CLEAR TO CIRCULAR POLARIZING PHOTOCHROMIC DEVICES AND METHODS OF MAKING THE SAME

• US 20090135462A1
• Filed: 12/18/2008
• Published: 05/28/2009
• Est. Priority Date: 07/01/2003
• Status: Active Grant

• Current Assignee: Transitions Optical, Inc. (EssilorLuxottica SA)
• Original Assignee: Transitions Optical, Inc. (EssilorLuxottica SA)
• Inventors: Blackburn, Forrest R., Kumar, Anil, Foller, Peter C., Furar, Elizabeth
• Granted Patent: US 8,089,678 B2
• Time in Patent Office: Days
• US Class Current: 359/243
• CPC Class Codes: B29D 11/00009 Production of simple or compound lenses
• CPC Class Codes: B29D 11/00644 polarizing
• CPC Class Codes: B29D 11/00653 photochromic
• CPC Class Codes: C09B 57/00 Other synthetic dyes of known constitution
• CPC Class Codes: C09B 57/02 Coumarine dyes
• CPC Class Codes: C09K 19/60 Pleochroic dyes
• CPC Class Codes: G02B 27/288 Filters employing polarising elements, e.g. Lyot or Solc filters G02B5/3016 takes precedence
• CPC Class Codes: G02B 5/23 Photochromic filters
• CPC Class Codes: G02B 5/3041 comprising multiple thin layers, e.g. multilayer stacks
• CPC Class Codes: G02B 5/3083 Birefringent or phase retarding elements G02B5/3008, G02B5/3016 take precedence; systems for polarisation control G02B27/286; manufacturing phase modulating patterns by lithographic processes G03F7/001
• CPC Class Codes: G02C 7/12 Polarisers
• CPC Class Codes: G02F 1/0126 Opto-optical modulation, i.e. control of one light beam by another light beam, not otherwise provided for in this subclass
• CPC Class Codes: G02F 1/1335 Structural association of cells with optical devices, e.g. polarisers or reflectors

Abstract

The present invention provides optical elements comprising a photochromic linear polarizing element and a birefringent layer that circularly or elliptically polarizes transmitted radiation. The photochromic linear polarizing element comprises a substrate and either: (1) a coating comprising an aligned, thermally reversible photochromic-dichroic compound having an average absorption ratio of at least 1.5 in an activated state, and being operable for switching from a first absorption state to a second absorption state in response to actinic radiation, to revert back to the first absorption state in response to thermal energy, and to linearly polarize transmitted radiation in at least one of the two states; or (2) an at least partially ordered polymeric sheet connected to the substrate; and a thermally reversible photochromic-dichroic compound that is at least partially aligned with the polymeric sheet and has an average absorption ratio greater than 2.3 in the activated state.

Claims

1. An optical element comprising:

(a) a photochromic linear polarizing element comprising;

(i) a substrate; and

(ii) at least one coating connected to the substrate, the coating having a first absorption state and a second absorption state and being operable for switching from the first absorption state to the second absorption state in response to actinic radiation, to revert back to the first absorption state in response to actinic radiation and/or thermal energy, and to linearly polarize transmitted radiation in the first absorption state and/or the second absorption state;

wherein the coating (ii) comprises an at least partially aligned, reversible photochromic-dichroic material having an average absorption ratio of at least 1.5 in an activated state; and

(b) at least one birefringent layer comprising a polymeric coating or polymeric sheet connected to the photochromic linear polarizing element (a), the birefringent layer being operable to circularly or elliptically polarize transmitted radiation.

2. The optical element of claim 1 wherein said photochromic-dichroic material comprises:

(a) at least one photochromic group PC chosen from a pyran, an oxazine, and a fulgide; and

(b) at least one lengthening agent L attached to the at least one photochromic group and represented by;

—

[S₁]_c-[Q₁-[S₂]_d]_d′

-[Q₂-[S₃]_e]_e′

-[Q₃-[S₄]_f]_f′

—

S₅—

P

wherein;

(i) each Q₁, Q₂, and Q₃ is independently chosen for each occurrence from;

a divalent group chosen from;

an unsubstituted or a substituted aromatic group, an unsubstituted or a substituted alicyclic group, an unsubstituted or a substituted heterocyclic group, and mixtures thereof, wherein substituents are chosen from;

a group represented by P, liquid crystal mesogens, halogen, poly(C₁-C₁₈ alkoxy), C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl, C₁-C₁₈alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy, perfluoro(C₁-C₁₈)alkoxycarbonyl, perfluoro(C₁-C₁₈)alkylcarbonyl, perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino, perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈acetyl, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain or branched C₁-C₁₈alkyl group that is mono-substituted with cyano, halo, or C₁-C₁₈ alkoxy, or poly-substituted with halo, and a group comprising one of the following formulae;

-M(T)_(t-1) and -M(OT)_(t-1), wherein M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and t is the valence of M;

(ii) c, d, e, and f are each independently chosen from an integer ranging from 1 to 20, inclusive; and

each S₁, S₂, S₃, S₄, and S₅ is independently chosen for each occurrence from a spacer unit chosen from;

(A) —

(CH₂)_g—

, —

(CF₂)_h—

, —

Si(CH₂)_g—

, —

(Si[(CH₃)₂]O)_h—

, wherein g is independently chosen for each occurrence from 1 to 20;

h is a whole number from 1 to 16 inclusive;

(B) —

N(Z)-, —

C(Z)=C(Z)-, —

C(Z)═

N—

, —

C(Z′

)-C(Z′

)- or a single bond, wherein Z is independently chosen for each occurrence from hydrogen, C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl, and Z′

is independently chosen for each occurrence from C₁-C₁₈ alkyl, C₃-C₁₀cycloalkyl and aryl; and

(C) —

O—

, —

C(O)—

, —

C≡

C—

, —

N═

N—

, —

S—

, —

S(O)—

, —

S(O)(O)—

, —

(O)S(O)O—

, —

O(O)S(O)O—

or straight-chain or branched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkylene residue being unsubstituted, mono-substituted by cyano or halo, or poly-substituted by halo;

provided that when two spacer units comprising heteroatoms are linked together the spacer units are linked so that heteroatoms are not directly linked to each other and when S₁ and S₅ are linked to PC and P, respectively, they are linked so that two heteroatoms are not directly linked to each other;

(iii) P is chosen from;

hydroxy, amino, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato, acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkyl aminocarbonyl, aminocarbonyl (C₁-C₁₈)alkyl, C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl, polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl, acryloyloxy(C₁-C₁₈)alkyl, methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl, 2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative, main-chain and side-chain liquid crystal polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, or substituted or unsubstituted chiral or non-chiral monovalent or divalent groups chosen from steroid radicals, terpenoid radicals, alkaloid radicals and mixtures thereof, wherein the substituents are independently chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is a structure having from 2 to 4 reactive groups or P is an unsubstituted or substituted ring opening metathesis polymerization precursor;

(iv) d′

, e′ and

f′

are each independently chosen from 0, 1, 2, 3, and 4, provided that a sum of d′

+e′

+f′

is at least 1.

3. The optical element of claim 1, further comprising at least one orientation facility having at least a first general direction connected to at least a portion of the substrate.

4. The optical element of claim 1 wherein the coating (ii) comprises two or more at least partially aligned reversible photochromic-dichroic materials, wherein the photochromic-dichroic materials have complementary absorption spectra and/or complementary linear polarization states.

5. The optical element of claim 1 wherein said coating (ii) comprises at least one self-assembling material.

6. The optical element of claim 5 wherein said self-assembling material is chosen from liquid crystal materials, block copolymers and mixtures thereof.

7. The optical element of claim 1 wherein the coating (ii) further comprises a phase-separated polymer comprising an at least partially ordered matrix phase and an at least partially ordered guest phase, wherein the guest phase comprises a reversible photochromic-dichroic compound that is at least partially aligned with the guest phase.

8. The optical element of claim 1 wherein the coating (ii) further comprises an interpenetrating polymer network comprising an at least partially ordered anisotropic material and a polymeric material, wherein the anisotropic material comprises a reversible photochromic-dichroic compound that is at least partially aligned with the anisotropic material.

9. The optical element of claim 1 wherein said coating (ii) comprises a coating having a first ordered region having a first general direction, and at least one second ordered region adjacent the first ordered region having a second general direction that is the same or different from the first general direction so as to form a desired pattern in the coating.

10. The optical element of claim 1 wherein said coating (ii) is adapted to transition from a first state to a second state in response to actinic radiation, and to linearly polarize transmitted radiation in at least the second state.

11. The optical element of claim 1 wherein the coating (ii) further comprises at least one additive chosen from dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical scavengers, gelators and adhesion promoters.

12. The optical element of claim 1 further comprising at least one additional at least partial coating chosen from photochromic coatings, anti-reflective coatings, linearly polarizing coatings, transitional coatings, primer coatings, adhesive coatings, mirrored coatings and protective coatings.

13. The optical element of claim 1 wherein said birefringent layer (b) comprises a layer having a first ordered region having a first general direction, and at least one second ordered region adjacent the first ordered region having a second general direction that is the same or different from the first general direction so as to form a desired pattern in the layer.

14. The optical element of claim 1 wherein said birefringent layer (b) comprises a polymeric coating chosen from self-assembling materials and film-forming materials.

15. The optical element of claim 1 wherein said birefringent layer (b) comprises a polymeric sheet comprising self-assembling materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane, polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.

16. The optical element of claim 1 wherein the birefringent layer (b) comprises a quarter-wave plate.

17. The optical element of claim 1, wherein the optical element comprises ophthalmic elements, display elements, windows, mirrors, packaging materials, and/or active and passive liquid crystal cell elements and devices.

18. The optical element of claim 17, wherein the ophthalmic element comprises corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, or visors.

19. The optical element of claim 17, wherein the display element comprises screens, monitors, and security elements.

20. The optical element of claim 1 wherein said substrate is formed from organic materials, inorganic materials, or combinations thereof.

21. The optical element of claim 20 wherein said substrate is at least translucent.

22. The optical element of claim 21 wherein said optical element is connected to a display element.

23. A composite optical element comprising:

(a) at least one photochromic linear polarizing element comprising;

(i) an at least partially ordered polymeric sheet; and

(ii) a reversible photochromic-dichroic material that is at least partially aligned with the polymeric sheet and has an average absorption ratio of at least 1.5 in the activated state; and

(b) at least one birefringent layer comprising a polymeric coating or polymeric sheet connected to the photochromic linear polarizing element (a), wherein the composite optical element is operable to circularly or elliptically polarize transmitted radiation.

24. The composite optical element of claim 23 wherein said photochromic-dichroic material is chosen from:

(1) 3-phenyl-3-(4-(4-(3-piperidin-4-yl-propyl)piperidino)phenyl)-13,13-dimethyl-indeno[2′

,3′

;

3,4]-naphtho[1,2-b]pyran;

(2) 3-phenyl-3-(4-(4-(3-(1-(2-hydroxyethyl)piperidin-4-yl)propyl)piperidino)phenyl)-13,13-dimethyl-indeno[2′

,3′

;

3,4]naphtho[1,2-b]pyran;

(3) 3-phenyl-3-(4-(4-(4-butyl-phenylcarbamoyl)-piperidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-phenyl-piperazin-1-yl)indeno[2′

,3′

;

3,4]naphtho[1,2-b]pyran;

(4) 3-phenyl-3-(4-([1,4′

]bipiperidinyl-1′

-yl)phenyl)-13,13-dimethyl-6-methoxy-7-([1,4′

]bipiperidinyl-1′

-yl)indeno[2′

,3′

;

3,4]naphtho[1,2-b]pyran;

(5) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)-piperidin-1-yl)indeno[2′

,3′

;

3,4]naphtho[1,2-b]pyran;

(6) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4′

-octyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)indeno[2′

,3′

;

3,4]naphtho[1,2-b]pyran;

25. The optical element of claim 23 wherein the polymeric sheet comprises self-assembling materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane, polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.

26. The composite optical element of claim 23 wherein the polymeric sheet (i) is chosen from a stretched polymer sheet, an at least partially ordered liquid crystal polymer sheet, and a photo-oriented polymer sheet.

27. The composite optical element of claim 23 wherein said polymeric sheet (i) comprises a sheet having a first ordered region having a first general direction, and at least one second ordered region adjacent the first ordered region having a second general direction that is the same or different from the first general direction so as to form a desired pattern in the sheet.

28. The composite optical element of claim 23 wherein said photochromic linear polarizing element is adapted to transition from a first state to a second state in response to actinic radiation, and to linearly polarize transmitted radiation in at least the second state.

29. The composite optical element of claim 23, wherein the birefringent layer (b) comprises a quarter-wave plate.

30. The composite optical element of claim 23 wherein said birefringent layer (b) comprises a polymeric coating chosen from self-assembling materials and film-forming materials.

31. The composite optical element of claim 23 wherein said birefringent layer (b) comprises a polymeric sheet comprising self-assembling materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane, polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, alkylene-vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.

(b) comprises a polymeric composition.

32. The composite optical element of claim 23 wherein said birefringent layer (b) comprises a layer having a first ordered region having a first general direction, and at least one second ordered region adjacent the first ordered region having a second general direction that is the same or different from the first general direction so as to form a desired pattern in the layer.

33. The composite optical element of claim 23 further comprises a substrate formed from organic materials, inorganic materials, or combinations thereof.

34. The composite optical element of claim 33 wherein said substrate is at least translucent.

35. The composite optical element of claim 33 wherein said substrate comprises untinted substrates, tinted substrates, photochromic substrates, tinted photochromic substrates, and linearly polarizing substrates.

36. The composite optical element of claim 23, wherein said optical element comprises ophthalmic elements, display elements, windows, mirrors, packaging materials and/or active and passive liquid crystal cell elements and devices.

37. The composite optical element of claim 36, wherein the ophthalmic element comprises corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, or visors.

38. The composite optical element of claim 36, wherein the display element comprises screens, monitors, and security elements.

39. The composite optical element of claim 23 connected to a display element.

40. The composite optical element of claim 39 further comprising at least one additional at least partial coating chosen from photochromic coatings, anti-reflective coatings, linearly polarizing coatings, transitional coatings, primer coatings, adhesive coatings, mirrored coatings and protective coatings.

41. An optical element comprising a circular polarizer connected to a substrate comprising packaging material for light-sensitive products wherein said circular polarizer comprises an assembly of a a quarter wave retarder and a linearly polarizing coating or an at least partially ordered polymeric sheet comprising an at least partially aligned reversible photochromic-dichroic material having an average absorption ratio of at least 1.5 in an activated state.