JPH03144543A - 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, 3, 4- 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 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 water-containing soft contact lenses are known as commonly used contact lenses. Although the water-containing rough 1-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 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.

<Means for Solving the Problems> According to the present invention, - Formula (I) (wherein R0, R2 and R3 are the same or different groups, and at least one group is a group containing a fluorine atom) represents 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 Q are each an integer of O to 4. A copolymer obtained by copolymerizing 2 to 95% by weight of one or more niepentene-2,3,4-tricarboxylic acid triester monomers represented by A contact lens is provided that includes a coalescence.

The present invention will be explained in more detail below.

The contact lens of the present invention has a specific l-pentene-2
, 3,4-tricarboxylic acid triester monomers as raw material monomers.

The 1-pentene-2,3,4,-1 to lyrylbonic acid triester monomer used in the present invention can be represented by the following formula (I), where R, , R2 and R3 are the same or different groups, and at least one group contains a fluorine atom, including a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, and a group having 3 to 12 carbon atoms. represents a cyclic alkyl group or aryl group, and n, m and aryl each represent an integer of O to 4.

The number of carbon atoms in at least one of R2 and R3 is 1
If the number is 3 or more, or if at least one of n, m, and 5 is 5 or more, manufacturing is difficult. Also R□
It is preferred that the number of fluorines contained in at least one group of , R2 and R1 is 3 or more. Examples of the 1-pentene-2,3,4-tricarboxylic acid triester monomer represented by formula (I) include 2-(2', 2'2'-1-lifluoroethoxycarbonyl) -3゜4-di(isopropyloxycarbonyl)-1-pentene, 2-(I,'
,1',],',3',3'3'-hexafluoroisopropyloxycarbonyl)-3,4-di(tert-butyloxycarbonyl)-1-pentene, 2-
(],',1'5'-trihydroperfluoropentyloxycarbonyl)-3,4-di(tert-butyloxycarbonyl)-1-pentene, 2-(I'1'
, 2', 2'-tetrahydroperfluorodecyloxycarbonylcarbonyl 2'-trifluoroethoxycarbonyl 4-di(]'
, 1', 1', 3', 3', 3'hexafluoroisopropyloxycarbonyl)-1-pentene, 2-(I', ]', 1', 3'3'
, 3'-hexafluoroisopropyloxycarbonyl)-3,4-di(2', 2', 2'trifluoroethyloxycarbonyl)-1-pentene, 2-(2'
, 2', 2'-trifluoroethoxycarbonyl)-3,4-di(I', 1'5'-trihydroperfluoropentyloxycarbonyl)-1-pentene, 2
-(I', l'2', 2'-tetrahydroperfluorodecyloxycarbonyl)-3,4-di(2',
2'2'-trifluoroethyloxycarbonyl)-1
-Pentene, 2,3.4-tri(2',2'2'-trifluoroethoxycarbonyl)-1-pentene, 2,
3.4-tri(I', 1', 1'3', 3',
3'-hexafluoroisopropyloxycarbonyl)-1-pentene, 2,4-di(2', 2', 2'
-1, trifluoroethoxycarbonyl)-3-(I'
, 1', 1', 3', 3'3'-hexafluoroisopropyloxycarbonyl)-1-pentene, 2
,4-di(2',2'2'-trifluoroethoxycarbonyl)-3-(I',1',5'-trihydroperfluorinyl)-1-pentene, etc. When used, they can be used alone or as a mixture. The content ratio of the 1-pentene-2,3,4-tricarboxylic acid triester monomer, which is the essential raw material component, is 2 to 95% of the total raw material monomers.
% by weight. If the content of the 1-pentene-2,3,4-tricarboxylic acid triester monomer is less than 2% by weight, the oxygen permeability will be extremely reduced, and if it exceeds 95% by weight, the strength of the contact lens will not be maintained. It disappears,
Moreover, since it contains fluorine atoms, it has high water repellency and cannot be used.

In the present invention, in order to prepare the above-mentioned 1-pentene-2.3.4-tricarboxylic acid triester represented by formula (I), which is an essential monomer component, six specific For example, an alkyl or fluoroalkyl acrylate and an alkyl or fluoroalkyl itaconate are dissolved in a solvent such as dioxane, and 3
It can be obtained by a method of reacting at about 90° C. for about 7 hours in the presence of a catalyst such as phosphine and an inert gas atmosphere.

In the contact lens of the present invention, if the copolymer is composed of the l-pentene-2,3,4-tricarboxylic acid triester monomer represented by formula (I) as an essential M family monomer component, 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 It is preferable to use a monomer selected from the group consisting of polymerizable vinyl monomers, silicon-containing vinyl monomers, fluorine-containing vinyl monomers, crosslinkable polyfunctional vinyl monomers, and mixtures thereof. the radically polymerizable vinyl monomer;
Silicon-free vinyl 7-mer, fluorine-containing vinyl 7-mer
Alternatively, examples of crosslinkable polyfunctional vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene. ,
p-methylstyrene, p-chlorostyrene, O-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl (meth)acrylate, allyl (meth)acrylate, 2,2.2-)-
Lifluoroethyl (meth)acrylate, ethyl vinyl ether, n-butyl vinyl ether, (meth)acrylic acid amide, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, vinylpyridine, allyl (
meth)acrylate, trimethylsilylmethyl(meth)
Acrylate, pentamethyldisiloxanyl methyl (meth)acrylate.

Methylbis(trimethylsiloxy)silylmethyl(meth)acrylate, Tris(trimethylsiloxy)silylmethyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate, Trimethylsilylethyl(meth)acrylate, Pentamethyldisiloxa Nylethyl (meth)acrylate, Methylbis(trimethylsiloxy)silylethyl(meth)acrylate, Tris(trimethylsiloxy)silylethyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylethyl(meth)acrylate, Trimethylsilylpropyl(meth)acrylate Acrylate, pentamethyldisiloxanyl (meth)acrylate,
Methylbis(trimethylsiloxy)silylpropyl(meth)acrylate, Tris(trimethylsiloxy)silylpropyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylpropyl(meth)acrylate, Methylbis(trimethylsiloxy)silylethylglycerol mono (meth)acrylate, tris(
trimethylsiloxy)silylethylglycerol mono(
Meta) acrylate.

Tris(pentamethyldisiloxanyloxy)silylethylglycerol mono(meth)acrylate, Methylbis(trimethylsiloxy)silylpropylglycerol mono(meth)acrylate, Tris(trimethylsiloxy)silylglycerol mono(meth)acrylate, Tris(pentamethyl Disiloxanyloxy)silylpropylglycerol mono(meth)acrylate, dimethyl(triphenylsiloxy)silylpropyl(meth)acrylate, 2,2.2-trifluoroethyl(meth)acrylate, 2,2.2-trifluoro -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)acryle-1~, 1,1,
2.2-Tetrahydroperfluorooctyl (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, triallyl diethylene glycol bisallyl carbonate, triallyl cyanurate, diiso-1-propyl itaconate, di-tert-butyl itaconate, di-2,2,2-fluoroethyl itaconate, ethyl-tristrimethyl Siloxysilylprobyl itaconate, diisopropyl mesaconate, ditertiarybutyl mesaconate, di2.

2,2-Fluoroethyl mesaconate, isopropyl-
1.1,2.2-tetrahydroperfluorodecyl mesaconate, isopropyl-tris-1-limethylsiloxysilylpropyl mesaconate, di-tert-butyl fumarate, di-2,2.2-fluoroethyl fumarate, isopropyl-3.

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

Examples include 9,9,10,10,10-heptadecafluorodecyl fumarate, tert-butyl-tristrimethylsiloxysilylprobyl fumarate, methacrylic acid, acrylic acid, itaconic acid, etc. When used alone or in combination with Can be used as a mixture. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, the blending ratio as a copolymer component is as follows:
A range of 5 to 85% by weight is desirable. In this case, if it is less than 5% by weight, sufficient thermal stability, mechanical strength, processability, etc. due to copolymerization cannot be obtained, and if it exceeds 85% by weight, the oxygen permeability of the contact lens will decrease significantly, which is not preferable. .

The contact lens of the present invention has a DK value of 6-1 5 X 1 0-10 mQ - to have excellent oxygen permeability.
cm
・wit (g is desirable. In this case, 6 X 1 0-1
Oxygen permeability is insufficient for long-term continuous wear at less than 1g of 0mQ-00/ci-see-iml;
5 X 1 0-”mQ-an/at ・sec-ma
1 (g) is not preferable as it deteriorates physical properties such as strength as a contact lens.

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 ll production method, the polymerization initiator used when polymerizing the monomer is selected to have a half-life temperature of 120 hrs.
1 of the group consisting of organic peroxides and azo compounds, etc. below ℃
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 1-butylperoxyisopropyl carbonate. 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 of the seven polymers 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 desirably 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 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 a wood-philic monomer by low-temperature plasma treatment.

<Effects of the Invention> The contact lens of the present invention has a specific 1-pentene-2
, 3,4-tricarboxylic acid triester polymer, it has higher oxygen permeability than conventional contact lenses and prevents deposition of proteins, lipids, and inorganic substances on the surface. It has excellent performance that improves the shortcomings of contact 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.

2.3.4-Tori (I', 1', 1', 3'3'
azobis(2,4-dimethyl Valeronitrile (1.0 part) 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
Product name: [MODEL 2110]
](Multirange Analyzer for
Dissolved Oxygen) in 0.9% physiological saline at 35°C with a diameter of 12.7 m and a thickness of 0.
The DK value (
nlQ-al/d-8eC·mmHg) was determined.

In Ai Chorai 0.2% egg white lysozyme aqueous solution, diameter 12.7 yen,
A test contact lens with a thickness Q of 2+m+ was immersed at 37° C. for 24 hours, and the change in absorbance at 280 nm was measured to determine the amount of the egg white lysozyme aqueous solution adhered.

The hardness was measured using a Terasawa type MM-2 ultra-micro hardness meter manufactured by Vickers (HV Taiyo Tester Co., Ltd.).

(2) Lid cutting: Two separately polymerized flat plate samples having a thickness of 50 mm and a width of 10 nm were measured in accordance with the JIS K7203 bending test method for hard plastics.

2-5 Ratio 1-3 By the same method as in Example 1, raw material monomers of various compositions shown in Table 1 were cured under the radical polymerization initiator and polymerization conditions shown in Table 1, and then contact lenses were produced, 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 Table 1 will be explained below.

TF3-A: 2,3.4-tri(2', 2', 2
1-pentene TF6-A: 2,3.4-1~(I',3-'
, 1'3', 3', 3'-hexafluoroisopropyloxycarbonyl)-"-pentene F8/DF6-A: 2-(I', 1', 5'-
trihydroperfluoropentyloxycarbonyl)-3,4-di(↓', 1' 1/, 3r, 3/, 3L-hexafluoroisopropyloxycarbonyl)-1-pentene F17/DE-A: 2- (] ' , 1.' ,
2', 2'-tetrahydroperfluorodecyloxycarbonyl)-3,4-di(ethoxycarbonyl)-1-pentene Si-MA Nidoristrimethylsiloxysilylpropyl methacrylate F17-MA: 1,1. ．． 2.2-Tetrahydroperfluorodecyl methacrylate F6-MA: 1,1,1,3,3.3-hexaf-1
'(- Luoloisoprobyl methacrylate F17-Fu: Isoprobyl-1,1,2,2 tetrahydroperfluorodecyl fumarate 5i-Fu: MMA: Methyl methacrylate EMA: Ethyl methacrylate A-MA: Allyl methacrylate V-MA: Vinyl methacrylate MA: To methacrylic acid A Niacrylic acid ABVN: Azobis(2,4-dimethylvaleronitrile) IPP diisopropyl peroxydicarbonate BPO: Benzoyl peroxide (blank below) 120 - Table (Units are parts by weight) Table 2 (* 2) kgf/mm2 (*3) N/1m2 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_2 and R_3 are the same or different groups, and at least one group has a fluorine atom. A group containing 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, where n, m and l are each 0. (indicates an integer of ~4)
A contact lens comprising a copolymer obtained by copolymerizing 2 to 95% by weight of 1-pentene-2,3,4-tricarboxylic acid triester monomers as essential raw material monomers.