JPH066609B2 - Contact lens material - Google Patents

Description

TECHNICAL FIELD The present invention relates to contact lens materials. More specifically, the present invention relates to a transparent contact lens material having excellent oxygen permeability.

[Prior Art and its Problems] In recent years, as polymer materials have been applied to the field of medical materials, interest in gas-permeable materials has been increasing, and particularly in the field of medical materials, materials for contact lenses and artificial corneas. Attention has been focused on a gas-permeable optical material applied to a material for a vehicle.

The contact lens material and the artificial cornea material have excellent gas permeability, particularly oxygen permeability, because it is necessary to supply a sufficient amount of oxygen to the cornea through the material so as not to impair the metabolic function of corneal tissue. Is required as one of the most important conditions.

Therefore, in order to improve gas permeability, (a) a method that is generally known as a material having excellent gas permeability, for example, a method of applying a silicone rubber material as a material, (b) known as a gas permeable monomer. The method of using as a material a copolymer containing a silicon-containing monomer such as siloxanyl methacrylate-based monomer as a material, and (c) the behavior of water impregnated in the material by increasing the water content of the material. There has been proposed a method for increasing gas permeability by utilizing it.

In the method of (a), there is a problem of water repellency peculiar to silicone rubber-based materials, and when used as a contact lens material, for example, it is not compatible with the corneal surface and tear fluid,
Further, since lipophilic stains are easily fixed on the surface, there is a problem that the corneal tissue is damaged and the material becomes opaque.

In the method (b), a material having an excellent gas permeability to some extent has been obtained, but when used as a contact lens material, it is still insufficient in terms of wearing for a long time.

Further, in the above method (c), since it absorbs water and is softened, the wearing feeling is good, and the gas permeability can be increased by increasing the water content. However, when the water content is increased, the mechanical strength when water is contained is significantly reduced and it may be damaged, resulting in a problem in durability.

[Problems to be Solved by the Invention] Accordingly, the inventors of the present invention have conducted extensive studies to solve the above-mentioned problems of the conventional technology, and as a result,
The present invention has been completed by finding out a transparent contact lens material having excellent oxygen permeability and moderate mechanical strength.

[Means for Solving Problems] That is, the present invention provides a compound represented by the general formula (I): (In the formula, R ₁ is a cyano group or a carbomethoxy group, R ₂
Represents a group selected from the group consisting of organooligosilanyl group, organooligosiloxanyl group, organooligosilanylalkyl group and organooligosiloxanylalkyl group). And a gas permeable material comprising a polymer.

[Operation and Examples] The contact lens material of the present invention has the general formula (I): (In the formula, R ₁ is a cyano group or a carbomethoxy group, R ₂
Represents a group selected from the group consisting of an organooligosilanyl group, an organooligosiloxanyl group, an organooligosilanylalkyl group and an organooligosiloxanylalkyl group). It consists of a polymer.

In the present invention, since the above-mentioned polymer is used, the rigid structure of the main chain exhibits self-reinforcing properties and a high separation coefficient, and at the same time, a chain substituent such as organosiloxane is introduced into the side chain. Therefore, the glass transition temperature is low, and high oxygen gas permeability is exhibited due to the effect of widening the main chain spacing.

In the general formula (I), R ₂ in the formula is selected from the group consisting of an organooligosilanyl group, an organooligosiloxanyl group, an organooligosilanylalkyl group and an organooligosiloxanylalkyl group as described above. It is a base.

Examples of the organooligosilanyl group include those represented by the general formula (In the formula, R ₃ , R ₄ and R ₅ are the same or different alkyl groups having 1 to 3 carbon atoms or trimethylsilyloxyl group, and m is an integer of 1 to 10); Examples of the nyl group include those represented by the general formula (Wherein R ₆ , R ₇₁ , R ₇₂ , R ₇₃ and R ₈ are the same or different alkyl groups having 1 to 3 carbon atoms or trimethylsilyloxyl groups, and n is an integer of 1 to 10) The above-mentioned organooligosilanylalkyl group is, for example, a compound represented by the general formula (In the formula, R ₉ , R ₁₀ and R ₁₁ are the same or different alkyl groups having 1 to 3 carbon atoms or a methylsilyloxyl group,
p and q are 1 to 10 and represent an integer satisfying p + q ≦ 11); the organooligosiloxanylalkyl group may be, for example, a general formula In the formula, R ₁₂ , R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₄ are the same or different alkyl groups having 1 to 3 carbon atoms or trimethylsilyloxyl groups, r and s are 1 to 10 and r + s
Group which represents an integer satisfying ≦ 11).

The norbornene derivative is subjected to polymerization in which one kind or two or more kinds is selected, and is made into a homopolymer or a copolymer.

The norbornene derivative represented by the general formula (I) can be obtained by the following method.

That is, there is obtained norbornene in which a cyano group or a carboester group is introduced at the 2-position by a Diels-Alder reaction of cyclopentadiene obtained by thermally decomposing dicyclopentadiene and acrylonitrile or various acrylic esters. Next, this can be obtained by reacting this with lithium diisopropylamide (LDA) to lithiate hydrogen at the 2-position and then reacting with various halogen compounds.

The norbornene derivative thus obtained undergoes ring-opening polymerization according to the following scheme.

Examples of the polymerization catalyst of the norbornene derivative used in the present invention include tungsten hexachloride, molybdenum pentachloride, niobium pentachloride, tantalum pentachloride, rhenium pentachloride,
Main catalysts such as metathesis polymerization catalysts such as ruthenium trichloride, osmium trichloride, iridium trichloride, etc.
Examples thereof include cocatalysts such as triethylaluminum, triisobutylaluminum, tetramethyltin, tetraethyltin, and tetrabutyltin, and these main catalysts and cocatalysts are usually used as a mixture. It is desirable that the ratio of the main catalyst to the cocatalyst be adjusted so that the cocatalyst is 1 to 5 parts by mole, preferably 2 to 4 parts by mole with respect to 1 part by mole of the main catalyst in order to increase the polymerization ratio. The ratio of the derivative to the main catalyst is preferably adjusted so as to be 0.001 to 0.1 part by mole of the main catalyst with respect to 1 part by mole of the norbornene derivative. If the main catalyst is used in excess of this range, the resulting polymer may be colored, and if it is less than this range, the polymerization yield tends to be low. Further, for the purpose of controlling the molecular weight of the polymer obtained, alkenes having a terminal double bond such as 1-octene and 1-nonene can be used as a chain transfer agent. Further, it is preferable to carry out the polymerization in a solvent in order to uniformly proceed the polymerization of the norbornene derivative. Chlorobenzene as the solvent,
Halogen compounds such as 1,2-dichloroethane and benzene,
An aromatic solvent such as toluene can be used.
The ratio of the solvent to the norbornene derivative is preferably 1 to 20 parts by volume of the solvent with respect to 1 part by volume of the norbornene derivative. The polymerization temperature is preferably 30 to 100 ° C. The reaction time varies depending on the type and concentration of the norbornene derivative, solvent, catalyst, etc., but is usually several minutes to
It is about 200 hours.

The molecular weight of the norbornene derivative polymer used in the present invention is preferably 100,000 to 1,000,000. If the molecular weight is smaller than the above range, it becomes difficult to form a film, or even if the film can be formed, the mechanical strength becomes small. On the other hand, if the molecular weight is too large, the molding becomes difficult or the molding method is limited, which is not preferable.

The contact lens material comprising the polymer of the norbornene derivative of the present invention thus obtained is usually dissolved in a solvent such as tetrahydrofuran, chloroform or dimethylformamide alone or in a mixture, the solution is cast, and the solvent is evaporated at an appropriate rate. By doing so, a molded body or film having a desired shape is molded.

Next, the contact lens material of the present invention will be described in more detail based on production examples and examples, but the present invention is not limited to these production examples and examples.

Production Example 1 50 g of dicyclopentadiene was pyrolyzed at 190 ° C. and distilled directly from the reactor to obtain 39 g of cyclopentadiene (boiling point: 40 to 42 ° C.). 49.2 g of methyl acrylate and 20 ml of anhydrous ethyl ether in a three-necked flask with an internal capacity of 200 ml.
Then, a solution of 35.8 g of cyclopentadiene dissolved in 20 ml of anhydrous ethyl ether was added dropwise at room temperature, and the mixture was refluxed for 2 hours. Next, the solvent was removed from the reaction solution, and the residue was distilled under reduced pressure to obtain 58.5 g of 2-carbomethoxy-5-norbornene (boiling point: 46 to 52 ° C./5 mmHg).

Diisopropylamine 4.0 in a 3-neck flask with an internal volume of 100 ml
Add 3g and 40ml of tetrahydrofuran, then add -78
The mixture was cooled to 0 ° C, then 15.0 g of a 15 wt% hexane solution of n-butyllithium was added dropwise, and then the mixture was stirred at 0 ° C for 30 minutes, and cooled again to -78 ° C. Then add 2-carbomethoxy-5-
After 5.15 g of norbornene was added dropwise and stirred for 2 hours, 3.80 g of trimethylchlorosilane was added, stirred for 1 hour, and further stirred at room temperature (about 20 ° C.) for 3 hours. After removing the solvent from the obtained reaction mixture, ethyl ether was added, the precipitate was filtered, and then 2-trimethylsilyl-2- was obtained by vacuum distillation.
Carbomethoxy-5-norbornene (boiling point: 77-78 ℃ / 7mm
Hg) 5.33 g was obtained. The yield and boiling point of the obtained norbornene are shown in Table 1.

Production Example 2 25 g of dicyclopentadiene was thermally decomposed at 190 ° C. and directly distilled from a reaction vessel to obtain 19.6 g of cyclopentadiene (boiling point: 40 to 42 ° C.).

20.1 g of acrylonitrile in a 3-neck flask with an internal volume of 100 ml
Add 25 ml of anhydrous ethyl ether and add cyclopentadiene.
After 19.3 g was added dropwise at room temperature (about 20 ° C.), the mixture was refluxed for 4 hours. After removing the solvent from the reaction solution, it was distilled under reduced pressure to give 5-norbornene-2-carbonitrile (boiling point: 47.0 to 4
9.7 ℃ / 1.8mmHg) 29.2g was obtained.

Diisopropylamine 36 in a three-necked flask with an internal volume of 100 ml.
2 g and 30 ml of anhydrous tetrahydrofuran were added, and the mixture was cooled to -78 ° C. Add 15% by weight n-butyllithium in hexane.
11.97 g was added dropwise, and then the mixture was stirred at 0 ° C for 30 minutes, and again -78
Cooled to ° C. Next, add this to anhydrous tetrahydrofuran 15
2.94 g of 5-norbornene-2-carbonitrile dissolved in ml
Was added dropwise, the mixture was stirred at the same temperature for 2 hours, and then 4.29 g of trimethylchlorosilane was added dropwise. After stirring for 1 hour, further at room temperature
It was stirred for 11 hours. The solvent was removed from the obtained reaction product, water was added, the mixture was extracted with ethyl ether, and then dried over anhydrous magnesium sulfate for a day. After filtering magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography (silica gel Wacogel C-200; Wako Pure Chemical Industries, Ltd., hexane: ethyl acetate (volume ratio) = 19: 1), and then further purified. Distilled under reduced pressure to 2-trimethylsilyl-5-norbornene-2-carbonitrile (boiling point: 61-65 ℃ / 0.33mmH
g) I got 3.58g. The yield and boiling point of the obtained norbornene are shown in Table 1.

Production Examples 3 to 7 Various chlorides were used in place of trichlorosilane and treated in the same manner as in Production Example 2 to prepare a norbornene derivative.
The yield and boiling point of the obtained norbornene are shown in Table 1.

Example 1 In a nitrogen-displaced 200 ml eggplant-shaped flask, 155 ml of an anhydrous chlorobenzene solution of tungsten hexachloride (0.00792 mo
l /), 17.7 ml (0.2083 mol /) of anhydrous chlorobenzene solution of triisobutylaluminum, and 6 ml (0.1034 mol /) of anhydrous chlorobenzene solution of 1-octene were added in this order to prepare a catalyst solution.

The catalyst solution obtained above in a nitrogen-substituted ampoule tube
10.5 ml was added, and then 2-pentamethyldisiloxanyl-5-norbornene-2-carbonitrile obtained in Production Example 3 was added.
After adding 9937 g, the tube was sealed under vacuum and polymerized at 80 ° C. for 45 hours. The obtained gel polymer was dissolved in tetrahydrofuran and poured into a large amount of methanol to collect the polymer as a precipitate. The recovered polymer is purified by reprecipitation by repeating tetrahydrofuran-methanol system several times,
0.375 g of a white polymer was obtained (yield: 38%).

Next, the polymer average molecular weight of the polymer obtained by gel permeation chromatography (hereinafter referred to as GPC) was measured and found to be 576,000.

0.1 g of the obtained polymer was dissolved in 4 ml of tetrahydrofuran, taken in a syringe, gently poured onto a glass plate with a diameter of 6 cm placed horizontally, and allowed to stand at room temperature for 12 hours, and then the film was peeled from the glass plate. After vacuum drying at room temperature (about 20 ° C) for 24 hours, a transparent and durable film with a thickness of 44 µm was obtained.

About this film Gas chromatograph method (Yanagimoto gas permeability measuring device, Model GTR-10; manufactured by Yanagimoto Manufacturing Co., Ltd. and Hitachi Gas Chromatograph K23 type; manufactured by Hitachi Manufacturing Co., Ltd.)
When the permeability of oxygen gas and nitrogen gas was evaluated by, the permeability coefficient of oxygen gas was 1.53 × 10 ^-9 cm ³ (STP) · cm /
[Cm ² · sec · cmHg], nitrogen gas permeability coefficient is 3.54 × 10
^-10 cm ³ (STP) · cm / [cm ² · sec · cmHg], separation factor 4.3
Was 2.

Examples 2 to 5 Polymerization and film formation were transparent in the same manner as in Example 1 except that norbornene derivatives shown in Table 2 were used instead of 2-pentamethyldicycloxanyl-5-norbornene-2-carbonitrile. To make a tough film. The permeation coefficient and separation coefficient of oxygen gas and nitrogen gas of the obtained film were obtained. The results are shown in Table 2.

Example 6 2-Pentamethyldisiloxanyl-5-obtained in Example 1
A polymer of norbornene-2-carbonitrile was formed into a film from a tetrahydrofuran solution to obtain a transparent and strong film having a thickness of 0.2 mm. This film was measured with an oxygen permeation meter manufactured by Rika Kagaku Kogyo Co., Ltd. in a 0.9% physiological saline solution at 35 ° C. to obtain an oxygen permeation coefficient of 75.5 × 10 ^-11 c
It was m ³ (STP) · cm / [cm ² · sec · cmHg].

As described above, the gas permeable materials obtained in the examples of the present invention have a large oxygen permeability coefficient and a separation coefficient that is about two times or more larger than the separation coefficient (about 2.1) of the conventional silicone rubber membrane. I understand.

EFFECT OF THE INVENTION The contact lens material of the present invention has a high oxygen permeability coefficient,
Since it is transparent and is a durable material, it can be suitably used as a contact lens material.

Claims (1)

[Claims] 1. General formula (I): (In the formula, R ₁ is a cyano group or a carbomethoxy group, R ₂
Is a group selected from the group consisting of an organooligosilanyl group, an organooligosiloxanyl group, an organooligosilanylalkyl group and an organooligosiloxanylalkyl group), and is obtained by polymerizing a norbornene derivative represented by Contact lens material made of polymer.