Long wearable soft contact lens

• US 6,867,245 B2
• Filed: 12/18/2000
• Issued: 03/15/2005
• Est. Priority Date: 12/16/1999
• Status: Expired due to Term

• Current Assignee: Coopervision International Limited (The Cooper Cos., Inc.)
• Original Assignee: AsahiKasei Aime Co. Ltd. (Asahi Kasei Corporation)
• Inventors: Iwata, Junichi, Hoki, Tsuneo, Ikawa, Seiichirou
• Primary Examiner(s): Peng, Kuo-Liang
• Application Number:
  US09/737,809
• Publication Number:
  US 20020016383A1
• Time in Patent Office: 1,548 Days
• Field of Search: 523/107, 528/499, 526/279, 623/4.1, 264/299, 351/159, 425/345
• US Class Current: 523/107
• CPC Class Codes: B29D 11/00125 Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
• CPC Class Codes: C08F 220/1806 C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 226/02 by a single or double bond to nitrogen
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/061 Polyesters; Polycarbonates
• CPC Class Codes: C08F 290/065 Polyamides; Polyesteramides; Polyimides
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 7/04 Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00

Abstract

The present invention relates to a soft contact lens, and provides a contact lens which shows small and stable contact angle to water at its surface in water as well as in air, little deposition in wearing, high oxygen permeability, no adhesion of lens to a cornea and superior extended-wearing characteristics. The present invention provides a hydrogel soft contact lens which has contact angle at a lens surface in a range of 10-50° by the captive bubble method in water and 30-90° by the sessile drop method in air, oxygen permeability of not less than 30 and water content of not less than 5%, and also a hydrogel soft contact lens consisting of a polymer comprising a hydrophilic siloxanyl monomer shown by a specified general formula.

Claims

1. A hydrogel soft contact lens with a surface contact angle in a range of 10-40°

and 30-80°

by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than a Dk value of 80 and water content of not less than 9% by weight.

2. The hydrogel soft contact lens according to claim 1, which is manufactured by a polymerization in a mold.

3. A method for manufacturing a contact lens according to claim 2, wherein the method is a polymerization in a mold.

4. The method according to claim 3, wherein a material of the mold is insoluble to a composition of polymerizable monomers and at least one side of the mold has a contact angle to water of 65-80°

by the sessile drop method.

5. The method according to claim 4, wherein said material of the mold comprises a resin selected from the group consisting of polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.

6. The method according to claim 4, wherein said material of the mold comprises ethylene-vinylalcohol copolymer.

7. The hydrogel soft contact lens according to claim 2, wherein a material of the mold is insoluble to a composition of polymerizable monomers and at least one side of the mold has a contact angle to water of 65-80°

by the sessile drop method.

8. The hydrogel soft contact lens according to claim 2, wherein a material of the mold comprises a resin selected from the group consisting of polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.

9. The hydrogel soft contact lens according to claim 8, wherein said material of the mold comprises ethylene-vinylalcohol copolymer.

10. A hydrogel soft contact lens with contact angle of a surface in a range of 10-50°

and 30-90°

by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than a Dk value of 30 and water content of not less than 5% by weight, comprising a copolymer obtained by a polymerization of at least one kind of hydrophilic siloxane monomer.

11. The hydrogel soft contact lens according to claim 10, wherein the hydrophilic siloxane monomer is a hydrophilic polysiloxane monomer shown by the following formula (1):

wherein, X1 is a polymerizable substituent shown by the following formula (2);

wherein, R5 is a hydrogen or a methyl group;

Z1 is a linking group selected from —

NHCOO—

, —

NHCONH—

, —

OCONH—

R6-NHCOO—

, —

NHCONH—

R7-NHCONH— and

—

OCONH—

R8-NHCONH—

(R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms);

m is 0-10;

n is 3-10;

p is 0 when m is 0 and 1 when m is not less than 1;

q is an integer of 0-20;

R1, R2, R3 and R4 are groups independently selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group; and

the structure [Y1] shows a polysiloxane backbone comprising not less than 2 sequential siloxane linkages.

12. The hydrogel soft contact lens according to claim 11, wherein the structure [Y1] is a structural unit shown by the following formula:

wherein, R9 and R10 are groups selected from hydrocarbon groups with 1-12 carbon atoms, hydrocarbon groups substituted with fluorine atom(s), trimethylsiloxy group and hydrophilic substituents, and R9 and R10 are the same or different from each other in the sequential chain; and

r is 7-1000.

13. The hydrogel soft contact lens according to claim 12, wherein the structural unit [Y1] according to claim 12 is a polysiloxane monomer with R9 and R10 being methyl group.

14. The hydrogel soft contact lens according to claim 11, wherein the structural unit [Y1] according to claim 11 comprises linked structural units (Ia) and (IIa) shown below, the linking ratio of the units (Ia) and (IIa) being 1:

10-10;

1, and the total number of the linking of (Ia) and (IIa) being 7-1000;

wherein, each of R11 and R12 is independently a hydrocarbon group with 1-12 carbon atoms, each of R13 and R14 is independently a hydrocarbon group with 1-12 carbon atoms or a hydrocarbon group substituted with fluorine atom(s), and at least one of R13 and R14 is a hydrocarbon group substituted with fluorine atom(s).

15. The hydrogel soft contact lens according to claim 14, wherein R11, R12 and R13 are methyl groups and R14 is a trifluoropropyl group in the structural unit [Y1] according to claim 14.

16. The hydrogel soft contact lens according to claim 11, wherein the structural unit [Y1] according to claim 4 comprises linked structural units (Ib) and (IIb) shown below, the linking ratio of the structural units (Ib) and (IIb) being (Ib)/(IIb)=0.1-200, and the total number of the linking of (Ib) and (IIb) being 7-1000:

wherein, each of R15 and R16 is a group independently selected from hydrocarbon group with 1-12 carbon atoms, hydrocarbon group with 1-12 carbon atoms substituted with fluorine atom(s) and trimethylsiloxy group, and R15 and R16 are the same or different from each other;

each of R17 and R18 is a group independently selected from hydrocarbon group with 1-12 carbon atoms, trimethylsiloxy group or hydrophilic groups; and

at least one of R17 and R18 groups is a hydrophilic group, wherein the hydrophilic group is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxy group and polyoxyalkylene group.

17. The hydrogel soft contact lens according to claim 16, wherein the hydrophilic substituent is shown by the following formula (4) or (5):

—

R20(OH)a 

 

(4)

wherein, R20 is a hydrocarbon group with 3-12 carbon atoms optionally including a group of —

O—

, —

CO—

or —

COO—

inserted between carbon atoms;

only one OH group can be substituted on one carbon atom; and

a is a number not less than 1,

—

R21-(OR22)^b—

OZ2 

 

(5)

wherein, R21 is a hydrocarbon group with 3-12 carbon atoms optionally including a group of —

O—

, —

CO—

or —

COO—

inserted between carbon atoms;

R22 is a hydrocarbon group with 2-4 carbon atoms, and the number of the carbon atoms are the same or different from each other when b is not less than 2;

b is 1-200;

Z2 is a group selected from hydrogen atom, hydrocarbon group with 1-12 carbon atoms and —

OCOR23 (R23 is a hydrocarbon group with 1-12 carbon atoms).

18. The hydrogel soft contact lens according to claim 16, wherein the hydrophilic substituent is selected from the group consisting of the following formulas (6), (7) and (8):

—

C₃H₆OH 

 

(6)

—

C₃H₆OCH₂CH(OH)CH₂OH 

 

(7)

—

C₃H₆OC₂H₄OH 

 

(8).

19. The hydrogel soft contact lens according to claim 16, wherein the hydrophilic substituent is selected from the group consisting of the following formulas (9) and (10):

—

C₃H₆(OC₂H₄)_cOH 

 

(9)

—

C₃H₆(OC₂H₄)_dOCH₃ 

 

(10)

wherein, c and d are 1-40.

20. The hydrogel soft contact lens according to claim 11, wherein the structural unit [Y1] according to claim 11 comprises linked structural units (Ic), (IIc) and (IIIc) shown by the following formulas:

wherein, R19 is a hydrophilic substituent which is a linear or cyclic hydrocarbon group linked with at least one substituent selected from hydroxy group and polyoxyalkylene group;

the linking ratio of the structural units (Ic), (IIc) and (IIIc) being ((Ic)+(IIc))/(IIIc)=0.5-100, (IIc)/(Ic)=0-1, and the total number of the linking of (Ic), (IIc) and (IIIc) being 7-1000.

21. The hydrogel soft contact lens according to claim 20, wherein the linking ratio of the structural units (Ic), (IIc) and (IIIc) in the structural unit [Y1] according to claim 10 is ((Ic)+(IIc))/(IIIc)=1-50, (IIc)/(Ic)=0.01-0.50, and the total number of the linking of (Ic), (IIc) and (IIIc) is 20-500.

22. The hydrogel soft contact lens according to claim 11, wherein the structural unit [Y1] in the hydrophilic polysiloxane monomer shown by the formula (1) according to claim 4 is expressed by the following formula (11):

wherein, Z3 is a linking group shown by the following formula (12);

—

A—

COHN—

R30-NHCOO—

R31-CONH—

R30-NHCO—

A—

 

 

(12)

wherein, R30 is a hydrocarbon group with 4-20 carbon atoms and optionally interrupted by oxygen atom;

R31 is polyoxyalkylene group or fluorine-substituted poly-oxyalkylene group;

the structural unit [Y2] means a polysiloxane backbone comprising not less than two sequential siloxane linkages;

A means —

O—

or —

NH—

linkage;

each of R24, R25, R26 and R27 is a group independently selected from hydrocarbon group with 1-12 carbon atoms and trimethylsiloxy group, each of R28 and R29 is a hydrocarbon group with 3-12 carbon atoms optionally interrupted by oxygen atom, respectively.

23. The hydrogel soft contact lens according to claim 22 consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R30 in the Z3 linking group shown by the formula (11) according to claim 15 is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R31 is selected from polyethylene glycol, polypropylene glycol and polybutylene glycol.

24. The hydrogel soft contact lens according to claim 11, wherein the polymerizable Z1 linking group shown by the formula (2) according to claim 4 is shown by the following formula (13):

—

B—

COHN—

R32-NHCOO—

R33-CONH—

R32-NHCO—

B—

 

 

(13)

wherein, R32 is a hydrocarbon group with 4-20 carbon atoms optionally interrupted by oxygen atom;

R33 is polyoxyalkylene or polyoxyfluoloalkylene group;

B means —

O—

or —

NH—

linkage.

25. The hydrogel soft contact lens according to claim 24 consisting of a polymer from a hydrophilic polysiloxane monomer, wherein R32 in the formula (13) is selected from hexamethylene, tetramethylene, dicyclohexylmethane, hydrogenated xylylene and isophorone groups and R33 is selected from polyethylene glycol, polypropylene glycol and polybutylene glycol.

26. The hydrogel soft contact lens according to claim 10, obtained by a polymerization of at least a crosslinkable monomer linked with urethane groups having no siloxane structure other than said hydrophilic siloxane monomer.

27. The hydrogel soft contact lens according to claim 26, wherein the crosslinkable monomer is shown by the following formula (14):

wherein, R34 and R35 are hydrogen or methyl group and R34 and R35 are the same or different from each other;

Z4 is —

NHCOO—

linking group;

R36 is selected from hydrocarbon groups with 2-10 carbon atoms or polyoxyethylene group shown by —

(C₂H₄O)_gC₂H₄—

(g is 2-40);

f is 0-10;

e is 0 when f is o and 1 when f is not less than 1.

28. The hydrogel soft contact lens according to claim 26, wherein the crosslinkable monomer is shown by the following formula (15):

29. The hydrogel soft contact lens according to claim 10, wherein the hydrophilic siloxanyl monomer is shown by the following formula (16):

wherein, R37 is hydrogen or methyl group;

R38Si is siloxanyl group; and

h is 0-20.

30. The hydrogel soft contact lens according to claim 29, comprising a copolymer obtained by a polymerization of at least said hydrophilic siloxanyl monomer, at least one kind of a hydrophilic monomer and at least one kind, of a crosslinkable monomer.

31. The hydrogel soft contact lens according to claim 30, wherein the hydrophilic monomer is an amide monomer containing N-vinyl group.

32. The hydrogel soft contact lens according to claim 31, wherein the amide monomer containing N-vinyl group is N-vinyl-N-methylacetamide or N-vinyl pyrrolidone.

33. The hydrogel soft contact lens according to claim 29, wherein the hydrophilic siloxanyl monomer according to claim 29 is shown by the following formula (17)

34. The hydrogel soft contact lens according to claim 29, comprising a copolymer obtained by a polymerization of at least said hydrophilic siloxanyl monomer, a siloxanyl monomer shown by the following formula (18), at least one kind of a hydrophilic monomer and at least one kind of a crosslinkable monomer:

wherein, R39 is hydrogen or methyl group;

R40Si is siloxanyl group; and

j is 0-4.

35. The hydrogel soft contact lens according to claim 34, wherein the siloxanyl monomer shown by the formula (18) is tris(trimethylsiloxy)silylpropyl methacrylate.

36. The hydrogel soft contact lens according to claim 29, prepared by processing a polymer comprising a hydrophilic siloxanyl monomer by lathe-cutting and polishing method followed by swelling with water.

37. A hydrogel soft contact lens consisting of a copolymer composed of 10-99% by weight of at least one kind of hydrophilic polysiloxane monomer of the formula (1):

wherein, X1 is a polymerizable substituent shown by the following formula (2);

wherein, R5 is a hydrogen or a methyl group;

Z1 is a linking group selected from —

NHCOO—

, —

NHCONH—

, —

OCONH—

R6-NHCOO—

, —

NHCONH—

R7-NHCONH— and

—

OCONH—

R8-NHCONH—

(R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms);

m is 0-10;

n is 3-10;

p is 0 when m is 0 and 1 when m is not less than 1;

q is an integer of 0-20;

R1, R2, R3 and R4 are groups independently selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group; and

the structure [Y1] shows a polysiloxane backbone comprising not less than 2 sequential siloxane linkages, 1-80% by weight at least one kind of an amide monomer containing N-vinyl group, and

other polymerizable monomers.

38. The hydrogel soft contact lens according to claim 37, consisting of a copolymer composed of 30-95% by weight of at least one kind of said hydrophilic polysiloxane monomer, 5-60% by weight of at least one kind of an amide monomer containing an N-vinyl group and other polymerizable monomers.

39. The hydrogel soft contact lens according to claim 37, wherein surface contact angle is in a range of 10-50°

and 30-90°

by the captive bubble method in water and by the sessile drop method in air, respectively, oxygen permeability is not less than a Dk value of 30 and water content is not less than 5% by weight.

40. The hydrogel soft contact lens according to claim 39, wherein surface contact angle is in a range of 10-40°

and 30-80°

by air bubble method in water and by droplet method in air, respectively, oxygen permeability is not less than a Dk value of 80 and water content is not less than 9% by weight.

41. The hydrogel soft contact lens according to claim 37, obtained by a polymerization of at least one kind of a crosslinkable monomer linked with urethane groups, having no siloxane structure other than said hydrophilic polysiloxane, and at least one kind of amide monomer containing N-vinyl group.

42. The hydrogel soft contact lens according to claim 37, manufactured by a polymerization in a mold.

43. The hydrogel soft contact lens according to claim 42, wherein a material of the mold is insoluble to a composition of polymerizable monomers and at least one side of the mold has a contact angle to water of 65-80°

by the sessile drop method.

44. The hydrogel soft contact lens according to claim 43, wherein said material of the mold comprises a resin selected from the group consisting of polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.

45. The hydrogel soft contact lens according to claim 43, wherein said material of the mold comprises ethylene-vinylalcohol copolymer.

46. A method for manufacturing a contact lens according to claim 37, wherein the method is a polymerization in a mold.

47. The method according to claim 46, wherein a material of the mold is insoluble to a composition of polymerizable monomers and at least one side of the mold has a contact angle to water of 65-80°

by the sessile drop method.

48. The method according to claim 47, wherein said material of the mold comprises a resin selected from the group consisting of polyamide, polyethylene terephthalate and ethylene-vinylalcohol copolymer.

49. The method according to claim 47, wherein said material of the mold comprises ethylene-vinylalcohol copolymer.

50. A hydrogel soft contact lens according to claim 37, wherein said amide monomer containing N-vinyl group is selected from the group consisting of N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, and N-vinyl caprolactam.

51. The hydrogel soft contact lens according to claim 37, wherein said amide monomer containing N-vinyl group is selected from the group consisting of N-vinyl-N-methylacetamide and N-vinylpyrrolidone.

52. A hydrogel soft contact lens manufactured by a polymerization in a mold, wherein a mold material is insoluble to a composition of polymerizable monomers and at least one side of the mold material consists of a resin with a contact angle to water of not higher than 90°

by the sessile drop method.

53. The hydrogel soft contact lens according to claim 52, wherein the mold material consists of a resin with a contact angle to water is 65-80°

by the sessile drop method.

54. The hydrogel soft contact lens according to claim 52, wherein the mold consists of a resin selected from nylon 66 and nylon 6, polyethylene terephthalate and ethylene-vinylalcohol copolymer.

55. The hydrogel soft contact lens according to claim 52, wherein the mold material consists of ethylene-vinylalcohol copolymer.

56. The hydrogel soft contact lens according to claim 55, which is manufactured by copolymerization of at least a kind of siloxane group-containing monomer and at least one kind of hydrophilic monomer.

57. The hydrogel soft contact lens according to claim 52, wherein contact angle of a surface is in a range of 10-50°

and 30-90°

by the captive bubble method in water and by the sessile drop method in air, respectively, and water content is not less than 5% by weight.

58. The hydrogel soft contact lens according to claim 52, wherein surface contact angle is in a range of 10-40°

and 30-80°

by the captive bubble method in water and by the sessile drop method in air, respectively, and water content is not less than 9% by weight.

59. A method for manufacturing a contact lens, comprising the steps of injecting a monomer composition into a mold which consists of a mold material consisting of a resin with a contact angle to water of not higher than 90°

by sessile drop method and forms a front or rear surface of said contact lens;

setting to said mold another mold which forms a surface opposite to said front or rear surface;

polymerizing said monomer composition by heating or irradiation with light; and

then taking the contact lens from the molds.

60. The method according to claim 59, wherein a monomer composition containing at least a kind of siloxane group-containing monomer and at least one kind of hydrophilic monomer is injected into a mold which consists of a resin comprising an ethylene vinyl alcohol copolymer;

said monomer composition is polymerized by heating or irradiation with light; and

then the contact lens is taken from the mold.

61. An ophthalmologic lens material, wherein contact angle of a surface is in a range of 10-40°

and 30-80°

by captive bubble method in water and by sessile drop method in air, respectively, oxygen permeability is not less than 80 as Dk value and water content is not less than 9% by weight.

62. An ophthalmologic lens material consisting of a copolymer composed of 10-99% by weight of at least one kind of hydrophilic polysiloxane monomer of the formula (1), 1-80% by weight of at least one kind of amide monomer containing N-vinyl group and other polymerizable monomers:

wherein, X1 is a polymerizable substituent shown by the following formula (2);

wherein, R5 is a hydrogen or a methyl group;

Z1 is a linking group selected from —

NHCOO—

, —

NHCONH—

, —

OCONH—

R6-NHCOO—

, —

NHCONH—

R7-NHCONH— and

—

OCONH—

R8-NHCONH—

(R6, R7 and R8 are hydrocarbon groups with 2-13 carbon atoms);

m is 0-10;

n is 3-10;

p is 0 when m is 0 and 1 when m is not less than 1;

q is an integer of 0-20;

R1, R2, R3 and R4 are groups independently selected from hydrocarbon groups with 1-12 carbon atoms or trimethylsiloxy group; and

the structure [Y1] shows a polysiloxane backbone comprising not less than 2 sequential siloxane linkages.

63. The ophthalmologic lens material according to claim 62, which consists of a copolymer composed of 30-95% by weight of at least one kind of said hydrophilic polysiloxane monomer, 5-60% by weight of at least one kind of amide monomer containing N-vinyl group and other polymerizable monomers.

64. A method for manufacturing an ophthalmologic lens, comprising the step of polymerizing the ophthalmologic lens material according to claim 62 in a mold which comprises a resin selected from the group consisting of Nylon 66, polyethylene terephthalate and an ethylene-vinyl alcohol copolymer.

65. A method for manufacturing an ophthalmologic lens, comprising the step of polymerizing the ophthalmologic lens material according to claim 62 in a mold which comprises a resin of an ethylene-vinyl alcohol copolymer.

66. The method according to claim 65, wherein said polymerizing is carried out by UV or visible light irradiation.

67. An ophthalmologic lens material manufactured by a polymerization in a mold, wherein a mold material is insoluble to a composition of polymerization monomers and at least one side of the mold material consists of a resin with a contact angle to water of not higher than 90°

by sessile drop method.

68. A hydrogel soft contact lens with contact angle of a surface in a range of 10-50°

and 30-90°

by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than a Dk value of 30 and water content of not less than 5% by weight, and the surface of the contact lens is not modified.

69. A hydrogel soft contact lens with contact angle of a surface in a range of 10-40°

and 30-80°

by the captive bubble method in water and the sessile drop method in air, respectively, oxygen permeability of not less than a Dk value of 30 and water content of not less than 5% by weight.

70. An ophthalmologic lens material, wherein contact angle of a surface is in a range of 10-40°

and 30-80°

by captive bubble method in water and by sessile drop method in air, respectively, oxygen permeability is not less than 30 as Dk value and water content is not less than 5% by weight.