JPH0728911B2 - Polymerizable dye for coloring eye lens, method for producing colored eye lens material using the same, and colored eye lens material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable dye used for coloring an ophthalmic lens such as a contact lens, an intraocular lens and an artificial cornea,
The present invention also relates to a method for producing a colored eye lens material using the same and a colored eye lens material.

(Background Art) Coloring an ophthalmic lens such as a contact lens, an intraocular lens, or an artificial cornea is easy to confirm when the lens is stored in water, and is easy to find when the lens is dropped,
In addition, it has many advantages such as improving the product image, making it easy to distinguish the lenses of our own products, and using it like sunglasses (eye protection, beauty, etc.).

By the way, conventionally, the methods for coloring such an ophthalmic lens are roughly classified into a method of dyeing after the lens is made (post-dyeing) and a method of coloring by adding a dye at the time of manufacturing the lens material (at the time of polymerization). Two methods are known.

First of all, regarding the former (post-dyeing) method, such a method is a method mainly used for water-containing soft contact lenses because it is necessary to allow the dye to penetrate into the lens. Some dyes cannot be applied to water-containing lenses because some dyes do not penetrate into the lens. In addition, even for highly water-containing contact lenses, the dye is likely to elute from the lens after dyeing, and the dyeing on the lens is limited to the surface of the lens, and the fastness, that is, durability against light and chemical agents. However, it is much inferior to the method of dyeing by adding a dye at the time of polymerization.

On the other hand, in the case of the latter method of coloring by adding a dye at the time of manufacturing the lens material (at the time of polymerization), the legal method conventionally used for coloring contact lenses, intraocular lenses, artificial corneas, and other ophthalmic lenses. Dyes (pigments) were not able to be sufficiently dispersed and solubilized in the monomers used as the main components of such lens materials. When it is stored in water for a long time and used, the dye may elute from the lens material with time. In particular,
In recent years, in a hard lens with high oxygen permeability, which has been attracting attention as a contact lens, the legal dye is added to a monomer such as siloxanyl methacrylate and / or fluoromethacrylate as a main component of the lens material. In many cases, even when trying to copolymerize, it is not possible to sufficiently disperse and solubilize these monomers, which are lens components,
Even if somehow dissolved and copolymerized, there was a problem that the dye was easily eluted from the lens material due to the large molecular gap of the obtained polymer. The same was true for highly water-containing contact lenses.

Further, as disclosed in JP-A-53-3836, a coupler monomer (coupler polymer) is copolymerized with a monomer constituting a component of a lens material, and then a contact lens made of such a copolymer is added. Although a method of permeating a diazonium salt, causing a reaction with such a coupler monomer to develop a color and dyeing has been clarified, such a method has the following problems.

In other words, the coupler monomer does not react 100%, the unreacted coupler remains in the lens and the reaction rate is not constant, so the color changes for each lens,
There is a problem that the color developed by the lens location is not uniform and the color changes irregularly.In addition, the unreacted coupler changes, which also causes the lens to change color over time. It was. Further, since the diazonium salt needs to be penetrated into the lens, such a method could not be adopted for hard type and non-hydrous lenses.

(Problems to be Solved) Here, the present invention has been made in view of such circumstances, and the problems to be solved are the problems inherent in the dyeing (coloring) methods described above. Which is soluble in various monomers such as siloxanyl methacrylate and fluoromethacrylate used in ophthalmic lenses, and which is either water-containing or hard system or non-water-containing ophthalmic lens. It can also be colored well, and there is no discoloration or discoloration of the ophthalmic lens due to elution of dye, etc., and it has excellent durability and fastness to light and chemical agents. An object of the present invention is to provide a polymerizable dye that can be uniformly colored and does not have a risk of color variation among lenses, and a method for advantageously producing a colored ophthalmic lens material using such a dye is proposed. And to provide such a colored ophthalmic lens material.

(Solution) In order to solve such a problem, the gist of the present invention is a polymerizable dye for coloring an ophthalmic lens, which is represented by the following general formula (I).

However, in the formula, R _{1 to} R ₇ are each independently, and any one of them is a polymerizable group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group. , Other are hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, hydroxyl group, chlorine atom,
And a substituent selected from the group consisting of bromine atoms, and R ₈ is a substituent selected from the group of the following general formulas (II) to (V).

(However, R _{9 to} R ₁₃ are each independently, and are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) (However, R _{14 to} R ₂₇ are each independently a substitution selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a chlorine atom, and a bromine atom. It is a base.) (However, R _{28 to} R ₃₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) Further, according to the present invention, in producing an ophthalmic lens material by polymerizing a vinyl-based monomer, a polymerizable dye represented by the general formula (I) is copolymerized to produce a colored ophthalmic lens material. The law is also its gist.

In the production of such a colored ophthalmic lens, preferably, the polymerizable dye is used in a proportion of 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the vinyl-based monomer, and copolymerized. Becomes

Further, a feature of the present invention is that the compound represented by the general formula (I) is
There is also a colored ophthalmic lens material composed of a vinyl polymer obtained by copolymerizing the polymerizable dye represented by

As described above, the polymerizable dye according to the present invention is soluble in various monomers as a component of the lens material, and any _one of R _{1 to} R _{7 in} the general formula (I) is used. Is a polymerizable group, and it will be copolymerized with the monomer that is a component of the lens material, so that it can be satisfactorily used for both water-containing and hard or non-water-containing ophthalmic lenses. In addition to being able to color uniformly, such dyes do not elute, preventing discoloration and discoloration of the colored lens due to dye elution, and durability and fastness to light and chemical agents. In addition, there is no variation in color depending on the lens or the location of the lens, and various uniformly colored ophthalmic lenses can be satisfactorily obtained.

Further, the problem of residual decomposition products of diazonium salts found in the invention disclosed in JP-A-53-3836 does not occur.

Further, such a polymerizable dye according to the present invention can give a color tone such as red, yellow, purple, and orange due to its chemical structure, and by combining a plurality of dyes at various concentrations, an ophthalmic lens can be obtained. It can be colored in various desired colors.

In the general formula (I), the substituent which is not a polymerizable group among R _{1 to} R ₇ is preferably selected from a hydrogen atom or a hydroxyl group, and the general formulas (II) and (IV)
In, the substituents R _{9 to} R ₁₃ and R _{28 to} R ₃₆ are a hydrogen atom,
It is preferably selected from an alkyl group having 1 to 12 carbon atoms and a hydroxyl group, and further, in the general formula (III), a substituent R ₁₄ to
R ₂₇ is preferably selected from a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, and a hydroxyl group.

Then, specific examples of the polymerizable dye according to the present invention include, for example, 1-phenylazo-4-methacryloyloxynaphthalene (yellow), 1-phenylazo-2-hydroxy-3-methacryloyloxynaphthalene (orange), 1-naphthylazo. -2-Hydroxy-3-methacryloyloxynaphthalene (red), 1-((4'-
(Phenylazo) phenyl) azo) -2-hydroxy-
Examples thereof include 3-methacryloyloxynaphthalene (red) and 1-anthrylazo-2-hydroxy-3-methacryloyloxynaphthalene (purple).

By the way, when forming an ophthalmic lens material, the polymerizable dye according to the present invention is added to a predetermined lens-forming monomer, mixed, and copolymerized. ), Variously proposed by those skilled in the art will be adopted. Then, as such a specific example, for example, the following monomers are listed, and one or two or more of them are selected and used.
In addition, hereinafter, (meth) acrylate represents acrylate or methacrylate, and other substances (meth)
The same applies to acrylic derivatives.

Acrylic acid and methacrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate,
tert-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, te
rt-pentyl (meth) acrylate, hexyl (meth)
Acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth)
Linear, branched, and cyclic acrylates, nonyl (meth) acrylates, decyl (meth) acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, cyclopentyl (meth) acrylates, cyclohexyl (meth) acrylates, etc. Alkyl (meth) acrylates; pentamethyldisiloxanylmethyl (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, methylbis (trimethylsiloxy) silylpropylglycerol (meth) acrylate, tris (trimethylsiloxy)
Silylpropyl glycerol (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl glycerol (meth) acrylate, trimethylsilylethyl tetramethyldisiloxanylpropyl glycerol (meth) acrylate, trimethylsilylmethyl (meth) Acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropylglycerol (meth) acrylate, pentamethyldisiloxanylpropylglycerol (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetra Methyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethy Silicon-containing (meth) acrylates such as triisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, Hexafluoroisopropyl (meth) acrylate, tetrafluoro-tert-pentyl (meth) acrylate, hexafluorobutyl (meth) acrylate, hexafluoro-tert-hexyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2,3, 4,5,5,5-hexafluoro-2,4
-Bis (trifluoromethyl) pentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, 2-hydroxyoctafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxydodecafluoro-8-trifluoromethylnonyl Fluorine-containing (meth) acrylates such as (meth) acrylate and 2-hydroxyhexadecafluoro-10-trifluoromethylundecyl (meth) acrylate; styrene, pentafluorostyrene, methylstyrene,
Trimethylstyrene, trifluoromethylstyrene,
Styrene derivatives such as (pentamethyl-3,3-bis (trimethylsiloxy) trisiloxanyl) styrene, (hexamethyl-3-trimethylsiloxytrisiloxanyl) styrene, dimethylaminostyrene; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate,
Hydroxyl group-containing (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate: N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone, N- Vinyllactams such as vinylcaprolactam and N- (meth) acryloylpyrrolidone; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (Meth) acrylamides such as dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl-N-aminoethyl (meth) acrylamide; aminoethyl (meth) acrylate, N-methyl-N-
Aminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate and the like Alkoxy group-containing (meth) acrylates; aromatic ring-containing (meth), such as benzyl (meth) acrylate
Acrylates; alkyl esters and substituted derivatives of itaconic acid, crotonic acid, maleic acid, fumaric acid and the like; glycidyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; 4-vinylpyridine; vinylimidazole, N-vinylpiperidone, N -Heterocyclic N-vinyl monomers such as vinylpiperidine and N-vinylsuccinimide; N- (meth) acryloylpiperidine; N- (meth) acryloylmorpholine; 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 UV-absorbing monomers such as ditroxy-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-based UV absorbing monomers such as benzotriazole and 2- (2'-hydroxy-5 '-(meth) acryloyloxypropyl-3'-tert-butylphenyl) -5-chloro-2H-benzotriazole.

In this way, the above lens-forming monomers are appropriately selected according to the target ophthalmic lens (contact lens or intraocular lens), blended in an arbitrary ratio, and then the desired color is imparted. The polymerizable dye according to the present invention is added in a predetermined amount, and after uniformly mixed, the mixture is subjected to copolymerization to obtain an objective ophthalmic lens material. For example, it is desired to obtain a lens material having good oxygen permeability. For example, as such a lens-forming monomer, silicon-containing (meth) acrylates, fluorine-containing (meth) acrylates, etc. are mainly preferably selected, and the lens is reinforced to obtain an ophthalmic lens material having good strength. Then, alkyl (meth) acrylates, styrene derivatives and the like are mainly preferably selected.

Then, in order to impart hydrophilicity to the lens or to obtain a water-containing flexible ophthalmic lens material, hydroxyalkyl (meth) acrylates, (meth) acrylamides,
A monomer having a hydrophilic group such as (meth) acrylic acid or vinyl lactam is mainly preferably selected, and if it is attempted to make the lens less likely to be contaminated with lipid, a fluorine-containing monomer, for example, a fluorine-containing (meth) An acrylate or a fluorine-containing styrene derivative will be mainly preferably selected.

Further, when the lens is required to have an ultraviolet absorbing ability or the light resistance of the dye is desired to be improved, the above-mentioned ultraviolet absorbing monomer is preferably selected.

It should be noted that one or more of the above lens-forming monomers may be selected and polymerized to form a macromonomer, which may be used as one of the lens-forming monomers.

Further, in order to improve the cross-linking effect, that is, the shape stability and durability (chemical resistance, solvent resistance, heat resistance), a cross-linking agent or at least two or more polymerizable groups are included in the molecule, if necessary. Macromonomers will also be selected.

Specific examples of the cross-linking agent include 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 and the like can be mentioned, and one or more of these are suitably selected and added.

By the way, the compounding ratio of the polymerizable dye according to the present invention is preferably in the range of 0.001 to 0.03 parts by weight with respect to 100 parts by weight of all the monomers of the lens component. If the blending ratio is lower than this, it makes no sense to add the polymerizable dye, and if the blending ratio is higher than this, the color tone is too dark to be practical, or it becomes difficult to transmit visible light. Of. And, such a polymerizable dye,
It is most suitable to use in a ratio of about 0.02 parts by weight.

Then, as a method for polymerizing the mixture of the lens-forming monomer and the polymerizable dye as described above, a method usually used in the technical field is adopted. For example, if necessary, a radical polymerization initiator may be added to such a mixture, and the mixture may be gradually heated in a temperature range of room temperature to 130 ° C or irradiated with electromagnetic waves such as microwaves, ultraviolet rays, and radiation (γ rays). Are polymerized by. The polymerization may be a bulk polymerization method, a solvent polymerization method using a solvent or the like, and in the case of heating polymerization, the temperature may be raised stepwise, and various other methods may be used. It can be adopted.

As a specific example of the radical polymerization initiator, for example,
Azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide and the like can be mentioned, and one or more of them can be selected. Will be used. The amount used is preferably in the range of about 0.01 to 1 part by weight with respect to 100 parts by weight of the total monomer mixture used for the polymerization.

Further, in the case of polymerizing / forming as an ophthalmic lens such as a contact lens or an intraocular lens, a molding method usually practiced by those skilled in the art can be adopted. For example, the polymerization is carried out in a suitable mold or container, a rod shape, After obtaining a block-shaped or plate-shaped material (polymer), machine it into a desired shape by mechanical processing such as cutting or polishing, or prepare a mold corresponding to the desired shape. Among them, a method is employed in which a monomer mixture is polymerized to obtain a molded product, and mechanically finishing is performed if necessary.

When forming an ophthalmic lens, it does not matter whether the lens supporting portion is formed separately from the lens and attached to the lens, or it is molded (integrally) with the lens.

(Examples) Hereinafter, several examples of the present invention will be shown to clarify the present invention more specifically, but the present invention does not impose any restrictions due to the description of such examples. Needless to say, it is not something to receive.

In addition to the following embodiments, the present invention further includes various changes and modifications based on the knowledge of those skilled in the art, in addition to the above specific description, without departing from the spirit of the present invention. It should be understood that improvements and the like can be added.

Example 1 (Synthesis of 1-phenylazo-4-methacryloyloxynaphthalene) Aniline: 3.72 g was dissolved in 0.5 N hydrochloric acid: 500 ml, and the solution was added with an aqueous sodium nitrite solution (concentration: 0.6
40 ml of 9 g / 10 ml) was added and the mixture was stirred for about 1 hour to prepare a diazonium salt aqueous solution. Next, α-naphthol: 5.56 g
It was dissolved in 0.5 N sodium hydroxide: 1 and the diazonium salt aqueous solution was added while vigorously stirring the solution.

After standing for 6 hours, hydrochloric acid was added to the aqueous solution to make it acidic, then made alkaline with a sodium hydroxide aqueous solution to about 1 N, washed with chloroform and then made acidic again, and the deposited precipitate was collected by filtration.

After drying such a precipitate, it is extracted with 1 ethanol,
The obtained extract: 4.15 g was dissolved in 200 ml of acetone, 10 g of triethylamine was further added, and the solution was cooled to 5 ° C. or lower, and then 50 ml of acetone was added with methacrylic acid chloride:
An acetone solution in which 2.15 g was dissolved was added dropwise to this solution over about 1 hour.

After stirring for 6 hours, the reaction mixture was evaporated to dryness and benzene 1 was added.
It was extracted with. Then, after drying again, 200 ml of hexane
It was recrystallized. As a result of analyzing the crystalline substance, the following results were obtained, and it was confirmed that the substance was 1-phenylazo-4-methacryloyloxynaphthalene.

Infrared absorption spectrum Wavenumber (cm ^-1 ) 1718: Carbonyl of methacryloyloxy group 1630: C = C double bond of methacryloyloxy group ¹ H-nuclear magnetic resonance spectrum δ value (ppm) 2.16: Methyl of methacryloyloxy group 5.81: Methacryloyl Methylene of oxy group 6.56: Methylene of methacryloyloxy group 7.2 to 9: Aromatic ring Visible light absorption spectrum λmax (nm) ε 375.5 1.35 × 10 ⁴ Example 2 (Synthesis of (1-phenylazo-2-hydroxy-3-methacryloyloxynaphthalene) ) Aniline: 3.72 g was dissolved in 0.5 N hydrochloric acid: 500 ml, and 40 ml of an aqueous sodium nitrite solution (concentration: 0.69 g / 10 ml) was added to the solution.
The mixture was added at a temperature of ~ 5 ° C and stirred for about 1 hour to prepare a diazonium salt aqueous solution.

On the other hand, 2-hydroxy-3-methacryloyloxynaphthalene (9.12 g) was dissolved in benzene (2), triethylamine (50 g) was added, and then the above diazonium salt aqueous solution was added with vigorous stirring.

The benzene layer was thoroughly washed with water and then dried to dryness, and the resulting solid was mixed with 100 parts of an organic solvent (chloroform: hexane = 1: 9).
It was dissolved in 0 ml under heat and left overnight to precipitate crystals.
As a result of analyzing the crystalline substance, the following results were obtained, and it was confirmed that the obtained substance was 1-phenylazo-2-hydroxy-3-methacryloyloxynaphthalene.

Infrared absorption spectrum Wave number (cm ^-1 ) 1735: Carbonyl of methacryloyloxy group 1637: C = C double bond of methacryloyloxy group ¹ H-nuclear magnetic resonance spectrum δ value (ppm) 2.12: Methyl of methacryloyloxy group 5.81: Methacryloyl Methylene of oxy group 6.44: Methylene of methacryloyloxy group 7.23 to 8.47: Aromatic ring 16.36: Hydroxyl group (hydrogen bond with azo group) ¹³ C-nuclear magnetic resonance spectrum δ value (ppm) 18.3: Methyl of methacryloyloxy group 117.8: Methacryloyloxy Methylene of the group Visible light absorption spectrum λmax (nm) ε 490.7 2.02 × 10 ⁴ Example 3 (Synthesis of 1-naphthylazo-2-hydroxy-3-methacryloyloxynaphthalene) Naphthylamine (1.43 g) was dissolved in 1N hydrochloric acid (100 ml). , 10ml of sodium nitrite aqueous solution (concentration: 0.69g / 10ml)
Was added at a temperature of 0 to 5 ° C., and the mixture was stirred for about 1 hour to prepare a diazonium salt aqueous solution.

On the other hand, 2-hydroxy-3-methacryloyloxynaphthalene (2.28 g) was dissolved in 500 ml of benzene, triethylamine (20 g) was added, and the above diazonium salt aqueous solution was added thereto while vigorously stirring.

After thoroughly washing the benzene layer with water, the solid was dried, and the solid obtained was washed with 1000 m of an organic solvent (chloroform: hexane = 1: 9).
It was dissolved in 1 l under heat and left overnight to precipitate crystals. As a result of analyzing the crystalline substance, the following results were obtained, and it was confirmed that the obtained substance was 1-naphthylazo-2-hydroxy-3-methacryloyloxynaphthalene.

Infrared absorption spectrum Wavenumber (cm ^-1 ) 1718: Carbonyl of methacryloyloxy group 1630: C = C double bond of methacryloyloxy group ¹ H-nuclear magnetic resonance spectrum δ value (ppm) 2.12: Methyl of methacryloyloxy group 5.18: Methacryloyl Methylene of oxy group 6.28: Methylene of methacryloyloxy group 7.22 to 8.30: Aromatic ring 17.26: Hydroxyl group (hydrogen bond with azo group) ¹³ C-nuclear magnetic resonance spectrum δ value (ppm) 18: Methyl of methacryloyloxy group 114: Methacryloyloxy Group methylene 121: methacryloyloxy group> C = 123 to 145: aromatic ring 178: methacryloyloxy group carbonyl visible light absorption spectrum λmax (nm) ε 524.0 1.94 × 10 ⁴ Example 4 (1-((4'- (Phenylazo) phenyl) azo)-
Synthesis of 2-hydroxy-3-methacryloyloxynaphthalene) p-aminoazobenzene: 1.97 g was dissolved in 1N hydrochloric acid: 100 ml, and sodium nitrite aqueous solution (concentration: 0.69 g / 10 m
10 ml of l) was added at a temperature of 0 to 5 ° C., and the mixture was stirred for about 3 hours to prepare a diazoniur salt aqueous solution.

On the other hand, 2-hydroxy-3-methacryloyloxynaphthalene (2.28 g) was dissolved in 200 ml of benzene, triethylamine (15 g) was added, and the above diazonium salt aqueous solution was added thereto while vigorously stirring.

After thoroughly washing the benzene layer with water, the solid was dried, and the solid obtained was washed with 1000 m of an organic solvent (chloroform: hexane = 1: 9).
It was dissolved in 1 l under heat and left overnight to precipitate crystals. As a result of analyzing the crystalline substance, the following results were obtained, and it was confirmed that the obtained substance was 1-((4 '-(phenylazo) phenyl) azo) -2-hydroxy-3-methacryloyloxynaphthalene. Was given.

Infrared absorption spectrum Wave number (cm ^-1 ) 1718: Carbonyl of methacryloyloxy group 1630: C = C double bond of methacryloyloxy group ¹ H-nuclear magnetic resonance spectrum δ value (ppm) 2.11: Methyl of methacryloyloxy group 5.86: Methacryloyl Methylene of oxy group 6.50: Methylene of methacryloyloxy group 7.29 to 8.43: Aromatic ring 16.39: Hydroxyl group (hydrogen bond with azo group) ¹³ C-nuclear magnetic resonance spectrum δ value (ppm) 18.8: Methyl of methacryloyloxy group 133: Methacryloyloxy Methylene of the group 124,126,131,133,155: aromatic ring visible light absorption spectrum λmax (nm) ε 518.0 3.72 × 10 ⁴ Example 5 (1- (α-anthrylazo) -2-hydroxy-3-
Synthesis of methacryloyloxynaphthalene) 1-aminoanthracene: 1.73 g is dissolved in 1N hydrochloric acid: 100 ml, and sodium nitrite aqueous solution (concentration: 0.69 / 10 ml) is dissolved in this.
Was added at a temperature of 0 to 5 ° C. and stirred for about 3 hours to prepare a diazonium salt aqueous solution.

On the other hand, 2-hydroxy-3-methacryloyloxynaphthalene (2.28 g) was dissolved in 200 ml of benzene, triethylamine (15 g) was added, and the above diazonium salt aqueous solution was added thereto while vigorously stirring.

The benzene layer was thoroughly washed with water, dried to dryness, and the obtained solid was dissolved in 50 ml of chloroform. 450 ml of hexane was vigorously stirred, and the chloroform solution was added to the powder substance to obtain 1- (α-anthrylazo). ) -2-Hydroxy-3-methacryloyloxynaphthalene.

Visible light absorption spectrum λmax (nm) ε 540.5 1.39 × 10 ⁴ Example 6 Tris (trimethylsiloxy) silylpropyl methacrylate: 71 parts by weight, hexafluoroisopropyl methacrylate: 29 parts by weight, ethylene glycol dimethacrylate: 6 parts by weight, methacrylic acid : 4.8 parts by weight, N-vinyl-
2-Pyrrolidone: 6.2 parts by weight, the polymerizable dye obtained in Example 1: 0.005 parts by weight, and azobisdimethylvaleronitrile as a polymerization initiator: 0.20 parts by weight were uniformly mixed and poured into a glass test tube. Sealed. Put this in a circulating constant temperature water tank, after 40 hours of reaction at a temperature of 35 ℃, in a circulation dryer, to 50 ~ 110 ℃ for about 12 hours,
Further reaction was carried out while gradually raising the temperature. The polymerization reaction proceeded well.

From the obtained rod-shaped copolymer, diameter: 12.5 mm, thickness: 0.5 m
A plate of m was cut out and both sides were polished to obtain a plate-shaped test piece (No. 1).

The obtained test piece was uniformly colored and yellow and transparent.

Example 7 The polymerizable dye obtained in Example 2 was used in place of the polymerizable dye used in Example 6 (the dye synthesized in Example 1), and the same operation as in Example 6 was performed. , A plate-shaped test piece (No. 2) was prepared. Polymerization proceeded satisfactorily, and the obtained test piece was uniformly colored and orange transparent.

Example 8 The polymerizable dye obtained in Example 3 was used in place of the polymerizable dye used in Example 6, and the same operation as in Example 6 was carried out to obtain a plate-shaped test piece (No. 3). It was created. The polymerization proceeded well, and the obtained plate was uniformly colored,
It was red and transparent.

Example 9 The polymerizable dye obtained in Example 4 was used in place of the polymerizable dye used in Example 6, and the same operation as in Example 6 was carried out to obtain a plate-shaped test piece (No. 4). It was created. The polymerization proceeded well, and the obtained plate was uniformly colored,
It was red and transparent.

Each of the test pieces obtained in Examples 6 to 9 is a material for ophthalmic lenses having high oxygen permeability.

Comparative Example 1 Instead of the polymerizable dye used in Example 6, a conventional dye D having no polymerizable group, D & C Green #, was used.
Using 6 (Ministry of Health and Welfare legal dye: Green No. 202), a plate-shaped test piece (No. 5) was prepared in the same manner as in Example 6.

Then, the light transmittances of the test pieces (Nos. 1 to 5) obtained in Examples 6 to 9 and Comparative Example 1 were measured, and then various durability tests as described below were performed. Further, the light transmittance was measured, the decolorization rate was calculated, and the test pieces (dye: synthesized in Examples 1 to 5) used in each Example were evaluated based on the results, and the results were shown. Are shown in Table 1.

The durability test of the material was performed as follows.

Acid resistance test Each test piece was immersed in 0.1N hydrochloric acid at a temperature of 50 ° C.
Soaking for a week.

Alkali resistance test Each test piece was immersed in a 0.1N sodium hydroxide aqueous solution at a temperature of 50 ° C for 1 week.

Boil resistance test A Each test piece was immersed in physiological saline and continuously boiled for 100 hours.

Boiling resistance test B Each test piece was left in an autoclave at 121 ° C for 1 hour while being immersed in physiological saline.

 Ethanol extraction test Each test piece was immersed in ethanol at 70 ° C for 24 hours.

Sodium hypochlorite aqueous solution extraction test Each test piece was treated with a sodium hypochlorite aqueous solution (concentration: 100 pp
Immersed in m) for 1 month.

 Hydrogen peroxide extraction test Each test piece was immersed in a 3% aqueous hydrogen peroxide solution for 1 month.

Light resistance test Each test piece was exposed to sunlight while being immersed in physiological saline for 1 month.

Further, regarding the method of measuring the light transmittance, using a self-recording spectrophotometer UV-240 manufactured by Shimadzu Corporation, first, the light transmittance of the test piece before various durability tests (visible light transmission spectrum)
After that, the light transmittance was similarly measured for the test pieces on which various durability tests were performed.

Next, the decolorization rate was calculated based on the following formula.

However, T is the minimum value of the light transmittance before the durability test in the visible region, and T ′ is the light transmittance measured after the durability test at the wavelength showing this minimum transmittance value.

Then, the performance of each test piece (dye) was evaluated as follows in consideration of the decolorization rate obtained from the visible light transmittance and the change in color tone depending on the appearance, and the results are shown in Table 1 below.

⊚: Decolorization rate of less than 5%, appearance is very good.

◯: Decolorization rate is 5% or more and less than 10%, and no change in appearance is observed with ordinary lenses.

Δ: Decolorization rate is 10% or more and less than 30%, and decolorization is observed in the appearance.

X: Decolorization rate of 30% or more, the appearance is in a state of deteriorating the product image

As is clear from the results, as compared with the comparative example, the test piece using the dye according to the present invention has dramatically improved durability, that is, fastness, and such dye hardly elutes. It was possible to prevent decolorization extremely well.

Comparative Example 2 It was attempted to prepare a plate-shaped test piece in the same manner as in Example 6 by using the phthalocyanine dye Blue No. 404 instead of the polymerizable dye used in Example 6, but this dye was used to form a lens. It was insoluble because it was not uniformly mixed with the monomer of siloxanyl type.

Comparative Example 3 Instead of the polymerizable dye used in Example 6, JP-A-62-26
An attempt was made to prepare a plate-shaped test piece in the same manner as in Example 6 using the dye having a phthalocyanine-based polymerizable group described in Japanese Patent No. 5357, but it was similarly insoluble.

Example 10 N-vinyl-2-pyrrolidone: 20 parts by weight, N, N-dimethylacrylamide: 60 parts by weight, methyl methacrylate: 15 parts by weight, ethylene glycol dimethacrylate: 0.3 parts by weight, having a polymerizable group in the molecule Methyl methacrylate polymer: 20 parts by weight, polymerizable dye obtained in Example 1:
0.01 parts by weight and 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator were uniformly mixed and injected into a polypropylene test tube and sealed. This was placed in a circulating constant temperature water bath, reacted at 35 ° C. for 64 hours and then at 50 ° C. for 40 hours, and then gradually heated to 60 to 110 ° C. for about 17 hours in a circulating dryer. The reaction was carried out. The polymerization reaction proceeded well, and a yellow transparent rod-shaped copolymer was obtained.

This copolymer is cut into a plate-shaped test piece,
After continuous boiling treatment for 300 hours and observing the color fading condition of the test piece, there was no problem such as color fading, and the colorability was good.

Example 11 A plate-shaped test piece was prepared in the same manner as in Example 10 except that the polymerizable dye obtained in Example 3 was used instead of the polymerizable dye used in Example 10. The polymerization proceeded well, and the obtained plate was uniformly colored and red and transparent.

Then, a boiling resistance test was conducted in the same manner as in Example 10, but there was no problem such as discoloration, and the colorability was good.

Example 12 In place of the polymerizable dye used in Example 10, the polymerizable dye obtained in Example 5 was used to prepare a plate-shaped test piece in the same manner as in Example 10. The polymerization proceeded satisfactorily, and the obtained plate was uniformly colored and was transparent in purple.

Then, a boiling resistance test was conducted in the same manner as in Example 10, but there was no problem such as discoloration, and the colorability was good.

Further, the obtained copolymer is formed into a chip and
1 g was boiled twice in 250 ml of water for 3 hours and then dried at 50 ° C. for 2 days. Using such a chip, an eluate test based on contact lenses as defined by the Ministry of Health and Welfare was carried out, and no elution of dye was observed.

The test pieces obtained in Examples 10 to 12 are all highly water-containing ophthalmic lens materials.

Example 13 Tris (trimethylsiloxy) silylpropyl methacrylate: 71 parts by weight, hexafluoroisopropyl methacrylate: 29 parts by weight, ethylene glycol dimethacrylate: 6 parts by weight, methacrylic acid: 4.8 parts by weight, N-vinyl-
2-Pyrrolidone: 6.2 parts by weight, UV-absorbing monomer 2-hydroxy-4-methacryloyloxybenzophenone: 0.7 parts by weight, polymerizable dye obtained in Example 1:
0.005 parts by weight and 0.20 parts by weight of azobisdimethylvaleronitrile as a polymerization initiator were uniformly blended, poured into a glass test tube and sealed. Put this in a circulating constant temperature water tank, after reacting at 35 ℃ for 40 hours, in a circulation dryer,
The reaction was carried out by gradually raising the temperature to 50 to 110 ° C. for about 12 hours. The polymerization reaction proceeded well.

From the obtained rod-shaped copolymer, similar to the above, diameter: 12.
A plate having a size of 5 mm and a thickness of 0.5 mm was cut out and subjected to polishing on both sides to obtain a plate-shaped test piece. The test piece was uniformly colored and yellow and transparent.

Example 14 Instead of the polymerizable dye used in Example 13, the polymerizable dye obtained in Example 2 was used to prepare a plate-shaped test piece in the same manner as in Example 13. Polymerization proceeded satisfactorily, and the obtained test piece was uniformly colored and orange transparent.

Example 15 Using the polymerizable dye obtained in Example 3 instead of the polymerizable dye used in Example 13, a plate-shaped test piece was prepared in the same manner as in Example 13. The polymerization proceeded well, and the obtained test piece was uniformly colored and red and transparent.

Example 16 Instead of the polymerizable dye used in Example 13, the polymerizable dye obtained in Example 4 was used to prepare a plate-shaped test piece in the same manner as in Example 13. The polymerization proceeded well, and the obtained test piece was uniformly colored and red and transparent.

Then, for each test piece obtained in Examples 13 to 16,
Of the above durability tests, a light resistance test () was performed, and the performance of the test piece (dye) was evaluated in the same manner as above. As a result, in all cases, a decolorization rate of less than 5% and a very good appearance were obtained,
From this, it was clarified that the light resistance was further improved by using the ultraviolet absorbing monomer together.

(Effects of the Invention) As is apparent from the above description, the polymerizable dye according to the present invention is soluble in various monomers that are components of the lens material, and has R _{1 to} R in the general formula (I). _Since any one of ₇ is a polymerizable group, it is copolymerized with a monomer that is a component of the lens material. Therefore, by using such a polymerizable dye, any of water-containing, and hard and non-water-containing ophthalmic lenses can be colored satisfactorily and uniformly, and since the dye is not eluted, It is possible to prevent discoloration and discoloration of the colored lens due to the elution of the dye, and it is also possible to effectively improve the durability and fastness to light and chemical agents. It is possible to satisfactorily obtain various types of uniformly colored ophthalmic lenses that do not vary in coloring depending on the location.

As described above, according to the present invention, it is possible to provide an excellent pigment for an ophthalmic lens and a colored ophthalmic lens that can solve the problems inherent in the conventional dyeing (coloring) methods. Therefore, the great significance of the present invention exists here.

Claims (4)

[Claims] 1. A polymerizable dye for coloring an ophthalmic lens represented by the following general formula (I). However, in the formula, R _{1 to} R ₇ are each independent, and any one of them is a polymerizable group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group. , Other are hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, hydroxyl group, chlorine atom,
And a substituent selected from the group consisting of bromine atoms, and R ₈ is a substituent selected from the group of the following general formulas (II) to (V). (However, R _{9 to} R ₁₃ are each independently selected from the group consisting of hydrogen atom, alkyl group having 1 to 18 carbon atoms, methoxy group, ethoxy group, hydroxyl group, nitro group, chlorine atom, and bromine atom. It is a substituted group.) (However, R _{14 to} R ₂₇ are each independently, a substituent selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a chlorine atom, and a bromine atom. It is a base.) (However, R _{28 to} R ₃₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) 2. A method for producing a colored ophthalmic lens material, characterized in that, when an ophthalmic lens material is produced by polymerizing a vinyl monomer, a polymerizable dye represented by the following general formula (I) is copolymerized. . However, in the formula, R _{1 to} R ₇ are each independently, and any one of them is a polymerizable group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group. , Other are hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, hydroxyl group, chlorine atom,
And a substituent selected from the group consisting of bromine atoms, and R ₈ is a substituent selected from the group of the following general formulas (II) to (V). (However, R _{9 to} R ₁₃ are each independently, and are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) (However, R _{14 to} R ₂₇ are each independently a substitution selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a chlorine atom, and a bromine atom. It is a base.) (However, R _{28 to} R ₃₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) 3. The method for producing a colored ophthalmic lens material according to claim 2, wherein the polymerizable dye is used in a proportion of 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the vinyl monomer. 4. A colored eye lens material comprising a vinyl polymer obtained by copolymerizing a polymerizable dye represented by the following general formula (I). However, in the formula, R _{1 to} R ₇ are each independently, and any one of them is a polymerizable group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group. , Other are hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, hydroxyl group, chlorine atom,
And a substituent selected from the group consisting of bromine atoms, and R ₈ is a substituent selected from the group of the following general formulas (II) to (V). (However, R _{9 to} R ₁₃ are each independently, and are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.) (However, R _{14 to} R ₂₇ are each independently a substitution selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a chlorine atom, and a bromine atom. It is a base.) (However, R _{28 to} R ₃₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a methoxy group, an ethoxy group, a hydroxyl group, a nitro group, a chlorine atom, and a bromine atom. It is a substituted group.)