JPH03179316A - Contact lens - Google Patents

Abstract

PURPOSE:To provide the contact lens which is excellent in sight correcting effect and has oxygen permeability and has excellent shape stability, contamination resistance and durability by incorporating a copolymer formed by copolymerizing a specific 1-butene-2, 4-diester dicarboxylate monomer as a raw material monomer. CONSTITUTION:The contact lens is constituted of the 1-butene-2, 4-diester dicarboxylate monomer which can be expressed by formula I. In the formula, A and B are respectively different groups; the one group denotes a straight chain or branched chain fluoroalkyl group expressed by -ChHkF2h+1-k; (h) denotes 2 to 18 integer; (k) denotes 1 to 2xh integer. The other group denotes formula II; X to Z are the same or different groups and denote a methyl group; (m) denotes 0 or 1; (n) denotes 1 to 3 integer; (l) denotes 2 to 4 integer. The high oxygen permeability is obtd. in this way and the deposition of protein, fats and inorg. materials, etc., on the surface is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a contact lens, and more particularly to a contact lens with excellent oxygen permeability and the like.

<Prior Art> Currently, oxygen permeable (hereinafter abbreviated as GP) hard contact lenses and water-containing soft contact lenses are known as contact lenses used for boat fishing. Although the water-containing soft contact lens has excellent wearing comfort, the oxygen permeability of the material is insufficient. Therefore, it is possible to increase the moisture content of the material in order to increase the oxygen permeability, but clinical results have shown that it is more likely to be contaminated with bacteria and cause serious complications for the cornea and conjunctiva. There is. On the other hand, GP hard contact lenses are highly evaluated for their high oxygen permeability, astigmatism correction effect, durability, and safety, and are becoming the mainstream contact lens. Along with this, research on GP hard contact lenses is also being actively conducted, but the reality is that each of the above GP hard contact lenses pursues only oxygen permeability, and does not have sufficient other properties required for contact lenses. .

For example, JP-A-62-8769, JP-A-62-6
The contact lenses described in Japanese Patent Publication No. 1928 and Japanese Patent Publication No. 63-36646 have good oxygen permeability, but have problems in shape stability and stain resistance. On the other hand, JP-A-62-
The dialkyl fumarates used in JP-A No. 99720 and JP-A No. 62-212618 have poor copolymerizability, and even if they can be copolymerized, they are very brittle and easily break, which is dangerous. Furthermore, the contact lens disclosed in Japanese Patent Application Laid-Open No. 61-176909 has low oxygen permeability and is unsuitable for continuous wear, which has attracted particular attention in recent years.

<Problems to be Solved by the Invention> The purpose of the present invention is to provide a contact lens that has excellent vision correction effects, has oxygen permeability that can be worn continuously for a long period of time, and has excellent shape stability, stain resistance, and durability. It is about providing.

According to the present invention, the following general formula (1) (wherein A and B are different groups, and one group is represented by -chHk F 2h +t- Represents a linear or branched fluoroalkyl group, where h is 2 to 1
An integer of 8, k represents an integer of 1 to 2Xh.

, X, Y and 2 are the same or different groups and represent a methyl group, m is O or 1, n is an integer of 1 to 3, and 2 is an integer of 2 to 4. 1-butene-2 containing both a fluorine atom and a silicon atom in the same molecule represented by
, 4-dicarboxylic acid diester monomers are copolymerized as essential raw materials, and a contact lens is provided.

The present invention will be explained in more detail below.

The contact lens of the present invention has a specific 1-butene-2,
It is characterized by containing a copolymer obtained by copolymerizing a 4-dicarboxylic acid diester monomer as a raw material monomer.

The 1-butene-2,4-dicarboxylic acid diester monomer used in the present invention can be represented by the following general formula (I).

In the formula, A and B are different groups, and one group is -
Ch HHF zl+ -1- represents a linear or branched fluoroalkyl group. However, h is 2 to 1
An integer of 8, k represents an integer of 1 to 2Xh.

, wherein X, Y and Z are the same or different groups, and are a methyl group.

shows. Also, m is O or 1, n is an integer from 1 to 3, C
represents an integer from 2 to 4.

When the above A or B is a linear or branched fluoroalkyl group represented by -Ch Hk F 2h+□-.

The larger h is, the more branched the 8ra elementary permeability becomes, but conversely, as h becomes larger, the shape stability decreases, and if h is 19 or more, it becomes difficult to manufacture, so it cannot be used. Furthermore, in the silicon-containing alkyl group introduced into the same molecule, if the total number of carbon atoms of X, Y and Z is 13 or more, m is 2 or more, n is 4 or more, and is difficult, and even if it can be synthesized, the shape stability will be reduced. Examples of the 1-butene-2,4-dicarboxylic acid diester monomer containing a fluorine atom and a silicon atom in the same molecule represented by the general formula (1) include, for example, 2-(2', 2', 2'-trifluoroethoxycarbonyl)-4-(trimethylsilylmethoxycarbonyl)-1-butene, 2-(trimethylsilylmethoxycarbonyl)-4-(2', 2', 2'
-trifluoroethoxycarbonyl)-1-butene,
2-(2',2'2'-trifluoroethoxycarbonyl)-4-pentamethyldisiloxanylmethoxycarbonyl)-1-butene, 2-(pentamethyldisiloxanylmethoxycarbonyl)-4- (2', 2'2
'-trifluoroethoxycarbonyl), 2-(2'
, 2', 2'-trifluoroethoxycarbonyl)
-4-(tris(trimethylsiloxy)silylpropyloxycarbonyl)-1-butene, 2-(tris(trimethylsiloxy)silylpropyloxycarbonyl)-
4-(2', 2'2'-trifluoroethoxycarbonyl), 2-(3', 3', 4', 4', 4'
-pentafluorobutoxycarbonyl)-4-(pentamethyldisiloxanylethoxycarbonyl)-1-butene, 2-(pentamethyldisiloxanylethoxycarbonyl)-4-(3', 3', 4',4',4
'-pentafluorobutoxycarbonyl)-1-butene,2-(3',3',4',4',4'-pentafluorobutoxycarbonyl)-4-(tris(trimethylsiloxy)silylpropyloxycarbonyl)
-1-butene, 2-(tris(trimethylsiloxy)silylpropyloxycarbonyl)-4-(3', 3'
, 4', 4', 4'-pentafluorobutoxycarbonyl)-l-butene, 2-(, 1', 1',
2', 2'-tetrahydroperfluorodecyloxycarbonyl)-4-(trimethylsilylmethoxycarbonyl)-1-butene, 2-(1-limethylsilylmethoxycarbonyl)-4-(1', 1', 2' ,2
'-tetrahydroperfluorodecyloxycarbonyl)-1-butene, 2-(3', 3', 4',
4', 4'-pentafluorobutoxycarbonyl)-
4-(methylbis(trimethylsiloxy)silylmethoxycarbonyl)-1-butene, 2-(methylbis(trimethylsiloxy)silylmethoxycarbonyl)-4-(
3',3',4',4',4'-pentafluorobutoxycarbonyl)-1-butene, 2-[1-(2
', 2'2'-trifluoroethoxy)-2-(
hydroxy)propyloxycarbonyl] -4-(trimethylsilylmethoxycarbonyl)-1-butene, 2
- (trimethylsilylmethoxycarbonyl)-4-[
1-(2',2'2'-trifluoroethoxy)-2
-(hydroxy)propyloxycarbonylco-1-butene, 2- (3', 3', 4', 4', 4'
-pentafluorobutoxycarbonyl)-4-[1-(
Pentamethyldisiloxanylethoxy)-2-(hydroxy)propyloxycarbonyl]-1-butene + 2
- [1-(pentamethyldisiloxanylethoxy)-
2-(Hydroxy)propyleneoxylponylco-4
-(3', 3', 4', 4'4'-pentafluorobutoxycarbonyl-butene, etc.),
When using.

It can be used alone or as a mixture.

The content of the l-butene-2,4-dicarboxylic acid diester monomer, which is the essential raw material component, is preferably in the range of 2 to 95% by weight based on the total raw material monomers.

If the content is less than 2% by weight, the oxygen permeability will be extremely reduced, and if it exceeds 95% by weight, it will not be possible to maintain the strength of the contact lens, which is not preferable.

In the present invention, the 1-butene-2,4-dicarboxylic acid diester represented by the general formula (1) can be produced by a known method.

Specifically, it can be obtained, for example, by dissolving a silicon-containing acrylic ester and a fluorine-containing acrylic ester in a solvent such as dioxane, and reacting them in the presence of a catalyst and in an inert gas atmosphere.

In the contact lens of the present invention, any copolymer containing the 1-butene-2,4-dicarboxylic acid diester monomer represented by the general formula (1) as an essential raw material monomer component can be used. It is also possible to copolymerize a polymerizable 7-mer, but in view of the thermal stability, mechanical strength, processability, etc. of the resulting contact lens, other copolymerizable monomers, such as radically polymerizable vinyl monomers, may be used. It is preferable to use a heptamer selected from the group consisting of a silicon-containing vinyl monomer, a fluorine-containing vinyl monomer, a crosslinkable polyfunctional vinyl monomer, and a mixture thereof. Examples of the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer include methyl (meth)
Acrylate, Ethyl (meth)acrylate, Isopropyl (meth)acrylate, Tert-butyl (meth)
Acrylate, cyclohexyl (meth)acrylate,
Benzyl (meth)acrylate, styrene, p-methylstyrene, p-chlorostyrene, O-chlorostyrene,
divinylbenzene, vinyl acetate, vinyl propionate,
Vinyl pivalate, vinyl (meth)acrylate, ethyl vinyl ether, n-butyl vinyl ether 5 (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, dipropylene glycol di(meth)acrylate, diallyl Phthalate, diallyl isofumarate, diallyl terephthalate, diethylene glycol bisallyl carbonate, triallyl trimellitate, triallyl cyanurate, diisopropyl itaconate, ditertiary butyl itaconate, ditertiary butyl fumarate, trimethylsilylmethyl (meth)acrylate, pentamethyl Disiloxanylmethyl(meth)acrylate, tris(trimethylsiloxy)silylmethyl(
meth)acrylate, tris(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate, trimethylsilylethyl(meth)acrylate, pentamethyldisiloxanylethyl(meth)acrylate, tris(trimethylsiloxy)silylethyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylethyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, pentamethyldisiloxanylpropyl(meth)acrylate, tris(trimethylsiloxy)silylpropyl(meth)acrylate, tris(penta methyldisiloxanyloxy)silylpropyl(meth)acrylate, ethyl-trimethylsilylethylitaconate, isopropyl-tris(trimethylsiloxy)silylethylitaconate, isopropyl-tris(pentamethyldisiloxanyloxy)silylmethylitaconate, Ethyl-tris(trimethylsiloxy)silylethyl itaconate, Isopropyl-tris(pentamethyldisiloxanyloxy)silylethyl itaconate, Tert-butyl-trimethylsilylpropyl itaconate, Isopropyl tris(trimethylsiloxy)silylpropyl itaconate, Tertiary Butylpentamethyldisiloxanylpropyl itaconate, isopropyl-tris(trimethylsiloxy)silylpropyl fumarate, tert-butyl-tris(trimethylsiloxy)silylpropyl fumarate.

Isopropyl-tris(pentamethyldisiloxanyloxy)silylmethyl fumarate, tert-butyl-pentamethyldisiloxanylpropyl fumarate, 2,2
．． 2-trifluoroethyl (meth)acrylate, 3,
3,4,4.4-pentafluorobutyl (meth)acrylate, 2゜2.3,3,4,4,5.5-octafluoropentyl (meth)acrylate, 2,2.2-)-
Lifluoro-1-trifluoromethyl (meth)acrylate, 1,1,2.2-tetrahydroperfluorodecyl (meth)acrylate, ethyl-2゜2.2-trifluoroethyl fumarate, isopropyl-3,3,4 ，
4,4-pentafluorobutyl (meth)acrylate,
Isopropyl-2゜2.3,3,4,4,5.5-octafluoropentyl fumarate, Isopropyl-2,2
, 2-trifluoro-1-trifluoromethyl fumarate 1-, isopropyl-1,1,2,2-tetrahydroperfluorodecyl fumarate, cyclohexyl-1,1
, 2,2-tetrahydroperfluorodecyl fumarate, tert-butyl-2,2゜2-trifluoro-l-
Trifluoromethyl fumarate, bis2. '2.2-Trifluoroethyl fumarate, methacrylic acid, acrylic acid, itaconic acid, etc. can be used alone or as a mixture. It is desirable to use the most preferable combination from the viewpoints of strength, workability, gas permeability, etc. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, it is preferably less than 95% by weight based on the entire raw material component, and particularly It is desirable to use it in a range of 5 to 85% by weight.

If it exceeds 95% by weight, the oxygen permeability of the contact lens will drop significantly, which is not preferable.

The contact lens of the present invention has a DK value of 5 to 20 x 10-''mQ・an/in order to have excellent oxygen permeability.
al ・see-mmHg is preferred, especially 8
10-"mQ・aIl/al-5ec-fflmHg or more is desirable. In this case, 5X10-"mQ・an/a(・s
If it is less than ec・mmHg, oxygen permeability will be insufficient during long-term continuous wear, and
Q-an/al ・Those exceeding see-mmHg are
It is not preferred as a contact lens because its physical properties such as strength deteriorate.

In order to prepare contact lenses in the present invention, known preparation methods can be used. Specifically, for example, a monomer raw material is polymerized together with a polymerization initiator in a suitable container such as a test tube to obtain a round bar or block, and then cutting,
A method of machining such as polishing, a method of injecting the monomer together with a polymerization initiator into a desired mold and directly forming a contact lens by mold polymerization, or a method of producing a polymer in advance by a radical polymerization method, etc. Examples include a method of obtaining a contact lens by dissolving the polymer in a suitable solvent and removing the solvent by a casting method.

In the above preparation method, the polymerization initiator used when polymerizing the monomer is selected to have a half-life temperature of 120' for 10 hours.
1 of the group consisting of organic peroxides below C and azo compounds, etc.
It can be selected from one species or two or more species. Examples of the organic peroxide or azo compound include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate,
Preferred examples include t-butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), and t-butylperoxyisopropyl carbonate. The amount of the polymerization initiator used is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the raw material.

In the above preparation method, the conditions for copolymerizing each monomer are preferably such that the polymerization system is appropriately replaced with an inert gas such as nitrogen, carbon dioxide, helium, etc. or under an atmosphere, or under deaerated conditions. The temperature during copolymerization varies depending on the type of polymerization initiator used, but is preferably in the range of 30 to 120°C. Further, the total time required for polymerization is preferably about 10 to 72 hours.

It is also possible to polymerize the raw materials by adding coloring agents such as dyes or additives such as ultraviolet absorbers to the raw materials.

In the present invention, the surface of the contact lens obtained by the above-mentioned preparation method can be modified by subjecting it to acid or alkali treatment or low-temperature plasma treatment. Furthermore, the wearing comfort can also be improved by performing graft polymerization of hydrophilic monomers by low-temperature plasma treatment.

<Effects of the Invention> The contact lenses of the present invention contain specific 1-butene-2,
Since it uses a 4-dicarboxylic acid diester polymer, it has higher oxygen permeability than conventional contact lenses.
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.

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

Note that the middle part of the example represents parts by weight.

40 parts of 2-(2',2',2'-)-lifluoroethoxycarbonyloxy)silylpropyloxycarbonyl)-1-butene, l,,1,2.2-tetrahydroperfluorodecy. 30 parts of methyl(meth)acrylate, methyl(meth)acrylate
1.5 parts of azobis(2,4-dimethylvaleronitrile) was mixed with 20 parts of acrylate, 5 parts of vinyl (meth)acrylate, and 5 parts of methacrylic acid, the mixture was placed in a glass sealed tube, and the inside was replaced with nitrogen. Deaeration was repeated and the product was sealed under vacuum. This sealed tube was polymerized by standing 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 produce contact lenses. Next, various physical properties of the obtained contact lenses were measured by the following methods.

, Toru' (DK Xertex Corp.
Product name: [MODEL 211]
0] (Multirange Analyzer for
35°C using
diameter 12, 7Iff11 in 0.9% saline.
, DK value (nIQ-aIl/d-sec・■m
ug) was calculated.

Ai Tosaku 0.2% egg white lysozyme aqueous solution, 12.7 m in diameter,
Test contact lenses with a thickness of 0.2 mm were heated at 37°C for 2 hours.
Soak for 4 hours. The amount of adhered egg white lysozyme aqueous solution was determined by measuring the change in absorbance at 280 nm.

2. Separately polymerized lid stand 2m thick, 50 parts long, 10+nm wide
Measurements were carried out on flat plate samples according to the JIS K7203 bending test method for hard plastics. After curing the raw material monomers under the radical polymerization initiators and polymerization conditions shown in Table 1, contact lenses were prepared and various physical properties were measured. The monomer blending ratio is shown in Table 1, and the measurement results are shown in Table 2.

Next, the abbreviations of each component shown in the topsoil will be explained below.

F3Si4-B: 2- (2', 2', 2'
-)-lifluoroethoxycarbonyl) 4-(tris(trimethylsiloxy)silylpropyloxycarbonyl)-1-butene F17Si-B:2- (1', 1', 2', 2
'tetrahydroperfluorodecyloxycarbonyl)-4 (trimethylsilylethoxycarbonyl)-1-butene5i2F5-B:2 (methylbis(trimethylsiloxy)silylmethoxycarbonyl)-4-(3', 3'4',4',4'-pentafluorobutoxycarbonyl)-1 monobutene Si-MAX tris(trimethylsiloxy)silylpropyl methacrylate-1-F3-MA: 2,2.2-1-lifluoroethyl methacrylate F6-MA: 1,1 , 1,3,3.3-hexafluoroisopropyl methacrylate F17-MA: 1,1,2.2-tetrahydroperfluorodecyl methacrylate FL7-Fu: Isoprobyl-1,,1,2,2-tetrahydroperfluorodecyl fuma Rate MMA: Methyl methacrylate EMA: Ethyl methacrylate A-MA: Allyl methacrylate V-MA: Vinyl methacrylate MA: Methacrylic acid AA Niacrylic acid ABVN: Azobis(2,4-dimethylvalero'nitrile) IPP diisopropyl peroxydicarbonate BP○ : Benzoyl peroxide table (units are parts by weight) Table (*1) Xl0-”mQ-an/a#・sec・mm
Hg (*2) kgf/rtn" (*3) N/rrn2 From the results in Table 2, the contact lenses of the present invention have a higher DK value and better oxygen permeability and stain resistance than the comparative example. Moreover, it was found that it maintains appropriate physical strength.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, A and B are different groups, and one group is -C_hH_kF_2_h_+_1_- _k represents a linear or branched fluoroalkyl group, where h represents an integer of 2 to 18, and k represents an integer of 1 to 2×h.The other group is represented by ▲mathematical formula, chemical formula, There are tables, etc. ▼ , where X, Y and Z are the same or different groups, methyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates. Also, m is 0 or 1, n is an integer from 1 to 3, l
represents an integer from 2 to 4) and contains both a fluorine atom and a silicon atom in the same molecule.
, 4-dicarboxylic acid diester monomer as an essential raw material monomer.