JPS63132216A - Contact lens - Google Patents

Abstract

PURPOSE:To obtain a contact lens which has an excellent sight correcting effect, permits long-period continuous use, has oxygen permeability and has a less tendency to dirt sticking by polymerizing or copolymerizing 1 or >=2 kinds of monomers of specific unsatd. diester dicarboxylate. CONSTITUTION:The contact lens consisting of the polymer obtd. by polymerizing 1 or >=2 kinds of the monomers of the unsatd. diester dicarboxylate expressed by the formula I or further copolymerizing the copolymerizable monomers or crosslinkable multifunctional monomers is obtd. In the formula, R1, R2 denote the same or different groups, at least one group of which denotes the fluorine- contg. group expressed by -CmHnF2m+1-n, m denotes 2-18 integer, n denotes 1-36 integer, the other group denotes an alkyl group, alkenyl group or cycloalkyl group. The high oxygen permeability is thereby obtd. and the deposit of protein, lipid and inorg. material on the surface is prevented; in addition, the penetration of water into the lens is prohibited.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a contact lens made of a polymer obtained by homopolymerizing or copolymerizing an unsaturated diester dicarboxylic acid having a fluoroalkyl group, and more specifically,
The present invention relates to a contact lens which is made by homopolymerizing or copolymerizing an unsaturated dicarboxylic acid diester having a fluoroalkyl group as an essential component, and has relatively high oxygen permeability, and is excellent in mechanical strength and stain prevention.

<Conventional technology and problems> Generally, there are two types of contact lenses: hard contact lenses and soft contact lenses.

As hard contact lenses, those containing polymethyl methacrylate as a main component have been widely used. Recently, (meth)acrylates (representing methacrylate or acrylate) having a siloxane group in the side chain, as disclosed in Japanese Patent Publication No. 56-39450, Japanese Patent Publication No. 56-40324, etc., have been developed as products with improved oxygen permeability.
and alkyl (meth)acrylate copolymers and JP-A-5
Copolymers containing fluoroalkyl (meth)acrylate as a main component, which are disclosed in JP-A No. 7-51705 and JP-A-57-211119, have also been studied.

These hard contact lenses are characterized by having excellent performance in terms of vision correction effect, durability, ease of handling, machinability, and the like. However, for example, contact lenses whose main component is polymethyl methacrylate have poor hydrophilicity, making them uncomfortable to wear, and their oxygen permeability is 0.5X 10-11 co?-cm in terms of oxygen permeability coefficient (DK value).
/ cJ sec-nmHg, which is low, so there are drawbacks such as damage to the cornea when worn for a long time. Furthermore, the oxygen permeability of contact lenses whose main component is a copolymer of (meth)acrylate and alkyl (meth)acrylate that has a siloxane bond in the side chain, or whose main component is fluoroalkyl (meth)acrylate, is Although improved, DK = I X 10'''11
˜40×10−”, which is not sufficient for long-term continuous wear.

On the other hand, soft contact lenses include hydrophilic water-containing contact lenses made by copolymerizing methyl methacrylate and 2-hydroxyethyl methacrylate or N-vinylpyrrolidone, and non-water-containing contact lenses made by copolymerizing butyl methacrylate and butyl acrylate. Sexual things are known.

Although hydrophilic soft contact lenses are comfortable to wear and have relatively high oxygen permeability, they have low mechanical strength and are difficult to handle, causing deposits of proteins, lipids, and inorganic substances, and bacterial growth. There are many problems such as these, and there is a limit to oxygen permeability, so it is unsuitable for long-term wear.

In addition, non-hydrous soft contact lenses have a DK value of 10.
~30 x 10-'', and although the oxygen permeability was relatively good, it was still insufficient in terms of long-term continuous wear.

<Object of the Invention> An object of the present invention is to provide a contact lens that has an excellent vision correction effect, has oxygen permeability that allows continuous wear for a long period of time, and is resistant to dirt.

<Means for Solving the Problems> According to the present invention, an unsaturated dicarboxylic acid diester represented by the following general formula (I) (wherein R and R2 are the same or different groups, R
engineering, at least one group of R2 is -c+5)(r+Fzm
+t-1 represents a fluorine-containing group, m is 2 to 1
8, n is an integer from 1 to 36, and only one of R1 and R2 is -C, HrlF2. +, , , , , the other group represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, or a cycloalkyl group having 3 to 12 carbon atoms). Alternatively, a contact lens made of a polymer obtained by further copolymerizing the monomer with a copolymerizable monomer or a crosslinkable polyfunctional monomer is provided.

The present invention will be explained in more detail below.

In the present invention, an unsaturated dicarboxylic acid diester represented by general formula (I) is used. At least one of the ester groups consists of a fluorine-containing saturated fluoroalkyl group represented by -C1lHnF2111+1-n, and the fluoroalkyl group has a carbon number m of an integer in the range of 2 to 18, and at least one A compound having a hydrogen atom (n is 1) is used. Outside this range, the polymer cannot be used because its thermal stability, mechanical strength and processability deteriorate. Note that since the maximum number of m is 18, n is in the range of 36 at most.

When one of the groups is an alkyl group, an alkenyl group, or a cycloalkyl group, those having 1 to 12 carbon atoms and 3 to 12 carbon atoms in the cycloalkyl group and cycloalkyl group, respectively, are used. If the number of carbon atoms is 13 or more, the polymerizability, heat resistance and mechanical strength will be significantly reduced, 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°4.4,5,5,6,6,6-nonafluorohexyfumarate, isopropyl-2,2
, 2-trifluoroethyl-fumarate, isopropyl-(2,2,2-trifluoro-1-trifluoromethyl)ethyl-fumarate, isopropyl-3,3,4,
4,4-pentafluorobutyl fumarate, isopropyl-3,3,4,4,5゜5.6,6.6-nonafluorohexyfumarate, isopropyl-(I,1,
2,2-tetrahydroperfluoro)octyl-fumarate, isopropyl-(I,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-(I,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-(I').

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(
I,1,2,2-tetrahydroperfluorooctyl) fumarate, di(I,1,2,2-tetrahydroperfluorodecyl) fumarate, 2,2.2-trifluoroethyl-(2',2', 2'-trifluoro-1'
-trifluoromethyl)ethyl-fumarate, (2゜2
．． 2-Trifluoro-1-trifluoromethyl)ethyl-3J, 31.4Z 4', 51.5Z 6'.

6',6'-nonafluorohexyl-fumarate, (2
, 2,2-trifluoro-1-trifluoromethyl)ethyl-1', 1', 2', 2'-tetrahydroperfluorodecyl-fumarate and similar corresponding malates. , homopolymerizability, and copolymerizability, fumarate, which is a trans form, is preferable to maleate, which is a cis form.

The contact lens of the present invention can be obtained by polymerizing or copolymerizing one or more monomers of the unsaturated dicarboxylic acid diester described above. On the other hand, it is also possible to copolymerize the unsaturated dicarboxylic acid diester with one or more other polymerizable vinyl monomers or crosslinkable polyfunctional monomers.

Examples of polymerizable vinyl monomers or crosslinkable polyfunctional monomers include styrene, p-methylstyrene, p-chlorostyrene, 0-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-vinylpyrrolidone, vinylpyridine, allyl (meth)acrylate, Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,
Examples include dipropylene glycol di(meth)acrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diethylene glycol bisallyl carbonate, triallyl trimellitate, triallyl cyanurate, triallyl isocyanurate, etc., but the heat of the resulting contact lens stability, mechanical strength,
For the purpose of improving processability, it is preferable to copolymerize with at least one crosslinkable polyfunctional vinyl monomer.

The copolymerization ratio of the above-mentioned copolymerizable vinyl hexamer or crosslinkable polyfunctional monomer to the unsaturated dicarboxylic diester of the present invention is 100% of the unsaturated dicarboxylic acid diester of the present invention.
It is preferably in the range of 300 to 0.1 part by weight, more preferably in the range of 200 to 1 part by weight. In this case, 30
If it exceeds 0 parts by weight, the oxygen permeability of the resulting contact lens will be extremely low, and if it is less than 0.1 part by weight, the effect of the copolymerization will not be sufficient.

In order to obtain the polymer or copolymer according to the present invention, a conventional radical polymerization method is selected. The polymerization initiator used in the polymerization is selected to have a half-life temperature of 120' for 10 hours.
One or more types of organic peroxides and azo compounds of C or less are used.

Examples of such initiators include benzoyl peroxide, diisopropyl peroxycarbonate, -butyl peroxy-2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy diisobutyrate, lauroyl peroxide, azo Examples 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, based on 100 parts by weight of the raw material.

The contact lenses of the present invention can be prepared by commonly used methods. For example, a raw material containing a polymerization initiator is polymerized or copolymerized in a suitable container such as a test tube to obtain a round bar or block, which is then cut,
The lens can be processed into a lens that matches the prescription by mechanical processing such as polishing. Alternatively, a method can be adopted in which a monomer containing a polymerization initiator is injected into the space created by two molds, and the contact lens is directly molded by mold polymerization. Furthermore, if the polymer is soluble in a solvent, a contact lens can also be obtained by dissolving it in a suitable solvent and removing the solvent by a casting method.

As for the conditions for polymerization or copolymerization when preparing contact lenses as mentioned above, it is preferable to replace the polymerization system with an inert gas such as nitrogen, carbon dioxide, helium, etc. or to put it in an atmosphere to carry out the polymerization or copolymerization. The temperature varies depending on the type of polymerization initiator used, but is 30-100°C.
Celsius is preferred. Further, the total time required for polymerization is about 10 to 72 hours.

It is also possible to add a coloring agent such as a dye or an additive such as an ultraviolet absorber to the raw material monomer for polymerization.

Furthermore, the surface of the finished lens is treated with acid or alkali, the lens surface is modified by low-temperature plasma treatment, and hydrophilic monomers are graft-polymerized by low-temperature plasma treatment to improve the wearing comfort. It can be improved.

<Effects of the Invention> The contact lens of the present invention has high oxygen permeability because it is obtained by polymerizing or copolymerizing an unsaturated dicarboxylic acid diester having a saturated fluoroalkyl group as an essential component.
It has excellent performance that improves the shortcomings of conventional contact lenses, such as preventing the deposition of proteins, lipids, and inorganic substances on the surface and preventing water from penetrating inside the lens.

<Examples> The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Note that the middle part of the example represents the polymerization part.

11 What is tert-butyl-(2,2,2-trifluoro-1-
0.3 parts of benzoyl peroxide was mixed with a raw material mixture containing 8 parts of trifluoromethyl)ethyl fumarate and 2 parts of diallylisophthalate, and the mixture was placed in a sealed glass tube, and the inside was replaced with nitrogen and degassed. This was repeated and sealed under vacuum. This sealed tube was left to polymerize in a constant temperature bath at 70° C. for 24 hours, and then heated at 100° C. for 2 hours. The obtained polymer was cut, then cut and polished to make contact lenses.

In addition, various physical properties were measured by the following methods.

■Oxygen permeability coefficient MODEL manufactured by Xertex Corporation
2110 (Multi-range Analyze
12.7 m in diameter in 0.9% physiological saline at 35°C using
DK value (c
c・GO/al-sac-nmal (g) was determined.

■Stain resistance 12.7m in diameter in 0.2% egg white lysozyme aqueous solution.
A test piece with a thickness of 0.2 nm was immersed at 37°C for 24 hours,
The amount of adhesion was determined from the change in absorbance at 280 nm.

By the same method as in Example 1, raw monomers of various compositions were cured using a predetermined radical initiator and under polymerization conditions, and then contact lenses were prepared. The results are shown in Table 1.

■ The size of the demand is t.

Claims (1)

[Claims] 1) An unsaturated dicarboxylic diester represented by the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 and R_2 are the same or different groups. At least one of R_1 and R_2 represents a fluorine-containing group represented by -CmHnF_2_m_+_1_-_n, m is an integer of 2 to 18, and n is 1 to 36.
and when only one of R_1 and R_2 is -CmHnF_2_m_+_1_-_n, the other group represents an alkyl group, alkenyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms). A contact lens made of a polymer obtained by polymerizing or copolymerizing one or more types. 2) Obtained by copolymerizing one or more monomers selected from unsaturated dicarboxylic diesters represented by general formula (I) with one or more monomers selected from copolymerizable vinyl monomers or crosslinkable polyfunctional monomers. Contact lenses made of polymers.