lightguide, at a glancing angle to the output surface.
- these light rays must then be turned substantially parallel to a viewing, or output, axis of the display device. This turning is usually accomplished using a turning lens or turning film.
- FIGs. 10-12 illustrate an illumination device including a turning film.
- the turning film can include the inventive material disclosed herein for form a durable turning film.
- a turning lens or turning film typically includes prism structures formed on an input surface, and the input surface is disposed adjacent the lightguide. The light rays exiting the lightguide at the glancing angle, usually less than 30 degrees to the output surface, encounter the prism structures. The light rays are refracted by a first surface of the prism structures and are reflected by a second surface of the prism structures such that they are directed by the turning lens or film in the desired direction, e.g., substantially parallel to a viewing axis of the display. Referring to FIG.
- an illumination system 510 includes optically coupled a light source 512; a light source reflector 514; a lightguide 516 with an output surface 518, a back surface 520, an input surface 521 and an end surface 522; a reflector 524 adjacent the back surface 520; a first light redirecting element 526 with an input surface 528 and an output surface 530; a second light redirecting element 532; and a reflective polarizer 534.
- the lightguide 516 may be a wedge or a modification thereof.
- the purpose of the lightguide is to provide for the uniform distribution of light from the light source 512 over an area much larger than the light source 512, and more particularly, substantially over an entire area formed by output surface 518.
- the lightguide 516 further preferably accomplishes these tasks in a compact, thin package.
- the light source 512 may be a CCFL that is edge coupled to the input surface 521 of the lightguide 516, and the lamp reflector 514 may be a reflective film that wraps around the light source 512 forming a lamp cavity.
- the reflector 524 backs the lightguide 516 and may be an efficient back reflector, e.g., a lambertian or a specular film or a combination.
- the edge-coupled light propagates from the input surface 521 toward the end surface 522, confined by TLR. The light is extracted from the lightguide 516 by frustration of the TLR.
- a ray confined within the lightguide 516 increases its angle of incidence relative to the plane of the top and bottom walls, due to the wedge angle, with each TIR bounce.
- the light eventually refracts out of each of the output surface 518 and the back surface 520 because it is no longer contained by TIR.
- the light refracting out of the back surface 520 is either specularly or diffusely reflected by the reflector 524 back toward and largely through the lightguide 516.
- the first light redirecting element 526 is arranged to redirect the light rays exiting the output surface 518 along a direction substantially parallel to a preferred viewing direction.
- the preferred viewing direction may be normal to the output surface 518, but will more typically be at some angle to the output surface 518. As shown in FIG.
- the first light redirecting element 526 is a light fransmissive optical fihn where the output surface 530 is substantially planar and the input surface 528 is formed with an array 536 of prisms 538, 540 and 542.
- the second light redirecting element 532 may also be a light fransmissive film, for example a brightness enhancing film such as the 3M Brightness Enhancement Film product (sold as BEFIII) available from Minnesota Mining and Manufacturing Company, St. Paul, Minn.
- the reflective polarizer 534 may be an inorganic, polymeric, cholesteric liquid crystal reflective polarizer or fihn.
- each prism 538, 540 and 542 may be formed with differing side angles as compared to its respective neighbor prisms. That is, prism 540 may be formed with different side angles (angles C and D) than prism 538 (angles A and B), and prism 542 (angles E and F). As shown, prisms 538 have a prism angle, i.e., the included angle, equal to the sum of the angles A and B.
- prisms 540 have a prism angle equal to the sum of the angles C and D
- prisms 542 have a prism angle equal to the sum of the angles E and F.
- array 536 is shown to include three different prism structures based upon different prism angle, it should be appreciated that virtually any number of different prisms may be used.
- Prisms 538, 540 and 542 may also be formed with a common prism angle but with a varied prism orientation.
- a prism axis " £ " is illustrated in FIG. 11 for prism 538.
- the prism axis £ may be arranged normal to the output surface 530, as shown for prism 538, or at an angle to the output surface either toward or away from the light source as illustrated by phantom axes " t “ and “ £ “ “, respectively, for prisms 540 and 542.
- Prisms 538, 540 and 542 may be arranged within a ⁇ ay 536 as shown in FIG. 11 in a regular repeating pattern or clusters 543 of prisms, and while the a ⁇ ay 536 is not shown to have like prisms adjacent like prisms, such a configuration may also be used.
- the prisms 538, 540 and 542 may change continuously from a first prism configuration, such as prism configuration 538, to a second prism configuration, such as prism configuration 540, and so on.
- the prism configuration may change in a gradient manner from the first prism configuration to the second prism configuration.
- the prisms may change in a step-wise manner, similar to the configuration shown in FIG. 11.
- the prisms have a prism pitch, which is selected to be smaller than the spatial ripple frequency.
- the clusters may have a regular cluster pitch.
- the prism array can be symmetrical as shown in FIG. 11 or the prism array can be non-symmetrical. While the array 536 shown in FIG.
- an array of prisms such as array 536' shown in FIG. 12 formed in light redirecting element 526', may be used.
- prisms 538' for example, has angle A' unequal to angle B'.
- angle C is unequal to angle A' and angle D'
- angle E' is unequal to either of angle A', angle C or angle F'.
- the array 536' may be advantageously formed using a single diamond cutting tool of a predetermined angle, and tilting the tool for each cut producing prisms of differing prism angle and symmetry.
- One purpose of the prism side angle variation is to spread and add variable amounts of optical power into the first light redirecting element 526.
- the varying configuration of prisms 538, 540 and 542 serves to provide substantially uniform sampling of the input aperture of the lightguide, which minimizes non-uniformities in the light extracted from the lightguide 516.
- FIG. 13 is a schematic flow diagram illustrating one method 600 to determine scratch contrast ratio.
- Tins method generally involves providing a microstructured article 610, forming a scratch in the microstructured article 620, illuminating the scratched optical film 630, measuring a plurality of scratch contrast ratios 640, and then determining a maximum scratch contrast ratio 650.
- the microstructured article can be any microstructured article described herein.
- Scratch creation 620 can be accomplished by any number of means. In general, to evaluate the durability of a microstructured article a consistent set of parameters are used to create the scratch.
- the scratched optical film can be illuminated 630 by any number of light sources such as, for example, a backlight.
- the light source can be a diffuse light source providing a near-lambertian light.
- a detector such as, for example, a camera can capture an optical image of the scratched microstructure surface and provide a measurement of a scratch contrast ratio along the length of the scratch 640.
- the detector and/or scratched film can be rotated such that the detector is off-axis with the scratched film in order to obtain the greatest contrast ratio.
- the contrast ratio data can then be manipulated (i.e., integrated, normalized, or the like) to determine a maximum contrast ratio 650 for the scratched film based the contrast ratio data provided by the detector.
- the data can be exported as an array of luminance values.
- One straightforward way to calculate the optical contrast of the scratches is to extract a luminance line profile across each scratch.
- This type of averaging increases sensitivity to spatially extended features that are of very low contrast but nevertheless are easily detected by the human image-processing mechanism.
- the averaging direction be the same as the scratch. Otherwise the scratch peak luminance is attenuated by being spread wider across the luminance profile. If a sample contains several scratches that are not at identical angles, then it is not possible to obtain an accurately averaged luminance peak value for each individual scratch using only one averaging direction. Therefore, the averaging algorithm carries out multiple one- dimensional averaging passes along different directions, recording the resulting profile for each. Then the highest scratch contrast ratio value calculated for each scratch is recorded.
- contrast ratio values that are calculated by the algorithm are plotted along with a composite, optimally ID-averaged profile. If the background is noisy, the algorithm may identify some spikes or bumps in the data as scratches even if they are not, and therefore it is useful to plot both the CR values and the composite luminance profile. By looking at the composite profile, one can quite easily determine which calculated contrast ratios values are from real scratches, and which ones are from other profile artifacts.
- One embodiment of durable optical film includes a polymerized optical film structure having a microstructured surface and a scratch contrast ratio value in a range of 1.0 to 1.15, or 1.0 to 1.12, or 1.0 to 1.10, or 1.0 to 1.05.
- the optical film can be formed from any of the material described herein.
- the optical film can include a plurality of surface modified colloidal nanoparticles of silica, zirconia, or mixtures thereof, as described herein.
- the optical film can have any microstructure described herein.
- the microstructure includes a plurality of ridges extending along a first surface. These ridges can be rounded to a radius in a range of 4 to 7 micrometers.
- a durable optical film includes a polymerized optical film structure having a microstructured surface including a plurality of rounded prism apexes extending along a first surface and a scratch contrast ratio value in a range of 1.0 to 1.65, or 1.0 to 1.4, or 1.0 to 1.10.
- the optical film can include a plurality of surface modified colloidal nanoparticles of silica, zirconia, or mixtures thereof, as described herein.
- the optical film can have any microstructure described herein.
- the microstructure includes a plurality of ridges extending along a first surface. These ridges can be rounded to a radius in a range of 4 to 7 micrometers.
- a durable optical film in another illustrative embodiment, includes a polymerized optical film structure having a microstructured surface including a plurality of surface modified colloidal nanoparticles of silica, zirconia, or mixtures thereof and a scratch contrast ratio value in a range of 1.0 to 1.65, or 1.0 to 1.4, or 1.0 to 1.10.
- the nanoparticles such as, for example, silica
- the durable optical film can include nanoparticles such as, for example, silica, from 10 to 60 wt% of the microstructured surface.
- the optical film can have any microstructure described herein.
- the microstructure includes a plurality of ridges extending along a first surface. These ridges can be rounded to a radius in a range of 4 to 7 micrometers.
- FIG. 14 is a schematic diagram of an illustrative apparatus 700 for determining scratch contrast ratio.
- the apparatus 700 generally includes a light source or backlight 710, a polymerized optical film structure having a microstructured surface and a scratch on the microstructured surface 720 disposed on the backlight 710, a detector 730 configured to acquire image data from the scratch.
- the detector 730 being disposed above the optical film 720 and a computer 740 configured to manipulate the image data and calculate a maximum contrast ratio for the scratched optical film 720.
- the light source 710 can be a diffuse or near-lambertian light source such as, for example, a Teflon light box.
- the detector 730 can be any device able to capture an optical image of the scratched microstructured surface and provide the optical image as data to a computer 740 for data manipulation.
- the detector 730 can be spaced away from the scratched microstructure surface any useful distance such as, for example, 5 to 40 cm, or 10 to 20 cm.
- the optical fihn 720 has an axis a-a orthogonal to the microstructured surface of the optical film 720.
- the detector 730 is capable of capturing image data off- axis by any angle ⁇ . In some embodiments, the scratch is most visible or detectable from an off-axis angle.
- This angle can be from 1 to 89 degrees, or from 20 to 70 degrees, or from 35 to 60 degrees, or from 40 to 50 degrees.
- the detector 730, and/or light source 720 (with associated platform) can rotate or move to achieve the angle ⁇ .
- the present invention should not be considered limited to the particular examples described herein, but rather should be understood to cover all aspects of the invention as fairly set out in the attached claims. Various modifications, equivalent processes, as well as numerous structures to which the present invention can be applicable will be readily apparent to those of skill in the art to which the present invention is directed upon review of the instant specification.
- micro-prismatic structures have a 90° apex angle as defined by the slope of the sides of the prisms with the mean distance between adjacent apices being about 50 micrometers.
- the prism vertices or apexes have a 7 micron radius rounding. All proportions shown in the examples are percent by weight unless otherwise specified.
- the process conditions are 0.002 mm radius probe tip with 160 degree included angles.
- the probe tip will be dragged across the sample prism film perpendicular to the prism groove direction or ridge length under a fixed load of 50 grams and at a speed of 10 feet per minute.
- the prism film sample is placed in the Plexiglas sample holder, making sure that the grooves are placed perpendicular to the stylus movement direction and secured with Scotch Magic Tape 810.
- the sample holder is then placed into the alignment frame and then onto a stage for scratch creation. Level the probe holder. Attach the 50 gram weight to the stylus, and place the diamond stylus in probe holder. Turn on the ANORAD
- Intelligent Axis Control System software enter the control speed (10 feet/min) and scratch length (0.25 inch.) Allow the ANORAD system to create the first scratch. Then wipe the probe tip with ethanol. Move the Plexiglas holder containing the scratched sample to the next position for scratching. Proceed as above to form another scratch about 1/8" from the first scratch to form a scratched sample having two scratch lines. Repeat these steps for each sample.
- Optical Scratch Measurement This test method describes an optical measurements procedure that evaluates a scratch formed on prism film with a stylus. The following materials and equipment are commonly commercially available unless otherwise noted. Optical Table Incandescent Light Source (Fiber-Lite Model No.
- the image will be stored in the Radiant software database.
- rotate the goinometer stage by entering a value of 1.000 in the position box and capture another image.
- images at angle ranges between 40 degrees to 50 degrees are taken at one degree increments. For additional samples, repeat these steps.
- Export the data files of each image captured in the Radiant software database by converting the files as a Luminance type file and export the Luminance file for each image for further data processing.
- the data can be exported as an array of luminance values.
- One straightforward way to calculate the optical contrast of the scratches is to extract a luminance line profile across each scratch. In some measurements there is enough noise in the data such that in any given line profile, the luminance spikes due to very faint scratches may be no larger than from random noise features. Therefore it may be necessary to apply some type of noise-reduction scheme to the data - ideally one that strongly reduces noise due to localized point defects without attenuating the luminance spike of the scratches. This can be accomplished by using a one-dimensional averaging method. Contrast ratio (CR) refers to a measure of visibility of the scratch on the prism fihn on a backlit source.
- Contrast ratio is a measure of the luminance of the light emitting from the scratched area compared to the background or non-scratched area. A contrast ratio of 1.00 is not visible to the human eye. The greater the value of the contrast ratio, the easier the scratch is to detect visually. The contrast ratio value can change as a function of viewing angle, and thus, the maximum contrast ratio value across all angles is selected as the contrast ratio for each sample. Since a scratch is a one dimensional feature, averaging along the direction of the scratch does not reduce the luminance peak of the scratch. However, this process effectively attenuates any 2-dimensional features because they have only limited extent along the averaging direction.
- This type of averaging increases sensitivity to spatially extended features that are of very low contrast but nevertheless are easily detected by the human image-processing mechanism.
- the averaging direction be the same as the scratch. Otherwise the scratch peak lummance is attenuated by being spread wider across the luminance profile. If a sample contains several scratches that are not at identical angles, then it is not possible to obtain an accurately averaged luminance peak value for each individual scratch using only one averaging direction. Therefore, the averaging algorithm can ⁇ es out multiple one- dimensional averaging passes along different directions, recording the resulting profile for each. Then the highest scratch contrast ratio value calculated for each scratch is recorded.
- An exemplary algorithm for calculating contrast ratio from the exported luminance data includes the following: 1) Load the luminance data file into memory. 2) Clip the file to exclude anything beyond the ends of the scratch lines. 3) Determine the angle at which the scratches are running in the sample with respect to the x and y axes of the camera/luminance file. 4) Sum (integrate) the luminance values in every line of pixels parallel to the scratches and record the individual numbers. These summation values can be relatively large numbers when the sum is performed on an area of the film that is scratched.
- Example 1 Nalco 2327(1200.00 g) was charged to a 2 liter Ehrlenmeyer flask. l-Methoxy-2- propanol (1350.3 g), Silane A174 (57.09 g), and PEG2TES (28.19 g) were mixed together and added to the colloidal dispersion while stirring. The contents of the flask were poured into three 32oz sealed jars. The jars were heated at 80°C for 16 hours. This resulted in a clear, low viscosity dispersion of surface modified colloidal silica nanoparticles.
- PEG2TES refers to N-(3-triethoxysilylpropyl) methoxyethoxyethyl carbamate.
- the resin dispersion contained approximately 38.5% SiO2 and approximately 2 % 1- methoxy-2-propanol as measured by gas chromatography. One percent by weight of Darocure 1173 was added to this resin dispersion. Tins example was photo-cured at 2 J/cm 2 .
- Example 2 Nalco 2327(224.17 lb) was charged to a large kettle. l-Methoxy-2-propanol (252.19 lb), Silane A174 (9.98 lb.), Silquest A1230 (8.62 lb.), and Prostab 5198 (1.81 g) was prepared and added to the Nalco 2327 while stirring. The kettle was sealed and heated to 90°C for 16 hours. This resulted in a clear, low viscosity dispersion of modified silica. 230 lbs. of water and alcohol were then removed from kettle via evaporation followed by the addition of 201.71 lbs of l-Methoxy-2-propanol into the kettle.
- Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 2 J/cm 2 .
- Example 4 0.5%) Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 1 J/cm 2 .
- Example 6 0.5% Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 2 J/cm 2 .
- Example 6 0.5% Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 2 J/cm 2 .
- Example 2 0.5%) Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 0.64 J/cm 2 .
- Example 2 0.5% Lucirin TPO-L was added per organic component to an aliquot of Example 2. This example was photo-cured at 1.28 J/cm 2 .
- Example 3 was diluted with SR 339 until the SiO2 content dropped to 33 wt. %. 1% Lucirin TPO-L per organic component was added to this dilution. This example was photo-cured at 2 J/cm 2 .
- Example 9
- Lucirin TPO-L was added to a 20/60/20 wt. % mix of SR339/RDX-51027/SR351. This example was photo-cured at 2 J/cm 2 .
- Comparative Example A VikuitiTM BEF II 90/50 film (BEF II), sold by 3M, St Paul, MN, is a microreplicated prismatic structured brightness enhancement film having a prism angle of 90 degree and a pitch (distance between prism peaks) of 50 micrometers. The prism peaks in Comparative Example A are sharp.
- Comparative Example B VikuitiTM Rounded Brightness Enhancement Film (RBEF) film, sold by 3M, St Paul, MN, is a microreplicated prismatic structured brightness enhancement film having a prism angle of 90 degree and a pitch of 50 micrometers.
- the prism peaks in Comparative Example B are rounded and have a peak radius of 8 microns.
- Examples 1 through 9 illustrate articles that posses scratch resistance properties. As described above, a scratch having a contrast ratio value of 1.00 is not visible to a human eye. Comparative Example A posses moderate scratch resistance while Comparative Example B shows poor scratch resistance.
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EP20100185280 EP2270558A2 (en) | 2003-09-12 | 2004-09-13 | Brightness enhancing film |
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US10/662,085 US7074463B2 (en) | 2003-09-12 | 2003-09-12 | Durable optical element |
US10/939,184 US7179513B2 (en) | 2003-09-12 | 2004-09-10 | Durable optical element |
PCT/US2004/029603 WO2005026793A1 (en) | 2003-09-12 | 2004-09-13 | Durable optical element |
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EP1664860A1 true EP1664860A1 (en) | 2006-06-07 |
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JP (1) | JP2007505359A (enrdf_load_stackoverflow) |
KR (1) | KR20060121919A (enrdf_load_stackoverflow) |
WO (1) | WO2005026793A1 (enrdf_load_stackoverflow) |
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WO2006133458A2 (en) | 2005-06-09 | 2006-12-14 | Ubright Optronics Corporation | Moire reducing optical substrates with irregular prism structures |
TWI417324B (zh) * | 2005-11-15 | 2013-12-01 | 3M Innovative Properties Co | 增亮膜及無機奈米粒子之表面處理方法 |
TWI339743B (en) * | 2005-12-06 | 2011-04-01 | Ubright Optronics Corp | A luminance enhancement film and manufacturing method thereof and method for enhancing brightness of an image |
JP5665214B2 (ja) | 2006-06-30 | 2015-02-04 | ユーブライト オプトロニクス コーポレイション | 光学上の欠陥を隠す構造を有する輝度増加光学基板 |
WO2008023612A1 (fr) * | 2006-08-25 | 2008-02-28 | National University Corporation The University Of Electro-Communications | Composition photosensible comprenant une microparticule composite organique/zircone |
WO2008120416A1 (ja) * | 2007-02-27 | 2008-10-09 | Konica Minolta Opto, Inc. | 光学用複合材料、その製造方法、及び光学用複合材料を用いた光学素子 |
JP2008249962A (ja) * | 2007-03-30 | 2008-10-16 | Nippon Carbide Ind Co Inc | 再帰反射シート |
KR101588073B1 (ko) | 2008-12-15 | 2016-01-22 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 표면 처리를 포함하는 고굴절률 무기 산화물 나노입자, 중합성 수지, 및 용품 |
US7957621B2 (en) * | 2008-12-17 | 2011-06-07 | 3M Innovative Properties Company | Light extraction film with nanoparticle coatings |
JP2018180099A (ja) | 2017-04-05 | 2018-11-15 | スリーエム イノベイティブ プロパティズ カンパニー | 親水性ハードコート積層体、及びその製造方法 |
KR102038143B1 (ko) * | 2018-04-16 | 2019-11-26 | 박성민 | 탈부착 사용이 가능한 빛 반사패치 |
WO2021152411A1 (en) * | 2020-01-29 | 2021-08-05 | 3M Innovative Properties Company | Retroreflective element and retroreflective film |
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JPH08217991A (ja) * | 1995-02-02 | 1996-08-27 | Minnesota Mining & Mfg Co <3M> | 放射線硬化性材料 |
US5626800A (en) * | 1995-02-03 | 1997-05-06 | Minnesota Mining And Manufacturing Company | Prevention of groove tip deformation in brightness enhancement film |
US5760126A (en) * | 1996-12-20 | 1998-06-02 | Minnesota Mining And Manufacturing Company | Aqueous fluorochemical compositions and abrasion-resistant coatings therefrom |
US5898523A (en) * | 1997-07-02 | 1999-04-27 | Minnesota Mining & Manufacturing Company | Tiled retroreflective sheeting composed of highly canted cube corner elements |
JP2001133607A (ja) * | 1999-08-25 | 2001-05-18 | Sumitomo Chem Co Ltd | 光散乱層、光散乱板、カラーフィルタおよびそれを用いた液晶表示装置 |
US6356391B1 (en) * | 1999-10-08 | 2002-03-12 | 3M Innovative Properties Company | Optical film with variable angle prisms |
US6896958B1 (en) * | 2000-11-29 | 2005-05-24 | Nanophase Technologies Corporation | Substantially transparent, abrasion-resistant films containing surface-treated nanocrystalline particles |
US6962946B2 (en) * | 2001-11-21 | 2005-11-08 | 3M Innovative Properties Company | Nanoparticles having a rutile-like crystalline phase and method of preparing same |
JP4177637B2 (ja) * | 2002-10-28 | 2008-11-05 | Tdk株式会社 | ノングレア処理された物体の製造方法 |
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- 2004-09-13 EP EP04788684A patent/EP1664860A1/en not_active Withdrawn
- 2004-09-13 JP JP2006526317A patent/JP2007505359A/ja active Pending
- 2004-09-13 KR KR1020067006977A patent/KR20060121919A/ko not_active Ceased
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