JPH0894979A - Oxygen permeable contact lens - Google Patents

Abstract

PURPOSE: To improve a wearing feel, oxygen permeability, contamination proofness, etc., by incorporating a polymer obtd. by polymerizing a polymerizable component contg. (meth)acrylate having specific urethane bonds as an indispensable component into the above contact lens. CONSTITUTION: This contact lens contains the polymer obtd. by polymerizing the polymerizable component contg. the (meth)acrylate having the urethane bonds expressed by formula as the indispensable component and having a copolymerizable vinyl monomer and/or crosslinkable multifunctional monomer at need. In the formula, R1 denotes a hydrogen atom or methyl group and R2 denotes 1 to 12C fluoroalkyl group. The (meth)acrylate group exhibits excellent polymerizability and is capable of decreasing the residual monomer quantity undesirable as a medical treatment material. The oxygen permeability, contaminationproofness, etc., are imparted to the contact lens by incorporating the fluoroalkyl group as R2 of the acrylate A. Further, the urethane bonds impart adequate hydrophilicity to the contact lens and contributes to an improvement in the wearing feel.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen permeable contact lens, and more particularly to an oxygen permeable contact lens such as a hard contact lens excellent in stain resistance, workability, mechanical strength, durability and wearing feeling. Regarding the lens.

[0002]

2. Description of the Related Art Generally, contact lenses are classified into hard contact lenses and soft contact lenses. Compared to hard contact lenses, soft contact lenses are easier to fit in the eyes and are more comfortable to wear.
As such a soft contact lens, one containing 2-hydroxyethyl methacrylate as a main component is used. This has excellent mechanical strength and workability, but has a water content of 40% or less, and has a drawback that oxygen permeability and wearing feeling are poor. Therefore, in recent years, high water content soft contact lenses have been proposed for continuous wear by increasing the water content of the lens material. For example, with N-vinylpyrrolidone as the main component, methyl methacrylate, 2
-There are copolymers of hydroxyethyl methacrylate and methacrylic acid. However, these high water content soft contact lenses have the drawback that stains tend to adhere and their strength decreases during use, and there are also various problems such as yellowing due to repeated sterilization treatment, which is essential for soft contact lenses. Therefore, it is usually necessary to perform boiling sterilization and to perform hygiene management by using care products such as bactericides and cleaning solutions.

On the other hand, as a hard contact lens,
Methylmethacrylate as a main component has been widely used from the past and is excellent in mechanical strength, wettability, workability, etc., but it has a drawback that it hardly permeates oxygen necessary for corneal physiology. Therefore, recently, in order to impart oxygen permeability, an oxygen-permeable hard contact lens containing methyl methacrylate, siloxanyl alkyl methacrylate, etc. as a monomer main component has been proposed (Japanese Patent Publication No. 52-33502). However, since this oxygen-permeable contact lens contains lipophilic silicone, it is apt to be contaminated with lipids and proteins in tear fluid and has a drawback in that it is uncomfortable to wear. Therefore, attempts have been made to add fluoroacrylate or the like as a means for solving this contamination (Japanese Patent Laid-Open No. 61-306646). More recently, a composition comprising a dimethacrylate monomer having a urethane bond and perfluorooxyalkylene (JP-A-58-127914) has been proposed, but such a dimethacrylate monomer is crosslinked. Since it is a polar monomer, it has a drawback that the usable range is limited.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oxygen permeable contact lens which has a feeling of wearing and oxygen permeability and is excellent in stain resistance, mechanical strength and workability. It is in.

[0005]

According to the present invention, a (meth) acrylate having a urethane bond represented by the following general formula (2) (hereinafter referred to as acrylate A) is contained as an essential component and, if necessary, a copolymerizable vinyl. There is provided an oxygen-permeable contact lens containing a polymer obtained by polymerizing a polymerizable component containing a monomer and / or a crosslinkable polyfunctional monomer.

[0006]

[Chemical 2]

The present invention will be described in detail below. The oxygen-permeable contact lens of the present invention contains a polymer obtained by polymerizing a polymerizable component containing acrylate A represented by the general formula 2 as an essential component.

In the acrylate A, the (meth) acrylate group exhibits excellent polymerizability and can reduce the amount of residual monomer which is not preferable as a medical material. When R ₂ of the acrylate A is a fluoroalkyl group, oxygen permeability and stain resistance can be imparted to the contact lens. Further, the urethane bond can impart appropriate hydrophilicity to the contact lens and improve the wearing feeling. When the carbon number of R ₂ is 13 or more, the production is difficult.

Specific examples of the acrylate A include 2,2,2-trifluoroethyloxycarbonylaminoethyl (meth) acrylate, 2- (trifluoromethyl) benzyloxycarbonylaminoethyl (meth) acrylate, and the like. 2,2,3,3-tetrafluoropropyloxycarbonylaminoethyl (meth)
Acrylate, 2,2,3,3,3-pentafluoropropyloxycarbonylaminoethyl (meth) acrylate, pentafluorophenyloxycarbonylaminoethyl (meth) acrylate, hexafluoroisopropyloxycarbonylaminoethyl (meth) acrylate, 2, 2,3,4,4,4-hexafluorobutyloxycarbonylaminoethyl (meth) acrylate,
2,2,3,3,4,4,5,5,6,6,7,7,
Preferable examples include 8,8,9,9,9-heptadecylfluorononyloxycarbonylaminoethyl (meth) acrylate and the like, and when used, they can be used alone or as a mixture.

To prepare the acrylate A, for example, JP-A-62-205045 and JP-A-5-251.
As described in JP-A-14, a (meth) acrylate having an isocyanate group represented by the following general formula 3 and a carbon number of 1 to 3 containing at least 3 or more fluorine atoms.
It can be obtained by a method of reacting a 12-alkyl group-containing fluorine-containing alcohol with a tertiary amine such as dimethylpiperazine or a catalyst such as an organic tin catalyst such as dibutyltin dilaurate in an equimolar amount.

[0011]

[Chemical 3]

At this time, either one of the raw material monomers may be present in an excessive amount, but it is preferable to use the above-mentioned fluorine-containing alcohol in an excessive amount from the viewpoint of preventing side reactions due to residual isocyanate groups. The reaction may be carried out in a solvent or without a solvent, and the solvent is not particularly limited as long as it does not react with an isocyanate group or an alcohol. Further, the reaction temperature is preferably 80 ° C. or lower in order to control side reactions such as polymerization.

The polymerizable component constituting the oxygen permeable contact lens of the present invention may contain a copolymerizable vinyl monomer and / or a crosslinkable polyfunctional monomer in addition to the acrylate A which is an essential component. .

The copolymerizable vinyl monomer is a component that adjusts the optical properties, mechanical strength, oxygen permeability, etc. of the contact lens obtained, and specifically, for example, styrene, methylstyrene, and methyl nucleus substitution. Styrene, chloro nucleus-substituted styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, trifluoroethyl (meth) acrylate, 1H-
Hexafluoroisopropyl (meth) acrylate,
(Meth) acrylic acid, (meth) acrylamide, N, N
-Dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyl propionate, vinyl pivalate, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, diethyl itaconate, Di-t-butyl fumarate, diisopropyl fumarate, isopropyl-tris-trimethoxysilylpropyl fumarate, isopropyl-1H-hexafluoropropyl fumarate, t-butyl trifluoroethyl fumarate, γ-methacryloxypropyl-tris ( Examples thereof include trimethylsiloxy) silane and t-butyloxycarbonyl fumaroyloxypropyl-tris (trimethylsiloxy) silane.

The crosslinkable polyfunctional monomer is a component for improving the heat resistance, processability, shape stability and the like of the obtained contact lens, and specifically, for example, allyl (meth) acrylate, ethylene glycol diester. (Meta)
Acrylate, diethyl glycol di (meth) acrylate, triethylene glycol (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, divinylbenzene, diallyl phthalate, diethylene glycol bisallyl carbonate, methylene bisacrylamide,
Triallyl trimellitate, triallyl cyanurate,
Examples thereof include divinyl adipate, and at the time of copolymerization, it is preferable to use at least one crosslinkable polyfunctional monomer.

In the oxygen-permeable contact lens of the present invention, when the acrylate A is used as the polymerizable component and the copolymerizable vinyl monomer and / or the crosslinkable polyfunctional monomer, the charging ratio is the acrylate A1.
The copolymerizable vinyl monomer and / or the crosslinkable polyfunctional monomer is preferably 5,000 to 1 part by weight, more preferably 2,000 to 5 parts by weight, based on 00 parts by weight. If the charged amount of the copolymerizable vinyl monomer and / or the crosslinkable polyfunctional monomer exceeds 5,000 parts by weight, the oxygen permeable contact lens obtained has insufficient oxygen permeability and stain resistance, and is less than 1 part by weight. Is not preferable because the effect of copolymerization is not sufficient. When both the copolymerizable vinyl monomer and the crosslinkable polyfunctional monomer are used, the compounding ratio is 10 to 1000 parts by weight of the copolymerizable vinyl monomer with respect to 100 parts by weight of the acrylate A. 1 to 30 parts by weight of the crosslinkable polyfunctional monomer is preferable with respect to a total of 100 parts by weight of the copolymerizable vinyl monomer.

To prepare the oxygen-permeable contact lens of the present invention, a polymerization initiator is added to the polymerizable component and mixed, and the mixture is mixed into a desired shape made of metal, glass or plastic, such as a test tube or a lens. After injecting into a thing, sealing it, obtaining a lens material or a lens-shaped object by a method of heating or polymerization by light, etc., and cutting the obtained material,
A desired contact lens can be obtained by a polishing method or the like. Incidentally, a method of directly forming a lens by a casting polymerization method, a method of casting while irradiating with light, or the like can be carried out.

As the above-mentioned polymerization initiator, an ordinary radical polymerization initiator or the like can be used. For example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-
Butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, lauroyl peroxide, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile)
Examples thereof include benzoin methyl ether and benzoin ethyl ether. The mixing ratio of the polymerization initiator is preferably 5 parts by weight or less, and particularly preferably 1 part by weight or less with respect to 100 parts by weight of the polymerizable component.

As the conditions of the above-mentioned polymerization reaction, it is desirable to replace the polymerization system with an inert gas such as nitrogen, helium, argon or the like at a suitable time or under an atmosphere. The polymerization temperature varies depending on the kind of the polymerization initiator. Usually 20-140
It is preferable to carry out the polymerization in the range of 0 ° C for a polymerization time of about 6 to 120 hours. It is also possible to add a colorant such as a dye, an additive such as an ultraviolet absorber or a monomer having a corresponding function to the polymerizable component for polymerization.

In the present invention, the above-mentioned polymer can be used not only as a contact lens but also as an intraocular lens having antifouling property and a medical material, and is also useful as various coating materials having water and oil repellency.

[0021]

The oxygen-permeable contact lens of the present invention is obtained by polymerizing or copolymerizing the above-mentioned polymerizable component containing acrylate A, so that the obtained contact lens is excellent in oxygen permeability and wearing sensation, and further is anti-staining. Excellent in mechanical properties, mechanical strength and workability. Therefore, it is useful for oxygen-permeable hard contact lenses and the like.

[0022]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0023]

Example 1 50 g of methyl methacrylate as a polymerizable component, 40 g of 2,2,2-trifluoroethyloxycarbonylaminoethyl methacrylate, 5 g of ethylene glycol dimethacrylate and 5 g of methacrylic acid,
Azobisisobutyronitrile as a polymerization initiator 0.3
A mixed liquid containing g was poured into a test tubular glass mold, the system was thoroughly replaced with nitrogen and deaeration was repeated, and the mold was sealed and then heat-cured. Heating is performed in a constant temperature room from 40 ℃ to 100 ℃ 7
The temperature was raised over 0 hours. After the polymerization was completed, the polymer was taken out of the mold. The polymer was a colorless and transparent material. The obtained polymer is cut and polished by a usual processing method to prepare a contact lens or a test piece having a diameter of 14 mm and a thickness of 0.3 mm, and the oxygen permeability, stain resistance, processability and hydrophilicity are measured. It was measured by the following method. The results are shown in Table 1.

(1) Oxygen permeability coefficient: A Kaken type film was used as an oxygen permeation measuring instrument (Rika Seiki Co., Ltd., trade name "K-").
316 IPI type ”) at 35 ° C. in 0.9% saline.

(2) Antifouling property: albumin 0.39% by weight, lysozyme 0.17% by weight and globulin 0.10
After immersing the contact lens in physiological saline containing 5% by weight at 35 ° C. for 2 weeks, the contact lens was washed with physiological saline and the protein was separated from the contact lens with a surfactant. A reagent for protein quantification (manufactured by Pierce, trade name "Micro BCA kit") was injected into the separated solution, and the amount of protein adsorbed on the contact lens was measured.

(3) Machinability: Evaluation of easiness of scratches and cracks and easiness of polishing by cutting and polishing by a usual method (○)
Good, △ normal, × bad) I went.

(4) Hydrophilicity: The contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science Co., Ltd., trade name "CA-A").

[0028]

Examples 2 to 8 and Comparative Examples 1 to 3 A contact lens and a test piece were prepared in the same manner as in Example 1 except that the polymerizable components having the compositions shown in Table 1 were used, and each physical property was measured.
The results are shown in Table 1.

From the above results, it was found that the contact lens of the present invention has excellent oxygen permeability, antifouling property, mechanical strength and wearing feeling.

[0030]

[Table 1]

Claims (2)

[Claims] 1. An oxygen-permeable contact lens containing a polymer obtained by polymerizing a polymerizable component containing, as an essential component, a (meth) acrylate having a urethane bond represented by the following general formula 1. [Chemical 1] 2. The oxygen-permeable contact lens according to claim 1, further comprising a copolymerizable vinyl monomer and / or a crosslinkable polyfunctional monomer as the polymerizable component.