JPS6332518A - Contact lens material - Google Patents

Abstract

PURPOSE:To obtain a contact lens material superior in oxygen permeability, hardness, rigidity, brittleness resistance, and hydrophilicness by forming a contact lens material made of a copolymer composed essentially of fumaric acid diester structural units each having a specified structure. CONSTITUTION:A contact lens material is made of fumaric acid diesters containing, as the structural units of 100mol% of it, 50-90mol% dialkyl fumarate and 5-30mol% alkyl(hydroxyalkyl) fumarate represented by the formula shown on the right in which R1 is 1-8C alkyl and R2 is 1-8C hydroxyalkyl. Said diesters may contain fumarates other than these in an amount of 5-45mol% of 100mol of it, and in addition, other kinds of monomers may be added to modify the properties of the polymer as the copolymer components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to contact lens materials. More specifically, the present invention relates to a contact lens material particularly having excellent oxygen permeability.

[Conventional technology and its problems] Conventionally, contact lens materials have been made mainly of polymethyl methacrylate, which has excellent machinability and elasticity, and silicone rubber, such as polydimethylsiloxane, which has excellent oxygen permeability. There are used materials in which machinability is imparted by introducing vinyl polymerizable groups into (poly)organone loxane and then polymerizing it with other vinyl monomers.

These contact lens materials are only useful for specific purposes depending on their properties, such as oxygen permeability,
It does not satisfy all properties such as hardness, and it also has drawbacks such as causing metabolic disorders in the corneal tissue when worn for a long time.

Therefore, the present inventors have discovered a copolymer containing fumaric acid diester as a main component as a contact lens material that can eliminate the above-mentioned drawbacks, that is, has excellent oxygen permeability and appropriate mechanical strength. Even when a copolymer containing fumaric acid diester as the main component is used, hydrophilicity has not been significantly improved, and in order to satisfy such hydrophilicity, the surface of contact lenses must be plasma treated. It was necessary to apply hydrophilic monomers such as 2-hydroxyethyl methacrylate or acrylic acid.

However, when plasma treatment is performed, the hydrophilicity decreases over time, and commonly used hydrophilic monomers such as 2-hydroxyethyl methacrylate and acrylic acid coexist with fumaric acid diester. When lightning strikes occur, there is a problem in that contact lenses often become cloudy.

[Problems to be Solved by the Invention] Therefore, in view of the above-mentioned problems, the present inventors have developed a hard contact lens made of a material that has desirable hardness and oxygen permeability as a hard contact lens, and also has excellent hydrophilicity. As a result of extensive research to develop lenses, we have developed a fumaric acid diester containing 50 to 90 mol parts of dialkyl fumarate and 5 to 30 mol parts of alkyl (hydroxyalkyl) fumarate per 100 mol parts of total ffl of fumaric acid diester. If a copolymer containing the main component is used as a contact lens material, it can be used as a contact lens material that not only has excellent properties such as oxygen permeability, hardness, hardness, and brittleness, but also has excellent hydrophilicity. After discovering this fact, we have completed the present invention.

[Means for Solving the Problems] That is, the present invention uses 50 to 90 mole parts of dialkyl fumarate and general formula (I):
20C-C1 (wherein R1 is an alkyl group having 1 to 8 carbon atoms, R2 is a hydroxyalkyl group having 1 to 8 carbon atoms) containing 5 to 30 mole parts of alkyl (hydroxyalkyl) fumarate; The present invention relates to a contact lens material made of a copolymer containing fumaric acid diester as a main component.

[Example] The contact lens material of the present invention contains 50 to 50 to 100 mole parts of dialkyl fumarate to 0,100 mole parts of the total diester fumarate.
90 mole parts and general formula (I); IICCOR+
(1) 5 to 30 mole parts of alkyl (hydroxyalkyl) fumarate represented by R20C-C11 (wherein R1 is an alkyl group having 1 to 8 carbon atoms, and R2 is a hydroxyalkyl group having 1 to 8 carbon atoms) It consists of a copolymer whose main component is fumaric acid diester containing

As the dialkyl fumarate, for example, the general formula (
■): 1IC-C0R4[11) 1230C-C11 (wherein R3 and R4 each represent a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms) is used. Specific examples of dialkyl fumarates include diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, ditertiary butyl fumarate, dialkyl fumarate, dioctyl fumarate, ditertiary amyl fumarate, didodecyl. Fumarate, linear or branched dialkyl fumarates such as di(2-ethylhexyl) fumarate, cyclic alkyl fumarates such as dicyclohexyl fumarate, di(tert-butylcyclohexyl) fumarate, bis(trimethylcyclohexyl) fumarate, etc. I can give it to you. Among these alkyl fumarates, ditertiary-butyl fumarate, ditertiary-amyl fumarate, diisopropyl fumarate, dicyclohexyl fumarate, etc. have a large number of hydrogen atoms at the β-position of the alkyl group and have excellent polymerizability, so they are preferred. Can be used. However, homopolymers of fumaric acid diesters having a large number of hydrogen atoms at the β-position of the alkyl group are generally hard and brittle, and therefore, for example, diethyl fumarate, di-n-butyl fumarate, di-n-octyl fumarate, etc. It is preferable to improve the mechanical strength (brittleness) by copolymerizing with a compound such as a resin.

Examples of the alkyl (hydroxyalkyl) fumarate represented by the general 2(r) include isopropyl (2-hydroxyethyl) fumarate, ethyl (2-hydroxyethyl) fumarate, n-butyl (2-hydroxyethyl) fumarate, and ethyl (2-hydroxyethyl) fumarate. -hydroxypropyl) fumarate, isopropyl (2-hydroxypropyl) fumarate, n-butyl (2-hydroquinepropyl) fumarate, ethyl (2-hydroxybutyl) fumarate, isopropyl (2-hydroquinebutyl) fumarate, n-
Examples include butyl (2-hydroxybutyl) fumarate, but among these, when R1 is an isopropyl group, fumaric acid diester can be easily obtained, and when R2 is 2-hydroxyalkyl A 2-hydroquinethyl group is particularly preferred because it has excellent polymerizability and compatibility with dialkyl fumarates.

The fumaric acid diesters other than the dialkyl fumarate and alkyl (hydroxyalkyl) fumarate used in the present invention include di(fluoroalkyl) fumarate, silicon-containing fumarate, alkyl (fluoroalkyl) fumarate, and alkyl (silicon-containing alkyl) fumarate 1. ~, fluoroalkyl (silicon-containing alkyl) fumarate, and the like.

(For fluoroalkyl, -Noshiro (Ill): (In the formula, R5 and R6 are
' a is an integer from 1 to 21, b is 0 or 1, and R2
each represents an integer of 0 to 3), and specific examples of such di(fluoroalkyl) fumarates include bis(trifluoroethyl) fumarate, bis(tetrafluoropropyl) fumarate, and bis(hexafluoropropyl) fumarate. Examples include fluoroisopropyl) fumarate and bis(dodecafluoropentyl) fumarate.

Among these di(fluoroalkyl) fumarates, monomers such as bis(trifluoroethyl) fumarate, bis(hexafluoroisopropyl) fumarate, and tetrafluoropropyl fumarate are easy to synthesize;
In addition, monomer raw materials are easily available, so they are preferably used.

As the silicon-containing fumarate, general II (IV)
: -2.

Medium 0=○ ■-0 (In the formula, R7 and R8 are each 1191 members xl 1is R9'h (Xl, Y+, and Zl are each -179 or 1?9 0-3i-Rs, R9 has 1 to 3 carbon atoms ), -3i-Y2 (X2, Y2, Z2 are each -R9Z (R9 is the same as above), -023 (Z3 is (R9 is the same as above, RIG is a carbon number of 1) ~3 alkyl group or phenyl group, r is an integer of 2 to 4)) !Oyobi10-3i Y+ (X+, Yl, Zl are the same as above) selected from l:T ),
-3t(O3i(C113)3) (O8ill
(Cl13)2) (+1 is 1 to 33-Q
(represents an integer of Q) and -23 (Z3 is the same as above), m+ and ff12 are each 1
Or 3, N+, j! = represents O or 1, and n represents 2 or 3), but
Specific examples of such silicon-containing furamates include bis(trimethylsilylpropyl) fumarate, bis(pentamethyldisiloxanyl brobyl) fumarate, bis(
(trimethylsilyloxy)tetramethyldisiloxanylpropyl) fumarate, bis((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl)fumarate, bis((tetrakis(trimethylsilyloxy)trimethyltrisiloxanyl)propyl)fumarate, bis(tetra Examples include methyltriisopropylcyclotetrasiloxanylpropyl) fumarate, bis(tetramethyltriisopropylcyclotetrasilyloxybis(trimethylsilyloxy)silylpropyl) fumarate, and the like.

Among these silicon-containing fumarates, bis((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl)fumarate is easily synthesized and produced, and is therefore preferably used.

Examples of the alkyl (fluoroalkyl) fumarate include Noshiro M.

11C-COI? u
(M11! 1?30C-CI+ (In the formula, 1?3 is the same as above.!?11 is +C112)
CII I" (wherein a and bs a
b 2a+1-b is the same as above, S represents one number from O to 3), and specific examples of such alkyl (fluoroalkyl) fumarates include methyl (trifluoroethyl) ) fumarate, ethyl (trifluoroethyl) fumarate, isopropyl (trifluoroethyl) fumarate, tert-butyl (trifluoroethyl) fumarate, octyl (trifluoroethyl) fumarate, cyclohexyl (trifluoroethyl) fumarate, methyl (hexafluoroisopropyl) ) fumarate, ethyl (hexafluoroisopropyl) fumarate, isopropyl (hexafluoroisopropyl) fumarate, ternary-butyl (hexafluoroinpropyl) fumarate, octyl (hexafluoroisopropyl) fumarate, cyclohexyl (hexafluoroisopropyl) fumarate, methyl (octafluoro) pentyl) fumarate, ethyl (octafluoropentyl)
Fumarate, isopropyl (octafluoropentyl)
Examples include fumarate, tert-butyl (octafluoropentyl) fumarate, octyl (octafluoropentyl) fumarate, and cyclohexyl (octafluoropentyl) fumarate.

As the alkyl (silicon-containing alkyl) fumarate, for example, general 2); 11C-CORI2
(171)1?30C-ell II (wherein R3 is the same as above. R12 represents 8-CH3 or 103i-C)13), but such alkyl (silicon-containing alkyl ) Specific examples of fumarate include methyl (trimethylnliluprovir) fumarate, ethyl (trimethylnliluprovir) fumarate, isopropyl (trimethylnliluprovir) fumarate, tert-butyl (trimethylnliluprovir) fumarate, octyl (trimethylnliluprovir) fumarate,
Trimethylnliluprovir) fumarate, cyclohexyl (trimethylnliluprovir) fumarate, methyl (
Pentamethyldisiloxanylpropyl) fumarate, Ethyl (pentamethyldisiloxanylpropyl) fumarate, Isopropyl (pentamethyldisiloxanylpropyl) fumarate, Tert-butyl (pentamethyldisiloxanylpropyl) Fumarate, octyl (pentamethyldisiloxanylpropyl) fumarate, cyclohexyl (pentamethyldisiloxanyl brobyl) fumarate, methyl (tetramethyl (trimethylsilyl oxane) cycloxanyl) propyl) fumarate, ethyl (
(tetramethyl(trimethylnryluoquine)cycloxanyl)propyl) fumarate, isopropyl((tetramethyl(trimethylnliluoquine)cycloxanyl)propyl) fumarate, tanyaly-butyl((tetramethyl(trimethylnlyluoquine)cycloxanyl)propyl) fumarate, Octyl ((tetramethyl(trimethylnryluoquine)cycloxanyl)propyl) fumarate, cyclohexyl ((tetramethyl(trimethylnliluoquine)cycloxanyl)propyl) fumarate,
Methyl ((trimethylbis(trimethylsilyloxy)
cycloxanyl)propyl) fumarate, ethyl((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, isopropyl((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, tert-butyl((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) ) fumarate, octyl ((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate! -, cyclohexyl ((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, etc.

As the fluoroalkyl (silicon-containing alkyl) fumarate, for example, general 2 (17 [D: % formula % (1
7[1 (wherein Rn and RI2 are the same as above) are used, and specific examples of such fluoroalkyl (silicon-containing alkyl) fumarates include trifluoroethyl (trimethylsilylpropyl) fumarate, hexafluoro Isopropyl (trimethylsilylpropyl) fumarate, octafluoropentyl (trimethylsilylpropyl) fumarate, trifluoroethyl (
(tetramethyl(trimethylsilyloxy)cycloxanyl)propyl) fumarate, hexafluoroisopropyl ((tetramethyl(trimethylsilyloxy)cycloxanyl)propyl) fumarate, octafluoropentyl ((tetramethyl(trimethylsilyloxy)cycloxanyl)propyl) fumarate, trifluoroethyl ((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, hexafluoroisopropyl ((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, octafluoropentyl ((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, etc. It will be done.

Among the fumaric acid diesters mentioned above, only dialkyl fumarates are homopolymerized, and di(
Fluoroalkyl) fumarates, silicon-containing fumarates, alkyl (fluoroalkyl) fumarates, alkyl (silicon-containing alkyl) fumarates and fluoroalkyl (silicon-containing alkyl) fumarates copolymerize with dialkyl fumarates, but not with di(fluoroalkyl) fumarates. Since copolymerization with silicon-containing fumarate is extremely difficult, the total amount of fumaric acid diester is 10
It is necessary to contain 50 to 90 mole parts of dialkyl fumarate in 0 mole part.

Furthermore, if the 8-self alkyl fumarate is less than 5 mol parts in 100 mol parts of the total fumaric acid diester, the hydrophilicity decreases. If it exceeds 30 mole parts, the oxygen permeability decreases, so it is preferably 5 to 30 mole parts, preferably <10 to 20 mole parts. Furthermore, fumaric acid diesters other than dialkyl fumarate and alkyl (hydroxyalkyl) fumarate must be used in an amount of 45 mol parts or less based on 100 mol parts of the total amount of fumaric acid diesters, and when used, their effects are 5 molar parts or more is required to obtain the desired effect.

In the copolymer according to the present invention, in addition to the above fumaric acid diester, various monomers can be used as copolymerization components to modify the properties of the copolymer in accordance with various purposes. . At this time, in order to prevent the oxygen permeability from decreasing, the amount of such copolymerization component is used in an amount of 35 mole parts or less based on 100 mole parts of the total amount of fumaric acid diester.

Crosslinking monomers are effective for the purpose of stabilizing the size, power (power), and shape of contact lenses, as well as improving chemical resistance. Specific examples of such bridge (1 pseudomonomers) include diallyl fumarate, allyl methacrylate, allyl acrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate,
Divinylbenzene and formula: % formula % (in the formula, 1z13.1n14 is independent 113, Rn, I
212, X is an ethylene group or (B is a methyl group or a trimethylsilyloxy group, S is O-5
Examples include crosslinking agents represented by (hereinafter referred to as fumaric acid crosslinking agents) (an integer of 5), and it is preferable to select and use one or more of these. Particularly preferred are diallyl fumarate and fumaric acid crosslinking agents. The amount used is preferably in the range of θ to about 20 parts by mole based on 00 parts by mole of the total monomer mixture to be subjected to copolymerization.

In addition, in the present invention, monomerized dyes such as Seikagen-O-Real Black (manufactured by Dainichiseika Chemical Co., Ltd.) and 2-hydroxy-5-acryloxyphenyl-2-hydroxybenzotriazole may be used as necessary. It is also possible to use monomerized UV absorbers. These components are preferably used in an amount of 5% by weight or less based on the total amount of monomers in order to maintain high oxygen permeability.

As a method for copolymerizing the monomer mixture, a conventional radical polymerization method may be used at a temperature range of 50 to 110°C.

Examples of polymerization initiators that can be used include benzoyl peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile, and one or two of these.
Select and use more than one species. The amount used is preferably 0.01 to 1.0 parts by mole per 100 parts by mole of the total amount of monomers.

The monomer mixture can be molded into a contact lens by a conventional method.

For example, the copolymerization reaction of the monomer mixture is carried out in a mold corresponding to the shape of a contact lens, the shape is directly molded into the shape of a contact lens, and if necessary, this is subjected to mechanical finishing processing such as cutting or polishing. can do.

In addition, after copolymerization is carried out in a suitable mold or container to obtain a block-shaped, plate-shaped or round bar-shaped material, the material is formed into a contact lens of a desired shape using ordinary mechanical processing methods such as cutting and polishing. Good too.

Alternatively, the polymer obtained by the above method may be dissolved in a suitable solvent, the resulting solution may be poured into a mold, the solvent may be removed, and the molded product may be subjected to mechanical processing. is also possible, and in this case, the oxygen permeability coefficient is slightly improved compared to a molding method that does not use a solvent.

The contact lenses obtained in this way exhibit hydrophilicity that is satisfactory for practical use, but if necessary, they may be further subjected to discharge treatment such as corona discharge or plasma discharge, or may be treated with (meth)acrylamide, (meth)acrylic acid, etc. after discharge treatment.
The hydrophilicity of the surface may be improved by graft polymerizing a hydrophilic monomer such as N-vinylpyrrolidone or by treating with a strong acid such as hydrochloric acid or nitric acid.

The contact lens obtained as described above not only exhibits excellent oxygen permeability and has appropriate mechanical strength, but also has excellent hydrophilicity.

Next, the contact lens material of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 60 mol parts of ditert-butyl fumarate, bis((
Trimethyl-1,1-bis(trimethylsilyloxy)
30 mole parts of cycloxanyl) gamma lopyl) fumarate and 1 part of isopropyl (2-hydroxyethyl) fumarate
After putting 0 mol part into a glass test tube and further adding 0.1 mol part of benzoyl peroxide as a polymerization initiator, the tube was sealed under reduced pressure (10' mmmm 1 l) and heated at 80°C for 24 hours and at 70°C for 24 hours. The container was heated to polymerize.Then, the package was opened and the polymerized product was taken out, and further heated at 100°C for 3 hours.

The obtained colorless and transparent polymer was machined by cutting and polishing to prepare a sample with a size of 15 mo + φX 2 mm, and then air bubbles were measured using a G-1 type goniometer complete contact angle measuring device (manufactured by Elma Optical ■). When the contact angle was measured by the method, it was 54.0', and when the contact angle was measured in the same manner after being immersed in distilled water for 1 hour, it was 48.8'.
Met.

Next, the sample was cut to a diameter of 15 mm +
A film with a thickness of 0°2 was prepared and the oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter, and it was found to be 110. Ox IQ-10 (Cl3(
STP)・cln/Cm2・scc-Inollg)
Met.

Examples 2 to 5 and Comparative Examples 1 to 2 Polymers were produced in the same manner as in Example 1, except that the type and composition ratio of fumaric acid diester were changed as shown in Table 1.
Samples and films were prepared by cutting, and the contact angle, hardness, and brittleness of the samples and the oxygen permeability coefficient of the films were measured. The results are shown in Table 1.

′ [Margin below] [Effects of the Invention] The contact lens material of the present invention has desirable hardness and oxygen permeability as a contact lens, and also has excellent hydrophilicity, and when applied to a contact lens, Since it is easily compatible with lachrymal fluid, it does not cause corneal metabolic disorders and can be used for a long time.

Claims (1)

[Scope of Claims] 1 50 to 90 mole parts of dialkyl fumarate and general formula (I
): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) alkyl) fumarate 5-3
A contact lens material comprising a copolymer containing fumaric acid diester as a main component containing 0 mole part. 2. The contact lens material according to claim 1, further comprising at most 45 mole parts of fumarate other than the above based on 100 mole parts of the total amount of diester fumarate.