photochromic article

专利摘要:
PHOTOCHROMIC ARTICLE. Photochromic articles are provided that include a substrate, a primary layer that includes a first photochromic compound, and a photochromic-dichroic layer on top of the primary layer that includes a photochromic-dichroic compound. The first photochromic compound and the photochromic-dichroic compound are each selected so that the dichroic photochromic compound has a minimum terminal wavelength in an inactivated state that is less than or equal to the minimum terminal absorbance in an inactivated state of the first photochromic compound. underlying. Photochromic articles additionally include a top coat layer over the photochromic-dichroic layer. The top coating layer can include a second photochromic compound that has a wavelength of minimum terminal absorbance in an inactivated state that is less than the wavelength of minimum terminal absorbance in an inactivated state of the underlying photochromic-dichroic compound. Photochromic articles provide, for example, a combination of linear polarizing properties, and reduce the percentage of transmittance of ultraviolet light and / or visible light when in an inactivated state, such as when exposed to sufficient actinic light.
公开号:BR112013031234B1
申请号:R112013031234-3
申请日:2011-11-16
公开日:2021-01-26
发明作者:Anil Kumar；Rachael L. Yoest；Chenguang Li；Delwin S. Jackson；Henry Nguyen
申请人:Transitions Optical, Inc.；
IPC主号:

专利说明:

[0001] [001] The present invention relates to photochromic articles that include a substrate, a primary layer that includes a first photochromic compound, and a photochromicadichrome layer on the primary layer that includes a photochromic-dichroic compound, in which the first photochromic compound and the photochromic-dichroic compound are each selected from that aforementioned photochromic-dichroic compound having a wavelength of the minimum terminal absorbance in an inactivated state that is less than the wavelength of the minimum terminal absorbance in an inactivated state of the first underlying photochromic compound. Background of the invention
[0002] [002] Conventional linearly polarizing elements, such as linearly polarizing lenses for sunglasses and linearly polarizing filters, are typically formed from stretched polymeric sheets containing a dichroic material, such as a dichroic dye. Consequently, conventional linearly polarizing elements are static elements having a unique linearly polarizing state. Consequently, when a linearly polarizing element is exposed to both randomly polarized radiation and reflected radiation of the appropriate wavelength, some percentage of the radiation transmitted through the element will be linearly polarized.
[0003] [003] Additionally, conventional linearly polarizing elements are typically dyed elements. That is, the conventional linearly polarizing elements contain a coloring agent and have an absorption spectrum that does not vary in response to actinic radiation. The color of the conventional linearly polarizing element will depend on the color of the coloring agent used to form the element and, more commonly, is a neutral color (for example, brown or gray). Thus, although linearly polarizing elements are useful for reducing reflected light shine, because of their tinting, they are not well suited for use under certain low light conditions. Furthermore, because conventional linearly polarizing elements have only a single linearly dyed polarizing state, they are limited in their ability to store or display information.
[0004] [004] Conventional linearly polarized elements are typically formed using sheets of stretched polymeric films containing a dichroic material. Correspondingly, although the dichroic materials are preferably capable of absorbing one of two polarized components of orthogonal planes of transmitted radiation, if the molecules of the dichroic material are not properly positioned or arranged, no net linear polarization of the transmitted radiation will be achieved. Without being linked to the theory, it is believed that this occurs due to the random positioning of the molecules of dichroic material, the selective absorption by individual molecules will cancel each one, in such a way that no net or global linear polarizing effect is achieved. Therefore, it is typically necessary to position or arrange the molecules of the dichroic material by aligning with another material in order to achieve a liquid linear polarization.
[0005] [005] A common method for aligning the molecules of a dichroic dye involves heating a sheet or layer of poly (vinyl alcohol) ("PVA") to soften the PVA and then stretching the sheet to guide the polymer chains of PVA. After that, the dichroic dye is impregnated in the stretched sheet, and the impregnated dye molecules adopt the orientation of the polymeric chains. That is, at least some of the dye molecules become aligned, so that the longitudinal geometric axis of each dye molecule is generally parallel to the oriented polymeric chains. Alternatively, the dichroic dye can first be impregnated in the PVA sheet and, after that, the sheet can be heated and stretched as described above to guide the polymeric PVA chains and the associated dye. In this way, the dichroic dye molecules can be properly positioned or arranged within the oriented polymeric chains of the PVA sheet, and a linear liquid polarization can be achieved accordingly. As a result, the PVA sheet can be made to linearly polarize the transmitted radiation and, correspondingly, a linearly polarizing filter can be formed.
[0006] [006] In contrast to the dichroic elements discussed above, conventional photochromic elements, such as photochromic lenses that are formed using thermally reversible photochromic materials, are generally capable of converting from a first state, for example, a "clear state", to a second state, for example, a "colored state", in response to actinic radiation, and revert back to the first state in response to thermal energy. Thus, conventional photochromic elements are generally well suited for use in both low light and bright conditions. However, conventional photochromic elements that do not include linearly polarizing filters are generally not adapted to linearly polarize radiation. The absorption ratio of conventional photochromic elements, in any state, is generally less than two. Therefore, conventional photochromic elements cannot reduce the brightness of the reflected light to the same extent as conventional linearly polarizing elements. In addition, conventional photochromic elements have a limited capacity to store or display information.
[0007] [007] Photochromic-dichroic compounds and materials have been developed in order to provide both photochromic and dichroic properties, if properly and, at least sufficiently aligned. When in a colored or darkened state, such as when exposed to actinic light, photochromic-dichroic compounds, however, typically have a higher percentage of transmittance than conventional or non-polarizing photochromic compounds at equivalent concentrations and in sample thickness. Although it is not intended to be linked to any theory, and based on the evidence at hand, it is believed that the increased percentage of transmittance of photochromicdichroic materials in the darkened or colored state is due to the percentage of transmittance being an average of the two polarized components in the plane orthogonal view of polarized radiation. A photochromic-dichroic material will more strongly absorb one of the two polarized components in the orthogonal plane of random radiation incidence, resulting in one of the planes of transmitted polarized light (passing through and out of the sample) having a higher percentage of transmittance than another polarized component in orthogonal plane. The average of two polarized components in an orthogonal plane typically results in a percentage of average transmittance of greater amplitude. In general, when a linearly polarizing efficiency, which can be quantified in terms of proportion and absorption, of photochromic-dichroic compounds increases, the percentage of transmittance associated with them also increases.
[0008] [008] 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 reduce the percentage of transmittance when in a colored or darkened state, such as when exposed to actinic light. Summary of the invention
[0009] [009] According to the present invention, a photochromic article is provided comprising a substrate and at least two layers thereof, including a primary layer positioned on the substrate, and a photochromic-dichroic layer positioned on the primary layer.
[0010] [010] The primary layer comprises a first photochromic compound having a first absorbance in an inactivated state greater than 0 at wavelengths from 340 nm to 380 nm, and a first wavelength of the minimum terminal absorbance in an inactive state greater than 380 nm.
[0011] [011] The photochromic-dichroic layer comprises a photochromic-dichroic compound having a second absorbance in an inactivated state greater than 0 over at least a portion of wavelengths from 340 nm to 380 nm, and a second wavelength of the minimum terminal absorbance in an inactivated state greater than 340 nm.
[0012] [012] The second wavelength of minimum terminal absorbance in an inactivated state (of the photochromic dichroic compound) is less than or equal to that of the first wavelength of minimum terminal absorbance in an inactivated state (of the first underlying photochromic compound).
[0013] [013] According to a further embodiment of the present invention, a photochromic article is provided that includes a substrate and at least three layers on it including, a primary layer that is positioned on the substrate, a photochromic-dichroic layer that is positioned on the primary layer, and a top coat layer that is positioned over the photochromic-dichroic layer.
[0014] [014] The primary layer includes a first photochromic compound having a first absorbance in an inactivated state greater than 0 and all wavelengths from 340 nm to 380 nm, and a first wavelength of the minimum terminal absorbance in an inactivated state greater than 380 nm.
[0015] [015] The photochromic-dichroic layer comprises a photochromic-dichroic compound having a second absorbance in an inactivated state greater than 0 over at least a portion of the wavelengths from 340 nm to 380 nm, and a second wavelength of the minimum terminal absorbance in an inactivated state greater than 340 nm.
[0016] [016] The top coating layer, of at least one three-layer embodiment, includes an optional ultraviolet light absorber, and a third inactivated absorbance greater than 0 over at least a portion of wavelengths from 330 nm to 380 nm, and a third length of minimum terminal absorbance in inactivated state greater than 330 nm.
[0017] [017] With an embodiment of at least three layers, the third wavelength of the minimum terminal absorbance in an inactivated state (of the second photochromic compound and the upper coating layer) is less than that of the second wavelength of the minimum terminal absorbance in inactivated state (of the photochromic-dichroic compound of the underlying coating layer), and the second wavelength of the minimum terminal absorbance in inactivated state (of the photochromic-dichroic compound of the coating layer) is less than or equal to that of the first wavelength minimum terminal absorbance (of the first photochromic compound in the underlying primary layer). Brief description of the drawings
[0018] [018] Figure 1 is a side cross-sectional view representative of a photochromic article according to the present invention, which includes graphical representations of the absorbance points versus the wavelength of the first photochromic compound of the primary layer, of the photochromic compound -dichroic of the photochromic-dichroic layer, and of the second photochromic compound of the upper coating layer;
[0019] [019] Figure 2 illustrates a graphical representation of the average delta absorbance as a function of wavelength (over a region of visible wavelength after activation with actinic radiation), and represents two mean differences in the absorption spectra obtained in two planes orthogonal to a photochromic-dichroic layer that includes a photochromic-dichroic compound that can be included in the photochromic articles of the present invention; and
[0020] [020] Figure 3 illustrates a graphical representation of element 41 in figure 1, in which the range of the y-axis has been changed from 0 to 3.5 (Figure 1) from 0 to 0.1 (Figure 3), for the purpose to better illustrate the absorbance versus the points of the wavelength. Detailed description of the invention
[0021] [021] As used here, the term "actinic radiation" means electromagnetic radiation that is capable of causing a response in a material, so that, but not limited to, transformation of a photochromic material from one form or state to another form or state, as will be discussed in further detail below.
[0022] [022] As used here, the term "photochromic" and similar terms, such as "photochromic compound" mean an absorption spectrum for at least one visible radiation that varies in response to the absorption of at least one actinic radiation. Furthermore, as used here, the term “photochromic material” means any substance that is adapted to have photochromic properties (that is, adapted to have an absorption spectrum for at least one visible radiation that varies in response to the absorption of at least one radiation actinic) and that includes at least one photochromic compound.
[0023] [023] As used here, the term “photochromic compound” includes thermally reversible photochromic compound and non-thermally reversible photochromic compound. The term "thermally reversible photochromic compound / material" as used here means a compound / material capable of converting from a first state, for example, a "transparent" state, to a second state, for example, a "colored state", in response to actinic radiation, and revert back to the first state in response to thermal energy. The term "non-thermally reversible photochromic compound / material" as used here means a compound / material capable of converting from a first state, for example, a "transparent state", to a second state, for example, "a colored state", in response to actinic radiation, and revert back to the first state in response to actinic radiation of substantially the same wavelength as that of the absorption of the colored state (e.g., discontinuous exposure to said actinic radiation).
[0024] [024] As used here, the term "dichroic" means capable of absorbing one of two polarized components from orthogonal planes of at least one radiation transmitted more strongly than the other.
[0025] [025] As used here, the term “photochromic-dichroic” and similar terms such as “photochromic-dichroic materials” and “dichroic photochromic compounds” mean materials and compounds that have and / or provide both photochromic properties (ie having an absorption spectrum for at least one visible radiation that varies in response to at least one actinic radiation), and dichroic properties (ie, capable of absorbing one of two polarized components in the orthogonal plane of at least one radiation transmitted more strongly than than another).
[0026] [026] As used here, As used here the term "absorption ratio" refers to the absorption ratio of linearly polarized radiation in the foreground to the absorption of radiation of the same wavelength polarized linearly in a plane orthogonal to the foreground , and the foreground is taken as the plane with the highest absorption.
[0027] [027] As used here, to modify the term "state", the terms "first" and "second" are not intended to refer to any particular order or chronology, but instead refer to two different conditions or two different properties . For the non-limiting purpose of the illustration, the first state and the second state of the photochromic-dichroic compound of the photochromic-dichroic layer may differ with respect to at least one optical property, such as, but not limited to, the linear absorption or polarization of visible radiation and / or of UV radiation. Thus, according to several non-limiting embodiments described here, the photochromic-dichroic compound of the photochromic-dichroic layer can have a different absorption spectrum in each, in the first and in the second state. For example, although not limiting here, the photochromic-dichroic compound of the photochromic-dichroic layer can be transparent in the first state and colored in a 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. Furthermore, as discussed below, in more detail, the photochromic-dichroic compound of the photochromic-dichroic layer can be non-linearly polarized (or “non-polarized”) in the first state, and linearly polarized in the second state.
[0028] [028] As used here, the term "optical" means belonging to or associated with light and / or vision. For example, according to various non-limiting embodiments described here, the optical article or optical element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and cell articles. active or passive liquid crystal, elements and devices.
[0029] [029] As used here, the term "ophthalmic" means belonging to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective lenses and non-corrective lenses, including single vision or multivision, which can be multivision or segmented or non-segmented lenses (such as, but not limited to bifocal lenses, trifocal lenses and progressive lenses) , as well as other elements used to correct, protect or intensify (cosmetically or otherwise) vision, including without limitation, contact lenses, intraocular lenses, magnification lenses, and protective lenses or visors.
[0030] [030] As used here, the term "ophthalmic substrate" means lenses, partially formed lenses, and white lenses.
[0031] [031] As used here, the term “display” means the representation of information visible or read by machine in words, numbers, symbols, designs or drawings. Non-limiting examples of items, display elements and devices, include screens, monitors and security elements, such as security tags.
[0032] [032] As used here, the term "window" means an opening adapted to allow the transmission of radiation through it. Non-limiting examples of windows include automotive and aeronautical transparencies, filters, shutters, and optical switches.
[0033] [033] As used here the term "mirror" means a surface that specifically reflects a large fraction of incident light.
[0034] [034] As used here the term "liquid crystal cell" refers to a structure containing a liquid crystal material that is capable of being ordered. Active liquid crystal cells are cells where the liquid crystal material is capable of being reversibly and controllably switched or converted between states, ordered and disordered, or between two ordered states, through the application of an external force, such as electric fields or magnetic. Passive liquid crystal cells are cells where the liquid crystal material maintains an ordered state. A non-limiting example of an active liquid crystal cell element or device is a liquid crystal display.
[0035] [035] As used here, the term "coating" means a supported film derived from a fluid composition, which may or may not have a uniform thickness and, specifically, exclude polymeric sheets. The primary layer, the photochromic-dichroic layer and the optional topcoat layer of the photochromic articles of the present invention can, in some embodiments, each be independently a coating.
[0036] [036] As used here, the term "foil" means a pre-formed film having a generally uniform thickness and capable of self-supporting.
[0037] [037] As used here, the term "connected to" means direct contact with an object or indirect contact with an object through one or more other structures or materials, at least one of which is in direct contact with the object . For the purpose of non-limiting illustration, the primary layer, for example, may be in direct contact (for example, abutting) with at least a portion of the substrate or it may be in indirect contact with at least one portion of the substrate through one or more other interposed structures or materials, such as a monomolecular layer of a coupling agent or adhesive. For example, although not limiting here, the primary layer may be in contact with one or more of the other interposed coatings, polymeric sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate.
[0038] [038] As used here, the term "photosensitive material" means materials that respond physically or chemically to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.
[0039] [039] As used here, the term "non-photosensitive materials" means materials that do not physically or chemically respond to electromagnetic radiation, including, but not limited to, static dyes.
[0040] [040] As used here, the molecular weight values of the polymers, such as the average molecular weight (Mw) and the average molecular weight (Mn), are determined by means of gel permeation chromatography using appropriate standards, such as polystyrene standard.
[0041] [041] As used here, the polydispersity value index (PDI) represents a ratio of the average molecular weight (Mw) to the average number of the molecular weight (Mn) of the polymer (ie Mw / Mn).
[0042] [042] As used here, the term "polymer" means homopolymers (for example, prepared from a single monomer species), copolymers (for example, prepared from at least two monomer species), and polymeric graft.
[0043] [043] As used here, the term "(meth) acrylate" and similar terms, such as "(meth) acrylic acid ester" means methacrylates and / or acrylate. As used herein, the term "(meth) acrylic acid" means methacrylic acid and / or acrylic acid.
[0044] [044] Unless otherwise indicated, all ranges or ratios described herein are to be understood to encompass any and all sub-ranges or sub-ratios sub-summed here. For example, a range or proportion declared from "1 to 10" should be considered including any and all sub-ranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all sub-ranges or sub-proportions belonging to the minimum value of 1 or more and ending with a maximum value of 10 or less, such as, but not limited to 1 to 6.1; 3.5 to 7.8; and 5.5 to 10.
[0045] [045] As used herein and in the claims, unless otherwise stated, left-to-right representations of linker groups, such as divalent linker groups, are inclusive of other appropriate guidelines, such as, but not limited to, right to left orientation. For the non-limiting purpose of the illustration, the left-to-right representation of the divalent link group
[0046] [046] As used here, the articles "one", "one", "o", "a" include reference to the plural unless otherwise expressly and unequivocally limited to a reference.
[0047] [047] As used here, the term “a first photochromic compound” means at least one photochromic compound. When two or more first photochromic compounds are present, they together have and provide a first (for example, medium) first length of the absorbance peak, a (for example, medium) first inactivated state absorbance greater than 0 over a length range of particular wave, a (for example, a medium) first wavelength of minimum terminal absorbance in an inactivated state, and a (for example, medium) first wavelength of minimum terminal absorbance in an inactivated state.
[0048] [048] As used here, the term “a photochromic-dichroic compound” means at least one photochromic-dichroic compound. When two or more photochromic dichroic compounds are present, they together have and provide one (for example, medium) second wavelength of the inactivated peak in an inactivated state, one (for example, medium) second inactivated absorbance greater than 0 over a particular wavelength range, one (for example, medium) second wavelength of the minimum terminal absorbance in an inactivated state, and one (for example, medium) second wavelength of the initial minimum absorbance in an inactivated state.
[0049] [049] As used here, the term "a second photochromic compound" means at least one second photochromic compound. When two or more photochromic compounds are present, they together have and provide a third (for example, medium) absorbance peak in an inactivated state, a (for example, medium) third wavelength of the absorbance in an inactivated state greater than 0 over a particular wavelength range, one (for example, medium) second wavelength of the minimum terminal absorbance in an inactivated state, and one (for example, medium) third wavelength of the initial minimum absorbance in an inactivated state; and a (for example, medium) third wavelength of the minimum initial absorbance in an inactivated state.
[0050] [050] As used here, the term “inactivated state” with respect to photochromic compounds, such as the first photochromic compound, the photochromic-dichroic compound and the second photochromic compound, means that the photochromic compound has been exposed to actinic radiation having sufficient energy to result in the photochromic compound having or producing: (i) measurable absorbance at wavelengths greater than or equal to 330 nm and less than or equal to 450 nm, such as less than or equal to 430 nm or less than or equal to 410 nm; and (ii) minimally or substantially non-measurable absorbance at wavelengths greater than 450 nm.
[0051] [051] As used here, the term “activated state” with respect to photochromic compounds, such as the first photochromic compound, the photochromic-dichroic compound and the second photochromic compound, and photochromic articles, means that the photochromic compound and / or photochromic article was exposed to actinic radiation having enough energy to result in the photochromic compound and / or photochromic article having or producing: (i) measurable absorbance at wavelengths greater than or equal to 300 nm and less than or equal to 450 nm, such as less than or equal to 430 nm or less than or equal to 410 nm; and (ii) measurable absorbance at wavelengths greater than 450 nm.
[0052] [052] As used here, the term “a first absorbance in an inactivated state greater than 0” over a given wavelength range, such as “above all wavelengths from 340 nm to 380 nm” means that the compound photochromic has an inactivated state absorbance greater than 0 over a certain wavelength range, as in all wavelengths from 340 nm to 380 nm.
[0053] [053] As used here, the term "a first wavelength of the absorbance peak in an inactivated state" means the wavelength at which the first photochromic compound (from the first primary layer), in an inactivated state, has a peak ( or maximum) of absorbance. The first wavelength of the absorbance peak in an inactivated state resides between 340 nm and 380 nm.
[0054] [054] As used here, the term “a first wavelength of the minimum terminal absorbance in an inactivated state” means that the wavelength at which the first photochromic compound (of the primary layer), in an inactivated state, has a minimum absorbance (or higher) terminal. The first wavelength of minimum terminal absorbance in an inactivated state is a wavelength greater than the first wavelength of the absorbance peak in an inactivated state.
[0055] [055] As used here, the term "a first wavelength of the minimum terminal absorbance in an inactivated state" means that the wavelength at which the first photochromic compound (of the primary layer), in an inactivated state, has an initial absorbance (or lower). The first wavelength of minimum absorbance in an inactivated state is a wavelength shorter than the first wavelength of the absorbance peak in an inactivated state.
[0056] [056] As used here, the term "a second absorbance in an inactivated state greater than 0" over a given wavelength range, such as "over at least a portion of wavelengths from 340 nm to 380 nm" means that the photochromic-dichroic has an inactivated state greater than 0 over a given wavelength range, such as over at least a portion of the wavelengths from 340 nm to 380 nm, such as from 340 nm to 370 nm, or from 350 nm to 380 nm, or from 340 nm to 380 nm.
[0057] [057] As used here, the term “over at least a portion of length from x nm to y nm” with respect to an inactivated state absorbance greater than 0, means over at least a portion of the consecutive wavelengths within the cited range, including the upper and lower wavelength values.
[0058] [058] As used here, the term “a second wavelength of the absorbance peak in an inactivated state” means that the wavelength at which the photochromic-dichroic compound (of the coating layer, or photochromic-dichroic coating layer), in an inactivated state, has a peak (or maximum) of absorbance. The second wavelength of the absorbance peak in an inactivated state is typically between 340 nm and 380 nm.
[0059] [059] As used here, the term “a second wavelength of the minimum terminal absorbance in an inactivated state” means that the wavelength at which the photochromic-dichroic compound (of the coating layer, or of the photochromic-dichroic coating layer) ), in an inactivated state, has a minimum (or higher) terminal absorbance. The second wavelength of the minimum terminal absorbance in an inactivated state is a wavelength greater than that of the second wavelength of the absorbance peak in an inactivated state.
[0060] [060] As used here, the term “a second wavelength of the minimum terminal absorbance in an inactivated state” means that the wavelength at which the photochromic-dichroic compound (of the photochromic-dichroic layer), in an inactivated state, has minimum initial absorbance (or higher). The second wavelength of the minimum terminal absorbance in an inactivated state is a shorter wavelength than that of the second wavelength of the absorbance peak in an inactivated state and the second wavelength of the minimum terminal absorbance in an inactivated state.
[0061] [061] As used here, the term “a third terminal minimum absorbance in an inactivated state greater than 0” over a given wavelength range, such as “over a portion of the wavelength from 330 nm to 380 nm” means that the second photochromic compound has an inactivated state absorbance greater than 0 over a certain wavelength range, such as over at least a portion of the wavelength from 330 nm to 380 nm, such as from 330 nm to 370 nm, or from 340 nm to 380 nm.
[0062] [062] As used here, the term “a third wavelength of the absorbance peak in an inactivated state” means the wavelength at which the second photochromic compound (from the upper coating layer), in an inactivated state, peaks absorbance (or maximum). The third wavelength of the absorbance peak in an inactivated state typically resides between 330 nm to 380 nm.
[0063] [063] As used here, the term "a third wavelength of the minimum terminal absorbance in an inactivated state" means the wavelength at which the second photochromic compound (from the top coating layer), in an inactivated state, has an absorbance minimum (or higher). The third wavelength of the minimum terminal absorbance in an inactivated state is at a wavelength greater than the third wavelength of the absorbance peak in an inactivated state.
[0064] [064] As used here, the term “a third wavelength of the initial minimum absorbance in an inactivated state” means that the wavelength at which the second photochromic compound (of the coating layer), in an inactivated state, has an absorbance minimum (or lower) threshold. The third wavelength of the minimum terminal absorbance in an inactivated state is a shorter wavelength than that of the third wavelength of the absorbance peak in an inactivated state and the third wavelength of the minimum terminal absorbance in an inactivated state.
[0065] [065] The wavelength values of the initial minimum absorbance in an inactivated state, such as the first, second and / or third wavelength values of the initial minimum absorbance in an inactivated state, can each be affected by the analytical method. and the equipment employed, and the substrate and / or the matrix, such as the coating matrix, in which the particular photochromic compound resides (which is referred to as a “USIMAWV Affect”). USIMAWV Affect can be more pronounced when the wavelength value of the initial minimum absorbance in an inactivated state is less than 360 nm. USIMAWV Affect can be additive or subtractive, resulting in higher or lower values of the initial minimum absorbance wavelength in an inactivated state. Alternatively or additionally, USIMAWV Affect can result in wavelength values of the initial minimum absorbance in an inactivated state having negative absorbance values. In addition, USIMAWV Affect can result in fixed positive and / or negative absorbance points, in particular, in wavelength values less than 360 nm. Although it is not intended to be linked to any theory, it is believed that, in the case of organic polymeric substrates and organic polymeric coatings, USIMAWV Affect should, at least in part, in the presence of aromatic rings, on the substrates and / or coating matrix , couple with instruments with respect to subtraction. With some embodiments, when the substrates are quartz, the USIMAWV Affect can be minized. Since substrates and coatings composed of organic polymeric materials, and the subtraction with reference to the instruments were used, it is believed that the first, second and third wavelength values of the minimum initial absorbance in inactivated state (65 , 68 and 71) as described in further details here with reference to figures 1 and 3, can be submitted to USIMAWV Affect.
[0066] [066] As used here, and unless otherwise stated, the “percent transmittance” was determined using a ULSTRASCAN PRO spectrometer obtained commercially from HunterLab, according to instructions provided in the spectrometer user manual.
[0067] [067] As used here, the term "linearly polarizes" means to confine the vibrations of the electric vector of electromagnetic waves, such as light waves, to a direction or plane.
[0068] [068] In addition to the operating examples, or when otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth, used in the specification and in the claims, should be understood as modified in all examples by the term “about”.
[0069] [069] As used here, the terms spatial or directional, such as "left", "right", "internal", "external", "above", "below", and the gender, related to the invention as it is represented in the figures in the drawings. However, it should be understood that the invention can take several alternative orientations and, consequently, such terms should not be considered as limiting.
[0070] [070] As used here, the terms "formed on", "deposited on", "provided on", "applied on", "residing on", or "positioned on", mean formed, deposited, provided, applied, residents or positioned on, but not necessarily in direct (or borderline) contact with the base element, or surface of the base element. For example, a layer “positioned on” a substrate does not exclude the presence of one or more other layers, coatings, or films thereof or a composition located between the positioned or formed layer and the substrate.
[0071] [071] All documents, such as, but not limited to, granted patents and patent applications, referred to herein, and unless otherwise indicated, should be considered as “incorporated by reference” in their entirety.
[0072] [072] With reference to figure 1, and for the purpose of non-limiting illustration, a photochromic article 2, according to the present invention is described. The photochromic article 2 includes a substrate 11 having a first surface 12 and a second surface 13, on which the first 12 and second 13 surfaces are opposite each other. The first surface 12 of the substrate 11 covers the incident actinic radiation represented by the arrow 15. The photochromic article 2 further includes a primary layer 14 on (for example, borderline) to the substrate 11 and in particular, on (for example borderline) to the first surface 12 of the substrate 11. The photochromic article 2 additionally includes a photochromic-dichroic layer 17 on the primary layer 14, and an optional topcoat layer 20 on the photochromic-dichroic layer 17. The photochromic article 2 of figure 1 includes other optional layers, which will be further described here.
[0073] [073] Primary layer 14 includes a first photochromic compound having the absorbance properties represented by graph 23, which is an absorbance point versus the wavelength for the first photochromic compound in an inactivated state. More particularly, the graph 23 is obtained from the analysis of the primary layer 14 applied on the substrate 11 in the absence of other underlying and overlapping layers. With reference to graph 23 of figure 1, the first photochromic compound has a first wavelength of the absorbance peak 26 in an inactivated state, a first wavelength of the minimum terminal absorbance 29 in an inactivated state, and a first wavelength of the absorbance. initial minimum 65 in inactivated state which is not shown in graph 23, but which is less than 340 nm. The first wavelength of the minimum terminal absorbance 29 in an inactivated state of the first photochromic compound is a wavelength greater than that of the first wavelength of the absorbance peak 26 in an inactivated state. The first initial minimum absorbance wavelength 65 in an inactivated state is at a shorter wavelength than that of the first wavelength of the absorbance peak 26 in an inactivated state.
[0074] [074] For the purpose of non-limiting illustration, and with additional reference to graph 23 of figure 1, the first wavelength of the absorbance peak 26 in inactivated state of the first photochromic compound in primary layer 14 is 355 nm, the first wavelength of the minimum terminal absorbance 29 in an inactivated state is 425 nm, and the first wavelength of the initial minimum absorbance 65 in an inactivated state is 333 nm (not shown).
[0075] [075] The wavelength values of the minimum terminal absorbance in activated state of the photochromic compounds and the photochromic-dichroic compounds of the photochromic articles of the present invention can be determined according to methods known in the art. In some embodiments, the activated state absorbance of the dichroic photochromic and photochromic compounds clearly drops to zero, and the zero-point wavelength is recorded. In other embodiments, the inactivated state absorbance of the photochromic compounds and the photochromic-dichroic compound drops to a minimum fixed value, which may not reach an absorbance measure of zero. In the case of a minimum fixed value, the wavelength value of the minimum terminal absorbance in an inactivated state is typically estimated. For the purposes of non-limiting illustration and with reference to figure 3, the third terminal minimum absorbance wavelength 47 in inactivated state is estimated by line extension, represented by the dotted line 62, from the linear portion 56 of the absorbance versus dashes the wavelength that remains to the left of (that is, at a shorter wavelength in relation to) the inflection point 59 of the trace. The point at which the extended line 62 intersects with the x-axis is recorded as the third wavelength value of the minimum terminal absorbance in an inactivated state. The wavelength points of the minimum terminal absorbance in the estimated inactivated state and the values as described can be determined by calculation (typically using a graphic computer program) or manually (for example, using an administrator). Unless otherwise indicated, the wavelength points of the minimum terminal absorbance in estimated inactivated state and values plotted and discussed with reference to figure 1 were manually determined.
[0076] [076] The wavelength values of the initial minimum absorbance in inactivated state can be estimated according to a method similar to that described with respect to the wavelength values of the terminal minimum absorbance. A line is extended from a linear portion of the absorbance versus wavelength traces that remains to the right of (that is, at the longest wavelength in relation to) the lower inflection point of the trace. With some embodiments, the initial minimum absorbance in an inactivated state clearly occurs at a zero absorbance value along the x-axis, and as such, cannot be estimated.
[0077] [077] The photochromic-dichroic layer 17 of the photochromic article 2 includes a photochromic-dichroic compound having absorbance properties represented by graph 32, which is a sketch of the absorbance versus the wavelength of the photochromic-dichroic compound. More particularly, Graph 32 is obtained from the analysis of the photochromic-dichroic compound 17 applied to substrate 11 in the absence of other underlying or overlapping layers. With reference to graph 32 in figure 1, the photochromic-dichroic compound has a second wavelength of the absorbance peak 35 in an inactivated state, the second wavelength of the minimum terminal absorbance 38 in an inactivated state, and the second initial minimum absorbance 68 in inactivated state. The second wavelength of the initial minimum absorbance 38 in an inactivated state of the photochromic-dichroic compound is a wavelength greater than that of the second wavelength of the absorbance peak 35 of the same. The second wavelength of the initial minimum absorbance 68 of the inactivated state of the photochromic-dichroic compound is a wavelength shorter than that of the second wavelength of the absorbance peak 35.
[0078] [078] For the purpose of non-limiting illustration, and with additional reference to graph 32 of figure 1, the second wavelength of the inactivated peak absorbance 35 of the photochromic-dichroic compound of the photochromic-dichroic layer 17 is 360 nm , the second wavelength of the minimum terminal absorbance in the inactivated state 38 is 417 nm, and the second wavelength of the initial minimum absorbance 68 in the inactivated state is 342 nm.
[0079] [079] The optional topcoat layer 20 of the photochromic article 2 may in some embodiments of the present invention include a second photochromic compound having absorbance properties represented by graph 41, which is an outline of the absorbance versus wavelength of the second photochromic compound. More particularly, the graph 41 is obtained from the analysis of the top coat layer 20 applied to the substrate 11 in the absence of other underlying or overlapping layers. With reference to graph 41 of figure 1 and figure 3, the second photochromic compound has a third absorbance peak in an inactivated state 44, a third wavelength length of the minimum terminal absorbance 47 in an inactivated state, and a third wavelength of the initial minimum absorbance 71, in inactivated state. The third wavelength of the minimum terminal absorbance 47 in an inactivated state of the second photochromic compound is at a wavelength greater than the third wavelength of the initial minimum absorbance peak 44 of the same. The third initial minimum absorbance wavelength 71 is at a lower wavelength shorter than the third wavelength of the absorbance peak 44 in an inactivated state.
[0080] [080] For the purpose of non-limiting illustration, and with additional reference to graph 41 of figure 1 and figure 23, the third wavelength of the absorbance peak 44 in inactivated state of the second photochromic compound of the top layer 20 is 364 nm, the minimum terminal absorbance wavelength in inactivated state 47 is 386 nm, and the third minimum initial wavelength in inactivated state 71 is 346 nm. In figure 3, the line or dotted line 74 is believed to be the result of the polymeric matrix of the top coating layer and / or the substrate, and is not believed to be the result of (or due to) the second photochromic compound. As such, stippling 74 is not considered when determining the third wavelength of the absorbance peak in an inactivated state, the third wavelength of the minimum terminal absorbance in an activated state, or the third wavelength of the initial minimum absorbance in an inactivated state. of the second photochromic compound of the upper coating layer.
[0081] [081] Graph 41 in figure 1 and 3 is the same, but the y-axis of graph 41 in figure 2 extends from 0 to 0.1, preferably from 0 to 3.5 as in figure 1, for the purpose of better illustrating and determining the peak value, the terminal minimum value, and initial minimum valleys associated with the second photochromic compound of the upper coating layer.
[0082] [082] Graphs 23, 32, and 41 in figure 1 and graph 41 in figure 2 each represent absorbance as a function of the wavelength from 340 nm to 4620 nm. As previously mentioned here, figure 1 and figure 3, including graphics 23, 32 and 41, are referred to for the purpose of non-limiting illustration. As such, the absorbance of the first photochromic compound, the first photochromic compound, the photochromic-dichroic compound, and the second photochromic compound in each case is not limited to that shown in figure 1 and figure 3.
[0083] [083] The first photochromic compound of the primary layer has a first absorbance in an inactivated state greater than 0 and all wavelengths from 340 nm to 380 nm, and the first wavelength of the minimum terminal absorbance in an inactivated state is greater than 380 nm. With some embodiments, the first photochromic compound of the first primary layer has a first absorbance in an inactivated state greater than 0 and all wavelengths from 340 nm to 400 nm, and the first wavelength of minimum terminal absorbance in an inactivated state is greater than 400 nm. With some embodiments, the first photochromic compound of the first primary layer has a first absorbance in an inactivated state greater than 0 in all wavelengths from 340 nm to 410 nm, and the first wavelength of minimum terminal absorbance in an inactivated state is greater than 410 nm. For the purpose of non-limiting illustration and with reference to graph 23 in figure 1, the first photochromic compound of the first layer 14 has a first absorbance in an inactivated state greater than 0 at all wavelengths from 340 nm to 380 nm, and a first wavelength of minimum terminal absorbance in an inactivated state that is greater than 380 nm. As previously discussed here, the first wavelength of minimum terminal absorbance in an inactivated state of the first photochromic compound of the primary layer 14 of the photochromic article 2 of figure 1 is 425 nm.
[0084] [084] The photochromic-dichroic compound of the photochromic-dichroic coating layer has a second absorbance in an inactivated state greater than 0 over at least a portion of the wavelength from 340 nm to 380 nm, and a second wavelength of the minimum absorbance terminal in an inactivated state that is greater than 340 nm. For the purpose of non-limiting illustration, the photochromic-dichroic compound can with some embodiments have: a second absorbance in an inactivated state greater than 0 over all wavelengths from 340 nm to 370 nm, and a second minimum absorbance wavelength terminal in an inactivated state that is greater than 370 nm; or a second absorbance in an inactivated state greater than 0 over all wavelengths from 350 nm to 380 nm, and a second wavelength of the minimum terminal absorbance in an inactivated state that is greater than 380 nm.
[0085] [085] With some embodiments, the photochromic-dichroic compound of the photochromic-dichroic coating layer has a second absorbance in an inactivated state greater than 0 over at least a portion of wavelength from 340 nm to 380 nm, and a second wavelength of minimum terminal absorbance in an inactivated state that is greater than 380 nm.
[0086] [086] With some additional embodiments, the photochromic-dichroic compound of the photochromic-dichroic coating layer has a second absorbance in an inactivated state greater than 0 at all (or over all) wavelengths from 340 nm to 380 nm, and a second length minimum absorbance waveform in an inactivated state that is greater than 380 nm.
[0087] [087] According to some embodiments of the present invention, the first wavelength of the minimum terminal absorbance in an inactivated state is greater than 380 nm and less than or equal to 450 nm, such as less than or equal to 440 nm, or less that or equal to 430 nm. With additional embodiments, the second minimum terminal absorbance wavelength in an inactivated state is greater than 340 nm and less than or equal to 450 nm, such as less than or equal to 440 nm, or less than or equal to 440 nm.
[0088] [088] The second wavelength of the minimum terminal absorbance in an inactivated state, with some embodiments of the present invention, is less than the first wavelength of the minimum terminal absorbance in an inactivated state.
[0089] [089] The photochromic-dichroic compound of the photochromic-dichroic layer 17 and the first photochromic compound of the underlying primary layer 14 are each selected to have the absorbance properties as described above. According to some embodiments of the present invention, they are selected so that the photochromic article has a transmittance percentage in an inactivated state of less than 5% in all lengths from 340 nm to 380 nm. The percentage of transmittance in an inactivated state at all wavelengths from 340 nm to 380 nm can, with some embodiments, be less than 4% or less than 3%, or less than 2%, or less than 1%, or less than 0.5%. With some embodiments, the percent transmittance in an inactivated state is substantially 0% at all wavelengths from 340 nm to 380 nm. The reduction or minimization of the percentage of electromagnetic radiation transmittance through the photochromic articles of the present invention at all wavelengths from 340 nm to 380 nm is desirable for the reasons including, but not limited to, protection of objects through the photochromic article, such like a human eye, for exposure to electromagnetic radiation having wavelengths from 340 nm to 380 nm. The percentage of transmittance over the aforementioned wavelength range or bands is determined according to the techniques recognized in the art using analytical equipment recognized by the state of the art and commercially available.
[0090] [090] With some additional embodiments, the photochromic article of the present invention has a transmittance percentage in an inactivated state of less than 5% at all wavelengths from 340 nm to 400 nm. The percentage of transmittance in inactivated state of all wavelengths from 340 nm to 400 nm can, with some embodiments, be less than 4% or less than 3%, or less than 2%, or less than 1%, or less than 0.5%. With some embodiments, the percentage of transmittance in an inactivated state is substantially 0% at all wavelengths from 340 nm to 400 nm. As discussed above, with respect to 340 nm to 380 nm, the reduction and minimization of the percentage of electromagnetic radiation transmittance through the photochromic articles of the present invention, at all wavelengths, from 340 nm to 400 nm is desirable for the reasons including, but not limited to, protection of objects through photochromic articles, such as a human eye, for exposure to electromagnetic radiation having odna lengths from 340 nm to 400 nm.
[0091] [091] When including the primary layer and the photochromic-dichroic layer as previously described here, the photochromic article with some embodiments of the present invention has an activated state optical density that is greater than an activated state control optical density of a photochromic article control comprising the substrate and the coating layer (ie photochromic-dichroic layer) in the absence of the primary layer. The substrate of the photochromic article and the photochromic control article are, in each case, substantially the same, and have substantially the same properties and thickness. The coating layers of the photochromic article and the photochromic control article are, in each case, substantially the same, and have substantially the same properties and thickness.
[0092] [092] Correspondingly, with the increased optical density, the photochromic articles of the present invention are typically darker, in an activated state, when exposed to the same level of incidence of actinic radiation when compared to photochromic articles, in an activated state, having, for example, a photochromic-dichroic layer containing a photochromic-dichroic compound in the absence of an underlying primary layer containing a first photochromic compound as described above.
[0093] [093] The optical density in the activated state of and the optical density in the activated state control are typically determined over at least a portion of the visible light spectrum. With some embodiments, the optical density in the activated state and the optical density in the activated state are each determined from 410 nm to 800 nm. Optical density is determined in accordance with methods recognized in the art using commercially available equipment known to the state of the art.
[0094] [094] With some embodiments, the photochromic article includes a top coat layer that remains over the photochromic-dichroic layer. The top coat layer may include an ultraviolet light absorber and / or a second photochromic compound. With some embodiments, the topcoat layer includes a second photochromic compound and, optionally, an ultraviolet light absorber. The top coat layer, with some embodiments, includes an ultraviolet light absorber and is free of photochromic compounds, such as the second photochromic compound. The top coat layer, with additional embodiments, includes a second photochromic compound and is free of an ultraviolet light absorber. The primary layer and the first photochromic compound, and the photochromic-dichroic layer and the photochromic-dichroic compound are each as previously described here.
[0095] [095] The second photochromic compound, from the primary coating layer, has a third absorbance in an inactivated state greater than 0 over at least a portion of wavelengths from 330 nm to 380 nm, and a third wavelength of minimum terminal absorbance. in inactivated state (of the second photochromic compound of the upper coating layer) less than that of the second wavelength of the minimum terminal absorbance (of the photochromic-dichroic compound of the photochromic-dichroic layer).
[0096] [096] With some embodiments, the third wavelength of minimum terminal absorbance in an inactivated state is greater than 330 nm and less than 380 nm. The third wavelength of minimum terminal absorbance in an inactivated state, with some additional embodiments, is greater than 330 nm and less than 370 nm.
[0097] [097] According to some additional embodiments of the photochromic articles of the present invention, the first wavelength of the minimum terminal absorbance in an inactivated state is greater than 380 nm and less than or equal to 450 nm; the second wavelength of minimum terminal absorbance in an inactivated state is greater than 340 nm and less than or equal to 450 nm; and the third wavelength of the minimum terminal absorbance in an inactivated state is greater than 330 nm and less than 380 nm.
[0098] [098] According to some embodiments of the photochromic articles of the present invention: the first minimum terminal absorbance wavelength in an inactivated state is greater than 380 nm and less than or equal to 450 nm; the second wavelength of the minimum terminal absorbance in an inactivated state is greater than 340 nm and less than or equal to 450 nm; and the third wavelength of the minimum terminal absorbance in an inactivated state is greater than 330 nm and less than 370 nm.
[0099] [099] The second photochromic compound of the top coating layer 20, the photochromic-dichroic compound of the photochromic-dichroic layer 17, and the first photochromic compound of the underlying primary layer 14 are each selected to have or provide absorbance properties. as described above According to some embodiments of the present invention, they are selected in such a way that the photochromic article has a percentage and transmittance in an inactivated state of less than 5% at all wavelengths from 340 nm to 380 nm. The percentage of transmittance in an inactivated state at all wavelengths from 340 nm to 380 nm may, with some embodiments, be less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%. With some embodiments, the percentage of transmittance in an inactivated state is substantially 0% at all wavelengths from 340 nm to 380 nm.
[0100] [100] With some additional embodiments, the photochromic article of the present invention, when including the top coating layer and the second photochromic compound, has an inactivated transmittance percentage of less than 5% at all wavelengths from 340 nm to 400 nm. The percentage of transmittance in an inactivated state at all wavelengths from 340 nm to 400 nm may, with some embodiments, be less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%. With some embodiments, the percentage of transmittance in an inactivated state is substantially 0% at all wavelengths from 340 nm to 400 nm.
[0101] [101] When including the top coat layer with the second photochromic compound, the photochromic-dichroic layer and the primary layer as previously described here, the photochromic article with some embodiments of the present invention has an optical density in an activated state that is greater than an activated state density control of a photochromic control article comprising the substrate and the coating layer (ie, the photochromic-dichroic layer) in the absence of both, the upper coating layer with the second photochromic compound and the primary layer. The substrate of the photochromic article and the photochromic control article are in each case substantially the same, and have substantially the same properties and thickness. The coating layer of the photochromic article and the photochromic control article are in each case substantially the same, and have substantially the same properties and thickness.
[0102] [102] Optical density in activated state and optical density in activated control state are each typically determined over at least a portion of the visible light spectrum. With some embodiments, the optical density in the activated state and the optical density in the activated state are each determined from 410 nm to 800 nm. Optical density is determined according to the state-of-the-art methods using commercially available and state-of-the-art equipment.
[0103] [103] Correspondingly, with the increased optical density, photochromic articles according to the present invention are typically dark, in an activated state, when exposed to the same level of incident actinic radiation when compared to photochromic articles, in an activated state, having, for example, a photochromic-dichroic layer containing a photochromic-dichroic compound in the absence of an overlay top layer containing a second photochromic compound, and an underlying primary layer containing the first photochromic compound as described above.
[0104] [104] With some embodiments of the photochromic articles of the present invention, the wavelength values of the inactivated peak absorbance of the first photochromic compound, the photochromic-dichroic compound and the optional second photochromic compound are not equivalent to each other. More particularly, the first wavelength of the absorbance peak in an inactivated state (of the first photochromic compound of the primary layer), the second wavelength of the absorbance peak (of the photochromic-dichroic compound of the photochromic-dichroic layer), and the third Wavelengths of the absorbance peak in an inactivated state (from the optional second photochromic compound of the additional top coating layer) are not equivalent with each other.
[0105] [105] The selection of the first photochromic compound, the photochromic-dichroic compound and the second optional photochromic compound as well as the wavelength values of the absorbance peak in inactivated state of the same not equivalent with each other is desirable, with some embodiments , for reasons including, but not limited to, increasing the total amount of radiation incidence (having wavelengths from 340 nm to 380 nm or from 340 nm to 400 nm that is absorbed by the photochromic article. When the wavelength values peak absorbance in inactivated state are not equivalent to each other, the amount of radiation incidence 9 having wavelengths from 340 nm to 380 nm or from 340 nm to 400 nm) which is absorbed by each of the optional second photochromic compound , the photochromic-dichroic compound and the first photochromic compound can be increased or optimized as the incidence of radiation passes through the optional top cladding layer 20, the photochromic-dichroic 17 and the primary layer 14. Increase and / or optimize the amount of radiation incidence (having wavelengths from 340 nm to 380 nm or from 340 nm to 400 nm) absorbed by each of the second photochromic compounds, the photochromic-dichroic compound and the first photochromic compound can increase and / or optimize the photochromic response and / or the photochromic-dichroic response of the aforementioned compounds and, correspondingly, improve the photochromic response and / or the photochromic-dichroic response and the properties of the articles photochromic elements of the present invention. Alternatively or in addition, the transmittance percentage of the radiation incidence has wavelengths from 340 nm to 380 nm or from 340 nm to 400 nm through the photochromic articles of the present invention can be minimized when the first, second, and third peak wavelengths in inactivated state are not equivalent and compensate as described above and in addition to this description.
[0106] [106] According to some embodiments, the difference between the second wavelength of the absorbance peak in an inactivated state and the first wavelength of the absorbance peak in an inactivated state is greater than or equal to 0.5 nm and less than or equal to 20 nm, or greater than or equal to 1 nm and less than or equal to 15 nm, or greater than or equal to 2 nm and less than or equal to 10 nm, or greater than or equal to 2 nm and less than or equal to 7nm, or any combination of these above and below wavelength values.
[0107] [107] The second wavelength of the absorbance peak in an inactivated state can be greater than or less than the first wavelength of the absorbance peak in an inactivated state. Correspondingly, the first wavelength of the absorbance peak in an inactivated state can be greater than or less than the second wavelength of the absorbance peak in an inactivated state. With some embodiments, the second wavelength of the absorbance peak in an inactivated state is greater than the first wavelength of the absorbance peak in an inactivated state and, consequently, the first wavelength of the absorbance peak in an inactivated state is less than the second wavelength of the absorbance peak in an inactivated state.
[0108] [108] According to some additional embodiments and, in addition to the first, second and third wavelength values of the absorbance peak in an inactivated state being not equivalent to each other, the difference between the third wavelength of the peak of absorbance in an inactivated state and the second wavelength of the absorbance peak in an inactivated state is greater than or equal to 0.5 nm and less than or equal to 20 nm, or less than or equal to 1 nm and less than or equal to 15 nm, or less than or equal to 2 nm and less than or equal to 10 nm, or greater than or equal to 2 nm and less than or equal to 7 nm, or any combination of these higher and lower wavelength values.
[0109] [109] In addition to the first, second and third wavelength values of the absorbance peak in inactivated state being not equivalent to each other, with some additional embodiments, the third wavelength of the absorbance peak in inactivated state can be greater than or less than the second wavelength of the absorbance peak in an inactivated state. Correspondingly, the second wavelength of the absorbance peak in an inactivated state can be greater than or less than the third wavelength of the absorbance peak in an inactivated state. With some embodiments, the third wavelength of the absorbance peak in an inactivated state is greater than the second wavelength of the absorbance peak in an inactivated state, and correspondingly, the second wavelength of the absorbance peak in an inactivated state is less than the third wavelength of the absorbance peak in an inactivated state.
[0110] [110] With some additional embodiments, in addition the first, second and third values of the absorbance peak wavelength in an inactivated state being not equivalent to each other, the first wavelength of the absorbance peak in an inactivated state is less than the second wavelength of the absorbance peak in an inactivated state; and the second wavelength of the absorbance peak in an inactivated state is less than the third wavelength of the absorbance peak in an inactivated state (when the upper coating layer and the second photochromic compound are present).
[0111] [111] The substrates from which the substrate of the photochromic articles of the present invention can be selected include, but are not limited to, substrates formed from organic materials, inorganic materials, or combinations thereof (for example, composite materials) . Non-limiting examples of substrates that can be used according to various non-limiting embodiments described here are described in greater detail below.
[0112] [112] 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, for example, homopolymers and copolymers, prepared from monomers and mixtures of monomers described in the United States patent No. 5,962,617 and U.S. Patent No. 5,658,501 from column 15, line 28 to column 16, line 17, the descriptions of said patents being specifically incorporated herein by reference. For example, such polymeric materials can be thermoplastic or thermosetting polymeric materials, can be transparent or optically transparent, and can have any required refractive index. Non-limiting examples of said described monomers and polymers include: polyol monomers (allyl carbonate), for example, allyl-diglycol carbonates, such as diethylene glycol bis (allyl carbonate), the monomer of which is sold under the trade name CR-39 by PPG Industries Inc .; polyurea-polyurethane polymers (polyurea-urethane), which are prepared, for example, by the reaction of a polyurethane prepolymer and a diamine curing agent, a composition for one of said polymers being sold under the trademark TRIVEX by PPG Industries Inc., polyol (meth) acryloyl terminated carbonate monomer; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; trimethylol propane ethoxylated triacrylate monomers; ethylene glycol bismethacrylate monomers; poly (ethylene glycol) bismethacrylate monomers; urethane acrylate monomers; poly (ethoxylated bisphenol A dimethacrylate); poly (vinyl acetate); poly (vinyl alcohol); polyvinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; polyurethanes; politiouretanos; thermoplastic polycarbonates, such as carbonate-bound resin derived from Bisphenol A and phosgene, one of which is being sold under the trade name LEXAN; polyester, such as material sold under the trade name MYLAR; polyethylene terephthalate); polyvinyl butyral; poly (methyl methacrylate), as well as the material sold under the trade name PLEXIGLAS, and polymers prepared by the reaction of polyfunctional isocyanates with polyisulfide or polyisulfide monomers, both homopolymerized and co- and / or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates and optionally ethylenically unsaturated or vinyl monomers containing aromatic halogenates. Also contemplated are the copolymers of said monomers and mixtures of the described polymers and copolymers with other polymers, for example, to form block copolymers or interpenetration mesh products.
[0113] [113] The substrate may, with some embodiments, be an ophthalmic substrate. Non-limiting examples of organic materials suitable for use in forming ophthalmic substrates include, but are not limited to, polymers recognized in the art that are useful as ophthalmic substrates, such as organic optical resins that are used to prepare optically transparent castings for optical applications , such as ophthalmic lenses.
[0114] [114] Other non-limiting examples of organic materials suitable for use in forming substrates of the photochromic articles of the present invention include both synthetic materials and organic materials, including, without limitation: opaque or translucent polymeric materials, synthetic or natural textiles, and cellulosic materials such as paper and wood.
[0115] [115] Non-limiting examples of organic materials suitable for use in forming substrates of the photochromic articles of the present invention include glass, minerals, ceramics, and metals. For example, in a non-limiting embodiment, the substrate may include glass. In another non-limiting embodiment, the substrate may have a reflective surface, for example, a polished ceramic substrate, metallic substrates, or mineral substrates. In other non-limiting embodiments, a reflective coating or layer may be deposited or otherwise applied to a surface of an inorganic substrate or an organic substrate to make it reflective or to improve its reflectivity.
[0116] [116] Furthermore, according to a certain non-limiting embodiment described here, the substrate may 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 their outer surface, because these surfaces tend to be quickly scratched, scraped, or worn. An example of such lens substrates is the GENTEXTM polycarbonate lens (available from Gentex Optics). Therefore, as used herein, the term "substrate" includes a substrate having a protective coating, such as, but not limited to, an abrasion resistant coating on its surface (s).
[0117] [117] In addition, the substrate of the photochromic article of the present invention may be unstained, colored, linearly polarized, circularly polarized, elliptically polarized, photochromic, or colored photochromic substrates. As used here with reference to substrates, the term "uncolored" means a substrate that is essentially free from the addition of coloring agent (such as, but not limited to, conventional dyes) and has an absorption spectrum for visible radiation that does not varies significantly in response to actinic radiation. Furthermore, with reference to substrates, the term "colored" means substrates that have the addition of a coloring agent (such as, but not limited to, conventional dyes) and an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation.
[0118] [118] As used here, the term "linearly polarized" with respect to the substrate means a substrate that has been adapted for linearly polarized radiation. As used here, the term "circularly polarized" with respect to the substrate means substrates that are adapted for circularly polarized radiation. As used here, the term "elliptically polarized" with respect to the substrate means substrates that are adapted to polarize elliptically in radiation. As used here, with the term “photochromic” in relation to a substrate, it means substrates having an absorption spectrum for visible radiation that varies in response to at least actinic radiation. Additionally, as used here with respect to the substrate, the term “colored photochromic” means substrates containing the addition of a coloring agent, as well as a photochromic material, and having an absorption spectrum for visible radiation that varies in response to at least one actinic radiation. Thus, for example, and without limitation, a colored photochromic substrate may have a first color characteristic of the coloring agent and a second color characteristic of the coloring agent combination of the photochromic material when exposed to actinic radiation.
[0119] [119] The photochromic articles of the present invention include a photochromic-dichroic layer that additionally includes a photochromic-dichroic compound. The photochromic-dichroic layer may, in some embodiments, be non-polarizing in a first state (ie, the coating will not confine the vibrations of the electric vector of light waves in one direction), and will be linearly polarized in a second state with relation to the transmitted radiation. As used here, the term "transmitted radiation" refers to radiation that is passed through at least a portion of an object. Although non-limiting, the transmitted radiation can be ultraviolet radiation, visible radiation, infrared radiation, or a combination thereof. Thus, according to various non-limiting embodiments, described here, the photochromic-dichroic layer can be non-polarizing in the first state and linearly polarizing transmitted ultraviolet radiation, transmitted visible radiation, or a combination of them in the second state.
[0120] [120] In addition to 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 polarizing in both, the first and the second state.
[0121] [121] With some embodiments, the photochromicdichroic layer can have an average proportion and absorption of at least 1.5 and at least one state. With some additional embodiments, the photochromic-dichroic layer can have an average absorption ratio ranging from at least 1.5 to 50 (or greater) in at least one state. The term “absorption ratio” refers to the proportion of the absorbance of linearly polarized radiation in the foreground to the absorbance of linearly polarized radiation in a plane orthogonal to the foreground, in which the foreground is taken as the plane with the most high absorbance. Thus, the absorption ratio (and the average absorption ratio that is described below) is an indication of how strongly one of the two polarized components in the orthogonal plane of radiation is absorbed by an object or material.
[0122] [122] The average absorption ratio of a photochromic-dichroic layer that includes a photochromic-dichroic compound can be determined as shown below. For example, to determine the proportion of the average absorption of a photochromic-dichroic layer that includes a photochromic-dichroic compound, a substrate having a coating is positioned on an optical bench and a coating is placed in a linearly polarizing state by activating the compound photochromic-dichroic. Activation was achieved by exposing the coating to UV radiation for a time sufficient to reach a saturated or close to saturated state (ie, a state where the absorption properties of the coating do not change substantially with respect to the time span during which measurements are made). Absorption measurements are taken over a period of time (typically 10 to 300 seconds) at 3-second intervals for light that is linearly polarized in a plane perpendicular to the optical bench (referred to as the O ° polarization plane or direction) and the light that is linearly polarized in a plane that is parallel to the optical bench (referred to as plane or direction and 90 ° polarization) in the following sequence; 0 °, 90 °, 90 °, 0 °, etc. The absorbance of linearly polarized light by the coating is measured at each time interval for all tested wavelengths and the inactivated absorbance (ie the absorbance of the coating in an inactivated state) in relation to the same wavelength range that is subtracted to obtain the absorption spectrum for the coating in an activated state in each of the 0 ° and 90 ° polarization planes to obtain a different average absorption spectrum in each polarization plane for the coating in the saturated or near saturated state.
[0123] [123] For example, with reference to figure 2, the different average absorption spectrum (usually indicated 4) is shown in a polarization plane that was obtained for a photochromic-dichroic layer according to a non-limiting embodiment described here. The average absorption spectrum (usually indicated 3) is the different average absorption spectrum obtained for the same photochromic-dichroic layer in the orthogonal polarization plane.
[0124] [124] Based on the different average absorption spectrum obtained for the photochromic-dichroic layer, the average absorption ratio for the photochromic-dichroic layer is obtained as follows. The absorption ratio of the photochromic layer at each wavelength in a predetermined wavelength range corresponding to λmaxvis +/- 5 nanometers (usually indicated as 5 in figure 2), where λmax-vis is the wavelength at which the coating had the highest average absorbance in any plane, it is calculated according to Equation (Eq.1) below: ARλi = Ab1λi / Ab2λi (Eq. 1) With reference to the equation Eq.1, ARλi is the absorption ratio at wavelength λ, Ab1 λi is the average absorption at wavelength λi in the direction of polarization (that is, 0 ° and 90 °) having the highest absorbance, and Ab2 λi is the mean absorbance at the wavelength λi, in the remaining direction of polarization. As previously discussed, the "absorption ratio" refers to the absorbance ratio of linearly polarized radiation in a first plane to the absorbance of the same wavelength of linearly polarized radiation in a plane orthogonal to the foreground, where the foreground is taken as the plane with the highest absorbance.
[0125] [125] The average absorbance ratio (“AR”) for the photochromic-dichroic layer is then calculated by averaging the individual proportions over the predetermined range of wavelengths (ie λmax-vis +/- 5 nanometers) according to with the equation (Eq. 2) below: AR = (ƩARλi) / ni (Eq. 2) With reference to the equation Eq.2, AR is the average absorption ratio for the coating, ARλ1 is the individual proportions (as determined above in Eq. 1) for each wavelength within the predetermined wavelength range, and ni is the number of individual proportions of absorption that averaged. A more detailed description of this method of determining the average absorption ratio is provided in the Examples of U.S. Patent No. US 7,256,921, in column 102, line 38 through column 103, line 15, the description of which is specifically incorporated herein by reference.
[0126] [126] With some embodiments, the photochromic-dichroic compound of the photochromic-dichroic layer can be at least partially aligned. As previously discussed, the term “photochromic-dichroic” means participating in both properties, photochromic and dichroic (that is, linearly polarizing) under certain conditions, in which the properties are at least detectable by instrumentation. Consequently, "photochromic-dichroic compounds" are compounds having both photochromic and dichroic (ie linearly polarizing) properties under certain conditions, whose properties are at least detectable by instrumentation. Thus, photochromic-dichroic compounds have an absorption spectrum for at least one visible radiation that varies in response to at least one actinic radiation and are capable of absorbing one of two polarized components in the orthogonal plane of at least one radiation transmitted more strongly than than the other. In addition, as with the conventional photochromic compounds discussed above, photochromic-dichroic compounds can change 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 substrate formed by the union of two or more elements, components, ingredients, or parts and includes, without limitation, molecules and macromolecules (for example, polymers and oligomers) formed by the union of two or more elements, components, ingredients, or parts.
[0127] [127] For example, the photochromic-dichroic layer can have a first state having a first absorption spectrum, a second state having a second absorption spectrum that is different from the first absorption spectrum, and can be adapted to change from a first state to the second state in response to at least one actinic radiation and revert back to the first state in response to thermal energy. Furthermore, the photochromic-dichroic compound can be dichroic (that is, linearly polarizing) in one or both, the first state and the second state. For example, although not required, the photochromic-dichroic compound can be linearly polarizing in an activated state and non-polarizing in the state of bleaching or fading (ie, not activated). As used herein, the term "activated state" refers to the photochromic-dichroic compound when exposed to sufficient actinic radiation to induce at least a portion of the photochromic-dichroic compound to change from a first state to a second state. In addition, although not required, the photochromic-dichroic compound can be dichroic in both the first and second states. Although not limiting here, for example, the photochromic-dichroic compound can polarize linearly in the visible radiation in both the activated and bleached states. In addition, the photochromic-dichroic compound can linearly polarize in visible radiation in an activated state, and can linearly polarize in UV radiation in the bleached state.
[0128] [128] Although not required, according to several non-limiting embodiments described here, the photochromic-dichroic compound of the photochromic-dichroic layer can have an average ratio and absorption of at least 1.5 in an activated state as determined according to the CELL METHOD. According to other non-limiting embodiments described here, at least one photochromic-dichroic compound can have an average absorption ratio greater than 2.3 in an activated state as determined according to the CELL METHOD. In accordance with yet another non-limiting embodiment, the photochromic-dichroic compound at least partially aligned with the photochromic-dichroic layer may have an average absorption ratio ranging from 1.5 to 50 in an activated state as determined according to the CELL METHOD. According to another non-limiting embodiment, the photochromic-dichroic compound of the photochromic-dichroic layer may have an average absorption ratio ranging from 4 to 20, it may also have an average absorption ratio ranging from 3 to 30, and may also have an average absorption ratio ranging from 2.5 to 50 in an activated state as determined according to the CELL METHOD. More typically, however, the average absorption ratio of the photochromic-dichroic compound at least partially aligned can be in any proportion of average absorption that is sufficient to impart the desired properties to the photochromic article of the present invention. Non-limiting examples of suitable photochromic dichroic compounds are described in detail below.
[0129] [129] The CELL METHOD for determining the average absorption ratio of the photochromic-dichroic compound is essentially the same as the method used to determine the average absorption ratio of the photochromic-dichroic layer, except that, instead of measuring absorbance of a coated substrate, a cell arrangement containing an aligned liquid crest material and the photochromic-dichroic compound is tested. More specifically, the cell arrangement includes two opposing glass substrates that are spaced from each other by 20 microns +/- 1 micron. The substrates are sealed at the two opposite edges to form a cell. The inner surface of each of the glass substrates is coated with a polyimide coating, the surface of which is at least partially rubbed. The alignment of the photochromic-dichroic compound is achieved by introducing the photochromic-dichroic compound and the liquid crystal medium into the cell arrangement, and allowing the liquid crystal medium and the photochromic-dichroic compound to align with the rubbed polyimide surface. Once the liquid crystal medium and the photochromic-dichroic compound are aligned, the cell arrangement is placed on an optical bench (which is described in detail in the Examples) and the proportion of the average absorption is determined in the manner previously described for the substrates. coated, except that the inactivated absorbance of the cell arrangement is subtracted from the activated absorbance to obtain the average difference in the absorption spectrum.
[0130] [130] As previously discussed, although dichroic compounds are capable of potentially absorbing one of two orthogonal components of light from the polarized plane, an appropriate position or arrangement of the molecules of a dichroic compound would generally be necessary in order to achieve an effect of liquid polarization. Similarly, it would generally be necessary to properly position or arrange the molecules of a photochromic-dichroic compound to achieve a liquid linear depolarization effect. That is, it would generally be necessary to align the molecules of the photochromic-dichroic compound so that the long axes of the molecules of the photochromic-dichroic compound in an activated state are generally parallel to each other. Therefore, as discussed above, according to the various non-limiting embodiments described herein, the photochromic-dichroic compound is at least partially aligned. Furthermore, if the activated state of the photochromic-dichroic compound corresponds to a dichroic state of the material, the photochromic-dichroic compound can be at least partially aligned so that the long axis of the molecules of the photochromic-dichroic compound in the activated state is aligned. As used here, the term "align" means to bring to an appropriate arrangement or appropriate position for interaction with another material, compound or structure.
[0131] [131] Furthermore, although not limiting here, the photochromic-dichroic layer of the photochromic article of the present invention can include a plurality of photochromic-dichroic compounds. While not limiting here, when two or more dichroic photochromic compounds are used in combination, the photochromic-dichroic compound can be chosen to complement another one to produce a desired color or shade. For example, mixtures of photochromic-dichroic compounds can be used according to certain non-limiting embodiments here, to bind certain activated colors, such as one close to neutral gray, or close to neutral brown. See, for example, U.S. Patent No. US 5,645,767, column 12, line 66 through column 13, line 19, the description of which being specifically incorporated by reference here, which describes the parameters that define the neutral gray colors and brown. In addition, or alternatively, the at least partial coating may comprise mixtures of photochromic-dichroic compounds having complementary linear polarization states. For example, the photochromic-dichroic compound can be chosen to have complementary linear polarization states with respect to the desired wavelength range to produce an optical element that is capable of polarizing light with respect to the desired wavelength range. Furthermore, mixtures of complementary photochromic-dichroic compounds having essentially the same polarization states at the same wavelength can be chosen to reinforce or improve the total linear polarization achieved. For example, according to a non-limiting embodiment, the photochromic-dichroic layer can include at least two photochromic-dichroic compounds at least partially aligned, in which each of the compounds at least partially aligned has: complementary colors; and / or states of complementary linear polarization.
[0132] [132] The photochromic-dichroic layer can also include at least one additive that can facilitate one or more processing steps, properties, or performance, at least partially of the coating. Non-limiting examples of said additives include dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polarization 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), free radical purgers, and promoters adhesion (such as hexanediol diacrylate and coupling agents).
[0133] [133] Examples of dyes that may be present in the photochromic-dichroic layer include, but are not limited to, organic dyes, which are capable of imparting a desired color or other optical property to the photochromic-dichroic layer.
[0134] [134] As used here, the term "alignment promoter" means an additive that can facilitate at least one of a rate and the alignment uniformity of a material to which it is added. Non-limiting examples of the alignment promoters that may be present in the photochromic-dichroic compound include, but are not limited to, those described in U.S. Patent No .: US 6,338,808 and in US Patent Application Publication No. 2002/0039627, which are specifically incorporated herein by reference here.
[0135] [135] Non-limiting examples of kinetic-enhancing additives that may be present in several layers of the photochromic article of the present invention, such as the photochromic-dichroic layer, include compounds containing epoxy, organic polyols, and / or plasticizers. More specific examples of said kinetics-enhancing additives are described in U.S. patent 6,433,043 and in patent application publication 2003/0045612, which are incorporated herein, specifically by reference.
[0136] [136] Non-limiting examples of photoinitiators that may be present in several layers of the photochromic article of the present invention, such as the primary layer, the photochromic-dichroic layer, and / or the top coat layer, include, but are not limited to , cleavage-type photoinitiators and abstraction-type photoinitiators. Non-limiting examples of cleavage-type photoinitiators include acetophenones, α-aminoalkylphenones, benzoyl ethers, benzoyl oximes, acylphosphine oxides and bisacylphosphine oxides or mixtures of such initiators. A commercial example of such a photoinitiator is DAROCURE® 4265, which is available from Ciba Chemicals, Inc. Non-limiting examples of abstraction type photoinitiators include benzophenones, Michler's ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures of such initiators .
[0137] [137] Another non-limiting example of a photoinitiator that can be present in one or more layers of the photochromic article of the present invention, such as the primary layer, the photochromic-dichroic layer, and / or an upper coating chamber, is a visible light photoinitiator. Non-limiting examples of suitable visible light photoinitiators are recorded in column 12, line 11 through column 13, line 21 of U.S. Patent 6,602,603, which is specifically incorporated by reference here.
[0138] [138] Non-limiting examples of thermal initiators include, but are not limited to, organic peroxy compounds and azobis (organonitrile) compounds. Examples of organic peroxy compounds that are useful as thermal initiators include peroxymonocarbonate esters, such as isopropyl tertiary butylperoxy carbonate; peroxydicarbonate esters, such as di (2-ethylhexyl) peroxydicarbonate, di (butyl secondary peroxydicarbonate) and diisopropyl peroxydicarbonate; diaciperoxides, such as 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzyl peroxide; peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate and t-butyl peroxyisobutyrate; methyl ethyl ketone peroxide; and acetylcyclohexane sulfonyl peroxide. In a non-limiting configuration, the thermal initiators used are those that do not discolor the resulting polymer. Non-limiting examples of azobis (organonitrile) compounds that can be used as thermal initiators include azobis (isobutyronitrile), azobis (2,4-dimethylvaleronitrile) or a mixture thereof.
[0139] [139] Non-limiting examples of polymerization inhibitors may include: nitrobenzene, 1,3,5-trinitrobenzene, ρ-benzoquinone, chloroanil, DPPH, FeCl3, CuCl2, oxygen, sulfur, aniline, phenol, ρ-dihydroxybenzene, 1,2 , 3-trihydroxybenzene, 2,4,6-trimethylphenol.
[0140] [140] Examples of solvents that may be present in the formation of several layers of the photochromic articles of the present invention, such as the primary layer, the photochromic-dichroic layer, and / or the top coat layer include, but are not limited to, those that they will dissolve the coating components, which are compatible with the coating and the elements and substrates and / or can guarantee uniform coverage of the external surface to which the coating is applied. Examples of solvent include, but are not limited to, the following: propylene glycol acetate monomethyl ether and its derivatives (sold as DOWANOL® industrial solvents), acetone, amyl propionate, anisol, benzene, butyl acetate, cyclohexane, dialkyl ethers of ethylene glycol, for example, diethylene glycol dimethyl ether and its derivatives (sold as industrial solvents CELLOSOLVE®), diethylene glycol dibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene, ethyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propylene glycol methyl ether, and mixtures thereof.
[0141] [141] 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, azomethines, indigoids, thioindigoids, merocyanins, indanas, quinophthalonic dyes, perylene, phthaloperins, triphenodiaxozins, indoloquinoxaline, imidazo-triazines, tetrazines, azozo and (poly) dyes. , naphthoquinones, anthroquinone and (poly) anthroquinones, anthropyrimidinones, iodine and iodates. In another non-limiting embodiment, the dichroic material can include at least one reactive functional group that is capable of forming at least one covalent bond with other materials. With some embodiments, the dichroic material can be a polymerizable dichroic compound. Correspondingly, the dichroic material can include at least one group that is capable of being polymerized (i.e., "polymerizable group"). For example, although not limiting here, in a non-limiting embodiment, the dichroic compound can have at least one alkoxy group, a polyalkoxy group, alkyl, or polyalkyl substituent terminated with at least one polymerizable group.
[0142] [142] With some embodiments, the photochromicdichroic layer can include at least one conventional photochromic compound. As used here, the term "conventional photochromic compound" includes both thermally reversible and non-thermally reversible (or photo-reversible) photochromic compounds. Generally, although not limiting here, when two or more conventional photochromic materials are used in combination with each other or with a photochromic-dichroic compound, the various materials can be chosen to complement each other to produce a desired color or shade. For example, mixtures of photochromic compounds can be used according to certain non-limiting embodiments here to bind certain activated colors, such as one close to neutral gray or one close to neutral brown. See, for example, U.S. Patent No. US 5,645,767, column 12, line 66 through column 13, line 19, the description of which is specifically incorporated herein by reference, which describes the parameters that define the neutral gray colors and neutral brown.
[0143] [143] According to some embodiments, the photochromic-dichroic layer is free of conventional photochromic compounds.
[0144] [144] The photochromic-dichroic layer may include one or more appropriate 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-ylpropyl) piperidino) phenyl) -13,13-dimethyl-3H, 13-indene [2 ', 3': 3 , 4] naphtho [1,2-b] pyran; (PCDC-2) 3-phenyl-3- (4- (4- (3- (1- (2-hydroxyethyl) piperidin-4-yl) propyl) piperidine) phenyl) -13,13-dimethyl-3H, 13H -indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-3) 3-phenyl-3- (4- (4- (4-butyl-phenylcarbamoyl) -piperidin1-yl) phenyl) -13,13-dimethyl-6-methoxy-7- (4-phenyl-piperazin -1- yl) - 3H, 13H-indene [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-indene [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-indene [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-indene [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-1Hcyclopenta [a] phenantren-3- iloxycarbonyloxy] -piperidin-1-yl} - 3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-8) 3-phenyl-3- (4- {4- [17- (1,5-dimethylhexyl) -10,13-dimethyl-2,3,4,7,8,9,10, 11,12,13,14,15,16,17-tetradecahydro1H-cyclopenta [a] phenanthren-3-yloxycarbonyloxy] -piperidin-1-yl} -phenyl) -13,13-dimethyl-6-methoxy-7- { 4- [17- (1,5-dimethylhexyl) -10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17- tetradecahydro-1H -cyclopenta [a] phenanthren-3-yloxycarbonyloxy] - piperidin-1-yl} -3H, 13H-indene [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-indene [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-indene [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-indene [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-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-13) 3-phenyl-3- (4- (pyrrolidin-1-yl) phenyl) -13,13-dimethyl6-methoxy-7- (4- (4-hexylbenzoyloxy) benzoyloxy) - 3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-14) 3-phenyl-3- (4- (pyrrolidin-1-yl) phenyl) -13,13-dimethyl6-methoxy-7- (4- (4- (4-hexylbenzoyloxy) benzoyloxy) benzoyloxy) - 3H, 13H-indene [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-yoyloxy) phenyl) piperazin-1-yl) - 3H, 13H-indene [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-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-17) 3-phenyl-3- {4- (pyrrolidin-1-yl) phenyl) -13- [17- (1,5-dimethylhexyl) -10,13-dimethyl2,3,4,7 , 8,9,10,11,12,13,14,15,16,17-tetradecahydro-1Hcyclopenta [a] phenanthren-3-yloxy] -13-ethyl-6-methoxy-7- (4- [17- (1,5-dimethyl-hexyl) -10,13-dimethyl2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta [a] phenantren-3-yloxycarbonyloxy] -piperadin-1-yl) - 3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-18) 3-phenyl-3- (4- {4- [17- (1,5-dimethylhexyl) -10,13-dimethyl-2,3,4,7,8,9,10, 11,12,13,14,15,16,17-tetradecahydro1H-cyclopenta [a] phenanthren-3-yloxycarbonyloxy] -piperidin-1-yl} -phenyl) -13-ethyl-13-hydroxy-6-methoxy-7 - {4- [17- (1,5-dimethylhexyl) -10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17- tetradecahydro -1H-cyclopenta [a] phenanthren-3-yloxycarbonyloxy] - piperidin-1-yl} -) - 3H, 13H-indene [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- (4- (3-phenyl- 3- {4- (pyrrolidin-1-yl) phenyl} - 13,13-dimethyl-6-methoxy-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran-7-yl ) -piperadin-1-yl) oxycarbonyl) phenyl) phenyl) cabonyloxy) -3H, 13H-indene [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-ylcarboxamido) 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-ylcarboxamido) phenyl) -3H-naphtho [2,1-b] pyran; (PCDC-22) 3- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl] -phenyl} -3-phenyl-7- (4-phenyl- (phen-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-ylcarboxamido) phenyl) -benzothieno [3 ', 2': 7.8] benzo [b] pyran; (PCDC-26) 7- {17- (1,5-dimethylhexyl) -10,13-dimethyl2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1Hcyclopenta [a] phenanthren-3-yloxycarbonyloxy} -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-ylcarboxamido) 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-ylcarboxamido) 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-ylcarboxamido) 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- pentadecafluoroheptiloxy-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-carbomethoxy-8- (N- (4-phenyl) phenyl ) carbamoyl-2H-naphtho [1,2-b] pyran; (PCDC-38) 2-phenyl-2- {4- [4- (4-methoxy-phenyl) -piperazin-1-yl] -phenyl} -5-carbomethoxy-8- (N- (4-phenyl) phenyl ) carbamoyl-2H-fluontene [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-dimethylhexyl) -10,13- dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta [a] fenantren -3-yloxycarbonyloxy} phenyl) -2H-fluontene [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-dioxolane [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-dioxolane [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] phenantren-3-yloxycarbonyloxy} phenyl) -6 '- (4- (4'-hexyloxy-biphenyl-4- carbonyloxy) -piperidin-1-yl) -spiro [indoline-2,3'-3Hnafto [2,1-b] [1,4] oxazine]; (PCDC-43) 1-butyl-3-ethyl-3-methyl-5-methoxy-7 '- (4- (4'-Hexyloxybiphenyl-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-9Hdioxolane [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-dioxolane [4 ”, 5”: 6,7] [indeno [2 ', 3': 3,4]] naphthus [ 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-9Hdioxolane [4 ”, 5”: 5,6] [indeno [2 ', 3': 3,4]] naphtho [1,2-b] pyran; (PCDC-47) 4- (4 - ((4-cyclohexylidene-1-ethyl-2,5-dioxopyrrolin-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-dioxopyrrolin-3-ylidene) ethyl) -2- thienyl) phenyl- (4-propyl) cyclohexylidene; (PCDC-49) 4- (4 - ((4-adamantan-2-ylidene-2,5-dioxo-1- (4- (4- (4- propylphenyl) piperazinyl) phenyl) pyrrolin-3-ylidene) ethyl ) -2-thienyl) phenyl (4-propyl) cyclohexylidene; (PCDC-50) 4- (4 - ((4-adamantan-2-ylidene-2,5-dioxo-1- (4- (4- (4- propylphenyl) piperazinyl) phenyl) pyrrolin-3-ylidene) ethyl ) -1- methylpyrrol-2-yl) phenyl (4-propyl) cyclohexylidene; (PCDC-51) 4- (4 - ((4-adamantan-2-ylidene-2,5-dioxo-1- (4- {17- (1,5-dimethyl-hexyl) -10,13-dimethyl2, 3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1Hcyclopenta [a] phenanthren-3-yloxycarbonyloxy} phenyl) pyrrolin-3-ylidene) ethyl) -1 -methylpyrrol-2-yl) phenyl (4-propyl) cyclohexylidene; (PCDC-52) 4- (4-methyl-5,7-dioxo-6- (4- (4- (4-propylphenyl) piperazinyl) phenyl) spiro [8,7adihydrothiapheno [4,5-f] isoindole-8 , 2'-adamentan] -2-yl) phenyl (4-propyl) phenyl cyclohexylidene; (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] phenantren-3-yloxycarbonyloxy} phenyl -6,7-dihydro-4-methyl-2-phenylpiro (5,6-benzo [b] thiophenodicarboxiimide-7,2 - tricycle [3.3.1.1] dean); (PCDC-54) N-cyanomethyl-6,7-dihydro-2- (4- (4- (4- propylphenyl) piperazinyl) phenyl) -4-methylpiro (5,6-benzo [b] thiophenodicarboxiimide-7,2 -tricycle [3.3.1.1] dean); (PCDC-55) N-phenylethyl-6,7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-methylpiro (5,6-benzo [b] thiophenodicarboxyimide-7,2-tricycle [3.3.1.1] decane); (PCDC-56) N-phenylethyl-6,7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-cyclopropylspir (5,6-benzo [b] thiophenodicarboxyimide-7,2-tricycle [3.3.1.1] decan); (PCDC-57) N-phenylethyl-6,7-dihydro-2- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-4-cyclopropyl spiro (5,6-benzo [b ] furodicarboxyimide-7,2-tricycle [3.3.1.1] dean); (PCDC-58) N-cyanomethyl-6,7-dihydro-4- (4- (4- (4-hexylbenzoyloxy) phenyl) piperazin-1-yl) phenyl-2-phenylpiro (5,6-benzo [b] thiophenodicarboxyimide-7,2-tricycle [3.3.1.1] decane); (PCDC-59) N- [17- (1,5-dimethylhexyl) -10,13-dimethyl2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1Hcyclopenta [a] phenanthren-3-yloxycarbonyl -6,7-dihydro-2- (4-methoxyphenyl) phenyl-4-methylpiro (5,6-benzo [b] thiophenodicarboxiimide-7,2-tricycle [3.3 .1.1] dean); (PCDC-60) N-cyanomethyl-2- (4- (6- (4-butylphenyl) carbonyloxi- (4,8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl -6,7- dihydro-4-cyclopropylspires (5,6-benzo [b] thiophenodicarboxiimide-7,2-tricycle [3.3.1.1] decane); (PCDC-61) 6,7-dihydro-N-methoxycarbonylmethyl-4- (4- (6- (4-butylphenyl) carbonyloxi- (4,8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl-2-phenylspiro (5,6-benzo [b] thiophenodicarboxyimide-7,2-tricycle [3.3.1.1] decane); and (PCDC-62) 3-phenyl-3- (4-pyrrolidinylphenyl) -13,13-dimethyl-6-methoxy-7- (4- (4- (4- (4- (6- (4- (4- (4-onylphenylcabonyloxy) phenyl) oxycarbonyl) phenoxy) hexyloxy) phenyl) piperazin-1-yl) indene [2 ', 3': 3,4] naphtho [1,2-b] pyran.
[0145] [145] With some additional embodiments, the photochromic-dichroic compounds of the photochromic articles of the present invention can be chosen from the following: (PCDC-a1) 3,3-Bis (4-methoxyphenyl) -10- [4- (4- (trans-4-pentylcyclohexyl) benzamido) phenyl] -13,13-dimethyl-12-bromo3,13-dihydro- indene [2 ′, 3 ′: 3,4] naphthus [1,2-b] pyran; (PCDC-a2) 3,3-Bis (4-methoxyphenyl) -10- [4 - ((4- (trans-4-pentylcyclohexyl) phenoxy) carbonyl) phenyl] -6,13,13-trimethyl3,13-dihydro - indene [2 ′, 3 ′: 3,4] naphthus [1,2-b] pyran; (PCDC-a3) 3- (4-Fluorophenyl) -3- (4-piperidinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6- trifluromethyl- 11,13,13-trimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a4) 3,3-Bis (4-methoxyphenyl) - 10- [4- (4- (trans-4-pentylcyclohexyl) benzamido) phenyl] -5,7-difluoro-13,13-dimethyl3,13- dihydro-indene [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) benzamido) phenyl] -5,7- difluoro-13,13-dimethyl-3,13-dihydroindene [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) benzamido) phenyl] -5,7- difluoro-13,13-dimethyl-3,13-dihydroindene [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-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a8) 3-Phenyl-3- (4-piperidinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -12-bromo5,7-difluoro- 13,13-dimethyl-3,13-dihydro-indene [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-bromo5,7-difluoro-13, 13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a10) 3- (4-Fluorophenyl) -3- (4-piperidinophenyl) - 10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -12- bromo- 13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a11) 3,3-Bis (4-methoxydinophenyl) -10- [4- (4- (4- (trans4-pentylcyclohexyl) phenyl) benzamido) phenyl] -12-bromo-6,7-dimethoxy-11 , 13,13-trimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a12) 3,3-Bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluromethyl-12-bromo-13 , 13-dimethyl-3,13-dihydro-indene [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) benzamido) phenyl] -6-trifluromethyl-13, 13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a14) 3,3-Bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -5,7-difluoro-13,13 - dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a15) 3,3-Bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluromethyl13,13-dimethyl-3 , 13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a16) 3,3-Bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -5,7-difluoro-12-bromo -13,13-dimethyl-3,13-dihydro-indene [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) benzamido) phenyl] -6- trifluoromethyl- 13-methyl-13-butyl-3,13-dihydroindene [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) benzamido) phenyl] -5,7- difluoro-12-bromo-13,13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a19) 3-Phenyl-3- (4-methoxyphenyl) -10- [4- (4- (4- (trans4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluoromethyl13,13-dimethyl-3, 13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a20) 3-Phenyl-3- (4-morpholinophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluoromethyl-13,13- dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a21) 3,3-Bis (4-fluorophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluoromethyl-12-bromo-13 , 13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a22) 3,3-Bis (4-fluorophenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluoromethyl13,13-dimethyl-3 , 13-dihydro-indene [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) benzamido) phenyl] -6- trifluoromethyl- 13,13-dimethyl-3,13-dihydroindene [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-ylcarboxamido) phenyl) -6- (trifluoromethyl) -3,13-dihydro-indene [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-ylcarboxamido) phenyl) -6- (trifluoromethyl) -3,13-dihydroindene [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-ylcarboxamido) phenyl) -3-phenyl-6- (trifluoromethyl) - 3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphthus [1,2- b] pyran; (PCDC-a27) 3- (4-Butoxyphenyl) -3- (4-fluorophenyl) -13,13-dimethyl-10- (4 - (((trans, trans-4'-pentyl- [1,1'- bi (cyclohexan)] - 4-yl) oxy) carbonyl) phenyl) -6- (trifluoromethyl) -3,13-dihydroindene [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-ylcarboxamido ) phenyl) -3- (4-butoxyphenyl) -6- (trifluoromethyl) - 3,13-dihydro indene [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-ylcarboxamido) phenyl ) -3- (4- (trifluoromethoxy) phenyl) -6- (trifluoromethyl) -3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a30) 3,3-Bis (4-hydroxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -6-trifluromethyl13,13-dimethyl-3 , 13-dihydro-indene [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 - ilcarboxamido) phenyl) -6- (trifluoromethyl) -3,13-dihydroindene [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-ylcarboxamido) phenyl) -6- (trifluoromethyl) -3,13-dihydroindene [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) benzamido) -6- (trifluoromethyl) -3,13- dihydro-indene [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-ylcarboxamido) phenyl) -3,13- dihydro-indene [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) benzamido) -6- (trifluoromethyl) -3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a43) 5,7-Dichloro-3,3-bis (4-hydroxyphenyl) -11-methoxy13,13-dimethyl-10- (4- (4 '- (trans-4-pentylcyclohexyl) - [1, 1'- biphenyl] -4-ylcarboxamido) phenyl) -3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a44) 6,8-Dichloro-3,3-bis (4-hydroxyphenyl) -11-methoxy13,13-dimethyl-10- (4- (4 '- (trans-4-pentylcyclohexyl) - [1, 1'- biphenyl] -4-ylcarboxamido) phenyl) -3,13-dihydroindene [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-ylcarboxamido) phenyl) -3,13-dihydro-indene [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-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a47) 3- (4-Morpholinophenyl) -3- (4-methoxyphenyl) -10,7- bis [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) phenyl] -5 -fluoro-13,13-dimethyl-3,13-dihydroindene [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) benzamido) -2- (trifluoromethyl) phenyl ] -13,13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-a49) 3, 3-Bis (4-methoxyphenyl) -10- [4- (4- (4- (trans-4-pentylcyclohexyl) phenyl) benzamido) -2- (trifluoromethyl) phenyl] - 13.13 -dimethyl-3,13-dihydro-indene [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) benzamido) -2- (trifluoromethyl) phenyl ] -13,13-dimethyl-3,13-dihydroindene [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) cyclohexanecarboxamido) phenyl) -3,13-dihydroindene [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-ylcarboxamido) -2- (trifluoromethyl) phenyl) -3,13-dihydroindene [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-ylcarboxamido) phenyl) -7- (4- (4- (trans-4-pentylcyclohexyl) benzamido) phenyl) -3,13-dihydroindene [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-ylcarboxamido) phenyl) - 3-phenyl -3,13-dihydro-indene [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'-pentylbi (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy) -10- (4- (4 '- (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamido) phenyl) -3,13-dihydroindene [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-1Hcyclopenta [a] phenanthren-3-yloxy) carbonyl) piperazin-1-yl) -3 - (4-methoxyphenyl) -13,13-dimethyl-3- (4-morpholinophenyl) - 3,13-dihydro-indene [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-ylcarboxamido) phenyl) - 3,13-dihydro-indene [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'- pentylbi (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy) -10- (4- (4 '- (trans-4-pentylcyclohexyl) biphenyl-4-ylcarboxamido) phenyl) -3,13-dihydro-indene [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-yloxy) carbonyl) phenyl) -3,13- dihydro-indene [2 ′, 3 ′: 3,4] naphthus [1,2-b] pyran.
[0146] [146] With some additional embodiments, the photochromic-dichroic compounds of the photochromic articles of the present invention, can be chosen from the following: (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-indene [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- (trans4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy) benzoyloxy)) - 3,13-dihydroindene [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-dihydroindene [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-dihydroindene [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-indene [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'-bi ( cyclohexane)] - 4-carbonyloxy) -3,13-dihydro-indene [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) - [1,1'-biphenyl] -4-carbonyloxy) - 3,13-dihydro-indene [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) - [1,1'-biphenyl] -4-carbonyloxy) -3,13-dihydroindene [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) - [1,1'-biphenyl] -4-carbonyloxy) -3,13-dihydroindene [2 ', 3': 3,4] naphthus [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- hydroxyethhoxy) benzoyloxy) - [1,1'-biphenyl] -4-carbonyloxy) - [1,1'-biphenyl] -4-carbonyloxy) -3,13-dihydroindene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-b11) 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (3-phenylpropioloyloxy) -3,13-dihydroindene [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-ylcarboxamido) phenyl) -3,13-dihydroindene [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'-bi (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1yl) -13-trifluoromethyl-3,13-dihydro-indene [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1yl) -13-hydroxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (PCDC-b15) 3,3-bis (4-methoxyphenyl) -6,7-di (4- (4- (trans, trans-4'-pentyl- [1,1'-bi (cyclohexane)] - 4 - carbonyloxy) phenyl) piperazin-1yl) -13-methoxy-13-trifluoromethyl-3,13-dihydro-indene [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'-bi (cyclohexane) ] -4-carbonyloxy) phenyl) piperazin-1-yl) -13-fluoro-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphthus [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-ylcarboxamido) phenyl) -11-trifluoromethyl13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -11-trifluoromethyl-13,13-dimethyl3,13-dihydro-indene [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- ilcarboxamido) phenyl) -10,12-difluoro-13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -10,12-difluoro-13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphthus [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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) benzamido) phenyl) phenyl) - 10 , 12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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) benzamido) benzamido) phenyl) -10 , 12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran ; (PCDC-b26) 3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexyl) benzamido) phenyl) phenyl) - 10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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 ' - bi (cyclohexane)] - 4-carboxamido) benzamido) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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) cyclohexanecarboxamido) phenyl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3, 4] naphtho [1,2-b] pyran; (PCDC-b29) 3- (4-N-morpholiniphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4 '- (trans-4-pentylcyclohexyl) - [1,1'- biphenyl] -4-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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) cyclohexanecarboxamido) phenyl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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 - ilcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphthus [1,2- b ] pyran; (PCDC-b34) 3-phenyl-3- (4- (piperidin-1-yl) phenyl) -6-methoxy7- (4- (4- (trans-4-pentylcyclohexyl) benzamido) -2- (trifluoromethyl) phenyl ) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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- iloxycarbonyl) cyclohexanocarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-b37) 3- (4- (piperidin-1-yl) phenyl) -3-phenyl-6-methoxy7- (trans-4- (4 '- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl] - 4-yloxycarbonyl) cyclohexanocarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-yloxycarbonyl) cyclohexanocarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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 '-bi (cyclohexane)] - 4-carbonyloxy) phenyl) benzoyloxy) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [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'-bi (cyclohexane) ] -4- carbonyloxy) phenyl) benzoyloxy) -10,12-di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphthus [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) benzoyloxy) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-yloxycarbonyl) cyclohexanocarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-yloxycarbonyl) cyclohexanocarbonyloxy) -13-ethyl-3,13-dihydro-indene [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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 ' - bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-yloxycarbonyl) cyclohexanocarbonyloxy) phenyl) piperazin-1-yl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [2 ′, 3 ′: 3,4] naphtho [1,2-b] pyran; (PCDC-b49) 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans-4- (4- (trans-4-pentylcyclohexyl) -phenyloxycarbonyl) - cyclohexanocarbonyloxy) phenyl ) piperazin-1-yl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydroindene [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-indene [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-ylcarboxamido) phenyl) -11-trifluoromethyl13,13-dimethyl-3,13-dihydro-indene [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-ylcarboxamido) phenyl) -11-trifluoromethyl-13,13-dimethyl3,13-dihydro-indene [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'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -11-trifluoromethyl13,13-dimethyl-3,13-dihydro-indene [2 ′, 3 ′: 3,4] naphtho [1,2- b] pyran; (PCDC-b54) 3- (4- (4-methoxyphenyl) piperazin-1-yl) -3-phenyl6-methoxy-7- (4 - ((4- (trans-4-propylcyclohexyl) phenoxy) carbonyl) phenyloxycarbonyl) -13,13- dimethyl-3,13-dihydro-indene [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-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran.
[0147] [147] More generally, the photochromic-dichroic compounds of the photochromic articles of the present invention include: (a) at least one photochromic group (PC), which can be chosen from, for example, pyranes, oxazins, and fulgides, and (b) at least one extending agent or group attached to the photochromic group. Said photochromic-dichroic compounds are described in detail in US Patent No. US 7,342,112 B1 in column 5, line 35 to column 14, line 54; and Table 1, the aforementioned portions of which are being incorporated here by reference. Other suitable photochromic compounds and reaction schemes for their preparation can be seen in U.S. Patent No. US 7,343,112 B1, in column 23, line 37 to column 78, line 13, the portions cited are being incorporated herein by reference.
[0148] [148] The photochromic-dichroic layer can include a single layer or multiple layers each including a photochromic-dichroic compound that can be the same or a different one. The photochromic-dichroic layer can be formed by the recognized methods of the technique including, but not limited to: lamination, such as one or more plastic sheets or films; mold formation, such as mold coating; film casting; and coating methods. With some embodiments, the dichroic photochromic layer is formed from a photochromic-dichroic composition and coating. The photochromic-dichroic coating composition can be a curable photochromic-dichroic coating composition, that is, curable by exposure to, for example, room temperatures, as in the case of a two-component coating composition; elevated temperatures (for example, 150 ° C to 190 ° C for 5 to 60 minutes), as in the case of thermally cured coating compositions; or actinic radiation, such as in the case of UV curable coating compositions.
[0149] [149] The photochromic-dichroic layer typically includes an organic matrix, such as a thermoplastic organic matrix and / or a cross-linking organic matrix. At least a portion of the organic matrix of the photochromic-dichroic layer may in some embodiments, include anisotropic materials, such as liquid crystal materials, additives, oligomers, and / or polymers, as will be discussed in detail below. In addition or alternatively, to an organic matrix, the photochromic-dichroic layer can include an inorganic matrix, including, for example, silane bonds, siloxane bonds, and / or titanate bonds. The organic matrix of the photochromic-dichroic layer includes, for example, acrylate residues (or monomeric units) and / or methacrylate residues; vinyl waste; ether bonds, sulfide bonds, including monosulfide bonds and / or polysulfide bonds; carboxylic ester bonds, carbonate bonds (for example, -O-C (O) -O-) urethane bonds (for example, -N (H) -C (O) -O-); and / or thio-urethane bonds (for example, -N (H) -C (O) -S-).
[0150] [150] The photochromic-dichroic layer can be any appropriate thickness. With some embodiments, the photochromic-dichroic layer has a thickness of 0.5 to 50 microns, such as from 1 to 45 microns, or from 2 to 40 microns, or from 5 to 30 microns, or from 10 to 25 microns.
[0151] [151] With some embodiments, the photochromic-dichroic layer of the photochromic article additionally includes a separate phase polymer that includes: a matrix phase that is at least partially ordered; and an exposure phase (“guest”) that is at least partially ordered. The exposure phase (“guest”) includes the photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the exposure phase (“guest”).
[0152] [152] In accordance with further embodiments of the present invention, the photochromic-dichroic layer further includes an interpenetrating polymer network that includes: an anisotropic material that is at least partially ordered, and a polymeric material. The anisotropic material includes the photochromic-dichroic compound that is at least partially aligned with at least a portion of the anisotropic material.
[0153] [153] With some embodiments of the present invention, the photochromic-dichroic layer also includes anisotropic material. As used here, the term “anisotropic” means having at least one property that differs in value when measured in at least a different direction. Consequently, “anisotropic materials” are materials that have at least one property that differs in 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 as liquid crystal materials as further described here with respect to the optional alignment layer of the photochromic articles of the present invention.
[0154] [154] With some embodiments, the photochromicdichroic layer: (i) includes liquid crystal oligomers and / or polymers prepared at least in part from monomeric mesogenic compounds; and / or (ii) includes the mesogenic compounds, in each case as described in Table 1 of U.S. Patent No. US 7,910,019 B2, in columns 43-90 thereof, the description of which is incorporated herein by reference.
[0155] [155] According to some embodiments of the present invention, the photochromic-dichroic compound, of the photochromic-dichroic layer, can be at least partially aligned by interaction with the anisotropic material, which itself is at least partially ordered. For example, although not limiting here, at least a portion of the photochromic-dichroic compound can be aligned so that the long geometric axis of the photochromic-dichroic compound in the dichroic state is essentially parallel to the general direction of the anisotropic material. Additionally, although not required, the photochromic-dichroic compound can be bonded to or reacted with at least a portion of at least one partially ordered anisotropic material.
[0156] [156] Methods of ordering, or order of introduction, the anisotropic material of the photochromic-dichroic layer include, but is not limited to, exposure of the anisotropic material to at least one of a magnetic field, an electric field, an ultraviolet radiation linearly polarized, linearly polarized infrared radiation, linearly polarized visible radiation, and a shear force. Alternatively or additionally, the anisotropic material can be at least partially ordered by aligning at least a portion of the anisotropic material with another material or structure. For example, the anisotropic material can be at least partially ordered by aligning the anisotropic material with an alignment layer (or an orientation facility) such as, but not limited to, those alignment layers as described in further details here below.
[0157] [157] By ordering at least a portion of the anisotropic material, it is possible to align, at least partially, a portion of the photochromic-dichroic compound that is contained within or otherwise connected to the anisotropic material of the photochromic-dichroic layer. Although not required, the photochromic-dichroic compound can be at least partially aligned while in an activated state. With some embodiments, the ordering of the anisotropic material and / or the alignment of the photochromic-dichroic compound can occur before, during, or after the application of the photochromic-dichroic layer on the primary layer.
[0158] [158] The photochromic-dichroic compound and anisotropic material can be aligned and ordered during the application of the photochromic-dichroic layer over the primary layer. For example, the photochromic-dichroic layer can be applied using a coating technique that introduces a shear force for the anisotropic material during application, such that the anisotropic material becomes at least partially ordered, generally parallel, to the direction of the applied shear. For the purposes of non-limiting illustration, a solution or mixture (optionally in a solvent or vehicle) including the photochromic-dichroic compound and the anisotropic material and the anisotropic material can be a canvas coating over the primary layer, so that the shear forces are introduced to the materials being applied due to the relative movement of the substrate surface with respect to the materials being applied. An example of a coating process that can introduce at least sufficient shear force is a web coating process. Shear forces can induce at least a portion of the anisotropic material to be ordered in a general direction that is substantially parallel to the direction of movement of the surface. As discussed above, by ordering at least a portion of the anisotropic material in this way, at least a portion of the photochromic-dichroic compound can be aligned. In addition and, optionally, by exposing at least a portion of the photochromic-dichroic compound to actinic radiation during the screen coating process, in order to convert the photochromic-dichroic compound into an activated state, at least partially aligned of the photochromic- dichroic while in the activated state can also be achieved.
[0159] [159] The photochromic-dichroic compound and anisotropic material can be aligned and ordered after the photochromic-dichroic layer is applied over the primary layer. For example, a solution or mixture of the photochromic dichroic compound and the anisotropic material (optionally in a solvent or carrier) can be coated by “spin” over at least a portion of the primary layer. Then, at least a portion of the anisotropic material can be ordered, for example, by exposing the anisotropic material to a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible radiation, and / or a shear force. Alternatively or additionally, the anisotropic material can be at least partially ordered by aligning it with another material or structure, such as an alignment layer.
[0160] [160] The photochromic-dichroic compound and anisotropic material can be aligned and ordered prior to the application of the photochromic-dichroic layer during the primary layer. For example, a solution or mixture (optionally in a solvent or carrier) of the photochromic-dichroic compound and the anisotropic material can be applied on an ordered polymeric sheet to form a layer on it. Then, at least a portion of the anisotropic material can be aligned with the underlying ordered polymeric sheet. The polymeric sheet can subsequently be applied over the primary layer by, for example, lamination recognized in the art or bonding methods. Alternatively, the photochromic-dichroic layer can be transferred from the polymeric sheet to / on the primary layer by methods recognized in the art, such as hot stamping.
[0161] [161] With some embodiments, the photochromicdichroic layer may include a phase-separated polymer that includes: a matrix phase; and an exposure phase (“guest”) distributed in a matrix phase. The exposure phase ("guest") can include an at least partially ordered anisotropic material and at least a portion of the photochromic-dichroic compound, which can be at least partially aligned. The photochromic-dichroic compound at least partially aligned can be at least partially aligned through interaction with an at least partially ordered anisotropic material.
[0162] [162] With some embodiments, a phase separation polymer system including, a matrix phase forming material that includes the anisotropic material and the photochromic-dichroic compound, is applied over the primary layer. After application of the phase separation 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 exposure phase are at least partially ordered, such that at least a portion of the photochromic compound -dichroic is aligned with at least a portion of the partially ordered anisotropic material from the exposure phase (“guest”). The methods of ordering the matrix phase forming material and the exposure phase forming material of the phase separation polymer system include, but are not limited to, exposure of the applied layer to at least one of: a magnetic field, a electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, and a shear force. Alternatively or additionally, the ordering of the matrix phase forming material and the exposure phase forming material may include aligning it by interacting with an underlying alignment layer, as described in further details here.
[0163] [163] After sorting the matrix phase forming material and the exposure phase forming material, the exposure phase forming material can be separated from the matrix phase forming material through polymerization-induced phase separation and / or solvent-induced phase separation. Although the separation of matrix phase and exposure phase forming materials is described here in relation to the exposure phase forming material separate from matrix phase forming material, it should be appreciated that this language is intended to cover any separation between the two phase-forming materials. That is, this language intends to cover the separation of the exposure phase forming material from the matrix phase forming material and separation of the matrix phase forming material from the exposure phase forming material, as well as simultaneous separation of both phase-forming materials and any combination thereof.
[0164] [164] According to some embodiments, the matrix phase forming material may include a liquid crystal material chosen from liquid crystal monomers, liquid crystal prepolymers, and liquid crystal polymers. The exposure phase forming material may, with some embodiments, include a liquid crystal material chosen 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 described here with respect to the optional alignment layer.
[0165] [165] With some embodiments, the phase separation polymer system may include a mixture of a matrix phase forming material that includes a liquid crystal monomer, an exposure phase forming material that includes liquid crystal mesogens and the photochromic-dichroic compound. With this embodiment, inducing the exposure phase forming material to separate from the matrix phase forming material, can include polymerization-induced phase separation. Typically, the liquid crystal monomer of the matrix phase can be polymerized and thereby separated from at least a portion of the liquid crystal mesogens of the exposure phase forming material. Examples of the polymerization methods include, but are not limited to, photo-induced polymerization and thermally-induced polymerization.
[0166] [166] With some additional embodiments, the polymeric phase separation system may include a mixture of a matrix phase forming material that includes a liquid crystal monomer, an exposure phase forming material that includes a liquid crest monomer of low viscosity having a different functionality from the liquid crystal monomer of the matrix phase, and the photochromic-dichroic compound. As used herein, the term "low viscosity liquid crystal monomer" refers to a mixture of liquid crystal monomer or solution that is free of flow at room temperature. Typically, induction of the exposure 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 phase monomer of the matrix phase can be polymerized under conditions that do not induce the liquid phase monomer of the exposure phase to be polymerized. During the polymerization of the matrix phase forming material, the exposure phase forming material typically separates from the matrix phase forming material. Then, the liquid crystal monomer of the exposure phase forming material can be polymerized in a separate polymerization process.
[0167] [167] The polymeric phase separation system may include, with some embodiments, a solution in at least one common solvent of a matrix phase forming material that includes a liquid crystal polymer, an exposure phase forming material that includes a liquid crystal polymer that is different from the liquid crystal polymer of the matrix phase forming material, and the photochromic-dichroic compound. The induction of the exposure phase forming material to separate from the matrix phase forming material typically includes solvent induced separation and phase. Typically, at least a portion of the common solvent is evaporated from the mixture of liquid crystal polymers, thereby inducing two phases to separate one from the other.
[0168] [168] With some additional embodiments, the photochromic-dichroic layer may include an interpenetrating polymer network. The at least partially ordered anisotropic material and a polymeric material can form an interpenetrating polymer network, in which at least a portion of the polymeric material interpenetrates with at least a portion of the at least partially ordered anisotropic material. As used herein, the term "interpenetrating polymer network" means a captured combination of polymers, at least one of which is cross-linked, which are bonded together. Thus, as used herein, the term interpenetrating polymer network includes semi-interpenetrating polymer networks. For example, see, L.H. Sperling, Introduction to Physical Polimer Science, John Wiley & Sons, New York (1986) on page 46. Additionally, at least a portion of at least one partially aligned photochromic-dichroic compound can be at least partially aligned with at least one anisotropic material partially ordered. In addition, the polymeric material can be isotropic or anisotropic, providing that in the whole, the photochromicadichroic layer is anisotropic. The methods of forming such photochromic-dichroic layers are described in more detail below.
[0169] [169] According to some embodiments, the anisotropic material can be adapted to allow the photochromic-dichroic compound to change from a first state to a second state at a desired rate. In general, photochromic-dichroic compounds can undergo a transformation from one isomeric form to another in response to actinic radiation, with each of the isomeric forms having a characteristic absorption spectrum. The photochromic-dichroic compounds of the photochromic articles of the present invention undergo a similar isomeric transformation. Without pretending to be linked to any theory, the rate or speed at which this isomeric transformation (and the reverse transformation) occurs depends, in part, on the properties of the local environment around the photochromic dichroic compound (ie, the “host”). Although not limiting here, it is believed that based on manual evidence of the transformation rate of the photochromic-dichroic compound depends, in part, on the flexibility of the host chain segments, and more particularly on the mobility or viscosity of the segments of the host. host chain. Correspondingly, it is believed, without pretending to be linked to any theory, that the transformation rate of the photochromic-dichroic compound is generally fast in hosts having more flexible chain segments in hosts having rigid or hard chain segments. As such, 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 various isomeric states at the desired rates. For example, the anisotropic material can be adapted by adjusting the molecular weight and / or the cross-linked density of the anisotropic material.
[0170] [170] With some embodiments, the photochromicdichroic layer includes a phase-separated polymer that includes a matrix phase including a liquid crystal polymer, and the exposure phase distributed within the matrix phase. The “guest” phase may include anisotropic material. Typically, a majority of the photochromic-dichroic compound can be contained within the phase of exposure of the phase-separated polymer. As previously discussed, because the transformation rate of the photochromic-dichroic compound depends, in part, on the host in which it is contained, the transformation rate of the photochromic-dichroic compound depends, substantially, on the properties of the "guest" phase.
[0171] [171] With some embodiments, and as discussed in further detail here, the photochromic articles of the present invention may include an alignment layer (also referred to as an alignment or orientation facility) that is interposed between the primary layer and the alignment layer. photochromic-dichroic compound. The phase-separated polymer of the photochromic-dichroic layer, can include a matrix phase, at least a portion of which is at least partially aligned with the alignment layer, and a "guest" phase including an anisotropic material, in which the exposure phase is dispersed within the matrix phase. At least a portion of the anisotropic material of the exposure phase can be at least partially aligned with at least a portion of the alignment layer, and the photochromic-dichroic compound can be at least partially aligned with at least a portion of the anisotropic material. In addition, the matrix phase of the phase-separated polymer can include a liquid crystal polymer, and the anisotropic material of the exposure phase ("guest") can be chosen from liquid crystal polymers and liquid crystal mesogens. Non-limiting examples of said materials are shown in detail above. When including a separate phase polymer as described, the photochromic-dichroic layer can be substantially free of opacity. Opacity is defined as the percentage of transmitted light that deviates from the incident account by more than 2.5 degrees from the average according to ASTM D 1003, from the standard test method (“Standard Test Method of Haze and Luminous Transmittance of Transparent Plastics” ). An example of an instrument in which opacity measurements according to ASTM D 1003 can be made from Haze-Gard PlusTM made by BIK-Gardener.
[0172] [172] According to some embodiments, the photochromic-dichroic compound can be encapsulated or overcoated with an anisotropic material having relatively flexible chain segments, such as a liquid crystal material, and then dispersed or distributed in another material having relatively rigid chain segments. The encapsulating anisotropic material can 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 chain segments and then the mixture can be applied to a substrate to form the photochromic dichroic layer.
[0173] [173] With the additional embodiments, the photochromic-dichroic layer can be a polymeric layer that contains a photochromic-dichroic compound. The polymeric sheet can be uniaxially or biaxially stretched. The stretching of the polymeric blade typically results in alignment and ordering of the photochromic-dichroic material in it. The photochromic-dichroic layer may, with some embodiments, include two or more polymeric sheets each containing a photochromic-dichroic compound, in which each of the sheets can be stretched in the same direction or in a different direction (for example, orthogonal).
[0174] [174] Examples of polymeric sheets that can be used as or to form the photochromic-dichroic layer include, but are not limited to stretched polymer sheets (for example, axially or biaxially stretched), polymer sheets of ordered liquid crystals, and polymer sheets. photo-oriented. Examples of polymeric materials, in addition to liquid crystal materials and photo-oriented materials that can be used in the formation of polymeric sheets of the photochromicdichroic layer include, but are not limited to: poly (vinyl alcohol), poly (vinyl chloride), polyurethane , polyacrylates, and polycaprolactam. Non-limiting examples of at least partially ordered polymer sheet methods are described in greater detail below.
[0175] [175] According to some embodiments, the photochromic-dichroic layer can be formed by applying at least one anisotropic material on the primary layer, embedded in the photochromic-dichroic compound in the previously applied anisotropic material, ordering the anisotropic material, and alignment photochromic-dichroic compound with at least a portion of the ordered anisotropic material. Anisotropic material can be ordered before, during or after being soaked with the photochromic-dichroic compound. The photochromic-dichroic compound can be aligned while in an activated state, with some embodiments.
[0176] [176] The act of soaking the photochromic-dichroic compound in the previously applied anisotropic material may involve, with some embodiments, the application of a solution or a mixture of the photochromic-dichroic compound in a carrier for the previously applied anisotropic material, and allow that the photochromic-dichroic compound diffuses into the anisotropic material, for example, with or without heating. The previously applied anisotropic material can be part of a phase-separated polymer coating, as described above.
[0177] [177] The photochromic articles of the present invention include a primary layer (for example, primary layer 14 of figure 1). The primary layer can include a single layer or multiple layers each including a first photochromic compound that can be the same or different. The primary layer typically includes an organic matrix, such as a thermoplastic organic matrix and / or a cross-linked organic matrix. Additionally or alternatively, in an organic matrix, the primary layer can include an inorganic matrix, including, for example, silane bonds, siloxane bonds and / or titanate bonds. The organic matrix can include, for example, acrylate residues (or monomer units) and / or methacrylate residues; vinyl waste; ether bonds, sulfide bonds, including monosulfide bonds and / or polysulfide bonds; carboxylic ester bonds; carbonate bonds (for example, -O-C (O) -O-), urethane bonds (for example, - N (H) -C (O) -O-); and / or thiourethane bonds (for example, - N (H) -C (O) -S-).
[0178] [178] The primary layer may be formed by methods known in the art including, but not limited to: lamination, such as one or more sheets or plastic films; mold forming, such as mold coating, film casting; and coating methods. Typically, the primary layer is formed from a primary coating composition. The primary coating composition can be a curable primary coating composition that is curable by exposing, for example, to room temperature, such as in the case of two component coating compositions; elevated temperatures (for example, 150 ° C to 190 ° C for 5 to 60 minutes), as in the case of UV-curable coating compositions.
[0179] [179] The primary layer can be any appropriate thickness. With some embodiments, the primary layer is 0.5 microns to 20 microns thick, such as 1 to 10 microns, or 2 to 8 microns, or 3 to 5 microns, including the quoted values.
[0180] [180] With some embodiments, the primary layer includes an organic matrix that includes urethane bonds. According to some embodiments, the primary layer containing the urethane bonds is formed from the curable coating composition which includes: a (meth) acrylate copolymer having active hydrogen functionality selected from hydroxyl, thiol, primary amine, secondary amine , and combinations thereof; blocked isocyanate, such as diisocyanate and / or triisocyanates blocked with an appropriate blocking or starting group, such as 3,5-dimethyl pyrazole; and one or more additives, including but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radical purgers, plasticizers, flow additives, and / or static inks or static dyes ( that is, paints or dyes that are not photochromic).
[0181] [181] Examples of (meth) acrylate monomers from which the functional active hydrogen of the (meth) acrylate copolymer can be prepared include, but are not limited to, (meth) acrylate C1-C20, (meth) acrylate -C20 having at least one active hydrogen group selected from hydroxyl, thiol, primary amine, and secondary amine. The (meth) acrylate C1-C20 groups can be selected from, for example, linear C1-C20 alkyl, branched C3-C20 alkyl, C3-C20 cycloalkyl, fused ring C3-C20 polycycloalkyl, C5-C20 aryl, and fused ring C10-C20 aryl.
[0182] [182] Additional polyols that can be used in the primary coating compositions from which the primary layer is prepared include, but are not limited to, materials recognized in the art, as described in U.S. Patent No. US 7,465,414, in column 15, line 22 to column 16, line 62, the description of which is incorporated herein by reference. Isocyanates that can be used in the primary coating compositions from which the primary layer is prepared include, but are not limited to, materials recognized in the art, such as those described in U.S. Patent No. US 7,465,414, in column 16 , line 63 to column 17, line 38, the description of which is incorporated herein by reference. Catalysts that can be used in the primary coating compositions from which the primary layer is prepared include, but are not limited to, the materials recognized in the art, as described in U.S. Patent No. US 7,465,414 in column 17, line 39-62 , the description of which is incorporated herein by reference.
[0183] [183] The primary layer may include additional additives that improve the performance of the first photochromic compound. Said additional additives may include, but are not limited to, ultraviolet light absorbers, stabilizers, such as hindered amine moon stabilizers (HALS), antioxidant, for example, polyphenolic antioxidants, asymmetric diaryloxalamide compounds (oxanilide), isolated oxygen repressors , for example, a nickel ion complex with an organic binder, and mixtures and / or combinations of said additive materials to improve photochromic performance.
[0184] [184] The primary layer can be applied to the substrate by the recognized methods of the technique including, but not limited to, spray application, spindle coating, medical blade application (or lowering), and canvas application.
[0185] [185] The primary layer may include at least partially hydrolyzed coupling agents and mixtures thereof. As used herein, "coupling agent" means a material having at least one group capable of reacting, bonding and / or associating with a group on at least one surface. With some embodiments, a coupling agent can serve as a molecular bridge at the interface of at least two surfaces that can be similar or non-similar surfaces. Coupling agents, with some additional embodiments, can be monomers, oligomers, prepolymers and / or polymers. Said materials include, but are not limited to, organo-metals such as silanes, titanates, zirconates, aluminates, zirconia aluminates, hydrolysates thereof and mixtures thereof. As used herein, the phrase "coupling agents at least partially hydrolyzed" means at least some of all hydrolyzable groups in the coupling agent are hydrolyzed.
[0186] [186] In addition or alternatively, the coupling agents and / or hydrolyzates of the coupling agent, the primary layer may include other adhesion-enhancing ingredients. For example, although not limiting here, the primary layer can still include an adhesion-improving amount of an epoxy-containing material. The adhesion-improving amounts of an epoxy-containing material when included in the primary layer, can improve the adhesion of a subsequently applied coating or layer. A class of an epoxy (or oxirane) functional adhesion promoter that can be included in the compositions from which the primary layer is formed includes, but is not limited to, functional alkyl-trialkoxysilanes, oxirane, such as gamma glycidoxypropyltrimethoxysilane, such as gammaglycidoxypropyltrimethoxysilane, and beta- (3,4- epoxycyclohexyl) ethyltrimethoxysilane.
[0187] [187] The first photochromic compound in the primary layer can be selected from the photochromic compounds recognized in the art. With some embodiments, the first photochromic compound is selected from indeno-fused naphthopyranes, naphtho [1,2-b] pyranes, naphtho [2,1-b] pyranes, spirofluoroene [1,2-b] pyranes, phenanthropirans, quinolinopyranes, fluoroantenopyranes, spiropyranes, benzoxazins, naphthoxazine, spiro (indoline) fluoranthenoxazins, spiro (indoline) quinoxazins, fulgides, fulgimidas, diariletenes, diarylalaquiletenes, diarylalkenylenes, thermoreversible, thermoreversible and reversible photochromic compounds.
[0188] [188] The first photochromic compound of the first layer can, with some embodiments, be selected from certain indeno-fused naphthopyran compounds, as described in U.S. Patent No. US 6,296,785, in column 3, lines 66 through column 10 , line 51, the description of which is incorporated herein by reference.
[0189] [189] More particular examples of the indeno-fused naphthopyran compounds from which the first photochromic compound can be selected include, but are not limited to: (Pa) 3,3-di (4-methoxyphenyl) -6,7,10,11-tetramethoxy-13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphthus [1, 2-b] pyran; (Pb) 3-phenyl-3- (4-morpholinophenyl) -6,7,10,11-tetramethoxy13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2 -b] pyran; (Pc) 3,3-di (4-methoxyphenyl) -6,7,10,11-tetramethoxy-13-hydroxy-13-ethyl-3H, 13H-indene [2 ', 3': 3,4] naphthus [ 1,2-b] pyran; (Pd) 3,3-di (4-methoxyphenyl) -6,7,11-trimethoxy-13,13-dimethyl3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (Pe) 3,3-di (4-methoxyphenyl) -6-methoxy-13-hydroxy-13-ethyl3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (Pf) 3,3-di (4-methoxyphenyl) -6,7,10,11-tetramethoxy-13,13-diethyl-3H, 13H-indene [2 ', 3': 3,4] naphthus [1, 2-b] pyran; (Pg) 3,3-di (4-methoxyphenyl) -6-morpholino-13-phenyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (Ph) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,11-dimethoxy-13-hydroxy-13-phenyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2- b] pyran; (Pi) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,11-dimethoxy13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2 -b] pyran; (Pj) 3- (4-methoxyphenyl) -3- (4-dimethylaminophenyl) -6,11- dimethoxy-13,13-dimethyl -3H, 13H-indene [2 ', 3': 3,4] naphtho [1 , 2- b] pyran; (Pk) 3,3-di (4-methoxyphenyl) -6,7,8-trimethoxy-13-phenyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (Pl) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7,10,11- tetramethoxy-13-hydroxy-13-ethyl-3H, 13H-indene [2 ', 3': 3 , 4] naphtho [1,2-b] pyran; (Pm) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7,10,11- tetramethoxy-13-hydroxy-13-butyl-3H, 13H-indene [2 ', 3': 3 , 4] naphtho [1,2-b] pyran; (Pn) 3- (4-morpholinophenyl) -3-phenyl-6,11-dimethoxy-13-hydroxy-13-ethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2 -b] pyran; (Po) 3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl-6,11- dimethoxy-13,13-dimethyl -3H, 13H-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran; (Pp) 3- (4-morpholinophenyl) -3-phenyl-6,11-dimethoxy-13-hydroxy-13-butyl-3H, 13H-indene [2 ', 3': 3,4] naphthus [1,2 -b] pyran; (Pq) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-13-hydroxy-13-ethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1 , 2-b] pyran; (Pr) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-diethylamino - 13-ethyl-13-methoxy-3H, 13H-indene [2 ', 3': 3,4] naphtho [1 , 2- b] pyran; (Ps) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,11-dimethoxy13-hydroxy-13-methyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1 , 2- b] pyran; (Pt) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6,7,8-trimethoxy-13-methoxy-13-methyl-3H, 13H-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran; and combinations of two or more of the same.
[0190] [190] The first photochromic compound of the primary layer can, with some additional embodiments, be selected from one or more indene-fused naphthopyran compounds having a pi-conjugated extension group, such as a halogen or substituted halogen group, attached to a position. 11 of naphthytophanes fused indene. Examples of indene-fused naphthopyran compounds having a pi-conjugation extension attached to position 11 thereof include, but are not limited to, those described in US patent application No. US 2011/0049445 A1 in paragraphs [0030] through [080].
[0191] [191] More particular examples of fused naphthopyran compounds having a pi conjugation extension attached to position 11 thereof, from which the first photochromic compound of the primary layer can be selected include, but is not limited to: (Pi) 3,3-di (4-methoxyphenyl) -6-methoxy-11- (4-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (P-ii) 3,3-di (4-methoxyphenyl) -6,7-dimethoxy-11- (3,5-bis (trifluoromethyl) phenyl) -13,13-dimethyl-3H, 13H-indene [2 ' , 3 ': 3,4] naphtho [1,2-b] pyran; (P-iii) 3,3-di (4-methoxyphenyl) -6,7-dimethoxy-11- (2-trifluoromethyl) phenyl-13,13-diethyl-3H, 13H-indene [2 ', 3': 3 , 4] naphtho [1,2-b] pyran; (P-iv) 3,3-di- (4-methoxyphenyl) -6-methoxy-7-piperidino-11- (4-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [2 ', 3 ': 3,4] naphtho [1,2-b] pyran; (Pv) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-11- (4-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [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-indene [ 2 ', 3': 3,4] naphtho [1,2-b] pyran; (P-vii) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-7-morpholine-11- (4-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [ 2 ', 3': 3,4] naphtho [1,2-b] pyran; (P-viii) 3,3-di (4-hydroxyphenyl) -6,7-dimethoxy-11- (3,5-bis (trifluoromethyl) phenyl) -13,13-dimethyl-3H, 13H-indene [2 ' , 3 ': 3,4] naphtho [1,2-b] pyran; (P-ix) 3,3-di- (4-methoxyphenyl-6-methoxy-7-morpholino-11- (4-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [2 ', 3' : 3.4] naphtho [1,2-b] pyran; (Px) 3,3-bis (4-methoxyphenyl) -7-methoxy-11- (2-trifluoromethyl) phenyl-13,13-dimethyl-3H, 13H-indene [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-indene [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-indene [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-indene [2 ', 3': 3,4] naphth [1,2-b] pyran; (P-xiv) 3- (4-butoxyphenyl) -3- (4-methoxyphenyl) -6,7-dimethoxy11- (3- (trifluoromethyl) pyridin-2-yl) -13,13-dimethyl-3H, 13H- indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; and combinations of two or more of the same.
[0192] [192] The first photochromic compound of the primary layer, with some embodiments, can be covalently linked to the matrix, like the organic matrix, of the primary layer. With some embodiments, the first photochromic compound can include one or more reactive groups, such as one or more polymerizable groups. With some embodiments, the first photochromic compound can be selected from 2Hnafto [1,2-b] pyran, 3H-naphtho [2,1-b] pyranes and / or indene [2,1- f] naphthus [1, 2-b] pyranes each having at least one functional group that is 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 per substituent which is capped (or finished) with a polymerizable group. Examples of said photochromic compounds from which the first photochromic compound can be selected include, but are not limited to, those described in U.S. Patent No. US 6,113,814, in column 2, lines 52 through column 8, line 40, whose description is hereby incorporated by reference.
[0193] [193] More particular examples of photochromic compounds having reactive functionality from which the first photochromic compound in the primary layer can be selected include, but is not limited to: (P-a ') 2,2-bis (4-methoxyphenyl) -5- (2-hydroxyethoxycarbonyl) -8-phenyl- [2H] -naphth [1,2-b] pyran; (P-b ') 2,2-bis (4-methoxyphenyl) -5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -8-phenyl- [2 H] -naphth [1,2-b] pyran; (P-c ') 3,3-di (4-methoxyphenyl) -6,11-dimethoxy-13-methyl-13- (2- (2-hydroxyethoxy) ethoxy) - 3H, 13H-indene [2', 3 ': 3,4] naphtho [1,2- b] pyran (P-d ') 3,3-di (4-methoxyphenyl) -6,11-dimethoxy-13-methyl-13- (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) - 3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran (P-e ') 3- (4- (2-hydroxyethoxy) phenyl) -3- (4-morpholinophenyl) -6-methoxy-11- (4-trifluoromethylphenyl) -13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran (P-f ') 3- (4- (2- (2- (2-hydroxyethioxy) ethoxy) ethoxy) phenyl) -3-phenyl-9-methoxycarbonyl-8-methoxy- [3H] -naphth [2, - 1-b] pyran; and combinations of two or more of the same.
[0194] [194] The photochromic articles of the present invention include a top coat layer (for example, top coat layer 20 of figure 1). The top coat layer can include a single layer or multiple layers, each including a second photochromic compound that can be the same or a different one. The top coating layer typically includes an organic matrix, such as a thermoplastic organic matrix and / or a cross-linked organic matrix. In addition, or alternatively, to an organic matrix, the top coating layer may include an inorganic matrix, including, for example, silane bonds, siloxane bonds and / or titanate bonds. The organic matrix can include, for example, acrylate residues (or monomer units) and / or methacrylate residues, vinyl residues, ether bonds, sulfide bonds, including monosulfide bonds and / or polysulfide bonds; carboxylic ester bonds, carbonate bonds (for example, -O-C (O) -O-) urethane bonds (for example, -N (H) -C (O) -O-); and / or thiourethane bonds (for example, -N (H) -C (O) -S-).
[0195] [195] The top coat layer may be formed by methods recognized in the art including, but not limited to: lamination, such as one or more plastic sheets or films; mold formation, such as mold coating; film casting; and coating methods. Typically, the top coat layer is formed from the top coat composition. The topcoat composition may be a curable coating composition, that is, curable through exposure to, for example, room temperature, as in the case of two-component coating compositions; elevated temperatures (for example, 150 ° C to 190 ° C for 5 to 60 minutes), as in the case of thermally cured coating compositions; or actinic radiation, as in the case of UV curable coating compositions.
[0196] [196] The top coating layer can be any appropriate thickness. With some embodiments, the top coating layer has a thickness of 0.5 microns to 10 microns, such as 1 to 8 microns, or 2 to 5 microns, including the values quoted.
[0197] [197] With some embodiments, the topcoat layers include an organic matrix formed from a radiation-cured acrylate-based composition and, correspondingly, the topcoat layer can be described as an acrylate-based topcoat layer .
[0198] [198] The acrylate-based topcoat layer can be prepared using (meth) acrylate monomers and / or (meth) acrylic acid monomers. The (meth) acrylate monomers can include one, two, three, four, or five (meth) acrylate groups. Additional copolymerizable monomers, such as epoxy monomers, for example, monomers containing an epoxy (or oxirane) functionality, monomers containing both, (meth) acrylate and epoxy functionality, etc., may also be present in the formulation used to prepare the layer top coat based on (meth) acrylate. The monomers used to prepare the coating layer based on (meth) acrylate include a plurality of, for example, a greater amount, i.e., more than 50 weight percent, of (meth) acrylate monomers; therefore, the designation “upper coating layer based on (meth) acrylate”. The formulations used to prepare the coating layer based on (meth) acrylate can also contain the components having at least one isocyanate group (-NCO), for example, organic monoisocyanates, organic diisocyanates, and organic triisocyanates, thus, the bonds of urethane can be incorporated within the top coat layer.
[0199] [199] The top layer of (meth) acrylate-based typically has physical properties including, for example, transparency, adherence to the underlying photochromic-dichroic layer, resistance to removal by aqueous alkali metal hydroxide, compatibility with a coating optional abrasion resistant, such as a hard coating, applied to its surface, and stretch resistance. With some embodiments, the top coating layer based on (meth) acrylate has a hardness that is greater than that of the photochromic-dichroic layer.
[0200] [200] Radiation curing of (meth) acrylate-based polymeric systems can be achieved with, for example, curing by electron (EB) and / or ultraviolet light (UV) radiation. Ultraviolet curing typically requires the presence of at least a photoinitiator, while EB curing does not require a photoinitiator. With the exception of the presence or absence of the photoinitiator, formulations based on (meth) acrylate, which are cured by either UV or EB radiation technology, may otherwise be identical.
[0201] [201] Radiation-curable (meth) acrylate-based polymer systems are well known in the art of polymers, and any of these systems can be used to produce the photochromic (meth) acrylate top coating layer of the present invention. According to some embodiments, the top coating layer based on (meth) acrylate is formed from a composition that includes a miscible combination or mixture of one or more free radical-initiated (meth) acrylate monomers and / or oligomers (meth) acrylate, and one or more cationic initiated epoxy monomers. When this monomer mixture is cured, a top layer of (meth) acrylate base, in the form of a polymer, is formed and includes a network of interpenetration of the polymeric components.
[0202] [202] Examples of (meth) acrylate monomers that can be included in compositions from which the top coating layer based on (meth) acrylate can be formed, includes, but is not limited to, polyfunctional (meth) acrylates having, for example, 1, 2, 3, 4, or 5 mono-functional (meth) acrylate, and (meth) acrylate groups, for example, a monomer containing a single (meth) acrylate group, substituted hydroxy (meth) acrylate and alkoxysilyl alkylacrylates, such as trialcoxysilylpropyl methacrylate. Other reactive monomers / diluents, such as monomers containing a functional ethylene group (in addition to other (meth) acrylate monomers) may also be present.
[0203] [203] The compositions from which the top coating layer based on (meth) acrylate can be formed, and methods of applying and curing said compositions, are described in column 16, line 14 through column 25, line 3 of U.S. Patent No. US 7,452,611 B2, the description of which is incorporated herein by reference.
[0204] [204] The compositions from which the top coat layer is formed may include one or more additives, including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, purgers. free radial, plasticizers, flow additives, and / or static inks or static dyes (ie paints or dyes that are not photochromic).
[0205] [205] With some embodiments, the compositions from which the top coating layer based on (meth) acrylate can be formed, can further include an adhesion promoter. The adhesion promoter can be selected from, for example, organosilanes, such as aminoorganosilanes, organic titanate coupling agents, organic zirconate coupling agents, and combinations thereof. Examples of adhesion promoters, which can be included in the compositions from which the top layer of the acrylate base can be formed, include, but are not limited to those described in column 5, line 52 through column 8, line 19 US Patent No. 7,410,691 B2, the description of which is incorporated herein by reference.
[0206] [206] The topcoat layer, in some embodiments, includes an ultraviolet light absorber and / or a second photochromic compound. With some embodiments, the top coating layer includes an ultraviolet light absorber, and is free of the second photochromic compound. With some embodiments, the top coating layer includes both an ultraviolet light absorber and the second photochromic compound. With some additional embodiments, the coating layer includes the second photochromic compound, and is free of an ultraviolet light absorber. The ultraviolet light absorber can be selected from one or more recognized classes of the ultraviolet light absorber technique, including, but not limited to: hindered amines, which may include, for example, one or more N-substituted piperidine groups 2, 2,6,6-tetramethyl; benzophenones; and / or benzotriazole. The ultraviolet light absorber is typically present in at least an effective amount, such as 0.1 to 10 weight percent, or 0.2 to 5 weight percent, or 0.3 to 3 weight percent , based on the total solids weight of the coating composition from which the top coating layer is prepared.
[0207] [207] The second photochromic compound can in some embodiments be selected from fused indene naphthytophans, [1,2-b] pyrane naphtha, [2,1-b] pyrane, spirofluorene [1,2-b] pyrane, phenanthropirans, quinolinopyranes, fluoroantenopyranes, spiropyranes, benzoxazins, naphthoxazine, spiro (indoline) naphtoxazine, spiro (indoline) pyridobenzoxazins, spiro (indoline) fluoranthenoxazines, spiro (indoline) quinoxazens, fulgent, diarrhea, dialysis, fulgent, dialysis , and non-thermally reversible photochromic compounds and mixtures thereof.
[0208] [208] The second photochromic compound of the top coat layer, with some embodiments, can be covalently attached to the matrix, such as the organic matrix, of the top coat layer. With some embodiments, the second photochromic compound can include one or more reactive groups, such as one or more polymerizable groups. With some embodiments, the second photochromic compound can include at least one functional group that is capable of forming a covalent bond with another functional group, such as at least one polymerizable group, such as at least one polyalkoxylated substituent, from 1 to 50 units alkoxy per substituent which is capped at the end (or finished) with a polymerizable group.
[0209] [209] The second photochromic compound, according to some additional embodiments, includes at least one open ring cyclic monomer. Examples of open ring monomers include, but are not limited to, cyclic esters, cyclic carbonates, cyclic ethers, and cyclic siloxanes. More particular examples of cyclic open ring monomers include, but are not limited to, e-caprolactone and 6-valerolactone.
[0210] [210] Photochromic compounds that include at least one open ring cyclic monomer, from which the second photochromic compound can be selected, include, but are not limited to, those described in column 2, row 32 through column 6, row 60 of U.S. Patent No. US 7,465,415 B2, the description of which is incorporated herein by reference. More particular examples of photochromic compounds having at least one open ring monomer covalently attached to it, from which the second photochromic compound can be selected, include, but are not limited to, those described in columns 86 through 103, and represented by the formulas 17 to 28 of U.S. Patent No. US 7,465,415 B2, the description of which is incorporated herein by reference.
[0211] [211] Examples of open ring cyclic monomers that can be used to form photochromic compounds having at least one open ring monomer covalently attached to it, from which the second photochromic compound can be selected include, but are not limited to, those described in column 10, line 43 through column 12, lines 26 of U.S. Patent No. US 7,465,415 B2, the description of which is incorporated herein by reference. Examples of the photochromic initiators that can be reacted with cyclic open ring monomers to form photochromic compounds having at least one open ring monomer covalently bonded to it, from which the second photochromic compound can be selected, includes, but does not include are limited to those described in Table 1 in columns 14 through 59 of U.S. Patent No. US 7,465,415 B2, the description of which is incorporated herein by reference.
[0212] [212] More particular examples of photochromic initiators that can be reacted with cyclic open ring monomers (including, but not limited to, cyclic esters, cyclic carbonates, cyclic ethers, and / or cyclic siloxanes as discussed above) in order to forming the photochromic compounds having at least one open ring monomer covalently attached to it, from which the second photochromic compound of the upper coating layer can be selected includes, but is not limited to the following: (TC-1) 3,3-di (4-methoxyphenyl) - 5-methoxycarbonyl-6-phenyl8,9-dimethoxy-2H-naphtho [1,2-b] pyran; (TC-2) 3,3-di (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-indene [2 ', 3': 3,4] naphthus [ 1,2-b] pyran (TC-7) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-13- (2-hydroxyethyl) - 3H, 13H-indene [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-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran; (TC-9) 2,2-diphenyl-5- (2,3-dihydroxy) propoxycarbonyl-8-methyl2H-naphtho [1,2-b] pyran; (TC-10) 2- (4- (2- (2-hydroxyethoxy) ethoxy) 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) ethoxyarbonyl) -8-methyl-2H-naphtho [1, - 2-b] pyran; (TC-12) 2,2-di (4-methoxyphenyl) -5- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxycarbonyl) -6-phenyl-2H-naphtho [1,2-b] pyran; (TC-13) 3,3-di (4-methoxyphenyl) -6-morpholino-3H-naphtho [2,1-b] pyran; (TC-14) 3,3-di (4-methoxyphenyl) -6-phenyl-3H-naphtho [2,1-b] pyran; (TC-15) 3,3-diphenyl-5-hydroxy-6- (2-hydroxyphenyl) -3Hnafto [2,1-b] pyran; and combinations of two or more of the same.
[0213] [213] The photochromic articles of the present invention may include, with some embodiments, an alignment layer that is interposed between the primary layer and the photochromic-dichroic layer. Referring to Figure 1 of the photochromic article 2 includes an alignment layer 50 which is interposed between the primary layer 14 and the photochromic dichroic layer 17. The alignment layer can also be referred to here as an orientation facility. The photochromic-dichroic compound of the photochromic-dichroic layer can be at least partially aligned by interaction with the underlying alignment layer.
[0214] [214] As used here, the term "alignment layer" means a layer that can facilitate the positioning of one or more other structures that are exposed, directly and / or indirectly, to at least a portion of it. As used here the term "order" means bringing about an appropriate arrangement or position, such as alignment with another structure or material, or by some other force or effect. Thus, as used here, the term “order” encompasses both the methods of ordering contact of a material, such as alignment with another structure or material, and methods of non-contact ordering of a material, such as by exposure to an external force or effect. The term order also encompasses combinations of contact and non-contact methods.
[0215] [215] For example, the photochromic-dichroic compound that is at least partially aligned by interaction with the alignment layer can be at least partially aligned, so that the longitudinal geometric axis of the photochromic-dichroic compound in the activated state is essentially parallel in at least a first general direction of the alignment layer. With some embodiments, the dichroic photochromic compound that is at least partially aligned by interaction with the alignment layer is bonded to or reacted with the alignment layer. As used here with reference to the order or alignment of a material or structure, the term "general direction" refers to the predominant arrangement or orientation of the material, compound or structure. In addition, it will be appreciated by those skilled in the art that a material, compound or structure may have a general direction even if there is some variation within the arrangement of the material, compound or structure, providing that the material, compound or structure has at least one predominant arrangement.
[0216] [216] The alignment layer can, with 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 a second ordered region adjacent to the first ordered region having a second general direction that is different from the first general direction. Furthermore, the alignment layer can have a plurality of regions, each of which has a general direction that is the same or different from the remaining regions in order to form a desired pattern or design. The alignment layer may include, for example, a coating including at least a partially ordered alignment means, a polymeric sheet at least partially ordered, a surface at least partially treated, Langmuir-Blodgett films, and combinations thereof.
[0217] [217] The alignment layer may, with some embodiments, include a coating that includes at least partially an ordered alignment means. Examples of suitable alignment means that can be used in conjunction with the alignment layer include, but are not limited to, photo-orientation materials, slip guidance materials, and liquid crystal materials. The methods of ordering at least a portion of the alignment means are described here in further detail.
[0218] [218] The alignment means of the alignment layer can be a liquid crystal material, and the alignment layer can be referred to as a liquid crystal alignment layer. Liquid crystal materials, due to their structure, are generally able to be ordered or aligned in order to take a general direction. More specifically, because liquid crystal molecules have disk- or rod-like structures, a long rigid axial axis, and strong dipoles, liquid crystal molecules can be ordered or aligned through interaction with an external force or other structure, such as the long geometric axis of molecules taken in an orientation that is generally parallel to a common axis. For example, it is possible to align the molecules of a liquid crystal material with a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, or shear forces. It is possible to align the liquid crystal molecules with an oriented surface. For example, liquid crystal molecules can be applied to a surface that has been oriented, for example, by polishing, grooving, or photo-alignment methods, and subsequently aligned so that the long geometric axis of each of the molecules of liquid crystal takes an orientation that is generally parallel to the general direction of orientation of the surface. 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 partially polymerized materials.
[0219] [219] Classes of liquid crystal monomers that are suitable for use in conjunction with the alignment layer include, but are not limited to, mono- as well as multi-functional liquid crystal monomers. Liquid crystal monomers can, with some embodiments, be selected from cross-linked liquid crystal monomers, such as photoreticulated liquid crystal monomers. As used herein, the term "photo-crosslinked" means a material, such as a monomer, prepolymer or polymer, that can be crosslinked upon exposure to actinic radiation. For example, photo-crosslinked liquid crystal monomers include, but are not limited to, those liquid crystal monomers that are crosslinkable on exposure to ultraviolet radiation and / or visible radiation, either with or without the use of polymerization initiators.
[0220] [220] Examples of cross-linked liquid crystal monomers, which can be included in the alignment layer include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylate, methacrylates, allyl, allyl ethers, alkines, amino, anhydrides, epoxides, hydroxides, isocyanate, blocked isocyanate, siloxane, thiocyanates, thiols, urea, vinyl, vinyl ethers, and mixtures thereof. Examples of photo-crosslinked liquid crystal monomers, which can be included in the alignment layer include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylate, methacrylates, alkines, epoxides, thiols, and mixtures thereof.
[0221] [221] Liquid crystal polymers and prepolymers that can be included in the alignment layer include, but are not limited to, main chain liquid crystal polymers and side chain and pre chain polymers and liquid crystal polymers -polymers. With main chain liquid crystal polymers and prepolymers, disc-type or stem-type liquid crystal mesogens are primarily located within the polymer's main chain. With side chain liquid crystal polymers and prepolymers, disc or rod type liquid crystal mesogens are located within the polymer side chains. In addition, the liquid crystal polymer or prepolymer can be crosslinkable, and in addition it can be photo crosslinkable.
[0222] [222] Examples of liquid crystal polymers or prepolymers, which may be included in the alignment layer, include but are not limited to, main or side chain polymers or prepolymers having functional groups chosen from acrylate , methacrylates, allyl, allyl esters, alkynes, amino, anhydride, epoxides, hydroxides, isocyanate, blocked isocyanate, siloxanes, thiocyanates, thiols, urea, vinyl, divinyl ethers, and mixtures thereof. Examples of photo-crosslinkable liquid crystal polymers and prepolymers, which can be included in the alignment layer, include, but are not limited to, polymers and prepolymers having functional groups chosen from acrylate, methacrylates, alkynes, epoxides , thiols, and mixtures thereof.
[0223] [223] Liquid crystal mesogens, which can 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 can be included in the alignment layer, include, but are not limited to, colummatic (or stem-type) liquid crystal mesogens and discotic (or disc-type) liquid crystal mesogens.
[0224] [224] Examples of photo-orientation materials, which can be included in the alignment layer, include, but are not limited to, a photo-oriented polymer network. More specific examples of photo-oriented polymer networks include, but are not aligned to, azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives and polyimides. With some embodiments, the alignment layer may include at least one ordered partially photo-oriented polymer network chosen from azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives, and / or polyimides. Examples of derivatives of cinnamic acid, which can be included in the alignment layer, include, but are not limited to, polyvinyl cinnamate and polyvinyl esters of parametoxicinamic acid.
[0225] [225] As used here, the term "polished orientation material" means a material that can be at least partially ordered by polishing at least a portion of a surface of the material with another material of an appropriate texture. For example, the polished orientation material can be polished with an appropriately textured fabric or a velvety brush. Examples of polished orientation materials, which can be included in the alignment layer, include, but are not limited to, (poly) imides, (poly) siloxane, (poly) acrylate, and (poly) coumarins. With some embodiments, the alignment layer can include a polyimide, and the alignment layer can be polished with a cotton fabric or velvety so that it is at least partially ordered from a portion of the surface of the alignment layer.
[0226] [226] With some embodiments, the alignment layer can include at least one partially ordered polymeric sheet. For example, a blade of polyvinyl alcohol can be at least partially ordered through the stretch (e.g., uniaxial stretch) of the blade, and then the drawn blade can be attached to at least a portion of an optical substrate surface to form ease of orientation. Alternatively, the ordered polymer sheet can be made by a method that at least partially sorts the polymer chains can be formed by casting or otherwise forming a sheet of a liquid crystal material and then at least partially ordered from the blade, for example, but exposing the blade to a magnetic field, an electric field, and / or a shear force. Furthermore, the at least partially ordered polymer sheet can be made using the photo-orientation methods. For example, the sheet of a photo-orientation material can be formed, for example, by casting and then at least partially ordered by exposure to linearly polarized ultraviolet radiation.
[0227] [227] The alignment layer of the photochromic articles of the present invention can include a surface that is at least partially treated. As used herein, the term "treated surface" refers to at least a portion of a surface that has been physically altered to create at least one ordered region on at least a portion of the surface. Examples of treated surfaces include, but are not limited to, polished surfaces, carved surfaces, and inlaid surfaces. In addition, the treated surfaces can be standardized, for example, using a photolithography process or an interferography process. With 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 (such as etched surfaces using a scanning tunnel microscope or an atomic force microscope), laser notch surface, and / or electron beam notch surface.
[0228] [228] According to some embodiments, when the alignment layer includes a treated surface, the treated surface can be formed by depositing a metallic salt (such as a metallic oxide or metal fluoride) on at least a portion of a surface ( for example, a surface of the alignment layer itself, or a surface of the primary layer), and then notch the deposit to form the treated surface. Methods recognized by the deposition technique and a metal salt include, but are not limited to, plasma vapor deposition, chemical vapor deposition, and sputtering. Polishing can be done according to the recognized methods of the art, such as those described here previously.
[0229] [229] As used here, the term "LangmuirBlodgett film" means one or more molecular films at least partially ordered on a surface. Langmuir-Blodgett films can be formed, for example, by immersing a substrate in a liquid one or more times so that it is at least partially covered by a molecular film and then removed from the substrate from the liquid, so that, due to the relative surface stresses of the liquid and the substrate, the molecules of the molecular film are at least partially ordered in substantially a general (or a single) direction. As used herein, the term molecular film refers to monomolecular films (i.e., monolayers) as well as films comprising more than one monolayer.
[0230] [230] The photochromic articles of the present invention may, with some embodiments, also include an alignment transfer material interposed between the alignment layer and the photochromic-dichroic layer. The alignment transfer material can be aligned by interaction with the alignment layer and, correspondingly, the photochromic-dichroic compound can be aligned by interaction with the alignment transfer material. The alignment transfer material can, with some embodiments, facilitate the propagation or transfer of an appropriate arrangement or position of the alignment layer of the photochromic-dichroic compound from the photochromic-dichroic layer.
[0231] [231] Examples of alignment transfer materials include, but are not limited to, those liquid crystal materials described above in conjunction with the alignment means described here. It is possible to align the molecules of a liquid crystal material with an oriented surface. For example, a liquid crystal material can be applied to a surface that has been oriented and subsequently aligned so that the longitudinal geometric axis of the liquid crystal molecules adopts an orientation that is generally parallel to the same general direction of the surface. The liquid crystal material of the alignment transfer material can be at least partially ordered by alignment with the alignment layer, so that the longitudinal geometric axis of the molecules of the liquid crystal material is generally parallel to, for example, a first direction general orientation facility. In this way, the general direction of the alignment layer can be transferred to the liquid crystal material, which can then 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 pattern or design, the pattern or pattern of which can be transferred to the liquid crystal material by aligning the liquid crystal material with several regions of the liquid layer. alignment. In addition, although not required, according to various non-limiting embodiments described here, at least a portion of the liquid crystal material of the alignment transfer material can be exposed to at least one of, a magnetic field, an electric field, radiation linearly polarized infrared, linearly polarized ultraviolet radiation, and linearly polarized visible radiation, while being at least partially aligned with at least a portion of the alignment layer.
[0232] [232] The photochromic articles of the present invention may, with some embodiments, include a durable coating layer that resides on the upper coating layer. With reference to figure 1, the photochromic article 2 includes a hard coating layer 53 which resides on the coating layer 20. The hard coating layer can include a single layer or multiple layers.
[0233] [233] The hard coating layer can be selected from abrasion resistant coatings including organosilanes, abrasion resistant coatings including thin films based on radiation cured acrylate, abrasion resistant coatings based on inorganic materials such as silica, titanite, / or zirconia, abrasion-resistant organic coatings of the type that are curable by ultraviolet light, coatings with oxygen barrier, coatings with UV protection, and combinations thereof. With some embodiments, the hard coating layer may include a first coating of a radiation-cured acrylate-based thin film and a second coating including an organosilanes. Non-limiting examples of commercial hard coating products include SILVUE® 124 and HI-GARD® coatings, available from SDS Coatings, Inc., and PPG Industries, Inc., respectively.
[0234] [234] The hard coating layer can be selected from art-recognized hard coating materials, such as organosilane abrasion resistant coatings. Organosilane abrasion resistant coatings, often referred to as hard coatings or silicone based hard coatings, are well known in the art, and are commercially available from various manufacturers, such as SDC Coatins, Inc., and PPG Industries, Inc Reference is made to U.S. Patent No. US 4,756,973 in column 5, lines 1-45; and in US patent 5,462,806 in column 1, lines 58 to column 2, line 8, and column 3, line 52 to column 5, line 50, the description of which has hard organosilane coatings and the description of which is incorporated herein by reference. Reference is also made to US Patent Nos .: US 4,731,264; US 5,134,191; US 5,231,156 and the publication of international application WO 94/20581 for the description of organosilane hard coatings, the description of which is also incorporated herein by reference. The hard coating layer can be applied using those coating methods as previously described here with respect to the primary layer, such as spindle coating.
[0235] [235] Other coatings that can be used to form the hard coating layer include, but are not limited to, polyfunctional acrylic hard coatings, melamine-based hard coatings, urethane-based hard coatings, alkyd-based coatings, coatings hard based on silica-sol or other inorganic / organic or organic hybrid hard coatings.
[0236] [236] The hard coating layer, with some embodiments, is selected from hard coatings of the organosilane type. Hard coatings of the organosilane type from which the hard coat layer of the photochromic articles of the present invention can be selected include, but are not limited to those described in column 24, line 46 through column 28, line 11 of the United States patent No. 7,465,414 B2, the description of which is incorporated herein by reference.
[0237] [237] The photochromic articles of the present invention may include additional coatings, such as anti-reflective coatings. With some embodiments, an anti-reflective coating can be applied over the hard coating layer. Examples of anti-reflective coatings are described in U.S. Patent No. US 6,175,450 and international publication No. WO 00/33111, the description of which is incorporated herein by reference.
[0238] [238] According to the further embodiments of the present invention, the photochromic articles of the present invention can be selected from ophthalmic articles or elements, display articles or elements, windows, mirror, packaging material, such as retractable film (“ shrinkwrap ”), and active or passive liquid crystal cell articles or elements.
[0239] [239] Examples of ophthalmic articles or elements include, but are not limited to, corrective lenses, non-corrective lenses, including monofocal or multifocal lenses, which can be either segmented or non-segmented multifocal lenses (such as, but not limited to , bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or improve (cosmetically or otherwise) vision, including without limitation, contact lenses, intraocular lenses, magnification lenses, protective lenses or displays.
[0240] [240] Examples of display articles, elements and devices include, but are not limited to, element screens, monitors, and security elements, including, without limitation, security marks and authentication marks.
[0241] [241] Examples of windows include, but are not limited to, automotive and aircraft transparencies, filters, shutters, and optical switches.
[0242] [242] With some embodiments, the photochromic article can be a security element. Examples of security elements include, but are not limited to, security tags and authentication tags that are connected to at least a portion of a substrate, such as: access cards and passes, for example, tickets, badges, credit cards identification or associate, eg promissory notes, checks, bonds, notes, certificates of deposit, stock certificates, etc .; government documents, eg, currency, licenses, identification cards, benefit cards, visas, passports, official certificates, deeds, etc .; consumer goods, eg, software, compact discs (“CDs”), digital video discs (“DVDs”), household items, consumer electronics, sporting goods, cars, etc .; credit cards; and labels, tags and packaging for goods.
[0243] [243] With additional embodiments, the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to additional embodiments in which a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can first be applied to at least a portion of the substrate before the safety mark is applied. applied to it. For example, a reflective aluminum coating can be applied to at least a portion of the substrate before forming the security element on it. Additionally or alternatively, the security element can be connected to at least a portion of a substrate chosen from non-colored substrates, colored substrates, photochromic substrates, colored photochromic substrates, linearly polarized substrates and circularly polarized substrates, and elliptically polarized substrates.
[0244] [244] In addition, the security elements according to the aforementioned embodiments may further include one or more other coatings or films or foils to form a reflective multi-layer security element with angle-dependent characteristics, as described in U.S. Patent No. 6,641,874.
[0245] [245] The present invention is more particularly described in the following examples, which are intended as illustrative only, since numerous modifications and variations here will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight. EXAMPLES
[0246] [246] Part 1 describes the preparation of the primary layer formulation (PLF). Part 2 describes the preparation of the liquid crystal alignment formulation (LCAF). Part 3 describes the preparation of the coating layer formulation (CLF). Part 4 describes the preparation of the top coat layer (TLF) formulation. Part 5 describes the procedures used for preparing the substrate and stacking the coatings listed in Table 1. Part 6 describes the photochromic performance tests including the proportion of absorption and optical response measures reported in Table 1 for Comparative Examples (CE) 1 to 4 and Examples 1 to 4. Part 1 - Preparing the PLF
[0247] [247] In a suitable container equipped with a magnetic stir bar the following materials were added in the indicated quantities: The polyacrylate polyol (14.69 g) (Composition D of Example 1, from US patent 6,187,444, whose description of the polyol is incorporated by reference, except that in Charge 2, the styrene was replaced with methyl methacrylate and 0.5% by weight, based on the total weight of the monomer, triphenyl phosphate was added); Polyalkylene diol carbonate (36.70 g) POLYMEG® 1000, from Great Lakes Chemical Corp; DESMODUR® PL 340 (48.23 g) from Bayer Material Science; TRIXENE® BI 7960 (34.39 g) from Baxenden; Polyether-modified polydimethyl siloxane (0.08 g) BYK®-333 from BYK-Chemie, USA; King Industries Urethane Catalyst (1.00 g) KKAT® 348; Gamma-glycidoxypropyl trimethoxysilane (3.96 g) A-187, from Momentive Performance Materials; Light stabilizer (8.07 g) TINUVIN® 928 from Ciba Specialty Chemicals; AROMATIC 100 (36.00g) a mixture of high temperature boiling solvents, available from Texaco; and 1-methyl-2-pyrrolidinone (61.88 g) from Sigma-Adrich.
[0248] [248] The mixture was stirred at room temperature for 2 hours to result in a solution having about 46.82% by weight of final solids based on the total weight of the solution. For this solution, the 3 photochromic compounds were added through mixers in approximately equal amounts for a total amount of 5 percent by weight, based on the total weight of the indicated resin solids:
[0249] [249] Photochromic compound - 1 (PC-1) is an indene naphthopyran that was prepared according to the procedure of U.S. Patent No. US 6,113,814, the description of which is incorporated herein by reference, and which during exposure to ultraviolet light (UV) showed an activated bluish green color. A UV spectrum was obtained in a photochromic square test containing PC-1 prepared as described in Part A of Example 10 of US patent 6,113,814. A Varian Cary 4000 UV-visible spectrometer was used with the following values in the method (unless otherwise indicated): range = 800-275 nm; average time = 0.100 s; data range = 1,100; and scan rate = 660 nm / minute. A simple average of the absorption values between 340 and 380 nm was determined to be 4.6. The first wavelength of minimum inactivated terminal absorbance, determined as described here for figure 3, was determined to be 422 ± 2 nm.
[0250] [250] PC-2 is a naphthopyran indene that was prepared according to the procedures of US Patent Publication 2006/0228557, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light and has shown a red color. -purple activated. A UV spectrum was obtained in a photochromic square test containing PC-2 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 2.2. The first wavelength of minimum inactivated terminal absorbance was determined to be 430 ± 2nm.
[0251] [251] PC-3 is a naphthopyran indene that has been prepared according to the procedures of US Patent publication 2011/0042629, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light has shown a brown color -yellow activated. A UV spectrum was obtained in a photochromic square test containing the PC-3 following the procedure done for the PC-1 except that ½ of the amount of the photochromic compound was used. The average of the absorption values between 340 and 380 nm was determined to be 3.5. The first wavelength of minimum inactivated terminal absorbance was determined to be 425 ± 2nm.
[0252] [252] The combination of PC-1, PC-2 and PC-3 in the primary layer produced an activated gray color. The inactivated absorption spectrum of the primary is shown as graph 23 of figure 1. The absorption spectrum of graph 23 was prepared from the photochromics containing PLF described above coated on a substrate and determined using a Varian Cary 4000 UVvisible spectrometer was used with the following values: range = 800-275 nm; average time = 0.100 s; data range = 1,100; and scan rate = 660 nm / minute. The substrate (a single view finished with 6 basic 70 mm diameter lenses made from the CR-39® monomer (FSVL) which was prepared as described in Part 5 and was coated with PLF only and heated for 1 hour at 125 ° C and then 105 ° C for 3 hours. PLF without the photochromic compounds was prepared for use in Examples 1 and 2 and Comparative Examples 1 and 2. Part 2 - Preparation of LCAF
[0253] [253] A solution of a photo alignment material of the type described in U.S. Patent Application No. US 12 / 959,467, filed on December 3, 2010, the description of which is incorporated herein by reference, was prepared by adding 6 by weight percent of the photo-alignment material to the cyclopentanone, based on the total weight of the solution. In addition, a purple dye at a level of about 0.02 weight percent, and a bluish purple dye at a level of 0.04 weight percent, both based on the weight of the total solution of the photoalignment material, were included. . Part 3 - Preparation of CLF
[0254] [254] The liquid crystal monomer (LCM) materials in the CLF were prepared as follows:
[0255] [255] LCM-1 is 1- (6- (6- (6- (6- (6- (6- (6- (6- (8- (4- (4- (4- (8-acryloyloxyhexyloxy)) benzoyloxy) phenyloxycarbonyl) phenoxy) octyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyl-6-oxohexyl ol, which was prepared in accordance with the procedures described in Example 17 of U.S. Relative No .: US 7,910,019, the description of which liquid crystal monomer is incorporated herein by reference.
[0256] [256] LCM-2 is commercially available as RM257, reported to be 4- (3-acryloyloxypropyloxy) benzoic acid, 2-methyl-1,4-phenylene ester, available from EMD Chemicals, Inc., having the molecular formula C33H32O10 .
[0257] [257] LCM-3 1- (6- (4- (4- (trans-4-pentylcyclohexyl) phenoxycarbonyl) phenoxy) hexyloxy) -2-methylprop-2-en-1-one, prepared according to the procedures of the Example 1, U.S. Patent No .: US 7,910,019; except that n = 0, the description of which has been incorporated by reference.
[0258] [258] LCM-4 is 1- (6- (6- (6- (6- (6- (6- (6- (8- (4- (4- (4- hexyloxybenzoyloxy) phenoxycarbonyl) -phenoxy) octyloxy ) -6- oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -2-methylprop-2-en-1-one, prepared according to the procedures of the US patent 7,910,019; whose description is hereby incorporated by reference.
[0259] [259] CLF was prepared as follows:
[0260] [260] In an appropriate flask, containing a mixture of anisole (3.99 g) and the additive BYK®-322 0.004g, reported to be an aralkyl modified polymethyl-alkyl siloxane, available from BYK Chemie, USA , LCM-1 (1.08g), LCM-2 (2.4 g), LCM-3 (1.08 g), LCM-4 (1.44 g), 4-methoxyphenol (0.006 g) were added, and IRGACURE® 819 (0.09 g, a photoinitiator available from Ciba-Geigy Corporation). The resulting mixture containing 60 weight percent solid monomers, based on the total weight of the mixture, was stirred for 2 hours at 80 ° C and cooled to about 26 ° C. A mixture of the photochromic / dichroic dyes that produce an activated gray color included as follows:
[0261] [261] PC-4 is a naftopyran indene that was prepared according to the procedures of US Patent publication 2011/0129678, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light and has shown a blue color - greenish activated and was used at a level of about 15 percent of the total amount of dye. A UV spectrum was obtained in a photochromic square test containing PC-4 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.9. The first wavelength of minimum inactivated terminal absorbance was determined to be 415 ± 2nm.
[0262] [262] PC-5 is a naftopyran indene that was prepared according to the procedures of US Patent publication 2011/0129678, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light, has shown a blue color activated and was used at a level of about 25 percent of the total amount of dye. A UV spectrum was obtained in a photochromic square test containing PC-5 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.4. The first wavelength of minimum inactivated terminal absorbance was determined to be 415 ± 2nm.
[0263] [263] PC-6 is a naftopyran indene that was prepared according to the procedures of US Patent publication 2011/0129678, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light and has shown a blue color activated and was used at a level of about 27 percent of the total amount of dye. A UV spectrum was obtained in a photochromic square test containing PC-6 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.9. The first wavelength of minimum inactivated terminal absorbance was determined to be 424 ± 2nm.
[0264] [264] PC-7 is a naftopyran indene that was prepared according to the procedures of US Patent publication 2011/0143141, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light and has shown a yellow color. activated and was used at a level of about 23 percent of the total amount of dye. A UV spectrum was obtained in a photochromic square test containing PC-7 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.4. The first wavelength of minimum inactivated terminal absorbance was determined to be 415 ± 2nm.
[0265] [265] PC-8 is a naftopyran indene that was prepared according to the procedures of US Patent publication 2011/0143141, the description of which is incorporated herein by reference, and which has been exposed to ultraviolet (UV) light, has shown a yellow color activated and was used at a level of about 10 percent of the total amount of dye. A UV spectrum was obtained in a photochromic square test containing PC-8 following the procedure performed for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.3. The first wavelength of minimum inactivated terminal absorbance was determined to be 415 ± 2nm.
[0266] [266] The photochromic compound PC-4, 5, 6, 7 and 8 were added to the CLF solutions of Example 1 and 3 and Comparative Examples 1 and 3 at a total level of 13 weight percent and to Examples 2 and 4 and CE 2 and 4 at a 6.5 weight percent level, all based on the total weight of the solution. The inactivated absorption spectrum for the CLF containing 6.5 weight percent of the photochromic compounds is included as graph 32 in figure 1. The spectrum was prepared using the same spectrometer and procedure described for the preparation of graph 23 in figure 1. The FSVL substrate was prepared as described in Part 5 and coated with the LCAF which was at least partially aligned before applying the CLF, all done as described in the coating procedures for the liquid crystal alignment layer and the coating layer of part 5 . Part 4: Preparation of the TLF:
[0267] [267] The TLF was prepared as follows:
[0268] [268] In a 50 ml amber glass bottle equipped with a magnetic stir bar, the following materials have been added: Hydroxy methacrylate (1.242 g) from Sigma-Aldrich; Neopentyl glycol diacrylate (13.7175 g) SR247 from Sartomer; Trimethylolpropane trimethacrolate (2.5825 g) SR350 from Sartomer; DESMODUR® PL 340 (5.02 g) from Bayer Material Science; IRGACURE®-819 (0.0628 g) from Ciba Specialty Chemicals; DAROCUR® TPO (0.0628 g) from Ciba Specialty Chemicals, Polybutyl acrylate (0.125 g), 3-Aminopropylpropyltrimethoxysilane (1.4570 g) A-1100 from Momentive Performance Materials; and Test anhydrous absolute 200 ethanol (1.4570 g) from Pharmaco-Aaper.
[0269] [269] The mixture was stirred at room temperature for 2 hours. For the TLF used for Examples 1 to 4, PC-9 was added at a level of 1 weight percent, based on the total weight of the solution. PC-9 was added in a 2H-naphthopyran compound that was prepared according to the procedures of US 5,458,814, the said patent is being incorporated here by reference, and in which during the exposure to ultraviolet (UV) light it demonstrated a red color activated. A UV spectrum was obtained in a photochromic square test containing PC-9 following the procedure done for PC-1 except that a Varian Cary 300 was used in an adjustment range below 700-275, mean time 0.100 seconds, time interval 1,100 data and classification rate of 450 nm / minutes. The average absorption value between 340 and 380 nm was determined to be 1.9. The first wavelength of minimum inactivated terminal absorbance was determined to be 384 ± 2 nm.
[0270] [270] The inactivated absorption spectrum for the TLF containing 1.0 weight percent of a PC-9 was induced as graph 41 of figure 1. The spectrum was prepared using the same spectrophotometer and the procedure described for the preparation of the graph 23 of figure 1. The FSVL substrate was prepared as described in Part 5 and coated only with TLF using the coating procedure for the top coating layer of Part 5. Part 5 - Procedures used for the preparation of the substrate and piles of coatings reported in table 1 Substrate Preparation:
[0271] [271] The finished monofocal contact lenses (6 bases, 70 mm) prepared from the CR-39® monomer were used as substrates. Each substrate was cleaned by a mop on a conveyor belt in a Tantec EST Serial No. 020270 System with Corona treatment equipment with HV 2000 series Power Generator with a high voltage transformer. The substrates were exposed to the Corona generated by 53.99 KV, 500 Watts while traveling on the conveyor belt at a speed of 3 feet / minute. Coating procedure for the primary layer:
[0272] [272] PLF was applied to the test substrates by spin coating on a portion of the test substrate surface, by dispersing approximately 1.5 mL of the solution. A spin processor from Laurell Tecnologies Corp. (WS-400B-6NPP / LITE) was used to rotate the coated substrates at 976 revolutions per minute (rpm) for 4 seconds, followed by 1.501 rpm for 2 seconds, followed by 2,500 rpm for 1 second. Then, the coated substrates were placed in an oven maintained at 125 ° C for 60 minutes. The coated substrates were cooled to about 26 ° C. The substrates were treated with corona by passing on a conveyor belt in Tantec EST System - Series 020270 - with HV 200 power generator in a series treatment by corona with a high voltage transformer. The primary dry layers were exposed to the corona generated by 53.00 KV, 500 Watts, while traveling on the conveyor belt at a speed of 3 feet / minute. Coating procedure for the liquid crystal alignment layer:
[0273] [273] The LCAF was applied to the test substrate by spin coating on a portion of the test substrate surface by dispersing approximately 1.0 mL of the solution and rotating the substrates at 800 revolutions per minute (rpm) for 3 seconds , followed by 1,000 rpm for 7 seconds, followed by 2,500 rpm for 4 minutes. A rotation processor from Laurell Technologies Corp. (WS-400B6NPP / LITE) was used for coating by rotation. Then, the coated substrates were placed in an oven maintained at 120 ° C for 30 minutes. The coated substrates were cooled to 26 ° C.
[0274] [274] The dry photo-alignment layer on each of the substrates was at least partially ordered by exposure to linearly polarized ultraviolet radiation. The light source was oriented so that the radiation was linearly polarized in a plane perpendicular to the surface of the substrate. The amount of ultraviolet radiation to which each photo-alignment layer was exposed was measured using a high-energy UV Poer PuckTM radiometer, from EIT, Inc., (No .: 2066 Series), and was as follows: UVA 0.018 W / cm2 and 5.361 J / cm2; UVB 0 W / cm2 and 0 J / cm2; UVC 0 W / cm2 and 0J / cm2; and UVV 0.005 W / cm2 and 1.541 J / cm2. After ordering at least a portion of the photo-oriented polymeric network, the substrates were cooled to about 26 ° C and kept covered. Coating procedure for the primary layer:
[0275] [275] The CLF was spun for coating at a rate of 400 revolutions per minute (rpm) for 6 seconds, followed by 800 rpm for 6 seconds on photo-alignment materials at least partially ordered on the test substrates. Each coated substrate was placed in an oven at 60 ° C for 30 minutes. They were then cured under two ultraviolet lamps on the UV Curing Oven machine, designed and built by Belcan Engineering, in a nitrogen atmosphere, while running on a conveyor belt at a speed of 2 feet / minute at a peak intensity of 0.388 Watts / cm2 of UVA and 0.165 Watts / cm2 of UVV and the UV dosage of 7.386 Joules / cm2 of UVA and 3.337 Joules / cm2 of UVV. If the coated substrate was successful in receiving a top coat layer, the cured layer was exposed to the corona generated by 53.00 KV, 500 Watts, while traveling on the conveyor belt at a speed of 3 feet / minute. If the coated substrate was not successful in receiving the top coat layer, post-cure was completed at 105 ° C for 3 hours. Coating procedure for the top coat layer:
[0276] [276] The TLF was coated by spinning at a rate of 1400 revolutions per minute (rpm) for 7 seconds, over the CLF coated substrates. Then, the substrates were cured under two ultraviolet lamps in the UV Curing Oven machine designed and built by Belcan Engineering, in a nitrogen atmosphere while running on a conveyor belt at a speed of 6 feet / minute, at a peak intensity of 1,887 Watts / cm2 of UVA and 0.694 Watts / cm2 of UVV and the UV dosage of 4,699 Joules / cm2 of UVA and 1,787 Joules / cm2 of UVV. The post-cure was completed at 105 ° C for 3 hours. Coating procedure for the top coat layer:
[0277] [277] TLF was coated by rotation at a rate of 1,400 revolutions per minute (rpm) for 7 seconds on cured CLF coated substrates. Then, the substrates were cured under two ultraviolet lamps in a UV Curing Oven machine, built by Belcan Engineering in a nitrogen atmosphere while running on a conveyor belt at a speed of 6 feet / minute at a peak intensity of 1,887 Watts / cm2 of UVA and 0.694 Watts / cm2 of UVV and a UV dosage of 4,699 Joules / cm2 of UVA and 1,787 Joules / cm2 of UVV. The post-cure was completed at 105 ° C for 3 hours. Part 6 - photochromic performance tests including absorption ratio and the measurement of optical response
[0278] [278] Before the response test on an optical bench, the substrates were conditioned by exposing them to 365 nm of ultraviolet light for 10 minutes at a distance of about 14 cm from the source in order to pre-activate the photochromic molecules. The UVA irradiation in the sample was measured with a Licor Model Li-1800 radiometer spectrum and found 22.2 Watts per square meter. The samples were then placed under a halogen lamp (500 W, 120 V) for about 10 minutes at a distance of about 36 cm from the lamp in order to whiten, or inactivate, the photochromic compound in the samples. The luminescence in the sample was measured with the Licor spectroradiometer and observed to be 21.9 Klux. The samples were then exposed to yellow fluorescent lamps for 30 minutes to provide additional visible light bleaching. The samples were then kept in a dark medium for at least 1 hour before testing in order to cool and continue to fade back into a crushed state.
[0279] [279] An optical bench was used to measure the optical properties of the coated substrates and derive the absorption ratios and photochromic properties. Each of the test samples was placed on the optical bench with an activation light source (a Xenon Newport / Oriel Model 66485 arc lamp, 300 Watts with a UNIBLITZ® VS-25, a high-speed computer controlled by a shutter that closed momentarily during data collection so that casual light would not interfere with the data collection process, a SCHOTT® 3mm KG-2 with a bandpass filter, which removed short wavelength radiation, the neutral density for attenuation of intensity and a condensation lens for collimation of the beam, positioned at an angle of 30 ° to 35 ° of incidence on the surface of the test sample.The arc lamp was equipped with a light intensity controller (Newport / Oriel Model 68950).
[0280] [280] A broadband light source for monitoring response measurements was positioned perpendicular to the sample surface. The increased signal of the short visible wavelengths was achieved by separately collecting and combining filtered light in a 100 Watt halogen-tungsten lamp (controlled by a constant voltage power source LAMBDA® UP60-14) with a fiber cable bifurcated optics with the split end. The light from one side of the tungsten-halogen lamp was filtered with a SCHOTT® KG1 filter to absorb heat and a HOYA® B-440 filter to allow the passage of shorter wavelengths. The other side of the light was either filtered with a SCHOTT® KG1 filter or unfiltered. The light was collected by focusing the light from each side of the lamp on a separate end of the split-end bifurcated optical fiber cable, and subsequently combined into a light source emerging from the single end of the cable. A 4 ”light tube was attached to one end of the cable to ensure proper mixing. The broadband light source was adjusted with a shutter controlled by a high-speed UNIBLITZ® VS-25 computer that was momentarily open during data collection.
[0281] [281] Polarization of the light source was achieved by passing the light at the single end of the cable through a Moxtek polarization aid, PROFLUX® on a computer, the motorized rotation stage (Model M-061-PD from Polytech, PI). The monitoring beam was arranged so that a polarization plane (0 ° C) was perpendicular to the plane of the optical bench table and the second polarization plane (90 °) was parallel to that of the optical bench table. The samples were run in air, at 23 ° C ± 0.1 ° C, maintained by a controlled temperature of the air cell.
[0282] [282] To align each sample, a second polarizer was added to the optical route. The second polarizer was arranged at 90 ° from the first polarizer. The sample was placed in an air cell in a self-centered retainer mounted in a rotation stage. A laser beam (Coherent –ULN 635 laser diode) was directed through the crossed polarizer and a sample. The sample was rotated (in 3 steps as the movement course and in 0.1º steps, as fine movements) to observe the minimum transmission. At this point, the sample was aligned both parallel and perpendicular to the Moxtek polarizer and the second polarizer as well as the laser beam from the diode were removed from the optical path. The sample was aligned within ± 0.5º before any activation.
[0283] [283] To conduct the measurements, each test sample was exposed to 6.7 W / m2 of UVA from the activation light source for 10 to 20 minutes to activate the photochromic compound. A Light Research Radiometer (Model IL-1700) with a detector system (Model SED033 detector, Filter B, and diffuser) was used to verify exposure at the beginning of each day. The light from the monitoring source that was polarized in the 0 ° polarization plane was then passed through the sample and focused on a 1 ”integration sphere, which was connected to an Ocean Optics® S2000 spectrophotometer using an optical single function fiber. Spectral information after passing through the sample was collected using Ocean Optics® OOIBase32 and OOIColor software, and PPG's patented software. While the photochromic material was activated, the position of the polarizing sheet was rotated to one side and the other to polarize the light from the monitoring light source to the 90 ° and back polarization plane. Data were collected for approximately 600 to 1200 seconds at 5-second intervals during activation. For each test, the rotation of the polarizers was adjusted to collect data in the following sequence of polarization planes: 0º, 90º, 90º, 0º, etc.
[0284] [284] The absorption spectrum was obtained and analyzed for each test sample using the Igor Pro software (available from WaveMetrics). The change in absorption in each direction of polarization for each test sample was calculated by subtracting time 0 (that is, not activated) of the absorption measurement for samples at each tested wavelength. The average absorbance values were obtained in the region of the activation profile where the photochromic response of the photochromic compound was saturated or approximately saturated (that is, the regions where the absorbance measurement did not increase or did not increase significantly with time) for each sample through of the absorbance average in each time interval in this region. The average absorbance value in a predetermined wavelength range corresponds to λmax-vis +/- 5 nm were extracted for polarizations of 0 ° and 90 ° and the absorption ratio for each wavelength in this range was calculated by dividing the higher mean absorbance by lower mean absorbance. For each wavelength extracted, 5 to 100 points of data were measured. The average absorption ratio for the photochromic compound was then calculated by averaging these individual absorption ratios.
[0285] [285] The change in optical density (∆OD) from the bleached state to the darkened state was determined by establishing the initial transmission, opening the Xenon lamp shutter to provide ultraviolet radiation to change the test lenses from the bleached state to an activated (ie darkened) state. The data were collected at the selected time intervals, measuring the transmittance in the activated state, and calculating the change in optical density according to the formula: ∆OD = log (% Tb /% Ta), where% Tb is the percentage of transmittance in the bleached state,% Ta is the percentage of transmittance in the activated state and the logarithm in base 10. The measurements were made in a heavy wavelength range corresponding to CIE Y, described in “CIE Technical Report Colorimtry” CIE 15 : 2004, 3rd Edition, published by the Commission Internationale De L'Eclairage, Vienna, Austria, whose publication is incorporated here by reference.
[0286] [286] The less intense half-life (T1 / 2) is the time interval in seconds for the ∆OD of the activated form of the photochromic compounds in the test samples to reach half of the ∆OD measured after fifteen minutes, or after saturation or close to saturation being achieved, at room temperature after removing the light activation source, for example, by closing the shutter. The results for Examples 1-4 and CE 1-4 are listed in Table 1. For Examples 1-4, the ∆OD of each was greater than that for CE 1-4 and the% of transmission of the activated substrate (% TA) was less than that for CE 1-4, as desired. The presence of photochromic compounds in both the primary layer and the top coat layer in Examples 3 and 4 and demonstrated a ∆OD greater and less than the% Ta of Examples 1 and 2 e, as well as CE 1-4. An “X” in the columns of table 1 indicated the presence of the photochromic compound in the primary layer and / or the top coat layer.
[0287] [287] The present invention has been described with reference to the specific details of particular embodiments. These details were not intended to limit the scope of protection of the invention, except to the extent that and extending those limitations that are included in the claims accompanying the process.

权利要求:
Claims (33)
[0001]
Photochromic article, characterized by the fact of understanding: - a substrate; - a primary layer comprising a first photochromic compound, said primary layer being positioned on said substrate, and said first photochromic compound having a first absorbance in an inactivated state greater than 0 and all wavelengths from 340 nm to 380 nm, and a first wavelength of minimum terminal absorbance in an inactivated state greater than 380 nm; and - a coating layer comprising a photochromic-dichroic compound, said coating layer being positioned on said primary layer, and said photochromic-dichroic compound having a second absorbance in an inactivated state greater than 0 over at least a portion of the wavelength from 340 nm to 380 nm, and a second wavelength of minimum terminal absorbance in an inactivated state greater than 340 nm, with said second wavelength of minimum terminal absorbance in an inactivated state being less than or equal to the first length minimum absorbance waveform in inactivated state.
[0002]
Photochromic article, according to claim 1, characterized by the fact that said second wavelength of the minimum terminal absorbance in inactivated state is greater than 380 nm.
[0003]
Photochromic article, according to claim 1, characterized by the fact that said second wavelength of the absorbance in inactivated state greater than 0 is in all wavelengths from 340 nm to 380 nm, and the aforementioned second wavelength of minimum terminal absorbance in inactivated state is greater than 380 nm.
[0004]
Photochromic article, according to claim 1, characterized by the fact that said first wavelength of the minimum terminal absorbance in inactivated state is greater than 380 nm and less than or equal to 450 nm, and said second wavelength of absorbance minimum terminal in inactivated state is greater than 340 nm and less than or equal to 450 nm.
[0005]
Photochromic article, according to claim 1, characterized by the fact that said second wavelength of the minimum terminal absorbance in an inactivated state is less than that of the said first wavelength of the minimum terminal absorbance in an inactivated state.
[0006]
Photochromic article, according to claim 1, characterized by the fact that said photochromic article has a percentage transmission in an inactivated state of less than 5% in all wavelengths from 340 nm to 380 nm.
[0007]
Photochromic article, according to claim 1, characterized by the fact that the photochromic article has an optical density in an activated state that is greater than an optical density in an activated state control of a photochromic control article comprising said substrate and the aforementioned coating layer in the absence of said primary layer.
[0008]
Photochromic article, according to claim 7, characterized by the fact that the aforementioned optical density in the activated state and the said optical density in the activated state are each determined from 410 nm to 800 nm.
[0009]
Photochromic article, according to claim 1, characterized by the fact that said primary layer also comprises an organic matrix containing polyurethane bonds.
[0010]
Photochromic article, according to claim 1, characterized by the fact that said photochromicdichroic layer comprises anisotropic material.
[0011]
Photochromic article according to claim 10, characterized in that said anisotropic material comprises a liquid crystal material.
[0012]
Photochromic article, according to claim 1, characterized by the fact that said photochromicdichroic compound is at least partially aligned.
[0013]
Photochromic article according to claim 1, characterized by the fact that the aforementioned photochromic photochromic layer comprises a polymer separated by phase containing: a matrix phase that is at least partially ordered, and an exposure phase that is at least partially ordered, said exposure phase comprising said photochromic-dichroic compound, and said photochromic-dichroic compound being at least partially aligned with at least a portion of said exposure phase.
[0014]
Photochromic article, according to claim 1, characterized by the fact that said photochromicdichroic layer further comprises an interpenetration polymer network containing: an anisotropic material that is at least partially ordered; and a polymeric material; an anisotropic material comprising said photochromic-dichroic compound, and said photochromic-dichroic compound is at least partially aligned with at least a portion of said anisotropic material.
[0015]
Photochromic article, according to claim 1, characterized by the fact that the aforementioned photochromic layer comprises, at least, one additive selected from dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold releasing agents, rheology controlling agents, leveling agents, free radical purgers, and adhesion promoters.
[0016]
Photochromic article, according to claim 1, characterized by the fact that the aforementioned photochromic layer comprises additionally at least one dichroic material chosen from azomethines, indigoids, thioindigoids, merocyanins, indanas, quinophthalonic, perylene, phthaloperins, triphenodioxazine dyes, indoloquinoxaline, imidazo-triazines, tetrazines, azo and (poly) azo dyes, benzoquinones, naphthoquinones, anthroquinone and (poly) anthroquinones, anthropirimidinones, and iodine and iodates
[0017]
Photochromic article, according to claim 1, characterized by the fact that the first photochromic compound and said photochromic-dichroic compound are each, independently, selected from naphttopirans indene fused, naphth [1,2-b] pirans, naphth [2,1-b] pyranes, spirofluoroene [1,2-b] pyranes, phenanthropirans, quinolinopyranes, fluoroanthenopyranes, spiropyranes, benoxazins, naphthoxazine, spiro (indoline) naphthoxazine, spiro (indoline) pyridobenzoxazine, spiro (indoline) fluorantenazine (indoline) quinoxazins, fulgides, fulgimides, diaethylenes, diarylalkylenes, diarylalkenylenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds and mixtures thereof.
[0018]
Photochromic article, according to claim 1, characterized by the fact that it also comprises an alignment layer interposed between said primary layer and the aforementioned photochromic-dichroic layer, and said photochromic-dichroic compound is at least partially aligned.
[0019]
Photochromic article, according to claim 1, characterized by the fact that it additionally comprises a top layer containing an ultraviolet light absorber, the top layer of which resides above the aforementioned photochromic-dichroic layer.
[0020]
Photochromic article according to claim 19, characterized in that it additionally contains a hard coating layer, the said hard coating layer residing above said upper coating layer.
[0021]
Photochromic article, according to claim 1, characterized by the fact that said photochromic article is selected from ophthalmic articles, display elements, windows, mirrors, and active liquid crystal cell articles, and liquid crystal cell articles passive.
[0022]
Photochromic article, according to claim 21, characterized by the fact that the photochromic article is selected from ophthalmic articles, and ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnification lenses, protective lenses, or viewfinders.
[0023]
Photochromic article, according to claim 21, characterized by the fact that the photochromic article is selected from the display element, and the aforementioned display article is selected from screens, monitors, and security elements.
[0024]
Photochromic article, according to claim 1, characterized by the fact that the substrate is selected from non-dyed substrates, dyed substrates, photochromic substrates, dyed photochromic substrates, and linearly polarized substrate.
[0025]
Photochromic article, according to claim 1, characterized by the fact that it additionally comprises: - a top coat layer comprising a second photochromic compound, said top coat layer being positioned on said photochromic dichroic layer, and said second photochromic compound having a third inactivated absorbance greater than 0 over at least a portion of the wavelength from 330 nm to 380 nm, and a third wavelength of minimum terminal absorbance in an inactivated state that is greater than 330 nm; the said third wavelength of the minimum terminal absorbance in inactivated state is less than the said second wavelength of the minimum terminal absorbance in inactivated state.
[0026]
Photochromic article, according to claim 25, characterized by the fact that the second absorbance in inactivated state is greater than 380 nm.
[0027]
Photochromic article, according to claim 25, characterized by the fact that said second absorbance in inactivated state greater than 0 is in all wavelengths from 340 nm to 380 nm, and said second wavelength of the minimum terminal absorbance in idle state is greater than 380 nm.
[0028]
Photochromic article, according to claim 25, characterized by the fact that said first wavelength of the minimum terminal absorbance in an inactivated state is greater than 380 nm and less than or equal to 450 nm, said second wavelength of the minimum terminal absorbance in inactivated state it is greater than 340 nm and less than or equal to 450 nm; and said third wavelength of the minimum terminal absorbance in an inactivated state is greater than 330 nm and less than 380 nm.
[0029]
Photochromic article according to claim 28, characterized in that said third absorbance in inactivated state is greater than 0 over at least a portion of the wavelengths of 330 nm to less than 370 nm; and said third wavelength of the minimum terminal absorbance in an inactivated state is greater than 330 nm and less than 370 nm.
[0030]
Photochromic article, according to claim 25, characterized by the fact that said second wavelength of the minimum terminal absorbance in inactivated state is less than that of said first wavelength of the minimum terminal absorbance in inactivated state.
[0031]
Photochromic article, according to claim 25, characterized by the fact that said photochromic article has a percentage transmittance in an inactivated state of less than 5% at all wavelengths from 340 nm to 380 nm.
[0032]
Photochromic article, according to claim 25, characterized by the fact that said first photochromic compound, said photochromic-dichroic compound, and said second photochromic compound are each, independently, selected from fused indene naphthytophans, naphthus [ 1,2-b] pyranes, naphtho [2,1-b] pyranes, spirofluoroene [1,2-b] pyranes, phenanthropirans, quinolinopyranes, fluoroanthenopyranes, spiropyranes, benoxazins, naphthoxazins, spiro (indoline) naphthoxazines, spiro (indoline) pyridobenzoxazins, spiro (indoline) fluoranthenoxazins, spiro (indoline) quinoxazins, fulgides, fulgimides, diarylenes, diarylalkylenes, diarylalkenylenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds and mixtures thereof.
[0033]
Photochromic article, according to claim 25, characterized in that the aforementioned top layer also comprises an ultraviolet light absorber.

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-11-17| B09A| Decision: intention to grant|

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2021-01-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/153,748|US8582192B2|2003-07-01|2011-06-06|Polarizing photochromic articles|

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US13/153,748|2011-06-06|

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US13/296,867|US8545015B2|2003-07-01|2011-11-15|Polarizing photochromic articles|

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US13/296,867|2011-11-15|

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PCT/US2011/060961|WO2012170066A1|2011-06-06|2011-11-16|Polarizing photochromic articles|

---