JPH01299560A - Contact lens material - Google Patents

Abstract

PURPOSE:To provide a contact lens which does not permeate ultraviolet rays and has excellent durability and light resistance, by a method wherein a polymerizable ultraviolet ray absorbent, having a polymerizable group selected a group consisting of on acryloil group, a methacryloil group, a vinyl group, an aryl group, and a isopropenyl group and a polymerizable pigment are copolymerized with an other copolymerizable lens forming monomer component. CONSTITUTION:A polymerizable ultraviolet ray absorbent used for a contact lens material is a polymerizable ultraviolet ray absorbent having a polymerizable group selected from a group consisting of an acryloil group, a methacryloil group, a vinyl group, an aryl group, and an isopropenyl group, but a polymerizable ultraviolet ray absorbent, e.g., benzophenon series, benzotriazole series, derivative salicylate series, is preferably employed. Azo series, anthraquinone series, nitro series, phthalocyanine aeries, are preferably employed as a polymerizable pigment having a polymerizable group selected from a similar group to that of the polymerizable ultraviolet ray absorbent. In relation to a lens forming monomer, methylmethacrylate is selected as the main component of a lens.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a novel intraocular lens material, and in particular, it has a light transmittance close to that of the natural crystalline lens and is free from the elution of ultraviolet absorbers and pigments used. This invention relates to an extremely rare intraocular lens material with excellent durability.

(Background Art) When an eye disease such as a cataract causes the natural crystalline lens to become cloudy, it is necessary to surgically remove the cloudy natural lens. After the crystalline lens is removed, eyeglass lenses, contact lenses, intraocular lenses, etc. for vision correction are adopted as appropriate to restore vision. Intraocular lenses that are implanted have been in the spotlight in recent years as a lens that can restore vision most naturally, and many of them are now being prescribed.

By the way, there is a difference in vision between an eye whose natural crystalline lens has been removed and an intraocular lens inserted and a normal eye.
Patients often complain that the eye with an intraocular lens inserted feels dazzling or looks bluish. This is because the natural crystalline lens has the property of not transmitting almost any ultraviolet rays, and also to some extent of visible light, mainly in the blue wavelength range (approximately 380 to 500 nm). This is because polymethyl methacrylate (PMMA), which is the most commonly used lens material for inner lenses, transmits not only visible light but also most of the light in the ultraviolet range (see Figure 6). .

In other words, the natural lens of the eye is thought to protect the retina from harmful rays such as ultraviolet rays. Therefore, after removing the natural lens of the eye, ultraviolet rays, etc. that should normally be absorbed by the crystalline lens are removed. There is a fear that it may reach the retina and damage it.

Therefore, recently, intraocular lenses having the property of absorbing ultraviolet rays have been studied, as proposed in Japanese Patent Laid-Open Nos. 60-232149 and 61-52873.

However, since these intraocular lenses are made by adding ultraviolet absorbers to the lens material, there have always been concerns about the elution and toxicity of the ultraviolet absorbers.
If ultraviolet absorbers or the like elute from the intraocular lens into the eye, it will cause serious damage to the patient.

Also, according to Japanese Patent Publication No. 52-48824, a lens-forming monomer is added with a visible light absorber that absorbs visible light to some extent, and a polymerizable ultraviolet absorber is mixed and polymerized. A UV absorbing contact lens is disclosed.

However, even with such lenses, the problem of elution of visible light absorbers cannot be avoided, and especially in the case of intraocular lenses, elution has a large effect on the eye, so such visible light absorbers must not be used. There is a strict requirement to prevent elution as much as possible.

(Problem to be solved) The present invention was made against the background of the above, and the problem to be solved is to prevent ultraviolet rays from passing through, similar to the natural crystalline lens of the eye. Also, the wavelength of visible light is mainly in the blue region (approximately 380 to 50
It has a light transmittance close to that of a natural crystalline lens, which prevents light rays (nearly 0 nm) from passing through to a certain degree, and it also has a light transmittance close to that of a natural crystalline lens. There is very little elution of
It is an object of the present invention to provide an intraocular lens that is excellent not only in the durability of the lens itself but also in durability such as the property of not transmitting ultraviolet rays, particularly in terms of durability against light rays (light resistance).

(Solution Means) The present invention provides a polymerizable ultraviolet absorber having a polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an isopropenyl group, and an acryloyl group and a methacryloyl group. , a polymerizable dye having a polymerizable group selected from the group consisting of a vinyl group, an allyl group, and an isopropenyl group, and another copolymerizable lens-forming monomer component. The gist is the inner lens material.

(Specific structure) By the way, the polymerizable ultraviolet absorber used in the intraocular lens material according to the present invention contains a polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an isopropenyl group. Of these polymerizable ultraviolet absorbers, it goes without saying that those with no or low toxicity to living organisms are advantageously selected. In addition, as such a polymerizable ultraviolet absorber, preferably, a polymerizable ultraviolet absorber such as a benzophenone type, a benzotriazole type, or a salicylic acid derivative type is employed.

More specifically, for example, benzophenone-based ultraviolet absorbers include those represented by the following general formula (1).

However, at least one of X, , X, □ is (CHz)
b It is a group represented by any one of C=CH2, and the rest are hydrogen atoms. Further, R1 is any group selected from -Hl-0H1-COOH and a halogen atom, and R and □ are -Hl
-0H1-COOH,C.

-C8 alkyl group, 01-CI+ alkoxy group, sulfo group, benzyloxy group, halogen atom, and R13 is -Hl-OH, C, -C
R14 is a C4-C8 alkylene group. Note that R' is -
H or -CH3, and a and b are each an integer of 0 or 1.

Specific examples of such compounds include 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
-hydroxy-3-(meth)acryloyloxypropoxy)benzophenone and the like. In addition,
Here, (meth)acryloyloxy means two compounds: acryloyloxy and methacryloyloxy (the same applies hereinafter). .

In addition, as a benzotriazole-based ultraviolet absorber,
There is one represented by the following general formula (II).

However, X11 is the same polymerizable group as Xll and X+Z, and RI5 is -H, C, ~C1l alkyl group, C3 to C8 alkoxy group, group similar to X13, carboxyl group, halogen An atom, a nitro group, a sulfo group, or a sulfonamide group. Furthermore, R1
& is any of the following: H, C+ to C8 alkyl group, c, '-c, alkoxy group, group similar to II3, carboxyl group, halogen atom, nitro group, sulfo group, sulfonamide group. R17 is the same group as GagaruRI6.

Such compounds include 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'-(meth)acryloyloxypropyl-3'-tert-butylphenyl)-5-chloro-2H-hensitriazole, and the like.

Further, as a salicylic acid derivative-based ultraviolet absorber, there is one represented by the following general formula (Ill).

However, X14, R111 and RI9 are each
It is the same group as the above-mentioned XI3, RI2 and R13.

Examples of such compounds include phenyl 2-hydroxy-4-methacryloyloxymethylbenzoate.

Furthermore, other ultraviolet absorbers include those represented by the following general formula (IV).

However, II5 is the same group as XI3 above, and R2° is -H or an alkyl group of C+-cll+.

Examples of such compounds include 2-cyano-3-phenyl-3-(3-(meth)acryloyloxydiphenyl)propenylic acid methyl ester.

Polymerizable ultraviolet absorbers such as those exemplified above copolymerize with monomers that are components of lens materials, so these ultraviolet absorbers almost never dissolve into the eye, and are resistant to chemical agents. It also has excellent properties such as durability and fastness. In addition, this ultraviolet absorber can effectively cut and absorb ultraviolet rays, and can advantageously prevent ultraviolet rays from reaching the retina.

It is desirable that this UV absorber has compatibility (chemical structure) with various monomers that are components of the lens material, and using such a UV absorber, the polymerization of the lens material can be carried out. By copolymerizing the UV absorber with other monomers, the UV absorber can be uniformly distributed and present in the intraocular lens components.

In addition to the above-mentioned polymerizable ultraviolet absorber, the intraocular lens material according to the present invention further includes a polymerizable ultraviolet absorber selected from the group consisting of an akuhaguchiyl group, a methacryloyl group, a vinyl group, an allyl group, and an isopropenyl group. A polymerizable dye having a functional group is copolymerized, and preferably, an azo-based, anthraquinone-based, nitro-based, phthalocyanine-based polymerizable dye, etc. is adopted as such a polymerizable dye,
In particular, those with no or low toxicity to living organisms are advantageously selected, and those with chemical structures that do not cause polymerization inhibiting effects are preferably employed. Of course, there is no problem in using Macro-Natsumer-1 containing these components, that is, a polymerizable polymer dye having a polymerizable group.

Specifically, for example, as an azo polymerizable dye, there is one represented by the following general formula (V).

However, X2. is a group represented by any one of R'OllCH2=C-C-0-, R'CH==C(CHz)m-, p', and Rm+ is
-Hl OH, CH3, CzHs, OCH:l, OC
zHs is any group of halogen atoms. Furthermore, R2□ is a substituent selected from the group consisting of benzene derivatives, naphthalene derivatives, and anthracene derivatives, in which some of the hydrogen atoms of their aromatic rings are 01 to C8 alkyl groups, -0H1OCH3, OCzHs ,−'−
t' group, a halogen atom, (R' is -Hl-CH3 or -3O,H), and furthermore, R11 is -Hl-〇H
1 halogen atom, any of the following groups. In addition, R' is -H or -CH3 as above, and n, m, ! ! .

are integers of 0 or 1, respectively, and Yl,
~Y14 is each -NH- or -0-.

Further, there is no problem even if some of the hydrogen atoms of the aromatic ring shown in the general formula (V) are substituted with the same substituent as R2+.

Such compounds include 1-phenylazo-4-(
meth)acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3-
(meth)acryloyloxynaphthalene, ■-anthryl azo 2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-R4-phenylazo)-phenyl)azo)-2-hydroxy-5-(meth)acryloyloxynaphthalene, 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, 2-(3-vinylanilino)-1-(4-nitro(phenylazo)-anilino)-6-chlor -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-) riazine, N-(1-orthotolylazo-2
-naphthyl)-3-vinylphthalic acid monoamide, N-(
1-Orthotolylazo-2-naphthyl)-6-vinylphthalic acid monoamide, 3-vinylphthalic acid-(4-parasulfophenylazo-1-naphthyl) monoester, 6-
Vinyl phthalic acid = (4-parasulfophenylazo-1-
(naphthyl) monoester, etc.

Further, some of the Ab type polymerizable dyes are represented by the following general formula (Vl).

However, X+t is the same group as XI6 above, R''
Rztl CH2=C-CH2-N-, R', R24 is the same group as R21 (excluding -H), and R2S is R2
A group similar to □, or one of the following groups. Furthermore, R26 and Rzt are
Each is -H or a lower alkyl group of CI'=C3, and Rzll is -Hl-NH2 or (however, R
' is the same group as above, and k is an integer of 0 or 1. ) Such compounds include 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-valatrylazophenol, 2-amino-4-(m-(2-hydroxy-1-naphthylazo)anilino)-6-isoprobenyl-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-Ituburovenyl 1,3. ,5-1-riazine,2
-amino-4-(N-methyl-p-(4-hydroxyphenylazo)anilino)-6-itupropenyl-1°3
．． 5-triazine, 2-amino-4-(m-(3-methyl-1-phenyl-5-hydroxyl 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-triazine, 2-amino-4-(p-phenylazoanilino)-6-itupropenyl 1. Examples include 3,5-) riazine.

Note: As an azo polymerizable dye, the following general formula (■)
Some are indicated by .

However, Xl is the same group as the above X16, RZQ,
R1° is the same group as the above Rz+ or -3
O, Na, R11 is the same group as RZt, and i and j are each an integer of 0 to 3.

Such compounds include 4-phenylazo-7-(
Examples include meth)acryloylamide-1-naphthol.

Next, as anthraquinone-based polymerizable dyes, there are those represented by the following general formula (■).

However, XIQ and X2゜ are each independently 0ORz
a CH2=C-CH, -NH-, X21 is a group represented by any one of R' CH2=C-CH2-Y, -, R' CHt =CCOY I'? −, is a group of any of the following. Moreover, R32 and Rff3 are each independently -NH2, -OH, -3O3H.

A nitro group, a halogen atom, a C1-C3 lower alkylamino group, a Cl-03 lower alkoxy group, a C1-C1 lower alkylamido group, and R34 is -H or C1
~C3 lower alkyl group. Furthermore, R3s is -H
, -CH, or -NHNH2, R3h, R3
7 is each independently a lower alkyl group of -H, C, =C3 or a lower alkoxy group of C3 to C1. Note that R' is the same group as above, h, d, and g are each an integer of 0 to 3, 0 or an integer of 1.0 to 4 (however, d+g≦4), and f is 0 or 1, e is O~6
is an integer.

Such compounds include 1,5-di(meth)acryloylamino-9,1O-anthraquinone, 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゜IO-anthraquinone, 1,4-bis-(
4'-vinylbenzoylamide)-9,10-anthraquinone, ■, 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
-(paravinylbenzoyloxyethylamino)-anthraquinone, ■-amino-4-(3'-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, l-amino-4-(4'-vinylphenylamino) )−
9,10-anthraquinone-2-sulfonic acid, 1-amino-4-(2'-vinylbenzylamino)-9,10-
Anthraquinone-2-sulfonic acid, ■-amino-4-(
3'-(meth)acryloylaminophenylamino)-
9,10-anthraquinone-2-sulfonic acid, 1-amino-4-(3'-(meth)acryloylaminobenzylamino)-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-benzoylamido-9,10-anthraquinone, 2-(3-(meth)acryloylamide-anilino)-4 -(3-(3-sulfo-4-aminoanthraquinon-1-yl)-amino-anilino)-6-chloro-1°3.5-)riazine, 2-(3-(meth)acryloylamide-anilino) -4-(3-(3-sulfo-4-aminoanthraquinon-1-yl)-aminoanilino)-6-hydrazino-1,3°5-triazine,
2,4-bis-((4-methoxyanthraquinone-1-
yl)-amino)-6-(3-vinylanilino)-1,
' 3.5-triazine, 2-(2-vinylphenoxy)-4-(4-(3-sulfo-4-aminoanthraquinon-1-yl-amino)-anilino)-6-chloro-1
゜3.5-1-Ryazine and the like can be mentioned.

In addition, as a nitro-based polymerizable dye, the following general formula (I
There is one shown in X).

However, R311% and R29 are each independently -H
or a C3 to C3 lower alkyl group, and p is 0 to 3
is an integer. Note that R' is the same group as described above.

Examples of such compounds include 0-nitroanilinomethyl (meth)acrylate.

Furthermore, examples of phthalocyanine-based polymerizable dyes include those represented by the following general formula (X).

R4t 4゜■ However, R4゜ to R4ff are -H or -Co-A, A is an alkyl group of 01 to CI'l, or one of R is a (meth)acryloyl group, and M is It is a metal atom (for example, Cu), and R' is the same group as described above.

Examples of such compounds include (meth)acryloylated tetraamino copper phthalocyanine, (meth)acryloylated (dodecanoylated tetraamino copper phthalocyanine), and the like.

Note that among the polymerizable dyes according to the present invention described above, yellow polymerizable dyes are particularly preferred. because,
Yellow pigments are mainly used for wavelengths in the blue region of visible light (approximately 380 to 500 nm) that cannot be cut by polymerizable ultraviolet absorbers.
This is because a part of the light rays in the vicinity of m) can be selectively and effectively cut, and visible light rays in other regions are not cut.

Of course, there is no problem in using dyes other than yellow, but in that case, light in other visible light ranges may also be blocked, so it is necessary to limit the amount of polymerizable dye used or to select the dye. There may be times when it is necessary to

Specific examples of polymerizable dyes according to the present invention have been described above, but such polymerizable dyes are suitable for wavelengths (mainly in the blue region) of visible light that cannot be cut by polymerizable ultraviolet absorbers.
It effectively cuts part of the light rays (about 380 to 500 nm), and it also has a polymerizable group and copolymerizes with the monomer that is a component of the lens material, so it can be used as a pigment (dye).
It is extremely safe as it does not elute into the eyes, and it also prevents decolorization and discoloration caused by dye elution, and it also has excellent durability and fastness against chemical agents. It is.

Furthermore, it is desirable that the dye be compatible (chemical structure) with the various monomers that will be the components of the lens material, which will be described later. By copolymerizing this dye with other monomers, it is possible to uniformly color the intraocular lens.

Furthermore, in the present invention, the light resistance of the polymerizable dye can be improved by using the above polymerizable dye and a polymerizable ultraviolet absorber together. In addition, compared to using a UV absorber alone, it can effectively cut the same amount of UV rays and a portion of visible light, mainly in the blue region, with a relatively small amount of usage.By using these in combination,
It is possible to enjoy the advantage that only a small amount of the polymerizable ultraviolet absorber and polymerizable dye can be used.

By the way, as the lens-forming monomer component used in the present invention, any of the various ones that have been proposed by those skilled in the art can be employed.Specifically, the monomers shown below may be used. One or more of these will be selected and used.

Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (
meth)acrylate, butyl(meth)acrylate, t
er t-Butyl (meth)acrylate, cyclohexyl (meth)acrylate, and other linear, branched, and cyclic alkyl (meth)acrylates; pentamethyldisiloxanylmethyl (meth)acrylate, pentamethyldisiloxa Silicon-containing (meth)acrylates such as nylpropyl (meth)acrylate, methylbis(trimethylsiloxy)silylpropyl(meth)acrylate, tris(trimethylsiloxy)silylpropyl(meth)acrylate; trifluoroethyl(meth)acrylate, tetrafluoro Fluorine-containing (meth)acrylates such as propyl (meth)acrylate, pentafluoropropyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate; styrene, pentafluorostyrene, methylstyrene, trimethylstyrene, trifluoromethylstyrene, ( Styrene derivatives such as pentamethyl-3,3-bis(trimethylsiloxy)trisiloxanyl)styrene, (hexamethyl-3-trimethylsiloxytrisiloxanyl)styrene, and dimethylaminostyrene; hydroxyethyl (meth)acrylate, hydroxypropyl (meth) Water such as acrylate, hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, dihydroxybutyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, etc. acid a
(meth)acrylates: (meth)acrylic acid: Vinyl lactams such as N-vinylpyrrolidone and α-methylene-N-methylpyrrolidone; (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl ( (meth)acrylamides such as meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and N,N-dimethyl(meth)acrylamide; (meth)acrylamides containing aromatic rings such as benzyl (meth)acrylate;
Acrylates.

In addition, as a crosslinking agent, 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,
Examples include methacryloyloxyethyl acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, and one or more of these may be selected as necessary. and will be used.

Alternatively, one or more of the above-mentioned components may be selected and polymerized to form a macromonomer, which may be used as one of the copolymerized components (lens components).

Then, depending on the intended intraocular lens, the above lens components are appropriately selected, blended in any proportion, and subjected to copolymerization.

For example, to obtain an intraocular lens material that is highly safe for living organisms, methyl methacrylate is selected as the main component of the lens, and it is necessary to reinforce the lens to obtain an intraocular lens material with excellent strength. If so, alkyl (meth)acrylates, styrene derivatives, etc. are mainly preferably selected.

In addition, if you want to add hydrophilicity to the lens or make a flexible, water-containing intraocular lens material, hydroxyalkyl (
meth)acrylates, (meth)acrylamides, (
Monomers having hydrophilic groups such as meth)acrylic acid and vinyl lactams are mainly preferably selected, and in order to make the lens resistant to lipid staining, fluorine-containing monomers such as fluorine-containing (meth)acrylate or Fluorine-containing styrene derivatives and the like are mainly preferably selected.

Furthermore, in order to improve the crosslinking effect, that is, shape stability, durability (chemical resistance, solvent resistance, heat resistance), etc., and to reduce eluates, at least two or more crosslinking agents or molecules are added to the crosslinking agent or in the molecule. It is desirable to use a macromonomer having a polymerizable group.

The crosslinking agent is preferably used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the lens component. If the amount is less than this, it is difficult to obtain a crosslinking effect,
This is because if the amount is too large, the material tends to become brittle.

Then, the above-mentioned lens-forming monomer, polymerizable ultraviolet absorber, and polymerizable dye are uniformly mixed and subjected to copolymerization.
When it is 0 parts by weight, the polymerizable ultraviolet absorber is 0.01~
Preferably, the amount is 10 parts by weight, and the polymerizable dye is blended in a range of 0.0005 to 1 part by weight.

If the amount of polymerizable ultraviolet absorber is too small, the effect of using the ultraviolet absorber will not be obtained, and if it is too large, the physical properties of the lens, such as strength, etc. will decrease, which is not only undesirable, but also considering its toxicity. Therefore, it is not preferable to be implanted in a living body. Note that a more preferable range is 0.05 to 7 parts by weight. In addition, if the amount of polymerizable dye is too low, the effect of using the dye cannot be obtained, and if it is too large, the coloring becomes too deep and the transparency decreases (it becomes difficult for visible light to pass through), and the physical properties of the lens deteriorate.
For example, it is not only undesirable because the strength etc. decreases, but also
Considering its toxicity, it is not preferable to implant it into a living body. Note that a more preferable range is 0.001 to 0.5 parts by weight.

In addition, when producing intraocular lens materials by polymerizing the monomer mixture as described above, the polymerization operation must be carried out to uniformly distribute the polymerizable ultraviolet absorber, polymerizable dye, other lens components, polymerization initiator, etc. It can be easily carried out by a method commonly used in the art.

For example, if necessary, a radical polymerization initiator is used and the material is gradually heated in a temperature range from room temperature to about 130°C, or irradiated with electromagnetic waves such as microwaves, infrared rays, ultraviolet rays, and radiation (γ rays). This will be implemented in various ways.

In addition, when carrying out heating polymerization, there is no problem in raising the temperature in stages, and the polymerization may be carried out by a bulk polymerization method, a solvent polymerization method using a solvent, etc., or various other methods may be used. It can be adopted.

In addition, as specific examples of the radical polymerization initiator, for example,
Examples include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and one or more of these may be selected. used. Also,
The amount used is 1/1 of the total monomer mixture to be subjected to polymerization.
00 parts by weight, a range of about 0.01 to 1 part by weight is suitable.

By the way, when molding the above monomer mixture into an intraocular lens, a molding method commonly used by those skilled in the art is employed. For example, after polymerization is performed in a suitable mold or container to obtain a rod-shaped, block-shaped, or plate-shaped material (polymer), it is processed into a desired shape by mechanical processing such as cutting or polishing, or Alternatively, a method is adopted in which a mold corresponding to the desired shape is prepared, the seven-mer mixture is polymerized in this mold to obtain a molded product, and mechanical finishing processing is performed as necessary.

In addition, when providing a suitable support part for an intraocular lens, even if such a support part for the lens is made separately from the lens and attached to the lens, it can be attached at the same time as the lens (integrally).
Even if it is molded, there is no difference.

Furthermore, a so-called plasma treatment for making the surface of the lens hydrophilic may be performed as necessary, and conventionally known conventional equipment and methods may be used as the treatment equipment and treatment method at that time. Ru. The processing conditions include inert gas such as helium, neon, argon, air, oxygen,
In an atmosphere of gases such as nitrogen, carbon oxide, carbon dioxide, etc.
Pressure crab approx. 0.0001 to several Torr, output crab approx. 10
It is preferable to process for several seconds to several tens of minutes under the condition of 0W, and more preferably, the gas is air, oxygen, or argon, the pressure is about 0.05 to 3 Torr, and the output is about 10
Processed under conditions of ~60W and several minutes.

The intraocular lens molded product thus produced is then sterilized, packaged, and used as the intended intraocular lens at the appropriate time.

(Examples) Below, some examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited in any way by the description of such examples. Needless to say, it is not something that can be accepted.

In addition to the following examples and the above-mentioned specific description, the present invention includes various changes, modifications, and changes based on the knowledge of those skilled in the art, as long as they do not depart from the spirit of the present invention. It should be understood that improvements and the like may be made.

Example l Methyl methacrylate = 96 parts by weight, ethylene glycol dimethacrylate = 3 parts by weight as a crosslinking agent, 2-hydroxy-4-methacryloyloxybenzophenone 20.3 parts by weight as a polymerizable ultraviolet absorber, l- as a polymerizable dye. 0.04 parts by weight of phenylazo-4-methacryloyloxynaphthalene and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator were uniformly blended, and then the blended solution was heated from 35°C to 110'C. The material was polymerized by raising the temperature to produce a rod-shaped intraocular lens material.

A plate with a thickness of 0.7 mm was cut from this rod-shaped intraocular lens material, and the surface was polished to prepare a plate-shaped test piece. Using the obtained test piece as a sample, the light transmittance at a wavelength of 190.0 to 780 nm was measured, and the chart thereof is shown in FIG. From the results shown in FIG.
It can be seen that some of the light rays (around 0 nm) are also cut off.

Further, a light resistance test and a dissolution test were conducted as follows. As a result, the discoloration rate was 0% even after one month, and no discoloration was observed, and the elution of the dye was 1% or less.

[Lightfastness test]

A plate-shaped test piece is stored in a transparent container in distilled water, exposed to sunlight, and the light transmittance is measured after a specified number of days.The fading rate is determined by comparing the light transmittance with the light transmittance before exposure to sunlight. Calculate.

[Dissolution test]

The intraocular lens material is pulverized to create a chip, part 3
g is extracted in 50 mj2 of acetone under reflux for 3 hours. Measure the absorbance of the extract, calculate the amount of extracted dye using a calibration curve created from the maximum absorption wavelength of an acetone solution of the dye, and calculate the elution rate of the dye by dividing the calculated value by the blended amount. calculate.

Example 2 Methyl methacrylate: 96 parts by weight, ethylene glycol dimethacrylate = 3 parts by weight as a crosslinking agent, 2-hydroxy-4-methacryloyloxybenzophenone as a polymerizable ultraviolet absorber: 1 part by weight, 1 part by weight as a polymerizable dye.
-(, ((4-phenylazo)-phenyl)azo)-2
-Hydroxy-3-methacryloyloxynaphthalene:
0.01 part by weight and 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator were uniformly blended, polymerization was carried out in the same manner as in Example 1, and a plate-shaped test piece was prepared.

Using the obtained test piece as a sample, wavelength: 190, (1
The light transmittance was measured up to 780.0 nm.

The chart is shown in Figure 2. From the results, 38
It can be seen that ultraviolet rays with a wavelength of 0 nm or less are reliably blocked, and a portion of visible light, mainly in the blue region (wavelength = around 380 to 500 nm), is also blocked.

Further, a light fastness test and a dissolution test were carried out in the same manner as in Example 1, and as a result, the discoloration rate was 0% even after - months, and the dissolution rate of the dye was 7%.

Example 3 296 parts by weight of methyl methacrylate, 3 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.5 parts by weight of 2-hydroxy-4-methacryloyloxybenzophenone as a polymerizable ultraviolet absorber, 1,5 parts by weight as a polymerizable dye. - 0.04 parts by weight of dimethacryloylamino-9,10-anthraquinone and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator,
Polymerization was carried out in the same manner as in Example 1, and a plate-shaped test piece was prepared.

Using the obtained test piece as a sample, wavelength: 190.0~
The light transmittance up to 780.0 nm was measured, and the chart is shown in FIG. The results show that ultraviolet rays with a wavelength of 380 nm or less are reliably blocked, and a portion of visible light, mainly in the blue region (wavelength: around 380 to 500 nm), is also blocked.

Further, a light fastness test and a dissolution test were carried out in the same manner as in Example 1, and as a result, the discoloration rate was 15% after - months, and the dissolution rate of the dye was 26%.

Example 4 Methyl methacrylate: 96 parts by weight, 13 parts by weight of ethylene glycol resin methacrylate as a crosslinking agent, 1 part by weight of 2-hydroxy=4-methacryloyloxybenzophenone as a polymerizable ultraviolet absorber, 1-/7thlylazo as a polymerizable dye 2-Hydroxy-3-methacryloyloxynaphthalene: 5 parts by weight of O,OO and 1 part by weight
-pheniazo 4-methacryloyloxynaph)rene:
o, o i heavy\1, mold part, azobisisobutyronitrile as a polymerization initiator:
0.1 part by weight was uniformly blended and polymerized in the same manner as in Example 1 to prepare a plate-shaped test piece.

Using the obtained test piece as a sample, wavelength: 190, 0~
780. The light transmittance up to Onm was measured and the chart is shown in FIG. The results show that ultraviolet rays with a wavelength of 380 nm or less are reliably blocked, and a portion of visible light, mainly in the blue region (wavelength: around 380 to 500 nm), is also blocked.

Comparative Example 1 (When using only a polymerizable ultraviolet absorber) Methyl methacrylate: 96 parts by weight, ethylene glycol dimethacrylate as a crosslinking agent: 3 parts by weight, 2-hydroxy-4-methacryloyloxybenzophenone as a polymerizable ultraviolet absorber: 1 part by weight and 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator were uniformly blended and polymerized in the same manner as in Example 1. Thickness: 0.7
A plate-shaped test piece with a diameter of mm was prepared.

Using this test piece as a sample, wavelength: 190. ．． 0-7
The light transmittance up to 80.0 nm was measured, and the chart is shown in FIG. As a result, the cutting rate of visible light (wavelength: around 380 to 500 nm) mainly in the ultraviolet region and blue region was found to be low even though 1 part by weight of UV absorber was used in this comparative example. This was lower than in Example 1, in which only 0.3 parts by weight of the agent was used.

Comparative Example 2 (When using only polymerizable dye) Methyl methacrylate = 96 parts by weight, ethylene glycol dimethacrylate: 3 parts by weight as a crosslinking agent, 1.5-dimethacryloylamino-9,10- as a polymerizable dye
Anthraquinone: 0.04 parts by weight and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator were uniformly blended, polymerized in the same manner as in Example 1, and a plate-shaped test piece was prepared. .

When this test piece was subjected to a light fastness test and a dissolution test in the same manner as in Example 1, the discoloration rate was 22% or more and the dye dissolution rate was 30%, which indicates that it is inferior to Example 3. understood.

Comparative Example 3 (Elution property of non-polymerizable ultraviolet absorber) Methyl methacrylate: 96 parts by weight, ethylene glycol dimethacrylate = 3 parts by weight as a crosslinking agent, Tinuvin P as an ultraviolet absorber (Switzerland: manufactured by Ciba Geigy: benzotriazole type) (trade name of ultraviolet absorber): 1 part by weight and 20.1 parts by weight of azobisisobutyronitrile as a polymerization initiator were uniformly blended, polymerized in the same manner as in Example 1, and a plate-shaped test piece was prepared. was created.

Using the obtained test piece as a sample, an ultraviolet absorber elution test was conducted as follows.

As a result, the elution rate of the ultraviolet absorber was as high as 98%, and it was found that most of the ultraviolet absorber was eluted.

[Dissolution test]

The obtained lens material is crushed to make a chip, and 1 g of the chip is made into 50mj! Extract with ethanol under reflux for 3 hours. Next, the absorbance of the extract was measured, and the elution rate of the extracted UV absorber or pigment was calculated using a calibration curve created from the maximum absorption wavelength of the ethanol solution of the UV absorber or pigment.

Comparative Example 4 [Elution of non-polymerizable dye] Methyl methacrylate: 96 parts by weight, ethylene glycol dimethacrylate as a crosslinking agent: 3 parts by weight, 2-hydroxy-4-methacryloyloxybenzophenone as a polymerizable ultraviolet absorber: 1 part by weight , r D as a dye
& CGGreen # 6 (Ministry of Health and Welfare legal pigment: Green 20
No. 2) 0.04 parts by weight of J and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator,
Polymerization was carried out in the same manner as in Example 1, and a plate-shaped test piece was prepared.

Using the obtained test piece as a sample, a dye elution test was conducted in the same manner as in Comparative Example 3. As a result, the dye elution rate was 9.
It was over 9%.

(Effects of the Invention) As is clear from the above description, the intraocular lens material according to the present invention does not transmit ultraviolet rays, similar to the athermal lens of the eye, and wavelengths of visible light mainly in the blue region ( Approximately 38
It has the property of not transmitting even light in the vicinity of 0 to 500 nm to a certain extent, and it is possible to provide an intraocular lens having light transmittance close to that of the natural crystalline lens.

Moreover, since it uses a polymerizable UV absorber and a polymerizable pigment, it can be chemically bonded to the lens material, and there is extremely little elution of the UV absorber or pigment (dye). By using a polymerizable ultraviolet absorber and a polymerizable dye together, the amount of these used can be extremely small, and as a result, not only the amount of elution of the ultraviolet absorber and dye is reduced, but also the intraocular lens is Considering the safety of the toxicity of additives such as ultraviolet absorbers and pigments (dyes), it can be an extremely good intraocular lens material.

Furthermore, not only the durability of the lens itself, but also the property of not transmitting ultraviolet rays, etc. made it possible to create a good intraocular lens material, especially in terms of the durability (light resistance) of the pigment against light rays.

[Brief explanation of the drawing]

1 to 4 are graphs showing the light transmittance according to wavelength of the intraocular lens materials according to the present invention obtained in Examples 1 to 4, respectively, and FIG. FIG. 6 is a graph showing the light transmittance according to wavelength of an intraocular lens material containing only a polymerizable ultraviolet absorber. It is a graph showing light transmittance according to each wavelength. Figure 1: Growth (nm) Figure 2: Concentration (nm) Figure 3: Concentration (nm) Figure 4: Mixture (nm) Figure 5: i'j [-t (nm) Figure 6: Depth length (nm) Procedures (Hoshosho (spontaneous) Yoshi, Commissioner of the Japan Patent Office 1) Fumi Qi Dong 1, Indication of the case 1988 Patent side No. 131036 2, Name of the invention Intraocular lens material 3° correction case Relationship with Patent Applicant Name Menicon Co., Ltd. 4, Agent (1) Column 6 of the detailed description of the invention in the specification, Contents of the amendment (1) "(Pigments/Dye)" on page 4, line 20 of the specification "etc." is corrected to "(pigment) etc." (2) Correct "sulfo group" in the 13th line from just below the 7th line to "sulfonic acid group". (3) “2-Hydroxy-4-
(2-hydroxy-3-(meth)acryloyloxypropoxy)benzophenone” to “2-hydroxy-4-
(2'-Hydroxy-3'-(meth)acryloyloxypropoxy)benzophenone". (4) Correct "sulfo group" in the fourth line from just below No. 8 to "sulfonic acid group". (5) "Sulfo group" in the first line of page 9 is corrected to "sulfonic acid group." (6) From the second line from the bottom of page 10 to the first line of page 11, “
2-cyano-3-phenyl-3-(3-(meth)acryloyloxyphenyl)propenylic acid methyl ester"
is corrected to "2-cyano-3=phenyl-3-(3'-(meth)acryloyloxyphenyl)propenylic acid methyl ester." (7) "1-Anthrylazo...monoester" on page 15, line 5 to page 16, line 9 is corrected as follows. rl-(α-anthryl azo)-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-)lylazo)-2'-naphthylamino)-1,3,5-triazine, 2-(m-vinylanilino)-4-((p-nitrophenylazo)-anilino) -6-chloro-1,3,5-triazine, 2-(
1'-(o-)lylazo)-2-naphthyloxy)-4
-(m-vinylanilino)-6-chloro-1,3,5-
Triazine, 2-(p-vinylanilino)-4-(1
'-(o-1 lyrua'/')-2'-naphthylanilino)-6-chloro-1,3,5-)riazine, N-(1
'-(.-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-pinylphthalic acid-(4'-(p-sulfophenylazo)-1'-naphthyl) monoester" ( 8) In the third line from the bottom of page 17, "is a group, and Ro is" is corrected to "is a group, Yls is -NH- or 10-, and R1, is". (9) “3-(
``Meta)acryloylamide...triazine'' is corrected as follows. [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-
) lylazo)-phenol, 2-niamino-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-itubropenyl 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-itupropenyl 1°3
．． 5-triazine, 2-amino-4-(N-methyl-p
-(3'-Methyl-1'-phenyl-5'-hydroxypyrazolylazo)anilino)-6-itupropenyl-1
, 3.5-) Reazin" 00) Same page 22, lines 9-10, after "It is an integer.", insert the following sentence without starting a new line. "In addition, YI6 and Y8. are respectively -NH- or -〇-." (II) "1,5-di(
meth)acryloylamino-9,10-anthraquinone" and "1,5-bis((meth)acryloylamino)-
9,10-Anthraquinone”. 02) “1-Methylamino-4-(paravinylbenzoyloxyethylamino)” on page 23, lines 19-20
-anthraquinone” to “1-methylamino-4-(4'
-vinylbenzoyloxyethylamino)-9,10
-Anthraquinone”. (+3) "r2-(3-...triazine" on page 24, line 18 to page 25, line 12) is corrected as follows. r2-(3'-(meth)acryloylamide-anilino) )-4-(3'-(3"-sulfo-41-aminoanthraquinon-1#-yl)-amino-anilino)-6
-Chloro-1,3,5-)riazine, 2-(3'-(
meth)acryloylamide-anilino)-4-(3'
-(3'-sulfo-4"-aminoanthraquinone-1"
-yl)-amino-anilino)-6-hydrazino-1,
3,5-triazine, 2,4-bis-((4"-methoxyanthraquinon-1"-yl)-amino) -6-(
3'-vinylanilino)-1,3,5-) riazine, 2
-(2'-vinylphenoxy)-4-(4'-(3
"-Sulfo-4"-aminoanthraquinone-19-yl-amino)-anilino)-6-chloro-1,3,5-triazine" side Same page 35, lines 2-3 "Transparency decreases (visible (becomes difficult to transmit light rays) or correct J to "becomes less transparent to visible light." Yes Same, on page 40, line 10, correct "acetone solution" to "acetone solution." 0ω N-( from page 40, line 19 to page 41, line 1)
((4-phenylazo)-phenyl)azo)-2-hydroxy-3-methacryloyloxynaphthalene" rl
-((4'-(phenylazo)-phenyl)azo)-
2-Hydroxy-3-methacryloyloxynaphthalene". 07) [1,5-dimethacryloylamino-9,10-anthraquinone] on page 42, lines 1-2
-Bis(methacryloylamino)-9,10-anthraquinone". (18) "1-anthryl azo-2-hydroxy-3-methacryloyloxynaphthalene" on page 43, lines 2-4 was corrected to "1-(α-anthryl azo)-2-hydroxy-3-methacryloyloxynaphthalene" do. 09) "1,5-dimethacryloylamino-9,10-anthraquinone" on page 44, lines 19-20 was replaced with [1,5-bis(methacryloylamino)-9,10-
Corrected to "Anthraquinone". that's all

Claims (1)

[Claims] A polymerizable ultraviolet absorber having a polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an isopropenyl group; 1. An intraocular lens material characterized by copolymerizing a polymerizable dye having a polymerizable group selected from the group consisting of: with other copolymerizable lens-forming monomer components.