JPH0651102A - Optical lens composition, optical lens, contact lens and intraocular lens - Google Patents

Abstract

(57) [Summary] [Purpose] To form an optical lens that has oxygen permeability, flexibility and stable ultraviolet absorption properties and is safe for the human body. The optical lens composition has an oxygen permeable resin containing a silicon atom, a polar group, and a molecular weight of 300 to 10.
00 benzotriazole-based UV absorber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical lens composition, an optical lens, a contact lens and an intraocular lens, particularly an optical lens composition containing an oxygen permeable resin containing a silicon atom, and an optical lens comprising the composition. , Contact lenses and intraocular lenses.

[0002]

2. Description of the Related Art As a medical optical lens such as a contact lens or an intraocular lens, one made of synthetic resin has been adopted. Regarding contact lenses, oxygen-permeable contact lenses have been developed that reduce the physiological burden on the cornea and can be worn continuously for a long time. Such an oxygen permeable contact lens is disclosed in, for example, JP-A-58-194.
014, JP-A-59-28127, JP-A-60-1
46219, JP-A-2-198415 and JP-A-2-19845.
No. 147613, etc., and generally comprises a polymer resin or copolymer resin of a monomer containing a silicon atom such as a siloxane compound.

On the other hand, the intraocular lens is used as a substitute for the lens of a cataract patient and is generally made of polymethylmethacrylate resin. However, since the intraocular lens made of polymethylmethacrylate resin is poor in flexibility, it is necessary to make a relatively large incision in the eyeball during a surgical operation for replacing the lens of a cataract patient. If a large incision is made in the eyeball, irregular sutures or incomplete fusion may occur, which may cause astigmatism or macroscopic aberration. Therefore, as for the intraocular lens, as a flexible one that can be inserted into the eyeball by a small incision, there is provided one made of a resin containing a silicon atom similar to that of a contact lens (for example, JP-A-63-2165).
74, JP-A-62-109564).

By the way, 300 to 400 contained in sunlight
It is known that ultraviolet rays having a wavelength in the nm region cause chemical changes in the lens and retina and cause damage. In order to avoid such an obstacle due to ultraviolet rays, US Pat. No. 3,141,869 discloses a spectacle lens in which an ultraviolet absorber is mixed. It is preferable that a contact lens and an intraocular lens made of a resin containing a silicon atom also contain an ultraviolet absorber in order to protect the crystalline lens and retina from ultraviolet rays.

However, when a contact lens or an intraocular lens is formed by mixing a UV absorber with an oxygen permeable resin composed of a polymer resin or a copolymer resin of a siloxane compound, the UV absorber is eluted or the lens is removed from the lens. Easy to bleed out. Further, the characteristics of the ultraviolet absorber are likely to deteriorate.
This is because the glass transition point of silicone is lower than room temperature and it is a rubbery polymer at room temperature. As a result, the molecular motion of the siloxane region is large in the polymer of the siloxane compound, and the ultraviolet absorber present in this part is It is thought that it is easy to move and disassemble. Therefore, if the content of the siloxane compound is increased in order to improve oxygen permeability and flexibility, such a problem is likely to occur. The elution, bleed-out and deterioration of the characteristics of the ultraviolet absorber may adversely affect the eyeball and pose a safety problem.

[0006] An object of the present invention is to provide an optical lens composition, which is capable of forming an optical lens having stable ultraviolet absorption characteristics while maintaining oxygen permeability and flexibility and safe for the human body. Another object of the present invention relates to optical lenses, contact lenses, and intraocular lenses, to provide stable ultraviolet absorption characteristics while maintaining oxygen permeability and flexibility, and to enhance safety to the human body.

[0007]

The optical lens composition according to the present invention comprises an oxygen permeable resin containing a silicon atom and a benzotriazole type ultraviolet absorber having a polar group and a molecular weight of 300 to 1000. I'm out. In this optical lens composition, the oxygen permeable resin has, for example, an oxygen permeability coefficient of 10 × 10 ⁻¹¹ cm ³ (STP) · cm ² · sec ·
mmHg or more. The oxygen permeable resin is, for example, a copolymer of a siloxane compound having a double bond and a compound having an acryloyl group. Here, the acryloyl group is a concept including a methacryloyl group. Furthermore, the amount of the benzotriazole-based ultraviolet absorber added is
For example, it is 0.01 to 10.0% by weight.

The optical lens, contact lens and intraocular lens according to the present invention are optical containing an oxygen permeable resin containing a silicon atom and a benzotriazole type ultraviolet absorber having a polar group and a molecular weight of 300 to 1000. Each is composed of a lens composition. Oxygen-permeable resin The oxygen-permeable resin used in the present invention is a polymer or copolymer containing a silicon atom. This polymer or copolymer contains a silicon atom in the main chain, side chain, or both of them, and is mainly composed of a polymer containing an organosilane group such as a siloxane bond or a trimethylsilyl group. It is a thing.

The polymer containing a silicon atom is preferably a long-chain polymer in which a silicon atom is contained in the polymer through a siloxane bond in order to obtain good oxygen permeability and flexibility. Specific examples of such a polymer include tris (trimethylsiloxy) silylpropyl methacrylate, polydimethylsiloxane having a double bond at both ends, a homopolymer using a silicone-containing acrylate, a silicone-containing methacrylate, and the above-mentioned silicon-containing monomer. And copolymers with other monomers.

The monomers copolymerizable with the silicon-containing monomer include acrylic monomers, methacrylic monomers,
Monofunctional monomers such as aromatic vinyl monomers and heterocyclic vinyl monomers, diacryl monomers, dimethacryl monomers, triacryl monomers, trimethacryl monomers, tetraacryl monomers, tetramethacryl monomers, aromatic divinyl monomers, aromatic diallyl monomers, etc. A polyfunctional monomer can be illustrated.

Here, as the acrylic monomer and methacrylic monomer, alkyl acrylates or alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, Hydroxyalkyl acrylates such as hydroxyethyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate, or hydroxyalkyl methacrylates, halogenated alkyl acrylates such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoroethyl acrylate, and tetrafluoroethyl methacrylate, or Halogenated alkyl methacrylate S, cyclohexyl acrylate, cycloalkyl acrylates or cycloalkyl methacrylates such as cyclohexyl methacrylate and the like. Of these, when methyl methacrylate is used, an optical lens having good mechanical properties can be obtained. When a fluoroalkyl acrylate or a fluoroalkyl methacrylate is used, an optical lens having good oxygen permeability and mechanical properties can be obtained.

Examples of aromatic vinyl monomers include vinylbenzene, vinylnaphthalene, vinylethylbenzene and the like. Examples of the heterocyclic vinyl monomer include vinylcarbazole, maleimide, maleic anhydride and the like. Among the above-mentioned monomers for copolymerization, an acrylate monomer or a methacrylate monomer is particularly preferable in terms of obtaining an optical lens having good copolymerizability and transparency. In particular, when methyl acrylate, methyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, acrylic acid or methacrylic acid is used, an optical lens having good mechanical strength, transparency and oxygen permeability can be obtained.

Among the above-mentioned polyfunctional monomers, examples of the bifunctional acrylic or methacrylic monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate and bisphenol A.
Diacrylate, bisphenol A dimethacrylate,
Examples thereof include ethylene oxide-added bisphenol A diacrylate, ethylene oxide-added dimethacrylate and urethane-modified acrylates or methacrylates thereof, glycerol diacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate and the like. As the trifunctional acrylic or methacrylic monomer,
Examples thereof include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Examples of the tetrafunctional acrylic or methacrylic monomer include tetramethylol methane tetraacrylate and tetramethylol methane tetramethacrylate. Examples of the aromatic divinyl compound include o-diallyl phthalate, m-diallyl phthalate, p-diallyl phthalate and the like. Specific examples of other polyfunctional monomers include bismaleimide, allyl acrylate, and allyl methacrylate. Note that diacrylate, dimethacrylate, triacrylate, trimethacrylate, tetraacrylate, and tetramethacrylate are preferable in order to improve good copolymerizability and transparency of the optical lens. In particular, in order to obtain an optical lens having good mechanical strength and transparency, it is preferable to use triacrylate or trimethacrylate.

Among the above-mentioned oxygen-permeable resins used in the present invention, the most preferable are the siloxane compound having a double bond and the acryloyl group or methacryloyl which can realize good transparency, oxygen permeability and mechanical properties. It is a copolymer with a compound having a group. In the oxygen permeable resin used in the present invention, silicon atoms may be present uniformly in the entire polymer or may be present in a non-uniform form having a so-called micro phase separation structure.

The oxygen permeable resin used in the present invention has an oxygen permeability coefficient of 10 × 10 ⁻¹¹ cm ³ (STP) · cm /
It is preferably at least cm ² · sec · mmHg. If the oxygen permeability coefficient is less than the above range, when a contact lens is formed, the contact lens cannot supply sufficient oxygen to the cornea. The oxygen permeability coefficient is
It can be measured by a known method such as an electrode method, a vacuum method and a pressure method. Ultraviolet Absorber The ultraviolet absorber used in the present invention is likely to cause a chemical change in the crystalline lens or retina of the human eye at 300 to 400 nm.
It is a benzotriazole-based UV absorber having excellent UV-absorbing properties in the wavelength range. It should be noted that benzophenone-based, salicylate-based, and cyanoacrylate-based ultraviolet absorbers have a maximum absorption wavelength in a shorter wavelength region than benzotriazole-based ultraviolet absorbers, and are not preferable for achieving the object of the present invention.

The benzotriazole type ultraviolet absorber used in the present invention has a polar group. here,
The benzotriazole-based ultraviolet absorber having a polar group refers to a polar group directly bonded to the benzotriazole skeleton, or a polar group bonded to the benzotriazole skeleton through a carbon chain. As the polar group bonded to the benzotriazole skeleton, a hydroxyl group, a carbonyl group, a carboxyl group, a thiocarboxyl group, an amino group, a nidro group, a nitroso group, a sulfo group, a sulfino group, an amide group, an imide group, a cyano group, Examples thereof include an isocyano group, a thiocyano group, an aldehyde group and a thiol group. Further, a polar heterocyclic compound can also be a polar group. Specific examples of the heterocyclic compound having polarity include:
Furan, tetrahydrofuran, dioxane, dioxolane, oxazole, isoxazole, xanthene, furazan, pyran, pyrimidine, pyrazine, pyrroline, pyrrolidine, imidazoline, triazine, pyrrole, imidazole, triazole, benzotriazole, pyrazole, pyridine, pyridazine, piperidine, pyrazolidine, Indole, quinoline, isoquinoline, quinoxaline, purine, pteridine, carbazole, phenanthridine, phenazine, phenanthroline, indoline, isoindoline, chroman, pyrazinocarbazole, pyridoxazine, imidazothiazole, pyrazinopyridazine, thiazole, isothiazole, thiophene. Etc. can be illustrated.

Further, a polymer having polarity can also be a polar group. Examples of polar polymers include hydrophilic polymers such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, and sodium polymethacrylate. The benzotriazole-based ultraviolet absorber used in the present invention has a molecular weight of 30.
0 to 1000. If the molecular weight is less than 300, the molecular size is small and the molecules easily move through the gaps of the polymer mesh of the oxygen permeable resin. Therefore, when the optical lens is formed, the ultraviolet absorbent is likely to be eluted or bleed out. Further, for the same reason, in particular, the molecular movement of the ultraviolet absorber becomes large, so that the ultraviolet absorber is easily decomposed, and the ultraviolet absorbing ability of the optical lens is likely to be lowered. On the contrary, when the molecular weight exceeds 1,000,
Since the molecular size becomes large, there is an advantage that elution and bleed-out of the ultraviolet absorber are less likely to occur,
The compatibility with the oxygen permeable resin or its monomer stock solution decreases. As a result, the optical lens may have reduced transparency or may become cloudy.

A specific example of the benzotriazole type ultraviolet absorber used in the present invention is 2- [2'-hydrosynoxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl)-. 5'-methylphenyl] -benzotriazole, methyl-3- [3-t-butyl-5
(2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2 , 2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol and the like.

The above various ultraviolet absorbers may be used alone or in combination of two or more in order to obtain more various ultraviolet absorbing properties. The method of adding the above-mentioned ultraviolet absorber to the oxygen-permeable resin is not particularly limited, but it is a method of adding in advance during the synthesis of the oxygen-permeable resin, a method of kneading by adding to the softened or melted oxygen-permeable resin, etc. Can be adopted.

The amount of the ultraviolet absorber added varies depending on the purpose of use of the optical lens formed by the optical lens composition of the present invention. For example, when used as a contact lens or an intraocular lens, it is preferable to adjust the addition amount so that the transmittance at the maximum absorption wavelength in the ultraviolet region of 200 to 400 nm is less than 20%. This addition amount can be determined in relation to the thickness of the optical lens in addition to the transmittance.

The general addition amount of the ultraviolet absorber is
It is 0.01 to 10% by weight with respect to the weight of the mixed liquid of the raw material monomers of the oxygen permeable resin. If the amount is less than 0.01% by weight, sufficient UV absorption characteristics cannot be obtained. On the contrary, if the addition amount exceeds 10% by weight, the polymerization rate of the oxygen permeable resin may be lowered and the mechanical strength may be lowered. Other Components The optical lens composition of the present invention may contain a colorant in order to adjust the absorption characteristics of the optical lens in the visible light region, in addition to the oxygen permeable resin and the ultraviolet absorber described above. As the colorant, a direct dye, an oil-soluble dye, an acid dye, a basic dye, a disperse dye, a vat dye or the like is used. Also,
Organic dyes such as monoazo, bisazo, anthraquinone, quinonaphthalone, xanthene, pyrazole, triphenylmethane, indigoid, fluorane and quinoline may be used. Use of Optical Lens Composition The optical lens composition of the present invention can be molded into a predetermined optical lens shape by a general molding method such as cast polymerization, injection molding, and extrusion molding. When the oxygen-permeable resin has three-dimensional cross-linking, cast polymerization is preferable. Further, in order to obtain a predetermined optical lens shape, a desired shape can be formed simultaneously with molding using an appropriate mold. When it is necessary to create a wide variety of shapes such as contact lenses and intraocular lenses, first create a cylindrical or flat plate shaped product, and shape this product into the desired shape by cutting or polishing. It is preferably formed.

The contact lens and intraocular lens obtained by the composition of the present invention are made of an oxygen permeable resin containing silicon atoms, and therefore have flexibility and oxygen permeability.
In addition, elution of the ultraviolet absorbent, bleed-out, and deterioration of the ultraviolet absorption characteristics are unlikely to occur, so that the safety is high.

[0023]

Example 1 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet was prepared, and 2,6-diisocyanatocaproic acid-β-isocyanatoethyl was added to the flask. 53.4 parts of ester, 52 parts of 2-hydroxyethyl methacrylate, and 0.0 of di-n-butyltin dilaurate.
1 part was charged, and the mixture was stirred under a nitrogen atmosphere while heating at 50 ° C. until the absorption of hydroxyl groups disappeared in the infrared absorption spectrum.

Next, 94.6 parts of polydimethylsiloxane modified with alcohol at both ends and having an average molecular weight of 946, represented by the following general formula (1), was added to the above-mentioned flask to obtain an isocyanate group of infrared absorption spectrum. The mixture was stirred under a nitrogen atmosphere while heating at 50 ° C until the absorption disappeared. As a result, a reaction product containing a siloxane macromer having two double bonds at each end as a main component was obtained.

[0025]

[Chemical 1]

Next, to 10 parts of this reaction product, 3 parts of methyl methacrylate, 0.055 part of trimethylolpropane trimethacrylate, and 0.004 part of azobismethylvaleronitrile were added. Furthermore, for this monomer mixture, 2- [2'- which is an ultraviolet absorber is used.
Hydroxyl-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -5'-methylphenyl] -benzotriazole 0.5 wt% was added, mixed and dissolved to give a uniform transparent A stock solution was obtained.

Next, the obtained transparent stock solution was placed in a rod-shaped glass container, the container was replaced with nitrogen, and the container was sealed. This glass container is placed in a constant temperature water bath at 40 ° C for 40 hours at 50 ° C.
-24 hours, 60 ° C-16 hours, 70 ° C-4 hours, 90
The treatment was carried out under 5 conditions of ℃ -2 hours. Then one more
It was heated in a circulating dryer at 30 ° C. for 3 hours to obtain a rod-shaped polymer. The obtained polymer had a Shore D hardness of 80 and was good in hardness, machinability and polishability.

The obtained polymer was made into small pieces with a mixer, and 1 g of the small pieces was immersed in 50 g of distilled water and heated at 100 ° C. for 30 hours. Then, when the elution amount of the ultraviolet absorber contained in the distilled water was examined spectroscopically, it was confirmed that only 1.7% of the ultraviolet absorber contained in 1 g of the strip was eluted. The polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm. Then, this disk was heat-treated under vacuum reduced pressure at 120 ° C. for 16 hours,
The decrease in absorbance due to the bleed-out of the ultraviolet absorber was examined spectroscopically, but no decrease in absorbance was observed.

Further, the polymer is 9 mm in diameter and 0.2 in thickness.
It was processed into a disc of mm, and the disc was heat-treated at 120 ° C. for 16 hours under vacuum reduced pressure. For this disc, use a fade meter at room temperature for 20
A 0-hour irradiation test was performed. The absorbance after irradiation was 92% of the absorbance before irradiation, and it was confirmed that this disc had excellent light resistance.

The oxygen permeability coefficient of the polymer was examined by using a Seikaken film oxygen permeability meter, and was found to be 20 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · se at 37 ° C.
It was c · mmHg. Experimental Example 2 Tris (trimethylsiloxy) silylpropyl methacrylate 50 parts by weight, trifluoroethyl methacrylate 50 parts by weight, asobisisobutyronitrile 0.05 parts by weight, and asobiscyclohexanecarbonitrile 0.1.
A monomer mixture containing 5 parts by weight was prepared. 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) as an ultraviolet absorber for this monomer mixture
0.09% by weight of -6- (2H-benzotriazol-2-yl) phenol was added and dissolved to obtain a uniform transparent polymerization stock solution.

Next, the obtained polymerization stock solution was sealed in a test tube. Then, the test tube is heated from 60 ° C to 110 ° C for 24 hours.
The temperature was raised over time, and then the temperature was maintained at 110 ° C. for 4 hours to obtain a polymer. With respect to the obtained polymer, the elution amount of the ultraviolet absorbent, the decrease in the absorbance due to the bleed-out of the ultraviolet absorbent, and the light resistance were examined by the same method as in Example 1. Elution amount of UV absorber is 1g of polymer strip
It was confirmed that the amount was 1.4%, which was extremely small among the ultraviolet absorbers contained in. The rate of decrease in absorbance due to bleed-out was 3.6%, which was extremely small. It was confirmed that the light resistance was excellent since the absorbance after light irradiation was 87% of the absorbance before light irradiation. Example 3 Polydimethylsiloxane 45 having double bonds at both ends
Parts by weight and trifluoroethyl methacrylate 47.5
Parts by weight, 3 parts by weight of methacrylic acid and 4.5 parts by weight of trimethylolpropane trimethacrylate are uniformly mixed, and further 0.05 part by weight of azobisisobutyronitrile and 0.15 part by weight of azobiscyclohexylcarbonitrile. Parts were added.

2- [2'-Hydroxy-3 '-(3 ",
0.5% by weight of 4 ", 5", 6 "-tetrahydrophthalimido-methyl) -5'-methylphenyl] -benzotriazole was added and mixed and dissolved to obtain a uniform transparent stock solution. Was placed in a rod-shaped glass container, the inside of the glass container was replaced with nitrogen, and the container was tightly closed, and the glass container was heated from 65 ° C. to 110 ° C. over 24 hours, and further held at 110 ° C. for 4 hours to obtain a polymer. Was given.
This polymer had a Shore D hardness of 70, and had good hardness, machinability, and polishability.

With respect to the obtained polymer, the elution amount of the ultraviolet absorbent, the decrease in the absorbance due to the bleed-out of the ultraviolet absorbent, the light resistance and the oxygen permeation coefficient were examined in the same manner as in Example 1. The elution amount of the ultraviolet absorber was 1.7% of the ultraviolet absorber contained in 1 g of the polymer strip.
It was confirmed that it was extremely small. No decrease in absorbance due to bleed-out was observed. Light resistance is
It was confirmed that the absorbance after irradiation was 92% of the absorbance before irradiation, which was excellent. Furthermore, the oxygen permeability coefficient is 1
30 × 10 ^-11 cm ³ (STP) · cm / cm ² · se
It was c · mmHg.

Further, it was confirmed that the polymer could be processed into a contact lens having a lens system of 9.0 mm, a base curve of 8.0 mm and a lens power of −3.00 D, and the cutting and polishing property was also good. As a reference, FIG. 1 shows an ultraviolet-visible absorption spectrum (transmittance) of a disk having a thickness of 0.2 mm used for the light resistance test. As is clear from FIG. 1, this disk has good ultraviolet absorption characteristics in the range of 300 to 400 nm.

[0035]

The optical lens composition according to the present invention contains a benzotriazole type ultraviolet absorber having a polar group and a molecular weight of 300 to 1000, and therefore has an oxygen permeability,
It is possible to form a safe optical lens for a human body that has both flexibility and stable ultraviolet absorption characteristics. Since the optical lens, contact lens and intraocular lens according to the present invention are composed of the optical lens composition of the present invention, they have both oxygen permeability, flexibility and stable ultraviolet absorption characteristics, and are highly safe for the human body.

[Brief description of drawings]

FIG. 1 is an ultraviolet absorption spectrum of a disk prepared in Example 3.

Claims (7)

[Claims] 1. An optical lens composition comprising an oxygen-permeable resin containing a silicon atom and a benzotriazole-based UV absorber having a polar group and having a molecular weight of 300 to 1,000. 2. The oxygen permeable resin has an oxygen permeability coefficient of 1.
0 × 10 ^-11 cm ³ (STP) · cm / cm ² · sec
-The optical lens composition according to claim 1, which has a viscosity of mmHg or more. 3. The optical lens composition according to claim 1, wherein the oxygen-permeable resin is a copolymer of a siloxane compound having a double bond and a compound having an acryloyl group. 4. The optical lens composition according to claim 1, wherein the benzotriazole-based ultraviolet absorber is added in an amount of 0.01 to 10.0% by weight. 5. An optical lens comprising an optical lens composition comprising an oxygen permeable resin containing a silicon atom and a benzotriazole type ultraviolet absorber having a polar group and having a molecular weight of 300 to 1000. 6. A contact lens comprising an optical lens composition containing an oxygen-permeable resin containing a silicon atom and a benzotriazole-based ultraviolet absorber having a polar group and having a molecular weight of 300 to 1,000. 7. An intraocular lens comprising an optical lens composition comprising an oxygen permeable resin containing a silicon atom and a benzotriazole type ultraviolet absorber having a polar group and having a molecular weight of 300 to 1000.