JPS62212618A - Contact lens material - Google Patents

Abstract

PURPOSE:To obtain a contact lens material which exhibits excellent oxygen permeability and has adequate mechanical strength by using a copolymer essentially consisting of >=2 kinds of fumaric diester, at least one kind of which is a dialkyl fumarate. CONSTITUTION:The copolymer essentially consisting of >=2 kind of the fumaric diester, at least one kind of which is the dialkyl fumarate, is used as the contact lens material. For example, the dialkyl fumarate expressed by the formula I (where, R1, R2 respectively denote a straight chain, branched or cyclic alkyl group of 1-13C) is used. A di (fluoroalkyl) fumarate, silicon-contg. fumarate, etc. are used as the fumaric diester except the dialkyl fumarate. The copolymer component is used at <=35 ml parts per 100mol parts total amt. of the fumaric diester in order to prevent the deterioration of the oxygen permeability, etc.

Description

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

[Prior art and its problems] Traditionally, glass materials have been mainly used as contact lens materials, but today, polymethyl methacrylate, which has superior machinability and elasticity than glass materials, and is lightweight. Contact lens materials are used.

However, since contact lens materials made of polymethyl methacrylate have low oxygen permeability, there is a problem in that when the contact lenses are worn for a long period of time, they cause metabolic disorders in the corneal tissue.

Therefore, in recent years, research has been carried out on contact lens materials with excellent oxygen permeability that can replace polymethyl methacrylate.
Various types of rubber have been developed, including those based on silicone rubber such as polydimethylsiloxane, and those in which vinyl polymerizable groups are introduced into (poly)organosiloxane, which are then directly combined with other vinyl monomers.

Contact lens abrasive materials mainly made of silicone rubber such as polydimethylsiloxane have excellent oxygen permeability, but they also exhibit water repellency, so they are usually used after being subjected to electrical discharge treatment.

However, even if the above-mentioned hydrophilic treatment is applied, the hydrophilicity decreases during use, and the material is flexible, so the phenomenon of adsorption to the eye is observed, causing corneal damage. There is a problem.

Introducing vinyl polymerization groups into (poly)organosiloxane,
In the case of copolymerized with other monomers, the oxygen permeability is mainly derived from the organosiloxane site, so the oxygen permeability is lower than that of silicone rubber, but the oxygen permeability of the hard and transparent acrylic resin is lower than that of silicone rubber. It is possible to improve oxygen absorption in the cornea when worn as a contact lens, and prevent a decline in corneal function due to oxygen deficiency.

However, in order to copolymerize (poly)organosiloxane with a vinyl polymerization group introduced with an acrylic monomer and provide contact lenses with sufficient oxygen permeability,
The monomer must be added in large quantities. As a result, the obtained copolymer has problems in that it has poor machinability during the production of contact lenses and also has poor lens toughness. On the other hand, in order to maintain a hard skin that can withstand machining during lens manufacturing, it is not possible to add a large amount of (poly)organosiloxane with vinyl polymerization groups introduced, and if the amount added is within that range, it will be continuous. Contact lens materials that have sufficient oxygen permeability to be worn have not been changed.

[Problems to be Solved by the Invention] Therefore, the present inventors solved the drawbacks of the conventional technology such as cooking, and created a material that has the hardness and stiffness desirable for a hard contact lens, and has improved brittleness. As a result of intensive research to develop a hard contact lens that has even higher oxygen permeability than conventional oxygen permeable hard contact lenses, we have found that at least one of them is dialkyl fumarate2. The present invention was completed based on the discovery that if a copolymer containing FJi or higher fumaric acid diester as a main component is used, a contact lens material that exhibits excellent oxygen permeability and has appropriate mechanical strength can be obtained. I ended up doing it.

[Means for Solving the Problems] That is, the present invention relates to a contact lens material comprising a copolymer mainly composed of 28 or more heptamalic acid diesters, at least one of which is a dialkyl fumarate.

[Example] The contact lens material of the present invention has at least I Pi
It consists of a copolymer whose main component is a diester of fumaric acid of 28 or more, which is a dialkyl fumarate.

As the dialkyl fumarate, for example, the general formula (
■): C1l-C-0-R2(T) R+ O'CC11 (wherein R1 and R2 each represent a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms) Specific examples of such dialkyl fumarates include diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, ditertiary butyl fumarate, dialkyl fumarate, dioctyl fumarate, ditertiary amyl fumarate. , linear or branched dialkyl fumarates such as didodecyl fumarate, di(2-ethylhexyl) fumarate, cyclic alkyls such as dicyclohexyl fumarate, di(tert-butylcyclohexyl) fumarate, bis(trimethylcyclohexyl) fumarate Examples include fumarate. Among these alkyl fumarates, ditertiary-butyl fumarate, ditertiary-amyl fumarate, diisopropyl fumarate, dicyclohexyl fumarate, etc. have a large number of hydrogen atoms in the β-position of the alkyl group and have excellent polymerizability, so they are preferred. Can be used. However, the 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 fumaric acid diesters other than dialkyl fumarate used in the present invention include di(fluoroalkyl) fumarate,
Silicon-containing fumarates and the like can be used.

The di(fluoroalkyl) fumarate has the general formula (I): (wherein A and B are 10aIlbP 2a+i-b' a
is an integer from 1 to 21, b is 0 or 1; kl and kl each represent an integer from θ to 3), and specific examples of such di(fluoroalkyl) fumarates include bis(trifluoroalkyl) fumarates. fluoroethyl) fumarate,
Examples include bis(tetrafluoropropyl) fumarate, bis(hexafluoroisopropyl) 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;
Moreover, since the monomer raw material is easily available, it can be suitably used.

The silicon-containing fumarate is expressed by the general formula (N): [blank space below] ~ Saturday, Sunday, and the following YI%Zl is -R3 or -0-, respectively
'3l-Rs, R3 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group), -8l-Y2 (X2, Y2, Z2 are each -1
? 3 (1?3 are the same as above), -'lx CZs (R3 is the same as above, R4 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, "represents an integer of 2 to 4)" and -0-8t-Y+ (X+, YI%Zl are the same as above), ÷O9i
(C113) 3) T: Completed @ OS I (Cl(i
)2) q (Q represents an integer from 1 to 3) and -Z
A group selected from the group consisting of 3 (Z3 is the same as above),
all, ■2 are each 1 or 3.11.12 are each 0 or 1, and n is 2 or 3. Specific examples of such silicon-containing furamates include bis(trimethylsilylpropyl) fumarate, bis(pentamethyldisiloxanyl brobyl) fumarate, bis((trimethylsilyloxy)). )
Tetramethyldisiloxanyl brobyl) fumarate, bis((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl) fumarate, bis((tetrakis(trimethylsilyloxy)trimethyltrisiloxanyl)propyl) fumarate, bis(tetramethyltriisopropyl) Examples include cyclotetrasiloxanylpropyl) fumarate, bis(tetramethyltriisopropylcyclotetrasilyloxybis(trimethylsilyloxy)silylpropyl) fumarate, and the like.

Among these silicon-containing fumarates, bis((trimethylbis(trimethylsilyloxy)cycloxanyl)propyl)fumarate can be preferably used because it is easy to synthesize and easy to purify.

Among the fumaric acid diesters mentioned above, only dialkyl fumarates are homopolymerized, and di(
Fluoroalkyl) fumarates and silicon-containing fumarates copolymerize with dialkyl fumarates, but di(fluoroalkyl) fumarates copolymerize with dialkyl fumarates;
Since copolymerization of (fluoroalkyl) fumarate and silicon-containing fumarate is extremely difficult, 5 mol of dialkyl fumarate is added to 100 mol parts of the total diester fumarate.
It is necessary to contain 0 mole part or more.

In the copolymer according to the present invention, in addition to the above fumaric acid diester, various hetamines may be used as copolymerization components to modify the properties of the copolymer in accordance with various purposes. I can do it. In this case, 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 the total m too mole parts of the fumaric acid diester.

Crosslinkable 7-termers 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 crosslinkable monomers include diallyl fumarate, allyl methacrylate, allyl acrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, vinylbenzene, and , A represents -o-sL-C)I3) C! 13 crosslinking agent (hereinafter referred to as B54PS8), and it is preferable to select and use one or more of these. Among others, diallyl fumarate °
or B54PS8 are preferable. In addition, the amount used is θ
A range of from about 20 mole parts is preferred.

In order to impart hydrophilicity to the resulting copolymer and obtain a hard contact lens with good water wettability, it is preferable to use a hydrophilic hexamer. Examples of such hydrophilic monomers include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 3-methyl-1-buten-3-ol, and one or more of these monomers. It is preferable to select and use. Further, the amount to be used is preferably in the range of about 0 to 20 parts by mole out of 100 parts by mole of the total monomer mixture to be subjected to copolymerization. It should be noted that if these hydrophilic monomers are used in an amount exceeding the above range, the oxygen permeability will decrease, which is not preferable.

Instead of or in addition to the use of the hydrophilic monomer, for example, the obtained hard contact lens may be subjected to an electric discharge treatment such as corona discharge or plasma discharge, or a hydrophilic monomer may be grafted after the electric discharge treatment, or hydrochloric acid or By treating with a strong acid such as nitric acid, it is also possible to impart hydrophilicity to the surface.

In addition, in the present invention, if necessary, monomerized dyes such as Seikagen-Real Black (manufactured by Dainichiseika Chemical Co., Ltd.) and 2-hydroxy-5-acryloxyphenyl-2-hydroxybenzotriazole may be used. It is also possible to use monomerized ultraviolet absorbers. In order to maintain high oxygen permeability with respect to the total amount of these monomers, it is preferable to use them in an amount of 5% by weight or less.

The copolymerization of the monomer mixture is carried out at a temperature range of 50 DEG to 110 DEG C. using a conventional radical polymerization method. Examples of the polymerization initiator that can be used include benzoyl peroxide, azobisisobutyronitrile, and azobisdimethylvaleronitrile, and one or more of these can be selected and used. In addition, the amount used is 0.01-1 parts by mole per 100 mole parts of the total amount of monomers.
．． Preferably it is 0 mole part.

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 oxygen permeable contact lens of the present invention thus obtained exhibits even better oxygen permeability than conventional oxygen permeable contact lenses, and also has appropriate mechanical strength.

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

Example 1 Ditert-butyl fumarate 0.022 mol (5
,0 g) and bis(2,2,2-trifluoroethyl) fumarate 0.022 mol (6,14 g>) in 50 m
1 into a glass ampoule, and azobisisobutyronitrile 4.39 Xl 0' as a polymerization initiator.
After adding moles (0,0072g), the pressure was reduced (to-3
(11 g) was sealed, and a polymerization reaction was carried out at 80° C. for 36 hours.

After the reaction was completed, the resulting polymer was dissolved in 100 ml of chloroform, and poured into a large pot of methanol to precipitate the resulting polymer, which was filtered and dried.

The number average molecular weight of the resulting polymer was measured by gel permeation chromatography (hereinafter referred to as GPC).
It was 9.5X 104. Note that the measurement was performed using Triro
torn I type GPC analyzer (manufactured by Kuchimoto Bunko ■), column is 5hodcx GPCA-80M type (manufactured by Showa Denko ■)
, using tetrahydrofuran as a solvent.

Next, the obtained polymer was dissolved in chloroform to prepare a polymer solution with a concentration of 0% by weight, and then 5 ml was cast onto a glass petri dish with a diameter of 50 mm, and the solvent was evaporated at room temperature to form a film. Further, after peeling, the film was dried under vacuum for 48 hours or more to obtain a colorless and transparent film.

The obtained film has a diameter of 15u* and a thickness of 0.204a.
After cutting to a value of m, the oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter, and it was found that the standard state (
STP) and 82.6X 10→O(el13(STP)
-am/csn3・See @aaHg).

Examples 2 to 23 The oxygen permeability coefficients of films obtained in the same manner as in Example 1 were measured, except that the fumaric acid diester, polymerization initiator, polymerization temperature, and polymerization time were changed as shown in Table 1. The results are shown in Table 1.

Examples 24 to 31 Films obtained in the same manner as in Example 1 except that the fumaric acid diester, polymerization initiator, polymerization temperature and polymerization time were changed as shown in Table 1, and diethyl ether was used as the solvent. The oxygen permeability coefficient was measured. The results are shown in Table 1.

[Leaving space] l - - L + 1 / ko゛; 2, '118 core + (tone + 8 core -!: ma mouth \ migo ... Example 32 55 mole parts of ditertiary-butyl fumarate, bis (3
- (3,3,3-trimethyl-1,1-bis((trimethylsilyl)oxy)disiloxanyl)propyl) 45 mol parts of fumarate and 0.1 mol part of benzoyl peroxide as a polymerization initiator are placed in a glass test tube, Reduced pressure (to
-3mal1g), sealed, and suspended at 70°C for 24 hours. After that, open the package, take out the m compound, and add 1
Heated at 00°C for 3 hours.

The obtained colorless and transparent copolymer was machined by cutting and grinding to obtain a hard contact lens.

The oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter in 0.9% physiological saline at 35°C.
■■ Measurements were made on a test piece with a thickness of 0.2 sm.

As a result, the oxygen permeability coefficient was 117. OX 110 [c
113(STP)・cIlZc12・soc-clII
g].

Examples 33 to 48 Rigid contact lenses were produced in the same manner as in Example 32, except that the composition of the fumaric acid diester was changed as shown in Table 2, and the oxygen permeability coefficient was measured in the same manner as in Example 32. The results are shown in Table 2.

[Margin below] Example 49 The film obtained in Example 1 was heated to an oxygen gas pressure of 0.40 dragon 1
It was placed in a reaction tube with a 1 g atmosphere and subjected to plasma discharge treatment at 50 W for 90 seconds using a 13.58M+1Z high frequency discharge device.

The contact angle between the obtained discharge-treated film and water droplets was determined by the liquid phase method and was approximately 0 degrees.

Next, the change in contact angle over time was determined when the sample was left in an atmosphere at room temperature (approximately 25° C.). The results are shown in Table 3.

Comparative Example 1 Using a conventionally commercially available oxygen-permeable lens (manufactured by Toyo Contact Lens ■, Menicon 02), the change over time of the contact angle between the lens and a water droplet was measured using fi1 in the same manner as in Example 49.
It was fixed at 1. The results are shown in Table 3.

Table 3 [Effects of the Invention] The contact lens material of the present invention exhibits better oxygen permeability than conventional contact lens materials, and also has moderate mechanical strength, so even when worn for a long time, the contact lens material It has the advantage that it does not cause problems such as metabolic disorders and can be suitably used in contact lenses.

[Brief explanation of drawings]

Figure 1 shows bis(trifluoroethyl) in an example of the present invention.
FIG. 3 is a diagram showing the relationship between the blending ratio of fumarate and the oxygen permeability coefficient. Patent applicant Tomey Sangyo Co., Ltd. Concentration of DTI F (mol%)

Claims (1)

[Claims] 1. A contact lens material comprising a copolymer containing two or more diesters of fumaric acid as main components, at least one of which is a dialkyl fumarate.