Rigid gas permeable lens material
View Patent ↗A copolymer useful as a rigid gas permeable contact lens material is the polymerization product of a monomeric mixture comprising a polysiloxane-containing urethane or urea prepolymer endcapped with polymerizable ethylenically unsaturated radicals.
1. A rigid gas permeable contact lens that is the polymerization product of a monomeric mixture comprising a polysiloxane-containing urethane or urea prepolymer endcapped with polymerizable ethylenically unsaturated radicals, said rigid gas permeable contact lens having an oxygen permeability of at least 100 barrers, a Rockwell hardness of at least 90 or a Shore D hardness of at least 70 and a modulus of at least 800 MPa.
2. The contact lens of claim 1 , having a toughness of at least 1.5 Mpa·mm/mm and a modulus of at least 800 Mpa.
3. The contact lens of claim 1 , having an oxygen permeability of at least 120 barrers.
4. The contact lens of claim 3 , having an oxygen permeability of at least 140 barrers.
5. The contact lens of claim 4 , having an oxygen permeability of at least 160 barrers.
6. The contact lens of claim 1 , wherein the monomer mixture further comprises a hydrophilic monomer.
7. The contact lens of claim 6 , wherein the monomer mixture comprises at least one member selected from the group consisting of N-vinylpyrrolidone and methacrylic acid.
8. The contact lens of claim 1 , wherein the monomer mixture further comprises a fluorinated monomer.
9. The contact lens of claim 8 , wherein the monomer mixture comprises at least one member selected from the group consisting of a fluorinated (meth)acrylate and a fluorinated itaconate.
10. The contact lens of claim 1 , wherein the monomer mixture further comprises a an ethylenically unsaturated monofunctional silicon-containing monomer.
11. The contact lens of claim 1 , wherein the monomer mixture further comprises a hardness modifying (meth)acrylate monomer.
12. The contact lens of claim 11 , wherein the monomer mixture comprises an alkyl (meth)acrylate monomer.
13. The contact lens of claim 1 , wherein the monomer mixture further comprises at least one member selected from the group consisting of a polymerization initiator, an ultraviolet blocking agent, and a colorant.
14. The contact lens of claim 1 , wherein the monomer mixture includes at least one prepolymer comprising blocks (I) and (II) and terminated at each end with an ethylenic unsaturated radical:
(*Dii*Diol*Dii*PS) x (I)
(*Dii*PS) y (II)
wherein:
each Dii is independently a diradical residue of a diisocyanate;
each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;
each PS is independently a diradical residue of a polysiloxane-diol or -diamine;
each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—;
x represents the number of blocks (I) and is at least 1, and
y represents the number of blocks (II) and is at least 1.
15. The contact lens of claim 1 , wherein the monomer mixture includes at least one prepolymer having the general formulae:
M(*Dii*Diol*Dii*PS) x (*Dii*PS) y *Dii*M (III) or
M(*Dii*Diol*Dii*PS) x (*Dii*PS) y *Dii*Diol*Dii*M (IV)
wherein Dii, Diol, PS, *, x and y are as defined above, and M is a polymerizable ethylenically unsaturated radical.
16. The contact lens of claim 1 , wherein the monomer mixture includes at least one prepolymer having the general formulae:
M(*Dii* PS) x *Dii*M (V)
M(*Dii*PS *Dii*Diol) x *Dii*PS *Dii*M (VI)
M(*Dii *Diol*Dii*PS) x *Dii*Diol*Dii*M (VII) or
M(*PS*Dii) x *PS*M (VIII)
wherein:
each Dii is independently a diradical residue of a diisocyanate;
each Diol is independently a diradlical residue of a diol having 1 to 10 carbon atoms;
each PS is independently a diradical residue of a polysiloxane-diol or -diamine;
each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—;
each M is independently a polymerizable ethylenically unsaturated radical; and
x represents the number of blocks (I) and is at least 1.
17. The contact lens of claim 1 , wherein the monomer mixture comprises: the urethane or urea prepolymer; a hydrophilic monomer; a fluorinated monomer; an ethylenically unsaturated monofunctional silicon-containing monomer; a hardness modifying (meth)acrylate monomer; and at least one member selected from the group consisting of a polymerization initiator, an ultraviolet blocking agent, and a colorant.
18. A copolymer useful as a rigid gas permeable contact lens material that is the polymerization product of a monomeric mixture comprising a polysiloxane-containing urethane or urea prepolymer endcapped with polymerizable ethylenically unsaturated radicals, and one or more hydrophilic monomers, to provide a rigid gas permeable contact lens having an oxygen permeability of at least 100 barrers, a Rockwell hardness of at least 90 or a Shore D hardness of at least 70 and a modulus of at least 800 MPa.
19. The copolymer of claim 18 , wherein the rigid gas permeable contact lens has a toughness of at least 1.5 Mpa·mm/mm and is optically clear.
20. The copolymer of claim 19 , wherein the rigid gas permeable contact lens has an oxygen permeability of at least 140 barrers.
21. The copolymer of claim 18 , wherein the monomer mixture further comprises: a fluorinated monomer; an ethylenically unsaturated monofunctional silicon-containing monomer; a hardness modifying (meth)acrylate monomer; and at least one member selected from the group consisting of a polymerization initiator, an ultraviolet blocking agent, and a colorant.
22. The copolymer of claim 18 , wherein the monomer mixture includes at least one prepolymer comprising blocks (I) and (II) and terminated at each end with an ethylenic unsaturated radical:
(*Dii*Diol*Dii*PS) x (I)
(*Dii*PS) y (II)
wherein:
each Dii is independently a diradical residue of a diisocyanate;
each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;
each PS is independently a diradical residue of a polysiloxane-diol or -diamine;
each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—;
x represents the number of blocks (I) and is at least 1, and
y represents the number of blocks (II) and is at least 1.
23. The copolymer of claim 22 , wherein the monomer mixture includes at least one prepolymer having the general formulae:
M(*Dii*Diol*Dii*PS) x (*Dii*PS) y *Dii*M (III) or
M(*Dii*Diol*Dii*PS) x (Dii*PS) y *Dii*Diol*Dii*M (IV)
wherein Dii, Diol, PS, *, x and y are as defined above, and M is a polymerizable ethylenically unsaturated radical.
24. The copolymer of claim 1 , wherein the monomer mixture includes at least one prepolymer having the general formulae:
M(*Dii* PS) x *Dii*M (V)
M(Dii*PS*Dii*Diol) x *Dii*PS*Dii*M (VI)
M(*Dii*Diol*Dii*PS) x *Dii*Diol*Dii*M (VII) or
M(*PS*Dii) x *PS*M (VIII)
wherein:
each Dii is independently a diradical residue of a diisocyanate; each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;
each PS is independently a diradical residue of a polysiloxane-diol or -diamine;
each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—;
each M is in dependently a polymerizable ethylenically unsaturated radical; and
x represents the number of blocks (I) and is at least 1.
25. The copolymer of claim 18 , having the shape of a cylindrical disk.
26. A combination comprising: a cylindrical disk formed from a copolymer that is the polymerization product of a monomeric mixture comprising a polysiloxane-containing urethane or urea prepolymer endcapped with polymerizable ethylenically unsaturated radicals, and one or more hydrophilic monomers; and packaged with the disk, printed instructions for lathing a rigid gas permeable contact lens from the disk, said rigid gas permeable contact lens having an oxygen permeability of at least 100 barrers, a Rockwell hardness of at least 90 or a Shore D hardness of at least 70 and a modulus of at least 800 MPa.