Method for making silicone hydrogel contact lenses

1. A lens-forming composition suitable for making silicone hydrogel contact lenses according to a curing method based on a spatial limitation of actinic radiation, comprising:

(1) from about 10% to about 50% by weight of at least one hydrophilic amide-type vinylic monomer;

(2) from about 10% to about 40% by weight of at least one siloxane-containing (meth)acrylamide of formula (1)

in which R is H or CH 3 R 3 and R 4 indeendentl of each other are H C 1 -C 6 alkyl, or a monovalent radical of formula (2)

in which Y is a C 1 -C 6 alkylene divalent radical or a C 1 -C 6 alkylene divalent radical containing one or more hydroxyl groups, m is an integer of 0 to 5, p is an integer of 1 to 6, and A 1 , A 2 and A 3 independent of each other are C 1 -C 6 alkyl, phenyl, benzyl, or a radical of formula (3)

in which B 1 , B 2 and B 3 independent of each other are C 1 -C 6 alkyl, phenyl, or benzyl, provided that at least one of R 3 and R 4 is a radical of formula (2), and provided that at least two of A 1 A 2 and A 3 are radicals of formula (3);

(3) from about 10% to about 40% by weight of a polysiloxane-containing vinylic macromere of formula (4);

Q-X 1 -G 1 -PDMS-G 2 X 2 -Q) r   (4)

in which

r is an integer of 1,

G 1 and G 2 independent of each other is a linear or branched C 1 -C 10 alkylene divalent radical, a divalent radical of alk′-O q alk- in which q is an integer of from 1 to 5 and alk and alk′ independent of each other is a C 1 -C 6 alkylene divalent radical, or a divalent radical of —R′ 1 —X 4 -E-X 5 —R′ 2 — in which R′ 1 and R′ 2 independent of each other is a linear or branched C 1 -C 10 alkylene divalent radical or a divalent radical of alk′-O q alk- as defined above, X 4 and X 5 independent of each other are a linkage selected from the group consisting of

 in

which R′ is H or C 1 -C 8 alkyl, E is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain,

X 1 and X 2 independent of each other are a linkage selected from the group consisting of a direct bond,

 in which R′ is H or C 1 -C 8 alkyl,

PDMS is a polysiloxane divalent radical of formula (5)

-D 1 U 1 -D 2 U 2 -D 3 ν ω   (5)

in which ν is 0 or 1, ω is an integer of from 0 to 5, U 1 and U 2 independent of each other represent a divalent radical of —R′ 1 —X 4 -E-X 5 —R′ 2 as defined above or a divalent radical of alk′-O q alk- as defined above, D 1 , D 2 and D 3 independently of each other are a divalent radical selected from the group consisting of —(CH 2 CH 2 O) t —CH 2 CH 2 — in which t is an integer of 3 to 40, —CF 2 —(OCF 2 ) a —(OCF 2 CF 2 ) b —OCF 2 — in which a and b independent of each other is an integer of 0 to 10 provided that a+b is a number in the range of 10 to 30, and a divalent group of formula (6)

in which R 3 , R 4 , R 5 ′, R 6 , R 7 , R 8 , R 9 and R 10 , independently of one another, are C 1 -C 8 -alkyl, C 1 -C 4 alkyl- or C 1 -C 4 - alkoxy-substituted phenyl, fluoro(C 1 -C 18 -alkyl), cyano(C 1 -C 12 -alkyl), -alk-(OCH 2 CH 2 ) n —OR 11 in which alk is C 1 -C 6 -alkylene divalent radical, R 11 is C 1 -C 6 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 2 to 698 and (m+p) is from 5 to 700, provided that at least one of D 1 , D 2 and D 3 is represented by formula (6), and

Q is an ethylenically unsaturated group of formula (7)

in which Z 1 and Z 2 independent of each other are a linear or branched C 1 -C 12 alkylene divalent radical, a linear or branched C 1 -C 12 alkylene divalent radical having one or more hydroxyl groups, a radical of —(CH 2 CH 2 O) d —CH 2 CH 2 in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituted phenylene divalent radical or C 7 -C 12 aralkylene divalent radical; A 5 is —O— or

 in which R′ is H or C 1 -C 8 alkyl; q 1 and q 2 independent of each other are an integer of 0 or 1; R 14 is hydrogen, C 1 -C 4 alkyl or halogen; R 15 and R 16 independent of each other are hydrogen, C 1 -C 4 alkyl, phenyl, carboxy, halogen, or a radical of

 in which X 3 is —O—,

 as defined above or —S— and R 17 is a C 1 -C 12 alkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl radical;

(4) from about 0.1% to about 1.3% by weight of a photoinitiator, and

(5) from 0 to about 5% by weight of a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent; provided that components (1) to (5) and any additional components add up to 100% by weight,

wherein if one or more methacrylate monomers are present in the lens-forming composition, the total amount of the methacrylate monomers is less than about 5% by weight, and wherein the lens forming composition is characterized by having a curing time of less than 30 seconds by a UV light having an UV-intensity of about 4.1 mW/cm 2 .

2. The lens-forming composition of claim 1 , wherein the siloxane-containing (meth)acrylamide monomeris selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris (dimethyl-phenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2- methyl acrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide; N,-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.

3. The lens-forming composition of claim 1 , wherein the monomer mixture comprises a polysiloxane-containing vinylic macromer of formula (4) in which D 1 , D 2 and D 3 independently of each other are a divalent radical of formula (6).

4. The lens-forming composition of claim 1 , wherein the monomer mixture comprises a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent in an amount from about 0.2% to about 5.0% by weight.

5. The lens-forming composition of claim 4 , wherein the monomer mixture comprises a polymerizable UV-absorbing agent which comprises a benzotriazole- and/or benzophenone-moiety.

6. The lens-forming composition of claim 5 , wherein the photoinitiator is a benzoylphosphine oxide photoinitiator.

7. The lens-forming composition of claim 4 , wherein the monomer mixture comprises a polymerizable latent UV-absorbing agent.

8. The lens-forming composition of claim 1 , wherein the hydrophilic amide-type vinylic monomer is selected from the group consisting of 2-acrylamidoglycolic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid or salt thereof, (3-acrylamidopropyl)-trimethylammonium chloride, 3-acryloylamino-1-propanol, N-(butoxymethyl)acrylamide, N-tert-butylacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-hydroxyethyl acrylamide, N-(hydroxymethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, methacrylamide, N-phenylacrylamide, N-[Tris(hydroxymethyl)methyl]acrylamide,N-methyl-3-methylene-2-pyrrolidone, and a mixture thereof.

9. The lens-forming composition of claim 8 , wherein the siloxane-containing (meth)acrylamide monomeris selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethyl-phenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N[2-hydroxy-3-(3-(t-butyldimethylsilyppropyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.

10. The lens-forming composition of claim 9 , wherein the monomer mixture comprises a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent in an amount from about 0.2% to about 5.0% by weight.

11. The lens-forming composition of claim 10 , wherein the monomer mixture comprises a polymerizable UV-absorbing agent which comprises a benzotriazole- and/or benzophenone-moiety.

12. The lens-forming composition of claim 10 , wherein the photoinitiator is a benzoylphosphine oxide photoinitiator.

13. The lens-forming composition of claim 10 , wherein the monomer mixture comprises a polymerizable latent UV-absorbing agent.