Patent Grant
10501446
Not applicable.
Not applicable.
Various non-limiting embodiments disclosed herein relate generally to photochromic compounds. Other non-limiting embodiments relate to devices and elements made using the photochromic compounds disclosed herein.
Conventional photochromic compounds have at least two states, a first state having a first absorption spectrum and a second state having a second absorption spectrum that differs from the first absorption spectrum, and are capable of switching between the two states in response to at least actinic radiation. Further, conventional photochromic compounds can be thermally reversible. That is, conventional photochromic compounds are capable of switching between a first state and a second state in response to at least actinic radiation and reverting back to the first state in response to thermal energy. As used herein “actinic radiation” means electromagnetic radiation, such as but not limited to ultraviolet and visible radiation that is capable of causing a response. More specifically, conventional photochromic compounds can undergo a transformation in response to actinic radiation from one isomer to another, with each isomer having a characteristic absorption spectrum, and can further revert back to the first isomer in response to thermal energy (i.e., be thermally reversible). For example, conventional thermally reversible photochromic compounds are generally capable of switching 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 “clear” state in response to thermal energy.
Dichroic compounds are compounds that are capable of absorbing one of two orthogonal plane polarized components of transmitted radiation more strongly than the other. Thus, dichroic compounds are capable of linearly polarizing transmitted radiation. As used herein, “linearly polarize” means to confine the vibrations of the electric vector of light waves to one direction or plane. However, although dichroic materials are capable of preferentially absorbing one of two orthogonal plane polarized components of transmitted radiation, if the molecules of the dichroic compound are not suitably positioned or arranged, no net linear polarization of transmitted radiation will be achieved. That is, due to the random positioning of the molecules of the dichroic compound, selective absorption by the individual molecules will cancel each other such that no net or overall linear polarizing effect is achieved. Thus, it is generally necessary to suitably position or arrange the molecules of the dichroic compound within another material in order to form a conventional linear polarizing element, such as a linearly polarizing filter or lens for sunglasses.
In contrast to the dichroic compounds, it is generally not necessary to position or arrange the molecules of conventional photochromic compounds to form a conventional photochromic element. Thus, for example, conventional photochromic elements, such as lenses for photochromic eyewear, can be formed, for example, by spin coating a solution containing a conventional photochromic compound and a “host” material onto the surface of the lens, and suitably curing the resultant coating or layer without arranging the photochromic compound in any particular orientation. Further, even if the molecules of the conventional photochromic compound were suitably positioned or arranged as discussed above with respect to the dichroic compounds, because conventional photochromic compounds do not strongly demonstrate dichroism, elements made therefrom are generally not strongly linearly polarizing.
It would be advantageous to provide photochromic compounds that can exhibit useful photochromic and/or dichroic properties in at least one state, and that can be used in a variety of applications to impart photochromic and/or dichroic properties.
Various non-limiting embodiments of the present invention will be better understood when read in conjunction with the drawings, in which:
As used in this specification and the appended claims, the articles “a,” “an,” and “the” include plural referents unless expressly and unequivocally limited to one referent.
Additionally, for the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other properties or parameters used in the specification are to be understood as being modified in all instances by the term “about.” Accordingly, unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.
Further, while the numerical ranges and parameters setting forth the broad scope of the invention are approximations as discussed above, the numerical values set forth in the Examples section are reported as precisely as possible. It should be understood, however, that such numerical values inherently contain certain errors resulting from the measurement equipment and/or measurement technique.
Various non-limiting embodiments of the invention will now be described. One non-limiting embodiment provides a thermally reversible, photochromic compound having a Q group at the position described hereinafter and optionally a Lengthening group L also described hereinafter. Another non-limiting embodiment provides a photochromic compound adapted to have at least a first state and a second state, wherein the thermally reversible, photochromic compound has an average absorption ratio greater than 2.3 in at least one state as determined according to the CELL METHOD, which is described in detail below. Further, according to various non-limiting embodiments, the thermally reversible, photochromic compound has an average absorption ratio greater than 2.3 in an activated state as determined according to the CELL METHOD. As used herein, the term “photochromic compound” (PC) includes thermally reversible photochromic compounds chosen from indeno[2′,3′-3,4]naphtho[1,2-b]pyran, indeno[3′,2′-3,4]naphtho[1,2-b]pyran, thiopheno[2′,3′-3,4]naphtho[1,2-b]pyran, thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran, benzothiopheno[2′,3′-3,4]naphtho[1,2-b]pyran, benzothiopheno[3′,2′-3,4]naphtho[1,2-b]pyran, furo[2′,3′-3,4]naphtho[1,2-b]pyran, furo[3′,2′-3,4]naphtho[1,2-b]pyran, benzofuro[2′,3′-3,4]naphtho[1,2-b]pyran, benzofuro[3′,2′-3,4]naphtho[1,2-b]pyran, 2H-naphtho[1,2-b]pyran, 3H-naphtho[2,1-b]pyran, a benzopyran, a spiro[1,3-dihydroindole-3,3′-naphtho[2,1-b][1,4]]oxazine, a spiro[1,3-dihydroindole-2,2′-naphtho[1,2-b][1,4]]floxazine a fulgide and mixtures thereof. As used herein with respect to photochromic compounds, the term “activated state” refers to the photochromic compound when exposed to sufficient actinic radiation to cause the at least a portion of the photochromic compound to switch states. Further, as used herein 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 macromolecules (for example polymers or oligomers) formed by the union of two or more elements, components, ingredients, or parts.
Generally speaking, the CELL METHOD of measuring average absorption ratio of a photochromic compound involves obtaining an absorption spectrum for the photochromic compound, in an activated or unactived state, in each of two orthogonal polarization directions while the photochromic compound is at least partially aligned in an aligned liquid crystal medium that is contained within a cell assembly. More specifically, the cell assembly comprises two opposing glass substrates that are spaced apart by 20 microns+/−1 micron. The substrates are sealed along two opposite edges to form the 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 compound is achieved by introducing the photochromic compound and a liquid crystal medium into the cell assembly and allowing the liquid crystal medium to align with the rubbed polyimide surface. Because the photochromic compound is contained within the liquid crystal medium, alignment of the liquid crystal medium causes the photochromic compound to be aligned. It will be appreciated by those skilled in the art that the choice of the liquid crystal medium and the temperature used during testing can affect the measured absorption ratio. Accordingly, as set forth in more detail in the Examples, for purposes of the CELL METHOD, absorption ratio measurements are taken at room temperature (73° F.+/−0.5° F. or better) and the liquid crystal medium is Licristal® E7 (which is reported to be a mixture of cyanobiphenyl and cyanoterphenyl liquid crystal compounds).
Once the liquid crystal medium and the photochromic compound are aligned, the cell assembly is placed on an optical bench (which is described in more detail in the Examples). To obtain the average absorption ratio in the activated state, activation of the photochromic compound is achieved by exposing the photochromic compound 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 photochromic compound 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 plane or direction) and light that is linearly polarized in a plane 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 cell is measured at each time interval for all of the wavelengths tested and the unactivated absorbance (i.e., the absorbance of the cell with the liquid crystal material and the unactivated photochromic compound) over the same range of wavelengths is subtracted to obtain absorption spectra for the photochromic compound in each of the 0° and 90° polarization planes to obtain an average difference absorption spectrum in each polarization plane for the photochromic compound in the saturated or near-saturated state.
For example, with reference to
Based on the average difference absorption spectra obtained for the photochromic compound, the average absorption ratio for the photochromic compound is obtained as follows. The absorption ratio of the photochromic compound at each wavelength in a predetermined range of wavelengths corresponding to λmax-vis+/−5 nanometers (generally indicated as 14 in
ARλi=Ab1λi/Ab2λi Eq. 1
The average absorption ratio (“AR”) for the photochromic compound is then calculated by averaging the individual absorption ratios obtained for the wavelengths within the predetermined range of wavelengths (i.e., λmax-vis+/−5 nanometers) according to the following equation:
AR=(ΣARλi)/ni Eq. 2
As previously discussed, conventional thermally reversible photochromic compounds are adapted to switch from a first state to a second state in response to actinic radiation, and to revert back to the first state in response to thermal energy. More specifically, conventional thermally reversible, photochromic compounds are capable of transforming from one isomeric form (for example and without limitation, a closed form) to another isomeric form (for example and without limitation, an open form) in response to actinic radiation, and reverting back to the closed form when exposed to thermal energy. However, as previously discussed, generally conventional thermally reversible photochromic compounds do not strongly demonstrate dichroism.
As discussed above, non-limiting embodiments disclosed herein provide a thermally reversible photochromic compound having an average absorption ratio greater than 2.3 in at least one state as determined according to CELL METHOD and/or a thermally reversible photochromic compound that can be used as an intermediate in the preparation of a photochromic compound having an absorption ratio greater than 2.3. Thus, the thermally reversible photochromic compound according to this non-limiting embodiment can display useful photochromic properties and/or useful photochromic and dichroic properties. That is, the thermally reversible, photochromic compound can be a thermally reversible, photochromic and/or photochromic-dichroic compound. As used herein with respect to the photochromic compounds described herein, the term “photochromic-dichroic” means displaying both photochromic and dichroic properties under certain conditions, which properties are at least detectable by instrumentation.
According to other non-limiting embodiments, the thermally reversible photochromic compounds can be thermally reversible photochromic-dichroic compounds having an average absorption ratio ranging from 4 to 20, from 3 to 30, or from 2.5 to 50 in at least one state as determined according to CELL METHOD. It will be appreciated by those skilled in the art that the higher the average absorption ratio of the photochromic compound the more linearly polarizing the photochromic compound will be. Therefore, according to various non-limiting embodiments, the thermally reversible photochromic compounds can have any average absorption ratio required to achieve a desired level of linear polarization.
Another non-limiting embodiment provides a thermally reversible, photochromic compound that is free of oxazines and adapted to have at least a first state and a second state, wherein the photochromic compound has an average absorption ratio of at least 1.5 in at least one state as determined according to CELL METHOD. Further, according to this non-limiting embodiment, the average average absorption ratio can range from 1.5 to 50 in at least one state as determined according to CELL METHOD.
In particular embodiments of the present invention, a photochromic material is provided comprising an indeno[2′,3′-3,4]naphtho[1,2-b]pyran, indeno[3′,2′-3,4]naphtho[1,2-b]pyran, thiopheno[2′,3′-3,4]naphtho[1,2-b]pyran, thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran, benzothiopheno[2′,3′-3,4]naphtho[1,2-b]pyran, benzothiopheno[3′,2′-3,4]naphtho[1,2-b]pyran, furo[2′,3′-3,4]naphtho[1,2-b]pyran, furo[3′,2′-3,4]naphtho[1,2-b]pyran, benzofuro[2′,3′-3,4]naphtho[1,2-b]pyran, benzofuro[3′,2′-3,4]naphtho[1,2-b]pyran, 2H-naphtho[1,2-b]pyran, 3H-naphtho[2,1-b]pyran, a benzopyran, a spiro[1,3-dihydroindole-3,3′-naphtho[2,1-b][1,4]]oxazine, a spiro[1,3-dihydroindole-2,2′-naphtho[1,2-b][1,4]]oxazine or a fulgide ; wherein:
As used herein, the term “attached” means directly bonded to or indirectly bonded to through another group. Thus, for example, according to various non-limiting embodiments disclosed herein, L can be directly bonded to PC as a substituent on PC, or L can be a substituent on another group (such as a group represented by R, which is discussed below) that is directly bonded to PC (i.e., L is indirectly bonded to PC). Although not limiting herein, according to various non-limiting embodiments, L can be attached to PC so as to extend or lengthen PC in an activated state such that the absorption ratio of the extended PC (i.e., the photochromic compound) is enhanced as compared to PC alone. Although not limiting herein, according to various non-limiting embodiments, the location of attachment of L on PC can be chosen such that L lengthens PC in at least one of a direction parallel to or a direction perpendicular to a theoretical transitional dipole moment of the activated form of PC. Regarding the position of L, it may be subsequently attached to the photochromic compound at the location of the Q group. The photochromic compound of the present invention can have at least one Q group at the position(s) indicated and optionally one or more L groups. As used herein the term “theoretical transitional dipole moment” refers to transient dipolar polarization created by interaction of electromagnetic radiation with the molecule. See, for example, IUPAC Compendium of Chemical Technology, 2nd Ed., International Union of Pure and Applied Chemistry (1997).
With reference to L above, each Q1, Q2, and Q3 can be independently chosen for each occurrence from: a divalent group chosen from: an unsubstituted or a substituted aromatic group, an unsubstituted or a substituted alicyclic group, an unsubstituted or a substituted heterocyclic group, and mixtures thereof, wherein substituents are chosen from: a group represented by P, liquid crystal mesogens, halogen, poly(C1-C18 alkoxy), C1-C18 alkoxycarbonyl, C1-C18 alkylcarbonyl, C1-C18 alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C1-C18)alkoxy, perfluoro(C1-C18)alkoxycarbonyl, perfluoro(C1-C18)alkylcarbonyl, perfluoro(C1-C18)alkylamino, di-(perfluoro(C1-C18)alkyl)amino, perfluoro(C1-C18)alkylthio, C1-C18 alkylthio, C1-C18 acetyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, a straight-chain or branched C1-C18 alkyl group that is mono-substituted with cyano, halo, or C1-C18 alkoxy, or poly-substituted with halo, and a group comprising one of the following formulae: -M(T)(t-1) and -M(OT)(t-1), wherein M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and t is the valence of M. As used herein, the prefix “poly” means at least two.
As discussed above, Q1, Q2, and Q3 can be independently chosen for each occurrence from a divalent group, such as an unsubstituted or a substituted aromatic group, unsubstituted or substituted heterocyclic group, and an unsubstituted or substituted alicylic group. Non-limiting examples of useful aromatic groups include: benzo, naphtho, phenanthro, biphenyl, tetrahydro naphtho, terphenyl, and anthraceno.
As used herein the term “heterocyclic group” means a compound having a ring of atoms, wherein at least one atom forming the ring is different than the other atoms forming the ring. Further, as used herein, the term heterocyclic group specifically excludes fused heterocyclic groups. Non-limiting examples of suitable heterocyclic groups from which Q1, Q2, and Q3 can be chosen include: isosorbitol, dibenzofuro, dibenzothieno, benzofuro, benzothieno, thieno, furo, dioxino, carbazolo, anthranilyl, azepinyl, benzoxazolyl, diazepinyl, dioazlyl, imidazolidinyl, imidazolyl, imidazolinyl, indazolyl, indoleninyl, indolinyl, indolizinyl, indolyl, indoxazinyl, isobenzazolyl, isoindolyl, isooxazolyl, isooxazyl, isopyrroyl, isoquinolyl, isothiazolyl, morpholino, morpholinyl, oxadiazolyl, oxathiazolyl, oxathiazyl, oxathiolyl, oxatriazolyl, oxazolyl, piperazinyl, piperazyl, piperidyl, purinyl, pyranopyrrolyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyrazyl, pyridazinyl, pyridazyl, pyridyl, pyrimidinyl, pyrimidyl, pyridenyl, pyrrolidinyl, pyrrolinyl, pyrroyl, quinolizinyl, quinuclidinyl, quinolyl, thiazolyl, triazolyl, triazyl, N-arylpiperazino, aziridino, arylpiperidino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, unsubstituted, mono- or di-substituted C4-C18 spirobicyclic amines, and unsubstituted, mono- or di-substituted C4-C18 spirotricyclic amines.
As discussed above, according to various non-limiting embodiments Q1, Q2, and Q3 can be chosen from mono- or di- substituted C4-C18 spirobicyclic amine and C4-C18 spirotricyclic amine. Non-limiting examples of suitable substituents include aryl, C1-C6 alkyl, C1-C6 alkoxy or phenyl (C1-C6)alkyl. Specific non-limiting examples of mono- or di-substituted spirobicyclic amines include: 2-azabicyclo[2.2.1]hept-2-yl; 3-azabicyclo[3.2.1]oct-3-yl; 2-azabicyclo[2.2.2]oct-2-yl; and 6-azabicyclo[3.2.2]nonan-6-yl. Specific non-limiting examples of mono- or di-substituted tricyclic amines include: 2-azatricyclo[3.3.1.1(3,7)]decan-2-yl; 4-benzyl-2-azatricyclo[3.3.1.1(3,7)]decan-2-yl; 4-methoxy-6-methyl-2-azatricyclo[3.3.1.1(3,7)]decan-2-yl; 4-azatricyclo[4.3.1.1(3,8)]undecan-4-yl; and 7-methyl-4-azatricyclo[4.3.1.1(3,8)]undecan-4-yl.
Examples of alicyclic groups from which Q1, Q2, and Q3 can be chosen include, without limitation, cyclohexyl, cyclopropyl, norbornenyl, decalinyl, adamantanyl, bicyclooctane, per-hydrofluorene, and cubanyl.
With continued reference to L, each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit chosen from:
According to various non-limiting embodiments disclosed herein, in L, c, d, e, and f each can be independently chosen from an integer ranging from 1 to 20, inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f is at least 1. According to other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 2. According to still other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f′each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 3. According to still other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f′each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 1.
Further, in L, P can be chosen from: hydroxy, amino, C2-C18 alkenyl, C2-C18 alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato, acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C1-C18 alkyl aminocarbonyl, aminocarbonyl(C1-C18)alkyl, C1-C18 alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy(C1-C18)alkyl, C1-C18 alkyl, C1-C18 alkoxy, amino(C1-C18)alkyl, C1-C18 alkylamino, di-(C1-C18)alkylamino, C1-C18 alkyl(C1-C18)alkoxy, C1-C18 alkoxy(C1-C18)alkoxy, nitro, poly(C1-C18)alkyl ether, (C1-C18)alkyl(C1-C18)alkoxy(C1-C18)alkyl, polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl, acryloyloxy(C1-C18)alkyl, methacryloyl, methacryloyloxy(C1-C18)alkyl, 2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato(C1-C18)alkyl, itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative, main-chain and side-chain liquid crystal polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, or substituted or unsubstituted chiral or non-chiral monovalent or divalent groups chosen from steroid radicals, terpenoid radicals, alkaloid radicals and mixtures thereof, wherein the substituents are independently chosen from C1-C18 alkyl, C1-C18 alkoxy, amino, C3-C10 cycloalkyl, C1-C18 alkyl(C1-C18)alkoxy, fluoro(C1-C18)alkyl, cyano, cyano(C1-C18)alkyl, cyano(C1-C18)alkoxy or mixtures thereof, or P is a structure having from 2 to 4 reactive groups or P is an unsubstituted or substituted ring opening metathesis polymerization precursor.
According to various non-limiting embodiments disclosed herein, when P is a polymerizable group, the polymerizable group can be any functional group adapted to participate in a polymerization reaction. Non-limiting examples of polymerization reactions include those described in the definition of “polymerization” in Hawley's Condensed Chemical Dictionary Thirteenth Edition, 1997, John Wiley & Sons, pages 901-902, which disclosure is incorporated herein by reference. For example, although not limiting herein, polymerization reactions include: “addition polymerization,” in which free radicals are the initiating agents that react with the double bond of a monomer by adding to it on one side at the same time producing a new free electron on the other side; “condensation polymerization,” in which two reacting molecules combine to form a larger molecule with elimination of a small molecule, such as a water molecule; and “oxidative coupling polymerization.” Further, non-limiting examples of polymerizable groups include hydroxy, acryloxy, methacryloxy, 2-(acryloxy)ethylcarbamyl, 2-(methacryloxy)ethylcarbamyl, isocyanate, aziridine, allylcarbonate, and epoxy, e.g., oxiranylmethyl.
According to one specific, non-limiting embodiment, P can be chosen from a main-chain or a side-chain liquid crystal polymer and a liquid crystal mesogen. As used herein, the term liquid crystal “mesogen” means rigid rod-like or disc-like liquid crystal molecules. Further, as used herein the term “main-chain liquid crystal polymer” refers to a polymer having liquid crystal mesogens within the backbone (i.e., the main chain) structure of the polymer. As used herein the term “side-chain liquid crystal polymer” refers to a polymer having liquid crystal mesogens attached to the polymer at the side chains. Although not limiting herein, generally, the mesogens are made up of two or more aromatic rings that restrict the movement of a liquid crystal polymer. Examples of suitable rod-like liquid crystal mesogens include without limitation: substituted or unsubstituted aromatic esters, substituted or unsubstituted linear aromatic compounds, and substituted or unsubstituted terphenyls.
According to another specific, non-limiting embodiment, P can be chosen from a steroid radical, for example and without limitation, a cholesterolic compound.
As is discussed above, various non-limiting embodiments disclosed herein provide a photochromic compound comprising (a) a photochromic group (PC) and (b) at least one Q group at the position described herein and optionally at least one lengthening agent (L) (above) attached to PC.
In alternative embodiments, the photochromic compound may be represented by the following graphic formula I, II, III, IVA, IVB, V or VI:
wherein: T is —S—, —O— or —N(R)—, J is a spiro-alicyclic ring and Q is the same as described hereinbefore.
According to one specific, non-limiting embodiment, wherein the photochromic group comprises at least two PCs, the PCs can be linked to one another via linking group substituents on the individual PCs. For example, the PCs can be polymerizable photochromic groups or photochromic groups that are adapted to be compatible with a host material (“compatibilized photochromic group”). Non-limiting examples of polymerizable photochromic groups from which PC can be chosen and that are useful in conjunction with various non-limiting embodiments disclosed herein are disclosed in U.S. Pat. No. 6,113,814, which is hereby specifically incorporated by reference herein. Non-limiting examples of compatibilized photochromic groups from which PC can be chosen and that are useful in conjunction with various non-limiting embodiments disclosed herein are disclosed in U.S. Pat. No. 6,555,028, which is hereby specifically incorporated by reference herein.
Other suitable photochromic groups and complementary photochromic groups are described in U.S. Pat. No. 6,080,338 at column 2, line 21 to column 14, line 43; U.S. Pat. No. 6,136,968 at column 2, line 43 to column 20, line 67; U.S. Pat. No. 6,296,785 at column 2, line 47 to column 31, line 5; U.S. Pat. No. 6,348,604 at column 3, line 26 to column 17, line 15; U.S. Pat. No. 6,353,102 at column 1, line 62 to column 11, line 64; and U.S. Pat. No. 6,630,597 at column 2, line 16 to column 16, line 23; the disclosures of the aforementioned patents are incorporated herein by reference.
Another non-limiting embodiment provides the aforementioned lengthening agent (L) attached to the at least one photochromic group, wherein the at least one lengthening agent is chosen from one of the following compounds listed (and graphically represented) below:
Another non-limiting embodiment disclosed herein provides a photochromic compound of graphic formula I represented by the following graphic formula:
Additionally, according to various non-limiting embodiments disclosed herein, the photochromic compound represented by Formulas I, II, III, IVA, IVB, V and VI may comprise one or more lengthening agents (L). As previously discussed, in L, c, d, e, and f each can be independently chosen from an integer ranging from 1 to 20, inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 1. According to other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f is at least 2. According to still other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f is at least 3. According to still other non-limiting embodiments disclosed herein, c, d, e, and f each can be independently chosen from an integer ranging from 0 to 20, inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 1.
Thus, for example, in Formulas I, II, III, IVA, IVB, V and VI, “i” can be at least 1 and at least one of the R groups can be a lengthening agent L. Additionally or alternatively, the photochromic compound can comprise at least one R group, at least one B group, or at least one B′ group that is substituted with a lengthening agent L. For example, although not limiting herein, in one non-limiting embodiment the photochromic compound can comprise a B group comprising a phenyl group that is mono-substituted with a lengthening agent L.
Moreover, although not limiting herein, according to various non-limiting embodiments disclosed herein, the lengthening agent (L) can be attached to a photochromic group (e.g., the pyran group of Formula I, II, III or V) at any available position such that L extends or lengthens the photochromic group in an activated state such that the absorption ratio of the extended photochromic group (i.e., the photochromic compound) is enhanced as compared to the unextended photochromic group. Thus, for example and without limitation, according to various non-limiting embodiments wherein the photochromic compound is represented by Formula I, II, III or V, L can be directly bonded to the pyran group, for example, wherein i is at least 1 and R is L, or it can be indirectly bonded to the pyran group, for example, as a substituent on an R group, B, or B′ group such that L extends the pyran group in an activated state such that the absorption ratio of the photochromic compound is enhanced as compared to the unextended pyran group.
Further, the photochromic compound according to various non-limiting embodiments disclosed herein and generally represented by Formula I, II, III, V and VI can have an average absorption ratio of at least 1.5 in an activated state as determined according to CELL METHOD. According to other non-limiting embodiments, the photochromic compound can have an average absorption ratio ranging from 4 to 20, 3 to 30, or 2.5 to 50 in an activated state as determined according to CELL METHOD. According to still other non-limiting embodiments, the photochromic compounds can have an average absorption ratio ranging from 1.5 to 50 in an activated state as determined according to CELL METHOD.
Reaction sequences for forming a photochromic compound according to various non-limiting embodiments disclosed herein having an L group are disclosed in Reaction Sequences A through J, K, M, N, P, Q, T in U.S. Pat. No. 7,342,112, which disclosure is incorporated herein by reference.
A general reaction scheme for preparing photochromic compounds represented by Formulas I, II, III, IVA, IVB, V and VI, is shown in
The following abbreviations were used for the chemicals listed in the reaction schemes and examples described hereinafter:
Another general reaction scheme for making Q-substituted naphthols and Q-substituted phenol intermediates for preparing photochromic compounds represented by Formulas I, II, III, IVA, IVB, and V, is shown in
Another non-limiting embodiment provides a photochromic compound chosen from:
Also provided by the present invention is a naphthol represented by one of the following graphic formulae:
In particular embodiments of the present invention, the naphthol may be represented by one of the following graphic formulae:
In another particular embodiment, the naphthol may be represented by the following graphic formula:
Further reaction schemes for preparing the naphthols of the present invention are described in
The thermally reversible photochromic compounds according to various non-limiting embodiments disclosed herein can be used in a variety of applications to provide photochromic and/or photochromic-dichroic properties.
One non-limiting embodiment provides a photochromic article comprising an organic host material and a photochromic composition of the present invention connected to at least a portion of the organic host material. As used herein 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. Further, according to this non-limiting embodiment, the photochromic compound can be connected to at least a portion of the host by incorporation into the host material or by application onto the host material, for example, as part of a coating or layer. In addition to the photochromic compound, the photochromic composition may further comprise at least one additive chosen from dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical scavengers, gelators and adhesion promoters.
Non-limiting examples of organic host materials that may be used in conjunction with various non-limiting embodiments disclosed herein include polymeric materials, for example, homopolymers and copolymers, prepared from the monomers and mixtures of monomers disclosed in U.S. Pat. No. 5,962,617 and in U.S. Pat. No. 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, an oligomeric material, a monomeric material or a mixture or combination thereof. 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(allyl carbonate) monomers, e.g., allyl diglycol carbonates such as diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39 by PPG Industries, Inc.; polyurea-polyurethane (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.; polyol(meth)acryloyl terminated carbonate monomer; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; ethoxylated trimethylol propane triacrylate monomers; ethylene glycol bismethacrylate monomers; poly(ethylene glycol) bismethacrylate monomers; urethane acrylate monomers; poly(ethoxylated bisphenol A dimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); poly(vinyl chloride); poly(vinylidene chloride); polyethylene; polypropylene; polyurethanes; polythiourethanes; thermoplastic polycarbonates, such as the carbonate-linked resin derived from bisphenol A and phosgene, one such material being sold under the trademark LEXAN; polyesters, such as the material sold under the trademark MYLAR; poly(ethylene terephthalate); polyvinyl butyral; poly(methyl methacrylate), such as the material sold under the trademark PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanates with polythiols or polyepisulfide monomers, either homopolymerized or co-and/or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates and optionally ethylenically unsaturated monomers or halogenated 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.
According to one specific non-limiting embodiment, the organic host material is chosen from polyacrylates, polymethacrylates, poly(C1-C12) alkyl methacrylates, polyoxy(alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethyl acrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate)monomers, mono-functional acrylate monomers, mono-functional methacrylate monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol monomers and diallylidene pentaerythritol monomers.
According to another specific non-limiting embodiment, the organic host material is a homopolymer or copolymer of monomer(s) chosen from acrylates, methacrylates, methyl methacrylate, ethylene glycol bis methacrylate, ethoxylated bisphenol A dimethacrylate, vinyl acetate, vinylbutyral, urethane, thiourethane, diethylene glycol bis(allyl carbonate), diethylene glycol dimethacrylate, diisopropenyl benzene, and ethoxylated trimethylol propane triacrylate. The polymeric material most often comprises self-assembling materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane, polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.
Further, according to various non-limiting embodiments disclosed herein, the organic host material can form an optical element or portion thereof. Non-limiting examples of optical elements include ophthalmic elements, display elements, windows, and mirrors. As used herein the term “optical” means pertaining to or associated with light and/or vision. For example, although not limiting herein, according to various non-limiting embodiments, the optical element or device can be chosen from ophthalmic elements and devices, display elements and devices, windows, mirrors, packaging material, and active and passive liquid crystal cell elements and devices.
As used herein the term “ophthalmic” means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic 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-ocular lenses, magnifying lenses, and protective lenses or visors. As used herein the term “display” means the visible or machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements and devices include screens, monitors, and security elements, including without limitation, security marks and authentication marks. As used herein the term “window” means an aperture adapted to permit the transmission of radiation therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, shutters, and optical switches. As used herein the term “mirror” means a surface that specularly reflects a large fraction of incident light.
For example, in one non-limiting embodiment, the organic host material is an ophthalmic element, and more particularly, is an ophthalmic lens.
Further, it is contemplated that the photochromic compounds disclosed herein can be used alone or in conjunction with at least one other complementary organic photochromic compound having at least one activated absorption maxima within the range of 300 nm to 1000 nm, inclusive (or substances containing the same). For example, the photochromic compound disclosed herein can be combined with at least one other conventional organic photochromic compound such that the combination of photochromic compound, when activated, exhibits a desired hue. Non-limiting examples of suitable conventional organic photochromic compounds include those photochromic pyrans, oxazines, and fulgides, set forth above. Other complementary photochromic compounds include, for example, the pyrans, oxazines, fulgides and fulgimides described hereinafter.
Non-limiting examples of thermally reversible complementary photochromic pyrans include benzopyrans, naphthopyrans, e.g., naphtho[1,2-b]pyrans, naphtho[2,1-b]pyrans, indeno-fused naphthopyrans, such as those disclosed in U.S. Pat. No. 5,645,767, and heterocyclic-fused naphthopyrans, such as those disclosed in U.S. Pat. Nos. 5,723,072, 5,698,141, 6,153,126, and 6,022,497, which are hereby incorporated by reference; spiro-9-fluoreno[1,2-b]pyrans; phenanthropyrans; quinopyrans; fluoroanthenopyrans; spiropyrans, e.g., spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans and spiro(indoline)pyrans. More specific examples of naphthopyrans and the complementary organic photochromic substances are described in U.S. Pat. No. 5,658,501, which are hereby specifically incorporated by reference herein. Spiro(indoline)pyrans are also described in the text, Techniques in Chemistry, Volume III, “Photochromism”, Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971, which is hereby incorporated by reference.
Non-limiting examples of thermally reversible complementary photochromic oxazines include benzoxazines, naphthoxazines, and spiro-oxazines, e.g., spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines, spiro(indoline)fluoranthenoxazine, and spiro(indoline)quinoxazine.
More non-limiting examples of thermally reversible complementary photochromic fulgides include: fulgimides, and the 3-furyl and 3-thienyl fulgides and fulgimides, which are disclosed in U.S. Pat. No. 4,931,220 (which are hereby specifically incorporated by reference) and mixtures of any of the aforementioned photochromic materials/compounds.
For example, it is contemplated that the photochromic compounds disclosed herein can be used alone or in conjunction with another conventional organic photochromic compound (as discussed above), in amounts or ratios such that the organic host material into which the photochromic compounds are incorporated, or onto which the organic host materials are applied, can exhibit a desired color or colors, either in an activated or a “bleached” state. Thus the amount of the photochromic compounds used is not critical provided that a sufficient amount is present to produce a desired photochromic effect. As used herein, the term “photochromic amount” refers to the amount of the photochromic compound necessary to produce the desired photochromic effect.
Another non-limiting embodiment provides a photochromic article comprising a substrate, and an at least partial coating of a coating composition having a photochromic amount of a photochromic compound of the present invention connected to at least a portion of at least one surface thereof of the substrate. Further, although not limiting herein, at least a portion of the at least partial coating can be at least partially set. As used herein the term “set” means to fix in a desired orientation.
For example, according to the above-mentioned non-limiting embodiment, the coating composition can be chosen from, without limitation, polymeric coating compositions, paints, and inks. Further, in addition to the photochromic compounds disclosed herein, the coating compositions according to various non-limiting embodiments can further comprise at least one other conventional organic photochromic compounds having at least one activated absorption maxima within the range of 300 nm to 1000 nm, inclusive.
Non-limiting examples of suitable substrates to which the coating composition comprising the photochromic amount of the photochromic compounds can be applied include glass, masonry, textiles, ceramics, metals, wood, paper and polymeric organic materials. Non-limiting examples of suitable polymeric organic materials are set forth above.
Still other non-limiting embodiments provide optical elements comprising a substrate and an at least partial coating comprising at least one photochromic compound of the present invention connected to at least a portion of the substrate. Non-limiting examples of optical elements include, ophthalmic elements, display elements, windows, and mirrors. For example, according to one non-limiting embodiment, the optical element is an ophthalmic element, and the substrate is an ophthalmic substrate chosen from corrective and non-corrective lenses, partially formed lenses, and lens blanks.
Although not limiting herein, the optical elements according to various non-limiting embodiments disclosed herein can comprise any amount of the photochromic compound necessary to achieve the desired optical properties, such as but not limited to, photochromic properties and dichroic properties.
Other non-limiting examples of substrates that are suitable for use in conjunction with the foregoing non-limiting embodiment include untinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing substrates, circularly polarizing substrates, elliptically polarizing substrates, and reflective substrates. As used herein with reference to substrates the term “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. Further, with reference to substrates 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.
As used herein the term “linearly polarizing” with reference to substrates refers to substrates that are adapted to linearly polarize radiation (i.e., confine the vibrations of the electric vector of light waves to one direction). As used herein the term “circularly polarizing” with reference to substrates refers to substrates that are adapted to circularly polarize radiation. As used herein the term “elliptically polarizing” with reference to substrates refers to substrates that are adapted to elliptically polarize radiation. As used herein with the term “photochromic” with reference to substrates refers to substrates having an absorption spectrum for visible radiation that varies in response to at least actinic radiation and is thermally reversible. Further, as used herein with reference to substrates, the term “tinted-photochromic” means substrates containing a coloring agent addition as well as a photochromic compound, and having an absorption spectrum for visible radiation that varies in response to at least actinic radiation and is thermally reversible. Thus for example, in one non-limiting embodiment, the 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 and the photochromic compound when exposed to actinic radiation.
One specific non-limiting embodiment provides an optical element comprising a substrate and an at least partial coating comprising at least one photochromic compound of the present invention connected to at least a portion of the substrate. Further, according to this non-limiting embodiment, the at least one thermally reversible photochromic compound can be a photochromic-dichroic compound having an average absorption ratio greater than 2.3 in an activated state as determined according to CELL METHOD.
As discussed above, the optical elements according to various non-limiting embodiments disclosed herein can be display elements, such as, but not limited to screens, monitors, and security elements. For example, one non-limiting embodiment provides a display element comprising a first substrate having a first surface, a second substrate having a second surface, wherein the second surface of the second substrate is opposite and spaced apart from the first surface of the first substrate so as to define a gap; and a fluid material comprising at least one photochromic compound of the present invention positioned within the gap defined by the first surface of the first substrate and the second surface of the second substrate. Further, the at least one photochromic compound can be a photochromic-dichroic compound having an average absorption ratio greater than 2.3 in an activated state as determined according to CELL METHOD.
Further, according to this non-limiting embodiment, the first and second substrates can be independently chosen from untinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing substrates, circularly polarizing substrates, elliptically polarizing substrates and reflective substrates.
Another non-limiting embodiment provides a security element comprising a substrate and at least one photochromic compound of the present invention connected to at least a portion of the substrate. Non-limiting examples of security elements include security marks and authentication marks that are connected to at least a portion of a substrate, such as and without limitation: 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.
Although not limiting herein, according to this non-limiting embodiment, the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to certain non-limiting embodiments wherein 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. For example, a reflective aluminum coating can be applied to the at least a portion of the substrate prior to forming the security element thereon. Still further, security element can be connected to at least a portion of a substrate chosen from untinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing, circularly polarizing substrates, and elliptically polarizing substrates.
Additionally, according to the aforementioned non-limiting embodiment the at least one photochromic compound can be a thermally reversible photochromic-dichroic compound having an average absorption ratio greater than 2.3 in the activated state as determined according to CELL METHOD.
Furthermore, security element according to the aforementioned non-limiting embodiment can further comprise one or more other coatings or sheets to form a multi-layer reflective security element with viewing angle dependent characteristics as described in U.S. Pat. No. 6,641,874, which is hereby specifically incorporated by reference herein.
The photochromic articles and optical elements described above can be formed by methods known in the art. Although not limiting herein, it is contemplated that the photochromic compounds disclosed herein can be connected to a substrate or host by incorporation into the host material or application onto the host or substrate, such as in the form of a coating.
For example, the photochromic-dichroic compound can be incorporated into an organic host material by dissolving or dispersing the photochromic compound within the host material, e.g., casting it in place by adding the photochromic compound to the monomeric host material prior to polymerization, imbibition of the photochromic compound into the host material by immersion of the host material in a hot solution of the photochromic compound or by thermal transfer. As used herein the term “imbibition” includes permeation of the photochromic compound alone into the host material, solvent assisted transfer of the photochromic compound into a porous polymer, vapor phase transfer, and other such transfer methods.
Additionally, the photochromic compound disclosed herein can be applied to the organic host material or other substrate as part of a coating composition (as discussed above) or a sheet comprising the photochromic compound. As used herein the term “coating” means a supported film derived from a flowable composition, which may or may not have a uniform thickness. As used herein the term “sheet” means a pre-formed film having a generally uniform thickness and capable of self-support.
Non-limiting methods of applying coating compositions comprising the photochromic compounds disclosed herein include those methods known in the art for applying coatings, such as, spin coating, spray coating, spray and spin coating, curtain coating, flow coating, dip coating, injection molding, casting, roll coating, wire coating, and overmolding. According to one non-limiting embodiment, a coating comprising the photochromic compound is applied to a mold and the substrate is formed on top of the coating (i.e., overmolding). Additionally or alternatively, a coating composition without the photochromic compound can be first applied to the substrate or organic host material using any of the aforementioned techniques and thereafter imbibed with the photochromic compound as described above.
Non-limiting methods of applying sheets comprising the photochromic compound disclosed herein to a substrate include, for example, at least one of: laminating, fusing, in-mold casting, and adhesively bonding the polymeric sheet to the at least a portion of the substrate. As used herein, the in-mold casting includes a variety of casting techniques, such as but not limited to: overmolding, wherein the sheet is placed in a mold and the substrate is formed (for example by casting) over at least a portion of the substrate; and injection molding, wherein the substrate is formed around the sheet. Further, it is contemplated that the photochromic compound can be applied to the sheet as a coating, incorporated into the sheet by imbibition or by other suitable methods, either prior to applying the sheet to the substrate or thereafter.
Moreover, as discussed above, the photochromic compounds disclosed herein can be incorporated or applied alone, or in combination with at least one other conventional organic photochromic compound, which can also be applied or incorporated into the host materials and substrates as described above. Additional coatings may be applied to the photochromic article including other photochromic coatings, anti-reflective coatings, linearly polarizing coatings, transitional coatings, alignment layers, primer coatings, adhesive coatings, mirrored coatings and protective coatings including antifogging coatings, oxygen barrier coatings and ultraviolet light absorbing coatings.
Various embodiments disclosed herein will now be illustrated in the following non-limiting examples.
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Part II: Testing
This application is a divisional of U.S. patent application Ser. No 15/219,434, filed Jul. 26, 2016, which is a divisional of U.S. patent application Ser. No. 14/174,978, filed Feb. 7, 2014, now U.S. Pat. No. 9,405,041 B2, which is a divisional of U.S. patent application Ser. No. 13/452,030, filed Apr. 20, 2012, now U.S. Pat. No. 8,705,160 B2, which is a divisional of U.S. patent application Ser. No. 12/329,092, filed Dec. 5, 2008, now U.S. Pat. No. 8,211,338 B2, which is a continuation-in-part of U.S. patent application Ser. No. 10/846,629, filed May 17, 2004, now U.S. Pat. No. 7,342,112 B2, which claims the benefit of U.S. Provisional Application No. 60/484,100, filed Jul. 1, 2003, all of which are hereby specifically incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 303673 | Small | Aug 1884 | A |
| 2319826 | Pellett | May 1943 | A |
| 2334446 | Serrell | Nov 1943 | A |
| 2475921 | Smith | Jul 1949 | A |
| 2481830 | Dreyer | Sep 1949 | A |
| 2544659 | Dreyer | Mar 1951 | A |
| 3276316 | Makas | Oct 1966 | A |
| 3361706 | Meriwether et al. | Jan 1968 | A |
| 3562172 | Ono et al. | Feb 1971 | A |
| 3567605 | Becker | Mar 1971 | A |
| 3578602 | Ono et al. | May 1971 | A |
| 3653863 | Araujo et al. | Apr 1972 | A |
| 4039254 | Harsch | Aug 1977 | A |
| 4043637 | Hovey | Aug 1977 | A |
| 4049338 | Slocum | Sep 1977 | A |
| 4166043 | Uhlmann et al. | Aug 1979 | A |
| 4190330 | Berreman | Feb 1980 | A |
| 4215010 | Hovey et al. | Jul 1980 | A |
| 4279474 | Belgorod | Jul 1981 | A |
| 4342668 | Hovey et al. | Aug 1982 | A |
| 4367170 | Uhlmann et al. | Jan 1983 | A |
| 4539048 | Cohen | Sep 1985 | A |
| 4539049 | Cohen | Sep 1985 | A |
| 4549894 | Araujo et al. | Oct 1985 | A |
| 4556605 | Mogami et al. | Dec 1985 | A |
| 4637698 | Kwak et al. | Jan 1987 | A |
| 4637896 | Shannon | Jan 1987 | A |
| 4648925 | Goepfert et al. | Mar 1987 | A |
| 4650526 | Claffey et al. | Mar 1987 | A |
| 4683153 | Goepfert et al. | Jul 1987 | A |
| 4685783 | Heller et al. | Aug 1987 | A |
| 4720356 | Chu | Jan 1988 | A |
| 4728173 | Toth | Mar 1988 | A |
| 4756605 | Okada et al. | Jul 1988 | A |
| 4756973 | Sakagami et al. | Jul 1988 | A |
| 4785097 | Kwak | Nov 1988 | A |
| 4810433 | Takayanagi et al. | Mar 1989 | A |
| 4816584 | Kwak et al. | Mar 1989 | A |
| 4818096 | Heller et al. | Apr 1989 | A |
| 4826977 | Heller et al. | May 1989 | A |
| 4838673 | Richards et al. | Jun 1989 | A |
| 4863763 | Takeda et al. | Sep 1989 | A |
| 4865668 | Goepfert et al. | Sep 1989 | A |
| 4873026 | Behre et al. | Oct 1989 | A |
| 4873029 | Blum | Oct 1989 | A |
| 4880667 | Welch | Nov 1989 | A |
| 4929693 | Akashi et al. | May 1990 | A |
| 4931219 | Kwiatkowski et al. | Jun 1990 | A |
| 4931220 | Haynes et al. | Jun 1990 | A |
| 4931221 | Heller | Jun 1990 | A |
| 4959471 | Melzig | Sep 1990 | A |
| 4962013 | Tateoka et al. | Oct 1990 | A |
| 4974941 | Gibbons et al. | Dec 1990 | A |
| 4977028 | Goepfert et al. | Dec 1990 | A |
| 4983479 | Broer et al. | Jan 1991 | A |
| 5024850 | Broer et al. | Jun 1991 | A |
| 5053302 | Makino et al. | Oct 1991 | A |
| 5066818 | Gemert et al. | Nov 1991 | A |
| 5067795 | Senatore | Nov 1991 | A |
| 5073294 | Shannon et al. | Dec 1991 | A |
| 5130058 | Tanaka et al. | Jul 1992 | A |
| 5130353 | Fischer et al. | Jul 1992 | A |
| 5139707 | Guglielmetti et al. | Aug 1992 | A |
| 5155607 | Inoue et al. | Oct 1992 | A |
| 5166345 | Akashi et al. | Nov 1992 | A |
| 5177227 | Fischer et al. | Jan 1993 | A |
| 5180470 | Smith et al. | Jan 1993 | A |
| 5180524 | Casilli et al. | Jan 1993 | A |
| 5185390 | Fischer et al. | Feb 1993 | A |
| 5186867 | Castaldi et al. | Feb 1993 | A |
| 5189448 | Yaguchi | Feb 1993 | A |
| 5194973 | Isogai et al. | Mar 1993 | A |
| 5200116 | Heller | Apr 1993 | A |
| 5202053 | Shannon | Apr 1993 | A |
| 5204850 | Obata | Apr 1993 | A |
| 5238931 | Yoshikawa et al. | Aug 1993 | A |
| 5238981 | Knowles | Aug 1993 | A |
| 5247377 | Omeis et al. | Sep 1993 | A |
| 5274132 | Van Gemert | Dec 1993 | A |
| 5289547 | Ligas et al. | Feb 1994 | A |
| 5359085 | Iwamoto et al. | Oct 1994 | A |
| 5359443 | Toyooka et al. | Oct 1994 | A |
| 5384077 | Knowles | Jan 1995 | A |
| 5389287 | Nishiyama et al. | Feb 1995 | A |
| 5389698 | Chigrinov et al. | Feb 1995 | A |
| 5391327 | Ligas et al. | Feb 1995 | A |
| 5395566 | Kobayakawa et al. | Mar 1995 | A |
| 5405958 | Van Gemert | Apr 1995 | A |
| 5464669 | Kang et al. | Nov 1995 | A |
| 5466398 | Van Gemert et al. | Nov 1995 | A |
| 5543267 | Stumpe et al. | Aug 1996 | A |
| 5543533 | Allegrini et al. | Aug 1996 | A |
| 5602661 | Schadt et al. | Feb 1997 | A |
| 5608567 | Grupp | Mar 1997 | A |
| 5641846 | Bieringer et al. | Jun 1997 | A |
| 5644416 | Morikawa et al. | Jul 1997 | A |
| 5645767 | Van Gemert | Jul 1997 | A |
| 5658501 | Kumar et al. | Aug 1997 | A |
| 5698141 | Kumar | Dec 1997 | A |
| 5707557 | Melzig et al. | Jan 1998 | A |
| 5723072 | Kumar | Mar 1998 | A |
| 5744070 | Kumar | Apr 1998 | A |
| 5746949 | Shen et al. | May 1998 | A |
| 5770115 | Misura | Jun 1998 | A |
| 5808100 | Momoda et al. | Sep 1998 | A |
| 5831090 | Paltchkov et al. | Nov 1998 | A |
| 5846452 | Gibbons et al. | Dec 1998 | A |
| 5869658 | Lin et al. | Feb 1999 | A |
| 5903330 | Funfschilling et al. | May 1999 | A |
| 5943104 | Moddel et al. | Aug 1999 | A |
| 5952515 | Melzig et al. | Sep 1999 | A |
| 5955520 | Heller et al. | Sep 1999 | A |
| 5961892 | Gemert et al. | Oct 1999 | A |
| 5962617 | Slagel | Oct 1999 | A |
| 6004486 | Chan | Dec 1999 | A |
| 6022497 | Kumar | Feb 2000 | A |
| 6025026 | Smith et al. | Feb 2000 | A |
| 6036890 | Melzig et al. | Mar 2000 | A |
| 6049428 | Khan et al. | Apr 2000 | A |
| 6060001 | Welch et al. | May 2000 | A |
| 6066797 | Toyomura et al. | May 2000 | A |
| 6080338 | Kumar | Jun 2000 | A |
| 6096375 | Ouderkirk et al. | Aug 2000 | A |
| 6106744 | Van Gemert et al. | Aug 2000 | A |
| 6113814 | Gemert et al. | Sep 2000 | A |
| 6136968 | Chamontin et al. | Oct 2000 | A |
| 6141135 | Nagoh et al. | Oct 2000 | A |
| 6146554 | Melzig et al. | Nov 2000 | A |
| 6150430 | Walters et al. | Nov 2000 | A |
| 6153126 | Kumar | Nov 2000 | A |
| 6160597 | Schadt et al. | Dec 2000 | A |
| 6177032 | Smith et al. | Jan 2001 | B1 |
| 6177932 | Galdes et al. | Jan 2001 | B1 |
| 6187444 | Bowles, III et al. | Feb 2001 | B1 |
| 6197225 | Tanizawa et al. | Mar 2001 | B1 |
| 6201588 | Walton et al. | Mar 2001 | B1 |
| 6208393 | Bawolek et al. | Mar 2001 | B1 |
| 6239778 | Palffy-Muhoray et al. | May 2001 | B1 |
| 6245399 | Sahouani et al. | Jun 2001 | B1 |
| 6256152 | Coldrey et al. | Jul 2001 | B1 |
| 6268055 | Walters et al. | Jul 2001 | B1 |
| 6281366 | Frigoli et al. | Aug 2001 | B1 |
| 6284418 | Trantolo | Sep 2001 | B1 |
| 6294112 | Clarke et al. | Sep 2001 | B1 |
| 6296785 | Nelson et al. | Oct 2001 | B1 |
| 6303673 | Clarke et al. | Oct 2001 | B1 |
| 6312811 | Frigoli et al. | Nov 2001 | B1 |
| 6334681 | Perrott et al. | Jan 2002 | B1 |
| 6337409 | Hughes et al. | Jan 2002 | B1 |
| 6338808 | Kawata et al. | Jan 2002 | B1 |
| 6340765 | Momoda et al. | Jan 2002 | B1 |
| 6340766 | Lin | Jan 2002 | B1 |
| 6348604 | Nelson et al. | Feb 2002 | B1 |
| 6353102 | Kumar | Mar 2002 | B1 |
| 6369869 | Schadt et al. | Apr 2002 | B2 |
| 6432544 | Stewart et al. | Aug 2002 | B1 |
| 6433043 | Misura et al. | Aug 2002 | B1 |
| 6436525 | Welch et al. | Aug 2002 | B1 |
| 6474695 | Schneider et al. | Nov 2002 | B1 |
| 6491990 | Parri et al. | Dec 2002 | B1 |
| 6506488 | Stewart et al. | Jan 2003 | B1 |
| 6531076 | Crano et al. | Mar 2003 | B2 |
| 6555028 | Walters et al. | Apr 2003 | B2 |
| 6555029 | Ruscio et al. | Apr 2003 | B1 |
| 6579422 | Kakinuma | Jun 2003 | B1 |
| 6597422 | Funfschilling et al. | Jul 2003 | B1 |
| 6602603 | Welch et al. | Aug 2003 | B2 |
| 6613433 | Yamamoto et al. | Sep 2003 | B2 |
| 6630597 | Lin et al. | Oct 2003 | B1 |
| 6641874 | Kuntz et al. | Nov 2003 | B2 |
| 6660727 | Mann et al. | Dec 2003 | B1 |
| 6683709 | Mann et al. | Jan 2004 | B2 |
| 6690495 | Kosa et al. | Feb 2004 | B1 |
| 6705569 | Sanders et al. | Mar 2004 | B1 |
| 6717644 | Schadt et al. | Apr 2004 | B2 |
| 6723859 | Kawabata et al. | Apr 2004 | B2 |
| 6736998 | Petrovskaia et al. | May 2004 | B2 |
| 6761452 | Moravec et al. | Jul 2004 | B2 |
| 6797383 | Nishizawa et al. | Sep 2004 | B2 |
| 6806930 | Moia | Oct 2004 | B2 |
| 6844686 | Schneck et al. | Jan 2005 | B1 |
| 6874888 | Dudai | Apr 2005 | B1 |
| 6891038 | Krongauz et al. | May 2005 | B2 |
| 6986946 | Nishizawa et al. | Jan 2006 | B2 |
| 7008568 | Qin | Mar 2006 | B2 |
| 7097303 | Kumar et al. | Aug 2006 | B2 |
| 7118806 | Nishizawa et al. | Oct 2006 | B2 |
| 7166357 | Kumar et al. | Jan 2007 | B2 |
| 7247262 | Evans et al. | Jul 2007 | B2 |
| 7256921 | Kumar et al. | Aug 2007 | B2 |
| 7262295 | Walters et al. | Aug 2007 | B2 |
| 7320826 | Kumar et al. | Jan 2008 | B2 |
| 7342112 | Kumar et al. | Mar 2008 | B2 |
| 7357503 | Mosse et al. | Apr 2008 | B2 |
| 7416682 | Frigoli et al. | Aug 2008 | B2 |
| 7465415 | Wang et al. | Dec 2008 | B2 |
| 7521004 | Momoda et al. | Apr 2009 | B2 |
| 7557206 | Kumar et al. | Jul 2009 | B2 |
| 7557208 | Walters et al. | Jul 2009 | B2 |
| 7560124 | Kumar | Jul 2009 | B2 |
| 7579022 | Kumar et al. | Aug 2009 | B2 |
| 7582749 | Kumar et al. | Sep 2009 | B2 |
| 8211338 | He | Jul 2012 | B2 |
| 8545984 | He et al. | Oct 2013 | B2 |
| 8697890 | Sukhomlinova et al. | Apr 2014 | B2 |
| 9034219 | He et al. | May 2015 | B2 |
| 20020039627 | Ichihashi et al. | Apr 2002 | A1 |
| 20020090516 | Loshak et al. | Jul 2002 | A1 |
| 20020167639 | Coates et al. | Nov 2002 | A1 |
| 20020180916 | Schadt et al. | Dec 2002 | A1 |
| 20030008958 | Momoda et al. | Jan 2003 | A1 |
| 20030045612 | Misura et al. | Mar 2003 | A1 |
| 20030189684 | Kuntz et al. | Oct 2003 | A1 |
| 20040046927 | Montgomery | Mar 2004 | A1 |
| 20040068071 | Hoff et al. | Apr 2004 | A1 |
| 20040090570 | Kosa et al. | May 2004 | A1 |
| 20040125337 | Boulineau et al. | Jul 2004 | A1 |
| 20040158028 | Buhler | Aug 2004 | A1 |
| 20040185255 | Walters et al. | Sep 2004 | A1 |
| 20040185268 | Kumar et al. | Sep 2004 | A1 |
| 20040186241 | Gemert | Sep 2004 | A1 |
| 20040191520 | Kumar et al. | Sep 2004 | A1 |
| 20040207809 | Blackburn et al. | Oct 2004 | A1 |
| 20040223221 | Sugimura et al. | Nov 2004 | A1 |
| 20040228817 | Simon et al. | Nov 2004 | A1 |
| 20040228818 | Simon et al. | Nov 2004 | A1 |
| 20050003107 | Kumar et al. | Jan 2005 | A1 |
| 20050004361 | Kumar et al. | Jan 2005 | A1 |
| 20050012998 | Kumar et al. | Jan 2005 | A1 |
| 20050146680 | Muisener et al. | Jul 2005 | A1 |
| 20050151926 | Kumar et al. | Jul 2005 | A1 |
| 20050202267 | Ha et al. | Sep 2005 | A1 |
| 20050276767 | Blin et al. | Dec 2005 | A1 |
| 20060022176 | Wang et al. | Feb 2006 | A1 |
| 20070041073 | Kumar et al. | Feb 2007 | A1 |
| 20070131362 | Buchert et al. | Jun 2007 | A1 |
| 20070188698 | Mosse et al. | Aug 2007 | A1 |
| 20070275234 | Lim et al. | Nov 2007 | A1 |
| 20090309076 | He et al. | Dec 2009 | A1 |
| 20090323011 | He et al. | Dec 2009 | A1 |
| 20100014010 | He et al. | Jan 2010 | A1 |
| 20110129678 | He et al. | Jun 2011 | A1 |
| 20110140056 | He et al. | Jun 2011 | A1 |
| 20110143141 | He et al. | Jun 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 2034316 | Jul 1991 | CA |
| 2549471 | Jul 2005 | CA |
| 0313941 | May 1989 | EP |
| 0315224 | May 1989 | EP |
| 0321563 | Jun 1989 | EP |
| 0331233 | Sep 1989 | EP |
| 0336193 | Oct 1989 | EP |
| 0397263 | Nov 1990 | EP |
| 0442166 | Aug 1991 | EP |
| 0446717 | Sep 1991 | EP |
| 0488164 | Jun 1992 | EP |
| 0543678 | May 1993 | EP |
| 0619358 | Oct 1994 | EP |
| 0686685 | Dec 1995 | EP |
| 0686686 | Dec 1995 | EP |
| 0770116 | May 1997 | EP |
| 0772069 | May 1997 | EP |
| 0926146 | Jun 1999 | EP |
| 0965626 | Dec 1999 | EP |
| 0965628 | Dec 1999 | EP |
| 1044979 | Oct 2000 | EP |
| 1162482 | Dec 2001 | EP |
| 1184379 | Mar 2002 | EP |
| 1203967 | May 2002 | EP |
| 1394595 | Mar 2004 | EP |
| 1674460 | Jun 2006 | EP |
| 583842 | Jan 1947 | GB |
| 2169417 | Jul 1986 | GB |
| 2189417 | Oct 1987 | GB |
| 59135428 | Aug 1984 | JP |
| 63175094 | Jul 1988 | JP |
| 63234084 | Sep 1988 | JP |
| 63250381 | Oct 1988 | JP |
| 63250382 | Oct 1988 | JP |
| 63275587 | Nov 1988 | JP |
| 6430744 | Feb 1989 | JP |
| 6490286 | Apr 1989 | JP |
| 1170904 | Jul 1989 | JP |
| 1258681 | Oct 1989 | JP |
| 280490 | Mar 1990 | JP |
| 2101080 | Apr 1990 | JP |
| 2194084 | Jul 1990 | JP |
| 2243694 | Sep 1990 | JP |
| 366692 | Mar 1991 | JP |
| 3137634 | Jun 1991 | JP |
| 3200118 | Sep 1991 | JP |
| 3200218 | Sep 1991 | JP |
| 3221563 | Sep 1991 | JP |
| 3227986 | Oct 1991 | JP |
| 3227988 | Oct 1991 | JP |
| 4117387 | Apr 1992 | JP |
| 4358117 | Dec 1992 | JP |
| 6214195 | Aug 1994 | JP |
| 6295687 | Oct 1994 | JP |
| 6306354 | Nov 1994 | JP |
| 741758 | Feb 1995 | JP |
| 762337 | Mar 1995 | JP |
| 7165762 | Jun 1995 | JP |
| 827155 | Jan 1996 | JP |
| 827461 | Jan 1996 | JP |
| 8157467 | Jun 1996 | JP |
| 8176139 | Jul 1996 | JP |
| 8209119 | Aug 1996 | JP |
| 8295690 | Nov 1996 | JP |
| 973149 | Mar 1997 | JP |
| 9124645 | May 1997 | JP |
| 11322739 | Nov 1999 | JP |
| 2001114775 | Apr 2001 | JP |
| 2001192378 | Jul 2001 | JP |
| 2002194084 | Jul 2002 | JP |
| 2005112772 | Apr 2005 | JP |
| 2005187420 | Jul 2005 | JP |
| 8905464 | Jun 1989 | WO |
| 8911674 | Nov 1989 | WO |
| 9201959 | Feb 1992 | WO |
| 9310112 | May 1993 | WO |
| 9317071 | Sep 1993 | WO |
| 9601684 | Jan 1996 | WO |
| 9601884 | Jan 1996 | WO |
| 9705213 | Feb 1997 | WO |
| 9706455 | Feb 1997 | WO |
| 9710241 | Mar 1997 | WO |
| 9722894 | Jun 1997 | WO |
| 9819207 | May 1998 | WO |
| 9920630 | Apr 1999 | WO |
| 9943666 | Sep 1999 | WO |
| 0015630 | Mar 2000 | WO |
| 0019252 | Apr 2000 | WO |
| 0035902 | Jun 2000 | WO |
| 0077559 | Dec 2000 | WO |
| 0102449 | Jan 2001 | WO |
| 0119813 | Mar 2001 | WO |
| 0155960 | Aug 2001 | WO |
| 0170719 | Sep 2001 | WO |
| 0177122 | Oct 2001 | WO |
| 0229489 | Apr 2002 | WO |
| 02058921 | Aug 2002 | WO |
| 03019270 | Mar 2003 | WO |
| 03032066 | Apr 2003 | WO |
| 2004003107 | Jan 2004 | WO |
| 2004011964 | Feb 2004 | WO |
| 2004041961 | May 2004 | WO |
| 2005005570 | Jan 2005 | WO |
| 2005084826 | Sep 2005 | WO |
| 2005085912 | Sep 2005 | WO |
| 2006060683 | Jun 2006 | WO |
| 2008051420 | May 2008 | WO |
| 2010065393 | Jun 2010 | WO |
| Entry |
|---|
| Chatterjea, “Syntheses of furano compounds. IX. A synthesis of alpha-brazan and the related quinone”, Journal of the Indian Chemical Society, 1956, pp. 447-454, vol. 33, (Abstract Only). |
| Araujo et al.; “Photochromism”; Techniques in Chemistry; 1971; pp. 734-853; vol. III; Chapter 3; Glenn H. Brown; Editor, Wiley-Interscience a Division of John Wiley & Sons, Inc. |
| Atassi et al.; “Reversible photoinduced modifications of polymers doped with photochromes: anisotropy, photo-assisted poling and surface gratings.”; Mol. Cryst. Liq. Cryst.; 1998; pp. 11-22; vol. 315. |
| Bachels et al.; “Novel Photo-Aligned LC-Polmer Wide-View Film for TN Displays”; Eurodisplay; 2002; pp. 183-186. |
| Castellano; “Surface Anchoring of Liquid Crystal Molecules on Various Substrates”; Mol. Cryst. Liq. Cryst.; 1983; pp. 33-41; vol. 94. |
| Chigrinov et al.; “New results on liquid crystal alignment by photopolymerization”; Proceedings of the SPIE—The Internationali Society for Optical Engineering, SPIE; 1995; pp. 130-140; vol. 2409. |
| “Choleric filters and films”; http://web.archive.org/web/20040325025143/http://rolic.com/050application/05223content.htm; Aug. 25, 2004. |
| Dyadyusha et al.; “Light-Induced Planar Orientation of a Nematic Liquid Crystal on an Anisotropic Surface Without Microrelief”; Ukr. fiz. zhurn; 1991; pp. 1059-1062; vol. 36:7. |
| Furrow et al.; “Practical Procedures for the Preparation of N-tert-Butyldimethylsilylhydrazones and Their Use in Modified Wolff-Kishner Reductions and in the Synthesis of Vinyl Halides and gem-Dihalides”; J. Am. Chem. Soc.; 2004; pp. 5436-5445; vol. 126. |
| Hattori et al.; “Facile Construction of the 1-Phenylnaphthyl Skeleton via an Ester-mediated Nucleophilic Aromatic Substitution Reaction. Applications to the Synthesis of Phenylnaphthalide Lignans”; J. Chem. Soc. Perkin Trans.; 1995; pp. 235-241. |
| Hattori et al.; “Practical Synthesis of 4′-Methylbiphenyl-2-carboxylic Acid”; Synthesis; 1995; pp. 41-43. |
| Hikmet et al.; “Gel layers for inducing adjustable pretilt angles in liquid crystal systems”; J. Appl. Phys.; 1991; pp. 1265-1269; vol. 70:3. |
| Huang et al.; “Effect of aligning layer thickness on photo-aligned ferroelectric liquid crystal displays”; Proceedings of the 6th Chinese Optoelectronics Symposium; Hong Kong, China; IEEE; (New York); 2003; pp. 231-234. |
| Ishihara et al.; “Regioselective Friedel-Crafts Acylation of 1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effects of NH Protective Groups and Ring Size”; J. Chem. Soc. Perkin Trans.; 1992, pp. 3401-3406. |
| Ishiyama et al.; “Palladium (0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters”; J. Org. Chem.; 1995; pp. 7508-7510; vol. 60. |
| Kozenkov et al.; “Photoanisotropic Effects in Poly (Vinyl-Cinnamate) Derivatives and Their Applications”; Mol. Cryst. Liq. Cryst.; 2004; pp. 251-267; vol. 409. |
| Kvasnikov et al.; “Birefringence in Polyvinylcinnamate Films Induced by Polarized Light”; Doklady Akademii nauk SSSR; 1977; pp. 633-636; vol. 237:3. |
| Moia et al.; “Optical LLP/LCD Devices: A new Generation of Optical Security Elements”; Proceedings of SPIE: Optical Security and Counterfeit Deterrence, Techniques III; Jan. 27-28, 2000; pp. 196-203; vol. 3973; San Jose, California. |
| Moia; “New coloured optical security elements using Rolic's LLP/LCP technology: devices for 1st to 3rd level inspection”; Proceedings of SPIE: Optical Security and Counterfeit Deterrence Techniques IV; Jan. 23-25, 2002; pp. 194-202; vol. 4677; San Jose, California. |
| Olah; “Friedel-Crafts and Related Reactions”; Interscience Publishers; 1964; pp. 1 vol. 3; Chapter XXXI (Aromatic Ketone Synthesis). |
| “Polymerization” in Hawley's Condensed Chemical Dictionary Thirteenth Edition; 1997; pp. 901-902; published by John Wiley & Sons, Inc., revised by Richard J. Lewis, Sr. |
| Schadt; “Liquid Crystal Displays and Novel Optical Thin Films Enabled by Photo-Alignment”; Mol. Cryst. and Liq. Cryst.; 2001; pp. 151-169; vol. 364. |
| Schadt; “Optics and Applications of Photo-Aligned Liquid Crystalline Surfaces”; Nonlinear Optics; 2000; pp. 1-12; vol. 25. |
| Schadt et al.; “Surface-Induced Parallel Alignment of Liquid Crystals by Lineraly Polymerized Photopolymers”; Jpn. J. Appl. Phys.; 1992; pp. 2155-2164; vol. 31. |
| Seiberle et al.; “Invited Paper: Photo-Aligned Anisotropic Optical Thin Films”; SID 03 Digest, Society of Information Displays; 2003; pp. 1162-1165. |
| Wang et al.; “Addition of Grignard Reagents to Aryl Acid Chlorides: An Efficient Synthesis of Aryl Ketones”; Organic Letters; 2005; pp. 5593-5595; vol. 7:25. |
| Chen et al., “Claisen rearrangement/Baylis-Hillman reaction/ring-closing metathesis as bases for the construction of substituted cyanonaphthalenes”, Tetrahedron, 2007, p. 2824-2828, vol. 63. |
| Flett, “Intensities of some group characteristic infra-red bands”, Spectrochimica Acta, 1962, pp. 1537-1556, vol. 18. |
| Kramer et al., “Development of a Selective Enzyme-Linked Immunosorbent Assay for 1-Naphthol—the Major Metabolite of Carbaryl (1-Naphthyl N-Methylcarbamate)”, Journal of Agricultural Food Chemistry, 1994, pp. 934-943, vol. 42. |
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|---|---|---|---|
| 20180291007 A1 | Oct 2018 | US |
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|---|---|---|---|
| 60484100 | Jul 2003 | US |
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