Fluorine containing polymeric compositions useful in contact lenses

• US 4,686,267 A
• Filed: 10/11/1985
• Issued: 08/11/1987
• Est. Priority Date: 10/11/1985
• Status: Expired due to Term

• Current Assignee: B&L International Holdings Corp.
• Original Assignee: Polymer Technology Group, Inc. (DSM-Firmenich AG)
• Inventors: Ellis, Jeanne Y., Ellis, Edward J.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): Mulcahy, Peter D.
• Application Number:
  US06/786,846
• Time in Patent Office: 669 Days
• Field of Search: 526/245, 526/246, 351/160 R, 351/160 H
• US Class Current: 526/245
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 290/062 Polyethers
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08L 35/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Improved contact lens compositions are achieved through incorporation of a fluorine containing mono or diester of itaconic acid in siloxane polymeric contact lens compositions. Copolymers include components which modify contact lens mechanical, optical and transport properties as well as surface characteristics to achieve at least some compositions having an oxygen permeability of at least DK35 with a refractive index of from 1.35 to 1.5 and a percent hydration below 2 percent of total weight. Contact lenses made of materials of this invention are highly permeable to oxygen and resistant to the deposition of tear components providing extended wear capability through improved biocompatibility.

Claims

1. An oxygen permeable dimensionally stable, hydrophilic, contact lens material of high transparency, comprising a polymer formed by free radical polymerization from

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having the structure:

##STR3## wherein;

Z₁ and Z₂ can be the same or different and are each of a group selected from among the following with at least one of Z₁ or Z₂ containing fluorine;

hydrogen,

straight chain alkyl groups or fluoro substituted alkyl groups containing from 1 to 18 carbon atoms,

branched chain alkyl groups or fluoro substituted alkyl groups containing from 4 to 18 carbon atoms,

cyclic alkyl groups or fluoro substituted cyclic alkyl groups containing from 5 to 18 carbon atoms,

phenyl groups and fluoro substituted phenyl groups, or

benzyl and fluoro substituted benzyl groups, phenethyl and fluoro substituted phenethyl groups,

ethers and polyethers of the general structure

space="preserve" listing-type="equation">(C.sub.x P.sub.2x O).sub.e -(C.sub.y P.sub.2y+1)

wherein;

"P" is hydrogen or fluorine

"x" is an integer from 1 to 4

"y" is an integer from 1 to 10

"e" is an integer from 1 to 10,

(B) 95 to 40% by weight of at least one organic comonomer of an ethylenically unsaturated organosiloxane having the following formula;

##EQU6## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy, vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical having from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms and a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety,

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups "R" and "b" may be the same or different within each "i" moiety.

2. A contact lens material in accordance with claim 1 wherein said material has an oxygen permeability of at least DK35 with a refractive index of from 1.35 to 1.5 and a percent hydration below 2% of total weight.

4. A contact lens material in accordance with claim 1 and further comprising an aromatic containing organic vinyl monomer and a refractive index of at least 1.5.

6. A contact lens material in accordance with claim 1 wherein from 5 to 30% of said ethylenically unsaturated organosiloxanes are multifunctional, unsaturated organosiloxanes.

7. A contact lens material in accordance with claim 1 and further comprising from about 5 to about 25% by weight of a hydrophilic organic monomer.

8. A contact lens material in accordance with claim 1 and further comprising from about 1 to about 10% by weight of a non-siloxane containing crosslinking monomer.

9. A contact lens material in accordance with claim 1 and further comprising from about 10 to about 25% by weight of a hardness modifying agent.

10. A contact lens material in accordance with claim 1 wherein Z₁ is hydrogen and Z₂ is a fluorinated alkyl group having from 1 to 8 carbon atoms.

11. A contact lens material in accordance with claim 1 wherein Z₁ and Z₂ are fluorinated alkyl groups having from 1 to 8 carbon atoms.

14. A contact lens material in accordance with claim 1 wherein said fluorine containing itaconate diester is bis(1,1,1,3,3,3-hexafluoro-2-propyl) itaconate.

23. The material of claim 1 in the form of a contact lens.

3. An oxygen permeable dimensionally stable hydrophilic, contact lens material of high transparency, comprising a polymer formed by free radical polymerization from

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having the structure:

##STR4## wherein;

Z₁ and Z₂ can be the same or different and are each of a group selected from among the following with at least one of Z₁ or Z₂ containing fluorine;

hydrogen,

straight chain alkyl groups or fluoro substituted alkyl groups containing from 1 to 18 carbon atoms,

branched chain alkyl groups or fluoro substituted alkyl groups containing from 4 to 18 carbon atoms

cyclic alkyl groups or fluoro substituted cyclic alkyl groups containing from 5 to 18 carbon atoms,

phenyl groups and fluoro substituted phenyl groups, or

benzyl and fluoro substituted benzyl groups,

phenethyl and fluoro substituted phenethyl groups,

ethers and polyethers of the general structure

space="preserve" listing-type="equation">(C.sub.x P.sub.2x O).sub.e -(C.sub.y P.sub.2y+1)

wherein;

"P" is hydrogen or fluorine

"x" is an integer from 1 to 4

"y" is an integer from 1 to 10

"e" is an integer from 1 to 10,

(B) from 95 to 40% by weight of at least one ethylenically unsaturated organosiloxane having the following formula;

##EQU7## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy, vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical having from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms and a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety,

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups, "R" and "b" may be the same or different within each "i" moiety,

(C) 0 to 55% by weight of the entire composition of a vinyl monomer hardness modifying agent,

(D) 0 to 55% by weight of the entire composition of a hydrophilic organic monomer,

(E) 0 to 20% by weight of the entire composition of a non-siloxane containing cross-linking monomer.

5. A contact lens material in accordance with claim 3 wherein said hardness modifying agent is selected from the class consisting of esters of acrylic acid, methacrylic acid and itaconic acid.

12. A contact lens material in accordance with claim 3 wherein said hardness modifying agent is not present and said hydrophilic organic monomer and non-siloxane containing crosslinking monomer are present.

13. A contact lens material in accordance with claim 3 wherein Z₁ and Z₂ are fluorinated alkyl groups containing from 1 to 8 carbon atoms.

15. An oxygen permeable dimensionally stable hydrophilic contact lens material in accordance with claim 3 wherein said organosiloxane is tris(trimethylsiloxy) silylpropyl methacrylate admixed with 1,3-bis(methacryloxypropyl)1,1,3,3-tetrakis (trimethyl siloxy) disiloxane.

17. A contact material in accordance with claim 3 wherein said hydrophilic organic monomer is present and is selected from the class consisting of acrylic acid, methacrylic acid, and monoesters of itaconic acid.

16. A contact lens material formed from polymerization of a monomeric mixture of bis(1,1,1,3,3,3-hexafluoro-2-propyl) itaconate, bis(methacryloxypropyl)1,1,3,3-tetrakis (trimethyl siloxy) disiloxane, tris(trimethylsiloxy) ilylpropyl methacrylate, methylmethacrylate, n-vinyl pyrrolidone, methacrylic acid and tetraethylene glycol dimethacrylate.

18. A contact lens formed from an oxygen permeable dimensionally stable, hydrophilic, contact lens material of high transparency, comprising a polymer formed by free radical polymerization from

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having the structure:

##STR5## wherein;

Z₁ and Z₂ can be the same or different and are each of a group selected from among the following with at least one of Z₁ or Z₂ containing fluorine;

hydrogen,

straight chain alkyl groups or fluoro substituted alkyl groups containing from 1 to 18 carbon atoms,

branched chain alkyl groups or fluoro substituted alkyl groups containing from 4 to 18 carbon atoms,

cyclic alkyl groups or fluoro substituted cyclic alkyl groups containing from 5 to 18 carbon atoms,

phenyl groups and fluoro substituted phenyl groups, or

benzyl and fluoro substituted benzyl groups, phenethyl and fluoro substituted phenethyl groups,

ethers and polyethers of the general structure

space="preserve" listing-type="equation">(C.sub.x P.sub.2x O).sub.e -(C.sub.y P.sub.2y+1)

wherein;

"P" is hydrogen or fluorine

"x" is an integer from 1 to 4

"y" is an integer from 1 to 10

"e" is an integer from 1 to 10,

(B) 95 to 40% by weight of at least one organic comonomer of an ethylenically unsaturated organosiloxane having the following formula;

##EQU8## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy and vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical having from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms, and a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups "R" and "b" may be the same or different within each "i" moiety.

19. A contact lens formed from a contact lens material in accordance with claim 18 wherein said material has an oxygen permeability of at least DK35 with a refractive index of from 1.35 to 1.5 and a percent hydration below 2% of total weight.

21. A contact lens formed from a contact lens material in accordance with claim 18 and further comprising an aromatic containing organic vinyl monomer and a refractive index of at least 1.5.

20. A contact lens formed from an oxygen permeable dimensionally stable hydrophilic, contact lens material of high transparency, comprising a polymer formed by free radical polymerization from

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having the structure:

##STR6## wherein;

Z₁ and Z₂ can be the same or different and are each of a group selected from among the following with at least one of Z₁ or Z₂ containing fluorine;

hydrogen,

straight chain alkyl groups or fluoro substituted alkyl groups containing from 1 to 18 carbon atoms,

branched chain alkyl groups or fluoro substituted alkyl groups containing from 4 to 18 carbon atoms

cyclic alkyl groups or fluoro substituted cyclic alkyl groups containing from 5 to 18 carbon atoms,

phenyl groups and fluoro substituted phenyl groups, or

benzyl and fluoro substituted benzyl groups,

phenethyl and fluoro substituted phenethyl groups,

ethers and polyethers of the general structure

space="preserve" listing-type="equation">(C.sub.x P.sub.2x O).sub.e -(C.sub.y P.sub.2y+1)

wherein;

"P" is hydrogen or fluorine

"x" is an integer from 1 to 4

"y" is an integer from 1 to 10

"e" is an integer from 1 to 10,

(B) from 30 to 95% by weight of at least one ethylenically unsaturated organosiloxane having the following formula;

##EQU9## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy and vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical having from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms, and a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety,

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, chain alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups "R" and "b" may be the same or different within each "i" moiety,

(C) 0 to 55% by weight of the entire composition of a vinyl monomer modifying agent,

(D) 0 to 55% by weight of the entire composition of a hydrophilic organic monomer,

(E) 0 to 20% by weight of the entire composition of a non-siloxane containing cross-linking monomer.

22. An oxygen permeable dimensionally stable, hydrophilic, contact lens material of high transparency, comprising a polymer formed by free radical polymerization from:

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having the structure;

##STR7## wherein;

Z₁ and Z₂ can be hydrogen or an organic group with at least one of Z₁ or Z₂ containing fluorine,

(B) 95 to 40% by weight of at least one organic comonomer of an ethylenically unsaturated organosiloxane having the following formula;

##EQU10## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy, vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical havng from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms, or a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety,

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups, "R" and "b" may be the same or different within each "i" moiety.

24. An oxygen permeable contact lens material of high transparency comprised of a polymer formed by free radical polymerization from

(A) 5 to 60% by weight of a fluorine containing itaconate mono or diester having a structure:

##STR8## wherein;

Z₁ and Z₂ can be hydrogen or an organic group with at least one of Z₁ or Z₂ containing fluorine,

(B) 95 to 10% by weight of at least one organic comonomer of an ethylenically unsaturated organosiloxane having the following formula;

##EQU11## wherein;

"X" is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy, vinyloxy, and carbovinyloxy,

"Y" represents no group or is selected from the group consisting of a divalent alkane radical having from 1 to 10 carbon atoms, a divalent alkene radical having 2 to 10 carbon atoms, or a phenylene radical,

"a" is an integer from 1 to 10,

"n" is an integer from 2 to 30,

"b" is an integer from 0 to 3 and may be the same or different within each "i" moiety,

"R" is selected from the class consisting of hydrogen, hydroxy, alkoxy, carboalkoxy, alkyl and substituted alkyl groups containing from 1 to 20 carbon atoms, cyclic alkyl or substituted cyclic alkyl groups containing from 5 to 10 carbon atoms, phenyl and substituted phenyl groups, benzyl and substituted benzyl groups and phenethyl and substituted phenethyl groups, "R" and "b" may be the same or different within each "i" moiety and

(C) from 85 to 20% by weight of a refractive index modifying aromatic group containing monomer.

25. A contact lens material in accordance with claim 24 wherein said aromatic group containing monomer is selected from the class consisting of styryls, vinyl naphthyls, arylacrylates, arylmethacrylates and arylitaconates and mixtures thereof.

26. A contact lens material in accordance with claim 24 wherein said contact lens material has a refractive index of at least 1.5 and a DK of at least 10.

27. Bis(1,1,1.3,3,3-hexafluoro-2-propyl) itaconate.

28. A contact lens material formed from polymerization of a monomeric mixture of bis(1,1,1,3,3,3-hexafluoro-2-propyl) itaconate, bis(methacryloxypropyl)1,1,3,3-tetrakis (trimethyl siloxy) disiloxane, tris(trimethylsiloxy) silylpropyl methacrylate, n-vinyl pyrrolidone, methacrylic acid and tetraethylene glycol dimethacrylate.

29. A contact lens material formed from polymerization of a monomeric mixture of bis(1,1,1,3,3,3-hexafluoro-2-propyl) itaconate, bis(methacryloxypropyl)1,1,3,3-tetrakis (trimethyl siloxy) disiloxane, tris(trimethylsiloxy) silylpropyl methacrylate, methylmethacrylate, methacrylic acid and tetraethylene glycol dimethacrylate.