HK1194476B

HK1194476B - Polarizing photochromic articles

Info

Publication number: HK1194476B
Application number: HK14107811.6A
Authority: HK
Inventors: A.库玛; R．L．约斯特; 李晨光; D.杰克逊; H．恩古彦
Original assignee: 光学转变公司
Priority date: 2011-06-06
Filing date: 2011-11-16
Publication date: 2017-06-16

Description

Polarized photochromic articles

Cross reference to related applications

This application is a continuation-in-part application of U.S. patent application No.13/153748 filed 6/2011, application No.13/153748 is a continuation-in-part application of U.S. patent application No.11/590055 filed 31/10/2006, application No.11/590055 is a division of U.S. patent application No.10/846650 filed 5/17/2004 (issued as US7256921B 2), application No.10/846650 claims and the benefit of priority granted to U.S. provisional patent application No.60/484100 filed 7/1/2003, each of which is hereby incorporated by reference in its entirety.

Technical Field

The present invention is directed to a photochromic article comprising a substrate, a primer layer comprising a first photochromic compound, and a photochromic-dichroic layer comprising a photochromic-dichroic compound on the primer layer, wherein the first photochromic compound and the photochromic-dichroic compound are each selected such that the photochromic-dichroic compound has an unactivated state terminal minimum absorbance wavelength that is less than or equal to the unactivated state terminal minimum absorbance wavelength of the underlying first photochromic compound.

Background

Conventional linear polarizing elements, such as linear polarizing lenses for sunglasses and linear polarizing filters, are typically formed from stretched polymer sheets containing dichroic materials, such as dichroic dyes. Thus, a conventional linear polarization element is a static element having a single linear polarization state. Thus, when a conventional linearly polarizing element is exposed to randomly polarized radiation of the appropriate wavelength or reflected radiation, some percentage of the radiation transmitted through the element will be linearly polarized.

In addition, conventional linear polarizing elements are typically colored. Typically, conventional linear polarizing elements comprise a colorant and have an absorption spectrum that does not change in response to actinic radiation. The color of a conventional linearly polarizing element will depend on the colorant used to form the element, and is most often a neutral color (e.g., brown or gray). Thus, while conventional linear polarizing elements may be used to reduce reflected glare, they are typically not well suited for use in low light conditions because of their color. Furthermore, because conventional linear polarizing elements have only a single colored linear polarization state, their ability to store or display information is limited.

Conventional linear polarizing elements are typically formed using stretched polymer films containing dichroic materials. Accordingly, while dichroic materials are capable of preferentially absorbing one of the two orthogonal plane polarization components of transmitted light, if the molecules of the dichroic material are not suitably positioned or aligned, a net linear polarization of the transmitted light will not be achieved. Without intending to be bound by any theory, it is believed that due to the random orientation of the molecules of the dichroic material, the selective absorption of the individual molecules will cancel each other out, thus not achieving a net or overall linear polarization effect. Also, it is typically necessary to position or align molecules of a dichroic material through the orientation of another material to achieve a net linear polarization.

One common method of orienting dichroic dye molecules involves heating a sheet or layer of polyvinyl alcohol ("PVA") to soften the PVA and then stretching the sheet to orient the PVA polymer chains. Thereafter, a dichroic dye is impregnated into the stretched sheet, and the impregnated dye molecules adopt the orientation of polymer chains. As a result, at least some of the dye molecules become oriented such that the long axis of each oriented dye molecule is generally parallel to the oriented polymer chain. Alternatively, the dichroic dye may be first impregnated into the PVA sheet, after which the sheet may be heated and stretched as described above to orient the PVA polymer chains and associated dyes. In this way, the molecules of the dichroic dye may be suitably positioned or aligned in the aligned polymer chains of the PVA sheet, and accordingly, a net linear polarization can be achieved. As a result, the PVA sheet can be made to linearly polarize transmitted light, and thus a corresponding linear polarization filter can be formed.

In contrast to the dichroic elements described above, conventional photochromic elements, such as photochromic lenses formed using conventional thermally reversible photochromic materials, are generally capable of transforming from a first state, such as a "clear state," to a second state, such as a "colored state," in response to actinic radiation, and reverting back to the first state in response to thermal energy. Thus, conventional photochromic elements are generally well suited for use in both low and bright light conditions. But conventional photochromic elements (which do not include a linear polarizing filter) generally cannot be linearly polarized radiation. Conventional photochromic elements typically have an absorption ratio of less than 2 in either state. The conventional photochromic element cannot reduce the reflected glare to the same extent as the conventional linear polarizing element. In addition, conventional photochromic elements have limited ability to store or display information.

Photochromic-dichroic compounds and materials have been developed that provide both photochromic and dichroic properties, if appropriate, and are at least sufficiently oriented. However, photochromic-dichroic compounds typically have a greater percent transmission when in a colored or darkened state, such as when exposed to actinic light, than non-polarizing or conventional photochromic compounds at equivalent concentrations and sample thicknesses. Without intending to be bound by any theory, and based on the evidence at hand, it is believed that the increased percent transmission of a photochromic-dichroic material in the darkened or colored state is due to the percent transmission being the average of the two orthogonal plane polarization components of polarized light. The photochromic-dichroic material will more strongly absorb one of the two orthogonal plane polarization components of incident random light, resulting in one of the planes of transmitted polarized light (passing through and out of the sample) having a greater percent transmission than the other orthogonal plane polarization component. Averaging of the two orthogonal plane polarization components typically yields an average percent transmission of a greater magnitude. Generally, as the linear polarization efficiency (which can be quantified in terms of absorption ratio) of a photochromic-dichroic compound increases, the percent transmittance associated therewith also increases.

It would be desirable to develop new polarizing photochromic articles that include photochromic-dichroic compounds and that provide a combination of linear polarizing properties and reduced percent transmittance when in a colored or darkened state, such as when exposed to actinic light.

Disclosure of Invention

In accordance with the present invention, a photochromic article is provided comprising a substrate and at least two layers thereof, including a primer layer on the substrate, and a photochromic-dichroic layer on the primer layer.

The primer layer includes a first photochromic compound having a first unactivated state absorbance greater than 0 at all wavelengths from 340nm to 380nm, and a first unactivated state end minimum absorbance wavelength greater than 380 nm.

The photochromic-dichroic layer comprises a photochromic-dichroic compound having a second unactivated state absorbance greater than 0 at least a portion of wavelengths ranging from 340nm to 380nm, and a second unactivated state terminal minimum absorbance wavelength greater than 340 nm.

The second unactivated state terminal minimum absorbance wavelength of the (photochromic-dichroic compound) is less than or equal to the first unactivated state terminal minimum absorbance wavelength of the (underlying first photochromic compound).

According to a further embodiment of the present invention, there is provided a photochromic article comprising a substrate and at least 3 layers thereon, including a primer layer on the substrate, a photochromic-dichroic layer on the primer layer, and a topcoat layer on the photochromic-dichroic layer.

The topcoat layer of the at least tri-layered embodiment includes an optional ultraviolet light absorber, and a third unactivated state absorbance of greater than 0 at least a portion of the wavelengths from 330nm to 380nm, and a third unactivated state terminal minimum absorbance wavelength of greater than 330 nm.

In at least a tri-layered embodiment, the third unactivated state terminal minimum absorbance wavelength of the (second photochromic compound of the top coat layer) is less than the second unactivated state terminal minimum absorbance wavelength of the (photochromic-dichroic compound of the underlying coat layer), and the second unactivated state terminal minimum absorbance wavelength of the (photochromic-dichroic compound of the coat layer) is less than or equal to the first terminal minimum absorbance wavelength of the (first photochromic compound of the underlying primer layer).

Drawings

FIG. 1 is a graphical representation of a side cross-sectional view of a photochromic article of the present invention comprising a graphical representation of the absorbance versus wavelength of a first photochromic compound of a primer layer, a photochromic-dichroic compound of a photochromic-dichroic layer, and a second photochromic compound of a topcoat layer; and

FIG. 2 is a graphical representation of average delta absorbance as a function of wavelength (over the visible wavelength region after activation with actinic radiation) and shows two average differential absorption spectra obtained with a photochromic-dichroic layer including a photochromic-dichroic compound, which may be included in a photochromic article of the present invention, and

FIG. 3 is a graphical representation of the graph 41 of FIG. 1, wherein the y-axis range has been varied from 0-3.5 (FIG. 1) to 0-0.1 (FIG. 3) in order to better illustrate the plot of absorbance versus wavelength.

Detailed Description

As used herein, the term "actinic radiation" means electromagnetic radiation capable of causing a response in a material, such as, but not limited to, converting a photochromic material from one form or state to another, as will be discussed in further detail herein.

As used herein, the term "photochromic" and similar terms, such as "photochromic compound," mean having an absorption spectrum for at least visible light that changes in response to the absorption of at least actinic radiation. Furthermore, as used herein, the term "photochromic material" means any substance that is suitable to exhibit photochromic properties (i.e., that is suitable to have an absorption spectrum for at least visible light that is variable in response to at least the absorption of actinic radiation) and that comprises at least one photochromic compound.

As used herein, the term "photochromic compound" includes both thermally reversible photochromic compounds and non-thermally reversible photochromic compounds. As used herein, the term "thermally reversible photochromic compound/material" refers to a compound/material that is capable of transforming from a first state, e.g., "clear state", to a second state, e.g., "colored state", in response to actinic radiation, and reverting back to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound/material" means a compound/material that is capable of converting from a first state, e.g., "clear state," to a second state, e.g., "colored state," in response to actinic radiation, and reverts back to the first state (e.g., ceases exposure to such actinic radiation) in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

As used herein, the term "dichroic" means one of two orthogonal plane polarization components capable of absorbing at least transmitted light more strongly than the other.

As used herein, the term "photochromic-dichroic" and similar terms, such as "photochromic-dichroic material" and "photochromic-dichroic compound," refer to materials and compounds that have and/or provide both photochromic properties (i.e., having an absorption spectrum for at least visible light that varies in response to at least actinic radiation) and dichroic properties (i.e., being capable of absorbing at least one of two orthogonal plane-polarized components of transmitted light more strongly than the other).

As used herein, the term "absorption ratio" refers to the ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of radiation of the same wavelength linearly polarized in a plane orthogonal to the first plane, where the first plane is the plane with the highest absorbance.

As used herein to modify the term "state," the terms "first" and "second" are not intended to indicate any particular order or chronological order, but instead indicate two different conditions or properties. For non-limiting illustration purposes, the first and second states of the photochromic-dichroic compound of the photochromic-dichroic layer can have at least one different optical property, such as, but not limited to, absorbing or linearly polarizing visible and/or UV light. Thus, according to various non-limiting embodiments disclosed herein, the photochromic-dichroic compound of the photochromic-dichroic layer can have a different absorption spectrum in each of the first and second states. For example, although not limited thereto, the photochromic-dichroic compound of the photochromic-dichroic layer can be transparent in the first state and colored in the second state. Alternatively, the photochromic-dichroic compound of the photochromic-dichroic layer can have a first color in the first state and a second color in the second state. In addition, as discussed in more detail below, the photochromic-dichroic compound of the photochromic-dichroic layer can be non-linearly polarized (or "unpolarized") in the first state, and linearly polarized in the second state.

As used herein, the term "optical" means pertaining to or related to light and/or vision. For example, the optical article or component or device may be selected from ophthalmic articles, components and devices, display articles, components and devices, windows, mirrors, and active and passive liquid crystal cell articles, components and devices according to the various non-limiting embodiments disclosed herein.

As used herein, the term "ophthalmic" means pertaining to or related to the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal, trifocal and progressive lenses), and other elements for correcting, protecting or enhancing (cosmetic or otherwise) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses and protective lenses or goggles.

As used herein, the term "ophthalmic substrate" refers to lenses, partially formed lenses, and lens blanks.

As used herein, the term "display" means a visual or machine-readable representation of information in the form of words, numbers, symbols, designs or drawings. Non-limiting examples of display articles, components and devices include screens, monitors and security elements, such as security markings.

As used herein, the term "window" means an aperture for allowing light to transmit therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, blinds and optical switches.

As used herein, the term "mirror" means a surface that specularly reflects most or a substantial portion of incident light.

As used herein, the term "liquid crystal cell" refers to a structure containing a liquid crystal material capable of orientation. An active liquid crystal cell is a cell in which the liquid crystal material is capable of reversible and controlled switching or switching between ordered and disordered states or between two ordered states by application of an external force, such as an electric or magnetic field. A passive liquid crystal cell is a cell in which the liquid crystal material remains in an ordered state. A non-limiting example of an active liquid crystal cell element or device is a liquid crystal display.

As used herein, the term "coating" means a supported film derived from a flowable composition, which may or may not have a uniform thickness, and specifically excludes polymer sheets. The primer layer, photochromic-dichroic layer, and optional topcoat layer of the photochromic articles of the present invention can each independently be a coating layer in some embodiments.

As used herein, the term "sheet" means a preformed film having a generally uniform thickness and being capable of being self-sustaining.

As used herein, the term "coupled to" means in direct contact with an object or in indirect contact with an object through one or more other structures or materials, at least one of which is in direct contact with an object. For non-limiting purposes of illustration, a primer layer can, for example, be in direct contact (e.g., contiguous contact) with at least a portion of the substrate or it can be in indirect contact with at least a portion of the substrate through one or more other intervening structures or materials, such as a monolayer of a coupling or bonding agent. For example, although not limiting herein, the primer layer can be in contact with one or more other intervening coating layers, polymeric sheets, or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate.

As used herein, the term "photosensitive material" refers to materials that respond physically or chemically to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.

As used herein, the term "non-photosensitive material" means a material that does not respond physically or chemically to electromagnetic radiation, including but not limited to static dyes.

As used herein, the molecular weight values of the polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are measured by gel permeation chromatography using appropriate standards, such as polystyrene standards.

As used herein, the polydispersity index (PDI) value represents the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/Mn).

As used herein, the term "polymer" means homopolymers (e.g., prepared from a single monomeric species), copolymers (e.g., prepared from at least two monomeric species), and graft polymers.

As used herein, the term "(meth) acrylate" and similar terms such as "(meth) acrylate" refer to methacrylates and/or acrylates. As used herein, the term "(meth) acrylic" means methacrylic and/or acrylic.

Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or sub-ratios subsumed therein. For example, a range or ratio of "1 to 10" should be considered to include any and all subranges between a minimum value of 1 and a maximum value of 10 (and including 1 and 10); i.e., all subranges or sub-ratios beginning with a minimum value of 1 or more and ending with a maximum of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein and in the claims, unless otherwise indicated, a left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as, but not limited to, fromRight to left direction. In a non-limiting illustration, a divalent linking groupOr equivalent-C (O) O-left to right representation includes right to left representation thereofOr equivalently-O (O) C-or-OC (O) -.

As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

As used herein, the term "first photochromic compound" means at least one photochromic compound. When two or more first photochromic compounds are present, they together have and provide (e.g., average) a first unactivated state peak absorbance wavelength, a (e.g., average) first unactivated state absorbance greater than 0 over a particular wavelength range, a (e.g., average) first unactivated state end minimum absorbance wavelength, and a (e.g., average) first unactivated state initial minimum absorbance wavelength.

As used herein, the term "photochromic-dichroic compound" means at least one photochromic-dichroic compound. When two or more photochromic-dichroic compounds are present, they together have and provide (e.g., average) a second unactivated state peak absorbance wavelength, a (e.g., average) second unactivated state absorbance greater than 0 over a particular wavelength range, a (e.g., average) second unactivated state terminal minimum absorbance wavelength, and a (e.g., average) second unactivated state initial minimum absorbance wavelength.

As used herein, the term "second photochromic compound" means at least one second photochromic compound. When two or more second photochromic compounds are present, they together have and provide (e.g., average) a third unactivated state peak absorbance, a third unactivated state absorbance wavelength greater than 0 over a particular wavelength range, (e.g., average) a third unactivated state end minimum absorbance wavelength, and (e.g., average) a third unactivated state initial minimum absorbance wavelength.

As used herein, the term "unactivated state" with respect to a photochromic compound, such as a first photochromic compound, a photochromic-dichroic compound, and a second photochromic compound, means that the photochromic compound has been exposed to actinic radiation of sufficient energy to cause the photochromic compound to have or produce: (i) absorbance measurable at wavelengths greater than or equal to 330nm and less than or equal to 450nm, e.g., less than or equal to 430nm or less than or equal to 410 nm; and (ii) minimal or substantially undetectable absorbance at wavelengths greater than 450 nm.

As used herein, the term "activated state" with respect to photochromic compounds, such as first photochromic compound, photochromic-dichroic compound, and second photochromic compound, and photochromic articles, means that the photochromic compounds and/or photochromic articles have been exposed to actinic radiation of sufficient energy to cause the photochromic compounds and/or photochromic articles to have or produce: (i) absorbance measurable at wavelengths greater than or equal to 330nm and less than or equal to 450nm, e.g., less than or equal to 430nm or less than or equal to 410 nm; and (ii) absorbance measurable at wavelengths greater than 450 nm.

As used herein, the term "first unactivated state absorbance of greater than 0" over some range of wavelengths, such as "over the entire wavelength range of 340nm to 380nm," means that the first photochromic compound has an unactivated state absorbance of greater than 0 over some range of wavelengths, such as over the entire wavelength range of 340nm to 380 nm.

As used herein, the term "first unactivated state peak absorbance wavelength" refers to a wavelength at which a first photochromic compound (of a primer layer) in an unactivated state has a peak (or maximum) absorbance. The first unactivated state peak absorbance wavelength is typically between 340nm and 380 nm.

As used herein, the term "first unactivated state terminal minimum absorbance wavelength" means a wavelength at which the first photochromic compound (of the primer layer) in the unactivated state has a terminal (or upper) minimum absorbance. The first unactivated state end minimum absorbance wavelength is at a higher wavelength than the first unactivated state peak absorbance wavelength.

As used herein, the term "first unactivated state initial minimum absorbance wavelength" means a wavelength at which a first photochromic compound (of a primer layer) in an unactivated state has an initial (or lower) minimum absorbance. The first unactivated state minimum absorbance wavelength is at a lower wavelength than the first unactivated state peak absorbance wavelength and the first unactivated state end minimum absorbance wavelength.

As used herein, the term "second unactivated state absorbance of greater than 0" over a certain range of wavelengths, such as "over at least a portion of wavelengths ranging from 340nm to 380 nm" means that the photochromic-dichroic compound has an unactivated state absorbance of greater than 0 over a certain range of wavelengths, such as over at least a portion of wavelengths ranging from 340nm to 380nm, such as 340nm to 370nm or 350nm to 380nm or 340nm to 380 nm.

As used herein, the term "wavelength in at least a portion of xnm-ynm" with respect to an unactivated state absorbance greater than 0 means a continuous wavelength in at least a portion of the range, including the upper and lower wavelength values.

As used herein, the term "second unactivated state peak absorbance wavelength" refers to a wavelength at which a photochromic-dichroic compound (of a coating or photochromic-dichroic coating) in an unactivated state has a peak (or maximum) absorbance. The second unactivated state peak absorbance wavelength is typically between 340nm and 380 nm.

As used herein, the term "second unactivated state terminal minimum absorbance wavelength" means a wavelength at which a photochromic-dichroic compound (of a coating or photochromic-dichroic coating) in an unactivated state has a terminal (or upper) minimum absorbance. The second unactivated state end minimum absorbance wavelength is at a higher wavelength than the second unactivated state peak absorbance wavelength.

As used herein, the term "second unactivated state initial minimum absorbance wavelength" refers to a wavelength at which a photochromic-dichroic compound (of a photochromic-dichroic layer) in an unactivated state has an initial (or lower) minimum absorbance. The second unactivated state minimum absorbance wavelength is at a lower wavelength than the second unactivated state peak absorbance wavelength and the second unactivated state end minimum absorbance wavelength.

As used herein, the term "third unactivated state absorbance of greater than 0" over a certain range of wavelengths, such as "over a portion of wavelengths from 330nm to 380 nm" means that the second photochromic compound has an unactivated state absorbance of greater than 0 over a certain range of wavelengths, such as at least a portion of wavelengths from 330nm to 380nm, such as from 330nm to 370nm, or from 340nm to 380 nm.

As used herein, the term "third unactivated state peak absorbance wavelength" means a wavelength at which the second photochromic compound (of the topcoat) in the unactivated state has a peak (or maximum) absorbance. The third unactivated state peak absorbance wavelength is typically between 330nm and 380 nm.

As used herein, the term "third unactivated state terminal minimum absorbance wavelength" means a wavelength at which the second photochromic compound (of the topcoat) in the unactivated state has a terminal (or upper) minimum absorbance. The third unactivated state end minimum absorbance wavelength is at a higher wavelength than the third unactivated state peak absorbance wavelength.

As used herein, the term "third unactivated state initial minimum absorbance wavelength" means the wavelength at which the second photochromic compound (of the topcoat) in the unactivated state has an initial (or lower) minimum absorbance. The third unactivated state minimum absorbance wavelength is at a lower wavelength than the third unactivated state peak absorbance wavelength and the third unactivated state end minimum absorbance wavelength.

The unactivated state initial minimum absorbance wavelength values, such as the first, second, and/or third unactivated state initial minimum absorbance wavelength values, may each be affected by the analytical methods and devices used, and the substrate and/or matrix, such as a coated substrate, in which the particular photochromic compound resides (which is referred to herein as the "USIMAWV effect"). The USIMAWV effect is more pronounced when the initial minimum absorbance wavelength value in the unactivated state is less than 360 nm. The USIMAWV effect can be additive or subtractive, resulting in higher or lower initial minimum absorbance wavelength values in the unactivated state. Alternatively or additionally, the USIMAWV effect may result in an unactivated state initial minimum absorbance wavelength value having a negative absorbance value. Still further, the USIMAWV effect can lead to positive and/or negative absorbance spikes, particularly at wavelengths less than 360 nm. While not intending to be bound by any theory, it is believed that in the case of organic polymeric substrates and organic polymeric coatings, the USIMAWV effect is at least partially attributed to the presence of aromatic rings in the substrate and/or coating matrix, plus the subtraction of the instrument reference. In some embodiments, the USIMAWV effect is minimal when the substrate is quartz. Because the substrate and coating comprise organic polymeric materials and subtraction of instrument reference values is used, it is believed that the first, second and third unactivated state initial minimum absorbance wavelength values (65, 68 and 71), described in further detail herein with reference to fig. 1 and 3, will experience the usimwv effect.

As used herein, and unless otherwise indicated, "percent transmission" is determined using the ULTRASCANPRO spectrometer commercially available from HunterLab, according to the instructions provided in the spectrometer user manual.

As used herein, the term "linearly polarize" means to confine the vibration of the electric vector of an electromagnetic wave, such as a light wave, to one direction or plane.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about".

As used herein, spatial or directional terms, such as "left," "right," "inner," "outer," "upper," "lower," and the like, relate to the invention as it is shown in the drawings. It is to be understood, however, that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.

As used herein, the terms "formed on …", "deposited on …", "provided on …", "applied on …", "residing on …" or "disposed on …" mean formed, deposited, provided, applied, residing on, or disposed on, but not necessarily in direct (or contiguous) contact with, an underlying element or underlying element surface. A layer "disposed on" for example does not preclude the presence of one or more other layers, coatings or films of the same or different composition located between the positioned or formed layer and the substrate.

All documents mentioned herein, such as but not limited to issued patents and patent applications, and unless otherwise indicated, are to be considered to be "incorporated by reference" in their entirety.

Referring to fig. 1, and for non-limiting purposes, a photochromic article 2 of the present invention is shown. The photochromic article 2 includes a substrate 11 having a first surface 12 and a second surface 13, wherein the first 12 and second 13 surfaces are opposite one another. The first surface 12 of the substrate 11 faces the incident actinic radiation as indicated by arrow 15. The photochromic article 2 further includes a primer layer 14 on (e.g., adjacent to) the substrate 11 and, in particular, on (e.g., adjacent to) the first surface 12 of the substrate 11. Photochromic article 2 further comprises photochromic-dichroic layer 17 (also referred to herein as photochromic-dichroic layer 17) on primer layer 14, and optional topcoat layer 20 on photochromic-dichroic layer 17. The photochromic article 2 of fig. 1 includes other optional layers, which will be further described herein.

Primer layer 14 includes a first photochromic compound having an absorbance property shown by plot 23, which is a representative plot of absorbance versus wavelength for the first photochromic compound in an unactivated state. More specifically, plot 23 is obtained from an analysis of the primer 14 applied to the substrate 11 in the absence of other underlying or overlying layers. Referring to plot 23 of FIG. 1, the first photochromic compound has a first unactivated state peak absorbance wavelength 26, a first unactivated state end minimum absorbance wavelength 29, and a first unactivated state initial minimum absorbance wavelength 65 (which is not illustrated in plot 23, but which is less than 340 nm). The first unactivated state end minimum absorbance wavelength 29 of the first photochromic compound is at a higher wavelength than its first unactivated state peak absorbance wavelength 26. The first unactivated state initial minimum absorbance wavelength 65 is at a lower wavelength than the first unactivated state peak absorbance wavelength 26.

For purposes of non-limiting illustration, and with further reference to plot 23 of FIG. 1, first unactivated state peak absorbance wavelength 26 of a first photochromic compound of primer layer 14 is 355nm, first unactivated state end minimum absorbance wavelength 29 is 425nm and first unactivated state initial minimum absorbance wavelength 65 is 333nm (not shown).

The end minimum absorbance wavelength values of the photochromic compounds and photochromic-dichroic compounds of the photochromic articles of the present invention in the unactivated state can be determined according to well known methods. In some embodiments, the unactivated state absorbance of the photochromic or photochromic-dichroic compound is substantially reduced to 0 and the wavelength at 0 point is recorded. In other embodiments, the unactivated state absorbance of the photochromic or photochromic-dichroic compound decreases to a minimum plateau value that fails to reach the measured 0 absorbance. In the case of the minimum plateau value, the unactivated state end minimum absorbance wavelength value is typically evaluated. For non-limiting illustration purposes and with reference to fig. 3, the third unactivated state end minimum absorbance wavelength 47 is evaluated by extending the line shown by dashed line 62 from the linear portion 56 of the absorbance versus wavelength trajectory, which is located to the left of inflection point 59 of the trajectory (i.e., at a lower wavelength relative to inflection point 59). The intersection of the extended line 62 with the x-axis is recorded as the third unactivated state end minimum absorbance wavelength value. The estimated unactivated state end minimum absorbance wavelength point and the value can be determined by calculation (typically using a computer graphics program) or manually (e.g., using a ruler). Unless otherwise indicated, the estimated unactivated state terminal minimum absorbance wavelength point and the values shown and discussed with reference to fig. 1 are determined manually.

The unactivated state initial minimum absorbance wavelength value may be estimated according to the methods described similar to the end minimum absorbance wavelength values. A line is extended from the linear portion of the absorbance versus wavelength trajectory, which is located to the right of the inflection point in the lower portion of the trajectory (i.e., at a higher wavelength relative to the inflection point). In some embodiments, the initial minimum absorbance in the unactivated state is significantly at the 0 absorbance value along the x-axis, and as such does not have to be estimated.

Photochromic-dichroic layer 17 of photochromic article 2 comprises a photochromic-dichroic compound having an absorbance property shown by plot 32, which is a plot of the absorbance versus wavelength of the photochromic-dichroic compound. More specifically, plot 32 results from an analysis of photochromic-dichroic layer 17 applied to substrate 11 in the absence of other underlying or overlying layers. Referring to plot 32 of fig. 1, the photochromic-dichroic compound has a second unactivated state peak absorbance wavelength 35, a second unactivated state end minimum absorbance wavelength 38, and a second unactivated state initial minimum absorbance 68. The unactivated state second end minimum absorbance wavelength 38 of the photochromic-dichroic compound is at a higher wavelength than its second peak absorbance wavelength 35. The unactivated state second initial minimum absorbance wavelength 68 of the photochromic-dichroic compound is at a lower wavelength than the second peak absorbance wavelength 35.

For purposes of non-limiting illustration, and with further reference to plot 32 of FIG. 1, the photochromic-dichroic compound of photochromic-dichroic layer 17 has a second unactivated state peak absorbance wavelength 35 of 360nm, a second unactivated state terminal minimum absorbance wavelength 38 of 417nm and a second unactivated state initial minimum absorbance wavelength 68 of 342 nm.

The optional topcoat layer 20 of the photochromic article 2 can include, in some embodiments of the present invention, a second photochromic compound having an absorbance property shown by plot 41, which is a plot of the absorbance versus wavelength of the second photochromic compound. More specifically, plot 41 is obtained from an analysis of the topcoat 20 applied to the substrate 11 in the absence of other underlying or overlying layers. Referring to plot 41 of fig. 1 and 3, the second photochromic compound has a third unactivated state peak absorbance 44, a third unactivated state end minimum absorbance wavelength 47, and a third unactivated state initial minimum absorbance wavelength 71. The third unactivated state end minimum absorbance wavelength 47 of the second photochromic compound is at a higher wavelength than its third unactivated state peak absorbance wavelength 44. The third unactivated state initial minimum absorbance wavelength 71 is at a lower wavelength than the third unactivated state peak absorbance wavelength 44.

For purposes of non-limiting illustration, and with further reference to plot 41 of fig. 1 and 3, the third unactivated state peak absorbance wavelength 44, the third unactivated state end minimum absorbance wavelength 47 of the second photochromic compound of the topcoat layer 20 is 386nm and the third unactivated state initial minimum absorbance wavelength 71 is 346 nm. In fig. 3, the lines or spikes 74 are believed to be the result of the polymer matrix and/or substrate of the topcoat and are not considered to be the result of (or due to) the second photochromic compound. Likewise, spike 74 is not considered when determining the third unactivated state peak absorbance wavelength, the third unactivated state end minimum absorbance wavelength, or the third unactivated state initial minimum absorbance wavelength of the second photochromic compound of the topcoat.

The plots 41 of fig. 1 and 3 are identical, but the y-axis of the plot 41 of fig. 3 extends from 0 to 0.1, rather than from 0 to 3.5 of fig. 1, for the purpose of better illustrating and determining the peak, end minimum and initial minimum values associated with the second photochromic compound of the topcoat.

Plots 23, 32 and 41 of FIG. 1 and plot 41 of FIG. 3 each represent absorbance as a function of wavelength from 340nm to 460 nm. As previously mentioned, FIGS. 1 and 3, including plots 23, 32 and 41, are mentioned for non-limiting illustrative purposes. Likewise, the absorbance of the first photochromic compound, photochromic-dichroic compound, and second photochromic compound as a function of wavelength in each case is not limited to that shown in fig. 1 and 3.

The first photochromic compound of the primer layer has a first unactivated state absorbance greater than 0 at all wavelengths from 340nm to 380nm, and the first unactivated state end minimum absorbance wavelength greater than 380 nm. In some embodiments, the first photochromic compound of the primer layer has a first unactivated state absorbance of greater than 0 at all wavelengths from 340nm to 400nm, and the first unactivated state end minimum absorbance wavelength is greater than 400 nm. In some further embodiments, the first photochromic compound of the primer layer has a first unactivated state absorbance greater than 0 at all wavelengths from 340nm to 410nm, and the first unactivated state terminal minimum absorbance wavelength is greater than 410 nm. For non-limiting purposes of illustration and with reference to plot 23 of fig. 1, the first photochromic compound of primer layer 14 has a first unactivated state absorbance of greater than 0 at all wavelengths from 340nm to 380nm, and a first unactivated state terminal minimum absorbance wavelength of greater than 380 nm. As previously described, the first unactivated state terminal minimum absorbance wavelength of the first photochromic compound of primer layer 14 of photochromic article 2 of fig. 1 is 425 nm.

The photochromic-dichroic compound of the photochromic-dichroic coating has a second unactivated state absorbance greater than 0 at least a portion of the wavelengths from 340nm to 380nm, and a second unactivated state terminal minimum absorbance wavelength greater than 340 nm. For non-limiting illustrative purposes, the photochromic-dichroic compound can have, in some embodiments: (ii) a second unactivated state absorbance of greater than 0 at all wavelengths from 340nm to 370nm, and a second unactivated state end minimum absorbance wavelength of greater than 370 nm; or a second unactivated state absorbance of greater than 0 at all wavelengths from 350nm to 380nm, and a second unactivated state end minimum absorbance wavelength of greater than 380 nm.

In some embodiments, the photochromic-dichroic compound of the photochromic-dichroic coating has a second unactivated state absorbance of greater than 0 at a wavelength of at least a portion of 340nm to 380nm, and a second unactivated state terminal minimum absorbance wavelength of greater than 380 nm.

In some further embodiments, the photochromic-dichroic compound of the photochromic-dichroic coating has a second unactivated state absorbance greater than 0 over all (or the entire) wavelengths ranging from 340nm to 380nm, and a second unactivated state terminal minimum absorbance wavelength greater than 380 nm.

According to some embodiments of the invention, the first unactivated state terminal minimum absorbance wavelength greater than 380nm and less than or equal to 450nm, such as less than or equal to 440nm, or less than or equal to 430 nm. In further embodiments, the second unactivated state terminal minimum absorbance wavelength greater than 340nm and less than or equal to 450nm, such as less than or equal to 440nm, or less than or equal to 440 nm.

The second unactivated state terminal minimum absorbance wavelength is less than the first unactivated state terminal minimum absorbance wavelength in some embodiments of the present invention.

The photochromic-dichroic compound of photochromic-dichroic layer 17 and the first photochromic compound of underlying primer layer 14 are each selected to have the above-described light absorption properties. According to some embodiments of the present invention, they are selected such that the photochromic article has a percent transmittance in the unactivated state of less than 5% at all wavelengths from 340nm to 380 nm. The percent unactivated state transmission at all wavelengths from 340nm to 380nm may be less than 4% or less than 3% or less than 2% or less than 1% or less than 0.5% in some embodiments. In some embodiments, the percent transmission in the unactivated state is substantially 0% at all wavelengths from 340nm to 380 nm. It is desirable to reduce and minimize the percent transmission of electromagnetic radiation through the photochromic articles of the present invention at all wavelengths from 340nm to 380nm, for reasons including, but not limited to, protecting objects, such as the human eye, behind the photochromic article from exposure to electromagnetic radiation at wavelengths from 340nm to 380 nm. The percent transmission over the wavelength range is determined according to known methods using known and commercially available analytical equipment.

In some further embodiments, the photochromic articles of the present invention have a percent transmittance in the unactivated state of less than 5% at all wavelengths from 340nm to 400 nm. The percent unactivated state transmission at all wavelengths from 340nm to 400nm may be less than 4% or less than 3% or less than 2% or less than 1% or less than 0.5% in some embodiments. In some embodiments, the unactivated state percent transmission is substantially 0% over all wavelengths 340nm to 400 nm. As described above with respect to 340nm to 380nm, it is desirable to reduce and minimize the percent transmission of electromagnetic radiation through the photochromic articles of the present invention at all wavelengths from 340nm to 400nm, for reasons including, but not limited to, protecting objects, such as the human eye, behind the photochromic article from exposure to electromagnetic radiation at wavelengths from 340nm to 400 nm.

When included with a primer layer and a photochromic-dichroic layer as described previously, in some embodiments of the present invention, the activated state optical density of the photochromic article is greater than the control activated state optical density of a control photochromic article comprising a substrate and a coating layer (i.e., a photochromic-dichroic layer), but without a primer layer. The substrates of the photochromic article and the control photochromic article were substantially the same in each case and had substantially the same properties and thicknesses. The coatings of the photochromic article and the control photochromic article were substantially the same in each case and had substantially the same properties and thicknesses.

Accordingly, as optical density increases, the photochromic articles of the present invention are typically darker in the activated state when exposed to the same level of incident actinic radiation as a comparative photochromic article in the activated state, the comparative sample having, for example, a photochromic-dichroic layer comprising a photochromic-dichroic compound, but without the underlying primer layer comprising the first photochromic compound described above.

The active state optical density of the present invention and the active state optical density of the control are typically measured over at least a portion of the visible light spectrum. In some embodiments, the activation state optical density and the control activation state optical density are each determined at 410nm to 800 nm. The optical density is determined according to known methods using known and commercially available equipment.

In some embodiments, the photochromic article includes a topcoat layer disposed over the photochromic-dichroic layer. The topcoat layer may include an ultraviolet light absorber and/or a second photochromic compound. In some embodiments, the topcoat layer includes a second photochromic compound and optionally an ultraviolet light absorber. The topcoat layer in some embodiments includes an ultraviolet light absorber and is free of a photochromic compound, such as the second photochromic compound. The topcoat layer in further embodiments includes a second photochromic compound and is free of an ultraviolet light absorber. The primer and the first photochromic compound and the photochromic-dichroic layer and photochromic-dichroic compound are each as previously described.

The second photochromic compound of the topcoat layer has a third unactivated state absorbance greater than 0 and a third unactivated state end minimum absorbance wavelength greater than 330nm over a wavelength of at least a portion of the 330nm to 380 nm. As previously described, the third unactivated state terminal minimum absorbance wavelength of the (second photochromic compound of the topcoat layer) is less than the second unactivated state terminal minimum absorbance wavelength of the (photochromic-dichroic compound of the photochromic-dichroic layer).

In some embodiments, the third unactivated state terminal minimum absorbance wavelength is greater than 330nm and less than 380 nm. The third unactivated state end minimum absorbance wavelength is greater than 330nm and less than 370nm in some further embodiments.

Some embodiments of the photochromic articles according to the present invention: a first unactivated state end minimum absorbance wavelength greater than 380nm and less than or equal to 450 nm; a second unactivated state end minimum absorbance wavelength greater than 340nm and less than or equal to 450 nm; and a third unactivated state end minimum absorbance wavelength greater than 330nm and less than 380 nm.

Some embodiments of the photochromic articles according to the present invention: a first unactivated state end minimum absorbance wavelength greater than 380nm and less than or equal to 450 nm; a second unactivated state end minimum absorbance wavelength greater than 340nm and less than or equal to 450 nm; and a third unactivated state end minimum absorbance wavelength greater than 330nm and less than 370 nm.

The second photochromic compound of the topcoat layer 20 and the photochromic-dichroic compound of the photochromic-dichroic layer 17 and the first photochromic compound of the underlying primer layer 14 are each selected to have or provide the above-described absorbance properties. According to some embodiments of the present invention, they are selected such that the photochromic article has a percent transmittance in the unactivated state of less than 5% at all wavelengths from 340nm to 380 nm. The percent unactivated state transmission at all wavelengths from 340nm to 380nm may be less than 4% or less than 3% or less than 2% or less than 1% or less than 0.5% in some embodiments. In some embodiments, the unactivated state percent transmission is substantially 0% at all wavelengths from 340nm to 380 nm.

In some further embodiments, the photochromic articles of the present invention, when comprising a topcoat layer and a second photochromic compound, have a percent transmittance in the unactivated state of less than 5% at all wavelengths from 340nm to 400 nm. The percent transmittance in the unactivated state at all wavelengths from 340nm to 400nm may be less than 4% or less than 3% or less than 2% or less than 1% or less than 0.5% in some embodiments. In some embodiments, the percent transmission in the unactivated state is substantially 0% at all wavelengths from 340nm to 400 nm.

When included with a topcoat layer, photochromic-dichroic layer, and primer layer having a second photochromic compound as described previously, the photochromic article in some embodiments of the present invention has an activated state optical density that is greater than the control activated state optical density of a control photochromic article comprising a substrate and a coating layer (i.e., photochromic-dichroic layer), but without both a topcoat layer and a primer layer having a second photochromic compound. The substrates of the photochromic article and the control photochromic article were substantially the same in each case and had substantially the same properties and thicknesses. The coatings of the photochromic article and the control photochromic article were substantially the same in each case, and had substantially the same properties and thicknesses.

The active state optical density and the control active state optical density are each typically measured over at least a portion of the visible light spectrum. In some embodiments, the activation state optical density and the control activation state optical density are each determined at from 410nm to 800 nm. The optical density is determined according to known methods using known and commercially available equipment.

Accordingly, as optical density increases, the photochromic articles of the present invention are typically darker in the activated state when exposed to the same level of incident actinic radiation as a comparative photochromic article in the activated state, the comparative sample having, for example, a photochromic-dichroic layer comprising a photochromic-dichroic compound, but without an overlying topcoat layer comprising a second photochromic compound, and an underlying primer layer comprising a first photochromic compound, as described above.

In some embodiments of the photochromic articles of the present invention, the unactivated state peak absorbance wavelength values of the first photochromic compound, the photochromic-dichroic compound, and the optional second photochromic compound are not equivalent to one another. More specifically, the first unactivated state peak absorbance wavelength of (the first photochromic compound of the primer layer), the second unactivated state peak absorbance wavelength of (the photochromic-dichroic compound of the photochromic-dichroic layer), and the third unactivated state peak absorbance wavelength of (the optional second photochromic compound of the optional topcoat layer) are not equivalent to each other.

In some embodiments, it is desirable to select the first photochromic compound, photochromic-dichroic compound, and optional second photochromic compound such that their unactivated state peak absorbance wavelength values are not equivalent to each other, for reasons including, but not limited to, increasing the total amount of incident radiation absorbed by the photochromic article (wavelengths ranging from 340nm to 380nm or from 340nm to 400 nm). When the values of peak absorbance wavelengths in the unactivated state are not equivalent to each other, the amount of incident radiation (wavelengths 340nm-380nm or 340nm-400nm) absorbed by each of the optional second photochromic compound, photochromic-dichroic compound, and first photochromic compound will increase or optimize as the incident radiation passes down through the optional topcoat layer (20), photochromic-dichroic layer (17), and primer layer (14). Increasing and/or optimizing the amount of incident radiation (wavelength 340nm to 380nm or 340nm to 400nm) absorbed by each of the optional second photochromic compound, photochromic-dichroic compound, and first photochromic compound can increase and/or optimize the photochromic and/or photochromic-dichroic response of the compounds, and correspondingly improve the photochromic and/or photochromic-dichroic response and performance of the photochromic articles of the present invention. Alternatively or additionally, the percent transmission of incident radiation having wavelengths of 340nm to 380nm or 340nm to 400nm through the photochromic articles of the present invention is minimized when the first, second, and third unactivated state peak wavelengths are not equivalent and shifted as described above and further herein.

According to some embodiments, the difference between the second unactivated state peak absorbance wavelength and the first unactivated state peak absorbance wavelength is greater than or equal to 0.5nm and less than or equal to 20nm, or greater than or equal to 1nm and less than or equal to 15nm, or greater than or equal to 2nm and less than or equal to 10nm, or greater than or equal to 2nm and less than or equal to 7nm, or any combination of these noted upper and lower wavelength values.

The second unactivated state peak absorbance wavelength may be greater than or less than the first unactivated state peak absorbance wavelength. Accordingly, the first unactivated state peak absorbance wavelength may be greater than or less than the second unactivated state peak absorbance wavelength. In some embodiments, the second unactivated state peak absorbance wavelength is greater than the first unactivated state peak absorbance wavelength, and correspondingly, the first unactivated state peak absorbance wavelength is less than the second unactivated state peak absorbance wavelength.

According to some further embodiments, and in addition to the first, second, and third unactivated state peak absorbance wavelength values being not equivalent to each other, the difference between the third unactivated state peak absorbance wavelength and the second unactivated state peak absorbance wavelength is greater than or equal to 0.5nm and less than or equal to 20nm, or greater than or equal to 1nm and less than or equal to 15nm, or greater than or equal to 2nm and less than or equal to 10nm, or greater than or equal to 2nm and less than or equal to 7nm, or any combination of these noted upper and lower wavelength values.

In addition to the first, second, and third unactivated state peak absorbance wavelength values not being equivalent to each other, in some further embodiments, the third unactivated state peak absorbance wavelength may be greater than or less than the second unactivated state peak absorbance wavelength. Accordingly, the second unactivated state peak absorbance wavelength may be greater than or less than the third unactivated state peak absorbance wavelength. In some embodiments, the third unactivated state peak absorbance wavelength is greater than the second unactivated state peak absorbance wavelength, and correspondingly, the second unactivated state peak absorbance wavelength is less than the third unactivated state peak absorbance wavelength.

In some further embodiments, in addition to the first, second, and third unactivated state peak absorbance wavelength values not being equivalent to each other: the first unactivated state peak absorbance wavelength is less than the second unactivated state peak absorbance wavelength; and the second unactivated state peak absorbance wavelength is less than the third unactivated state peak absorbance wavelength (when the topcoat and the second photochromic compound are present).

The substrate from which the photochromic articles of the present invention can be selected includes, but is not limited to, substrates formed from organic materials, inorganic materials, or combinations thereof (e.g., composites). Non-limiting examples of substrates that can be used in accordance with the various non-limiting embodiments disclosed herein are described in more detail below.

Non-limiting examples of organic materials that can be used to form the substrate of the photochromic articles of the present invention include polymeric materials such as homopolymers and copolymers prepared from the monomers and monomer mixtures disclosed in U.S. patent 5962617 and U.S. patent 5658501 at column 15, line 28 to column 16, line 17, the disclosures of which are expressly incorporated herein by reference. Such polymeric materials may be, for example, thermoplastic or thermoset polymeric materials, may be transparent or optically transparent, and may have any desired refractive index. Non-limiting examples of such disclosed monomers and polymers include: a polyol (allyl carbonate) monomer, such as allyl diglycol carbonate, for example diethylene glycol bis (allyl carbonate), sold under the trademark CR-39 by PPGIndustries, inc; polyurea-polyurethane (polyurea-urethane) polymers, prepared for example by reaction of a polyurethane prepolymer and a diamine curing agent, the composition for one such polymer being sold under the trade mark TRIVEX by ppginindustries, inc; a polyol (meth) acryloyl-terminated carbonate monomer; diethylene glycol dimethacrylate monomer; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomer; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol dimethacrylate monomer; a poly (ethylene glycol) dimethacrylate monomer; a urethane acrylate monomer; poly (ethoxylated bisphenol a dimethacrylate); poly (vinyl acetate); poly (vinyl alcohol); poly (vinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; a polyurethane; a polythiourethane; thermoplastic polycarbonates, such as the carbonate-linked resins derived from bisphenol a and phosgene, one such material being sold under the trademark LEXAN; polyester, such as the material sold under the trademark MYLAR; poly (ethylene terephthalate); polyvinyl butyral; poly (methyl methacrylate), such as the material sold under the trademark PLEXIGLAS, and polymers prepared as follows: polyfunctional isocyanates are reacted with polythiol or polyepisulfide monomers, homo-or co-and/or ter-polymerizing with polythiol, polyisocyanate, polyisothiocyanate and optionally ethylenically unsaturated monomers or vinyl monomers containing halogenated aryl groups. Also contemplated are such monomer copolymers and blends of the polymers and copolymers with other polymers, for example to form block copolymers or interpenetrating network products.

The substrate may be an ophthalmic substrate in some embodiments. Non-limiting examples of organic materials suitable for forming ophthalmic substrates include, but are not limited to, well-known polymers that can be used as ophthalmic substrates, such as organic optical resins, for making optically transparent castings for optical applications, such as ophthalmic lenses.

Other non-limiting examples of organic materials suitable for use in forming the substrate of the photochromic articles of the present invention include both synthetic and natural organic materials, including but not limited to: opaque or transparent polymeric materials, natural and synthetic textiles, and cellulosic materials such as paper and wood.

Non-limiting examples of inorganic materials suitable for forming the substrate of the photochromic articles of the present invention include glass, minerals, ceramics, and metals. For example, in one non-limiting embodiment, the substrate can comprise glass. In other non-limiting embodiments, the substrate can have a reflective surface, such as a polished ceramic substrate, a metal substrate, or a mineral substrate. In other non-limiting embodiments, a reflective coating or layer can be deposited or applied onto the surface of an inorganic or organic substrate to make it reflective or to enhance its reflectivity.

Further, in accordance with certain non-limiting embodiments disclosed herein, the substrate can have a protective coating, such as, but not limited to, an abrasion resistant coating, such as a "hard coating" on its outer surface. For example, commercially available thermoplastic polycarbonate ophthalmic lens substrates are often sold with an abrasion resistant coating already applied to its outer surface because these surfaces tend to be easily scratched, rubbed, or abraded. An example of such a lens substrate is GENTEX^TMPolycarbonate lenses (available from genetex optics). Thus, as used herein, the term "substrate" includes substrates having a protective coating, such as, but not limited to, an abrasion resistant coating on a surface thereof.

Still further, the substrate of the photochromic articles of the present invention can be an uncolored, colored, linearly polarized, circularly polarized, elliptically polarized, photochromic, or colored photochromic substrate. As used herein with reference to a substrate, the term "uncolored" means a substrate that is substantially free of added colorants (such as, but not limited to, conventional dyes) and has an absorption spectrum for visible light that does not change significantly in response to actinic radiation. Further, the term "colored" when referring to a substrate means a substrate having an added colorant (such as, but not limited to, a conventional dye) and an absorption spectrum for visible light that does not change significantly in response to actinic radiation.

As used herein, the term "linearly polarized" with reference to a substrate means a substrate suitable for linearly polarized radiation. As used herein, the term "circularly polarized" with reference to a substrate means a substrate suitable for circularly polarized radiation. As used herein, the term "elliptically polarized" with reference to a substrate refers to a substrate suitable for elliptically polarized radiation. As used herein, the term "photochromic" in reference to a substrate means a substrate having an absorption spectrum for visible light that changes in response to at least actinic radiation. Further, as used herein with reference to a substrate, the term "tinted-photochromic" means a substrate that contains an added colorant as well as a photochromic material and has an absorption spectrum for visible light that changes in response to at least actinic radiation. Thus, for example and without limitation, a colored-photochromic substrate may have a first color characteristic of a colorant and a second color characteristic of the combination of the colorant and the photochromic material when exposed to actinic radiation.

The photochromic articles of the present invention comprise a photochromic-dichroic layer that further comprises a photochromic-dichroic compound. The photochromic-dichroic layer can be unpolarized in a first state (i.e., the coating will not confine the vibration of the electric vector of a light wave to one direction), and linearly polarized in a second state involving transmitted light in some embodiments. As used herein, the term "transmitted light" refers to radiation that passes through at least a portion of an object. Although not limiting herein, the transmitted light may be ultraviolet light, visible light, infrared light, or a combination thereof. Thus, according to various non-limiting embodiments disclosed herein, the photochromic-dichroic layer can be unpolarized in the first state and linearly polarized transmitted ultraviolet light, transmitted visible light, or a combination thereof in the second state.

According to still other non-limiting embodiments, the photochromic-dichroic layer can have a first absorption spectrum in the first state, a second absorption spectrum in the second state, and can be linearly polarized in both the first and second states.

In some embodiments, the photochromic-dichroic layer can have an average absorption ratio of at least 1.5 in at least one state. In some further embodiments, the average absorption ratio of the photochromic-dichroic layer in at least one state can be at least 1.5 to 50 (or greater). The term "absorption ratio" refers to the ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of radiation linearly polarized in a plane orthogonal to the first plane, where the first plane is taken as the plane of highest absorbance. Thus, the absorption ratio (and average absorption ratio described below) is an indication of how strongly one of the two orthogonal plane-polarized components of radiation is absorbed by an object or material.

The average absorption ratio of a photochromic-dichroic layer comprising a photochromic-dichroic compound can be determined as described below. For example, to determine the average absorption ratio of a photochromic-dichroic layer comprising a photochromic-dichroic compound, a substrate having a coating is disposed on an optical bench and the coating is placed in a linear polarization state activated by the photochromic-dichroic compound. Activation is achieved by exposing the coating to UV radiation for a sufficient time to achieve a saturated or near saturated state (i.e., a state in which the absorption properties of the coating do not change significantly over the time interval during which the measurement is taken). For light linearly polarized perpendicular to the plane of the optical table (referred to as the 0 ° plane or direction of polarization) and light linearly polarized in a plane parallel to the optical table (referred to as the 90 ° plane or direction of polarization), the absorption measurements are taken over a period of time (typically 10-300 seconds), at 3 second intervals in the following order: 0 °, 90 °, 90 °, 0 °, etc. The absorbance of linearly polarized light passing through the coating is measured at each time interval for all wavelengths tested, and the obtained absorbance spectrum of the coating in the activated state at each of the 0 ° and 90 ° polarization planes is subtracted from the unactivated absorbance at the same wavelength range (i.e., the absorbance of the coating in the unactivated state) in each of the 0 ° and 90 ° polarization planes to obtain the average differential absorption spectrum of the coating in the saturated or near saturated state in each polarization plane.

For example, referring to FIG. 2, an average differential absorption spectrum (generally designated 4) at one polarization plane is shown, which is obtained for a photochromic-dichroic layer according to one non-limiting embodiment disclosed herein. The average absorption spectrum (generally designated 3) is the average differential absorption spectrum obtained for the same photochromic-dichroic layer in the orthogonal polarization planes.

The average absorption ratio of the photochromic-dichroic layer is obtained as follows based on the average differential absorption spectrum obtained for the photochromic-dichroic layer. The photochromic-dichroic layer has an absorption ratio corresponding to λ at each wavelength in a predetermined wavelength range_max-vis+/-5 nanometers (generally indicated as 5 in FIG. 2), where λ_max-visIs the wavelength at which the coating has the highest average absorbance in any plane, which is calculated according to the following equation (Eq.1):

AR_λi=Ab¹ _λi/Ab² _λiEq.1

with respect to equation Eq.1, AR_λiAt a wavelength λ_iAbsorption ratio of (A) Ab¹ _λiIs at a wavelength λ in the polarization direction (i.e., 0 ° or 90 °) having higher absorbance_iAverage absorption of, and Ab² _λiIs at a wavelength λ in the remaining polarization direction_iAverage absorption over time. As previously mentioned, "absorption ratio" refers to the ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of radiation of the same wavelength linearly polarized in a plane orthogonal to the first plane, where the first plane is taken as the plane of highest absorbance.

The average absorption ratio ("AR") of the photochromic-dichroic layer is thus calculated by averaging the individual absorption ratios according to the following equation (eq.2) over a predetermined wavelength range (i.e., λ @_max-vis+/-5 nm):

AR=(ΣAR_λi)/n_iEq.2

referring to the equation Eq.2, AR is the average absorption ratio of the coating, AR_λiIs a single absorption ratio (as determined by eq.1 above) for each wavelength within a predetermined wavelength range,and n_iIs the number of average individual absorptances. A more detailed description of this method of determining the average absorption ratio is provided in the examples at column 102, line 38 to column 103, line 15 of U.S. Pat. No.7256921, the disclosure of which is expressly incorporated herein by reference.

In some embodiments, the photochromic-dichroic compound of the photochromic-dichroic layer can be at least partially aligned. As previously mentioned, the term "photochromic-dichroic" means that under certain conditions both photochromic and dichroic (i.e., linearly polarizing) properties are exhibited, which properties are at least detectable 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 detectable by an instrument. Thus, photochromic-dichroic compounds have an absorption spectrum for at least visible light that changes in response to at least actinic radiation and is capable of absorbing at least one of two orthogonal plane-polarized components of transmitted light more strongly than the other. Further, as with the conventional photochromic compounds described above, the photochromic-dichroic compounds disclosed herein can be thermally reversible. That is, the photochromic-dichroic compound 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. As used herein, the term "compound" means a substance formed by the combination 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 combination of two or more elements, components, ingredients, or moieties.

For example, the photochromic-dichroic layer can have a first state (which has a first absorption spectrum), a second state (which has a second absorption spectrum different from the first absorption spectrum), and can be adapted to switch 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 the photochromic-dichroic compound causing at least a portion of the photochromic-dichroic compound to switch from a first state to a second state when exposed to sufficient actinic radiation. Further, although not required, the photochromic-dichroic compound can be dichroic in both the first and second states. Although not limited thereto, for example, the photochromic-dichroic compound can linearly polarize visible light in both the activated state and the bleached state. Further, the photochromic-dichroic compound can linearly polarize visible light in an activated state, and can linearly polarize UV radiation in a bleached state.

Although not required, according to various non-limiting embodiments disclosed herein, the photochromic-dichroic compound of the photochromic-dichroic layer can have an average absorption ratio in the activated state of at least 1.5, as measured according to CELL method. According to other non-limiting embodiments disclosed herein, the photochromic-dichroic compound can have an average absorption ratio greater than 2.3 in the activated state as measured according to the CELL method. According to still other non-limiting embodiments, the photochromic-dichroic layer at least partially aligned photochromic-dichroic compound can have an average absorption ratio ranging from 1.5 to 50 in the activated state, as measured according to CELL method. According to other non-limiting embodiments, the at least partially aligned photochromic-dichroic compound of the photochromic-dichroic layer can have an average absorption ratio of 4 to 20, can further have an average absorption ratio of 3 to 30, and can still further have an average absorption ratio of 2.5 to 50, as measured in the activated state according to the CELL method. More typically, however, the average absorption ratio of the at least partially aligned photochromic-dichroic compound can be any average absorption ratio sufficient to impart the desired properties to the photochromic articles of the present invention. Non-limiting examples of suitable photochromic-dichroic compounds are described in detail herein below.

The CELL method for determining the average absorption ratio of photochromic-dichroic compounds is essentially the same as the method for determining the average absorption ratio of photochromic-dichroic layers, except that instead of measuring the absorbance of the coated substrate, a CELL assembly containing an oriented liquid crystal material and a photochromic-dichroic compound is tested. More specifically, the cartridge assembly includes two opposing glass substrates that are spaced 20 microns +/-1 micron apart. The substrate is sealed along two opposing edges to form a cassette. The inner surface of each glass substrate is coated with a polyimide coating, the surface of which has been at least partially ordered by wiping. The photochromic-dichroic compound is oriented by introducing the photochromic-dichroic compound and a liquid crystal medium into the cell assembly, and allowing the liquid crystal medium to orient with the rubbed polyimide surface. Once the liquid crystal medium and photochromic-dichroic compound are oriented, the cell assembly is placed on an optical bench (which is described in detail in the examples) and the average absorbance is determined in the manner previously described for the coated substrate, except that the unactivated absorbance of the cell assembly is subtracted from the activated absorbance to obtain the average differential absorbance spectrum.

As previously mentioned, while dichroic compounds are capable of preferentially absorbing one of the two orthogonal components of plane polarized light, it is generally necessary to properly arrange or arrange the molecules of the dichroic compound to achieve a net linear polarization effect. Similarly, it is often necessary to properly arrange or align the molecules of the photochromic-dichroic compound to achieve a net linear polarizing effect. That is, it is generally necessary to orient the molecules of the photochromic-dichroic compound such that the long axes of the molecules of the photochromic-dichroic compound in the activated state are generally parallel to each other. Thus, as described above, the photochromic-dichroic compounds are at least partially aligned according to the various non-limiting embodiments disclosed herein. Further, if the activated state of the photochromic-dichroic compound corresponds to the dichroic state of the material, the photochromic-dichroic compound can be at least partially aligned such that the long axes of the photochromic-dichroic compound molecules in the activated state are aligned. As used herein, the term "oriented" means in a suitable arrangement or position through interaction with another material, compound or structure.

Further, although not limited herein, the photochromic-dichroic layer of the photochromic articles of the present invention can include a plurality of photochromic-dichroic compounds. Although not limited herein, when two or more photochromic-dichroic compounds are used in combination, the photochromic-dichroic compounds can be selected to complement each other to produce a desired color or shade. For example, according to certain non-limiting embodiments disclosed herein, a mixture photochromic-dichroic compound can be used to achieve certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. patent 5645767, column 12, line 66-column 13, line 19, the disclosure of which is expressly incorporated herein by reference, which describes parameters defining neutral gray and brown. Additionally or alternatively, the at least partial coating may comprise a mixture of photochromic-dichroic compounds having complementary linear polarization states. For example, the photochromic-dichroic compounds can be selected to have complementary linear polarization states over a desired wavelength range to produce an optical element capable of polarizing light over the desired wavelength range. Still further, a mixture of complementary photochromic-dichroic compounds having substantially the same polarization state at the same wavelength may be selected to enhance or enhance the overall linear polarization achieved. For example, according to one non-limiting embodiment, the photochromic-dichroic layer can comprise at least two at least partially aligned photochromic-dichroic compounds, wherein each at least partially aligned photochromic-dichroic compound has: a complementary color; and/or complementary linear polarization states.

The photochromic-dichroic layer can further include at least one additive that can facilitate one or more processing, properties, or characteristics of at least a portion of the coating. Non-limiting examples of such additives include dyes, orientation promoters, kinetic enhancing additives, photoinitiators, 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)), thermal stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), radical quenchers, and adhesion promoters (such as hexanediol diacrylate and coupling agents).

Examples of dyes that can be present in the photochromic-dichroic layer include, but are not limited to, organic dyes that can impart a desired color or other optical properties to the photochromic-dichroic layer.

As used herein, the term "orientation promoter" means an additive capable of promoting at least one of orientation rate and orientation uniformity of a material to which it is added. Non-limiting examples of alignment promoters that can be present in the photochromic-dichroic layer include, but are not limited to, those described in U.S. patent 6338808 and U.S. patent publication No.2002/0039627, which are expressly incorporated herein by reference.

Non-limiting examples of kinetic enhancing additives that can be present in the different layers (e.g., photochromic-dichroic layers) of the photochromic articles of the present invention include epoxy-containing compounds, organic polyols, and/or plasticizers. More specific examples of such power enhancing additives are disclosed in U.S. patent 6433043 and U.S. patent publication No.2003/0045612, which are expressly incorporated herein by reference.

Non-limiting examples of photoinitiators that can be present in the various layers of the photochromic articles of the present invention (e.g., the primer layer, the photochromic-dichroic layer, and/or the topcoat layer) include, but are not limited to, cleavage type photoinitiators and extraction type photoinitiators non-limiting examples of cleavage type photoinitiators include acetophenone, α -aminoalkylphenone, benzoin ether, benzoyl oxime, acyl phosphine oxide, and bisacyl phosphine oxide or mixtures of such initiatorsObtained from ciba chemicals, Inc. Non-limiting examples of abstraction-type photoinitiators include benzophenone, Michler's ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures of such initiators.

Another non-limiting example of a photoinitiator that can be present in one or more layers of the photochromic articles of the present invention (e.g., the primer layer, the photochromic-dichroic layer, and/or the topcoat layer) is a visible light photoinitiator. Non-limiting examples of suitable visible light photoinitiators are illustrated in U.S. patent 6602603, column 12, line 11-column 13, line 21, which is expressly incorporated herein by reference.

Examples of thermal initiators include, but are not limited to, organic peroxide compounds and azobis (organonitrile) compounds. Examples of organic peroxide compounds that can be used as thermal initiators include, but are not limited to, peroxymonocarbonate esters, such as t-butyl peroxyisopropyl carbonate; peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate, di (sec-butyl) peroxydicarbonate and diisopropylperoxydicarbonate; diacyl peroxides such as benzoyl 2, 4-dichloroperoxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide; peroxyesters such as t-butylperoxytrimethyl acetate, t-butylperoxyoctanoate and t-butylperoxyisobutyrate; methyl ethyl ketone peroxide and acetyl cyclohexane sulfonyl peroxide. In a non-limiting embodiment, the thermal initiators used are those that do not discolor the polymer formed. Examples of azobis (organonitrile) compounds that can be used as thermal initiators include, but are not limited to, azobis (isobutyronitrile), azobis (2, 4-dimethylvaleronitrile), or mixtures thereof.

Examples of polymerization inhibitors include, but are not limited to: nitrobenzene, 1,3, 5-trinitrobenzene, p-benzoquinone, chloranil, DPPH, FeCl₃，CuCl₂Oxygen, sulfur, aniline, phenol, p-dihydroxyPhenyl, 1,2, 3-trihydroxybenzene and 2,4, 6-trimethylphenol.

Examples of solvents that can be present in the formation of the different layers (e.g., primer layer, photochromic-dichroic layer, and/or topcoat layer) of the photochromic articles of the present invention include, but are not limited to, those that will dissolve the solid components of the coating, which are compatible with the coating and the element and substrate, and/or can ensure uniform coverage of the outer surface to which the coating is applied. Examples of solvents include, but are not limited to, the following: propylene glycol monomethyl ether acetates and their derivatives (asSold as industrial solvents), acetone, amyl propionate, anisole, benzene, butyl acetate, cyclohexane, dialkyl ethers of ethylene glycol such as diethylene glycol dimethyl ether and derivatives thereof (asCommercial solvent sales), diethylene glycol dibenzoate, dimethyl sulfoxide, dimethylformamide, dimethoxybenzene, ethyl acetate, isopropanol, methylcyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propanediol methyl ether, and mixtures thereof.

In another non-limiting embodiment, the photochromic-dichroic layer can include at least one conventional dichroic compound. Examples of suitable conventional dichroic compounds include, but are not limited to, azomethine, indigo, thioindigo, merocyanine, indane, quinophthalone dyes, perylene, phthalidyl, triphenodioxazine, indoloquinoxaline, imidazotriazine, tetrazine, azo and (poly) azo dyes, benzoquinone, naphthoquinone, anthraquinone and (poly) anthraquinone, anthrapyrimidinone, iodine and iodate salts. In another non-limiting embodiment, the dichroic material can include at least one reactive functional group capable of forming at least one covalent bond with another material. In some embodiments, the dichroic material may be a polymerizable dichroic compound. Accordingly, the dichroic material may include at least one group capable of polymerization (i.e., "polymerizable group"). For example, although not limited thereto, in one non-limiting embodiment, the dichroic compound can have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent terminating with at least one polymerizable group.

In some embodiments, the photochromic-dichroic layer can include at least one conventional photochromic compound. As used herein, the term "conventional photochromic compounds" includes both thermally reversible and non-thermally reversible (or photo-reversible) photochromic compounds. In general, while not limited herein, when two or more conventional photochromic materials are used in combination with each other or with a photochromic-dichroic compound, the different materials can be selected to complement each other to produce a desired color or shade. For example, according to certain non-limiting embodiments disclosed herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near neutral gray or near neutral brown. See, for example, U.S. patent 5645767, column 12, line 66-column 13, line 19, the disclosure of which is expressly incorporated herein by reference, which describes parameters defining neutral gray and brown colors.

According to some embodiments, the photochromic-dichroic layer is free of conventional photochromic compounds.

The photochromic-dichroic layer can include one or more suitable photochromic-dichroic compounds. Examples of photochromic-dichroic compounds that can be included in the photochromic-dichroic layer of the photochromic articles of the present invention include, but are not limited to, the following:

(PCDC-1) 3-phenyl-3- (4- (4- (3-piperidin-4-yl-propyl) piperidino) phenyl) -13, 13-dimethyl-3H, 13-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-2) 3-phenyl-3- (4- (4- (3- (1- (2-hydroxyethyl) piperidin-4-yl) propyl) piperidino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-3) 3-phenyl-3- (4- (4- (4-butyl-phenylcarbamoyl) -piperidin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4-phenyl-piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-4) 3-phenyl-3- (4- ([1,4'] bipiperidinyl-1' -yl) phenyl) -13, 13-dimethyl-6-methoxy-7- ([1,4'] bipiperidinyl-1' -yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-5) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4-hexylbenzoyloxy) -piperidin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-6) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4' -octyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl) -3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-7) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidin-1-yl } -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-8) 3-phenyl-3- (4- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidin-1-yl } -phenyl) -13, 13-dimethyl-6-methoxy-7- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidin-1-yl 3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-9) 3-phenyl-3- (4- (4-phenylpiperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (4' -octyloxy-biphenyl-4-carbonyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-10) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (4-hexyloxyphenylcarbonyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-11) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (4- (2-fluorobenzoyloxy) benzoyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-12) 3-phenyl-3- (4- (pyrrolidin-1-yl) phenyl) -13-hydroxy-13-ethyl-6-methoxy-7- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-13) 3-phenyl-3- (4- (pyrrolidin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4-hexylbenzoyloxy) benzoyloxy) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-14) 3-phenyl-3- (4- (pyrrolidin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (4-hexylbenzoyloxy) benzoyloxy) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-15) 3-phenyl-3- (4- (4-methoxyphenyl) -piperazin-1-yl)) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (3-phenylprop-2-ynyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-16)3- (4-methoxyphenyl) -3- (4- (4-methoxyphenyl) piperazin-1-yl) phenyl) -13-ethyl-13-hydroxy-6-methoxy-7- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-17) 3-phenyl-3- {4- (pyrrolidin-1-yl) phenyl) -13- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxy ] -13-ethyl-6-methoxy-7- (4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidin-1-yl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-18) 3-phenyl-3- (4- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidin-1-yl } -phenyl) -13-ethyl-13-hydroxy-6-methoxy-7- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy ] -piperidine- 1-yl } -) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-19) 3-phenyl-3- {4- (pyrrolidin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (3-phenyl-3- {4- (pyrrolidin-1-yl) phenyl } -13, 13-dimethyl-6-methoxy-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran-7-yl) -piperidin-1-yl) oxycarbonyl) phenyl) carbonyloxy) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-20)3- { 2-methylphenyl } -3-phenyl-5- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3H-naphtho [2,1-b ] pyran;

(PCDC-21)3- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -3-phenyl-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3H-naphtho [2,1-b ] pyran;

(PCDC-22)3- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -3-phenyl-7- (4-phenyl- (benzene-1-oxy) carbonyl) -3H-naphtho [2,1-b ] pyran;

(PCDC-23)3- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -3-phenyl-7- (N- (4- ((4-dimethylamino) phenyl) diazenyl) phenyl) carbamoyl-3H-naphtho [2,1-b ] pyran;

(PCDC-24) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -benzofuro [ 3', 2': 7,8] benzo [ b ] pyran;

(PCDC-25) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -benzothieno [ 3', 2': 7,8] benzo [ b ] pyran;

(PCDC-26)7- {17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy } -2-phenyl-2- (4-pyrrolidin-1-yl-phenyl) -6-methoxycarbonyl-2H-benzo [ b ] pyran;

(PCDC-27) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -9-hydroxy-8-methoxycarbonyl-2H-naphtho [1,2-b ] pyran;

(PCDC-28) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -9-hydroxy-8- (N- (4-butyl-phenyl)) carbamoyl-2H-naphtho [1,2-b ] pyran;

(PCDC-29) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -9-hydroxy-8- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -2H-naphtho [1,2-b ] pyran;

(PCDC-30)1,3, 3-trimethyl-6 '- (4-ethoxycarbonyl) -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-31)1,3, 3-trimethyl-6 '- (4- [ N- (4-butylphenyl) carbamoyl ] -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-32)1,3, 3-trimethyl-6 '- (4- (4-methoxyphenyl) piperazin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-33)1,3, 3-trimethyl-6 '- (4- (4' - (trans-4-pentylcyclohexyl) - [1,1 '-biphenyl ] -4-ylcarboxamide) phenyl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-34)1,3,3,5, 6-pentamethyl-7 '- (4- (4' - (trans-4-pentylcyclohexyl) - [1,1 '-biphenyl ] -4-ylcarboxamide) phenyl)) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-35)1, 3-diethyl-3-methyl-5-methoxy-6 ' - (4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-36)1, 3-diethyl-3-methyl-5- [4- (4-pentadecafluoroheptyloxy-phenylcarbamoyl) -benzyloxy ] -6 ' - (4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-37) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -5-carbo-methoxy-8- (N- (4-phenyl) carbamoyl-2H-naphtho [1,2-b ] pyran;

(PCDC-38) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -5-carbo-methoxy-8- (N- (4-phenyl) carbamoyl-2H-fluorantheno [1,2-b ] pyran;

(PCDC-39) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -5-carbomethoxy-11- (4- {17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy } phenyl) -2H-fluorantheno [1,2-b ] pyran;

(PCDC-40)1- (4-carboxybutyl) -6- (4- (4-propylphenyl) carbonyloxy) phenyl) -3, 3-dimethyl-6 ' - (4-ethoxycarbonyl) -piperidin-1-yl) -spiro [ (1, 2-dihydro-9H-dioxolano [ 4', 5 ': 6,7] indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-41)1- (4-carboxybutyl) -6- (4- (4-propylphenyl) carbonyloxy) phenyl) -3, 3-dimethyl-7 ' - (4-ethoxycarbonyl) -piperidin-1-yl) -spiro [ (1, 2-dihydro-9H-dioxolano [ 4', 5 ': 6,7] indoline-2, 3' -3H-naphtho [1,2-b ] [1,4] oxazine ];

(PCDC-42)1, 3-diethyl-3-methyl-5- (4- {17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy } phenyl) -6 ' - (4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [2,1-b ] [1,4] oxazine ];

(PCDC-43) 1-butyl-3-ethyl-3-methyl-5-methoxy-7 ' - (4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl) -spiro [ indoline-2, 3' -3H-naphtho [1,2-b ] [1,4] oxazine ];

(PCDC-44) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl ] -phenyl } -5-methoxycarbonyl-6-methyl-2H-9- (4- (4-propylphenyl) carbonyloxy) phenyl) - (1, 2-dihydro-9H-dioxolano [ 4', 5': 6, 7)) naphtho [1,2-b ] pyran;

(PCDC-45)3- (4-methoxyphenyl) -3- (4- (4-methoxyphenyl) piperazin-1-yl) phenyl) -13-ethyl-13-hydroxy-6-methoxy-7- (4- (4-propylphenyl) carbonyloxy) phenyl) -3H,13H- [1, 2-dihydro-9H-dioxolano [4 ", 5": 6,7] [ indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-46) 3-phenyl-3- (4- (4-methoxyphenyl) piperazin-1-yl) phenyl) -13-ethyl-13-hydroxy-6-methoxy-7- (4- (4-hexylphenyl) carbonyloxy) phenyl) -3H,13H- [1, 2-dihydro-9H-dioxolano [4 ", 5": 5,6] [ indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-47)4- (4- ((4-cyclohexylidene-1-ethyl-2, 5-dioxapyrrolin-3-ylidene) ethyl) -2-thienyl) phenyl- (4-propyl) benzoate;

(PCDC-48)4- (4- ((4-adamantan-2-ylidene-1- (4- (4-hexylphenyl) carbonyloxy) phenyl) -2, 5-dioxapyrrolin-3-ylidene) ethyl) -2-thienyl) phenyl- (4-propyl) benzoate;

(PCDC-49)4- (4- ((4-adamantan-2-ylidene-2, 5-dioxa-1- (4- (4- (4-propylphenyl) piperazinyl) phenyl) pyrrolin-3-ylidene) ethyl) -2-thienyl) phenyl (4-propyl) benzoate;

(PCDC-50)4- (4- ((4-adamantan-2-ylidene-2, 5-dioxa-1- (4- (4- (4-propylphenyl) piperazinyl) phenyl) pyrrolin-3-ylidene) ethyl) -1-methylpyrrol-2-yl) phenyl (4-propyl) benzoate;

(PCDC-51)4- (4- ((4-adamantan-2-ylidene-2, 5-dioxa-1- (4- {17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy } phenyl) pyrrolin-3-ylidene) ethyl) -1-methylpyrrol-2-yl) phenyl (4-propyl) benzoate;

(PCDC-52)4- (4-methyl-5, 7-dioxa-6- (4- (4- (4-propylphenyl) piperazinyl) phenyl) spiro [8, 7 a-dihydrothieno [4, 5-f ] isoindol-8, 2' -adamantan ] -2-yl) phenyl (4-propyl) phenylbenzoate;

(PCDC-53) N- (4- {17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyloxy } phenyl-6, 7-dihydro-4-methyl-2-phenylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-54) N-cyanomethyl-6, 7-dihydro-2- (4- (4- (4-propylphenyl) piperazinyl) phenyl) -4-methylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-55) N-phenylethyl-6, 7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-methylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-56) N-phenylethyl-6, 7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-cyclopropylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyiimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-57) N-phenylethyl-6, 7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-cyclopropylspiro (5, 6-benzo [ b ] fluorocarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-58) N-cyanomethyl-6, 7-dihydro-4- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-2-phenylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-59) N- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxycarbonyl-6, 7-dihydro-2- (4-methoxyphenyl) phenyl-4-methylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-60) N-cyanomethyl-2- (4- (6- (4-butylphenyl) carbonyloxy- (4, 8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl-6, 7-dihydro-4-cyclopropylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane);

(PCDC-61)6, 7-dihydro-N-methoxycarbonylmethyl-4- (4- (6- (4-butylphenyl) carbonyloxy- (4, 8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl-2-phenylspiro (5, 6-benzo [ b ] thiothiophenedicarboxyimide-7, 2-tricyclo [3.3.1.1] decane); and

(PCDC-62) 3-phenyl-3- (4-pyrrolidinylphenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4- (4- (6- (4- (4- (4-nonylphenylcarbonyloxy) phenyl) oxycarbonyl) phenoxy) hexyloxy) phenyl) piperazin-1-yl) indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran.

In some further embodiments, the photochromic-dichroic compound of the photochromic articles of the present invention may be selected from the following:

(PCDC-a1)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl ] -13, 13-dimethyl-12-bromo-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a2)3, 3-bis (4-methoxyphenyl) -10- [4- ((4- (trans-4-pentylcyclohexyl) phenoxy) carbonyl) phenyl ] -6,13, 13-trimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a3)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-11, 13, 13-trimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a4)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl ] -5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a5)3- (4-methoxyphenyl) -3- (4-piperidinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a6)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a7)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -10- [4- ((4- (trans-4-pentylcyclohexyl) phenoxy) carbonyl) phenyl ] -12-bromo-5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a8) 3-phenyl-3- (4-piperidinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -12-bromo-5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a9) 3-phenyl-3- (4-piperidinophenyl) -10- [4- ((4- (trans-4-pentylcyclohexyl) phenoxy) carbonyl) phenyl ] -12-bromo-5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a10)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -12-bromo-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a11)3, 3-bis (4-methoxydinonylphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -12-bromo-6, 7-dimethoxy-11, 13, 13-trimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a12)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-12-bromo-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a13)3, 3-bis (4-methoxyphenyl) -10, 12-bis [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a14)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5, 7-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a15)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a16)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5, 7-difluoro-12-bromo-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a17)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13-methyl-13-butyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a18)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5, 7-difluoro-12-bromo-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a19) 3-phenyl-3- (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a20) 3-phenyl-3- (4-morpholinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a21)3, 3-bis (4-fluorophenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-12-bromo-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a22)3, 3-bis (4-fluorophenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a23)3- (4-methoxyphenyl) -3- (4-butoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a24)3- (4-fluorophenyl) -13, 13-dimethyl-3- (4-morpholinophenyl) -10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a25)3- (4-butoxyphenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a26)3- (4- (4- (4-methoxyphenyl) piperazin-1-yl) phenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3-phenyl-6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a27)3- (4-butoxyphenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- (((trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-yl) oxy) carbonyl) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a28)3- (4-fluorophenyl) -13-hydroxy-13-methyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3- (4-butoxyphenyl) -6- (trifluoromethyl) -3, 13-dihydroindeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a29)3- (4-methoxyphenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3- (4- (trifluoromethoxy) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a30)3, 3-bis (4-hydroxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -6-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a31)3- (4-morpholinophenyl) -3-phenyl-13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a32)3- (4-morpholinophenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a40) 12-bromo-3- (4-butoxyphenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- ((4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) oxy) benzamide) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a41)3- (4-butoxyphenyl) -5, 7-dichloro-11-methoxy-3- (4-methoxyphenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a42)3- (4-butoxyphenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- ((4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) oxy) benzamide) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a43)5, 7-dichloro-3, 3-bis (4-hydroxyphenyl) -11-methoxy-13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a44)6, 8-dichloro-3, 3-bis (4-hydroxyphenyl) -11-methoxy-13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a45)3- (4-butoxyphenyl) -5, 8-difluoro-3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a46)3- (4-butoxyphenyl) -3- (4-fluorophenyl) -13, 13-dimethyl-10- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) piperazin-1-yl) -6- (trifluoromethyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a47)3- (4-morpholinophenyl) -3- (4-methoxyphenyl) -10, 7-bis [4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) phenyl ] -5-fluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a48)3- (4-morpholinophenyl) -3- (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) -2- (trifluoromethyl) phenyl ] -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a49)3, 3-bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) -2- (trifluoromethyl) phenyl ] -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a50)3- (4-morpholinophenyl) -3- (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamide) -2- (trifluoromethyl) phenyl ] -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a51)3, 3-bis (4-methoxyphenyl) -13, 13-dimethyl-10- (2-methyl-4- (trans-4- ((4' - ((trans-4-pentylcyclohexyl) biphenyl-4-yloxy) carbonyl) cyclohexanecarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a52)3- (4- (4- (4-butylphenyl) piperazin-1-yl) phenyl) -3- (4-methoxyphenyl) -13, 13-dimethyl-10- (4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) -2- (trifluoromethyl) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a53)3- (4- (4- (4-butylphenyl) piperazin-1-yl) phenyl) -3- (4-methoxyphenyl) -13, 13-dimethyl-10- (2-methyl-4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) phenyl) -7- (4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a54)3- (4-methoxyphenyl) -13, 13-dimethyl-7, 10-bis (4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) phenyl) -3-phenyl-3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a55) 3-p-tolyl-3- (4-methoxyphenyl) -6-methoxy-13, 13-dimethyl-7- (4' - (trans, trans-4 ' -pentylbis (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy) -10- (4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a56)10- (4- (((3S,8S,9S,10R,13R,14S,17R) -10, 13-dimethyl-17- ((R) -6-methylheptan-2-yl) -2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthrene-3-oxy) carbonyl) piperazin-1-yl) -3- (4-methoxyphenyl) -13, 13-dimethyl-3- (4-morpholinophenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a57) 6-methoxy-3- (4-methoxyphenyl) -13, 13-dimethyl-3- (4- ((S) -2-methylbutoxy) phenyl) -10- (4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-a58) 6-methoxy-3- (4-methoxyphenyl) -13, 13-dimethyl-3- (4- ((S) -2-methylbutoxy) phenyl) -7- (4' - (trans, trans-4 ' -pentylbis (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy) -10- (4- (4' - (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran; and

(PCDC-a59) 6-methoxy-3- (4-methoxyphenyl) -13, 13-dimethyl-3- (4- ((S) -2-methylbutoxy) phenyl) -10- (4- (((3R,3aS,6S,6aS) -6- (4' - (trans-4-pentylcyclohexyl) biphenylcarbonyloxy) hexahydrofuro [3, 2-b ] furan-3-oxy) carbonyl) phenyl) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyrans.

(PCDC-b1)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4'- ((4- (trans-4-pentylcyclohexyl) benzoyl) oxy) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b2)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4- (4'- (4- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy) benzoyloxy)) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b3)3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4'- ((4- (trans-4-pentylcyclohexyl) benzoyl) oxy) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b4)3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4- (4'- (4- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy) benzoyloxy)) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b5)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4'- (4- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy)) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b6)3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b7)3, 3-bis (4-fluorophenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4' - (4' - (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b8)3- (4-methoxyphenyl) -3- (4- (piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4' - (4' - (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b9)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4' - (4' - (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b10)3- (4- (4-methoxyphenyl) piperazin-1-yl) -3-phenyl-13-methoxy-13-ethyl-6-methoxy-7- (4'- (4- (2-hydroxyethoxy) benzoyloxy) - [1,1' -biphenyl ] -4-carbonyloxy) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b11)3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (3-phenylpropoxy) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b12)3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b13)3, 3-bis (4-methoxyphenyl) -6, 13-dimethoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -13-trifluoromethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b14)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -13-hydroxy-13-trifluoromethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b15)3, 3-bis (4-methoxyphenyl) -6, 7-bis (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -13-methoxy-13-trifluoromethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b16)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -13-fluoro-13-trifluoromethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b17)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -11-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b18)3- (4-butoxyphenyl) -3- (4-methoxyphenyl) -7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -11-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b19)3- (4- (N-morpholinyl) phenyl) -3-phenyl-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b20)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-difluoro-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b21)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b22)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b23)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b24)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b25)3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b26)3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4- (trans-4-pentylcyclohexyl) benzamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b27)3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carboxamide) benzamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b28)3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (trans-4- (((4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-yl) oxy) carbonyl) cyclohexanecarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b29)3- (4-N-morpholinylphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b30)3- (4-N-morpholinophenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (trans-4- (((4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-yl) oxy) carbonyl) cyclohexanecarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b31)3- (4-N-morpholinophenyl) -3-phenyl-6-methoxy-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b32)3- (4-N-morpholinophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b33)3- (4-N-morpholinophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b34) 3-phenyl-3- (4- (piperidin-1-yl) phenyl) -6-methoxy-7- (4- (4- (trans-4-pentylcyclohexyl) benzamide) -2- (trifluoromethyl) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b35)3, 3-bis (4-fluorophenyl) -6-methoxy-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b36)3, 3-bis (4-fluorophenyl) -6-methoxy-7- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b37)3- (4- (piperidin-1-yl) phenyl) -3-phenyl-6-methoxy-7- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b38)3- (4- (N-morpholino) phenyl) -3-phenyl-6-methoxy-7- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b39)3- (4- (N-morpholino) phenyl) -3-phenyl-6-methoxy-7- (4- (4- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) benzoyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b40)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) benzoyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b41)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -6-methoxy-7- (4- (4- ((trans, trans) -4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) benzoyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b42)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -6-methoxy-7- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b43)3, 3-bis (4-methoxyphenyl) -6, 13-dimethoxy-7- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) -13-ethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b44)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b45)3, 3-bis (4-hydroxyphenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b46)3, 3-bis (4-fluorophenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b47)3- (4-methoxyphenyl) -3- (4-N-morpholinophenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b48)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans-4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-oxycarbonyl) cyclohexanecarbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b49)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans-4-pentylcyclohexyl) -phenoxycarbonyl) -cyclohexanecarbonyloxy) phenyl) piperazin-1-yl) -10, 12-bis (trifluoromethyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b50)3, 3-bis (4-methoxyphenyl) -7- (4- (4- (trans-4-pentylcyclohexyl) phenoxycarbonyl) phenyl) -11-methyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b51)3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -6-methyl-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -11-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b52)3, 3-bis (4-hydroxyphenyl) -6-methyl-7- (4- (4'- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamide) phenyl) -11-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b53)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -11-trifluoromethyl-13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(PCDC-b54)3- (4- (4-methoxyphenyl) piperazin-1-yl) -3-phenyl-6-methoxy-7- (4- ((4- (trans-4-propylcyclohexyl) phenoxy) carbonyl) phenoxycarbonyl) -13, 13-dimethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran; and

(PCDC-b55)3, 3-bis (4-methoxyphenyl) -7- (4- ([1,1 ': 4',1 "-terphenyl ] -4-ylcarbamoyl) piperazin-1-yl) -6, 13-dimethoxy-13-trifluoromethyl-3, 13-dihydro-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyrans.

More generally, the photochromic-dichroic compounds of the photochromic articles of the present invention comprise: (a) at least one photochromic group (PC) which may be chosen, for example, from pyrans, oxazines and fulgides; and (b) at least one lengthening agent or group attached to the photochromic group. Such photochromic-dichroic compounds are described in detail at column 5, line 35-column 14, line 54 of U.S. patent No. 7342112B1; and table 1, the portions of which are incorporated herein by reference. Other suitable photochromic compounds and reaction schemes for preparing them can be found in U.S. patent No.7342112B1, column 23, line 37-column 78, line 13, the portions of which are incorporated herein by reference.

The photochromic-dichroic layer can comprise a single layer or multiple layers, each comprising the same or different photochromic-dichroic compounds. The photochromic-dichroic layer can be formed by well known methods including, but not limited to: lamination, such as one or more plastic sheets or films; in-mold formation, such as in-mold coating; film casting; and a coating method. In some embodiments, the photochromic-dichroic layer is formed from a photochromic-dichroic coating composition. The photochromic-dichroic coating composition can be a curable photochromic-dichroic coating composition that can be cured by exposure to, for example: ambient temperature, for example in the case of a two-component coating composition; elevated temperatures (e.g., 150 ℃ to 190 ℃ for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, for example in the case of uv-curable coating compositions.

The photochromic-dichroic layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a crosslinked organic matrix. The organic matrix of at least a portion of the photochromic-dichroic layer can, in some embodiments, include anisotropic materials, such as liquid crystal materials, additives, oligomers, and/or polymers, as discussed in further detail herein. In addition or as an alternative to an organic matrix, the photochromic-dichroic layer may include an inorganic matrix including, for example, silane linkages, siloxane linkages, and/or titanate linkages. The organic matrix of the photochromic-dichroic layer can include, for example: acrylate residues (or monomer units) and/or methacrylate residues; a vinyl residue; an ether linkage; sulfide linkages, including mono-sulfide linkages and/or polysulfide linkages; (ii) a carboxylate linkage; carbonate linkages (e.g., -O-C (O) -O-) carbamate linkages (e.g., -N (H) -C (O) -O-); and/or a thiourethane linkage (e.g., -N (H) -C (O) -S-).

The photochromic-dichroic layer can have any suitable thickness. In some embodiments, the photochromic-dichroic layer has a thickness of 0.5 to 50 microns, such as 1 to 45 microns or 2 to 40 microns, or 5 to 30 microns, or 10 to 25 microns.

In some embodiments, the photochromic-dichroic layer of the photochromic article further comprises a phase-separated polymer comprising: an at least partially ordered matrix phase; and an at least partially ordered guest phase. The guest phase includes a photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the guest phase.

According to additional embodiments of the present invention, the photochromic-dichroic layer further comprises an interpenetrating polymer network comprising: an anisotropic material that is at least partially ordered, and a polymeric material. The anisotropic material includes a photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the anisotropic material.

In some embodiments of the present invention, the photochromic-dichroic layer further comprises an anisotropic material. As used herein, the term "anisotropy" means a property having at least one different value when measured in at least one different direction. Thus, an "anisotropic material" is a material that has at least one property of different value when measured in at least one different direction. Non-limiting examples of anisotropic materials that can be included in the photochromic-dichroic layer include, but are not limited to, those liquid crystal materials described herein further with respect to the optional alignment layer of the photochromic article of the present invention.

In some embodiments, the photochromic-dichroic layer: (i) comprising liquid crystalline oligomers and/or polymers which are at least partially prepared from monomeric mesogenic compounds; and/or (ii) comprises a mesogenic compound, in each case as disclosed in U.S. patent No.7910019B2 in table 1 at columns 43-90 thereof, the disclosure of which is incorporated herein by reference.

According to some embodiments of the present invention, the photochromic-dichroic compounds of the photochromic-dichroic layer may be at least partially oriented by interacting with the anisotropic material, which itself is at least partially ordered. For example, although not limited herein, at least a portion of the photochromic-dichroic compound can be oriented such that the long axis of the photochromic-dichroic compound is substantially parallel to the general direction of the anisotropic material when in the dichroic state. Further, although not required, the photochromic-dichroic compound can be bonded to or otherwise react with at least a portion of the at least partially ordered anisotropic material.

Methods of orienting or introducing orientation into the anisotropic material of the photochromic-dichroic layer include, but are not limited to, exposing the anisotropic material to at least one of a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible light, and shear force. Alternatively or additionally, the anisotropic material may be at least partially ordered by orienting at least a portion of the anisotropic material with another material or structure. For example, the anisotropic material may be at least partially ordered as follows: the anisotropic material is oriented with an orientation layer (or orientation means) such as, but not limited to, those described in further detail below.

By orienting at least a portion of the anisotropic material, at least a portion of the photochromic-dichroic compound contained on or attached to the anisotropic material of the photochromic-dichroic layer can be at least partially oriented. Although not required, the photochromic-dichroic compound can be at least partially oriented while still in an activated state. In some embodiments, orienting the anisotropic material and/or orienting the photochromic-dichroic compound may be performed before, during, or after the photochromic-dichroic layer is applied on the primer layer.

The photochromic-dichroic compound and anisotropic material can be oriented and ordered during application of the photochromic-dichroic layer onto the primer layer. For example, the photochromic-dichroic layer can be applied using a coating technique that introduces a shear force into the anisotropic material during application, such that the anisotropic material becomes at least partially ordered generally parallel to the direction of the applied shear force. For non-limiting purposes of illustration, a solution or mixture (optionally in a solvent or carrier) comprising the photochromic-dichroic compound and an anisotropic material can be curtain coated onto the primer layer such that shear forces are introduced onto the material to be applied due to the relative movement of the substrate surface with respect to the material to be applied. One example of a coating method that is capable of introducing at least sufficient shear force is a curtain coating method. The shear force causes at least a portion of the anisotropic material to order in a general direction substantially parallel to the direction of surface movement. As described above, by orienting at least a portion of the anisotropic material in this manner, at least a portion of the photochromic-dichroic compound can be oriented. Additionally, and optionally, at least partial orientation of the photochromic-dichroic compound while in an activated state can also be achieved by exposing at least a portion of the photochromic-dichroic compound to actinic radiation during the curtain coating process to convert the photochromic-dichroic compound to an activated state.

The photochromic-dichroic compound and anisotropic material can be oriented and ordered after the photochromic-dichroic layer is applied to the primer layer. For example, a solution or mixture of the photochromic-dichroic compound and anisotropic material (optionally in a solvent or carrier) can be spin coated onto at least a portion of the primer layer. Thereafter, at least a portion of the anisotropic material can be ordered by, for example, exposing the anisotropic material to a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible light, and/or shear forces. Alternatively or additionally, the anisotropic material may be at least partially ordered by its orientation with another material or structure, such as an alignment layer.

The photochromic-dichroic compound and anisotropic material can be oriented and ordered prior to application of the photochromic-dichroic layer onto the primer layer. For example, a solution or mixture of the photochromic-dichroic compound and anisotropic material (optionally in a solvent or carrier) may be applied to an ordered polymeric sheet to form a layer thereon. Thereafter, at least a portion of the anisotropic material may be allowed to orient with the underlying ordered polymer sheet. The polymer sheet may be subsequently applied to the primer layer, for example, by known lamination or bonding methods. Alternatively, the ordered photochromic-dichroic layer can be transferred from the polymer sheet onto the primer layer by known methods such as hot stamping.

In some embodiments, the photochromic-dichroic layer can include a phase-separated polymer comprising: a matrix phase; and a guest phase distributed in the matrix phase. The matrix phase may comprise an at least partially ordered liquid crystal polymer. The guest phase may include an anisotropic material that is at least partially ordered and at least a portion of the photochromic-dichroic compound, which may be at least partially aligned. The at least partially aligned photochromic-dichroic compound can be at least partially aligned by interacting with an anisotropic material that is at least partially ordered.

In some embodiments, a phase separated polymer system including a matrix phase forming material (which includes a liquid crystal material) and a guest phase forming material (which includes an anisotropic material and a photochromic-dichroic compound) is applied over the primer layer. After application of the phase separated polymer system, at least a portion of the liquid crystal material of the matrix phase and at least a portion of the anisotropic material of the guest phase are at least partially ordered such that at least a portion of the photochromic-dichroic compound is oriented with the anisotropic material of at least a portion of the guest phase being at least partially ordered. Methods of orienting the matrix phase forming material and the guest phase forming material of the phase separated polymer system include, but are not limited to, exposing the applied layer to at least one of the following: magnetic fields, electric fields, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible light, and shear forces. Alternatively or additionally, orienting the matrix phase forming material and guest phase forming material may include their orientation through interaction with an underlying orientation layer, as described in further detail herein.

After orienting the matrix phase-forming material and the guest phase-forming material, the guest phase-forming material may be separated from the matrix phase-forming material by polymerization-induced phase separation and/or solvent-induced phase separation. Although separation of the matrix and guest phase forming materials is described herein as being separate from the guest phase forming material and the matrix phase forming material, it should be understood that this language is intended to cover any separation between the two phase forming materials. That is, the purpose of this language is to cover the separation of the guest phase forming material from the matrix phase forming material and the separation of the matrix phase forming material from the guest phase forming material, as well as the simultaneous separation of both phase forming materials and any combination thereof.

According to some embodiments, the matrix phase forming material may comprise a liquid crystal material selected from liquid crystal monomers, liquid crystal prepolymers, and liquid crystal polymers. The guest phase forming material may in some embodiments comprise a liquid crystal material selected from liquid crystal mesogens, liquid crystal monomers and liquid crystal polymers and prepolymers. Examples of such materials include, but are not limited to, those described above, and further herein directed to optional alignment layers.

In some embodiments, the phase-separated polymer system may include a mixture of matrix phase-forming materials (which include liquid crystal monomers), guest phase-forming materials (which include liquid crystal mesogens and photochromic-dichroic compounds). In such embodiments, causing the guest phase-forming material to separate from the matrix phase-forming material may include polymerization-induced phase separation. Typically, the liquid crystal monomer of the matrix phase may polymerize and thereby mesomorphically separate from at least a portion of the liquid crystal of the guest phase forming material. Examples of polymerization methods include, but are not limited to, photo-induced polymerization and heat-induced polymerization.

In some further embodiments, the phase-separated polymer system may comprise a mixture of: a matrix phase forming material (which includes a liquid crystal monomer), a guest phase forming material (which includes a low viscosity liquid crystal monomer functionally different from the liquid crystal monomer of the matrix phase, and a photochromic-dichroic compound). As used herein, the term "low viscosity liquid crystalline monomer" refers to a liquid crystalline monomer mixture or solution that is free flowing at room temperature. Typically, causing the guest phase forming material to separate from the matrix phase forming material includes polymerization-induced phase separation. For example, at least a portion of the liquid crystal monomer of the matrix phase may be polymerized under conditions that do not cause polymerization of the liquid crystal monomer of the guest phase. The guest phase forming material typically separates from the matrix phase forming material during polymerization of the matrix phase forming material. Thereafter, the liquid crystal monomers of the guest phase forming material may be polymerized in separate polymerization methods.

The phase separated polymer system may in some embodiments include a solution in at least one co-solvent of a matrix phase forming material (which includes a liquid crystal polymer), a guest phase forming material (which includes a liquid crystal polymer different from the liquid crystal polymer of the matrix phase forming material, and a photochromic-dichroic compound). Causing the guest phase-forming material to separate from the matrix phase-forming material typically involves solvent-induced phase separation. Typically, at least a portion of the common solvent evaporates from the mixture of liquid crystalline polymers, thereby causing the two phases to separate from each other.

In further embodiments, the photochromic-dichroic layer can include an interpenetrating polymer network. The at least partially ordered anisotropic material and the polymeric material can form an interpenetrating polymer network wherein at least a portion of the polymeric material is interpenetrating with at least a portion of the at least partially ordered anisotropic material. As used herein, the term "interpenetrating polymer network" means an entangled combination of polymers, at least one of which is crosslinked, which are bonded to each other. Thus, as used herein, the term interpenetrating polymer network includes semi-interpenetrating polymer networks. See, e.g., L.H.Sperling, introduction to physical Polymer science, John Wiley & Sons, New York (1986), page 46. Additionally, at least a portion of the at least one at least partially aligned photochromic-dichroic compound can be at least partially aligned with an anisotropic material that is at least partially ordered. Still further, the polymeric material may be isotropic or anisotropic, defining the photochromic-dichroic layer as a whole to be anisotropic. Methods of forming such photochromic-dichroic layers are described in more detail below.

According to some embodiments, the anisotropic material may be adapted to cause the photochromic-dichroic compound to switch from the first state to the second state at a desired rate. In general, conventional photochromic compounds can undergo a transformation from one isomeric form to another in response to actinic radiation, and each isomeric form has a characteristic absorption spectrum. The photochromic-dichroic compounds of the photochromic articles of the present invention undergo a similar isomer transformation. Without intending to be bound by any theory, the rate or speed at which such isomers are converted (and inversely converted) depends in part on the properties of the local environment surrounding the photochromic-dichroic compound (i.e., the "host"). Although not limited herein, it is believed that the rate of conversion of the photochromic-dichroic compound is dependent, in part, on the flexibility of the segments of the host, and more specifically on the mobility or viscosity of the segments of the host, based on the evidence at hand. Accordingly, without intending to be bound by any theory, it is believed that for the rate of conversion of the photochromic-dichroic compound, hosts having soft segments are generally faster than hosts having rigid or hard segments. Also, and according to some embodiments, when the anisotropic material is a host, the anisotropic material can be adapted to allow the photochromic-dichroic compound to transform between different isomeric states at a desired rate. For example, the anisotropic material can be adapted by adjusting the molecular weight and/or the crosslink density of the anisotropic material.

In some embodiments, the photochromic-dichroic layer includes a phase separated polymer including a matrix phase (which includes a liquid crystal polymer) and a guest phase dispersed in the matrix phase. The guest phase may include an anisotropic material. Typically, a majority of the photochromic-dichroic compound may be contained within the guest phase of the phase-separated polymer. As previously discussed, because the conversion rate of the photochromic-dichroic compound is dependent in part on the host in which it is included, the conversion rate of the photochromic-dichroic compound is essentially dependent on the properties of the guest phase.

In some embodiments, and as discussed in further detail herein, the photochromic articles of the present invention can include an alignment layer (also referred to as an alignment or orientation facility) interposed between the primer layer and the photochromic-dichroic compound layer. The phase separated polymer of the photochromic-dichroic layer may include a matrix phase (at least a portion of which is at least partially aligned with the alignment layer) and a guest phase (which includes an anisotropic material), wherein the guest phase is dispersed in the matrix phase. The at least a portion of the anisotropic material of the guest phase may be at least partially aligned with at least a portion of the alignment layer, and the photochromic-dichroic compound may be at least partially aligned with at least a portion of the anisotropic material. In addition, the matrix phase of the phase-separated polymer may include a liquid crystal polymer, and the anisotropic material of the guest phaseMay be selected from liquid crystalline polymers and liquid crystalline mesogens. Non-limiting examples of such materials are described in more detail above. When the phase separation polymer is included, the photochromic-dichroic layer can be substantially haze-free. Haze is defined as the percentage of transmitted light that deviates on average from the incident beam by more than 2.5 degrees according to standard test methods for haze and luminous transmittance of transparent plastics according to astm d 1003. One example of an instrument on which Haze can be measured according to ASTM D1003 is Haze-GardnPlus manufactured by BYK-Gardener^TM。

According to some embodiments, the photochromic-dichroic compound may be encapsulated or overcoated with an anisotropic material, such as a liquid crystal material, having relatively soft segments, and then dispersed or distributed into another material having relatively rigid segments. The encapsulating anisotropic material may be at least partially ordered. For example, the encapsulated photochromic-dichroic compound can be dispersed or distributed in a liquid crystal polymer having relatively rigid segments, after which the mixture can be applied to a substrate to form the photochromic-dichroic layer.

In further embodiments, the photochromic-dichroic layer can be a polymeric sheet comprising a photochromic-dichroic compound. The polymer sheet may be uniaxially or biaxially stretched. Stretching of the polymer sheet typically results in orientation and orientation within the photochromic-dichroic material. The photochromic-dichroic layer can include in some embodiments two or more polymer sheets, each containing a photochromic-dichroic compound, wherein each sheet can be stretched in the same direction or in different (e.g., orthogonal) directions.

Examples of polymer sheets that can be used as or to form a photochromic-dichroic layer include, but are not limited to, stretched (e.g., uniaxially or biaxially stretched) polymer sheets, ordered liquid crystal polymer sheets, and photo-oriented polymer sheets. Examples of polymeric materials (which are different from the liquid crystal materials and photo-alignment materials that can be used to form the polymeric sheet of the photochromic-dichroic layer) include, but are not limited to: polyvinyl alcohol, polyvinyl chloride, polyurethane, polyacrylate, and polycaprolactam. Non-limiting examples of methods for at least partially orienting polymer sheets are described in more detail below.

According to some embodiments, the photochromic-dichroic layer may be formed as follows: applying at least one anisotropic material onto the primer layer, absorbing the photochromic-dichroic compound onto the previously applied anisotropic material, orienting the anisotropic material, and orienting the photochromic-dichroic compound with at least a portion of the ordered anisotropic material. The anisotropic material may be ordered before, during or after absorption with the photochromic-dichroic compound. In some embodiments, the photochromic-dichroic compound can be oriented while in an activated state.

In some embodiments, imbibing the photochromic-dichroic compound into a previously applied anisotropic material can include applying a solution or mixture of the photochromic-dichroic compound in a carrier to the previously applied anisotropic material, and allowing the photochromic-dichroic compound to diffuse into the anisotropic material, e.g., with or without the use of heat. The previously applied anisotropic material may be part of a phase separated polymer coating, as described above.

The photochromic articles of the present invention comprise a primer layer (e.g., primer layer 14 of fig. 1). The primer layer may comprise a single layer or multiple layers, each of which comprises a first photochromic compound, which may be the same or different. The primer layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a crosslinked organic matrix. In addition or as an alternative to organic substrates, the primer layer may include an inorganic substrate including, for example, silane, siloxane, and/or titanate linkages. The organic matrix may include, for example: acrylate residues (or monomer units) and/or methacrylate residues; a vinyl residue; an ether linkage; sulfide linkages, including monosulfide linkages and/or polysulfide linkages; (ii) a carboxylate linkage; carbonate linkages (e.g., -O-C (O) -O-) carbamate linkages (e.g., -N (H) -C (O) -O-); and/or a thiourethane linkage (e.g., -N (H) -C (O) -S-).

The primer layer may be formed by known methods including, but not limited to: lamination, such as lamination of one or more plastic sheets or films; in-mold formation, such as in-mold coating; film casting; and a coating method. Typically, the primer layer is formed from a primer coating composition. The primer coating composition may be a curable primer coating composition that can be cured by exposure to, for example: ambient temperature, for example in the case of a two-component coating composition; elevated temperatures (e.g., 150 ℃ to 190 ℃ for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, for example in the case of uv-curable coating compositions.

The primer layer can have any suitable thickness. In some embodiments, the primer has a thickness of 0.5 microns to 20 microns, such as 1 to 10 microns or 2 to 8 microns or 3 to 5 microns, inclusive.

In some embodiments, the primer layer includes an organic matrix that includes urethane linkages. According to some embodiments, the urethane connection-containing primer layer is formed from a curable coating composition comprising: (meth) acrylate copolymers having active hydrogen functionality selected from the group consisting of hydroxyl, thiol, primary amine, secondary amine, and combinations thereof; blocked isocyanates, for example diisocyanates and/or triisocyanates blocked with suitable blocking or elimination groups, such as 3, 5-dimethylpyrazole; and one or more additives including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, radical quenchers, plasticizers, flow additives, and/or static colorants or static dyes (i.e., non-photochromic colorants or dyes).

Examples of (meth) acrylate monomers from which active hydrogen-functionalized (meth) acrylate copolymers may be prepared include, but are not limited to, C₁-C₂₀(meth) acrylic acid ester, C₁-C₂₀(meth) acrylates having a structure selected from the group consisting of hydroxyl, thiol, primary amineAnd at least one active hydrogen group of a secondary amine. C of (meth) acrylic acid ester₁-C₂₀The radicals may be selected, for example, from C₁-C₂₀Linear alkyl radical, C₃-C₂₀Branched alkyl, C₃-C₂₀Cycloalkyl radical, C₃-C₂₀Fused cyclopolycycloalkyl, C₅-C₂₀Aryl and C₁₀-C₂₀A fused cyclic aryl group.

Additional polyols, which may be used in the primer coating composition for making the primer layer, include, but are not limited to, well-known materials, such as those described in U.S. Pat. No.7465414, column 15, line 22-column 16, line 62, the disclosure of which is incorporated herein by reference. Isocyanates (which may be used in the primer coating composition for making the primer layer) include, but are not limited to, well known materials such as those described in U.S. Pat. No.7465414, column 16, line 63-column 17, line 38, the disclosure of which is incorporated herein by reference. Catalysts, which may be used in the primer coating composition for making the primer layer, include, but are not limited to, well-known materials, such as those described in U.S. Pat. No.7465414, column 17, lines 39-62, the disclosure of which is incorporated herein by reference.

The primer layer may include additional additives that enhance the performance of the first photochromic compound. Such additional additives may include, but are not limited to, ultraviolet light absorbers, stabilizers such as Hindered Amine Light Stabilizers (HALS), antioxidants such as polyphenol antioxidants, asymmetric diaryloxamide (oxanilide) compounds, singlet oxygen quenchers such as nickel iron complexes with organic ligands, and mixtures and/or combinations of such photochromic performance enhancing additive materials.

The primer layer may be applied to the substrate by known methods including, but not limited to, spray coating, spin coating, doctor blade (or doctor blade) coating, and curtain coating.

The primer layer may include at least partial hydrolysis products of the coupling agent and mixtures thereof. As used herein, "coupling agent" means a material having at least one group capable of reacting, binding and/or associating with a group on at least one surface. In some embodiments, the coupling agent may act as a molecular bridge at the interface of at least two surfaces, which may be similar or dissimilar surfaces. In further embodiments, the coupling agent may be a monomer, oligomer, prepolymer, and/or polymer. Such materials include, but are not limited to, organometallics such as silanes, titanates, zirconates, aluminates, zircoaluminates, hydrolysates thereof, and mixtures thereof. As used herein, the phrase "at least partial hydrolysis product of the coupling agent" means that at least some to all of the hydrolyzable groups on the coupling agent have been hydrolyzed.

In addition or as an alternative to the coupling agent and/or coupling agent hydrolysate, the primer layer may include other adhesion promoting ingredients. For example, although not limited thereto, the primer layer may further include an adhesion-promoting amount of an epoxy-containing material. An adhesion-promoting amount of an epoxy-containing material, when included in the primer layer, can improve the adhesion of subsequently applied coatings or layers. One class of epoxy (or oxirane) functional adhesion promoters that may be included in the composition used to form the primer layer include, but are not limited to, oxirane-functional alkyl-trialkoxysilanes, such as gamma-glycidoxypropyltrimethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

The first photochromic compound of the primer layer may be selected from known photochromic compounds. In some embodiments, the first photochromic compound is selected from indeno-fused naphthopyrans, naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, spirofluoreno [1,2-b ] pyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, spiropyrans, benzoxazines, phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) fluoranthenoxazines, spiro (indoline) quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds and non-thermally reversible photochromic compounds and mixtures thereof.

The first photochromic compound of the primer layer may be selected from certain indeno-fused naphthopyran compounds in some embodiments, such as described in U.S. patent No.6296785, column 3, line 66-column 10, line 51, the disclosure of which is incorporated herein by reference.

More specific examples of indeno-fused naphthopyran compounds from which the first photochromic compound can be selected include, but are not limited to:

(P-a)3, 3-bis (4-methoxyphenyl) -6,7,10, 11-tetramethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-b) 3-phenyl-3- (4-morpholinophenyl) -6,7,10, 11-tetramethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-c)3, 3-bis (4-methoxyphenyl) -6,7,10, 11-tetramethoxy-13-hydroxy-13-ethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-d)3, 3-bis (4-methoxyphenyl) -6,7, 11-trimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-e)3, 3-bis (4-methoxyphenyl) -6-methoxy-13-hydroxy-13-ethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-f)3, 3-bis (4-methoxyphenyl) -6,7,10, 11-tetramethoxy-13, 13-diethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-g)3, 3-bis (4-methoxyphenyl) -6-morpholino-13-phenyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-H)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6, 11-dimethoxy-13-hydroxy-13-phenyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-i)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-j)3- (4-methoxyphenyl) -3- (4-dimethylaminophenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-k)3, 3-bis (4-methoxyphenyl) -6,7, 8-trimethoxy-13-phenyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-l)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7,10, 11-tetramethoxy-13-hydroxy-13-ethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-m)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7,10, 11-tetramethoxy-13-hydroxy-13-butyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-n)3- (4-morpholinophenyl) -3-phenyl-6, 11-dimethoxy-13-hydroxy-13-ethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-o)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl-6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-P)3- (4-morpholinophenyl) -3-phenyl-6, 11-dimethoxy-13-hydroxy-13-butyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-q)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-13-hydroxy-13-ethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-r)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-diethylamino-13-ethyl-13-methoxy-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-s)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6, 11-dimethoxy-13-hydroxy-13-methyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-t)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7, 8-trimethoxy-13-methoxy-13-methyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran; and combinations of two or more thereof.

The first photochromic compound of the primer layer may be selected from one or more indeno-fused naphthopyran compounds having pi-conjugated elongated groups, such as halogens or halogen-substituted groups, bonded to the 11-position of the indeno-fused naphthopyran in some additional embodiments. Examples of indeno-fused naphthopyran compounds having a pi-conjugated lengthened group bonded to the 11-position thereof include, but are not limited to, those disclosed in U.S. patent application publication No. US2011/0049445A1 in paragraphs [0030] - [0080 ].

More specific examples of indeno-fused naphthopyran compounds having pi-conjugated elongated groups bonded to the 11-position thereof (from which the first photochromic compound of the primer layer may be selected) include, but are not limited to:

(P-i)3, 3-bis (4-methoxyphenyl) -6-methoxy-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-ii)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-11- (3, 5-bis (trifluoromethyl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-iii)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-11- (2-trifluoromethyl) phenyl-13, 13-diethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-iv)3, 3-bis- (4-methoxyphenyl) -6-methoxy-7-piperidino-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-v)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-vi)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-7-piperidino-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-vii)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-7-morpholino-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-viii)3, 3-bis (4-hydroxyphenyl) -6, 7-dimethoxy-11- (3, 5-bis (trifluoromethyl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-ix)3, 3-bis- (4-methoxyphenyl-6-methoxy-7-morpholino-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-x)3, 3-bis (4-methoxyphenyl) -7-methoxy-11- (2-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-xi)3- (4-methoxyphenyl) -3- (2-hydroxyethoxy) phenyl-6-methoxy-7-piperidino-11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-xii) 3-phenyl-3 ' - (4-morpholinophenyl) -11- (4-trifluoromethyl) phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyran;

(P-xiii)3- (4-morpholinophenyl) -3-phenyl-11- (2-trifluoromethyl) -phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(P-xiv)3- (4-butoxyphenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-11- (3- (trifluoromethyl) pyridin-2-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran; and combinations of two or more thereof.

In some embodiments, the first photochromic compound of the primer layer may be covalently bonded to the substrate of the primer layer, e.g., the organic substrate. In some embodiments, the first photochromic compound can include one or more reactive groups, such as one or more polymerizable groups. In some embodiments, the first photochromic compound can be selected from 2H-naphtho [1,2-b ] pyran, 3H-naphtho [2,1-b ] pyran and/or indeno [2,1-f ] naphtho [1,2-b ] pyran, each of which has at least one functional group capable of forming a covalent bond with another functional group, such as at least one polymerizable group, for example at least one polyalkoxylated substituent of 1 to 50 alkoxy units/substituent, which is capped (or terminated) with a polymerizable group. Examples of such photochromic compounds from which the first photochromic compound may be selected include, but are not limited to, those disclosed in U.S. patent No.6113814, column 2, line 52-column 8, line 40, the disclosure of which is incorporated herein by reference.

More specific examples of photochromic compounds having reactive functionality from which the first photochromic compound of the primer layer may be selected include, but are not limited to:

(P-a') 2, 2-bis (4-methoxyphenyl) -5- (2-hydroxyethoxycarbonyl) -8-phenyl- [2H ] -naphtho [1,2-b ] pyran;

(P-b') 2, 2-bis (4-methoxyphenyl) -5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -8-phenyl- [2H ] -naphtho [1,2-b ] pyran;

(P-c ') 3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-methyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyrans

(P-d ') 3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-methyl-13- (2- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyrans

(P-e ') 3- (4- (2-hydroxyethoxy) phenyl) -3- (4-morpholinophenyl) -6-methoxy-11- (4-trifluoromethylphenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3 ': 3,4] naphtho [1,2-b ] pyrans

(P-f') 3- (4- (2- (2- (2-hydroxyethoxy) ethoxy) phenyl) -3-phenyl-9-methoxycarbonyl-8-methoxy- [3H ] -naphtho [2, -1-b ] pyran; and combinations of two or more thereof.

The photochromic articles of the present invention comprise a topcoat layer (e.g., topcoat layer 20 of fig. 1). The topcoat layer may comprise a single layer or multiple layers, each comprising a second photochromic compound, which may be the same or different. The topcoat typically includes an organic matrix, such as a thermoplastic organic matrix and/or a crosslinked organic matrix. In addition or as an alternative to organic matrices, the top coat may comprise an inorganic matrix comprising, for example, silane linkages, siloxane linkages and/or titanate linkages. The organic matrix may include, for example: acrylate residues (or monomer units) and/or methacrylate residues; a vinyl residue; an ether linkage; sulfide linkages, including mono-sulfide linkages and/or polysulfide linkages; (ii) a carboxylate linkage; carbonate linkages (e.g., -O-C (O) -O-) carbamate linkages (e.g., -N (H) -C (O) -O-); and/or a thiourethane linkage (e.g., -N (H) -C (O) -S-).

The topcoat may be formed by known methods including, but not limited to: lamination, such as lamination of one or more plastic sheets or films; in-mold formation, such as in-mold coating; film casting; and a coating method. Typically, the top coat is formed from a top coat coating composition. The topcoat coating composition may be a curable topcoat coating composition that can be cured by exposure to, for example: ambient temperature, for example in the case of a two-component coating composition; elevated temperatures (e.g., 150 ℃ to 190 ℃ for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, for example in the case of uv-curable coating compositions.

The top coat may have any suitable thickness. In some embodiments, the thickness of the top coat is from 0.5 microns to 10 microns, such as from 1 to 8 microns or from 2 to 5 microns, inclusive.

In some embodiments, the topcoat layer includes an organic matrix formed from a radiation-cured acrylate-based composition, and accordingly, the topcoat layer may be described as an acrylate-based topcoat layer.

The acrylate-based topcoat layer may be prepared using a (meth) acrylate monomer and/or a (meth) acrylic acid monomer. The (meth) acrylate monomer may include one, two, three, four, or five (meth) acrylate groups. Additional copolymerizable monomers, for example, epoxy monomers such as monomers containing epoxy (or oxirane) functionality, monomers containing both (meth) acrylate and epoxy functionalities, and the like, may also be present in the formulation used to prepare the (meth) acrylate-based topcoat. The monomers used to prepare the (meth) acrylate-based topcoat layer include a major amount, e.g., a major amount (i.e., greater than 50 weight percent) of (meth) acrylate monomers; hence the name "(meth) acrylate based topcoat". The formulations used to prepare the (meth) acrylate-based topcoats may also contain components having at least one isocyanate (-NCO) group, such as organic monoisocyanates, organic diisocyanates and organic triisocyanates, whereby urethane linkages may be incorporated into the topcoats.

The (meth) acrylate-based topcoat typically has physical properties including, for example, transparency, adhesion to the underlying photochromic-dichroic layer, aqueous alkali metal hydroxide removability, compatibility with an optional abrasion resistant coating applied to its surface, such as a hard coat, and scratch resistance. In some embodiments, the hardness of the (meth) acrylate-based topcoat is greater than the hardness of the photochromic-dichroic layer.

Radiation curing of (meth) acrylate-based polymer systems can be achieved, for example, with electron beam curing (EB) and/or Ultraviolet (UV) radiation. Uv curing typically requires the presence of at least one photoinitiator, whereas EB curing techniques do not require a photoinitiator. The (meth) acrylate-based formulation (which is cured by UV or EB radiation process) may be the same except for the presence or absence of a photoinitiator.

Radiation curable (meth) acrylate-based polymer systems are well known in the polymer art, and any such system can be used to produce the (meth) acrylate-based topcoat of the photochromic articles of the present invention. According to some embodiments, the (meth) acrylate-based topcoat is formed from a composition comprising a combination or miscible blend of one or more free-radically initiated (meth) acrylate monomers and/or (meth) acrylate oligomers, and one or more cationically initiated epoxy monomers. When this monomer blend is cured, a (meth) acrylate-based topcoat in polymeric form is formed and includes an interpenetrating network of polymer components.

Examples of (meth) acrylate monomers that can be included in the composition capable of forming a (meth) acrylate-based topcoat layer include, but are not limited to, multifunctional (meth) acrylates having, for example, 1,2,3, 4, or 5 (meth) acrylate groups, and monofunctional (meth) acrylates, such as monomers containing a single (meth) acrylate group, hydroxyl-substituted (meth) acrylates, and alkoxysilylalkyl acrylates, such as trialkoxysilylpropyl methacrylate. Other reactive monomers/diluents such as monomers containing olefinic functionality (in addition to the (meth) acrylate monomers) may also be present.

Compositions that can form (meth) acrylate-based topcoats and methods of applying and curing such compositions are disclosed in U.S. patent No.7452611B2, column 16, line 14-column 25, line 3, the disclosure of which is incorporated herein by reference.

The topcoat-forming coating composition may include one or more additives including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, heat stabilizers, catalysts, free radical quenchers, plasticizers, flow additives, and/or static colorants or static dyes (i.e., non-photochromic colorants or dyes).

In some embodiments, the composition that may form a (meth) acrylate-based topcoat may further include an adhesion promoter. The adhesion promoter may be selected from, for example, organosilanes, such as aminoorganosilanes, organotitanate coupling agents, organozirconate coupling agents, and combinations thereof. Examples of adhesion promoters, which may be included in the composition capable of forming an acrylate-based topcoat, include, but are not limited to, those disclosed in U.S. patent No.7410691B2, column 5, line 52-column 8, line 19, the disclosure of which is incorporated herein by reference.

In some embodiments, the topcoat layer includes an ultraviolet light absorber and/or a second photochromic compound. In some embodiments, the topcoat layer includes an ultraviolet light absorber and is free of the second photochromic compound. In some further embodiments, the topcoat layer includes both an ultraviolet light absorber and a second photochromic compound. In some further embodiments, the topcoat layer includes a second photochromic compound and is free of an ultraviolet light absorber. The ultraviolet light absorber may be selected from one or more known classes of ultraviolet light absorbers, including but not limited to: hindered amines which may include, for example, one or more 2, 2, 6, 6-tetramethyl N-substituted piperidine groups; a benzophenone; and/or benzotriazole. The ultraviolet light absorber is typically present in at least an effective amount, for example, from 0.1 to 10 weight percent, alternatively from 0.2 to 5 weight percent, alternatively from 0.3 to 3 weight percent, based on the total solids weight of the coating composition from which the topcoat layer is made.

In some embodiments the second photochromic compound may be selected from indeno-fused naphthopyrans, naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, spirofluoreno [1,2-b ] pyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, spiropyrans, benzoxazines, phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) fluoranthenoxazines, spiro (indoline) quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds and non-thermally reversible photochromic compounds and mixtures thereof.

The second photochromic compound of the topcoat layer may in some embodiments be covalently bonded to a substrate, such as an organic substrate, of the topcoat layer. In some embodiments, the second photochromic compound can include one or more reactive groups, such as one or more polymerizable groups. In some embodiments, the second photochromic compound can include at least one functional group capable of forming a covalent bond with another functional group, such as at least one polymerizable group, such as at least one polyalkoxylated substituent of 1 to 50 alkoxy units/substituent, which is end-capped (or terminated) with a polymerizable group.

According to some further embodiments, the second photochromic compound comprises at least one ring-opened cyclic monomer. Examples of ring-opened cyclic monomers include, but are not limited to, cyclic esters, cyclic carbonates, cyclic ethers, and cyclosiloxanes. More specific examples of ring-opened cyclic monomers include, but are not limited to, e-caprolactone and 6-valerolactone.

The photochromic compounds from which the second photochromic compound is selected (which includes at least one ring-opened cyclic monomer) include, but are not limited to, those disclosed in U.S. patent No.7465415B2, column 2, line 32 to column 6, line 60, the disclosure of which is incorporated herein by reference. More specific examples of photochromic compounds from which the second photochromic compound is selected (which have covalently bonded thereto at least one ring-opened monomer) include, but are not limited to, those disclosed in columns 86-103 of U.S. patent No.7465415B2 and shown in formulas 17-28, the disclosures of which are incorporated herein by reference.

Examples of ring-opened cyclic monomers that can be used to form photochromic compounds having covalently bonded thereto at least one ring-opened monomer from which a second photochromic compound can be selected include, but are not limited to, those disclosed in U.S. patent No.7465415B2, column 10, line 43 to column 12, line 26, the disclosure of which is incorporated herein by reference. Examples of photochromic initiators capable of reacting with the ring-opened cyclic monomer to form a photochromic compound having covalently bonded thereto at least one ring-opened monomer from which a second photochromic compound may be selected include, but are not limited to, those disclosed in table 1 at columns 14-59 of U.S. patent No.7465415B2, the disclosure of which is incorporated herein by reference.

More specific examples of photochromic initiators capable of reacting with ring-opened cyclic monomers (including but not limited to the cyclic esters, cyclic carbonates, cyclic ethers, and/or cyclic siloxanes described above) to form photochromic compounds (which have covalently bonded thereto at least one ring-opened monomer from which the second photochromic compound of the topcoat may be selected) include, but are not limited to, the following:

(TC-1)3, 3-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-phenyl-8, 9-dimethoxy-2H-naphtho [1,2-b ] pyran;

(TC-2)3, 3-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (4-methoxyphenyl) -2H-naphtho [1,2-b ] pyran;

(TC-3)3- (4- (2-hydroxyethoxy) phenyl) -3- (4-fluorophenyl) -5-methoxycarbonyl-6- (4-methoxyphenyl) -2H-naphtho [1,2-b ] pyran;

(TC-4) 3-phenyl-3- (4-ethoxyphenyl) -6-methoxy-5-methoxycarbonyl-2H-naphtho [1,2-b ] pyran;

(TC-5)3- (4-methoxyphenyl) -3- (4-fluorophenyl) -7-methyl-5-methoxycarbonyl-2H-naphtho [1,2-b ] pyran;

(TC-6) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyrans

(TC-7) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-13- (2-hydroxyethyl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(TC-8) 3-phenyl-3- (4-morpholinophenyl) -6, 7-dimethoxy-13-hydroxymethyl-13- (2-hydroxyethyl) -3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran;

(TC-9)2, 2-diphenyl-5- (2, 3-dihydroxy) propoxycarbonyl-8-methyl-2H-naphtho [1,2-b ] pyran;

(TC-10)2- (4- (2- (2-hydroxyethoxy) ethoxy) phenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-9-methoxy-2H-naphtho [1,2-b ] pyran;

(TC-11)2, 2-diphenyl-5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -8-methyl-2H-naphtho [1, -2-b ] pyran;

(TC-12)2, 2-bis (4-methoxyphenyl) -5- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxycarbonyl) -6-phenyl-2H-naphtho [1,2-b ] pyran;

(TC-13)3, 3-bis (4-methoxyphenyl) -6-morpholino-3H-naphtho [2,1-b ] pyran;

(TC-14)3, 3-bis (4-methoxyphenyl) -6-phenyl-3H-naphtho [2,1-b ] pyran;

(TC-15)3, 3-diphenyl-5-hydroxy-6- (2-hydroxyphenyl) -3H-naphtho [2,1-b ] pyran; and combinations of two or more thereof.

In some embodiments, the photochromic articles of the present invention can comprise an alignment layer interposed between the primer layer and the photochromic-dichroic layer. Referring to fig. 1, the photochromic article 2 includes an alignment layer 50 interposed between the primer layer 14 and the photochromic-dichroic layer 17. The orientation layer may also be referred to herein as an orientation facility. The photochromic-dichroic compounds of the photochromic-dichroic layer can be at least partially aligned by interaction of the underlying alignment layers.

As used herein, the term "alignment layer" means a layer that is capable of facilitating the positioning of one or more other structures directly and/or indirectly exposed to at least a portion thereof. As used herein, the term "oriented" means brought into a suitable arrangement or position, such as by another structure or material, or by some other force or effect. Thus, as used herein, the term "orienting" includes both contact methods of orienting a material, such as by orientation with another structure or material, and non-contact methods of orienting a material, such as by exposure to an external force or effect. The term orientation also includes combinations of contact and non-contact methods.

For example, the photochromic-dichroic compound (which is at least partially aligned by interaction with the alignment layer) can be at least partially aligned such that the long axis of the photochromic-dichroic compound in the activated state is substantially parallel to at least the first general direction of the alignment layer. In some embodiments, the photochromic-dichroic compound (which is at least partially aligned by interaction with the alignment layer) is bonded to or reacts with the alignment layer. As used herein, the term "generally direction" refers to the predominant arrangement or orientation of a material, compound, or structure with respect to the orientation or orientation of that material or structure. Further, those skilled in the art will appreciate that a material, compound, or structure can have a general orientation that dictates at least one preferred arrangement of the material, compound, or structure, even if there is some deviation in the arrangement of the material, compound, or structure.

The alignment layer may in some embodiments have at least a first general direction. For example, the alignment layer may include a first ordered region having a first general direction and at least one second ordered region having a second general direction (which is different from the first general direction) adjacent to the first ordered region. Further, the alignment layer may have a plurality of regions, each having the same or different general direction as the remaining regions, to form a desired pattern or design. The alignment layer can include, for example, a coating comprising an at least partially ordered alignment medium, an at least partially ordered polymer sheet, an at least partially treated surface, a Langmuir-Blodgett film, and combinations thereof.

In some embodiments, the alignment layer may comprise a coating comprising an at least partially ordered alignment medium. Examples of suitable alignment media (which may be used in combination with an alignment layer) include, but are not limited to, photo-alignment materials, rubbing-alignment materials and liquid crystal materials. Methods of orienting at least a portion of the oriented media are described in more detail below.

The alignment medium of the alignment layer may be a liquid crystal material, and the alignment layer may be referred to as a liquid crystal alignment layer. Liquid crystal materials, due to their structure, are generally capable of being ordered or oriented to adopt a general direction. More specifically, because the liquid crystal molecules have a rod-like or disk-like structure, a rigid long axis, and a strong dipole, the liquid crystal molecules can be ordered or oriented by interaction with an external force or another structure such that the long axes of the molecules are oriented in a direction generally parallel to the common axis. For example, magnetic fields, electric fields, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible light, or shear forces may be used to orient the molecules of the liquid crystal material. The liquid crystal molecules may also be oriented with an orientation surface. For example, the liquid crystal molecules may be applied to a surface that has been oriented by, for example, rubbing, notching or photo-alignment methods, and then aligned such that the long axis of each liquid crystal molecule adopts an orientation generally parallel to the general direction of surface orientation. Examples of liquid crystal materials suitable for use as an alignment medium include, but are not limited to, liquid crystal polymers, liquid crystal prepolymers, liquid crystal monomers, and liquid crystal mesogens. As used herein, the term "prepolymer" means a partially polymerized material.

Suitable classes of liquid crystal monomers for combination with the alignment layer include, but are not limited to, mono-and poly-functional liquid crystal monomers. The liquid crystal monomer may in some embodiments be selected from crosslinkable liquid crystal monomers, for example photo-crosslinkable liquid crystal monomers. As used herein, the term "photocrosslinkable" refers to materials such as monomers, prepolymers, or polymers that can be crosslinked by exposure to actinic radiation. For example, photo-crosslinkable liquid crystal monomers include, but are not limited to, those liquid crystal monomers that can be crosslinked by exposure to ultraviolet radiation and/or visible light, with or without the use of a polymerization initiator.

Examples of crosslinkable liquid crystalline monomers (which may be included in the alignment layer) include, but are not limited to, liquid crystalline monomers having functional groups selected from the group consisting of: acrylates, methacrylates, allyl ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siloxanes, thiocyanates, thiols, ureas, vinyl ethers, and blends thereof. Examples of photo-crosslinkable liquid crystal monomers (which may be included in the alignment layer) include, but are not limited to, liquid crystal monomers having functional groups selected from the group consisting of: acrylates, methacrylates, alkynes, epoxides, thiols, and blends thereof.

Liquid crystal polymers and prepolymers (which may be included in the alignment layer) include, but are not limited to, backbone liquid crystal polymers and prepolymers and side chain liquid crystal polymers and prepolymers. In the main chain liquid crystalline polymers and prepolymers, rod-like or discotic liquid crystalline mesogens are mainly located within the main chain of the polymer. In side chain liquid crystalline polymers and prepolymers, rod-like or discotic liquid crystalline mesogens are mainly located in the side chains of the polymer. Further, the liquid crystal polymer or prepolymer may be crosslinkable, and further may be photo-crosslinkable.

Examples of liquid crystal polymers and prepolymers (which may be included in the alignment layer) include, but are not limited to, backbone and side chain polymers and prepolymers having functional groups selected from the group consisting of: acrylates, methacrylates, allyl ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siloxanes, thiocyanates, thiols, ureas, vinyl ethers, and blends thereof. Examples of photo-crosslinkable liquid crystalline polymers and prepolymers (which may be included in the alignment layer) include, but are not limited to, those polymers and prepolymers having functional groups selected from: acrylates, methacrylates, alkynes, epoxides, thiols, and blends thereof.

Liquid crystal mesogens (which may be included in the alignment layer) include, but are not limited to, thermotropic liquid crystal mesogens and lyotropic liquid crystal mesogens. Additional classes of liquid crystal mesogens (which may be included in the alignment layer) include, but are not limited to, columnar and discotic liquid crystal mesogens.

Examples of photo-orientable materials (which may be included in the orientation layer) include, but are not limited to, photo-orientable polymer networks. More specific examples of photo-orientable polymer networks include, but are not limited to, azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives and polyimides. In some embodiments, the alignment layer may comprise an at least partially ordered photo-orientable polymer network selected from azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives and/or polyimides. Examples of cinnamic acid derivatives, which may be included in the alignment layer, include, but are not limited to, polyvinyl cinnamate and polyvinyl esters of p-methoxycinnamic acid.

As used herein, the term "wipe orientation material" means a material that can be at least partially ordered by wiping at least a portion of the surface of the material with another suitable textured material. For example, the wipe-oriented material may be wiped with a suitable textured cloth or velvet brush. Examples of wipe orientation materials, which may be included in the orientation layer, include, but are not limited to, (poly) imides, (poly) siloxanes, (poly) acrylates, and (poly) coumarins. In some embodiments, the alignment layer may comprise polyimide, and the alignment layer may be wiped with velvet or cotton to at least partially orient at least a portion of the surface of the alignment layer.

In some embodiments, the alignment layer may comprise at least partially ordered polymer sheets. A sheet of, for example, polyvinyl alcohol, may be at least partially ordered by stretching (e.g., uniaxially stretching) the sheet, after which the stretched sheet may be bonded to at least a portion of the surface of an optical substrate to form an orientation facility. Alternatively, ordered polymer sheets can be made by a process that at least partially orients the polymer chains during the manufacturing process, such as by extrusion. Further, the at least partially ordered polymer sheet may be formed as follows: by casting or otherwise forming a sheet of liquid crystal material, and thereafter at least partially orienting the sheet, such as, but not limited to, exposing the sheet to a magnetic field, electric field, and/or shear force. Still further, the at least partially ordered polymer sheet may be fabricated using a photo-orientation process. For example, a sheet of photo-orientable material may be formed, for example by casting, and thereafter at least partially ordered by exposure to linearly polarised ultraviolet light.

The alignment layer of the photochromic articles of the present invention can comprise an at least partially treated surface. As used herein, the term "treated surface" refers to at least a portion of a surface that has been physically altered to produce at least one ordered region on at least a portion of the surface. Examples of treated surfaces include, but are not limited to, wiped surfaces, etched surfaces, and embossed surfaces. Furthermore, the treated surface may be patterned, for example using a photolithographic or interferographic method. In some embodiments, the surface of the alignment layer may be a treated surface selected from, for example: chemically etched surfaces, plasma etched surfaces, nano-etched surfaces (e.g., surface etching using a scanning tunneling microscope or atomic force microscope), laser etched surfaces, and/or electron beam etched surfaces.

According to some embodiments, when the orientation layer comprises a treated surface, the treated surface may be formed by: depositing a metal salt (e.g. a metal oxide or metal fluoride) onto at least a portion of the surface (e.g. the surface of the alignment layer itself, or the surface of the primer layer), and thereafter etching the deposit to form a treated surface. Well known methods of depositing metal salts include, but are not limited to, plasma vapor deposition, chemical vapor deposition, and sputtering. The etching may be performed according to known methods, such as those described hereinbefore.

As used herein, the term "Langmuir-Blodgett film" means one or more at least partially ordered molecular films on a surface. The Langmuir-Blodgett film may be formed, for example, as follows: the substrate is immersed one or more times in the liquid so that it is at least partially covered with a molecular film, and then the substrate is removed from the liquid so that the molecules of the molecular film are at least partially ordered in substantially one (or single) general direction due to the relative surface tension of the liquid and the substrate. As used herein, the term molecular film refers to monomolecular films (i.e., monolayers) as well as films comprising more than one monolayer.

The photochromic articles of the present invention may further comprise an orientation transfer material interposed between the alignment layer and the photochromic-dichroic layer in some embodiments. The orientation transfer material may be oriented by interacting with the alignment layer, and the corresponding photochromic-dichroic compound may be oriented by interacting with the orientation transfer material. The orientation transfer material may, in some embodiments, facilitate the propagation or transfer of a suitable arrangement or location from the alignment layer to the photochromic-dichroic compound of the photochromic-dichroic layer.

Examples of orientation transfer materials include, but are not limited to, those liquid crystal materials described above in connection with the orientation media disclosed above. The molecules of the liquid crystal material may be oriented with an orientation surface. For example, the liquid crystal material may be applied to a surface that has been oriented and subsequently oriented such that the long axes of the liquid crystal molecules adopt an orientation that is generally parallel to the same general direction as the surface orientation. The liquid crystal material of the orientation transfer material may be at least partially ordered as follows: the alignment is performed with an alignment layer such that the long axes of the molecules of the liquid crystal material are generally parallel to a first general direction of, for example, an alignment facility. In this way, the general direction of the alignment layer may be transferred to the liquid crystal material, which in turn may transfer the general direction to another structure or material. Furthermore, if the alignment layer includes a plurality of regions having general directions that together form a design or pattern, the design or pattern may be transferred to the liquid crystal material by orienting the liquid crystal material with different regions of the alignment layer. Additionally, although not required, according to various non-limiting embodiments disclosed herein, at least a portion of the liquid crystal material of the orientation transfer material can be exposed to at least one of a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, and linearly polarized visible light while at least partially orienting with at least a portion of the alignment layer.

The photochromic articles of the present invention may, in some embodiments, comprise a hardcoat layer disposed on the topcoat layer. Referring to fig. 1, the photochromic article 2 includes a hard coat layer 53 on the top coat layer 20. The hard coating may comprise a single layer or multiple layers.

The hard coating may be selected from the group consisting of an abrasion resistant coating comprising an organosilane, an abrasion resistant coating comprising a radiation cured acrylate based film, an abrasion resistant coating based on inorganic materials such as silica, titania and/or zirconia, an organic abrasion resistant coating of the ultraviolet light curable type, an oxygen barrier coating, a UV screening coating and combinations thereof. In some embodiments, the hard coating may include a first coating of a radiation-cured acrylate-based film and a second coating including an organosilane. Non-limiting examples of commercially available hard coat products include124 andcoatings, available from sdccotings, inc. and PPGIndustries, inc.

The hard coating may be selected from known hard coating materials, such as organosilane abrasion resistant coatings. Organosilane abrasion resistant coatings, often referred to as hardcoats or silicone-based hardcoats, are well known in the art and are commercially available from various manufacturers, such as SDCCoatings, inc. See column 5, lines 1-45 of U.S. Pat. No. 4756973; and see U.S. patent No.5462806, column 1, line 58-column 2, line 8 and column 3, line 52-column 5, line 50, the disclosure of which describes organosilane hardcoats and the disclosure of which is incorporated herein by reference. Reference may also be made to U.S. Pat. Nos. 4731264, 5134191,5231156 and International patent publication WO94/20581, the disclosures of which are also incorporated herein by reference, for the use of organosilane hardcoats. The hard coat layer may be applied by coating methods such as those previously described with respect to the primer layer, such as spin coating.

Other coatings (which may be used to form a hard coating) include, but are not limited to, multi-functional acrylic hard coatings, melamine-based hard coatings, urethane-based hard coatings, alkyd-based coatings, silica sol-based hard coatings, or other organic or inorganic/organic hybrid hard coatings.

In some embodiments, the hard coating is selected from an organosilane type of hard coating. The hard coating of the photochromic articles of the present invention may be selected from the organosilane type hard coatings from which they are selected, including but not limited to those disclosed in U.S. patent No.7465414B2, column 24, line 46 to column 28, line 11, the disclosure of which is incorporated herein by reference.

The photochromic articles of the present invention can include additional coatings such as antireflective coatings. In some embodiments, an antireflective coating may be applied over the hard coat layer. Examples of anti-reflective coatings are described in U.S. patent No.6175450 and international patent publication WO00/33111, the disclosures of which are incorporated herein by reference.

According to further embodiments of the present invention, the photochromic articles of the present invention may be selected from ophthalmic articles or components, display articles or components, windows, mirrors, packaging materials such as creped paper, and active and passive liquid crystal cell articles or components.

Examples of ophthalmic articles or elements include, but are not limited to, corrective and non-corrective lenses, including single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal, trifocal and progressive lenses), and other elements for correcting, protecting or enhancing (cosmetic or otherwise) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses and protective lenses or goggles.

Examples of display articles, components and devices include, but are not limited to, screens, monitors and security components, including, but not limited to, security marks and authentication marks.

Examples of windows include, but are not limited to, automotive and aircraft transparency windows, optical filters, shutters and optical switches.

In some embodiments, the photochromic article can be a security element. Examples of security elements include, but are not limited to, security and authentication marks attached to at least a portion of a substrate, such as: access cards and tickets, such as tickets, certificates, identification or membership cards, debit cards, and the like; negotiable instruments and non-negotiable instruments such as drafts, checks, keys, tickets, proof of deposit, stocks, etc.; government documents such as currency, licenses, identification cards, benefit cards, visas, passports, official certificates, deeds, and the like; consumer goods such as software, compact discs ("CDs"), digital video discs ("DVDs"), appliances, consumer electronics, sporting goods, cars, etc.; a credit card; and merchandise labels, logos and packaging.

In a further embodiment, the security element may be attached to at least a portion of a substrate selected from the group consisting of transparent substrates and reflective substrates. Alternatively, according to further embodiments in which a reflective substrate is desired, if the substrate is not reflective or sufficiently reflective for the intended application, the reflective material may be first applied to at least a portion of the substrate before the security symbol is applied thereto. For example, a reflective aluminum coating may be applied to at least a portion of the substrate prior to forming the security element thereon. Additionally or alternatively, the security element may be attached to a substrate selected from at least a portion of: an uncolored substrate, a colored substrate, a photochromic substrate, a colored photochromic substrate, a linearly polarizing, circularly polarizing substrate, and an elliptically polarizing substrate.

Furthermore, the security element according to the previous embodiments may further comprise one or more other coatings or films or sheets to form a multilayer reflective security element with visually dependent properties, as described in us patent 6641874.

The present invention is more particularly described in the following examples that are intended to be illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. All parts and all percentages are by weight unless otherwise indicated.

Examples

Section 1 describes the preparation of a Primer Layer Formulation (PLF). Section 2 describes the preparation of liquid crystal orientation formulations (LCAF). Section 3 describes the preparation of a coating formulation (CLF). Section 4 describes the preparation of a top coat formulation (TLF). Section 5 describes the procedure used to prepare the substrates and coating stacks listed in table 1. Section 6 describes the photochromic performance tests of Comparative Examples (CE)1-4 and examples 1-4, including the absorption ratio and optical response measurements reported in table 1.

Part 1-preparation of PLF

To a suitable vessel equipped with a magnetic stir bar, the following materials were added by the weights indicated:

polyacrylate polyol (14.69g) (composition D of example 1 of U.S. patent 6187444, the disclosure of the polyol of which is incorporated herein by reference, except that in charge 2, the styrene was replaced with methyl methacrylate and 0.5 weight percent of triphenyl phosphite based on total monomer weight was added);

polyalkylene carbonate glycol (36.70g)From great lakes chemical corp;

PL340(48.23g), from Bayer MaterialScience;

BI7960(34.39g), from Baxenden;

polyether modified polydimethylsiloxane (0.08g)From BYK-Chemie, USA;

carbamate catalyst (1.00g)From King industries;

gamma-glycidoxypropyltrimethoxysilane (3.96g) A-187 from MomentivePerformance materials;

light stabilizer (8.07g)From Ciba specialty Chemicals;

aromaticc 100(36.00g), a mixture of high boiling solvents, available from Texaco; and

1-methyl-2-pyrrolidone (61.88g) from Sigma-Aldrich).

The mixture was stirred at room temperature for 2h to yield a solution having a final solids of about 46.82 wt%, based on the total weight of the solution. To this solution was added and mixed the following approximately equal amounts of the total of 5 weight percent of 3 photochromic compounds, based on the total weight of resin solids:

photochromic Compound-1 (PC-1) is an indenonaphthopyran, which is prepared according to the procedure of U.S. Pat. No.6113814, the disclosure of which is incorporated herein by reference, and which exhibits an activated blue-green color upon exposure to Ultraviolet (UV) light. The UV spectra were obtained on a photochromic test cube containing PC-1, prepared as described in part A of example 10 of U.S. Pat. No. 6113814. A varian cary4000 UV-visible light spectrometer was used, which had the following values in the process (unless otherwise indicated): range = 800-; mean time =0.100 s; data interval = 1.100; and scan rate =660 nm/min. A simple average determination of the absorbance at 340-380nm was 4.6. The first unactivated terminal minimum absorbance wavelength determined as described herein in fig. 3 was determined to be 422 ± 2 nm.

PC-2 is an indenonaphthopyran that is prepared according to the procedure of U.S. patent publication 2006/0228557, the disclosure of which is incorporated herein by reference, and which exhibits an activated magenta color upon exposure to Ultraviolet (UV) light. The UV spectrum was obtained on a photochromic test block containing PC-2 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 2.2. The first unactivated terminal minimum absorbance wavelength was determined to be 430 ± 2 nm.

PC-3 is an indenonaphthopyran that is prepared according to the procedure of U.S. patent publication 2011/0042629, the disclosure of which is incorporated herein by reference, and which exhibits an activated yellow-brown color upon exposure to ultraviolet light (UV). The UV spectrum was obtained on a photochromic test cube containing PC-3 following the procedure performed for PC-1, except that an amount of 1/2 of the photochromic compound was used. The average measurement of the absorbance at 340-380nm was 3.5. The first unactivated terminal minimum absorbance wavelength was determined to be 425 ± 2 nm.

The combination of PC-1, PC-2, and PC-3 in the primer produced an activated gray color. The unactivated absorption spectrum of the primer is shown as plot 23 in fig. 1. The absorption spectrum of plot 23 was prepared from the above described photochromic-containing PLF coated onto a substrate and was determined using a variancay 4000 UV-visible spectrophotometer to have the following values: range = 800-; mean time =0.100 s; data interval = 1.100; and scan rate =660 nm/min. Substrate (composed ofFinal single vision 6 base lens 70mm in diameter made of monomer (FSVL) was prepared as described in part 5 and coated with PLF only and heated at 125 ℃ for 1 hour, then 105 ℃ for 3 hours. PLF without photochromic compound was prepared for examples 1 and 2 and comparative examples 1 and 2.

Part 2-preparation of LCAF

A photo-alignment material solution of the type described in U.S. patent application serial No.12/959467, filed on 3/12/2010 (which application is incorporated herein by reference), was prepared by adding 6 wt% photo-alignment material to cyclopentanone, based on the total weight of the solution. Also included are violet dye in an amount of about 0.02% by weight and blue-violet dye in an amount of about 0.04% by weight, both based on the total solution weight of the photo-alignment material.

Part 3-preparation of CLF

The Liquid Crystal Monomer (LCM) material in CLF was prepared as follows:

LCM-1 is 1- (6- (6- (6- (6- (6- (6- (8- (4- (4- (8-acryloyloxyhexyloxy) benzoyloxy) phenoxycarbonyl) phenoxy) octyloxy) -6-oxohexyloxy) -6-oxohex-an-1-ol prepared according to the procedure described in example 17 of U.S. Pat. No.7910019, the disclosure of which is incorporated herein by reference.

LCM-2 is a commercially available RM257, reported to be 4- (3-acryloxypropoxy) -benzoic acid 2-methyl-1, 4-phenylene ester, available from EMDCchemicals, Inc., having the formula C₃₃H₃₂O₁₀。

LCM-3 is 1- (6- (4- (4- (trans-4-pentylcyclohexyl) phenoxycarbonyl) phenoxy) hexyloxy) -2-methylpropan-2-en-1-one, prepared according to the procedure of example 1 of U.S. patent 7910019, the disclosure of which is incorporated herein by reference, except that n =0.

LCM-4 is 1- (6- (6- (6- (6- (6- (6- (8- (4- (4- (4-hexyloxybenzoyloxy) phenoxycarbonyl) -phenoxy) octyloxy) -6-oxohexyloxy) -2-methylprop-2-en-1-one prepared according to the procedure of U.S. Pat. No.7910019, the disclosure of which is incorporated herein by reference.

CLF was prepared as follows:

to a suitable flask containing anisole (3.99g) and0.004g of the additive was added to the mixture,additives are reported to be aralkyl modified poly-methyl-alkyl-siloxanes from BYKChemie, USA with addition of LCM-1(1.08g), LCM-2(2.4g), LCM-3(1.08g), LCM-4(1.44g), 4-methoxyphenol (0.006g) and(0.09g, a photoinitiator, available from Ciba-Geigy corporation). The resulting mixture, which contains 60 wt% monomer solids based on the total weight of the mixture, was stirred at 80 ℃ for 2 hours and cooled to about 26 ℃. The mixture of photochromic/dichroic dyes (which produces an activated gray color) includes the following:

PC-4 is an indenonaphthopyran prepared according to the procedure of U.S. patent publication 2011/0129678, the disclosure of which is incorporated herein by reference, which exhibits an activated blue-green color upon exposure to Ultraviolet (UV) light and is used in an amount of about 15% of the total dye amount. The UV spectrum was obtained on a photochromic test block containing PC-4 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 4.9. The first unactivated terminal minimum absorbance wavelength was determined to be 415 ± 2 nm.

PC-5 is an indenonaphthopyran prepared according to the procedure of U.S. patent publication 2011/0129678, the disclosure of which is incorporated herein by reference, that exhibits an activated blue color upon exposure to Ultraviolet (UV) light, and is used in an amount of about 25% of the total dye amount. The UV spectrum was obtained on a photochromic test block containing PC-5 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 4.4. The first unactivated terminal minimum absorbance wavelength was determined to be 415 ± 2 nm.

PC-6 is an indenonaphthopyran prepared according to the procedure of U.S. patent publication 2011/0129678, the disclosure of which is incorporated herein by reference, which exhibits an activated blue color upon exposure to Ultraviolet (UV) light and is used in an amount of about 27% of the total dye amount. The UV spectrum was obtained on a photochromic test block containing PC-6 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 4.9. The first unactivated terminal minimum absorbance wavelength was determined to be 424 ± 2 nm.

PC-7 is an indenonaphthopyran prepared according to the procedure of U.S. patent publication 2011/0143141, the disclosure of which is incorporated herein by reference, which exhibits an activated yellow color upon exposure to Ultraviolet (UV) light and is used in an amount of about 23% of the total dye amount. The UV spectrum was obtained on a photochromic test block containing PC-7 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 4.4. The first unactivated terminal minimum absorbance wavelength was determined to be 415 ± 2 nm.

PC-8 is an indenonaphthopyran prepared according to the procedure of U.S. patent publication 2011/0143141, the disclosure of which is incorporated herein by reference, which exhibits an activated blue color upon exposure to Ultraviolet (UV) light and is used in an amount of about 10% of the total dye amount. The UV spectrum was obtained on a photochromic test block containing PC-8 following the procedure performed for PC-1. The average measurement of the absorbance at 340-380nm was 4.3. The first unactivated terminal minimum absorbance wavelength was determined to be 415 ± 2 nm.

The photochromic compounds PC-4, 5,6, 7 and 8 were added to the CLF solutions of examples 1 and 3 and comparative examples 1 and 3 in a total amount of 13% by weight and to the CLF solutions of examples 2 and 4 and CE2 and 4 in an amount of 6.5% by weight, all based on the total weight of the solutions. The unactivated absorption spectrum of a CLF containing 6.5 weight percent of the photochromic compound is included in graph 32 of fig. 1. The spectra were prepared using the same spectrometer and procedure used to prepare plot 23 of fig. 1. The FSVL substrate was prepared as described in part 5 and coated with LCAF, which was at least partially oriented prior to CLF application, all as described in the coating procedure for the liquid crystal alignment layer and coating of part 5.

Part 4: preparation of TLF

TLF was prepared as follows:

in a50 mL amber glass vial equipped with a magnetic stir bar were added the following materials:

hydroxy methacrylate (1.242g), from Sigma-Aldrich;

neopentyl glycol diacrylate (13.7175g) SR247 from Sartomer;

trimethylolpropane trimethacrylate (2.5825g) SR350 from Sartomer;

PL340(5.02g), from Bayer MaterialScience;

from Ciba speciality Chemicals;

TPO (0.0628 g; from Ciba speciality Chemicals,

polybutylacrylate (0.125g),

3-aminopropylpropyltrimethoxysilane (1.4570g) A-1100, from MomentivePerformance materials; and

200 Standard Strength Absolute Anhydrous ethanol (1.4570g), from Pharmaco-Aoper.

The mixture was stirred at room temperature for 2 h. PC-9 was added to the TLF used in examples 1-4 in an amount of 1% by weight, based on the total solution weight. PC-9 is a 2H-naphthopyran compound, prepared according to the procedure of U.S. Pat. No. 5458814, incorporated herein by reference, which exhibits an activated red color upon exposure to Ultraviolet (UV) light. UV spectra were obtained on photochromic test squares containing PC-9 following the procedure performed for PC-1, except that Varian Cary 300-range 700 and 275 were used with the following settings, average time 0.100s, data interval 1.100 and scan rate 450 nm/min. The average measurement of the absorbance at 340-380nm was 1.9. The first unactivated terminal minimum absorbance wavelength was determined to be 384 ± 2 nm.

The unactivated absorption spectrum of a TLF containing 1.0 wt.% PC-9 is included as plot 41 of FIG. 1. The spectra were prepared using the same spectrometer and procedure used to prepare plot 23 of fig. 1. The FSVL substrate was prepared as described in section 5 and coated with only TLF using the coating procedure for the top coat of section 5.

And part 5: procedure for preparing the substrates and the coating stacks reported in table 1

Substrate preparation

Will be composed ofThe final single vision lens (6 substrate, 70mm) prepared from the monomer was used as the substrate. Each substrate was cleaned by wiping with a gauze soaked with acetone and dried with an air stream and corona treated by passing on a conveyor belt of a TantecEST system series No.020270 generator HV2000 series corona treatment device with a high voltage transformer. The substrate was exposed to a corona generated by 53.99KV, 500 watts while being transported on a conveyor belt at a belt speed of 3 ft/min.

Procedure for coating a primer layer

PLF was applied to a test substrate by spin coating onto a portion of the surface of the test substrate as follows: approximately 1.5mL of this solution was dispensed. The substrate was spin coated using a spin coating processor from Laurel technologies Corp. (WS-400B-6NPP/LITE) as follows: 976 revolutions per minute (rpm) for 4s, followed by 1501rpm for 2s, followed by 2500rpm for 1 s. Thereafter, the coated substrate was placed in an oven maintained at 125 ℃ for 60 minutes. The coated substrate was cooled to about 26 ℃. The substrate was corona treated by passing it over a conveyor belt of a TantecEST System series No.020270 Generator HV2000 series corona treatment apparatus having a high voltage transformer. The dried primer layer was exposed to a corona generated by 53.00KV, 500 watts while being transported on a conveyor belt at a belt speed of 3 ft/min.

Coating procedure for liquid crystal alignment layers

The LCAF was applied to the test substrate by spin coating onto a portion of the surface of the test substrate as follows: approximately 1.0mL of the solution was dispensed and the substrate was spun at 800 revolutions per minute (rpm) for 3s, then at 1000rpm for 7s, then at 2500rpm for 4 s. Spin coating was performed using a spin coating machine from Laurel technologies Corp. (WS-400B-6 NPP/LITE). Thereafter, the coated substrate was placed in an oven maintained at 120 ℃ for 30 minutes. The coated substrate was cooled to about 26 ℃.

The dried photo-alignment layer on each substrate is at least partially ordered by exposure to linearly polarized ultraviolet radiation. The light source is oriented such that the radiation is linearly polarized in a plane perpendicular to the substrate surface. The amount of ultraviolet radiation to which each photo-alignment layer is exposed is measured using a UVPowerPuck (TM) high energy radiometer from EITInc (series No.2066) and is as follows: UVA0.018W/cm²And 5.361J/cm²；UVB0W/cm²And 0J/cm²；UVC0W/cm²And 0J/cm²(ii) a And UVV0.005W/cm²And 1.541J/cm². After orienting at least a portion of the photo-orientable polymer network, the substrate is cooled to about 26 ℃ and remains covered.

Coating method for coating

CLF was spin coated onto at least partially ordered photo-alignment material on the test substrate at a rate of 400 revolutions per minute (rpm) for 6s, followed by a rate of 800rpm for 6 s. Each coated substrate was placed in an oven at 60 ℃ for 30 minutes. Thereafter, they were cured under two ultraviolet lamps under a nitrogen atmosphere in a UV curing oven designed and built by Belcan engineering while moving on a conveyor at a speed of 2ft/min with a peak intensity of 0.388W/cm²UVA and 0.165W/cm²UVV and UV dose of 7.386J/cm²UVA and 3.337J/cm²UVV of (1). If the coated substrate is intended to receive a topcoat, the cured layer is exposed to a corona generated by 53.00KV, 500 Watts while being transported on a conveyor belt at a belt speed of 3 ft/min. If the coated substrate is not intended to receive a topcoat, post-curing is accomplished at 105 ℃ for 3 hours.

Coating procedure for top coat

The TLF was spin coated onto the coated substrate of the cured CLF at a rate of 1400 revolutions per minute (rpm) for 7 s. The substrate was thereafter cured under two ultraviolet lamps under a nitrogen atmosphere in a UV curing oven designed and built by Belcan engineering while moving on a conveyor at a speed of 6ft/min with a peak intensity of 1.887W/cm²UVA and 0.694W/cm²UVV and UV dose of 4.699J/cm²UVA and 1.787J/cm²UVV of (1). The post-curing was carried out at 105 ℃ for 3 hours.

Part 6-photochromic Performance test, including absorption ratio and optical response measurements

Prior to response testing on the optical bench, the substrate was conditioned as follows: they were exposed to 365nm uv light for 10 minutes at a distance of about 14cm from the light source to pre-activate the photochromic molecules. UVA illumination at the sample was measured with a Licor Model Li-1800 spectrophotometer and found to be 22.2W/m². The sample was then placed under a high intensity halogen lamp (500W, 120V) for about 10 minutes at a distance of about 36cm from the lamp to bleach or deactivate the photochromic compounds in the sample. The illuminance at the sample was measured with a Licor spectrophotometer and found to be 21.9 Klux. The sample was exposed to a yellow fluorescent lamp for 30 minutes to provide further visible light bleaching. The samples were then kept in a dark environment for at least 1 hour prior to testing to cool and continue to fade back to background.

The optical bench was used to measure the optical properties of the coated substrate and derive the absorption ratio and photochromic properties. Will each beThe test specimens were placed on an optical bench with an activated light source (Newport/Oriel model 66485300-watt xenon arc lamp, fitted with an installed light source) at an incident angle of 30-35 DEG on the surface of the test specimensA high speed computer controlled shutter that closes momentarily during data collection, so that stray light will not interfere with the data collection method,KG-2 pass band filters, which remove short wavelength radiation, medium density filters for intensity attenuation and focusing lenses for beam aiming). The arc lamp is equipped with a light intensity controller (Newport/Oriel model 68950).

The broadband light source for monitoring the response measurement is positioned perpendicular to the surface of the test sample. The increased signal of shorter visible wavelengths was obtained by separately collecting and combining filtered light (controlled by a constant voltage power supply) from 100 watt tungsten halogen lamps with split-end, two-part fiber optic cables. Using light from one side of a tungsten halogen lampFiltering with filters to absorb heat and useA B-440 filter to allow shorter wavelengths to pass. Using light from the other sideKG1 filter filtered or unfiltered. This light was collected as follows: light from each side of the lamp is focused at the split end, the respective ends of the two-part fiber optic cable, and then combined into one light source, which emerges from a single end of the cable. A4 "or 6" light pipe is connected to a single end of the cable to ensure proper mixing. The broadband light source is provided withVS-25 high speed computer controlled shutter which opens instantaneously during data collection.

The light source was polarized by sending light from a single end of the cable through Moxtek held at a computer driven motorized rotation stage,polarizer (model M-061-PD, from Polytech, PI or equivalent). The monitoring beam is set such that one plane of polarization (0) is perpendicular to the plane of the optical table and the second plane of polarization (90) is parallel to the plane of the optical table. The samples were run in air at 23 ℃. + -. 0.1 ℃ maintained by a temperature controlled balloon.

To orient each sample, a second polarizer was added to the optical path. The second polarizer was set to 90 ° of the first polarizer. The sample was placed in a balloon mounted in a self-centering holder on a rotating stage. A laser beam (Coherent-ULN 635 diode laser) is directed through the crossed polarizers and the sample. The sample was rotated (coarse movement in 3o steps and fine movement in 0.1o steps) to find the minimum transmission. At this point, the sample was oriented parallel or perpendicular to the Moxtek polarizer and the second polarizer and diode laser beam were removed from the optical path. The samples were oriented ± 0.5 ° prior to any activation.

To perform this measurement, each test sample was exposed to 6.7W/m from an activating light source²UVA10-20 minutes to activate the photochromic compound. An International LightResearch radiometer (model IL-1700) with a detector system (model SED033 detector, B filter, and diffuser) was used to qualify the exposure at the beginning of the day. Light from a monitoring source, polarized in the 0 ° plane of polarization, was then sent through the coated sample and collected into a1 "integrating sphere, which was connected to using a single function fiber optic cableSpectrophotometer or equivalent. Using OCEANOOIBase32 and OOIColor software and PPG proprietary software collect spectral information after the sample is sent. When the photochromic material is activated, the position of the polarizers are rotated back and forth to polarize the light from the monitoring light source into the 90 ° polarization plane and back. Data was collected at 5 second intervals for approximately 600-1200 seconds during activation. For each test, the rotation of the polarizer was adjusted to collect data for the following sequence of polarization planes: 0 °, 90 °, 90 °, 0 °, etc.

Absorption spectra were obtained and each test sample was analyzed using IgorPro software (obtained from WaveMetrics). The change in absorbance for each test sample in each polarization direction was calculated at each test wavelength of the sample minus the 0-time (i.e., unactivated) absorbance measurement. For each sample, the average absorbance value is obtained by averaging the absorbance in the activation profile region for each time interval in the region where the photochromic response of the photochromic compound is saturated or nearly saturated (i.e., the region where the measured absorbance does not increase or does not increase significantly over time). In a direction corresponding to λ_max-visThe average absorbance values in a predetermined wavelength range of +/-5nm are extracted at 0 ° and 90 ° polarizations, and the absorbance ratio for each wavelength in this range is calculated by dividing the small average absorbance by the larger average absorbance. For each extracted wavelength, 5-100 data points were averaged. The average absorption ratio of the photochromic compound is then calculated by averaging the individual absorption ratios.

The change in optical density (Δ OD) from bleached to darkened state is determined as follows: the initial transmittance was established and the baffle of the xenon lamp was opened to provide ultraviolet radiation to change the test lens from a bleached state to an activated (i.e., darkened) state. Data is collected at selected time intervals, the transmittance of the activated state is measured, and the transmittance is measured according to the formula: Δ OD = log (% Tb/% Ta) the change in optical density is calculated, where% Tb is the percent transmission in the bleached state,% Ta is the percent transmission in the activated state, and the base of the logarithm is 10. The measurements are made over a range of metrology wavelengths corresponding to CIEY, which is described in cietechnical report, colorometry, CIE 15: 2004, 3 rd edition, published by Commission International Del' Eclairage, Vienna, Austria, which publication is incorporated herein by reference.

The fade half-life (T1/2) is the time interval (seconds) for the photochromic compound in activated form in the test sample to reach a Δ OD that is half the Δ OD measured at 15 minutes or after saturation or near saturation is achieved after removal of the activating light source, e.g., by closing the shutter, at room temperature. The results of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 1. Each of examples 1-4 had a Δ OD greater than comparative examples 1-4 and the% transmission (% Ta) of the activated substrate was less than comparative examples 1-4, as expected. The presence of the photochromic compound in both the primer layer and the topcoat of examples 3 and 4 exhibited a greater Δ OD and a lesser% Ta than examples 1 and 2 and comparative examples 1-4. The "X" in the columns in table 1 indicates the presence of photochromic compounds in the primer and/or topcoat.

Table 1-photochromic performance and absorption ratio of the coating stacks of examples 1-4 and comparative examples 1-4

The invention has been described with reference to specific details of specific embodiments thereof. It is not intended that such details 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

1. A photochromic article comprising:

a substrate;

a primer layer comprising a first photochromic compound, the primer layer being on the substrate, and the first photochromic compound having a first unactivated state absorbance of greater than 0 at all wavelengths from 340nm to 380nm, and a first unactivated state end minimum absorbance wavelength of greater than 380 nm; and

a coating layer comprising a photochromic-dichroic compound, said coating layer being disposed on said primer layer, and said photochromic-dichroic compound having a second unactivated state absorbance greater than 0 at least a portion of wavelengths from 340nm to 380nm, and a second unactivated state end minimum absorbance wavelength greater than 340nm,

wherein the second unactivated state end minimum absorbance wavelength is less than or equal to the first unactivated state end minimum absorbance wavelength.

2. The photochromic article of claim 1 wherein said second unactivated state terminal minimum absorbance wavelength is greater than 380 nm.

3. The photochromic article of claim 1 wherein said second unactivated state absorbance is greater than 0 at all wavelengths from 340nm to 380nm and said second unactivated state end minimum absorbance wavelength is greater than 380 nm.

4. The photochromic article of claim 1, wherein said first unactivated state terminal minimum absorbance wavelength is greater than 380nm and less than or equal to 450nm and said second unactivated state terminal minimum absorbance wavelength is greater than 340nm and less than or equal to 450 nm.

5. The photochromic article of claim 1, wherein said second unactivated state terminal minimum absorbance wavelength is less than said first unactivated state terminal minimum absorbance wavelength.

6. The photochromic article of claim 1 wherein said photochromic article has an unactivated state percent transmission of less than 5% at all wavelengths from 340nm to 380 nm.

7. The photochromic article of claim 1 wherein the activated state optical density of said photochromic article is greater than the control activated state optical density of a control photochromic article comprising said substrate and said coating layer but lacking said primer layer.

8. The photochromic article of claim 7 wherein said activated state optical density and said control activated state optical density are both determined from 410nm to 800 nm.

9. The photochromic article of claim 1, wherein said primer layer further comprises an organic matrix comprising polyurethane linkages.

10. The photochromic article of claim 1, wherein said photochromic-dichroic layer further comprises an anisotropic material.

11. The photochromic article of claim 10 wherein said anisotropic material comprises a liquid crystal material.

12. The photochromic article of claim 1, wherein said photochromic-dichroic compound is at least partially aligned.

13. The photochromic article of claim 1 wherein said photochromic-dichroic layer further comprises a phase-separated polymer comprising:

an at least partially ordered matrix phase, and

an at least partially ordered guest phase,

wherein the guest phase comprises the photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the guest phase.

14. The photochromic article of claim 1 wherein said photochromic-dichroic layer further comprises an interpenetrating polymer network comprising:

an anisotropic material that is at least partially ordered, and

a polymeric material, which is a mixture of a polymeric material,

wherein the anisotropic material comprises the photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the anisotropic material.

15. The photochromic article of claim 1, wherein said photochromic-dichroic layer further comprises at least one additive selected from the group consisting of: dyes, orientation promoters, dynamic enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical quenchers, and adhesion promoters.

16. The photochromic article of claim 1, wherein said photochromic-dichroic layer further comprises at least one dichroic material selected from the group consisting of: azomethine, indigoid, thioindigoid, merocyanine, indane, quinophthalone dyes, perylene, phthalin, triphenodioxazine, indoloquinoxaline, imidazotriazine, tetrazine, azo and polyazo dyes, benzoquinone, naphthoquinone, anthraquinone and polyanthraquinone, anthrapyrimidinone, iodine and iodate.

17. The photochromic article of claim 1, wherein the first photochromic compound and the photochromic-dichroic compound are each independently selected from indeno-fused naphthopyrans, naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, spirofluoreno [1,2-b ] pyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, spiropyrans, benzoxazines, phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) fluoranthenoxazines, spiro (indoline) quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof.

18. The photochromic article of claim 1, further comprising an alignment layer interposed between said primer layer and said photochromic-dichroic layer, and said photochromic-dichroic compound is at least partially aligned.

19. The photochromic article of claim 1 further comprising a topcoat layer comprising an ultraviolet light absorber, wherein said topcoat layer is disposed over said photochromic-dichroic layer.

20. The photochromic article of claim 19 further comprising a hard coat layer, wherein said hard coat layer is disposed on said topcoat layer.

21. The photochromic article of claim 1 wherein said photochromic article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, and active liquid crystal cell articles and passive liquid crystal cell articles.

22. The photochromic article of claim 21 wherein said photochromic article is selected from the group consisting of ophthalmic articles and said ophthalmic articles are selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.

23. The photochromic article of claim 21 wherein said photochromic article is selected from the group consisting of display articles, and said display article is selected from the group consisting of screens, monitors, and security elements.

24. The photochromic article of claim 1 wherein the substrate is selected from the group consisting of an uncolored substrate, a colored substrate, a photochromic substrate, a colored-photochromic substrate, and a linearly polarizing substrate.

25. A photochromic article comprising:

a substrate;

a topcoat layer comprising a second photochromic compound, the topcoat layer being disposed on the photochromic-dichroic layer, and the second photochromic compound having a third unactivated state absorbance greater than 0 at least a portion of the wavelengths from 330nm to 380nm, and a third unactivated state terminal minimum absorbance wavelength greater than 330nm,

wherein the third unactivated state end minimum absorbance wavelength is less than the second unactivated state end minimum absorbance wavelength and the second unactivated state end minimum absorbance wavelength is less than or equal to the first unactivated state end minimum absorbance wavelength.

26. The photochromic article of claim 25 wherein said second unactivated state terminal minimum absorbance wavelength is greater than 380 nm.

27. The photochromic article of claim 25, wherein said second unactivated state absorbance is greater than 0 at all wavelengths from 340nm to 380nm and said second unactivated state end minimum absorbance wavelength is greater than 380 nm.

28. The photochromic article of claim 25 wherein,

the first unactivated state end minimum absorbance wavelength is greater than 380nm and less than or equal to 450nm,

said second unactivated state end minimum absorbance wavelength is greater than 340nm and less than or equal to 450nm, and

the third unactivated state end minimum absorbance wavelength is greater than 330nm and less than 380 nm.

29. The photochromic article of claim 28 wherein,

the third unactivated state absorbance is greater than 0 at least a portion of wavelengths from 330nm to less than 370nm, and

the third unactivated state end minimum absorbance wavelength is greater than 330nm and less than 370 nm.

30. The photochromic article of claim 25, wherein said second unactivated state terminal minimum absorbance wavelength is less than said first unactivated state terminal minimum absorbance wavelength.

31. The photochromic article of claim 25 wherein said photochromic article has a percent transmittance in the unactivated state of less than 5% at all wavelengths from 340nm to 380 nm.

32. The photochromic article of claim 25, wherein said first photochromic compound, said photochromic-dichroic compound, and said second photochromic compound are each independently selected from the group consisting of indeno-fused naphthopyrans, naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, spirofluoreno [1,2-b ] pyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, spiropyrans, benzoxazines, phenoxazines, spiro (indolino) phenoxazines, spiro (indolino) pyridobenzoxazines, spiro (indolino) fluoranthenoxazines, spiro (indolino) quinolinooxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds and non-thermally reversible photochromic compounds and mixtures thereof.

33. The photochromic article of claim 25, wherein said topcoat further comprises an ultraviolet light absorber.