US20080074613A1 - Method of making a thermoplastic-based article and a thermoplastic-based article made thereby - Google Patents
Method of making a thermoplastic-based article and a thermoplastic-based article made thereby Download PDFInfo
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- US20080074613A1 US20080074613A1 US11/998,509 US99850907A US2008074613A1 US 20080074613 A1 US20080074613 A1 US 20080074613A1 US 99850907 A US99850907 A US 99850907A US 2008074613 A1 US2008074613 A1 US 2008074613A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/12—Polarisers
Definitions
- the present invention generally relates to the field of manufacturing.
- the present invention is directed to a method of making a photochromic thermoplastic-based article and a thermoplastic-based article made thereby.
- a material having one or more properties suited for use in a particular article of manufacture cannot be used because that material is not compatible with the process that is the most desirable for making the article.
- a flexible polarizer to a rigid substrate to make a composite and then thermoform the composite to provide the curvature(s) necessary for the type of lens, e.g., piano, powered, multi-focal, etc., for which the composite will be used.
- the composite may then be finished, e.g., by appropriately shaping its periphery to suit the finished lens and/or applying one or more optical coatings, such as a hardcoat, to the surfaces of the composite.
- thermoformed composite may be used as pre-curved polarizing insert for a lens that, when finished, will include one or more additional optical layers attached to the insert.
- the resulting multilayer lens may then be finished in a manner similar to the manner mentioned, e.g., by appropriately shaping the periphery of the lens and/or applying one or more optical coatings to the surfaces of the lens.
- polarizers used in ophthalmic lenses are often a sandwich of three thermoplastic layers.
- the middle layer is the polarizing layer, which frequently comprises a polyvinyl alcohol (PVA) layer containing either a hydrophilic dichroic dye or iodine that provides the polarizing property.
- PVA polyvinyl alcohol
- the outer two layers are often made of the same material as each other, typically a cellulose-based polymer, such as cellulose acetobutyrate (CAB).
- CAB cellulose acetobutyrate
- Such polarizers provide very good polarizing performance, but they must not be heated to temperatures equal to or greater than their “minimum degradation temperature,” i.e., the temperature at which their performance/quality noticeably degrades due to physical changes caused by the elevated temperature. If these polarizers are heated to their minimum degradation temperature or higher, particularly for a sustained period, they will often become unsuitable for use because the degradation caused by the elevated temperature will reach or exceed an acceptable limit.
- a conventional CAB-PVA-CAB polarizer sandwich typically has a minimum degradation temperature in a range of about 95° C. to about 120° C., depending upon the particular formulation of the various layers.
- the amount and type of degradation generally depends on time and the internal constituents of the CAB.
- the CAB degrades, typically by yellowing in the first instance, followed by the development of air bubbles and/or blisters and increased stiffness. Similar degradation also occurs with cellulosetriacetate (CTA) but at slightly higher temperatures. Other degradation may also occur, depending upon the makeup of the polarizer.
- CTA cellulosetriacetate
- the bond may separate in places and cause blisters among the layers.
- iodine is the polarizing substance incorporated into the PVA
- the iodine's ability to provide a polarizing effect begins to irreversibly degrade at a temperature of about 100° C. (the minimum degradation temperature) by changing color. Moisture affects the amount and speed of the degradation; the higher the moisture content, the greater and faster is the degradation. Starting around 120° C., the polarizer begins to fade and lose polarizing efficiency.
- thermoplastics for the substrate based on their optical and durability properties, e.g., pure polycarbonates and some pure methacrylates, e.g., poly (methyl methacrylate) (PMMA), have glass transition temperatures that are higher than the minimum degradation temperatures of the polarizers.
- a pure polycarbonate typically has a glass transition temperature in a range of about 135° C. to about 155° C.
- a pure methacrylate typically has a glass transition temperature in a range of about 105° C. to about 110° C.
- thermoforming the substrate and polarizer together with one another which generally requires the substrate to be heated to its glass transition temperature or higher, would not be suitable because this temperature is higher than the minimum degradation temperature of the polarizer. Consequently, the polarizer would degrade, likely to an unacceptable extent. It is noted that in a thermoforming process that includes heating the article to a temperature lower than the glass transition temperature at issue and subjecting it to relatively large pressure is often not an acceptable alternative for ophthalmic lenses due to the residual stresses that this process imparts into article. Besides, even the lower temperatures used in this alternative are often higher than the minimum degradation temperature of the polarizer.
- a first aspect of the invention is a method of making a photochromic lens article.
- the method includes supporting at least one photochromic substance in operable relationship with a substrate, the photochromic substance having a minimum degradation temperature.
- the method also includes forming the substrate as a polymer blend that contains a first polymer having a first glass transition temperature higher than the minimum degradation temperature.
- the polymer blend has a second glass transition temperature lower than the minimum degradation temperature.
- the method also includes thermoforming the substrate and the at least one photochromic substance at a temperature below the minimum degradation temperature so as not to degrade the at least one photochromic substance.
- the photochromic substance is in the form of a photochromic dye incorporated into the substrate.
- Another aspect of the invention is a method of making a photochromic lens article that includes a substrate and at least one photochromic substance having a minimum degradation temperature.
- the method includes forming the substrate by providing a first polymer having a first glass transition temperature higher than the minimum degradation temperature, and blending a second polymer with the first polymer to form a blended polymer having a second glass transition temperature lower than the minimum degradation temperature.
- the method also includes placing the at least one photochromic substance in operable relationship to the substrate.
- the method further includes thermoforming the at least photochromic substance and the substrate at a temperature lower than the minimum degradation temperature so as to form the photochromic lens article while avoiding degrading the at least one photochromic substance.
- the lens article includes at least one photochromic substance having a minimum degradation temperature.
- the lens article also includes a substrate.
- the substrate is arranged in working relation with the at least one photochromic substance.
- the substrate is formed from a blend of a first polymer and a second polymer, with the first polymer having a first glass transition temperature greater than the minimum degradation temperature.
- the second polymer is selected to cause the blended-polymer substrate to have a second glass transition temperature lower than the minimum degradation temperature. This allows the at least one photochromic substance and the substrate to be thermoformed at a temperature lower than the minimum degradation temperature so as not to degrade the at least one photochromic substance when forming the lens article.
- FIG. 1 is a perspective view of a thermoplastic-based article of the present invention
- FIG. 2 is a partial cross-sectional view of a mold assembly and the thermoplastic-based article of FIG. 1 taken along line 2 - 2 of FIG. 1 ;
- FIG. 3 is a partial cross-sectional view of an alternative thermoplastic-based article of the present invention.
- FIG. 4 is a partial cross-sectional view of a mold assembly and another alternative thermoplastic-based article of the present invention.
- FIG. 5 is a partial cross-sectional view of the mold assembly of FIG. 2 and yet another alternative thermoplastic-based article of the present invention.
- thermoplastic-based article such as, e.g., the ophthalmic lens article 10 shown in FIG. 1 .
- Ophthalmic lens “article” 10 is referred to as such because it can be either a lens in and of itself or, alternatively, an insert for incorporating into a finished lens, e.g., as described below in connection with FIG. 4 .
- Ophthalmic lens “article” 10 is referred to as such because it can be either a lens in and of itself or, alternatively, an insert for incorporating into a finished lens, e.g., as described below in connection with FIG. 4 .
- elevated temperatures may be due to any one or more of the following: molding, thermoforming, extrusion and annealing, among others.
- thermoplastics have properties that are well-suited to a particular application.
- polycarbonate is well-suited for ophthalmic lenses due to various desirable characteristics, such as its optical clarity, hardness, toughness and relatively high index of refraction.
- polycarbonate may be desirable for reasons relating to its optical and durability characteristics
- certain properties of polycarbonate such as its glass-transition temperature, can increase the difficulty of incorporating various desirable features into lens article 10 .
- lens article 10 may be desirable to provide lens article 10 with a filter 14 comprising a filtering layer 18 placed in working relation with a substrate 22 in any suitable manner known in the art.
- Filtering layer 18 may be provided with at least one of a polarizing function or a photochromic function, among others.
- filter layer 18 may comprise a suitable thermoplastic, such as a polyvinyl alcohol (PVA), e.g., polyvinylene, or polyacetelyne, containing iodine or a dichroic substance, such as Chloratine Fas Red, Chrysophenine, Sirius Yellow, Bensopurpurine, Direct Fast Red, Brilliant Blue 6B, Chlorasol Black BH, Direct Blue 2B, Direct Sky Blue, Diamine Green, Congo Red and Acid Black, among others, or mixtures thereof, that provides this layer with a polarizing ability.
- PVA polyvinyl alcohol
- a dichroic substance such as Chloratine Fas Red, Chrysophenine, Sirius Yellow, Bensopurpurine, Direct Fast Red, Brilliant Blue 6B, Chlorasol Black BH, Direct Blue 2B, Direct Sky Blue, Diamine Green, Congo Red and Acid Black, among others, or mixtures thereof, that provides this layer with a polarizing ability.
- Filter layer 18 may be sandwiched between two protective layers 26 made of, e.g., a cellulosic material, such as cellulose acetobutyrate (CAB), among others, so as to form a standalone filter laminate.
- a cellulosic material such as cellulose acetobutyrate (CAB)
- CAB cellulose acetobutyrate
- filter 14 is attached to substrate 22 , which generally provides a relatively robust structure for supporting the filter, which is typically relatively thin and flexible, as those skilled in the art will appreciate.
- filter 14 is a photochromic filter
- a suitable photochromic substance such as naphthopyrans, spironapthopyrans, fulgides, fulgimides, salicylates, triazoles, oxazoles, azobenzenes and silver halide, among others, may be incorporated into filtering layer 18 , which may also include a material, e.g., CAB, polypropylene, poly(vinyl chloride) and poly(vinyl acetate), among others, suitable for containing or supporting the selected substance.
- Such a photochromic filtering layer 18 may be attached to substrate 22 directly or, optionally, first sandwiched between protective layers 26 if necessary, before being attached to the substrate by appropriate means, such as adhesive bonding.
- substrate 22 is provided in flat sheet or flat plate form, and filter 14 is attached to the flat substrate to form the article prior to providing the article with its desired contour(s), such as curvature(s) or stepped multi-focal contour(s), e.g., by thermoforming.
- desired contour(s) such as curvature(s) or stepped multi-focal contour(s)
- thermoforming e.g., by thermoforming.
- the convex side 30 and the concave side 32 may be provided with the same or different curvature as required to achieve a particular result.
- iodine-based polarizers such as a polarizing version of filter 14
- the iodine in a PVA/iodine polarizer generally begins to deteriorate at a temperature (i.e., the minimum degradation temperature) in a range of about 95° C. to about 120° C., thereby degrading or destroying the polarizer's polarizing ability.
- CAB layers of a CAB/PVA/CAB polarizer generally begin to degrade at a temperature in a range of about 95° C. to about 120° C., typically by yellowing in the first instance, thereby rendering the polarizer unsuitable.
- elevated temperatures can cause the protective layers and/or filter to blister. Such blistering would render lens article 10 unacceptable for its intended purpose.
- Polycarbonates e.g., those sold under the trademarks LEXAN® and MAKROLON® by General Electric Corporation and Bayer Corporation, respectively, generally have a glass-transition temperature in a range of about 135° C. to about 155° C. Consequently, if substrate 22 were made of one of these polycarbonates, it would generally be necessary to raise the temperature of the substrate and filter 14 to at least the glass transition temperature of that polycarbonate, i.e., about 135° C. or higher, in order to thermoform and/or anneal lens article 10 . However, heating filter 14 to such a temperature would exceed its minimum degradation temperature. Therefore, despite polycarbonate being a highly desirable material from optical and durability viewpoints, it is generally not desirable from a manufacturability viewpoint.
- the pure polycarbonate i.e., the first polymer
- the pure polycarbonate may be blended, or copolymerized, with a second polymer other than polycarbonate, e.g., polyethylene teraphthalate, so as to essentially reduce the glass transition temperature of the polycarbonate to an adjusted glass transition temperature that will allow lens article 10 to be thermoformed and/or annealed at a temperature lower than the minimum degradation temperature of filter 14 .
- This concept may be readily extended not only to carbonates other than polycarbonate (see below), but also to other polymers generally.
- the second polymer blended with the first polymer that provides the desirable characteristics is typically, but not necessarily, not from the same group as the first polymer. For example, if the first polymer is a carbonate, the second polymer is typically, but again not necessarily, not a carbonate.
- carbonate blends having glass-transition temperatures lower than pure polycarbonate and lower than the temperature at which filter 14 would start to degrade include certain ones of the blends made of aliphatic polyester-carbonates incorporating “diaryl carbonates” disclosed in U.S. Pat. No. 5,654,380 (e.g., the carbonate blend disclosed in Example 1 has a glass-transition temperature of 104° C.) and the blend disclosed in U.S. Pat. No. 5,410,014, which discloses a copolymer of aromatic-aliphatic polycarbonate having a glass transition temperature of about 119° C.
- U.S. Pat. Nos. 5,654,380 and 5,410,014 are incorporated herein by reference in their entireties.
- substrate 22 may comprise a blend of 70 parts of polycarbonate to 30 parts of polyethylene teraphthalate that has an adjusted glass transition temperature of about 121° C.
- This blend is commercially available under the trademark XYLEX® from the General Electric Company. It has been observed that sheets of this blend can be thermoformed at temperatures between about 120° C. and about 140° C.
- this particular blend is not suitable for use with an iodine/PVA-based polarizer, which has a minimum degradation temperature in a range of about 95° C. to about 120° C. based on the presence of iodine.
- the lower end of the range may be suitable for such a polarizing layer. That said, experiments performed to date have shown that thermoforming at the lower end of the range can be non-uniform.
- substrate 22 comprises a 50 parts to 50 parts blend of polycarbonate and polyethylene teraphthalate (also available from General Electric under the trademark XYLEX®) having an adjusted glass transition temperature of about 87° C.
- polycarbonate and polyethylene teraphthalate also available from General Electric under the trademark XYLEX®
- XYLEX® polyethylene teraphthalate
- FIG. 2 the curvatures of sides 30 , 32 of lens article 10 thermoformed at 95° C. using the thermoforming assembly 36 of FIG. 2 matched, respectively, the curvatures of surfaces 40 , 42 of the thermoforming assembly.
- This relatively low thermoforming temperature is suitable for avoiding degradation of the iodine/PVA-based polarizer discussed in the preceding paragraph.
- lens article 10 is to be a lens, as opposed to an insert, one or more optical coatings, such as hardcoat layers 46 , may be provided to the article on each of sides 30 , 32 . This would typically be done after lens article 10 has been thermoformed.
- one or more dichroic dyes may be incorporated directly into substrate 22 .
- filter 14 need not be provided.
- the photochromic dye(s) could be incorporated only in substrate 22 .
- some photochromic dyes have been reported to not perform well in polymers with high glass transition temperatures and perform better in polymers with lower glass transition temperatures.
- Some photochromic dyes have two geometrical forms, e.g., one form “open” and the other form “closed,” and the photochromic action is accompanied by opening and closing the molecule.
- substrate 22 in this scenario could be a polymer blend having a glass transition temperature adjusted in the manner described above in connection with the embodiment incorporating filter.
- the glass transition temperature of substrate 22 may be adjusted prior to adding any photochromic dyes thereto.
- Suitable polymer blends for supporting direct addition of one or more photochromic dyes may include any of the exemplary blends discussed above, including the methacrylate/butyldyene blend and the polycarbonate/polyethylene teraphthalate blend, among others.
- FIG. 3 shows an alternative lens article 10 ′ of the present invention that may also be used as a filtering lens or a filtering insert in manner similar to the manner described above relative to lens article of FIGS. 1 and 2 .
- lens article 10 ′ of FIG. 3 includes two blended-polymer layers 22 ′ attached to opposite sides of a filter 14 ′. Similar to lens article 10 ′ of FIGS. 1 and 2 , lens article 10 ′ of FIG. 3 would typically be assembled with substrates 22 ′ in flat-plate form, such that the entire article, including filter 14 ′, would need to be thermoformed in order achieve the contours shown in FIG. 3 .
- Filter 14 ′ may be any filter suitable for lens article 10 ′, such as the polarizer-type or photochromic filter 14 shown and described above relative to FIG. 2 .
- each substrates 22 ′ of FIG. 3 may contain a polymer blend that includes a first polymer selected primarily for its ability to provide lens article 10 ′ with one or more desirable characteristics as discussed above. Also similar to the discussion above, each substrate 22 ′ further includes a second polymer blended with the first polymer in a predetermined amount so as to essentially lower the glass transition temperature of the first polymer so that lens article 10 ′ can be thermally processed, e.g., thermoformed and/or annealed, at a temperature that will not unacceptably degrade filter 14 ′, or any of its components.
- FIG. 4 illustrates lens article 10 of FIGS. 1 and 2 being used as a filtering insert for an ophthalmic lens 100 .
- lens 100 is made by placing lens article 10 between mold parts 104 of an injection molding or injection/coining machine (not shown) and injecting or injecting/coining a high-impact polymer layer 108 against the concave side of the article.
- high-impact polymer layer 108 may be formed on the convex side of lens article 10 .
- a greater impact strength can be achieved by forming layer 108 on the concave side.
- High-impact polymer layer 108 may be made of any suitable polymer or polymer blend, including a polymer blend, including the polycarbonate/polyethylene teraphthalate blend or methacrylate/butyldyene blend described above, that is made in accordance with the present invention, i.e., generally, by first selecting a first polymer based on its ability to provide one or more desirable characteristics and then blending the first polymer with a second polymer so as to create a blend having both good characteristics and a glass transition temperature lower than the glass transition temperature of the polymer originally selected for its ability to provide the desirable characteristic(s).
- high-impact polymer layer is molded at a suitable molding temperature, which is generally between about 415° F. and about 480° F. for polycarbonate copolymers and about 400° F. for the acrylic copolymer.
- FIG. 5 shows a lens article 10 ′′ that is similar to lens article 10 of FIG. 2 , except that substrate 22 is located on the convex side 30 of the article rather than the concave side 32 , as shown in FIG. 2 .
- This may be achieved, e.g., simply by flipping the flat filter 14 /substrate 22 precursor to article 10 side 30 for side 32 in thermoforming assembly 36 relative to FIG. 2 prior to thermoforming. All other aspects of article 10 ′′ may be the same as described above relative to lens article 10 .
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick LEXAN polycarbonate to form the composite structure. Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 95° C. for 8 minutes. The curvature of the composite rectangles was very irregular and minimal. However the iodine-based polarizer did not show any degradation during the process. Similar results were obtained when the LEXAN polycarbonate sheets were replaced with sheets of polycarbonate from the Mobay Corp.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick LEXAN polycarbonate to form a composite structure. Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 140° C. for 8 minutes. The composite rectangles had an irregular curvature that was less than the mold surface curvature. The iodine polarizer was degraded and the cellulose acetobutyrate layers were yellowed and blistered. Similar results were obtained when the sheets of LEXAN polycarbonate were replaced with sheets of polycarbonate from the Mobay Corp.
- Rectangles approximately 60 mm by 70 mm were cut from a sheet (substrate) of 0.5 mm thick blend of 70/30 polycarbonate/polyethylene teraphthalate (XYLEX).
- the rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm.
- the rectangles were heated in the thermoformer to 120° C. for 8 minutes.
- the resultant curvature of the rectangles was irregular.
- the polarizer showed slight degradation and the cellulose acetobutyrate showed slight yellowing.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick blend of 70/30 polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 120° C. for 8 minutes. The resultant curvature of the rectangles was irregular. Further, the polarizer showed slight degradation and the cellulose acetobutyrate showed slight yellowing.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick blend of 50/50 polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 100° C. for 8 minutes. The resultant curvature of the composite rectangles was regular and closely matched the curvature of the mold surface. Further, the iodine polarizer showed no degradation and the cellulose acetobutyrate layers did not yellow or blister. This article can be used as a stand-alone polarizing lens.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one layer (substrate) of 50/50 blend of polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60 ⁇ 70 mm were cut from the composite structure and were then heated in the thermoformer to 100° C. for 8 minutes. Upon removal from the thermoformer the curvature of the rectangles closely approximated the curvature of the mold surfaces and was uniform. This article was then used as an insert for an injection molded polarized lens.
Abstract
A lens article containing a photochromic substance, such as a photochromic dye, having a minimum degradation temperature arranged relative to a substrate, such as by being incorporated into the substrate. The substrate is formed from a blend of first and second thermoplastic polymers. The first polymer has a glass transition temperature higher than the minimum degradation temperature of the photochromic substance. The second polymer is blended with the first polymer to provide the substrate with an adjusted glass transition temperature lower than the minimum degradation temperature. This allows the combined photochromic substance and substrate to be thermoformed at a temperature greater than or equal to the adjusted glass transition temperature but below the minimum degradation temperature so that the photochromic substance is not degraded during fabrication of the lens article.
Description
- This application claims priority from and is a continuation of U.S. patent application Ser. No. 11/023,790, now U.S. Pat. No. ______, which is a continuation-in-part application of U.S. patent application Ser. No. 10/331,062, filed Dec. 27, 2002 and titled, “Thermoformable Polarized Lens with Substrate Having Adjusted Glass Transition Temperature,” now U.S. Pat. No. 6,834,956, which patents are incorporated by reference herein in their entirety.
- The present invention generally relates to the field of manufacturing. In particular, the present invention is directed to a method of making a photochromic thermoplastic-based article and a thermoplastic-based article made thereby.
- Sometimes a material having one or more properties suited for use in a particular article of manufacture cannot be used because that material is not compatible with the process that is the most desirable for making the article. For example, in the context of polarized ophthalmic lenses, it is often desirable to attach a flexible polarizer to a rigid substrate to make a composite and then thermoform the composite to provide the curvature(s) necessary for the type of lens, e.g., piano, powered, multi-focal, etc., for which the composite will be used. After thermoforming, the composite may then be finished, e.g., by appropriately shaping its periphery to suit the finished lens and/or applying one or more optical coatings, such as a hardcoat, to the surfaces of the composite. Alternatively, the thermoformed composite may be used as pre-curved polarizing insert for a lens that, when finished, will include one or more additional optical layers attached to the insert. The resulting multilayer lens may then be finished in a manner similar to the manner mentioned, e.g., by appropriately shaping the periphery of the lens and/or applying one or more optical coatings to the surfaces of the lens.
- Conventional polarizers used in ophthalmic lenses are often a sandwich of three thermoplastic layers. The middle layer is the polarizing layer, which frequently comprises a polyvinyl alcohol (PVA) layer containing either a hydrophilic dichroic dye or iodine that provides the polarizing property. The outer two layers are often made of the same material as each other, typically a cellulose-based polymer, such as cellulose acetobutyrate (CAB). Such polarizers provide very good polarizing performance, but they must not be heated to temperatures equal to or greater than their “minimum degradation temperature,” i.e., the temperature at which their performance/quality noticeably degrades due to physical changes caused by the elevated temperature. If these polarizers are heated to their minimum degradation temperature or higher, particularly for a sustained period, they will often become unsuitable for use because the degradation caused by the elevated temperature will reach or exceed an acceptable limit.
- For example, a conventional CAB-PVA-CAB polarizer sandwich typically has a minimum degradation temperature in a range of about 95° C. to about 120° C., depending upon the particular formulation of the various layers. Relative to the CAB part of the polarizer, the amount and type of degradation generally depends on time and the internal constituents of the CAB. When such a polarizer is heated to or above its minimum degradation temperature, the CAB degrades, typically by yellowing in the first instance, followed by the development of air bubbles and/or blisters and increased stiffness. Similar degradation also occurs with cellulosetriacetate (CTA) but at slightly higher temperatures. Other degradation may also occur, depending upon the makeup of the polarizer. For example, depending upon the adhesive used bond the CAB layers to the PVA layer, the bond may separate in places and cause blisters among the layers. In another example wherein iodine is the polarizing substance incorporated into the PVA, the iodine's ability to provide a polarizing effect begins to irreversibly degrade at a temperature of about 100° C. (the minimum degradation temperature) by changing color. Moisture affects the amount and speed of the degradation; the higher the moisture content, the greater and faster is the degradation. Starting around 120° C., the polarizer begins to fade and lose polarizing efficiency.
- Unfortunately, some of the most desirable thermoplastics for the substrate, based on their optical and durability properties, e.g., pure polycarbonates and some pure methacrylates, e.g., poly (methyl methacrylate) (PMMA), have glass transition temperatures that are higher than the minimum degradation temperatures of the polarizers. For example, a pure polycarbonate typically has a glass transition temperature in a range of about 135° C. to about 155° C., and a pure methacrylate typically has a glass transition temperature in a range of about 105° C. to about 110° C. Therefore, a manufacturing process that includes thermoforming the substrate and polarizer together with one another, which generally requires the substrate to be heated to its glass transition temperature or higher, would not be suitable because this temperature is higher than the minimum degradation temperature of the polarizer. Consequently, the polarizer would degrade, likely to an unacceptable extent. It is noted that in a thermoforming process that includes heating the article to a temperature lower than the glass transition temperature at issue and subjecting it to relatively large pressure is often not an acceptable alternative for ophthalmic lenses due to the residual stresses that this process imparts into article. Besides, even the lower temperatures used in this alternative are often higher than the minimum degradation temperature of the polarizer.
- A first aspect of the invention is a method of making a photochromic lens article. The method includes supporting at least one photochromic substance in operable relationship with a substrate, the photochromic substance having a minimum degradation temperature. The method also includes forming the substrate as a polymer blend that contains a first polymer having a first glass transition temperature higher than the minimum degradation temperature. The polymer blend has a second glass transition temperature lower than the minimum degradation temperature. The method also includes thermoforming the substrate and the at least one photochromic substance at a temperature below the minimum degradation temperature so as not to degrade the at least one photochromic substance. In one example, the photochromic substance is in the form of a photochromic dye incorporated into the substrate.
- Another aspect of the invention is a method of making a photochromic lens article that includes a substrate and at least one photochromic substance having a minimum degradation temperature. The method includes forming the substrate by providing a first polymer having a first glass transition temperature higher than the minimum degradation temperature, and blending a second polymer with the first polymer to form a blended polymer having a second glass transition temperature lower than the minimum degradation temperature. The method also includes placing the at least one photochromic substance in operable relationship to the substrate. The method further includes thermoforming the at least photochromic substance and the substrate at a temperature lower than the minimum degradation temperature so as to form the photochromic lens article while avoiding degrading the at least one photochromic substance.
- Another aspect of the invention is a photochromic lens article. The lens article includes at least one photochromic substance having a minimum degradation temperature. The lens article also includes a substrate. The substrate is arranged in working relation with the at least one photochromic substance. The substrate is formed from a blend of a first polymer and a second polymer, with the first polymer having a first glass transition temperature greater than the minimum degradation temperature. The second polymer is selected to cause the blended-polymer substrate to have a second glass transition temperature lower than the minimum degradation temperature. This allows the at least one photochromic substance and the substrate to be thermoformed at a temperature lower than the minimum degradation temperature so as not to degrade the at least one photochromic substance when forming the lens article.
- For the purpose of illustrating the invention, the drawings illustrate forms of the invention that are presently preferred. However, it should be understood that the present invention is not limited to the precise arrangements and instrumentalities shown in the drawings, wherein:
-
FIG. 1 is a perspective view of a thermoplastic-based article of the present invention; -
FIG. 2 is a partial cross-sectional view of a mold assembly and the thermoplastic-based article ofFIG. 1 taken along line 2-2 ofFIG. 1 ; -
FIG. 3 is a partial cross-sectional view of an alternative thermoplastic-based article of the present invention; -
FIG. 4 is a partial cross-sectional view of a mold assembly and another alternative thermoplastic-based article of the present invention; and -
FIG. 5 is a partial cross-sectional view of the mold assembly ofFIG. 2 and yet another alternative thermoplastic-based article of the present invention. - In the following detailed description of various embodiments of the invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that changes may be made without departing from the scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention may be determined from the appended claims.
- Referring now to the drawings, in general the present invention is directed to a method of making a thermoplastic-based article, such as, e.g., the
ophthalmic lens article 10 shown inFIG. 1 . Ophthalmic lens “article” 10 is referred to as such because it can be either a lens in and of itself or, alternatively, an insert for incorporating into a finished lens, e.g., as described below in connection withFIG. 4 . Like all thermoplastic articles, duringmanufacturing lens article 10 or a portion thereof is subjected to one or more elevated temperatures that are generally significantly higher than the temperatures that the article will experience during its intended use. These elevated temperatures may be due to any one or more of the following: molding, thermoforming, extrusion and annealing, among others. - As noted in the Background section above, certain thermoplastics have properties that are well-suited to a particular application. For example, in the context of
lens article 10, it is known that polycarbonate is well-suited for ophthalmic lenses due to various desirable characteristics, such as its optical clarity, hardness, toughness and relatively high index of refraction. However, while polycarbonate may be desirable for reasons relating to its optical and durability characteristics, certain properties of polycarbonate, such as its glass-transition temperature, can increase the difficulty of incorporating various desirable features intolens article 10. - For example, as illustrated in
FIG. 2 , it may be desirable to providelens article 10 with afilter 14 comprising a filtering layer 18 placed in working relation with asubstrate 22 in any suitable manner known in the art. Filtering layer 18 may be provided with at least one of a polarizing function or a photochromic function, among others. In the context of polarizing, filter layer 18 may comprise a suitable thermoplastic, such as a polyvinyl alcohol (PVA), e.g., polyvinylene, or polyacetelyne, containing iodine or a dichroic substance, such as Chloratine Fas Red, Chrysophenine, Sirius Yellow, Bensopurpurine, Direct Fast Red, Brilliant Blue 6B, Chlorasol Black BH, Direct Blue 2B, Direct Sky Blue, Diamine Green, Congo Red and Acid Black, among others, or mixtures thereof, that provides this layer with a polarizing ability. Filter layer 18 may be sandwiched between twoprotective layers 26 made of, e.g., a cellulosic material, such as cellulose acetobutyrate (CAB), among others, so as to form a standalone filter laminate. Generally,filter 14 is attached tosubstrate 22, which generally provides a relatively robust structure for supporting the filter, which is typically relatively thin and flexible, as those skilled in the art will appreciate. Whenfilter 14 is a photochromic filter, a suitable photochromic substance, such as naphthopyrans, spironapthopyrans, fulgides, fulgimides, salicylates, triazoles, oxazoles, azobenzenes and silver halide, among others, may be incorporated into filtering layer 18, which may also include a material, e.g., CAB, polypropylene, poly(vinyl chloride) and poly(vinyl acetate), among others, suitable for containing or supporting the selected substance. Such a photochromic filtering layer 18 may be attached tosubstrate 22 directly or, optionally, first sandwiched betweenprotective layers 26 if necessary, before being attached to the substrate by appropriate means, such as adhesive bonding. - In one method of
manufacturing lens article 10,substrate 22 is provided in flat sheet or flat plate form, and filter 14 is attached to the flat substrate to form the article prior to providing the article with its desired contour(s), such as curvature(s) or stepped multi-focal contour(s), e.g., by thermoforming. (It is noted that theconvex side 30 and theconcave side 32 may be provided with the same or different curvature as required to achieve a particular result. It is also noted that it may be desirable to anneallens article 10 after thermoforming in order to relieve residual stresses in the article.) As discussed in the Background section above, it is well-known that iodine-based polarizers, such as a polarizing version offilter 14, can be damaged by exposure to elevated temperatures. For example, the iodine in a PVA/iodine polarizer generally begins to deteriorate at a temperature (i.e., the minimum degradation temperature) in a range of about 95° C. to about 120° C., thereby degrading or destroying the polarizer's polarizing ability. - Higher temperatures can also be detrimental to
protective layers 26. For example, the CAB layers of a CAB/PVA/CAB polarizer generally begin to degrade at a temperature in a range of about 95° C. to about 120° C., typically by yellowing in the first instance, thereby rendering the polarizer unsuitable. In addition, depending on the adhesive (not shown) used to bond theprotective layers 26 to filter layer 18 and/or filter 14 tosubstrate 22, elevated temperatures can cause the protective layers and/or filter to blister. Such blistering would renderlens article 10 unacceptable for its intended purpose. - Polycarbonates, e.g., those sold under the trademarks LEXAN® and MAKROLON® by General Electric Corporation and Bayer Corporation, respectively, generally have a glass-transition temperature in a range of about 135° C. to about 155° C. Consequently, if
substrate 22 were made of one of these polycarbonates, it would generally be necessary to raise the temperature of the substrate and filter 14 to at least the glass transition temperature of that polycarbonate, i.e., about 135° C. or higher, in order to thermoform and/oranneal lens article 10. However,heating filter 14 to such a temperature would exceed its minimum degradation temperature. Therefore, despite polycarbonate being a highly desirable material from optical and durability viewpoints, it is generally not desirable from a manufacturability viewpoint. - Although a pure polycarbonate would generally not be suitable for use as
substrate 22 in the manufacturing process described above due to the deterioration of filter caused during thermoforming and/or annealing, the pure polycarbonate (i.e., the first polymer) may be blended, or copolymerized, with a second polymer other than polycarbonate, e.g., polyethylene teraphthalate, so as to essentially reduce the glass transition temperature of the polycarbonate to an adjusted glass transition temperature that will allowlens article 10 to be thermoformed and/or annealed at a temperature lower than the minimum degradation temperature offilter 14. This concept may be readily extended not only to carbonates other than polycarbonate (see below), but also to other polymers generally. Those skilled in the art will readily understand how to apply the basic concepts of the present invention to myriad other polymers based on the particular thermoplastic-based article being considered and the characteristics that are desirable for the component of that article at issue. Consequently, it is not necessary to provide an exhaustive list of all permutations of polymer blends. However, a few examples are provided herein for a more robust disclosure. It is noted that the second polymer blended with the first polymer that provides the desirable characteristics is typically, but not necessarily, not from the same group as the first polymer. For example, if the first polymer is a carbonate, the second polymer is typically, but again not necessarily, not a carbonate. - Other examples of carbonate blends having glass-transition temperatures lower than pure polycarbonate and lower than the temperature at which filter 14 would start to degrade include certain ones of the blends made of aliphatic polyester-carbonates incorporating “diaryl carbonates” disclosed in U.S. Pat. No. 5,654,380 (e.g., the carbonate blend disclosed in Example 1 has a glass-transition temperature of 104° C.) and the blend disclosed in U.S. Pat. No. 5,410,014, which discloses a copolymer of aromatic-aliphatic polycarbonate having a glass transition temperature of about 119° C. Each of U.S. Pat. Nos. 5,654,380 and 5,410,014 are incorporated herein by reference in their entireties.
- In one particular embodiment,
substrate 22 may comprise a blend of 70 parts of polycarbonate to 30 parts of polyethylene teraphthalate that has an adjusted glass transition temperature of about 121° C. This blend is commercially available under the trademark XYLEX® from the General Electric Company. It has been observed that sheets of this blend can be thermoformed at temperatures between about 120° C. and about 140° C. Clearly, at the upper end of this range this particular blend is not suitable for use with an iodine/PVA-based polarizer, which has a minimum degradation temperature in a range of about 95° C. to about 120° C. based on the presence of iodine. However, the lower end of the range may be suitable for such a polarizing layer. That said, experiments performed to date have shown that thermoforming at the lower end of the range can be non-uniform. - In another embodiment in which
substrate 22 comprises a 50 parts to 50 parts blend of polycarbonate and polyethylene teraphthalate (also available from General Electric under the trademark XYLEX®) having an adjusted glass transition temperature of about 87° C., it has been observed that sheets of this blend can be readily thermoformed at about 95° C. Referring toFIG. 2 , the curvatures ofsides lens article 10 thermoformed at 95° C. using thethermoforming assembly 36 ofFIG. 2 matched, respectively, the curvatures ofsurfaces - If
lens article 10 is to be a lens, as opposed to an insert, one or more optical coatings, such as hardcoat layers 46, may be provided to the article on each ofsides lens article 10 has been thermoformed. - In addition, or alternatively, to one or more dichroic dyes being incorporated into
filter 14, one or more dichroic dyes may be incorporated directly intosubstrate 22. Indeed, in alternative embodiments ofarticle 10 having photochromic properties without polarizing properties, filter 14 need not be provided. In this case, the photochromic dye(s) could be incorporated only insubstrate 22. In this connection, some photochromic dyes have been reported to not perform well in polymers with high glass transition temperatures and perform better in polymers with lower glass transition temperatures. Some photochromic dyes have two geometrical forms, e.g., one form “open” and the other form “closed,” and the photochromic action is accompanied by opening and closing the molecule. In a matrix having a low glass transition temperature, the matrix has greater mobility and the photochromic molecule can change forms more readily. Consequently,substrate 22 in this scenario could be a polymer blend having a glass transition temperature adjusted in the manner described above in connection with the embodiment incorporating filter. In this case, the glass transition temperature ofsubstrate 22 may be adjusted prior to adding any photochromic dyes thereto. Suitable polymer blends for supporting direct addition of one or more photochromic dyes may include any of the exemplary blends discussed above, including the methacrylate/butyldyene blend and the polycarbonate/polyethylene teraphthalate blend, among others. -
FIG. 3 shows analternative lens article 10′ of the present invention that may also be used as a filtering lens or a filtering insert in manner similar to the manner described above relative to lens article ofFIGS. 1 and 2 . Rather than having a single blended-polymer substrate 22 to whichfilter 14 is attached as withlens article 10 ofFIG. 2 ,lens article 10′ ofFIG. 3 includes two blended-polymer layers 22′ attached to opposite sides of afilter 14′. Similar tolens article 10′ ofFIGS. 1 and 2 ,lens article 10′ ofFIG. 3 would typically be assembled withsubstrates 22′ in flat-plate form, such that the entire article, includingfilter 14′, would need to be thermoformed in order achieve the contours shown inFIG. 3 .Filter 14′ may be any filter suitable forlens article 10′, such as the polarizer-type orphotochromic filter 14 shown and described above relative toFIG. 2 . - Like
substrate 22 ofFIG. 2 , eachsubstrates 22′ ofFIG. 3 may contain a polymer blend that includes a first polymer selected primarily for its ability to providelens article 10′ with one or more desirable characteristics as discussed above. Also similar to the discussion above, eachsubstrate 22′ further includes a second polymer blended with the first polymer in a predetermined amount so as to essentially lower the glass transition temperature of the first polymer so thatlens article 10′ can be thermally processed, e.g., thermoformed and/or annealed, at a temperature that will not unacceptably degradefilter 14′, or any of its components. -
FIG. 4 illustrateslens article 10 ofFIGS. 1 and 2 being used as a filtering insert for anophthalmic lens 100. In one embodiment,lens 100 is made by placinglens article 10 betweenmold parts 104 of an injection molding or injection/coining machine (not shown) and injecting or injecting/coining a high-impact polymer layer 108 against the concave side of the article. In an alternative embodiment, high-impact polymer layer 108 may be formed on the convex side oflens article 10. However, it appears that a greater impact strength can be achieved by forminglayer 108 on the concave side. - A suitable method of forming high-
impact polymer layer 108 is the injection/coining process disclosed in detail in U.S. Pat. No. 6,270,698 to Pope, which is incorporated by reference herein in its entirety. High-impact polymer layer 108 may be made of any suitable polymer or polymer blend, including a polymer blend, including the polycarbonate/polyethylene teraphthalate blend or methacrylate/butyldyene blend described above, that is made in accordance with the present invention, i.e., generally, by first selecting a first polymer based on its ability to provide one or more desirable characteristics and then blending the first polymer with a second polymer so as to create a blend having both good characteristics and a glass transition temperature lower than the glass transition temperature of the polymer originally selected for its ability to provide the desirable characteristic(s). During the injection/coining process, high-impact polymer layer is molded at a suitable molding temperature, which is generally between about 415° F. and about 480° F. for polycarbonate copolymers and about 400° F. for the acrylic copolymer. - Using the injection/coining process of the Pope patent, using a polycarbonate/polyethylene teraphthalate blend for each of
substrate 22 and high-impact polymer layer 108 and using iodine/PVA for filtering layer 18, it was seen that the high-impact polymer layer bonded very well to the substrate and filtering layer did not degrade. In addition, use of this process resulted in minimal residual stress inlayer 108. In a particular specimen oflens 100 made using the Pope process with the materials just cited, the overall thickness of the lens was approximately 2 mm. This specimen passed the tests set forth in the American National Standards Institute (ANSI) Z78 Standard for Eye and Face Protection. Specimens oflens 100 thinner than 2.4 mm can also pass these tests, depending upon the materials selected for the various layers of the lens and the level of residual internal stresses remaining in the lens after its manufacture. -
FIG. 5 shows alens article 10″ that is similar tolens article 10 ofFIG. 2 , except thatsubstrate 22 is located on theconvex side 30 of the article rather than theconcave side 32, as shown inFIG. 2 . This may be achieved, e.g., simply by flipping theflat filter 14/substrate 22 precursor toarticle 10side 30 forside 32 inthermoforming assembly 36 relative toFIG. 2 prior to thermoforming. All other aspects ofarticle 10″ may be the same as described above relative tolens article 10. - The following six examples outline results obtained from different experiments to form example embodiments of
article 10 of the present invention. The experiments were carried out to determine the proper process and structure for articles suitable for use as stand-alone polarized lenses, or as inserts for injection-molded polarized lenses. - An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick LEXAN polycarbonate to form the composite structure. Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 95° C. for 8 minutes. The curvature of the composite rectangles was very irregular and minimal. However the iodine-based polarizer did not show any degradation during the process. Similar results were obtained when the LEXAN polycarbonate sheets were replaced with sheets of polycarbonate from the Mobay Corp.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick LEXAN polycarbonate to form a composite structure. Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 140° C. for 8 minutes. The composite rectangles had an irregular curvature that was less than the mold surface curvature. The iodine polarizer was degraded and the cellulose acetobutyrate layers were yellowed and blistered. Similar results were obtained when the sheets of LEXAN polycarbonate were replaced with sheets of polycarbonate from the Mobay Corp.
- Rectangles approximately 60 mm by 70 mm were cut from a sheet (substrate) of 0.5 mm thick blend of 70/30 polycarbonate/polyethylene teraphthalate (XYLEX). The rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The rectangles were heated in the thermoformer to 120° C. for 8 minutes. The resultant curvature of the rectangles was irregular. Further, the polarizer showed slight degradation and the cellulose acetobutyrate showed slight yellowing.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick blend of 70/30 polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 120° C. for 8 minutes. The resultant curvature of the rectangles was irregular. Further, the polarizer showed slight degradation and the cellulose acetobutyrate showed slight yellowing.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one sheet (substrate) of 0.5 mm thick blend of 50/50 polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60 mm by 70 mm were cut from the composite structure. The composite rectangles were placed in a conventional vacuum thermoformer with spherical cups having a radius of 90 mm. The composite rectangles were heated in the thermoformer to 100° C. for 8 minutes. The resultant curvature of the composite rectangles was regular and closely matched the curvature of the mold surface. Further, the iodine polarizer showed no degradation and the cellulose acetobutyrate layers did not yellow or blister. This article can be used as a stand-alone polarizing lens.
- An iodine-based polarizer having transmittance for visible light of 37% was bonded between two layers of cellulose acetobutyrate, then bonded to one layer (substrate) of 50/50 blend of polycarbonate/polyethylene teraphthalate (XYLEX). Rectangles approximately 60×70 mm were cut from the composite structure and were then heated in the thermoformer to 100° C. for 8 minutes. Upon removal from the thermoformer the curvature of the rectangles closely approximated the curvature of the mold surfaces and was uniform. This article was then used as an insert for an injection molded polarized lens.
- Although the invention has been described and illustrated with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions and additions may be made therein and thereto, without parting from the spirit and scope of the present invention. For example, although the present invention has been described above in connection with ophthalmic lenses, those skilled in the art that the present invention will also be suitable in other optical applications, such as filters for electronic display devices and enclosures (filters) for lamps.
Claims (20)
1. A method of making a photochromic lens article, comprising:
a) providing at least one photochromic substance in operable relationship with a substrate, the photochromic substance having a minimum degradation temperature;
b) forming the substrate as a polymer blend that contains a first polymer having a first glass transition temperature higher than said minimum degradation temperature, said polymer blend having a second glass transition temperature lower than said minimum degradation temperature; and
c) thermoforming the substrate and at least one photochromic substance at a temperature below said minimum degradation temperature so as not to degrade the at least one photochromic substance.
2. A method according to claim 1 , wherein the photochromic substance includes at least one such substance selected from the group comprising: naphthopyrans, spironapthopyrans, fulgides, fulgimides, salicylates, triazoles, oxazoles, azobenzenes and silver halide.
3. A method according to claim 1 , including supporting the photochromic substance adjacent the substrate using a filtering layer.
4. A method of claim 3 , including providing at least one protective layer adjacent the filtering layer.
5. A method of claim 4 , wherein the filtering layer includes at least one of CAB, polypropylene, poly(vinyl chloride) and poly(vinyl acetate).
6. A method of claim 1 , wherein step b) includes forming said polymer blend by blending a second polymer with the first polymer in a predetermined amount that lowers said first glass transition to said second glass transition temperature.
7. A method of claim 1 , wherein the at least one photochromic substance is incorporated into the substrate.
8. A method according to claim 7 , wherein the at least one photochromic substance includes a photochromic dye.
9. A method according to claim 1 , wherein step c) includes thermoforming the substrate and at least one photochromic substance into one of an ophthalmic lens and a pre-contoured ophthalmic lens insert.
10. A method according to claim 1 , wherein the step b) of forming the substrate as a polymer blend is performed prior to the step a) of providing and supporting the least one photochromic substance in operable relationship with the substrate.
11. A method of making a photochromic lens article that includes a substrate and at least one photochromic substance having a minimum degradation temperature, the method comprising:
a) forming the substrate by:
i) providing a first polymer having a first glass transition temperature higher than the minimum degradation temperature; and
ii) blending a second polymer with said first polymer to form a blended polymer having a second glass transition temperature lower than said minimum degradation temperature;
b) placing the at least one photochromic substance in operable relationship to the substrate; and
c) thermoforming the at least photochromic substance and the substrate at a temperature lower than said minimum degradation temperature so as to form said photochromic lens article while avoiding degrading the at least one photochromic substance.
12. A method according to claim 11 , including supporting the at least one photochromic substance in a filter layer
13. The method of claim 12 , including sandwiching the filter layer between two protective layers.
14. A method according to claim 11 , wherein the first polymer includes at least one of a carbonate polymer and an acrylic polymer
15. A method according to claim 12 , wherein the at least one photochromic substance includes a photochromic dye.
16. A method according to claim 12 , wherein the at least one photochromic substance is incorporated into the substrate.
17. A photochromic lens article, comprising:
a) at least one photochromic substance having a minimum degradation temperature; and
b) a substrate arranged in working relation with the at least one photochromic substance, said substrate comprising a blend of a first polymer and a second polymer, said first polymer having a first glass transition temperature greater than the minimum degradation temperature, the second polymer selected to cause the blended-polymer substrate to have a second glass transition temperature lower than said minimum degradation temperature so that the at least one photochromic substance and the substrate are thermoformable at a temperature lower than the minimum degradation temperature so as not to degrade the at least one photochromic substance when forming the lens article.
18. The lens article of claim 17 , wherein the at least one photochromic substance includes a photochromic dye.
19. The lens article of claim 17 , wherein the at least one photochromic substance is incorporated into the substrate.
20. The lens article of claim 17 , wherein said first polymer is a poly(methyl methacrylate) and said second polymer is a butyldyene.
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US11/998,509 US20080074613A1 (en) | 2002-12-27 | 2007-11-30 | Method of making a thermoplastic-based article and a thermoplastic-based article made thereby |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5188930A (en) * | 1989-10-18 | 1993-02-23 | Idemitsu Kosan Co., Ltd. | Photographic film of syndiotactic styrene polymer |
US6280808B1 (en) * | 1999-05-25 | 2001-08-28 | Rohm And Haas Company | Process and apparatus for forming plastic sheet |
US20020006469A1 (en) * | 1996-08-14 | 2002-01-17 | Gilles Baillet | Method for incorporating additives in an ophthalmic article by means of a supercritical fluid |
US6352761B1 (en) * | 1998-01-13 | 2002-03-05 | 3M Innovative Properties Company | Modified copolyesters and improved multilayer reflective films |
US6432327B2 (en) * | 1999-12-29 | 2002-08-13 | Younger Mfg. Co. | Formed polyethylene terephthalate polarizing film for incorporation in optical-grade plastic parts |
US20040015187A1 (en) * | 2002-04-18 | 2004-01-22 | Mnemoscience Corporation | Biodegradable shape memory polymeric sutures |
US6719812B1 (en) * | 2000-04-11 | 2004-04-13 | Gentex Optics, Inc. | Infusion of dye using a plasticizer |
US7311399B2 (en) * | 2002-12-27 | 2007-12-25 | Optical Enterprise, Inc. | Method of making a thermoplastic-based article and a thermoplastic-based article made thereby |
Family Cites Families (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2237567A (en) | 1939-05-04 | 1941-04-08 | Polaroid Corp | Light polarizer and process of manufacturing the same |
US2445555A (en) | 1945-04-16 | 1948-07-20 | Polaroid Corp | Light-polarizing polyvinyl sheet containing polyvinyl compoundboric acid complex |
US2674159A (en) | 1951-03-16 | 1954-04-06 | Polaroid Corp | Process for the manufacture of light-polarizing sheets |
FR2118305A5 (en) | 1970-12-14 | 1972-07-28 | Vergo Sa | |
US3940304A (en) | 1972-05-02 | 1976-02-24 | Polaroid Corporation | Method of making composite light-polarizing element |
US4090830A (en) | 1974-07-03 | 1978-05-23 | American Optical Corporation | Mold for producing polarizing optical devices |
US4035527A (en) | 1974-11-29 | 1977-07-12 | American Optical Corporation | Method of providing a phototropic layer on a carrier |
JPS62295001A (en) | 1986-06-14 | 1987-12-22 | Nippon Sheet Glass Co Ltd | Multi-focus spherical lens made of synthetic resin and its production |
JPH0339903A (en) | 1989-04-27 | 1991-02-20 | Mitsubishi Gas Chem Co Inc | Antidazzle polarizing plate made of polycarbonate |
US5246728A (en) | 1991-01-29 | 1993-09-21 | Bmc Industries, Inc. | Scratch-resistant coating and method of making coated lenses |
US5223862A (en) | 1991-04-08 | 1993-06-29 | Corning Incorporated | High-index, organic lens member |
JPH06214670A (en) * | 1991-04-29 | 1994-08-05 | Intel Corp | Computer system and method for initializing it |
US5164228A (en) | 1991-05-20 | 1992-11-17 | Bmc Industries, Inc. | Method of applying scratch-resistant coatings to plastic ophthalmic lenses |
US5286419A (en) | 1992-02-20 | 1994-02-15 | Bmc Industries, Inc. | Process for making a light polarizing spectacle lens |
US5351100A (en) | 1992-12-09 | 1994-09-27 | Bmc Industries, Inc. | Glass multifocal ophthalmic lens with polarizing element and method of making |
DE4244008C2 (en) | 1992-12-24 | 1997-04-24 | Bayer Ag | Process for the production of aliphatic-aromatic polycarbonates |
US5550599A (en) | 1994-01-10 | 1996-08-27 | Oakley, Inc. | Surface modified lens |
NZ260250A (en) | 1993-05-25 | 1997-11-24 | James Henry Jannard | Lens system for eyeglasses; peripheral zone of lens has its surface modified by grooving |
US5434707A (en) | 1993-09-14 | 1995-07-18 | Polaroid Corporation | Shaped plastic light-polarizing lens and method of making same |
US5531940A (en) | 1993-12-10 | 1996-07-02 | Innotech, Inc. | Method for manufacturing photochromic lenses |
US6498683B2 (en) * | 1999-11-22 | 2002-12-24 | 3M Innovative Properties Company | Multilayer optical bodies |
US5654380A (en) | 1994-05-23 | 1997-08-05 | Mitsubishi Gas Chemical Company, Inc. | Aliphatic polyester carbonate and process for producing the same |
JP3372665B2 (en) * | 1994-08-12 | 2003-02-04 | 山本光学株式会社 | Polycarbonate polarized lenses for eyeglasses |
US5757459A (en) | 1995-03-03 | 1998-05-26 | Vision-Ease Lens, Inc. | Multifocal optical elements |
US5753145A (en) * | 1995-06-02 | 1998-05-19 | Hoecst Celanese Corp. | Polarizer films with high thermal and hygroscopic stability |
US5815848A (en) | 1995-07-14 | 1998-10-06 | Oakley, Inc. | Impact resistant face shield for sporting helmets |
US5648832A (en) | 1995-12-05 | 1997-07-15 | Oakley, Inc. | Decentered noncorrective lens for eyewear |
AUPN718195A0 (en) | 1995-12-18 | 1996-01-18 | Sola International Holdings Ltd | Laminate wafers |
US5805336A (en) * | 1996-04-05 | 1998-09-08 | Polaroid Corporation | Optical lens blank with polarizer aligned between plastic birefringent sheets |
AUPO625797A0 (en) | 1997-04-17 | 1997-05-15 | Sola International Holdings Ltd | Spectacles bearing sunglass lenses |
US6627300B1 (en) * | 1997-10-12 | 2003-09-30 | 3M Innovative Properties Company | Optical device containing polymeric material domains having different degrees of randomness |
US6808658B2 (en) * | 1998-01-13 | 2004-10-26 | 3M Innovative Properties Company | Method for making texture multilayer optical films |
US6065836A (en) * | 1998-07-30 | 2000-05-23 | Bayer Corporation | Photochromic ophthalmic lens |
US7002744B2 (en) * | 1999-11-22 | 2006-02-21 | Younger Mfg. Co. Dba Younger Optics | Polarized optical part using high impact polyurethane-based material |
US6270698B1 (en) | 1999-05-25 | 2001-08-07 | American Greetings Corp. | Stress-relieved acrylic optical lenses and methods for manufacture by injection coining molding |
US6220703B1 (en) | 1999-12-29 | 2001-04-24 | Younger Manufacturing Co., Inc. | Ophthalmic lenses utilizing polyethylene terephthalate polarizing films |
JP2001166112A (en) * | 1999-12-08 | 2001-06-22 | Nitto Denko Corp | Optical film and optical device |
US6375776B1 (en) * | 2000-01-24 | 2002-04-23 | Avery Dennison Corporation | Method for forming multi-layer laminates with microstructures |
JP4633906B2 (en) * | 2000-05-23 | 2011-02-16 | Jx日鉱日石エネルギー株式会社 | Circularly polarizing plate and liquid crystal display device |
JP4220652B2 (en) * | 2000-05-02 | 2009-02-04 | 山本光学株式会社 | Manufacturing method of sunglasses, goggles or correction lenses |
JP3795727B2 (en) | 2000-05-02 | 2006-07-12 | 山本光学株式会社 | Manufacturing method of sunglasses, goggles, or corrective lenses |
JP4455743B2 (en) | 2000-09-12 | 2010-04-21 | 山本光学株式会社 | Manufacturing method of polarizing lens |
US6638450B2 (en) | 2000-11-02 | 2003-10-28 | Vtec Technologies, Inc. | Method for manufacturing an injection molded thermoplastic ophthalmic lens having an encapsulated light polarizing element |
US7087195B2 (en) * | 2000-12-13 | 2006-08-08 | Tokuyama Corporation | Photochromic curable composition and cured articles thereof |
JP2002192554A (en) | 2000-12-22 | 2002-07-10 | Yasunobu Nakakoshi | Method for molding and manufacturing polyurethane polarizing lens |
US20030118750A1 (en) * | 2001-12-14 | 2003-06-26 | Eastman Kodak Company | Microvoided light diffuser containing optical contact layer |
US6801360B2 (en) | 2002-10-28 | 2004-10-05 | International Polarizer, Inc. | Polarized lens formed by injection/coining injection molding process |
US6926405B2 (en) * | 2003-06-06 | 2005-08-09 | Younger Mfg. Co. | Eyewear lens having selective spectral response |
-
2002
- 2002-12-27 US US10/331,062 patent/US6834956B2/en not_active Expired - Fee Related
-
2003
- 2003-12-24 EP EP03258171A patent/EP1434064A3/en not_active Ceased
- 2003-12-25 TW TW092136835A patent/TWI293131B/en active
- 2003-12-26 JP JP2003432714A patent/JP2004213001A/en active Pending
-
2004
- 2004-12-28 US US11/023,790 patent/US7311399B2/en not_active Expired - Fee Related
-
2007
- 2007-11-30 US US11/998,509 patent/US20080074613A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5188930A (en) * | 1989-10-18 | 1993-02-23 | Idemitsu Kosan Co., Ltd. | Photographic film of syndiotactic styrene polymer |
US20020006469A1 (en) * | 1996-08-14 | 2002-01-17 | Gilles Baillet | Method for incorporating additives in an ophthalmic article by means of a supercritical fluid |
US6352761B1 (en) * | 1998-01-13 | 2002-03-05 | 3M Innovative Properties Company | Modified copolyesters and improved multilayer reflective films |
US6280808B1 (en) * | 1999-05-25 | 2001-08-28 | Rohm And Haas Company | Process and apparatus for forming plastic sheet |
US6432327B2 (en) * | 1999-12-29 | 2002-08-13 | Younger Mfg. Co. | Formed polyethylene terephthalate polarizing film for incorporation in optical-grade plastic parts |
US6719812B1 (en) * | 2000-04-11 | 2004-04-13 | Gentex Optics, Inc. | Infusion of dye using a plasticizer |
US20040015187A1 (en) * | 2002-04-18 | 2004-01-22 | Mnemoscience Corporation | Biodegradable shape memory polymeric sutures |
US7311399B2 (en) * | 2002-12-27 | 2007-12-25 | Optical Enterprise, Inc. | Method of making a thermoplastic-based article and a thermoplastic-based article made thereby |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100014144A1 (en) * | 2008-07-17 | 2010-01-21 | Hoya Corporation | Plastic lens and manufacturing method thereof |
US8092014B2 (en) * | 2008-07-17 | 2012-01-10 | Hoya Corporation | Plastic lens and manufacturing method thereof |
US20110199680A1 (en) * | 2010-01-22 | 2011-08-18 | Oakley, Inc. | Eyewear with three-dimensional viewing capability |
US20110205626A1 (en) * | 2010-01-22 | 2011-08-25 | Oakley, Inc. | Lenses for 3d eyewear |
US8547635B2 (en) | 2010-01-22 | 2013-10-01 | Oakley, Inc. | Lenses for 3D eyewear |
US10976574B2 (en) | 2010-04-15 | 2021-04-13 | Oakley, Inc. | Eyewear with chroma enhancement |
US11397337B2 (en) | 2010-04-15 | 2022-07-26 | Oakley, Inc. | Eyewear with chroma enhancement |
US8770749B2 (en) | 2010-04-15 | 2014-07-08 | Oakley, Inc. | Eyewear with chroma enhancement |
US11474382B2 (en) | 2010-04-15 | 2022-10-18 | Oakley, Inc. | Eyewear with chroma enhancement |
US10401652B2 (en) | 2010-04-15 | 2019-09-03 | Oakley, Inc. | Eyewear with chroma enhancement |
US10345623B2 (en) | 2010-04-15 | 2019-07-09 | Oakley, Inc. | Eyewear with chroma enhancement |
US9383594B2 (en) | 2010-04-15 | 2016-07-05 | Oakley, Inc. | Eyewear with chroma enhancement |
US20120309187A1 (en) * | 2011-05-30 | 2012-12-06 | International Business Machines Corporation | Conformal Coining of Solder Joints in Electronic Packages |
US9134547B2 (en) | 2011-10-20 | 2015-09-15 | Oakley, Inc. | Eyewear with chroma enhancement |
CN104040412A (en) * | 2011-10-20 | 2014-09-10 | 奥克利有限公司 | Eyewear with chroma enhancement |
WO2013070417A1 (en) * | 2011-10-20 | 2013-05-16 | Oakley, Inc. | Eyewear with chroma enhancement |
US11579470B2 (en) | 2012-05-10 | 2023-02-14 | Oakley, Inc. | Lens with anti-fog element |
US9939657B2 (en) | 2013-03-15 | 2018-04-10 | Johnson & Johnson Vision Care, Inc. | Thermoformed ophthalmic insert devices |
US9069186B2 (en) | 2013-03-15 | 2015-06-30 | Johnson & Johnson Vision Care, Inc. | Thermoformed ophthalmic insert devices |
US11099408B2 (en) | 2014-01-10 | 2021-08-24 | Oakley, Inc. | Eyewear with chroma enhancement |
US11762221B2 (en) | 2014-01-10 | 2023-09-19 | Oakley, Inc. | Eyewear with chroma enhancement |
US10871661B2 (en) | 2014-05-23 | 2020-12-22 | Oakley, Inc. | Eyewear and lenses with multiple molded lens components |
US11048103B2 (en) | 2014-11-13 | 2021-06-29 | Oakley, Inc. | Eyewear with variable optical characteristics |
US11112622B2 (en) | 2018-02-01 | 2021-09-07 | Luxottica S.R.L. | Eyewear and lenses with multiple molded lens components |
CN112123684A (en) * | 2019-06-25 | 2020-12-25 | 江苏想靓眼镜有限公司 | Processing technology of multiple color-changing sunglasses |
Also Published As
Publication number | Publication date |
---|---|
US7311399B2 (en) | 2007-12-25 |
EP1434064A3 (en) | 2004-12-22 |
TWI293131B (en) | 2008-02-01 |
EP1434064A2 (en) | 2004-06-30 |
JP2004213001A (en) | 2004-07-29 |
US20040125339A1 (en) | 2004-07-01 |
US20050117113A1 (en) | 2005-06-02 |
US6834956B2 (en) | 2004-12-28 |
TW200506433A (en) | 2005-02-16 |
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