JPH02294616A - Contact lens - Google Patents

Abstract

PURPOSE:To improve oxygen permeability and resistance to staining, etc., by using a specific 1-butene-2, 4-dicarboxylate monomer. CONSTITUTION:This lens contains a copolymer contg. 2 to 95wt.% 1-butene-2, 4-dicarboxylate monomer expressed by formula I as an essential raw material monomer. In the formula, R1, R2 are the same or different groups and denote a hydrogen atom, 1 to 12C alkyl group, 1 to 12C alkenyl group, 3 to 12C cyclic alkyl group; m denotes 0 or 1; n denotes 0 to 3 integer; l denotes 2 to 4 integer. The contact lens which has the oxygen permeability to allow long-term continuous wearing and is improved in shape stability, resistance to staining 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.

<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 soft contact lenses are comfortable to wear, 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 easily contaminated with bacteria and causes serious complications for the cornea and cord. ing. In contrast, 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 been attracting 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 an excellent vision correction effect, 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, the following general formula (I) (wherein R1 and R2 are the same or different groups, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, Alkenyl group having 1 to 12 carbon atoms, cyclic Y having 3 to 12 carbon atoms, where X, Y and 2 are the same or different groups and represent a methyl group; m is 0 or 1; n is O ~3 integer, Q
represents an integer from 2 to 4), 1-butene-2,
A contact lens is provided that includes a copolymer containing 2 to 95% by weight of a 4-dicarboxylic acid diester monomer as an essential raw material monomer.

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 containing 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), where R1 and R2 are the same or different groups, and a hydrogen atom, Alkyl group having 1 to 12 carbon atoms, alkenyl group having 1 to 12 carbon atoms, cyclic X having 3 to 12 carbon atoms The X, Y and Z are the same or different groups, and represent a methyl group. Also, m is 0 or 1, n is an integer from 0 to 3, and Q
indicates an integer between 2 and 4. When the number of carbon atoms in R and/or R2 is 13 or more, m is 2 or more, n is 4 or more, and Q
If is 5 or more, manufacturing is difficult. The general formula (
Examples of the 1-butene-2,4-dicarboxylic acid diester monomer represented by I) include 2-(methoxylponylethyl)tert-butyl acrylate, 2-(
ethoxycanolebonylethyl) tert-butyl acrylate, 2-(tert-butyloxytriponylethyl) tert-butyl acrylate, 2-(allyloxytriponylethyl) tert-butyl acrylate, 2-(methoxycanolebonylethyl) trimethylsilylmethyl Acrylate. 2-(Methoxyluponylethyl)methylbis(trimethylsiloxy)silylmethylacrylate, 2-(Ethoxyluponylethyl)trimethylsilylmethylacrylate, 2-(Ethoxyluponylethyl)pentamethylsiloxyxaninolemethylacrylate, 2-(Ethoxycanolebonyl) ethyl)methylbis(trimethylsiloxy)silylmethylacrylate, 2-(isoprobyloxycarponylethyl)pentamethyldisiloxanylmethylacrylate, 2-(isoprobyloxycarponylethyl)trimethylsilylmethylacrylate 2-(isoprobyloxycarponylethyl) Methylbis(trimethylsiloxy)silylmethylacrylate, 2-(isoprobyloxycarponylethynole)tris(trimethylsiloxy)silylmethylacrylate, 2-(isoprobyloxycarponylethyl)bis(trimethylsiloxy)(pentamethyldisiloxanyl) oxy)silyl methyl acrylate, 2
-(tert-butyloxyproponylethyl)trimethylsilylmethylacrylate, 2-(tert-butyloxyproponylethyl)trimethylsilylbutyl acrylate, 2-(tert-butyloxyproponylethyl)pentamethyloxyxanyl Methyl acrylate, 2-(tert-butyloxylponylethyl)tris(trimethylsiloxy)silylbutylene acrylate, 2-(2'-ethylhexylhexyloxylponylethyl)trimethylsilylmethyl acrylate, 2-(2'-ethylhexyloxycano) levoninolethyl)bis(trimethylsiloxy)(pentamethyldisyxanyloxy)silylmethylacrylate, 2-
(cyclohexyloxylponylethyl)tris(trimethylsiloxy)silylpyl acrylate, 2-
(cyclohexyloxylponylethyl)tris(trimethylsiloxy)silylmethylacrylate, 2-(
Trimethylsilylmethoxyruponylethyl)methyl acrylate, 2-(pentamethyldisiloxanylmethoxyluponylethyl)methyl acrylate, 2-(pentamethyldisiloxanylmethoxycanolevonylethyl)ethyl acrylate. 2- (tris(trimethylsiloxy)silyloxymethylethyl)
Ethyl acrylate. 2-(trimethylsilyloxypropylene ethyl)isopropylacrylate, 2-(tris(trimethylsiloxy)silylpropylphyloxypropylene ethyl)isopropylacrylate,
2-(Pentamethyldisymethoxylponylethyl)tert-butyl acrylate. 2- (}-
Lis(trimethylsiloxy)silylbutyloxytriponylethyl)-2'-ethylhexyl acrylate,
2-(pentamethylmethoxylponylethyl)cyclohexylmethylacrylate, 2-methoxycanolevonylethyl-(2'-hydroxy-3'
monotrimethylsilylethoxy) probyl acrylate,
2-ethoxylponylethyl-(2'-hydroxy-
37-Pentamethyldisiacyxanyl ethoxy) probyl acrylate, 2-ethoxylic acid probyl acrylate [
2'-Hydroxy-3'-tris(trimethylsiloxy)silylpropylacrylate, 2-
Isoprobyloxycarponylethyl-[2'-hydroxy-3'-tris(trimethylsiloxy)silylbutyloxy]butyl acrylate, 2-tert-butoxycarponylethyl-(2'-hydroxy-3'-trimethylsilylethoxy)propylene Building acrylate, 2
-Cyclohexyloxycarbonylethyl-[2'-hydroxy-3'-tris(trimethylsiloxy)silyloxy]pyropylacrylate, 2-trimethylsilyloxycarbonylethyl(2'
-hydroxy-3'methoxy)probyl acrylate,
2-tris(trimethylsiloxy)silylboxypropyl ethyl(2'-hydroxy-3'monoethoxy)propyl acrylate, 2-trimethylsilylboxypropyl ethyl(2'-hydroxy-
3'-isopropyloxy)propyl acrylate, 2
-Pentamethyldisymethoxylponylethynole (2'-hydroxy-3'-tert-butoxy)
Propyl acrylate, 2-tris(trimethylsiloxy)silyloxypyloxypropyl ethyl[2'-
Hydroxy-3'-(2'-ethylhexyloxy) ester acrylate, 2-(trimethylsilylmethoxylponylethyl)trimethylsilylmethyl acrylate, 2-(trimethylsilyl methoxylponylethyl)trimethylsilyl ester acrylate, 2
Examples include -(pentamethyldisyxanylmethoxylponylethyl)pentamethyldisyxanylmethyl acrylate, 2-(pentamethyldisyxanylpropyloxycarbonylethyl)pentamethyldisyxanylmethoxycarbonyl acrylate, etc., and when used,
It can be used alone or as a mixture. The content of the 1-butene to 2,4-dicarboxylic acid diester monomer, which is the essential raw material component, is in the range of 2 to 95% by weight based on the total raw material heptanomer. 1-butene-2,
If the content of the 4-dicarboxylic acid diester monomer is less than 2% by weight, the oxygen permeability is extremely low, and if it exceeds 95% by weight, the contact lens cannot maintain its strength and cannot be used.

In the present invention, to prepare the 1-butene-2,4-carboxylic acid diester represented by the general formula (I),
It can be obtained by a known method.

Specifically, it can be obtained, for example, by a method in which a dioxane solution of a silicon-containing acrylic ester is reacted in the presence of a catalyst and an inert gas atmosphere. The contact lens of the present invention can be made of any other copolymerizable polymer as long as it contains the 1-butene-2,4-dicarboxylic acid diester monomer represented by the general formula (I) as an essential raw material monomer. Monomers can be copolymerized, but in view of the thermal stability, mechanical strength, processability, etc. of the resulting contact lenses, other copolymerizable monomers, such as radically polymerizable vinyl monomers and silicon-containing vinyl monomers, are recommended. It is preferable to use a monomer selected from the group consisting of fluorine-containing vinyl heptanomeric crosslinkable polyfunctional vinyl monomers, mixtures thereof, and the like. 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, and tert-butyl (meth)acrylate. , cyclohexyl (meth)acrylate, benzyl (meth)
Acrylate, styrene, p-methylstyrene, p-chlorostyrene, 0-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl piperate, vinyl (meth)acrylate, ethyl vinyl ether, n-butyl vinyl ether, ( meth)acrylic acid amide, 2-hydroxyethyl (meth)acrylate,
N-vinylpyrrolidone, vinylpyridine, furyl (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, diisobutyl itaconate, ditertiary butyl itaconate, ditertiary butyl fuma trimethylsilylmethyl(meth)acrylate, pentamethyldisiloxanylmethyl(meth)acrylate, tris(trimethylsiloxy)silylmethyl(meth)acrylate, tris(pentamethyldidyloxanyloxy)silylmethyl(meth)acrylate, trimethylsilylethyl (meth)acrylate, pentamethyldisysilylethyl (meth)acrylate, tris(trimethylsiloxy)silylethyl(meth)acrylate, tris(
Pentamethyldisiloxanyloxy)silylethyl (meth)acrylate, trimethylsilylpipil (meth)
Acrylate. Pentamethyl disyxanil pill (
meth)acrylate, tris(trimethylsiloxy)silylpyl(meth)acrylate, 1-lis(pentamethyldisyxanyloxy)silylpyl(meth)
Acrylate, ethyl trimethylsilylethyl itaconate, isobropyrutris (trimethylsiloxy)
Silylethyl itaconate, inpropyl-tris(pentamethyldisiloxanyloxy)silylmethyl itaconate, ethyl-tris(trimethylsiloxy)silylethyl itaconate, isopropyl-tris(pentamethyldisiloxanyloxy)silylethyl itaconate, tert-butyltrimethylsilyl Propyl itaconate, isopropyl lutris (trimethylsiloxy)
Silylbutyl itaconate, tert-butyl pentamethyldisyxanyl itaconate, isopropyl lutris (trimethylsiloxy) silylbyl itaconate, tert-butyl lutris (trimethylsiloxy) silyl pyrufumarate, isopropyl lutris (pentamethyl disyxanyloxy) Silylmethyl fumarate, tert-butyl-pentamethyldisyxanylbutylphumarate, 2,2.2-trifluoroethyl (meth)acrylate, 3,3,4,4.4-
Pentafluorobutyl (meth)acrylate, 2,2,
3,3,4,4,5,5-octafluorobentyl (meth)acrylate, 2,2.2-trifluoro 1-1
-Refluoromethyl (meth)acrylate, 1,1.2
．． 2-tetrahydride perfluorodecyl (meth)acrylate, ethyl-2.2.2-1-refluorethyl fumato, isoprobyl-3.3,4,4,4-pentafluorobutyl (meth)acrylate, isoprobyl- 2
．． 2,3,3,4,4,5,5-octafluoro-pentyl fumarate, isoprobyl-2.2.2-trifluoro-1-trifluoromethyl fumarate, isobrobyl-1,1,2,2-tetrahydride Perfluorodecyl fumarate, cyclohexyl-1,1,2,2-tetrahydride perfluorodecyl fumarate, tert-butyl-2,2,2-trifluoro-1-trifluoromethyl fumarate. Bis-2.2.2-trifluoroethyl fumarate, methacrylic acid, acrylic acid, itaconic acid, etc. can be mentioned, and they can be used alone or as a mixture. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, it is desirable to use it in a range of 5 to 85% by weight. 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 to 1 2
l/d-sec-LDIIHg is preferred, especially 7 to 1
1X1 0-”mQ-atr/al-see-mmHg
is desirable. In this case, 6 X 1 0-”mQ-am/a
J sec ・mm}Ig, oxygen permeability is insufficient for long-term continuous wear, and 1 2
-"a1Q-cs/al-sac .mmHg is not preferable because physical properties such as strength of the contact lens deteriorate.

In order to prepare contact lenses in the present invention, known preparation methods can be used. Specifically, for example, the monomer raw materials are copolymerized together with a polymerization initiator in a suitable container such as a test tube to obtain a round piece or block, and then mechanical processing such as cutting and polishing is performed to adjust the composition to the formulation. A method for processing a contact lens, a method in which the monomer is injected together with a polymerization initiator into a single desired mold, and a contact lens is directly molded by mold polymerization, or a copolymer is produced in advance by a radical polymerization method, etc. Afterwards, the copolymer is dissolved in a suitable solvent and the solvent is removed by a casting method to obtain a contact lens. In the above preparation method, the polymerization initiator used when polymerizing the monomer is selected to have a half-life temperature of 12 hours.
It can be selected from one or more of the group consisting of organic peroxides and azo compounds at temperatures below 0°C. Examples of the organic peroxide or azo compound include penzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxydi-2-ethylhexanoate, t-butylperoxypipalate, di-butylperoxydiisobutyrate, Lauroyl peroxide, azobisisobutyronitrile. Preferred examples include azobis(2,4-dimethylbenolenitrile), t-butylbenoleoxyisobutylene carbonate, and the like. The amount of the polymerization initiator used is based on 100 parts by weight of the raw material monomer. It is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.

In addition, in the above preparation method, the conditions for copolymerizing each heptanomer are that the polymerization system is appropriately replaced with an inert gas such as nitrogen, carbon dioxide, helium, etc., or the polymerization is performed in an atmosphere or under deaerated conditions. is preferable. 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 material monomers by adding coloring agents such as dyes or additives such as ultraviolet absorbers.

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 hydrophilic monomers by low-temperature plasma treatment.

Effects of the Invention> The contact lens of the present invention has a specific 1-butene-2,
Since it uses a 4-dicarboxylic acid ester I11rik compound, 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 has improved its shortcomings.

<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-isoprobyloxycarponylethyl tris(trimethylsiloxy)silylpyl acrylate, 15 parts of tristrimethylsiloxysilyl methacrylate
parts, 30 parts of 1,1,2.2-tetrahydride perfluorodecyl methacrylate, 20 parts of ethyl methacrylate,
5 parts of allyl methacrylate and 5 parts of methacrylic acid are mixed with 1.0 part of azobis(2,4-dimethylbaret nitrile), charged into a sealed glass tube, replaced with nitrogen, repeated deaeration, and melted under vacuum. It was sealed. 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. Next, the obtained polymer was cut and then cut. A contact lens was prepared by i'fm. Various physical properties of the obtained contact lenses were measured by the following methods. Table 1 shows the blending ratio of each raw material monomer and polymerization initiator, and Table 2 shows the measurement results. XerteyCorp
Oration Manufactured by Shisha Product Name [MO[)EL 21
10 pieces (Multirange A nalyzer
for Dissolved Oxygen)
12.7 m in diameter and 0.0 m in thickness in 0.9% saline at 5°C. DK value measured for 2mn+ test contact lens (p・am/aj・SQC・wound Hg)
I asked for

15 Elephant blood 0.2% egg white lysozyme aqueous solution, diameter 12.7 m,
Test contact lenses with a thickness of 0.2 mm were heated at 37°C for 24 hours.
The sample was immersed for a period of time, and the change in absorbance at 280 nm was measured to determine the amount of the egg white lysozyme aqueous solution attached.

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

1 Separately polymerized blood powder with a thickness of 2 mm and a length of 50 nm. Width 10+um
A flat plate sample was measured in accordance with JIS K7203 bending test method for hard plastics. After curing the raw material monomers of the composition using the radical polymerization initiator shown in Table 1, contact lenses were produced and various physical properties were measured. Table 1 shows the blending ratios of raw material monomers and polymerization initiators, and Table 2 shows the measurement results. (Left below) Table (Thursday 1) XIO-”mQ-an/aJ-secam
n+}Ig (Thursday 2) kgf/Sono 2 (Thursday 3) N/rmz From the results in Table 2, the contact lenses of the present invention have extremely excellent oxygen permeability and are also excellent in stain resistance, etc. It turns out.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 and R_2 are the same or different groups,
Hydrogen atom, alkyl group having 1 to 12 carbon atoms, 1 to 1 carbon number
2 alkenyl group, cyclic alkyl group having 3 to 12 carbon atoms,
Indicates an aryl group or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the X, Y and Z are the same or different groups, and 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 0 to 3, l
represents an integer from 2 to 4), 1-butene-2,
A contact lens comprising a copolymer containing 2 to 95% by weight of a 4-dicarboxylic acid diester monomer as an essential raw material monomer.