JP3084161B2 - Ophthalmic lens materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to ophthalmic lens materials. More specifically, it is optically uniform and transparent, has suitable oxygen permeability and stain resistance, and is more excellent in impact resistance, such as contact lenses, intraocular lenses,
The present invention relates to an ophthalmic lens material that can be suitably used for an artificial cornea and the like.

[0002]

2. Description of the Related Art Conventionally, various ophthalmic lens materials have been proposed as contact lens materials, intraocular lens materials, and the like. Development of ophthalmic lens materials that can provide a contact lens that is difficult to adhere to and that can be worn for a long time has been advanced.

[0003] Therefore, in order to obtain such an ophthalmic lens material, a method for producing an oxygen-permeable polymer material characterized by copolymerizing two kinds of fluorine-containing polymerizable monomers (Japanese Patent Laid-Open Publication No.
No. 145108) and contact lens materials obtained from perfluoropolyether di (meth) acrylate monomers (JP-A-3-28819, JP-A-3-3819).
No. 9928).

[0004] However, although the above-mentioned polymer materials and contact lens materials do have good oxygen permeability and stain resistance, their impact resistance is not improved, and they are excellent in practical use. Development of an ophthalmic lens material that has both oxygen permeability and contamination resistance and excellent impact resistance has been awaited.

[0005]

Therefore, in view of the above prior art, the present inventors have, of course, not only excellent transparency, oxygen permeability and contamination resistance, but also superior impact resistance. As a result of intensive studies on the ophthalmic lens materials as much as possible, such materials were finally found, and the present invention was completed.

[0006]

That is, the present invention relates to a silicon-containing styrene derivative in an amount of 30 to 99% by weight, represented by the general formula (I):

[0007]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or a methyl group, n and m each independently represent an integer of 1-3, and p represents an integer of 2-6) The present invention relates to an ophthalmic lens material obtained by copolymerizing a copolymer component containing 0.1 to 20% by weight of a fluorine-containing crosslinkable monomer represented by the following formula and 0 to 70% by weight of a fluorine-containing non-crosslinkable monomer.

[0009]

Operation and Examples As described above, the ophthalmic lens material according to the present invention has a silicon-containing styrene derivative in an amount of 30 to 99% by weight and a general formula (I):

[0010]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or a methyl group, n and m each independently represent an integer of 1-3, and p represents an integer of 2-6) Can be obtained by copolymerizing a copolymer component containing 0.1 to 20% by weight of a fluorine-containing crosslinkable monomer represented by the formula (1) and 0 to 70% by weight of a fluorine-containing non-crosslinkable monomer.

[0012] The silicon-containing styrene derivative (hereinafter, referred to as
The monomer (A)) is a component for improving the oxygen permeability and mechanical strength of the obtained ophthalmic lens material and obtaining a material having a high refractive index.

The monomer (A) includes, for example, a compound represented by the following general formula (II):

[0014]

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Wherein s is an integer of 1 to 15, q is 0 or 1, and r is an integer of 1 to 15 (provided that q = 0 and r =
Compounds represented by the following formulas are excluded.

In the compound represented by the general formula (II), when s or r is an integer of 16 or more, purification or synthesis of the compound becomes difficult, and q is an integer of 2 or more. In such cases, their synthesis tends to be difficult.

Representative examples of the compound represented by the general formula (II) include, for example, tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, tris (trimethylsiloxy) Siloxydimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxy] dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, heneicosamethyldecasiloxa Nylstyrene, heptacosamethyltridecasiloxanylstyrene, hentriacontamethylpentadecasiloxanylstyrene, trimethylsiloxypentamethyldisiloxymethylsilylstyrene, Lis (pentamethyldisiloxy) silylstyrene, (tristrimethylsiloxy) siloxybis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris [methylbis (trimethylsiloxy) siloxy] silylstyrene, trimethylsiloxybis [ Tris (trimethylsiloxy) siloxy] silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris [tris (trimethylsiloxy) siloxy] silylstyrene, tris (trimethylsiloxy) ) Hexamethyltetrasiloxy (tristrimethylsiloxy) siloxy trimethylsiloxysilylstyrene, nonakis (trimethylsilyl) Carboxymethyl)
Tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene And the like, either alone or in 2
Although it is possible to use a mixture of more than one species, among these, it is possible to further improve the mechanical strength of the obtained ophthalmic lens material, and to obtain a material having a high oxygen permeability and a high refractive index. Tris (trimethylsiloxy) silylstyrene is preferred.

The amount of the monomer (A) is desirably 30 to 99% by weight, preferably 40 to 85% by weight of the total amount of the copolymer components. When the amount of the monomer (A) is less than 30% by weight, it becomes difficult to obtain an ophthalmic lens material having a satisfactory high oxygen permeability, and more than 99% by weight. In such a case, the mechanical strength of the obtained ophthalmic lens material is reduced.

The fluorine-containing crosslinkable monomer represented by the above general formula (I) (hereinafter referred to as monomer (B)) improves the mechanical strength of the obtained ophthalmic lens material without significantly lowering its oxygen permeability. Component.

Specific examples of the monomer (B) include, for example, 3,3,4,4,5,5,6,6-octafluoro-1,8-octanediol di (meth) acrylate, 2,2,2 3,3,4,4-hexafluoro-1,5
Pentanediol di (meth) acrylate, 2,2,
3,3,4,4,5,5-octafluoro-1,6-hexanediol di (meth) acrylate, 3,3,4
4,5,5,6,6-octafluoro-1,8-octanediol di (α-fluoro) (meth) acrylate,
3,3,4,4,5,5,6,6,7,7-decafluoro-1,9-nonanediol di (meth) acrylate, etc., and these may be used alone or in combination of two or more. Can be used.

The amount of the monomer (B) is desirably 0.1 to 20% by weight, preferably 0.5 to 15% by weight of the total amount of the copolymer components. The amount of the monomer (B) is
If it is less than 0.1% by weight, it becomes difficult to obtain an ophthalmic lens material having satisfactory mechanical strength, and if it exceeds 20% by weight, the oxygen transmission of the obtained ophthalmic lens material becomes difficult. And impact resistance are reduced.

The term "-(meth) acrylate" as used herein means "-acrylate and / or methacrylate", and the same applies to other (meth) acrylate derivatives.

The above-mentioned fluorine-containing non-crosslinkable monomer (hereinafter, referred to as
The monomer (C) is a component for improving the oxygen permeability and stain resistance of the obtained ophthalmic lens material.

As the monomer (C), for example, a compound represented by the following general formula (III):

[0025]

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(Wherein R ³ is a hydrogen atom or a methyl group;
R ⁴ is a linear or branched fluoroalkyl group having 2 to 21 fluorine atoms, i is 0 or 1, and j is 0 to
A fluorine-containing (meth) acrylate represented by an integer of 3) or a fluorine-containing styrene derivative.

Representative examples of the fluorine-containing (meth) acrylate represented by the general formula (III) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (Meta)
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,
2,3,3,4,4,5,5,6,6,7,7,7,7-tridecafluoroheptyl (meth) acrylate;
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-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 (meth) acrylate, 3,3,4,4,5,5
6,6,7,7,8,8,9,9,10,10,11,11,1
2,12-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, 11, 11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate.

Specific examples of the fluorine-containing styrene derivative include, for example, 4-vinylbenzyl-2 ', 2', 2
'-Trifluoroethyl ether, 4-vinylbenzyl-2', 2 ', 3', 3 ', 4', 4 ', 4'-heptafluorobutylether, 4-vinylbenzyl-3',
3 ', 3'-trifluoropropyl ether, 4-vinylbenzyl-3', 3 ', 4', 4 ', 5', 5 ', 6
', 6', 6'-Nonafluorohexyl ether, o-
Fluorostyrene, m-fluorostyrene, p-fluorostyrene, trifluorostyrene, perfluorostyrene, o-trifluoromethylstyrene, m-trifluoromethylstyrene, p-trifluoromethylstyrene, 2,2,2-trifluoro Ethyl (4'-vinylphenyl) acetate, 2,2,2-trifluoro-1-
Trifluoromethylethyl (4'-vinylphenyl) acetate, 2,2,3,3,4,4,5,5-octafluoropentyl (4'-vinylphenyl) acetate,
2,2,2-trifluoroethyl (4'-vinylbenzoate), 2,2,2-trifluoro-1-trifluoromethylethyl (4'-vinylbenzoate), 2,
2,3,3,4,4,5,5-octafluoropentyl (4'-vinylbenzoate) and the like.

These monomers (C) can be used alone or in admixture of two or more. Among them, the resulting ophthalmic lens material is further improved in stain resistance and has high oxygen permeability. 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoro-1-trifluoromethylethyl (meth) acrylate and 2,2,2- Trifluoro-1-trifluoromethylethyl (4'-vinylbenzoate) is preferred.

The amount of the monomer (C) is preferably from 0 to 70% by weight, more preferably from 10 to 60% by weight, based on the total amount of the copolymer components. When the amount of the monomer (C) exceeds 70% by weight, the refractive index and oxygen permeability of the obtained ophthalmic lens material are reduced.

In the present invention, in order to further improve the oxygen permeability of the obtained ophthalmic lens material, a silicon-containing (meth) acrylate (hereinafter, referred to as a monomer (D)) can be used as an optional component.

Examples of the monomer (D) include pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, and tris ( Trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methylbis (trimethyl) Siloxy) silylpropylglycerol (meth) acrylate, tris (trimethylsiloxy)
Silylpropyl glycerol (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropylglycerol (meth) acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglycerol (meth) acrylate, trimethylsilylmethyl (meth) Acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropylglycerol (meth) acrylate, pentamethyldisiloxanylpropylglycerol (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetra Methyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyl Such as triisopropyl cyclotetra siloxy bis (trimethyl siloxy) silyl propyl (meth) acrylate and the like. These may be used alone or in admixture of two or more.

The amount of the monomer (D) is preferably 50% by weight or less, more preferably 10 to 40% by weight, based on the total amount of the copolymer components. If the amount of the monomer (D) exceeds 50% by weight, the resulting ophthalmic lens material tends to have a reduced impact resistance.

In the present invention, in addition to the monomer (B), an ordinary crosslinking agent may be used in addition to the monomer (B) in consideration of the type and blending amount of the copolymer component used, the material of the target ophthalmic lens material, and the like. Can be used.

Specific examples of the crosslinking agent include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. Meth) acrylate, allyl (meth) acrylate,
Vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, 4-vinylbenzyl (meth) acrylate, diallyl adipate, 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- (meta ) Acryloyloxyhexafluoroisopropyl) benzene,
1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-bis (2-
(Meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2-
(Meth) acryloyloxyisopropyl) benzene,
Examples thereof include 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene, which can be used alone or in combination of two or more. Among them, ethylene glycol di (meth) Acrylate and 4-vinylbenzyl (meth) acrylate are preferred.

The amount of the crosslinking agent is preferably adjusted so as not to exceed the amount of the monomer (B) so that the effect of using the monomer (B) is sufficiently exhibited. It is preferably about 0 to 10% by weight of the total amount of the polymerization components.

In the present invention, the monomer (A), the monomer (B) and the monomer (C), and if necessary, the copolymerization component containing the monomer (D) and a crosslinking agent are copolymerized. A polymer is obtained,
In addition to these, other copolymer components can be appropriately used depending on the material of the objective ophthalmic lens material.

As the other copolymer component, for example, when it is intended to reinforce the mechanical strength of the obtained ophthalmic lens material, a reinforcing monomer can be used.

Specific examples of the reinforcing monomer include (meth) acrylic acid; styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene.
Ethylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, trimethylstyrene, tert-butylstyrene, perbromostyrene,
Styrene derivatives such as dimethylaminostyrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) A) acrylate, n-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,
Linear, branched and cyclic alkyl (meth) acrylates such as dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate; aromatic rings such as benzyl (meth) acrylate Included (meth) acrylates; alkyl esters such as itaconic acid, crotonic acid, maleic acid, and fumaric acid, and the like, and these can be used alone or as a mixture of two or more.

For example, when it is desired to impart hydrophilicity to the obtained ophthalmic lens material, a hydrophilic monomer can be used.

Specific examples of the hydrophilic monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and dihydroxypropyl (meth) acrylate.
Acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate,
Hydroxyl-containing (meth) acrylates such as triethylene glycol mono (meth) acrylate and dipropylene glycol mono (meth) acrylate; (meth) acrylic acid; N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone, N-vinylcaprolactam , N- (meta)
Vinyl lactams such as acryloylpyrrolidone; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, (Meth) acrylamides such as N-diethyl (meth) acrylamide and N-ethylaminoethyl (meth) acrylamide; aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) ) Aminoalkyl (meth) acrylates such as acrylates; alkoxy group-containing (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxydiethylene glycol (meth) acrylate Etc. can be mentioned, these can be used alone or in admixture of two or more.

The amount of other copolymer components such as the reinforcing monomer and hydrophilic monomer may be arbitrarily determined according to the intended use of the obtained ophthalmic lens material. 50% by weight or less, especially 10-30% by weight
It is preferred that If the amount exceeds 50% by weight, the oxygen permeability of the obtained ophthalmic lens material tends to decrease.

Further, in order to impart ultraviolet absorption to the obtained ophthalmic lens material, other copolymerizable components such as a polymerizable ultraviolet absorber may be used.

Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, Benzophenone-based polymerizable ultraviolet absorption such as hydroxy-4- (meth) acryloyloxy-2 ', 4'-dichlorobenzophenone, 2-hydroxy-4- (2'-hydroxy-3'-(meth) acryloyloxypropoxy) benzophenone Agent; 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
-(2'-hydroxy-5 '-(2 "-(meth) acryloyloxyethoxy) -3'-tert-butylphenyl)
Benzotriazole-based polymerizable ultraviolet absorbers such as -5-methyl-2H-benzotriazole; 2-hydroxy-
Salicylic acid derivative-based polymerizable ultraviolet absorbers such as phenyl 4-methacryloyloxymethyl benzoate;
And polymerizable ultraviolet absorbers such as cyano-3-phenyl-3- (3 '-(meth) acryloyloxyphenyl) propenyl acid methyl ester. These polymerizable ultraviolet absorbers may be used alone or in combination of two or more. Are used as a mixture.

The amount of the polymerizable ultraviolet absorber greatly depends on the thickness of the lens, but is usually preferably 3% by weight or less, more preferably 0.01 to 2% by weight of the total amount of the copolymer components. When the amount is more than 3% by weight, the physical properties of the obtained lens, such as mechanical strength, tend to be reduced. It tends to be unsuitable as a material for an ophthalmic lens such as a lens or an intraocular lens implanted in a living body.

In the present invention, the monomer (A),
An ophthalmic lens material can be obtained by copolymerizing copolymerizable components such as monomer (B) and monomer (C), monomer (D), a crosslinking agent, and other copolymerizable components.

As a method for producing the ophthalmic lens material of the present invention, for example, a method of uniformly blending the respective components, adding a polymerization initiator, and subjecting the mixture to polymerization by a conventional method to obtain a copolymer, etc. There is.

As a method for obtaining the above-mentioned copolymer, for example, a method in which a radical polymerization initiator is added to each component, and then the temperature is gradually raised from room temperature to about 130 ° C. in about 10 hours to complete the polymerization (heating weight) After the photopolymerization initiator is blended with each component, polymerization is performed by irradiating light rays having a wavelength corresponding to the absorption band of the photopolymerization initiator, for example, electromagnetic waves such as microwaves, ultraviolet rays, and radiation (γ rays). Method (photopolymerization method), a method combining the heat polymerization method and the photopolymerization method, and the like.

When the above-mentioned heat polymerization method is performed, heating may be performed in a thermostatic chamber or a thermostatic chamber, for example, irradiation with electromagnetic waves such as microwaves, and such heating may be performed stepwise. When the photopolymerization method is used, a sensitizer may be further added.

The production of the ophthalmic lens material can be carried out by, for example, a bulk polymerization method or a solution polymerization method. In order to efficiently produce the material, it is preferable to employ a usual bulk polymerization method.

Specific examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, te
rt-butyl hydroperoxide, cumene peroxide, benzoyl peroxide and the like.

Specific examples of the photopolymerization initiator include, for example, benzoin, methyl orthobenzoyl benzoate, methyl orthobenzoin benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-isobutyl ether. n-
Benzoin-based photopolymerization initiators such as butyl ether; 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, p-isopropyl-α-hydroxyisobutyrophenone, p-tert-butyltrichloroacetophenone,
2,2-dimethoxy-2-phenylacetophenone,
α, α-dichloro-4-phenoxyacetophenone,
Phenone-based photopolymerization initiators such as 4,4'-bisdiethylaminobenzophenone; 1-hydroxycyclohexylphenyl ketone; 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) .oxime;
Thioxanthone-based photopolymerization initiators such as chlorothioxanthone and 2-methylthioxanthone; dibenzosubalone;
2-ethylanthraquinone; benzophenone acrylate; benzophenone; benzyl and the like.

As the radical polymerization initiator or the photopolymerization initiator, one or more of them can be selected and used. The amount of such a polymerization initiator may be any amount that is sufficient to start the polymerization, and is usually about 0.01 to about 100 parts (parts by weight, hereinafter the same) based on the total amount of the copolymerization components.
It is preferably 1 part, especially about 0.05 to 0.5 part.

When molding the ophthalmic lens material thus obtained into an ophthalmic lens such as a contact lens or an intraocular lens, a molding method generally used by those skilled in the art is employed. Examples of such a molding method include a cutting method and a mold method. In the 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 processed into a desired shape by mechanical processing such as cutting or polishing. Is the way. The mold method is a method of preparing a mold corresponding to the shape of a desired ophthalmic lens, polymerizing the lens components in the mold to obtain a molded product, and mechanically finishing the product as necessary. It is.

Further, when the ophthalmic lens material of the present invention is used as an intraocular lens, a supporting portion of the lens may be manufactured separately from the lens and attached to the lens, or may be simultaneously (integrally) with the lens. It may be molded.

The ophthalmic lens material of the present invention may be subjected to a plasma treatment as required. As a processing apparatus and a processing method used for such plasma processing, conventionally known apparatuses and methods are employed, and processing conditions include, for example, an inert gas such as helium, neon, or argon, or air, oxygen, chip, or the like. In general, a condition that the treatment is performed for several seconds to several tens of minutes at a pressure of about 0.0001 to several Torr and an output of several V to about 100 V under an atmosphere of a gas such as carbon dioxide, carbon monoxide, and carbon dioxide. . More preferably, it is possible to employ a condition that the treatment is performed for several minutes at a pressure of about 0.05 to 3 Torr and an output of about 10 to 60 V in an atmosphere of a gas such as air, oxygen or argon.

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 95 parts of tris (trimethylsiloxy) silylstyrene,
3,3,4,4,5,5,6,6-octafluoro-
0.5 parts of 1,8-octanediol dimethacrylate,
4.5 parts of 2,2,2-trifluoroethyl methacrylate and 2,2'-azobis (2,4-
(Dimethylvaleronitrile) 0.1 part was uniformly mixed to obtain a mixed solution. About 50 ml of the compound solution was poured into a glass test tube and sealed.

Next, the test tube was transferred into a constant temperature water bath at 35 ° C. and preliminarily polymerized for 40 hours. Then, the test tube was transferred into a circulating drier at 50 ° C. for 6 hours, and then at a rate of 10 ° C. per 1 to 1.5 hours. The temperature is raised to 130 ° C and heat polymerization is performed.
Was obtained as a rod-shaped copolymer.

The obtained rod-shaped copolymer was cut and subjected to cutting and polishing to prepare a test piece. The obtained test piece had no distortion and was preferable as an ophthalmic lens material. The physical properties of this test piece were examined according to the following methods. Table 1 shows the results.

(A) Transparency The appearance of the test piece was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) 透明: Transparent. Δ: slightly cloudy X: considerably cloudy.

(B) Stain resistance An artificial tear (pH 7.3 buffer, lysozyme: 1.2 mg / ml, albumin: 3.88 mg / ml, imino) prepared in accordance with the FDA guidelines (CLASS III, 1985) A poly (methyl methacrylate) (PMMA) plate was immersed in globulin (1.61 mg / ml, sodium chloride: 9 mg / ml, calcium ion: 0.04 mg / ml) for 24 hours and washed with running water. The surface of the test piece and the surface of the PMMA plate were observed using a stereo microscope (× 20), and evaluated based on the following evaluation criteria.

(Evaluation Criteria) ：: There is no difference as compared with the PMMA plate, and no stain is observed on the surface of the test piece. Δ: There is a slight difference compared to the PMMA plate, and slight adhesion of dirt on the test piece surface is observed. X: There is a difference as compared with the PMMA plate, and remarkable adhesion of dirt is observed on the surface of the test piece.

(C) Oxygen Permeability Coefficient The oxygen permeability coefficient of a test piece having a thickness of 2 mm was measured in physiological saline at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Co., Ltd. The unit of the oxygen permeability coefficient is (ml (STP) · cm) / (cm ² · sec · mmHg).
The oxygen permeability coefficient in the figure is a value obtained by multiplying the value of the original oxygen permeability coefficient by 10 ¹¹ .

In the present invention, the oxygen permeability coefficient is 30.
A sample with a value of (ml (STP) · cm) / (cm ² · sec · mmHg) or more was judged as passing (shown by ○ in Table 1), and a sample with less than that was rejected (shown by × in Table 1). I do.

(D) Impact strength A steel ball having a load of 6.75 g was dropped on a test piece having a thickness of 0.5 mm.
The height (mm) when the test piece was broken was measured.

In the present invention, those having a height of 20 mm or more are regarded as acceptable (shown by ○ in Table 1), and those having a height less than 20 mm are unacceptable (shown by × in Table 1).

Examples 2 to 6 and Comparative Examples 1 to 4 In the same manner as in Example 1, except that each component was changed to have the composition shown in Table 1, the components were blended and copolymerized. Then, after obtaining a rod-shaped copolymer, this was subjected to cutting and polishing to obtain a test piece. Each physical property of the obtained test piece was examined in the same manner as in Example 1. Table 1 shows the results.

The test pieces obtained in Examples 2 to 6 were free from distortion as in the case of Example 1, and were preferred as ophthalmic lens materials.

[0071]

[Table 1]

The abbreviations in Table 1 are as follows.

SiSt: tris (trimethylsiloxy)
Silylstyrene 8FDMA: 3,3,4,4,5,5,6,6-octafluoro-1,8-octanediol dimethacrylate 3FE: 2,2,2-trifluoroethyl methacrylate 6FP: 2,2,2 -Trifluoro-1-trifluoromethylethyl methacrylate SiMA: tris (trimethylsiloxy) silylpropyl methacrylate MMA: methyl methacrylate EDMA: ethylene glycol dimethacrylate V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) As is clear from the results shown in Table 1, Examples 1 to 6
The obtained ophthalmic lens material has high oxygen permeability coefficient and impact strength, excellent transparency and stain resistance,
It can be seen that the impact strength is particularly large as compared with the ophthalmic lens materials obtained in Comparative Examples 1 to 4. In particular, Examples 1 to
The material obtained in Comparative Example 6 has a considerably higher impact strength as compared with the material comprising only the monomer (A) obtained in Comparative Example 4, while the composition of the monomer (B) obtained in Comparative Examples 2 and 3 It can be seen that the impact strength is high even when compared with a material having an excessive amount.

[0074]

The ophthalmic lens material of the present invention is optically uniform and transparent, and has not only excellent oxygen permeability and stain resistance, but also excellent impact resistance.
For example, when a contact lens is formed, the metabolic function of the cornea is not impaired, the surface is less sticky, dirt such as lipids is less likely to adhere, and the lens is less likely to be damaged by various physical treatments.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Eri Ito 3-12-7 Biwajima, Nishi-ku, Nagoya-shi, Aichi Prefecture Inside Menicon Biwajima Research Laboratories (72) Inventor Shoji Ichinohe 1 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 1 No. 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Yasushi Yamamoto 1-10, Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Toshio Yamazaki 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (56) References JP-A-4-190213 (JP, A) JP-A-4-168415 (JP , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02C 1/00-13/00 CA (STN)

Claims (2)

(57) [Claims] 1. A silicon-containing styrene derivative in an amount of 30 to 99% by weight, represented by the general formula (I): (Wherein R ¹ and R ² are each independently a hydrogen atom,
A fluorine atom or a methyl group, n and m each independently represent an integer of 1 to 3, and p represents an integer of 2 to 6) 0.1 to 20% by weight of a fluorine-containing crosslinkable monomer represented by the following formula: An ophthalmic lens material obtained by copolymerizing a copolymer component containing 0 to 70% by weight. 2. The ophthalmic lens material according to claim 1, wherein the copolymer component contains a silicon-containing (meth) acrylate.