JP2001188204A - Soft ocular lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft ocular lens which is small in the surface tacky adhesiveness of the soft acrylic material itself and commonly has pliability and shape restorability adequate as the ocular lens. SOLUTION: This soft ocular lens consists of a copolymer containing the trimer acid ester of higher unsaturated fatty acid or the dimer acid ester and trimer acid ester of the higher unsaturated fatty acid as constitution components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft ophthalmic lens, and more particularly, to a soft ophthalmic lens having extremely small tackiness on the lens surface and excellent lens shape recovery.

[0002]

2. Description of the Related Art Various soft eye lenses have been developed at present. The advantages of a soft ophthalmic lens are numerous, for example, if it is an intraocular lens, the lens can be folded into small pieces so that the insertion of the intraocular lens can be made by a small surgical incision. In addition, if it is a contact lens, it has a great merit such as being excellent in wearing feeling. As the soft ophthalmic lens, an acrylic material is generally used, for example, because there is little breeding of bacteria that cause serious problems to the eyes, and it also has appropriate flexibility and shape recovery.

[0003] However, soft acrylic materials have some disadvantages, and the surface of the material is apt to be tacky, which causes a bad influence when handling or wearing the lens. For example, in the case of an intraocular lens, the handling of the intraocular lens when the intraocular lens is inserted is inadequate due to the adhesiveness of the surface, which requires a great deal of labor and time. Further, even a contact lens may cause serious obstacles such as sticking to the cornea due to the tackiness of the lens surface.

[0004] In order to solve the problem of stickiness, Japanese Patent Publication No. 7-507356 discloses a plasma treatment. However, there is a problem that it is difficult to completely reduce the adhesiveness only by the plasma treatment, and the effect is not maintained. In addition, radicals generated on the lens surface by the plasma treatment may remain even when worn, which is not so preferable as an ophthalmic lens.

In Japanese Patent Application Laid-Open No. Hei 10-24097, in order to improve the tackiness of the surface of a soft ophthalmic lens, a thermal polymerization initiator and a photopolymerization initiator are mixed in a polymerization component, and after a molded article is polymerized by heat. And a method of performing light irradiation. However, in this method, after the lens molded body is manufactured by thermal polymerization, the lens molded body is further irradiated with light, which complicates the working process.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a soft acrylic material having a low surface tackiness, a high strength, and a flexibility and shape recovery suitable for an ophthalmic lens. It is to provide a lens for use.

[0007]

The present invention is characterized by comprising a trimer ester of a higher unsaturated fatty acid or a copolymer containing dimer acid ester and trimer ester of a higher unsaturated fatty acid as constituents. This is a soft ophthalmic lens.

Further, the present invention provides a trimer ester of a higher unsaturated fatty acid, or a dimer ester and a trimer ester of a higher unsaturated fatty acid in an amount of 1 to 40 parts by weight, an alkyl acrylate in an amount of 30 to 90 parts by weight, and copolymerization thereof. A soft ophthalmic lens comprising a copolymer of possible monomers.

The present invention also relates to a method for preparing a trimer acid ester of a higher unsaturated fatty acid or a dimer acid ester and a trimer acid ester of a higher unsaturated fatty acid in an amount of 1 to 40 parts by weight, 30 to 90 parts by weight of an alkyl acrylate, A soft eye comprising 5 to 80 parts by weight of a monomer having at least one radically polymerizable functional group in a molecule at 10 to 50%, and a copolymer of a monomer copolymerizable therewith; Lens.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The trimer esters of higher unsaturated fatty acids, or the dimer esters and trimer esters of higher unsaturated fatty acids used in the present invention, are dimers or trimers of higher unsaturated fatty acids or their esters. It can be obtained by subjecting a polyhydric alcohol obtained by reducing the body to (meth) acrylic esterification.

The higher unsaturated fatty acids used in the present invention include oleic acid, linolenic acid, linoleic acid, etc. In addition, octadecenoic acid, elaidic acid, branched octadecenoic acid, isooleic acid, eicosenoic acid, docosenoic acid And undecylenic acid. Examples of the esters of higher unsaturated fatty acids include esters of the higher unsaturated fatty acids and the like with methanol, ethanol, propanol, butanol, isopropanol, and the like. These higher unsaturated fatty acids or esters thereof may be used alone or in combination of two or more. It can be mixed and used.

The dimer acid or trimer acid can be obtained as a mixture by a generally known production method such as thermal polymerization of the above-mentioned higher unsaturated fatty acid or its ester using montmorillonite-based activated clay as a catalyst.

As a method for separating dimer acid and trimer acid, for example, unreacted substances and the like are distilled off by distilling the above-mentioned synthetic mixture under reduced pressure. Thereafter, the dimer acid component is distilled off, and the distillation is further continued to obtain the trimer acid component.

[0014] Other separation methods include thin-film distillation, molecular distillation, extraction, and chromatographic separation.

The obtained dimer acid or trimer acid is alcoholized by a known reduction operation using lithium aluminum hydride or the like, and then the alcoholated dimer acid or trimer acid is esterified with (meth) acrylic acid. The dimer acid esters represented by the following formulas (1), (2), (3), (4) and (5) used in the present invention, or the following formulas (1), (2) and (3) A trimer ester obtained by reacting the compound represented by the formula (6) with the compound represented by the following formula (6) at each unsaturated bond site can be obtained.

[0016]

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In the present invention, the trimer acid ester is used alone or in any ratio between the dimer acid ester and the trimer acid ester.

Generally, the more flexible the acrylic polymer, the more the tackiness tends to increase. However, it is known that the tackiness is greatly reduced when the material components are crosslinked. When the tackiness is reduced, the physical adhesion amount of dirt is reduced, and the handling of the lens is facilitated. By using the trimer acid ester, or the dimer acid ester and the trimer acid ester, it is possible to bring about a cross-linking effect while having sufficient flexibility as a soft acrylic material. Results in reduced stickiness. In addition, the shape-recovering property is improved by an appropriate crosslinking effect.

The dimer acid ester and trimer acid ester of higher unsaturated fatty acid have the same polarity as a linear alkyl (meth) acrylate such as stearyl (meth) acrylate, but have a branched chain in the molecule. Has two or three radically polymerizable functional groups, and has higher mechanical strength than linear alkyl (meth) acrylates with similar carbon numbers. It is very preferable as an ophthalmic lens material. Also,
Rather than using dimer acid alone, the use of trimer acid, which has a complicated branched chain structure or cyclic structure in the molecule and has a large number of radically polymerizable functional groups, alone or in combination with dimer acid, further enhances mechanical properties. Ophthalmic lens with excellent target strength.

The above is an effect that can be expected even when the dimer acid ester is used alone. However, a trimer acid ester having a higher cross-linking effect and a more complex branched or cyclic structure in the molecule can be obtained. When used alone or in combination with a dimer acid ester, it becomes possible to obtain an ophthalmic lens material which is more flexible, has less surface tackiness, and is excellent in shape recovery and mechanical strength.

Trimer esters of higher unsaturated fatty acids,
Alternatively, the amount of the dimer acid ester and trimer acid ester of a higher unsaturated fatty acid to be used is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the copolymer.

Specific examples of the alkyl acrylate used in the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, pentyl acrylate, and the like.
Trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, hexyl acrylate, 2
-Ethylhexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, 3-methyltridecyl acrylate, 6- Methyl tridecyl acrylate, 7-methyl tridecyl acrylate, 2,11-dimethyl dodecyl acrylate, 2,7-dimethyl-4,5-diethyloctyl acrylate, pentadecyl acrylate, stearyl acrylate, i-stearyl acrylate, allyl acrylate, phenyl Acrylate, phenoxyethyl acrylate Benzyl acrylate, isobornyl acrylate linear, alkyl acrylates branched or cyclic.

In addition to the above acrylate, a fluorine atom-containing alkyl acrylate can be used to improve the stain resistance. Generally, a fluorine atom-containing alkyl acrylate is used as a component for reducing tackiness in order to reduce the material surface energy. However, in the present invention, since the tackiness is sufficiently reduced even without using a fluorine atom-containing alkyl acrylate, it is used for the purpose of improving stain resistance. Specific examples include trifluoroethyl acrylate, tetrafluoropropyl acrylate,
Tetrafluoropentyl acrylate, hexafluorobis (trifluoromethyl) pentyl acrylate, hexafluoroisopropyl acrylate, heptafluorobutyl acrylate, octafluoropentyl acrylate, nonafluoropentyl acrylate, dodecafluorooctyl acrylate, tridecafluorooctyl acrylate, tridecafluoro Heptyl acrylate, heptadecafluorodecyl acrylate, octadecafluoroundecyl acrylate, eicosafluorododecyl acrylate and the like can be mentioned.

The above-mentioned alkyl acrylates can be used alone or in combination of two or more depending on the purpose. The use amount of these alkyl acrylates is preferably 30 to 90 parts by weight based on 100 parts by weight of the copolymer.

Further, various copolymer components can be used depending on the intended use of the ophthalmic lens and required properties.

In order to improve oxygen permeability as a contact lens, a monomer having a silicon atom content of 10 to 50% and having at least one radically polymerizable functional group in a molecule is used. Specific examples include pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, and methylbis (trimethylsiloxy) silylpropyl (meth) ) Acrylate, isobutylhexamethyltrisiloxanylmethyl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropylglycerol (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl Glycerol (meth) acrylate, tris (trimethylsiloxy) silylstyrene, 2-methyl-4-tris (trimethylsiloxy) silyls Ren, trimethylsilyl styrene, 2-methyl-4-trimethylsilyl styrene, pentamethyl disiloxanyl styrene, 2-
Methyl-4-pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene, 2-methyl-4
-Heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, 2-methyl-4-nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, 2-methyl-4-pentadecamethylhepta Siloxanylstyrene, bis (trimethylsiloxy) methylsilylstyrene, 2-methyl-4-
Bis (trimethylsiloxy) methylsilylstyrene,
(Trimethylsiloxy) (pentamethyldisiloxy) methylsilylstyrene, 2-methyl-4- (trimethylsiloxy) (pentamethyldisiloxy) methylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, 2-methyl-4- Tris (pentamethyldisiloxy) silylstyrene, (Tris (trimethylsiloxy)
Siloxanyl) (bis (trimethylsiloxy)) silylstyrene, 2-methyl-4- (tris (trimethylsiloxy) siloxanyl) (bis (trimethylsiloxy))
Silylstyrene, (bis (heptamethyltrisiloxy)) methylsilylstyrene, 2-methyl-4- (bis (heptamethyltrisiloxy)) methylsilylstyrene, tris (tris (trimethylsiloxy) siloxy)
Silyl styrene, 2-methyl-4-tris (tris (trimethylsiloxy) siloxy) silylstyrene and the like can be mentioned. The amount of these silicon monomers to be used is preferably 5 to 80 parts by weight, more preferably 30 to 60 parts by weight, per 100 parts by weight of the copolymer.

In order to impart hydrophilicity to the obtained contact lens, (meth) acrylic acid,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diethylene glycol mono (meth)
Acrylate, triethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, acrylamide, dimethylacrylamide, N-
A hydrophilic monomer such as vinylpyrrolidone can be used, and a radically polymerizable (meth) acrylate having a urethane bond can be used to further improve the mechanical strength. Further, depending on the intended flexibility, strength, etc., linear, branched or cyclic alkyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate ,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Various polyfunctional (meth) acrylates and the like can also be used. However,
The polyfunctional (meth) acrylate is different from the dimer acid ester and the trimer acid ester of higher unsaturated fatty acids, because if the compounding amount is large, the flexibility and elasticity required for the intended soft ophthalmic lens are likely to be impaired. Copolymer 1
It is preferable to use 3 parts by weight or less in 00 parts by weight.

Further, a soft ophthalmic lens having a low specific gravity can be produced by appropriately combining the copolymer component with the trimer acid ester or the dimer acid ester and the trimer acid ester.

The copolymerization in the present invention can be thermal polymerization or ultraviolet polymerization. Examples of the initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, p-isopropyl-α-hydroxyisobutyl ketone, 2,2-dimethoxy-2-phenylacetophenone, α, α -Dichloro-4-phenoxyacetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,2'-azobisisobutyronitrile, 1,
1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4
Dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2,4,4-trimethylpentane), benzoyl peroxide, diisopropylperoxydicarbonate, lauroyl peroxide, stearoyl peroxide, Tert-butyl peroxybivalate, bis (4-tert-butylcyclohexyl) peroxydicarbonate,
α, α'-bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5
-Dimethyl-2,5-bis (tert-butylperoxy) hexane and the like.

Further, radiation polymerization in which high energy radiation or the like is irradiated is also within the scope of the present invention.

The polymerization can be carried out by injecting a monomer mixture containing a polymerization initiator into a mold in which the shape of the lens is adjusted in advance, or after the polymerization in a tubular mold. A method of cutting and polishing the lens shape to be formed is also possible. If the ophthalmic lens of the present invention is applied to an intraocular lens, it is possible to attach a lens support to the lens after molding the lens, or to integrally mold the lens and the support. .

In the present invention, the surface of the soft ophthalmic lens can be subjected to a hydrophilic treatment in order to further improve the hydrophilicity and stain resistance. Plasma in the hydrophilization treatment,
Ultraviolet rays, electron beams, heat and the like can be used.

The ophthalmic lens of the present invention can contain an ultraviolet absorber.

Specific examples of the ultraviolet absorber include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, 2- (2'- Hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- Phenyl hydroxy-4-methacryloyloxymethylbenzoate;

[0035]

The present invention will be described below with reference to examples.

(Synthesis Example) 75 parts by weight of methyl oleate
Starting from a highly unsaturated fatty acid methyl ester containing 15 parts by weight of methyl linoleate and 9 parts by weight of methyl stearate, using 8 parts by weight of montmorillonite-based activated clay as a catalyst, 230 ° C. for 5 hours in a heat-resistant container Dimerization and trimerization reactions were performed. Next, after removing the catalyst from the reaction product solution by filtration, 230 ° C., 133.32 Pa (1 m
mHg) was distilled under reduced pressure to distill unreacted substances and the like. Thereafter, the residue was cooled to 230 ° C. and 13.332 Pa (0.1 mm
Dimer acid dimethyl ester was obtained by molecular distillation under Hg) conditions, and trimer acid trimethyl ester was obtained as a distillation residue.

The dimer acid dimethyl ester and trimer acid trimethyl ester obtained by separation were diluted with diethyl ether, and the diluted solution was added to a diethyl ether solution in which lithium aluminum hydride was dispersed at 5 mL / min. At a speed of. At this time, the reaction was performed while maintaining the temperature of the reaction system at 30 ° C. After the completion of the dropwise addition, the mixture was allowed to stand for 1 hour, and then pure water was added dropwise to the reaction solution, and then slowly transferred into a container containing ice. Further, an aqueous solution of 10% by weight sulfuric acid was added thereto, followed by adding an appropriate amount of diethyl ether to extract an ether layer, and washing with pure water until the waste liquid became neutral.
The solvent was distilled off under reduced pressure to obtain dimer diol and trimer triol.

The obtained dimer diol and trimer triol, methacrylic acid, p-methoxyphenol, and p-toluenesulfonic acid as an acid catalyst were mixed at 90 ° C. while stirring in a three-neck flask using cyclohexane as a solvent.
For 6 hours. During this time, the reaction was continued while removing the water generated by the esterification reaction. After the reaction was completed, the reaction product was allowed to stand for 1 hour, then the reaction product was dissolved in an appropriate amount of diethyl ether, neutralized with a 10% by weight aqueous sodium hydroxide solution, and the aqueous layer was separated and removed. Then, the mixture was neutralized with a 10% by weight aqueous solution of sodium hydrogencarbonate, the aqueous layer was separated and removed, and the ether layer was washed with pure water until the waste liquid became neutral. After the washing, the aqueous layer was separated and removed, and magnesium sulfate was added to the remaining ether layer and allowed to stand overnight, whereby water was completely removed from the ether layer. Thereafter, magnesium sulfate in the ether layer was removed by filtration, and then the solvent was distilled off under reduced pressure to obtain dimer acid dimethacrylate (DiMA) and trimer acid trimethacrylate (TriMA) used in the present invention.

Example 1 Trimer acid trimethacrylate (TriMA), dimer acid dimethacrylate (Di)
MA), trifluoroethyl acrylate (3FE
A), phenoxyethyl acrylate (POA), 2-
Ethylhexyl acrylate (EHA) and 2- (2 ′
-Hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole (HMB) was prepared as shown in Table 1, and 0.2 part by weight of 1-hydroxycyclohexyl-phenyl ketone was mixed.

After sufficiently stirring the above components so as to be uniform, they were poured into a polypropylene mold having a diameter of 6 mm and a thickness of 1 mm. The mold was irradiated with ultraviolet light to obtain a molded body.

With respect to such a molded lens, the recoverability of the lens shape and the tackiness of the surface were evaluated based on the following methods. The evaluation results are shown in Table 1.

Evaluation: Shape Recovery and Adhesion of Lens Surface A 500 g weight was placed on the lens molded body after folding it into four pieces, held for 1 minute, and then the weight was removed to evaluate the behavior at that time.

[Lens Shape Recovery] ○: Returns to the original shape within 10 seconds.

Δ: Returns to the original shape within one hour.

X: Shape recovery is not possible.

[Lens Surface Adhesion] A: No adhesion between lenses.

Δ: The lenses adhere to each other but can be easily peeled off.

X: The lenses are completely adhered to each other and cannot be peeled off.

(Examples 2 to 7) Molded ophthalmic lenses were obtained in the same manner as in Example 1 except that mixtures having the compositions shown in Table 1 were used. Table 1 also shows the results of evaluating the molded body for lens shape recovery and surface tackiness.

(Comparative Examples 1 to 7) Instead of using no trimer ester, dimer ester (DiMA),
Example 1 used ethylene glycol dimethacrylate (ED) or hydroxypropylene glycol acrylate methacrylate (GAMA), and the other composition and process were as described in Example 1.
In the same manner as in the above, an ophthalmic lens molded body was obtained. Table 1 also shows the results of evaluating the molded body for lens shape recovery and surface tackiness.

[0051]

[Table 1]

From Table 1, it can be seen that the ophthalmic lens molded product using the higher unsaturated fatty acid trimer acid ester or the higher unsaturated fatty acid dimer acid ester and trimer acid ester is as follows:
It can be seen that the adhesion of the lens surface is small and the shape recovery is excellent.

[0053]

According to the present invention, a soft ophthalmic lens having excellent non-adhesiveness and strength, and having both flexibility and shape recovery properties has been made possible.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 (72) Inventor Kenji Uno 2-40-2 Hongo 2-chome, Bunkyo-ku, Tokyo Stock F-term in company seed (reference) 2H006 BB01 BB06 BB10 4C081 AB22 AB23 BB04 BB07 BB08 BC02 CA081 CA271 CC01 4J100 AB07R AJ02S AL03Q AL04Q AL05Q AL08Q AL08R AL08S AL09S AL62P AL62S AL63S AL65P AL66S AL66P AL66S AL65P AL67S BA08Q BA72R BA80R BB10S BC04P BC04Q BC23P BC36P BC43Q BC43S CA05 CA06 DA44 DA49 JA33 JA34

Claims (3)

[Claims] 1. A soft ophthalmic lens comprising a trimer acid ester of a higher unsaturated fatty acid or a copolymer containing a dimer acid ester and a trimer acid ester of a higher unsaturated fatty acid as constituents. 2. A trimer ester of a higher unsaturated fatty acid, or 1 to 40 parts by weight of a dimer acid ester and a trimer acid ester of a higher unsaturated fatty acid, 30 to 90 parts by weight of an alkyl acrylate, and a monomer copolymerizable therewith. A soft ophthalmic lens comprising a body copolymer. 3. A trimer acid ester of a higher unsaturated fatty acid, or 1 to 40 parts by weight of a dimer acid ester and a trimer acid ester of a higher unsaturated fatty acid, 30 to 90 parts by weight of an alkyl acrylate, and a silicon atom content of 10 to 50 parts.
%. A soft ophthalmic lens comprising 5-80 parts by weight of a monomer having at least one radically polymerizable functional group in a molecule, and a copolymer of a monomer copolymerizable therewith.