HK1139701B - Optical element having light influencing property - Google Patents

Description

Optical element with light influencing properties

Cross Reference to Related Applications

This application claims priority to U.S. provisional patent application No. 60/884,424 filed on 11/1/2007 and U.S. provisional patent application No. 60/956,204 filed on 16/8/2007.

Technical Field

The present invention relates to an optical element. More particularly, the present invention relates to optical elements comprised of multiple polymer film layers, one of which has a light-influencing property.

This application claims priority to U.S. provisional patent application No. 60/884,424 filed on 11/1/2007 and U.S. provisional patent application No. 60/956,204 filed on 16/8/2007.

The present invention relates to an optical element comprising at least (a) a supporting polymer film layer having opposing first and second sides, the polymer film layer comprising a film material, (b) a second polymer film layer having opposing first and second sides, the second polymer film layer comprising a film material and exhibiting light influencing properties, and (c) optionally, a tie layer interposed between and connected to at least a portion of the first side of the supporting polymer film layer (a) and the second side of the second polymer film layer (b), wherein the film material constituting the supporting polymer film layer (a) and the film material constituting the second polymer film layer (b) are the same or different.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

Moreover, for the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth, and other properties or parameters used in the specification are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, it is understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

In addition, notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the examples section are reported as precisely as possible. It should be understood, however, that these numerical values inherently contain certain errors resulting from the measurement equipment and/or measurement techniques.

As previously mentioned, the present invention relates to an optical element comprising at least (a) a supporting polymer film layer having opposing first and second sides, said layer comprising a film material, (b) a second polymer film layer having opposing first and second sides, said second polymer film layer comprising a film material and exhibiting light influencing properties, and optionally, (c) a tie layer interposed between and connected to at least a portion of the first side of the supporting polymer film layer (a) and the second side of the second polymer film layer (b), wherein the film material constituting the supporting polymer film layer (a) and the film material constituting the second polymer film layer (b) are the same or different. In one embodiment of the present invention, the supporting polymer film layer (a) and the second polymer film layer (b) comprise the same film material. In another embodiment, the supporting polymer film layer (a) and the second polymer film layer (b) comprise different film materials.

The term "light influencing property" or similar terms refer to a material being described, such as a film layer, that can be modified by absorbing (or filtering) incident light radiation, such as visible, Ultraviolet (UV) and/or Infrared (IR) radiation, impinging on the material. In alternative embodiments, the light influencing property may be light polarization, for example by means of a polarizer and/or a dichroic dye; a change in light absorption properties, for example by using chromophores that change color when exposed to actinic radiation, such as photochromic materials; only a portion of the incident light radiation is transmitted, for example, by using a fixed tint (fixed tint) such as a conventional dye; or a combination of one or more of these light influencing functions.

The term "linearly polarize" as used herein refers to confining the vibration of a light wave charge vector to one direction or plane. The term "dichroic" as used herein refers to one of two orthogonal plane polarization components that are capable of absorbing at least penetrating radiation more strongly than the other component. Thus, although dichroic materials are capable of preferentially absorbing one of the two orthogonal plane polarization components of penetrating radiation, if the molecules of the dichroic material are not properly arranged or aligned, net linear polarization of penetrating radiation is not achieved. That is, due to the random arrangement of the molecules of the dichroic material, the selective absorption of the individual molecules will cancel each other out so that no net or overall linear polarization effect is achieved. Thus, in order to achieve a net linear polarization, it is generally necessary to properly arrange or align the molecules of the dichroic material.

The term "photochromic" as used herein means having an absorption spectrum for at least visible radiation that changes in response to at least actinic radiation. Thus, conventional photochromic elements are generally well suited for use in low light and brightness conditions. It should be noted that conventional photochromic elements (not including linear polarizing filters) are generally not adapted to linearly polarized radiation. That is, conventional photochromic elements generally have an absorption ratio of less than 2 in either state. As used herein, the term "absorptance" refers to the ratio of the absorptance of radiation linearly polarized in a first plane to the absorptance of radiation of the same wavelength linearly polarized in a plane orthogonal to the first plane, where the first plane is considered to be the plane having the highest absorptance. Therefore, conventional photochromic elements generally cannot reduce reflected glare (light glare) to the same extent as conventional linear polarizing elements.

The term "coating" as used herein refers to a supported polymer layer obtained from a flowable composition, which may or may not have a uniform thickness, and specifically excludes the polymer films defined below. The term "polymer film" as used herein refers to a preformed polymer layer having a generally uniform thickness and being capable of being self-supporting (i.e., it is free-standing) and specifically excludes the coatings defined above. Furthermore, as used herein, the terms "connected with," "attached with," or the like, refer to being in direct contact with an object or being in indirect contact with an object via one or more other structures or materials or layers, at least one of which is in direct contact with the object.

The term "optical" as used herein refers to or in relation to light and/or vision. For example, optical elements or devices may include ophthalmic elements and devices, display elements and devices, windows, mirrors, and/or active and passive liquid crystal cell elements and devices. The term "ophthalmic" as used herein refers to or in relation to the eye and/or vision. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including single or multi-dimensional vision lenses, which may be segmented or non-segmented multi-dimensional vision lenses (such as, but not limited to, bifocal, trifocal, and progressive addition lenses), and other elements for correcting, protecting, or enhancing (cosmetic or other) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, protective lenses, or goggles. The term "display" as used herein refers to a visual or machine-readable representation of information in the form of words, values, indicia, structures or pictures. Non-limiting examples of display elements and devices include screens, monitors, and security elements, such as security markers. The term "window" as used herein refers to an aperture adapted to allow radiation to pass therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, shutters (shetters), and optical switches. The term "mirror" as used herein refers to a surface that specularly reflects a substantial portion of incident light.

The supporting polymer film layer (a) may comprise a polymer film composed of any of a number of film materials, including thermoset and thermoplastic materials. For example, the support layer (a) may comprise polycarbonate, polycycloolefin, polyurethane, poly (urea) urethane, polythiourethane, polythiourea urethane, polyol (allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyester, polysulfone, polyolefin, copolymers thereof, or mixtures thereof. In a particular embodiment of the invention, the supporting polymer film layer (a) may comprise cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate and/or cellulose acetate butyrate.

The supporting polymer film layer (a) may further comprise any of a number of additives to affect or enhance one or more of the processing and/or performance characteristics of the layer. Non-limiting examples of such additives may include dyes, photoinitiator thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers such as Hindered Amine Light Stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, and adhesion promoters (such as hexanediol diacrylate and/or coupling agents).

In a particular embodiment, the supporting polymer film layer (a) may further comprise ultraviolet light absorbers which may include, for example, 2-hydroxybenzophenones, 2-hydroxyphenylbenzotriazoles, oxanilides, 2-hydroxyphenyltriazines, cinnamates, salicylates, and/or formamidines. Specific examples of suitable ultraviolet light absorbers may include those disclosed in U.S.5,770,115, column 4, lines 2-14, the citation of which is incorporated herein by reference. Suitable ultraviolet light stabilizers may include, but are not limited to, those available from CibaThose obtained under the trade name.

It should be mentioned that the supporting polymer film layer (a) may consist of a single layer or sheet of any of the above materials, or the supporting polymer film layer (a) may consist of multiple layers of different materials, such as any of those mentioned hereinbefore. The thickness of the supporting polymer film layer (a) may vary widely depending on the type of material comprising the supporting layer (a) and the desired end use of the optical element it is composed of. Typically, the supporting polymer film layer (a) has a thickness of 10-2000 microns, such as 20-1000 microns, or 50-500 microns, or 75-300 microns. The thickness of the supporting polymer film layer (a) may range between any of the values recited, inclusive.

The optical element of the present invention also includes a second polymeric film layer (b) having opposing first and second sides and comprising a film material (as described herein). The second polymer film layer (b) comprises a film exhibiting light influencing properties.

The second polymeric film layer (b) may comprise any of a number of materials, for example, any of those materials previously described with respect to the support layer (a). In one embodiment of the present invention, the second polymer film layer (b) is linearly polarized. In such embodiments, the second polymer film layer (b) may also comprise a dichroic material as discussed below, and may be oriented, as discussed below, in one or more directions.

In a particular embodiment of the invention, the second polymer film layer (b) is linearly polarized and comprises a polymer component comprising polyvinyl alcohol, polyvinyl butyral, polyethylene terephthalate, cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, polyurethane, polyether, polyester, polyamide, polyalkyl (meth) acrylate, mixtures thereof and/or copolymers thereof.

The second polymer film layer (b) may be linearly polarizing and may comprise an optical film consisting of a dispersed phase of polymer particles disposed within a continuous birefringent matrix, which film may be oriented in one or more directions. The size and shape of the disperse phase particles, the volume fraction of the disperse phase, the film thickness and the amount of dispersion are selected to achieve the desired degree of total transmission and diffuse reflection of the desired wavelength of radiation in the film. Such membranes and their preparation are described in U.S.5,867,316, column 6, line 47 to column 20, line 51, the citation of which is incorporated herein by reference. The second layer (b), when linearly polarized, may also comprise a birefringent multilayer optical film as described in U.S.5,882,774 column 2, line 63 to column 18, line 31, the citation of which is incorporated herein by reference. In addition, the second layer (b) may also comprise a two-component polarizer (i.e. dichroic and reflective polarizing component), such as the two-component polarizers described in U.S.6,096,375 column 3, line 7 to column 19, line 46, the citation of which is incorporated herein by reference.

In addition, the second polymer film layer (b) may be linearly polarized and may include an oriented film of polyvinyl alcohol, vinyl butyral, polyethylene terephthalate, polyalkyl (meth) acrylate, polyamide, poly (amide-ether) block copolymer, poly (ester-ether) block copolymer, poly (ether-urethane) block copolymer, poly (ester-urethane) block copolymer, and/or poly (ether-urea) block copolymer. The term "oriented film" as used with respect to the linearly polarizing second polymer film layer (b) means that the film has at least a first general direction (orientation) such that one or more other structures or components comprising the sheet are arranged or suitably aligned along the same general direction. For example, the orientation or ordering of the dichroic compound along the long axis of the dichroic compound is substantially parallel to at least the first general direction of the film or layer. The term "general direction" as used herein with reference to the ordering or orientation of materials or structures refers to the predominant arrangement or orientation of materials, compounds, or structures. Further, those skilled in the art will recognize that materials, compounds, or structures may have a general orientation even if there is some variation in the arrangement of the materials, compounds, or structures, provided that the materials, compounds, or structures have at least one predominant arrangement.

The polarizing second polymer film layer (b) may also comprise a "K-type" polarizer, wherein the dichroic material is prepared, for example, by dehydration of polyvinyl alcohol. Such polarizers are often referred to as intrinsic polarizers (intrinsic polarizers) because the absorbing chromophores are the result of conjugation in the polymer backbone, and not due to dichroic materials such as dichroic dyes added to the polymer composition. Such K-type polarizers may comprise a film of oriented polyvinyl alcohol having light polarizing (dichroic) molecules composed of conjugated blocks such as poly (acetylene) blocks (i.e., - [ CH ═ CH-]_n) Composition of the film by heating an oriented polyvinyl alcohol film in the presence of a dehydration catalyst such as the vapor of aqueous hydrochloric acidThereby forming the composite material. The K-type polarizer may also be formed as follows: an acid donor layer comprising a photoacid generator is fixed to a film of oriented polyvinyl alcohol and exposed to radiant energy at a temperature sufficient to effect partial dehydration of the vinyl alcohol polymer to a vinyl alcohol/poly (acetylene) copolymer. See, for example, U.S.6,808,657.

As previously mentioned, the second polymer film layer (b) may comprise a dichroic material when polarized. Non-limiting examples of suitable dichroic materials may include, but are not limited to, compounds such as azomethines, indigoids, thioindigoids, merocyanines, indanes, quinophthalone dyes, perylenes, phthalimidines, triphendioxazines, indoloquinoxalines, imidazotriazines, tetrazines, azo and polyazo dyes, benzoquinones, naphthoquinones, anthraquinones, (poly) anthraquinones, anthrapyrimidinones, iodine and/or iodates. The term "compound" as used herein refers to a substance formed by the association of two or more elements, components, ingredients or moieties and includes, but is not limited to, molecules and macromolecules (e.g., polymers and oligomers) formed by the association of two or more elements, components, ingredients or moieties.

The dichroic material may also include a polymerizable dichroic compound. That is, the dichroic material may comprise at least one group capable of being polymerized (i.e., "polymerizable group"). For example, although not limited herein, in one non-limiting embodiment, the dichroic compound can have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent terminated by at least one polymerizable group.

The dichroic material may also include a photochromic-dichroic compound. The term "photochromic-dichroic" refers to exhibiting both photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least perceptible by an instrument. Thus, a "photochromic-dichroic compound" is a compound that exhibits both photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least perceptible by an instrument. Thus, photochromic-dichroic compounds have an absorption spectrum for at least visible radiation that changes in response to at least actinic radiation, and are capable of absorbing at least one of the two orthogonal plane-polarized components of penetrating radiation more strongly than the other component (i.e., are capable of exhibiting dichroism). Further, the photochromic-dichroic compounds disclosed herein can be thermally reversible, as with conventional photochromic compounds discussed below. That is, such photochromic-dichroic compounds can switch from a first state to a second state in response to actinic radiation and revert back to the first state in response to thermal energy.

For example, according to various non-limiting embodiments disclosed herein, a photochromic-dichroic compound can have a first state having a first absorption spectrum, a second state having a second absorption spectrum different from the first absorption spectrum, and can be adapted to transition from the first state to the second state in response to at least actinic radiation and to revert back to the first state in response to thermal energy. Further, the photochromic-dichroic compound can be dichroic (i.e., linearly polarizing) in one or both of the first and second states. For example, although not required, the photochromic-dichroic compound can be linearly polarizing in the activated state and unpolarized in the bleached or bleached (i.e., unactivated) state. As used herein, the term "activated state" refers to a photochromic-dichroic compound when exposed to sufficient actinic radiation to cause at least a portion of the photochromic-dichroic compound to switch from a first state to a second state. Further, although not required, the photochromic-dichroic compound can be dichroic in both the first and second states. Although not limited herein, for example, the photochromic-dichroic compound can linearly polarize visible radiation in both the activated and bleached states. Further, photochromic-dichroic compounds can linearly polarize visible radiation in the activated state and can polarize UV radiation in the bleached state.

Examples of photochromic-dichroic compounds suitable for use in the present invention can include, but are not limited to, those described in detail in U.S. patent application publication No. 2005/0012998a1 paragraphs [0089] - [0339], the disclosure of which is incorporated herein by reference.

As previously mentioned, the second polymer film layer (b) may be polarizing and may comprise an oriented polymer film. The polymer components used to prepare such polymer films and the dichroic materials (including the dichroic-photochromic materials described above) and any other components that may be included, may be blended together and then subjected to any of a number of processing techniques known in the art to form a film. These techniques may include, for example, extrusion, solvent casting, calendering, blow molding, or a combination of these techniques. Alternatively, the compositions used to prepare the polymer components may be blended together and processed to form a film by any of a number of processing techniques known in the art. Once the film is formed, a solution containing the dichroic material may be incorporated into the film, for example by a imbibing process as is well known in the art, and the imbibed film may then be oriented to orient the dichroic material.

The membrane may be secured in the oriented configuration by any of a number of securing means known in the art. For example, a film oriented by stretching may be fixed in an oriented configuration by mechanical fixing means (e.g., by using a jig) to prevent the sheet from returning to the pre-stretched configuration. Other means may include thermal fixing or thermal annealing, i.e., fixing the alignment film by heating. When a film is prepared from reactive (e.g., crosslinkable) polymeric components, the film may be formed, for example, by extrusion or solvent casting, in a manner such that the components do not react. Once formed, the film can be oriented and then fixed in this oriented configuration by reacting (e.g., crosslinking, including self-crosslinking) the polymer components. For example, such crosslinking may be accomplished as follows: the oriented film is subjected to conditions that promote the reaction of the functional groups of any reactive polymer component, for example, subjecting the oriented sheet to heat or radiation, including actinic (ultraviolet) and/or ionizing (electron beam) radiation.

Further, as previously mentioned, the second polymer film layer (b) may be photochromic. That is, the second polymer film layer (b) may comprise a photochromic material (in addition to or in place of the photochromic-dichroic material described above). The term "photochromic material" as used herein includes both thermally reversible photochromic compounds and non-thermally reversible (or photo-reversible) photochromic compounds. Generally, although not limited thereto, when two or more photochromic materials are used in combination with each other or with a photochromic-dichroic compound (such as those described above), numerous materials can be selected to complement each other to produce a desired color or shade. For example, mixtures of photochromic compounds may be used according to certain non-limiting embodiments disclosed herein to obtain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Pat. No. 5,645,767, column 12, line 66 to column 13, line 19, the disclosure of which is expressly incorporated herein by reference, which describes parameters defining neutral gray and brown.

The photochromic material can include any of a wide variety of organic and inorganic photochromic materials. Photochromic materials may include, but are not limited to, the following types of materials: chromenes, such as naphthopyrans, benzopyrans, indenonaphthopyrans, phenanthropyrans, or mixtures thereof; spiropyrans, such as spiro (benzindoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, spiro (indoline) quinopyrans and spiro (indoline) pyrans; oxazines, such as spiro (indoline) phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) phenoxazines and spiro (indoline) benzoxazines; mercuric dithiozonates, fulgides, fulgimides and mixtures of these photochromic compounds.

These photochromic materials and complementary photochromic materials are described in U.S. Pat. No. 4,931,220 at column 8, line 52 to column 22, line 40; U.S. Pat. No. 5,645,767, column 1, line 10 to column 12, line 57; line 64 of column 1 to line 17 of column 13 of U.S. Pat. No. 8,5,658,501(ii) a U.S. patent 6,153,126, column 2, line 18 to column 8, line 60; U.S. patent 6,296,785, column 2, line 47 to column 31, line 5; U.S. patent 6,348,604, column 3, line 26 to column 17, line 15; U.S. patent 6,353,102, column 1, line 62 to column 11, line 64, the disclosure of which is incorporated herein by reference. Spiro (indoline) pyrans are also describedTechniques in ChemistryVolumeIII, "Photochromysm", Chapter 3, Glenn H.Brown, Editor, John Wiley and Sons, Inc., New York, 1971.

In another non-limiting embodiment, the photochromic material can be a polymerizable photochromic material, such as polymerizable naphthoxazines disclosed in U.S. Pat. No. 5,166,345 at column 3, line 36 to column 14, line 3; polymerizable spirobenzopyrans disclosed in U.S. Pat. No. 5,236,958, column 1, line 45 to column 6, line 65; polymerizable spirobenzopyrans and spirobenzothiopyrans disclosed in U.S. Pat. No. 5,252,742 at column 1, line 45 to column 6, line 65; polymerizable fulgides disclosed in U.S. Pat. No. 5,359,085, column 5, line 25 to line 19, line 55; polymerizable naphthonaphthalenediones disclosed in U.S. Pat. No. 5,488,119 at column 1, line 29 to column 7, line 65; polymerizable spirooxazines disclosed in U.S. Pat. No. 5,821,287 at column 3, line 5 to column 11, line 39; polymerizable polyalkoxylated naphthopyrans disclosed in U.S. Pat. No. 6,113,814 at column 2, line 23 to column 23, line 29; and WO97/05213 and U.S. Pat. No. 6,555,028, column 1, line 16 to column 24, line 56. The disclosures of polymerizable photochromic materials in the above-mentioned patents are incorporated herein by reference.

Other suitable photochromic materials may include organometallic dithiozonates, such as (arylazo) -thiocarboxylic arylhydrazidates (hydrazidates), such as mercury dithiozonates, which are described, for example, in U.S. Pat. No. 3,361,706 at column 2, lines 27 to 8, lines 43; and fulgides and fulgimides, such as 3-furyl and 3-thienyl fulgides and fulgimides, which are described in U.S. Pat. No. 4,931,220 at column 1, line 39 to column 22, line 41, the disclosures of which are incorporated herein by reference.

When used, the additional photochromic materials can include organic photochromic materials that are resistant to the effects of polymerization initiators. These organic photochromic materials include photochromic compounds mixed with a resin material that has been formed into particles and encapsulated in a metal oxide, which are described in U.S. Pat. Nos. 4,166,043 and 4,367,170 at column 1, line 36 to column 7, line 12, the disclosures of which are incorporated herein by reference.

The photochromic material can include a single photochromic compound; a mixture of photochromic compounds; a material containing at least one photochromic compound, such as a plastic polymer resin or an organic monomer or oligomer solution; a material such as a monomer or a polymer to which at least one photochromic compound is chemically bonded; a material comprising and/or having chemically bonded thereto at least one photochromic compound, the outer surface of which is encapsulated (encapsulation being in a coated form) with, for example, a polymeric resin or a protective coating such as a metal oxide, said polymeric resin or protective coating preventing the photochromic material from coming into contact with external materials having a negative impact on the photochromic material, such as oxygen, moisture and/or chemical substances, such materials may be formed into particles prior to the application of the protective coating, as described in U.S. Pat. nos. 4,166,043 and 4,367,170; photochromic polymers, such as photochromic polymers comprising photochromic compounds bonded together; or mixtures thereof.

Suitable photochromic materials can also include polymerizable polyalkoxylated naphthopyrans disclosed in U.S. Pat. No. 6,113,814 at column 2, line 24 to column 23, line 29, the citation of which is incorporated herein by reference. Further, suitable photochromic materials can include polymer matrix-compatibilized naphthopyran compounds, such as those disclosed in U.S.6,555,028b2, column 2, line 40 to column 24, line 56, the citation of which is incorporated herein by reference.

Further, in a particular embodiment of the present invention, the photochromic material may comprise the reaction product of at least one ring-opened cyclic monomer comprising a cyclic ester and/or cyclic carbonate and a photochromic initiator. Such materials and their preparation are described in detail in U.S. patent application publication No. 2006/0022176A1, paragraphs [0007] to [0088], the citation of which is incorporated herein by reference.

One or more art-recognized plasticizers may also be used in combination with the photochromic material in order to enhance the kinetics of any photochromic material present in any of layers (a) and/or (b), and/or layers (c) and/or (d), as described below. Suitable plasticizers useful in the present invention may include generally known types of plasticizers. Examples of Plasticizers of this type are listed in Table 117 of Plasticizer Evaluation and Performance, Chemical Names of Plasticizers and the air Brand Names, pp 140-;Ullmann’s Encyclopedia of Industrial Chemistryvol.20, pp 439-458, 1992 and model Plastics Encyclopedia, Mid-November 1998, Vol.75, No. 12, ppC-105 to C-115.

Various types of plasticizers contemplated for use herein may include, but are not limited to: rosin acid esters such as methyl abietate; acetates, such as glycidyl triacetate; adipates, such as dibutyl adipate; azelaic acid esters such as diisooctyl azelate; benzoates, such as polyethylene glycol dibenzoate; biphenyls such as camphor; octanoates, for example, butanediol dicaprylate; citric acid esters, such as triethyl citrate; dodecanedioic acid esters, such as dioctyl dodecanedioate; ethers, for example, benzyl ether; fumarates, such as dioctyl fumarate; glutarates, such as diisodecyl glutarate; glycolates, such as di (2-ethylhexyl) diglycolate; isophthalates, such as dimethyl isophthalate; laurates, such as poly (ethylene glycol) monolaurate; maleates, such as dibutyl maleate; myristates such as isopropyl myristate; oleates, such as methyl oleate; palmitate esters, such as tetrahydrofurfuryl palmitate; alkane derivatives, such as chloromethane alkanes; phosphoric acid esters such as 2-ethylhexyl diphenyl phosphate and triphenyl phosphate; phthalic acid esters such as diethyl phthalate and dioctyl phthalate; ricinoleates, such as methoxyethyl ricinoleate; sebacates, such as diethyl sebacate; stearates, such as methyl pentachlorosulfate; sulfonamides, such as toluene sulfonamide; tartrates, such as butyl tartrate; terephthalates, such as dioctyl terephthalate; trimellitates, such as trioctyl trimellitate; and mixtures of these plasticizers.

Examples of suitable plasticizers may also include, if appropriate, organic polyols such as: a polyester polyol; a polyether polyol; an amide-containing polyol; a polyhydroxy polyvinyl alcohol; and mixtures of these polyols. These organic polyols and their preparation are well known in the art.

The second polymeric film layer (b) may also contain, if appropriate, any of a number of additives such as any of those previously discussed with respect to the supporting polymeric film layer (a). In a particular embodiment, the second polymer film layer (b) may further comprise stabilizers such as light stabilizers and/or antioxidants. Suitable stabilizers may include, but are not limited to, those available under the trade name Ciba(e.g., TINUVIN111, TINUVIN123, TINUVIN 144, TINUVIN 765 and/or TINUVIN 770), and an antioxidant, such as may be obtained from Ciba under the trade name(e.g., IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1081, IRGANOX1135, and/or IRGANOX 1330).

The second polymer film (b) may consist of a single layer or sheet of any of the above materials, or the second polymer film layer (b) may consist of multiple layers of one of the above materials, or the second polymer film layer (b) may consist of multiple layers of different materials. The thickness of the second polymer film layer (b) may vary widely depending on the type of material comprising the second polymer film layer (b) and the desired end use of the optical element it is composed of. Typically, the thickness of the second polymer film layer (b) may be 5 to 1000 microns, for example 5 to 500 microns, or 7 to 200 microns, or 10 to 100 microns, or 10 to 75 microns. The thickness of the second polymer film layer (b) may range between any of the values recited, inclusive.

Optionally, the optical element of the present invention may further comprise an adhesive layer (c) interposed between and connected to at least a portion of the first side of the supporting polymer film layer (a) and the second side of the second polymer film layer (b). The optional tie layer (c) may comprise any of a number of adhesive materials known in the art, provided that the adhesive materials do not adversely affect the optical quality (e.g., transparency) of the resulting optical element.

For example, pressure sensitive adhesive materials may be used to form tie layer (c), including self-tack adhesives (self-tack adhesive) or those requiring the addition of tackifiers. These materials may include, but are not limited to, tackified natural rubber, tackified synthetic rubber, tackified styrenic block copolymers, self-adhesive or tackified acrylate or methacrylate copolymers, self-adhesive or tackified polyolefins, and tackified silicones. Non-limiting examples of suitable pressure sensitive adhesives include those described in the following documents: encyclopedia of Polymer Science and engineering, vol.13, Wiley-Interscience Publishers, New York, 1988; the Encyclopedia of Polymer Science and Technology, vol.1, Interscience Publishers, New York, 1964; and Handbook of pressure Sensitive Adhesives, D.Satas, Editor, 2 nd edition, Von Nostrand Reinhold, New Yourk, 1989. Suitable pressure sensitive adhesives may include those known under the trade name DURO-That on saleSome, it may be from National Starch&Chemical is commercially available.

Other suitable adhesives may include, but are not limited to, curable flexible laminating adhesives such as OP-40, OP-44 ULTRA FAST, commercially available from Dymax Corporation of Torrington, CT^TMAnd OP-44 ULTRA FAST^TMA photocurable adhesive; and OPT 5053, OPT 5001, and OPT 5012 epoxy-based adhesives commercially available from Intertronic of Oxfordshire, England.

It should be noted that in one embodiment of the present invention, the second polymer film layer (b) may be directly connected to the supporting polymer film layer (a) in the absence of the interlayer tie layer (c). In such embodiments, the first side of the support polymer film layer (a) is directly connected to the second side of the second polymer film layer (b) by means other than adhesive bonding with an adhesive material. The layers may be joined, for example, by at least one of lamination, fusion, and in-mold casting, wherein the second polymer film layer (b) is joined to at least a portion of the supporting polymer film layer (a).

The optical element of the present disclosure may further include a protective polymer film layer (d) having opposing first and second sides, wherein the second side of the protective polymer film layer (d) is attached to at least a portion of the first side of the second polymer film layer (b). The protective polymeric film layer (d) may comprise any of a number of polymeric materials, including any of those discussed above with respect to the supporting polymeric film layer (a) and, if appropriate, the second polymeric film layer (b). For example, the protective polymer film layer (d) may comprise polycarbonate, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyester, polyurethane, poly (urea) urethane, polythiourethane, polythiourea urethane, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.

The protective polymeric film layer (d) may further comprise any of a number of additives to affect or enhance one or more of the processing and/or performance characteristics of the layer. Non-limiting examples of such additives may include any of those previously mentioned with respect to the supporting polymer film layer (a).

It should be mentioned that the protective polymer film layer (d) may consist of a single layer or sheet of any of the above materials, or the protective polymer film layer (d) may consist of multiple layers of one of the above materials, or the protective polymer film layer (d) may consist of multiple layers of different materials. The thickness of the protective polymer film layer (d) can vary widely depending on the type of material from which the protective polymer film layer (d) is constructed and the desired end use of the optical element from which it is constructed. Typically, the protective polymeric film layer (d) has a thickness of 10 to 2000 microns, such as 20 to 1000 microns, or 50 to 500 microns, or 75 to 300 microns. The thickness of the protective polymer film layer (d) can range between any of the recited values, inclusive.

The protective polymer film layer (d) and the second polymer film layer (b) can be joined by any means known in the art, provided, of course, that the optical and other physical properties of the optical element are not negatively affected. For example, layers (d) and (b) may be joined by any of the art-recognized lamination, fusion, adhesive bonding, and/or in-mold casting methods.

In any of the optical elements of the present invention, the supporting polymer film layer (a) and/or the optional tie layer (c) and/or the protective polymer film layer (d) may comprise a photochromic material.

As previously mentioned, the optical element of the present invention may include (a) a support layer having opposing first and second sides; (b) a linear polarizing layer having opposing first and second sides; (c) optionally, an adhesive layer interposed between and connected to at least a portion of the first side of the support layer (a) and the second side of the polarizing layer (b); and (d) a protective layer having opposing first and second sides, wherein the second side of the protective layer (d) is attached to at least a portion of the first side of the polarizing layer (b), and wherein at least one of (a), (b), and (d) comprises a photochromic material. In one such embodiment, the protective layer (d) comprises a photochromic material, the support layer (a) does not comprise a photochromic material, and the polarizing layer (b) does not comprise a photochromic material.

In one non-limiting embodiment of the invention, the optical element does not include the protective film layer (d) and the second polymeric film layer (b) further includes a protective coating applied to at least a portion of the first side of the second polymeric film layer (b). The protective coating can include, for example, an abrasion resistant coating, an oxygen barrier coating, a UV shielding coating, an anti-reflective coating, an anti-fog coating, a mirror coating, or a combination thereof, coupled to at least a portion of the first side of the second film layer (b).

When the optical element includes the protective film layer (d), the protective film layer (d) may further include a protective coating applied to at least a portion of the first side of the protective film layer (d). The protective coating may include any of those just mentioned above.

The optical elements of the present invention may be used as ophthalmic elements and devices, display elements and devices, windows, mirrors and/or active and passive liquid crystal cell elements and devices (all of which are described above) or components thereof to provide both photochromic and polarizing properties to such elements and devices.

The invention will be further described in conjunction with the following examples, which are to be regarded as illustrative rather than restrictive; wherein, unless otherwise specified, all parts are parts by weight and all percentages are percentages by weight.Examples Example 1 Step 1-preparation of triacetyl cellulose solutionA triacetyl cellulose (TAC) solution was prepared by adding TAC (20 wt% based on the total weight percent of the mixture) to a container containing dichloromethane equipped with a mixer and a heater. It should be noted that all weight percent values reported herein are based on the total weight of the mixture, solution or resin, unless otherwise indicated. The resulting mixture was heated at 50 ℃ with stirring until TAC was dissolved. Triphenyl phosphate (15 wt% based on TAC solids level) is added with mixing.Step 2-addition of photochromic dyesThe following mixture of photochromic dyes (0.15 wt% based on the weight of TAC solids) was added to the solution of step 1 with mixing.

Photochromic dyes	Weight percent of the total dye mixture
		Photochromic A(1)	50
Photochromic B(2)	30
		Photochromic C(3)	20

(1) Photochromic a is an indenonaphthopyran reported to produce a blue activated color. (2) Photochromic B is an indenonaphthopyran reported to produce an activated color of light green. (3) Photochromic C is an indenonaphthopyran reported to produce a reddish activated color.Step 3-preparation of photochromic TAC filmThe photochromic TAC solution of step 2 was cast onto a glass plate using a 16 mil draw down bar. Two to three casts were performed to produce a film having a thickness of about 3 mils after evaporation of the methylene chloride in an oven maintained at 60 ℃.Example 2The procedure of example 1 was followed except that Cellulose Acetate Butyrate (CAB) was used instead of TAC; acetone was used instead of dichloromethane; TPP was used at a level of 20% based on solids weight of CAB.Example 3The procedure of example 1 was followed except that Cellulose Diacetate (CDA) was used instead of TAC; acetone was used instead of dichloromethane.Example 4 Step 1-preparation of cellulose diacetate solutionThe procedure of example 1, step 1, was followed except that a Cellulose Diacetate (CDA) solution was used instead of TAC; acetone was used instead of dichloromethane; TPP was used at a level of 20% based on solids weight of CAB; and a Hindered Amine (HALS) light stabilizer is used in a weight ratio of 4: 1 to the photochromic dye.Step 2-addition of photochromic dyesThe procedure of example 1, step 2 was followed.Step 3-preparation of photochromic CDA filmThe photochromic CDA solution of step 2 was cast onto a stainless steel belt to produce a film having a thickness of about 7 mils after evaporation of the acetone.Step 4-lamination stepThe photochromic CDA film of step 3 was used with other films to form laminated photochromic and polarizing samples. The order of the membranes was as follows: #1-7 mil transparent CDA film. # 2-photochromic 7 mil CDA film of step 3. # 3-iodine-treated polarization-stretched polyvinyl alcohol film. # 4-A14 mil transparent CDA film was prepared by laminating two 7 mil films. # 5-A14 mil transparent CDA film was prepared by laminating two 7 mil films. Each CDA film used in the above stack (except for #1 and #2 films) contains a UV absorber that provides the film with a transmittance at 400nm of about 1% or less. The #1 film and the #2 film were laminated using acetone to cause adhesion. The lamination was performed by passing a pair of CDA films between a pair of nip rollers, with a bead of acetone spread between the interface of the two films. The contact time of acetone and two CDA films was less than one second. The exterior of the #1 film was coated with an ultraviolet (uv) curable acrylic-based optical quality hardcoat available from Exopack, LLC Corp to produce a hardcoat thickness of about 4 microns. The surface of #2 membrane was subjected to hydrolysis treatment as follows: immersion in 20 wt% sodium hydroxide at 120 ° F (49 ℃) for 15 seconds; immersed in water at 70-75 deg.F (21-24 deg.C) for 20-25 seconds and dried at 150-155 deg.F (65-68 deg.C) for 35-40 seconds. The resulting composite was laminated to a #3 film, a polyvinyl alcohol film, the #3 film being stretched 4 times when laminated to a #2 film. When #2 and #3 films were laminated and rolled in the same manner as that performed with acetone205 (reported to be partially hydrolyzed polyvinyl alcohol) to cause adhesion between #2 and #3 films. The outer surface of the #3 film was treated to polarize it as follows: immersing in a first aqueous solution of iodine (0.32 wt%) and potassium iodide (8.6 wt%) maintained at 70 ° F (21 ℃) for 10-11 seconds; immersing in water maintained at a temperature of 60-70 ° F (16-21 ℃) for 4 seconds; boric acid (7.5 wt%) and iodine maintained at a temperature of 125 ° F (52 ℃), andimmersing potassium (3.3 wt%) in a second aqueous solution for 10-11 seconds; immersing in water maintained at a temperature of 60-70 ° F (16-21 ℃) for 4 seconds; and dried at 150 ℃ and 155 ℃ F. (65-68) for 35-40 seconds. Before laminating the composite of films #1-3 to the #4 and #5 films, the #4 and 5 films were subjected to the above-described hydrolysis treatment. Using 5% by weight of the composition as described hereinbefore205 laminates of films #1-3 to a #4 film and then to a #5 film using the same process.Photochromic example testThe photochromic and polarizing laminated test samples prepared in examples 1-4 were cut into approximately 5 x 5 cm squares and tested for photochromic response as described herein on a Bench scale for Measuring photochromic (BMP) optical Bench manufactured by esilor, France. Each photochromic test sample was exposed to 365 nm uv light for about 10 minutes to activate the photochromic compound at a distance of about 14 cm prior to testing on the optical bench. UVA (315 to 380nm) irradiance at the sample was measured using a Licor Model Li-1800 spectroradiometer and found to be 22.2 watts/square meter. The test sample was then placed under a high intensity halogen lamp for about 10 minutes at a distance of about 36 cm to bleach (deactivate) the photochromic compound. The illuminance at the sample was measured with a Licor spectroradiometer and found to be 21.9 Klux. Each test sample was then kept covered for at least 1 hour prior to testing on the optical bench. The BMP comprises a flat metal surface provided with two 150 watt xenon arc lamps arranged 90 degrees apart (one lamp providing UV/VIS light and one providing an additional contribution to visible light). The slightly collimated output beams of the xenon arc lamps were combined and directed through an 50/50 beam splitter to an irradiance detector and to a sample cell. Each lamp was filtered and individually shielded from light and further shielded from light after blending before entering the sample cell. Each lamp was filtered with a Schott 3mm KG-2 bandpass filter. The lamp used to supplement the visible light was also filtered with a 400nm cut-off filter. The software equipped equipment, i.e., bmpsofft version 4.0c, was used to control timing, irradiance, air chamber and sample temperature, shading, filter selection and response measurement. To be determined atThe irradiance adjustment within the settings provides a software program that is limited via an optical feedback unit that in turn makes minor adjustments to the lamp wattage and subsequent lamp output. If the selected irradiance cannot be reached within the limits of the ZEISS spectrophotometer, the program indicates that the selection of neutral density filters for each optical path needs to be changed. Photopic response measurements were collected because multiple photochromic compounds were used in the stack. The setting of the BMP software requires a correlation factor between the spectral radiance spectrum measurements at the samples using ZEISS spectrophotometer model MCS 501. The BMP software uses this correlation factor to set the operating irradiance on the optical bench. The test cell was equipped with a quartz window and a self-centering sample holder. The temperature in the cell was controlled at 23 ℃ via the software using a modified facility, model FX-10 environmental simulator. The power output of the optical bench (e.g., the dose of light to which the test sample will be exposed) was adjusted to 6.7 watts per square meter (W/m)²). The visible light output is always maintained at 50 kilolux. A Zeiss spectrophotometer model MCS 501 (with fiber optic cable carrying light from a tungsten halogen lamp and through the sample) was used for photochromic response and color measurements. The collimated monitoring beam from the fiber optic cable is maintained perpendicular to the test sample while the beam is directed through the sample and into a receiving fiber optic cable assembly connected to a spectrophotometer. The precise point in the sample cell at which the sample is placed is where the activated xenon arc beam and the monitoring beam intersect to form two concentric apertures. The incident angle of the xenon arc beam at the sample placement point is approximately 20 degrees from perpendicular. Response measurements (in terms of change in optical density (Δ OD) from an unactivated or bleached state to an activated or darkened state) were determined as follows: the initial unactivated transmittance was determined, the shutter of the xenon lamp was opened and the transmittance through activation was measured at selected time intervals. The change in optical density was determined according to the formula Δ OD ═ log (% Tb/% Ta), where% Tb is the percentage transmission in the bleached state and% Ta is the percentage transmission in the activated state, with the base 10 logarithm. Optical density measurements were performed at photopic wavelengths. The percent transmission in the bleached (% Tb) and activated (% Ta) states are listed in table 1. Fade half-life (T1/2) is the delta OD of the activated form of the photochromic material in the test square to 23 deg.CFifteen minutes after the next activation (after removal of the activating light source, e.g., by closing the shutter), a time interval (seconds) of half the Δ OD measured. The results of examples 1-3, prepared from a single photochromic film, are not expected to change when assembled in a composite having at least one transparent film. If assembled in a composite such as example 4, the photochromic fade half-life results would not be expected to change, but the percent transmission would be expected to be different.TABLE 1 photochromic Properties and percent transmittance (activation)&Bleaching)

Example #	％Tb	％Ta	T1/2
				1	81	22	80 seconds
2	81	10	100 seconds
				3	90	30	125 seconds
4	40	16	80 seconds

While the present invention has been described in detail with respect to certain embodiments thereof, it is not intended that such detail be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are included in the accompanying claims.

Claims (14)

1. An optical element comprising at least

(a) A supporting polymeric film layer having opposed first and second sides, said layer comprising a film material,

(b) a second polymeric film layer having opposing first and second sides, the second layer comprising a film material and exhibiting light influencing properties, and

(c) optionally, a tie layer interposed between and connected to at least a portion of the first side of the supporting polymer film layer (a) and the second side of the second polymer film layer (b),

wherein the film material constituting the supporting polymer film layer (a) and the film material constituting the second polymer film layer (b) are the same or different, and

wherein the supporting polymer film layer (a) and/or the second polymer film layer (b) comprises cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate and/or cellulose acetate butyrate,

wherein the second polymer film layer (b) is photochromic and comprises a photochromic material comprising a naphthopyran,Oxazines, phenanthropyrans, benzopyrans, metal-dithizone salts; fulgides and/or fulgimides,

wherein the second polymer film layer (b) is linearly polarized and comprises a dichroic material, and

wherein the second polymer film layer consists of a monolayer.

2. The optical element of claim 1 wherein the dichroic material comprises azomethines, indigoids, thioindigoids, merocyanines, indanes, quinophthalone dyes, perylenes, phthalidines, triphendioxanesAzines, indoloquinoxalines, imidazotriazines, tetrazines, azo and polyazo dyes, benzoquinones, naphthoquinones, anthraquinones, (poly) anthraquinones, anthrapyrimidinones, iodine and/or iodates.

3. The optical element of claim 1 wherein the dichroic material comprises a photochromic-dichroic compound.

4. The optical element of claim 1 wherein the dichroic material comprises a K-type polarizer.

5. The optical element of claim 1, wherein the film material constituting the supporting polymer film layer (a) and the film material constituting the second polymer film layer (b) are different.

6. The optical element of claim 1, wherein the film material constituting the supporting polymer film layer (a) and the film material constituting the second polymer film layer (b) are the same.

7. The optical element of claim 1 wherein the optical element further comprises a protective polymer film layer (d) having opposing first and second sides, wherein the second side of the protective polymer film layer (d) is attached to at least a portion of the first side of the second polymer film layer (b).

8. The optical element of claim 7 wherein the protective polymeric film layer (d) comprises polycarbonate, polycycloolefin, polyurethane, poly (urea) urethane, polythiourethane, polythiourea urethane, polyol (allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyester, polysulfone, polyolefin, copolymers thereof, or mixtures thereof.

9. The optical element of claim 8 wherein the protective polymer film layer (d) comprises cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, cellulose diacetate, and/or cellulose triacetate.

10. The optical element of claim 8 wherein the protective polymeric film layer (d) further comprises a protective coating attached to at least a portion of the first side of the protective layer (d), the protective coating comprising an abrasion resistant coating, an oxygen barrier coating, a UV shielding coating, an anti-reflective coating, an anti-fog coating, a mirror coating, or a combination thereof.

11. The optical element of claim 1 wherein the first side of the supporting polymer film layer (a) is directly connected to the second side of the second polymer film layer (b).

12. The optical element of claim 11, wherein the optical element further comprises a protective coating attached to at least a portion of the first side of the second polymer film layer (b), the protective coating comprising an abrasion resistant coating, an oxygen barrier coating, a UV shielding coating, an anti-reflective coating, an anti-fog coating, a mirror coating, or a combination thereof.

13. The optical element of claim 1, wherein the optical element comprises ophthalmic elements, display elements, windows, mirrors, and/or active and passive liquid crystal cell elements and devices.

14. The optical element of claim 13, wherein the ophthalmic element comprises a corrective lens, a non-corrective lens, a contact lens, an intraocular lens, a magnifying lens, a protective lens, or a goggle.