JPH03144542A - Contact lens - Google Patents

Abstract

PURPOSE:To obtain the contact lens which has high oxygen permeability and can prevent the deposition of protein, lipid and inorg. matter, etc., onto the surface by using a specific polymer. CONSTITUTION:A copolymer formed by copolymerizing the 1-pentene-2, 4, 5- triester tricarboxylate monomer expressed by formula I as a raw material monomer is incorporated into this contact lens. In the formula, R1 to R3 denote a hydrogen atom, 1 to 12C alkyl group, 1 to 12C alkenyl group, 3 to 12C cyclic alkyl group or aryl group, at least one group of which contain a fluorine atom; n, m and l respectively denote 0 to 4 integer. The number of the fluorine incorporated into at least one group of R1 to R3 is preferably >=3. The contact lens which has an excellent visual power correcting effect, has the oxygen permeability to allow long-term continuous wearing and has the excellent shape stability, contamination resistance and durability is obtd. in this way.

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 hydrous rough 1-contact lenses are known as commonly used contact lenses. 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 has been actively conducted, but the reality is that each of the above GP contact lenses pursues only oxygen permeability and does not have the other properties required for contact lenses. It is.

For example, JP-A-62-8769, JP-A-62-6
The contact lens 1 described in Japanese Patent Publication No. 1928 and Japanese Patent Publication No. 63-36646 has good oxygen permeability, but
There are problems with shape stability and stain resistance. On the other hand, time opening F@6
The dialkyl fumarates used in JP-A No. 2-99720 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. Also, JP-A-61-17690
The contact lens disclosed in Publication No. 9 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, - General formula (I) (wherein R□, R2 and Rj are the same or different groups, and at least one group contains a fluorine atom) A hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
It represents an alkenyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or an aryl group, and n, m and 0 each represent an integer of 0 to 4. ) is copolymerized with 2 to 95% by weight of one or more 1-pentene-2,4,,5-1 carboxylic acid triester monomers as essential raw material monomers. Contact lenses are provided that include the copolymers.

The present invention will be explained in more detail below.

The contact lens of the present invention has a specific l-pentene-2
, 4,5-1~ is characterized in that it contains a copolymer formed by copolymerizing a tricarboxylic acid triester monomer as a raw material monomer.

The 1-pentene-2,4,5-1-licarboxylic acid l-lyester monomer used in the present invention can be represented by the following general formula (I), where R, R2 and R3 are the same as - or a different group, in which at least one group contains a fluorine atom, such as a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms. group or an aryl group, and n, m and α each represent an integer of 0 to 4. Said R work, R2 and/or R1
If the number of carbon atoms is 13 or more, or if at least one of n, m, and the above is 5 or more, manufacturing is difficult. Also R1. The number of fluorines contained in at least one group of R2 and R3 is preferably 3 or more. 1-pentene- represented by the general formula (I)
Examples of 2,4,5-tricarboxylic acid 1-lyester monomers include 1, for example, 2-(2',2'2'-trifluoroethoxycarbonyl)-4゜5-di(isopropyloxycarbonyl)-1= Pentene, 2-(I', 1
．． ', 1. ',3',3'3'-hexafluoroisopropyloxycarbonyl)-4,5-di(tert-butyloxycarbonyl)-1-pentene, 2-
(I', 1'5'-trihydroperfluoropentyloxycarbonyl)-4,5-di(tert-butyloxycarbonyl)-1-pentene, 2- (I'1'
,2',2'-tetrahydroperfluorodecyloxycarbonyl)-4,,5-di(ethoxycarbonyl)-1-pentene,2-(2',2'2'-trifluoroethyloxycarbonyl)-4, 5-di(I'
, 1', 1', 3', 3'3'-hexafluoroisopropyloxycarbonyl)-1-pentene, 2-
(I', 1', 1'3', 3', 3'-hexafluorisopropyloxycarbonyl)-4,5-
di(2',2'2'-trifluoroethyloxycarbonyl)1-pentene, 2-(2',2',2'
-trifluoroethyloxycarbonyl)-4,5-
di(I', 1', 5'-trihydroperfluoropentyloxycarbonyl)-1-pentene, 2-(I
',1',2',2'-tetrahydroperfluorodecyloxycarbonyl)-4,5-di(2'
, 2', 2'-trifluoroethyloxycarbonyl)-1-pentene, 2,4.5-tri(2', 2'
, 2'-trifluoroethyloxycarbonyl)-
1-pentene, 2,4.5-tri(I', 1', 1
',3',3',3'-hexafluoroinpropyloxycarbonylpentene,2,5-di(2',
2', 2'-trifluoroethyloxycarbonyl)-4- (I'1', 1', 3', 3', 3
'-hexafluoroisopropyloxycarbonyl)
-1-pentene, 2,5-di(2', 2', 2'
-trifluoroethyloxycarbonyl) -4- (
Examples include I', 1'5'-trihydroperfluoropentyloxycarbonyl)-1-pentene, which can be used alone or as a mixture. 1-pentene, which is the essential raw material component
2.4.5-7 The content of the tricarboxylic acid triester monomer is 2 to 95% by weight based on the total raw material monomers.
is within the range of 1-pentene-2.4. , the content of 5-1-ricarboxylic acid triester monomer is 2% by weight
If it is less than 95% by weight, the oxygen permeability will be extremely reduced, and if it exceeds 95% by weight, it will not be able to maintain its strength as a contact lens, and since it contains fluorine atoms, its water repellency will be too high, making it unusable.

In the present invention, 1-pentene-2 represented by the above general formula (I) is an essential heptamer component.

To prepare 4,5-tricarboxylic acid triester,
- Can be obtained by known methods. Specifically, for example, an alkyl or fluoroalkyl acrylate and an alkyl or fluoroalkyl itaconate are dissolved in a solvent such as dioxane, and the mixture is heated at about 90°C for about 7 hours in the presence of a catalyst such as tertiary phosphine and an inert gas atmosphere. It can be obtained by a reaction method, etc.

In the contact lens of the present invention, if the copolymer is composed of the 1-pentene-2.4.5-tricarboxylic acid triester monomer represented by the general formula (I) as an essential raw material, Although any other copolymerizable monomers can be copolymerized, considering the thermal stability, mechanical strength, processability, etc. of the resulting contact lenses, other copolymerizable monomers, such as radical polymerizable monomers, may be used. It is preferred to use monomers selected from the group consisting of vinyl monomers, silicon-containing vinyl monomers, fluorine-containing vinyl monomers, crosslinkable polyfunctional vinyl monomers, and mixtures 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-6-butyl (meth)acrylate, cyclohexyl (meth)acrylate
Acrylate, benzyl (meth)acrylate, styrene, p-methylstyrene, p-chlorostyrene, O-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl (meth)acrylate, allyl (meth)acrylate, 2 ,2.2-
Trifluoroethyl (meth)acrylate-1-, ethyl vinyl ether, n-butyl vinyl ether, (meth)acrylic acid amide, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, vinylpyridine, allyl (meth)acrylate, trimethylsilyl Methyl(meth)acrylate, Pentamethyldisiloxanylmethyl(meth)acrylate, Methylbis(trimethylsiloxy)silylmethyl(meth)acrylate, Tris(]・
] Limethylsiloxysilylmethyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate, Trimethylsilylethyl(meth)acrylate, Pentamethyldisiloxanylethyl(meth)acrylate, Methylbis(trimethylsiloxy) ) silylethyl (meth)acrylate, tris(
trimethylsiloxy)silylethyl(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylethyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, pentamethyldisiloxanyl(meth)acrylate, methylbis(trimethylsiloxy)silylpropyl (meth)acrylate, tris(
trimethylsiloxy)silylpropyl(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylpropylta)acrylate, methylbis(trimethylsiloxy)silylethylglycerol mono(meth)acrylate, tris(trimethylsiloxy)silylethylglycerol mono( meth)acrylate, tris(pentamethyldisiloxanyloxy)silylethylglycerol mono(meth)acrylate, methylbis(trimethylsiloxy)silylpropylglycerol mono(meth)acrylate.

Tris(I-limethylsiloxy)silylglycerol mono(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylpropylglycerol mono(meth)acrylate, Dimethyl(triphenylsiloxy)
Silylpropyl (meth)acrylate, 2,2.2-trifluoroethyl (meth)acrylate, 2,2.2-
1\Lifluoro-1-trifluoromethyl (meth)acrylate, 3,3,4,4,5,5,6,6.6-nonafluorohexyl (meth)acrylate, 2,2.

3,3,4,4,5.5-octafluoropentyl (meth)acrylate, 1,1,2,2-tetrahydroperfluorooctyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Acrylate, triethylene glycol di(
meth)acrylate, dipropylene glycol di(meth)acrylate, diallyl phthalate, diallyl isofumarate, diallyl terephthalate, diethylene glycol bisallyl carbonate, triallyl trimellitic acid 11-acid, triallyl cyanurate, diisopropyl itaconate, ditertiary butyl itaconate , di2,2.2-fluoroethyl itaconate, ethyl-tristrimethylsiloxysilylprobyl itaconate,
Diisopropyl mesaconate, ditertiary butyl mesaconate, di2.

2,2-Fluoroethyl mesaconate, isopropyl-
1. , 1,2.2-tetrahydroperfluorodecyl mesaconate, isopropyl-tristrimethylsiloxysilylpropyl mesaconate, di-tert-butyl fumarate, di-2,2.2-fluoroethyl fumarate, isopropyl-3.

3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8.

9,9,10,10.10-hebutadecafluorodecyl fumarate, tert-butyl-tris 1-lymethylsiloxysilylpropyl fumarate, methacrylic acid. Examples include acrylic acid and itaconic acid, which can be used alone or as a mixture. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, 2-fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, the blending ratio as a copolymer component is 5 to 5.
A range of 85% by weight is desirable. In this case, if it is less than 5% by weight, sufficient thermal stability, mechanical strength, processability, etc. can not be obtained by copolymerization, and if it exceeds 85% by weight, the oxygen permeability of the contact lens will be significantly reduced, so it is preferable. do not have.

The contact lens of the present invention has a DK value of 6 to 15 × 10 to 10 mQ・(
! l X d-sec-smog is preferred, especially 8-
14×1 0-10mQ-an/ai-see-iv
Hg is preferred. In this case, 6 X 1 0-”mQ ・a
m/al-sec-mm) less than 1 g, oxygen permeability is insufficient for long-term continuous wear, and l 5
0-”mQ ・(!l/(!If ・sec ・mmH
If it exceeds g, the physical properties such as strength as a contact lens will deteriorate, so it is not preferable.

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°C for 10 hours.
It can be selected from one or more of the following organic peroxides and azo compounds. Examples of the organic peroxide or azo compound include benzoyl peroxide, diisopropyl peroxydicarbonate,
t-Butylperoxy-2-ethylhexanoate, t
-Butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 1-butylperoxyisopropyl carbonate 15- Preferred examples include: can. 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 monomer.

In addition, in the above preparation method, the conditions for copolymerizing each monomer are as follows:
It is preferable to carry out the polymerization under an atmosphere of substitution or degassing with carbon dioxide, helium, etc., and the temperature during copolymerization is in the range of 30 to 120°C, although it varies depending on the type of polymerization initiator used. preferable. Also,
The total time required for polymerization is. It is desirable that the heating time be about 10 to 72 hours.

It is also possible to polymerize by adding a coloring agent such as a dye or an additive such as an ultraviolet absorber to the raw material monomer.

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 be improved by graft polymerizing a 16-hydrophilic monomer by low-temperature plasma treatment.

<Effects of the Invention> The contact lens of the present invention has a specific 1-pentene-2
．． Because it uses a 4.5-tricarboxylic acid triester polymer, it has higher oxygen permeability than conventional contact lenses, and can prevent the deposition of proteins, lipids, and inorganic substances on the surface. It has excellent performance that improves the drawbacks of lenses.

<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.

2, 4.5-)-ri (I', 1', 1', 3'3
, 3'-hexafluoroisopropyloxycarbonyl)-1-pentene, 35 parts of tristrimethylsiloxysilylpropyl methacrylate, 20 parts of methyl methacrylate, 5 parts of allyl methacrylate, and 5 parts of methacrylic acid; 1.0 part of dimethylvaleronitrile) was mixed, and this mixture was placed in a glass sealed tube, and the inside was repeatedly purged with nitrogen and degassed, and then melt-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.

' DK Xertex Corporation
manufactured by Oration) Product name [NODEL 211
0] (Multirange Analyzer for
35°C using
In 0.9% physiological saline, the diameter is 12, 7, and the thickness is Q.
, 2m test contact lenses were measured to determine the DK value (-.am/cd-see.s+mHg).

12.7 m in diameter in a 0.2% egg white lysozyme aqueous solution.
Test contact lenses with a thickness of 0.2 mm were heated at 37°C for 2 hours.
The sample was immersed for 4 hours, and the change in absorbance at 280 nm was measured to determine the amount of the egg white lysozyme aqueous solution attached.

Picker 2 11th row point - 1 Measurement was performed using a Terasawa type MM-2 ultra-micro hardness meter manufactured by Shishichichitsuichi Taiyo Tester Co., Ltd.

Separately polymerized thickness: 2IIll, length: 50m++, width: 10cm
+nm flat plate samples were measured in accordance with JIS K7203 hard plastic bending test method. 2-5 Ratio 1-3 By the same method as in Example 1, raw monomers of various compositions shown in Table 1 were measured. was cured using the radical polymerization initiator shown in Table 1 under the polymerization conditions, 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 I@ name of each component shown in Table 1 will be explained below.

TF3-A: 2,4.5-)-li(2', 2',
2'-trifluoroethoxycarbonyl)-1-pentene TF6-A: 2,4. ．． 5-tri(I', ],'
, 1'3', 3', 3'-hexafluoroisopropyloxycarbonyl)-1°-pentene F8/DF6-A: 2- (I,', 1.'
, 5'-trihydroperfluoropentyloxycarbonyl)-4,,5-di(I', 1'1', 3'
, 3', 3'-hexafluoroisopropyloxycarbonyl)-1-pentene F17/DE-A: 2- (I,', 1', 2'
. Fluorodecyl methacrylate 19-F6-MA: 1,1,1,3,3.3-hexafluoroisopropyl methacrylate F17 Fu: Isoprobyl-1.1,2.2-te1
-Rahydroperfluorodecyl fumarate Si-Fu: MMA: Methyl methacrylate EMA: Ethyl methacrylate A-MA: Allyl methacrylate V-MA: Vinyl methacrylate MA: Methacrylic acid AA Niacrylic acid ABVN: Azobis(2,4-dimethylvaleronitrile) ) IPP diisopropyl peroxydicarbonate BPO: benzoyl peroxide (blank below) Table (Units are parts by weight) Table 2 (Kyo1) X 10-”mQ-cn/al ・sec
・mmHg (ne2) kd/d (ne3) N/d 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] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) (In the formula, R_1, R_ and R_3 are the same or different groups, and at least one group has a fluorine atom. a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or an aryl group, and n, m and l are each 0. 2 to 95% by weight of one or two or more 1-pentene-2,4,5-tricarboxylic acid triester monomers represented by A contact lens containing a copolymer made of