Photochromic article

• US 7,465,414 B2
• Filed: 11/14/2002
• Issued: 12/16/2008
• Est. Priority Date: 11/14/2002
• Status: Expired due to Term

• Current Assignee: Transitions Optical, Inc. (EssilorLuxottica SA)
• Original Assignee: Transitions Optical, Inc. (EssilorLuxottica SA)
• Inventors: Knox, Carol L., McDonald, William H.
• Primary Examiner(s): Tran; Thao T.
• Application Number:
  US10/294,058
• Publication Number:
  US 20040096666A1
• Time in Patent Office: 2,224 Days
• Field of Search: 428/412, 428/423.1, 428/423.3, 428/424.4, 428/424.6, 252/586, 359/238
• US Class Current: 252/586
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C03C 17/3405 with at least two coatings of organic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3225 Polyamines
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/664 with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/6674 with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: G02B 1/041 Lenses
• CPC Class Codes: G02B 1/105 Protective coatings
• CPC Class Codes: G02B 1/11 Anti-reflection coatings
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31554 Next to second layer of polyamidoester
• CPC Class Codes: Y10T 428/31576 Ester monomer type [polyvinylacetate, etc.]
• CPC Class Codes: Y10T 428/3158 Halide monomer type [polyvinyl chloride, etc.]

Abstract

Describes an optical article, e.g., an ophthalmic photochromic article, such as a lens, in which the article includes: (1) a transparent substrate, such as a thermoset or thermoplastic plastic substrate, (2) a multiply laminate adjacent to at least one surface of the substrate, the laminate comprising (i) a transparent, thermoplastic polyurethane film, the thermoplastic, polyurethane film providing a desirable light filtering property, e.g., photochromism, and being juxtaposed to the surface of the substrate, the polyurethane being formed from a material comprising polyether-based polyurethane or polycarbonate-based polyurethane, and (ii) a transparent protective film of polymeric material, e.g., polycarbonate film, adjacent to the thermoplastic polyurethane film. Describes also the aforedescribed optical article having an abrasion-resistant coating affixed to the protective film, e.g., an organo-silane abrasion-resistant coating; and an optical article having an antireflective coating adhered to the abrasion-resistant coating.

Claims

1. A photochromic article consisting essentially of:

(a) a transparent solid substrate having a front surface and a back surface, wherein said substrate is prepared from compositions selected from the group consisting of polymerizable allyl glycol carbonate monomer(s), thermoplastic polycarbonate, polyurea urethane, compositions comprising the reaction product of polyfunctional isocyanate(s) and polythiol monomer(s), compositions comprising the reaction product of polyfunctional isocyanate(s) and polyepisulfide monomer(s), optical quality mineral glass, and combinations thereof,

(b) a transparent photochromic thermoplastic polyurethane film adjacent to at least one surface of said substrate, said polyurethane film having (i) a thickness of 2 to 15 mils, (ii) a flexural modulus of less than 2.5 GPa, and (iii) being formed from polyurethane material selected from the group consisting of polyether-based polyurethane, polycarbonate-based polyurethane and mixtures of such polyurethane materials, said polyurethane film containing at least one organic photochromic material that is soluble in the polyurethane film, and

(c) transparent protective film of thermoplastic polymeric organic material superposed on said polyurethane film, said photochromic article exhibiting (1) a change in color when exposed to activating ultraviolet light radiation, and (2) a color fading half life (T½

) of not more than 500 seconds when the ultraviolet light radiation is removed.

2. The article of claim 1 wherein the protective film of thermoplastic polymeric organic material is selected from nylon, poly(vinyl acetate), vinyl chloride-vinyl acetate copolymer, poly (lower alkyl) acrylates, poly (lower alkyl) methacrylates, styrene-butadiene copolymer resin, polyurea urethane, lightly cross-linked thermoplastic polyurethane and thermoplastic polycarbonate material.

3. The article of claim 1 wherein the protective film of polymeric material has a thickness of from 1 to 20 mils.

4. The article of claim 1 wherein an abrasion resistant coating is superposed on said protective film.

5. The article of claim 4 wherein the abrasion resistant coating is selected from polyfunctional acrylic hard coatings, melamine-based hard coatings, urethane-based hard coatings, alkyd-based hard coatings, silica sol-based hard coatings and organo-silane type hard coatings.

6. The article of claim 5 wherein the abrasion resistant coating comprises an organo-silane type abrasion resistant coating or a silica-sol-based hard coating.

7. The article of claim 4 wherein an anti-reflective coating is superposed on said abrasion resistant coating.

8. The article of claim 1 wherein a polarizing film pervious to ultraviolet light radiation is interposed between the photochromic thermoplastic polyurethane film and the protective film of thermoplastic polymeric organic material.

9. The article of claim 1 wherein the organic photochromic material is selected from benzoxazines, naphthoxazines, spiro(indolino)pyridobenzoxazines, benzopyrans, naphthopyrans, spiro-9-fluorenopyrans, phenanthropyrans, quinopyrans, indeno-fused naphthopyrans, fulgides, metal dithizonates, fulgimides and mixtures of such photochromic materials.

10. The article of claim 9 wherein the organic photochromic material comprises (a) at least one organic photochromic material having a visible lambda max of from 400 to less than 550 nanometers, and (b) at least one organic photochromic material having a visible lambda max of from 550 to 700 nanometers.

11. The article of claim 1 wherein a polarizing film impervious to ultraviolet light radiation is interposed between the transparent solid substrate and the photochromic thermoplastic polyurethane film.

12. The article of claim 1 wherein organic photochromic material is present in the polyurethane film in amounts of from 0.2 to 20 weight percent.

13. The article of claim 1 wherein the article is an optical article.

14. The article of claim 13 wherein the optical article is a lens having a refractive index of from 1.48 to 1.90.

15. The photochromic article of claim 2 wherein the article is an optical article and wherein organic photochromic material is present in the polyurethane film in amounts of from 0.2 to 10 weight percent.

16. The optical article of claim 15 wherein the article is a lens having a refractive index of from 1.48 to 1.75, and the polymeric protective film has a thickness of from 1 to 20 mils and a flexural modulus of from 0.1 to 5 GPa.

26. The photochromic optical lens of claim 16 wherein:

(a) the lens substrate has a refractive index of from 1.50 to 1.67, said substrate having a convex surface and a concave surface, the lens substrate being prepared from compositions selected from the group consisting of polymerizable allyl glycol carbonate monomer(s), thermoplastic polycarbonates, substrates prepared from polyurea urethanes, and combinations thereof,

(b) the transparent thermoplastic photochromic polyurethane film is attached to the convex surface of the lens substrate, and

(c) the transparent thermoplastic protective film of polymeric organic material has a thickness of from 5 to 10 mils.

27. The photochromic lens of claim 26 wherein organic photochromic material is present in amounts of from 0.3 to 5 weight percent, the organic photochromic material comprises naphthoxazines, spiro(indolino)pyridobenzoxazines, naphthopyrans, spiro-9-fluorenopyrans, phenanthropyrans, indeno-fused naphthopyrans or mixtures of such photochromic materials, and the polymeric protective film is comprised of nylon, polyurea urethanes, lightly cross-linked thermoplastic polyurethane and/or thermoplastic polycarbonate material.

28. The photochromic lens of claim 27 wherein the lens substrate and the protective film each comprise thermoplastic polycarbonate material.

29. The photochromic lens of claim 27 wherein the protective film of polymeric material has a melting temperature of greater than 120°

C., a light transmission value of greater than 80%, a flexural modulus of from 0.5 to 3 GPa, and an abrasion resistance that is greater than the polyurethane film.

30. The photochromic lens of claim 27 wherein an abrasion resistant coating is appended to the polymeric protective film and the abrasion resistant coating is selected from coatings comprising an organo-silane type hard coating and a silica sol-based hard coating.

31. The photochromic lens of claim 30 wherein an antireflective coating is appended to the abrasion resistant coating.

32. The optical article of claim 14 wherein the optical article is a high index photochromic lens wherein:

(a) the transparent solid optical polymeric substrate has a refractive index of at least 1.60, said substrate being prepared from compositions selected from the group consisting of polyurea urethane, the reaction product of polyfunctional isocyanate(s) and polythiol monomer(s), the reaction product of polyfunctional isocyanates and polyepisulfide monomer(s), and combinations thereof,

(b) the transparent thermoplastic photochromic polyurethane film is appended to at least one surface of said lens, and

(c) said optical lens being substantially free of interference fringes.

33. The lens of claim 32 wherein the polyurethane film contains from 0.3 to 5 weight percent of at least one organic photochromic material comprising naphthoxazines, spiro(indolino)pyridobenzoxazines, naphthopyrans, spiro-9-fluorenopyrans, phenanthropyrans, indeno-fused naphthopyrans or mixtures of such photochromic materials, and wherein the protective polymeric film has a thickness of from 5 to 10 mils and comprises nylon, polyurea urethanes, lightly cross-linked thermoplastic polyurethane or thermoplastic polycarbonate.

34. The lens of claim 33 wherein an abrasion resistant coating is appended to the protective polymeric film, and the abrasion resistant coating comprises organo-silane type abrasion resistant coatings and/or silica sol-based hard coatings.

35. The lens of claim 34 wherein an antireflective coating is appended to the abrasion resistant coating.

17. An ophthalmic photochromic article consisting essentially of:

(a) a transparent solid optical polymeric substrate having a front surface and a back surface, wherein the solid optical substrate is prepared from compositions selected from the group consisting of polyurea urethane, the reaction product of polyfunctional isocyanate(s) and polythiol monomer(s), the reaction product of polyfunctional isocyanate(s) and polyepisulfide monomer(s), and combinations thereof,

(b) a transparent thermoplastic photochromic polyurethane film contiguous to one surface of said substrate, said polyurethane film having (i) a light transmission of at least 80%, (ii) a flexural modulus of less than 2.5 GPa, (iii) a thickness of from 2 to 15 mils, and (iv) being formed from polyurethane material comprising polyether-based polyurethane, polycarbonate-based-polyurethane or mixtures of such polyurethane materials, said polyurethane film further containing a photochromic amount of at least one organic photochromic material that is soluble in the polyurethane film, and

(c) a transparent thermoplastic protective film of polymeric organic material superposed on said polyurethane film, said polymeric protective film having a light transmission of at least 80%, a thickness of from 1 to 20 mils and a flexural modulus of from 0.5 to 3 Gpa, said ophthalmic photochromic article exhibiting a change in color from colorless to colored when exposed to activating ultraviolet light radiation, and a color fading half-life (T½

) of not more than 500 seconds when the ultraviolet light radiation is removed.

18. The ophthalmic article of claim 17 wherein the substrate is a lens having a refractive index of from 1.48 to 1.75.

19. The ophthalmic article of claim 18 wherein the lens is a plano lens, a single vision lens, a multi-focal lens, an aspheric lens, an aspheric multi-focal lens, or a semi-finished single vision lens.

20. The ophthalmic article of claim 17 wherein the organic photochromic material is chosen from benzoxazines, naphthoxazines, spiro(indolino)pyridobenzoxazines, benzopyrans, naphthopyrans, spiro-9-fluorenopyrans, phenanthropyrans, quinopyrans, indeno-fused naphthopyrans, fulgides, fulgimides, metal dithizonates, and mixtures of such photochromic materials.

21. The ophthalmic article of claim 20 wherein organic photochromic material is present in amounts of from 0.2 to 20 weight percent.

22. The ophthalmic article of claim 20 wherein the protective film comprises nylon, poly(vinyl acetate), vinyl chloride-vinyl acetate copolymer, poly (lower alkyl) acrylates, poly (lower alkyl) methacrylates, styrene-butadiene copolymer resin, polyurea urethanes, lightly cross-linked thermoplastic polyurethane and/or thermoplastic polycarbonate.

23. The ophthalmic article of claim 17 wherein an abrasion resistant coating is superposed on the protective polymeric film.

24. The ophthalmic article of claim 23 wherein the abrasion resistant coating comprises polyfunctional acrylic hard coatings, melamine-based hard coatings, urethane-based hard coatings, alkyd-based hard coatings, silica sol-based hard coatings and/or organo-silane type hard coatings.

25. The ophthalmic article of claim 17 wherein a polarizing film pervious to ultraviolet light radiation is interposed between the polyurethane film and the protective film of thermoplastic polymeric organic material.

36. A photochromic optical article comprising, in combination:

(a) a transparent solid optical polyurea urethane substrate having a front surface and a back surface;

(b) transparent thermoplastic photochromic polyurethane film appended to at least one surface of the optical substrate, said polyurethane film having (i) a thickness of 2 to 15 mils, (ii) a flexural modulus of less than 2.5 GPa, and (iii) being formed from polyurethane material selected from polyether-based polyurethane materials, polycarbonate-based polyurethane materials and mixtures of said polyurethane materials, said polyurethane film further containing from 0.2 to 10 weight percent of at least one organic photochromic material that is soluble in the polyurethane film, said photochromic material being chosen from naphthoxazines, spiro(indolino) pyridobenzoxazines, naphthopyrans, spiro-9-fluorenopyrans, phenanthropyrans, indeno-fused naphthopyrans and mixtures of such photochromic materials; and

(c) transparent thermoplastic protective film of polymeric organic material superposed on said polyurethane film, said polymeric protective film having a flexural modulus of from 0.1 to 5 GPa, said polymeric protective film being selected from nylon, poly(vinyl acetate), vinyl chloride-vinyl acetate copolymer, poly(lower alkyl)acrylates, poly(lower alkyl)methacrylates, styrene-butadiene copolymer resin, polyurea urethane, lightly cross-linked thermoplastic polyurethane and thermoplastic polycarbonate material, said photochromic optical article exhibiting (1) a change in color when exposed to activating ultraviolet light radiation, and (2) a color fading half-life (T½

) of not more than 500 seconds when the ultraviolet light radiation is removed.

37. The optical article of claim 36 wherein the polymeric protective film is thermoplastic polycarbonate.