Inorganic polymer material with tantalic acid anhydride base, in particular with high refractive index, mechanically abrasionproof, method of manufacture, optical materials comprising such material

• US 6,387,517 B1
• Filed: 09/14/1999
• Issued: 05/14/2002
• Est. Priority Date: 02/10/1997
• Status: Expired due to Term

• Current Assignee: Commissariat a L'Energie Atomique (AES Corporation)
• Original Assignee: Commissariat a L'Energie Atomique (AES Corporation)
• Inventors: Belleville, Philippe, Prene, Philippe, Floch, Hervé
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): STEIN, STEPHEN J
• Application Number:
  US09/355,763
• Time in Patent Office: 973 Days
• Field of Search: 428/212, 428/446, 428/432, 428/447, 428/448, 428/450, 428/470, 428/472, 428/697, 427/515, 427/162, 427/299, 427/407.1, 427/419.3, 106/286.2, 106/287.18, 525/16
• US Class Current: 428/447
• CPC Class Codes: C01G 35/00 Compounds of tantalum
• CPC Class Codes: C01P 2002/84 by UV- or VIS- data
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/80 Compositional purity
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 17/3452 comprising a fluoride
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 2217/218 V2O5, Nb2O5, Ta2O5
• CPC Class Codes: C03C 2217/734 comprising an alternation of high and low refractive indexes
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The invention relates to an inorganic polymer material based on tantalum oxide, notably with a high refractive index and mechanically resistant to abrasion, its method of manufacture, in particular making use of precursors based on chlorinated derivatives of tantalum, and optical materials such as antiglare materials and reflecting materials manufactured from this material.

Claims

1. A polymeric inorganic material characterized in that said material is a material based on tantalum oxide, densified or cross-linked by a heat treatment at a temperature less than 200°

C., or by an exposure to ultra-violet rays and in that said material comprises in addition residual halide ions.

2. The polymeric material according to claim 1, characterized in that said material comprises an inorganic, densified or cross-linked, tantalum oxy-hydroxide polymer.

3. The polymeric material according to claim 1, characterized in that said halide ions are chloride ions.

4. The polymeric material according to claim 1, characterized in that it comprises, apart from tantalum oxide, at least one other metal or metalloid oxide selected from the group consisting of titanium oxide, yttrium oxide, scandium oxide, zirconium oxide, hafnium oxide, thorium oxide, niobium oxide, lanthanum oxide, aluminum oxide, magnesium oxide and silicon oxide.

5. The polymeric material according to claim 1, characterized in that the one or more other metal or metalloid oxides are present in a proportion from about 1 to 99% by mass, with respect to the total mass of metal and metalloid oxides.

6. The polymeric material according to claim 1, characterized in that said inorganic polymeric material is a material with a high refractive index.

7. A method of preparation and of deposition of the inorganic polymeric material according to claim 1, characterized in that said method comprises the steps of:

preparing a first solution comprising a solvent and a tantalum molecular precursor compound selected from the group consisting of tantalum pentahalides of the formula TaX₅ wherein X is F, Br, I or Cl and TaCl₂(OEt)₃;

optionally mixing said first solution with a second solution comprising a second solvent of the same kind and one or more other metal or metalloid compound other than tantalum thereby obtaining a third solution;

depositing the first solution or the third solution onto a support wherein said depositing forms a uniform layer of polymeric material based on tantalum oxide; and

cross-linking or densifying said uniform polymeric layer based on tantalum oxide, the cross-linking or densifying being accomplished by a heat treatment at a temperature below 200°

C., or by an exposure to ultra-violet rays; and

optionally said cross-linking or densifying is followed by an annealing step or a post-treatment heating step.

8. The method according to claim 7, characterized in that said heat treatment is carried out at a temperature of from 100 to 200°

C. for a period of from 2 to 150 minutes.

9. The method according to claim 7, characterized in that said exposure to ultra-violet rays is carried out with an energy of from 5 to 10 J/cm² for a period of from 10 seconds to 10 minutes.

10. The method according to claim 7, characterized in that the solvent is a saturated aliphatic alcohol of the formula ROH, where R represents an alkyl group with from 1 to 5 carbon atoms.

11. The method according to claim 7, characterized in that the annealing step, or the post-treatment heat treatment is carried out at a temperature of from 80 to 200°

C. for 10 to 60 minutes.

12. The method according to claim 7, further comprising the step of removing the excess halide ions from the first solution.

13. The method according to claim 12, characterized in that the excess halide ions in the first solution are removed by evaporation under reduced pressure and then redissolution.

14. The method according to claim 12, characterized in that the excess halide ions in the first solution are removed by chemical neutralization.

15. The method according to claim 7, characterized in that the solvent of the first solution is ethanol, optionally neutralized by NH₃, and the tantalum molecular precursor compound is selected from the group consisting of tantalum pentachloride and TaCl₂(OEt)₃.

16. An optical material, characterized in that it comprises an organic or inorganic substrate covered by at least one layer of the inorganic polymeric material based on tantalum oxide according to claim 1.

17. An optical material, characterized in that comprises an organic or inorganic substrate covered by at least one layer of the inorganic polymeric material based on tantalum oxide according to claim 6.

18. The optical material according to claim 17, characterized in that it further comprises at least one layer selected from the group consisting of:

a layer with a low refractive index comprising a component selected from the group consisting of colloids of silicon oxide, colloids of silicon oxide encased in a siloxane binder, colloids of calcium fluoride, colloids of calcium fluoride encased in a siloxane binder, colloids of magnesium fluoride, colloids of magnesium fluoride encased in a siloxane binder, silicon oxide in polymeric form and magnesium oxide in polymeric form;

a layer with a medium refractive index formed from a polymeric material based on tantalum oxide and another metal oxide; and

an anti-abrasive layer, based on a fluorinated silane.

19. The optical material according to claim 18, characterized in that the layers with low or medium refractive index are densified or cross-linked polymeric layers.

20. The optical material according to claim 18, having anti-glare properties with a wide spectral band, characterized in that it comprises an organic or inorganic substrate covered successively by:

a layer with a medium refractive index;

a layer with a high refractive index;

a layer with a low refractive index; and

optionally an anti-abrasive layer.

21. The optical material according to claim 18, having anti-glare properties with a narrow spectral band, characterized in that it comprises an organic or inorganic substrate covered successively by:

a layer with a high refractive index;

a layer with a low refractive index; and

optionally an anti-abrasive layer.

22. The optical material according to claim 18, having reflecting properties, characterized in that it comprises an organic or inorganic substrate covered successively by at least one sequence of two layers wherein the layers are selected from the group consisting of:

a layer with a low refractive index;

a layer with a high refractive index; and

optionally an anti-abrasive layer.

23. The optical material according to claim 18 characterized in that the substrate is an organic substrate covered by a lacquer.

24. The optical material according to claim 18 characterized in that the layer with a medium refractive index is formed from a polymeric material based on tantalum oxide and silicon oxide or based on tantalum oxide and magnesium oxide, wherein the refractive index can be modulated at will by varying the relative proportions in tantalum oxide and silicon oxide equivalents, or in tantalum oxide and magnesium oxide equivalents.

25. The optical material according to claim 18 characterized in that the layer with a low refractive index is a layer formed from polymeric silicon oxide selected from the group consisting of polymeric silicon oxide prepared in an HCl medium, polymeric silicon oxide prepared in an HNO₃ medium, and oligomeric silicon oxide.

26. The optical material according to claim 18, characterized in that the anti-abrasive layer is formed from C₆F₁₃—

CH₂CH₂—

Si(OEt)₃ or C₆F₁₃—

CH₂CH₂—

SiCl₃.

27. A method of preparing an anti-glare material with a wide spectral band according to claim 20, characterized in that it comprises the following steps:

cleaning-scouring the substrate;

depositing on the cleaned substrate the layer with medium refractive index;

optionally thermal cross-linking or densifying the deposited layer with a medium refractive index;

cleaning-scouring;

depositing the layer with a high refractive index based on Ta₂O_5];

optionally thermal cross-linking or densifying the deposited layer with a high refractive index;

cleaning-scouring as previously;

depositing the layer with a low refractive index;

optionally thermal cross-linking or densifying the deposited layer with a low refractive index;

applying the anti-abrasive layer onto the layer with a low index; and

heat treatment.

28. The method according to claim 27, characterized in that, following the deposition of the layer with a high refractive index based on Ta₂O₅, the cross-linking or densification of this layer-and the cleaning and scouring of this layer, a period of from 1 to 24 hours is allowed to pass before carrying out a second scouring of the layer with a high refractive index and depositing the layer with a low refractive index.

29. The method according to claim 27, characterized in that, following the deposition of the layer with a high refractive index based on Ta₂O₅, a treatment is carried out of rinsing the deposited layer with a mixture of ammonia and ethanol;

a heat treatment is then carried out under reduced pressure and the rinsing with ammonia/ethanol is repeated and then the cross-linking or densification of the layer with a high refractive index before depositing the layer with a low refractive index.

30. The method according to claim 29, characterized in that a period of from 1 to 24 hours is allowed to pass following the final rinsing with the ammonia/ethanol mixture before carrying out the deposition of the layer with a low index.

31. A method of preparing an anti-glare material with a wide spectral band according to claim 20, characterized in that it comprises the following steps:

cleaning-scouring the substrate;

depositing on the cleaned substrate the layer with medium refractive index,

optionally cross-linking or densifying the deposited layer with a medium refractive index by exposure to ultra-violet rays;

depositing the layer with a high refractive index based on Ta₂O₅;

optionally cross-linking or densifying the deposited layer with a high refractive index by exposure to ultra-violet rays;

depositing the layer with a low refractive index;

cross-linking or densifying the deposited layer with a low refractive index by exposure to ultra-violet rays;

applying the anti-abrasive layer onto the layer with a low index; and

heat treatment of the whole of the applied layers and the substrate.

41. The polymeric material according to claim 5 characterized in that said inorganic polymeric material is a material with a high refractive index.

42. An optical material, characterized in that it comprises an organic or inorganic substrate covered by at least one layer of the inorganic polymeric material based on tantalum oxide according to claim 5.

43. The optical material according to claim 20 characterized in that the substrate is an organic substrate covered by a lacquer.

44. The optical material according to claim 21 characterized in that the substrate is an organic substrate covered by a lacquer.

45. The optical material according to claim 22 characterized in that the substrate is an organic substrate covered by a lacquer.

46. The optical material according to claim 20 characterized in that the layer with a medium refractive index is formed from a polymeric material based on tantalum oxide and silicon oxide or based on tantalum oxide and magnesium oxide, wherein the refractive index can be modulated at will by varying the relative proportions in tantalum oxide and silicon oxide equivalents, or in tantalum oxide and magnesium oxide equivalents.

47. The optical material according to claim 21 characterized in that the layer with a medium refractive index is formed from a polymeric material based on tantalum oxide and silicon oxide or based on tantalum oxide and magnesium oxide, wherein the refractive index can be modulated at will by varying the relative proportions in tantalum oxide and silicon oxide equivalents, or in tantalum oxide and magnesium oxide equivalents.

48. The optical material according to claim 22 characterized in that the layer with a medium refractive index is formed from a polymeric material based on tantalum oxide and silicon oxide or based on tantalum oxide and magnesium oxide, wherein the refractive index can be modulated at will by varying the relative proportions in tantalum oxide and silicon oxide equivalents, or in tantalum oxide and magnesium oxide equivalents.

49. The optical material according to claim 20 characterized in that the layer with a low refractive index is a layer formed from polymeric silicon oxide selected from the group consisting of polymeric silicon oxide prepared in an HCl medium, polymeric silicon oxide prepared in an HNO₃ medium, and oligomeric silicon oxide.

50. The optical material according to claim 21 characterized in that the layer with a low refractive index is a layer formed from polymeric silicon oxide selected from the group consisting of polymeric silicon oxide prepared in an HCl medium, polymeric silicon oxide prepared in an HNO₃ medium, and oligomeric silicon oxide.

51. The optical material according to claim 22 characterized in that the layer with a low refractive index is a layer formed from polymeric silicon oxide selected from the group consisting of polymeric silicon oxide prepared in an HCl medium, polymeric silicon oxide prepared in an HNO₃ medium, and oligomeric silicon oxide.

52. The optical material according to claim 20 characterized in that the anti-abrasive layer is formed from C₆F₁₃—

CH₂CH₂—

Si(OEt)₃ or C₆F₁₃—

CH₂CH₂—

SiCl₃.

53. The optical material according to claim 21 characterized in that the anti-abrasive layer is formed from C₆F₁₃—

CH₂CH₂—

Si(OEt)₃ or C₆F₁₃—

CH₂CH₂—

SiCl₃.

32. A solution comprising

a solvent;

a tantalum molecular precursor compound selected from the group consisting of tantalum pentahalides of the formula TaX₅ wherein X is F, Br, I or Cl, and TaCl₂(OEt)₃; and

one or more other metal or metalloid compounds selected from the group consisting of titanium, silicon, yttrium, scandium, zirconium, hafnium, thorium, niobium, lanthanum, aluminum and magnesium.

33. The solution according to claim 32, in which said solvent is a saturated aliphatic alcohol of the formula ROH, where R represents an alkyl group of from 1 to 5 carbon atoms.

34. The solution according to claim 32, in which said one or more other metal or metalloid compounds are selected from the group consisting of alkoxide and halide metalloid compounds.

35. The solution according to claim 32, in which the concentration of the tantalum molecular precursor and said one or more other metal or metalloid compounds comprises from 1 to 20% by mass expressed as an oxide of the tantalum molecular precursor or the metal or metalloid compounds.

36. The solution according to claim 33 characterized in that the residual halide ions in the solution are removed from it.

37. The solution according to claim 36, characterized in that the residual halide ions in the solution are removed by evaporation under reduced pressure and then redissolution.

38. The solution according to claim 36, characterized in that the residual halide ions in the solution are removed by chemical neutralization.

55. The solution according to claim 35 characterized in that the residual halide ions in the solution are removed from it.

56. The solution according to claim 35, in which the concentration of the tantalum molecular precursor and said one or more other metal or metalloid compounds comprises from 5 to 10% by mass expressed as an oxide of the tantalum molecular precursor or the metal or metalloid compounds.

39. The solution in ethanol, optionally neutralized with NH₃, of a tantalum molecular precursor compound selected from the group consisting of tantalum pentachloride and TaCl₂(OEt)₃.

40. A solution of TaCL₂(OEt)₃ in ethanol at a concentration of from 5 to 10% in mass equivalent of Ta₂O₅.

54. The optical material according to claim characterized in that the anti-abrasive layer is formed from C₆F₁₃—

CH₂CH₂—

Si(OEt)₃ or C₆F₁₃—

CH₂CH₂—

SiCl₃.