Facebook Patent | Substituted propane-core monomers and polymers thereof for volume bragg gratings

小编映维 | 分类：Meta | 2022年5月19日

Patent: Substituted propane-core monomers and polymers thereof for volume bragg gratings

Publication Number: 20220153895

Publication Date: 20220519

Applicant: Facebook

Abstract

The disclosure provides recording materials including propane derivatized monomers and polymers for use in volume Bragg gratings, including, but not limited to, volume Bragg gratings for holography applications. Several structures are disclosed for propane derivatized monomers and polymers for use in Bragg gratings applications, leading to materials with higher refractive index, low birefringence, and high transparency. The disclosed propane derivatized monomers and polymers thereof can be used in any volume Bragg gratings materials, including two-stage polymer materials where a matrix is cured in a first step, and then the volume Bragg grating is written by way of a second curing step of a monomer.

Claims

A compound of Formula I: ##STR00079## wherein in Formula I: R is at each independent occurrence hydrogen or a substituent comprising one or more groups selected from optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, optionally substituted epoxide, optionally substituted glycidyl, optionally substituted acrylate, optionally substituted methacrylate, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a, –S(O).sub.tR.sup.a, –S(O).sub.tOR.sup.a, –S(O).sub.tN(R.sup.a).sub.2, –S(O).sub.tN(R.sup.a)C(O)R.sup.a, –O(O)P(OR.sup.a).sub.2, and –O(S)P(OR.sup.a).sub.2; t is 1 or 2; R.sup.a is independently selected at each occurrence from hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, and optionally substituted heteroarylalkyl; and wherein the compound of Formula I comprises at least one R substituent comprising at least one polymerizable or crosslinkable group.
The compound of claim 1, having a Formula IIa or Formula IIb: ##STR00080## wherein in Formula IIa and Formula IIb: R.sub.20 is a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; R.sub.21 and R.sub.22 are each independently an optionally substituted aryl or C(R.sub.23).sub.3; and R.sub.23 is at each independent occurrence is an optionally substituted aryl.
The compound of claim 1, having a Formula III: ##STR00081## wherein in Formula III: R.sub.30 is alkyl; R.sub.31 and R.sub.32 are each independently a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; R.sub.33 is independently a group of one, two, three, four, or five independently selected –SR.sup.a substituents; and L is a linking group selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, (S)P(O–).sub.3, and combinations thereof.
The compound of claim 1, having a Formula IV: ##STR00082## wherein in Formula IV: ##STR00083## is CR.sub.43 or ##STR00084## each R.sub.40, R.sub.41, and R.sub.42 is independently a group of one, two, three, four, or five independently selected substituents, wherein one or more of the substituents comprise ##STR00085## and one or more of the substituents comprise an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; and/or wherein one or more of the substituents comprise ##STR00086## R.sub.43 is H or alkyl; R.sub.44 is a linking group selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, (S)P(O–).sub.3, and combinations thereof; R.sub.45, R.sub.46, and R.sub.48 are each independently optionally substituted aryl; and R.sub.47 is a substituent comprising at least one polymerizable or crosslinkable group.
The compound of claim 1, having a Formula V: ##STR00087## wherein in Formula V: R.sub.50 and R.sub.51 are each independently selected from hydrogen and alkyl; R.sub.52, R.sub.54, R.sub.55, and R.sub.57 are each independently halo; and R.sub.53 and R.sub.56 are each independently a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof.
The compound of claim 1, wherein the substituent comprises one or more linking groups selected from wherein the substituent comprises one or more linking groups selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, and (S)P(O–).sub.3.
The compound of claim 1, wherein the substituent comprises at least an aryl group Ar, wherein Ar is selected from substituted phenyl, substituted naphthyl, substituted anthracenyl, substituted phenanthrenyl, substituted phenalenyl, substituted tetracenyl, substituted chrysenyl, substituted triphenylenyl, and substituted pyrenyl.
The compound of claim 1, wherein the substituent comprises one or more groups selected from ##STR00088##
The compound of claim 1, wherein the substituent comprises one or more groups selected from ##STR00089##
The compound of claim 1, wherein the compound comprises one or more groups selected from: ##STR00090## ##STR00091##
The compound of claim 1, wherein the compound comprises one or more groups selected from: ##STR00092##
The compound of claim 2, wherein the compound is selected from: ##STR00093##
The compound of claim 3, wherein the compound is selected from: ##STR00094##
The compound of claim 4, wherein the compound is selected from: ##STR00095## ##STR00096##
The compound of claim 5, wherein the compound is ##STR00097##
A recording material for writing a volume Bragg grating, the material comprising a resin mixture comprising a first polymer precursor comprising the compound of claim 1, wherein the first polymer precursor is partially or totally polymerized or crosslinked.
A volume Bragg grating recorded on the recording material of claim 16, wherein the grating is characterized by a Q parameter equal to or greater than 1, wherein Q = 2 .times. .pi. .times. .lamda. 0 .times. d n 0 .times. .LAMBDA. 2 ##EQU00005## and wherein .lamda..sub.0 is a recording wavelength, d is the thickness of the recording material, n.sub.0 is a refractive index of the recording material, and .LAMBDA. is a grating constant.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to U.S. Provisional Patent Application No. 63/113,738, filed Nov. 13, 2020, which is incorporated by reference herein in its entirety.

FIELD

[0002] Described herein are recording materials for volume holograms, volume holographic elements, volume holographic gratings, and the like, as well as the volume holograms, volume holographic elements, volume holographic gratings produced by writing or recording such recording materials.

BACKGROUND

[0003] Polymeric substrates are disclosed in the art of holographic recording media, including for example photosensitive polymer films. See, e.g., Smothers et al., “Photopolymers for Holography,” SPIE OE/Laser Conference, 1212-03, Los Angeles, Calif., 1990. The holographic recording media described in this article contain a photoimageable system containing a liquid monomer material (the photoactive monomer) and a photoinitiator (which promotes the polymerization of the monomer upon exposure to light), where the photoimageable system is in an organic polymer host matrix that is substantially inert to the exposure light. During writing (recording) of information into the material (by passing recording light through an array representing data), the monomer polymerizes in the exposed regions. Due to the lowering of the monomer concentration caused by the polymerization, monomer from the dark, unexposed regions of the material diffuses to the exposed regions. See, e.g., Colburn and Haines, “Volume Hologram Formation in Photopolymer Materials,” Appl. Opt. 10, 1636-1641, 1971. The polymerization and resulting diffusion create a refractive index change, referred to as .DELTA.n, thus forming the hologram (holographic grating) representing the data.

[0004] Chain length and degree of polymerization are usually maximized and driven to completion in photopolymer systems used in conventional applications such as coatings, sealants, adhesives, etc., usually by using high light intensities, multifunctional monomers, high concentrations of monomers, heat, etc. Similar approaches were used in holographic recording media known in the art by using organic photopolymer formulations high in monomer concentration. See, for example, U.S. Pat. Nos. 5,874,187 and 5,759,721, disclosing “one-component” organic photopolymer systems. However, such one-component systems typically have large Bragg detuning values if they are not precured with light to some extent.

[0005] Improvements in holographic photopolymer media have been made by separating the formation of a polymeric matrix from the photochemistry used to record holographic information. See, for example, U.S. Pat. Nos. 6,103,454 and 6,482,551, disclosing “two-component” organic photopolymer systems. Two-component organic photopolymer systems allow for more uniform starting conditions (e.g., regarding the recording process), more convenient processing and packaging options, and the ability to obtain higher dynamic range media with less shrinkage or Bragg detuning.

[0006] Such two-component systems have various issues that need improvement. For example, the performance of a holographic photopolymer is determined strongly by how species diffuse during polymerization. Usually, polymerization and diffusion are occurring simultaneously in a relatively uncontrolled fashion within the exposed areas. This leads to several undesirable effects: for example, polymers that are not bound to the matrix after polymerization initiation or termination reactions are free to diffuse out of exposed regions of the film into unexposed areas, which “blurs” the resulting fringes, reducing .DELTA.n and diffraction efficiency of the final hologram. The buildup of .DELTA.n during exposure means that subsequent exposures can scatter light from these gratings, leading to the formation of noise gratings. These create haze and a loss of clarity in the final waveguide display. As described herein, for a series of multiplexed exposures with constant dose/exposure, the first exposures will consume most of the monomer, leading to an exponential decrease in diffraction efficiency with each exposure. A complicated “dose scheduling” procedure is required to balance the diffraction efficiency of all of the holograms.

[0007] Generally, the storage capacity of a holographic medium is proportional to the medium’s thickness. Deposition onto a substrate of a pre-formed matrix material containing the photoimageable system typically requires use of a solvent, and the thickness of the material is therefore limited, e.g., to no more than about 150 .mu.m, to allow enough evaporation of the solvent to attain a stable material and reduce void formation. Thus, the need for solvent removal inhibits the storage capacity of a medium.

[0008] In contrast, in volume holography, the media thickness is generally greater than the fringe spacing, and the Klein-Cook Q parameter is greater than 1. See Klein and Cook, “Unified approach to ultrasonic light diffraction,” IEEE Transaction on Sonics and Ultrasonics, SU-14, 123-134, 1967. Recording mediums formed by polymerizing matrix material in situ from a fluid mixture of organic oligomer matrix precursor and a photoimageable system are also known. Because little or no solvent is typically required for deposition of these matrix materials, greater thicknesses are possible, e.g., 200 .mu.m and above. However, while useful results are obtained by such processes, the possibility exists for reaction between the precursors to the matrix polymer and the photoactive monomer. Such reaction would reduce the refractive index contrast between the matrix and the polymerized photoactive monomer, thereby affecting to an extent the strength of the stored hologram.

SUMMARY

[0009] In some embodiments, the disclosure provides a compound of Formula I:

STR00001

[0010] wherein in Formula I: R is at each independent occurrence hydrogen or a substituent comprising one or more groups selected from optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, optionally substituted epoxide, optionally substituted glycidyl, optionally substituted acrylate, optionally substituted methacrylate, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a, –S(O).sub.tR.sup.a, –S(O).sub.tOR.sup.a, –S(O).sub.tN(R.sup.a).sub.2, –S(O).sub.tN(R.sup.a)C(O)R.sup.a, –O(O)P(OR.sup.a).sub.2, and –O(S)P(OR.sup.a).sub.2; t is 1 or 2; R.sup.a is independently selected at each occurrence from hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, and optionally substituted heteroarylalkyl; and wherein the compound of Formula I comprises at least one R substituent comprising at least one polymerizable or crosslinkable group.

[0011] In one embodiment, the substituent comprises one or more linking groups selected from wherein the substituent comprises one or more linking groups selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, and (S)P(O–).sub.3. In one embodiment, the substituent comprises at least an aryl group Ar, wherein Ar is selected from substituted phenyl, substituted naphthyl, substituted anthracenyl, substituted phenanthrenyl, substituted phenalenyl, substituted tetracenyl, substituted chrysenyl, substituted triphenylenyl, and substituted pyrenyl. In one embodiment, the substituent comprises one or more groups selected from:

STR00002## ##STR00003

In one embodiment, the substituent comprises one or more groups selected from:

STR00004

In one embodiment, the compound comprises one or more groups selected from:

STR00005## ##STR00006

In one embodiment, the compound comprises one or more groups selected from:

STR00007

[0012] In one embodiment, the disclosure provides a compound of Formula IIa or Formula IIb:

STR00008

wherein in Formula IIa and Formula IIb: R.sub.20 is a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; R.sub.21 and R.sub.22 are each independently an optionally substituted aryl or C(R.sub.23).sub.3; and R.sub.23 is at each independent occurrence is an optionally substituted aryl.

[0013] In one embodiment, the compound of Formula IIa or Formula IIb is selected from:

STR00009## ##STR00010

[0014] In one embodiment, the disclosure provides a compound having a Formula III:

STR00011

wherein in Formula III: R.sub.30 is alkyl; R.sub.31 and R.sub.32 are each independently a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; R.sub.33 is independently a group of one, two, three, four, or five independently selected –SR.sup.a substituents; and L is a linking group selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, (S)P(O–).sub.3, and combinations thereof.

[0015] In one embodiment, the compound of Formula III is selected from:

STR00012

[0016] In one embodiment, the disclosure provides a compound having a Formula IV:

STR00013

wherein in Formula IV:

STR00014

is CR.sub.43 or

STR00015

[0017] each R.sub.40, R.sub.41, and R.sub.42 is independently a group of one, two, three, four, or five independently selected substituents, wherein one or more of the substituents comprise

STR00016

and one or more of the substituents comprise an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof; and/or wherein one or more of the substituents comprise

STR00017

R.sub.43 is H or alkyl; R.sub.44 is a linking group selected from –(CH.sub.2)–, –(CH.sub.2).sub.2–, –(CH.sub.2).sub.3–, –(CH.sub.2).sub.4–, –(CH.sub.2).sub.5–, –(CH.sub.2).sub.6–, 1,4 disubstituted phenyl, disubstituted glycidyl, trisubstituted glycidyl, –CH.dbd.CH–, –O–, –C(O)–, –C(O)O–, –OC(O)–, –NH–, –C(O)NH–, –NHC(O)–, –OC(O)NH–, –NHC(O)O–, –SC(O)NH–, –NHC(O)S–, and (S)P(O–).sub.3, and combinations thereof; R.sub.45, R.sub.46, and R.sub.48 are each independently optionally substituted aryl; and R.sub.47 is a substituent comprising at least one polymerizable or crosslinkable group.

[0018] In one embodiment, the compound of Formula IV is selected from:

STR00018## ##STR00019

[0019] In one embodiment, the disclosure provides a compound having a Formula V:

STR00020

wherein in Formula V: R.sub.50 and R.sub.51 are each independently selected from hydrogen and alkyl; R.sub.52, R.sub.54, R.sub.55, and R.sub.57 are each independently halo; and R.sub.53 and R.sub.56 are each independently a substituent comprising an optionally substituted acrylate, an optionally substituted methacrylate, or a combination thereof.

[0020] In one embodiment, the compound of Formula V is:

STR00021

[0021] In one embodiment, the disclosure provides a recording material for writing a volume Bragg grating, the material comprising a resin mixture comprising a first polymer precursor comprising the compound of claim 1, wherein the first polymer precursor is partially or totally polymerized or crosslinked.

[0022] In one embodiment, the disclosure also provides a volume Bragg grating recorded on a recording material disclosed herein, wherein the grating is characterized by a Q parameter equal to or greater than 1, wherein

Q = 2 .times. .pi. .times. .lamda. 0 .times. d n 0 .times. .LAMBDA. 2 ##EQU00001##

[0023] and wherein .lamda..sub.0 is a recording wavelength, d is the thickness of the recording material, n.sub.0 is a refractive index of the recording material, and .LAMBDA. is a grating constant.

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The foregoing summary, as well as the following detailed description of the present disclosure, will be better understood when read in conjunction with the appended drawings.

[0025] FIG. 1 illustrates generic steps for forming a volume Bragg grating (VBG). A raw material can be formed by mixing two different of precursors, e.g., a matrix precursor, and a photopolymerizable imaging precursor. The raw material can be formed into a film by curing or crosslinking, or partially curing or crosslinking the matrix precursor. Finally, holographic exposure initiates the curing or crosslinking of the photopolymerizable precursor which is the main step of the holographic recording process of making a VBG.

[0026] FIG. 2 is a schematic illustrating the various steps included in a controlled radical polymerization for holography applications. The general goals for such applications is the design of a photopolymer material that is sensitive to visible light, produces a large .DELTA.n response, and controls the reaction/diffusion of the photopolymer such that chain transfer and termination reactions are reduced or suppressed. The polymerization reaction that occurs inside traditional photopolymer materials is known as a free radical polymerization, which has several characteristics: radical species are produced immediately upon exposure, radicals initiate polymerization and propagate by adding monomer to chain ends, radicals also react with matrix by hydrogen abstraction and chain transfer reactions, and radicals can terminate by combining with other radicals or reacting with inhibiting species (e.g., O.sub.2).

[0027] FIGS. 3A-3C illustrate generally the concept of using a two-stage photopolymer recording material for volume Bragg gratings, the material including a polymeric matrix (crosslinked lines), and recording, photopolymerizable monomers (circles). As the material is exposed to a light source (arrows, FIG. 3A), the monomer begins to react and polymerize. Ideally, polymerization occurs only in the light exposed areas, leading to a drop in monomer concentration. As the monomer polymerizes, a gradient of monomer concentration is created, resulting in monomer diffusing from high monomer concentration areas, toward low monomer concentration areas (FIG. 3B). As monomer diffuses into exposed regions, stress builds up in the surrounding matrix polymer as it swells and “diffuses” to the dark region (FIG. 3C). If the matrix becomes too stressed and cannot swell to accommodate more monomer, diffusion to exposed areas will stop, even if there is a concentration gradient for unreacted monomer. This typically limits the maximum dynamic range of the photopolymer, since the buildup of .DELTA.n depends on unreacted monomer diffusing into bright regions.

[0028] FIG. 4 illustrates an example of an optical see-through augmented reality system using a waveguide display that includes an optical combiner according to certain embodiments.

[0029] FIG. 5A illustrates an example of a volume Bragg grating. FIG. 5B illustrates the Bragg condition for the volume Bragg grating shown in FIG. 5A.

[0030] FIG. 6A illustrates the recording light beams for recording a volume Bragg grating according to certain embodiments. FIG. 6B is an example of a holography momentum diagram illustrating the wave vectors of recording beams and reconstruction beams and the grating vector of the recorded volume Bragg grating according to certain embodiments.

[0031] FIG. 7 illustrates an example of a holographic recording system for recording holographic optical elements according to certain embodiments.

DETAILED DESCRIPTION

[0032] Volume gratings, usually produced by holographic technique and known as volume holographic gratings (VHG), volume Bragg gratings (VBG), or volume holograms, are diffractive optical elements based on material with periodic phase or absorption modulation throughout the entire volume of the material. When an incident light satisfies Bragg condition, it is diffracted by the grating. The diffraction occurs within a range of wavelength and incidence angles. In turn, the grating has no effect on the light from the off-Bragg angular and spectral range. These gratings also have multiplexing ability. Due to these properties, VHG/VBG are of great interest for various applications in optics such as data storage and diffractive optical elements for displays, fiber optic communication, spectroscopy, etc.

[0033] Achieving of the Bragg regime of a diffraction grating is usually determined by Klein parameter Q:

Q = 2 .times. .pi..lamda. .times. .times. d n .times. .LAMBDA. 2 , ##EQU00002##

where d is a thickness of the grating, .lamda. is the wavelength of light, .LAMBDA. is the grating period, and n is the refractive index of the recording medium. As a rule, Bragg conditions are achieved if Q>>1, typically, Q.gtoreq.10. Thus, to meet Bragg conditions, thickness of diffraction grating should be higher than some value determined by parameters of grating, recording medium and light. Because of this, VBG are also called thick gratings. On the contrary, gratings with Q<1 are considered thin, which typically demonstrates many diffraction orders (Raman-Nath diffraction regime).

Definitions

[0034] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this disclosure belongs. All patents and publications referred to herein are incorporated by reference in their entireties.

[0035] When ranges are used herein to describe, for example, physical or chemical properties such as molecular weight or chemical formulae, all combinations and subcombinations of ranges and specific embodiments therein are intended to be included. Use of the term “about” when referring to a number or a numerical range means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error), and thus the number or numerical range may vary. The variation is typically from 0% to 15%, or from 0% to 10%, or from 0% to 5% of the stated number or numerical range. The term “including” (and related terms such as “comprise” or “comprises” or “having” or “including”) includes those embodiments such as, for example, an embodiment of any composition of matter, method or process that “consist of” or “consist essentially of” the described features.

[0036] As used herein, the term “light source” refers to any source of electromagnetic radiation of any wavelength. In some embodiments, a light source can be a laser of a particular wavelength.

[0037] As used herein, the term “photoinitiating light source” refers to a light source that activates a photoinitiator, a photoactive polymerizable material, or both. Photoinitiating light sources include recording light, but are not so limited.

[0038] As used herein, the term “spatial light intensity” refers to a light intensity distribution or patterns of varying light intensity within a given volume of space.

[0039] As used herein, the terms “volume Bragg grating,” “volume holographic grating,” “holographic grating,” and “hologram,” are interchangeably used to refer to a recorded interference pattern formed when a signal beam and a reference beam interfere with each other. In some embodiments, and in cases where digital data is recorded, the signal beam is encoded with a spatial light modulator.

[0040] As used herein, the term “holographic recording” refers to a holographic grating after it is recorded in the holographic recording medium.

[0041] As used herein, the term “holographic recording medium” refers to an article that is capable of recording and storing, in three dimensions, one or more holographic gratings. In some embodiments, the term refers to an article that is capable of recording and storing, in three dimensions, one or more holographic gratings as one or more pages as patterns of varying refractive index imprinted into an article.

[0042] As used herein, the term “data page” or “page” refers to the conventional meaning of data page as used with respect to holography. For example, a data page may be a page of data, one or more pictures, etc., to be recorded in a holographic recording medium, such as an article described herein.

[0043] As used herein, the term “recording light” refers to a light source used to record into a holographic medium. The spatial light intensity pattern of the recording light is what is recorded. Thus, if the recording light is a simple noncoherent beam of light, then a waveguide may be created, or if it is two interfering laser beams, then interference patterns will be recorded.

[0044] As used herein, the term “recording data” refers to storing holographic representations of one or more pages as patterns of varying refractive index.

[0045] As used herein, the term “reading data” refers to retrieving data stored as holographic representations.

[0046] As used herein, the term “exposure” refers to when a holographic recording medium was exposed to recording light, e.g., when the holographic grating was recorded in the medium.

[0047] As used herein, the terms “time period of exposure” and “exposure time” refer interchangeably to how long the holographic recording medium was exposed to recording light, e.g., how long the recording light was on during the recording of a holographic grating in the holographic recording medium. “Exposure time” can refer to the time required to record a single hologram or the cumulative time for recording a plurality of holograms in a given volume.

[0048] As used herein, the term “schedule” refers to the pattern, plan, scheme, sequence, etc., of the exposures relative to the cumulative exposure time in recording holographic gratings in a medium. In general, the schedule allows one to predict the time (or light energy) needed for each single exposure, in a set of plural exposures, to give a predetermined diffraction efficiency.

[0049] As used herein, the term “function” when used with the term “schedule” refers to a graphical plot or mathematical expression that defines or describes a schedule of exposures versus cumulative exposure time in recording plural holographic gratings.

[0050] As used herein, the term “substantially linear function” when used with the term “schedule” refers to a graphical plot of the schedule of exposures versus exposure time that provides a straight line or substantially a straight line.

[0051] As used herein, the term “support matrix” refers to the material, medium, substance, etc., in which the polymerizable component is dissolved, dispersed, embedded, enclosed, etc. In some embodiments, the support matrix is typically a low T.sub.g polymer. The polymer may be organic, inorganic, or a mixture of the two. Without being particularly limited, the polymer may be a thermoset or thermoplastic.

[0052] As used herein, the term “different form” refers to an article of the present disclosure being processed to form a product having a different form such as processing an article comprising a block of material, powder of material, chips of material, etc., into a molded product, a sheet, a free flexible film, a stiff card, a flexible card, an extruded product, a film deposited on a substrate, etc.

[0053] As used herein, the term “particle material” refers to a material that is made by grinding, shredding, fragmenting or otherwise subdividing an article into smaller components or to a material that is comprised of small components such as a powder.

[0054] As used herein, the term “free flexible film” refers to a thin sheet of flexible material that maintains its form without being supported on a substrate. Examples of free flexible films include, without limitation, various types of plastic wraps used in food storage.

[0055] As used herein, the term “stiff article” refers to an article that may crack or crease when bent. Stiff articles include, without limitation, plastic credit cards, DVDs, transparencies, wrapping paper, shipping boxes, etc.

[0056] As used herein, the term “volatile compound” refers to any chemical with a high vapor pressure and/or a boiling point below about 150.degree. C. Examples of volatile compounds include: acetone, methylene chloride, toluene, etc. An article, mixture or component is “volatile compound free” if the article, mixture or component does not include a volatile compound.

[0057] As used herein, the term “oligomer” refers to a polymer having a limited number of repeating units, for example, but without limitation, approximately 30 repeat units or less, or any large molecule able to diffuse at least about 100 nm in approximately 2 minutes at room temperature when dissolved in an article of the present disclosure. Such oligomers may contain one or more polymerizable groups whereby the polymerizable groups may be the same or different from other possible monomers in the polymerizable component. Furthermore, when more than one polymerizable group is present on the oligomer, they may be the same or different. Additionally, oligomers may be dendritic. Oligomers are considered herein to be photoactive monomers, although they are sometimes referred to as “photoactive oligomer(s)”.

[0058] As used herein, the term “photopolymerization” refers to any polymerization reaction caused by exposure to a photoinitiating light source.

[0059] As used herein, the term “resistant to further polymerization” refers to the unpolymerized portion of the polymerizable component having a deliberately controlled and substantially reduced rate of polymerization when not exposed to a photoinitiating light source such that dark reactions are minimized, reduced, diminished, eliminated, etc. A substantial reduction in the rate of polymerization of the unpolymerized portion of the polymerizable component according to the present disclosure can be achieved by any suitable composition, compound, molecule, method, mechanism, etc., or any combination thereof; including using one or more of the following: (1) a polymerization retarder; (2) a polymerization inhibitor; (3) a chain transfer agent; (4) metastable reactive centers; (5) a light or heat labile phototerminator; (6) photo-acid generators, photo-base generators or photogenerated radicals; (7) polarity or solvation effects; (8) counter ion effects; and (9) changes in monomer reactivity.

[0060] As used herein, the term “substantially reduced rate” refers to a lowering of the polymerization rate to a rate approaching zero, and ideally a rate of zero, within seconds after the photoinitiating light source is off or absent. The rate of polymerization should typically be reduced enough to prevent the loss in fidelity of previously recorded holograms.

[0061] As used herein, the term “dark reaction” refers to any polymerization reaction that occurs in absence of a photoinitiating light source. In some embodiments, and without limitation, dark reactions can deplete unused monomer, can cause loss of dynamic range, can cause noise gratings, can cause stray light gratings, or can cause unpredictability in the scheduling used for recording additional holograms.

[0062] As used herein, the term “free radical polymerization” refers to any polymerization reaction that is initiated by any molecule comprising a free radical or radicals.

[0063] As used herein, the term “cationic polymerization” refers to any polymerization reaction that is initiated by any molecule comprising a cationic moiety or moieties.

[0064] As used herein, the term “anionic polymerization” refers to any polymerization reaction that is initiated by any molecule comprising an anionic moiety or moieties.

[0065] As used herein, the term “photoinitiator” refers to the conventional meaning of the term photoinitiator and also refers to sensitizers and dyes. In general, a photoinitiator causes the light initiated polymerization of a material, such as a photoactive oligomer or monomer, when the material containing the photoinitiator is exposed to light of a wavelength that activates the photoinitiator, e.g., a photoinitiating light source. The photoinitiator may refer to a combination of components, some of which individually are not light sensitive, yet in combination are capable of curing the photoactive oligomer or monomer, examples of which include a dye/amine, a sensitizer/iodonium salt, a dye/borate salt, etc.

[0066] As used herein, the term “photoinitiator component” refers to a single photoinitiator or a combination of two or more photoinitiators. For example, two or more photoinitiators may be used in the photoinitiator component of the present disclosure to allow recording at two or more different wavelengths of light.

[0067] As used herein, the term “polymerizable component” refers to one or more photoactive polymerizable materials, and possibly one or more additional polymerizable materials, e.g., monomers and/or oligomers, that are capable of forming a polymer.

[0068] As used herein, the term “polymerizable moiety” refers to a chemical group capable of participating in a polymerization reaction, at any level, for example, initiation, propagation, etc. Polymerizable moieties include, but are not limited to, addition polymerizable moieties and condensation polymerizable moieties. Polymerizable moieties include, but are not limited to, double bonds, triple bonds, and the like.

[0069] As used herein, the term “photoactive polymerizable material” refers to a monomer, an oligomer and combinations thereof that polymerize in the presence of a photoinitiator that has been activated by being exposed to a photoinitiating light source, e.g., recording light. In reference to the functional group that undergoes curing, the photoactive polymerizable material comprises at least one such functional group. It is also understood that there exist photoactive polymerizable materials that are also photoinitiators, such as N-methylmaleimide, derivatized acetophenones, etc., and that in such a case, it is understood that the photoactive monomer and/or oligomer of the present disclosure may also be a photoinitiator.

[0070] As used herein, the term “photopolymer” refers to a polymer formed by one or more photoactive polymerizable materials, and possibly one or more additional monomers and/or oligomers.

[0071] As used herein, the term “polymerization retarder” refers to one or more compositions, compounds, molecules, etc., that are capable of slowing, reducing, etc., the rate of polymerization while the photoinitiating light source is off or absent, or inhibiting the polymerization of the polymerizable component when the photoinitiating light source is off or absent. A polymerization retarder is typically slow to react with a radical (compared to an inhibitor), thus while the photoinitiating light source is on, polymerization continues at a reduced rate because some of the radicals are effectively terminated by the retarder. In some embodiments, at high enough concentrations, a polymerization retarder can potentially behave as a polymerization inhibitor. In some embodiments, it is desirable to be within the concentration range that allows for retardation of polymerization to occur, rather than inhibition of polymerization.

[0072] As used herein, the term “polymerization inhibitor” refers to one or more compositions, compounds, molecules, etc., that are capable of inhibiting or substantially inhibiting the polymerization of the polymerizable component when the photoinitiating light source is on or off. Polymerization inhibitors typically react very quickly with radicals and effectively stop a polymerization reaction. Inhibitors cause an inhibition time during which little to no photopolymer forms, e.g., only very small chains. Typically, photopolymerization occurs only after nearly 100% of the inhibitor is reacted.

[0073] As used herein, the term “chain transfer agent” refers to one or more compositions, compounds, molecules, etc. that are capable of interrupting the growth of a polymeric molecular chain by formation of a new radical that may react as a new nucleus for forming a new polymeric molecular chain. Typically, chain transfer agents cause the formation of a higher proportion of shorter polymer chains, relative to polymerization reactions that occur in the absence of chain transfer agents. In some embodiments, certain chain transfer agents can behave as retarders or inhibitors if they do not efficiently reinitiate polymerization.

[0074] As used herein, the term “metastable reactive centers” refers to one or more compositions, compounds, molecules, etc., that have the ability to create pseudo-living radical polymerizations with certain polymerizable components. It is also understood that infrared light or heat may be used to activate metastable reactive centers towards polymerization.

[0075] As used herein, the term “light or heat labile phototerminators” refers to one or more compositions, compounds, components, materials, molecules, etc., capable of undergoing reversible termination reactions using a light source and/or heat.

[0076] As used herein, the terms “photo-acid generators,” “photo-base generators,” and “photogenerated radicals,” refer to one or more compositions, compounds, molecules, etc., that, when exposed to a light source, generate one or more compositions, compounds, molecules, etc., that are acidic, basic, or a free radical.

[0077] As used herein, the term “polarity or solvation effects” refers to an effect or effects that the solvent or the polarity of the medium has on the polymerization rate. This effect is most pronounced for ionic polymerizations where the proximity of the counter ion to the reactive chain end influences the polymerization rate.

[0078] As used herein, the term “counter ion effects” refers to the effect that counter ion, in ionic polymerizations, has on the kinetic chain length. Good counter ions allow for very long kinetic chain lengths, whereas poor counter ions tend to collapse with the reactive chain end, thus terminating the kinetic chain (e.g., causing smaller chains to be formed).

[0079] As used herein, the term “plasticizer” refers to the conventional meaning of the term plasticizer. In general, a plasticizer is a compound added to a polymer both to facilitate processing and to increase the flexibility and/or toughness of a product by internal modification (solvation) of a polymer molecule.

[0080] As used herein, the term “thermoplastic” refers to the conventional meaning of thermoplastic, e.g., a composition, compound, substance, etc., that exhibits the property of a material, such as a high polymer, that softens when exposed to heat and generally returns to its original condition when cooled to room temperature. Examples of thermoplastics include, but are not limited to: poly(methyl vinyl ether-alt-maleic anhydride), poly(vinyl acetate), poly(styrene), poly(propylene), poly(ethylene oxide), linear nylons, linear polyesters, linear polycarbonates, linear polyurethanes, etc.

[0081] As used herein, the term “room temperature thermoplastic” refers to a thermoplastic that is solid at room temperature, e.g., will not cold flow at room temperature.

[0082] As used herein, the term “room temperature” refers to the commonly accepted meaning of room temperature.

[0083] As used herein, the term “thermoset” refers to the conventional meaning of thermoset, e.g., a composition, compound, substance, etc., that is crosslinked such that it does not have a melting temperature. Examples of thermosets are crosslinked poly(urethanes), crosslinked poly(acrylates), crosslinked poly(styrene), etc.

[0084] Unless otherwise stated, the chemical structures depicted herein are intended to include compounds which differ only in the presence of one or more isotopically enriched atoms. For example, compounds where one or more hydrogen atoms is replaced by deuterium or tritium, or where one or more carbon atoms is replaced by .sup.13C- or .sup.14C-enriched carbons, are within the scope of this disclosure.

[0085] “Alkyl” refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to ten carbon atoms (e.g., (C.sub.1-10)alkyl or C.sub.1-10 alkyl). Whenever it appears herein, a numerical range such as “1 to 10” refers to each integer in the given range–e.g., “1 to 10 carbon atoms” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms, although the definition is also intended to cover the occurrence of the term “alkyl” where no numerical range is specifically designated. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl and decyl. The alkyl moiety may be attached to the rest of the molecule by a single bond, such as for example, methyl (Me), ethyl (Et), n-propyl (Pr), 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl) and 3-methylhexyl. Unless stated otherwise specifically in the specification, an alkyl group is optionally substituted by one or more of substituents which are independently heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2 where each R.sup.a is independently hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0086] “Alkylaryl” refers to an -(alkyl)aryl radical where aryl and alkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for aryl and alkyl respectively.

[0087] “Alkylhetaryl” refers to an -(alkyl)hetaryl radical where hetaryl and alkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for aryl and alkyl respectively.

[0088] “Alkylheterocycloalkyl” refers to an -(alkyl) heterocyclyl radical where alkyl and heterocycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for heterocycloalkyl and alkyl respectively.

[0089] An “alkene” moiety refers to a group consisting of at least two carbon atoms and at least one carbon-carbon double bond, and an “alkyne” moiety refers to a group consisting of at least two carbon atoms and at least one carbon-carbon triple bond. The alkyl moiety, whether saturated or unsaturated, may be branched, straight chain, or cyclic.

[0090] “Alkenyl” refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond, and having from two to ten carbon atoms (e.g., (C.sub.2-10)alkenyl or C.sub.2-10 alkenyl). Whenever it appears herein, a numerical range such as “2 to 10” refers to each integer in the given range–e.g., “2 to 10 carbon atoms” means that the alkenyl group may consist of 2 carbon atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms. The alkenyl moiety may be attached to the rest of the molecule by a single bond, such as for example, ethenyl (e.g., vinyl), prop-1-enyl (e.g., allyl), but-1-enyl, pent-1-enyl and penta-1,4-dienyl. Unless stated otherwise specifically in the specification, an alkenyl group is optionally substituted by one or more substituents which are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0091] “Alkenyl-cycloalkyl” refers to an -(alkenyl)cycloalkyl radical where alkenyl and cycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for alkenyl and cycloalkyl respectively.

[0092] “Alkynyl” refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to ten carbon atoms (e.g., (C.sub.2-10)alkynyl or C.sub.2-10 alkynyl). Whenever it appears herein, a numerical range such as “2 to 10” refers to each integer in the given range–e.g., “2 to 10 carbon atoms” means that the alkynyl group may consist of 2 carbon atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms. The alkynyl may be attached to the rest of the molecule by a single bond, for example, ethynyl, propynyl, butynyl, pentynyl and hexynyl. Unless stated otherwise specifically in the specification, an alkynyl group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0093] “Alkynyl-cycloalkyl” refers to an -(alkynyl)cycloalkyl radical where alkynyl and cycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for alkynyl and cycloalkyl respectively.

[0094] “Carboxaldehyde” refers to a –(C.dbd.O)H radical.

[0095] “Carboxyl” refers to a –(C.dbd.O)OH radical.

[0096] “Cyano” refers to a –CN radical.

[0097] “Cycloalkyl” refers to a monocyclic or polycyclic radical that contains only carbon and hydrogen, and may be saturated, or partially unsaturated. Cycloalkyl groups include groups having from 3 to 10 ring atoms (e.g. (C.sub.3-10)cycloalkyl or C.sub.3-10 cycloalkyl). Whenever it appears herein, a numerical range such as “3 to 10” refers to each integer in the given range–e.g., “3 to 10 carbon atoms” means that the cycloalkyl group may consist of 3 carbon atoms, etc., up to and including 10 carbon atoms. Illustrative examples of cycloalkyl groups include, but are not limited to the following moieties: cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and the like. Unless stated otherwise specifically in the specification, a cycloalkyl group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0098] “Cycloalkyl-alkenyl” refers to a -(cycloalkyl)alkenyl radical where cycloalkyl and alkenyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for cycloalkyl and alkenyl, respectively.

[0099] “Cycloalkyl-heterocycloalkyl” refers to a -(cycloalkyl)heterocycloalkyl radical where cycloalkyl and heterocycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for cycloalkyl and heterocycloalkyl, respectively.

[0100] “Cycloalkyl-heteroaryl” refers to a -(cycloalkyl)heteroaryl radical where cycloalkyl and heteroaryl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for cycloalkyl and heteroaryl, respectively.

[0101] The term “alkoxy” refers to the group –O-alkyl, including from 1 to 8 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy and cyclohexyloxy. “Lower alkoxy” refers to alkoxy groups containing one to six carbons.

[0102] The term “substituted alkoxy” refers to alkoxy where the alkyl constituent is substituted (e.g., –O-(substituted alkyl)). Unless stated otherwise specifically in the specification, the alkyl moiety of an alkoxy group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0103] The term “alkoxycarbonyl” refers to a group of the formula (alkoxy)(C.dbd.O)– attached through the carbonyl carbon where the alkoxy group has the indicated number of carbon atoms. Thus a (C.sub.1-6)alkoxycarbonyl group is an alkoxy group having from 1 to 6 carbon atoms attached through its oxygen to a carbonyl linker. “Lower alkoxycarbonyl” refers to an alkoxycarbonyl group where the alkoxy group is a lower alkoxy group.

[0104] The term “substituted alkoxycarbonyl” refers to the group (substituted alkyl)-O–C(O)– where the group is attached to the parent structure through the carbonyl functionality. Unless stated otherwise specifically in the specification, the alkyl moiety of an alkoxycarbonyl group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0105] “Acyl” refers to the groups (alkyl)-C(O)–, (aryl)-C(O)–, (heteroaryl)-C(O)–, (heteroalkyl)-C(O)– and (heterocycloalkyl)-C(O)–, where the group is attached to the parent structure through the carbonyl functionality. If the R radical is heteroaryl or heterocycloalkyl, the hetero ring or chain atoms contribute to the total number of chain or ring atoms. Unless stated otherwise specifically in the specification, the alkyl, aryl or heteroaryl moiety of the acyl group is optionally substituted by one or more substituents which are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.b (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0106] “Acyloxy” refers to a R(C.dbd.O)O– radical where R is alkyl, aryl, heteroaryl, heteroalkyl or heterocycloalkyl, which are as described herein. If the R radical is heteroaryl or heterocycloalkyl, the hetero ring or chain atoms contribute to the total number of chain or ring atoms. Unless stated otherwise specifically in the specification, the R of an acyloxy group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0107] “Amino” or “amine” refers to a –N(R.sup.a).sub.2 radical group, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl, unless stated otherwise specifically in the specification. When a –N(R.sup.a).sub.2 group has two R.sup.a substituents other than hydrogen, they can be combined with the nitrogen atom to form a 4-, 5-, 6- or 7-membered ring. For example, –N(R.sup.a).sub.2 is intended to include, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. Unless stated otherwise specifically in the specification, an amino group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0108] The term “substituted amino” also refers to N-oxides of the groups –NHR.sup.d, and –NR.sup.dR.sup.d each as described above. N-oxides can be prepared by treatment of the corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid.

[0109] “Amide” or “amido” refers to a chemical moiety with formula –C(O)N(R).sub.2 or –NHC(O)R, where R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon), each of which moiety may itself be optionally substituted. The R.sub.2 of –N(R).sub.2 of the amide may optionally be taken together with the nitrogen to which it is attached to form a 4-, 5-, 6- or 7-membered ring. Unless stated otherwise specifically in the specification, an amido group is optionally substituted independently by one or more of the substituents as described herein for alkyl, cycloalkyl, aryl, heteroaryl, or heterocycloalkyl. An amide may be an amino acid or a peptide molecule attached to a compound disclosed herein, thereby forming a prodrug. The procedures and specific groups to make such amides are known to those of skill in the art and can readily be found in seminal sources such as Greene and Wuts, Protective Groups in Organic Synthesis, 3.sup.rd Ed., John Wiley & Sons, New York, N.Y., 1999, which is incorporated herein by reference in its entirety.

[0110] “Aromatic” or “aryl” or “Ar” refers to an aromatic radical with six to ten ring atoms (e.g., C.sub.6-C.sub.10 aromatic or C.sub.6-C.sub.10 aryl) which has at least one ring having a conjugated pi electron system which is carbocyclic (e.g., phenyl, fluorenyl, and naphthyl). Bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals. Bivalent radicals derived from univalent polycyclic hydrocarbon radicals whose names end in “-yl” by removal of one hydrogen atom from the carbon atom with the free valence are named by adding “-idene” to the name of the corresponding univalent radical, e.g., a naphthyl group with two points of attachment is termed naphthylidene. Whenever it appears herein, a numerical range such as “6 to 10” refers to each integer in the given range; e.g., “6 to 10 ring atoms” means that the aryl group may consist of 6 ring atoms, 7 ring atoms, etc., up to and including 10 ring atoms. The term includes monocyclic or fused-ring polycyclic (e.g., rings which share adjacent pairs of ring atoms) groups. Unless stated otherwise specifically in the specification, an aryl moiety is optionally substituted by one or more substituents which are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl. It is understood that a substituent R attached to an aromatic ring at an unspecified position,

STR00022

includes one or more, and up to the maximum number of possible substituents.

[0111] The term “aryloxy” refers to the group –O-aryl.

[0112] The term “substituted aryloxy” refers to aryloxy where the aryl substituent is substituted (e.g., –O-(substituted aryl)). Unless stated otherwise specifically in the specification, the aryl moiety of an aryloxy group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0113] “Aralkyl” or “arylalkyl” refers to an (aryl)alkyl-radical where aryl and alkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for aryl and alkyl respectively.

[0114] “Ester” refers to a chemical radical of formula –COOR, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon). The procedures and specific groups to make esters are known to those of skill in the art and can readily be found in seminal sources such as Greene and Wuts, Protective Groups in Organic Synthesis, 3.sup.rd Ed., John Wiley & Sons, New York, N.Y., 1999, which is incorporated herein by reference in its entirety. Unless stated otherwise specifically in the specification, an ester group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0115] “Fluoroalkyl” refers to an alkyl radical, as defined above, that is substituted by one or more fluoro radicals, as defined above, for example, trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, and the like. The alkyl part of the fluoroalkyl radical may be optionally substituted as defined above for an alkyl group.

[0116] “Halo,” “halide,” or, alternatively, “halogen” is intended to mean fluoro, chloro, bromo or iodo. The terms “haloalkyl,” “haloalkenyl,” “haloalkynyl,” and “haloalkoxy” include alkyl, alkenyl, alkynyl and alkoxy structures that are substituted with one or more halo groups or with combinations thereof. For example, the terms “fluoroalkyl” and “fluoroalkoxy” include haloalkyl and haloalkoxy groups, respectively, in which the halo is fluorine.

[0117] “Heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” refer to optionally substituted alkyl, alkenyl and alkynyl radicals and which have one or more skeletal chain atoms selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus or combinations thereof. A numerical range may be given–e.g., C.sub.1-C.sub.4 heteroalkyl which refers to the chain length in total, which in this example is 4 atoms long. A heteroalkyl group may be substituted with one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0118] “Heteroalkylaryl” refers to an -(heteroalkyl)aryl radical where heteroalkyl and aryl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for heteroalkyl and aryl, respectively.

[0119] “Heteroalkylheteroaryl” refers to an -(heteroalkyl)heteroaryl radical where heteroalkyl and heteroaryl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for heteroalkyl and heteroaryl, respectively.

[0120] “Heteroalkylheterocycloalkyl” refers to an -(heteroalkyl)heterocycloalkyl radical where heteroalkyl and heterocycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for heteroalkyl and heterocycloalkyl, respectively.

[0121] “Heteroalkylcycloalkyl” refers to an -(heteroalkyl)cycloalkyl radical where heteroalkyl and cycloalkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for heteroalkyl and cycloalkyl, respectively.

[0122] “Heteroaryl” or “heteroaromatic” or “HetAr” refers to a 5- to 18-membered aromatic radical (e.g., C.sub.5-C.sub.13 heteroaryl) that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, and which may be a monocyclic, bicyclic, tricyclic or tetracyclic ring system. Whenever it appears herein, a numerical range such as “5 to 18” refers to each integer in the given range–e.g., “5 to 18 ring atoms” means that the heteroaryl group may consist of 5 ring atoms, 6 ring atoms, etc., up to and including 18 ring atoms. Bivalent radicals derived from univalent heteroaryl radicals whose names end in “-yl” by removal of one hydrogen atom from the atom with the free valence are named by adding “-idene” to the name of the corresponding univalent radical–e.g., a pyridyl group with two points of attachment is a pyridylidene. A N-containing “heteroaromatic” or “heteroaryl” moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. The polycyclic heteroaryl group may be fused or non-fused. The heteroatom(s) in the heteroaryl radical are optionally oxidized. One or more nitrogen atoms, if present, are optionally quaternized. The heteroaryl may be attached to the rest of the molecule through any atom of the ring(s). Examples of heteroaryls include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzindolyl, 1,3-benzodioxolyl, benzofuranyl, benzooxazolyl, benzo[d]thiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzoxazolyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzofurazanyl, benzothiazolyl, benzothienyl(benzothiophenyl), benzothieno[3,2-d]pyrimidinyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl, cinnolinyl, cyclopenta[d]pyrimidinyl, 6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidinyl, 5,6-dihydrobenzo[h]quinazolinyl, 5,6-dihydrobenzo[h]cinnolinyl, 6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridazinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furazanyl, furanonyl, furo[3,2-c]pyridinyl, 5,6,7,8,9,10-hexahydrocycloocta[d]pyrimidinyl, 5,6,7,8,9,10-hexahydrocycloocta[d]pyridazinyl, 5,6,7,8,9,10-hexahydrocycloocta[d]pyridinyl, isothiazolyl, imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indolinyl, isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, 5,8-methano-5,6,7,8-tetrahydroquinazolinyl, naphthyridinyl, 1,6-naphthyridinonyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 5,6,6a,7,8,9,10,10a-octahydrobenzo[h]quinazolinyl, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrrolyl, pyrazolyl, pyrazolo[3,4-d]pyrimidinyl, pyridinyl, pyrido[3,2-d]pyrimidinyl, pyrido[3,4-d]pyrimidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrrolyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, 5,6,7,8-tetrahydroquinazolinyl, 5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidinyl, 6,7,8,9-tetrahydro-5H-cyclohepta[4,5]thieno[2,3-d]pyrimidinyl, 5,6,7,8-tetrahydropyrido[4,5-c]pyridazinyl, thiazolyl, thiadiazolyl, thiapyranyl, triazolyl, tetrazolyl, triazinyl, thieno[2,3-d]pyrimidinyl, thieno[3,2-d]pyrimidinyl, thieno[2,3-c]pyridinyl, and thiophenyl (e.g., thienyl). Unless stated otherwise specifically in the specification, a heteroaryl moiety is optionally substituted by one or more substituents which are independently: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0123] Substituted heteroaryl also includes ring systems substituted with one or more oxide (–O–) substituents, such as, for example, pyridinyl N-oxides.

[0124] “Heteroarylalkyl” refers to a moiety having an aryl moiety, as described herein, connected to an alkylene moiety, as described herein, where the connection to the remainder of the molecule is through the alkylene group.

[0125] “Heterocycloalkyl” refers to a stable 3- to 18-membered non-aromatic ring radical that comprises two to twelve carbon atoms and from one to six heteroatoms selected from nitrogen, oxygen and sulfur. Whenever it appears herein, a numerical range such as “3 to 18” refers to each integer in the given range–e.g., “3 to 18 ring atoms” means that the heterocycloalkyl group may consist of 3 ring atoms, 4 ring atoms, etc., up to and including 18 ring atoms. Unless stated otherwise specifically in the specification, the heterocycloalkyl radical is a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which may include fused or bridged ring systems. The heteroatoms in the heterocycloalkyl radical may be optionally oxidized. One or more nitrogen atoms, if present, are optionally quaternized. The heterocycloalkyl radical is partially or fully saturated. The heterocycloalkyl may be attached to the rest of the molecule through any atom of the ring(s). Examples of such heterocycloalkyl radicals include, but are not limited to, dioxolanyl, thienyl[1,3]dithianyl, decahydroisoquinolyl, imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl, piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl, quinuclidinyl, thiazolidinyl, tetrahydrofuryl, trithianyl, tetrahydropyranyl, thiomorpholinyl, thiamorpholinyl, 1-oxo-thiomorpholinyl, and 1,1-dioxo-thiomorpholinyl. Unless stated otherwise specifically in the specification, a heterocycloalkyl moiety is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, –OR.sup.a, –SR.sup.a, –OC(O)–R.sup.a, –N(R.sup.a).sub.2, –C(O)R.sup.a, –C(O)OR.sup.a, –C(O)SR.sup.a, –SC(O)R.sup.a, –OC(O)N(R.sup.a).sub.2, –C(O)N(R.sup.a).sub.2, –N(R.sup.a)C(O)OR.sup.a, –N(R.sup.a)C(O)R.sup.a, –N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, –N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tR.sup.a (where t is 1 or 2), –S(O).sub.tOR.sup.a (where t is 1 or 2), –S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), –S(O).sub.tN(R.sup.a)C(O)R.sup.a (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0126] “Heterocycloalkyl” also includes bicyclic ring systems where one non-aromatic ring, usually with 3 to 7 ring atoms, contains at least 2 carbon atoms in addition to 1-3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, as well as combinations including at least one of the foregoing heteroatoms; and the other ring, usually with 3 to 7 ring atoms, optionally contains 1-3 heteroatoms independently selected from oxygen, sulfur, and nitrogen and is not aromatic.

[0127] “Nitro” refers to the –NO.sub.2 radical.

[0128] “Oxa” refers to the –O– radical.

[0129] “Oxo” refers to the .dbd.O radical.

[0130] “Isomers” are different compounds that have the same molecular formula. “Stereoisomers” are isomers that differ only in the way the atoms are arranged in space–e.g., having a different stereochemical configuration. “Enantiomers” are a pair of stereoisomers that are non-superimposable mirror images of each other. A 1:1 mixture of a pair of enantiomers is a “racemic” mixture. The term “(.+-.)” is used to designate a racemic mixture where appropriate. “Diastereoisomers” are stereoisomers that have at least two asymmetric atoms, but which are not mirror-images of each other. The absolute stereochemistry is specified according to the Cahn-Ingold-Prelog R-S system. When a compound is a pure enantiomer the stereochemistry at each chiral carbon can be specified by either (R) or (S). Resolved compounds whose absolute configuration is unknown can be designated (+) or (-) depending on the direction (dextro- or levorotatory) which they rotate plane polarized light at the wavelength of the sodium D line. Certain of the compounds described herein contain one or more asymmetric centers and can thus give rise to enantiomers, diastereomers, and other stereoisomeric forms that can be defined, in terms of absolute stereochemistry, as (R) or (S). The present chemical entities, compositions and methods are meant to include all such possible isomers, including racemic mixtures, optically pure forms and intermediate mixtures. Optically active (R)- and (S)-isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. When the compounds described herein contain olefinic double bonds or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers.

[0131] “Enantiomeric purity” as used herein refers to the relative amounts, expressed as a percentage, of the presence of a specific enantiomer relative to the other enantiomer. For example, if a compound, which may potentially have an (R)- or an (S)-isomeric configuration, is present as a racemic mixture, the enantiomeric purity is about 50% with respect to either the (R)- or (S)-isomer. If that compound has one isomeric form predominant over the other, for example, 80% (S)-isomer and 20% (R)-isomer, the enantiomeric purity of the compound with respect to the (S)-isomeric form is 80%. The enantiomeric purity of a compound can be determined in a number of ways known in the art, including but not limited to chromatography using a chiral support, polarimetric measurement of the rotation of polarized light, nuclear magnetic resonance spectroscopy using chiral shift reagents which include but are not limited to lanthanide containing chiral complexes or Pirkle’s reagents, or derivatization of a compounds using a chiral compound such as Mosher’s acid followed by chromatography or nuclear magnetic resonance spectroscopy.

[0132] In some embodiments, enantiomerically enriched compositions have different properties than the racemic mixture of that composition. Enantiomers can be isolated from mixtures by methods known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts; or preferred enantiomers can be prepared by asymmetric syntheses. See, for example, Jacques, et al., Enantiomers, Racemates and Resolutions, Wiley Interscience, New York (1981); E. L. Eliel, Stereochemistry of Carbon Compounds, McGraw-Hill, New York (1962); and E. L. Eliel and S. H. Wilen, Stereochemistry of Organic Compounds, Wiley-Interscience, New York (1994).

[0133] The terms “enantiomerically enriched” and “non-racemic,” as used herein, refer to compositions in which the percent by weight of one enantiomer is greater than the amount of that one enantiomer in a control mixture of the racemic composition (e.g., greater than 1:1 by weight). For example, an enantiomerically enriched preparation of the (S)-enantiomer, means a preparation of the compound having greater than 50% by weight of the (S)-enantiomer relative to the (R)-enantiomer, such as at least 75% by weight, or such as at least 80% by weight. In some embodiments, the enrichment can be significantly greater than 80% by weight, providing a “substantially enantiomerically enriched” or a “substantially non-racemic” preparation, which refers to preparations of compositions which have at least 85% by weight of one enantiomer relative to other enantiomer, such as at least 90% by weight, or such as at least 95% by weight. The terms “enantiomerically pure” or “substantially enantiomerically pure” refers to a composition that comprises at least 98% of a single enantiomer and less than 2% of the opposite enantiomer.

[0134] “Moiety” refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.

[0135] “Tautomers” are structurally distinct isomers that interconvert by tautomerization. “Tautomerization” is a form of isomerization and includes prototropic or proton-shift tautomerization, which is considered a subset of acid-base chemistry. “Prototropic tautomerization” or “proton-shift tautomerization” involves the migration of a proton accompanied by changes in bond order, often the interchange of a single bond with an adjacent double bond. Where tautomerization is possible (e.g., in solution), a chemical equilibrium of tautomers can be reached. An example of tautomerization is keto-enol tautomerization. A specific example of keto-enol tautomerization is the interconversion of pentane-2,4-dione and 4-hydroxypent-3-en-2-one tautomers. Another example of tautomerization is phenol-keto tautomerization. A specific example of phenol-keto tautomerization is the interconversion of pyridin-4-ol and pyridin-4(1H)-one tautomers.

[0136] A “leaving group or atom” is any group or atom that will, under selected reaction conditions, cleave from the starting material, thus promoting reaction at a specified site. Examples of such groups, unless otherwise specified, include halogen atoms and mesyloxy, p-nitrobenzensulphonyloxy and tosyloxy groups.

[0137] “Protecting group” is intended to mean a group that selectively blocks one or more reactive sites in a multifunctional compound such that a chemical reaction can be carried out selectively on another unprotected reactive site and the group can then be readily removed or deprotected after the selective reaction is complete. A variety of protecting groups are disclosed, for example, in T. H. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, Third Edition, John Wiley & Sons, New York (1999).

[0138] “Solvate” refers to a compound in physical association with one or more molecules of a pharmaceutically acceptable solvent.

[0139] “Substituted” means that the referenced group may have attached one or more additional groups, radicals or moieties individually and independently selected from, for example, acyl, alkyl, alkylaryl, cycloalkyl, aralkyl, aryl, carbohydrate, carbonate, heteroaryl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, ester, thiocarbonyl, isocyanato, thiocyanato, isothiocyanato, nitro, oxo, perhaloalkyl, perfluoroalkyl, phosphate, silyl, sulfinyl, sulfonyl, sulfonamidyl, sulfoxyl, sulfonate, urea, and amino, including mono- and di-substituted amino groups, and protected derivatives thereof. The substituents themselves may be substituted, for example, a cycloalkyl substituent may itself have a halide substituent at one or more of its ring carbons. The term “optionally substituted” means optional substitution with the specified groups, radicals or moieties.

[0140] “Sulfanyl” refers to groups that include –S-(optionally substituted alkyl), –S-(optionally substituted aryl), –S-(optionally substituted heteroaryl) and –S-(optionally substituted heterocycloalkyl).

[0141] “Sulfinyl” refers to groups that include –S(O)–H, –S(O)-(optionally substituted alkyl), –S(O)-(optionally substituted amino), –S(O)-(optionally substituted aryl), –S(O)-(optionally substituted heteroaryl) and –S(O)-(optionally substituted heterocycloalkyl).

[0142] “Sulfonyl” refers to groups that include –S(O.sub.2)–H, –S(O.sub.2)-(optionally substituted alkyl), –S(O.sub.2)-(optionally substituted amino), –S(O.sub.2)-(optionally substituted aryl), –S(O.sub.2)-(optionally substituted heteroaryl), and –S(O.sub.2)-(optionally substituted heterocycloalkyl).

[0143] “Sulfonamidyl” or “sulfonamido” refers to a –S(.dbd.O).sub.2–NRR radical, where each R is selected independently from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon). The R groups in –NRR of the –S(.dbd.O).sub.2–NRR radical may be taken together with the nitrogen to which it is attached to form a 4-, 5-, 6- or 7-membered ring. A sulfonamido group is optionally substituted by one or more of the substituents described for alkyl, cycloalkyl, aryl, heteroaryl, respectively.

[0144] “Sulfoxyl” refers to a –S(.dbd.O).sub.2OH radical.

[0145] “Sulfonate” refers to a –S(.dbd.O).sub.2–OR radical, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon). A sulfonate group is optionally substituted on R by one or more of the substituents described for alkyl, cycloalkyl, aryl, heteroaryl, respectively.

[0146] Compounds of the present disclosure also include crystalline and amorphous forms of those compounds, including, for example, polymorphs, pseudopolymorphs, solvates, hydrates, unsolvated polymorphs (including anhydrates), conformational polymorphs, and amorphous forms of the compounds, as well as mixtures thereof. “Crystalline form” and “polymorph” are intended to include all crystalline and amorphous forms of the compound, including, for example, polymorphs, pseudopolymorphs, solvates, hydrates, unsolvated polymorphs (including anhydrates), conformational polymorphs, and amorphous forms, as well as mixtures thereof, unless a particular crystalline or amorphous form is referred to.

[0147] For the avoidance of doubt, it is intended herein that particular features (for example integers, characteristics, values, uses, diseases, formulae, compounds or groups) described in conjunction with a particular aspect, embodiment or example of the disclosure are to be understood as applicable to any other aspect, embodiment or example described herein unless incompatible therewith. Thus, such features may be used where appropriate in conjunction with any of the definition, claims or embodiments defined herein. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of the features and/or steps are mutually exclusive. The present disclosure is not restricted to any details of any disclosed embodiments. The present disclosure extends to any novel one, or novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Volume Holography

[0148] A holographic recording medium described herein can be used in a holographic system. Formation of a hologram, waveguide, or other optical article relies on a refractive index contrast (An) between exposed and unexposed regions of a medium. The amount of information capable of being stored in a holographic medium is a function of the product of: the refractive index contrast, .DELTA.n, of the photorecording material, and the thickness, d, of the photorecording material. The refractive index contrast, .DELTA.n, is conventionally known, and is defined as the amplitude of the sinusoidal variations in the refractive index of a material in which a plane-wave, volume hologram has been written. The refractive index varies as:

n(x)=n.sub.0+.DELTA.n cos(K.sub.x)

where n(x) is the spatially varying refractive index, x is the position vector, K is the grating wave vector, and n.sub.0 is the baseline refractive index of the medium. See, e.g., P. Hariharan, Optical Holography: Principles, Techniques and Applications, Cambridge University Press, Cambridge, 1991, at 44, the disclosure of which is hereby incorporated by reference. The .DELTA.n of a material is typically calculated from the diffraction efficiency or efficiencies of a single volume hologram or a multiplexed set of volume holograms recorded in a medium. The .DELTA.n is associated with a medium before writing, but is observed by measurement performed after recording. Advantageously, the photorecording material of the present disclosure exhibits a .DELTA.n of 3.times.10.sup.-3 or higher.

[0149] In some embodiments, this contrast is at least partly due to monomer/oligomer diffusion to exposed regions. See, e.g., Colburn and Haines, “Volume Hologram Formation in Photopolymer Materials,” Appl. Opt. 10, 1636-1641, 1971; Lesnichii et al., “Study of diffusion in bulk polymer films below glass transition: evidences of dynamical heterogeneities,” J. Phys.: Conf Ser. 1062 012020, 2018. High index contrast is generally desired because it provides improved signal strength when reading a hologram, and provides efficient confinement of an optical wave in a waveguide. In some embodiments, one way to provide high index contrast in the present disclosure is to use a photoactive monomer/oligomer having moieties, referred to for example as index-contrasting moieties, that are substantially absent from the support matrix, and that exhibit a refractive index substantially different from the index exhibited by the bulk of the support matrix. In some embodiments, high contrast may be obtained by using a support matrix that contains primarily aliphatic or saturated alicyclic moieties with a low concentration of heavy atoms and conjugated double bonds providing low index, and a photoactive monomer/oligomer made up primarily of aromatic or similar high-index moieties.

[0150] As described herein, a holographic recording medium is formed such that holographic writing and reading to the medium are possible. Typically, fabrication of the medium involves depositing a combination, blend, mixture, etc., of the support matrix/polymerizable component/photoinitiator component, as well as any composition, compound, molecule, etc., used to control or substantially reduce the rate of polymerization in the absence of a photoinitiating light source (e.g., polymerization retarder), between two plates using, for example, a gasket to contain the mixture. The plates are typically glass, but it is also possible to use other materials transparent to the radiation used to write data, e.g., a plastic such as polycarbonate or poly(methyl methacrylate). It is possible to use spacers between the plates to maintain a desired thickness for the recording medium. In applications requiring optical flatness, the liquid mixture may shrink during cooling (if a thermoplastic) or curing (if a thermoset) and thus distort the optical flatness of the article. To reduce such effects, it is useful to place the article between plates in an apparatus containing mounts, e.g., vacuum chucks, capable of being adjusted in response to changes in parallelism and/or spacing. In such an apparatus, it is possible to monitor the parallelism in real-time by use of conventional interferometric methods, and to make any necessary adjustments to the heating/cooling process. In some embodiments, an article or substrate of the present disclosure may have an antireflective coating and/or be edge sealed to exclude water and/or oxygen. An antireflective coating may be deposited on an article or substrate by various processes such as chemical vapor deposition and an article or substrate may be edge sealed using known methods. In some embodiments, the photorecording material is also capable of being supported in other ways. More conventional polymer processing can also be used, e.g., closed mold formation or sheet extrusion. A stratified medium can also be used, e.g., a medium containing multiple substrates, e.g., glass, with layers of photorecording material disposed between the substrates.

[0151] In some embodiments, a holographic film described herein is a film composite consisting of one or more substrate films, one or more photopolymer films and one or more protective films in any desired arrangement. In some embodiments, materials or material composites of the substrate layer are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulphone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. In addition, material composites, such as film laminates or coextrudates, can be used as substrate film. Examples of material composites are duplex and triplex films having a structure according to one of the schemes A/B, A/B/A or A/B/C, such as PC/PET, PET/PC/PET and PC/TPU (TPU=thermoplastic polyurethane). In some embodiments, PC and PET are used as substrate film. Transparent substrate films which are optically clear, e.g. not hazy, can be used in some embodiments. The haze is measurable via the haze value, which is less than 3.5%, or less than 1%, or less than 0.3%. The haze value describes the fraction of transmitted light which is scattered in a forward direction by the sample through which radiation has passed. Thus, it is a measure of the opacity or haze of transparent materials and quantifies material defects, particles, inhomogeneities or crystalline phase boundaries in the material or its surface that interfere with the transparency. The method for measuring the haze is described in the standard ASTM D 1003.

[0152] In some embodiments, the substrate film has an optical retardation that is not too high, e.g. a mean optical retardation of less than 1000 nm, or of less than 700 nm, or of less than 300 nm. The automatic and objective measurement of the optical retardation is effected using an imaging polarimeter. The optical retardation is measured in perpendicular incidence. The retardation values stated for the substrate film are lateral mean values.

[0153] In some embodiments, the substrate film, including possible coatings on one or both sides, has a thickness of 5 to 2000 .mu.m, or of 8 to 300 .mu.m, or of 30 to 200, or of 125 to 175 .mu.m, or of 30 to 45 .mu.m.

[0154] In some embodiments, the film composite can have one or more covering layers on the photopolymer layer in order to protect it from dirt and environmental influences. Plastics films or film composite systems, but also clearcoats can be used for this purpose. In some embodiments, covering layers are film materials analogous to the materials used in the substrate film, having a thickness of 5 to 200 .mu.m, or of 8 to 125 .mu.m, or of 20 to 50 .mu.m. In some embodiments, covering layers having as smooth a surface as possible are preferred. The roughness can be determined according to DIN EN ISO 4288. In some embodiments, roughness is in the region of less than or equal to 2 .mu.m, or less than or equal to 0.5 .mu.m. In some embodiments, PE or PET films having a thickness of 20 to 60 .mu.m can be used as laminating films. In some embodiments, a polyethylene film of 40 .mu.m thickness can be used. In some embodiments, further protective layers, for example a backing of the substrate film, may be used.

[0155] In some embodiments, an article described herein can exhibit thermoplastic properties, and can heated above its melting temperature and processed in ways described herein for the combination, blend, mixture, etc., of the support matrix/polymerizable component/photoinitiator component/polymerization retarder.

[0156] Examples of other optical articles include beam filters, beam steerers or deflectors, and optical couplers. See, e.g., Solymar and Cooke, “Volume Holography and Volume Gratings,” Academic Press, 315-327, 1981, incorporated herein by reference. A beam filter separates part of an incident laser beam that is traveling along a particular angle from the rest of the beam. Specifically, the Bragg selectivity of a thick transmission hologram is able to selectively diffract light along a particular angle of incidence, while light along other angles travels undeflected through the hologram. See, e.g., Ludman et al., “Very thick holographic nonspatial filtering of laser beams,” Optical Engineering, Vol. 36, No. 6, 1700, 1997, incorporated herein by reference. A beam steerer is a hologram that deflects light incident at the Bragg angle. An optical coupler is typically a combination of beam deflectors that steer light from a source to a target. These articles, typically referred to as holographic optical elements, are fabricated by imaging a particular optical interference pattern within a recording medium, as discussed previously with respect to data storage. Media for these holographic optical elements are capable of being formed by the techniques discussed herein for recording media or waveguides.

[0157] Materials principles discussed herein are applicable not only to hologram formation, but also to formation of optical transmission devices such as waveguides. Polymeric optical waveguides are discussed for example in Booth, “Optical Interconnection Polymers,” in Polymers for Lightwave and Integrated Optics, Technology and Applications, Hornak, ed., Marcel Dekker, Inc. (1992); U.S. Pat. No. 5,292,620 (Booth et al.), issued Mar. 18, 1994; and U.S. Pat. No. 5,219,710 (Horn et al.), issued Jun. 15, 1993, incorporated herein by reference. In some embodiments, a recording material described herein is irradiated in a desired waveguide pattern to provide refractive index contrast between the waveguide pattern and the surrounding (cladding) material. It is possible for exposure to be performed, for example, by a focused laser light or by use of a mask with a non-focused light source. Generally, a single layer is exposed in this manner to provide the waveguide pattern, and additional layers are added to complete the cladding, thereby completing the waveguide.

[0158] In one embodiment of the present disclosure, using conventional molding techniques, it is possible to mold the combination, blend, mixture, etc., of the support matrix/polymerizable component/photoinitiator component/polymerization retarder thus realizing a variety of shapes prior to formation of the article by cooling to room temperature. For example, the combination, blend, mixture, etc., of the support matrix/polymerizable component/photoinitiator component/polymerization retarder can be molded into ridge waveguides, where a plurality of refractive index patterns are then written into the molded structures. It is thereby possible to easily form structures such as Bragg gratings. This feature of the present disclosure increases the breadth of applications in which such polymeric waveguides would be useful.

Two-Stage Photopolymers

[0159] The purpose of a photopolymer is to faithfully record both phase and amplitude of a three-dimensional optical pattern. During the exposure process, the optical pattern is recorded as modulations in refractive index inside of the photopolymer film. Light is converted to variations in refractive index by a photopolymerization reaction, which causes high and low-index species to diffuse to bright and dark fringes, respectively.

[0160] A two-stage photopolymer refers to a material that is “cured” twice (FIGS. 3A-3C). It typically consists of (at least) three materials: i) the matrix: typically a low refractive index rubbery polymer (like a polyurethane) that is thermally cured (1st stage) to provide mechanical support during the holographic exposure and ensure the refractive index modulation is permanently preserved; ii) the writing monomer: typically a high index acrylate monomer that reacts with a photoinitiator and polymerizes quickly; and iii) the photoinitiator (PI) system: the compound or group of compounds that react with light and initiate the polymerization of the writing monomer. For visible light polymerization, the PI system usually consists of two compounds that work together. The “dye” or “sensitizer” absorbs light and transfers energy or some reactive species to the “coinitiator,” which actually initiates the polymerization reaction.

[0161] The performance of a holographic photopolymer is determined strongly by how species diffuse during polymerization. Usually, polymerization & diffusion are occurring simultaneously in a relatively uncontrolled fashion within the exposed areas. This leads to several undesirable effects. Polymers that are not bound to the matrix after initiation or termination reactions are free to diffuse out of exposed regions of the film into unexposed areas. This “blurs” the resulting fringes, reducing .DELTA.n and diffraction efficiency of the final hologram. The buildup of .DELTA.n during exposure means that subsequent exposures can scatter light from these gratings, leading to the formation of noise gratings. These create haze and a loss of clarity in the final waveguide display. For a series of multiplexed exposures with constant dose/exposure, the first exposures will consume most of the monomer, leading to an exponential decrease in diffraction efficiency with each exposure. A complicated “dose scheduling” procedure is required to balance the diffraction efficiency of all of the holograms.

[0162] As shown in FIG. 2, controlled radical polymerization can be used in holography applications. The general goals for such applications is the design of a photopolymer material that is sensitive to visible light, produces a large .DELTA.n response, and controls the reaction/diffusion of the photopolymer such that chain transfer and termination reactions are reduced or suppressed. The polymerization reaction that occurs inside traditional photopolymer materials is known as a free radical polymerization, which has several characteristics: radical species are produced immediately upon exposure, radicals initiate polymerization and propagate by adding monomer to chain ends, radicals also react with matrix by hydrogen abstraction and chain transfer reactions, and radicals can terminate by combining with other radicals or reacting with inhibiting species (e.g., O.sub.2). Controlled radical polymerization that can be used include Atom Transfer Radical Polymerization (ATRP), Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT), and Nitroxide-mediated Polymerization (NMP).

[0163] The matrix is a solid polymer formed in situ from a matrix precursor by a curing step (curing indicating a step of inducing reaction of the precursor to form the polymeric matrix). It is possible for the precursor to be one or more monomers, one or more oligomers, or a mixture of monomer and oligomer. In addition, it is possible for there to be greater than one type of precursor functional group, either on a single precursor molecule or in a group of precursor molecules. Precursor functional groups are the group or groups on a precursor molecule that are the reaction sites for polymerization during matrix cure. To promote mixing with the photoactive monomer, in some embodiments the precursor is liquid at some temperature between about -50.degree. C. and about 80.degree. C. In some embodiments, the matrix polymerization is capable of being performed at room temperature. In some embodiments, the polymerization is capable of being performed in a time period less than 300 minutes, for example between about 5 and about 200 minutes. In some embodiments, the glass transition temperature (T.sub.g) of the photorecording material is low enough to permit sufficient diffusion and chemical reaction of the photoactive monomer during a holographic recording process. Generally, the T.sub.g is not more than 50.degree. C. above the temperature at which holographic recording is performed, which, for typical holographic recording, means a T.sub.g between about 80.degree. C. and about -130.degree. C. (as measured by conventional methods). In some embodiments, the matrix exhibits a three-dimensional network structure, as opposed to a linear structure, to provide the desired modulus described herein.

[0164] In some embodiments, use of a matrix precursor, e.g., the one or more compounds from which the matrix is formed, and a photoactive monomer that polymerize by independent reactions, substantially prevents both cross-reaction between the photoactive monomer and the matrix precursor during the cure, and inhibition of subsequent monomer polymerization. Use of a matrix precursor and photoactive monomer that form compatible polymers substantially avoids phase separation, and in situ formation allows fabrication of media with desirable thicknesses. These material properties are also useful for forming a variety of optical articles (optical articles being articles that rely on the formation of refractive index patterns or modulations in the refractive index to control or modify light that is directed at them). In addition to recording media, such articles include, but are not limited to, optical waveguides, beam steerers, and optical filters.

[0165] In some embodiments, independent reactions indicate: (a) the reactions proceed by different types of reaction intermediates, e.g., ionic vs. free radical, (b) neither the intermediate nor the conditions by which the matrix is polymerized will induce substantial polymerization of the photoactive monomer functional groups, e.g., the group or groups on a photoactive monomer that are the reaction sites for polymerization during the pattern (e.g., hologram) writing process (substantial polymerization indicates polymerization of more than 20% of the monomer functional groups), and (c) neither the intermediate nor the conditions by which the matrix is polymerized will induce a non-polymerization reaction of the monomer functional groups that either causes cross-reaction between monomer functional groups and the matrix or inhibits later polymerization of the monomer functional groups.

[0166] In some embodiments, polymers are considered to be compatible if a blend of the polymers is characterized, in 90.degree. light scattering of a wavelength used for hologram formation, by a Rayleigh ratio (R.sub.90.degree.) less than 7.times.10.sup.-3 cm.sup.-1. The Rayleigh ratio (R.sub..theta.) is a conventionally known property, and is defined as the energy scattered by a unit volume in the direction .theta., per steradian, when a medium is illuminated with a unit intensity of unpolarized light, as discussed in Kerker, “The Scattering of Light and Other Electromagnetic Radiation,” Academic Press, San Diego, 1969, at 38. The light source used for the measurement is generally a laser having a wavelength in the visible part of the spectrum. Normally, the wavelength intended for use in writing holograms is used. The scattering measurements are made upon a photorecording material that has been flood exposed. The scattered light is collected at an angle of 90.degree. from the incident light, typically by a photodetector. It is possible to place a narrowband filter, centered at the laser wavelength, in front of such a photodetector to block fluorescent light, although such a step is not required. The Rayleigh ratio is typically obtained by comparison to the energy scatter of a reference material having a known Rayleigh ratio. Polymers considered miscible, e.g., according to conventional tests such as exhibition of a single glass transition temperature, will typically be compatible as well. But polymers that are compatible will not necessarily be miscible. In situ indicates that the matrix is cured in the presence of the photoimageable system. A useful photorecording material, e.g., the matrix material plus the photoactive monomer, photoinitiator, and/or other additives, is attained, the material capable of being formed in thicknesses greater than 200 .mu.m, in some embodiments greater than 500 .mu.m, and, upon flood exposure, exhibiting light scattering properties such that the Rayleigh ratio, R.sub.90, is less than 7.times.10.sup.-3 cm.sup.-1. In some embodiments, flood exposure is exposure of the entire photorecording material by incoherent light at wavelengths suitable to induce substantially complete polymerization of the photoactive monomer throughout the material.

[0167] Polymer blends considered miscible, e.g., according to conventional tests such as exhibition of a single glass transition temperature, will also typically be compatible, e.g., miscibility is a subset of compatibility. Standard miscibility guidelines and tables are therefore useful in selecting a compatible blend. However, it is possible for polymer blends that are immiscible to be compatible according to the light scattering described herein.

[0168] A polymer blend is generally considered miscible if the blend exhibits a single glass transition temperature, T.sub.g, as measured by conventional methods. An immiscible blend will typically exhibit two glass transition temperatures corresponding to the T.sub.g values of the individual polymers. T.sub.g testing is most commonly performed by differential scanning calorimetry (DSC), which shows the T.sub.g as a step change in the heat flow (typically the ordinate). The reported T.sub.g is typically the temperature at which the ordinate reaches the mid-point between extrapolated baselines before and after the transition. It is also possible to use Dynamic Mechanical Analysis (DMA) to measure T.sub.g. DMA measures the storage modulus of a material, which drops several orders of magnitude in the glass transition region. It is possible in certain cases for the polymers of a blend to have individual T.sub.g values that are close to each other. In such cases, conventional methods for resolving such overlapping T.sub.g should be used, such as discussed in Brinke et al., “The thermal characterization of multi-component systems by enthalpy relaxation,” Thermochimica Acta., 238, 75, 1994.

[0169] Matrix polymer and photopolymer that exhibit miscibility are capable of being selected in several ways. For example, several published compilations of miscible polymers are available, such as Olabisi et al., “Polymer-Polymer Miscibility,” Academic Press, New York, 1979; Robeson, MMI. Press Symp. Ser., 2, 177, 1982; Utracki, “Polymer Alloys and Blends: Thermodynamics and Rheology,” Hanser Publishers, Munich, 1989; and S. Krause in Polymer Handbook, J. Brandrup and E. H. Immergut, Eds.; 3rd Ed., Wiley Interscience, New York, 1989, pp. VI 347-370, incorporated herein by reference. Even if a particular polymer of interest is not found in such references, the approach specified allows determination of a compatible photorecording material by employing a control sample.

[0170] Determination of miscible or compatible blends is further aided by intermolecular interaction considerations that typically drive miscibility. For example, polystyrene and poly(methylvinylether) are miscible because of an attractive interaction between the methyl ether group and the phenyl ring. It is therefore possible to promote miscibility, or at least compatibility, of two polymers by using a methyl ether group in one polymer and a phenyl group in the other polymer. Immiscible polymers are also capable of being made miscible by the incorporation of appropriate functional groups that can provide ionic interactions. See Zhou and Eisenberg, J. Polym. Sci., Polym. Phys. Ed., 21 (4), 595, 1983; Murali and Eisenberg, J. Polym. Sci., Part B: Polym. Phys., 26 (7), 1385, 1988; and Natansohn et al., Makromol. Chem., Macromol. Symp., 16, 175, 1988. For example, polyisoprene and polystyrene are immiscible. However, when polyisoprene is partially sulfonated (5%), and 4-vinyl pyridine is copolymerized with the polystyrene, the blend of these two functionalized polymers is miscible. Without wishing to be bound by any particular theory, it is contemplated that the ionic interaction between the sulfonated groups and the pyridine group (proton transfer) is the driving force that makes this blend miscible. Similarly, polystyrene and poly(ethyl acrylate), which are normally immiscible, have been made miscible by lightly sulfonating the polystyrene. See Taylor-Smith and Register, Macromolecules, 26, 2802, 1993. Charge-transfer has also been used to make miscible polymers that are otherwise immiscible. For example it has been demonstrated that, although poly(methyl acrylate) and poly(methyl methacrylate) are immiscible, blends in which the former is copolymerized with (N-ethylcarbazol-3-yl)methyl acrylate (electron donor) and the latter is copolymerized with 2-[(3,5-dinitrobenzoyl)oxy]ethyl methacrylate (electron acceptor) are miscible, provided the right amounts of donor and acceptor are used. See Piton and Natansohn, Macromolecules, 28, 15, 1995. Poly(methyl methacrylate) and polystyrene are also capable of being made miscible using the corresponding donor-acceptor co-monomers. See Piton and Natansohn, Macromolecules, 28, 1605, 1995.

[0171] A variety of test methods exist for evaluating the miscibility or compatibility of polymers, as reflected in the recent overview published in Hale and Bair, Ch. 4-“Polymer Blends and Block Copolymers,” Thermal Characterization of Polymeric Materials, 2nd Ed., Academic Press, 1997. For example, in the realm of optical methods, opacity typically indicates a two-phase material, whereas clarity generally indicates a compatible system. Other methods for evaluating miscibility include neutron scattering, infrared spectroscopy (IR), nuclear magnetic resonance (NMR), x-ray scattering and diffraction, fluorescence, Brillouin scattering, melt titration, calorimetry, and chemilluminescence. See, generally, Robeson, herein; Krause, Chemtracts–Macromol. Chem., 2, 367, 1991; Vesely in Polymer Blends and Alloys, Folkes and Hope, Eds., Blackie Academic and Professional, Glasgow, pp. 103-125; Coleman et al. Specific Interactions and the Miscibility of Polymer Blends, Technomic Publishing, Lancaster, Pa., 1991; Garton, Infrared Spectroscopy of Polymer Blends Composites and Surfaces, Hanser, New York, 1992; Kelts et al., Macromolecules, 26, 2941, 1993; White and Mirau, Macromolecules, 26, 3049, 1993; White and Mirau, Macromolecules, 27, 1648, 1994; and Cruz et al., Macromolecules, 12, 726, 1979; Landry et al., Macromolecules, 26, 35, 1993.

[0172] In some embodiments, compatibility has also been promoted in otherwise incompatible polymers by incorporating reactive groups into the polymer matrix, where such groups are capable of reacting with the photoactive monomer during the holographic recording step. Some of the photoactive monomer will thereby be grafted onto the matrix during recording. If there are enough of these grafts, it is possible to prevent or reduce phase separation during recording. However, if the refractive index of the grafted moiety and of the monomer are relatively similar, too many grafts, e.g., more than 30% of monomers grafted to the matrix, will tend to undesirably reduce refractive index contrast.

[0173] The optical article of the present disclosure is formed by steps including mixing a matrix precursor and a photoactive monomer, and curing the mixture to form the matrix in situ. In some embodiments, the reaction by which the matrix precursor is polymerized during the cure is independent from the reaction by which the photoactive monomer is later polymerized during writing of a pattern, e.g., data or waveguide form, and, in addition, the matrix polymer and the polymer resulting from polymerization of the photoactive monomer, e.g., the photopolymer, are compatible with each other. The matrix is considered to be formed when the photorecording material exhibits an elastic modulus of at least about 10.sup.5 Pa. In some embodiments, the matrix is considered to be formed when the photorecording material, e.g., the matrix material plus the photoactive monomer, photoinitiator, and/or other additives, exhibits an elastic modulus of at least about 10.sup.5 Pa. In some embodiments, the matrix is considered to be formed when the photorecording material, e.g., the matrix material plus the photoactive monomer, photoinitiator, and/or other additives, exhibits an elastic modulus of about 10.sup.5 Pa to about 10.sup.9 Pa. In some embodiments, the matrix is considered to be formed when the photorecording material, e.g., the matrix material plus the photoactive monomer, photoinitiator, and/or other additives, exhibits an elastic modulus of about 10.sup.6 Pa to about 10.sup.8 Pa.

[0174] In some embodiments, an optical article described herein contains a three-dimensional crosslinked polymer matrix and one or more photoactive monomers. At least one photoactive monomer contains one or more moieties, excluding the monomer functional groups, that are substantially absent from the polymer matrix. Substantially absent indicates that it is possible to find a moiety in the photoactive monomer such that no more than 20% of all such moieties in the photorecording material are present, e.g., covalently bonded, in the matrix. The resulting independence between the host matrix and the monomer offers useful recording properties in holographic media and desirable properties in waveguides such as enabling formation of large modulations in the refractive index without the need for high concentrations of the photoactive monomer. Moreover, it is possible to form the material without solvent development.

[0175] In some embodiments, media that utilize a matrix precursor and photoactive monomer that polymerize by non-independent reactions can be used, resulting in substantial cross-reaction between the precursor and the photoactive monomer during the matrix cure (e.g., greater than 20% of the monomer is attached to the matrix after cure), or other reactions that inhibit polymerization of the photoactive monomer. Cross-reaction tends to reduce the refractive index contrast between the matrix and the photoactive monomer and is capable of affecting the subsequent polymerization of the photoactive monomer, and inhibition of monomer polymerization clearly affects the process of writing holograms. As for compatibility, previous work has been concerned with the compatibility of the photoactive monomer in a matrix polymer, not the compatibility of the resulting photopolymer in the matrix. Yet, where the photopolymer and matrix polymer are not compatible, phase separation typically occurs during hologram formation. It is possible for such phase separation to lead to increased light scattering, reflected in haziness or opacity, thereby degrading the quality of the medium, and the fidelity with which stored data is capable of being recovered.

[0176] In one embodiment, the support matrix is thermoplastic and allows an article described herein to behave as if the entire article was a thermoplastic. That is, the support matrix allows the article to be processed similar to the way that a thermoplastic is processed, e.g., molded into a shaped article, blown into a film, deposited in liquid form on a substrate, extruded, rolled, pressed, made into a sheet of material, etc. and then allowed to harden at room temperature to take on a stable shape or form. The support matrix may comprise one or more thermoplastics. Suitable thermoplastics include poly(methyl vinyl ether-alt-maleic anhydride), poly(vinyl acetate), poly(styrene), poly(propylene), poly(ethylene oxide), linear nylons, linear polyesters, linear polycarbonates, linear polyurethanes, poly(vinyl chloride), poly(vinyl alcohol-co-vinyl acetate), and the like. In some embodiments, polymerization reactions that can be used for forming matrix polymers include cationic epoxy polymerization, cationic vinyl ether polymerization, cationic alkenyl ether polymerization, cationic allene ether polymerization, cationic ketene acetal polymerization, epoxy-amine step polymerization, epoxy-mercaptan step polymerization, unsaturated ester-amine step polymerization (e.g., via Michael addition), unsaturated ester-mercaptan step polymerization (e.g., via Michael addition), vinyl-silicon hydride step polymerization (hydrosilylation), isocyanate-hydroxyl step polymerization (e.g., urethane formation), isocyanate-amine step polymerization (e.g., urea formation), and the like.

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