multilayer optical films

专利摘要:
MULTIPLE LAYER OPTICAL FILMSThe present invention relates to a multilayer optical film (10) comprising optical layers that reflect at least 50 percent of UV light incident on specified wavelength bands. The modalities of multilayer optical films are useful, for example, as a UV protective coating.
公开号:BR112012011654A2
申请号:R112012011654-1
申请日:2010-11-11
公开日:2020-08-25
发明作者:Timothy J. Hebrink；Mark A. Roehrig；Mark D. Weigel
申请人:3M Innovantive Properties Company；
IPC主号:

专利说明:

e) and 1/58 “MULTIPLE LAYER OPTICAL FILMS” Background The degradation by ultraviolet (UV) light of materials is a significant problem for many materials.
Although there are a number of UV protective materials known in the art, there is a need for further improvements in such materials, and preferably more effective UV light blocking materials, especially those that provide long-term protection (i.e., at least 10 years) for articles intended to have a long service life outdoors.
In particular, materials (for example, films) made with polymers that contain aromatic compounds (for example, aromatic polyesters, aromatic polycarbonates, polystyrenes, 2.6 naphthalate polyethylene, and certain polyimides (for example, those - available under the trade names) “ULTEM” with Sabic Innovative Plastics, Pittsfield, MA, and “KAPTON” with El
DuPont de Nemours, Wilmington, DE, USA) need: substantial UV protection to last more than 10 years outdoors.
Summary In one aspect, the present description describes a UV-stable multilayer optical film comprising at least a plurality of first and second optical layers that collectively reflect at least 50 (in some embodiments, at least 55, 60, 65, 70 , 75, 80, 85, 90, 95, 96, 97, or even at least 98) percent of incident UV light across a wavelength range of at least 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, | 90, 95, or even at least 100) nanometers in a wavelength range of | at least 300 nanometers to 400 nanometers, some of which at least one of the first or second optical layers (in some modalities at least 50] percent by number of first and / or second optical layers, in some modalities all from at least first or second layers) comprises a UV absorber.
In another aspect, the present description describes a multilayer optical film that comprises a plurality of at least first and second optical layers that have a main surface and collectively reflect at least 50 (in some embodiments, at least 55, 60, 65 , 70, 75, 80, 85, 90, 95, 96, 97, or even at least 98) per cent of UV light incident over a wavelength range of at least 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100) nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, and a third optical layer that has first and second main surfaces in general opposite and that absorbs at least 50 (in some modalities, at least 55.60, 65.70, 75.80, 85, 90, or even at least 95) percent of incident UV light through at least a wavelength range of 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at
“* 2/58 minus 100) nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is adjacent (that is, no more than 1 mm, in some embodiments, no more than 0.75 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.45 mm, 0.1 mm, or even not greater than 0.05mm; in some modalities, in contact) to the first main surface of the third optical layer, and in which there is no other multilayer optical film adjacent to the second surface of the third optical layer.
Optionally, at least some of the first and / or second layers (in some embodiments at least 50 per cent per number of the first and / or second layers, in some embodiments all of the at least one of the first or second layers) comprise a UV absorber ,. In another aspect, the present description describes a multilayer optical film that comprises a first plurality of at least first and second optical layers that have a main surface and collectively reflect at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, or even at least 98) percent of incident UV light across a wavelength range of at least 30 (in some embodiments, at least 35 , 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100) nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, and a third optical layer that has first and second among the first and second main surfaces generally opposite and collectively absorbs at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, or even at least least 95) per incident UV light center through at least one strip | wavelength of 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100) nanometers in a range of 'wavelength of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is adjacent (that is, at 1 mm, in some embodiments, no more than 0.75 mm, 0, 5 mm, 0.4 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.15 mm, 0.1 mm, or even 0.05 mm; in some modalities, in contact) at first main surface of the third optical layer, and in which there is a second plurality of first and second optical layers that have a main surface and collectively reflect at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, or even at least 98) percent of incident UV light across a wavelength range of at least 30 (in some embodiments, at least 35, 40, 45, 50, 55 , 60, 65, 70, 75, 80, 85, 90, 9 5, or even at least 100) nanometers in a wavelength range of at least 300 nanometers to 400 nanometers adjacent (that is, at 1 mm, in some embodiments, no more than 0.75 mm, 0.5 mm, 0 , 4 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.415 mm, 0.1 mm, or even 0.05 mm; in some modalities, in contact) to the second main surface of the third optical layer.
Optionally, at least some x "= 3/58 among the first and / or second layers (in some embodiments, at least 50 per cent in number of the first and / or second layers, in some embodiments all within at least one of the first or second layers) comprises a UV absorber.
In another aspect, the present description describes a multilayer optical film that comprises a plurality of at least first and second optical layers that have opposing first and second main surfaces and collectively reflects at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, or even at least 98) percent of incident UV light across at least a wavelength range of 30 (in some embodiments, at least minus 35, 40, 45, 50, 55, 60, 65, 70.75, 80.85, 90.95, or even at least 100) nanometers in a length range. at least 300 nanometers to 400 nanometers, a third optical layer that has a main surface and absorbs at least 50 (in some embodiments, at least + 55, 60, 65, 70, 75, 80, 85, 90, or even at least 95) percent of incident UV light across at least a wavelength range of 30 (in some embodiments, at least 35.40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100) nanometers in a wavelength range of at least 300 nanometers to 400 nanometers adjacent (that is, at 1 mm, in some embodiments, no more than 0.75 mm, 0 , 5 mm, 0.4 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.15 mm, 0.1 mm, or even at 0.05 mm; in some modalities, in contact) with first main surface of the plurality of at least first and second optical layers, and a fourth optical layer that absorbs at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, or even at least at least 95) percent of incident UV light through at least least one wavelength range of 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at: minus 100) nanometers at a wavelength of at least 300 nanometers at - 400 nanometers adjacent (that is, at 1 mm, in some embodiments, no more than 0.75 mm, 0.5 mm, 0.4 mm, 0.3 mm , 0.25 mm, 0.2 mm, 0.15 mm, 0.1 mm, or even at 0.05 mm; in some modalities, in contact) to the second main surface of the plurality of at least | first and second optical layers.
Optionally, at least some of the first | and / or second layers (in some embodiments at least 50 per cent per number of the first and / or second layers, in some embodiments all of at least one of the first or second layers) comprise a UV absorber.
In another aspect, the present description describes an optical film of multiple | layers comprising at least first and second optical layers that reflect at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, or at least 98) of incident light over a wavelength range of 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, or even at least 130) nanometers in a length range of
«" ”4/58 wave from 300 nanometers to 430 nanometers, optionally a third optical layer that absorbs at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, or even at minus 95) percent of incident light over a wavelength range of at least 30 (in some embodiments, at least 35, 40, 45, 50, 55, 60, 65, 70, 75,80,85,90 , 95,100, 110, 120, or even at least 130) nanometers in a wavelength range of at least 300 nanometers to 430 nanometers and a fourth optical layer comprising polyethylene naphthalate, with at least one of the first, second or third optical layers absorb at least 50 percent of incident light over a wavelength range of at least 30 (in some embodiments, at least 35.40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, or even at least 130) nanometers in a wavelength range of at least 300 nanometers to 430 nanometers. at least some of the first and / or second layers: (in some modalities at least 50 per cent per number of the first and / or second layers, in some modalities all of at least one of the first or second layers) comprise a UV absorber. In some embodiments, a plurality of fourth optical layers collectively absorb at least 50 (in some embodiments, at least 55, 60, 65, 70, 75, 80, 85, 90, or even at least 95) percent of incident light over a wavelength range of at least 30 (35, 40, 45, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1,000 , 1,100, 1,200, 1,300, — 1,400,1,500,1,600, 1,700, 1,800, 1,900, 2,000, or even 2,100) nanometers in a wavelength range from 400 nanometers to 2,500 nanometers.
In some embodiments, the multilayer optical films described in this document, the transmission of incident UV light through at least the first, Ú second, third (if present), and fourth (if present) optical layers is less than 5 per percent (in some embodiments, less than 4, 3, 2, or less than 1 percent) in a wavelength range of at least 300 nanometers to 400 nanometers. And in some embodiments, the multilayer optical films described in this document, the transmission of incident UV light through at least the first, second, third (if present), and fourth (if present) optical layers is less than 5 percent (in some embodiments, less than 4, 3.2, or even less than 1 percent) over a wavelength range of at least 300 nanometers to 430 nanometers.
The multilayer optical films described in this document are useful, for example, as a UV protective coating. For example, the present description features a composite article comprising a substrate having a main surface and a multilayer optical film described in the present document on at least a portion of the main surface; aA vehicle window (for example, an automobile or a truck) comprising a multilayer optical film described in this document; commercial graphics (that is, an image for signs or fleets designed to communicate a brand or promotional message); a light assembly comprising a multilayer optical film described in this document; a signage comprising a multilayer optical film described in this document; a crystallized liquid (LCD) screen comprising a multilayer optical film described in the present invention; a building exterior comprising a multilayer optical film described in the present invention and an activated photovoltaic module (for example, a flexible module) comprising a multilayer optical film described in the present invention.
Brief Description of the Drawings Figures 1 to 3 are seen in schematic cross section of exemplary multilayer optical films described in this document. Figure 4 is a schematic cross-sectional view of an exemplary automobile windshield comprising the multilayer optical film described in the present document.
Figure 5 is a schematic cross-sectional view of an example window comprising the multilayer optical film described in the present invention.
Figure 6 is a schematic cross-sectional view of an exemplary liquid crystal display cell comprising the multilayer optical film - described in the present invention.
Figure 7 is a schematic cross-sectional view of an example signaling comprising multilayer optical film described in this document.
Figure 8 is a schematic cross-sectional view of an exemplary light signaling comprising multilayer optical film described in this document.
Figures 9 to 11 are a schematic cross-section of an exemplary photovoltaic cell comprising the multilayer optical films described here.
Detailed Description Referring to figure 1, the exemplary multilayer optical film 10 includes at least one hundred first optical layers 11A, 11B ... 11, and second optical layers 12A, 12B ... 12º, third optical layers 13A, 13B, optional adhesive layer 15, and optional hard coating layer 14 alternating, wherein at least some of the third optical layers include a UV absorber. In some embodiments, at least some of the first and / or second layers include a UV absorber.
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Referring to figure 2, the exemplary multilayer optical film 20 includes at least the first hundred optical layers 21A, 21B ... 21h and second alternating optical layers 22A, 22B ... 22, at least some of which at least one of the first or second optical layers includes a UV absorber. The exemplary multilayer optical film 20 optionally includes an adhesive layer 25 and a hard coating layer 24. In some embodiments, the hard coating layer 24 includes a UV absorber. : Referring to figure 3, the exemplary multilayer optical film 30 includes at least the first hundred optical layers 31A, 31B ... 31y and second | 10 optical layers 32A, 32B ... 32º, optional third optical layers 33A, 33B, layer: optional adhesive 35, and optional hard coating layer 34, and fourth alternating layer (polyethylene naphthalate) 36, at least some of which the first, * second, and / or third layers include a UV absorber. "Ultraviolet" (also "UV"), for use in the present invention, refers to electromagnetic radiation that has wavelengths up to 400 nm. In general, the optical multilayer optical films described in this document comprise at least 100 (typically in a range of 100 to 2000 total layers or more).
The first and second alternating layers of the multilayer optical films have a difference in the refractive index of at least 0.04 (in some embodiments, at least 0.05, 0.06, 0.07, 0.08, 0, 09, 0.1, 0.125, 0.15, 0.175, 0.2, 0.225, 0.25, 0.275, or even at least 0.3). In some embodiments, the first optical layer is birefringent and comprises a birefringent polymer. In some embodiments, at least one of the first, second, or third (if present) optical layer is at least one of fluoropolymer, silicone polymer, urethane polymer, or acrylate polymer (including mixtures thereof), and, preferably, it is UV stable (that is, after a 3,000 hour exposure to a weatherometer-type xenon arc chamber and lamp | according to ASTM G155-05a (October, 2005), the description of which is incorporated herein by reference) has a change: 30 emb * less than 5 units and was measured with a spectrophotometer (available from Perkin-Elmer, Inc., Waltham, MA, USA, under the trade name “LAMBDA 950”)) .
Exemplary materials for making reflective optical layers (for example, the first and second optical layers) include polymers (for example, polyesters, copolyesters, and modified copolyesters). In this context, the term "polymer" will be. 35 understood to include homopolymers and copolymers, as well as polymers or copolymers that can be formed into a miscible mixture, for example, by co-extrusion or by reaction, including transternernification. The terms "polymer" and "copolymer" include both random and block copolymers. Polyesters suitable for use in some exemplary multilayer optical films constructed in accordance with the present description generally include dicarboxylate ester and glycol subunits and can be generated by reactions of carboxylate monomer molecules with glycol. Each dicarboxylate ester monomer molecule has two or more functional groups of ester or carboxylic acid and each molecule of glycol monomer has two or more hydroxy functional groups. The dicarboxylate ester monomer molecules can all be the same or there can be two or more different types of molecules. The same applies to monomeric glycol molecules. Also included in the term "polyester" are polycarbonates - derived from the reaction of glycol monomer molecules with carbonic acid esters.
Examples of dicarboxylic acid monomer molecules suitable for use in forming carboxylate subunits of the polyester layers include 2,6-naphthalene dicarboxylic acid and isomers thereof; terephthalic acid; isophthalic acid; phthalic acid; azelaic acid; adipic acid; sebacic acid; norbornenodicarboxylic acid; bi-cyclooctane dicarboxylic acid; 1,4-cyclohexanedicarboxylic acid and isomers thereof; t-butylisophthalic acid, trimellitic acid, sodium sulphonated isophthalic acid; 4.4 "acid - dicarboxylic biphenyl and isomers thereof; and lower alkyl esters of these acids, such as methyl or ethyl esters. The term" lower alkyl "refers, in this context, to C1- normal or branched chain alkyl groups. Ç;..
Examples of glycol monomer molecules suitable for use in forming glycol subunits of polyester layers include ethylene glycol; propylene glycol; 1,4-butane diol and isomers thereof; 1,6-hexane diol; neopentyl glycol; polyethylene glycol; glycolic diethylene; tricyclodecanediol; 1,4-cyclohexane dimethanol and isomers thereof; norbornanediol; 'biciclooctanodio !; trimethylol propane; pentaerythritol; 1,4-benzenedimethanol and isomers thereof; bisphenol A; 1,8-dihydroxybiphenyl and isomers thereof; and 1,3-bis (2-hydroxy ethoxy) benzene.
Another exemplary birefringent polymer useful for the reflective layer (s) is polyethylene terephthalate (PET), which can be manufactured, for example, by reacting dicarboxylic terephthalic acid with ethylene glycol! L: Its refractive index for polarized incident light of 550 nm in wavelength increases when the plane of polarization is parallel to the direction of extension from about 1.57 to about 1.69. Increasing the molecular orientation increases the birefringence of PET. The molecular orientation can be increased by stretching the material for greater extension ratios and maintaining other fixed stretching conditions. PET Copolymers (CoPET), such as those described in US Patent No. 6,744,561 (Condo et al.) And US Patent No. 6,449,093 (Hebrink et al.), The descriptions of which are —incorporated as a reference , are particularly useful for their processing capacity at relatively low temperatures (typically below 250ºC), making them more compatible for coextrusion with less thermally stable second polymers.
'Other semi-crystalline polyesters suitable as birefringent polymers include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and copolymers thereof, such as those described in US patent No. 6,449,093 B2 (Hebrink et al.) Or Publication of US Patent No. 20060084780 (Hebrink et al.), The descriptions of which are incorporated herein by reference. Another useful birefringent polymer is syndiotactic polystyrene (sSPS).
In addition, for example, the second polymer (of the second layer) of the multilayer optical film can be manufactured from a variety of polymers that have glass transition temperatures compatible with those of the first layer and have a refractive index similar to the index refractive index of the birefringent polymer. Examples of other polymers suitable for use in optical films and, particularly, in the second. polymer, include vinyl polymers and copolymers made from monomers such as vinyl naphthalenes, styrene, maleic anhydride, acrylates, and methacrylates. Examples of such polymers include polyacrylates, polymethacrylates, such as poly (methyl methacrylate) (PMMA), and isotactic or syndiotactic polystyrene. Other polymers include condensation polymers, such as —polysulfones, polyamides, polyurethanes, polyamic acids and polyimides. In addition, the second polymer can be formed from homopolymers and copolymers of polyesters, polycarbonates, fluoropolymers, and polydimethyl siloxanes, and mixtures thereof.
The third optical layer (s) (UV absorber), if present, and fourth layer (s) (UV absorber), if present, comprise a polymer of an absorber of UV, and preferably serves as a UV protective layer. Typically, the polymer is a thermoplastic polymer. Examples of suitable polymers include polyesters (for example, polyethylene terephthalate), fluoropolymers, acrylics (for example, polymethyl methacrylate), silicone polymers (for example, thermoplastic silicone polymers), 'styrenic polymers, polyolefins, olefinic copolymers (by example, copolymers of ethylene and norbomene available as “TOPAS COC” from Topas Advanced Polymers of Florence, i KY), silicone copolymers, fluoropolymers, and combinations thereof (for example, a mixture of polymethyl methacrylate and polyvinylidene fluoride) .
Other exemplary polymers for the optical layers, especially for use in the second layer, include polymethyl methacrylate (PMMA) homopolymers, such as those available from Ineos Acrylics, Inc., Wilmington, DE, USA, under the trade names “CP71” and “CP80;” and polyethyl methacrylate (PEMA), which has a lower glass transition temperature than PMMA. Additional useful polymers include PMMA copolymers (COoPMMA), such as a CoPMMA made from 75% by weight, methyl methacrylate (MMA) monomers and 25% by weight, ethyl acrylate (EA), Í monomers (available together) to Ineos Acrylics, Inc., under the trade name “PERSPEX CP63" or Arkema, Philadelphia, PA, USA, under the trade name “ATOGLAS 510”), a COoPMMA formed with MMA comonomer units and methacrylate comonomer units n-butyl (nBMA), or a mixture of PMMA and poly (vinylidene fluoride) (PVDF).
Additional suitable polymers for the optical layers, especially for use in the second layer, include polyolefin copolymers, such as poly (ethylene-co-octene) '5 (PE-PO) available from Dow Elastomers, Midland, Ml, USA, under the designation | commercial "ENGAGE 8200," poly (prolylene-co-ethylene) (PPPE) available from Atofina | Petrochemicals, Inc., Houston, TX, USA, under the trade name “Z9470 /" and an atactic polypropylene (aPP) and isotactic polypropylene (iPP) copolymer. Multilayer optical films may also include, for example , in the second layers, a functionalized polyolefin, such as low density, linear maleic anhydride-graft-polyethylene (LLDPE-g-MA), such as that available from El duPont de Nemours & Co., Inc., Wilmington, DE, USA, under the trade name “BYNEL 4105.” Preferred polymer compositions for the third layer and / or second layers in alternating layers with at least one birefringent polymer include PMMA, CoPMMA, segmented copolymer based on poly (dimethyl siloxane oxamide) (SPOX), fluoropolymers including homopolymers such as PVDF and copolymers such as those derived from tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV), mixtures of PVDF / PMMA, acrylate, styrene copolymers, styrene copolymers, silicone copolymers, polycarbonate, polycarbonate mixtures, polycarbonate mixtures, polycarbonate, polycarbonate mixtures polycarbonate and styrene maleic anhydride, and cyclic olefin copolymers. 'The selection of polymer combinations used in creating the multilayer optical film depends, for example, on the bandwidth you want to reflect. between the birefringent polymer and the second polymer creates more 'optical power, thus allowing a wide the most reflective band. On the other hand, additional layers can be used to provide more optical power. Preferred combinations of birefringent layers and second polymer layers can include, for example, the following: PET / THV, PET / SPOX, PEN / THV, PEN / SPOX, PEN / PMMA, PET / COPMMA, PEN / COPMMA, CoPEN / PMMA , CoPEN / SPOX, sPS / SPOX, sPS / THV, CoPEN / THV, PET / fluoroelastomers, sPS / fluoroelastomers and CoPEN / fluoroelastomers. In one embodiment, two or more multilayer optical mirrors with different reflection bands are laminated together to enlarge the reflection band. For example, a PET / COPMMA multi-layer reflective mirror that reflects 98% of light from 350 nm to 420 nm would be laminated to a PET / COPMMA multi-layer reflective mirror that reflects 90% of light from 900 nm at 1200 nm to create a UV stabilizing IR mirror that reflects light from 900 nm to 1200 nm. In another example, a multi-layer reflective mirror of PET / CoPMMA that reflects 96.8% of light from 370 nm to 800 nm could be laminated to a multi-layer reflective mirror that reflects 96.8% of light from 700 nm to 1300 nm to create a wider band mirror that reflects light from 400 nm to 1300 nm. Preferred material combinations for making optical layers that reflect UV light (for example, the first and second optical layers) include PMMA (for example, first layer / THV (for example, second layer), PC (polycarbonate) (for example , first layer / PMMA (for example, second layer), and PET (for example, first layer / CoPMMA (for example, second layer). The exemplary material for the manufacture of optical layers that absorb UV light (for example, the third optical layer) includes PET, CoPET, PC, PMMA, CoPMMA, or mixtures of PMMA and PVDF .. A UV absorbing layer (for example, a UV protective layer) assists in protecting the visible reflective / IR optical layer stack from damage / degradation caused by UV light over time by absorbing UV light (preferably any UV light) that can pass through the stack of UV reflecting optical layer. In general, the UV absorbing layer (s) can include any polymeric composition (ie polymer plus additives), including pressure sensitive adhesive compositions that are able to resist UV light for an extended period of time.
Sunlight, in particular ultraviolet radiation from 280 to 400 nm, can induce the degradation of plastics, which, in turn, results in color change and deterioration of mechanical and optical properties. Inhibition of photo-oxidant degradation is important for outdoor applications where long-term durability is mandatory. The absorption of UV light by polyethylene terephthalates, for example, starts at about 360 nm, increases markedly below 320 nm, and is very marked below 300 nm. Polyethylene naphthalates' strongly absorb UV light in the 310-370 nm range, with an absorbing tail that dries. 25 extends to about 410 nm, and the maximum absorption occurs at 352 nm and 337 nm. Chain cleavage occurs in the presence of oxygen, and the predominant photooxidation products are carbon monoxide, carbon dioxide, and carboxylic acids. In addition to direct photolysis of the ester groups, oxidation reactions are taken into account, which likewise form carbon dioxide through peroxide radicals.
A UV-absorbing layer can protect the multilayer optical film by reflecting UV light, absorbing UV light, diffusing UV, or a combination of them. In general, a UV absorbing layer can include any polymeric composition that is capable of withstanding UV radiation for an extended period of time while it either reflects, diffuses, or absorbs UV radiation. Examples of such polymers include PMMA, CoPMMA, silicone thermoplastics, fluoropolymers and their copolymers, and mixtures thereof. An exemplary UV-absorbing layer comprises PMMA / PVDF mixtures.
A variety of optional additives can be incorporated into an optical layer to make it UV absorbing. Examples of such additives include at least one of an ultraviolet absorber (s), a hindered amine-based photo-stabilizer (s), or an anti-oxidant (s) thereof.
Particularly desirable UV absorbers are red shifted UV absorbers (RUVA) that absorb at least 70% (in some embodiments, at least 80%, particularly preferably more than 90% of UV light in the 180 wavelength region) nm to 400 nm Typically, it is desirable for RUVA to be highly soluble in polymers, highly absorbable, photo-permanent and thermally stable in the temperature range of 200 ° C to 300 ° C for the extrusion process to form the protective layer. may be highly suitable if it can be copolymerized with monomers to form the protective coating layer by UV curing, gamma ray curing, electronic beam curing, or thermal curing processes. RUVAs typically have enhanced spectral coverage in the Long-wave UV, allowing it to block high-wavelength UV light that can cause yellowing of polyesters. Typical UV protective layers are thick in one from 13 micrometers to 380 micrometers (0.5 thousand to 15 thousand) with a RUVA loading level of 2 to 10% by weight. One of the most effective RUVA is a benzotriazole compound, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-S-tert-octyl phenol) -2H-benzotriazole (sold under the trade name “CGL-0139" with Ciba Specialty Chemicals Corporation, Tarryton, NY, USA) Other preferred benzotriazoles include 2- (2-hydroxy-3,5-di-alpha-cumylphenyl) -2H-benzotriazo |, 5-chloro-2- (2- hydroxy-3-ter-butyl-5-methylphenyl) -2H-benzothiazole, S5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2 H-benzotriazole, 2- (2- hydroxy-3,5-di- 'tert-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-alpha-cumyl-S-tert-octyl phenol) -2H-benzotriazo |, 2- 2- (3 -ter-butyl-2-hydroxy-S-methylphenyl) -S-chloro-2H-benzotriazole.Additionally preferred RUVA includes 2 (-4,6-diphenyl-1-3,5-triazin-2-yl) -5- hexyloxy-phenol. Other exemplary UV absorbers include those available from Ciba Specialty Chemicals Corporation under the trade name “TINUVIN 1577,” “TINÚVIN 900," and “TINUVIN 777.” Other exemplary UV absorbers are available in a master polyester lot from Sukano Polymers Corporation, Dunkin SC, under the trade name “TA07-07 MB.” An exemplary UV absorber for polycarbonate is a master batch with Sukano Polymers Corporation, Dunkin SC, under the trade name “TA28-09 MBO1.” In addition, UV absorbers can be used in combination with hindered amine-based photostabilizers (HALS) and antioxidants. Exemplifying HALS include those available from Ciba Specialty Chemicals Corporation, under the trade name: “CHIMASSORB 944" and "“ TINUVIN 123 ”Exemplifying antioxidants include those obtained under the trade names IRGANOX 1010” and “ULTRANOX 626”, also available from Ciba Specialty Chemicals Corporation.
In some embodiments, the third UV-absorbing (protective) layer is a multilayer optical film that reflects wavelengths from about 350 to about 400 nm (in some modalities from 300 nm to 400 nm). In these embodiments, the polymers for the UV light absorbing layer do not preferably absorb UV light in the range of 300 nm to 400 nm.
Examples of materials that are desirable for such modalities include PET / THV, PMMA / THV, PET / SPOX, PMMA / SPOX, sPS / THV, sPS / SPOX, THV, TPU / THV and TPU / modified polyolefin copolymers (EVA) SPOX.
In an exemplary way, THV is available under the trade name “DYNEON THV. 220 GRADE "and" DYNEON THV 2030 GRADE "with Dyneon LLC, Oakdale, MN, are used with PMMA for multi-layer UV mirrors reflecting 300 to '400 nm or with PET for multi-layer mirrors reflecting 350 to 400 nm.
Other additives can be included in a UV absorbing layer (for example, a protective UV layer). Small particle non-pigmented zinc oxide and titanium oxide can also be used as blocking or diffusing additives in a UV-absorbing layer.
For example, nanoscale particles can be dispersed on polymer or coating substrates to minimize degradation by UV radiation.
The nanoscale particles are transparent to visible light while either diffusing or absorbing harmful UV radiation, thus reducing damage to thermoplastics.
US Patent No. 5,504,134 (Palmer et al.) Describes the attenuation of polymer substrate degradation due to ultraviolet radiation through the use of metal oxide particles in a size range from about 0.001 micrometer to 'about 0, 2 micrometer in diameter, and most preferably about. 25 0.01 micrometer to about 0.15 micrometer in diameter.
US patent No. 5,876,688 (Laundon) describes a method for producing micronized Zinc oxide that is small enough to be transparent when incorporated as a UV blocker and / or diffusing agent in paints, coatings, finishes, plastic articles, cosmetics and the like that are suitable for use in the present invention.
These fine particles, such as zinc oxide and titanium oxide with particle size ranging from 10 to 100 nm, that can attenuate UV radiation are available, for example, from Kobo Products, Inc.
South Plainfield, NJ, USA.
Flame retardants can also be incorporated as an additive in a UV protective layer.
In addition to adding UV absorbers, HALS, nanoscale particles, flame retardants, and anti-oxidants to a UV absorbing layer, UV absorbers, HALS, nanoscale particles, flame retardants and anti-oxidants can be added to multilayer optical films, and any optional durable coating layers. Fluorescent molecules and optical bleaches can also be added to a UV absorbing layer, to the multilayer optical layers, an optional hard coating layer, or a combination thereof. The desired thickness of a UV protective layer is typically dependent on an optical density target at specific wavelengths, as calculated by Beers Law. In some embodiments, the UV protective layer has an optical density greater than 3.5, 3 , 8, or 4 at 380 nm; greater than 1.7 to 390 nm; and greater than 0.5 nm to 400 nm. Elements of common skill in the art recognize that optical densities should typically remain reasonably constant — through the extended life of the article to provide the intended protective function. . The UV protective layer, and any optional additives, can be selected to achieve the desired protective functions, such as UV protection. Those of ordinary skill in the art recognize that there are multiple ways to reach the indicated objects in the UV protective layer. For example, additives that are very soluble in certain polymers can be added to the composition. Particularly important is the permanence of the additives in the polymer. The additives should not degrade or migrate out of the polymer. In addition, the thickness of the layer can be varied to achieve the desired protective results. For example, thicker UV protective layers would allow for the same level of UV absorbance with lower concentrations of UV absorbers, and would provide more UV absorber permanence attributable to a lower actuation force for UV absorber migration. One mechanism for detecting changes in physical characteristics is the use of the wear cycle by atmospheric agents described in ASTM G155-05a (October, 2005) and a D65 light source operated in reflected mode. Under the test 'indicated, and when the UV protective layer is applied to the article, should the article withstand 2 25 to an exposure of at least 18,700 kJ / m at 340 nm before the space of the b * value obtained with the use of CIE L * a * b * increases by 5 or less, 4 or less, 3 or less, or 2 or less before the beginning of cracking, detachment, delamination significant opacity or opacity. The fourth optical layer, which in some embodiments is optional, comprising polyethyl enenaphthalate, can be made, for example, as described in Example 15, below. Multilayer optical films described in the present invention can be made using general processing techniques, such as those described in US Patent no.
6,783,349 (Neavin et al.), The description of which is incorporated herein by reference. Desirable techniques for providing a multilayer optical film with a controlled spectrum include the use of an axial rod heater control of the layer thickness values of coextruded polymer layers, as described, for example, in US patent No. 6,783,349 ( Neavin et al.); feedback of point thickness profile during production from a layer thickness measurement tool, such as an atomic force microscope (AFM), a transmission electron microscope, or a scanning electron microscope; optical modeling to generate the desired layer thickness profile; and the repetition of axial shank adjustments based on the difference between the measured layer profile and the desired layer profile.
The basic process for controlling the layer thickness profile involves adjusting the power settings of the axial shank zone based on the difference in the target layer thickness profile and the measured layer profile. The increase in axial shaft power required to adjust the layer thickness values in a given feed block zone can first be calibrated in terms of watts of heat input per nanometer of thickness change resulting from the layers. generated in that heating zone. For example, detailed spectrum control is possible with the use of 24 axial stem zones for 275 layers. Once calibrated, 7 the required power settings can be calculated once a target profile and a measured profile are given. The procedure is repeated until the two profiles converge.
The layer thickness profile (layer thickness values) of the multilayer optical film described in the present invention that reflects at least 50 percent of the incident UV light over a specified wavelength range can be adjusted to be approximately one linear profile with the first optical layers (thinner) adjusted to have about an optical wave thickness of 1/4 (index times physical thickness) for 300nm light progressing to the thicker layers, which would be adjusted to have about 1 / 4 wavelength optical thickness for 400 nm light.
Optionally, a hard coating can be provided by techniques known in the art, including those described in U.S. Patent No. 7,153,588 (McMan), the description of which is incorporated herein by reference. The use of hard coatings 25 can, for example, reduce or prevent premature degradation of the article due to exposure to elements from external environments. The hard coating is, in general, resistant to abrasion and impact and does not interfere with the primary function of reflecting a selected bandwidth of electromagnetic radiation. A hard coating can also provide mechanical durability to the article.
- Some mechanisms for measuring mechanical durability may have resistance to impact or abrasion. Taber abrasion is a test to determine a film's resistance to abrasion, and abrasion resistance is defined as the ability of a material to withstand mechanical action such as rubbing, scraping or erosion. According to the test method of ASTM D1044-08 (2008), a load of 500 grams is placed on top of a wheel - abrasive CS-10 and allowed to spin for 50 revolutions in a test specimen of 25.8 in (4 inches ). The reflectivity of the sample before and after the Taber abrasion test is measured, and the results are expressed by changes in the% reflectivity. For the hi Ri 15/58 purpose of this invention, it is expected that the change in the% of reflectivity is less than 20%, preferably less than 10% and particularly more preferential, less than 5%.
Other tests suitable for mechanical durability include break elongation, brush hardness, sandblasting testing and sand agitation abrasion. The appropriate UV absorbers and UV stabilizers described above can be added to the top cover to stabilize the coating, as well as to protect the substrates. Substrates coated with such a durable hard cover are thermoformable before being fully cured at an elevated temperature, and a durable hard cover can then be formed by curing after 80ºC for 15 to 30 minutes. In addition, the “siloxane components used as a durable top coat are hydrophobic in nature and can. provide an easy surface cleaning function for the articles disclosed in that invention. Due to outdoor application, weathering is a desirable feature of the article. Studies on accelerated weathering are an option for qualifying the article's performance. Accelerated weather wear studies are generally performed on films using techniques similar to those described in ASTM G-155-05a (October, 2005), “Standard practice for exposing non-metallic materials in accelerated test devices that use laboratory light sources ”. The ASTM technique indicated is considered as a sound predictor of outdoor durability, that is, classifying the performance of materials correctly.
The hard coating layers may include at least one of PMMA / PVDF blends, thermoplastic polyurethanes, curable or crosslinked polyurethanes, CoPET, cyclic olefin copolymers (COC's), fluoropolymers and their copolymers such as PVDF, ETFE, FEP, and THV, thermoplastic acrylates curable, crosslinked acrylates, crosslinked urethanes, crosslinked urethanes, curable or crosslinked polyepoxides or silicones. 25 lattices. Disposable polypropylene copolymer films can also be used. On the other hand, for example, a silane silica sol copolymer hard coating can be applied to improve scratch resistance. The hard coating may contain UV absorbers, HALS, and anti-oxidants as described above. Optionally, a fixation layer can be interposed between the outer surface of the first and second layers and the UV protective layer, a hard coating layer, etc. to assist in grip and provide long-term stability in use. Examples of attachment layers include: hot-melt adhesives, and COPETs that include modifications such as with sulfonic acid functional groups, PMMA / PVDF blends, modified olefins with functional comonomers such as maleic anhydride, acrylic acid, —methacrylic acid or vinyl acetate. In addition, thermally curable or UV acrylates, silicone acrylates, epoxies, siloxanes, urethane can be suitable as fixing layers. The fixation layers can optionally contain UV absorbers as
16/58 | described above. The fixation layers can optionally contain plasticizers, conventional tachifiers or combinations thereof. The fixing layer can be applied using conventional film forming techniques.
It is within the scope of the present disclosure to include UV absorbing layers (e.g., UV protective layers) on both main surfaces of the stack of the first and second optical layers. Also, in some embodiments, it may be desirable to have a UV absorbing layer (e.g., UV protective layer) on the opposite side of the stack of the first and second optical layers for a specific application requirement. In some embodiments, it may be desirable to provide a UV absorbing layer (for example, UV protective layer) only on the optical film of: multiple layers in order to provide protection at the rear against UV radiation. Other potential embodiments may include a carbon black layer or an IR absorber layer on one or more of the main surfaces of the stack of the first and second optical layers. In another embodiment, an anti-reflective coating can be on the back of the stack of the first and second optical layers to reduce or prevent IR reflection on the back. Fixation layers, such as those discussed above, can be used to provide these additional exemplary modalities.
Some modalities of multilayer optical films described here have a UV transmission band edge in a range of 10 to 90 percent transmission spanning less than 20 (in some embodiments, less than 10) nanometers.
The exemplary thicknesses of multilayer optical films described here have a thickness in the range of 25 micrometers to 250 micrometers. The exemplary thicknesses of optical layers (for example, the third optical layer) that 'absorb' have a collective thickness in a range of 10 micrometers to 200 micrometers.
. 25 The multilayer optical films described here are useful, for example, as a UV protective coating. For example, the present description features a composite article comprising a substrate having a main surface and a multilayer optical film described in the present document on at least a portion of the main surface; a vehicle window (for example, an automobile or a truck) comprising a multilayer optical film described in this document; commercial graphic (that is, an image for signs or fleets designed to communicate a brand or promotional message); a light assembly comprising a multilayer optical film described in this document; a signage comprising a multilayer optical film described in this document; an LCD comprising a multilayer optical film described in the present invention; a building exterior comprising a multilayer optical film described in the present invention and a photovoltaic module (for example, a flexible module) comprising a multilayer optical film described in the present invention.
Referring to Figure 4, the exemplary automobile windshield 30 includes automobile windshield glass 41, 42, exemplary multilayer optical film described here 43, mirror layer against 44, and adhesive layers 45, 46, 47 The multilayer optical film can be incorporated into the construction of an automobile window using techniques of general knowledge in the art.
Referring to figure 5, the exemplary architectural window 50 includes window glass 51, 52, exemplary multilayer optical film described herein 53, mirror layer against IR 55, adhesive layers 57, 58, and optional hard coat layer 56. The multilayer optical film can be incorporated into automobile window constructions using techniques well known in the art.
Referring to figure 6, the exemplifying liquid crystal display device 60 includes liquid crystal display 61, exemplary multilayer optical film described herein 63, and mirror layer against IR 65, adhesive layers 67, 68, and coating layer optional drive 66. The multilayer optical film can be incorporated into liquid crystal display devices using techniques of general skill in the art.
Referring to Figure 7, commercial graphic signage 70 includes signage 71, exemplary multilayer optical film described here 73, adhesive layer 75, and optional hard coat layer 76. The multilayer optical film can be incorporated into signage constructions commercial graphics with the use of techniques of general knowledge in the technique.
Referring to figure 8, signage 80 includes light signaling 81, exemplary multilayer optical film described here 83, adhesive layer 85, and optional hard coating layer 86. The multilayer optical film can be incorporated into light signaling constructions with the use of techniques of general knowledge in the art.
With reference to figure 9, the photovoltaic module 90 includes photovoltaic module cell 91, exemplary multi-layer optical film described here 93, adhesive layer 95, and optional hard coating layer 96. With reference to figure 10, the photovoltaic module 100 includes photovoltaic module cell 101, example multilayer optical film described here 103, adhesive layer 105, and optional antireflective surface structure 109. Referring to Figure 11, photovoltaic module 110 includes photovoltaic module cell 111, multilayer optical film example described here 113, adhesive layer 115, | optional vapor barrier layer 118, and optional antireflective surface structure 119. - Multilayered film can be incorporated into photovoltaic modules using techniques well known in the art.
Solar energy conversion devices that have front side layers of polymer or flat glass typically lose 3 to 5% of available solar energy due to front side surface reflections and therefore preferably include a anti-reflective surface.
Preferably, a surface layer with an anti-reflective structure minimizes surface reflections. The incident sunrays are particularly reflected off | 5 of the sloping surfaces of the structured surface. However, these partially reflected sunrays reflect on the adjacent surface structure where they are | refracted directly to the solar energy conversion device, or are fully | reflected internally to the solar energy conversion device. Almost all of the incident sun rays eventually reach the solar energy conversion device, thereby increasing its efficiency.
Exemplary structured layers include those that have a structured surface that comprises a series of structures. The structured layer can be a single material or it can be a multilayer construction, where the structured layer comprises a formulation of a material, and a base film and adhesive comprise different formulations of material. In addition, the adhesive layers themselves and the film could comprise multiple layers. In general, the structured layer has a structured surface, where a substantial portion of the reflected light intersects with another structure on the surface. In some embodiments, the series of structures comprises a series of essentially parallel peaks separated by a series of essentially parallel valleys. In the cross section, the structured layer can adopt a variety of waveforms. For example, the cross section may adopt a symmetrical sawtooth pattern in which each of the peaks is identical as are each of the valleys; a series of parallel peaks having different heights, separated by a series of parallel valleys; or a sawtooth pattern of alternating, parallel, asymmetric peaks separated by a series of parallel, - asymmetric valleys. In some modalities, the peaks and valleys are continuous and, in other modalities, a discontinuous pattern of peaks and valleys is also contemplated. In this way, for example, the peaks and valleys can end for a portion of the article. Valleys may narrow or widen as the peak or valley advances from one end of the article to the other. Furthermore, the height and / or width of a given peak or valley may change as the peak or valley advances from one end of the article to the other.
In some embodiments, the structured surface is opposite the energy conversion device, and the structured surface is anti-reflective. A significant anti-reflective structured surface, for the purpose of the present patent application, that the reflection, on average over all angles of incidence, is less than it would be on a corresponding flat surface, for example, is less than 50% of the reflection outside of the flat surface (in some modalities, less than 60%, 70% or even less than 80% of the reflection outside the flat surface).
Peak dimensions, in general, have a height of at least about 10 micrometers (0.0004 inch). In some embodiments, the peaks are up to about 250 micrometers (0.010 inches) high. In one embodiment, for example, the peaks are at least about 20 micrometers (0.0008 inch) high, and in another exemplary embodiment, the peaks are up to about 150 micrometers (0.006 inch) high. The peak-to-peak spacing between adjacent peaks is, in general, at least about micrometers (0.0004 inch). In another embodiment, the spacing is up to about 250 micrometers (0.010 inches). In one embodiment, the spacing is at least about 20 micrometers (0.0008 inch), and in some embodiments, the spacing is up to about 1050 micrometers (0.006 inch). The angle included between adjacent peaks can also vary. The valleys can be flat, round, parabolic or V-shaped. The peaks are generally V-shaped and have an apex angle less than 60 degrees (in some modalities, less than 50 degrees or even less than 40 degrees ). The present order is also aimed at peaks that have a radius of curvature at the tip, and this —modality has an apex angle measured by the line of best fit to the sides.
In some embodiments, the series of structures are non-uniform structures. For example, structures differ in height, base width, gap, apex angle or other structural aspect. In such modalities, the angular coefficient of the structures from the plane of the surface presents an average superior to that of the surface in less than 30 degrees of the normal. In other embodiments, for example, the structures are substantially symmetrical in a dimension around a perpendicular to the surface.
The structured surface can comprise, for example, a structured polyurethane layer. This polyurethane layer can be prepared, for example, from the condensation polymerization of a reaction mixture comprising a polyol, a polysocyanate and a catalyst. The reaction mixture can also contain additional components that are not polymerizable by condensation and, in general, contains at least one UV stabilizer. As will be described below, the polymerization reaction by condensation or curing, in general, is performed outside a mold or tool to generate the structured surface on the cured surface.
For the polyurethane polymers described in that disclosure that are formed from the condensation reaction of a polyol and a polyisocyanate they contain at least polyurethane bonds. The polyurethane polymers formed in this disclosure may contain only polyurethane bonds or may contain other optional bonds such as polyurea bonds, polyester bonds, polyamide bonds, silicone bonds, acrylic bonds and the like. As described above, these other optional bonds may appear in the polyurethane polymer due to the fact that they are present in the polyol or the polyisocyanate materials that are used to form the polyurethane polymer. The polyurethane polymers in this disclosure are not cured by free radical polymerizations.
For example, polyurethane oligomeric molecules with vinyl groups or other radically free polymerizable end groups are known materials, and the polymers formed by free radical polymerization of these molecules are often called "polyurethanes", but these polymers are outside of the scope of that revelation.
A wide variety of polyols can be used.
The term polyol includes functional hydroxyl materials that generally comprise at least 2 terminal hydroxyl groups and can generally be described by the HO-B-OH structure, where the group B can be an aliphatic group, an aromatic group or a group containing a combination of groups aromatic and aliphatic, and may contain a variety of linkages or functional groups, including additional terminal hydroxyl groups.
Typically, HO-B-OH is a diol or hydroxyl-terminated prepolymer such as a polyurethane, polyester, polyamide, silicone, acrylic or polyurea prepolymer.
Examples of such useful polyols include polyester polyols (such as lactose polyols), polyether polyols (such as polyoxy alkylene polyols), polyalkylene polyols, mixtures thereof, and copolymers thereof.
Polyester polyols are particularly useful.
Among the useful polyester polyols are linear and non-linear polyester polyols that include those produced from polyethylene adipate, polybutylene succinate, polyhexamethylene sebacate, polyhexamethylene dodecanedioate, polyneopentyl adipate, polypropylene adipate, polycyclohexanxine and polycyclohexanxine. poly e-caprolactone.
Particularly useful aliphatic polyester polyols are available from King Industries, Nonvalk, CT, USA, under the trade name “K-FLEX” (for example, “K-FLEX 188" and “K-FLEX A308”). Where HO-B-OH is a hydroxyl-terminated prepolymer, a wide variety of precursor molecules can be used to produce the desired HO-B-OH prepolymer.
For example, the reaction of polyols with lower stoichiometric amounts of diisocyanates can produce a hydroxyl-terminated polyurethane prepolymer.
Examples of suitable diisocyanates include, for example, aromatic diisocyanates, such as 2,6-toluene diisocyanate, 2,5-toluene diisocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, methylene bis (o-chlorophenyl diisocyanate), 4,4 'methylenediphenylene diisocyanate, polycarbodiimide modified methylenediphenylene diisocyanate, (4,4-diisocyanate-3,3,5, - S'-tetraethyl) -biphenylmethane, - 4 , 4'-diisocyanate-3,3'-dimethoxybiphenyl, S-chloro-2,4-toluene diisocyanate, 1-chloromethyl-2 4-benzene diisocyanate, aromatic aliphatic diisocyanates such as m-xylylene diisocyanate, tetramethyl-m diisocyanate -xylene, aliphatic diisocyanates, such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, 2-methyl-1,5 diisocyanatopentane and cycloaliphatic diisocyanates such as methylene-dicyclohexylene-4,4'-diisocyanate and cyclohexyl 3-isocyanatomethyl-3,5,5-trimethyl isocyanate (isophorone diisocyanate). For reasons of resistance to exposure to the elements, aliphatic and cycloaliphatic diisocyanates are generally used.
An example of the synthesis of a HO-B-OH prepolymer is shown in Reaction Scheme 1 (where (CO) represents a carbonyl group C = O) below: 2 HO-RI-OH + OCN — RENEW Ho RL otic -oN — RE-NiC = 0) o-RE-obl-n HA "Reaction Scheme 1 where n is one or greater, depending on the ratio between polyol and diisocyanate, for example, when the ratio is 2: 1, n is 1. Similar reactions between polyols and dicarboxylic acids or dianhydrides can obtain HO-B-OH prepolymers with ester bonding groups.
Polyols with more than two hydroxyl groups per molecule will lead to a resin - reticulated by reacting with functionally larger di or isocyanates.
Crosslinking prevents deformation of the polymer formed and helps maintain the desired structure.
Typically, the polyol is an aliphatic polyester polyol like those available from King Industries, Nonwvalk, CT, USA, under the trade name “K-FLEX” (for example, “K-FLEX 188” and “K-FLEX A308” ). A wide variety of polyisocyanates can be used.
The term polyisocyanate includes functional isocyanate materials that generally comprise at least 2 terminal isocyanate groups, such as diisocyanates that can generally be described by the OCN-Z-NCO structure, where the Z group can be an aliphatic group, an aromatic group or a group containing a combination of aromatic and aliphatic groups.
Examples of suitable diisocyanates include, for example, aromatic diisocyanates, such as 2,6-toluene diisocyanate, 2,5-toluene disocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, methylene bis (o-chlorophenyl diisocyanate), methylenediphenylene-4,4'-diisocyanate, methylenediphenylene diisocyanate modified with polycarbodiimide, (4,4'-diisocyanate-3,3,5, 5'-tetraethyl) biphenylmethane, 4,4 '-diisocyanato-3,3'-dimethoxybiphenyl, 5-chloro-2,4-toluene diisocyanate, 1-chloromethyl-2 4-diisocyanate benzene, aromatic aliphatic diisocyanates such as mxlylene diisocyanate, tetrametik-m-xylates diisocyanate, diis aliphatics such as 1,4 diisocyanatobutane, 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, 2-methyl-1,5-diisocyanatopentane, and cycloaliphatic diisocyanates such as methylene-dicyclohexylene-4.4 "- diisocyanate, and 3- isocyanate isocyanatomethyl-3,5,5-trimethyl-cyclohexyl (isophorone diisocyanate). For reasons of resistance to exposure to the elements, generally, aliphatic diisocyanates and —cycloaliphatics are used.
Some degree of crosslinking is useful in maintaining the desired structured surface.
One approach is to use polyisocyanates with functionality greater than 2.0. A particularly suitable aliphatic polyisocyanate is available under the trade name “DESMODUR N3300A” from Bayer, Pittsburgh, PA, USA.
Typically, the structured polyurethane layer is of sufficient size to produce the desired optical effect. The polyurethane layer is generally no more than 10mm thick, typically thinner. For economic reasons, it is generally desirable to use a structured polyurethane layer that is as thin as possible. It may be desirable to maximize the amount of polyurethane material that is contained in the structures and to minimize the amount of polyurethane material that forms the base of the structured but unstructured polyurethane layer. In some cases, this base portion is often called "the land" since it is analogous to the land from which the mountains arise.
Aliphatic polyurethanes show good stability for ultraviolet wear, but the addition of UV stabilizers can further improve their stability when exposed to the environment. Examples of suitable UV stabilizers include ultraviolet absorbers (UVAs), hindered amine light stabilizers (HALS) and antioxidants. It has been shown that it is useful to choose additives that are soluble in the reactive mixture, specifically, in the polyol. Benzotriazole UVAs (available, for example, under the trade names "TINUVIN P 213," "TINÚVIN P 234," "TINÚVIN P 326," "TINUVIN P 327," "TINÚVIN P 328," and "TINUVIN P 571" with Ciba, Tarrytown, NY, USA), hydroxyphenyl triazines such as (available, for example, under the trade names “TINUVIN 400" and “TINÚVIN 405” with Ciba); HALS (available, for example, under the trade names “TINUVIN 123,” “TINÚVIN 144,” “TINUÚVIN 622," “TINÚVIN 765,” and “TINUVIN 770” from Ciba); and antioxidants (available, for example, under the trade names “RGANOX 1010,” “IRGANOX 1135,” and “IRGANOX 1076” from Ciba) The material available under the trade name "TINUVIN B75," a product containing UVA, HALS and antioxidant available from Ciba is also suitable .
The reactive mixture used to form the structured polyurethane layer may also contain additional additives, if desired, as long as the additive does not interfere with the urethane polymerization reaction or adversely affects the optical properties of the formed polyurethane layer. Additives can be added to aid mixing, processing or coating the reactive mixture or to assist the final properties of the formed structured polyurethane layer. Examples of additives include: particles, including nanoparticles or larger particles; mold release agents; low surface energy agents; anti-mold agents; fungicidal agents; anti-foaming agents; anti-static agents; and coupling agents such as amino silanes and silane isocyanate. Additive combinations can also be used.
In some embodiments, the structured layer has a variable crosslink density across the entire thickness of the layer. For example, there may be a higher crosslink density on the surface of the structured layer. The crosslink density can be increased on the film surface of the structured surface with the use of electron beam irradiation at a relatively low voltage such as 100 kV to 150 kV.
In some embodiments, for example, the reaction of polyol and polyisocyanate can proceed without a catalyst, and accelerated cross-linking by free radicals is formed by means of electron beam irradiation. This can be advantageous, in that the catalysts can contribute to the oxidative degradation and photodegradation of the polyurethane polymer. In another embodiment, the reactive mixture is polymerized with the above preferred catalysts and then additionally cross-linked with electron beam irradiation. The higher crosslinking densities achieved with electron beam irradiation can increase the durability of the polyurethane, specifically, to abrasion such as from falling sand. Electron beam irradiation can be controlled to provide crosslink density — higher on the surface of the structured polyurethane surface than on the volume of the polyurethane article. The high crosslink density has the desirable effect of minimizing transmission losses from abrasion. For example, the exposure of surface structured aliphatic polyurethanes to a dosage of 30 megarads at 120 kV reduces transmission losses to less than 3%. Transmission increases of 4 to 5% were measured with the exemplified surface structures along the flat glass surfaces before abrasion. Since the demonstrated benefit of the surface structure is to provide a higher transmission than flat glass, it is desirable to have transmission losses of no more than 3% of the abrasion. The cross-linked structured surface polyurethanes exemplifying this invention maintain a higher transmission than flat glass after abrasion from sand fall.
Barrier layers useful for the practice of the present disclosure can be selected from a variety of constructions. Barrier layers are typically selected such that they have oxygen and water transmission rates at a specified level as required by the patent application. In some embodiments, the barrier layer has a water vapor transmission rate (WVTR) less than about — from 0.005 g / media at 38ºC and 100% relative humidity; in some modalities, less than about 0.0005 gimº / day at 38ºC and 100% relative humidity; and in some modalities, less than about 0.00005 g / mº / day at 38ºC and 100% relative humidity. In some embodiments, the flexible barrier layer has a WVTR less than about 0.05, 0.005, 00005 or 0.00005 g / m / Day at 50 ° C and 100% relative humidity or even less than about 0.005, 00005 , 000005 g / min / day at 85ºC and 100% relative humidity. In some embodiments, the barrier layer has an oxygen transmission rate of less than about 0.005 gimildia at 23ºC and 90% relative humidity; in some modalities, less
| 24/58 | that about 0.0005 g / m / day at 23ºC and 90% relative humidity; and in some modalities, less than about 0.00005 g / mº / day at 23ºC and 90% relative humidity. Useful exemplary barrier layers include inorganic films prepared by atomic layer deposition, thermal evaporation, ion bombardment and chemical vapor deposition. Useful barrier layers are typically flexible and transparent. In some embodiments, useful barrier layers comprise inorganic / organic multilayers. Ultra-flexible barrier layers comprising organic / inorganic multilayers are described, for example, in U.S. patent no.
7,018,713 (Padiyath et al.). Such ultra-flexible barrier layers may have a first polymeric layer disposed on a polymeric filament substrate which is overcoated with two or more inorganic barrier layers separated by at least a second polymer layer. In some embodiments, the barrier layer comprises an inorganic barrier layer interposed between the first polymer layer disposed on the polymeric film substrate and a second polymer layer.
The first and second layers of polymer can be formed independently by applying a layer of a monomer or oligomer and crosslinking the layer to form the polymer locally, for example, by flash evaporation and vapor deposition of a radiation crosslinkable monomer followed by crosslinking , for example, using an electron beam apparatus, UV light source, electrical discharge apparatus or other suitable device. The first polymer layer is applied over the polymeric film substrate, and the second polymer layer is typically applied to the inorganic barrier layer. The materials and methods useful during the formation of the first and second polymer layers can be selected independently to be the same or different. Techniques useful for flash evaporation and vapor deposition followed by crosslinking locally can be found, for example, in US Patent Nos. 4,696,719 (Bischoff), 4,722,515 (Ham), 4,842,893 (Yializis et al.), 4,954,371 (Yializis),
5,018,048 (Shaw et al.), 5,032,461 (Shaw et al.), 5,097,800 (Shaw et al.), 5,125,138 (Shaw et al.), 5,440,446 (Shaw et al.), 5,547,908 (Furuzawa et al.), 6,045,864 (Lyons et al.), 6,231,939 (Shaw et al.), And 6,214,422 (Yializis); in published PCT patent application No. WO 00/26973 (Delta V Technologies, Inc); in D. G. Shaw and M. G. Langlois, “A New Vapor Deposition Process for Coating Paper and Polymer Webs”, 6th International Vacuum Coating Conference (1992); in D. G. Shaw and M. G. Langlois, “A New High Speed Process for Vapor Depositing Acrylate Thin Films: An Update”, Society of Vacuum Coaters 36th Annual Technical Conference Proceedings (1993); in D. G. Shaw and M. G. Langlois, “Use of Vapor Deposited Acrylate Coatings to Improve the Barrier Properties of Metallized Film”, Society of Vacuum Coaters 37th Annual Technical Conference Proceedings (1994); in D. G. Shaw, M. Roehria, M. G. Langlois and C. Sheehan, “Use of Evaporated Acrylate Coatings to Smooth the Surface of
Polyester and Polypropylene Film Substrates ”, RadTech (1996); in J. Affinito, P. Martin, M. Gross, C. Coronado and E. Greenwell, “Vacuum deposited polymer / metal multilayer films for optical application”, Thin Solid Films 270, 43 to 48 (1995); and in JD Affinito, ME Gross, CA Coronado, GL Graff, EN Greenwell and PM Martin, "Polymer-Oxide Transparent Barrier Layers", Society of Vacuum Coaters 39th Annual Technical Conference Proceedings (1996). In some embodiments, the polymer layers and the inorganic barrier layer are sequentially deposited in a single-pass vacuum coating operation without interrupting the coating process.The coating efficiency of the first polymeric layer can be improved, for example, by cooling the polymeric film substrate Similar techniques can also be used to improve the coating efficiency of the second polymeric layer The monomer or oligomer useful to form the first and / or second polymeric layer can also be applied using conventional coating methods such as cylinder (eg engraving cylinder coating) or spray coating (eg coating electrostatic spraying). The first and / or second polymer layer can also be formed by applying a layer containing an oligomer or polymer in solvent and then removing the solvent using conventional techniques (for example, at least one among heat or vacuum). Plasma polymerization can also be employed.
The volatilizable acrylate and methacrylate monomers are useful for the formation of the first and second polymer layers. In some embodiments, volatilizable acrylates are used. The volatilizable acrylate and methacrylate monomers can have a molecular weight in the range of about 150 grams per mole to about 600 grams per mole, or, in some embodiments, from about 200 grams per mole to about 400 grams per mole. In some embodiments, the volatilizable acrylate and methacrylate monomers have a value of the ratio between the molecular weight and the number of (meta) acrylate functional groups per molecule in the range of about 150 grams per mol to about 600 g / mol / group (meta) acrylate, in some embodiments, from about 200 grams per mol to about 400 g / mol / group (meta) acrylate. Fluorinated acrylates and methacrylates can be used in ranges or ratios of higher molecular weight, for example, molecular weight of about 400 per mo! to about 3,000 grams or about 400 to about 3,000 g / mol / group (meta) acrylate. Useful volatilizable acrylates and methacrylates exemplifying include hexane diol diacrylate, ethyl ethoxy acrylate, ethyl phenoxy acrylate, cyanoethyl (mono) acrylate, isobornyl acrylate, isobornyl methacrylate, octadecyl acrylate, isodecyl acrylate, isodecyl acrylate, isodecyl acrylate beta-carboxy ethyl, tetrahydrofurfuryl acrylate, dinitrile acrylate, pentafluorophenyl acrylate, nitrophenyl acrylate, 2-phenoxy ethyl acrylate, 2-phenoxy ethyl methacrylate, 2,2,2- (meth) acrylate
, MO 26/58 trifluoromethyl, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, diacrylate glycol and diacrylate, polyoxyl glycol and diacrylate, propoxylated tetraethylene glycol, bisphenol A epoxy diacrylate, 1,6-hexane diol dimethacrylate, propyl trimethylol triacrylate, ethoxylated trimethylol propane triacrylate, propyl propyl trimethylol triethylate (2-hydrochloride) trisilate, ethylene hydrochloride; , phenylticoethyl acrylate, naphthyloxy ethyl acrylate, cyclic diacrylates (for example, available under the trade name “EB-130” from Cytec Industries Inc.) and trichiciodecane dimethanol diacrylate (for example, available under the trade name SR8338S ”together to Sartomer Co.), epoxy acrylate (for example, available under the trade name “RDX80095” from Cytec Industries Inc.), and mixtures thereof.
Monomers useful to form the first and second layers of polymer are available from several commercial sources and include urethane acrylates (for example, available from Sartomer Co., Exton, PA under the trade names “CN-968” and “CN -983 ”), isobornyl acrylate (for example, available from Sartomer Co. under the trade name“ SR-506 ”), dipentaerythritol pentaacrylates (for example, available from Sartomer Co. under the trade name“ SR-399 ”), Epoxy acrylates blended with styrene (for example, available from Sartomer Co. under the trade name“ CN-120S80 ”), di-trimethylol propane tetraacrylates (for example, available from Sartomer Co. under the trade name "SR-355"), glycolic diethylene diacrylates! (for example, available from Sartomer Co. under the trade name “SR-230”), 1,3-butylene glycol diacrylate (for example, available from Sartomer Co. under the trade name “SR-212”) , pentaacrylate esters (for example, available from Sartomer Co. under the trade name “SR-9041”), pentaerythritol tetraacrylates (for example, available from Sartomer Co. under the trade name “SR-295”), triacrylates pentaerythritol (for example, available from Sartomer Co. under the trade name "SR-444"), (3) ethoxylated trimethylolpropane triacrylates (for example, available from Sartomer Co. under the trade name "SR-454") , (3) | ethoxylated trimethylolpropane triacrylates (for example, available from Sartomer Co. under the trade name “SR-454HP”), alkoxylated trifunctional acrylate esters (for example, available from Sartomer Co. under the trade name “SR-9008”) , dipropylene glycol diacrylates (for example, available from Sartomer Co. under the trade name “SR-508”), neopentyl glycol diacrylates (for example, available. from Sartomer Co. under the trade name “SR-247” ), (4) bisphenol to ethoxylated dimethacrylates (for example, available from Sartomer Co. under the trade name “CD-450”), cyclohexane dimethanol diacrylate esters (for example, available from Sartomer Co. under the name “CD-406”), isobornyl methacrylate (for example, available from Sartomer Co. under the trade name “SR-423"), cyclic diacrylates (for example, available from UCB Chemical, Smyma, GA, under trade name “IRR-214”) and triacrylat o of tris (2-hydroxy ethyl) isocyanurate (by | example; available from Sartomer Co. under the trade name “SR-368"), acrylates among the aforementioned methacrylates and methacrylates among the aforementioned acrylates.
Other monomers that are useful to form the first and / or the second layer | of polymer include vinyl ethers, vinyl naphthalene, acrylonitrile, and mixtures thereof. The desired chemical composition and thickness of the first polymeric layer will depend, in part, on the nature and surface topography of the support. The thickness of the first and / or second polymer layers will typically be sufficient to provide a smooth, defect-free surface to which the inorganic barrier layer can be applied subsequently. For example, the first polymer layer can have a thickness of a few nm (for example, 2 nm or 3 nm) to about 5 micrometers or more. The thickness of the second polymer layer can also be in this range and can, in some embodiments, be thinner than the first polymer layer.
The visible light transmissive inorganic barrier layer can be formed from a variety of materials. Useful materials include metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxiborides, and combinations thereof. Exemplary metal oxides include silicon oxides such as silica, aluminum oxides such as alumina, titanium oxides such as titanium oxide, indium oxides, tin oxides, indium and tin oxide (ITO), tantalum oxide, zirconium oxide, niobium oxide, and combinations thereof. Other exemplary materials include boron carbide, tungsten carbide, silicon carbide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxinitride, “boro oxynitride, zirconium oxide, titanium oxide, and combinations thereof. In some embodiments, the visible light transmissive inorganic barrier layer comprises at least one of ITO, silicon oxide, or aluminum oxide. In some modalities, with the proper selection of the relative proportions of each elementary constituent, ITO can be electrically conductive. Inorganic barrier layers, for example, can be formed using techniques employed in the film metallization technique such as ion bombardment (for example, cathode ion bombardment or flat magnetron, ion bombardment of double AC flat magnetron or ion bombardment double rotating magnetron), evaporation (for example, resistive or electron beam evaporation and enhanced energy analogues of resistive evaporation or electron beam including plasma and ion beam assisted deposition, chemical vapor deposition, deposition plasma-enhanced steam chemistry, and leafing. In some embodiments, inorganic barrier layers are formed using
PDD Lc - ces  + sas = "= = DM o 28/58 ion bombardment (eg reactive ion bombardment). The enhanced barrier properties can be observed when the inorganic layer is formed by a superior energy deposition technique such as ion bombardment compared to lower energy techniques such as conventional vapor deposition processes. Without adhering to the theory, it is believed that the enhancement of properties is due to the condensation of species that settle on the substrate with greater kinetic energy, leading to a lower empty space fraction as a result of compaction.
The desired thickness and chemical composition of each inorganic barrier layer will depend, in part, on the nature and surface topography of the underlying layer and the desired optical properties of the barrier layer. The inorganic barrier layers are typically thick enough to be continuous, and thin enough to ensure that the barrier layers and assemblies presented in the present invention will have the desired degree of visible light transmission and flexibility. The physical thickness (as opposed to the optical thickness) of each inorganic barrier layer can be. For example, from about 3 nm to about 150 nm (in some embodiments, from about 4 nm to about 75 nm). The term "visible light transmissive" for use in the present invention that describes the inorganic barrier layer can mean the fact that there is an average transmission over the visible portion of the spectrum of at least about 75 (in some embodiments, at least about 80, 85, 90, 92, 95, 97, or 98) percent measured along the normal geometric axis. In some embodiments, the inorganic barrier layer has an average transmission over the 400 nm to 1400 nm range of at least about 75 (in some embodiments, at least about 80, 85, 90, 92, 95, 97, or 98) percent. As | transmissive inorganic barrier layers of visible light are those that do not interfere with the absorption of visible light, for example, by photovoltaic cells.
Additional inorganic barrier layers and polymer layers can be present if desired. In modalities where more than one inorganic barrier layer is present, the inorganic barrier layers do not have to be the same, or have the same thickness. When more than one inorganic barrier layer is present, the inorganic barrier layers can, respectively , be called the "first layer of inorganic barrier" and "second layer of inorganic barrier". Additional "polymer layers" may be present between the additional inorganic barrier layers. For example, the barrier layer can have several alternating inorganic barrier layers and polymer layers. Each unit of inorganic barrier layer combined with a polymer layer is called a dyad, and the barrier layer can include any number of dyads. Several types of optional layers can also be included between the dyads.
Surface treatments or fixation layers can be applied between any of the polymer layers or inorganic barrier layers, for example, to optimize smoothness or adhesion.
Useful surface treatments include electrical discharge in the presence of an appropriate reactive or non-reactive atmosphere (for example, plasma, luminescent discharge, corona discharge, dielectric barrier discharge, or atmospheric pressure discharge); chemical pre-treatment; or flame pretreatment.
A separate adhesion promoting layer can also be formed between the main surface of the polymeric film substrate and the barrier layer.
The adhesion-promoting layer can be, for example, a separate polymeric layer or a layer containing metal such as a layer of metal, metal oxide, metal nitride or metal oxynitride.
The adhesion-promoting layer can be a few nanometers (nm) thick (for example, 1 nm or 2 nm) at about 50 nm or more.
In some embodiments, the useful barrier layers comprise polymer layers deposited in plasma (e.g., diamond-like layers) such as those disclosed in the U.S. patent application.
No. 2007-0020451 (Padiyath et al.). For example, the barrier layers can be made by overcoating a first polymer layer on the flexible visible light transmissive substrate, and a polymer layer deposited in overcoated plasma on the first polymer layer.
The first polymer layer can be as described in any of the above embodiments of the first polymer layer.
The polymer layer deposited in plasma can be, for example, a diamond-like carbon layer or a diamond-like glass.
The term "overcoated" describes the position of a layer in relation to a substrate or other element of a barrier layer, refers to the layer as being on top of the substrate or another element, but not necessarily adjacent to the substrate or another element.
The term “diamond-like glass” (DLG) refers to a substantial or completely amorphous glass that includes carbon and silicon, and optionally includes one or more additional components selected from the group that includes hydrogen, nitrogen, oxygen, fluorine , sulfur, titanium and copper.
Other elements may be present in certain modalities.
Amorphous diamond-type glass films may contain grouping of atoms that promote a short-range order, but are essentially devoid of medium and long-range ordering that leads to micro or macro crystallinity, which can adversely disperse radiation of 180 nm to 800 nm wave.
The term “diamond-like carbon” (DLC) refers to an amorphous film or coating that comprises approximately 50 to 90 carbon in atomic percentage and approximately 10 to 50 hydrogen in atomic percentage, with an atom-gram density between approximately 0.20 and approximately 0.28 gram atoms per cubic centimeter, and | composed of approximately 50% to approximately 90% of tetrahedron bonds. i |
In some embodiments, the barrier layer may have multiple layers produced from alternating layers of DLG or DLC and polymer layers (e.g., first and second layers of polymer as described above) overcoated on the flexible visible light transmissive substrate. Each unit including a combination of a polymer layer and a DLG or DLC layer is called a dyad, and the set can include numerous dyads. Several types of optional layers can also be included between the dyads. Adding more layers to the barrier layer can increase its impenetrability to oxygen, moisture or other contaminants and can also help to cover or encapsulate defects in the layers.
In some embodiments, diamond-type glass comprises, on a hydrogen-free basis, at least 30% carbon, a substantial amount of silicon (typically at least 25%) and no more than 45% oxygen. The unique combination of a reasonably high silicon content with a significant oxygen content and a substantial carbon content makes these films highly transparent and flexible. Thin films of diamond-like glass can have a variety of light-transmitting properties. Depending on the composition, thin films can have increased transmissive properties at various frequencies. However, in some embodiments, thin film (when approximately one micrometer thick) is at least 70% transmissive to radiation at substantially all wavelengths from about 250 nm to about 800 nm (for example, 400 nm to about 800 nm). A 70% transmission of a one micron thick film corresponds to an extinction coefficient (k) less than 0.02 in the visible wavelength range between 400 nm and 800 nm.
In the creation of a diamond-type glass film, several additional components can be incorporated in order to alter and intensify the properties that the typical glass film gives to the substrate (for example, barrier and surface properties). Additional components may include one or more of hydrogen, nitrogen, fluorine, sulfur, titanium or copper. Additional components can also be beneficial. The addition of hydrogen promotes the formation of tetrahedral bonds. The addition of fluorine can enhance the barrier and surface properties of the diamond-type glass film, including the ability to be dispersed in an incompatible matrix. Fluoride sources include compounds such as carbon tetrafluoride (CF), sulfur hexafluoride (SFs), CoF6, C3Fg, & CaFio. The addition of nitrogen can be used to increase resistance to oxidation and to increase electrical conductivity, nitrogen sources include nitrogen gas (N>), ammonia (NH;) and hydrazine (NxH; s). The addition of sulfur can enhance adhesion. The addition of titanium tends to enhance adhesion and diffusion and barrier properties.
Various additives can be used for the DLC film. In addition to nitrogen or fluorine, which can be added for the reasons described above in relation to diamond-type glass,
oxygen and silicon can be added.
The addition of silicon and oxygen to the DLC coating tends to optimize the optical transparency and thermal stability of the coating.
Oxygen sources include oxygen gas (Oz), water vapor, ethanol, and hydrogen peroxide.
Sources of silicon preferably include silanes such as SiH, SioH; s, and hexamethyl disiloxane.
The DLG or DLC film additives described above can be incorporated into the diamond-like matrix or attached to the atomic surface layer.
If additives are incorporated into the diamond-like matrix, they may cause irregularities in density and / or structure, but the resulting material will essentially be a compactly packed net with characteristics of diamond-like carbon (chemical inertness, hardness content and properties of barceira)) If the additive concentration is very large (for example, greater than 50 in atomic percentage in relation to the carbon concentration), the density will be affected, and the beneficial properties of the diamond-like carbon network will be lost.
If additives are attached to the atomic surface layers, they will only change the structure and properties of the surface.
The volume properties of the diamond-like carbon network will be preserved.
Polymers deposited in plasma such as diamond-like glass and diamond-like carbon can be synthesized from a plasma through the use of precursor monomers in the gas phase at low temperatures.
The precursor molecules are decomposed by energetic electrons present in the plasma to form free radical species.
These free radical species react with the substrate surface and lead to the growth of the polymeric film film.
Due to the lack of specification of the reaction processes in both the gas phase and the substrate, the resulting polymer films are typically highly cross-linked and amorphous in nature.
For additional information related to polymers deposited in plasma, see, for example, H.
Yasuda, "Plasma Polymerization," Academic Press Inc, New York, USA (1985); Rd'Agostino (Ed), “Plasma Deposition, Treatment & Etching of Polymers," Academic Press, New York, USA (1990); and H.
Biederman and Y.
Osada, “Plasma Polymerization Processes," Elsever, New York, USA (1992). Typically, the plasma deposited polymer layers described here are organic in nature due to the presence of hydrocarbons and functional carbonaceous groups such as CH; 3, CH72, CH, Si-C, Si-CH; 3, AFC, Si-O-CH ;, etc.
The polymer layers deposited in plasma are substantially substoichiometric in their inorganic component and substantially rich in.
In films containing silicon, for example, the oxygen ratio | for silicon is typically below 1.8 (silicon dioxide has a ratio of 2.0), plus | typically below 1.5 for DLG, and the carbon content is at least about 10%. In some embodiments, the carbon content is at least about 20% or 25%. Amorphous diamond-type films formed by chemical plama and ion intensified vapor deposition (PECVD) using silicone oil and an optional silane source to form plasma as described, for example, in U.S. Patent Application 2008-
0196664 (David et al.), Can also be useful in barrier layers. The terms "silicone", "silicone oil" or "siloxanes" are used interchangeably and refer to higher molecular weight and oligomeric molecules that have a structural unit R, 8SiO in which R is independently selected from hydrogen, (Cr-Cs) alkyl, (Cs-Cis) aryl, (Cçs-Cosarylalkyl or (Cs-Cos) alkyl aryl. They may also be called polyorganosiloxanes and include alternating silicon and oxygen chains (- O-Si-O- Si-O-) with free valences of silicon atoms usually joined to R groups, but can also be joined (crosslinked) to oxygen atoms and silicon atoms of a second chain, forming a network (high PM) In some embodiments, a source of siloxane such as vaporized silicone oil is introduced in such a way that the resulting plasma-formed coatings are flexible and have high optical transmission Any additional useful process gases, such as oxygen , nitrogen and / or ammonia, for example, can be used with siloxane and optional silane to assist in plasma maintenance and to modify the properties of amorphous diamond film layers.
In some embodiments, combinations of two or more different polymers deposited in plasma can be used. For example, different layers of polymer deposited in plasma formed by changing or pulsating the process gas that forms the plasma to deposit the polymer layer. In another example, a first layer of a first amorphous diamond-type film can be formed and then a second layer of a second amorphous diamond-type film can be formed on the first layer, where the first layer has a different composition than the second layer . In some embodiments, a first layer of amorphous diamond-type film is formed from a silicone oil plasma and then a second layer of amorphous diamond-type film is formed from a silicone oil and silane plasma. In other embodiments, two or more layers of the amorphous diamond type film of alternative composition are formed to create the amorphous diamond type film.
Polymers deposited in plasma such as diamond-like glass and diamond-like carbon can have any useful thickness. In some embodiments, the polymer deposited in plasma can have a thickness of at least 500 angstroms, or at least 1,000 angstroms. In some embodiments, the polymer deposited in plasma can have a thickness in the range of 1,000 angstroms to 50,000 angstroms, from
1,000 angstrons to 25,000 angstrons, or 1,000 angstrons to 10,000 angstrons.
Other plasma deposition processes for preparing useful barrier layers 120 such as carbon-rich films, films containing silicon or combinations thereof are disclosed, for example, in U.S. Patent No. 6,348,237 (Kohler et al.). Carbon-rich films can contain at least an atomic percentage of carbon equal to 50 and, | typically, an atomic carbon percentage of about 70 to 95 an atomic nitrogen percentage of 0.1 to 20 an atomic oxygen percentage of 0.1 to 15, and an atomic hydrogen percentage of 0.1 to 40. Such carbon-rich films can be classified as "amorphous", "hydrogenated amorphous", "graphitic", "i-carbon", or "diamond type", depending on their chemical and physical properties. Films containing silicon are usually polymeric and | 5 contain, in random composition, silicon, carbon, hydrogen, oxygen and nitrogen.
Carbon-rich films and films containing silicon can be formed by interacting plasma with a vaporized organic material, which is usually a liquid at room temperature and pressure. The vaporized organic material is typically capable of condensing in a vacuum of less than about 130 Pa (1 Torr). The vapors are directed to the flexible visible light transmitting substrate in a vacuum (for example, in a conventional vacuum chamber) on a negatively charged electrode as described above for deposition of polymer in plasma. A plasma (for example, an argon plasma or a carbon-rich plasma as described in U.S. patent no.
5,464,667 (Kohler et al.)) And at least one vaporized organic material interact during film formation. Plasma is one that is capable of activating the vaporized organic material. Plasma and vaporized organic material can interact on the surface of the substrate or before coming into contact with the surface of the substrate. Either way, the interaction of the vaporized organic material and the plasma provides a reactive form of the organic material (for example, loss of the methyl group of the silicone) to allow the material to densify through the formation of the film as a result of polymerization and / or halftone, for example. Significantly, these films are prepared without the need for solvents.
Such formed films may be uniform multicomponent films (for example, layer films produced from multiple starting materials), uniform one-component films and / or multilayer films (for example, alternating layers of carbon-rich material and silicone). For example, with the use of a carbon-rich plasma in a stream from a first source and a high molecular weight organic liquid vaporized like dimethyl siloxane oil in another stream from a second source, a pass deposition procedure can result in a multilayered construction of the film (for example, a layer of a carbon-rich material, a layer of dimethyl siloxane that is at least partially polymerized and an intermediate or interfacial layer of a carbon / dimethyl siloxane composite). Variations in system layouts result in controlled formation of uniform multicomponent films or layered films with gradual or abrupt changes in properties and composition as desired. Uniform coatings of a material can also be formed from a carrier gas plasma (eg, argon), and a vaporized high molecular weight organic liquid (eg, dimethyl siloxane oil). | |
Other useful barrier layers comprise films that have a graduated composition coating like those described in the U.S. patent.
No. 7,015,640 (Schaepkens et al.). Films that have a graduated composition coating can be produced through the deposition reaction or species reaction recombination products on polymeric film substrate.
The variation in the relative supply rates or the change in the identities of the reactive species results in a coating that has a composition that can be classified along its thickness.
Suitable coating compositions are organic, inorganic or ceramic materials.
These materials are typically products of the reaction or recombination of reactive plasma species, and are deposited on the substrate surface. Organic coating materials typically comprise carbon, hydrogen, oxygen, and, optionally, other smaller elements, such as sulfur, nitrogen, silicon, etc., depending on the types of reagents.
Suitable reagents that result in inorganic compositions in the coating are linear or branched alkanes, alkenes, alkynes, alcohols, aldehydes, ethers, alkylene oxides, aromatics, etc., having up to 15 carbon atoms.
Inorganic and ceramic coating materials typically comprise oxide; nitride; carbide; boride; or combinations thereof of elements from Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB and IIB; metals of Groups IIIB, IVB and VB; and rare earth metals.
For example, a silicon carbide can be deposited on a substrate by recombining plasmas generated from silane (SiH) and an organic material, such as methane or xylene.
Silicon oxycarbide can be deposited from plasmas generated from silane, methane, and oxygen, or silane and propylene oxide.
Silicon oxycarbide can also be deposited from plasmas generated from organosilicone precursors, such as tetraethoxysilane (TEOS), hexamethyl disiloxane (HMDSO), hexamethyldisilazane (HMDSN), or octamethyl cyclotetrasiloxane (D4). Silicon nitride can be deposited from plasmas generated from silane and ammonia.
Aluminum oxycarbonitride can be deposited from a plasma generated from a mixture of aluminum tartrate and ammonia.
Other combinations of reagents can be selected to obtain a desired coating composition.
The choice of specific reagents is within the scope of the practice of those skilled in the art.
A classified composition of the coating can be obtained by changing the compositions of the reagents fed to the reactor chamber during the deposition of reaction products to form the coating, or by using overlapping deposition zones, for example, in a blanket process .
The coating can be formed by one of many deposition techniques, such as plasma-enhanced chemical vapor deposition (PECVD), radio-frequency plasma-enhanced chemical deposition (RFPECVD), thermally expanding plasma chemical vapor deposition (ETPCVD) ), ion bombardment including reactive ion bombardment, plasma-enhanced chemical vapor deposition with electron cyclotron resonance (ECRPECVD), inductively coupled plasma-enhanced chemical vapor deposition (ICPECVD), or combinations thereof. The coating thickness is typically in the range of about 10 nm to about 10,000 nm, in some embodiments, from about 10 nm to about 1,000 nm, and, in some embodiments, from about 10 nm to about 200 nm. The barrier layer can have an average transmission over the visible portion of the spectrum of at least about 75 (in some embodiments, at least about 80, 85, 90, 92, 95, 97 or 98) measured over the normal axis. In some embodiments, the barrier layer has an average transmission over a range from 400 nm to 1400 nm of at least about 75 (in some embodiments, at least about 80, 85, 90, 92, 95, 97 or 98) Percent.
Other suitable barrier layers include thin and flexible glass laminated to a polymer film, and glass deposited on a polymeric film.
For additional details on the barrier layers, see also, for example, a co-pending order that has U.S. serial number 61 / 262,406, filed on November 18, 2009, the description of which is incorporated herein by reference.
Exemplifying modalities
1. A UV-stable multilayer optical film that comprises at least a plurality of first and second optical layers that collectively reflect at least 50 percent of UV light incident over at least a 30 nanometer wavelength range in a range wavelength of at least 300 nanometers to 400 nanometers, where at least one of the first or second optical layers comprises a UV absorber.
2. The multilayer optical film of mode 1, in which transmission of incident UV light through at least the plurality of first and second optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 400 nanometers.
3. The multilayer optical film of any of the previous embodiments, in which the transmission of incident light through at least the plurality of first and second optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 430 nanometers.
4. The multilayer optical film of any of the previous embodiments that has a UV transmission band edge in a range of 10 to 90 percent transmission spanning less than 20 nanometers.
5. The multilayer optical film of any of the modalities 1 to 3 that has a UV transmission band edge in a 10 to 90 percent transmission range spanning less than 10 nanometers.
6. The multilayer optical film of any of the previous modalities that has a thickness in a range of 25 micrometers to 250 micrometers.
7. The multilayer optical film of any of the previous modalities, in which the plurality of the first and second optical layers has a collective thickness in a range of 15 micrometers to 25 micrometers
8. The multilayer optical film of any of the above embodiments, wherein the at least first optical layer comprises PMMA, PC or PET, and the second optical layer comprises THV, PMMA or CoPMMA.
9. A set comprising the multilayer optical film of any of the previous embodiments and a barrier layer.
10. Mode 9 as a whole, wherein the barrier layer comprises at least 10 minus first and second polymer layers separated by an inorganic barrier layer.
11. A composite article comprising a substrate having a main surface, and the assembly of any embodiment 9 or 10 on at least a portion of the main surface. | 12 12. A vehicle window comprising all of the | modalities 9 or 10. | 13. A commercial graphic signage comprising all of the 9 or 10 modes.
14. A set of light comprising the set of any of the 9 or 10 modes.
15. A signal that comprises all of the 9 or 10 modes.
16. An LCD comprising all 9 or 10 modes.
17. A building exterior comprising all 9 or 10 modes.
18. A photovoltaic module that comprises all of the 9 or 10 modes.
19. The photovoltaic module of modality 18, which is a flexible module.
20. A composite article comprising a substrate having a main surface, and the film of any one of embodiments 1 to 8 on at least a portion of the main surface.
21. A vehicle window comprising the film of any of the J modalities 1 to 8.
22. A commercial graphic signage that includes the film of any of the modalities 1 to 8.
23. A set of light that comprises the end of any of the | modalities 1 to 8. |
24. A sign that comprises the film of any of the modalities 1 to 8. | À | |
25, An LCD that comprises the film of any of the modalities 1 to 8.
26. A building exterior that comprises the film of any of the modalities 1 to 8.
27. A photovoltaic module that comprises the film of any one of the - modalities 1 to 8.
28. The photovoltaic module of modality 27, which is a flexible module.
29. A multilayer optical film that comprises a plurality of at least first and second optical layers that has a main surface and that collectively reflects at least 50 percent of UV light incident on at least one wavelength band of 30 nanometers over a wavelength range of at least 300 nanometers to 400 nanometers, and a third optical layer that has first and second among the first and second generally opposite surfaces and that absorbs at least 50 percent of UV light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is close to the first main surface of the third optical layer, and where there is no other multilayer optical film near the second surface of the third optical layer.
30. The multilayer optical film of modality 29, wherein the main surface of the plurality of first and second optical layers is in contact with the first main surface of the third optical layer.
31. The multilayer optical film of any of the 30 or 31 modalities, in which the transmission of incident UV light through at least the first, second and third optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 400 nanometers.
32. The multilayer optical film of any of the 29 or 30 modalities, in which the transmission of incident light through at least the first, second and third optical layers is less than 5 percent over a hair wavelength range. minus 300 nanometers to 430 nanometers.
33. The multilayer optical film of any of the modalities 29 to 32 that has a UV transmission band edge in a range of 10 to 90 percent transmission spanning less than 20 nanometers.
34. The multilayer optical film of any of the modalities 29 to 32 that has a UV transmission band edge in a range of 10 to 90 percent transmission spanning less than 10 nanometers.
35. The multilayer optical film of any of the modalities 29 to 34 that has a thickness in a range of 25 micrometers to 250 micrometers.
36. The multilayer optical film of any of the modalities 29 to 35, in which the at least first and second optical layers have a collective thickness in a range of 15 micrometers to 25 micrometers
37. The multilayer optical film of any of the modalities 29 a! 5 36, in which at least the first optical layer comprises PMMA, PC or PET, e! the second optical layer comprising THV, PMMA or COPMMA.
38. The multilayer optical film of any of the modalities 29 to 36, in which the at least first and second optical layers comprise PMMA and THV,
39. The multilayer optical film of any of the modalities 29 to 38, in which at least the third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
40. The multilayer optical film of any of the modalities 29 to 39, in which the third optical layer comprises at least one of PET, CoPET, PC, PMMA, CoPMMA or blends of PMMA and PVDF.
41. The multilayer optical film of any of the modalities 29 to 40, wherein at least one of the first or second optical layers comprises a UV absorber.
42. An assembly comprising the multilayer optical film of any of the modalities 29 to 41 and a barrier layer,
43. The whole of embodiment 42, wherein the barrier layer comprises at least first and second layers of polymer separated by an inorganic barrier layer.
| 44. A composite article comprising a substrate having a main surface, and the combination of any one of embodiments 42 or 43 on at least a portion of the main surface.
45. A vehicle window comprising all of the 42 or 43 modes.
46. A commercial graphic signage comprising all of the 42 or 43 modes.
47. A set of light comprising all 42 or 43 modes. | 48, A signal comprising all of the 42 or 43 modes.
49. An LCD comprising all 42 or 43 modes. |
50. A building exterior comprising any of the 42 or 43 modes.
51. A photovoltaic module comprising all of the 42 or 43 modes.
52. The photovoltaic module of modality 51, which is a flexible module.
53. A composite article comprising a substrate having a main surface, and the film of any of the embodiments 29 to 41 on at least a portion of the main surface.
54, A vehicle window comprising the film of any of the modalities 29 to 41.
55. A commercial graphic signage that includes the film of any of the modalities 29 to 41.
56. A set of light that comprises the film of any of the modalities 29 to 41.
57. A sign that comprises the film of any of the modalities 29 to 41.
58. An LCD that comprises the film of any of the modalities 29 to 41.
59. A building exterior that comprises the film of any of the modalities 29 to 41.
60. A photovoltaic module that comprises the film of any of the modalities 29 to 41.
61. The photovoltaic module of modality 60, which is a flexible module.
62. A multilayer optical film comprising a first plurality of at least first and second optical layers having a main surface and which collectively reflects at least 50 percent of UV light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, and a third optical layer that has first and second among the first and second generally opposite surfaces and that collectively absorb at least 50 percent of UV light incident on at least one wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is close to the first main surface of the third optical layer, and where there is a second plurality of first and second optical layers that have a main surface and that ref collectively cast at least 50 percent of UV light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers near the second main surface of the third optical layer.
63. The multilayer optical film of modality 62, in which the main surface of the plurality of first and second optical layers is in contact with the first main surface of the third optical layer, and where the main surface of the second plurality of first and second layers second optical layers are in contact with | second main surface! of the third optical layer.
64. Multilayer optical film of any of the 62 or 63 modes, in which transmission of incident UV light through at least the first, second and third optical layers is less than 5 percent over a hair wavelength range minus 300 nanometers to 400 nanometers.
65, The multilayer optical film of any of the 62 or 63 modalities, in which the transmission of incident light through at least the first, second and third optical layers is less than 5 percent in a hair wavelength range. minus 300 nanometers to 430 nanometers.
66. The multilayer optical film of any of the modalities 62 to 65, in which the third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
67. The multilayer optical film of any of the modalities 62 to 66, in which the at least first optical layer comprises at least one of PMMA, PC or PET, and in which the second optical layers comprise at least one of THV, PMMA or COPMMA.
68. The multilayer optical film of any of the modalities 62 to 67, wherein the third optical layer comprises at least one among PET, CoPET, PC, PMMA, CoPMMA or blends of PMMA and PVDF.
69. The multilayer optical film of any of the modalities 62 to 68 has an edge of UV transmission band in a range of 10 to 90 percent transmission spanning less than 20 nanometers.
70. The multilayer optical film of any of the 62 to 69 modes that has a UV transmission band edge in a 10 to 90 percent transmission range spanning less than 10 nanometers.
71. The multilayer optical film of any of the modalities 62 to 70 that has a thickness in a range of 25 micrometers to 250 micrometers.
72. The multilayer optical film of any of the modalities 62 to 71, in which each one has the pluralities of first and second optical layers having a collective thickness in a range of 15 micrometers to 25 micrometers.
73. The multilayer optical film of any of the modalities 62 to 72, in which the at least third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
74. The multilayer optical film of any of the modalities 62 to 73, wherein part of at least one of the first or second optical layers comprises a UV absorber.
75. An assembly comprising the multilayer optical film of any of the modalities 62 to 74 and a barrier layer.
Pa FE MM MM MM 41/58 | 76. Mode 75 as a whole, wherein the barrier layer comprises at least first and second layers of polymer separated by an inorganic barrier layer,
77. A composite article comprising a substrate having a main surface, and the assembly of any of the modalities 75 or 76 on at least a portion of the main surface.
78. A vehicle window comprising all 75 or 76 modes.
79. A commercial graphic signage comprising all 75 or 76 modalities.
80. A set of light comprising all 75 or 76 modes.
81. A sign comprising all 75 or 76 modes.
82. An LCD comprising all 75 or 76 modes.
83. A building exterior comprising any of the 75 or 76 modes.
84. A photovoltaic module comprising all 75 or 76 modes.
85. The photovoltaic module of modality 84, which is a flexible module. | 86. A composite article comprising a substrate having a main surface, and the film of any of the modalities 62 to 74 on at least a portion of the main surface.
87. A vehicle window comprising the film of any of the | modalities 62 to 74,: 25 88. A commercial graphic signage comprising the film of any one of modalities 62 to 74. | 89. A set of light that comprises the film of any of the 'modalities 62 to 74.
90. A sign that comprises the film of any of the modalities 62 to 74.
91. An LCD that comprises the film of any of the modalities 62 to 74.
92. A building exterior that comprises the film of any of the modalities 62 to 74.
93. A photovoltaic module that comprises the film of any of the modes 62 to 74.
94. The photovoltaic module of modality 93, which is a flexible module.
95. A multilayer optical film comprising a plurality of at least first and second optical layers having first and second surfaces
| . '| 42/58 main opposites and which collectively reflects at least 50 percent of incident UV light | over at least a wavelength range of 30 nanometers in a range of | wavelength of at least 300 nanometers to 400 nanometers, a third optical layer that has a main surface and absorbs at least 50 percent of UV light | 5 incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers near the first main surface of the plurality of at least first and second optical layers, and a fourth optical layer which absorbs at least 50 percent of UV light incident over at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers near the second main surface of the plurality of at least first and second layers optics.
96. Mode 95 multilayer optical film, where the surface | main layer of the third layer is in contact with the first main surface of | plurality of first and second optical layers, and the main surface | 15 of the fourth layer is in contact with the second main surface of the plurality of | first and second optical layers.
97. Multilayer optical film of any of the 95 or 96 modes, in which transmission of incident UV light through at least the first, second and third optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 400 nanometers. . 98. Multilayer optical film of any of the 95 or 96 modes, in which the transmission of incident light through at least the first, second, third and fourth optical layers is less than 5 percent over a wavelength range at least 300 nanometers to 430 nanometers.
99. The multilayer optical film of any of the modes 95 to 98, in which the third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
100. The multilayer optical film of any of the modes 95 to 99, in which the fourth optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
101. The multilayer optical film of any of the modes 95 to 100, in which the at least first optical layer comprises at least one among PMMA, PC or PET, and the second optical layers comprise at least one among THV, PMMA or CoPMMA.
102. The multilayer optical film of any of the modalities 95 to 101, in which the third and fourth optical layers independently comprise at least one of PET, CoPET, PC, PMMA, COPMMA or blends of PMMA and PVDF.
103. The multilayer optical film of any of the 95 to 102 modalities that has a UV transmission band edge in a 10 to 90 percent transmission range spanning less than 20 nanometers.
104. The multilayer optical film of any of the 95 to 103 modes that has a UV transmission band edge in a 10 to 90 percent transmission range spanning less than 10 nanometers.
105. The multilayer optical film of any of the modes 95 to 104 that has a thickness in a range of 25 micrometers to 250 micrometers.
106. The multilayer optical film of any of the modalities 95 to 105, in which each one has the pluralities of first and second optical layers having a collective thickness in a range of 15 micrometers to 25 micrometers.
107. The multilayer optical film of any of the modes 95 to 106, in which the at least third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
108. The multilayer optical film of any of the modalities 95 to 107, wherein part of at least one of the first or second optical layers comprises a UV absorber.
109. An assembly comprising the multilayer optical film of any of the modes 95 to 108 and a barrier layer.
110. The 109 mode assembly, wherein the barrier layer comprises at least first and second layers of polymer separated by an inorganic barrier layer.
111. A composite article comprising a substrate having a main surface, and the assembly of any of the modalities 109 or 110 on at least a portion of the main surface.
112. A vehicle window comprising all 109 or 110 modes.
113. A commercial graphic signage comprising all 109 or 110 modalities.
114. A set of light comprising the set of any of the 109 or 110 modes.
115. A sign comprising all of the 109 or 110 modalities.
116. An LCD comprising all 1090u110 modes.
117. A building exterior comprising all 109 or 110 modes. Í Í
118. A photovoltaic module comprising all 109 or 110 modes.
119. The photovoltaic module of modality 118, which is a flexible module.
120. A composite article comprising a substrate having a main surface, and the film of any one of embodiments 95 to 107 on at least a portion of the main surface.
121. A vehicle window comprising the film of any of the modes 95 to 107.
122. A commercial graphic signage comprising the film of any of the modes 95 to 107.
123. A set of light that comprises the film of any of the modalities 95 to 107.
124. A signal that comprises the film of any of the modalities 95 to 107.
125. An LCD that comprises the film of any of the modes 95 to 107.
126. A building exterior comprising the film of any of the 95 to 107 modalities.
127. A photovoltaic module that comprises the film of any of the modalities 95 to 107.
128. The 127 mode photovoltaic module, which is a flexible module.
129. A multilayer optical film comprising at least first and second optical layers that reflect at least 50 percent of light incident over a wavelength range of 30 nanometers over a wavelength range of 300 nanometers to 430 nanometers , optionally a third optical layer that absorbs at least 50 percent of light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 430 nanometers and a fourth optical layer comprising polyethylene naphthalate, in which at least one of the first, second or third optical layers absorbs at least 50 percent of light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 430 nanometers.
130. Mode 129 multilayer optical film, where transmission of incident UV light through at least the first, second and third optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 400 nanometers.
131. Multilayer optical film of modality 130, in which the transmission of incident light through at least the first, second and third optical layers is less than 5 percent over a wavelength range of at least 300 nanometers to 430 nanometers. | 132. The multilayer optical film of any of the modalities 129 to 131, in which the third optical layer has a collective thickness in a range of micrometers to 200 micrometers.
133. The multilayer optical film of any of the modalities 129 to 131, in which the at least first optical layers comprise at least one among PMMA, PC, or PET, and the second optical layers comprise at least one among THV , PMMA or CoPMMA.
10 132, The multilayer optical film of any of the modalities 129 to 133, wherein the third optical layer comprises at least one of PET, CoPET, PC, PMMA, CoPMMA or blends of PMMA and PVDF.
133. Multilayer optical film of any of 129 to 132 modes that has a UV transmission band border in a 10 to 90 percent transmission range spanning less than 20 nanometers.
134. The multilayer optical film of any of the 129 to 132 modes that has a UV transmission band edge in a 10 to 90 percent transmission range spanning less than 10 nanometers.
135. The multilayer optical film of any of the 129 to 134 modes has a thickness in a range of 25 micrometers to 250 micrometers.
136. The multilayer optical film of any of the modalities 129 to 135, in which each one has the pluralities of first and second optical layers having a collective thickness in a range of 15 micrometers to 25 micrometers.
137. The multilayer optical film of any of the 129 to 133 modalities, in which at least the third optical layer has a collective thickness in a range of 10 micrometers to 200 micrometers.
138. The multilayer optical film of any of the modalities 129 to 137, wherein part of at least one of the first or second optical layers comprises a UV absorber.
139. An assembly comprising the multilayer optical film of any of the modalities 129 to 138 and a barrier layer.
140. Mode 139 as a whole, wherein the barrier layer comprises at least first and second polymer layers separated by an inorganic barrier layer.
141. A composite article comprising a substrate having a main surface, and the combination of any of the 139 or 140 modalities on at least a portion of the main surface.
142. A vehicle window comprising all 139 or 140 modes,
143. A commercial graphic signage comprising all 139 or 140 modalities.
144. A set of light comprising the set of any of the 139 or 140 modalities.
145. A sign comprising all 139 or 140 modalities.
146. An LCD comprising all 1390uU140 modes.
147. A building exterior comprising all 139 or 140 modalities.
148. A photovoltaic module comprising all 139 or 140 modes.
149. The 148 mode photovoltaic module which is a flexible module.
150. A composite article comprising a substrate having a main surface, and the film of any of the embodiments 129 to 136 on at least a portion of the main surface.
151. A vehicle window comprising the film of any of the 129a136 modalities.
152. A commercial graphic signage that comprises the film of any of the modalities 129 to 136.
153. A set of light that comprises the film of any of the modalities 129 to 136.
154. A sign that comprises the film of any of the modalities 129 to 136.
155. An LCD that comprises the film of any of the modalities 129 to 136.
156. A building exterior that comprises the film of any of the modalities 129 to 136.
157. A photovoltaic module that comprises the film of any of the modalities 129a136.
158. The 157-mode photovoltaic module, which is a flexible module.
The advantages and modalities of this invention are further illustrated by the following examples, however, the specific materials and quantities mentioned in these examples, as well as the conditions and details, should not be unduly interpreted as limiting this invention. All parts and percentages are measured by weight, unless otherwise indicated.
Comparative example A
»A multilayer optical film was produced with the first optical layers of polyethylene 2.6 naphthalate (PEN) and second optical layers of polymethyl methacrylate (PMMA1) (obtained from Arkema Inc. Philadelphia, PA, USA, under the trade name “PEXIGLAS VO44" ”). Polyethylene 2,6 naphthalate (PEN) was synthesized in a batch reactor with the following raw material charge: 2,6 dimethyl naphthalene dicarboxylate (136 kg), ethylene glycol! ( 73 kg), manganese (II) acetate (27 grams), cobalt acetate (!!) (27 grams) and antimony acetate (ll!) (48 grams), under a pressure of 166.7 kPa (1520 torr) or 2x10º N / m (2 atm.)), this mixture was heated to 254ºC during the removal of methanol (a by-product of the transesterification reaction). After 35 kg of methane! had been removed, 49 grams of triethyl phosphonoacetate were removed. loaded in the reactor and the pressure was gradually reduced to 0.13 kPa ((131 N / mº [1 torr]) during heating to 290ºC. The reaction by-product Condensing agent, ethylene glycol, was continuously removed until a polymer with an intrinsic viscosity of 0.48 dl / g (as measured at 60/40% by weight of phenol / o-dichlorobenzene) was produced.
PEN and PMMA1 were coextruded through a multilayer polymer melt pipeline to create a multilayer melt stream that has 530 alternating first and second optical layers. In addition to the first and second optical layers, a pair of non-optical layers also made up of PEN was coextruded as protective film layers on both sides of the optical layer stack. This flow of coextruded, multi-layered molten material was molded onto a cooled cylinder at 22 meters per minute creating a multi-layered molded network about 1.075 micrometers (43 mils) thick.
| The multi-layer molded mesh was then heated in a tenter oven at 145ºC for 10 seconds before being biaxially oriented at a 3.8x3.8 stretch ratio. The oriented multilayer film was further heated to 225 ° C for 10 seconds to increase the crystallinity of the PEN layers. The reflectivity of this multilayer visible mirror film was measured with a spectrophotometer (obtained from Perkin-Elmer, Inc., Waltham, MA, USA, under the trade name “LAMBDA 950”) to have an average reflectivity of 98.5 % over a bandwidth of 390 to 850nm. After 3,000 hours of exposure to a chamber with a xenon arc lamp of the weatherometer type according to ASTM G155-05a (October, 2005), a change in b * of 5 units was measured with the spectrophotometer (“LAMBDA 950").
Comparative example B A multilayer optical film against ultraviolet (UV) was produced with the first optical layers of polyethylene terephthalalt (PET1) (obtained from Eastman Chemical, Kingsport, TN, USA, under the trade name “EASTAPAK 7452”) and the second optical layers of a copolymer of 75 percent by weight of methyl methacrylate and 25 percent by weight of ethyl acrylate (coPMMA1) (obtained from Ineos Acrylics, Inc., Memphis, TN, USA , under the trade name “PERSPEX CP63”). PETI and coPMMA1 were coextruded through a multilayer polymer melt pipe to form a stack of 224 optical layers. The layer thickness profile (layer thickness values) of this UV reflector has been adjusted to be approximately a linear profile with the first (thinner) optical layers adjusted to have about * á of optical wave thickness (index times thickness physics) for 350 nm light and progressing to the thicker layers which are adjusted to be about 74 thick optical wavelength for 410 nm light. The layer thickness profiles of such films have been adjusted to provide enhanced spectral characteristics with the use of the axial rod apparatus reported in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference, combined with layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the non-optical protective film layers of PETI1 (thickness of 260 micrometers each) were coextruded on both sides of the optical stack. This multilayered coextruded melt flow was molded onto a cooled cylinder at 5.4 meters per minute creating a molded multilayer network about 500 micrometers (20 mils) thick. The multi-layer molded mesh was then preheated for about 10 seconds at 95ºC and biaxially oriented at 3.5x3.7 stretch ratios. The oriented multilayer film was further heated to 225 ° C for 10 seconds to increase the crystallinity of the PET layers.
The UV reflective multilayer optical film (Film 1) was measured with the spectrophotometer (“LAMBDA 950”) to transmit less than 1 percent of the UV light over a 350 to 400 nm bandwidth.
After 3,000 hours of exposure to a chamber with a xenon arc lamp of the weatherometer type, according to ASTM G155-05, a change in b * of 3.5 units was measured with the spectrophotometer (“LAMBDA 950”).
Example 1 A multilayer optical film reflective against UV was produced with the first optical layers of PET1 and second optical layers of coPMMA1. PET1 and coPMMA1 were coextruded through a multilayer polymer melt pipe to form a stack of 224 optical layers. The layer thickness profile (layer thickness values) of this UV reflector was adjusted to be approximately a linear profile with the first optical (thinner) layers adjusted to about 50% optical wave thickness (index times physical thickness) for light. 350 nm and progressing to the thicker layers which are adjusted to be about 4 thick optical wavelength for 400 nm light. The layer thickness profiles of such films were adjusted to provide enhanced spectral characteristics with the use of the axial rod apparatus taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference, combined with | layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the non-optical protective film layers of PET1 (thickness of 260 micrometers each) were coextruded on both sides of the optical stack. 2% by weight of the UV absorber (obtained from Ciba Specialty Chemicals Corporation, Tarryton, NY, USA, under the trade name “TINÚVIN 1577 UVA") was combined in these protective PET film layers.
This flow of molten material - coextruded from multiple layers was molded on a cooled cylinder at 5.4 meters per minute, creating a molded multilayer network approximately 500 micrometers (20 mils) thick.
The multi-layer molded mesh was then preheated for about 10 seconds at 95ºC and biaxially oriented at 3.5x3.7 stretch ratios. The oriented multilayer film was further heated to 225 ° C for 10 seconds to increase the crystallinity of the PET layers.
The UV reflective multilayer optical film (Film 1) was measured with the spectrophotometer (“LAMBDA 950”) to transmit less than 2 percent of the UV light over a 350 to 400 nm bandwidth.
After 3,000 hours of exposure to a chamber with a xenon arc lamp dotipoweatherometer according to ASTM G155-05a (October, 2005), a change in b * less than 1 unit was measured with the spectrophotometer (“LAMBDA 950”). Example 2 A multi-layer optical film reflective against UV was produced with the first optical layers of PET1 and second optical layers of coPMMA1. PET1 and —coPMMAI1 were coextruded through a multilayer polymer melt pipe to form a 224 stack of optical layers.
The layer thickness profile (layer thickness values) of this UV reflector was adjusted to be approximately a linear profile with the first (thinner) optical layers adjusted to have about A of optical wave thickness (index times physical thickness ) for 350nm light progressing to the thicker layers that are adjusted to be about 4% thick optical wavelength for 400 nm light.
The layer thickness profiles of such films were adjusted to provide enhanced spectral characteristics with the use of the axial rod apparatus taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference, combined with layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the PET1 non-optical protective film layers (thickness of 260 micrometers each) were coextruded on both sides of the optical stack. 2% by weight of UV absorber ("TINUVIN 1577 UVA”) was combined in these protective PET film layers. This flow of coextruded multi-layer molten material was molded on a cooled cylinder at 5.4 meters per minute, creating a network multi-layered molding of approximately 500 micrometers (20 mils) in thickness The multi-layered molded net was then preheated for about 10 seconds at 95ºC and biaxially oriented in a stretch ratio of 3.5x3.7. oriented multi-layer film was additionally heated to 225ºC for 10 seconds to increase the crystallinity of the PET layers.The multi-layered UV-reflective optical film (Film 1) was measured with the spectrophotometer (“LAMBDA 950”) to transmit less than 2 percent of UV light over a 350 to 400 nm bandwidth.
Film 1 was laminated using an optically transparent adhesive (available from 3M Company, St. Paul, MN, USA, under the trade name “OPTICALLY CLEAR LAMINATING ADHESIVE PSA 8171”) on a 75 micron thick sheet surface made of polymethyl methacrylate (PMMA2) (obtained from Ineos Acrylics, Inc. Wilmington, DE, USA, under the trade name “CP82” which has been combined with 3% by weight UV absorber (“TINUVIN 1577 UVA”) Another sample of Film 1 was laminated to the second surface of PMMA2 with the same 8171 laminating adhesive.
Reflective laminated reflective UV absorption Film 2 was measured with the spectrophotometer ((LAMBDA 950 ") to transmit less than 0.1 percent of the UV light over a 350 to 400 nm bandwidth.
After 3,000 hours of exposure to a chamber with a xenon arc lamp of the weatherometer type according to ASTM G155-05a (October, 2005), a change in b * less than 1 unit was measured with the spectrophotometer (“LAMBDA 950” ).
Example 3 (A Prophetic Example) An article can be laminated on or coextruded with a multilayer UV mirror made with transparent UV polymers such as PMMA (for example, PMMAÍ or PMMAZ2) and THV. These multilayer UV reflective mirrors can be made with the first optical layers of PMMA and second layers of polymer from a fluoropolymer (for example, available from Dyneon, Oakdale, MN, USA, under the trade name “THV2030”). PMMA and fluoropolymer can be coextruded through a multilayer polymer melt tubing to create a multilayer melt stream that has 150 alternating first and second polymer layers. In addition, a pair of non-optical layers also made up of PMMA can be coextruded as protective film layers on both sides of the optical layer stack. These PMMA skin layers can be composed by extruding 2% by weight of a UV absorber (for example, “TINUVIN 1577”). This multilayer coextruded melt flow can be molded onto a cooled cylinder at 22 meters per minute, creating a multi-layer molded net approximately 300 micrometers (12 mils) thick The multi-layer molded net is then heated in a tenter oven at 135ºC for 10 seconds before being biaxially oriented at a stretching ratio of 3.8x3.8. Example 4 (A Prophetic Example) A multi-layer optical film reflective against UV can be produced with the first optical layers of PET1 and second optical layers of coPMMA1. PET1 and coPMMA1 can be coextruded through a multilayer polymer melt tubing to form a stack of 224 layers of optical layers.
The layer thickness profile (layer thickness values) of this UV reflector can be adjusted to be approximately a linear profile with the first layers | (thinner) optics adjusted to be about 74 optical wave thickness (index times physical thickness) for 300 nm light and progressing to the thicker layers | 15 that can be adjusted to be about 4 thick optical wavelength for 400 nm light.
The layer thickness profiles of such films can be adjusted to | provide enhanced spectral characteristics with the use of the axial rod device | disclosed in US patent No. 6,783,349 (Neavin et al.), the description of which is here | incorporated by reference, combined with layer profile information obtainable with atomic force microscope techniques. 20% by weight of the master batch absorber | UV (for example, available under the trade name “SUKANO TA07-07 MB” from | Sukano Polymers Corp, Duncan, SC, USA) can be composed of extrusion in both the first optical layers (PET1) and second optical layers ( coPMMA1). | In addition to these optical layers, the PETI non-optical protective film layers (thickness of 260 micrometers each) can be coextruded into | both sides of the optical stack. 20% by weight of the UV master batch absorber (for example, “SUKANO TA07-07 MB”) can be combined in these protective PET film layers.
This multi-layered coextruded melt flow can be molded onto a cooled cylinder at 5.4 meters per minute, creating a network | 30 multi-layer molded approximately 500 micrometers (20 mils) of | thickness The multi-layer molded net can then be preheated for about 10 seconds at 95ºC and biaxially oriented in the stretch ratio of | 3.5x3.7. The oriented multilayer film can be additionally heated to 225ºC for 10 seconds to increase the crystallinity of the PET layers. | 35 Example 5 (A Prophetic Example) | An article can be laminated on, or coextruded with, a multilayer UV mirror made with transparent UV polymers such as PMMA (for example, |
PMMA1 or PMMA2) and THV. This multi-layer reflective UV mirror can be made with the first optical layers of PMMA that have been combined by extruding 3% by weight of the absorber (eg “TINUVIN 1577 UV”) second layers of polymer from a fluoropolymer (eg , “THV2030”). PMMA and fluoropolymer can be coextruded through a multilayer polymer melt tubing to create a multilayer melt stream that has 550 alternating first and second polymer layers. In addition, a pair of non-optical layers also made up of PMMA can be coextruded as protective film layers on both sides of the optical layer stack. These PMMA skin layers can be composed by extruding 2% by weight of a UV absorber (for example, “TINUVIN 1577”). This multi-layer coextruded melt flow can be molded onto a cooled cylinder at 22 meters per minute, creating a multi-layer molded net approximately 500 micrometers (20 mils) thick The multi-layer molded net is then heated in a tenter-type oven at 135ºC for 10 seconds before being biaxially oriented at a stretching ratio of 3.8x3.8.
Example 6 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
An almost infrared reflective multilayer optical Film 4 can be made with the first optical layers of PETI and second optical layers of coPMMA1. PET1 and coPMMA1 can be coextruded through a multilayer polymer melt pipeline to form a stack of 550 optical layers. The layer thickness profile (layer thickness values) of this near-infrared reflector can be adjusted to be approximately one profile | linear with the first (thinner) optical layers adjusted to have about 4 optical wave thickness (index times physical thickness) for 900 nm light and progressing to the thicker layers that can be adjusted to be about 4 thick thick wave optics for 1150 nm light. The layer thickness profiles of these films can be adjusted to provide enhanced spectral characteristics with the use of the axial rod apparatus taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference, combined with the layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the PET1 non-optical protective film layers (thickness of 260 micrometers each) can be coextruded on both sides of the optical stack. This flow of coextruded multilayer cast material can be molded onto a cooled cylinder at 3.23 meters per minute, creating a molded multilayer network approximately 1,800 micrometers (73 mils) thick. The multilayer molded mesh can then , be preheated for about 10 seconds at 95ºC and oriented non-axially towards the machine in a 3.3: 1 stretch ratio. The multi-layer molded mesh can then be heated in a tenter type oven at 95ºC for about 10 seconds before being oriented non-axially in the transverse direction at a 3.5: 1 stretch ratio. The oriented multilayer film can be additionally heated to 225ºC for seconds to increase the crystallinity of the PET layers. Film 3 and Film 4 can be laminated together using an optically transparent adhesive 10 (for example, available from 3M Company, St. Paul, MN, USA, under the trade name “OPTICALLY CLEAR LAMINATING ADHESIVE PSA 8171") and then laminated inside a windshield with PVB (polyvinyl butyral) adhesive.
Example 7 (A Prophetic Example) An UV-reflective multilayer optical film 3 can be made as described in Example 4. i An almost infrared reflective multilayer optical film 4 can be made with the first PETI optical layers and second layers coPMMA1 optics. PET1 and coPMMA1 can be coextruded through a multilayer polymer melt pipeline to form a stack of 550 optical layers. The layer thickness profile (layer thickness values) of this near-infrared reflector can be adjusted to be approximately a linear profile with the first (thinner) optical layers adjusted to have about 4 optical wave thickness (index times thickness physical) for 900 nm light and progressing to the thicker layers that can be adjusted to be about 4 thick optical wavelength for 1150 nm light. The layer thickness profiles of such films can be adjusted to provide enhanced spectral characteristics using the axial rod device taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference , combined with layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the PET1 non-optical protective film layers (thickness of 260 micrometers each) can be coextruded on both sides of the optical stack. This flow of coextruded multilayer cast material can be molded onto a cooled cylinder at 3.23 meters per minute, creating a molded multilayer network approximately 1,800 micrometers (73 mils) thick. The multilayer molded mesh can then , be preheated for about 10 seconds at 95ºC and oriented non-axially towards the machine in a 3.3: 1 stretch ratio. The multi-layer molded mesh can then be heated in a tenter type oven at 95ºC for about 10 seconds before being oriented non-axially in the transverse direction at a 3.5: 1 stretch ratio. The oriented multilayer film can be additionally heated to 225ºC for 10 seconds to increase the crystallinity of the PET layers.
Film 3 and Film 4 can be laminated together using an optically transparent adhesive (for example, “OPTICALLY CLEAR LAMINATING ADHESIVE PSA 8171”) and then laminated inside a window with the same optically transparent adhesive.
Example 8 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
Film 3 can then be laminated to a liquid crystal display using an optically transparent adhesive (for example, “OPTICALLY CLEAR LAMINATING ADHESIVE PSA 8171") for outdoor use.
Example 9 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
An almost infrared reflective multilayer optical Film 4 can be made with the first ones. optical layers of PET1 and second optical layers of coPMMA1. PET1 and coPMMA1 can be coextruded through a multilayer polymer melt pipeline to form a stack of 550 optical layers. The layer thickness profile (layer thickness values) of this near-infrared reflector can be adjusted to be approximately a linear profile with the first (thinner) optical layers adjusted to have about 4 optical wave thickness (index times thickness physical) for 900 nm light and progressing to the thicker layers that can be adjusted to be about 4 thick optical wavelength for 1150 nm light. The layer thickness profiles of such films can be adjusted to provide enhanced spectral characteristics using the axial rod device taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference , combined with layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the PET1 non-optical protective film layers (thickness of 260 micrometers each) can be coextruded on both sides of the optical stack. This flow of coextruded multilayer cast material can be molded onto a cooled cylinder at 3.23 meters per minute, creating a molded multilayer network approximately 1,800 micrometers (73 mils) thick. The multilayer molded mesh can then , be preheated for about 10 seconds at 95ºC and oriented non-axially towards the machine in a 3.3: 1 stretch ratio. The multi-layer molded mesh can then be heated in a tenter type oven at 95ºC for about 10 seconds before being oriented non-axially in the transverse direction at a 3.5: 1 stretch ratio. The oriented multilayer film can be additionally heated to 225ºC for seconds to increase the crystallinity of the PET layers. | Film 3 and Film 4 can be laminated together using an 'optically transparent' adhesive (for example, “OPTICALLY CLEAR LAMINATING ADHESIVE | PSA 8171”) and then laminated inside a liquid crystal screen with the same 10 adhesive optically transparent. Example 10 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
Film 3 can then be laminated to a commercial graph using a | 15 optically transparent adhesive (eg “OPTICALLY CLEAR LAMINATING | ADHESIVE PSA 8171”) for outdoor use.
Example 11 (A Prophetic Example) A UV reflective multilayer optical film 3 can be made | as described in Example 4.
Film 3 can then be laminated to a light box sign using an optically transparent adhesive (eg “OPTICALLY CLEAR: LAMINATING ADHESIVE PSA 8171”) for outdoor use.
Example 12 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
The multi-layer reflective optical film against UV can then be laminated to a photovoltaic module using crosslinkable adhesives.
Example 13 (A Prophetic Example) A UV reflective multilayer optical Film 3 can be made as described in Example 4.
A micro-replication casting tool was manufactured using a diamond with an apex angle of 53 degrees to cut a copper cylinder with linear prism grooves over a 100 micron range. That roller tool | micro-replication metal casting was then used to make a tool | Linear prism polypropylene polymer film with 53 degrees “rib” type with the same pattern, by continuously extruding and abruptly cooling the polypropylene molded on the metal casting tool.
Polyurethane films can be prepared using a notched bar flatbed coating apparatus and the following procedure: A helicoidal mixer can be used to mix 1,368 grams of a urethane monomer (for example, available from King Industries, Nonwalk, CT, USA under the trade name “KFLEX 188 with 288 grams of a UV absorber (for example, available from Ciba Specialty Chemicals Corporation under the trade name“ TINUVIN 405 "), 144 grams of HALS (for example, available from Ciba Specialty Chemicals Corporation under the trade name “TINUVIN 123”), and 4.3 grams of a catalyst (for example, available from Air Products And Chemicals, Inc., Allentown, PA, USA, under the trade name “DABCO T12”) —for about 10 minutes. This polyol mixture can be degassed in a vacuum oven at 60ºC for 15 hours, then loaded in plastic Part A dispensing cartridges and kept warm at 50 ºC. A polyisocyanate (for example, available from Bayer, Pittsburgh, PA, USA, under the trade name “DESMODUR N3300A”) can be loaded in Part B dispensing cartridges and also kept warm at 50 ° C. A variable drive pump can be configured to have a Part A: Part B volumetric ratio of 100: 77. A 30.5 cm (12 inch) long static mixer could be used to blend the two components before coating. UV reflective Film 3 could be loaded onto the bottom unwinding and coated at a linear speed of 1.5 m / min.
(5 feet per minute). The heated plate oven could have 5 zones, each 1.2 m (4 feet) long. a temperature of the first 4 zones can be adjusted to 71ºC (160ºF) while the last zone could be at room temperature. The unwinding tension for the upper and lower linings, and the unwinding tension for the resulting coated film can all be adjusted to 89 N (20 lbs). The gap between the two liners in the choke | formed by the notched bar and the flat bed can be adjusted to 0.075 mm (3 mils). After | 25 acura, the polyfime can be removed to produce a cross-linked microstructured polyurethane “rib” type in the UV reflective film.
The multi-layered UV-reflective optical film with an anti-reflective surface structure can then be laminated to a photovoltaic module using crosslinkable adhesives.
Prophetic Example 14 (A Prophetic Example) UV reflective multilayer optical film 3 with antireflective surface structure made as described in Example 4 can be additionally coated with alternating moisture barrier layers of aluminum oxide and acrylate polymer opposite the layer with anti-reflective surface structure.
The multi-layered UV-reflective light barrier layer with a reflective surface structure can then be laminated to a photovoltaic module using crosslinkable adhesives.
Example 15 (A Prophetic Example A UV 5 reflective multilayer optical film can be made with first V optical layers of PET1 and second optical layers of coPMMA1. PET1 and coPMMA1 can be coextruded through a tubing of melted polymer material. multiple layers to form a stack of 224 optical layers. The layer thickness profile (layer thickness values) of this UV reflector can be adjusted to be approximately a linear profile with the first (thinner) optical layers adjusted to have about of 74 optical wave thickness index times physical thickness) for 370 nm light and progressing to the thicker layers that can be adjusted to be around 430 nm optical thick wave thickness. The layer thickness profile of such films can be adjusted to provide enhanced spectral characteristics with the use of the axial rod apparatus taught in US patent No. 6,783,349 (Neavin et al.), The description of which is incorporated herein by reference , combined with layer profile information obtained with atomic force microscope techniques.
In addition to these optical layers, the protective PET1 film layers (thickness of 260 micrometers each) can be coextruded on both sides of the optical stack. 2% by weight of UV absorber ("TINUVIN 1577 UVA") can be formulated in these layers of PET protective hair. This flow of coextruded multi-layer melt can be molded on a cylinder cooled to S54A4 meters per minute creating a network multi-layered molding of approximately 500 micrometers (20 mils) in thickness The molded net can then be preheated for about 10 seconds at 95ºC and is biaxially oriented in a ratio of 3.5x3.7. oriented layers can be additionally heated to 225ºC for 10 seconds to increase the crystallinity of the PET layers.
The polyethylenonaphthalate (Film 6) can be made with the same PEN as described in Comparative Example A through the extrusion of polymer on a cylinder Í cooled to 5.4 meters per minute creating a modified network of about 500 micrometers (20 mils) of thickness The molded net can then be heated in a tenter oven at 145ºC for 10 seconds before being biaxially oriented at a stretching ratio of 3.8x3.8. The oriented multilayer film can then be further heated to 225ºC for 10 seconds to increase the crystallinity of the PEN layers.
Film 5 can then be laminated to Film 6 with the use of optically transparent adhesive (for example, “OPTICALLY CLEAR LAMINATING ADHESIVE - PSAB8B171”) for outdoor use, Example 16 (A Prophetic Example
A UV 3 reflective multilayer optical film can be made as described in Example 4 and coated with crosslinked abrasion resistant polyurethane coatings.
Polyurethane films can be prepared using a notched bar flat bed coating apparatus and the following procedure: a helicoidal mixer can be used to mix 1368 grams of a urethane monomer (“KFLEX 188") to 288 grams of UV absorber ("TINUVIN 405"), 144 grams of HALS ("TINUVIN 123"), and 4.3 grams of a "DABCO T12" catalyst for about 10 minutes. This polyol mixture can be degassed in a vacuum oven at 60ºC for 15 hours, then loaded in plastic Part A dispensing cartridges and kept heated to 50ºC. A “DESMODUR N3300A” polyisocyanate can be loaded in Part B dispensing cartridges and also kept heated to 50ºC. A variable drive pump would be adjusted to have a Part A: Part B volumetric ratio of 100: 77. A 30.5 cm (12 inch) long static mixer would be used to blend the two components before coating. The UV reflective film would be coated at a line speed of 1.5 m / min. (5 feet per minute). The heated platen oven would have 5 zones, each being 1.2 m (4 feet) long. The temperature of the first 4 zones would be adjusted to 71ºC (160ºF) while the last zone would be at room temperature. The unwinding tension for the top and bottom linings, and the resulting rewinding tension for the coated film would all be adjusted to 89 N (20 lbs.). The gap between the two liners: in the contact line formed by the notched bar and the flat bed would be adjusted to 0.075 mm (3 mils). The UV 3 reflective multilayer optical film would then have an approximately 0.075 mm (3 mils) UV stable cross-linked polyurethane coating. Predictable modifications and alterations to this invention will be evident to those skilled in the art - technical without departing from the scope and nature of this invention. This invention should not be restricted to the modalities that are demonstrated in this application for illustrative purposes.

权利要求:
Claims (9)
[1]
1. UV-stable multilayer optical film, FEATURED by the fact that it comprises at least a plurality of first and second optical layers that collectively reflect at least 50 percent of UV light incident on at least one wavelength range of 30 nanometers over a wavelength range of at least 300 nanometers to 400 nanometers, where part of at least one of the first or second optical layers comprises a UV absorber.
[2]
2. Multilayer optical film, CHARACTERIZED by the fact that it comprises a plurality of at least first and second optical layers that | 10 have a main surface and collectively reflect at least 50 percent of UV light incident over at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, and a third layer optics having first and second generally opposite first and second surfaces and which absorb at least 50 percent of UV light incident over at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is close to the first main surface of the third optical layer, and where there is no other multilayer optical film close to the second surface of the third optical layer.
[3]
3. Multilayer optical film according to claim 2, CHARACTERIZED by the fact that at least one of the first or second optical layers comprises a UV absorber.
[4]
4. Multilayer optical film, CHARACTERIZED by the fact that it comprises a first plurality of at least first and second optical layers that have a main surface and that collectively reflect at least 50 percent of UV light incident over at least one strip of length nanometer wavelengths in a wavelength range of at least 300 nanometers to 400 nanometers, and a third optical layer that has first and second generally opposite first and second main surfaces and that collectively absorb at least 30 percent 50 light UV incident on at least a wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, where the main surface of the plurality of first and second optical layers is close to the first main surface of the third optical layer, and in which there is a second plurality of first and second optical layers that have a s main surface and that collectively reflect at least 50 percent of UV light incident on at least a wavelength range of | |
30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers near the second main surface of the third optical layer.
[5]
5. Multilayer optical film according to claim 4, CHARACTERIZED by the fact that part of at least one of the first or second optical layers comprises a UV absorber.
[6]
6. Multilayer optical film, CHARACTERIZED by the fact that it comprises a plurality of at least first and second optical layers that have opposing first and second main surfaces and that collectively reflect at least 50 percent of UV light incident on at least one band wavelength range of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers, a third optical layer that has a main surface and absorbs at least 50 percent of UV light incident on at least a range of wavelength of 30 nanometers in a wavelength range of at least 300 nanometers to 400 nanometers near the first main surface of the plurality of at least first and second optical layers, and a fourth optical layer that absorbs at least 50 percent of UV light incident on at least a wavelength range of 30 nanometers in a wavelength range of at least in the 300 nanometers to 400 nanometers near the second main surface of the plurality of at least first and second optical layers.
[7]
7. Multilayer optical film according to claim 6, CHARACTERIZED by the fact that part of at least one of the first or second optical layers comprises a UV absorber.
[8]
8. Multilayer optical film, CHARACTERIZED by the fact that it comprises at least first and second optical layers that reflect at least 50 percent of light incident over a wavelength range of 30 nanometers in a wavelength range of 300 nanometers to 430 nanometers, optionally a third optical layer that absorbs at least 50 percent of light incident on at least a wavelength range of 30 nanometers over a wavelength range of at least 300 nanometers to 430 nanometers and a fourth optical layer comprising polyethylene naphthalate, where at least one of the first, second or third optical layers absorbs at least 50 percent of light incident on at least a wavelength range of 30 nanometers in a wavelength range at least 300 nanometers to 430 nanometers.
[9]
9. Multilayer optical film, according to claim 8, - CHARACTERIZED by the fact that part of at least one of the first or second optical layers comprises a UV absorber.

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同族专利:

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公开号 | 公开日

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US20160209562A1|2016-07-21|

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KR20120106953A|2012-09-27|

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EP2502100B1|2020-09-16|

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US20120229893A1|2012-09-13|

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KR20170015548A|2017-02-08|

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CN102754000A|2012-10-24|

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JP2013511746A|2013-04-04|

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CN107390300A|2017-11-24|

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JP5940980B2|2016-06-29|

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US10514482B2|2019-12-24|

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KR102013045B1|2019-08-21|

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US9459386B2|2016-10-04|

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JP2016026323A|2016-02-12|

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WO2011062836A1|2011-05-26|

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JP6212091B2|2017-10-11|

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EP2502100A1|2012-09-26|

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法律状态:
2020-09-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 9A ANUIDADE. |

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2020-12-22| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

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2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US26241709P| true| 2009-11-18|2009-11-18|

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US61/262,417|2009-11-18|

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PCT/US2010/056390|WO2011062836A1|2009-11-18|2010-11-11|Multi-layer optical films|

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