JP2565316B2 - contact lens - Google Patents

Description

TECHNICAL FIELD The present invention relates to a contact lens comprising a polymer obtained by homopolymerizing or copolymerizing an unsaturated dicarboxylic acid diester having a fluoroalkyl group, and more specifically, The present invention relates to a contact lens having a relatively high oxygen permeability obtained by homopolymerizing or copolymerizing an unsaturated dicarboxylic acid diester having a fluoroalkyl group as an essential component, and having excellent mechanical strength and stain adhesion prevention.

<Conventional Technology and Problems> Generally, contact lenses are classified into two types, hard contact lenses and soft contact lenses.

As a hard contact lens, one having polymethyl methacrylate as a main component has been widely used. Recently, as those having improved oxygen permeability, a (meth) acrylate (representing methacrylate or acrylate) having a siloxane group as a side chain as disclosed in JP-B-56-39450, JP-B-56-40324, etc. (Meth) acrylate copolymers and JP-A-57-51705,
Copolymers containing a fluoroalkyl (meth) acrylate as the main component disclosed in JP-A-57-211119 and the like have also been investigated.

These hard contact lenses are characterized by having excellent performance in terms of visual acuity correction effect, durability, ease of handling, machinability, and the like. However, for example, contact lenses containing polymethylmetallate as a main component have poor hydrophilicity and thus have a poor feeling of wearing, and have an oxygen permeability of 0.5 × 10 ^-11 cm ³ · cm / cm ^{2 as an} oxygen permeability coefficient (DK value). Since it is as low as sec · mm Hg, it has drawbacks such as damage to the cornea when worn for a long time. Furthermore, the oxygen permeability is also high for the contact lens containing a copolymer of (meth) acrylate having a siloxane bond in the side chain and an alkyl (meth) acrylate as a main component and the contact lens containing a fluoroalkyl (meth) acrylate as a main component. Although improved, DK = 1
It cannot be said to be sufficient at × 10 ^-11 to 40 × 10 ^-11 , which is insufficient for continuous wear for a long period of time.

On the other hand, as the soft contact lens, a hydrophilic water-containing contact lens obtained by copolymerizing methyl methacrylate and 2-hydroxyethyl methacrylate or N-vinylpyrrolidone, or a non-water-containing contact lens obtained by copolymerizing butyl methacrylate and butyl acrylate. Are known.

Hydrophilic water-containing soft contact lenses have the characteristics of excellent wearing comfort and relatively high oxygen permeability, but low mechanical strength, difficulty in handling, deposition of proteins and lipid minerals, bacterial growth, etc. Since there are many problems and the oxygen permeability is limited, it is not suitable for long-term wear.

For non-hydrous soft contact lenses, the DK value is 10-
Although it was 30 + 10 ^-11 and had relatively good oxygen permeability, it was still insufficient in terms of long-term continuous wear.

<Object of the Invention> The present invention is to provide a contact lens which has an excellent effect of correcting visual acuity, has oxygen permeability that can be continuously worn for a long period of time, and is less likely to have dirt attached thereto.

<Means for Solving Problems> According to the present invention, an unsaturated dicarboxylic acid diester represented by the following general formula (I) is used. (In the formula, R ₁ and R ₂ are the same or different groups, and at least _one of R ₁ and R ₂ represents a fluorine-containing group represented by —CmHnF _{2m + 1-n} , and m is 2 to 18 , N is an integer of 1 to 36, and when only _one of R ₁ and R ₂ is —CmHnF _{2m + 1-n} , the other group is an alkyl group having 1 to 12 carbon atoms, an alkenyl group or a carbon number. 3 to 12 cycloalkyl groups)
There is provided a contact lens made of a polymer obtained by polymerizing one or two or more or a copolymerizable monomer other than dialkyl fumarate or a crosslinkable polyfunctional monomer obtained by copolymerizing the monomer with the monomer.

 Hereinafter, the present invention will be described in more detail.

In the present invention, the unsaturated dicarboxylic acid diester represented by the general formula (I) is used. At least one of the ester groups is a saturated fluoroalkyl group having fluorine represented by -CmHnF2m _{+ 1-n} , and the fluoroalkyl group is an integer having a carbon number m in the range of 2 to 18, and at least The one having one hydrogen atom (n is 1) is used. If it is out of this range, the thermal stability, mechanical strength and processability of the polymer deteriorate, so that it cannot be used. Since the maximum number of m is 18, n
Is a maximum of 36.

When one is an alkyl group, an alkenyl group, or a cycloalkyl group, an alkyl group or an alkenyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms are used. When the carbon number is 13 or more, the polymerizability, heat resistance and mechanical strength are remarkably lowered, which is not preferable.

Examples of unsaturated dicarboxylic acid diesters that can be used in the present invention include methyl-2,2,2-trifluoroethyl-fumarate, allyl- (2,2,2-trifluoro-1-trifluoromethyl) ethyl- Fumarate, allyl-3,3,4,4,5,5,6,6-nonafluorohexyl-fumarate, isopropyl-2,2,2-trifluoroethyl-fumarate, isopropyl- (2,2,2-tri Fluoro-1
-Trifluoromethyl) ethyl fumarate, isopropyl-3,3,4,4,4-pentafluorobutyl fumarate, isopropyl-3,3,4,4,5,5,6,6,6-nonafluorohexyl -Fumarate, isopropyl- (1,1,2,2-tetrahydropa-fluoro) octyl-fumarate, isopropyl- (1,1,2,2-tetrahydroperfluoro) decyl-fumarate, tert-butyl-2,2, 2-trifluoroethyl-fumarate, tert-butyl- (2,2,
2-trifluoro-1-trifluoromethyl) ethyl-
Fumarate, tert-butyl-3,3,4,4,4-pentafluorobutyl-fumarate, tert-butyl- (1,1,1,
2,2-Tetrahydroperfluoro) decyl-fumarate, 2-ethylhexyl- (2 ', 2', 2'-trifluoroethyl) -fumarate, 2-ethylhexyl-
(2 ', 2', 2'-Trifluoro-1'-trifluoromethyl) ethyl fumarate, 2-ethylhexyl-
(1 ', 1', 2 ', 2'-Tetrahydroperfluoro) octyl-fumarate, cyclohexyl-2,2,2-trifluoroethyl-fumarate, cyclohexyl- (2,2,2-
Trifluoro-1-trifluoromethyl) ethyl-fumarate, cyclohexyl-3,3,4,4,4-pentafluorobutyl-fumarate, di- (2,2,2-trifluoroethyl) fumarate, di- (2 , 2,2-Trifluoro-1-trifluoromethylethyl) fumarate, di- (3,3,4,4,
4-pentafluorobutyl) fumarate, di- (3,3,4,
4,5,5,6,6,6-nonafluorohexyl) fumarate, di- (1,1,2,2, -tetrahydroperfluorooctyl) fumarate, di- (1,1,2,2-tetrahydroper) Fluorodecyl) fumarate, 2,2,2-trifluoroethyl-
(2 ', 2', 2'-trifluoro-1'-trifluoromethyl) ethyl fumarate, (2,2,2-trifluoro-
1-trifluoromethyl) ethyl-3 ', 3', 4 ', 4',
5 ', 5', 6 ', 6', 6'-nonafluorohexyl-fumarate, (2,2,2-trifluoro-1-trifluoromethyl) ethyl-1 ', 1', 2 ', 2' Examples thereof include fumarates such as tetrahydroperfluorodecyl-fumarate and similar corresponding malates, but trans-form fumarates are preferable to cis-form malates because of their homopolymerizability and copolymerizability.

The contact lens of the present invention can be obtained by polymerizing or copolymerizing at least one monomer of the unsaturated dicarboxylic acid diester. On the other hand, the unsaturated dicarboxylic acid diester may be further copolymerized with one or more copolymerizable vinyl monomers or crosslinkable polyfunctional monomers other than the other dialkyl fumarate.

Among the polymerizable vinyl monomers or crosslinkable polyfunctional monomers, the monomers other than dialkyl fumarate include styrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl pivalate. , Methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, ethyl vinyl ether, n-butyl vinyl ether, (meth) acrylic acid amide, 2-hydroxyethyl (meth) acrylate, N
-Vinyl pyrrolidone, vinyl pyridine, allyl (meth)
Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diethylene glycol bisallyl carbonate, triallyl trimellitate, triallyl cyanurate, triallyl isocyanurate, etc. However, for the purpose of improving the thermal stability, mechanical strength and processability of the obtained contact lens, it is preferable to copolymerize with at least one crosslinkable polyfunctional vinyl monomer.

The copolymerization composition ratio of the copolymerizable vinyl monomer or crosslinkable polyfunctional monomer excluding the dialkyl fumarate to the unsaturated dicarboxylic acid diester of the present invention is 300 to 0.1 parts by weight with respect to 100 parts by weight of the unsaturated dicarboxylic acid diester. Is more preferable, and the range of 200 to 1 part by weight is more preferable. In this case, if the amount exceeds 300 parts by weight, the oxygen permeability of the obtained contact lens becomes remarkably low, and if it is less than 0.1 part by weight, the effect of copolymerization is not sufficient.

In order to obtain a polymer or a copolymer according to the present invention, a usual radical polymerization method is selected. As the polymerization initiator used in the polymerization, one or more of an organic peroxide and an azo compound having a selected 10-hour half-life temperature of 120 ° C. or less are used.

Examples of such initiators are benzoyl peroxide, diisopropylperoxycarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azo. Examples thereof include bisisobutyronitrile. The amount of the polymerization initiator used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of the raw material monomer.

For the preparation of the contact lens of the present invention, a commonly used method can be used. For example, a monomer material containing a polymerization initiator is polymerized or copolymerized in an appropriate container such as a test tube, and a round bar or a block is obtained. What is necessary is just to process it into a lens. Further, a method in which a monomer containing a polymerization initiator is injected into a space formed by two molds and molded directly into a contact lens by mold polymerization can also be adopted. Furthermore, a contact lens can be obtained by dissolving the polymer in a solvent and dissolving it in an appropriate solvent and removing the solvent by a casting method.

As the conditions for the polymerization or copolymerization in the case of preparing the contact lens, it is preferable to replace the polymerization system with an inert gas such as nitrogen, carbon dioxide, or helium at appropriate times or to carry out the polymerization or copolymerization. The temperature varies depending on the type of polymerization initiator used, but it is 30-100 ° C.
Is preferred. Also, the total time required for polymerization is
It is about 10 to 72 hours.

It is also possible to add a colorant such as a dye or an additive such as an ultraviolet absorber to the raw material monomer to carry out polymerization.

Furthermore, the finished lens is treated with acid or alkali, the surface of the lens is modified by low-temperature plasma treatment, or the hydrophilic monomer is graft-polymerized by low-temperature plasma treatment to improve the feeling of wearing. Can be improved.

<Effects of the Invention> The contact lens of the present invention is obtained by polymerizing or copolymerizing an unsaturated dicarboxylic acid diester having a saturated fluoroalkyl group as an essential component, and thus has high oxygen permeability, and has a high surface area for proteins, lipids and It can prevent inorganic deposits,
It has excellent performance by improving the drawbacks of conventional contact lenses, such as alienating the penetration of water into the lens.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

 Incidentally, the middle part of the examples represents a polymerized part.

Example 1 0.3 part of benzoyl peroxide was mixed with a raw material mixed monomer consisting of 8 parts of tert-butyl- (2,2,2-trifluoro-1-trifluoromethyl) ethyl fumarate and 2 parts of diallyl isophthalate. The mixture was placed in a glass sealed tube, the inside was replaced with nitrogen and deaeration was repeated, and the mixture was sealed under vacuum. This sealed tube was allowed to stand and polymerize in a constant temperature bath at 70 ° C. for 24 hours, and further heated at 100 ° C. for 2 hours. The obtained polymer was cut, then cut and polished to form a contact lens.

 The various physical properties were measured by the following methods.

Oxygen permeability coefficient MODEL 2110 (Multirange Ana) manufactured by Xertex Corporation
lyzer for Dissolved Oxygen) at 35 ° C. in 0.9% physiological saline to measure a test piece having a diameter of 12.7 mm and a thickness of 0.2 mm, and the DK value (cc · cm / cm ² · sec · mmHg) was obtained.

Stain resistance 0.2% egg white lysozyme solution in water, diameter 12.7mm, thickness 0.2
A test specimen of mm was immersed at 37 ° C. for 24 hours, and the amount of adhesion was determined from the change in absorbance at 280 nm.

Examples 2 to 8 By the same method as in Example 1, raw material monomers having various compositions were cured under predetermined radical initiator and polymerization conditions to prepare contact lenses. The results are shown in Table 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Kubota 3-3-5 Yamato, Suwa-shi Seiko Epson Co., Ltd. (72) Inventor Takao Mogami 3-3-5 Yamato, Suwa-shi Seiko Epson Co., Ltd. ( 56) References Japanese Patent Laid-Open No. 63-11908 (JP, A)

Claims (2)

(57) [Claims] 1. An unsaturated dicarboxylic acid diester represented by the general formula (I). (In the formula, R ₁ and R ₂ are the same or different groups, and at least one group of R ₁ and R ₂ represents a fluorine-containing group represented by —CmHnF _{2m + 1-n} , and m is 2-18. An integer, n is an integer of 1 to 36, and when only _one of R ₁ and R ₂ is —CmHnF _{2m + 1-n} , the other group is an alkyl group having 1 to 12 carbon atoms, an alkenyl group or 3 carbon atoms. A contact lens comprising a polymer obtained by polymerizing or copolymerizing one or two or more monomers (having 12 to 12 cycloalkyl groups). 2. An unsaturated dicarboxylic acid diester represented by the general formula (I) (In the formula, R ₁ and R ₂ are the same or different groups, and at least one group of R ₁ and R ₂ represents a fluorine-containing group represented by —CmHnF _{2m + 1-n} , and m is 2-18. An integer, n is an integer of 1 to 36, and when only _one of R ₁ and R ₂ is —CmHnF _{2m + 1-n} , the other group is an alkyl group having 1 to 12 carbon atoms, an alkenyl group or 3 carbon atoms. To 12 cycloalkyl groups) to a copolymerizable vinyl monomer other than dialkyl fumarate or one or more monomers selected from crosslinkable polyfunctional monomers. A contact lens made of a polymer.