Crosslinking of silicones presence of functionalized silicones

• US 7,241,009 B2
• Filed: 06/17/2004
• Issued: 07/10/2007
• Est. Priority Date: 11/21/2001
• Status: Expired due to Term

• Current Assignee: RxSight, Inc.
• Original Assignee: Calhoun Vision, Inc.
• Inventors: Grubbs, Robert H., Kornfield, Julia A., Jethmalani, Jagdish M., Chang, Shiao H.
• Primary Examiner(s): MANUEL, GEORGE C
• Application Number:
  US10/871,686
• Publication Number:
  US 20050018310A1
• Time in Patent Office: 1,118 Days
• Field of Search: 359/642, 623/901, 528/21, 564/18, 351/159
• US Class Current: 351/159
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61F 2/1613 having special lens configurations, e.g. multipart lenses; having particular optical properties, e.g. pseudo-accommodative lenses, lenses having aberration corrections, diffractive lenses, lenses for variably absorbing electromagnetic radiation, lenses having variable focus
• CPC Class Codes: A61F 2/1627 for changing index of refraction, e.g. by external means or by tilting
• CPC Class Codes: A61F 2/1635 for changing shape
• CPC Class Codes: A61F 2002/1699 Additional features not otherwise provided for
• CPC Class Codes: B29D 11/00442 Curing the lens material
• CPC Class Codes: B29D 11/023 Implants for natural eyes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 2202/14 Photorefractive lens material

Abstract

Methods and materials are disclosed for the production of optical elements, in particular intraocular lenses (IOL) that incorporate any amount (0 to 99%) of refraction and/or shape modulating compound into a substantially crosslinked first polymeric matrix. The materials produced according to the inventive methods exhibit certain rheological parameters useful in defining medical lenses. These medical lenses have the ability to change their refractive power via changing the refractive index and/or by altering the shape by stimulus induced polymerization.

Claims

1. A method for fabricating an optical element comprising;

(a) preparing a first composite comprising a first precursor and a refraction- and/or shape- modifying composition (RSMC);

(b) preparing a second composite comprising a second precursor and a catalyst for the first and second precursors;

(c) combining the first and the second composites to form a reaction mixture;

(d) placing the reaction mixture into a mold;

(e) forming a substantially cross-linked first polymer matrix from said reaction mixture, said substantially crosslinked first polymer matrix having said RSMC dispersed therein, and;

(f) removing the optical element from the mold.

2. The process according to claim 1 further comprising the step of adding at least one third composite, the third composite comprising a third precursor further comprising a crosslinking agent.

3. The process according to claim 2 further comprising the step of forming the substantially crossed linked first polymer matrix under pressures.

4. The process according to claim 3 wherein the pressure is from about atmospheric pressure up to about 20,000 pounds per square inch.

5. The process according to claim 4 wherein the pressure is in the range of about 10,000 to about 20,000 pounds per square inch.

6. The process according to claim 3 wherein the pressure is constant, variable or a combination of constant and variable pressures.

7. The method of claim 2 wherein the cross-linking agent is selected from the group consisting of vinyl silicone compounds having at least three vinyl groups per molecule and silicone compounds having at least three silicone hydride moieties per molecule.

8. The method of claim 7 wherein the crosslinking agent is present is an amount of up to 15% by weight.

9. The process according to claim 1 further comprising the step of forming the reaction mixture in the mold at a temperature from above the freezing temperature of the reaction mixture to the decomposition temperature of the catalyst.

10. The process according to claim 9 wherein the temperature is in the range of about 30°

C. to about 40°

C.

11. The process according to claim 1 further comprising the step of forming the reaction mixture in the mold at a temperature in the range of from about room temperature to about 50°

C.

12. The process according to claim 1 further comprising the step of forming the reaction mixture in the mold at a constant temperature, over a variable temperature range or a combination of constant temperature and variable temperature ranges.

13. The method of claim 1 wherein the first precursor comprises at least one polyorganosiloxane molecule having at least two silicone-bonded vinyl radials per molecule.

14. The method of claim 1 wherein the second precursor comprises at least one polyorganosiloxane molecule having at least three silicone-bonded hydride groups with the proviso that no single silicone atom has more than two Si-H bonded groups.

15. The method of claim 1 wherein the catalyst is a platinum group metal-containing catalyst known to catalyze the addition of silicone bonded hydrides to silicone-bonded vinyl radicals.

16. The method according to claim 15 wherein the catalyst is present in the reaction mixture sufficient to provide at least about 0.1 parts per million by weight of platinum group metal, calculated as elemental metal.

17. The method of claim 1 wherein the RSMC is bio-compatible.

18. The method of claim 1 wherein the RSMC comprises polysiloxanes.

19. The method of claim 18 wherein the polysiloxane contains a functional group capable of stimulus-induced polymerization.

20. The method of claim 19 wherein the functional group is selected from the group comprising acrylate, alkoxy, cinnanmoyl, methacrylate, stibenyl, and vinyl.

21. The method of claim 1 wherein the refraction and/or shape modifying composition further comprises a photoinitiator.

22. The method of claim 21 wherein the photoinitiator is selected from the group comprising:

acetophenone, 2,4-dichioromethyl-1,3,5 triazines, benzoin methyl ethers, O-benzoylyoximino-ketone and silicone derivatives thereof.

23. The method of claim 1 further comprising the step of energetically stimulating the optical element thereby causing the RSMC to form a reaction product.

24. The method of claim 23 wherein said reaction product is polymeric or an interpenetrating polymer network.

25. The method of claim 1 wherein the RSMC comprises a macromer of the formula

x-Y-x¹

and a photoinitiator wherein Y is

wherein:

m and n are each independently an integer and R¹, R², R³, R⁴, R⁵, and R⁶ are each independently selected from the group consisting hydrogen, alkyl, aryl, and heteroaryl; and

Z is a photopolymerizable The method of claim 25 wherein said R¹, R², and R³, R⁵, and R⁶ are selected from the group consisting of methyl, ethyl, and propyl, and R⁴ is pThe method of claim 1 wherein the RSMC comprises up to about 45% by weight of the optical element.

26. An optical element prepared according to any one of claims 1-25.

27. An intraocular lens prepared according to anyone of claims 1-25.

28. A fabricated optical element, comprising a reaction product of:

(a) a first composite, said first composite further comprising at least one polyorganosiloxane molecule having at least two silicone-bonded vinyl radicals per molecule;

(b) a second precursor comprising at least one polyorganosiloxane molecule having at least three silicone-hydride groups per molecule;

(c) a platinum group metal-containing catalysts known to catalyze the addition of silicone-bonded hydrides to silicone-vinyl radicals;

(d) a refraction and/or shape-modifying composition;

said reaction product exhibiting a shear loss modulus, between 1×

10⁴ to about 1.25×

10⁵ Pa over a testing frequency range of from 0.01 radians/second to about 100 radians/second.

(e) a UV-absorber(s).

29. The fabricated optical element of claim 28 further comprising a cross-linking agent selected from the group of silicone compounds having at least three vinyl groups per molecule, silicone compounds having at least three silicone hydride moieties per molecule, said hydrides being on different silicon atoms, or combinations thereof, said crosslinking-agent being present in an amount up to about 15 weight percent of the optical element.

30. The fabricated optical element of claim 28 wherein the fabricated optical element exhibits a shear loss modulus, G″

of at least about 1×

10⁴.