UV-absorbing vinylic monomers and uses thereof

1. A UV-absorbing vinylic monomer of any one of formula (I) to (III)

in which:

R O is H or CH 3 ;

R 1 and R 2 independent of each other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , or NR′R″ in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl;

R 3 and R 4 independent of each other are H or a first hydrophilic group which is *—CH 2 —(OC 2 H 4 ) n1 —OCH 3 , *—CH 2 —(OC 2 H 4 ) n1 —OH,

provided that at least one of R 3 and R 4 is the first hydrophilic group;

R 5 is H, *—COOH, *—CONH—C 2 H 4 —(OC 2 H 4 ) n1 —OCH 3 , or —CONH—C 2 H 4 —(OC 2 H 4 ) n1 —OH;

one of R 6 and R 7 is H or a second hydrophilic group which is *—CH 2 —(OC 2 H 4 ) n1 —OCH 3 , *—CH 2 —(OC 2 H 4 ) n1 —OH,

while the other of R 6 and R 7 is

R 8 is CH 3 , C 2 H 5 ,

R 10 is methyl or ethyl;

Y 1 is a C 2 -C 4 alkylene divalent radical;

Q1 is a (meth)acryloylamido or (meth)acryloyloxy group;

and

n1 is an integer of 2 to 20.

2. The UV-absorbing vinylic monomer of claim 1 , being a vinylic monomer of formula (I).

3. The UV-absorbing vinylic monomer of claim 2 , being selected from a vinylic monomer of any one of the following formula:

in which: Q 1 is (meth)acryloylamido or (meth)acryloyloxy group; Y 1 is an ethylene or propylene divalent radical; R 1 and R 2 independent of each other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , or NR′R″ in which R′ and R″ independent of each other are H, methyl or ethyl.

4. The UV-absorbing vinylic monomer of claim 1 , being a vinylic monomer of formula (II).

5. The UV-absorbing vinylic monomer of claim 4 , being selected from a vinylic monomer of any one of the following formula:

in which: Q 1 is (meth)acryloylamido or (meth)acryloyloxy group; Y 1 is an ethylene or propylene divalent radical; R 1 and R 2 independent of each other are CH 3 , CCl 3 , CF 3 , Cl, Br, NR′R″, OH, or OCH 3 ; R′ and R″ independent of each other are H, methyl or ethyl;

R 3 and R 4 independent of each other are *—CH 2 —(OC 2 H 4 ) n1 —OCH 3 , *—CH 2 —(OC 2 H 4 ) n1 —OH,

R 10 is methyl or ethyl.

6. The UV-absorbing vinylic monomer of claim 1 , being a vinylic monomer of formula (III).

7. The UV-absorbing vinylic monomer of claim 6 , being selected from a vinylic monomer of any one of the following formula:

in which: Q 1 is (meth)acryloylamido or (meth)acryloyloxy group; Y 1 is an ethylene or propylene divalent radical; R 1 and R 2 independent of each other are CH 3 , CCl 3 , CF 3 , Cl, Br, NR′R″ OH, or OCH 3 ; in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl; R 8 is CH 3 , C 2 H 5 ,

R 10 is methyl or ethyl.

8. A hydrogel contact lens, comprising a crosslinked polymeric material which comprises repeating units of a UV-absorbing vinylic monomer of any one of formula (I) to (VII),

in which:

R O is H or CH 3 ;

R 1 , R 2 and R 2 ′ independent of one other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , or NR′R″ in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl;

R 1 ′ independent of each other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , SO 3 H, SO 3 Na, or NR′R″ in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl;

R 3 and R 4 independent of each other are H or a first hydrophilic group which is *—CH 2 —(OC 2 H 4 ) n1 —OCH 3 , *—CH 2 —(OC 2 H 4 ) n1 —OH,

provided that at least one of R 3 and R 4 is the first hydrophilic group;

R 5 is H, *—COOH, *—CONH—C 2 H 4 —(OC 2 H 4 ) n1 —OCH 3 or —CONH—C 2 H 4 —(oC 2 H 4 ) n1 —OH;

one of R 6 and R 7 is H or a second hydrophilic group which is *—CH 2 —(O 2 H 4 ) n1 —OCH 3 ,*—CH 2 —(OC 2 H 4 ) n1 —OH,

while the other of R 6 and R 7 is

R 8 is CH 3 , C 2 H 5 ,

R 9 ′ is H, SO 3 Na,

R 10 is methyl or ethyl;

L1 is a direct bond or a linkage of

L2 is a linkage of *—CH 2 —*,*—C 2 H 4 —*,*—C 3 H 6 —*, *—C 3 H 6 —S—C 2 H 4 —*, *—C 3 H 6 —S—C 3 H 6 —* or

Y 1 , Y 2 , and Y 3 independent of one another are a C 2 -C 4 alkylene divalent radical;

Q1, Q2, and Q3 independent of one another are a (meth)acryloylamido or (meth)acryloyloxy group;

m1 is zero or 1, provided that if m1 is zero, then Q 2 is a (meth)acryloylamido group; and

n1 is an integer of 2 to 20,

wherein the hydrogel contact lens has: an UVB transmittance (designated as UVB % T) of about 10% or less between 280 and 315 nanometers; an UVA transmittance (designated as UVA % T) of about 30% or less between 315 and 380 nanometers;

optionally a Violet transmittance (designated as Violet % T) of about 60% or less between 380 nm and 440 nm; and a water content of from about 15% to about 80% by weight (at room temperature, about 22° C. to 28° C.) when being fully hydrated.

9. The hydrogel contact lens of claim 8 , wherein the hydrogel contact lens is a silicone hydrogel contact lens, wherein the crosslinked polymeric material which comprises repeating units of at least one hydrophilic vinylic monomer and repeating units of at least one siloxane-containing vinylic monomer and/or macromer.

10. The hydrogel contact lens of claim 8 , wherein the crosslinked polymeric material which comprises repeating units of an actinically-crosslinkable polyvinyl alcohol prepolymer.

11. The hydrogel contact lens of claim 10 , wherein the actinically-crosslinkable polyvinyl alcohol prepolymer comprises repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

R 11 is hydrogen or C 1 -C 6 alkyl;

R 12 is an ethylenically unsaturated group of

in which q1 and q2 independently of each another are zero or one, and R 16 and R 17 independently of each another are a C 2 -C 8 alkylene divalent radical, R 18 is C 2 -C 8 alkenyl;

R 13 can be hydrogen or a C 1 -C 6 alkyl group; and

R 14 is a C 1 -C 6 alkylene divalent radical.

12. A method for producing UV-absorbing contact lenses, comprising the steps of:

(1) obtaining a lens formulation comprising

(a) from about 0.1% to about 4% by weight of a UV-absorbing vinylic monomer of any one of formula (I) to (VII),

in which:

R 0 is H or CH 3 ;

R 1 , R 2 and R 2 ′ independent of one other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , or NR′R″ in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl;

R 1 ′ independent of each other are H, CH 3 , CCl 3 , CF 3 , Cl, Br, OH, OCH 3 , SO 3 H, SO 3 Na, or NR′R″ in which R′ and R″ independent of each other are H or C 1 -C 4 alkyl;

R 3 and R 4 independent of each other are H or a first hydrophilic group which is *—CH 2 —(OC 2 H 4 ) n1 —OCH 3 , *—CH 2 —(OC 2 H 4 ) n1 —OH,

provided that at least one of R 3 and R 4 is the first hydrophilic group;

R 5 is H, *—COOH, *—CONH—C 2 H 4 —(OC 2 H 4 ) n1 —OCH 3 or —CONH—C 2 H 4 —(OC 2 H 4 ) n1 —OH;

one of R 6 and R 7 is H or a second hydrophilic group which is *—CH 2 —

while the other of R 6 and R 7 is

R 8 is CH 3 , C 2 H 5 ,

R 9 ′ is H, SO 3 Na,

R 10 is methyl or ethyl;

L1 is a direct bond or a linkage of

L2 is a linkage of *—CH 2 —*, *—C 2 H 4 —*, *—C 3 H 6 —*, *—C 3 H 6 —S—C 2 H 4 —*, *—C 3 H 6 —S—C 3 H 6 —* or

Y 1 , Y 2 , and Y 3 independent of one another are a C 2 -C 4 alkylene divalent radical;

Q1, Q2, and Q3 independent of one another are a (meth)acryloylamido or (meth)acryloyloxy group;

m1 is zero or 1, provided that if m1 is zero, then Q 2 is a (meth)acryloylamido group; and

n1 is an integer of 2 to 20,

(b) from about 0.1% to about 2.0% by weight of at least one free-radical initiator, and

(c) at least one polymerizable components selected from the group consisting of a hydrophilic vinylic monomer, a water-soluble silicone-free prepolymer, a silicone-containing prepolymer, a non-silicone hydrophobic vinylic monomer, a siloxane-containing vinylic monomer, a siloxane-containing vinylic macromer, a vinylic crosslinking agent, and combinations thereof;

(2) introducing the lens formulation into a mold for making a soft contact lens, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens and a second mold half with a second molding surface defining the posterior surface of the contact lens, wherein said first and second mold halves are configured to receive each other such that a cavity is formed between said first and second molding surfaces; and

(3) curing thermally or actinically the lens formulation in the mold to form the UV-absorbing contact lens, wherein the formed UV-absorbing contact lens is characterized by having a UVB % T of about 10% or less between 280 and 315 nanometers and a UVA % T of about 30% or less between 315 and 380 nanometers and and optionally a Violet % T of about 60% or less between 380 nm and 440 nm.

13. The method of claim 12 , wherein the free-radical initiator is a thermal initiator, wherein the step of curing is carried out thermally.

14. The method of claim 12 , wherein the free-radical initiator is a photoinitiator, wherein the step of curing is carried out by irradiation with a light having a wavelength within the range from 380 nm to 500 nm.

15. The method of claim 13 , wherein the lens formulation is a water-based lens formulation comprising at least one actinically-crosslinkable polyvinyl alcohol prepolymer, wherein the actinically-crosslinkable polyvinyl alcohol prepolymer comprises repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

R 11 is hydrogen or C 1 -C 6 alkyl;

R 12 is an ethylenically unsaturated group of

in which q1 and q2 independently of each another are zero or one, and R 16 and R 17 independently of each another are a C 2 -C 8 alkylene divalent radical, R 18 is C 2 -C 8 alkenyl;

R 13 can be hydrogen or a C 1 -C 6 alkyl group; and

R 14 is a C 1 -C 6 alkylene divalent radical.

16. The method of claim 14 , wherein the lens formulation is a water-based lens formulation comprising at least one actinically-crosslinkable polyvinyl alcohol prepolymer, wherein the actinically-crosslinkable polyvinyl alcohol prepolymer comprises repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

R 11 is hydrogen or C 1 -C 6 alkyl;

R 12 is an ethylenically unsaturated group of

in which q1 and q2 independently of each another are zero or one, and R 16 and R 17 independently of each another are a C 2 -C 8 alkylene divalent radical, R 18 is C 2 -C 8 alkenyl;

R 13 can be hydrogen or a C 1 -C 6 alkyl group; and

R 14 is a C 1 -C 6 alkylene divalent radical.