WO2012170066A1 - Polarizing photochromic articles - Google Patents
Polarizing photochromic articles Download PDFInfo
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- WO2012170066A1 WO2012170066A1 PCT/US2011/060961 US2011060961W WO2012170066A1 WO 2012170066 A1 WO2012170066 A1 WO 2012170066A1 US 2011060961 W US2011060961 W US 2011060961W WO 2012170066 A1 WO2012170066 A1 WO 2012170066A1
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- WIPO (PCT)
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- photochromic
- dichroic
- unactivated state
- compound
- layer
- Prior art date
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
- G02C7/102—Photochromic filters
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/12—Polarisers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
- A61F2/1613—Intraocular lenses having special lens configurations, e.g. multipart lenses; having particular optical properties, e.g. pseudo-accommodative lenses, lenses having aberration corrections, diffractive lenses, lenses for variably absorbing electromagnetic radiation, lenses having variable focus
- A61F2/1659—Intraocular lenses having special lens configurations, e.g. multipart lenses; having particular optical properties, e.g. pseudo-accommodative lenses, lenses having aberration corrections, diffractive lenses, lenses for variably absorbing electromagnetic radiation, lenses having variable focus having variable absorption coefficient for electromagnetic radiation, e.g. photochromic lenses
Definitions
- the present invention relates to phoiochromic articles thai inciude a substrate, a primer laye that includes a first phoiochromic compound, and a photochromic-dichroic layer over the primer layer that includes a photochromic-dichroic compound, in which the first phoiochromic compound and the photochromic-dichroic compound are each selected such that the photochromic-dichroic compound has an unactivaied state terminal minimum absorbance wavelength that is less than or equal to the unactivaied state terminal minimum absorbance wavelength of the underlying first photochromic compound.
- linearly polarizing elements such as linearly polarizing lenses for sunglasses and linearly polarizing filters
- linearly polarizing elements are typically formed from stretched polymer sheets containing a dichroic material, such as a dichroic dye. Consequently, conventional linearly polarizing elements are static elements having a single, linearly polarizing state. Accordingly, when a conventional linearly polarizing element is exposed to either randomly polarized radiailon or reflected radiation of the appropriate wavelength, some percentage of the radiation transmitted through the element will be linearly polarized.
- linearly polarizing elements are typically tinted.
- conventional linearly polarizing elements typically 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 upon the coloring agent used to form the element,, and most commonly, is a neutral color (for example, brown or gray).
- conventional linearly poiarizsng: elements are useful in reducing reflected light glare, because of their tint, they are typically not well suited for use under low-light conditions.
- conventional linearly polarizing elements have only a single, tinted iinearly polarizing state, ihey are limited in their ability to store or display information.
- a common method of aligning the molecules of a dichroic dye involves heating a sheet or layer of polyvinyl alcohol (“PVA”) to soften the PVA and then stretching the sheet to orient the PVA polymer chains. Thereafter, the dichroic dye is impregnated into the stretched sheet, and the impregnated dye molecules adopt the orientation of the polymer chains. Resuitantiy, at least some of the dye molecules become aligned, such that the long axis of each aligned dye molecule is generally parallel to the oriented polymer chains.
- the dichroic dye can be first impregnated into the PVA sheet, and thereafter the sheet can be heated and stretched as described above to orient the PVA polymer chains and associated dye.
- the molecules of the dichroic dye can be suitably positioned or arranged amongst the oriented polymer chains of the PVA sheet, and a net iinear polarization can be correspondingly achieved.
- the PVA sheet can be made to Iinearly polarize transmitted radiation, and correspondingly a Iinearly polarizing filter can thus be formed.
- conventional photochromic elements such as photochromic lenses that are formed using conventional 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 reverting back to the first state in response to thermal energy.
- conventional photochromic elements are generally well suited for use in both low-light and bright conditions.
- Conventional photochromic elements, however, that do not include linearly polarizing filters are generally not capable of linearly polarizing radiation.
- the absorption ratio of conventional photochromic elements, in either state is generally less than two. Therefore, conventional photochromic elements are not capable of reducing reflected light glare to the same extent as conventional linearly polarizing elements.
- conventional photochromic elements have a limited ability to store or display information
- Photochromic-dichroic compounds and materials have been developed that provide both photochromic properties and dichroic properties, If properly and at least sufficiently aligned.
- photochromic-dichroic compounds typically have a larger percent transmittance than non-polarizing or conventional photochromic compounds at equivalent concentrations and sample thickness, While not intending to be bound by any theory, and based on the evidence at hand, it is believed that the increased percent transmittance of photochromic-dichroic materials in the darkened or colored state is due to the percent transmittance being an average of the two orthogonal plane polarized components of the polarized radiation.
- a photochromic-dichroic material will more strongly absorb one of the two orthogonal plane polarized components of the incident random radiation, resulting in one of the planes of transmitted polarized light (passing through and out of the sample) having a greater percent transmittance than the other orthogonal plane polarized component.
- the average of the two orthogonal plane polarized components typically results In an average percent transmittance of greater magnitude.
- the linearly polarizing efficiency which can be quantified in terms of absorption ratio, of photochromic-dichroic compounds increases, the percent transmittance associated therewith also increases,
- St would be desirable to develop new polarizing photochromic articles that include photochromic-dichroic compounds, and which provide a combination of linear polarizing properties, and reduced percent transmittance when in a colored or darkened state, such as when exposed to actinic light.
- a photochromic article comprising a substrate and at least two layers thereof including, a primer layer positioned over the substrate, and a photochromic-dichroic layer positioned over the primer layer.
- the primer layer comprises a first photochromic compound having a first unactivated state absorbance of greater than 0 at all wavelengths from 340 nm to 380 nm, and a first unactivated state terminal minimum absorbance wavelength of greater than 380 nm.
- the photochromic-dichroic layer comprises a photochromic-dichroic compound having a second unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 340 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength of greater than 340 nm.
- the second unactivated state terminal minimum absorbance wavelength (of the photochromic-dichroic compound) is less than or equal to the first unactivated state terminal minimum absorbance wavelength (of the underlying first photocnromic compound).
- a photochrome article that includes, a substrate and at least three layers thereover including, a primer layer that is positioned over the substrate, a photochromic-dichroic layer that is positioned over the primer layer, and a topcoat layer that is positioned over the photochromic- dichroic layer.
- the primer layer includes a first photochromic compound having a first unaclivated state absorbance of greater than 0 at all wavelengths from 340 nm to 380 nm, and a first unactivated state terminal minimum absorbance wavelength of greater than 380 nm.
- the photochromic-dichroic layer comprises a photochromic-dichroic compound having a second unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 340 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength of greater than 340 nm.
- the topcoat layer includes a optional ultraviolet light absorber, and a third unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 330 nm to 380 nm, and a third unactivated state terminal minimum absorbance wavelength that is greater than 330 nm.
- the third unactivated state terminal minimum absorbance wavelength (of the second photocnromic compound of the topcoat layer) is less than the second unactivated state terminal minimum absorbance wavelength (of the photochromic-dichroic compound of the underlying coating layer), and the second unactivated state terminal minimum absorbance wavelength (of the photochromic-dichroic compound of the coating layer) is less than or equal to the first terminal minimum absorbance wavelength (of the first photochromic compound of the underlying primer layer).
- FIG. 1 is a representative side elevation sectional view of a photochromic article according to the present invention, which includes graphical representations of plots of absorbance vs. wavelength for the first photochromic compound of the primer layer, the photochromic-dichroic compound of the photochromic-dichroic layer, and the second photochromic compound of the topcoat layer;
- FIG. 2 is a graphical representation of average delta absorbance as a function of wavelength (over a visible wavelength region after activation with actinic radiation), and depicts two average difference absorption spectra obtained in two orthogonal planes for a photochromic-dichroic layer that includes a photochromic-dichroic compound that can be included in the photochromic articles of the present invention; and
- FIG. 3 is a graphical representation of graph 41 of FSG. 1 , in which the y-axis range has been changed from 0 to 3,5 ⁇ FIG. 1 ) to 0 to 0.1 (FSG. 3), for purposes of better illustrating the absorbance vs. wavelength plot,
- actinic radiation means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another as will be discussed in further detail herein.
- photochromic compound means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation.
- photochromic material means any substance thai is adapted to display photochromtc properties (i.e. adapted to have an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation) and which includes at least one photochromic compound,
- photochromic compound includes thermally reversible photochromic compounds and non-thermalfy reversible photochromic compounds.
- thermally reversible photochromic compounds/materials as used herein means compounds/materials 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 reverting back to the first state in response to thermal energy.
- non-thermaliy reversible photochromic compounds/materials as used herein means compounds/materials 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 reverting back to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorptions) of the colored state (e.g., discontinuing exposure to such actinic radiation),
- dichroic means capable of absorbing one of two orthogonal plane polarized components of at least transmitted radiation more strongly than the other.
- photochromic-dichroic As used herein, the term "photochromic-dichroic" and similar terms, such as
- photochromic-dichroic materials and “photochromic-dichroic compounds” means materials and compounds that possess and/or provide both photochrome properties (i.e., having an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation), and dichroic properties (i.e., capable of absorbing one of two orthogonal plane polarized components of at least transmitted radiation more strongly than the other).
- the term “absorption ratio” refers to the ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of the same wavelength radiation linearly polarized in a plane orthogonal to the first plane, in which the first plane is taken as the plane with the highest absorbance.
- the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties.
- the first state and the second state of the photochromic-dichroic compound of the photochromic- dichroic layer can differ with respect to at least one optical property, such as but not limited to the absorption or linearly polarization of visible and/or UV radiation.
- the photochromic- dichroic compound of the photochromic-dichroic Iayer can have a different absorption spectrum in each of the first and second state.
- the photochromic-dichroic compound of the photochromic-dichroic layer can be clear in the first state and colored in the second state.
- the photochromic-dichroic compound of the photochromic-dichroic Iayer can have a first color in the first state and a second color in the second state.
- the photochromic-dichroic compound of the photochromic-dichroic layer can be non ⁇ iinear!y polarizing (or "non-polarizing") in the first state, and linearly polarizing in the second state.
- the term "optical” means pertaining to or associated with light and/or vision.
- the optica! article or element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and actsve and passive liquid crystal ceil articles, elements and devices.
- ophthalmic means pertaining to or associated with the eye and vision
- ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which may be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intra-ocufar lenses, magnifying lenses, and protective lenses or visors,
- ophthalmic substrate means lenses, partially formed lenses, and lens blanks.
- display means the visible or machine-readable representation of information in words, numbers, symbols, designs or drawings.
- Non- limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
- window means an aperture adapted to permit the transmission of radiation therethrough.
- windows include automotive and aircraft transparencies, filters, shutters, and optical switches.
- mirror means a surface that specularly reflects a large or substantial fraction of incident light.
- liquid crystal cell refers to a structure containing a liquid crystal material that is capable of being ordered.
- Active liquid crystal cells are cells in which the liquid crystal material is capable of being reversibly and controllabiy switched or converted between ordered and disordered states, or between two ordered states by the application of an external force, such as electric or magnetic fields.
- Passive liquid crystal cells are cells in which 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.
- coating means a supported film derived from a flowable composition, which may or may not have a uniform thickness, and specifically excludes polymeric sheets.
- the primer layer, the photochromlc-dichroic layer and the optional topcoat layer of the photochrome articles of the present invention can, in some embodiments, each independently be a coating,
- sheet means a pre-formed film having a generally uniform thickness and capable of self-support.
- the term "connected to" means in 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.
- the primer layer for example, can be in direct contact (e.g., abutting contact) with at least a portion of the substrate or it can be in indirect contact with at least a portion of the substrate through one or more other interposed structures or materials, such as a monomolecular layer of a coupling or adhesive agent.
- the primer layer can be in contact with one or more other Interposed coatings, polymer sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate,
- photosensitive material means materials that physically or chemically respond to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.
- non-photosensitive materials means materials that do not physically or chemically respond to electromagnetic radiation, including, but not limited to, static dyes.
- molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mrs) are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
- polydispersity index (PDi) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/fvin).
- polymer means bomopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least, two monomer species), and graft polymers.
- (meth)acryiic acid ester means methacrylates and/or acrylaies
- (meth)acrylic acid means methacryhc acid and/or acrylic acid.
- a stated range or ratio of "1 to 10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, ail subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but ⁇ limited to, 1 to 6.1 , 3.5 to 7.8, and 5.5 to 10.
- feft-to-right representations of finking groups are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
- 0 group C O or equivendedly -C(Q)G- is inclusive of the right-to-left o representation thereof,— o c— -—— , or equivendedly -0(0)C- or -OC(O)-.
- a first photochromic compound means at least one first photochromic compound.
- first photochromic compounds When iwo or more first photochromic compounds are present, they together have and provide a (e.g. , an average) first unactivated state peak absorbance wavelength, a (e.g. , an average) first unactivated state absorbance of greater than 0 over a particular wavelength range, a (e.g. , an average) first unactivated state terminal minimum absorbance wavelength, and a (e.g., an average) first unactivated state initial minimum absorbance wavelength.
- a pbotochromic-dichroic compound means at least one photochromic-dichroic compound.
- photochromic-dichrolc compounds When two or more photochromic-dichrolc compounds are present, they together have and provide a (e.g., an average) second unactivated state peak absorbance wavelength, a (e.g., an average) second unactivated state absorbance of greater than 0 over a particular wavelength range, a (e.g., an average) second unactivated state terminal minimum absorbance wavelength, and a (e.g., an average) second unactivated state initial minimum absorbance wavelength.
- a second photochromic compound means at least one second photochromic compound.
- two or more second photochromic compounds When two or more second photochromic compounds are present, they together have and provide a (e.g., an average) third ⁇ activated state peak absorbance, a ⁇ e.g., an average) third unactivated state absorbance wavelength of greater than 0 over a particular wavelength range, a ⁇ e.g., an average) third unactivated state terminal minimum absorbance wavelength, and a (e.g., an average) third unactivated state initial minimum absorbance wavelength.
- a third ⁇ activated state peak absorbance e.g., an average third unactivated state absorbance wavelength of greater than 0 over a particular wavelength range
- a ⁇ e.g., an average third unactivated state terminal minimum absorbance wavelength e.g., an average third unactivated state initial minimum absorbance wavelength
- the term "unactivated state" with regard to photochromic compounds means 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 of 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 (si) minimal or substantially no measurable absorbance at wavelengths of greater than 450 nm.
- the term "activated state" with regard to photochromic compounds, such as the first photochromic compound, the photochromic-dichroic compound and the second photochromic compound, and photochromic articles means the photochromic compound and/or photochromic article has been exposed to actinic radiation having sufficient energy to result in the photochromic compound and/or photochromic article having or producing: (i) measurable absorbance at wavelengths of 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) measurable absorbance at wavelengths of greater than 450 nm.
- a first unactivated state absorbance of greater than 0" over a certain wavelength range such as “over all wavelengths from 340 nm to 380 nm” means the first photochromic compound has an unactivated state absorbance of greater than 0 over a certain wavelength range, such as at all wavelengths from 340 nm to 380 nm.
- a first unactivated state peak absorbance wavelength means the wavelength at which the first photochromic compound (of the primer layer), in an unactivated state, has a peak (or maximum) absorbance.
- the first unactivated state peak absorbance waveiength typically resides between 340 nm and 380 nm.
- a first unactivated state terminal minimum absorbance wavelength means the wavelength at which the first photochromic compound ⁇ of the primer layer), in an unactivated state, has a terminal (or upper) minimum absorbance.
- the first unactivated state terminal minimum absorbance wavelength is at higher wavelength than the first unactivated state peak absorbance waveiength.
- a first unactivated state initial minimum absorbance waveiength means the wavelength at which the first photochromic compound (of the primer layer), in an unactivated state, has an initial (or lower) minimum absorbance.
- the first unactivated state minimum absorbance wavelength is at lower wavelength than the first unactivated state peak absorbance wavelength and the first unactivated state terminal minimum absorbance waveiength.
- a second unactivated state absorbance of greater than 0" over a certain waveiength range such as “over at least a portion of wavelengths from 340 nm to 380 nm” means the photochromic-dichroic has an unactivated state absorbance of greater than 0 over a certain wavelength range, such as over at least a portion of 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.
- the term "over at least a portion of wavelengths from x nm to y nm" with regard to an unactivated state absorbance of greater than 0 means over at least a portion of consecutive wavelengths within the recited range, inclusive of the recited upper and lower wavelength values.
- a second unactivated state peak absorbance wavelength means the waveiength at which the photochromic-dichroic compound (of the coating layer, or photochromic-dichroic coating layer), in an unactivated state, has a peak (or maximum) absorbance.
- the second unactivated state peak absorbance wavelength typicaliy resides between 340 nm and 380 nm.
- a second unactivated state terminal minimum absorbance waveiength means the wavelength at which the photochromic-dichroic compound (of the coating layer, or photochromic-dichroic coating layer), in an unactivated state, has a terminal (or upper) minimum absorbance.
- the second unactivated state terminal minimum absorbance wavelength is at higher wavelength than the second unactivated state peak absorbance wavelength.
- a second unactivated state initial minimum absorbance wavelength means the wavelength at which the photochromic-dichroic compound (of the photochromic-dichroic layer), in an unactivated state, has an initial (or lower) minimum absorbance.
- the second unactivated state minimum absorbance wavelength is at sower wavelength than the second unactivated state peak absorbance wavelength and the second unactivated state terminal minimum absorbance wavelength,
- a third unactivated state absorbance of greater than 0" over a certain wavelength range means the second photochromic compound has an unactivated state absorbance of greater than 0 over a certain wavelength range, such as over at least a portion of wavelengths from 330 nm to 380 nm, such as from 330 nm to 370 nm, or from 340 nm to 380 nm.
- a third unactivated state peak absorbance wavelength means the wavelength at which the second photochromic compound (of the topcoat layer), in an unactivated state, has a peak (or maximum) absorbance.
- the third unactivated state peak absorbance wavelength typically resides between 330 nm and 380 nm.
- a third unactivated state terminal minimum absorbance wavelength means the wavelength at which the second photochromic compound (of the topcoat layer), in an unactivated state, has a terminal (or upper) minimum absorbance.
- the third unactivated state terminal minimum absorbance wavelength is at higher wavelength than the third unactivated state peak absorbance wavelength.
- a third unactivated state initial minimum absorbance wavelength means the wavelength at which the second photochromic compound (of the topcoat layer), in an unactivated state, has an initial (or lower) minimum absorbance.
- the third unactivated state minimum absorbance wavelength is at lower wavelength than the third unactivated state peak absorbance wavelength and the third unactivated state terminal minimum absorbance wavelength.
- the unactivated state initial minimum absorbance wavelength values can each be affected by the analytical method and equipment employed , and the substrate and/or the matrix, such as the coating matrix, in which the particular photochromic compound resides (which is referred herein as a "USIMAWV affect").
- the USI AWV affect can be more pronounced when the unactivated state initial minimum absorbance wavelength value is less than 360 nrn.
- the USIMAWV affect can be additive or subtractive, resulting in higher or lower unactivated state initial minimum absorbance wavelength values. Alternatively or additionally, the USIMAWV affect can result in unactivated state initial minimum absorbance wavelength values having negative absorbance values.
- the USIMAWV affect can result in positive and/or negative absorbance spikes, in particular at wavelength values less than 360 nrn. While not intending to be bound by any theory, it is believed that, in the case of organic polymer substrates and organic polymer coatings, the USIMAWV affect is due, at least in part, to the presence of aromatic rings in the substrate and/or the coating matrix, coupled with instrument reference subtraction. With some embodiments, when the substrate is quartz, the USIMAWV affect can be minimized .
- first, second and third unactivated state initial minimum absorbance wavelength values (65, 68 and 71 ) as described in further detail herein with reference to FIG's 1 and 3, may have been subject to the USIMAWV affect.
- percent transmittance was determined using an ULTRASCAN PRO spectrometer obtained commercially from HunterLab, in accordance with instructions provided in the spectrometer user manual.
- the term 'linearly polarize means to confine the vibrations of the electric vector of electromagnetic waves, such as light waves, to one direction or plane.
- “applied over,” residing over,” or “positioned over,” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct (or abutting) contact with the underlying eiement, or surface of the underlying element.
- a layer "positioned over" a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
- Photochromic article 2 includes a substrate 1 1 having a first surface 12 and a second surface 13, in which the first 1 and second 13 surfaces are opposed to each other. First surface 12 of substrate 1 faces Incident actinic radiation depicted by arrow 5. Photochromic article 2 further includes a primer layer 14 over (e.g., abutting) substrate 1 and in particular over (e.g., abutting) first surface 12 of substrate 1 1.
- Photochromic article 2 further includes a coating layer 17 (which is also referred to herein as a photochromic-dichroic layer 17) over primer layer 14, and an optional topcoat layer 20 over photochromic-dichroic layer 17.
- Photochromic article 2 of FIG. 1 includes other optional layers, which will be described further herein.
- Primer layer 14 includes a first photochromic compound having absorbance properties represented by graph 23, which is a representative plot of absorbance vs. wavelength for the first photochromic compound in an unactivated state. More particularly, graph 23 is obtained from analysis of primer 1 applied to substrate 11 In the absence of other underlying or overlying layers. With reference to graph 23 of FIG. 1 , the first photochromic compound has a first unactivated state peak absorbance wavelength 26, a first unactivated state terminal minimum absorbance wavelength 29, and a first unactivated state initial minimum absorbance wavelength 65 that is not depicted in graph 23, but which is less than 340 nm.
- the first unactivated state terminal minimum absorbance wavelength 29 of the first photochromic compound is at higher wavelength than the first unactivated state peak absorbance wavelength 28 thereof.
- the first unactivated state initial minimum absorbance wavelength 65 is at Sower wavelength than the first unactivated state peak absorbance wavelength 26.
- the first unactivated state peak absorbance wavelength 28 of the first photochromic compound of primer layer 14 is 355 nm
- the first unactivated state terminal minimum absorbance wavelength 29 is 425 nm
- the first unactivated state initial minimum absorbance wavelength 65 Is 333 nm ⁇ not depicted).
- the unactivated state terminal minimum absorbance wavelength values of the photochromic compounds and photochromic-dichroic compounds of the photochromic articles of the present invention can be determined in accordance with art-recognized methods.
- the unactivated state absorbance of the phoiochromic or photochromic-dichroic compounds clearly drops to zero, and the wavelength at the zero point is recorded.
- the unactivated state absorbance of the photochromic or photochromic-dichroic compound drops to a minimum plateau value, which may not reach a measured absorbance of zero. In the case of a minimum plateau value, the unactivated state terminal minimum absorbance wavelength values are typically estimated, For purposes of non-limiting illustration and with reference to FIG.
- the third unactivated state terminal minimum absorbance wavelength 47 is estimated by extending a fine, represented by dashed line 62, from a linear portion 56 of the absorbance vs. wavelength trace that resides to the left of ⁇ i.e., at lower wavelength relative to) the inflection point 59 of the trace.
- the point at which the extended line 62 intersects the x-axis is recorded as the third unactivated state terminal minimum absorbance wavelength value.
- the estimated unactivated state terminal minimum absorbance wavelength points and values as described can be determined by calculation (typically with the use of a computer graphing program) or manually (e.g., using a ruler). Unless otherwise indicated, the estimated unactivated state terminal minimum absorbance wavelength points and values depicted and discussed with reference to FIG. 1 were determined manually.
- the unactivated state Initial minimum absorbance wavelength values can be estimated in accordance with a method similar to that described with regard to the terminal minimum absorbance wavelength values.
- a line is extended from a linear portion of the absorbance vs. wavelength trace that resides to the right of (i.e., at higher wavelength relative to) the lower Inflection point of the trace.
- the unactivated state initial minimum absorbance clearly occurs at a value of zero absorbance along the x-axis, and as such does not have to be estimated.
- Photochromic-dichroic layer 17 of photochromic article 2 includes a photochromic-dichroic compound having absorbance properties represented by graph 32, which is a plot of absorbance vs. wavelength for the photochromic-dichroic compound. More particularly, graph 32 is obtained from analysis of photochromic-dichroic layer 17 applied to substrate 1 1 in the absence of other underlying or overlying layers. With reference to graph 82 of FIG, 1 , the photochromic-dichroic compound has a second unactivated state peak absorbance wavelength 35, a second unactivated state terminal minimum absorbance wavelength 38, and a second unactivated state initial minimum absorbance 68.
- the unactivated state second terminal minimum absorbance wavelength 38 of the photochromic-dichroic compound is at higher wavelength than the second peak absorbance wavelength 35 thereof.
- the unactivated state second initial minimum absorbance wavelength 68 of the photochromic-dichroic compound is at lower wavelength than the second peak absorbance wavelength 35.
- the second unactivated state peak absorbance wavelength 35 of the photochromic-dichroic compound of photochromic-dichroic layer 17 is 360 nm
- the second unactivated state Initial minimum absorbance wavelength 68 is 342 nm.
- the optional topcoat layer 20 of photochromic article 2 can in some embodiments of the present Invention include a second photochromic compound having absorbance properties represented by graph 41 , which is a plot of absorbance vs. wavelength for the second photochromic compound. More particularly, graph 41 is obtained from analysis of topcoat layer 20 applied to substraie 11 in the absence of other underlying or overlying layers. With reference to graph 41 of FIG. 1 and FIG. 3, the second photochromic compound has a third unactivated state peak absorbance 44, a third unactivated state terminal minimum absorbance wavelength 47, and a third unactivated state initial minimum absorbance wavelength 71.
- the third unactivated state terminal minimum absorbance wavelength 47 of the second photochromic compound is at higher wavelength than the third unactivated state peak absorbance wavelength 44 thereof.
- the third unactivated state initial minimum absorbance wavelength 71 Is at lower wavelength than third unactivated state peak absorbance wavelength 44.
- the third unactivated state peak absorbance wavelength 44 of the second photochromic compound of topcoat layer 20 is 364 nm
- the third unactivated state terminal minimum absorbance wavelength 47 is 386 nm
- the third unactivated state initial minimum absorbance wavelength 71 is 346 nm.
- line or spike 74 is believed to be the result of the polymer matrix of the topcoat layer and/or the substrate, and is not believed to be the result of (or due to) the second photochromic compound. As such, spike 74 is not considered when determining the third unactivated state peak absorbance wavelength, the third unactivated state terminal minimum absorbance wavelength, or the third unactivated state initial minimum absorbance wavelength of the second photochromic compound of the topcoat layer.
- FIG. 3 extends from 0 to 0.1 rather than from 0 to 3.5 as in FiG . 1 , for purposes of better illustrating and determining the peak, terminal minimum, and initial minimum values associated with the second photochromic compound of the topcoat layer.
- Graphs 23, 32, and 41 of FiG. 1 , and graph 41 of FIG. 3 each depict absorbance as a function of wavelength from 340 nm to 460 nm.
- FiG. 1 and FIG. 3, including graphs 23, 32, and 41 are referenced for purposes of non-limiting illustration.
- absorbance as a function of wavelength of the first photochromic compound, the photochromic-dichroic compound, and the second photochromic compound in each case is not limited to thai depicted In FIG. 1 and FIG. 3.
- the first photochromic compound of the primer layer has a first unactivated state absorbance of greater than 0 at all wavelengths from 340 nm to 380 nm, and the first unactivated state terminal minimum absorbance wavelength is greater than 380 nm.
- the first photochromic compound of the primer layer has a first unactivated state absorbance of greater than 0 at all wavelengths from 340 nm to 400 nm, and the first unactivated state terminal minimum absorbance wavelength Is greater than 400 nm.
- the first photochromic compound of the primer layer has a first unactivated state absorbance of greater than 0 at all wavelengths from 340 nm to 410 nm, and the first unactivated state terminal minimum absorbance wavelength is greater than 410 nm.
- the first photochromic compound of primer layer 14 has a first unactivated state absorbance of greater than 0 at. all wavelengths from 340 nm to 380 nm, and a first unactivated state terminal minimum absorbance wavelength that is greater than 380 nm .
- the first unactivated state terminal minimum absorbance wavelength of the first phoiochromic compound of the primer layer 14 of photochromtc article 2 of FIG. 1 is 425 nm.
- the phoiochromic-dichroic compound of the photochromic-dichroic coating layer has a second unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 340 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength that Is greater than 340 nm.
- ihe photochromic-dichroic compound can, with some embodiments, have; a second unactivated state absorbance of greater than 0 over all wavelengths from 340 nm to 370 nm, and a second unactivated state terminal minimum absorbance wavelength that is greater than 370 nm; or a second unactivated state absorbance of greater than 0 over all wavelengths from 350 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength that is greater than 380 nm.
- the photochromic-dichroic compound of the photochromic-dichroic coating layer has a second unactivated state absorbance of greater than 0 over at least a portion of wavelengths from. 340 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength that is greater than 380 nm.
- the phoiochromic-dichroic compound of the photochromic-dichroic coating layer has a second unactivated state absorbance of greater than 0 at ail (or, over all) wavelengths from 340 nm to 380 nm, and a second unactivated state terminal minimum absorbance wavelength that is greater than 380 nm.
- the first unactivated state terminal minimum absorbance wavelength is greater than 380 nm and less than or equal to 450 nm, such as less than or equal to 440 nm, or less than or equal to 430 nm.
- the second unactivated state terminal minimum absorbance wavelength Is greater than 340 nm and less than or equal to 450 nm, such as less than or equal to 440 nm, or iess than or equal to 440 nm.
- the second unactivated state terminal minimum absorbance wavelength is less than the first unactivated state terminal minimum absorbance wavelength.
- the photochromic-dichroic compound of photochromic-dichroic layer 1 ? and the first photochromic compound of the underlying primer iayer 14 are each selected so as to have the absorbance properties as described above. According to some embodiments of the present invention, they are selected such that the photochromic article has an unactivated state percent transmittance of less than 5% at all wavelengths from 340 nm to 380 nm.
- the unactivated state percent transmittance 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 unactivated state percent transmittance is substantially 0% at all wavelengths from 340 nm to 380 nm. Reducing and minimizing the percent transmittance of electromagnetic radiation through the photochromic articles of the present invention at all wavelengths from 340 nm to 380 nm is desirable for reasons including, but not limited to, protecting objects behind the photochromic article, such as a human eye, from exposure to electromagnetic radiation having wavelengths from 340 nm to 380 nm. Percent transmittance over the recited wavelength range or ranges is determined in accordance with art-recognized methods using art-recognized and commercially available analytical equipment.
- the photochromic article of the present invention has an unactivated state percent transmittance of less than 5% at all wavelengths from 340 nm to 400 nm.
- the unactivated state percent transmittance at ail 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%.
- the unactivated state percent transmittance is substantially 0% at all wavelengths from 340 nm to 400 nm.
- reducing and minimizing the percent transmittance of electromagnetic radiation through the photochromic articles of the present invention at all wavelengths from 340 nm to 400 nm is desirable for reasons including, but not limited to, protecting objects behind the photochromic article, such as a human eye, from exposure to electromagnetic radiation having wavelengths from 340 nm to 400 nm.
- the photochromic article with some embodiments of the present invention has an activated state optical density that Is greater than a control activated state optica! density of a control photochromic article comprising the substrate and the coating iayer (i.e., photochromic-dichroic layer) in the absence of the primer layer,
- the substrate of the photochromic article and the control photochromic article is in each case substantially the same, and has substantially the same properties and thickness.
- the coating layers of the photochromic article and the control photochromic article are in each case substantially the same, and have substantially the same properties and thickness.
- photochromic articles according to the present invention are typically darker, in an activated state, when exposed to the same level of Incident actinic radiation as comparative photochromic articles, in an activated state, having, for example, a photochromic-dichroic layer containing a photochromic-dichroic compound in the absence of an underlying primer Iayer containing a first photochromic compound as described above,
- the activated state optical density of the and the control activated state optical density are typically determined over at least a portion of the visible light spectrum. With some embodiments, the activated state optical density and the control activated state optical density are each determined from 410 nm to 800 nm, Optical density is determined in accordance with art-recognized methods using art-recognized and commercially available equipment.
- the photochromic article includes a topcoat Iayer that resides over the photochromic-dichroic layer.
- the topcoat layer can include an ultraviolet light absorber and/or a second photochromic compound.
- the topcoat layer includes a second photochromic compound and optionally an ultraviolet light absorber.
- the topcoat Iayer includes an ultraviolet light absorber and is free of photochromic compounds, such as the second photochromic compound.
- the topcoat layer includes a second photochromic compound and is free of an ultraviolet light absorber.
- the primer and first photochromic compound, and the photochromic-dichroic Iayer and photochromic-dichroic compound are each as described previously herein.
- the second photochromic compound, of the topcoat Iayer has a third unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 330 nm to 380 nm, and a third unactivated state terminal minimum absorbance wavelength that is greater than 330 nm.
- the third unactivated state terminal minimum absorbance wavelength (of the second photochromic compound of the topcoat layer) is less than the second unactivated state terminal minimum absorbance wavelength (of the photochromic-dichroic compound of the photochromic-dichroic iayer).
- the third unaciivated state terminal minimum absorbance wavelength is greater than 330 nm and less than 380 nm.
- the third unactivaied state terminal minimum absorbance wavelength is greater than 330 nm and less than 370 nm.
- the first unactivaied state terminal minimum absorbance wavelength is greater than 380 nm and less than or equal to 450 nm; the second unaciivated state terminal minimum absorbance wavelength is greater than 340 nm and less than or equal to 450 nm; and the third unactivaied state terminal minimum absorbance wavelength is greater than 330 nm and less than 380 nm,
- the first unaciivated state terminal minimum absorbance wavelength is greater than 380 nrn and less than or equal to 450 nm; the second unaciivated state terminal minimum absorbance wavelength is greater than 340 nm and less than or equal to 450 nm; and the third unaciivated state terminal minimum absorbance wavelength is greater than 330 nm and less than 370 nm.
- the second photochromic compound of the topcoat layer 20, the photochromic-dichroic compound of photochromic-dichroic layer 17, and the first photochromic compound of the underlying primer layer 14 are each selected so as to have or provide the absorbance properties as described above. According to some embodiments of the present Invention, they are selected such that the photochromic article has an unactivaied state percent transmittance of less than 5% at ail wavelengths from 340 nm to 380 nm.
- the unactivaied state percent transmittance at ail 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 unactivaied state percent transmittance is substantially 0% at ail wavelengths from 340 nm to 380 nm.
- the photochromic article of the present invention when including the topcoat layer and second photochromic compound, has an unactivaied state percent transmittance of less than 5% at all wavelengths from 340 nm to 400 nm.
- the unactivaied state percent transmittance at all wavelengths from 340 nm ⁇ 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%.
- the unactivated stale percent transmittance is substantially 0% at al! wavelengths from 340 nm to 400 nm.
- the phoiochromic article with some embodiments of the present invention has an activated state optical density that is greater than a control activated state optical density of a control photochromic article that comprises the substrate and the coating layer (i.e., photochromic-dichroic layer) in the absence of both of the topcoat layer with the second photochromic compound and the primer layer,
- the substrate of the photochromic article and the control photochromic article is in each case substantially the same, and has substantially the same properties and thickness.
- the coating layer of the photochromic article and the control phoiochromic article are in each case substantially the same, and have substantially the same properties and thickness.
- the activated state optical density and the control activated state optical density are each typically determined over at least a portion of the visible light spectrum. With some embodiments, the activated state optical density and the control activated state optical density are each determined from 410 nm to 800 nm. Optical density is determined in accordance with art-recognized methods using art-recognized and commercially available equipment.
- photochromic articles according to the present invention are typically darker, in an activated state, when exposed to the same level of incident actinic radiation as comparative photochromic articles, in an activated state, having, for example, a photochromic-dichroic layer containing a photochromic-dichroic compound in the absence of a overlying topcoat layer containing a second photochromic compound, and an underlying primer layer containing & first photochromic compound as described above.
- the unactivated state peak absorbance wavelength values of the first photochromic compound , the photochromic-dichroic compound and the optional second photochromic compound are not equivalent to each other. More particularly, the first unactivated state peak absorbance wavelength (of the first photochromic compound of the primer layer), the second unactivated state peak absorbance wavelength (of the photochromic-dichroic compound of the photochromic-dichroic layer), and the third unactivated state peak absorbance wavelength (of the optional second photochromic compound of the optional topcoat iayer) are not equivalent to each other.
- the amount of incident radiation (having wavelengths from 340 nm to 380 nm or from 340 nm to 400 nm) thai 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 incident radiation passes down through the optional topcoat !ayer (20), the photochromic-dichroic layer (17) and the primer layer (14).
- the photochromic-dichrotc compound and the first photochromic compound can increase and/or optimize the photochromic and/or photochromic-dichroic response of the recited compounds, and correspondingly improve the photochromic and/or photochromic-dichroic response and properties of the photochromic articles of the present invention.
- the percent transmittance of incident radiation having 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 unactivated state peak wavelengths are non-equivalent and offset as described above and further herein.
- the difference between the second unactivated state peak absorbance wavelength and the first unactivated state peak absorbance wavelength is greater than or equal to 0,5 nm and less than or equal to 20 nm, or greater than or equal to 1 nm and iess 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 7 nm, or any combination of these recited upper and lower wavelength values.
- the second unactivated state peak absorbance wavelength can be greater than or less than the first unactivated state peak absorbance wavelength.
- the first unactivated state peak absorbance wavelength can be greater than or less than the second unactivated state peak absorbance wavelength.
- the second unactivated state peak absorbance wavelength is greater than the first unactivated state peak absorbance wavelength, and correspondingly, the first unactivated state peak absorbance wavelength is less than the second unactivated state peak absorbance wavelength.
- the difference between the third unactivated state peak absorbance wavelength and the second unactivated state peak absorbance wavelength Is greater than or equal to 0.5 nm and less than or equal to 20 nm, or greater than or equal to 1 nm and less than or equai to 15 nm, o greater than or equai to 2 nm and iess than or equai to 10 nm, or greater than or equal to 2 nm and less than or equal to 7 nm, or any combination of these recited upper and lower wavelength values.
- the third unactivated state peak absorbance wavelength can be greater than or less than the second unactivated state peak absorbance wavelength.
- the second unactivated state peak absorbance wavelength can be greater than or less than the third unactivated state peak absorbance wavelength.
- the third unactivated state peak absorbance wavelength is greater than the second unactivated state peak absorbance wavelength, and correspondingly, the second unactivated state peak absorbance wavelength is less than the third unactivated state peak absorbance wavelength.
- the first unactivated state peak absorbance wavelength is less than the second unactivated state peak absorbance wavelength; and the second unactivated state peak absorbance wavelength is less than the third unactivated state peak absorbance wavelength (when the topcoat and second photochrome compound are present).
- 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 in accordance with various non-limiting embodiments disclosed herein are described in more detail below.
- Non-limiting examples of organic materials that can be used to form the substrate of the photochromic articles of the present invention include polymeric materials, for example, homopolymers and copolymers, prepared from the monomers and mixtures of monomers disclosed in U.S. Patent 5,962,617 and in U .S. Patent 5,658,501 from column 15, line 28 to column 16, line 17, the disclosures of which U.S. patents are specifically incorporated herein by reference.
- polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any refractive index required.
- Non-limiting examples of such disclosed monomers and polymers include: polyol(aliy! carbonate) monomers, e.g., ally!
- digiycol carbonates such as diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39 by PPG industries, inc.; poSyurea-po!yurethane (polyurea-urethane) polymers, which are prepared , for example, by the reaction of a polyurethane prepolymer and a diamine curing agent, a composition for one such polymer being sold under the trademark TRIVEX by PPG Industries, Inc.; po!yoi(rneth)acryfoyl terminated carbonate monomer; diethylene glycol dimetnacryiate monomers; ethoxylated phenol methacry!ate monomers; ditsopropenyl benzene monomers; ethoxylated irimethylol propane triacrylate monomers; ethylene glycol bismethacry!ate monomers; po!y(ethyiene glycol) bismethacrytate monomers; urethane acryi
- polyesters such as the material sold under the trademark MYLAR; poly(ethylene terephtha!ate); polyvinyl butyrai; poly(methyS methacrylate), such as the materia! sold under the trademark PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanates with polythiols or po!yepisulfide monomers, either homopo!ymerized or co-and/or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates and optionally ethylenlcaily unsaturated monomers or ha!ogenated aromatic-containing vinyl monomers. Also contemplated are copolymers of such monomers and blends of the described polymers and copolymers with other polymers, for example, to form block copolymers or interpenetrating network products.
- the substrate can, 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, the art-recognized polymers that are useful as ophthalmic substrates, such as organic optical resins that are used to prepare optically clear castings for optical applications, such as ophthalmic lenses.
- organic materials suitable for use in forming the substrate of the photochromic articles of the present invention include both synthetic and natural organic materials, including without limitation: opaque or transluscent polymeric materials, natural and synthetic textiles, and va!ulosic materials such as, paper and wood .
- Non-limiting examples of inorganic materials suitable for use in forming the substrate of the photochromic articles of the present invention include glasses, minerals, ceramics, and metals.
- the substrate can include glass
- the substrate can have a reflective surface, for example, a polished ceramic substrate, metal substrate, or mineral substrate.
- a reflective coating or layer can be deposited or otherwise applied to a surface of an inorganic or an organic substrate to make it reflective or to enhance its reflectivity.
- the substrate can have a protective coating, such as, but not limited to, an abrasion- resistant coating, such as a "hard coat," on its exterior surfaces.
- a protective coating such as, but not limited to, an abrasion- resistant coating, such as a "hard coat”
- a protective coating such as, but not limited to, an abrasion-resistant coating, such as a "hard coat”
- an abrasion-resistant coating such as a "hard coat”
- a protective coating such as, but not limited to, an abrasion-resistant coating, on its surface(s).
- the substrate of the photochromic article of the present invention can be untinted, tinted, linearly polarizing, circularly polarizing, e!liptically polarizing, photochromic, or tinted-photochromic substrates.
- untinted means substrates that are essentially free of coloring agent additions ⁇ such as, but not limited to, conventional dyes) and have an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation
- the term "tinted” means substrates that have a coloring agent addition (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.
- linearly polarizing with regard to the substrate means substrates that are adapted to linearly polarize radiation.
- circularly polarizing with regard to the substrate means substrates that are adapted to circularly polarize radiation.
- eliiptica!ly polarizing with regard to the substrate means substrates that are adapted to eliipticaily polarize radiation.
- photochromic with regard to the substrate means substrates having an absorption spectrum for visible radiation that varies in response to at least actinic radiation.
- tinted- photochiomic means substrates containing a co!oring agent addition as well as a photochromic material, and having an absorption spectrum for visible radiation that varies in response to at least actinic radiation.
- a tinted- photochromic substrate can have a first color characteristic of the coloring agent and a second color characteristic of the combination of the coloring agent the photochromic material when exposed to aclinic radiation.
- the photochromic articles of the present invention include a photochromic- dichroic layer that further includes a photochromic-dichroic compound .
- the photochromic-dichroic layer can, in some embodiments, be non-polarizing in a first state (that is, the coating will not confine the vibrations of the electric vector of light waves to one direction), and be linearly polarizing in a second state with regard to transmitted radiation.
- transmitted radiation refers to radiation that is passed through at least a portion of an object.
- the transmitted radiation can be ultraviolet radiation, visible radiation, infrared radiation, or a combination thereof-
- the photochromic-dichroic layer can be non-polarizing in the first state and linearly polarizing transmitted ultraviolet radiation, transmitted visible radiation, or a combination thereof in the second state.
- the photochromic-dschroic 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 second states.
- the photochromic-dichroic iayer can have an average absorption ratio of at least 1 .5 in at least one state.
- the photochromic-diehrolc 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 ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of radiation linearly polarized in a plane orthogonal to the first plane, in which the first plane is taken as the piane with the highest absorbance.
- the absorption ratio (and the average absorption ratio which is described below) is an indication of how strongly one of two orthogonal plane polarized components of radiation is absorbed by an object or material.
- the average absorption ratio of a photochromic-dichroic Iayer that includes a photochromic-dichroic compound can be determined as set forth be!ow.
- a substrate having a coating is positioned on an optical bench and the coating is placed in a linearly polarizing state by activation of the photochromic-dichroic compound.
- Activation is achieved by exposing the coating to UV radiation for a time sufficient to reach a saturated or near saturated state (that is, a state wherein the absorption properties of the coating do not substantially change over the interval of time during which the 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 0° polarization piane or direction) and light that is linearly polarized in a piane that is parallel to the optical bench (referred to as the 90° polarization plane or direction) in the following sequence: 0°, 90°, 90°, 0° etc.
- the absorbance of the linearly polarized light by the coating is measured at each time interval for all of the wavelengths tested and the unactivated absorbance (I.e., the absorbance of the coating in an unactivated state) over the same range of wavelengths Is subtracted to obtain absorption spectra for the coating in an activated state in each of the 0° and 90° polarization planes to obtain an average difference absorption spectrum in each polarization plane for the coating in the saturated or near-saturated state.
- the average difference absorption spectrum (generally indicated 4) in one polarization plane thai was obtained for a phoiochromic-dichroic layer according to one non-limiting embodiment disclosed herein.
- the average absorption spectrum (generally indicated 3) is the average difference absorption spectrum obtained for the, same phoiochromic-dichroic Iayer in the orthogonal polarization plane.
- the average absorption ratio for the photochromic-dichroic Iayer is obtained as follows.
- the absorption ratio of the phoiochromic-dichroic Iayer at each wavelength in a predetermined range of wavelengths corresponding to X max .. V i S +/- 5 nanometers (generally Indicated as 5 In FIG. 2), wherein max-Vis is the wavelength at which the coating had the highest average absorbance in any plane, is calculated according to the following equation (Eq. 1 ):
- AR 3 ⁇ 4i is the absorpiion ratio at wavelength 3 ⁇ 4, Ab ; Is the average absorption at wavelength ⁇ , in the polarization direction ⁇ I.e., 0° or 90°) having the higher absorbance, and Ab 2 y Is the average absorption at wavelength ⁇ , in the remaining polarization direction.
- the "absorption ratio” refers to the ratio of the absorbance of radiation linearly polarized in a first plane to the absorbance of the same wavelength radiation linearly polarized in a plane orthogonal to the first plane, wherein the first plane is taken as the plane with the highest absorbance.
- the average absorption ratio ("AR") for the photochromic-dichroic Iayer is then calculated by averaging the individual absorption ratios over the predetermined range of wavelengths (i.e., +/- 5 nanometers) according to the following equation (Eq . 2):
- AR is average absorption ratio for the coating
- j are the individual absorption ratios (as determined above in Eq, 1 ) for each wavelength within the predetermined range of wavelengths
- n is the number of individual absorption ratios averaged
- the photochromic-dichroic compound of the photochromic-dichroic layer can be at least partially aligned.
- photochromic-dichroic means displaying both photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least deteciibie by instrumentation.
- photochromic-dichroic compounds are compounds displaying both photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least deteciibie by instrumentation.
- photochromic-dichroic compounds have an absorption spectrum for at Ieast visible radiation that varies in response to at ieast actinic radiation and are capable of absorbing one of two orthogonal plane polarized components of at Ieast transmitted radiation more strongiy than the other.
- the photochromic-dichroic compounds disclosed herein can be thermally reversible. That Is, the photochromic-dichroic compounds can switch from a first state to a second state in response to actinic radiation and revert back to the first state in response to thermal energy.
- the term "compound” means a substance formed by the union of two or more elements, components, ingredients, or parts and includes, without limitation, molecules and rnacromo!ecules ⁇ for example polymers and oligomers) formed by the union of two or more elements, components, Ingredients, or parts.
- 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 switch from the first state to the second state in response to at least actinic radiation and to revert back to the first state in response to thermal energy.
- the photochromic-dichroic compound can be dichroic (i.e., linearly polarizing) in one or both of the first state and the second state.
- the photochromic-dichroic compound can be linearly polarizing in an activated state and non-polarizing In the bleached or faded (i.e., not activated) state.
- the term "activated state” refers to the photochromic-dichroic compound when exposed to sufficient actinic radiation to cause at ieast a portion of the photochromic-dichroic compound to switch from a first state to a second state,
- the photochromic-dichroic compound can be dichroic in both the first and second states. While not limiting herein, for example, the photochromic-dichroic compound can linearly polarize visible radiation in both the activated state and the bleached state. Further, the photochromic-dichroic compound can linearly polarize visible radiation in an activated state, and can linearly polarize UV radiation in the bleached state.
- the photochromic-dichroic compound of the photochromic-dichroic layer can have an average absorption ratio of at least 1.5 in an activated state as determined according to the CELL METHOD.
- the photochromic-dichroic compound can have an average absorption ratio greater than 2,3 in an activated state as determined according to the CELL METHOD.
- the at least partially aligned photochromic-dichroic compound of the photochromic-dichroic layer can have an average absorption ratio ranging from 1 .5 to 50 in an activated state as determined according to the CELL ETHOD.
- the at least partially aligned photochromic-dichroic compound of the photochromic-dichroic layer can have an average absorption ratio ranging from 4 to 20, can further have an average absorption ratio ranging from 3 to 30, and can still further 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 at least partially aligned photochromic-dichroic compound can be any average absorption ratio that is sufficient to impart the desired properties to the photochrome article of the present invention.
- suitable photochromic-dichroic compounds are described in detail herein below.
- 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 the absorbance of a coated substrate, a cell assembly containing an aligned liquid crystal material and the photochromic-dichroic compound is tested. More specifically, the cell assembly Includes two opposing glass substrates that are spaced apart by 20 microns +/- 1 micron. The substrates are sealed along 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 has been at least partially ordered by rubbing.
- Alignment of the photochromic-dichroic compound is achieved by introducing the photochrornic- dichroic compound and the liquid crystai medium into the ceil assembly, and allowing the liquid crystal medium to align with the rubbed polyimide surface. Once the liquid crystal medium and the photochromic-dichroic compound are aligned, the eel! assembly is placed on an optical bench (which is described in detail in the Examples) and the average absorption ratio is determined in the manner previously described for the coated substrates, except that the unactivated absorbance of the ceil assembly is subtracted from the activated absorbance to obtain the average difference absorption spectra.
- white dichrosc compounds are capable of preferentially absorbing one of two orthogonal components of plane polarized light, it is generally necessary to suitably position or arrange the molecules of a dichroic compound in order to achieve a net linear polarization effect.
- the photochromic-dichroic compound is at least partially aligned.
- the activated state of the photochromic-dichroic compound corresponds to a dichroic state of the materia!
- the photochromic-dichroic compound can be at least partially aligned such that the long axis of the molecules of the photochromic- dichroic compound in the activated state are aligned.
- align means to bring into suitable arrangement or position by interaction with another material, compound or structure.
- the photochromic-dichroic layer of the photoc . hromic article of the present invention can include a plurality of photochromic- dichroic compounds.
- the photochromic-dichroic compounds can be chosen to complement one another to produce a desired color or hue.
- mixtures photochromic-dichroic compounds can be used according to certain non-limiting embodiments disclosed herein to attain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S.
- the at least partial coating can comprise mixtures of photochromic-dichroic compounds having complementary linear polarization states.
- the photochromic-dichroic compounds can be chosen to have complementary linear polarization states over a desired range of wavelengths to produce an optical element that is capable of polarizing !ight over the desired range of wavelengths.
- mixtures of complementary photochromic-dichroic compounds having essentially the same polarization states at the same wavelengths can be chosen to reinforce or enhance the overall linear polarization achieved.
- the photochromic-dichroic layer can include at least two at least partially aligned photochromic-dichroic compounds, in which each at least partially aligned photochromic-dichroic compounds have: complementary colors; and/or complementary linear polarization states.
- the photochromic-dichroic laye can further include at least one additive that may facilitate one or more of the processing, the properties, or the performance of the at least partial coating.
- additives include dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polymerization Inhibitors, solvents, Sight stabilizers (such as, but not.
- Iimited to ultraviolet Iight absorbers and Iight stabilizers, such as hindered amine Sight stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not Iimited to, surfactants), free radical scavengers, and adhesion promoters (such as hexanediol diacrylate and coupling agents).
- HALS hindered amine Sight stabilizers
- leveling agents such as, but not Iimited to, surfactants
- free radical scavengers free radical scavengers
- adhesion promoters such as hexanediol diacrylate and coupling agents.
- Examples of dyes that can be present in the photochromic-dichroic layer include, but are not iimited to, organic dyes that are capable of imparting a desired color or other optical property to the photochromic-dichroic layer.
- alignment promoter means an additive that can facilitate at least one of the rate and uniformity of the alignment of a material to which it is added.
- alignment promoters that can be present in the photochromic-dichroic layer include, but are not limited to, those described in U .S. Patent 6,338,808 and U.S. Patent Publication No. 2002/0039627, which are hereby specifically incorporated by reference herein.
- Non-limiting examples of kinetic enhancing additives that can be present in the various layers of the photochromic article of the present invention, such as the photochromic-dichroic layer, include epoxy-containing compounds, organic polyo s, and/or plasticizers. More specific examples of such kinetic enhancing additives are disclosed in U.S. Patent 6,433,043 and U.S. Patent Publication No. 2003/0045612, which are hereby specifically incorporated by reference herein.
- Non-limiting examples of photoinitiators that can be present in the various layers of the photochromic article of the present invention, such as the primer layer, the photochromtc-dichroic layer, and/or the topcoat layer include, but are not limited to, cleavage-type photoinitiators and abstraction-type photoinitiators.
- Non-limiting examples of c!eavage-type photoinitiators include acetophenones, ct-aminoalkylphenones, benzoin ethers, benzoyl oximes, acylphosphine oxides and blsacyiphosphine 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 benzophenone, ichler ' s ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures of such initiators.
- a photoinitiator that can be present In one or more of the layers of the photochromic article of the present invention, such as the primer layer, the photochromic-dichroic layer, and/or the topcoat layer, is a visible light photoinitiator.
- a visible light photoinitiator is set. forth at column 12, line 1 1 to column 13, line 21 of U.S. Patent 6,602,603, which is specifically incorporated by reference herein.
- thermal initiators include, but are not limited to, organic peroxy compounds and azobis(organonitrile) compounds.
- organic peroxy compounds thai are useful as thermal initiators include, but are not limited to, peroxymonocarbona e esters, such as tertlarybutylperoxy isopropyi carbonate; peroxydicarbonate esters, such as di(2-ethylhexyi) peroxydicarbonate, di ⁇ secondary butyl) peroxydicarbonate and diisopropylperoxydicarbonate; diacyperoxides, such as 2,4- dichJorobenzoyl peroxide, isobutyryl peroxide, decanoyi peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzoy!
- thermal initiators used are those that do not discolor the resulting polymerizate.
- thermal initiators include, but are not limited to, azobis(isobutyronitrile), azobis(2. s 4-dimethyiva!eronitrile) or a mixture thereof.
- polymerization inhibitors include, but are not limited to: nitrobenzene, 1 ,3,5,-trinitrobenzene, p-benzoquinone, chloranil, DPPH, FeCf 3 , CuCI 2 , oxygen, sulfur, aniline, phenol, p-dihydroxybenzene, 1 ,2,3-tnhydroxybenzene, and 2,4,6- trimethyiphenoi.
- solvents that can be present in forming the various layers of the phptochromic articles of the present invention, such as the primer layer, the photochromic-dichroic layer, and/or the topcoat layer, include, but are not limited to, those that will dissolve solid components of the coating, that are compatible with the coating and the elements and substrates, and/or can ensure uniform coverage of the exterior surface(s) to which the coating is applied.
- solvents include, but are not limited to, the following: propylene glycol rnonomethyi ether acetate and their derivates (sold as DOWANOL ® industrial solvents), acetone, amy!
- propionate aniso!e, benzene, butyl acetate, cyciohexane, dia!kyi ethers of ethylene glycol, e.g., diethy!ene glycol dimethyl ether and their derivates (sold as CELLOSOLVE ® industrial solvents), dlethylene glycol dibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene, ethyl acetate, isopropyl alcohol, methyl cyc!ohexanone, cyc!opentanone, methyl ethyl ketone, methyi isobutyi ketone, methyl propionate, propylene carbonate, ietrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propyiene glycol methyl ether, and mixtures thereof.
- the photochromic-dichroic layer can include at least one conventional dichroic compound.
- suitable conventional dichroic compounds include, but are not limited to, azomethmes, indigoids, thioindigoids, merocyanines, indans, quinophthalonic dyes, pery!enes, phthaloperines, triphenodi . oxazines, indoioquinoxaiines, imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthroquinone and (poly)anthroquinones, anthropyrimidinones, iodine and iodates.
- the dichroic material can include at ieast one reactive functional group that is capable of forming at least one covalent bond with another materials.
- the dichroic material can be a polymenzable dichroic compound.
- the dichroic material can include at least one group that is capable of being polymerized (i.e., a "po!ymerizabie group").
- the dichroic compound can have at least one aikoxy, poiyalkoxy, alkyi, or polyaikyl substituent terminated with at least one polymerizable group.
- the photochromic-dichroic layer cars include at least one conventional photochromic compound.
- conventional photochromic compound includes both thermally reversible and non-therma!iy reversible (or photo-reversible ⁇ photochromic compounds.
- the various materials can be chosen to complement one another to produce a dessred color or hue.
- mixtures of photochromic compounds can be used according to certain non-iimiting embodiments disclosed herein to attain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Patent 5,845,787, column 12, line 86 to column 13, line 19, the disclosure of which is specifically incorporated by reference herein, which describes the parameters that define eutral gray and brown colors.
- the photochromic-dichroic layer is free of conventional photochromic compounds.
- the photochromic-dichroic layer can include one or more suitable photochromic-dichroic compounds.
- 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:
- the photochromic-dichroic compounds of the phoiochromic articles of the present invention can be chosen from the following: (PCDC-a1 ) 3,3-Bis(4-methoxyph . enyl)-1 G ⁇ [4- ⁇ 4- ⁇ trans-4-penty!cyciohexyl)ben2amido)pheriyl]- 13,13-dimeihyj-12-bromo.-3,13-dihydro- indeno[2',3':3 ( 4]naphtho 1 ,2-bjpyran;
- the photochromic-dichrcic compounds of the photochromic articles of the present invention can be chosen from the following:
- 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, pyrans, oxazines, and fuigides; and (b) at least one lengthening agent or group attached to the photochromic group.
- PC photochromic group
- Such photochromic- dichroic compounds are described in detail in United States Patent No. 7,342,1 12 B1 at column 5, line 35 to column 14, line 54; and Table 1 , the cited portions of which are Incorporated by reference herein.
- Other suitable photochromic compounds and reaction schemes for their preparation can be found in United States Patent No. 7,342,1 12 B1 at column 23, line 37 to column 78, fine 13, the cited portions of which are incorporated by reference herein.
- the photochromic-dichroic layer can include a single layer or multiple layers each including a photochromic-dichroic compound that can be the same or different.
- the photochromic-dichroic layer can be formed by art- recognized methods including, but not limited to; lamination, such as of one or more plastic sheets or films; in-mold formation, such as in-rnoid coating; film casting; and coating methods.
- the photochromic-dichroic layer is formed from a photochromic-dichroic coating composition.
- the photochromic-dichroic coating composition can be a curable photochromic-dichroic coating composition, that is curable by exposure to, for example: ambient temperatures, such as in the case of two component coating compositions; elevated temperatures (e.g., 150°C to 190°C for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, such as in the case of ultraviolet light curable coating compositions.
- ambient temperatures such as in the case of two component coating compositions
- elevated temperatures e.g., 150°C to 190°C for 5 to 60 minutes
- actinic radiation such as in the case of ultraviolet light curable coating compositions.
- the photochromic-dichroic layer typically Includes an organic matrix, such as a thermoplastic organic matrix and/or a cross!inked organic matrix. At least a portion of the organic matrix of the photochromic-dichroic layer can in some embodiments include anisotropic materials, such as liquid crystal materials, additives, oligomers, and/or polymers, as will be discussed in further detail herein. Additionally or alternatively to an organic matrix, the photochromic-dichroic layer can include an inorganic matrix, including, for example, siiane linkages, si!oxane linkages and/or titanate linkages.
- the organic matrix of the photochromic-dichroic layer can include, for example; acrylate residues (or monomer units) and/or methacryiate residues; vinyl residues; ether linkages; sulfide linkages, including monosu!fide linkages and/or pqlysu!flde linkages; carboxylic ester linkages; carbonate linkages (e.g., -O-C(O)-O-) urethane linkages (e.g., -N(H) ⁇ C(0 ⁇ -0-); and/or thiourethane linkages (e.g., -N(H)-C(0) ⁇ S-).
- the photochromic-dichroic iayer can have any suitable thickness.
- the photochromic-dichroic layer has a thickness of from 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.
- the photochromic-dichroic Iayer of the photochromic article, further includes a phase-separated polymer that Includes: a matrix phase that is at least, partially ordered; and a guest phase that is at least partially ordered.
- the guest phase includes the photochromic-dichroic compound, and the photochromic- dichroic compound is at least partially aligned with at least a portion of the guest phase.
- the photochromic-dichroic Iayer 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, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the anisotropic material.
- the photochromic- dichroic !ayer also includes an anisotropic material
- anisotropic means having at least one property thai differs in va ue when measured in at least one different direction.
- anisotropic materials are materials that have at (east one property that differs in value when measured in at least one different direction.
- anisotropic materials that can be included in the photochromic- dichroic laye include, but are not limited to, those liquid crystal materials as described further herein with regard to the optional alignment layer of the photochromic articles of the present invention.
- the photochromic-dichroic Iayer includes liquid crystal oligomers and/or polymers prepared at least in part from the monomeric mesogenic compounds; and/or (si) includes the mesogenic compounds, in each case as disclosed in Table 1 of United States Patent No. 7,910 s 019 B2 at columns 43 -90 thereof, which disclosure is incorporated herein by reference.
- 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.
- the photochromic-dichroic compound can be aligned such that the long-axis of the photochromic-dichroic compound in the dichroic state is essentially parallel to the general direction of the anisotropic material.
- the photochromic- dichroic compound can be bound to or reacted with at least a portion of the at least partially ordered anisotropic material.
- Methods of ordering, or introducing order into, the anisotropic materia! of the photochromic-dichroic layer include, but are not limited to, exposing the anisotropic material to at least one of a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible radiation, and a shear force.
- the anisotropic material can be at least partially ordered by aligning at least a portion of the anisotropic material with another material or structure.
- 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 detail herein below.
- the anisotropic material By ordering at least a portion of the anisotropic material, it is possible to at least partially align at least 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, ordering of the anisotropic materia ' ! and/or aligning the photochromic-dichroic compound can occur prior to, during, or after application of the photochromic-dichroic layer over the primer layer,
- the photochromic-dichroic compound and the anisotropic material can be aligned and ordered during application of the photochromic-dichroic layer over the primer layer.
- the photochromic-dichroic layer can be applied using a coating technique thai introduces a shear force to the anisotropic material during application, such that the anisotropic material becomes at least partially ordered generally parallel to the direction of the applied shear force.
- a solution or mixture (optionally in a solvent or carrier) including the phoiochromic-dichroic compound and the anisotropic material can be curtain coated over the primer layer, such that shear forces are introduced to the materials being applied due to relative movement of the surface of the substrate with respect to the materials being applied.
- An example of a coating process that can introduce at least sufficient shear forces is a curtain coating process. The shear forces can cause at least a portion of the anisotropic material to be ordered in a general direction that is substantially parallel to the direction of the movement of the surface.
- At least a portion of the photochromic-dichroic compound ca be aligned, in addition, and optionally, by exposing at least a portion of the photochromic-dichrosc compound to actinic radiation during the curtain coating process, so as to convert the photochromic-dichroic compound to an activated state, at least partial alignment of the photochromic-dichroic compound while in the activated state can also be achieved,
- the photochromic-dichroic compound and the anisotropic materia! can be aligned and ordered after application of the photochromic-dichroic layer over the primer layer.
- a solution or mixture of the photochromic-dichroic compound and the anisotropic material ⁇ optionally in a solvent or carrier) can be spin-coated over at least a portion of the primer layer.
- at least a portion of the anisotropic materia! 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.
- the anisotropic materia! can be at least partially ordered by alignment thereof with another material or structure, such as an alignment layer.
- the photochromic-dichroic compound and the anisotropic material can be aligned and ordered prior to application of the photochromic-dichroic layer over the primer layer.
- a solution or mixture (optionally in a solvent or carrier) of the photochromic-dichroic compound and the anisotropic material can be applied over an ordered polymeric sheet to form a layer thereover. Thereafter, at least a portion of the anisotropic material can be allowed to align with the underlying ordered polymeric sheet.
- the polymeric sheet can be subsequently applied over the primer layer by, for example, art-recognized laminating or bonding methods.
- the ordered photochromic- dichroic layer can be transferred from the polymeric sheet to / over the primer layer by art-recognized method, such as hot stamping.
- the photochromic-dichroic layer can include a phase-separated polymer that includes: a matrix phase; and a guest phase distributed in the matrix phase.
- the matrix phase can include an at least partially ordered liquid crystal polymer.
- the guest phase can include the at least partially ordered anisotropic material and at least a portion of the photochromic-dichroic compound, which can be at least partially aligned.
- the at least partially aligned photochromic-dichroic compound can be at least partially aligned by interaction with the at least partially ordered anisotropic material, [0183]
- a phase-separating polymer system including, a matrix phase forming material that includes a liquid crystal material, and a guest phase forming material that includes the anisotropic material and the photochromic-dichroic compound, is applied over the primer layer.
- At least portion of the liquid crystal material of the matrix phase and at least a portion of the anisotropic material of the guest phase are at least partially ordered, such that at least a portion of the photochromic-dichroic compound is aligned with at least a portion of the at least partially ordered anisotropic material of the guest phase.
- Methods of ordering the matrix phase forming materiai and the guest phase forming materiai of the phase-separating polymer system include, but are not limited to, exposing the applied layer to at least one of: a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, and a shear force.
- ordering the matrix phase forming material and the guest phase forming materia! can include alignment thereof by interaction with an underlying alignment layer, as described in further detail herein.
- the guest phase forming material can be separated from the matrix phase forming material by polymerization induced phase separation and/or solvent induced phase separation.
- polymerization induced phase separation and/or solvent induced phase separation.
- this language is intended to cover any separation between the two phase forming materials. That is, this language is intended to cover separation of the guest phase forming material from the matrix phase forming material and separation of the matrix phase forming material from the guest phase forming material, as well as, simu!taneous separation of both phase forming materials and any combination thereof.
- the matrix phase forming materia! can include a iiqusd crystal material chosen form liquid crystal monomers, liquid crystal pre- poiymers, and liquid crystal polymers.
- the guest phase forming material cart include a liquid crystal material chosen from liquid crystal mesogens, liquid crystal monomers, and liquid crystal polymers and pre-polymers. Examples of such materials include, but are not limited to, those described above, and further herein with regard to the optional alignment layer.
- the phase-separating polymer system can include, a mixture of a matrix phase forming materia! that includes a liquid crystal monomer, a guest phase forming material that includes liquid crystal mesogens and the photochromic-dicbroic compound.
- causing the guest phase forming material to separate from the matrix phase forming material can include polymerization induced phase-separation.
- the liquid crystal monomer of the matrix phase can be poiymerized and thereby separated from at least a portion of the liquid crystal mesogens of the guest phase forming material. Examples of polymerization methods include, but are not limited to, photo-induced polymerization and thermally- induced polymerization,
- the phase-separating polymer system can include, a mixture of a matrix phase forming material that includes a liquid crystal monomer, a guest phase forming material that includes a low viscosity liquid crystal monomer having a different funciionaiity from the liquid crystal monomer of the matrix phase, and the photochromic-dichroic compound,
- the term "low viscosity liquid crystal monomer” refers to a liquid crystal monomer mixture or solution that Is freely flowing at room temperature.
- causing the guest phase forming material to separate from the matrix phase forming material includes polymerization induced phase-separation.
- the liquid crystal monomer of the matrix phase can be polymerized under conditions that do not cause the liquid crystal monomer of the guest phase to polymerize.
- the guest phase forming materia! typically separates from the matrix phase forming material. Thereafter, the liquid crystal monomer of the guest phase forming material can be polymerized in a separate polymerization process.
- the phase-separating polymer system can include, with some embodiments, a solution in at least one common solvent of a matrix phase forming material that includes a liquid crystal polymer, a guest phase forming material that includes a liquid crystal polymer that is different from the liquid crystal poiymer of the matrix phase forming material, and the photochromic-dichroic compound.
- Causing the guest phase forming material to separaie from the matrix phase forming materia! typically includes solvent induced phase-separation.
- Typicaiiy at least a portion of the common solvent is evaporated from the mixture of liquid crystal polymers, thereby causing the two phases to separate from each other,
- the photochromic-dichroic layer can 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.
- the term 'Interpenetrating polymer network means an entangled combination of polymers, at least one of which is cross- linked, that are not bonded to each other.
- the term interpenetrating polymer network includes semi-interpenetrating polymer networks. For example, see L.H. Sperling, Introduction to Physical Polymer Science.
- At least a portion of the at least one at least partially aligned photochromic-dichroic compound can be at least partially aligned with the at least partially ordered anisotropic material.
- the polymeric materia! can be isotropic or anisotropic, provided that, on the whole, the photochromic-dichroic layer is anisotropic. Methods of forming such photochromic-dichroic layers are described in more detail herein below,
- the anisotropic material can be adapted to allow the photochromic-dichroic compound to switch from a first state to a second state at a desired rate.
- conventional photochrome compounds can undergo a transformation from one isomeric form to another in response to actinic radiation, with each isomeric form having a characteristic absorption spectrum.
- the photochromic- dichroic compounds of the photochrome articles of the present invention undergo a similar isomeric transformation. Without intending to be bound by any theory, the rate or speed at which this isomeric transformation (and the reverse transformation) occurs depends, In part, upon the properties of the local environment surrounding the photochromic-dichroic compound (i.e., the "host").
- the rate of transformation of the photochromic-dichroic compound depends, In part, upon the flexibility of the chain segments of the host, and more particularly on the mobility or viscosity of the chain segments of the host.
- the rate of transformation of the photochromic-dichroic compound is generally faster in hosts having flexible chain segments than in hosts having stiff or rigid chain segments.
- the anisotropic material 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 desired rates.
- the anisotropic material can be adapted by adjusting the molecular weight and/or the crosslink density of the anisotropic material.
- the photochromic-dichroic layer includes a phase- separated polymer that includes a matrix phase including a liquid crystal polymer, and guest phase distributed within the matrix phase.
- the guest phase can include the anisotropic material.
- a majority of the photochromic-dichroic compound can be contained within the guest phase of the phase-separated polymer.
- the photochromic articles of the present invention can include an alignment layer (also referred to as an alignment or orientation facility) that is interposed between the primer layer and the photochromic-dichroic compound layer.
- 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 guest phase is dispersed within the matrix phase.
- the anisotropic material of the guest phase can be at least partially aligned with at least 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.
- the matrix phase of the phase-separated polymer can include a liquid crystal polymer, and the anisotropic material of the guest phase can be chosen from liquid crystal polymers and liquid crystal mesogens. Non-limiting examples of such materials are set forth In detail above.
- the photochromic-dichroic layer can be substantially haze-free.
- Haze is defined as the percentage of transmitted light that deviates from the incident beam by more than 2.5 degrees on average according to ASTM D 1003 Standard Test Method of Haze and Luminous Transmittance of Transparent Plastics.
- An example of an instrument on which haze measurements according to ASTM D 1003 can be made is Haze-Gard PlusTM made by BYK-Gardener,
- 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 thereafter dispersed or distributed in another material having relatively rigid chain segments,
- the encapsulating anisotropic material can be at least partially ordered.
- the encapsulated photochromic-dichroic compound can be dispersed or distributed in a liquid crystal polymer having relatively rigid chain segments and thereafter the mixture can be applied to a substrate to form the photochromic-dichroic layer,
- the photochromic-dichroic layer can be a polymeric sheet that contains a photochromic-dichroic compound.
- the polymeric sheet can be uniaxiaiiy or biaxlaiSy stretched. Stretching of the polymeric sheet typically results in alignment and ordering of the photochromic-dichroic material therein.
- the photochromic-dichroic layer can, with some embodiments, include two or more polymeric sheets each containing a photochromic-dichroic compound, in which each sheet can be stretched in the same direction or in different (e.g.., orthogonal) directions.
- Examples of polymeric sheets that can be used as or to form the photochromic-dichroic layer include, but are not limited to, stretched ⁇ e.g., uniaxiaiiy or biaxia!ly stretched) polymer sheets, ordered liquid crystal polymer sheets, and photo- oriented polymer sheets.
- Examples of polymeric materials, other than liquid crystal materials and photo-orientation materials that can be used in forming polymeric sheets of the photochromic-dichroic layer include, but are not limited to: polyvinyl alcohol, polyvinyl chloride, polyurethane, po!yacrylaie, and pofycaprofactam.
- Non-limiting examples of methods of at least partially ordering polymeric sheets are described below in more detail.
- the photochromic-dichroic iayer can be formed by applying at least one anisotropic material over the primer Iayer, imbibing the photochromic-dichroic compound into the previously applied anisotropic material, ordering the anisotropic material, and aligning the photochromic-dichroic compound with at least a portion of the ordered anisotropic material.
- the anisotropic material can be ordered before, during or after imbibition with the photochromic-dichroic compound.
- the photochromic-dichroic compound can be aligned while in an activated state, with some embodiments.
- imbibing the photochromic-dichroic compound into the previously applied anisotropic material can involve, with some embodiments, applying a solution or mixture of the photochromic-dichroic compound in a carrier to the previously applied anisotropic materia!, and ailowing the photochromic-dichroic compound to diffuse 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 describe above,
- the photochrome articles of the present invention include a primer layer
- the primer layer can include a single layer or multiple layers each including a first photochrome compound that can be the same or different.
- the primer layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a cross!inked organic matrix. Additionally or alternatively to an organic matrix, the primer layer can include an inorganic matrix, including, for example, si!ane linkages, siloxane linkages and/or titanate linkages.
- the organic matrix can include, for example: acrylate residues (or monomer units) and/or meihacrylate residues; vinyl residues; ether linkages; sulfide linkages, including monosulfide linkages and/or polysulfide linkages; carboxylic ester linkages; carbonate linkages (e.g., -O-C(O)-O-) urethane linkages (e.g., - (H)-C(0)-O-);; and/or thiourethane linkages (e.g., -N(H)-C(0) ⁇ S-).
- the primer layer can be formed by art-recognized methods including, but not limited to: lamination, such as of one or more plastic sheets or films; in-moSd formation, such as in-moid coating; film casting; and coating methods.
- the primer layer is formed from a primer coating composition.
- the primer coating composition can be a curable primer coating composition, that is curable by exposure to, for example: ambient temperatures, such as in the case of two component coating compositions; elevated temperatures (e.g., 150°C to 190°C for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, such as in the case of ultraviolet light curable coating compositions.
- the primer layer can have any suitable thickness.
- the primer has a thickness of from 0.5 microns to 20 microns, such as from 1 to 10 microns, or from 2 to 8 microns, or from 3 to 5 microns, inclusive of the recited values.
- the primer layer includes an organic matrix that includes urethane linkages.
- the primer layer containing urethane linkages is formed from a curable coating composition that includes: a (meth)acryfate copolymer having active hydrogen functionality selected from hydroxy!, thiol, primary amine, secondary amine, and combinations thereof; blocked isocyanate, such as diisocyanate and/or triisocyanate blocked with a suitable blocking or leaving group, such as, 3,5-dimeihy!
- additives including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radical scavengers, piasticizers, flow additives, and/or static tints or static dyes (i.e., tints or dyes that are not phoiochromic),
- Examples of (meth)acry!ate monomers from which the active hydrogen functional (meth)acrylate copolymer can be prepared include, but are not limited to, C r ⁇ C20 (meth)acrylates, C C20 (meth)acrylates having at least one active hydrogen group selected from hydroxy! , thiol, primary amine, and secondary amine.
- the CTC 20 groups of the (meth)acry!ates can be selected from, for example, C C 20 linear aikyl, C3-C20 branched aikyl, C 3 ⁇ C 2 o cycioalkyi, C 3 -C 20 fused ring polycycloalkyl, C 3 -C 2 o aryi, and C10- C 20 fused ring aryl.
- Additional polyois that can be used in the primer coating compositions from which the primer layer is prepared include, but are not limited to, art-recognized materials, such as described in United States Patent No. 7,465,414 at. column 15, line 22 through column 16, line 62. which disclosure is Incorporated herein by reference.
- Isocyanates that can be used in the primer coating compositions from which the primer layer is prepared include, but are not limited to, art- ecognized materials, such as described in United States Patent No. 7,465,414 at column 16, line 63 through column 17, line 38, which disclosure is incorporated herein by reference.
- Catalysts that can be used in the primer coating compositions from which the primer layer is prepared include, but are not limited to, art-recognized materials, such as described in United States Patent No. 7,465,414 at column 17, lines 39-62, which disclosure is incorporated herein by reference.
- the primer layer can include further additives that enhance the performance of the first photochromic compound.
- Such further additives can include, but are not limited to, ultraviolet light absorbers, stabilizers, such as hindered amine light stabilizers (HALS), antioxidants, e.g., polyphenols antioxidants, asymmetric diaryloxa!amide (oxanilide) compounds, singlet oxygen quenchers, e.g., a nickel ion complex with an organic ligand, and mixtures and/or combinations of such photochromic performance enhancing additive materials.
- HALS hindered amine light stabilizers
- antioxidants e.g., polyphenols antioxidants, asymmetric diaryloxa!amide (oxanilide) compounds
- singlet oxygen quenchers e.g., a nickel ion complex with an organic ligand
- mixtures and/or combinations of such photochromic performance enhancing additive materials e.g., a nickel ion complex with an organic ligand
- the primer layer can include at least partial hydrolysates of coupling agents, and mixtures thereof.
- coupling agent means a material having at least one grou capable of reacting, binding and/or associating with a group on at least one surface.
- a coupiing agent can serve as a molecular bridge at the interface of at least two surfaces that can be similar or dissimilar surfaces.
- Coupling agents can be monomers, oligomers, pre-polymers and/or polymers.
- Such materials include, but are not limited to, organo-metailics such as silanes, titanates, zirconates, aiuminates, zirconium aluminates, hydrolysates thereof and mixtures thereof.
- organo-metailics such as silanes, titanates, zirconates, aiuminates, zirconium aluminates, hydrolysates thereof and mixtures thereof.
- at least partial hydrolysates of coupling agents means that at least some to all of the hydroiyzabie groups on the coupling agent are hydro!yzed.
- the primer layer can include other adhesion enhancing ingredients.
- the primer layer can further include an adhesion- enhancing amount of an epoxy-containing material. Adhesion-enhancing amounts of an epoxy-containing materials when included Irs the primer layer, can improve the adhesion of a subsequently applied coating or layer.
- a class of an epoxy (or oxirane) functional adhesion promoters that can be inciuded In compositions from which the primer laye is formed include, but are not limited to, oxirane-functionai-a!kyi-triaikoxysiianes, such as gamma-glycidoxypropyltrimethoxysilane, and beta-(3,4 ⁇
- photochrome compound is selected from Indeno-fused naphthopyrans, naphtho[1 ,2- b]pyrans, naphtho[2,1 -b3pyrans, spirofiuoroeno[1 ,2-bjpyrans, phenanthropyrans, quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines, naphihoxazines, spiro ⁇ indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,
- the first photochromic compound of the primer layer can, with some embodiments, be selected from certain indeno-fused napthopyran compounds, such as described in United States Patent No. 6,296,785, at column 3, lines 66 through column 10, line 51 , which disclosure is incorporated herein by reference.
- indeno-fused naphthopyran compounds from which the first photochromic compound can be selected include, but are not limited to: (P ⁇ a) 3,3-di(4-methoxyphenyl)-6,7,10, 11-tetramethoxy-13, 13-dimethyl-3H,13H- indeno[2 , ,3':3,4]naphthoil,2-b]pyran;
- the first photochromic compound of the primer iayer can with some further embodiments be selected from one or more indeno-fused naphthopyran compounds having a pi-conjugation extending group, such as a halogen or halogen substituted group, bonded to the 1 1 -position of the indeno-fused naphthopyran.
- indeno-fused naphthopyran compounds having a pi-conjugalion extending bonded to the 1 1-position thereof include, but are not limited to, those disclosed in United States Patent Appiication Publication No. US 201 1 /0049445 A1 at paragraphs [0030] through [0080],
- indeno-fused naphthopyran compounds having a pi-conjugation extending bonded to the 1 1-position thereof, from which the first photochromic compound of the primer Iayer can be selected include, but are not limited to:
- the first photochromic compound of the primer layer can be covalent'y bonded to the matrix, such as the organic matrix, of the primer layer.
- the first photochromic compound can include one or more reactive groups, such as one or more poiymerizabie groups.
- the first photochromic compound can be selected from 2H-naphtho[1 ,2- bjpyrans, 3H-naphtho[2,1 -b]pyrans and/or indeno[2,1 -f]naphtho[1 ,2 ⁇ b]pyrans each having at least one functional group that is capable of forming a covending bond with another functional group, such as at least one poiymerizabie group, such as at least one polyalkoxylated substituent of from 1 to 50 alkoxy units per substituent which is end- capped ⁇ or terminated) with a poiymerizabie group.
- photochromic compounds from which the first photochromic compound can be selected include, but are not limited to, those disclosed in United States Patent No. 6,1 13,814, at column 2, line 52 through column 8, line 40, which disclosure is incorporated herein by reference.
- photochromic compounds having reactive functionality from which the first photochromic compound of the primer layer can be selected include, taut are not limited to:
- the photochromic articles of the present invention include a topcoat layer
- the topcoat layer can include a single layer or multiple layers each including a second photochromic compound that can be the same or different.
- the topcoat layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a crosslinked organic matrix.
- the topcoat layer can include an inorganic matrix, Including, for example, si!ane linkages, siloxane linkages and/or titanate linkages
- the organic matrix can include, for example: acrylate residues (or monomer units) and/or methacryiate residues; vinyl residues; ether linkages; sulfide linkages, including monosulfide linkages and/or polysulfide linkages; carboxyiic ester linkages; carbonate linkages (e.g., -O-C(O)-O-) urethane linkages (e.g., -N(H)-C(0)-0-); and/or thiourethane linkages (e.g., -N(H) ⁇ C(0)-
- topcoat layer can be formed by art-recognized methods including, but not limited to: lamination, such as of one or more plastic sheets or films; in-mold formation, such as in-mold coating; film casting; and coating methods.
- the topcoat layer is formed from a topcoat coating composition.
- the topcoat coating composition can be a curable topcoat coating composition, that is curable by exposure to, for example: ambient temperatures, such as in the case of two component coating compositions; elevated temperatures (e.g., 150°C to 19 OX for 5 to 60 minutes), such as in the case of thermally cured coating compositions; or actinic radiation, such as in the case of ultraviolet light curable coating compositions.
- the topcoat layer can have any suitable thickness. With some embodiments, the topcoat has a thickness of from 0.5 microns to 10 microns, such as from 1 to 8 microns, or from 2 to 5 microns, inclusive of the recited values.
- the topcoat layer includes an organic matrix formed from a radiation-cured acryiate-based composition, and correspondingly, the topcoat layer can be described as an acryiate-based topcoat layer.
- the acryiate-based topcoat layer can be prepared using (meth)acryiate monomers and/or (meth)acrylic acid monomers.
- the (meth)acryiate monomers can include one, two, three, four, or five (meth)acrylate groups.
- Additional co-polymerizabie monomers such as epoxy monomers, e.g., monomers containing a epoxy (or oxirane) functionality, monomers containing both (meth)acry!ate and epoxy functionalities, etc., can also be present in the formuiation used to prepare the ⁇ meth)acryiate-based topcoat layer.
- the monomers used to prepare the (meth)acrylate-based topcoat layer include a plurality, e.g., a major amount, i.e., more than 50 weight percent, of (meth)acrylate monomers; hence the designation "(metb)acryiate-based topcoat layer.”
- the formulations used to prepare the (meth)acry!ate-based topcoat layer can aiso contain components having at least one isocyanate (-NCO) group, e.g., organic monoisocyanates, organic diisocyanates, and organic triisocyanates, whereby urethane linkages can be incorporated into the topcoat layer.
- -NCO isocyanate
- the (meth)acrylate-based topcoat layer typically possesses physical properties including, for example, transparency, adherence to the underlying photochromic-dichroic layer, resistance to removal by aqueous alkali metal hydroxide, compatibility with an optional abrasion-resistant coating, such as a hardcoat, applied to its surface, and scratch resistance.
- the (meth)acry!ate-based topcoat layer has a hardness that is greater than that of the photochromic-dichroic layer.
- Radiation curing of (methjacrylate-based polymeric systems can be achieved with, for example, electron beam curing (EB) and/or ultraviolet light (UV) radiation.
- EB electron beam curing
- UV ultraviolet light
- UV curing typically requires the presence of at least one photoinitiator, whereas curing by EB techniques does not require a photoinitiator.
- the (meth)acry!ate- based formulations which are cured by either UV or EB radiation technology, can otherwise be identical.
- Radiation-curable (meth)acry!ate -based polymeric systems are weli known in the polymeric art, and any such system may be used to produce the (meth)acrylate- based topcoat layer of the photochromic article of the present invention.
- the (meth)acrylate-based topcoat layer is formed from a composition that includes a combination or miscibie blend of one or more free-radical initiated (meth)acryiate monomers and/or (meth)acryiate oligomers, and one or more cationic initiated epoxy monomers.
- a (meth)acryiate-based topcoat layer in the form of a polymerizate, is formed and includes an interpenetrating network of polymer components.
- Examples of (meth)acry!ate monomers that can be included in compositions from which the ⁇ meth)acrylate-based topcoat layer can be formed include, but are not limited to, polyfunctional (meth)acrylates having, for example, 1 , 2, 3, 4, or 5 (meth)acryiate groups, and monofunctional (meth)acrylates, e.g., a monomer containing a single (meth)acrylate group, hydroxy-substituted (meth)acrylates and alkoxysilyi alkylacrylates, such as trialkoxyssfylpropyimethacrySate.
- Other reactive monomers/diluents such as monomers containing an ethylenic functiona! group (other than the (meth)acrylate monomers) can also be present.
- compositions from which the (meth)acrylate-based topcoat layer can be formed are disclosed at column 16, line 14 through column 25, line 3 of United Sates Patent No. 7,452,611 B2, which disclosure is incorporated herein by reference.
- compositions from which the topcoat layer is formed can include one or more additives, including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radical scavengers, plasficizers, flow additives, and/or static tints or static dyes (i.e., tints or dyes that are not photochromic).
- additives including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radical scavengers, plasficizers, flow additives, and/or static tints or static dyes (i.e., tints or dyes that are not photochromic).
- the compositions from which the ⁇ meth)acrylate » based topcoat layer can be formed can further include an adhesion promoter.
- the adhesion promoter can be selected from, for example, organo-sllanes, such as aminoorganosilanes, organic titanate coupling agents, organic zirconate coupling agents, and combinations thereof.
- adhesion promoters which can be Included in the compositions from which the acrylate-based topcoat layer can be formed, inciude, but are not limited to, those disclosed at column 5, line 52 through column 8, line 19 of United Sates Patent No. 7,410,691 B2, which disclosure is incorporated herein by reference.
- the topcoat layer includes an ultraviolet light absorber and/or a second photochrome compound.
- the topcoat layer includes an ultraviolet light absorber, and is free of the second photochromic compound.
- the topcoat layer includes both an ultraviolet light absorber and the second photochromic compound.
- the topcoat layer includes the second photochromic compound, and is free of an ultraviolet light absorber.
- the ultraviolet Sight absorber can be selected from one or more art- recognized classes of ultraviolet light absorbers, including, but not limited to: hindered amines, which can include, for example, one or more 2,2,6,6- tetramethyl N -subslituted piperidine groups; benzophenones; and/or benzotriazoles.
- the ultraviolet light absorber is typically present in at least an effective amount, such as from 0,1 to 10 percent by weight, or 0,2 to 5 percent by weight, or from 0.3 to 3 percent by weight, based on the total solids weight of the coating composition from which the topcoat layer is prepared.
- the second photochromic compound can in some embodiments be selected from indeno-fused naphthopyrans, naphtho[1 : 2-b]pyrans, naphtho[2,1 -b]pyrans,. spirofluoroeno[1 ,2-b]pyrans, phenanthropyrans, quinolinopyrans, fSuoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(lndoline)naphthoxazines,
- the second photochromic compound of the topcoat layer can be covalently bonded to the matrix, such as the organic matrix, of the topcoat layer.
- the second photochromic compound can Include one or more reactive groups, such as one or more polymerizable groups.
- the second photochromic compound can include at least one functional group that is capable of forming a covarri bond with another functional group, such as at least one polymerizable group, such as at least one polyalkoxylated substituent of from 1 to 50 aikoxy units per substituent which is end-capped (or terminated) with a polymerizable group.
- the second photochromic compound includes at least one ring-opened cyclic monomer.
- ring- opening cyclic monomers include, but are not limited to, cyclic esters, cyclic carbonates. cyclic ethers, and cyclic siioxanes. More particular examples of ring-opening cyclic monomers include, but are not limited to, e ⁇ caprolactone and 6-valerolactone.
- Photochromic compounds that include at least one ring-opened cyclic monomer, from which the second photochromic compound can be selected include, but are not limited to, those disclosed at column 2, line 32 through column 6, line 60 of United States Patent No. 7,485,415 B2, which disclosure is incorporated herein by reference. More particular examples of photochromic compounds having at least one ring-opened monomer covalentiy bonded thereto, from which the second photochromic compound can be selected, include, but are not limited to, those disclosed at columns 86 through 103, and represented by Formulas 17 through 28 of United States Patent No. 7,465,415 B2, which disclosure is incorporated herein by reference.
- Examples of ring-opening cyclic monomers that can be used to form photochromic compounds having at least one ring-opened monomer covalentiy bonded thereto, from which the second photochromic compound can be selected include, but are not limited to, those disclosed at column 10, line 43 through column 12, lines 28 of United States Patent No. 7,465,415 B2, which disclosure is incorporated herein by reference.
- photochromic initiators that can be reacted with ring-opening cyclic monomers so as to form photochromic compounds having at least one ring-opened monomer covalentiy bonded thereto, from which the second photochromic compound can be selected, include, but are not limited to, those disclosed in Table 1 at columns 14 through 59 of United States Patent No, 7,465,415 B2, which disclosure is incorporated herein by reference.
- photochromic Initiators that can be reacted with ring-opening cyclic monomers (including, but not limited to, cyclic esters, cyclic carbonates, cyclic ethers, and/or cyclic siioxanes as discussed above) so as to form photochromic compounds having at least one ring-opened monomer covalentiy bonded thereto, from which the second photochromic compound of the topcoat layer can be selected, include, but are not limited to, the following:
- TC-9 2,2-diphenyl-5-(2,3-dihydroxy)propoxycarboriyl-8-methyl-2H-naphiho[1 ,2-b]pyran;
- TC-10) 2-(4-(2-(2-hydroxyethoxy)ethoxy)ethoxy)pheny!)-2-phenyl-5-methoxycarbonyl-6- methyl-9 ⁇ methoxy-2H-naphtho[1 ,2-b]pyran;
- the photochrome articles of the present invention can include, with some embodiments, an alignment iayer that is interposed between the primer layer and the photochromic-dichroic iayer.
- photochrome article 2 includes an alignment layer 50 that is interposed between primer Iayer 14 and photochromic-dichroic iayer 17.
- the alignment iayer can also be referred to herein as an orientation facility.
- the photochromic-dichroic compound of the photochromic-dichroic Iayer can be at least partially aligned by interaction with the underlying alignment Iayer.
- the term “alignment layer” means a Iayer that can facilitate the positioning of one or more other structures that are exposed, directly and/or indirectly, to at least a portion thereof.
- the term “order” means bring into a suitable arrangement or position, such as aligning with another structure or material, or by some other force or effect.
- the term “order” encompasses both contact methods of ordering a material, such as by aligning with another structure or material, and non-contact methods of ordering a material, such as by exposure to an external force or effect.
- order also encompasses combinations of contact and non-contact methods.
- the photochromic-dichroic compound that is at least partially aligned by interaction with the alignment layer can be at least partially aligned such that the long-axis of the photochromic-dichroic compound in the activated state is essentially parallel to at least the first general direction of the alignment layer.
- the photochromic-dichroic compound that is at least partially aligned by interaction with the alignment layer is bound to or reacted with the alignment layer.
- general direction refers to the predominant arrangement or orientation of the material, compound or structure. Further, it will be appreciated by those skilled in the art that a material, compound or structure can have a general direction even though there is some variation within the arrangement of the material, compound or structure, provided that the material, compound or structure has at least one predominate arrangement.
- the alignment layer can, with some embodiments, have at least a first general direction.
- the alignment layer can include a first ordered region having a first general direction and at least one second ordered region adjacent the first ordered region having a second general direction that is different from the first general direction.
- 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 so as to form a desired pattern or design.
- the alignment layer can include, for example, a coating including an at least partially ordered alignment medium, an at least partially ordered polymer sheet, an at least partially treated surface, Langmuir-Blodgett films, and combinations thereof.
- the alignment layer can include, with some embodiments, a coating that includes an at least partially ordered alignment medium.
- suitable alignment media include, but are not limited to, photo-orientation materials, rubbed-orientation materials, and liquid crystal materials. Methods of ordering at least a portion of the alignment medium are described herein below in further detail.
- the alignment medium 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 because of their structure, are generally capable of being ordered or aligned so as to take on a general direction. More specifically, because liquid crystal molecules have rod- or disc-like structures, a rigid long axis, and strong dipoles, liquid crystal molecules can be ordered or aligned by interaction with an external force or another structure such that the long axis of the molecules takes on an orientation that is generally parallel to a common axis.
- liquid crystal molecules can be aligned with a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, or shear forces, St is also possible to align liquid crystal molecules with an oriented surface.
- liquid crystal molecules can be applied to a surface thai has been oriented, for example by rubbing, grooving, or photo-alignment methods, and subsequently aligned such that the long axis of each of the liquid crystal molecules takes on an orientation that is generally parallel to the general direction of orientation of the surface.
- liquid crystal materials suitable for use as alignment media include, but are not limited to, liquid crystal polymers, liquid crystal pre-po ' iymers, Hquid crystal monomers, and liquid crystal mesogens.
- pre-polymer means partially polymerized materials.
- Classes of liquid crystal monomers that are suitable for use in conjunction with the alignment laye include, but are not limited to, mono- as well as multi-functional liquid crystal monomers.
- the liquid crystal monomers can, with some embodiments, be selected from cross-linkable liquid crystal monomers, such as photocross-iinkable liquid crystal monomers.
- photocross-iinkable means a material, such as a monomer, a pre-polymer or a polymer, that can be cross-linked on exposure to actinic radiation.
- photocross-iinkable liquid crystal monomers include, but are not limited to, those liquid crystal monomers that are cross-iinkabie on exposure to ultraviolet radiation and/or visible radiation, either with or without the use of polymerization initiators.
- cross-linkable liquid crystal monomers examples include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylates, methacrylates, ally i , ailyl ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers and blends thereof.
- photocross- iinkable liquid crystal monomers that can be included In the alignment layer, include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylates, methacrylates, alkynes, epoxides, thiols, and blends thereof.
- Liquid crystal poiymers and pre-polymers that can be included in the alignment layer, include, but are not limited to, main-chain liquid crystal polymers and pre-polymers and side-chain liquid crystal polymers and pre-poiymers. With main-chain liquid crystal polymers and pre-polymers, rod- or disc-like liquid crystal mesogens are primarily located within the polymer backbone.
- the rod- or disc-like liquid crystal mesogens primarily are located within the side chains of the polymer.
- the liquid crystal polymer or pre-polymer can be cross-linkable, and further can be photocross-linkabie,
- liquid crystal polymers and pre-polymers that can be included in the alignment layer, include, but are not limited to, main-chain and side-chain polymers and pre-poiymers having functional groups chosen from acry!ates, methacryiaf.es, ally!, aiiyi ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siioxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers, and blends thereof.
- main-chain and side-chain polymers and pre-poiymers having functional groups chosen from acry!ates, methacryiaf.es, ally!, aiiyi ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siioxanes, thiocyanates, thio
- photocross-linkabie liquid crystal polymers and pre-poiymers that can be included in the alignment layer, include, but are not limited to, those polymers and pre- polymers having functional groups chosen from acrylates, methacrylates, alkynes, epoxides, thiols, and blends thereof.
- Liquid crystal mesogens that 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, that can be included in the alignment layer, include, but are not limited to, co!urnaiic (or rod-like) liquid crystal mesogens and discotic (or disc-like) liquid crystal mesogens.
- the alignment layer can include an at least partially ordered photo-orientabie polymer network chosen from azobenzene derivatives, cinnarnic acid derivatives, coumarine derivatives, ferulic acid derivatives, and/or poiyimides.
- Examples of cinnarnic acid derivatives, that can be included in the alignment layer, inciude but are not limited to, polyvinyl cinnamate and polyvinyl esters of paramethoxycinnamic acid,
- the term "rubbed- orientation material” means a material that can be at least partially ordered by rubbing at least a portion of a surface of the material with another suitably textured material.
- the rubbed-orientation material can be rubbed with a suitably textured cloth or a velvet brush.
- rubbed- orientation materials that can be included in the alignment layer, include, but are not limited to, (poly)imides, (poly)siloxanes, (poly)acrylates, and (poly)coumarines.
- the alignment layer can include a polyimide, and the alignment layer can be rubbed with a velvet or a cotton cloth so as to at least partially order at least a portion of the surface of the alignment layer,
- the alignment layer can include an at least partially ordered polymer sheet.
- a sheet of polyvinyl alcohol can be at least partially ordered by stretching (e.g., untaxiaily stretching) the sheet, and there-after the stretched sheet can be bonded to the at least a portion a surface of the optical substrate to form the orientation facility.
- the ordered polymer sheet can be made by a method that at least partially orders the polymer chains during fabrication, for example, by extrusion.
- the at least partially ordered polymer sheet can be formed by casting or otherwise forming a sheet of a liquid crystal material and thereafter at least partially ordering the sheet for example, but exposing the sheet to a magnetic field, an electric field, and/or a shear force.
- the at least partially ordered polymer sheet can be made using photo-orientation methods.
- a sheet of a photo-orientation material can be formed, for example by casting, and thereafter at least partially ordered by exposure to linearly polarized ultraviolet radiation.
- the alignment layer of the photochrome articles of the present invention can include an at least partially treated surface.
- 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 least a portion of the surface. Examples of treated surfaces include, but are not limited to, rubbed surfaces, etched surfaces, and embossed surfaces. Further, the treated surfaces can be patterned, for example using a photolithographic or an interferographic process.
- the surface of the alignment layer can be a treated surface selected from, for example, chemically etched surfaces, plasma etched surfaces, nanoetched surfaces (such as surfaces etched using a scanning tunneling microscope or an atomic force microscope), laser etched surfaces, and/or electron-beam etched surfaces.
- the treated surface when the alignment layer includes a treated surface, can be formed by depositing a metal salt (such as a metal oxide or metal fluoride) onto at least a portion of a surface (e.g., a surface of the alignment layer itself, or a surface of the primer layer), and thereafter etching the deposit to form the treated surface.
- a metal salt such as a metal oxide or metal fluoride
- Art-recognized methods of depositing a metal sa!t include, but are not imited to, plasma vapor deposition, chemical vapor deposition, and sputtering. Etching can be undertaken in accordance with art-recognized methods, such as those described previously herein.
- Lir-Blodgett films means one or more at least partially ordered molecular films on a surface.
- Langmuir-Blodgett films can be formed, for example, by dipping a substrate into a liquid one or more times so that it is at least partially covered by a molecular film and then removing the substrate from the liquid such that, due to the relative surface tensions of the liquid and the substrate, the molecules of the molecular film are at least partially ordered in substantially one (or a single) general direction.
- molecular film refers to monomo!ecufar films (i.e., monolayers) as well as films comprising more than one monolayer.
- the photochromic articles of the present invention can, with some embodiments, further 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 aiignment transfer material.
- the alignment transfe material can, with some embodiments, facilitate the propagation or transfer of a suitable arrangement or position from the alignment layer to the photochromic-dichroic compound of the photochromic-dichroic layer.
- alignment transfer materials include, but are not limited to, those liquid crystal materials described above in connection with the alignment media disclosed herein. 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 such that the long axis of the liquid crystal molecules adopts an orientation that is generally parallel to the same general direction of orientation of the surface.
- the liquid crystal material of the alignment transfer material can be at least partially ordered by alignment with the alignment layer, such that the long axis of the molecules of the liquid crystal material are generally parallel to, for example, a first general direction of the orientation facility.
- the general direction of the aiignment layer can be transferred to the liquid crystal material, which in turn can transfer the general direction to another structure or material.
- the alignment layer includes a plurality of regions having general directions that together form a design or pattern, that design or pattern can be transferred to the liquid crystal material by aligning the liquid crystal material with the various regions of the alignment layer.
- 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, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, and linearly polarized visible radiation while being at least partially aligned with at least a portion of the alignment layer.
- the photochromic articles of the present invention can, with some embodiments, include a hard coat layer that resides over the topcoat layer.
- photochromic article 2 includes a hard coat layer 53 that resides over topcoat layer 20.
- the hard coat layer can include a single layer or multiple layers.
- the hard coat layer can be selected from abrasion-resistant coatings including organo si!anes, abrasion-resistant coatings including radiation-cured acrylate- based thin films, abrasion-resistant coatings based on inorganic materials such as silica, titania and/or ztrconia, organic abrasion-resistant coatings of the type that are ultraviolet Sight curable, oxygen barrier-coatings, UV ⁇ shieldlng coatings, and combinations thereof.
- the hard coat layer can include a first coating of a radiation- cured acrylate-based thin film and a second coating including an organo-silane.
- Non- limiting examples of commercial hard coating products include SILVUE® 124 and Hl- 6ARD ⁇ coatings, available from SDC Coatings, Inc. and PPG Industries, Inc., respectively.
- the hard coat layer can be selected from art-recognized hard coat materials, such as organo-silane abrasion-resistant coatings.
- Organo-silane abrasion- resistant coatings often referred to as hard coats or silicone-based hard coatings, are well known in the art, and are commercially available from various manufacturers, such as SDC Coatings, Inc. and PPG industries, Inc.
- SDC Coatings, Inc. and PPG industries, Inc. Reference is made to U.S. Pat. No. 4,756,973 at column 5, lines 1-45; and to U.S. Pat. No. 5,462,806 at column 1 , lines 58 through column 2, line 8, and column 3, line 52 through column 5, line 50, which disclosures describe organo-silane hard coatings and which disclosures are incorporated herein by reference.
- Other coatings that can be used to form the hard coat layer include, but are not limited to, polyfunctions! acrylic hard coatings, melamine-based hard coatings, urethane-based hard coatings, aikyd-based coatings, silica sol-based hard coatings or other organic or inorganic/organic hybrid hard coatings.
- the hard coat, layer is selected from organo- siiane type hard coatings
- Organo-siiane type hard coatings from which the hard coat layer of the photochromic articles of the present invention can be selected include, but are not limited to, those disclosed at column 24, line 46 through column 28, line 11 of United States Patent No. 7,465,414 B2, which disclosure is incorporated herein by- reference.
- the photochromic articles of the present Invention can include additional coatings, such as a nti reflective coatings.
- additional coatings such as a nti reflective coatings.
- an antireflective coating can be applied over the hard coat layer. Examples of antireflective coatings are described in U.S. Pat No. 6,175,450 and International Patent Publication WO 00/33111 , the disclosures of which are incorporated herein by reference.
- the photochromic articles of the present Invention can be selected from ophthalmic articles or elements, display articles or elements, windows, mirrors, packaging material such as shrinkwrap, and active and passive liquid crystal cell articles or elements.
- ophthalmic articles or elements include, but are not limited to, corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact Senses, intraocular lenses, magnifying lenses, and protective lenses or visors.
- corrective and non-corrective lenses including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact Senses, intraocular lenses, magnifying lenses, and protective lenses or visors.
- Examples of display articles, elements and devices include, but are not limited to, screens, monitors, and security elements, including without limitation, security marks and authentication marks.
- the photochrome article can be a security element.
- security elements include, but are not limited to, security marks and authentication marks that are connected to at least a portion of a substrate, such as: access cards and passes, e.g., tickets, badges, identification or membership cards, debit cards, etc; negotiable instruments and non-negotiable instruments e.g., drafts, checks, bonds, notes, certificates of deposit, stock certificates, etc; government documents, e.g., currency, licenses, identification cards, benefit cards, visas, passports, official certificates, deeds etc.; consumer goods, e.g., software, compact discs ("CDs”), digital-video discs ("DVDs”), appliances, consumer electronics, sporting goods, cars, etc. ; credit cards; and merchandise tags, labels and packaging,
- the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate.
- a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can be first applied to at least a portion of the substrate before the security mark is applied thereto.
- a reflective aluminum coating can be applied to the at least a portion of the substrate prior to forming the security element thereon.
- the security element can be connected to at least a portion of a substrate chosen from hereinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing, circularly polarizing substrates, and el!ipticaliy polarizing substrates.
- security elements according to the aforementioned embodiments can further include one or more other coatings or films or sheets to form a multi-layer reflective security element with viewing angle dependent characteristics, such as described in U.S. Patent 6,641 ,874.
- Part 1 describes the preparation of the primer layer formulation (PLF)
- Part 2 describes the preparation o the liquid crystal alignment formulation (LCAF).
- Part 3 describes the preparation of the coating layer formulation (CLF).
- Part 4 describes the preparation of the topcoat layer formulation (TLF).
- Part 5 describes the procedures used for preparing the substrate and stack of coatings listed in Table 1 .
- Part 6 describes the photochromic performance tests including the absorption ratio and optical response measurements reported in Table 1 for Comparative Examples (CE) 1 to 4 and Examples 1 to 4.
- Polyacryiate polyol 14,69 g
- Charge 2 the styrene was replaced with methyl methacrylate and 0.5 % by weight, based on the total monomer weight, of triphenyl phosphite was added
- Po!yalkyienecarbonate dio! (36.70 g) POLY EG ® 1000 from Great Lakes Chemical Corp; DESMODUR ® PL 340 (48.23 g) from Bayer Material Science;
- AROMATIC 100 (36.00 g) a mixture of high temperature boiling solvents available from Texaco;
- Photochromic Compound --- 1 (PC-1 ) is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent 6,1 13,814, which disclosure is incorporated herein by reference, and which upon exposure to ultraviolet light (UV) demonstrated an activated bluish green color.
- a UV spectrum was obtained on a photochromic test square containing PC-1 prepared as described in Part A of Example 10 of U.S. Patent 6,113,814.
- a simple average of the absorption values between 340 and 380 nm was determined to be 4.6.
- the first unactivated terminal minimum absorbance wavelength, determined as described herein for FIG. 3. was determined to be 422 ⁇ 2 nm.
- PC-2 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 2006/0228557, which disclosure is incorporated herein by reference, and which upon exposure to ultraviolet light (UV) demonstrated an activated purplish red color.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-2 following the procedure done for PC-1 , The average of the absorption values between 340 and 380 nm was determined to be 2.2. The first unactivated terminal minimum absorbance wavelength was determined to be 430 ⁇ 2 nm.
- PC-3 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 201 1/0042629, which disclosure is incorporated herein by reference, and which upon exposure to ultraviolet light (UV) demonstrated an activated yellowish brown color.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-3 following the procedure done for PC-1 except that 1 ⁇ 2 of the amount of photochromic compound was used.
- the average of the absorption vaiues between 340 and 380 nm was determined to be 3.5,
- the first unactivated terminal minimum absorbance wavelength was determined to be 425 ⁇ 2 nm,
- the combination of PC-1 , PC-2 and PC-3 in the primer produced an activated gray color.
- the unactivated absorption spectrum of the primer is shown as graph 23 of FIG. 1 .
- the absorption spectrum of graph 23 was prepared from the photochromic containing PLF described above coated onto a substrate and determined using a Varian Gary 4000 UV-Visible spectrophotometer with the following values; range - 800-275 nm; ave. time. ⁇ - 0.100 s; data interval - 1 .100; and scan rate - 660 nm / min.
- the substrate (a finished single vision 6 base lens 70 mm in diameter made of CR-39 ® monomer (FSVL)) that was prepared as described in Part 5 and was coated only with the PLF and heated for 1 hour at 125°C and then 1 Q5 C C for 3 hours. PLF without photochromic compounds was prepared for use in Examples 1 and 2 and Comparative Examples 1 and 2. Part 2 - Preparation of LCAF
- LCM-1 is 1 ⁇ (6- ⁇ 6- ⁇ 6-(6-(6- ⁇ 6-(6-(8- ⁇ 4-(4 ⁇ 4-(8 acryioy!oxyhexyl!oxy)benzoyloxy) phenyloxycarbonyl)phenoxy)octyioxy)-6-oxohexyloxy)-6-oxohexyloxy)-6 oxohexyioxy)-6- oxohexyioxy)-6 oxohexyioxy)-6 oxohexyioxy)-6 oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexan-1-ol which was prepared according to the procedures described in Example 17 of U.S. Patent 7.910,019, which liquid crystal monomer disclosure is incorporated herein by reference.
- LCM-2 is commercially available R 257 reported to be 4-(3- acryioyioxypropyioxy)-benzoic acid 2-methyl-1 ,4-phenylene ester, avaiiabie from E D Chemicals, Inc., having the molecular formula of C33M 2O10.
- LCM-4 is 1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4- ⁇ 4-(4- hexy!oxybenzoylcxy)phenoxycarbony!- phenoxy)octyloxy)-6-oxohexyloxy)-6- oxohexyioxy)-6-oxohexyfoxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy ⁇ -6- oxohexyloxy )-2-methylprop-2 ⁇ en- -one prepared according to the procedures of U.S. Patent 7,9 0,019, which disclosure is incorporated herein by reference.
- CLF was prepared as follows;
- PC-4 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 201 1/0129678, which disclosure is incorporated herein by reference, which upon exposure to ultraviolet light (UV) demonstrated an activated blue-green color and was used at a level of about 15 percent of the total dye amount.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-4 following the procedure done for PC-1 , The average of the absorption values between 340 and 380 nm was determined to be 4.9.
- the first unactivated terminal minimum absorbance wavelength was determined to be 415 + 2 nm.
- PC-5 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 2011/0129676, which disclosure is incorporated herein by reference, which upon exposure to ultraviolet light (UV) demonstrated an activated blue color and was used at a level of about 25 percent of the total dye amount.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-5 following the procedure done for PC-1. The average of the absorption values between 340 and 380 nm was determined to be 4.4. The first unactivated terminal minimum absorbance wavelength was determined to be 415 ⁇ 2 nm.
- PC-6 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 201 /0129678, which disclosure is incorporated herein by reference, which upon exposure to ultraviolet light (UV) demonstrated an activated blue color and was used at a level of about 27 percent of the total dye amount.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-8 following the procedure done for PC- .
- the average of the absorption values between 340 and 380 nm was determined to be 4.9.
- the first unactivated terminal minimum absorbance wavelength was determined to be 424 ⁇ 2 nm.
- PC ⁇ 7 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 201 1/0143141 , which disclosure is incorporated herein by reference, which upon exposure to ultraviolet light (UV) demonstrated an activated yellow color and was used at a level of about 23 percent of the total dye amount.
- UV ultraviolet light
- a UV spectrum was obtained on a photochromic test square containing PC-7 following the procedure done for PC- .
- the average of the absorption values between 340 and 380 nm was determined to be 4.4.
- the first unactivated terminal minimum absorbance wavelength was determined to be 415 ⁇ 2 nm.
- PC-8 is an indenonaphthopyran which was prepared according to the procedures of U.S. Patent Publication 2011/0143141 , which disclosure is incorporated herein by- reference, which upon exposiire to ultraviolet light (UV) demonstrated an activated blue color and was used at a levei of about 10 percent of the total dye amount.
- a UV spectrum was obtained on a photochrome test square containing PC-8 following the procedure done for PC- .
- the average of the absorption values between 340 and 380 nm was determined to be 4.3.
- the first unactivated terminal minimum absorbance wavelength was determined to be 415 ⁇ 2 nm.
- the photochrome compounds PC-4, 6, 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 level of 6.5 weight percent, all based on the total weight of the solution.
- the unactivated absorption spectrum for the CLF containing 6.5 weight percent photochrome compounds is included as graph 32 of FIG. 1 .
- the spectrum was prepared using the same spectrophotometer and procedure described for the preparation of graph 23 of FIG. 1 .
- the FSVL substrate was prepared as described in Part 5 and coated with the LCAF which was at least partially aligned prior to application of the CLF, ail done as described in the Coating Procedures for the Liquid Crystal Alignment Layer and Coating Layer of Part 5.
- Neopentyl glycol diacryiate (13.7 75 g) SR247 from Sartomer;
- DAROCUR ® TPO (0.0628 g; from Ciba Speciality Chemicals,
- PC-9 is a 2H-naphthopyran compound which was prepared according to the procedures of U.S. 5,458,814, which patent is incorporated herein by reference, and which upon exposure to ultraviolet iighf (UV) demonstrated an activated red color.
- a UV spectrum was obtained on a photochromic test square containing PC-9 following the procedure done for PC-1 except that a Varian Cary 300 was used at the following settings - range 700-275, avg..
- the average of the absorption values between 340 and 380 nm was determined to be 1 .9.
- the first unaclivated terminal minimum absorbance wavelength was determined to be 384 ⁇ 2 nm .
- the unactivated absorption spectrum for the TLF containing 1 .0 weight percent of a PC-9 is included as graph 41 of FIG. 1 .
- the spectrum was prepared using the same spectrophotometer and procedure described for the preparation of graph 23 of FIG. 1.
- the FSVL substrate was prepared as described in Part 5 and coated only with the TLF using the Coating Procedure for the Topcoat Layer of Part 5.
- Finished single vision lenses (6 base, 70 mm) prepared from CR-39® monomer were used as substrates. Each substrate was cleaned by wiping with a tissue soaked with acetone and dried with a stream of air and corona treated by passing on a conveyor beit in Tantec EST Systems Serial No. 020270 Power Generator HV 2000 series corona treatment equipment with a high voltage transformer. The substrates were exposed to corona generated by 53.99 KV, 500 Watts while traveling on a conveyor at a belt speed 3 ft min.
- the PLF was applied to the test substrates by spin-coating on a portion of the surface of the test substrate by dispensing approximately 1 .5 mL of the solution.
- a spin processor from Laurel! Technologies Corp. (WS-400B-6NPP/L1TE) was used for spin coating the substrates at 976 revolutions per minute (rpm) for 4 seconds, followed by 1501 rpm for 2 seconds, followed by 2500 rpm for 1 second. Afterwards, the coated substrates were placed in an oven maintained at 125°C for 80 minutes. The coated substrates were cooled to about 26°C.
- the substrate was corona treated by passing on a conveyor belt in Tantec EST Systems Serial No. 020270 Power Generator HV 2000 series corona treatment equipment with a high voltage transformer. The dried primer layers were exposed to corona generated by 53.00 KV, 500 Watts while traveling on a conveyor at a belt speed 3 ft/min.
- the LCAF was applied to the test substrates by spin-coating on a portion of the surface of the test substrate by dispensing approximately 1.0 mL of the solution and spinning 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 seconds.
- a spin processor from Laurel! Technologies Corp. (WS-400B-6NPP/LITE) was used for spin coating. Afterwards, the coated substrates were piaced in an oven maintained at 120 C C for 30 minutes. The coated substrates were cooled to about 26°C.
- the dried photoaiignment layer on each of the substrates was at least partially ordered by exposure to linearly polarized ultraviolet radiation.
- the light source was oriented such that the radiation was linearly polarized in a plane perpendicular to the surface of the substrate.
- the amount of ultraviolet radiation that each photoaiignment layer was exposed to was measured using a UV Power PuckT High energy radiometer from EST e ⁇ Serial No. 2066) and was as follows: UVA 0.018W/cm2 and 5.361 J/cm2; UVB 0 W/cm2 and 0 J/cm2; UVC 0 W/cm2 and 0 J/cm2; and UW 0.005 W/cm2 and 1.541 J/cm2.
- the substrates were cooled to about 26°C and kept covered.
- the CLF was spin coated at a rate of 400 revolutions per minute (rpm) for 6 seconds, followed by 800 rpm for 6 seconds onto the at least partially ordered photoaiignment materials on the test substrates. Each coated substrate was placed in an oven at 60°C for 30 minutes.
- UV Curing Oven Machine designed and built by Belcan Engineering in nitrogen atmosphere while running on a conveyor belt at 2 ft/min speed at peak intensity of 0.388 Watts/cm2 of UVA and 0,165 Watfs/cm2 of UVV and UV dosage of 7.386 Jouies/cm2 of UVA and 3.337 Joules/cm2 of UVV, If the coated substrate was going to receive a topcoat layer the cured layer was exposed to corona generated by 53.00 KV, 500 Watts while traveling on a conveyor at a belt speed 3 ft/min. If the coated substrate was not going to receive a topcoat layer, the post curing was completed ai 105°C for 3 hours.
- the TLF was spin coated at a rate of 1 ,400 revolutions per minute (rpm) for 7 seconds onto the cured CLF coated substrates. Afterwards the substrates were cured under two ultraviolet lamps in the UV Curing Oven Machine designed and built by Befcan Engineering in nitrogen atmosphere white running on a conveyor belt at 6 ft/min speed at peak intensity of 1 .887 Watts/cm2 of UVA and 0.694 Watts/cm2 of UVV and UV dosage of 4.699 Jou!es/cm2 of UVA and 1 .787 Joules/cm2 of UVV. Post curing was completed at 105°C for 3 hours.
- the substrates Prior to response testing on an optical bench, the substrates were conditioned by exposing them to 365 nm ultraviolet light for 10 minutes at a distance of about 14 cm from the source in order to pre-activate the photochrornic molecules.
- the UVA irradiance at the sample was measured with a Licor Model Li-1800 spectroradiometer and found to be 22.2 Watts per square meter.
- the samples were then placed under a high intensity halogen lamp ⁇ 500 W, 120 V) for about 10 minutes at a distance of about 36 cm from the lamp in order to bleach, or inactivate, the photochrornic compound in the samples.
- the illuminance at the sample was measured with the Licor spectroradiometer and found to be 21 .9 Klux.
- the samples were exposed to yellow fluorescent lamps for 30 minutes to provide further visible light bleaching.
- the samples were then kept in a dark environment for at least 1 hour prior to testing in order to cool and continue to fade back to a ground state.
- An optical bench was used to measure the optical properties of the coated substrates and derive the absorption ratio and photochrornic properties.
- Each test sample was placed on the optical bench with an activating light source (a Newport/Oriel Model 66485 300-Waii Xenon arc lamp fitted with a UNIBLITZ ® VS-25 high-speed computer controlled shutter that momentarily closed during data collection so that stray light would not interfere with the data collection process, a SCHOTT ® 3 mm KG--2 bandpass filter, which removed short wavelength radiation, neutral density filter(s) for intensity attenuation and a condensing lens for beam collimation) positioned at a 30" to 35° angie of incidence to the surface of the test sample.
- the arc lamp was equipped with a light intensity controller (Newport/Oriel model 68950).
- a broadband light source for monitoring response measurements was positioned in a perpendicular manner to a surface of the test sample. Increased signal of shorter visible wavelengths was obtained by collecting and combining separately filtered light from a 100-Watt tungsten haiogen lamp (controlled by a constant voltage powder supply) with a split-end, bifurcated fiber optical cable. Light from one side of the tungsten haiogen lamp was filtered with a SCHOTT ® KG1 filter to absorb heat and a HOYA ® B-440 filter to allow passage of the shorter wavelengths. The other side of the light was either filtered with a SCHOTT ® KG1 filter or unfl!tered.
- the light was collected by focusing light from each side of the lamp onto a separate end of the split-end, bifurcated fiber optic cable, and subsequently combined into one light source emerging from the single end of the cable.
- a 4" or 6" light pipe was attached to the single end of the cable to insure proper mixing.
- the broad band light source was fitted with a UNIBLITZ ® VS-25 highspeed computer controlled shutter that momentarily opened during data collection.
- Polarization of the light source was achieved by passing the light from the single end of the cable through a Moxtek, PROFLUX ® Polarizer held in a computer driven, motorized rotation stage (Model M-061 -PD from Polytech, PI or equivalent).
- the monitoring beam was set so that the one polarization plane (0°) was perpendicuiar to the plane of the optical bench table and the second polarization plane (90°) was parallel to the plane of the optical bench table.
- the samples were run in air, at 23°C ⁇ 0.1 °C maintained by a temperature controlled air cell.
- a second polarizer was added to the optical path.
- the second polarizer was set to 90° of the first polarizer.
- the sample was placed in an air cell in a self-centering holder mounted on a rotation stage.
- a laser beam (Coherent -ULN 635 diode laser) was directed through the crossed polarizers and sample.
- the sample was rotated (in 3° steps as coarse moves and in 0.1° steps as fine moves) to find the minimum transmission.
- the sample was aligned either parallel or perpendicular to the Moxtek polarizer and the second polarizer as well as the diode laser beam was removed from the optical path.
- the sample was aligned within ⁇ 0.5° prior to any activation.
- each test sample was exposed to 6,7 W/m 2 of UVA from the activating light source for 10 to 20 minutes to activate the photochromic compound.
- An International Light Research Radiometer (Model IL-17Q0) with a detector system (Model SED033 detector, B Filter, and diffuse;- ⁇ was used to verify exposure at the beginning of each day.
- Light from the monitoring source that was polarized to the 0° polarization plane was then passed through the coated sample and focused into a 1" integrating sphere, which was connected to an OCEAN OPTICS ® S2000 spectrophotometer or equivalent using a single function fiber optic cable.
- the average absorbance values in a predetermined range of wavelengths corresponding A r iax-Vis +/- 5 nm were extracted for the 0° and 90° polarizations, and the absorption ratio for each wavelength in this range was calculated by dividing the larger- average absorbance by the small average absorbance. For each wavelength extracted, 5 to 100 data points were averaged. The average absorption ratio for the photochromic compound was then calculated by averaging these individual absorption ratios,
- the fade half life (T1 /2) is the time interval in seconds for the &QD of the activated form of the phoiochromsc compounds in the test samples to reach one half the OO measured after fifteen minutes, or after saturation or near-saturation was achieved, at room temperature after removal of the source of activating light, e.g., by closing the shutter.
- the results for Examples 1 -4 and CE 1 -4 are listed in Table 1 .
- the ADD of each was greater than that for CE 1 -4 and the % Transmission of the activated substrate (%Ta) was less than that for CE 1 -4, as desired.
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Abstract
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KR1020147000105A KR101542021B1 (en) | 2011-06-06 | 2011-11-16 | Polarizing photochromic articles |
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US20120120473A1 (en) * | 2003-07-01 | 2012-05-17 | Transitions Optical, Inc. | Polarizing photochromic articles |
EP2804030A1 (en) * | 2013-05-13 | 2014-11-19 | Kilolambda Technologies Ltd. | Layered Photochromic Composition and Device |
US9311545B2 (en) | 2013-09-18 | 2016-04-12 | Blackberry Limited | Multicolor biometric scanning user interface |
US9418273B2 (en) | 2013-09-18 | 2016-08-16 | Blackberry Limited | Structure for multicolor biometric scanning user interface |
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Also Published As
Publication number | Publication date |
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CN103649789A (en) | 2014-03-19 |
KR20140029511A (en) | 2014-03-10 |
EP2718754B1 (en) | 2024-01-24 |
JP5932027B2 (en) | 2016-06-08 |
BR112013031234A2 (en) | 2017-01-31 |
AU2011370482B2 (en) | 2014-08-28 |
ZA201309044B (en) | 2016-02-24 |
JP2014524040A (en) | 2014-09-18 |
BR112013031234B1 (en) | 2021-01-26 |
EP2718754A1 (en) | 2014-04-16 |
KR101542021B1 (en) | 2015-08-04 |
MX363608B (en) | 2019-03-27 |
MX2013014445A (en) | 2014-02-27 |
CA2836743C (en) | 2016-06-14 |
HK1194476A1 (en) | 2014-10-17 |
ES2973880T3 (en) | 2024-06-24 |
CA2836743A1 (en) | 2012-12-13 |
CN103649789B (en) | 2016-03-16 |
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