JPS63172117A - Soft contact lens - Google Patents

Abstract

PURPOSE:To make a contact lens unhydrous, to facilitate machining work, and to improve the oxygen permeability of the contact lens by molding a polymer having vinyl groups bonding directly to Si atoms, then subjecting the molded product to hydrosilylating reaction. CONSTITUTION:After molding a polymer having vinyl groups bonded directly to Si atoms, the molded product is hydrosilylated. The monomer to be copolymerized with a monomer having a vinyl group bonded directly to an Si atom is pref. one having easily polymerizable group, forming a polymer having high machinability, appropriate hardness and least brittleness, such as methacrylic monomer. The hydrosilylating reaction proceeds by heating hydrosilane in an appropriate solvent in the presence of a catalyst. Suitable example for the hydrosilane is 1,1,3,3-tetramethyl-1-hexyl disiloxane, etc. By this constitution, a soft contact lens having high machinability and higher oxygen permeability than conventional contact lens is provided.

Description

[Detailed description of the invention] [Industrial application fields] FIELD OF THE INVENTION The present invention relates to soft contact lenses.

More specifically, it is water-free and can be mechanically processed.
This invention relates to soft contact lenses with excellent oxygen permeability.

[Prior Art] Contact lenses include node contact lenses made of hard materials and soft contact lenses made of soft materials, but soft contact lenses are superior in terms of comfort.

Many soft contact lenses are known to be made of hydrogel that contains a large amount of water in order to increase oxygen permeability, but in the case of these contact lenses, the soft lens body contains water and is therefore susceptible to bacteria and mold. etc., and must be sterilized by boiling every day.

On the other hand, soft contact lenses made of non-water-containing materials that are free from bacteria and mold are known to be made of silicone rubber and polyalkyl acrylate.

Soft contact lenses made of silicone rubber have been known for a relatively long time and are water-free but have high oxygen permeability. However, its surface is extremely water-repellent, and it has been reported that this causes serious eye damage.

Furthermore, since contact lenses made of polyalkyl acrylate are non-hydrous, they cannot be expected to become softer due to water content, so in order to obtain soft contact lenses, the material itself needs to be soft. However, it is difficult to mechanically process soft materials, so it is necessary to polymerize methacrylic acid, harden it, then mechanically process it, and then alkylate it through an esterification reaction to obtain soft contact lenses. It is known (Tokuko Sho 53-3)
(See Publication No. 1189). However, there is a problem in that the alkyl methacrylate material obtained in this way cannot provide sufficient oxygen permeability.

[Problems to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to provide a soft contact lens that is substantially water-free, easy to mechanically process, and has excellent oxygen permeability. be.

[Means for Solving the Problems] The present invention relates to a non-water-containing soft contact lens obtained by molding a polymer having a vinyl group directly bonded to a silicon atom and then subjecting the molded product to a hydrosilylation reaction.

[Example] The polymer having a vinyl group directly bonded to a silicon atom may be a homopolymer of a monomer having a vinyl group directly bonded to a silicon atom, but shape stability and hydrophilicity can be imparted by forming it into a copolymer. Therefore, a polymer obtained by copolymerizing a monomer having a vinyl group directly bonded to a silicon atom with another monomer is preferred.

The monomer copolymerized with the monomer having a vinyl group directly bonded to a silicon atom has a polymerizable group that easily polymerizes, has excellent mechanical processability, is moderately hard, and is not brittle. Monomers are preferred.

In such a copolymer, the blending ratio of the monomer having a vinyl group directly bonded to a silicon atom and the methacrylic monomer is 100:0 to 100:400, preferably 70:0.
;30-30;70, blending ratio 100:40
If a monomer having a vinyl group directly bonded to a silicon atom is blended in an amount less than 0, the oxygen permeability tends to be low.

If the chain of the monomer having a vinyl group directly bonded to a silicon atom is too long, the mechanical processability of the polymer will be poor and cutting will not be possible, so the number of siloxane units is preferably about 2 to 4. Examples of the hexamers that can be used in the present invention include 1-, which is represented by the formula (V): CH3C83CH3 (wherein m is 1 or an integer of 3 to 5, and n is an integer of 1 to 3); methacryloyloxypropyl-5-vinyl-1,1,3,3,5,5-hexamethyltrisiloxane, ■-methacryloyloxymethyl-5-vinyl-1,1,3,3,5,5-hexamethyltrisiloxane siloxane, -methacryloyloxybenzene-3-vinyl-1,1,3,3-tetramethyldisiloxane, etc., and 1-methacryloyloxypropyl-3-vinyl-1,1, which is represented by formula (vI): 3,3
-Tetramethyldisiloxane (hereinafter referred to as VSMA)
, can be given.

Examples of monomers copolymerized with the above monomers include alkyl methacrylates such as methyl methacrylate (hereinafter referred to as HMA), lauvyl methacrylate (hereinafter referred to as LMA), and n-butyl methacrylate (hereinafter referred to as nBuMA), trifluoroethyl Examples include fluoroalkyl methacrylates such as methacrylate (hereinafter referred to as 3FB) and hexafluoroisopropyl methacrylate.

Further, in order to stabilize the specifications of contact lenses, crosslinking agents such as ethylene glycol dimethacrylate (hereinafter referred to as EDMA) and allyl methacrylate are added. The blending amount thereof is preferably 0.01 to 2.0 parts by weight.

After blending these monomers, a polymerization reaction is performed.

Moreover, the polymerization form in this reaction is generally bulk polymerization.

As a polymerization catalyst for starting polymerization, azobisisobutyronitrile, azobisdimethylvaleronitrile (
(hereinafter referred to as V-65), Hensyl peroxide, and other radical polymerization catalysts. Its blending amount is 0.
001 to 1.0 parts by weight is preferred.

The polymerization temperature varies depending on the catalyst used, but is 30 to 150
℃, and it is possible to accelerate the polymerization by increasing the temperature in stages (7℃).Also, if necessary, after the polymerization is completed, the material can be heated again to about 90 to 110℃ before processing. It is also possible to eliminate distortion.

The polymerization time is approximately 2 hours to 48 hours, but the polymerization time can be further extended if the polymerization is not completed.

Polymerization over a short period of several hours is not preferable because the polymer may foam.

The hydrosilylation reaction proceeds by heating the hydrosilane in a suitable solvent in the presence of a catalyst.

Examples of hydrosilanes used in the present invention include 1.1.3
．． 3-tetramethyl-1-hexyldisiloxane (hereinafter referred to as II S-2'), 1,1.3.3-tetramethyl-1-methoxyethoxyethoxyethoxyprobyl disiloxane (hereinafter referred to as ll5-1), 1,
1°3.3-Tetramethyl-1-octyldisiloxane, 1.1.3.3-tetramethyl-1-decyldisiloxane and 1.1.3.3-tetramethyl-1-methoxyethoxyethoxypropyldisiloxane Examples include siloxane. In order to improve the hydrophilicity of the polymer, its-
A hydrosilane having an ether bond like 1 is preferable, and in order to improve the mechanical strength of the polymer, 2 is preferable.
Alkylhydrosilanes such as S-2 are preferred.

Furthermore, in order to improve hydrophilicity, a hydrosilane having an ether bond may be reacted as described above.
For example, trimethylsiloxyethoxyethoxypropyl-1 represented by 2 (IVY: C113CH3 CI!3 ■ I3 (in the formula, q represents an integer of 1 to 4)),
A method may be used in which 1,3,3-tetramethyldisiloxanehydrosilane is reacted and then detrimethylsilylated to return to a hydroxyl group to improve hydrophilicity.

In addition, if a nonpolar solvent such as cyclohexane, hexane, xylene, or toluene is used as the solvent, the film will easily swell, and the hydrosilane dissolved in the solvent will penetrate into the inside of the contact lens, and the hydrosilylation reaction will be completed quickly. preferable. Among these, cyclohexane having a boiling point suitable for the hydrosilylation reaction is particularly preferred.

Examples of catalysts include peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and platinum catalysts such as chloroplatinic acid. However, since peroxides involve decomposition of siloxane bonds, chloroplatinic acid is preferable. .

In addition, the reaction temperature is preferably 60 to 120°C, more preferably 70°C because the reaction does not proceed at temperatures lower than 60°C, and side reactions may occur at temperatures higher than 120°C.
The temperature is 5-85°C. Further, the reaction time is approximately 5 to 24 hours.

(Synthesis of VSMA) 1,3-bis(chloropropyl)-1,1,
3,3-tetramethyldisiloxane 0.8 mol (17
2.2g), methacrylic acid 1.4mol (208,
4g), triethylamine 1.3IIlol (242
, 4g), DMP (dimethylformamide > 540
g, 3 g of hydroquinone, and 3 g of NN-di-2-naphthyl-p-phenylenediamine, and heated to 130°C.
The mixture was allowed to react for 6 hours. Triethylamine hydrochloride was removed from this by suction filtration. The precipitated triethylamine hydrochloride was washed several times with n-hexane and mixed with the filtrate.

700 ml of water was added to the mixed solution, and further 50 g of sodium carbonate was added. 500 ml of n-hexane was added to this to extract the product. Repeat this extraction two more times,
The n-hexane layer was dried over anhydrous magnesium sulfate and decolorized using activated carbon.

The solvent was completely removed by evaporation to obtain 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetramethyldisiloxane. Then, in a 500 ml Erlenmeyer flask, 74.4 g (0.4 mol) of 1,3-bisvinyl-1,1,3,3-tetramethyldisiloxane and 1,
3-bis(methacryloyloxypropyl)-1,1,
3,3-tetramethyldisiloxane 154.4g (0
, 4 mol) and 4 g of concentrated sulfuric acid was added thereto. The mixture was stirred with a magnetic stirrer at room temperature for 24 hours. It was confirmed by gas chromatographic analysis that this reaction solution had reached equilibrium. Thereafter, 800 ml of n-hexane was added to the reaction solution, washed with a 10% aqueous sodium carbonate solution of 700011 and 700 ml of water, and dried over anhydrous magnesium sulfate. Next, n-hexane was removed by evaporation and distilled under reduced pressure to 79-81°C/0.
A fraction of 15 mm and 11 g was collected to obtain VSMA.

(Synthesis of Its-1) In a 2 g three-neck flask equipped with a cooling tube and a dropping funnel, 200 g of anhydrous ethyl ether and og of sodium metal were added. Add 80g (0.5mol) of diethylene glycol monomethyl ether to this.
was added dropwise over about 3 hours. Furthermore, as it is,
This was left for 48 hours to allow the metallic sodium to react completely.

Next, 38.3g of allyl chloride (0.5m
ol) was added over 1 hour with stirring. The reaction was completed after further stirring for 2 hours. This reaction solution was filtered with suction to separate the produced salt, and the filtrate was distilled to 85°C/
A fraction of 12 mmHg was collected to obtain diethylene glycol allyl methyl ether. Next, the cooling pipe, thermometer,
In a 500 ml four-neck flask equipped with a dropping funnel and a stirrer, diethylene glycol methyl allyl ether 80 [(0,5+++ol) and cyclohexane were added.
100 ml was added and heated to 50°C. To this was added 5 drops (approximately 0.2 ml) of a solution of 1 g of chloroplatinic acid dissolved in 3 mm of inpropanol, the isopropanol removed by heating under reduced pressure, and mixed with 10 ml of cyclohexane. To this, tetramethyldisiloxane 67
g (0.5 mol) was added dropwise over 2 hours. The reaction solution was directly distilled, and a fraction at 116°C/1.5 mmHg was collected to obtain 115-1.

(Synthesis of MS-2) 1-hexene 12B+ was placed in a 500 ml four-bottle flask equipped with a condenser, thermometer, dropping funnel, and stirrer.
r (1.5 mol) and heated to 50°C. To this, 5 drops (approximately 0.2 ml) of a solution of 1 g of chloroplatinic acid dissolved in 30 ml of isopropanol were heated under reduced pressure to remove isopropanol, and the mixture was mixed with 10 ml of cyclohexane and added. To this, 201 g (1.5 mol) of tetramethyldisiloxane was added dropwise over 2 hours. The reaction solution was directly distilled to obtain 76-b.

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

Example 1 40 parts by weight of VSMA, 20 parts by weight of HMA, 40 parts by weight of nBuMA and 0.5 parts by weight of EDMA shown in FIG.
Parts by weight were placed in a glass test tube, 0.1 parts by weight of ■-650 as a polymerization catalyst was added, and polymerization was carried out in a constant temperature water bath at 40°C for 48 hours. After that, it was placed in a circulation dryer (manufactured by Chuo Rikaki ■) at 50°C for 6 hours.
60℃, 70℃, 80℃, 90℃, 100℃, 110℃
C for 1.5 hours each to complete the polymerization.

The resulting rod-shaped polymer was taken out of the glass test tube, heated for 2 hours in a circulation dryer at 90°C, and then cut into pieces with a diameter of 11 to 12 mm and a thickness of about 0.
, 211111 sample film was obtained.

Place the sample film in a perforated Teflon case.
The whole Teflon case was placed in a wide-mouth Erlenmeyer flask. Add 5 drops of a solution of 40 g of cyclohexane and 1 g of chloroplatinic acid dissolved in 30 ml of isopropanol (approx.
1) and 10g of HS-1 and heated at 88°C for about 15 hours.
The mixture was heated to reflux. After the hydrosilylation reaction is complete, take out the sample film along with the case and add 100 m of ethanol.
After washing 3 times with 500ml of ethanol,
boiled for an hour. Furthermore, it was dried overnight in a drying mold at 60°C. The weight of the sample film was measured before and after the hydrosilylation reaction to determine the reaction rate of hydrosilane to the sample film.

The sample film subjected to the hydrosilylation reaction was measured for oxygen permeability coefficient, punching load, elongation rate, and thickness, and visually inspected for appearance. The oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter (manufactured by Rika Seiki Kogyo ■) at a measurement temperature of 35°C, and the punch-through load was measured using an Instron type compression tester. A pressure needle (indenter) with a diameter of 1/16 inch is applied to the center, and the load at breakage is measured at room temperature.The elongation rate is determined by measuring the radius of the sample sandwiched between O-rings before measurement, dl, and measuring the elongation rate at the point where the sample breaks. The length from the center of the sample immediately before the O-ring to the O-ring was determined as d2 using the following formula (see Japanese Patent Application No. 81-182528). The measurement results are shown in Table 1.

Examples 2 to 17 Sample films were obtained in the same manner as in Example 1, except that the types and blending ratios of monomers were changed as shown in Table 1. Then, the reaction rate of hydrosilane was determined in the same manner as in Example 1, and the oxygen permeability coefficient, punching load, elongation rate, and thickness were similarly measured, and the appearance was visually inspected. The results are shown in Table 1.

Comparative Examples 1 to 3 1-(γ-methacryloisooxybrobyl αα) obtained by reacting VSMA with II S-1 instead of VSMA
γγ-tetramethyldisiloxane)-2-(γ′-methoxyethoxyethoxyethoxyprobyl-α°α゛
A sample was obtained in the same manner as in Example 1, except that γ'γ'-tetramethyldisiloxanylethane (hereinafter referred to as SSM) was used. That is, the examples are reactions in which monomers are polymerized and then hydrosilylated, and the comparative examples are reactions in which monomers are hydrosilylated and then polymerized.

Then, in the same manner as in Example 1, the oxygen permeability coefficient, punching load, elongation rate, and thickness were measured, and the appearance was visually inspected. The results are shown in Table 1.

[Margins below] [Effects of the Invention] The soft contact lens of the present invention is a soft contact lens that can be mechanically processed and has higher oxygen permeability than conventional contact lenses.

Furthermore, since the soft contact lens of the present invention is non-hydrostatic, it has the effect of eliminating the drawback that the lens is contaminated by inorganic and organic substances in tear fluid.

Furthermore, since the soft contact lens of the present invention has hydrophilicity, it solves the problem of water repellency seen in lenses made from silicone rubber.

Patent applicant: Toyo Contact Lenses Co., Ltd. and 1 other person ・I", ・- ″ノ；・Go-1

Claims (1)

[Scope of Claims] 1. A non-hydrous soft contact lens obtained by molding a polymer having a vinyl group directly bonded to a silicon atom, and then subjecting the molded product to a hydrosilylation reaction. 2 A polymer having a vinyl group directly bonded to a silicon atom has the formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, m is 1 or an integer from 3 to 5, and n is 1 to 2. The soft contact lens according to claim 1, which contains a monomer unit represented by the following integer 3). 3. The software according to claim 1, wherein the polymer having a vinyl group directly bonded to a silicon atom contains a monomer unit represented by formula (II): contact lens. 4 The hydrosilylation reaction is expressed by formula (III): ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, X is an alkyl group having 4 to 12 carbon atoms or -(C
H_2)-_3O-(CH_2CH_2O)-_PCH
The soft contact lens according to claim 1, which is a reaction for adding a compound represented by _3 (wherein P represents an integer of 1 to 4).