JP3040259B2 - Ophthalmic lens materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to ophthalmic lens materials. More specifically, the present invention relates to an ophthalmic lens material having high gas permeability, high mechanical strength, and excellent mechanical workability, and which can be suitably used as a contact lens, an ophthalmic lens, an artificial cornea, and the like.

[0002]

2. Description of the Related Art In recent years, silicon-containing styrene derivatives such as tris (trimethylsiloxy) silylstyrene and fluorinated alkyl ether-containing styrene derivatives have been used as contact lens materials having high oxygen permeability and rigidity and a high refractive index. (JP-A-2-198415).

[0003] The above-mentioned contact lens material is excellent in oxygen permeability and rigidity, but if the amount of the silicon-containing styrene derivative is increased in order to further improve oxygen permeability, The mechanical strength of the resulting contact lens material is reduced, while when the amount of the fluorinated alkyl ether-containing styrene derivative is increased, the oxygen permeability coefficient may decrease, resulting in better gas permeability. The development of ophthalmic lens materials that can be suitably used for contact lenses, etc., which has excellent properties, especially excellent oxygen permeability and better mechanical strength, and also has excellent mechanical workability. Long-awaited.

[0004]

In view of the above-mentioned problems, the present inventors have developed an eye which simultaneously has high mechanical strength and high gas permeability, especially high oxygen permeability and excellent mechanical workability. As a result of intensive studies on lens materials for ophthalmology, the inventors finally found an ophthalmic lens material having these various properties at the same time, and completed the present invention.

[0005]

That is, the present invention provides a compound represented by the following general formula (I):

[0006]

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Wherein R represents a linear or branched hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by fluorine atoms. The present invention relates to an ophthalmic lens material made of a copolymer comprising, as a copolymerization component, a styrene derivative contained therein and a monomer having an unsaturated double bond copolymerizable therewith.

[0008]

Operation and Examples As described above, the ophthalmic lens material of the present invention has the general formula (I):

[0009]

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Wherein R represents a linear or branched hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by fluorine atoms. The copolymer is made of a copolymer containing a styrene derivative and a monomer having an unsaturated double bond copolymerizable therewith.

The fluorinated alkyl ester-containing styrene derivative imparts higher oxygen permeability and higher mechanical strength to the obtained ophthalmic lens material than the fluorinated alkyl ether-containing styrene derivative, and furthermore, provides mechanical processing. In the present invention, a component represented by the general formula (I) is used.

In the general formula (I), R is a linear or branched C1-C5 hydrocarbon group in which some or all of the hydrogen atoms are substituted with fluorine atoms. When the carbon number of R is 6 or more, the hardness of the obtained ophthalmic lens material decreases. Representative examples of R include, for example, a linear or branched C1-C5 fluoroalkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms.

Specific examples of the fluorinated alkyl ester-containing styrene derivative represented by the general formula (I) include, for example, 2,2,2-trifluoroethyl (4-vinylphenyl)
Acetate, 2,2,2,3,3,3-hexafluoroisopropyl (4-vinylphenyl) acetate, 2,2,3,3,4,4,5,5-octafluoropentyl (4-vinylphenyl) Acetate, etc., and these compounds are usually used alone or
A mixture of more than one species is used.

The amount of the fluorinated alkyl ester-containing styrene derivative is 5 to 95 parts, preferably 20 to 80 parts, more preferably 30 to 70 parts, per 100 parts (parts by weight, hereinafter the same) of the copolymer component. It is desirable that When the amount is less than 5 parts, the mechanical strength of the obtained ophthalmic lens material tends to decrease. When the amount exceeds 95 parts, a material having high oxygen permeability is obtained. Tends to be difficult.

Examples of the monomer having an unsaturated double bond copolymerizable with the fluorinated alkyl ester-containing styrene derivative (hereinafter referred to as other copolymer component) include, for example, a silicon-containing styrene derivative. Representative examples of the contained styrene derivative include, for example, those represented by the general formula
(II):

[0016]

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Wherein p is an integer of 1 to 15, q is 0 or 1, and r is an integer of 1 to 15; and the like. Such silicon-containing styrene derivatives,
It is a component that gives the obtained ophthalmic lens material high gas permeability, especially high oxygen permeability and high refractive index, and facilitates mechanical processing of the material.

In the general formula (II), when p or r is an integer of 16 or more, it becomes difficult to purify or synthesize the silicon-containing styrene derivative, and further, the hardness of the obtained ophthalmic lens material decreases. When q is an integer of 2 or more, synthesis of the silicon-containing styrene derivative tends to be difficult.

Among the compounds represented by the general formula (II), a compound which is easily available and most suitable for achieving the object of the present invention is, for example, a compound represented by the general formula (III):

[0020]

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(Wherein m is 0 or 1 and n is an integer of 0 to 3).

Specific examples of the compound represented by the general formula (III) include, for example, tris (trimethylsiloxy)
Silylstyrene (when m in the general formula (III) is 0 and n is 3), bis (trimethylsiloxy) methylsilylstyrene (when m in the general formula (III) is 0 and n is 2), (trimethyl Siloxy) dimethylsilylstyrene (general formula (II
In formula (I), m is 0 and n is 1), trimethylsilylstyrene (when m is 0 and n in formula (III) is 0), tris (trimethylsiloxy) siloxanyldimethylsilylstyrene (formula (III)) (When m in Formula (III) is 1 and n is 3), [bis (trimethylsiloxy) methylsiloxanyl] dimethylsilylstyrene (when m in Formula (III) is 1 and n is 2), penta Methyldisiloxanylstyrene (when m in the general formula (III) is 1 and n is 0), heptamethyltrisiloxanylstyrene (when m in the general formula (III) is 1 and n is 1) And so on.

Specific examples of the silicon-containing styrene derivative represented by the general formula (II) other than the compound represented by the general formula (III) include, for example, nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanyl Styrene, heneicosamethyl decasiloxanyl styrene, heptacosa methyl tridecasiloxanyl styrene,
Hentriacontamethylpentadecasiloxanylstyrene, trimethylsiloxypentamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, (tristrimethylsiloxy) siloxanylbis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) ) Methylsilyl styrene,
Tris (methylbistrimethylsiloxysiloxy) silylstyrene, trimethylsiloxybis (tristrimethylsiloxysiloxy) silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris (tris (Trimethylsiloxysiloxy) silylstyrene, (tristrimethylsiloxyhexamethyl) tetrasiloxy (tristrimethylsiloxy) siloxytrimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, Heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsilo Shi) silyl styrene, such as tripropyl tetramethylcyclotetrasiloxane siloxanyl styrene and the like, one or two or more from among these materials are selected.

The amount of the silicon-containing styrene derivative is 5 to 95 parts, preferably 20 parts, per 100 parts of the copolymer component.
It is desirable that the amount be from 80 to 80 parts, more preferably from 30 to 70 parts. When the amount is less than 5 parts, the refractive index and oxygen permeability of the obtained ophthalmic lens material tend to decrease, and when the amount exceeds 95 parts, the mechanical strength decreases. Tend.

Further, other copolymer components other than the silicon-containing styrene derivative include, for example, (meth) acrylic monomers, styrene monomers, vinyl monomers other than the styrene monomers, and the like. The type and amount of the monomer can be appropriately selected according to the physical properties of the intended 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, and n-butyl (meth) acrylate. A) 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,
Linear, branched, and cyclic alkyl (meth) acrylates such as decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate; pentamethyldiacrylate Siloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate,
Tris (trimethylsiloxy) silylpropyl (meth)
Acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methyl [bis (trimethylsiloxy)] silylpropylglyceryl (Meth) acrylate, tris (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglyceryl (Meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, Methylsilylpropylglyceryl (meth) acrylate, pentamethyldisiloxanylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanyl Silicon-containing (meth) acrylates such as propyl (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-trifluoromethylethyl (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-octafluoropentyl (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 , 8,8,9,9,10,1
0-hexadecafluorodecyl (meth) acrylate, 3,
3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl (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 (meta)
Acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,1
1,11,12,12-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 , 5,5,6,6,7,7,8,8,9,9,10,11,1
Fluorine-containing (meth) such as 1,11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate
Acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth)
Hydroxyl-containing (meth) acrylates such as acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate; (meth)
Acrylic acid; N- (meth) acryloylpyrrolidone; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide , N, N-diethyl (meth) acrylamide,
(Meth) acrylamides such as N-ethylaminoethyl (meth) acrylamide; aminoalkyl (such as aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate (Meth) acrylates; 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-tert-butylbenzophenone, 2-hydroxy-4- (meth) acryloyloxy-
2 ', 4'-dichlorobenzophenone, 2-hydroxy-4- (2
Benzophenone-based polymerizable ultraviolet absorbers such as -hydroxy-3- (meth) acryloyloxypropoxy) 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 Polymerizable ultraviolet absorbers based on salicylic acid derivatives such as phenyl- (meth) acryloyloxymethyl benzoate; such as methyl ester of 2-cyano-3-phenyl-3- (3- (meth) acryloyloxyphenyl) propenylate 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (Meth) acryloyloxynaphthalene, 1- (α
-Anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4 '-(phenylazo) -phenyl) azo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ', 4'-Xylylazo) -2- (meth)
Acryloyloxynaphthalene, 1- (o-tolylazo) -2-
(Meth) acryloyloxynaphthalene, 2- (m- (meth)
Acryloylamide-anilino) -4,6-bis (1 ′-(o-tolylazo) -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- (p-tolylazo) phenol, 4-phenylazo-7- (meth) acryloylamide-1-
Azo polymerizable dyes such as naphthol; 1,5-bis ((meth) acryloylamino) -9,10-anthraquinone, 1-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 ″ -aminoanthraquinone-1 ″ -yl)-
Anthraquinone-based polymerizable dyes such as amino-anilino) -6-hydrazino-1,3,5-triazine; nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate; (meth) acryloylated tetra Phthalocyanine-based polymerizable dyes such as amino copper phthalocyanine and (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine); 2,4-dihydroxy-3- (p- (meth) acryloyloxymethylphenylazo) benzophenone; 4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p-
(Meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-
Dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5-
(p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth)
Acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) Benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4- Dihydroxy-5- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3-
(p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy
-5- (p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy
-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy
-5- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy
-3- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloyloxyethylamino ) Phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-
Dihydroxy-5- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone,
2,4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloyl Amino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o-
Polymerizable ultraviolet-absorbing dyes such as (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone and the like can be mentioned, and one or more of them can be selected and used.

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

Specific examples of vinyl monomers other than the styrene monomer include N-vinylpyrrolidone and α
N-vinyllactams such as -methylene-N-methylpyrrolidone and N-vinylcaprolactam; 4-vinylpyridine; heterocyclic N-vinyl monomers such as vinylimidazole, N-vinylpiperidone, N-vinylpiperidine and N-vinylsuccinimide 2- (m-vinylanilino) -4-((p-nitrophenylazo) -anilino) -6-chloro-1,3,5-triazine;
2- (1 '-(o-tolylazo) -2-naphthyloxy) -4- (m-vinylanilino) -6-chloro-1,3,5-triazine, 2- (p-vinylanilino) -4- (1 '-(O-Tolylazo) -2'-naphthylanilino) -6-chloro-1,3,5-triazine, N- (1'-(o-tolylazo) -2'-naphthyl) -3-vinylphthalic acid Monoamide, N- (1 ′-(o-tolylazo) -2′-naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4- (p-sulfophenylazo) -1′-naphthyl) monoester, 6-vinylphthalic acid-(4 '-(p-sulfophenylazo) -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-triazine, 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'-
Azo such as hydroxypyrazolylazo) anilino) -6-isopropenyl-1,3,5-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- (4'-vinylbenzoyloxyethylamino) -9,10-
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) -6-chloro-1,3,5-triazine and other anthraquinone-based polymerizable dyes; 2,4-dihydroxy-3- (p-styrenoazo ) Polymerizable ultraviolet absorbing dyes such as benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, and phenyl 2-hydroxy-4- (p-styrenoazo) benzoate. One or two or more are selected and used depending on the conditions.

In the present invention, as described above, other copolymer components such as the above-mentioned various monomers are appropriately selected depending on the intended ophthalmic lens material such as a contact lens material and an intraocular lens material. Used as

For example, when oxygen permeability is additionally provided to the obtained ophthalmic lens material, one or two of the above-mentioned silicon-containing (meth) acrylate and fluorine-containing (meth) acrylate may be used. The above is selectively used. The amount of these other copolymer components is 2 to 50 parts, preferably 5 parts, per 100 parts of the copolymer components.
It is desirable that the amount be from 40 to 40 parts, more preferably from 10 to 30 parts. When the amount is less than 2 parts, the effect of improving the oxygen permeability by adding the other copolymer component tends to be hardly expected. In general, the blending amount of the fluorinated alkyl ester-containing styrene derivative is reduced, and the mechanical strength tends to decrease.

In order to obtain an ophthalmic lens material having excellent mechanical strength, for example, the above-mentioned alkyl (meth) acrylate, styrene derivative, (meth)
One or more of acrylic acid and the like are selected and used. The amount of these other copolymer components is
It is desirable that the amount is 3 to 60 parts, preferably 5 to 50 parts, more preferably 5 to 40 parts per 100 parts. When the amount is less than 3 parts, the effect of adding the other copolymer component tends not to be sufficiently exerted. There is a tendency that the blending amount of the fluorinated alkyl ester-containing styrene derivative is reduced and oxygen permeability is reduced.

In order to impart hydrophilicity to the obtained ophthalmic lens material or to obtain a water-containing and soft ophthalmic lens material, a monomer having a hydrophilic group may be used. Other copolymerization components may be blended. 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, (meth) acrylic acid, and N-vinyl lactam. And one or more of these are selected and used. The amount of the monomer having a hydrophilic group is 3 to 20 parts, preferably 5 to 15 parts, per 100 parts of the copolymer component.
Part is desirable. When the amount is less than 3 parts, the expression of hydrophilicity on the surface of the obtained ophthalmic lens material tends to decrease, and when the amount exceeds 20 parts, the obtained ophthalmic lens material tends to decrease. Tend to absorb water and become soft or turbid.

In order to make the obtained ophthalmic lens material less likely to be contaminated with lipids, for example, the above-mentioned fluorine-containing (meth) acrylate may be blended. The amount of the fluorine-containing (meth) acrylate is determined by the amount of the copolymer component.
It is desirable that the amount be 5 to 80 parts, preferably 10 to 60 parts, more preferably 30 to 50 parts per 100 parts. When the amount is less than 5 parts, the effect of the addition of the other copolymer component tends to be insufficiently exhibited. There is a tendency that the blending amount of the fluorinated alkyl ester-containing styrene derivative decreases and the mechanical strength decreases.

In order to obtain an ophthalmic lens material having a higher refractive index, a monomer containing an aromatic ring, for example, a styrene monomer may be blended.
Representative examples of the styrene-based monomer include, for example, the styrene derivatives, and one or more of these are selected and used. The amount of the styrene derivative is from 2 to 50 per 100 parts of the copolymer component.
Parts, preferably 5 to 40 parts, more preferably 10 to 30 parts. When the amount is less than 2 parts, the effect of adding the other copolymer component tends to be insufficient, and when the amount exceeds 50 parts, the relative amount is relatively small. There is a tendency that the blending amount of the fluorinated alkyl ester-containing styrene derivative is reduced and oxygen permeability is reduced.

In the case where the obtained ophthalmic lens material is to be provided with an ultraviolet absorbing property or the ophthalmic lens material is to be colored, the polymerizable ultraviolet absorbing agent, the polymerizable dye and the polymerizable ultraviolet light are used. One kind or two or more kinds are selected from the absorbing dyes and used. The amount of these other copolymer components is greatly affected by the thickness of the lens,
The amount is preferably 3 parts or less, more preferably 0.1 to 2 parts, per 100 parts of the copolymer component. If the amount is more than 3 parts, physical properties such as mechanical strength tend to decrease, and in consideration of the toxicity of ultraviolet absorbers and dyes, contact that directly contacts biological tissues It tends to be unsuitable as an ophthalmic lens material used for a lens or an intraocular lens implanted in a living body. Further, particularly in the case of pigments, if the amount is too large, the color of the ophthalmic lens material becomes too deep, the transparency is lowered, and the obtained lens tends to be difficult to transmit visible light.

The copolymer component used in the ophthalmic lens material of the present invention may contain a crosslinking agent.

The above-mentioned crosslinking agent is a component which makes the obtained ophthalmic lens material tough, improves mechanical strength and hardness, and provides a material having excellent optical properties which is uniform, has no distortion, and is transparent and free from cloudiness. The crosslinking 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 the amount of eluted substances.

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, triethylene glycol di (meth) 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, diallyl adipate, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, 2,2-bis (p- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (m-
(Meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (o- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (p- (meth) acryloyloxyphenyl) propane, 2,2 -Bis (m- (meth) acryloyloxyphenyl) propane,
2,2-bis (o- (meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyhexa) Fluoroisopropyl)
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 these can be selected. Used as

When a (meth) acrylic monomer is used as a copolymer component, among the above-mentioned crosslinking agents,
Especially 4-vinylbenzyl (meth) acrylate and
3-Vinylbenzyl (meth) acrylate is such that the (meth) acryloyl group in these molecules has excellent compatibility with the (meth) acrylic monomer, and the vinyl group bonded to the benzene ring, the so-called styrene skeleton Has excellent compatibility with styrene monomers. Further, there is usually a difference in the polymerization rate between the (meth) acryloyl group of the (meth) acrylic monomer and the vinyl group of the styrene monomer, but in the case of the vinylbenzyl (meth) acrylate, The polymerization rate of the (meth) acryloyl group and the vinyl group bonded to the benzene ring in the molecule is the same as the polymerization rate of the (meth) acryloyl group and the vinyl group bonded to the benzene ring in another molecule blended as a copolymerization component. Almost match.

Therefore, even in the copolymerization of a mixture containing a (meth) acrylic monomer and a styrene monomer, when the vinylbenzyl (meth) acrylate is used, the copolymerization proceeds smoothly. As a result, a crosslinked structure is formed, and a material that is tough, has improved mechanical strength and hardness, is uniform, has no distortion, and is transparent and has excellent optical properties without clouding.

The compounding amount of the crosslinking agent is the same as that of the copolymer component 1
About 0.5 to 20 parts, more preferably 2 to 20 parts
Desirably 15 parts. The amount of such a crosslinking agent is 0.
When the amount is less than 5 parts, the effect exerted by using the cross-linking agent tends to be small, and when the amount is more than 20 parts, the physical properties improved by other components subjected to copolymerization, for example, Oxygen permeability and the like are reduced, and the obtained ophthalmic lens material tends to be brittle and weak against stress such as impact.

In the present invention, a desired amount of the fluorinated alkyl ester-containing styrene derivative and other copolymer components is adjusted within the above-mentioned range, and a polymerization initiator is added thereto to polymerize the copolymer. A polymer can be obtained.

Representative examples of the copolymerization method include a bulk polymerization method and a solution polymerization method using a solvent.

The copolymerization may be carried out, for example, by using a radical polymerization initiator as required, gradually heating the blended solution in a temperature range from room temperature to about 130 ° C., or using microwaves, ultraviolet rays, radiation (γ
The polymerization can be carried out by irradiating electromagnetic waves such as When heating and polymerizing, the temperature may be raised stepwise.

Specific examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, te
Examples thereof include rt-butyl hydroperoxide, cumene hydroperoxide, and benzoyl peroxide, and one or more of these are selected and used.

The amount of the polymerization initiator used is determined by the amount of the copolymer component 10
It is desirably about 0.01 to 1 part, preferably 0.1 to 0.5 part with respect to 0 parts. When the amount is less than 0.01 part, the polymerization tends to be difficult to complete, and when the amount exceeds 1 part, the obtained copolymer contains bubbles and strain. Tend.

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 and polishing. Is a method of processing into a desired shape.

The mold method is a method in which a mold corresponding to a desired ophthalmic lens shape is prepared, and polymerization is performed in this mold to obtain a molded product. Finishing is performed mechanically.

Further, when the ophthalmic lens material of the present invention is used as an intraocular lens material, a supporting portion of the lens may be manufactured separately from the lens and attached to the lens. At the same time, they may be molded (integrally).

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

The ophthalmic lens material of the present invention thus obtained has advantages such as high gas permeability (high oxygen permeability), desirable mechanical strength as an ophthalmic lens material, and easy mechanical processing. It has both.

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

Example 1 [Preparation of copolymer] 61 parts of 2,2,2,3,3,3-hexafluoroisopropyl (4-vinylphenyl) acetate, 39 parts of tris (trimethylsiloxy) silylstyrene, N- 5.6 parts of vinylpyrrolidone,
4.4 parts of methacrylic acid, 6 parts of 4-vinylbenzyl methacrylate and 1 part of ethylene glycol dimethacrylate are uniformly mixed, and 0.1 part of azobisdimethylvaleronitrile is added to prepare a liquid mixture. The liquid mixture is placed in a glass test tube. Injected and sealed.

The above-mentioned mixture was placed in a thermostatic water bath at 35 ° C. for 40 hours.
After prepolymerization at 50 ° C for 8 hours, transfer the test tube into a circulating drier, heat at 50 ° C for 5 hours, and then raise the temperature to 120 ° C at a rate of 10 ° C per 1 to 1.5 hours, and mix the solution. 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 was transparent in appearance and free from distortion, and was preferable for obtaining an ophthalmic lens material.

Next, the oxygen permeability coefficient,
Rockwell hardness and impact strength were measured according to the methods shown below. Table 1 shows the results.

(A) Oxygen Permeability Coefficient Oxygen permeability coefficient of a film having a thickness of 0.2 mm was measured in physiological saline at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Industry Co., Ltd. The unit is [ml (S
TP) · cm] / [cm ² · sec · mmHg], and Table 1 shows a value obtained by multiplying the original value of the oxygen permeability coefficient by 10 ¹¹ .

(B) Rockwell hardness (30X) Using a test piece having a thickness of 4.0 mm, a Rockwell superficial hardness tester (ASD manufactured by Akashi Seisakusho Co., Ltd., ASD) was used to load 30 kg, indenter 1/4 inch, It was measured under measurement conditions of 25 ° C.

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

Examples 2 to 3 In the same manner as in Example 1, the components shown in Table 1 were uniformly mixed and polymerized to obtain a copolymer, which was subjected to mechanical processing to obtain a test piece. Various physical properties of the test piece were measured in Example 1.
The measurement was performed in the same manner as described above. Table 1 shows the results.

The mechanical working 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.

Comparative Examples 1-2 In the same manner as in Example 1, a fluorinated alkyl ether-containing styrene derivative (Comparative Example 1) or a fluorine-containing alkyl methacrylate (Comparative Example 2) was used instead of the fluorinated alkyl ester-containing styrene derivative. The components shown in Table 1 were uniformly mixed and polymerized to obtain a copolymer, which was subjected to mechanical processing to obtain a test piece. Various physical properties of the test piece were measured in the same manner as in Example 1. Table 1 shows the results.
Shown in

The abbreviations in Table 1 mean the following.

FSt1: 2,2,2,3,3,3-hexafluoroisopropyl (4-vinylphenyl) acetate FSt2: p-vinylbenzyl-1,1,1-trifluoroisopropylether SiSt: tris (trimethylsiloxy) ) Silylstyrene SiMA: tris (trimethylsiloxy) silylpropyl methacrylate FMA: 2,2,2,3,3,3-hexafluoroisopropyl methacrylate N-VP: N-vinylpyrrolidone MAA: methacrylic acid MMA: methyl methacrylate VBMA: 4 -Vinylbenzyl methacrylate EDMA: Ethylene glycol dimethacrylate DVBZ: Divinylbenzene V-65: Azobisdimethylvaleronitrile Also, the unit of the amount of each compounding component is part.

[0067]

[Table 1]

Examples 1 to 3 and Comparative Examples 1 and 2 shown in Table 1
As apparent from comparison of the results of Examples 1 to 3 of the present invention,
The ophthalmic lens material obtained in No. 3 has a higher oxygen permeation coefficient, Rockwell hardness and hardness than those obtained in Conventional Comparative Examples 1 and 2.
It can be seen that all of the impact strengths are excellent.

[0069]

The ophthalmic lens material of the present invention is a transparent ophthalmic lens material having high oxygen permeability, high mechanical strength and good mechanical workability at the same time.

Therefore, the ophthalmic lens material of the present invention is
Since it has high gas permeability and is particularly excellent in oxygen permeability, when it is used as a contact lens, there is an effect that the metabolic function of the cornea is not impaired.

Moreover, since the ophthalmic lens material of the present invention has excellent mechanical strength, it has an effect that the shape of the lens is stable and the lens is hardly damaged by various physical treatments.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A61L 27/00 G02B 1/04 G02C 7/04

Claims (1)

(57) [Claims] [Claim 1] General formula (I): (Wherein, R represents a linear or branched C1-C5 hydrocarbon group in which some or all of the hydrogen atoms have been substituted with fluorine atoms). An ophthalmic lens material comprising a copolymer comprising, as a copolymerization component, a monomer having an unsaturated double bond copolymerizable therewith.