compound containing mesogen, composition, article of manufacture and method for forming an ophthalmi

专利摘要:
COMPOSITE CONTAINING MESOGEN, COPOLYMER COMPOSITION, POLYMER COMPOSITION, LIQUID CRYSTAL COMPOSITION, MANUFACTURING ARTICLE, OPTICAL ELEMENT, LIQUID CRYSTAL CELL AND METHOD TO FORM AN OPHTHALMIC ELEMENT. Compounds are disclosed including at least one mesogenic substructure and at least one long flexible segment and methods for synthesizing them. Formulations are also disclosed that include various incorporations of compounds containing mesogen and their use in manufacturing articles and ophthalmic devices.
公开号:BR112013021046B1
申请号:R112013021046-0
申请日:2012-03-07
公开日:2021-03-02
发明作者:Meng He；Anil Kumar
申请人:Transitions Optical, Inc；
IPC主号:

专利说明:

Historic
[0001] In general, the present invention relates to compounds containing mesogen, formulations thereof, optical elements, liquid crystal polymers and methods of preparing them.
[0002] Liquid crystal (“LC”) molecules tend to align with each other in a preferred direction, producing a fluid material with anisotropic, electromagnetic, and mechanical optical properties. The mesogen is the fundamental unit of an LC that induces the structural order in liquid crystals.
[0003] Liquid crystal polymers ("LCPs") are polymers capable of forming regions of very ordered structure while in a liquid phase. LCPs have a wide range of uses, ranging from strong engineering plastics to delicate gels for LC displays. The structure of the LCPs can consist of densely packed fibrous polymer chains that provide self-reinforcement practically at the melting point of the polymer.
[0004] Dichroism in LCs can occur due to the optical anisotropy of the molecular structure or the presence of impurities or the presence of dichroic dyes. When used here, the term "dichroism" means the ability to absorb one of two polarized components in orthogonal planes of at least one radiation transmitted more strongly than the other.
[0005] Conventionally linearly polarized elements, such as linearly polarized lenses for sunglasses and linearly polarized filters, are typically formed from stretched polymeric sheets containing a dichroic material, such as a dichroic dye. Consequently, conventional linearly polarized elements are static elements having a single linearly polarized state. Therefore, when a linearly conventionally polarized element is exposed to randomly polarized radiation or reflected radiation of the appropriate wavelength, some percentage of the radiation transmitted through the element will be linearly polarized. When used here, the term "linearly polarize" means to confine the vibrations of the electric light wave vector to a direction or plane.
[0006] In addition, conventional linearly polarized elements are typically colored. That is, linearly conventionally polarized elements contain a coloring agent (i.e., the dichroic material) and have an absorption spectrum that does not vary in response to actinic radiation. When used here, the term "actinic radiation" means electromagnetic radiation, such as ultraviolet and visible radiation that is capable of causing a response. The color of the linearly conventionally polarized element will depend on the coloring agent used to form the element, and very commonly, it is a neutral color (for example, brown or gray). Thus, although conventional linearly polarized elements are useful for reducing the glare of reflected light, because of their color, they are not well suited for use in certain low light conditions. In addition, as conventional linearly polarized elements have a single linearly colored polarized state, they are limited in their ability to store or display information.
[0007] As discussed above, linearly conventionally polarized elements are typically formed using stretched polymeric film sheets containing a dichroic material. When used here, the term "dichroic" means capable of absorbing one of two polarized components in orthogonal planes of at least one radiation transmitted more strongly than the other. Therefore, although the dichroic materials are able to preferentially absorb one of two polarized components in orthogonal planes of transmitted radiation, if the molecules of the dichroic material are not properly positioned or arranged, the final linear polarization of transmitted radiation will not be achieved. That is, due to the random positioning of the molecules of the dichroic material, the selective absorption by individual molecules will cancel each other so that no global or final polarization effect is achieved. Consequently, it is generally necessary to properly position or arrange the molecules of the dichroic material by aligning it with another material in order to achieve a final linear polarization.
[0008] Unlike the dichroic elements discussed above, conventional photochromatic elements, such as photochromic lenses that are formed using conventional thermally reversible photochromic materials, are generally capable of converting from a first state, for example, a "colorless state", to a second state, for example, a "colored state", in response to actinic radiation, then return to the first state in response to thermal energy. When used here, the term "photochromatic" means having an absorption spectrum for at least visible radiation that varies in response to less actinic radiation. Therefore, conventional photochromic elements are generally well suited for use in both low light and high light conditions. However, conventional photochromatic elements that do not include linearly polarized filters generally do not adapt to linearly polarized radiation. That is, the absorption ratio of conventional photochromatic elements, in either state, is generally less than two. When used here, the term “absorption ratio” refers to the absorbance ratio of linearly polarized radiation in an orthogonal plane to the foreground, with the foreground being considered the plane of maximum absorbance. Therefore, conventional photochromatic elements cannot reduce glare from reflected light to the same extent as conventional linearly polarized elements. Thus, photochromatic / dichroic materials were developed. Photochromatic / dichroic materials are materials that exhibit photochromatic properties (that is, having an absorption spectrum of at least visible radiation that varies in response to at least actinic radiation) and dichroic properties (that is, capable of absorbing one of two polarized components in orthogonal planes of at least radiation transmitted more strongly than the other).
[0009] Photochromatic materials and photochromatic / dichroic materials can be incorporated into a substrate or an organic material, for example, a polymeric substrate, including LCP substrates. When photochromatic materials and photochromatic / dichroic materials undergo a change from one state to another, the molecules of the photochromatic compound or the photochromatic / dichroic compound may undergo a change in conformation from a conformation state to a second conformation state. This change in conformation can result in a change in the amount of space that the compound occupies. However, for certain photochromatic / dichroic elements to effectively change from one state to another, for example, to change from a colorless state to a colored state, to change from a colored state to a colorless state, to change from an unpolarized state to a state polarized, and / or to change from a polarized state to a non-polarized state, the photochromatic compound or the photochromatic / dichroic compound must be in a chemical environment that is flexible enough to allow the compound to change from a conformation state to the second state of conformation at a rate that is sufficient to provide the desired response within an acceptable time frame. Therefore, new polymeric materials, such as new LCPs, and materials are needed to form these new materials to further develop photochromatic and photochromatic / dichroic substrates and materials. Brief summary of disclosure
[0010] Several aspects of the present disclosure relate to new compounds containing mesogen and formulations formed with them, optical elements, liquid crystal polymers and methods for preparing them.
[0011] The present disclosure provides a compound containing mesogen represented by one of the following structures

in which: (a) each X is independently: (I) a group R, (II) a group represented by - (L) yR, (III) a group represented by - (L) -R, (IV) a group represented by
or (V) a group represented by - (L) yP; (b) each P is independently selected from hydrogen, aryl, alkyl, alkoxy, alkyl alkoxy, alkoxy alkoxy, polyalkyl ether, (C1-C6 alkyl) (C1-C6 alkoxy) (C1-C6 alkyl), polyethyleneoxy and polypropyleneoxy; (c) each L can be the same or different and is chosen independently from a single bond, a monosubstituted, polysubstituted, unsubstituted or branched spacer chosen independently from arylene, C1-C30 alkylene, (C1-C30 alkylene) carbonyloxy, (C1-C30 alkylene) amino, C1-C30 alkyleneoxy, C1-C30 alkylene perfluor, C1-C30 alkyleneoxy perfluor, (C1-C30 alkylene) silyl, (C1-C30 dialkylene) siloxyl, (alkylene of C1-C30) carbonyl, (C1-C30 alkyleneoxy) carbonyl, (C1-C30 alkylene) amino carbonyl, (C1-C30 alkylene) amino carbonyl, (C1-C30 alkylene) amino carbonyl thio, C1- alkenylene C30, C1-C30 alkenylene thio, (C1-C30 alkylene) sulfone, or C1-C30 alkenylene sulfoxide, each substituent being chosen independently from C1-C5 alkyl, C1-C5 alkoxide, fluorine, chlorine , chromium, cyano, C1-C5 alkanoate ester, isocyanate, thio isocyanate, or phenyl; note that L can also be trivalent as shown in some structures of the mesogen-containing compound of the present invention; (d) the group R is selected from hydrogen, C1-C18 alkyl, C1-C18 alkoxy, (C1- C18 alkoxy) carbonyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, poly (C1- alkoxy C18), or a normal or branched C1-C18 alkyl group that is unsubstituted or substituted with cyan, fluorine, chlorine, bromine, or C1-C18 alkoxy, or polysubstituted with fluorine, chlorine, or bromine; and (e) the Mesogen-1 and Mesogen-2 groups are independently a liquid crystal group as a rigid straight stem, a liquid crystal group as a rigid curved stem, or a liquid crystal group as a hard disk; where w is an integer from 1 to 26, y is an integer from 2 to 25, z is 1 or 2, provided that when: (I) the group X is represented by R, then w is an integer of 2 to 25, ez is 1; (II) the group X is represented by - (L) yR, so w is 1, y is an integer from 2 to 25, and z is 1; (III) group X is represented by - (L) wR, so w is an integer from 3 to 26, and z is 2: (IV) group X is represented by
then w is 1, y is an integer from 2 to 25, with the proviso that - (L) y- comprises at least two groups L that are different from a single bond and z is 1; (V) the group X is represented by - (L) yP, so w is 1, y is an integer from 2 to 25, ez is 1 and - (L) y- comprises a linear sequence of at least 25 connections between the mesogen and P; and in - (L) y- and - (L) w- there are no two arylene groups connected by a single bond. Brief description of the various views of the drawings
[0012] Aspects of the present disclosure will be better understood when read together with the figures, in which: Figures 1-7 illustrate exemplary methods to synthesize certain incorporations of the compounds containing mesogen described herein. In particular: Figure 1 illustrates a process for synthesizing a non-mesogenous L group and using it to connect mesogens according to the present invention; Figure 2 illustrates a process for synthesizing a compound containing two mesogens using an L group such as polycaprolactone diol; Figure 3 illustrates a process for synthesizing a compound containing two mesogens using an L group such as polycarbonate diol; Figure 4 illustrates a process for the synthesis of a compound containing a single mesogen having an L group at one end using a base-catalyzed or Lewis acid-catalyzed process with excess caprolactone; Figure 5 illustrates a process for the synthesis of a compound containing a single mesogen having an L group at one end using a base-catalyzed or Lewis acid-catalyzed process with excess cyclic carbonate; Figure 6 illustrates a process for the synthesis of a compound containing a single mesogen having a double-ended L group using a base-catalyzed or Lewis acid-catalyzed process with excess caprolactone; and Figure 7 illustrates a process for synthesizing a compound containing a single mesogen having a branching L group using caprolactone. Detailed description of the incorporations
[0013] Compounds containing mesogens and liquid crystal compositions and formulations containing compounds containing mesogens in accordance with the present disclosure will now be described. The mesogen-containing compounds disclosed herein provide new structures that can be used for a variety of applications, including, for example, formulations and compositions that can be used, for example, liquid crystal polymers ("LCPs"), in optical elements including, for example, ophthalmic elements, display elements, windows, and mirrors. According to certain aspects of the present disclosure, the mesogen-containing compounds of the present disclosure can act as monomers for the formation of LCPs.
[0014] The mesogen is the fundamental unit of a liquid crystal ("LC"), which induces the structural order in the liquid crystal. The mesogenic portion of the LC typically comprises a rigid portion that aligns with other mesogenic components in the LC composition, thereby aligning the LC molecules in one direction. The rigid portion of the mesogen may consist of a rigid molecular structure, such as a mono or polycyclic ring structure, including, for example, mono or polycyclic aromatic ring structures. Examples of potential mesogens are shown here in more detail and include those mesogenic compounds shown in Demus et al., “Flüssige Kristalle in Tabellen”, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1974 and “Flüssige Kristalle in Tabellen II”, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1984. LCs can also include one or more flexible portions in the LC molecule. One or more flexible portions can give fluidity to the LC. LCs can exist in an unordered state or in an ordered (aligned) state. LC molecules in the unordered state will adopt an essentially random orientation, that is, there will be no general orientation for LC molecules. In the ordered or aligned state, the LC molecules will generally adopt an orientation where the mesogenic portions of the LC molecules are at least partially aligned in all the LC material. When used here, the terms "align" or "aligned" mean putting in an appropriate arrangement or position by interacting with another material, compound or structure. In certain embodiments, the mesogenic portions of the LC molecules may be at least partially aligned in a parallel orientation. In other embodiments, the mesogenic portions of the LC molecules can be at least partially aligned in a helical orientation, such as in a reflecting polarizer.
[0015] The mesogen-containing compounds of the present disclosure can be used in a variety of functions including LC compositions. The mesogen-containing compounds of the present disclosure can act as non-monomeric components, such as non-monomeric LC components. When used herein, the term “compound” means a substance formed by the union of two or more elements, components, ingredients, or parts and includes molecules and macromolecules (for example, polymers and oligomers) formed by the union of two or more elements, components , ingredients, or parts. The compositions formed by the mesogen-containing compounds can have a variety of uses, including as layers, such as films and coatings cured on at least a portion of a substrate, which can impart certain desired characteristics to the substrate, and as manufacturing articles, such as molded articles, assembled articles and cast articles. For example, compositions formed by compounds containing mesogen can be used, for example, as at least partial layers, coatings or films on at least a portion of a substrate that can impart certain desired characteristics to the substrate, such as for use in applications storage of optical data, such as photo covers, as decorative pigments; in cosmetics and for safety applications (see, for example, U.S. Patent No. 6,217,948); as curable resins for medical, dental, adhesive and lithographic stereo applications (see, for example, U.S. Patent No. 7,238,831); such as manufacturing articles, such as molded, cast or cast articles for use in the aforementioned applications and various similar devices.
[0016] Compositions containing mesogen can be formulated in LCs and / or LCPs that can be used or incorporated in optical elements such as, for example, ophthalmic elements, display elements, windows, mirrors, cells, elements and liquid crystal devices assets and liabilities, and other items of interest containing LC or LCP, such as polarizers, optical compensators (see, for example, US patent No. 7,169,448), optical retarders (see, for example, reissued US patent no. ° RE 39,605 E), color filters, and wave plates for light wave circuits (see, for example, US patent No. 7,058,249). For example, LCPs can be used to form optical films such as retarders, waveguides, reflectors, circular polarizers, films with a wide viewing angle, etc. Specific incorporations of the compounds containing mesogen find particular use in the formation of ophthalmic elements that comprise at least one photochromatic or photochromatic / dichroic compound or material. As will be described in more detail here, the mesogen-containing materials of various embodiments of the present disclosure may be particularly suitable for giving the desired kinetic properties for certain photochromatic or photochromatic / dichroic materials, such as ophthalmic elements and optical elements. In other embodiments, LCPs can also be used as a host material for dyes, such as photosensitive and non-photosensitive materials. Photosensitive materials may include organic photochromic materials such as thermally or non-reversible materials, as well as photochromic / dichroic materials, inorganic photochromatic materials, fluorescent or phosphorescent materials and non-linear optical materials (“NLOs”). Non-photosensitive materials can include fixed color dyes, dichroic materials, thermochroic materials, and pigments.
[0017] The mesogen-containing compounds of the present disclosure generally comprise at least one mesogenic unit and at least one flexible linker group that can be from 1 to 500 atomic bonds in linear length and therefore can act as LCs, which can be incorporated into materials or compositions that exhibit LP properties or can be used as LC monomers, for example, for the formation of LCPs.
[0018] According to an embodiment, the compounds containing mesogens of the present disclosure can be represented by a compound having Formula I:

[0019] In Formula I, each X can be represented independently by: (I) a group -R, (II) a group represented by - (L) yR, (III) a group represented by - (L) -R, (IV) a group represented by the structure:
or (V) a group represented by - (L) yP. In addition, in Formula I, each group P represents a group as defined above.
[0020] As described here and with reference to Formula I, the groups L, (L) y or (L) w represent a linking group connecting 2 to 3 groups, typically having a linear length of 1 to 500 atomic bonds. That is, for the general FLE structure, the maximum linear length of the linker group between groups F and E (where each of the groups F and E generally represents any of the groups P, R, X, or a mesogen) can range from 1 to 500 bonds (including intermediate atoms). It should be understood that when discussing the linear length of the linker group, the skilled technician will understand that the length of the linker group can be calculated by determining the length of each of the links in the linear sequence and the distance occupied by the various intermediate atoms in the linear sequence of the linker group and totaling the values. In certain embodiments, the longest linear link sequence can be at least 25 links between linked groups. In other embodiments, the longest linear sequence of connections can be at least 30 connections. In yet other incorporations, the longest linear sequence of connections can be at least 50 connections. It has been found that, in certain embodiments, an L-linker group with at least 25 bonds improves a variety of benefits of the resulting mesogen-containing compound. For example, a linker group of at least 25 bonds can improve the solubilities of additives, such as photochromatic compounds in compositions comprising compounds containing mesogens; it can provide improved or faster alignment properties of the compositions comprising the compounds containing mesogens; and / or can decrease the viscosity of a composition comprising the compound containing mesogen.
[0021] In each occurrence each L group can be the same or different and an unsubstituted, monosubstituted or polysubstituted spacer as defined above can be chosen independently of a single bond; “W” is an integer from 1 to 26, “y” is an integer from 2 to 25, and “z” is 1 or 2. It should be noted that when more than one group L occurs in the sequence, for example , in the (L) y or (L) w structure where “y” and / or “w” is a number greater than 1, then the adjacent L groups may or may not have the same structure. That is, for example, in a linking group having the structure - (L) 3 or -LLL- (that is, where “y” or “w” is 3), each group -L- can be chosen independently from any of the L groups mentioned above and adjacent -L- groups may or may not have the same structure. For example, in an exemplary embodiment, -LLL- can represent -C1-C30 alkylene-C1-C30 alkylene-C1-C30 alkylene- (i.e., where each occurrence of -L- is represented by C1-C30 alkylene , where each adjacent C1-C30 alkylene group can have the same number or different numbers of carbons in the alkylene group). In another exemplary embodiment, -L-L-L- can represent -arylene- (C1-C30 alkyl) silylene-C1-C30- alkenoxy (i.e., where each occurrence of -L- differs from the adjacent -L- groups). Therefore, the structure of (L) y or (L) w should be understood as covering all possible combinations of the various sequences of the -L- linker groups including those where some or all of the adjacent -L- groups are the same and where all adjacent -L- groups are different, as long as none of the two arylene groups are linked by a single bond. L can also be trivalent such that it can serve as a group that can be linked to other L groups as well as to groups P, R, X and / or mesogenous groups.
[0022] Still with reference to Formula I, the group R represents a terminal group as defined above. Also with reference to Formula I, each of the Mesogen-1 and Mesogen-2 groups is, independently, a liquid crystal group as a rigid straight stem, a liquid crystal group as a rigid curved stem, or a liquid crystal group as a disk hard. The structures for Mesogen-1 and Mesogen-2 can be any appropriate mesogenic group known in the art, for example, any of those mentioned in Demus et al., “Flüssige Kristalle in Tabellen”, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1974 and “Flüssige Kristalle in Tabellen II”, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1984. In addition, according to certain incorporations, the groups Mesogen-1 and Mesogen-2 can have, independently, a structure represented by: 1 12 23 34 5 - [S] c- [G - [S] d] d '- [G - [S] e] e' - [G - [S] f] f'-S -
[0023] The mesogenous structure above is further defined such that in each occurrence each group G1, G2, and G3 can be chosen independently from: a divalent group chosen from: an unsubstituted or substituted aromatic group, an alicyclic group not substituted or substituted, an unsubstituted or substituted heterocyclic group, and mixtures thereof, the substituents being chosen from: thiol, hydroxy (C1-C18 alkyl), isocyanate (C1-C18 alkyl), acryloyloxy, acryloyloxy (alkyl (C1-C18 alkoxy), halogen, C1-C18 alkoxy, poly (C1-C18 alkoxy), amino (C1-C18 alkylene), (C1-C18 alkyl) amino, C1-C18 alkyl, C2C18 alkenyl , C2-C18 alkynyl, (C1-C18 alkyl) (C1-C18 alkoxy), (C1-C18 alkoxy) carbonyl, (C1-C18 alkyl) carbonyl, (C1-C18 alkoxy) carbonyloxy, ( C1- C18 alkyloxy) carbonyloxy, aryloxy carbonyloxy, perfluoro (C1- C18 alkyl) amino, di (perfluoro (C1-C18 alkyl)) amino, C1-C18 acetyl, C3-C10 cycloalkyl, cycloalkoxy C3-C10, isocyanate, starch, cyano, nitro, a normal or branched chain C1-C18 alkyl group that is monosubstituted with cyan, halogen, or C1-C18 alkoxy, or polysubstituted with halogen, and a group comprising one of following formulas: -M (T) (t-1) and -M (OT) (t-1), in which M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, et is the valence of M. Furthermore, in the mesogenic structure, c, d, e, and f can be chosen independently from an integer ranging from 0 to 20, including e d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least equal to 1. Still with reference to the mesogenic structure above, the S groups represent spacer groups such that at each occurrence, each of the groups S1, S2, S3, S4, and S5 can be esc viewed independently of a spacer unit chosen from: (A) - (CH2) g-, - (CF2) h-, -Si (CH2) g-, or - (Si (CH3) 2O) h-, for each occurrence, “g” is chosen independently from 1 to 20 and “h” is an integer from 1 to 16, inclusive; (B) -N (Z) -, -C (Z) = C (Z) -, -C (Z) = N-, -C (Z ') 2-C (Z') 2-, or a bond simple, being that in each occurrence, Z is chosen independently of hydrogen, C1-C6 alkyl, cycloalkyl and aryl, and Z ', in each occurrence, is chosen independently of C1-C6 alkyl, cycloalkyl and aryl; or (C) -O-, -C (O) -, -C = C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - ( O) S (O) O-, -O (O) S (O) O- or C1-C24 alkylene residue of normal or branched chain being unsubstituted, monosubstituted by cyan or halogen, or polysubstituted by halogen; as long as when two spacer units comprising heteroatoms come together, the spacer units bond so that the heteroatoms do not bond directly to each other and when S1 and S5 bond to another group, they bond so that two heteroatoms do not connect directly to each other.
[0024] According to several incorporations disclosed here, in the structure of the above mesogen, c, d, e, and f are chosen independently of an integer ranging from 1 to 20, inclusive; and d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least equal to 1. According to other embodiments disclosed here, c, d, e, and f are chosen independently of an integer ranging from 0 to 20, inclusive; d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least equal to 2. According to still other embodiments disclosed here, c, d, e, and f are chosen independently of an integer ranging from 0 to 20, inclusive; d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least equal to 3. According to still other embodiments disclosed here, c, d, e, and f are chosen independently of an integer ranging from 0 to 20, inclusive; d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least equal to 1.
[0025] Finally, with reference to Formula I, the structure of the mesogen-containing compound requires that: (I) the group X is represented by R, so w is an integer from 2 to 25, and z is 1; (II) the group X is represented by - (L) yR, so w is 1, y is an integer from 2 to 25, and z is 1; (III) Group X is represented by - (L) wR, so w is an integer from 3 to 26, and z is 2; (IV) group X is represented by
then w is 1, y is an integer from 2 to 25, with the proviso that - (L) y- comprises at least two groups L that are different from a single bond and z is 1; (V) the group X is represented by - (L) yP, so w is 1, y is an integer from 2 to 25, ez is 1 and - (L) y- comprises a linear sequence of at least 25 bonds, preferably at least 30 connections between the mesogen and P; and in - (L) y- and - (L) w- neither of the two arylene groups is connected by a simple bond.
[0026] According to certain incorporations of the compound containing mesogen, the compound containing mesogen may be a compound containing mono mesogen (ie, a compound containing mesogen that has a mesogenic structure). According to an embodiment, the compound containing mono mesogen can have a structure represented by Formula I, in which the group X is represented by -R, "w" is an integer from 2 to 25, and "z" is 1. According to another embodiment, the compound containing mono mesogen can have a structure represented by Formula I, in which the group X is represented by - (L) yR, “w” is 1, “y” is an integer from 2 to 25, and “z” is 1.
[0027] According to other incorporations of the compound containing mesogen it can be a compound containing bi mesogen (that is, a compound that contains two mesogenic structures (which can be the same or different)). For several incorporations, the structures of the compound containing bi mesogen will have a long chain linker group between the two mesogenic units. According to an embodiment, the compound containing bi mesogen can have a structure represented by Formula I, in which the group X is represented by
where w is 1, y is an integer from 2 to 25, with the proviso that - (L) y- comprises at least two groups L that are different from a single bond and z is 1.
[0028] According to several incorporations, the mesogen-containing compound of the present disclosure represented by Formula I, may be a compound of liquid crystals. When used herein, the term "liquid crystal compound" means a compound that can exhibit liquid crystal properties. That is, the liquid crystal compound can exhibit liquid crystal properties alone and / or after being added to a polymer or copolymer to form an LCP.
[0029] Consequently, embodiments of the present disclosure also consider a polymer or copolymer that comprises the compound containing mesogen according to the various embodiments described herein. For example, according to an embodiment, the polymer or copolymer can comprise the mesogen-containing compound that is suspended or mixed in the polymer or copolymer composition. According to certain embodiments, the polymeric compositions comprising the compounds containing mesogens, as described herein, can be liquid crystal polymers. For example, the LCP can be an anisotropic LCP, an isotropic LCP, a thermotropic LCP, or a liotropic LCP. In various embodiments, the LCPs may exhibit at least one of a nematic phase, an emetic phase, a chiral nematic phase (i.e., a cholesteric phase), a discotic phase (including chiral discotic), a discontinuous cubic phase, a hexagonal phase , a bicontinuous cubic phase, a lamellar phase, a reverse hexagonal columnar phase, or an inverse cubic phase. In addition, in certain LCPs of the present disclosure, the LC monomers or residues thereof may change from one phase to another, for example, in response to thermal energy or actinic radiation.
[0030] In particular incorporations, the present disclosure provides a liquid crystal compound represented by the structure according to Formula II or Formula III:


[0031] According to these incorporations, the group P in either Formula II or III may be a group such as those shown in the listing for P described above. In addition, either in Formula II or III, in each occurrence, the groups (L) can be chosen independently, which can be the same or different, from the list of possible groups (L) shown here. Whether in Formula II or III, group R can be selected from the list of possible R groups presented here. The component mesogen of either Formula II or III may be a liquid crystal group as a rigid straight stem, a liquid crystal group as a rigid curved stem, or a liquid crystal group as a hard disk, such as the mesogens presented herein, including those having the structure: 1 12 23 34 5 - [S] c- [G - [S] d] d '- [G - [S] e] e' - [G - [S] f] f'-S - as defined herein. In addition, in Formulas II and III, "w" can be an integer ranging from 2 to 25 and "y" can be an integer ranging from 2 to 25.
[0032] In other embodiments, the present disclosure provides a bi-mesogen liquid crystal compound represented by the structure according to Formula IV or Formula V:

[0033] According to these incorporations, each group P in either Formula IV or V can be independently, a group such as those shown in the listing for P here described above. In addition, either in Formula IV or V, at each occurrence, the groups (L) can be chosen independently, which can be the same or different, from the list of possible groups (L) shown here. Whether in Formula IV or V, each R group can be selected independently from the list of possible R groups shown here. The component mesogens, either in Formula IV or V, may have liquid crystal groups as a rigid straight stem, liquid crystal groups as a rigid curved stem, liquid crystal groups as a hard disk, or a combination thereof. Thus, Mesogen-1 and Mesogen-2 of either Formula IV or V can be selected independently of the mesogenic structures shown here including those having the structure: 1 12 23 34 5 - [S] c- [G - [S] d] d '- [G - [S] e] e' - [G - [S] f] f'-S - as defined herein. In addition, in Formulas IV and V, “w” can be an integer ranging from 2 to 25.
[0034] In additional embodiments, the present disclosure provides a liquid crystal compound represented by the structure according to Formula VI:
defined above with respect to the structure according to Formula I in which X is - (L) yP.
[0035] According to the various embodiments of the mesogen-containing compounds disclosed herein, the structure of the mesogen-containing compound, for example, represented by Formulas I-VI described in detail here, can be designed to include a long flexible linker group between one or more portions of the compound. For example, in the various structures of the mesogen-containing compounds disclosed herein, the linker groups - (L) y- and / or - (L) w- and in certain cases the group - (L) - (for example, when - (L ) - comprises at least 25 linear bonds) may be a long flexible linker group comprising a long linear sequence of chemical bonds, ranging from 25 to 500 chemical bonds in length, between the two or three groups linked by the linker group. In certain embodiments, the linker groups may comprise a long linear sequence of chemical bonds ranging from 30 to 500 chemical bonds in length between the two or three groups. In other embodiments, the linker groups may comprise a long linear sequence of chemical bonds ranging from 50 to 500 chemical bonds in length between the two or three groups. When used with reference to the linker group, the chemical bonds in the linear sequence between the groups linked by the linker group may be polar or covalent covalent chemical bonds, such as polar or covalent covalent bonds and may also include one or more n-bonds ( although n-bonds are not included when calculating the length of chemical bonds in the linear sequence). In addition, those skilled in the art will understand that the linker group also comprises those intermediate atoms through which the linear sequence of bonds are associated.
[0036] As will be described in more detail here, it is believed that the one or more linking groups in the compounds containing mesogens disclosed herein confer desirable characteristics to the compound and compositions, such as cured compositions formed with them. For example, while not wishing to be bound by any interpretation, it is believed that the one or more flexible linker groups in the compound containing mesogen or residue therefrom may result in cured compositions prepared with the same having a "softer" structure. When used herein, with reference to the character of cured compositions, such as LCPs, layers, coatings, and coated articles made from the compounds, the term "softer" refers to compositions exhibiting a Fischer microhardness typically less than 150 N / mm2, for example, from 0 to 149.9 N / mm2. Cured compositions having a softer structure may exhibit desired or improved characteristics, for example, improved LC character, improved photochromatic performance, and improved dichroic performance. For example, for cured compositions such as a polymer, a copolymer or mixtures of (co) polymers, it may be desirable to have hard and soft components or segments in the polymer. The concept that cured polymers can be composed of hard and soft components or segments is known in the art (see, for example, “Structure-Property-Relationship in Polyurethanes”, Polyurethane Handbook, G. Oertel, 2nd edition, Hanser Publishers, 1994, pp 37-53). Typically, the hard component or segment includes a crystalline or semi-crystalline region within the cured polymeric structure, while the component or soft segment includes a more amorphous, non-crystalline or rubbery region. In certain embodiments, the contribution of the structure of a component or monomeric residue in a polymer to either the hardness or softness of the resulting polymer can be determined, for example, by measuring the Fischer microhardness of the resulting cured polymer. The physical properties of polymers are derived from their molecular structure and are determined by the choice of building blocks, for example, the choice of monomer and other reagents, additives, the ratio of hard and soft segments, and the supramolecular structures caused by atomic interactions between polymer chains. Materials and methods for the preparation of polymers, such as polyurethanes, are described in Ullmann’s Encyclopedia of Industrial Chemistry, 5th edition, 1992, Vol. A21, pages 665-716.
[0037] For example, in the photochromic and / or dichroic materials and coatings and cured layers described herein, it is believed that the components or soft segments of the polymeric material or cured coatings and layers can provide an improved solubilization environment for photochromatic materials, photochromatic / dichroic, and / or dichroic to transform reversibly from a first state to a second state, while the components or hard segments of the polymeric material or coating provide structural integrity for the material or coating and / or prevent migration of the transformable compounds. In an application of photochromic and / or dichroic materials, a balance of soft and hard components in the polymer can achieve desired advantages of a suitable cured material or cured coating or layer, i.e., a material, layer, or coating having a varying Fischer microhardness 0 to 150 N / mm2 which also exhibits good photochromatic and / or dichroic response characteristics. In another application, the photochromic and / or dichroic material may be located in a cured polymeric material having a Fischer microhardness less than 60 N / mm2, for example, from 0 to 59.9 N / mm2, or alternatively from 5 to 25 N / mm2, and coated with or contained within a harder polymeric material that provides structural strength. In a further application, the photochromic and / or dichroic material may already be contained within a soft polymeric material such as a soft polymeric coating that can be incorporated into a hard polymeric material or coating, for example, a material having a Fischer microhardness greater than 150 N / mm2, for example, greater than or equal to 200 N / mm2.
[0038] Other embodiments of the present disclosure provide compositions, articles of manufacture, optical elements, LC compositions, LC cells, and the like, comprising at least one compound containing mesogen represented by the structure of Formula I as described in detail herein.
[0039] In accordance with certain embodiments, the present disclosure provides a liquid crystal (LC) composition comprising a compound containing mesogen, as described herein.
[0040] LC compositions may further comprise a liquid crystal polymer including, for example, a cured LCP. The liquid crystal polymer may contain a compound containing mesogen represented by the structure of Formula I as defined herein. In specific embodiments, the LCP can be a copolymer, the copolymer comprising the compound containing mesogen being suspended or mixed in the copolymer.
[0041] General synthetic methods have been developed to synthesize the structures of the compounds containing mesogens represented by Formulas I-VI. Exemplary embodiments of approaches to the structures of the Formulas are illustrated in Figures 1-7. For example, referring to Figure 1, a group L was prepared in a stepwise process using Williamson ether esterification and synthesis reactions. Through the Steglich esterification reaction, the diacid obtained was used to form the compound containing bi mesogen represented by Formula I when z is 2 or by Formulas IV and / or V. Compounds containing similar bi mesogen were also prepared from commercially obtainable materials that were used to form L represented in Figures 2 and 3. Polycaprolactone diol in Figure 2 and polycarbonate diol in Figure 3 are also commercially obtainable. Figure 2 illustrates a Mitsunobu reaction that was used to form ether bonds. Figure 3 illustrates the Steglich esterification reaction that was used to form ester bonds.
[0042] Figures 4 to 7 illustrate the synthesis of compounds containing a single mesogen that can be represented by Formula I when z is 1 or by Formulas II, III, and IV. Figure 4 shows the formation of a soft polycaprolactone chain starting on one side of the mesogen by a Lewis acid catalyzed process or a base catalyzed process using excess caprolactone. The product reacted with propionyl chloride to form a non-reactive end group. It must be understood that this reaction is not limited to the use of propionyl chloride. For example, other materials that can be used include, but are not limited to: alkyl carboxylic acid chlorides, aryl carboxylic acid chlorides, alkyl chloroformates, aryl chloroformates, alkyl isocyanates and aryl isocyanates.
[0043] Figure 5 shows the formation of a soft polycarbonate chain starting at one end of the mesogen by a Lewis acid catalyzed process using excess cyclic carbonate. The product reacted with propionyl chloride to form a non-reactive end group. As mentioned above, it must be understood that this reaction is not limited to the use of propionyl chloride.
[0044] Figure 6 shows a mesogen having two reactive groups at both ends of the molecule. Soft chains were developed from both ends of the mesogen by a Lewis acid catalyzed process or a base catalyzed process using excess caprolactone. Then, the product reacted with propionyl chloride to form a non-reactive group. As mentioned above, this reaction is not limited to propionyl chloride. The product is represented by Formula I when z is 1 or by Formulas III and VI.
[0045] Figure 7 shows a method for forming a branched soft chain. In this approach, one of the three hydroxyl groups of a commercially obtainable triol reacted with a mesogen using Steglich esterification. The other two hydroxyl groups were used to develop a soft polycaprolactone chain via a Lewis acid catalyzed process using excess caprolactone. The product reacted with propionyl chloride to form terminal non-reactive groups. As mentioned above, this reaction is not limited to propionyl chloride. The product obtained has an L-branched structure and is represented by Formula I when z is 1 or by Formulas II, III, and VI.
[0046] It should be understood that the synthetic schemes shown in Figures 1-7 are presented for purposes of illustration and do not suggest any preferred approach for the synthesis of compounds containing mesogens represented by Formulas I-VI. Those of ordinary skill in the organic synthesis technique will recognize that numerous other synthetic approaches are possible based on the structure of the target compound containing mesogen. Such alternative synthetic approaches are within the scope of the present disclosure.
[0047] In specific embodiments, the polymer may or may not be a block copolymer comprising the compound containing mesogen. In certain embodiments, the block copolymer may comprise hard blocks and soft blocks. According to these incorporations, the compound containing mesogen can be dissolved (but not incorporated) in the hard block, in the soft block, or in both the hard block and the soft block. In other embodiments, the polymer may be a non-block copolymer (i.e., a copolymer that does not have large blocks of specific monomer residues), such as a random copolymer, an alternating copolymer, a periodic copolymer, and a statistical copolymer. For example, the mesogen-containing compound can be dissolved (but not incorporated) in the non-block copolymer. The present disclosure is also intended to cover copolymers of more than two different types of comonomer residues.
[0048] As defined herein, according to particular incorporations, the cured LCP can be a "soft" or "hard" polymer. For example, in certain embodiments, the LCP may have a Fischer microhardness less than 0 to 200 N / mm2. In other embodiments, the LCP may have an average number of at least 20 links between intra- or inter-spun crosslinks in a polymeric backbone. That is, in a linear sequence of bonds in a polymeric backbone, there is at least one linear sequence of 20 bonds between one crosslink and the next crosslink. While not wishing to be bound by any interpretation, it is believed that the intra- or inter-spun crosslinks in the main chain of a polymer, such as a cured LCP described herein, that differ from each other, for example, by at least 20 bonds , produces resulting rows of polymer that are more flexible and the resulting polymer has “softer” characteristics. As described herein, a polymer with "soft" characteristics may be desirable in certain applications, such as ophthalmic applications, for example, photochromatic applications.
[0049] In certain embodiments of the LC compositions of the present disclosure, the LC compositions may further comprise at least one of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, a non-photosensitive material, and a or more additives. According to these embodiments, the one or more additives can be a liquid crystal, a liquid crystal property control additive, a non-linear optical material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, an initiator thermal, a surfactant, a polymerization inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology control agent, a gelator, a leveling agent, a free radical purger, a coupling, a tilt control agent, a polymeric material in blocks or not in blocks, or adhesion promoter. When used here, the term “photochromatic compound” includes thermally reversible photochromic materials and thermally irreversible materials, which are generally capable of changing from a first state, for example, a “colorless state”, to a second state, for example, a “ colored state ”in response to actinic radiation, and return to the first state in response to thermal energy and actinic radiation, respectively. When used here, the term "photochromatic" means having an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation. When used here, the term "actinic radiation" means electromagnetic radiation, such as ultraviolet radiation and visible radiation that is capable of causing a response. When used here, the term "dichroic" means capable of absorbing one of two polarized components from orthogonal planes of at least transmitted radiation than the other. When used herein, the term "photosensitive material" includes materials that respond physically or chemically to electromagnetic radiation, such as, for example, phosphorescent materials or fluorescent materials. When used here, the term "non-photosensitive materials" includes materials that do not respond to electromagnetic radiation, such as fixed colored dyes or thermochromatic materials.
[0050] According to those incorporations in which the LC compositions comprise at least one of a photochromatic compound, a dichroic compound or a photochromatic / dichroic compound, the photochromatic compound may comprise a photochromatic group chosen from a thermally reversible or irreversible pyran, a thermally reversible or irreversible oxazins, or flashes thermally reversible or irreversible. Also included are inorganic photochromic materials. When used here, the term "thermally irreversible" means adapted to change from a first state to a second state in response to actinic radiation, and to return to the first state in response to actinic radiation.
[0051] Examples of thermally reversible photochromatic pyranes from which the photochromatic compound can be chosen and which can be used together with the various embodiments disclosed herein include benzopyranes, naphthopyranes, for example, naphthus [1,2-b] pyranes, naphthus [ 2,1- b] pyranes, fused indene naphthytophans, such as those disclosed in US Patent No. 5,645,767 in column 2, line 16 through column 12, line 57; and fused heterocyclic naphthopyranes, such as those disclosed in U.S. Patent Nos. 5,723,072 in column 2, row 27 through column 15, row 55; 5,698,141 in column 2, line 11 through column 19, line 45; 6,153,126 in column 2, row 26 through column 8, row 60; and 6,022,497 in column 2, line 21 through column 11, line 46; spiro-9-fluorene [1,2-b] pyran; phenanthropirans; quinopiranos; antenopyran fluorine; spiro piranos, for example, spiro (benzindoline) naphthopyran, spiro (indoline) benzopyran, spiro (indoline) naphthopyran, spiro (indoline) quinopyran, and spiro (indoline) piranos. More specific examples of naphthytophanes and complementary organic photochromatic substances are described in US patent No. 5,658,501 in column 1, line 64 through column 13, line 17. Spiro (indoline) pyranes are also described in the text “Techniques in Chemistry ”, Volume III,“ Photochromism ”, chapter 3, Glenn H. Brown, Editor, John Wiley & Sons, Inc., New York, 1971.
[0052] Non-limiting examples of thermally reversible photochromatic oxazins include benzoxazins, naphthoxazins, and spiro-oxazines, for example, spiro (indoline) naphthoxysins, spiro (indoline) pyridobenzoxazins, spiro (benzindoline) pyridobenzoxazins, spiro (benzindoline), spiro (benzindoline) naftox indoline) benzoxazines, spiro (indoline) fluoro antenoxazine, and spiro (indoline) quinoxazine.
[0053] Examples of thermally reversible photochromic fulgides from which photochromatic compounds can be chosen and which can be used together with the various embodiments disclosed herein include: fulgimides and 3-furyl and 3-thienyl fulgides and fulgimides, which are disclosed in the patent US No. 4,931,220 in column 2, line 51 through column 10, line 7, and mixtures of any of the aforementioned photochromic compounds / materials. Examples of thermally irreversible photochromic materials from which photochromatic compounds can be chosen and which can be used in conjunction with various embodiments disclosed herein include the photochromatic compounds disclosed in US patent application publication 2005/0004361 in paragraphs [0314] to [0317 ].
[0054] In certain embodiments, the photochromatic compound may be an inorganic photochromatic compound. Examples of inorganic photochromatic compounds include silver halide, cadmium halide and / or copper halide crystallites. Other examples of inorganic photochromatic compounds can be prepared by adding europium (II) and / or cerium (II) to a mineral glass, such as a soda / silica glass. According to an embodiment, the inorganic photochromatic compounds can be added in molten glass and molded into particles which are incorporated in the compositions of the present disclosure to form microparticles comprising such particulates. Glass particulates can be formed by any of a number of various methods known in the art. Inorganic photochromatic compounds are further described in Kirk Othmer Encyclopedia of Chemical Technology, 4th edition, volume 6, pages 322-325.
[0055] Other embodiments of the compositions may comprise a photosensitive material, including luminescent dyes, such as a phosphorescent dye or a fluorescent dye. Those skilled in the art know that after activation, phosphorescent and fluorescent dyes emit visible radiation when an atom or molecule changes from an upper to a lower electronic state. A difference between the two types of dyes is that the emission of luminescence after exposure to radiation from the fluorescent dye occurs more quickly than that of a phosphorescent dye.
[0056] Fluorescent dyes known to those skilled in the art can be used as photosensitive materials in various embodiments of the present disclosure. For a list of various fluorescent dyes, see, Haugland, RP “Molecular Probes Handbook for Fluorescent Probes and Research Chemicals”, 6th edition, 1996. Examples of fluorescent dyes include tetracene anthracenes, pentacenes, rodamides, benzophenones, coumarins, fluoresceins, perylenes, and mixtures thereof.
[0057] Phosphorescent dyes known to those skilled in the art can be used as photosensitive materials in various embodiments of the present disclosure. Suitable examples of phosphorescent dyes include metal binder complexes such as tris (2-phenyl pyridine) iridium, [Ir (ppy) 3], and 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II), [PtOEP]; and organic dyes such as eosin (2 ', 4', 5 ', 7'-tetrabromo fluorescein), 2,2'-bipyridine and erythrosine (2', 4 ', 5', 7'-fluorescein tetraiodine). Examples of non-photosensitive materials suitable for use in the compositions of the present disclosure include fixed color dyes. Examples of suitable fixed color dyes can include nitrobenzene dyes, azo dyes, anthraquinone dyes, naphthoquinone dyes, benzoquinone dyes, phenothiazine dyes, indigoid dyes, xanthene dyes, phenanthridine dyes, phthalocyanine dyes and dye derivatives triaryl methane. These fixed color dyes can be used alone or as mixtures with other fixed color dyes or with other chromophoric compounds (such as photochromatic compounds).
[0058] Suitable examples of dyes used with other chemicals suitable for preparing thermochromatic materials include substituted fluorans and phenyl methanes, such as 3,3'-dimethoxy fluorane (yellow); 3-chloro-6-phenylamino fluorane (orange); 3-diethylamino-6-methyl-7-chloro fluorane (red-scarlet color); 3-diethyl-78,8-benzo fluorane (pink); crystal violet lactone (blue); 3.3 ’, 3” -tris (p-dimethylamino phenyl) phthalide (purplish blue); malachite green lactone (green); 3,3-bis (p-dimethylamino phenyl phthalide (green); 3-detylamino-6-methyl-7-phenylamino fluoran (black), indolyl phthalides, spiro pyranes, coumarins, fulgides, etc. In addition, thermochromatic materials can also include cholesteric liquid crystals and mixtures of cholesteric liquid crystals and nematic liquid crystals.
[0059] According to a specific incorporation, the photochromatic compound can comprise at least two photochromatic groups, the photochromatic groups being linked to each other via linker group substituents on the individual photochromatic groups. For example, photochromatic groups can be polymerizable photochromatic groups or photochromatic groups that are adapted to be compatible with a host material ("compatible photochromatic group"). Examples of polymerizable photochromatic groups that can be chosen and which are useful together with various embodiments disclosed herein are disclosed in US Patent No. 6,113,814 in column 2, line 24 through column 22, line 7. Examples of compatible photochromatic groups which can be chosen and which are useful together with the various embodiments disclosed herein, in US Patent No. 6,555,028 in column 2, line 40 to column 24, line 56.
Other suitable photochromatic groups and complementary photochromatic groups are described in U.S. Patent Nos. 6,080,338 in column 2, line 21 through column 14, line 43; 6,136,968 in column 2, line 43 to column 20, line 67; 6,296,785 in column 2, line 47 to column 31, line 5; 6,348,604 in column 3, row 26 through column 17, row 15; 6,353,102 in column 1, line 62 to column column 11, 16, line line 64; 23. and 6,630,597 in column 2, line 16 to the
[0061] As shown above, in certain embodiments, the photochromatic compound may be a photochromatic pyran. According to these incorporations, the photochromic compound can be represented by Formula IX:

[0062] With reference to Formula IX, A is an unsubstituted or substituted aromatic ring or an unsubstituted or substituted fused aromatic ring chosen from: naphtha, benzo, phenantro, fluoranthene, antenna, quinoline, thieno, bore, indoline, indene benzofuro, benzothien, thiophene, fused indene naphtha, fused heterocyclic naphtha, and fused heterocyclic benzo. According to these incorporations, the possible substituents on the fused aromatic or aromatic ring are disclosed in US Patent Nos. 5,458,814, 5,466,398, 5,514,817, 5,573,712, 5,578,252, 5,637,262, 5,650. 098, 5,651,923, 5,698,141, 5,723,072, 5,891,368, 6,022,495, 6,022,497, 6,106,744, 6,149,841, 6,248,264, 6,348,604, 6,736,998, 7,094,368, 7,262,295 and 7,320,826. According to Formula IX, "i" can be the number of substituents R 'attached to ring A, and can range from 0 to 10. Furthermore, with reference to Formula IX, B and B' can independently represent a chosen group from: a metallocenyl group (such as those described in US patent application publication 2007/0278460 in paragraphs [0008] to [0036]); an aryl group that is monosubstituted with a reactive substituent or compatibilizing substituent (such as those discussed in US patent application publication 2007/0278460 in paragraphs [0037] to [0059]); 9- julolidinyl, an unsubstituted, mono, di or tri-substituted aryl group chosen from phenyl and naphthyl, an unsubstituted, mono or disubstituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoil, benzopyridyl, indolinyl and fluorenyl, with each of the aryl and heteroaromatic substituents chosen independently from: hydroxy, aryl, (C1- mono or dialcoxy) C12) aryl, (C1-C12 mono or dialkyl) aryl, haloaryl, (C3-C7 cycloalkyl) aryl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, (C3-C7 cycloalkoxy) C1-C12 alkyl , (C3-C7 cycloalkoxy) C1-C12 alkoxy, aryl (C1-C12 alkyl), aryl (C1-C12 alkoxy), aryloxy, aryloxy (C1-C12 alkyl), aryloxy (C1-C12 alkoxy ), (C1C12 mono or dialkyl) aryl (C1-C12 alkyl), (C1C12 mono or dialkoxy) aryl (C1-C12 alkyl), (C1C12 mono or dialkoxy) aryl (C1-C12 alkoxy), amino , (C1-C12 mono or dialkyl) amino, diarylamino, piperazine, N- (C1-C20 alkyl) piperazine, N-aryl-piperazine, aziridine, indoline, piperidine, morpholino, thiomorpholino, tetrahydroquinoline, tetrahydroquinoline, pyrrolidine, pyrrolidine, pyrrolidine C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkoxy, mono (C1C20 alkoxy) (C1-C20 alkyl), acryloxy, methacryloxy, halogen or - C (= O) R1, in which R1 represents a group, such as, -OR2, - N (R3) R4, piperidine or morpholino, where R2 represents a group, such as, allyl, C1-C6 alkyl, phenyl, phenyl substituted with C1-C6 monoalkyl, phenyl substituted with C1-C6 monoalkoxy, phenyl (C1-C3 alkyl), phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkyl, phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkox, ( C1- C6 alkoxy) (C2-C4 alkyl) or C1-C6 haloalkyl, and each of R3 and R4 represents a group, such as C1-C6 alkyl, C5-C7 cycloalkyl, or unsubstituted phenyl or replaced, and said subs phenyl substituents are independently C1-C6 alkyl or C1-C6 alkoxy; an unsubstituted or monosubstituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidine, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, said substituents being independently C1-C12 alkyl, C1-C12 alkoxy, phenyl or halogen; a phenyl group substituted in position 4, the substituent being a dicarboxylic acid residue or derivative thereof, a polyol residue or derivative thereof, - (CH2) -, - (CH2) k- or - [O- (CH2) k] q, where "k" represents an integer ranging from 2 to 6 and "q" represents an integer ranging from 1 to 50, and the substituting one binds to an aryl group of another photochromatic material; a group represented by:

where W represents a group, such as -CH2- or oxygen; Y represents a group such as oxygen or substituted nitrogen, provided that when Y represents substituted nitrogen, W will represent -CH2-, the substituted nitrogen substituents being hydrogen, C1-C12 alkyl or C1-C12 acyl; each R5 independently represents a group, such as C1-C12 alkyl, C1-C12 alkoxy, hydroxy or halogen; each R6 and R7 independently represents a group, such as hydrogen or C1-C12 alkyl; and "j" represents an integer ranging from 0 to 2; or a group represented by;
R8 R9 in which R8 represents a group, such as hydrogen or C1-C12 alkyl, and R9 represents a group, such as an unsubstituted, mono or disubstituted naphthyl, phenyl, furanyl or thienyl group, said naphthyl substituents , phenyl, furanyl and thienyl are, independently, C1-C12 alkyl, C1-C12 alkoxy or halogen. Alternatively, B and B 'may represent groups that together form a mono- or disubstituted fluoren-9-ylidene or fluoren-9-ylidene, each of said fluoren-9-ylidene substituents being independently C1-C12 alkyl, C1 alkoxy -C12 or halogen.
[0063] Furthermore, with reference to Formula IX, R 'can be a substituent on a ring in Formula IX, and if R' is a substituent on a sp3 hybridized carbon, each R 'can be independently selected from: a metallocenyl group; a reactive substituent or a compatibilizing substituent; C1-C10 perhaloalkyl, C2-C10 perhaloalkenyl, C3-C10 perhaloalkyl, C1C10 perhaloalkoxy, or C3-C10 perhaloalkyl; a group represented by —O (CH2) to (CJ2) bCK3, in which K is halogen, J is hydrogen or halogen, “a” is an integer ranging from 1 to 10, and “b” is an integer ranging from 1 to 10; a group containing silicon represented by one in which each of
R10, R11, and R12 are independently C1-C10 alkyl, C1-C10 alkoxy, or phenyl; hydrogen, hydroxy, C1-C8 alkyl, chlorine, fluorine, C3-C7 cycloalkyl, C1-C8 allyl or haloalkyl; morpholino, piperidino, pyrrolidino, an unsubstituted, mono or disubstituted amino, said amino substituents being independently C1-C6 alkyl, phenyl, benzyl or naphthyl; an unsubstituted, mono, di or tri-substituted aryl group chosen from phenyl, naphthyl, benzyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, being the ar substitutents independently. halogen, C1-C6 alkyl or C1-C6 alkoxy; -C (= O) R13, in which R13 is hydrogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 amino, mono or dialkylamino, morpholino, piperidine, pyrrolidine, a non-phenyl or naphthyl group substituted, mono or disubstituted, substituted, mono or disubstituted phenoxy, substituted, mono or disubstituted phenylamino, each of said phenyl, naphthyl, phenoxy and phenylamino substituents being independently C1-C6 alkyl or C1-C6 alkoxy; -OR14, in which R14 is C1-C6 alkyl, C1-C3 phenyl (alkyl), C1-C3 monoalkyl substituted phenyl (alkyl), C1-C3 monoalkoxy substituted phenyl (alkyl) C1-C6, (C1-C6 alkoxy) C2-C4 alkyl, C3-C7 cycloalkyl, C3-C7 cycloalkyl substituted with C1-C4 monoalkyl, C1-C8 chloroalkyl, C1-C8 fluoroalkyl, allyl or acyl of C1-C6, -CH (R15) R16, in which R15 is hydrogen or C1-C3 alkyl, and R16 is -CN, —CF3 or -COOR17, in which R17 is hydrogen or C1-C3 alkyl, or -C (= O) R18 in which R18 is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 amino, mono or dialkylamino, unsubstituted, mono or disubstituted phenyl or naphthyl, substituted, mono or disubstituted phenoxy , substituted, mono or disubstituted phenylamino, each of said substituents for phenyl, naphthyl, phenoxy and phenylamino being independently, C1-C6 alkyl or C1-C6 alkoxy; a phenyl group substituted in position 4, the substituent being a dicarboxylic acid residue or derivative thereof, a polyol residue or derivative thereof, - (CH2) -, - (CH2) k- or - [O- (CH2) k] q, where "k" represents an integer ranging from 2 to 6 and "q" represents an integer ranging from 1 to 50, and the substituting one binds to an aryl group of another photochromatic material; -CH (R19) 2, in which R19 is -CN or - COOR20, in which R20 is hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl (C1-C3 alkyl), phenyl (C1- alkyl C3) substituted by C1-C6 monoalkyl, phenyl (C1-C3 alkyl) substituted by C1-C6 monoalkoxy or unsubstituted, mono or disubstituted phenyl or naphthyl, said phenyl and naphthyl substituents being independently C1 alkyl -C6 or C1-C6 alkoxy; -CH (R21) R22 in which R21 is hydrogen, C1-C6 alkyl or unsubstituted, mono or disubstituted phenyl or naphthyl, said phenyl and naphthyl substituents being independently C1-C6 alkyl or C1-C6 alkoxy , and R22 is -C (= O) OR23, - C (= O) R24, or -CH2OR25, where R23 is hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl (C1-C3 alkyl) , phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkyl, phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkoxy or unsubstituted, mono or disubstituted phenyl or naphthyl, said phenyl substituents and naphthyl are independently C1-C6 alkyl or C1-C6 alkoxy, R24 is hydrogen, C1-C6 alkyl, amino, C1-C6 monoalkylamino, C1-C6 dialkylamino, phenylamino, diphenylamino, (phenyl substituted with mono or C1-C6 dialkyl) amino, (phenyl substituted with mono or C1-C6 dialkoxy) amino, morpholino, piperidino or an unsubstituted, mono or disubstituted phenyl or naphthyl group, where said phenyl or naphthyl substituents are C1-C6 alkyl or C1-C6 alkoxy, and R25 is hydrogen, -C (= O) OR23, C1-C6 alkyl, (C1- C3 alkoxy) C1- alkyl C6, phenyl (C1-C3 alkyl), phenyl (C1-C3 alkyl) substituted with monoalkoxy or unsubstituted, mono or disubstituted phenyl or naphthyl, said phenyl and naphthyl substituents being independently C1-C6 alkyl or C1-C6 alkoxy; or two R 'groups on the same atom together form an oxo group, a spiro-carbocyclic group containing from 3 to 6 carbon atoms or a spiro-heterocyclic group containing from 1 to 2 oxygen atoms and from 3 to 6 carbon atoms including the spiro-carbon atom, said spiro-carbocyclic and spiro-heterocyclic groups forming rings with 0, 1 or 2 benzene rings; or when R 'is a substituent on a sp2 hybrid carbon, each R' may be independently: hydrogen, C1-C6 alkyl; chlorine; fluorine; bromine; C3-C7 cycloalkyl; unsubstituted, mono- or disubstituted phenyl, said phenyl substituents being independently C1C6 alkyl or C1-C6 alkoxy; -OR26 or -OC (= O) R26 in which R26 is hydrogen, amine, alkylene glycol, poly (alkylenic glycol), C1-C6 alkyl, phenyl (C1-C3 alkyl), phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkyl, phenyl (C1-C3 alkyl) substituted with C1-C6 monoalkoxy, (C1-C6 alkoxy) C2-C4 alkyl, C3-C7 cycloalkyl, C3-C7 cycloalkyl substituted with C1-C4 monoalkyl, or unsubstituted, mono or disubstituted phenyl, said phenyl substituents being independently C1-C6 alkyl or C1-C6 alkoxy; a reactive substituent or a compatibilizing substituent; a phenyl group substituted in position 4, the substituent being a dicarboxylic acid residue or derivative thereof, a polyol residue or derivative thereof, - (CH2) -, - (CH2) k- or - [O- (CH2) k] q, where "k" represents an integer ranging from 2 to 6 and "q" represents an integer ranging from 1 to 50, and the substituting one binds to an aryl group of another photochromatic material; -N (R27) R28, where R27 and R28 are independently hydrogen, C1-C8 alkyl, naphthyl phenyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzotien-2-yl, benzotien- 3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, (C1- C8 alkyl) aryl, C3-C8 cycloalkyl, C4-C16 bicycloalkyl, C5-C20 tricycloalkyl or (C1-C20 alkoxy) C1C6 alkyl or R27 and R28 join with the nitrogen atom to form a C3-C20 straight-bicycloalkyl ring or a C4-C20 straight-tricycloalkyl ring; a nitrogen-containing ring represented by:
where in each occurrence, each -V- is chosen independently from -CH2-, -CH (R29) -, -C (R29) 2-, - CH (aryl) -, -CH (aryl) 2- and -CH (R29) (aryl) -, each R29 being independently phenyl or naphthyl; -U- is -V-, -O-, -S-, -S (O) -, -SO2-, -NH-, -N (R29) - or -N (aryl) -; "S" is an integer ranging from 1 to 3; and "r" is an integer ranging from 0 to 3, provided that if "r" is 0 (zero) then -U- and -V- will be the same; a group represented by: in which each R30 is independently, C1-C6 alkyl, C1-C6 alkoxy, fluorine or chlorine; R31, R32 and R33 are, independently, hydrogen, C1-C6 alkyl, phenyl or naphthyl, or R31 and R32 together form a ring of 5 to 8 carbon atoms; and "p" is an integer ranging from 0 to 3 or an unsubstituted or substituted C4-C18 spiro-bicyclic amine or an unsubstituted or substituted C4-C18 spiro-tricyclic amine, said substituents being independently aryl, alkyl C1-C6, C1-C6 alkoxy or phenyl (C1-C6 alkyl); or R 'can be a metallocenyl group; alkyl perfluor or alkoxy perfluor; -C (= O) R34 or -SO2R34, where each R34 is independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or unsubstituted, mono or disubstituted phenyl, and said phenyl substituents are independently C1-C6 alkyl or C1-C6 alkoxy; -C (= C (R38) 2) R39, where each R38 is independently, -C (= O) R34, -OR35, -OC (= O) R35, -NR36R37, hydrogen, halogen, cyano, C1- alkyl C6, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or an unsubstituted, mono or disubstituted phenyl group, said phenyl substituents being independently C1-C6 alkyl or C1-C6 alkoxy; and R39 is hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or an unsubstituted, mono or disubstituted phenyl group, said phenyl substituents being independently C1-C6 alkyl or C1C6 alkoxy; or -C = CR40 or -C = N, where R40 is -C (= O) R34, hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, or an unsubstituted, mono or disubstituted phenyl group, with said phenyl substituents are independently C1C6 alkyl or C1-C6 alkoxy; or at least a pair of adjacent R 'groups together form a group represented by:
in which each R30 is independently, C1-C6 alkyl, C1-C6 alkoxy, fluorine or chlorine; R31, R32 and R33 are, independently, hydrogen, C1-C6 alkyl, phenyl or naphthyl, or R31 and R32 together form a ring of 5 to 8 carbon atoms; and "p" is an integer ranging from 0 to 3 or an unsubstituted or substituted C4-C18 spiro-bicyclic amine or an unsubstituted or substituted C4-C18 spiro-tricyclic amine, said substituents being independently aryl, alkyl C1-C6, C1-C6 alkoxy or phenyl (C1-C6 alkyl); or R 'can be a metallocenyl group; alkyl perfluor or alkoxy perfluor; -C (= O) R34 or –SO2R34, where each R34 is independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or unsubstituted, mono or disubstituted phenyl, and said phenyl substituents are independently C1-C6 alkyl or C1-C6 alkoxy; -C (= C (R38) 2) R39, where each R38 is independently, -C (= O) R34, -OR35, -OC (= O) R35, -NR36R37, hydrogen, halogen, cyano, C1- alkyl C6, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or an unsubstituted, mono or disubstituted phenyl group, said phenyl substituents being independently C1-C6 alkyl or C1-C6 alkoxy; and R39 is hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, alkylene glycol, poly (alkylene glycol) or an unsubstituted, mono or disubstituted phenyl group, said phenyl substituents being independently C1-C6 alkyl or C 1 -C 6 alkoxy; or -C≡CR40 or -C≡N, where R40 is –C (= O) R34, hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, or an unsubstituted, mono or disubstituted phenyl group, with said phenyl substituents are independently C1-C6 alkyl or C1-C6 alkoxy; or at least a pair of adjacent R 'groups together form a group represented by:
where D and D 'are, independently, oxygen or the group - NR27-; or two R 'groups on adjacent atoms together form a fused aromatic or heteroaromatic group, said fused group being benzo, indene, dihydronaphthalene, indole, benzofuran, benzopyrans or thianaftene.
[0064] In other embodiments, the LC compositions of the present disclosure may comprise a dichroic compound. Suitable dichroic compounds are described in detail in US Patent No. 7,097,303 in column 7, lines 6 to 60. Other examples of suitable conventional dichroic compounds include azomethines, indigoids, thioindigoids, merocyanins, indanes, quinophthalonic dyes, perylenes, phthaloperins, triphenodioxazins , indoloquinoxaline, imidazo-triazines, tetrazines, azo and poly (azo) dyes, benzoquinones, naphthoquinones, anthraquinone and (poly) anthraquinones, anthropirimidinones, iodine and iodates. In another embodiment, the dichroic material can be a polymerizable dichroic compound. That is, according to this incorporation, the dichroic material can comprise at least one group that is capable of being polymerized (i.e., a "polymerizable group" or "reactive group"). For example, in an embodiment, the at least one dichroic compound can have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent terminated with at least one polymerizable group. When used here, the term "dichroic" means capable of absorbing one of two polarized components in orthogonal planes of at least radiation transmitted more strongly than the other. When used here, the terms "linearly polarize" or "linear polarization" mean to confine the vibrations of the electric light wave vector in one direction. Consequently, dichroic dyes are able to absorb one of two polarized components in orthogonal planes of at least transmitted radiation more strongly than the other, thus resulting in linear polarization of the transmitted radiation. However, although dichroic dyes are able to preferentially absorb one of two components polarized in orthogonal planes of transmitted radiation, if the dichroic dye molecules are not aligned, no final linear polarization of transmitted radiation will be achieved. That is, due to the random placement of the dichroic dye molecules, selective absorption by the individual molecules can be canceled such that no final or global polarizing effect is achieved. Thus, it is generally necessary to align the dichroic dye molecules in order to achieve a final linear polarization. An alignment means as described in US patent application publication 2005/0003107 in paragraphs [0008] to [0126], can be used to facilitate the positioning of an optically anisotropic dye, such as a dichroic dye, thus achieving an effect or desired optical property.
[0065] Still other embodiments of the LC compositions here may comprise a photochromatic / dichroic compound. When used here, the term "photochromatic / dichroic" means to exhibit both photochromatic and dichroic properties (that is, linearly polarize) under certain conditions, which are at least detectable by instrumentation. Consequently, “photochromatic / dichroic compounds” are compounds that exhibit both photochromatic and dichroic properties (ie, linear polarization) under certain conditions, which are at least detectable by instrumentation. Thus, photochromatic / dichroic compounds have an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation and are capable of absorbing one of two polarized components in orthogonal planes of at least transmitted radiation more strongly than the other. In addition, as with the photochromatic compounds discussed above, the photochromatic / dichroic compounds disclosed herein can be thermally reversible. That is, photochromatic / dichroic compounds can change from a first state to a second state in response to actinic radiation and return to the first state in response to thermal energy.
[0066] In addition, according to various embodiments disclosed herein, the mesogen-containing material can be adapted to allow at least one photochromatic compound, dichroic compound, or photochromatic / dichroic compound to change from a first state to a second state at a rate desired. Generally speaking, conventional photochromatic / dichroic compounds can undergo a transformation from one isomeric form to another in response to actinic radiation, with each isomeric form having a characteristic absorption spectrum and / or characteristic polarization. The photochromatic compound, dichroic compound, or photochromatic / dichroic compound according to the various embodiments disclosed herein undergo a similar isomeric transformation. The rate or speed at which this isomeric transformation occurs (and the inverse transformation) depends, in part, on the properties of the cured layer comprising the mesogen-containing compound surrounding the photochromatic compound, dichroic compound, or photochromatic / dichroic compound (ie, the “ host"). The inventors believe that the transformation rate of the photochromatic / dichroic compounds will depend, in part, on the flexibility of the host chain segments, that is, on the mobility or viscosity of the host chain segments. In particular, it is believed that the transformation rate of the photochromatic compound, dichroic compound, or photochromatic / dichroic compound will generally be faster in hosts that have flexible chain segments than in hosts that have rigid or hard chain segments. Therefore, according to certain embodiments disclosed herein, in which the at least partial layer comprising a composition comprising the mesogen-containing compound is a host, the composition can be adapted to allow the photochromatic compound, dichroic compound, or photochromatic / dichroic compound to become transform between various isomeric states at desired rates. For example, the composition can be adapted by adjusting one or more of the molecular weight and crosslinking density of the mesogen-containing compound.
[0067] For example, according to various embodiments disclosed herein, the at least one photochromatic / dichroic compound can have a first state having a first absorption spectrum, a second state having a second absorption spectrum that is different from the first spectrum of absorption absorption, and can be adapted to change from the first state to the second state in response to actinic radiation and return to the first state in response to thermal energy. In addition, the photochromatic / dichroic compound can be dichroic (i.e., linearly polarized) in one or both of the first and second states. For example, although not required, the photochromatic / dichroic compound can be linearly polarized in an activated state and non-polarized in the bleached or faded (i.e., not activated) state. When used herein, the term "activated state" refers to the photochromatic / dichroic compound when exposed to sufficient actinic radiation to cause at least a portion of the photochromatic / dichroic compound to change from a first state to a second state. In addition, although not required, the photochromatic / dichroic compound can be dichroic in both the first and the second states. For example, the photochromatic / dichroic compound can linearly polarize visible radiation in both the activated and non-activated states. In addition, the photochromatic / dichroic compound can linearly polarize visible radiation in an activated state, and can linearly polarize UV radiation in the non-activated state. Examples of suitable photochromatic / dichroic compounds that can be included in the LC compositions described herein include those disclosed in U.S. patent application publication 2005/0012998 in paragraphs [0089] to [0339]. In addition, a general structure for certain photochromatic / dichroic compounds is provided in U.S. Patent No. 7,342,112 in column 5, line 35 through column 31, line 3 and Table V covering columns 97-102.
[0068] For example, it is considered that the photochromatic compounds and / or photochromatic / dichroic compounds disclosed herein can be used alone or together with another conventional organic photochromatic compound (as discussed above), in amounts or reasons such that the compositions of LCs in which the photochromatic or photochromatic / dichroic compounds are incorporated, or on which the LC compositions (for example, the substrate) are applied, may exhibit desired color or colors, which in an activated state or in an unactivated state. Thus, the amount of the photochromatic or photochromatic / dichroic compounds is not critical as long as a sufficient amount is present to produce a desired photochromatic effect. When used here, the term "photochromatic amount" refers to the amount of the photochromatic or photochromatic / dichroic compound needed to produce the desired photochromatic effect.
[0069] LC compositions and other articles according to the various embodiments disclosed herein may comprise any amount of the photochromatic compound, dichroic compound and / or photochromatic / dichroic compound necessary to dye the desired optical properties, such as photochromatic properties or dichroic properties .
[0070] According to specific embodiments of the LC compositions, the compositions may further comprise an additive selected from a liquid crystal, a liquid crystal property control agent, a non-linear optical material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, a thermal initiator, a surfactant, a polymerization inhibitor, a solvent, a light stabilizer (such as ultraviolet light absorbers and light stabilizers such as hindered amine light stabilizers (HALS)), a thermal stabilizer, release agent, rheology-controlling agent, gelator, leveling agent (such as a surfactant), free radical scavenger, or adhesion promoter (such as hexanediol diacrylate and coupling agents) .
[0071] Liquid crystal materials used here can be chosen from liquid crystal polymers, liquid crystal prepolymers, and liquid crystal monomers. When used herein, the term "prepolymer" means partially polymerized materials.
[0072] Liquid crystal monomers that are suitable for use in conjunction with the various embodiments disclosed herein include monofunctional as well as polyfunctional liquid crystal monomers. In addition, according to the various embodiments disclosed herein, the liquid crystal monomer can be a cross-linkable liquid crystal monomer, and it can also be a photoreticulable liquid crystal monomer. When used herein, the term “photoreticulable” means a material, such as a monomer, a prepolymer or a polymer, which can be cross-linked by exposure to actinic radiation.
[0073] Examples of crosslinkable liquid crystal monomers suitable for use according to the various embodiments disclosed herein include liquid crystal monomers having functional groups chosen from acrylates, methacrylates, allyl, allyl ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers and mixtures thereof. Examples of crosslinkable liquid crystal monomers suitable for use in accordance with the various embodiments disclosed herein include liquid crystal monomers having functional groups chosen from acrylates, methacrylates, alkali, epoxides, hydroxides, thiols and mixtures thereof. Those skilled in the art know other suitable cross-linking functional groups.
[0074] Liquid crystal polymers and prepolymers that are suitable for use in conjunction with various embodiments disclosed herein include thermotropic liquid crystal prepolymers and polymers, and lyotropic liquid crystal polymers and prepolymers. In addition, liquid crystal polymers and prepolymers can be main chain polymers and prepolymers or side chain polymers and prepolymers. In addition, according to the various embodiments disclosed herein, liquid crystal polymers and prepolymers can be cross-linked, and can also be photoreticulable.
[0075] Examples of suitable liquid crystal polymers and prepolymers that are suitable for use in accordance with the various embodiments disclosed herein include main and side chain polymers and prepolymers having functional groups chosen from acrylates, methacrylates, allyl, allyl ethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates, siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers and mixtures thereof. Examples of crosslinkable liquid crystal polymers and prepolymers that are suitable for use in accordance with the various embodiments disclosed herein include those liquid crystal polymers and prepolymers having functional groups chosen from acrylates, methacrylates, alkines, epoxides, hydroxides, thiols and mixtures thereof.
[0076] In certain incorporations, one or more surfactants can be used. Surfactants include materials known differently as wetting agents, defoaming agents, emulsifiers, dispersing agents, leveling agents, etc. Surfactants can be anionic, cationic and non-ionic, and many surfactants of each type are commercially available. Examples of nonionic surfactants that can be used include ethoxylated alkyl phenols, such as IGEPAL® DM surfactants or octyl-phenoxy polyethoxy ethanol sold as TRITON® X-100, ethoxylated acetylenic diols such as the SURFYNOL® 400 series surfactants, fluorinated surfactants, such as the FLUORAD® series of fluorinated chemical surfactants, and capped non-ionic surfactants such as benzyl capped octyl phenol ethoxylates sold as TRITON® CF87, propylene oxide capped alkyl ethoxylates, which are obtainable as a series of PLURAFAC® RA surfactants, octyl phenoxy hexadecyl ethoxy benzyl ether, copolymer of polyester modified dimethyl polysiloxane in solvent sold as an additive BYK®-306 by Byk Chemie and mixtures of such mentioned surfactants.
[0077] Incorporations of nonlinear materials (NLO) can include substantially any organic material that exhibits nonlinear optical properties and forms crystals, which are obtainable at present or which may be synthesized in the future. Examples include the following organic compounds: N- (4-nitro phenyl) - (L) -prolinol (NPP); 4-N, N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST); 2-methyl-4-nitro aniline (MNA); 2-amino-5-nitro pyridine (2A5NP); p-chlorophenyl urea (PCPU); and 4- (N, N-dimethylamino) -3-nitrobenzene acetamido (DAN). Additional examples of suitable NLO materials are disclosed in U.S. Patent No. 6,941,051 in column 4, lines 4-37.
[0078] Examples of thermal stabilizers may include a basic nitrogen-containing compound, for example, biurea, allantoin or a metal salt thereof, a carboxylic acid hydrazide, for example, an aliphatic or aromatic carboxylic acid hydrazide, a metal salt of an organic carboxylic acid, an alkali or alkaline earth metal compound, a hydrotalcite, a zeolite and an acidic compound (for example, boric acid, a nitrogen-containing cyclic compound having a hydroxyl group, a carboxyl-containing compound, a (poly) phenol, butylated hydroxy-toluene, and an amino carboxylic acid) or mixtures thereof.
[0079] Examples of release agents include esters of long-chain aliphatic acids and alcohols such as pentaerythritol, Guerbet alcohols, long-chain ketones, siloxanes, alpha-olefinic polymers, long-chain alkanes and hydrocarbons having 15 to 600 atoms carbon.
[0080] Rheology control agents are thickeners that are typically powders that can be inorganic, such as silica, organic, such as microcrystalline cellulose or particulate polymeric materials. Gelifiers or gelling agents are often organic materials that can also affect the thixotropy of the material to which they are added. Examples of suitable gelling agents or gelling agents include natural gums, starches, pectins, agar, and gelatines. Often, gelling agents or gelling agents are based on polysaccharides or proteins.
[0081] Free radical scavengers include synthetic pseudopeptides resistant to hydrolysis such as carcinin chloride; lipoic amino acids such as L-lysine lauroyl methionine; plant extracts containing an active hydrogen such as -OH, -SH, or -NRH group. Additional examples of free radical scavengers are chosen from the group of sterically hindered amines (HALS = hindered amine light stabilizer) which, unlike the usual light protection agents, are not based on the absorption of radiated light or the tempering of absorbed light. , but essentially in the ability to purge or replace free radicals and hydroperoxides formed during the photodegradation of polymeric and antioxidant materials.
[0082] Adhesion promoters include organic silane materials adhesion promoters, such as organic amino silane materials, silane coupling agents, organic titanate coupling agents and organic zirconate coupling agents described in the US patent application publication 2004/0207809 in paragraphs [0033] to [0042]. Additional examples of adhesion promoters include zirco-aluminate adhesion promoters that are commercially obtainable from Rhone-Poulenc. The preparation of aluminum / zirconium complexes is described in U.S. Patent Nos. 4,539,048 and 4,539,049. These patents describe zirco-aluminate complex reaction products corresponding to the empirical formula: (Al2 (OR1O) aAbBc) x (OC (R2) O) y (ZrAdBe) z, in which x, y and z are at least 1, R1 is an alkyl, alkenyl, amino alkyl, carboxy alkyl, alkyl mercapto, or epoxy alkyl group, having from 2 to 17 carbon atoms, and the ratio of x: z is from about 2: 1 to about 5: 1. Additional zirco-aluminate complexes are described in U.S. Patent No. 4,650,526.
[0083] Examples of dyes that can be present in the at least partial coating, according to various embodiments disclosed herein include organic dyes that are capable of imparting a desired color or other optical property to the at least partial coating.
[0084] When used here, the term "alignment promoter" means an additive that can facilitate at least one of the rate and uniformity of the alignment of a material to which it is added. Examples of alignment promoters that may be present in at least partial coatings according to various embodiments disclosed herein include those described in U.S. Patent No. 6,338,808 and in U.S. Patent Publication No. 2002/0039627.
[0085] Examples of kinetic enhancing additives that may be present in at least partial coatings according to various embodiments disclosed herein include compounds containing epoxy, organic polyols and / or plasticizers. More specific examples of such kinetic enhancing additives are disclosed in U.S. Patent No. 6,433,043 and U.S. Patent Publication No. 2003/0045612.
[0086] Examples of photoinitiators that can be present in at least partial coatings according to various embodiments disclosed herein include cleavage-type photoinitiators and abstraction-type photoinitiators. Examples of cleavage-type photoinitiators include acetophenones, α-amino alkyl phenones, benzoyl ethers, benzoyl oximes, acyl phosphine oxides and bis acyl phosphine oxides or mixtures of such initiators. A commercial example of such a photoinitiator is DAROCURE® 4265, which is obtainable from Ciba Chemicals, Inc. Examples of abstraction-type photoinitiators include benzophenone, Michler's ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocumaine or mixtures of such initiators.
[0087] Another example of a photoinitiator that can be present in the LC compositions according to several incorporations disclosed here is a visible light photoinitiator. Examples of suitable visible light photoinitiators are shown in column 12, line 11 through column 13, line 21 of U.S. Patent No. 6,602,603.
[0088] Examples of thermal initiators include organic peroxy and organic nitrile azobis. Specific examples of organic peroxy that are useful as thermal initiators include peroxy monocarbonates, such as terciobutyl peroxy isopropyl carbonate; peroxy dicarbonates, such as di (2-ethyl hexyl) peroxy dicarbonate, di-secbutyl peroxy dicarbonate and diisopropyl peroxy dicarbonate; diaciperoxides, such as 2,4-dichloro benzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and benzoyl p-chloride peroxide; peroxy esters such as terciobutyl peroxy pivalate, tertiobutyl peroxy octylate, and terciobutyl peroxy isobutyrate; methyl ethyl ketone peroxide, and acetyl cyclohexane sulfonyl peroxide. In an embodiment, the thermal initiators used are those that do not discolor the resulting polymer. Examples of organic nitrile azobis that can be used as organic initiators include azobis (isobutyron nitrile), azobis (2,4-dimethyl valero nitrile) or a mixture thereof.
[0089] Examples of polymerization inhibitors include: nitrobenzene, 1,3,5-trinitrobenzene, p-benzoquinone, chloranyl, DPPH, FeCl3, CuCl2, oxygen, sulfur, aniline, phenol, p-dihydroxy-benzene, 1,2, 3-trihydroxy-benzene, and 2,4,6-trimethyl phenol.
[0090] Examples of solvents that may be present in the LC compositions according to various embodiments disclosed herein include those that will dissolve solid components of the LC compositions, and / or can guarantee uniform coverage of a surface on which the LC composition is applied . Potential solvents include the following: propylene glycol acetate monomethyl ether and its derivatives (sold as DOWANOL® industrial solvents), acetone, amyl propionate, anisol, benzene, butyl acetate, cyclohexane, ethylene glycol dialkyl ethers, for example , diethylene glycol dimethyl ether and its derivatives (sold as CELLOSOLVE® industrial solvents), diethylene glycol dibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxy benzene, atyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxy ethyl ether, 3-propylene glycol methyl ether, and mixtures thereof.
[0091] In certain embodiments, the LC compositions of the present disclosure may further comprise at least one additional polymeric material. Suitable examples of additional polymeric materials that can be used in conjunction with various embodiments disclosed herein include, for example, homopolymers and copolymers prepared from the monomers and mixtures of monomers disclosed in U.S. Patent No. 5,962,617 and US Patent No. 5,658. 501 from column 15, line 28 to column 16, line 17. For example, such polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any required index of refraction. Examples of such disclosed monomers and polymers include: polyol monomers (allyl carbonate), for example, allyl diglycol carbonates such as diethylene glycol bis (allyl carbonate), the monomer of which is sold under the trade name CR-39 by PPG Industries , Inc .; poly (urea / urethane) polymers which are prepared, for example, by the reaction of a polyurethane prepolymer and a diamine curing agent, a composition for such polymer being sold under the trade name TRIVEX by PPG Industries, Inc. ; polyol (meth) acryloyl terminated carbonate monomer; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol bis methacrylate monomers; poly (ethylene glycol) bis methacrylate monomers; urethane acrylate monomers; poly (ethoxylated bisphenol A dimethacrylate); poly (vinyl acetate); poly (vinyl alcohol); polyvinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; polyurethanes; poly (thiourethanes); thermoplastic polycarbonates, such as carbonate-bound resin derived from bisphenol A and phosgene, such material being sold under the trade name LEXAN; polyesters, such as the material sold under the trade name MYLAR; poly (ethylene terephthalate); poly (butyral vinyl); poly (methyl methacrylate), such material sold under the trade name PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanates with poly (episulfide) polythiols or monomers, whether homopolymerized or copolymerized and / or terpolymerized with polythiols, polyisocyanates, polyisothiotates and optional polyisothiotates. ethylenically or vinyl monomers containing halogenated aromatics. Copolymers of such monomers and mixtures of the described polymers and copolymers with other polymers are also considered, for example, to form block copolymers or interpenetration mesh products.
[0092] According to a specific incorporation, the additional polymeric material is chosen from polyacrylates, polymethacrylates, poly (C1-C12 alkyl methacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate , cellulose triacetate, cellulose propionate acetate, cellulose butyrate acetate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl pyrrolidone), poly ( (meth) acrylamide), poly (dimethyl acrylamide), poly (hydroxyethyl methacrylate), poly ((meth) acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, poly (thiourethanes), poly (ethylene terephthalate), polystyrene, poly (α-methyl styrene), copoly (styrene / methyl methacrylate), copoli (styrene / acrylonitrile), poly (vinyl butyral) and group member polymers consisting of polyol monomers (allyl carbonate), monofunctional acrylate monomers, monofunctional methacrylate monomers, mo polyfunctional acrylate numbers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, benzene diisopropenyl monomers, alkoxylated polyhydric alcohol monomers and pentaerythritol diallylene monomers.
[0093] According to another specific incorporation, the at least one additional polymeric material can be a homopolymer or copolymer of monomers chosen from acrylates, methacrylates, methyl methacrylate, ethylene glycol bis methacrylate, ethoxylated bisphenol A dimethacrylate, vinyl acetate , butyral vinyl, urethane, thiourethane, bis (allyl carbonate) diethylene glycol, diethylene glycol dimethacrylate, diisopropenyl benzene and ethoxylated trimethylolpropane triacrylate.
[0094] Other incorporations of the present disclosure still provide optical elements. The optical elements comprise a substrate and an at least partial layer on at least a portion of the substrate. When used herein, the term "layer" includes layers, coatings, and films, which can be cured. According to these embodiments, the at least partial layer comprises the compound containing mesogen as described according to various embodiments of the present disclosure, such as those having a structure according to Formulas I, II, III, IV, V, VI or mixtures thereof. In other embodiments, the partial layer may comprise the LC compositions in accordance with the various embodiments disclosed herein. When used here, the term "optical" means referring to or associated with light and / or vision. For example, according to various embodiments, the optical element or device can be chosen from ophthalmic elements and devices, display elements and devices, windows, mirrors, and active and passive liquid crystal cell devices and elements.
[0095] When used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material capable of being ordered. Active liquid crystal cells are cells in which the liquid crystal material is able to change from an ordered state to a disordered state and vice versa or to change from an ordered state to another ordered state by the application of an external force, such as electric or magnetic hoods. Passive liquid crystal cells are cells in which the liquid crystal material maintains an orderly state. An example of an active liquid crystal cell device or element is a liquid crystal display.
[0096] When used here, the term "ophthalmic" means to refer to or associated with the eye and vision. Examples of ophthalmic elements include corrective and non-corrective lenses, including monofocal and multifocal lenses, which can be segmented or non-segmented multifocal lenses (such as, but not limited to bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used for correct, protect, or improve (cosmetically or differently) vision, including without limitation, contact lenses, intraocular lenses, magnifying lenses, and protective visors or lenses; and may also include partially formed lenses and lens glasses. When used here, the term “display” means the machine-readable or visible representation of information in words, numbers, symbols, drawings or figures. Non-limiting examples of display elements include screens, monitors, and security elements, such as security tags. When used here, the term "window" means an opening adapted to allow the transmission of radiation through it. Non-limiting examples of windows include automotive and aircraft windshields, automotive and aircraft transparencies, for example, T-roofs, side lights and tail lights, filters, shutters, and optical switches. When used here, the term “mirror” means a surface that speculatively reflects a large fraction of incident light.
[0097] According to specific incorporations of the optical elements, the at least partial layer, for example, a cured coating layer, can further comprise at least one of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a material photosensitive, a non-photosensitive material, and / or one or more additives. The one or more additives can be chosen from a liquid crystal, a liquid crystal property control additive, a non-linear optical material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, a thermal initiator, a surfactant , a polymerization inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology control agent, a gelator, a leveling agent, a free radical purger, and / or an adhesion promoter . Specific examples of photochromatic compounds, dichroic compounds, photochromatic / dichroic compounds, photosensitive materials, non-photosensitive materials, and additives suitable for use in the various incorporations of ophthalmic elements are discussed in detail elsewhere in the present disclosure.
[0098] Although the dichroic compounds are able to preferentially absorb one of two orthogonal components of the polarized light plane, it is generally necessary to properly position or arrange the molecules of a dichroic compound in order to achieve a total linear polarization effect. Similarly, it is often necessary to properly position or arrange the molecules of a dichroic or photochromatic / dichroic compound to achieve a full linear polarization effect. That is, it is generally necessary to align the molecules of the dichroic or photochromatic / dichroic compound such that the long axes of the molecules of the dichroic or photochromatic / dichroic compound in an activated state are parallel to each other. Therefore, according to several incorporations disclosed herein, the at least one dichroic or photochromatic / dichroic compound is at least partially aligned. In addition, if the activated state of the dichroic or photochromatic / dichroic compound corresponds to a dichroic state of the material, the dichroic or photochromatic / dichroic compound may be at least partially aligned such that the long axes of the dichroic or photochromatic / dichroic compound molecules are aligned. When used here, the term "align" means to place in an appropriate position or arrangement by interacting with another material, compound or structure.
[0099] In certain embodiments, the dichroic compound and / or the photochromatic / dichroic compound or other anisotropic material (such as certain incorporations of the compounds containing mesogens described herein) may be at least partially aligned. At least partial alignment of compositions, such as those comprising a dichroic compound, a photochromatic / dichroic compound or other anisotropic material, can be carried out by at least one of exposing at least a portion of the composition to a shear force, exposing at least at least a portion of the composition to an electric field, exposing at least a portion of the composition to ultraviolet radiation from the polarized plane, exposing at least a portion of the composition to infrared radiation, drying at least a portion of the composition, cauterizing at least a portion of the composition, rubbing at least a portion of the composition, and aligning at least a portion of the composition with another structure or material, such as at least partially ordered alignment means. It is also possible to align the dichroic compound and / or the photochromatic / dichroic compound or other anisotropic material (such as certain embodiments of the compounds containing mesogens described herein) with an oriented surface. That is, liquid crystal molecules can be applied to a surface that has been guided, for example, by friction, notch, or photo-alignment methods, and subsequently aligned such that the long axis of each of the liquid crystal molecules acquires a orientation that is generally parallel to the general direction of orientation of the surface. Examples of liquid crystal materials suitable for use as alignment means according to the various embodiments disclosed herein include compounds containing mesogens, liquid crystal polymers, liquid crystal prepolymers, liquid crystal monomers, and liquid crystal mesogens. When used herein, the term "prepolymer" means partially polarized materials.
[0100] For example, according to embodiments where the optical element comprises a cured layer comprising a photochromatic compound, or a photochromatic / dichroic compound, the coating can be adapted to change from a first state to a second state in response to at least actinic radiation and still be able to return to the first state in response to thermal energy. In other embodiments, the coating can be adapted to linearly polarize at least the radiation transmitted in at least one of the first and second states. In certain embodiments, the coating can linearly polarize at least the radiation transmitted in both the first and second states.
[0101] As discussed above, an embodiment provides, in part, an optical element comprising an at least partial coating or layer having a first state and a second state connected to at least a portion of at least one surface of a substrate. When used herein, the term "coating" means a supported film derived from a flowable composition, which may or may not have a uniform thickness, and specifically excludes polymeric sheets. The layer or coating can be cured after application to the surface of the optical element to form a coating or cured layer. When used herein, the term "sheet" means a pre-formed film having a generally uniform thickness and capable of supporting itself. In addition, when used here, the term "connected to" means in direct contact with an object or in indirect contact with an object through one or more structures or materials, at least one of which is in direct contact with the object. Thus, according to various embodiments disclosed herein, the at least partial coating may be in direct contact with at least a portion of the substrate or it may be in indirect contact with at least a portion of the substrate through at least one or more other coatings partial, polymeric sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate.
[0102] According to certain embodiments, the at least partial layer can be at least partially aligned. Appropriate methods for aligning at least partially the first at least partial layer include at least one of exposing at least a portion of the composition to a magnetic cap, exposing at least a portion of the composition to a shear force, exposing to at least one portion of the composition to an electric field, exposing at least a portion of the composition to flat polarized ultraviolet radiation, exposing at least a portion of the composition to infrared radiation, drying at least a portion of the composition, cauterizing at least a portion of the composition, rubbing at least a portion of the composition, and aligning at least a portion of the composition with another structure or material, such as at least partially ordered alignment means. Appropriate alignment methods for layers are described in more detail in U.S. Patent No. 7,097,303, from column 27, row 17 to column 28, row 45.
[0103] According to certain embodiments of the optical element, the at least partial layer, for example, a coating or cured layer, may further comprise at least one of a photochromic compound, a dichroic compound at least partially aligned, a photochromatic compound / dichroic at least partially aligned, a photosensitive material, a non-photosensitive material, and one or more additives. The one or more additives may include a liquid crystal, a liquid crystal property control additive, a NLO material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, a thermal initiator, a surfactant, an inhibitor of polymerization, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology controlling agent, a gelator, a leveling agent, a free radical purger, a coupling agent, a tilt control additive and an adhesion promoter. Suitable examples of these compounds, materials, and additives are described in greater detail elsewhere elsewhere, for example, those described with reference to the LC compositions of the present disclosure.
[0104] According to certain embodiments of the optical elements described here, the at least partial layer can be adapted to change from a first state to a second state in response to at least actinic radiation and return to the first state in response to thermal energy . For example, in those embodiments where the at least partial layer comprises a photochromatic compound or a photochromatic / dichroic compound, the at least partial layer can be adapted to change from a first uncolored or light state to a second state in response to at least radiation. actinic and return to the first state in response to thermal energy. In other embodiments where the at least partial layer can be adapted to linearly polarize at least radiation transmitted in at least one of the first and second states. For example, the at least partial layer can transmit linearly polarized radiation in certain embodiments that comprise a dichroic compound or photochromatic / dichroic compound.
[0105] According to specific embodiments of the optical elements of the present disclosure, the at least partial layer may comprise a polymer or copolymer comprising one or more compounds containing mesogens described herein. The at least partial layer comprising a polymer or copolymer comprising a compound containing mesogen can be a cured at least partial layer. In other embodiments, the at least partial layer may comprise a liquid crystal phase. The liquid crystal phase can be a nematic phase, a smectic phase, a chiral nematic phase, or a discotic phase.
[0106] According to another embodiment, the present disclosure provides an ophthalmic element comprising a substrate and an at least partial layer on at least a portion of a substrate surface. The at least partial layer may comprise at least one of a dichroic compound, a photochromatic compound or a photochromatic / dichroic compound, one or more additives, a first polymer having a Fischer microhardness ranging from 0 N / mm2 to 150 N / mm2 ( and in certain embodiments of 50 N / mm2 to 150 N / mm2), and a liquid crystal compound represented by any of Formulas I, II, III, IV, V, or VI, described herein. According to specific embodiments, the dichroic compound and / or the photochromatic / dichroic compound can be at least partially aligned. In other embodiments, the liquid crystal compound can be aligned at least partially. Additives can be selected from a liquid crystal, a liquid crystal property control additive, a NLO material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, a thermal initiator, a surfactant, a polymerization inhibitor , a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology controlling agent, a gelator, a leveling agent, a free radical scavenger, a coupling agent, a tilt control additive and a adhesion promoter. Dichroic compounds, photochromatic compounds, photochromatic / dichroic compounds and appropriate additives are described in detail herein, such as when describing the liquid crystal compositions and optical elements of the present disclosure.
[0107] When used here to modify the term "state", the terms "first" and "second" are not intended to refer to any particular order or chronology, but instead refer to two conditions or properties many different. For example, the first state and the second state of the coating may differ with respect to at least one optical property, such as the absorption or linear polarization of visible and / or UV radiation. According to certain embodiments of the ophthalmic elements described herein, the at least partial layer can be adapted to change from a first state to a second state in response to at least actinic radiation and return to the first state in response to thermal energy. For example, in those embodiments where the at least partial layer comprises a photochromatic compound or a photochromatic / dichroic compound, the at least partial layer can be adapted to change from a first uncolored or light state to a second colored state in response to at least actinic radiation and return to the first uncolored state in response to thermal energy. Alternatively, the at least partial coating can be adapted to have a first color in the first state and a second color in the second state. In other embodiments where the at least partial layer can be adapted to linearly polarize at least one radiation transmitted in at least one of the first and second states. For example, the at least partial layer can transmit linearly polarized radiation in certain embodiments comprising a dichroic compound or a photochromatic / dichroic compound. In other embodiments, the at least partial layer may comprise a liquid crystal phase. The liquid crystal phase can be a nematic phase, a smectic phase, a chiral nematic phase, or a discotic phase. According to yet other embodiments, the at least partial coating having a first state and a second state can be adapted to have a first absorption spectrum in the first state, a second absorption spectrum in the second state, and be linearly polarized in both. States.
[0108] Other embodiments of the present disclosure also come from a liquid crystal cell. According to these embodiments, the liquid crystal cell can comprise a first substrate having a first surface; a second substrate having a second surface; and a mesogen-containing compound represented by any of Formulas I, II, III, IV, V, or VI, described herein. Referring further to the liquid crystal cell, the second surface of the second substrate may be opposite and away from the first surface of the first substrate in order to define a region. The mesogen-containing compound can be placed in the region between the first substrate and the second substrate. Alternatively, the mesogen-containing compound can be incorporated in an at least partial layer on at least one of the first surface of the first substrate, the second surface of the second substrate, or both on the first and the second surface. The liquid crystal cell can be used, for example, as display elements, including screens, monitors, or security elements.
[0109] According to certain embodiments, the liquid crystal cell can further comprise at least one of a photochromatic compound, a dichroic compound or a photochromatic / dichroic compound. Photochromatic compounds, dichroic compounds or appropriate photochromatic / dichroic compounds are described in detail herein, as when describing the liquid crystal compositions and optical elements of the present disclosure. In other embodiments, the liquid crystal cells may further comprise an at least partial layer connected to at least a portion of a surface of at least one of the first substrate and the second substrate, such as, the first surface and / or the second surface. The at least partial layer may be a linearly polarized layer, a circularly polarized layer, an elliptically polarized layer, a photochromatic layer, a reflective layer, a colored layer, a retarding layer, and a wide-angle vision layer.
[0110] According to certain incorporations, the liquid crystal cell can be a pixelated cell. When used here, the term "pixelated (a)" means that an article, such as a display element or liquid crystal cell, can be broken up into a plurality of individual pixels (that is, a single point occupying a specific location within a display, image or cell). In certain embodiments, the liquid crystal cell can be a pixelated cell comprising a plurality of regions or compartments (i.e., pixels). The characteristics of individual pixels, such as color, polarization and the like can be controlled in relation to other pixels in the display element, liquid crystal, or article.
[0111] In accordance with yet other embodiments, the present disclosure provides articles of manufacture comprising a composition including a compound containing mesogen represented by any of Formulas I, II, III, IV, V, or VI, described herein. Specific manufacturing articles include molded articles, assembled articles and cast articles.
[0112] Additionally, the present disclosure also provides methods for forming liquid crystal compositions, optical elements, ophthalmic elements, liquid crystal cells and articles of manufacture, such as those described herein.
[0113] For example, according to an embodiment, the present disclosure provides methods for forming an optical element, including an ophthalmic element. The methods comprise the step of formulating a liquid crystal composition; coating at least a portion of a substrate with the liquid crystal composition; at least partially aligning at least a portion of the liquid crystal composition in the coating layer; and curing the liquid crystal coating layer. The liquid crystal composition can be as described herein. For example, in an embodiment, the liquid crystal can comprise at least one composition containing mesogen, at least one photochromatic compound, dichroic compound or photochromatic / dichroic compound, and at least one additive. The mesogen-containing composition can be represented by any of Formulas I, II, III, IV, V, or VI, described herein. The at least one photochromatic compound, dichroic compound or photochromatic / dichroic compound, and at least one additive are as described herein.
[0114] Methods for at least partially aligning at least a portion of the liquid crystal composition in the coating are described herein and in U.S. Patent No. 7,097,303 in column 27, line 17 through column 28, line 45.
[0115] Curing of the liquid crystal coating layer may include polymerizing the liquid crystal composition at least partially. Methods for at least partially polymerizing a liquid crystal composition include exposing at least a portion of the liquid crystal composition to at least one of thermal energy (for example, activating a thermal initiator); infrared radiation, ultraviolet radiation, visible radiation, gamma radiation, microwave radiation or combinations thereof in order to initiate the polymerization reaction of the polymerizable or reticular components with or without a catalyst or initiator. If desired or required, this can be followed by a heating step. According to certain embodiments, the liquid crystal coating layer can be cured to a specific hardness. For example, in certain embodiments, the liquid crystal coating layer can be cured to have a Fischer microhardness ranging from 0 to 150 N / mm2 which also exhibits good photochromatic and / or dichroic response characteristics. In another embodiment, the liquid crystal composition can be cured to a Fischer microhardness less than 60 N / mm2, for example, from 0 to 59.9 N / mm2, or alternatively from 5 to 25 N / mm2. In still other embodiments, the liquid crystal coating layer can be cured to have a Fischer microhardness ranging from 150 N / mm2 to 250 N / mm2 or alternatively from 150 N / mm2 to 200 N / mm2.
[0116] According to specific embodiments, the at least one additive can be adapted to affect a property of the liquid crystal composition, such as the free crystal temperature of the liquid crystal composition, decrease the viscosity of the liquid crystal composition, enlarge a phase temperature for a nematic phase of the liquid crystal composition, to stabilize a phase of the liquid crystal composition or to control the slope of the liquid crystal composition.
[0117] Specific methods for forming optical elements, such as ophthalmic elements comprising at least a partial layer, such as a layer comprising a liquid crystal composition as described herein, on at least a portion of a substrate surface, are described in detail in US patent No. 7,342,112 in column 83, line 16 to column 84, line 10. These disclosed methods include methods for forming articles, such as optical elements and ophthalmic elements, which may also include at least one of a compound photochromatic, a dichroic compound, or a photochromatic / dichroic compound, by a variety of methods known in the art, such as soaking, coating, overmolding, rotation coating, spray coating, spray and rotation coating, curtain coating, coating flow, dip coating, injection molding, casting, lamination and wire coating.
[0118] Generally speaking, substrates that are suitable for use together with the various embodiments disclosed herein include substrates formed from organic materials, inorganic materials, or combinations thereof (for example, composite materials). Examples of materials that can be used in accordance with the various embodiments disclosed herein are described in more detail below.
[0119] Specific examples of organic materials that can be used to form the substrates disclosed herein include polymeric materials, such as those discussed in detail above, for example, homopolymers and copolymers prepared from monomers and mixtures of monomers disclosed in the US patent. No. 5,962,617 and US Patent No. 5,658,501 from column 15, line 28 to column 16, line 17. For example, such polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any required index of refraction. Examples of such disclosed monomers and polymers include: polyol monomers (allyl carbonate), for example, allyl diglycol carbonates such as diethylene glycol bis (allyl carbonate), the monomer of which is sold under the trade name CR-39 by PPG Industries , Inc .; polyurea / polyurethane polymers (polymers of poly (urea / urethane)), which are prepared, for example, by the reaction of polyurethane prepolymer and a diamine curing agent, a composition for such polymer being sold under the trade name TRIVEX by PPG Industries, Inc .; carbonate comonomer terminated with (meth) acryloyl polyol, diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol bis methacrylate monomers; poly (ethylene glycol) bis methacrylate monomers; urethane acrylate monomers; poly monomers (ethoxylated bisphenol A dimethacrylate); poly (vinyl acetate); poly (vinyl alcohol); polyvinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; polyurethanes; poly (thiourethanes); thermoplastic polycarbonates; such as carbonate-bonded resin derived from bisphenol A and phosgene, such material being sold under the trade name LEXAN; polyesters, such as the material sold under the trade name MYLAR; poly (ethylene terephthalate); poly (butyral vinyl); poly (methyl methacrylate), such as the material sold under the trade name PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanates with polyisol or polyisulfide monomers, whether homopolymerized and / or copolymerized and / or terpolymerized with polythiols, polyisocyanates and polyisotopes and polyisotopes and polyisotopes and polyisotopes ethylenically unsaturated or vinyl monomers containing halogenated aromatics. Copolymers of such monomers and mixtures of the described polymers and copolymers with other polymers are also considered to form block copolymers or interpenetrated network products.
[0120] According to several incorporations disclosed here, the substrate can be an ophthalmic substrate. When used here, the term "ophthalmic substrate" means lenses, partially formed lenses and blank lenses. Examples of organic materials suitable for use in forming ophthalmic substrates according to various embodiments disclosed herein include polymers recognized in the art that are useful as ophthalmic substrates, for example, organic optical resins that are used to prepare optically clear leaks for optical applications, such as like ophthalmic lenses.
[0121] Other examples of organic materials suitable for use in forming substrates according to various embodiments disclosed herein include both synthetic and natural materials, including: opaque or translucent polymeric materials, natural and synthetic textiles, and cellulosic materials such as paper and wood.
[0122] Examples of inorganic materials suitable for use in forming substrates according to various embodiments disclosed herein include glass, minerals, ceramics, and metals. For example, in an embodiment, the substrate comprises glass. In other embodiments, the substrate may have a reflective surface, for example, a ceramic substrate, metallic substrate, or polished mineral substrate. In other embodiments, a reflective layer or coating can be deposited or applied differently to a surface of an organic or inorganic substrate to make it reflective or to improve its reflection.
[0123] Additionally, according to certain embodiments disclosed here, substrates may have a protective coating, such as an abrasion resistant coating, such as a "hard coating" on their external surfaces. For example, commercially obtainable thermoplastic polycarbonate ophthalmic lens substrates are often sold with an abrasion resistant coating already applied to their outer surfaces because these surfaces tend to be quickly scratched, scraped or scratched. An example of such a lens substrate is the GENTEX ™ polycarbonate lens (obtainable from Gentex Optics). Therefore, when used herein, the term "substrate" includes a substrate having a protective coating, such as an abrasion resistant coating, on its surfaces.
[0124] In addition, the substrates according to various embodiments disclosed herein may be non-dyed, dyed, linearly polarized, circularly polarized, elliptically polarized, photochromatic, or dyed photochromatic substrates. When used herein with reference to substrates, the term "undyed" means substrates that are essentially free of coloring agent additions (such as conventional dyes) and have an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation . In addition, with reference to substrates, the term "dyed" means substrates that have a coloring agent (such as conventional dyes) and an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation.
[0125] When used here with reference to substrates, the term "linearly polarized" refers to substrates that are adapted to polarize radiation linearly (that is, to confine the vibrations of the electrical vector of light waves in one direction). When used herein with reference to substrates, the term "circularly polarized" refers to substrates that are adapted to circularly polarize radiation. When used herein with reference to substrates, the term "elliptically polarized" refers to substrates that are adapted to polarize elliptically radiation. In addition, when used herein with reference to substrates, the term "dyed photochromatic" means substrates containing added coloring agent as well as a photochromatic material, having an absorption spectrum for visible radiation that varies in response to at least actinic radiation. Consequently, for example, the dyed photochromatic substrate may have a first color characteristic of the coloring agent and a second color characteristic of the combination of the coloring agent and the photochromatic material when exposed to actinic radiation.
[0126] As described here, in certain embodiments the optical element can be a security element. Examples of security elements include security marks or authentication marks that connect to at least a portion of a substrate, such as: cards and access passes, for example, tickets, badges, identification or membership cards, identity cards. debit and / or credit, etc .; negotiable instruments and non-negotiable instruments, for example, drafts of contracts, checks, policies, bank notes (cash), certificates of deposit, certificates of stock, etc .; official documents, for example, money, licenses, identification cards, benefit cards, visas, passports, official certificates, property deeds, etc .; consumer goods, for example, software, CDs, DVDs, furniture, electronic devices, sporting goods, etc .; credit cards; and labels, tags and packaging.
[0127] The security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to certain embodiments in which a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can be applied to at least a portion of the substrate before applying to security mark on it. For example, a reflective aluminum coating can be applied to at least a portion of the substrate before the security element is formed on the substrate. Additionally, the security element can be connected to at least a portion of a substrate chosen from non-dyed substrates, dyed substrates, photochromatic substrates, dyed photochromatic substrates, linearly polarized substrates, circularly polarized substrates, and elliptically polarized substrates.
[0128] In addition, the security element according to the aforementioned embodiment can comprise one or more other coatings or sheets to form a multilayer reflective security element with characteristics dependent on the angle of view as described in US patent no. 6,641,874.
[0129] The optical elements according to the various embodiments disclosed herein may further comprise at least one additional at least partial coating that can facilitate bonding, adhesion, or wetting of any of the various coatings connected to the substrate of the optical element. For example, according to an embodiment, the optical element can comprise a primer layer at least partial between the at least partial coating having the first state and the second state and a portion of the substrate. In addition, in some embodiments disclosed herein, the primer coating can serve as a barrier to prevent interaction of the coating ingredients with the substrate or element surface and vice versa.
[0130] Examples of primer coatings that can be used in conjunction with various embodiments disclosed herein include coatings comprising coupling agents, at least partial hydrolysates of coupling agents, and mixtures thereof. When used herein, the term "coupling agent" means a material having at least one group capable of reacting, bonding and / or associating with a group on at least one surface. In an embodiment, a coupling agent can serve as a molecular bridge at the interface of at least two surfaces that can be similar or different. In another embodiment, the coupling agents can be monomers, oligomers, prepolymers and / or polymers. Such materials include organometallic such as silanes, titanates, zirconates, aluminates, zirconium aluminates, hydrolysates thereof and mixtures thereof. When used herein, the phrase "at least partial coupling agent hydrolyzates" means that at least some even all hydrolyzable groups in the coupling agent are hydrolyzed. In addition to the coupling agents and / or the coupling agent hydrolysates, the primer layers may comprise other adhesion-enhancing ingredients. For example, the primer coating may further comprise an amount of improved adhesion of an epoxy-containing material. Adhesive improvement amounts of an epoxy containing material when added to the coating composition containing coupling agent can improve the adhesion of a coating applied subsequently when compared to a coating composition containing coupling agent that is essentially free of the epoxy containing material. Other examples of primer coatings that are suitable for use in conjunction with the various embodiments disclosed herein include those described in U.S. Patent Nos. 6,602,603, and 6,150,430.
[0131] According to various embodiments disclosed herein, optical elements may further comprise at least one additional at least partial coating chosen from conventional photochromatic coatings, anti-reflective coatings, linearly polarized coatings, circularly polarized coatings, elliptically polarized coatings, transition coatings, primer coatings (such as those discussed above), and protective coatings connected to at least a portion of the substrate. For example, the at least one additional at least partial coating can be on at least a portion of the at least partial coating having the first state and the second state, that is, as an overcoat; or under at least a portion of the at least partial coating, that is, as a lower layer .. Additionally or alternatively, the at least partial coating having the first state and the second state can be connected to at least a portion of a first surface of the substrate and the at least one additional at least partial coating may be connected to at least a portion of a second surface of the substrate, the first surface being opposite the second surface.
[0132] Examples of conventional photochromatic coating include coating comprising any of the conventional photochromatic compounds which are discussed in detail below. For example, photochromic coatings can be photochromic polyurethane coatings, such as those described in U.S. Patent No. 6,187,444; photochromic coatings of aminoplastic resin, such as those described in U.S. Patent Nos. 4,756,973, 6,432,544 and 6,506,488; photochromic polysilane coatings, such as those described in U.S. Patent No. 4,556,605; photochromic poly (meth) acrylate coatings, such as those described in U.S. Patent Nos. 6,602,603, 6,150,430 and 6,025,026 and WO 01/02449; photochromic polyanhydride coatings, such as those described in U.S. Patent No. 6,436,525; photochromatic polyacrylamide coatings, such as those described in U.S. Patent No. 6,060,001; photochromic epoxy resin coatings, such as those described in U.S. Patent Nos. 4,756,973 and 6,268,055; and photochromic poly (urea / urethane) coatings, such as those described in U.S. Patent No. 6,531,076.
[0133] Examples of linearly polarized coatings include coatings comprising conventional dichroic compounds such as those discussed above.
[0134] When used here, the term "transition coating" means a coating that assists in creating a gradient in properties between two coatings. For example, a transition coating can assist in creating a gradient in hardness between a relatively hard coating and a relatively soft coating. Examples of transition coatings include thin, radiation-cured acrylate-based films.
[0135] Examples of protective coatings include abrasion resistant coatings comprising organic silanes, abrasion resistant coatings comprising radiation-cured acrylate thin films, abrasion resistant coatings based on inorganic materials such as silica, titania and / or zirconia, abrasion resistant coatings of the type that are ultraviolet curable, oxygen barrier coatings, UV shield coatings, and combinations thereof. For example, according to an embodiment, the protective coating may comprise a first coating of a thin film based on radiation cured acrylate having UV shielding properties and a second coating comprising an organic silane. Examples of commercial protective coatings include SILVUE® 124 and HI-GARD® coatings obtainable, respectively, from SDC Coatings, Inc. and PPG Industries, Inc., respectively.
[0136] According to a specific embodiment, the present disclosure provides compounds containing mesogen having the following structures disclosed in Table 1. Table 1: Structure of compounds containing specific mesogens
EXAMPLES
[0137] Examples 1-3 describe the preparation of the materials of the present invention. Example 4 describes the methods for measuring the melting points and phase transition temperatures of Examples 1-3.
[0138] The following abbreviations were used for the chemicals listed in the Examples and Figures: Al (OiPr) 3 - aluminum triisopropylate; DHP - 3,4-dihydro-2H-pyran; DCC - dicyclohexyl carbodiimide; DIAD - diisopropyl azo dicarboxylate; DMAP - 4-dimethylamino pyridine; PPh3 - triphenyl phosphine; PPTS - pyridine p-toluene sulfonate; NMP - N-methyl pyrrolidone; NMR - proton nuclear magnetic resonance; TDB - 1,5,7-triazabiciclo [4.4.0] dec-5-ene; THF - tetrahydrofuran. Example 1 Step 1
[0139] In a reaction flask, 4-hydroxy benzoic acid (20 g), 3-chloro-1-propanol (34 g), N-methyl pyrrolidone (NMP) (200 ml), and potassium carbonate (50 g) were added. g) and the mixture was vigorously stirred at 110 ° C for 4 hours. The resulting mixture was extracted using a 1/1 volume ratio of ethyl acetate / hexanes (1 L) and water (500 ml). The separated organic layer was washed several times with water to remove NMP and was then dried over magnesium sulfate. After concentration, the recovered oil (40 g) was used directly in the next step. Step 2
[0140] In a reaction flask, the product from Step 1 (40 g), succinic anhydride (40 g), DMPA (0.5 g) and THF (200 ml) were added and the resulting mixture was refluxed for 4 hours. hours. Extraction was performed using ethyl acetate (1 L) and water (1 L). The organic layer was separated, dried over magnesium sulfate and concentrated. The resulting product was purified by separation on a silica column using a mixture of ethyl acetate / hexane (8/2 volume / volume (v / v)). A clear oil (36.6 g) was obtained as product. NMR showed that the product had a structure consistent with 4- (3 - ((4- ((3-carboxy propanoyl) oxy) propoxy) benzoyl) oxy) propoxy) -4-oxo butanoic acid. Step 3
[0141] In a reaction flask, 6-chloro-1-hexanol (50 g), methylene chloride (200 ml) and p-toluene sulfonic acid monohydrate (0.5 g) were added. The mixture was stirred at room temperature. DHP (33.5 g) was added via a dropper funnel over an interval of 20 minutes. The resulting mixture was stirred at room temperature for one hour and then concentrated. The recovered clear oil (79 g) was used directly in the next step. Step 4
[0142] In the reaction flask containing the product from Step 3 (78.2 g), ethyl 4-hydroxy benzoate (65 g), potassium carbonate (147 g) and NMP (700 ml) were added. The mixture was stirred at 120 ° C for six hours and then poured into 1.5 L of water. The mixture was extracted with hexane (1.5 L). The separated organic layer was washed with water, dried over magnesium sulfate and concentrated. The recovered clear oil (126.7 g) was used directly in the next step. Step 5
[0143] In the reaction flask containing the product from Step 4 (126.7 g), aqueous sodium hydroxide solution (64 g of a 50 percent by weight solution, based on the total weight of the solution) was added, methanol (300 ml) and water (200 ml). The mixture was refluxed for 2 hours and most of the methanol was removed using a rotary evaporator. Water (1.5 L) was added to the resulting mixture and a clear solution was obtained. The pH of the solution was adjusted to ~ 7 by the slow addition of 3M HCl (~ 270 ml was used). A large amount of an unwanted precipitate was formed. The resulting mixture was extracted twice with ethyl acetate (500 ml each time). The separated organic layer was washed with water, dried over magnesium sulfate and concentrated to the beginning of solid formation. Hexanes (1 L) were added for further crystallization of the product. The resulting crystals were collected by filtration and dried in a vacuum oven. White crystals were obtained as product (89.7 g). NMR showed that the product had a structure consistent with 4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) benzoic acid. Step 6
[0144] 4- (trans-4-propyl cyclohexyl) phenol (4.78 g), 4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) benzoic acid were added to a reaction flask (7.068 g) from Step 5, N, N'-dicyclohexyl carbodiimide (5 g), 4-dimethylamino pyridine (0.25 g) and methylene chloride (100 ml). The mixture was stirred at room temperature for 4 hours. The solid by-product that was formed was filtered. The resulting solution was concentrated and ethanol (100 ml), 1,2-dichloroethane (100 ml) and pyridinium p-toluene sulfonate (1 g) were added. The resulting mixture was refluxed for 2 days and then concentrated. The product was purified by separation on a silica column using methylene chloride / acetone (50/1 v / v) followed by recrystallization from methanol. White crystals (6.47 g) were obtained as a product. NMR showed that the product had a structure consistent with 4- (trans-4-propyl cyclohexyl) phenyl 4 - ((6-hydroxy hexyl) oxy) benzoate. Step 7
[0145] In a reaction flask, 4- (trans-4-propyl cyclohexyl) phenyl (1.47 g) from Step 6, 4- ((6-hydroxy hexyl) oxy) benzoate) was added 3 - (((4 - (((3-carboxy propanoyl) oxy) propoxy) benzoyl) oxy) propoxy) -4-oxo butanoic (0.76 g) from Step 2, N, N'-dicyclohexyl carbodiimide (0, 72 g), 4-dimethylamino pyridine (0.03 g) and methylene chloride (20 ml). The mixture was stirred at room temperature for 4 hours. The solid by-product that was formed was filtered. The solution was concentrated and the product was purified by separating on a silica column using methylene chloride / acetone (50/1 v / v) followed by recrystallization from a methylene chloride / ethanol mixture. A white solid (0.97) was obtained as product. NMR showed that the product had a structure consistent with 1- {3- (4- (3- (4- (6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexyloxy- 4-oxo butanoyloxy) propyloxy) benzoyloxy) propyloxy} -4- {6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexyloxy) butane-1,4-dione. Example 2 Step 1
[0146] In a reaction flask, 4-hydroxy benzoic acid (90 g, 0.65 mol), ethyl ether (1000 mL) and p-toluene sulfonic acid (2 g) were added. The resulting suspension was stirred at room temperature. 3,3-dihydro-2H-pyran (DHP) (66 g, 0.8 mol) was added to the mixture. The suspension became transparent shortly after the addition of DHP and a white crystalline precipitate was formed. Then, the mixture was stirred at room temperature overnight. The resulting precipitate was collected by vacuum filtration and washed with ethyl ether. White crystals (90 g) were recovered as a product. NMR showed that the product had a structure consistent with 4- (tetrahydro-2H-pyran-2-yloxy) benzoic acid. Step 2
[0147] 4- (tetrahydro-2H-pyran-2-yloxy) benzoic acid (17 g) from Step 1, 4- (trans-4-propyl cyclohexyl) phenol (15, 1 g), dicyclohexyl carbodiimide (DCC) (15.7 g), 4-dimethylamino pyridine (DMAP) (0.8 g) and methylene chloride (100 ml). The resulting mixture was stirred at room temperature for 2 hours. The resulting solid by-product was filtered. The solution was concentrated and methanol (100 ml), 1,2-dichloroethane (100 ml) and pyridine p-toluene sulfonate (PPTS) (2 g) were added. The resulting mixture was heated to reflux and reflux was maintained for 6 hours. The solvent was removed and the resulting product was purified by separating on a silica column using a mixture of ethyl acetate / hexane (2/8 v / v). A white solid (16 g) was obtained as a product. NMR showed that the product had a structure consistent with 4- (trans-4-propyl cyclohexyl) phenyl 4-hydroxy benzoate. Step 3
[0148] In a reaction flask, the product from Step 2 (4.98 g), polycaprolactone diol (2.6 g, Aldrich catalog number 189405), triphenyl phosphine (3.86 g), THF (40 mL) and diisopropyl azo dicarboxylate (2.98 g). The resulting mixture was stirred at room temperature for 20 hours. After concentration, a rapid silica gel separation column was used employing a mixture of ethyl acetate / hexanes to collect the major components of the products. A white solid (3.2 g) was recovered as a product. NMR showed that the product had a structure consistent with 2,2'-bis (6- (6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexanoyloxy) -6-hexanoyloxy) diethyl ether with each n having an average distribution of 2.2. Example 3 Step 1
[0149] 4-Nonyl benzoyl chloride (15 g) was added to a reaction flask containing a mixture of pyridine (110 mL) and hydroquinone (33.2 g) and the resulting mixture was stirred for four hours, poured into water (3 L) and the pH was adjusted to ~ 3 with slow addition of 12N HCl. The resulting solution was extracted with hexane (200 ml). The resulting hexane solution was washed with water, dried and concentrated. Methanol (100 ml) was added and the undesirable solid by-product formed was filtered. The methanol solution was collected, concentrated and dried. A white solid (17 g) was obtained as a product. NMR showed that the product had a structure consistent with 4-nonyl benzoate and 4-hydroxy phenyl. Step 2
[0150] In a reaction flask, 4-nonyl benzoate of 4-hydroxy phenyl (9.22 g) from Step 1, 4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) benzoic acid ( 7.94 g) from Step 5 of Example 1, N, N'-dicyclohexyl carbodiimide (6.1 g), 4-dimethylamino pyridine (0.3 g) and methylene chloride (100 ml). The mixture was stirred at room temperature for 24 hours. The solid by-product formed was filtered. The resulting solution was concentrated to the beginning of solid formation. Methanol (100 ml) was added for further crystallization of the product. White crystals (13.41 g) were collected by vacuum filtration and dried. NMR showed that the product had a structure consistent with 4 - ((6 - ((tetrahydro-2H-pyran-2-yl) oxy) hexyl) oxy) 4 - ((4-nonyl benzoyl) oxy) phenyl benzoate. Step 3
[0151] In a reaction flask, the product of Step 2 (13.41 g), methanol (80 ml), chloroform (200 ml) and pyridinium p-toluene sulfonate (0.52 g) were added. The resulting white solid (11 g) was collected as the product. NMR showed that the product had a structure consistent with 4 - ((4 - ((6-hydroxy hexyl) oxy) benzoyl) oxy) phenyl 4-nonyl benzoate. Step 4
[0152] In a reaction flask, the product of Step 3 (5.56 g), succinic anhydride (1.98 g), DMAP (0.04 g) and THF (100 ml) were added. The resulting mixture was refluxed for 4 hours and poured into water (1 L). The formed precipitate was collected and purified by separation on a silica column using an ethyl acetate / hexane (5/5 v / v) mixture. A white solid (5.77 g) was obtained as a product. NMR showed that the product had a structure consistent with 4- ((6- (4 - ((4 - ((4-nonyl benzoyl) oxy) phenoxy) carbonyl) phenoxy) hexyl) oxy-4-oxo butanoic acid.
[0153] Step 4 product (4 g), poly (hexamethylene carbonate) diol (1.7 g, Mn 860, Aldrich catalog number 461172), N, N'-dicycle were added to a reaction flask -hexyl carbodiimide (1.26 g), 4-dimethylamino pyridine (0.06 g) and methylene chloride (20 ml). The mixture was stirred at room temperature for 24 hours. The solid by-product formed was filtered. The resulting mixture was poured into a mixture of water (3 L) and sodium bicarbonate (10 g) and stirred for another 24 hours. Methylene chloride (200 ml) was added. The separated organic layer was collected, dried over magnesium sulfate and concentrated. The recovered solid was stirred in methanol for 2 hours. A white solid (3 g) was collected and dried as the product. NMR showed that the product had a structure consistent with 1- {6- (6- (6- (6- (6- (6- (6- (4- (6- (4- (4- (4-nonyl benzoyloxy ) phenoxy carbonyl) phenoxy) hexyloxy-4-oxo butanoyloxy) hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonoloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyl ) -4- {6- (4- (6- (4- (4- (4-nonyl benzoyloxy) phenoxy carbonyl) phenoxy) hexyloxy} butane-1,4-dione. Example 4
[0154] Measurement of melting points and liquid crystal phase transition temperatures. Approximately 0.1-5 mg of a sample from each of Examples 1-3 was applied to a Vista Vision ™ VWR object slide. A FISHERFINEST® Premium cover glass was applied to the sample. The resulting object-holder slide was placed on the INSTEC® HCS302 hot stage mounted on the sample stage of an OLYMPUS® BX51 polarized light microscope so that the sample point was in the optical path of the microscope. The microscope was also equipped with an INSTEC® STC200 temperature controller to control the temperature of the hot stage and with a 11.2 colored mosaic camera from DIAGNOSTIC INSTRUMENTS in order to be able to observe the phase transitions of a computer display. Melting points of non-liquid crystals and phase transition temperatures of liquid crystal materials were measured by observing the samples during heating at a rate of 1 ° C / min starting at 25 ° C. Melting points and phases below 25 ° C have not been measured unless otherwise indicated. In some cases, the sample was heated until it reached the isotropic phase and then cooled at a rate of 1 ° C / min to determine the phase transition temperatures during the cooling process as indicated in Table 2. the phases of the liquid crystals according to the texture that appeared during the heating and cooling processes. “Textures of Liquid Crystals” by Dietrich Demus and Lothar Richter, published by Verlag Chemie, Weinheim & New York in 1978, were used to identify the different phases of liquid crystals listed in Table 2. Table 2: Transition temperature data of phase

[0155] In the Table above, the following abbreviations were used: N represents the nematic phase; I represents the isotropic phase; K represents the crystalline structure; and glass represents an amorphous state with no ordered structure. Note that all numbers represent the temperature in ° C at which the abbreviation for adjacent phase occurred. Each measured phase is separated by // meaning that the phase has extended to the next listed temperature or temperature range. Observation of the sample phase started at room temperature (25 ° C) and the next phase transition temperature was reported unless otherwise indicated.
[0156] It is understood that the present description illustrates relevant aspects of the invention for a clear understanding of it. Certain aspects of the invention that would be obvious to those skilled in the art and that, therefore, would not facilitate a better understanding of the invention have not been presented in order to simplify the present description. Although the present invention has been described with respect to certain embodiments, the present invention is not limited to the particular embodiments disclosed, but is intended to cover modifications that are within the spirit and scope of the invention, defined by the appended claims.

权利要求:
Claims (14)
[0001]
1. Compound containing mesogen, characterized by the fact that it is represented by one of the following structures:
[0002]
2. Compound containing mesogen, according to claim 1, characterized in that the groups Mesogen-1 and C1-C18, poly (C1-C18 alkoxy), amino (C1-C18 alkylene), (C1 alkyl -C18) amino, C1-C18 alkyl, C2C18 alkenyl, C2-C18 alkynyl, (C1-C18 alkyl) (C1-C18 alkoxy), (C1-C18 alkoxy) carbonyl, (C1- alkyl C18) carbonyl, (C1-C18 alkoxy) carbonyloxy, (C1- C18 alkyloxy) carbonyloxy, aryloxy carbonyloxy, perfluorine (C1- C18 alkyl) amino, di (perfluorine (C1-C18 alkyl)) amino, acetyl C1-C18, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, isocyanate, starch, cyan, nitro, a normal or branched chain C1-C18 alkyl group that is monosubstituted with cyan, halogen, or C1-C18 alkoxy , or polysubstituted with halogen, and a group comprising one of the following formulas: -M (T) (t-1) and -M (OT) (t-1), in which M is chosen from aluminum, antimony, tantalum, titanium , zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbons, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and t is the valence of M; (II) c, d, e, and f are chosen independently of an integer ranging from 0 to 20, inclusive; d ', e' and f 'are independently an integer from 0 to 4 as long as the sum of d' + and '+ f' is at least 2; and at each occurrence, each of S1, S2, S3, S4, and S5 is chosen independently from a spacer unit chosen from: (A) - (CH2) g-, - (CF2) h-, -Si (CH2 ) g-, or - (Si (CH3) 2O) h-, where in each occurrence, g is chosen independently from 1 to 20 and h is an integer from 1 to 16, inclusive; (B) -N (Z) -, -C (Z) = C (Z) -, -C (Z) = N-, -C (Z ') 2- C (Z') 2-, or a bond simple, being that in each occurrence, Z is chosen independently of hydrogen, C1-C6 alkyl, cycloalkyl and aryl, and Z ', in each occurrence, is chosen independently of C1-C6 alkyl, cycloalkyl and aryl; (C) -O-, -C (O) -, -C = C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - (O ) S (O) O-, -O (O) S (O) O- or C1-C24 alkylene residue of normal or branched chain being unsubstituted, monosubstituted by cyan or halogen, or polysubstituted by halogen; provided that when two spacer units comprising heteroatoms bond, the spacer units bond so that the heteroatoms do not bond directly to each other and when S1 and S5 bond to another group, they bond so that two heteroatoms do not bond connect directly to each other.
[0003]
3. Compound containing mesogen, according to claim 1, characterized by the fact that it is selected from the following group of compounds: (a) 1- {3- (4- (3- (4- (6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexyloxy-4-oxo butanoyloxy) propyloxy) benzoyloxy) propyloxy} -4- {6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexyloxy) butado-1,4-dione; (b) 2,2'-bis (6- (6- (4- (4- (trans-4-propyl cyclohexyl) phenoxy carbonyl) phenoxy) hexanoyloxy) -6-hexanoyloxy) diethyl ether; and (c) 1- {6- (6- (6- (6- (6- (6- (6- (4- (6- (4- (4- (4-nonyl benzoyloxy) phenoxy carbonyl) phenoxy) hexyloxy-4-oxo butanoyloxy) hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonoloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyloxy hexyloxy) -6-carbonyloxy hexyloxy) -4- {6 - (4- (6- (4- (4- (4-nonyl benzoyloxy) phenoxy carbonyl) phenoxy) hexyloxy} butane-1,4-dione.
[0004]
4. Compound containing mesogen, according to claim 1, characterized by the fact that it is a liquid crystal compound.
[0005]
5. Composition, comprising the compound containing mesogen, as defined in claim 1, characterized by the fact that it is selected from: (a) a copolymer composition; (b) a polymer composition; and (c) a liquid crystal composition.
[0006]
6. Composition according to claim 5, characterized in that it comprises a liquid crystal polymer.
[0007]
Composition according to claim 6, characterized in that the liquid crystal polymer is present and is a block copolymer or a non-block copolymer comprising the compound containing mesogen; or the composition further comprises at least one of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, a non-photosensitive material, and one or more additives, the one or more additives being chosen from the group consisting of of a liquid crystal, a liquid crystal property control additive, a non-linear optical material, a dye, an alignment promoter, a kinetic enhancer, a photoinitiator, a thermal initiator, a surfactant, a polymerization inhibitor, a solvent , a light stabilizer, a thermal stabilizer, a release agent, a rheology controlling agent, a gelator, a leveling agent, a free radical purger, a coupling agent, a tilt control additive, a polymeric material in blocks or not blocks, and an adhesion promoter; preferably, the at least one photochromatic compound or photochromatic / dichroic compound is chosen from the group consisting of fused indene naphthopyranes, [1,2-b] pyrane naphtha, [2,1-b] pyrane, fluorene spiro [ 1,2-b] pyranes, phenanthropirans, quinolinopyranes, fluoranthrenopyranes, spiro pyranes, benzoxazins, naphthoxazins, spiro (indoline) naphtoxazins, spiro (indoline) pyridobenzoxazins, spiro (indoline) fluoranthrenopyranes, spiro (indoline), quulgine, fulgine, quulgine ethenes, diaryl alkyl ethenes, diaryl alkenyl ethenes, non-thermally reversible photochromatic compounds, and mixtures thereof.
[0008]
8. Article of manufacture, characterized by the fact that it comprises a compound containing mesogen, as defined by claim 1 and is selected from: (a) an optical element comprising: - a substrate; and - a layer at least partial on at least a portion of the substrate, the layer comprising said compound containing mesogen; and (b) a liquid crystal cell comprising: 1. a first substrate having a first surface; 2. a second substrate having a second surface, the second surface of the second substrate being opposite and away from the first surface of the first substrate in order to define a region, and 3. the said compound containing mesogen positioned within the region defined by a first surface and second surface.
[0009]
9. Article according to claim 8, characterized in that the liquid crystal (b) has at least a partial layer chosen from linearly polarized layers, circularly polarized layers, elliptically polarized layers, photochromatic layers, reflective layers, colored layers, retardant layers, and wide-angle view layers, attached to at least a portion of a surface of at least one of the first substrate and the second substrate.
[0010]
10. Article according to claim 8, characterized in that the liquid crystal (b) has a pixel cell comprising a plurality of regions or compartments.
[0011]
11. Article according to claim 8, characterized in that the optical element: (a) has, the at least partial layer is at least partially aligned, exposing at least a portion of the layer to at least one of a magnetic field, an electric field, linearly polarized radiation, and shear force; or (b) have, the at least partial layer be adapted to change from a first state to a second state in response to at least actinic radiation and return to the first state in response to thermal energy; or (c) have, the at least partial layer comprise a liquid crystal phase having at least one of the nematic phase, smectic phase, or chiral nematic phase; or (d) have, the optical element be chosen from an ophthalmic element, a display element, a window, a mirror, and an active and passive liquid crystal cell element.
[0012]
12. Article according to claim 11, characterized in that the at least partial layer (b) is adapted to linearly polarize at least the radiation transmitted in at least one of the first state and the second state.
[0013]
13. Article according to claim 11, characterized in that the ophthalmic element (d) is chosen from a correction lens, a non-correction lens, a contact lens, an intraocular lens, a magnifying glass, a protective lens, and a visor.
[0014]
14. Method for forming an ophthalmic element, using the mesogen-containing compound, as defined in claim 1 and characterized by the fact that it comprises: - formulating a liquid crystal composition comprising the mesogen compound; - coating at least a portion of a substrate with the liquid crystal composition; - at least partially aligning at least a portion of the liquid crystal composition in the coating; and - curing the liquid crystal coating layer.

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引用文献:

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/051,130|2011-03-18|

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US13/051,130|US8628685B2|2008-06-27|2011-03-18|Mesogen-containing compounds|

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PCT/US2012/028025|WO2012128944A1|2011-03-18|2012-03-07|Mesogen-containing compounds|

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