JPS6261927B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel hydrous contact lens and a method for manufacturing the same. More specifically, the present invention relates to a water-containing contact lens that can be worn continuously for a long time and is made of a methacrylate having a sugar in the side chain or a copolymer having an acrylate unit, and a method for producing the same. A variety of water-containing contact lenses have been known, among them those with a water content of 30 to 40% (by weight, 2-hydroxyethyl methacrylate).
The same applies hereafter) are widely used.
However, water-containing contact lenses made mainly of 2-hydroxyethyl methacrylate do not have sufficient permeability for the physiologically required amount of oxygen in the cornea of the eye, so they are used for approximately 16 hours a day. There is a limit to how much the lens can be worn, and wearing exceeding this limit is dangerous as it may cause tissue damage to the cornea. For this reason, research has been carried out on various high water content contact lenses with the aim of increasing the water content and supplying the cornea with the physiologically necessary amount of oxygen from the atmosphere through the large amount of water impregnated into the contact lens material. is being actively carried out. The most common material for highly water-containing contact lenses is made by copolymerizing N-vinylpyrrolidone with a methacrylate compound, such as an alkyl methacrylate such as methyl methacrylate or 2-hydroxyethyl methacrylate. It is a copolymer. These copolymers usually have about 50 to 80
% water holding capacity. Therefore, most of these high water content contact lenses are capable of supplying the cornea with the amount of oxygen required by the cornea from the atmosphere through the lens material. However, due to their high water content, these contact lenses have drawbacks such as reduced material strength and instability of the standard shape of the lens, and have not been widely used. In addition, when these high water content contact lenses made mainly of N-vinylpyrrolidone are worn on the eyes, diffuse superficial keratitis tends to occur frequently, and this fact also prevents the spread of high water content contact lenses. This is a major cause. As described above, the oxygen permeability of the contact lens material is a necessary but not sufficient condition for providing a hydrous contact lens that can be worn continuously for a long period of time. In order to provide hydrous contact lenses that can be worn continuously for long periods of time, it is known that in addition to the oxygen permeability of the lens material, the affinity of the lens material for the eye tissue, especially the corneal tissue, is a major factor. There is. However, there are no fixed standards for determining the affinity of lens materials for eye tissue, and this makes it more difficult to develop better water-containing contact lenses. The present inventors focused on the biocompatibility of sugars, which have never been used as components of hydrous contact lenses, and conducted various studies in order to develop hydrous contact lenses that can be worn continuously for long periods of time. As a result, for at least one monosaccharide of the group consisting of D-galactose, D-glucose, and D-mannose, four out of five hydroxyl groups of the monosaccharide were reacted with a ketone to form a ketal. A polymerizable group is introduced into the remaining hydroxyl group, and this is copolymerized with other copolymerizable monomers such as hydrophilic monomers and hydrophobic monomers, and then the ketal group is converted back into a hydroxyl group. It was discovered that the obtained copolymer treated with acid has excellent properties as a material for water-containing contact lenses, and the present invention was completed. That is, the present invention comprises a methacrylate or acrylate unit having at least one sugar selected from the group consisting of D-galactose, D-glucose and D-mannose in its side chain, and a hydrophilic monomer and/or a hydrophobic monomer. The present invention provides a water-containing contact lens made of a copolymer consisting essentially of mer units and a method for producing the same. The ester of ketalized sugar and acrylic acid or methacrylic acid [hereinafter collectively referred to as ketalized sugar (meth)acrylate] used to produce the hydrous contact lens of the present invention is D-galactose, D-glucose or D-mannose is ketalized with a ketone compound such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, or methyl isobutyl ketone, and then the ketalized sugar thus obtained is reacted with acrylic acid halide or methacrylic acid halide to form the remaining one hydroxyl group. It can be obtained by introducing a polymerizable group. Hereinafter, as sugar, D-galactose,
A general method for producing ketalized sugar (meth)acrylate will be explained with reference to the case where acetone is used as a ketone compound and methacrylic acid chloride is used as an acid halide.
-Mannose is produced in the same way. The ketalization of D-galactose is, for example, D
- Galactose, zinc chloride, sulfuric acid, ferric chloride,
This can be carried out by reaction with a ketone, for example acetone, in the presence of a catalyst such as phosphoric acid or copper sulfate. This can be expressed as a reaction formula as follows. Thus the 1st, 2nd and 3rd positions of D-galactose
The hydroxyl groups at position and 4 are replaced with isopropylidene groups to synthesize 1,2:3,4-di-O-isopropylidene-D-galactopyranose. The resulting 1,2:3,4-di-O-isopropylidene-D-galactopyranose is then reacted with, for example, methacrylic acid chloride to introduce a polymerizable group (methacrylic group in this case) into the 6-position. and polymerizable 1,2:3,4-di-
O-isopropylidene-6-O-methacryloyl-D-galactopyranoside (also known as: 1,2:3,
4-di-O-isopropylidene-6-O-methacryloyl-D-galactose. Below, 6-
(called MDIGa). This can be expressed as a reaction formula as follows. The above esterification reaction is preferably carried out in the presence of triethylamine, pyridine, etc. in order to remove by-produced hydrochloric acid. 1 if the starting material is D-glucose,
2:5,6-di-O-isopropylidene-3-O
-methacryloyl-D-glucofuranoside (also known as 1,2:5,6-di-O-isopropylidene-3-O-methacryloyl-D-glucose; hereinafter referred to as 3-MDIGLu) is obtained, and the starting material is In the case of D-mannose, 1-O-methacryloyl-2,3:5,6-di-O-isopropylidene-D-mannofuranoside (also known as 1-O-methacryloyl-2,3:5,6-di -O-isopropylidene-D-mannose.Hereinafter, 1-MDIMa
) can be obtained. 6-MDIGa and 1-MDIMa each have a melting point of 62 ~
63.5℃, 105-106.5℃, and 3-MDIGLu has a boiling point of 113℃/0.12℃.
Produces in liquid form with mmHg. In the same manner as above, by using various acrylic acid or methacrylic acid halides and ketone compounds, D-galactose, D-glucose,
Various ketalized sugars (meth) from D-mannose
You can make acrylate. These ketalized sugar (meth)acrylates may be used alone or in combination of two or more. Ketalized sugar (meth) obtained in this way
Acrylate can be copolymerized with various monomers, and the material for the water-containing contact lens of the present invention is prepared by copolymerizing with at least one of a hydrophilic monomer and a hydrophobic monomer. be able to. Desirable hydrophilic monomers include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, acrylamide, methacrylamide. , dimethylacrylamide, dimethylmethacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, etc., and one or more of these are selected and used. By copolymerizing ketalized sugar (meth)acrylate with these hydrophilic monomers, a contact lens formed from the resulting copolymer is deketalized in an acid aqueous solution to convert the ketal groups into hydroxyl groups. During the conversion, the acid solution can be uniformly and effectively penetrated into the lens material, allowing the desired deketalization reaction to occur efficiently. Furthermore, in the case of hydrophilic monomers such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate whose homopolymers have a relatively low water-containing capacity, ketalized sugar (meth)acrylate can be added to these hydrophilic monomers. It is also possible to control to some extent the water content of the final water-containing contact lens obtained by copolymerizing with. Desirable hydrophobic monomers used in the present invention include, for example, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, amyl methacrylate, amyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, octyl methacrylate, Octyl acrylate, decyl methacrylate, decyl acrylate, undecyl methacrylate, undecyl acrylate,
Alkyl esters of methacrylic acid or acrylic acid such as lauryl methacrylate and lauryl acrylate (however, if the alkyl group has 1 to 15 carbon atoms)
), styrene, vinyl acetate, vinyl propionate, acrylonitrile, etc., and one or more of these are selected and used. The use of hydrophobic monomers controls the water content of the resulting hydrous contact lens material and
It is particularly effective for increasing the strength and durability of products. The amount of ketalized sugar (meth)acrylate used in the present invention is 100 parts (parts by weight) of the ketalized sugar (meth)acrylate, the hydrophilic monomer, and/or the hydrophobic monomer. , hereinafter the same), preferably in the range of 5 to 97 parts, preferably 20 to 80 parts, and more preferably 40 to 70 parts. Ketalized sugar (meth)acrylate is copolymerized with at least one of a hydrophilic monomer and a hydrophobic monomer, but when a hydrophilic monomer is used,
The amount used is in the range of 3 to 95 parts, preferably 20 to 85 parts, and more preferably 30 to 60 parts out of 100 parts of the total amount of the monomer used. In such cases, the amount used is suitably in the range of 1 to 40 parts, preferably 3 to 20 parts, and more preferably 5 to 12 parts. If the amount of ketalized sugar (meth)acrylate used is more than 97 parts, the strength of the resulting contact lens will be weakened, and if it is less than 5 parts, the effect of its use will be poor, and in any case. Undesirable. In addition, if the amount of hydrophilic monomer used is more than 95 parts, the effect of using ketalized sugar (meth)acrylate will be poor, and if the amount of hydrophobic monomer used is more than 40 parts, This makes it difficult for the deketalization reaction by acid treatment to proceed smoothly. The above three types of monomers are appropriately selected from the above ranges for each monomer so that the total amount of monomers used among these monomers is 100 parts. However, depending on the type of ketalized sugar (meth)acrylate, there is a certain limit in its compatibility with hydrophilic monomers. for example,
6-MDDIGa and 1-MDIMa have limited compatibility with hydrophilic monomers, and the total amount with hydrophilic monomers is limited.
For every 100 parts by weight, 6-MDDIGa should be used in an amount of about 70 parts by weight or less and 1-MDDIMa should be used in an amount of about 25 parts by weight or less. 3-MDIGLu is compatible with hydrophilic monomers in any proportion. Furthermore, in the present invention, from the viewpoint of stabilizing the shape of the resulting contact lens and improving solvent resistance, a crosslinkable monomer having two or more polymerizable functional groups may be used as necessary. good.
Examples of such crosslinkable monomers include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples include triethylene glycol diacrylate, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, divinylbenzene, diallyl phthalate, trimethylolpropane trimethacrylate, and one or more selected from these are used. . The amount used is the total amount of the monomers used.
A range of 0.01 to 2 parts per 100 parts is suitable. In polymerizing the monomer mixture, a radical polymerization initiator commonly used in the polymerization of unsaturated hydrocarbon compounds can be used. Examples of such radical polymerization initiators include benzoyl peroxide, azobisisobutyronitrile, and azobisdimethylvaleronitrile, and one or more of these may be selected and used.
The amount of these polymerization initiators used is preferably in the range of about 0.05 to 1 part based on 100 parts of the total monomer mixture to be copolymerized. During copolymerization, for example, ethylene glycol,
A water-soluble substance inert to the polymerization reaction, such as propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, or glycerin, is present as a wetting agent in the monomer mixture in an amount of about 2 to 45%. Good too. Although the use of such a wetting agent is not essential, when the copolymerization reaction is carried out in the presence of a wetting agent by a bulk polymerization method,
Since a wetting agent is contained in the resulting copolymer, it is very effective in acid treatment of the copolymer for deketalization. That is, by using a wetting agent, even if the proportion of hydrophilic monomer used is small or not used at all, in the process of acid-treating a contact lens molded from the resulting copolymer, Since the acid solution can be effectively penetrated through the wetting agent impregnated into the lens material, the deketalization reaction can be carried out efficiently. Such a wetting agent can be easily obtained by, for example, neutralizing a hydrous contact lens in an alkaline solution after acid treatment, then immersing it in water or physiological saline, and further boiling it if desired. can be replaced with If the amount of the wetting agent used is more than 45%, it is not preferable because problems such as the lens material becoming cloudy after acid treatment and a decrease in optical properties tend to occur. Polymerization and molding into a contact lens shape can be carried out using conventional polymerization techniques and molding techniques.
For example, polymerization can be carried out in a mold corresponding to the shape of a contact lens to directly form the shape of a contact lens, which can then be mechanically finished if necessary. Alternatively, polymerization may be carried out in a suitable mold or container to obtain a block-shaped, plate-shaped or round bar-shaped material, which is then formed into a contact lens of a desired shape by ordinary mechanical processing such as cutting and polishing. You can also do it. The contact lenses thus formed are acid-treated with various organic or inorganic acids to convert the ketal groups in the copolymer into hydroxyl groups. For example, as shown in the following reaction formula, isopropylidene groups are removed by hydrolysis to make the copolymer hydrophilic. Examples of acids used in the acid treatment include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, and trifluoroacetic acid. If the concentration of the acid used is high, there is a risk of deterioration of the lens material or cracks, so it is preferable to carry out the acid treatment by gradually or stepwise increasing the concentration of the treatment liquid. Appropriate acid concentration and immersion time vary depending on the material of the lens to be treated and the type of acid used, and cannot be determined unconditionally. time,
In the case of formic acid or acetic acid, at a concentration of about 30 to 90%, the temperature is kept at room temperature for about 2 hours to 20 days, and in the case of trifluoroacetic acid, at a concentration of about 80 to 90%, it is kept at room temperature for about 1 hour to 20 days.
~2 hours of treatment is preferred. If the material of the lens to be treated is not copolymerized with a hydrophilic monomer and is not impregnated with a wetting agent, rapid excitation of the deketalization reaction is likely to cause cracks in the contact lens, so acid treatment is particularly recommended. It is preferable to carry out the treatment by gradually or stepwise increasing the acid concentration of the treatment liquid. In this case, the contact lens is first immersed in a low concentration acid aqueous solution of about 5% for several hours to several days, and then transferred to a high concentration acid aqueous solution for acid treatment. The reaction by acid treatment is particularly advantageous in industrial implementation because it can be carried out with good reproducibility within a certain tolerance range without being strictly regulated by standard treatment methods and standard treatment times. The acid-treated contact lens may be neutralized by immersing it in an alkaline aqueous solution such as sodium carbonate, or it may be immersed or boiled in water or physiological saline. The contact lens of the present invention has a high water content, excellent oxygen permeability, softness and flexibility, and excellent affinity for eye tissue, so it can be worn continuously for a long period of time. Furthermore, the contact lens of the present invention has excellent optical properties, and can be sterilized by boiling in water without impairing the excellent properties of the contact lens. Next, the contact lens of the present invention and the method for manufacturing the same will be explained in detail with reference to Examples. Further, reference examples are attached to explain the production of the ketalized sugar (meth)acrylate used in the present invention. Reference Example 1 (Synthesis of 6-MDIGa) (i) Isopropylideneation 21.6 g of anhydrous zinc chloride was added to an Erlenmeyer flask containing 225 ml of acetone, suspended with stirring, and 0.72 ml of concentrated sulfuric acid was added. and stirred vigorously. Powdered anhydrous D-
18 g of galactose was quickly added, the container was sealed, and the reaction was allowed to proceed. After stirring for 4 hours, a suspension of 36 g of anhydrous sodium carbonate in 63 ml of water was added dropwise to the reaction solution as quickly as possible. After stirring was continued until zinc ions were liberated, the reaction solution was filtered by suction. The filtrate was concentrated under reduced pressure until no acetone flowed out, and an oil layer was released. The oil layer was extracted with ether, dried, concentrated, and purified by distillation under reduced pressure.
2:3,4-di-O-isopropylidene-D-
15.1g of galactopyranose was obtained (yield 58.0
%). The boiling point of the compound is 131-135℃/0.2mmHg
It was hot. (ii) Methacrylation 51 g of 1,2:3,4-di-O-isopropylidene-D-galactopyranose was mixed with 200 g of ether.
Triethylamine as a dehydrochlorination agent dissolved in ml
20g of methacrylic acid chloride was added thereto, and while the reaction solution was kept ice-cooled at 0 to 5°C, a mixture of 20.5g of methacrylic acid chloride diluted with a small amount of ether was added dropwise to react. After continued stirring for 1 hour, the reaction solution was filtered under suction to remove the precipitate, and the ether was distilled off under reduced pressure. Further, a small amount of n-hexane was added to remove the polymer produced during the reaction, and the n-hexane solution was concentrated to obtain a syrupy liquid. The syrupy liquid was recrystallized from a mixture of water and methanol (90:10) to form a white powder of 6-
Obtained 26.8g of MDIGa. The product yield was 40.9% and the melting point was 62-63.5°C. Reference Example 2 (Synthesis of 3-MDIGLu) (i) Isopropylideneation Anhydrous D-glucose in 1000 ml of anhydrous acetone
120 g of anhydrous zinc chloride containing 7.5 g of 85% phosphoric acid was added under stirring, and stirring was continued for 30 hours at room temperature. After that, water was added to the reaction solution from which undissolved D-glucose had been removed to neutralize the acid.
A solution of 85 g of sodium hydroxide dissolved in 85 ml was added to make it alkaline. Then, the inorganic salts were removed, and the solution was concentrated under reduced pressure and extracted with chloroform. After that, chloroform was distilled off to obtain a solid substance. The solid was taken out and recrystallized from ligroin (boiling point 90°C) to give 1,2:5,6-
73.8 g of di-O-isopropylidene-D-glucofuranose was obtained (yield 34.1%). The melting point of the compound was 110-111°C. (ii) Methacrylation 1,2: In place of 3,4-di-O-isopropylidene-D-galactopyranose, 1,2:
An experiment was carried out in the same manner as in Reference Example 1 except that 5,6-di-O-isopropylidene-D-glucofuranose was used and 500 ml of acetone was used instead of 200 ml of ether to obtain a syrupy liquid. The syrupy liquid was purified by distillation under reduced pressure to obtain 17.2 g of 3-MDIGLu. (Yield 26.2
%). The boiling point of the product was 113°C/0.12mmHg. Reference Example 3 (Synthesis of 1-MDIMa) (i) Isopropylidene 1500 ml of anhydrous acetone containing 35 ml of concentrated sulfuric acid and D-
This was mixed with 50 g of mannose and stirred. Approximately 2~
After 3 hours, D-mannose was completely dissolved and turned into a pale yellow solution, which was then neutralized with anhydrous sodium carbonate. After filtering the reaction solution, a small amount of activated carbon and anhydrous sodium carbonate were added, and the mixture was refluxed for 1 hour, filtered again, and concentrated under reduced pressure to obtain a solid. The solid was removed and recrystallized from petroleum ether to yield 32.0 g of 2,3:5,6-di-O-isopropylidene-D-mannofuranose (yield 44.3%). The melting point of the compound is 122-123
It was warm at ℃. (ii) Methacrylation 1,2: 2,3: in place of 5,6-di-O-isopropylidene-D-glucofuranose
An experiment was carried out in the same manner as in Reference Example 2 except that 5,6-di-O-isopropylidene-D-mannofuranose was used, and a solid product was obtained. The solid was recrystallized from a water-methanol (75:25) mixture to obtain 24.2 g of 1-MDIMa (yield 36.9%). The boiling point of the product was 105-106.5°C. Example 1 28.6 g of 6-MDIGa obtained in Reference Example 1, 64.3 g of 2-hydroxyethyl methacrylate (2-HEMA)
g, 3.6 g of lauryl methacrylate (LMA), 3.6 g of methyl methacrylate (MMA), and 0.045 g of a,a'-azobisdimethylvaleronitrile (ADMVN) as a polymerization initiator were mixed and dissolved, placed in a test tube, and placed in a constant temperature water bath. Polymerize at 40℃ for 48 hours, and then polymerize at 50℃ for 16 hours in a hot air circulation dryer.
The polymerization was carried out stepwise by heating at 90°C for 4 hours and then at 90°C for 4 hours to obtain a rod-shaped polymer. The obtained polymer was hard, colorless and transparent. Cut this thing by the usual method,
After polishing and forming into the shape of a contact lens, it was soaked in a 50% formic acid solution for 30 minutes and in a 6N hydrochloric acid solution for 2 hours (or in a 50% formic acid solution for 30 minutes and in a 3.6N hydrochloric acid solution for 6 hours). The lens was soaked to make it hydrophilic, and then immersed in a 0.024% aqueous sodium carbonate solution to neutralize it, yielding the desired contact lens. This contact lens is soft and flexible, has a water content of 47.6%, an oxygen transmission coefficient of 1.30×10 ^-10 cc・cm/cm ²・sec・mmHg, a refractive index (n ²⁰ _D ) of 1.414, and a visible light transmittance. It was greater than 90%. The oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter manufactured by Rika Seiki Kogyo Co., Ltd. at 35°C.
The test was carried out using a platinum electrode method in a 0.9% sodium chloride aqueous solution. In addition, the measurement of visible light transmittance is made by Shimadzu Corporation.
UV-210 was used in the wavelength range of 780 to 380 nm between quartz plates. The refractive index was measured on a disk-shaped test piece using an Atsube refractometer manufactured by Elma Optical Co., Ltd. Examples 2 to 5 Water-containing contact lenses were obtained by carrying out experiments in the same manner as in Example 1, except that each component in the copolymerization was used in the amounts shown in Table 1. The results are shown in Table 1.
In Table 1, AMA represents allyl methacrylate. Regarding the 6-MDIGa copolymer of Example 3, the infrared absorption spectra before and after the hydrophilic treatment were measured using A-202 manufactured by JASCO Corporation at a wave number of 4000 to 400 cm. The results measured in ^{the -1} region are shown as A and B in FIG. 1, respectively. In FIG. 1, from the absorption of OH groups at around 3400 cm ^-1 , a clear increase in the number of hydroxyl groups in the 6-MDIGa copolymer after the hydrophilic treatment is observed.

【table】

[Table] Example 6 50 g of 3-MDIGLu obtained in Reference Example 2, 2-hydroxyethyl methacrylate (2-HEMA) 25
g, methyl methacrylate (MMA) 25 g, ethylene glycol dimethacrylate (EDMA) 0.25
g and 0.1 g of a,a'-azobisdimethylvaleronitrile (ADMVN) as a polymerization initiator were mixed and dissolved, placed in a test tube, and heated at 40℃ for 24 hours in a constant temperature water bath.
Polymerization was carried out for 1 hour, and heat polymerization was further carried out stepwise in a hot air circulation dryer at 50℃ for 8 hours, 60℃ for 6 hours, 80℃ for 6 hours, 100℃ for 3 hours, and 110℃ for 3 hours. A transparent rod-shaped polymer was obtained. This material was cut and polished using a conventional method to form a contact lens shape, and then subjected to hydrophilic treatment under the same conditions as in Example 1 to obtain the intended hydrous contact lens. This contact lens has a water content of 77.9% and an oxygen permeability coefficient of 4.10×10 ^-10 cc・cm/cm ²・
sec·mmHg, refractive index (n ²⁰ _D ) of 1.366, and visible light transmittance of more than 90%. Examples 7 to 9 Water-containing contact lenses were obtained by carrying out experiments in the same manner as in Example 6, except that each component in the copolymerization was used in the amounts shown in Table 2. The results are shown in Table 2.

[Table] Example 10 1-MDIMa17g, 2-hydroxyethyl methacrylate (2-HEMA) obtained in Reference Example 378
g, 5 g of lauryl methacrylate (LMA) and 0.07 g of a,a'-azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed and dissolved, placed in a test tube, and polymerized in a constant temperature water bath at 35°C for 48 hours. , further 16 hours at 50 °C in a hot air circulation dryer, 70
The polymerization was carried out by heating at 90°C for 4 hours and 90°C for 4 hours to obtain a colorless and transparent rod-shaped polymer. This product was cut and polished in a conventional manner to form a contact lens shape, and then subjected to hydrophilic treatment under the same conditions as in Example 1 to obtain the desired hydrophilic contact lens. This contact lens has a water content of 45.5
%, oxygen permeability coefficient 1.62×10 ^-10 cc・cm/cm ²・sec・
mmHg, refractive index (n ²⁰ _D ) 1.412, visible light transmittance 90
%. Examples 11-12 Water-containing contact lenses were obtained by conducting an experiment in the same manner as in Example 10, except that each component in the copolymerization was used in the amounts shown in Table 3. The results are shown in Table 3.

[Table] Example 13 Monomer consisting of 55.6 g of 3-MDIGLu obtained in Reference Example 2, 27.8 g of methyl methacrylate (MMA), 12.4 g of 2-hydroxyethyl methacrylate (2-HEMA), and 0.2 g of allyl methacrylate (AMA) 4.2 g of ethylene glycol (EG) as a wetting agent and 0.04 g of azobisdimethylvaleronitrile (ADMVN) as a polymerization initiator were added to the mixture, mixed and dissolved, and then placed in a test tube and placed in a constant temperature water bath at 35°C for 48 hours. , and further in a hot air circulation dryer.
Heating polymerization was carried out at 50°C for 4 hours and at 60°C for 8 hours to obtain a rod-shaped polymer. Cut this thing by the usual method,
After polishing and forming it into the shape of a contact lens, it was immersed in a 50% formic acid aqueous solution for 30 minutes, a 20% hydrochloric acid aqueous solution for 2 hours, and then a 0.024% sodium carbonate aqueous solution to remove the acid inside the contact lens. The target water-containing contact lens was obtained by neutralizing, immersing in 0.9% physiological saline, and boiling for 3 hours twice. This contact lens has a water content of 89.6% and an oxygen permeability coefficient of 4.50×10 ^-10 cc.
cm/cm ² ·sec · mmHg, refractive index (n ²⁰ _D ) of 1.350, and visible light transmittance of more than 90%. Examples 14-15 Water-containing contact lenses were obtained in the same manner as in Example 13, except that each component in the copolymerization was used in the amounts shown in Table 4. The results are shown in Table 4.

[Table] Example 16 95 g of 3-MDIGLu obtained in Reference Example 2, 5.0 g of lauryl methacrylate, 0.5 g of allyl methacrylate
and ethylene glycol dimethacrylate 0.2
Add 0.1 g of azobisdimethylvaleronitrile as a polymerization initiator to the monomer mixture consisting of
48 hours at 35℃, then 50℃ in a hot air circulation dryer
16 hours at 70℃, 4 hours at 90℃, 110℃
The polymerization was carried out stepwise for 4 hours to obtain a rod-shaped polymer. After cutting and polishing this material using conventional methods and forming it into the shape of a contact lens, 50%
Hydrophilic treatment was performed by immersing in formic acid aqueous solution for 6 hours and 6N hydrochloric acid aqueous solution for 20 hours, and further 0.024%
The desired water-containing contact lens was obtained by immersing it in an aqueous sodium carbonate solution for neutralization.
This contact lens has a water content of 76.8%, an oxygen permeability coefficient of 3.83×10 ^-10 cc・cm/cm ²・sec・mmHg, a refractive index (n ²⁰ _D ) of 1.369, and a visible light transmittance of 90%.
It was bigger. Example 17 3-MDIGLu92g, lauryl methacrylate 3
A water-containing contact lens was obtained in the same manner as in Example 16, except that a monomer mixture consisting of G, 5 g of methyl methacrylate, 0.5 g of allyl methacrylate, and 0.2 g of ethylene glycol dimethacrylate was used. This contact lens has a water content of 74.8
%, oxygen permeability coefficient 3.79×10 ^-10 cc・cm/cm ²・sec・
mmHg, refractive index (n ²⁰ _D ) of 1.370, and visible light transmittance was greater than 90%. When the contact lenses obtained in Example 9 were worn continuously on the right eyes of three white rabbits for 21 days,
No abnormalities were observed on the corneal surface, no significant decrease in glycogen content was observed, and histological findings showed no neovascularization, substantial edema, or inflammatory cell infiltration. No significant morphological changes were observed between the eyes.

[Brief explanation of the drawing]

FIG. 1 shows infrared absorption spectra of the 6-MDIGa copolymer of the present invention before and after acid treatment.

Claims (1)

[Claims] 1 D-galactose, D-glucose and D
- A copolymer consisting essentially of a methacrylate or acrylate unit having at least one type of sugar selected from the group consisting of mannose in its side chain, and a hydrophilic monomer unit and/or a hydrophobic monomer unit. Water-containing contact lenses. 2 Hydrophilic monomer is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
selected from the group consisting of 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, acrylamide, methacrylamide, dimethylacrylamide, dimethylmethacrylamide, acrylic acid, methacrylic acid and N-vinylpyrrolidone The water-containing contact lens according to claim 1, which is one or more kinds of compounds. 3 The hydrophobic monomer is one or more selected from the group consisting of methacrylic acid or acrylic acid alkyl ester (alkyl group has 1 to 15 carbon atoms), styrene, vinyl acetate, and vinyl propionate. Claim 1 which is a compound of
Water-containing contact lenses as described in section. 4 Ketalized sugar, acrylic acid or methacrylic acid ester, hydrophilic monomer and/or
A contact lens made of a copolymer obtained by copolymerizing a monomer mixture consisting essentially of hydrophobic monomers is molded, and then the contact lens is treated with an acid to form a water-containing contact lens. A method for producing a water-containing contact lens, comprising replacing the acid impregnated with water or physiological saline. 5. The method for producing a water-containing contact lens according to claim 4, wherein the copolymerization is carried out in the presence of a wetting agent.