Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains

• US 4,259,467 A
• Filed: 12/10/1979
• Issued: 03/31/1981
• Est. Priority Date: 12/10/1979
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Kunzler, Jay F., Keogh, Philip L., Niu, Gregory C. C.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/102,010
• Time in Patent Office: 477 Days
• Field of Search: 351/160 R, 351/160 H, 264/1.2, 204/159.13, 528/12, 528/25, 528/31, 528/32, 526/279, 556/437
• US Class Current: 526/279
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08F 30/08 containing silicon
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

A hydrolytically stable, biologically inert, transparent, hydrophilic, contact lens comprising a polysiloxane containing hydrophilic sidechains is disclosed.

Claims

1. A hydrophilic, hydrolytically stable, biologically inert contact lens with the capability of transporting oxygen sufficiently to meet the requirements of the human cornea, comprising a polysiloxane monomer having the following formula:

##STR91## wherein Y₁ and Y₂ equal the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms,

X is selected from the group consisting of a hydroxyl radical, a monovalent hydrocarbon having from 1 to 20 carbon atoms, halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, ##STR92## wherein R is a monovalent hydrocarbon having from 1 to 20 carbon atoms, R₁ is a monovalent hydrocarbon having from 1 to 20 carbon atoms, n₁ is an integer from zero to 1 and n₂ is an integer from 1 to 3, ##STR93## wherein R₂ and R₃ are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and n₃ is an integer from zero to 1,

space="preserve" listing-type="equation">--R.sub.4 --A

wherein R₄ is a divalent hydrocarbon having from 1 to about 22 carbon atoms and A is a free radical polymerizably activated monovalent unsaturated group,

a is at least 1, b is zero or at least 2, c is 1 if b is zero and c is zero if b is at least 2, d is at least 1, except when b is zero and a is 1 then d is zero or greater, e is at least 1 and f is zero or greater,

Z₁ through Z₇ are the same or different and at least one of Z₁ through Z₇ is equal to a hydrophilic sidechain, said Z₁ through Z₇ are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms, a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms and a hydrophilic sidechain with the following formulas selected from the group consisting of ##STR94## wherein R₅ is a divalent hydrocarbon having from 1 to 10 carbon atoms, R₆ is selected from the group consisting of methyl and hydrogen, R₇ is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms, ##STR95## wherein R₈ is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and hydrogen, and n₄ is at least 1,

space="preserve" listing-type="equation">--R.sub.9 --OH).sub.n.sbsb.5

wherein R₉ is a hydrocarbon having from 1 to 20 carbon atoms and a valence of n₅ +1, n₅ is at least 1, there cannot be an --OH group on an aliphatic carbon atom beta to the Si atom, and there cannot be more than one OH group on any one carbon atom, ##STR96## wherein R₁₀ is a divalent hydrocarbon having from 1 to 10 carbon atoms, R₁₁ is selected from the group consisting of hydrogen and methyl and R₁₂ is a hydrocarbon having from 2 to 20 carbon atoms and a valance of n₈ +1 and can have no more than one oxygen atom attached to any one carbon atom, n₆ is zero or greater, n₇ is an integer from zero to 1 and n₈ is at least 1, ##STR97## wherein R₁₃ is a divalent hydrocarbon having from 2 to 10 carbon atoms and the ##STR98## group is not attached to a carbon atom of R₁₃ which is alpha to the Si atom, R₁₄ and R₁₅ can be the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms, hydrogen, --CH₂ --CH₂)_n.sbsb.9 OH wherein n₉ is an integer from 1 to 3 and ##STR99## wherein R₁₆ and R₁₇ are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n₁₀ is an integer from 1 to 5, ##STR100## wherein R₁₈ is a divalent hydrocarbon having from 1 to 20 carbon atoms and R₁₉ and R₂₀ are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, ##STR101## wherein R₂₁ is a divalent or trivalent hydrocarbon having from 1 to 10 carbon atoms and the S atom is not attached to R₂₁ by an aliphatic carbon atom beta to the Si atom, R₂₁ may or may not be attached to R₂₂ to form a ring which contains more than 3 carbon atoms and R₂₂ is selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and --O.sup.⊖

M.sup.⊕

where M is selected from the group consisting of a monovalent metal ion and a quaternery ammonium ion, and n₁₁ is an integer from 1 to 2, ##STR102## wherein R₂₃ is a divalent hydrocarbon having from 3 to 10 carbon atoms and the N.sup.⊕

must be attached to a carbon atom of R₂₃ which is at least 2 carbon atoms away from the Si atom, R₂₄, R₂₅ and R₂₆ are the same or different and are monovalent hydrocarbons having from 1 to 10 carbon atoms, X₁.sup.⊖

is a monovalent anion selected from the group consisting of halides, R₂₇ --COO.sup.⊖

wherein R₂₇ is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 10 carbon atoms and R₂₈ --SO₃.sup.⊖

wherein R₂₈ is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 10 carbon atoms, ##STR103## wherein R₂₉ is a divalent hydrocarbon having from 1 to 10 carbon atoms and n₁₂ is an integer from 0 to 1 and when n₁₂ is 1 the oxygen cannot be attached to an aliphatic carbon atom in R₂₉ which is beta to the Si atom, R₃₀ is a divalent hydrocarbon having from 1 to 10 carbon atoms, R₃₁ is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n₁₃ +1 and can have no more than one oxygen atom attached to any one carbon atom and n₁₃ is at least 1, ##STR104## wherein R₃₂ is a divalent hydrocarbon having from 1 to 10 carbon atoms and the ester oxygen atom bonded to R₃₂ cannot be attached to an aliphatic carbon atom in R₃₂ which is beta to the Si atom, R₃₃ is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n₁₄ +1 and can have no more than one oxygen atom attached to any one carbon atom and n₁₄ is an integer of at least 1, ##STR105## wherein R₃₄ is a divalent hydrocarbon having from 1 to 10 carbon atoms, ##STR106## wherein R₃₅ is a divalent hydrocarbon having from 2 to 10 carbon atoms and n₁₅ is an integer from 1 to 10, ##STR107## wherein R₃₆ is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group is not attached to a carbon atom alpha to the Si atom, R₃₇ is selected from the group consisting of methyl and hydrogen, R₃₈ is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and ##STR108## wherein R₃₉ is a monovalent hydrocarbon having from 1 to 10 carbon atoms and n₁₆ is at least 1, ##STR109## wherein R₄₀ is a divalent hydrocarbon having from 1 to 10 carbon atoms, R₄₁ and R₄₂ can be the same or different and are selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and --CH₂)_n.sbsb.17 OH wherein n₁₇ is an integer from 2 to 4, ##STR110## wherein R₄₃ is a divalent hydrocarbon having from 2 to 10 carbon atoms and the S atom cannot be attached to a carbon atom of R₄₃ which is alpha to the Si atom, R₄₄ and R₄₅ can be the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, ##STR111## wherein R₄₆ is a divalent hydrocarbon having from 1 to 10 carbon atoms and n₁₈ is an integer from zero to 3, ##STR112## wherein R₄₇ and R₄₈ are selected from the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 0 to 10 carbon atoms and R₄₉ is selected from the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and only one of R₄₇, R₄₈ and R₄₉ must be a divalent hydrocarbon and attached to the Si atom, R₅₀ is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and --CH₂)_n.sbsb.20 OH where n₂₀ is an integer from 2 to 4, and n₁₉ is an integer from zero to 3, ##STR113## wherein R₅₁ is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R₅₁ alpha to the Si atom and X₂.sup.⊕

is a monovalent cation selected from the group consisting of monovalent metal cations and ##STR114## wherein R₅₂, R₅₃, R₅₄ and R₅₅ can be the same or different and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, and ##STR115## wherein R₅₆ is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R₅₆ which is alpha to the Si atom, R₅₇ is a divalent hydrocarbon having from one to 10 carbon atoms, R₅₈ is selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n₂₁ is an integer from zero to 10, polymerized to form a polymer in a crosslinked network.

2. The contact lens according to claim 1 wherein said hydrophilic sidechains are selected from the group consisting of ##STR116## wherein n₂₂ is an integer from 2 to 3, ##STR117## wherein R₅₉ and R₆₀ are the same or different and are selected from the group consisting of hydrogen, methyl and --CH₂ --CH₂ --OH, ##STR118## and R₆₁ is selected from the group consisting of hydrogen and methyl, ##STR119## wherein n₂₃ is an integer from 2 to 3 ##STR120##

3. The contact lens according to claim 1 wherein X is selected from the group consisting of ##STR121## wherein n₂₄ is an integer from 0 to 2, --CH═

CH₂ and --R₆₂ --G wherein R₆₂ is --CH₂)_n.sbsb.25 wherein n₂₅ is an integer from 3 to 4 and G is ##STR122## wherein R₆₃ is selected from the group consisting of hydrogen and methyl.

4. The contact lens according to claim 1 wherein X is ##STR123## wherein R₆₄ is selected from the group consisting of hydrogen and methyl.

5. The polysiloxane monomer according to claim 1 wherein Y₁ and Y₂ are methyl.

6. The polysiloxane monomer according to claim 1 wherein Y₁ is methyl and Y₂ is phenyl.

7. The contact lens according to claim 1 wherein only one of Z₁, Z₂, Z₅ and Z₆ is a hydrophilic sidechain and wherein a is equal to 1 to about 1,000, b is equal to zero, c is equal to 1, d is equal to 1 to about 1,000, and f is equal to zero.

8. The contact lens according to claim 7 wherein a is equal to about 10 to about 500, b is equal to zero, c is equal to 1, d is equal to about 10 to about 500, e is equal to 1 and f is equal to zero.

9. The contact lens according to claim 8 wherein said contact lens is soft and flexible and a is equal to about 75 to about 150, b is equal to zero, c is equal to 1, d is equal to about 25 to about 50, e is equal to one and f is equal to zero.

10. The soft and flexible contact lens according to claim 9 wherein a is equal to about 75, b is equal to zero, c is equal to 1, d is equal to about 25, e is equal to 1 and f is equal to zero.

11. The contact lens according to claim 10 wherein Z₁, Z₂ and Z₅ are methyls, and Z₆ is selected from the group consisting of --CH₂)₃ (O--CH₂ --CH₂)_n.sbsb.26 O--CH₃ wherein n₂₆ is an integer from 2 to 3, ##STR124## wherein R₆₅ is selected from the group consisting of methyl and hydrogen, R₆₆ is selected from the group consisting of methyl, hydrogen and --CH₂ --CH₂ --OH, Y₁ and Y₂ equal methyl and X equals ##STR125## wherein n₂₇ is an integer from 3 to 4.

12. The contact lens according to claim 1 wherein only one of Z₁ through Z₇ is a hydrophilic sidechain and wherein a is equal to 1, b is equal to about 2 to about 4, c is equal to zero, d is equal to 1, e is equal to about 25 to about 500 and f is equal to about 5 to about 500.

13. The contact lens according to claim 12 wherein said contact lens is soft and flexible and a is equal to 1, b is equal to about 2 to about 3, c is equal to zero, d is equal to 1, e is equal to about 25 to about 250 and f is equal to about 10 to about 250.

14. The soft and flexible contact lens according to claim 13 wherein a is equal to 1, b is equal to about 2 to about 3, d is equal to 1, c is equal to zero, e is equal to from about 50 to about 100 and f is equal to from about 10 to about 100.

15. The soft and flexible contact lens according to claim 14 wherein a is equal to 1, b is equal to from about 2 to about 3, c is equal to zero, d is equal to 1, e is equal to from about 50 to about 75 and f is equal to from about 10 to about 75.

16. The soft and flexible contact lens according to claim 15 wherein Z₁, Z₂, Z₅, Z₆, Z₇, Y₁ and Y₂ equal methyl, and Z₄ equals hydrogen, and at least one of the Z₃ '"'"'s in the methylene bridge is equal ##STR126## and the other Z₃ '"'"'s in that bridge equal hydrogen, and X equals ##STR127##