JP2804279B2 - Ophthalmic lens materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an ophthalmic lens material used for a contact lens, an intraocular lens, an artificial cornea and the like. More specifically, the present invention relates to an ophthalmic lens material having an optically high refractive index and exhibiting high gas permeability and excellent mechanical strength.

[Conventional technology]

In recent years, as a contact lens having high oxygen permeability and rigidity and a high refractive index, a contact lens comprising a silicon-containing styrene monomer such as tris (trimethylsiloxy) silylstyrene or trimethylsilylstyrene and perfluoroalkyl methacrylate. Materials have been introduced (JP-A-60-142324). However, such a contact lens material decreases the optical properties, particularly the refractive index, which is one of the functions of the contact lens when the amount of perfluoroalkyl methacrylate is increased, while increasing the amount of silicon-containing styrene increases the contact. There is a disadvantage that the mechanical strength of the lens, particularly the breaking strength, is reduced, and sufficient strength cannot be provided as a contact lens.

[Problems to be solved by the invention]

The inventors of the present invention have conducted intensive studies to obtain an ophthalmic lens material having high refractive index, high mechanical strength, high gas permeability, and excellent mechanical workability at the same time. For the first time, they found an ophthalmic lens material provided and completed the present invention.

[Means for solving the problem]

That is, the present invention provides a silicon-containing styrene derivative and a compound represented by the general formula (II): (In the formula, j represents an integer of 1 to 3, and k represents an integer of 0 to 7.)
The present invention relates to an ophthalmic lens material comprising a copolymer containing a fluorine-containing styrene derivative represented by the following formula as an essential copolymer component.

[Operation and Examples]

As described above, the ophthalmic lens material of the present invention comprises a silicon-containing styrene derivative and a compound represented by the general formula (II): (In the formula, j represents an integer of 1 to 3, and k represents an integer of 0 to 7.)
And a copolymer containing a fluorine-containing styrene derivative represented by the following formula as an essential copolymerization component.

As the silicon-containing styrene derivative, for example, a compound represented by the general formula (III): (Where p is an integer of 1 to 15, q is 0 or 1, r is 1 to
And an integer of 15).

In the general formula (III), when p or r is an integer of 16 or more, purification and synthesis of the silicon-containing styrene derivative are difficult, and the hardness of the obtained ophthalmic lens material tends to decrease. When q is an integer of 2 or more, the synthesis of the silicon-containing styrene derivative tends to be difficult.

Among the compounds represented by the general formula (III), compounds that are usually easily available and most suitable for achieving the object of the present invention include, for example, general formula (I): (Wherein, m represents 0 or 1, and n represents an integer of 0 to 3).

Representative examples of the compound represented by the general formula (I) include, for example, tris (trimethylsiloquine) silylstyrene (when m in the general formula (I) is 0 and n is 3), bis (trimethylsiloquine) Methylsilylstyrene (when m in the general formula (I) is 0 and n is 2), (trimethylsiloquine) dimethylsilylstyrene (when m in the general formula (I) is 0 and n is 1), trimethylsilyl Styrene (when m in formula (I) is 0 and n is 0), tris (trimethylsiloquin) siloxanyldimethylsilylstyrene (when m in formula (I) is 1 and n is 3) , [Bis (trimethylsiloquin) methylsiloxanyl] dimethylsilylstyrene (when m in Formula (I) is 1 and n is 2), pentamethyldisiloxanylstyrene (in Formula (I) m is 1 and n is 0 When), when m in heptamethyltrisiloxane siloxanyl styrene (general formula (I) is 1, n is 1), and the like.

Specific examples of the silicon-containing styrene derivative represented by the general formula (III) other than the compound represented by the general formula (I) include, for example, nonamethyltetrasiloxanylstyrene, petadecamethylheptasiloxanylstyrene,
Heineicosamethyl decasiloxanyl styrene, heptacosa methyl tridecasiloxanyl styrene, hentria contamethyl pentadecasiloxanyl styrene, trimethylsiloxypentamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene (Tristrimethylsiloxy) siloxanylbis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbistrimethylsiloxysiloxy) silylstyrene, trimethylsiloxybis (tristrimethylsiloxysiloxy) silylstyrene, heptakis ( Trimethylsiloxy) trisiloxanylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris (Tristrimethylsiloxysiloxy) silylstyrene, (tristrimethylsiloxyhexamethyl) tetrasiloxy (tristrimethylsiloxy) siloxytrimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene , Heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene, and the like. One or more kinds are selected from these. Used as

The silicon-containing styrene derivative is a component that imparts a high refractive index and high gas permeability to the obtained ophthalmic lens material and facilitates mechanical processing.

The preferred amount of the silicon-containing styrene derivative is 5 to 95 parts by weight, preferably 30 to 80 parts by weight, particularly preferably 100 parts by weight of the essential copolymer component.
40 to 70 parts by weight. If the amount is more than the above range, the mechanical strength of the obtained material tends to decrease, and if the amount is less than the above range, the refractive index and oxygen permeability tend to decrease.

The fluorine-containing styrene derivative has the general formula (II): (In the formula, j represents an integer of 1 to 3, and k represents an integer of 0 to 7.)
It is a compound represented by these.

In the general formula (II), when j is 0, the synthesis of the fluorine-containing styrene derivative tends to be difficult, and when j is an integer of 4 or more, or when k is an integer of 8 or more. However, the hardness of the obtained ophthalmic lens material tends to decrease.

Specific examples of the fluorine-containing styrene derivative represented by the general formula (II) include, for example, 4-vinylbenzyl-
2 ', 2', 2'-trifluoroethyl ether (when j in formula (II) is 1 and k is 0), 4-vinylbenzyl-2 ', 2', 3 ', 3', 4 ', 4', 4'-heptafluorobutyl ether (when j in formula (II) is 1 and k is 2), 4-vinylbenzyl-3 ', 3', 3'-trifluoropropyl ether (general In the formula (II), j is 2 and k is 0
), 4-vinylbenzyl-3 ', 3', 4 ', 4',
5 ′, 5 ′, 6 ′, 6 ′, 6′-nonafluorohexyl ether (when j in the general formula (II) is 2 and k is 3).

The fluorine-containing styrene derivative represented by the general formula (II) used in the present invention has a high refractive index, a high mechanical strength,
It is a component for obtaining an ophthalmic lens material having both high gas permeability and excellent mechanical workability at the same time. In particular, the fluorine-containing styrene derivative is used in the obtained ophthalmic lens material in comparison with fluoroalkyl methacrylate. It is a component that imparts a high refractive index and a high mechanical strength, and also facilitates mechanical processing.

The amount of the fluorine-containing styrene derivative to be used is 5 to 95 parts by weight, preferably 20 to 70 parts by weight, particularly preferably 30 to 60 parts by weight, based on 100 parts by weight of the essential copolymer component. If the amount is more than the above range, the oxygen permeability of the obtained material tends to decrease, and if it is less than the above range, the mechanical strength tends to decrease.

In the present invention, since the silicon-containing styrene derivative and the specific fluorine-containing styrene derivative represented by the general formula (II) are used in combination, the physical properties aimed at by the present invention are effectively exhibited by a synergistic effect of both. It is done.

In addition to the essential copolymer components, various monomers may be used for various purposes. Such monomers include:
For example, there are (meth) acrylic monomers, styrene monomers and monomers other than these. The kind, number and amount of the monomers are arbitrarily selected and set depending on the physical properties and properties of the objective ophthalmic lens material.

Specific examples of the (meth) acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, tert-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-methylbutyl (meth) acrylate, heptyl (meth) acrylate, octyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cycle Linear, branched or cyclic alkyl (meth) acrylates such as hexyl (meth) acrylate; pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethyl) (Siloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate , Methyl bis (trimethylsiloxy)
Silylpropyl glycerol (meth) acrylate, tris (trimethylsiloxy) silylpropyl glycerol (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropylglycerol (meth) acrylate, trimethylsilylethyltetramethyldisiloxa Nylpropyl glycerol (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropyl glycerol (meth) acrylate, pentamethyldisiloxanylpropyl glycerol (meth) acrylate, methyl bis (trimethylsiloxy) silylethyl Tetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltri Silicon-containing (meth) acrylates such as isopropylcyclotetrasiloxanylpropyl (meth) acrylate and tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate; 2,2,2-trifluoroethyl ( (Meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,2-trifluoro-1-tri Fluoromethylethyl (meth) acrylate, 2,2,3,3-tetrafluoro-tert-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2 , 3,3,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-
Hexafluoro-tert-hexyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5-octa Fluoropentyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4, 5,5,5-nonafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,
7,7-dodecafluoroheptyl (meth) acrylate,
3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7, 7,8,8,8−
Tridecafluorooctyl (meth) acrylate, 2,2,
3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7 , 8,8,9,9,
10,10-hexadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro Decyl (meth) acrylate, 3,3,4,4,5,5,
6,6,7,7,8,8,9,9,10,10,11,11-octadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5,6,6, 7,7,
8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8, 8,9,9,
10,10,11,11,12,12-eicosafluorododecyl (meth) acrylate, 2-hydroxy-4,4,5,5,6,7,7,7
-Octafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxy-4,4,5,5,6,6,
7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl (meth) acrylate, 2-hydroxy-4,4,
Fluorine-containing (meth) such as 5,5,6,6,7,7,8,8,9,9,10,11,11,11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate Acrylates: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) A) acrylates, hydroxy-containing (meth) acrylates such as dipropylene glycol mono (meth) acrylate; (meth) acrylic acid; N- (meth) acryloylpyrrolidone; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (Meth) acrylamide, N-hydroxy Ethyl (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- diethyl (meth) acrylamide, N-
(Meth) acrylamides such as ethylaminoethyl (meth) acrylamide; aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate,
Aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; alkoxy group-containing (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxydiethylene glycol (meth) acrylate; Aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate; 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4
-(Meth) acryloyloxy-5-tret-butylbenzophenone, 2-hydroxy-4- (meth) acryloyloxy-2 ', 4'-dichlorobenzophenone, 2-hydroxy-4- (2-hydroxy-3- (meta) ) Acryloyloxypropoxy) benzophenone-based polymerizable ultraviolet absorbers such as benzophenone; 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl- (2H) -benzotriazole, 2- (2′-hydroxy) -5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2-
(2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2-
Benzotriazole polymerizable ultraviolet absorbers such as (2'-hydroxy-5 '-(meth) acryloyloxypropyl-3'-tert-butylphenyl) -5-chloro-2H-benzotriazole; 2-hydroxy-4 -(Meta)
Salicylic acid derivative-based polymerizable ultraviolet absorbers such as phenyl acryloyloxymethyl benzoate; 2-cyano-3-
Polymerizable ultraviolet absorbers other than the above, such as phenyl-3- (3- (meth) acryloyloxyphenyl) propenyl acid methyl ester; 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2 -Hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3-
(Meth) acryloyloxynaphthalene, 1-anthrylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4- (phenylazo) -phenyl) azo) -2-hydroxy-3- (meth) acryloyloxy Naphthalene, 1- (2 ', 4'-xylylazo) -2-naphthol (meth) acrylate, 1- (orthotolylazo) -2-naphthol (meth) acrylate, 2- (3- (meth) acryloylamide-anilino)- 4,6-bis (1-orthotolylazo-2-naphthylamino) -1,3,5-triazine, 3- (meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4- (8 -Hydroxy-3,6
-Disulfo-1-naphthylazo) -phenol, 3-
(Meth) acryloylamide-4- (1-phenylazo-2-naphthylazo) -phenol, 3- (meth) acryloylamide-4-paratolylazophenol, 4-
Phenylazo-7- (meth) acryloylamide-1-
Azo-based polymerizable dyes such as naphthol; 1,5-bis ((meth) acryloylamide) -9,10-anthraquinone,-
Amino-4- (3 '-(meth) acryloylaminophenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (3' (meth) acryloylaminobenzylamino) -9,10- Anthraquinone-2-sulfonic acid, 2- (3- (meth) acryloylamide-anilino) -4- (3- (3-sulfo-4-aminoanthraquinone-1-yl) -amino-anilino) -6-chloro- 1,3,5-triazine, 2- (3- (meth) acryloylamide-anilino) -4- (3- (3-sulfo-4-
Anthraquinone-based polymerizable dyes such as aminoanthraquinone-1-yl) -amino-aniline) -6-hydrazino-1,3,5-triazine; nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate Pigment;
Phthalocyanine-based polymerizable dyes such as (meth) acryloylated tetraamino copper phthalocyanine and (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine); 2,4-dihydroxy-3-p- (meth) acryloyloxymethylphenyl azo Benzophenone, 2,4-
Dihydroxy-5-p-meth) acryloyloxymethylphenylazobenzophenone, 2,4-dihydroxy-
3-p- (meth) acryloyloxyethylphenylazobenzophenone, 2,4-dihydroxy-5-p- (meth) acryloyloxyethylphenylazobenzophenone, 2,4-dihydroxy-3-p (meth) acryloyloxypropylphenyl Azobenzophenone, 2,4-
Dihydroxy-5-p- (meth) acryloyloxypropylphenylazobenzophenone, 2,4-dihydroxy-3-o- (meth) acryloyloxymethylphenylazobenzophenone, 2,4-dihydroxy-5-o-
(Meth) acryloyloxymethylphenylazobenzophenone, 2,4-dihydroxy-3-o- (meth) acryloyloxyethylphenylazobenzophenone,
4-dihydroxy-5-o- (meth) acryloyloxyethylphenylazobenzophenone, 2,4-dihydroxy-3-o- (meth) acryloyloxypropylphenylazobenzophenone, 2,4-dihydroxy-5
o- (meth) acryloyloxypropylphenylazobenzophenone, 2,4-dihydroxy-3-p-N, N-di (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-5-p-N, N-di (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-3-o-N, N-di (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-5-o- N, N-di (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-3-p-N-ethyl-N- (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-5 −
p-N-ethyl-N- (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-3-o-N-ethyl-N- (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4
-Dihydroxy-5-o-N-ethyl-N- (meth) acryloyloxyethylaminophenylazobenzophenone, 2,4-dihydroxy-3-p-N-ethyl-N-
(Meth) acryloylaminophenylazobenzophenone, 2,4-dihydroxy-5-p-N-ethyl-N-
(Meth) acryloylaminophenylazobenzophenone, 2,4-dihydroxy-3-o-N-ethyl-N-
(Meth) acryloylaminophenylazobenzophenone, 2,4-dihydroxy-5-o-N-ethyl-N-
Examples thereof include polymerizable ultraviolet absorbing dyes such as (meth) acryloylaminophenylazobenzophenone, and one or more of these are selected and used.

Specific examples of the styrene monomer include, for example, styrene, o-methylstyrene, m-methylstyrene,
-Methylstyrene, p-ethylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, trimethylstyrene, tert-butylstyrene, perbromostyrene, dimethylaminostyrene, α
Styrene derivatives such as -methylstyrene; and one or more of these are selected and used.

In addition, a vinyl-based monomer contained in a vinyl group or the like other than the styrene-based monomer may be treated in the same manner as the styrene-based monomer.

Specific examples of the vinyl monomer include N-
N-vinyl lactams such as vinylpyrrolidone, α-methylene-N-methylpyrrolidone and N-vinylcaprolactam; 4-vinylpyridine; heterogeneous such as vinylimidazole, N-vinylpyropidone, N-vinylpiperidine and N-vinylsuccinimide Cyclic N-vinyl monomer; 2-
(3-vinylanilino) -4- (nitro (phenylazo) -anilino) -6-chloro-1,3,5-triazine,
2- (1-orthotolylazo-2-naphthyloxy)-
4- (3-vinylanilino) -6-chloro-1,3,5-triazine, 2- (4-vinylanilino) -4-orthotolylazo-2-naphthylanilino) -6-chloro-1,3,
5-triazine, N- (1-orthotolylazo-2-naphthyl) -3-vinylphthalic acid monoamide, N- (1-
Ortho-tolylazo-2-naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4-parasulfophenylazo-1-naphthyl) monoester, 6-vinylphthalic acid- (4-parasulfophenylazo-1-naphthyl) Monoester, 2-amino-4- (m- (2-hydroxy-1-naphthylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N
-Methyl-p- (2-hydroxy-1-naphthylazo)
Anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (m- (4-hydroxy-1-phenylazo) anilino) -6-isopropenyl-1,3,5
-Triazine, 2-amino-4- (N-methyl-p-
(4-hydroxyphenylazo) anilino-6-isopropenyl-1,3,5-triazone, 2-amino-4- (m
-(3-Methyl-1-phenyl-5-hydroxy-4-
Pyrazolylazo) anilino) -6-isopropenyl-1,
3,5-triazine, 2-amino-4- (N-methyl-p
-(3-methyl-1-phenyl-5-hydroxypyrazolylazo) anilino) -6-isopropenyl-1,3,5-
Azo polymerizable dyes such as triazine and 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1,3,5-triazine; 1- (4'-vinylbenzoylamide) -9 , 10-Anthraquinone, 4-amino-1-
(4'-vinylbenzoylamide) -9,10-anthraquinone, 5-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1- (4 '
-Vinylbenzoylamide) -9,10-anthraquinone,
4-nitro-1- (4'-vinylbenzoylamide)-
9,10-anthraquinone, 4-hydroxy-1- (4'-
Vinylbenzoylamide) -9,10) -anthraquinone,
1- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1- (2'-vinylbenzoylamide) -9,
10-anthraquinone, 1- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (3'-
Isopropenylbenzoylamide) -9,10-anthraquinone, 1- (2'-isopropenylbenzoylamide)
-9,10-anthraquinone, 1,4-bis- (4'-vinylbenzoylamide) -9,10-anthraquinone, 1,4-bis- (4'-isopropenylbenzoylamide) -9,10
-Anthraquinone, 1,5-bis- (4'-vinylbenzoylamide) -9,10-anthraquinone, 1,5-bis-
(4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4- (paravinylbenzoyloxy Ethylamino) -anthraquinone, 1-amino-4-
(3'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (4'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino- 4- (2'-vinylbenzylamino) -9,10-anthraquinone-2-sulfonic acid, 1-
(Β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1- (β-carboxyallylamino) -9,
10-anthraquinone, 1,5-di- (β-carboxyallylamino) -9,10-anthraquinone, 1- (β-isopropoxycarbonylallylamino) -5-benzoylamide-9,10-anthraquinone, 2,4 -Bis ((4-methoxyanthraquinone-1-yl) -amino) -6- (3
-Vinylanilino) -1,3,5-triazine, 2- (2-
Vinylphenoxy) -4- (4- (3-sulfo-4-aminoanthraquinone-1-yl-amino) -anilino)
Anthraquinone-based polymerizable dyes such as -6-chloro-1,3,5-triazine; 2,4-dihydroxy-3-p-styrenoazobenzophenone, 2,4-dihydroxy-5-p-
Styrenoazobenzophenone, 2-hydroxy-4-p
And polymerizable ultraviolet absorbing dyes such as phenyl styrenoazobenzoate, and one or more of these may be selected and used as needed.

As described above, in the present invention, the above-mentioned various fillers are appropriately selected according to the intended ophthalmic lens material such as a contact lens material and an intraocular lens material, and the essential components are formed at an arbitrary mixing ratio. It can be added to the copolymerization component and subjected to copolymerization.

In order to obtain a contact lens material having excellent oxygen permeability, for example, the silicon-containing (meth)
It is preferable to select and mix one or more of acrylates and the fluorine-containing (meth) acrylates.

In order to obtain an ophthalmic lens material having excellent mechanical strength by providing an auxiliary property, for example, one kind of the alkyl (meth) acrylate, the styrene derivative, the (meth) acrylic acid, etc. Alternatively, it is preferable to select and mix two or more kinds.

Also, to impart hydrophilicity to the ophthalmic lens material, or to obtain a water-containing and soft ophthalmic lens material,
It is preferable to further incorporate a monomer having a hydrophilic group.

Representative examples of such a monomer having a hydrophilic group include, for example, the hydroxyl group-containing (meth) acrylate, the (meth) acrylamides, the aminoalkyl (meth) acrylate, the (meth) acrylic acid, and the N-vinyl. Lactam and the like, and one or more of these are selected and blended.

However, when the purpose is to impart hydrophilicity to the surface of the hard ophthalmic lens material, the amount of the monomer having a hydrophilic group used is based on 100 parts by weight of the essential copolymer component. The amount is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight. When the amount is less than the above range, the expression of hydrophilicity on the surface of the obtained material tends to be small, and when the amount is more than the above range,
The resulting material tends to absorb water and become soft or turbid.

Further, in order to make the obtained ophthalmic lens material less likely to be contaminated with lipids, it is preferable to mix, for example, the above-mentioned fluorine-containing (meth) acrylate.

In order to obtain an ophthalmic lens material having a higher refractive index, it is preferable to blend a monomer containing an aromatic ring, such as the styrene-based monomer.

Specific examples of the styrene-based monomer include, for example, the above-mentioned styrene derivatives, and one or more of these are selected and blended.

In addition, when imparting to an ophthalmic lens material capable of obtaining ultraviolet absorption or coloring the material, the polymerizable ultraviolet absorber, the polymerizable dye and the polymerizable ultraviolet absorbing dye may be used. From 1 and 2 as required
It is preferred to select more than one species and mix them further.

It should be noted that a crosslinking agent may be used in the ophthalmic lens material of the present invention.

The cross-linking agent forms a bridged structure in the ophthalmic lens material, thereby toughening the obtained ophthalmic lens material, improving mechanical strength and hardness, and being uniform, distortion-free, and transparent. In addition, it is a component that is a material having high optical properties without clouding. In addition, such a cross-linking agent also has the properties of improving the durability of the obtained ophthalmic lens material, such as chemical resistance, heat resistance, solvent resistance, and shape stability, and reducing elution.

Specific examples of the crosslinking agent include, for example, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. Acrylate,
Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl acrylate, divinylbenzene, diallyl phthalate, adipine Acid diallyl, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, 2,2-bis (4- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (3-
(Meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (2- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (4
-(Meth) acryloyloxyphenyl) propane, 2,
2-bis (3- (meth) acryloyloxyphenyl)
Propane, 2,2-bis (2- (meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyl Oxyhexafluoroisopropyl) benzene, 1,2-bis (2-
(Meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2
-Bis (2- (meth) acryloyloxyisopropyl) benzene and the like, and one or more of them are selected and used.

Among the crosslinking agents, especially, 4-vinylbenzyl (meth) acrylate and 3-vinylbenzyl (meth) acrylate have a (meth) acryloyl group in these molecules whose compatibility with a (meth) acrylic monomer is high. Further, the vinyl group bonded to the benzene ring, that is, the so-called styrene skeleton portion is excellent in compatibility with the styrene monomer. Further, there is a difference in the polymerization rate between the (meth) acryloyl group of the (meth) acrylic monomer and the vinyl group of the styrene monomer, The (meth) acryloyl group and the vinyl group bonded to the benzene ring have almost the same polymerization rates as the (meth) acryloyl group and the vinyl group bonded to the benzene ring in the copolymer component.

Therefore, in the copolymerization of a mixture containing a (meth) acrylic monomer and a styrene monomer as a component, if the vinylbenzyl (meth) acrylate is used, the copolymerization proceeds smoothly to form a bridged structure. As a result, the material can be made tough and have improved mechanical strength and hardness, and can be a material that is uniform, has no distortion, and is transparent and rich in optical properties without clouding.

The amount of the crosslinking agent used is preferably about 0.5 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the essential copolymer component. If the amount of the crosslinking agent is too large, the physical properties improved by other components used for copolymerization, for example, the oxygen permeability is reduced, and the obtained material becomes brittle, and the stress such as impact is increased. When the amount is less than the above range, the effect of using the crosslinking agent tends to be small.

In the present invention, the essential copolymerization component is uniformly mixed with other copolymerization components such as the (meth) acrylic monomer and the styrene monomer, and a polymerization initiator is added thereto. It is subjected to copolymerization by a method commonly used in the art.

Specific examples of the above method include, for example, using a radical polymerization initiator as needed, gradually heating the blended solution in a temperature range from room temperature to about 130 ° C., or using microwaves, ultraviolet rays, radiation (γ-rays). For example, a method in which polymerization is performed by irradiating an electromagnetic wave. When heating and polymerizing, the temperature may be raised stepwise. The copolymerization may be a bulk polymerization method, a solvent polymerization method using a solvent or the like, or various other methods.

Specific examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and the like. One or two or more are selected and used.

The amount of the polymerization initiator to be used is about 0.01 to 1 part by weight, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total monomer mixture subjected to the polymerization.

If the amount is more than the above range, the obtained copolymer tends to contain bubbles and strain, and if the amount is less than the above range, the polymerization tends to be difficult to complete. is there.

When the obtained copolymer is used for an ophthalmic lens material such as a contact lens material or an intraocular lens material, a molding method commonly used by those skilled in the art can be employed. Examples of such a molding method include a cutting method and a mold method. In the above cutting method, polymerization is performed in an appropriate mold or container, and a rod-shaped, block-shaped, or plate-shaped material (polymer) is obtained, and then subjected to mechanical processing such as cutting, polishing, or the like. This is a method of processing into a shape. The mold method is a method of preparing a mold corresponding to the shape of a desired ophthalmic lens, and performing polymerization in the mold to obtain a molded product. Is subjected to finishing.

Further, when the ophthalmic lens material of the present invention is used for an intraocular lens material, the lens support may be manufactured separately from the lens, and the lens may be attached. It may be (integrally) molded.

If necessary, a plasma treatment may be applied to the ophthalmic lens material. As a processing apparatus and a processing method, conventionally known ordinary apparatuses and methods are employed. The processing conditions of the plasma processing include, for example, an inert gas such as helium, neon, or argon, air, oxygen, nitrogen,
Under an atmosphere of a gas such as carbon monoxide and carbon dioxide, the pressure is about 0.0001 to several Torr, the output is about several to 100 W, and the time is several seconds to several tens of minutes. Preferably, the gas species is air, oxygen, argon, the pressure is about 0.05-3 Torr, the power is about 10-60 W, and the time is a few minutes.

Since the thus obtained ophthalmic lens material of the present invention has an optically high refractive index, it is possible to make a thinner lens with the same power, thereby improving both the feeling of wearing and the oxygen permeability. It has desirable mechanical strength as an ophthalmic lens material, and has high gas permeability, especially in oxygen permeability, having higher oxygen permeability than conventional oxygen-permeable ophthalmic lens materials, It also has advantages such as easy mechanical processing.

Next, the ophthalmic lens material of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 [Production of copolymer] 65 parts by weight of tris (trimethylsiloxy) silylstyrene, 35 parts by weight of 4-vinylbenzyl-2 ', 2', 2'-trifluoroethyl ether, 6 parts by weight of ethylene glycol dimethacrylate , N-vinylpyrrolidone 6.2 parts by weight,
4.8 parts by weight of methacrylic acid were uniformly mixed, and 0.3 parts by weight of azobisdimethylvaleronitrile was added to prepare a liquid mixture. The liquid mixture was poured into a glass test tube and sealed.

After pre-polymerizing the compounded solution in a constant temperature water bath at 35 ° C. for 40 hours, the test tube was transferred into a circulating drier, and was heated at 50 ° C. for 6 hours.
Thereafter, the temperature was increased to 130 ° C. at a rate of 10 ° C. per 1 to 1.5 hours, and the mixture was heated and polymerized to obtain a rod-shaped copolymer.

The rod-shaped copolymer was cut and subjected to mechanical processing by cutting and polishing to prepare block-shaped and film-shaped test pieces having a diameter of 12.7 mm. Such mechanical processing could be performed very easily.

The obtained test piece had a transparent appearance and no distortion, and was preferable for obtaining an ophthalmic lens material.

Next, as physical properties of the test piece, Rockwell hardness, oxygen permeability coefficient, refractive index, and impact strength were measured according to the following methods. Table 1 shows the results.

[Rockwell hardness] Using a 4 mm-thick block-shaped test piece, load was 30 kg, indenter 1/4 inch, and temperature was 25 ° C by a Rockwell superficial hardness tester (ASD, manufactured by Akashi Seisakusho Co., Ltd.).
Was measured under the above measurement conditions.

[Oxygen Permeability Coefficient] Using several types of film-shaped test pieces having different thicknesses, the measurement was performed in physiological saline at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Co., Ltd. Units It is.

The oxygen permeability coefficient in Tables 1 and 2 is a value obtained by multiplying the original oxygen permeability coefficient by 10 ¹¹ .

[Refractive index] The refractive index of the test piece (▲ n
²⁰ _D ▼) with Abe refraction system (Atago Co., Ltd., trade name: 1-
T).

[Impact strength] A steel ball with a load of 6.75 g is dropped on a 0.5 mm thick test piece,
The height (mm) at which the test piece was broken was measured as impact strength.

Comparative Example 1 A hard contact lens that can be worn continuously and has excellent oxygen permeability (trade name: Menicon EX,
Example 1 was added to a rod-shaped copolymer for production (manufactured by Menicon Corporation).
A test piece was prepared in the same manner as described above, and its various physical properties were measured. The results are shown in Table 1.

In addition, in Table 1 and Table 2, each abbreviation means the following.

SiSt1: tris (trimethylsiloxy) silylstyrene SiSt2: trimethylsilylstyrene FSt1: 4-vinylbenzyl-2, '2', 2'-trifluoroethylether FSt2: 4-vinylbenzyl-2 ', 2', 3 ', 3 ′, 4 ′, 4 ′,
4'-Heptafluorobutyl ether FSt3: 4-vinylbenzyl-3 ', 3', 3'-trifluoropropylether FSt4: 4-vinylbenzyl-3 ', 3', 4 ', 4', 5 ', 5' ,
6 ', 6', 6'-Nonafluorohexyl ether EDMA: Ethylene glycol dimethacrylate VBMA: 4-vinylbenzyl methacrylate DVBz: Divinylbenzene N-VP: N-vinylpyrrolidone MAA: Methacrylic acid V-65: Azobisdimethylvalero Nitrile Further, the unit of the amount of each compounding component is part by weight.

As is clear from comparison between Example 1 and Comparative Example 1, the contact lens obtained in Example 1 of the present invention has a much higher oxygen permeability coefficient and a higher refractive index than conventional high oxygen permeable contact lenses. It can be seen that they are high and have excellent impact strength.

Examples 2 to 13 In the same manner as in Example 1, the components shown in Table 2 were uniformly blended and polymerized to obtain a copolymer, which was mechanically processed to obtain a test piece. Various physical properties of the test piece were measured in the same manner as in Example 1. Table 2 shows the results.

Such mechanical processing could be performed very easily. Further, the obtained test piece was transparent in appearance and free from distortion, and was extremely preferable in obtaining an ophthalmic lens material.

From the above results, the refractive index obtained in Comparative Example 1 was
1.438 (▲ n ²⁰ _D ▼), whereas the a, those obtained in Examples 1 to 13 of the present invention are all 1.440 (▲ n ²⁰ _D ▼) or more and high can be seen.

Also. It can be seen that the impact strength obtained in Comparative Example 1 was 22 mm, whereas that obtained in Examples 1 to 13 of the present invention was as high as 27 mm or more.

The oxygen permeability coefficient obtained in Comparative Example 1 was 52
× to 10 ^-11 is the (unit Domae), those obtained in Examples 1 to 13 of the present invention is seen to be very high and both 80 × 10 ^-11 (unit Domae) or more.

[Effects of the Invention] The ophthalmic lens material of the present invention is a transparent ophthalmic lens material which has a particularly high optical refractive index, excellent mechanical strength, high oxygen permeability and easy mechanical processing. is there.

Therefore, the ophthalmic lens material of the present invention has an optically high refractive index, so that it is possible to obtain a thinner contact lens, and it is possible to improve both the feeling of wearing and the oxygen permeability by making it thin. Has advantages.

Further, since the ophthalmic lens material of the present invention is excellent in mechanical strength, it has an effect that the shape of the lens is stable and the lens is not damaged by various physical treatments.

Furthermore, since the ophthalmic lens material of the present invention has high gas permeability, and particularly excellent oxygen permeability, it has an effect of not impairing the metabolic function of the cornea when used as a contact lens.

──────────────────────────────────────────────────続 き Continued on the front page (72) Yasushi Yamamoto 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (72) Inventor Hiroshi Yoshioka Annaka-shi, Gunma 2-13-1 Isobe Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (56) References JP-A-60-142324 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) ) G02C 7/04 C08F 12/14

Claims (3)

(57) [Claims] 1. A silicon-containing styrene derivative and a compound represented by the general formula (II): (In the formula, j represents an integer of 1 to 3, and k represents an integer of 0 to 7.)
An ophthalmic lens material comprising a copolymer containing a fluorine-containing styrene derivative represented by the following as an essential copolymer component. 2. The method according to claim 1, wherein the silicon-containing styrene derivative has the general formula (III) (Where p is an integer of 1 to 15, q is 0 or 1, r is 1 to
The ophthalmic lens material according to claim 1, which is a compound represented by the following formula: 3. The method according to claim 1, wherein the silicon-containing styrene derivative has the general formula (I) The ophthalmic lens material according to claim 1, wherein the compound is a compound represented by the formula: wherein m is 0 or 1, and n is an integer of 0 to 3.