Ophthalmic and otorhinolaryngological device materials

1. A polymeric ophthalmic or otorhinolaryngological device material comprising

a) 70 to 98% (w/w) of a monofunctional monomer of formula [1]:

wherein

B═—O(CH 2 ) n —, —(OCH 2 CH 2 ) n —, —NH(CH 2 ) n —, or —NCH 3 (CH 2 ) n —;

R 1 ═H, CH 3 , CH 2 CH 3 , or CH 2 OH;

n=0-12;

A=C 6 H 5 or O(CH 2 ) m C 6 H 5 , where the C 6 H 5 group is optionally substituted with —(CH 2 ) n H, —O(CH 2 ) n H, —CH(CH 3 ) 2 , —C 6 H 5 , —OC 6 H 5 , —CH 2 C 6 H 5 , F, Cl, Br, or I; and

m=0-18;

b) a difunctional cross-linking monomer of formula [2]:

wherein

R 2 , R 3 independently=H, CH 3 , CH 2 CH 3 , or CH 2 OH;

W, W′ independently=O(CH 2 ) d , NH(CH 2 ) d , NCH 3 (CH 2 ) d , O(CH 2 ) d C 6 H 4 , O(CH 2 CH 2 O) d CH 2 , O(CH 2 CH 2 CH 2 O) d CH 2 , O(CH 2 CH 2 CH 2 CH 2 O) d CH 2 , or nothing;

J=(CH 2 ) a , O(CH 2 CH 2 O) b , O, or nothing, provided that if W and W′=nothing, then J ≠ nothing;

d=0-12;

a=1-12; and

b=1-24;

and

c) 0.5 to 15% (w/w) of a copolymer additive of formula [3]:

wherein for formula [3]:

D=OCH 2 CH 2 S, SCH 2 C═O, CH 3 CH(OH)CH 2 S, SCH 2 CH(OH)CH 2 O, S(CH 2 ) 11 O, S(CH 2 ) 10 C═O, S(CH 2 ) 14 C═O, S(CH 2 ) 15 C═O, SC 6 H 4 CH 2 O, CH 3 CH(S)C═O, S(CH 2 CH 2 CH 2 )O, CH 3 CH(S)CH(O)CH 3 , OCH 2 CH 2 C(CH 3 ) 2 S, SCH 2 CH 2 C═O, S(CH 2 ) 4 O, SC 6 H 4 CH 2 C═O, SC 6 H 4 C═O, S(CH 2 ) 11 C═O, CH 3 CH(O)CH(S)CH 3 , SC 6 H 4 C═O, S(CH 2 ) 6 OC 6 H 4 CH 2 O, S(CH 2 ) 6 O, S(CH 2 ) 5 C═O, S(CH 2 ) 7 C═O, S(CH 2 ) 9 O, C(CH 3 ) 2 C(═O)NHCH 2 CH 2 O, C(CH 3 ) 2 C(═NH)NHCH 2 CH 2 C═O, C(CH 3 ) 2 C(═O)NHCH(CH 2 CH 3 )(CH 2 O), C(CH 3 ) 2 CN, C(CH 3 )(CN)CH 2 C(OCH 3 )(CH 3 CH 3 ) , C(CH 3 ) 2 C(═O)NHCH 2 CH═CH 2 , C(CH 3 )(CN)CH 2 C(CH 3 ) 2 (OCH 3 ), C(CH 3 )(CN)CH 2 CH(CH 3 ) 2 , C(CH 3 ) 2 C(═O)OCH 3 , C(CH 3 )(CN)CH 2 CH 3 , C(CN)(CH 2 ) 5 , C(CH 3 ) 2 C(═O)NHCH 2 CH 2 CH 2 CH 3 , or C(CH 3 ) 2 C(═O)NHC 6 H 11 ;

E=nothing, O(CH 2 ) n NH, (OCH 2 CH 2 ) n NH, O(CH 2 ) n NHC═O, HN(CH 2 ) n NH, OH, or H; provided that if D=C(CH 3 ) 2 CN, C(CH 3 )(CN)CH 2 C(OCH 3 )(CH 3 CH 3 ), C(CH 3 ) 2 C(═O)NHCH 2 CH═CH 2 , C(CH 3 )(CN)CH 2 C(CH 3 ) 2 (OCH 3 ), C(CH 3 )(CN)CH 2 CH(CH 3 ) 2 , C(CH 3 ) 2 C(═O)OCH 3 , C(CH 3 )(CN)CH 2 CH 3 , C(CN)(CH 2 ) 5 , C(CH 3 ) 2 C(═O)NHCH 2 CH 2 CH 2 CH 3 , or C(CH 3 ) 2 C(═O)NHC 6 H 11 , then E=F=nothing;

n=1-5;

if D≠C(CH 3 ) 2 CN, C(CH 3 )(CN)CH 2 C(OCH 3 )(CH 3 CH 3 ), C(CH 3 ) 2 C(═O)NHCH 2 CH═H 2 , C(CH 3 )(CN)CH 2 C(CH 3 ) 2 (OCH 3 ), C(CH 3 )(CN)CH 2 CH(CH 3 ) 2 , C(CH 3 ) 2 C(O)OCH 3 , C(CH 3 )(CH)CH 2 CH 3 , C(CN)(CH 2 ) 5 , C(CH 3 ) 2 C(═O)NHCH 2 CH 2 CH 2 CH 3 , or C(CH 3 ) 2 C(O)NHC 6 H 11 then

if E=H or OH, then F=nothing;

if E≠H or OH, then F═C(═O)C(CH 3 )═CH 2 , C(═O)CH═CH 2 , C(═O)C(CH 2 CH 3 )═CH 2 , C(═O)C(CH 2 OH)═CH 2 , C(═O)NHCH 2 CH 2 OC(═O)C(CH 3 )═CH 2 , or C(═O)NHC(CH 3 ) 2 C 6 H 4 C(═CH 2 )CH 3 ;

R 4 , R 5 , and R 6 independently=H or CH 3 ;

t, u, and v represent molar fraction values and t+u+v=1;

t and u independently=0-0.95; provided that t+u=0.8-0.95;

v=0.05-0.2;

W═H, CH 3 , C(═O)C(CH 3 )═CH 2 , C(═O)CH═CH 2 , C(═O)C(CH 2 CH 3 )═CH 2 , C(═O)C(CH 2 OH)═CH 2 , C(═O)NHCH 2 CH 2 OC(═O)C(CH 3 )═CH 2 , or C(═O)NHC(CH 3 ) 2 C 6 H 4 C(═CH 2 )CH 3 ; provided that if F=nothing, then W═C(═O)C(CH 3 )═CH 2 , C(═O)CH═CH 2 , C(═O)C(CH 2 CH 3 )═CH 2 , C(═O)C(CH 2 OH)═CH 2 , C(═O)NHCH 2 CH 2 OC(═O)C(CH 3 )═CH 2 , or C(═O)NHC(CH 3 ) 2 C 6 H 4 C(═CH 2 )CH 3 ;

y 1 , y 2 , and y 3 independently=4-200; and

x=1-100;

wherein the polymeric device material has an equilibrium water content of 0.5-3.0%.

2. The polymeric device material of claim 1 wherein for the monomer of formula [I]:

B═—O(CH 2 ) n — or —(OCH 2 CH 2 ) n —;

R 1 ═—H or —CH 3 ;

n=1-5;

A=—C 6 H 5 , O(CH 2 ) m C 6 H 5 ; and

m=0-4.

3. The polymeric device material of claim 1 wherein for the monomer of formula [2]:

R 2 , R 3 independently=H or CH 3 ;

W, W′ independently=O(CH 2 ) d , O(CH 2 ) d C 6 H 4 , or nothing;

J=O(CH 2 CH 2 O) b or nothing, provided that if W and W′=nothing, then J≠nothing;

d=0-6; and

b=1-10.

4. The polymeric device material of claim 1 wherein the copolymer additive of formula [3] has a number average molecular weight (M n ) from 3,000 to 10,000 Daltons.

5. The polymeric device material of claim 1 wherein for the copolymer additive of formula [3]:

D=OCH2CH2S or OCH2CH2CH2S;

E=nothing, H, or OH;

if E=H or OH, then F=nothing;

if E≠H or OH, then F═C(═O)C(CH3)=CH2;

R4=R5=R6=CH3;

W═C(═O)C(CH3)=CH2;

t and u independently=0-0.95; provided that t+u=0.85-0.95;

v=0.05-0.15;

y1, y2, and y3 independently=4-20; and

x=5-50.

6. The polymeric device material of claim 5 wherein for the copolymer additive of formula [3]:

D=OCH2CH2S;

E=nothing;

F═C(═O)C(CH3)=CH2;

R4=R5=R6=CH3;

W═C(═O)C(CH3)=CH2;

t and u independently=0-0.9; provided that t+u=0.85-0.9;

v=0.1-0.15;

y=4-20; and

x=5-50.

7. The polymeric device material of claim 1 wherein the monomer of formula [1] is selected from the group consisting of benzyl methacrylate; 2-phenylethyl methacrylate; 3-phenylpropyl methacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-phenoxyethyl methacrylate; 2-(2-phenoxyethoxy)ethyl methacrylate; 2-benzyloxyethyl methacrylate; 2-(2-(benzyloxy)ethoxy)ethyl methacrylate; 3-benzyloxypropyl methacrylate; benzyl acrylate; 2-phenylethyl acrylate; 3-phenylpropyl acrylate; 4-phenylbutyl acrylate; 5-phenylpentyl acrylate; 2-phenoxyethyl acrylate; 2-(2-phenoxyethoxy)ethyl acrylate; 2-benzyloxyethyl acrylate; 2-(2-(benzyloxy)ethoxy)ethyl acrylate; and 3-benzyloxypropyl acrylate.

8. The polymeric device material of claim 1 wherein the monomer of formula [2] is selected from the group consisting of ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate; 1,4-benzenedimethanol dimethacrylate; ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; 1,6-hexanediol diacrylate; 1,4-butanediol diacrylate; and 1,4-benzenedimethanol diacrylate.

9. The polymeric device material of claim 1 wherein the amount of monomer [1] is 80 to 95% (w/w).

10. The polymeric device material of claim 1 wherein the amount of monomer [2] is 0.5 to 3% (w/w).

11. The polymeric device material of claim 1 wherein the amount of copolymer additive [3] is 1 to 10% (w/w).

12. The polymeric device material of claim 11 wherein the amount of copolymer additive [3] is 1 to 5% (w/w).

13. The polymeric device material of claim 12 wherein the amount of copolymer additive [3] is 2 to 4% (w/w).

14. The polymeric device material of claim 1 further comprising an ingredient selected from the group consisting of a polymerizable UV absorbers and a polymerizable colorants.

15. The polymeric device material of claim 14 comprising 0.1-5% (w/w) of a polymerizable UV absorber and 0.01-0.5% (w/w) of a polymerizable colorant.

16. An ophthalmic or otorhinolaryngological device comprising the polymeric device material of claim 1 wherein the ophthalmic or otorhinolaryngological device is selected from the group consisting of intraocular lenses; contact lenses; keratoprostheses; corneal inlays or rings; otological ventilation tubes; and nasal implants.

17. The ophthalmic or otorhinolaryngological device of claim 16 wherein the ophthalmic or otorhinolaryngological device is an intraocular lens.