KR20120069054A - A modifying method of hydrogel contact lens - Google Patents

Abstract

PURPOSE: A surface modifying method for a hydrogel contact lens is provided to remove the residual monomer and non-reacting intermediates remaining in the inner structure and surface of a contact lens by using solvent used for dissolving oligosaccharides. CONSTITUTION: A contact lens material is expanded to an expansion ratio of 10-50%. The expanded contact lens material is dipped in oligosaccharide solution, which includes dissolved oligosaccharide with an average molecular weight(Mw) of 100-200,000, in order to modify the surface of a contact lens. An expansion medium for the expansion of the contact lens material is selected among alcohol with a carbon number of 1 to 6, sodium bicarbonate solution with a concentration of 1.0 to 1.0 weight% and their mixture. The oligosaccharide solution includes oligosaccharides dissolved to a concentration of 0.001 to 1 weight% in solvent with a polarity index of 3 to 7.

Description

Surface modifying method of contact lens {A modifying method of hydrogel contact lens}

The present invention relates to a surface modification method of a contact lens, and more particularly, by performing a surface modification process of swelling in a oligosaccharide solution after swelling a contact lens substrate prepared by polymerizing a conventional polymer material, IPN of a contact lens It efficiently removes cytotoxic substances such as unreacted monomers and side reaction intermediates contained in the network structure, removes residual monomers bound to the contact lens surface, and forms a wettable oligosaccharide film on the contact lens surface to reduce contact angle and wettability. The present invention relates to a method of modifying the surface of a contact lens, which has an effect of remarkably improving the efficiency.

In the 21st century, which is defined as the digital and information age beyond the industrial age, eye health is threatened by the increase of near field work using reading and computers. Hydrogel materials most commonly used as raw materials for contact lenses are polymer materials in which monomers are connected at regular intervals by a crosslinking agent to be bonded in a chain to form a network. The first hydrogel material used as a contact lens material was poly (2-hydroxyethylmethacrylate (polyHEMA, also commonly referred to as HEMA), first developed by Wichterle in the 1960s. polyHEMA is a homopolymer in which hydroxyethyl methacrylate monomers are combined in the simplest way by a crosslinking agent (EGDMA) PolyHEMA has a very flexible structure and is relatively stable to changes in pH and temperature as well as contact lenses. Because it is easily made and easy to produce, it is most commonly used as a material for contact lenses. However, there is a limit to increase oxygen permeability of the lens, and in many cases, congestion or eye disease may be caused by side effects of lens wearing for a long time.

Attempts to address the side effects of contact lenses reported to date are as follows.

In order to increase the oxygen transmittance of the contact lens, Korean Patent No. 214748 is grafted acrylamide, a hydrophilic monomer, on the contact lens surface to adjust the contact angle in the range of 13 to 19 ° to maintain the wettability of the lens surface for a comfortable fit It was. However, the method of modifying the lens surface by grafting has a long reaction time, a complicated process, and may cause eye redness or disease due to the remaining reducing agent.

In order to remove the unreacted substance of the contact lens, International Patent Publication No. WO 02/36669 used a solvent contained within the range of Hansen Solubility Parameter. However, there is no secondary treatment effect on the surface of the unreacted contact lens, which may cause eye redness or disease.

In order to reduce the ocular side effects that occur during long-term wearing of contact lenses, a technique for removing foreign substances adhered while wearing contact lenses mainly by developing a cleaning solution or a storage solution composition of contact lenses [Japanese Patent No. 4255,656; Japanese Patent No. 3754751; Japanese Patent Application No. 2001-559516; US Patent No. 5765579; International Patent Publication No. WO 09/096038 has been published. However, the ocular side effects may be due to the presence of unreacted monomers, modified intermediates, additives, etc. used in the manufacture of the contact lens substrate, in addition to the foreign matter attached during the wearing and storage of the contact lens. In particular, since color contact lenses are added with dyes unlike general contact lenses, eye side effects are more serious when wearing contact lenses for a long time. Ocular side effects from long-term wear of contact lenses have been demonstrated in cytotoxicity and clinical trials.

It is an object of the present invention to completely eliminate foreign substances such as unreacted monomers, side reaction intermediates, and additives remaining in the IPN network structure of a contact lens to solve a cytotoxic problem.

An object of the present invention is to form an oligosaccharide film on the surface of the contact lens to improve the fit, and to prevent foreign matters such as proteins and inorganic elements from being deposited on the contact lens during lens wearing and storage to solve the problem of ocular side effects. It is done.

In order to solve the above problems, the present invention comprises the steps of swelling the contact lens substrate in a swelling ratio of 10 to 50% range; And modifying the lens surface by immersing the swollen contact lens substrate in an oligosaccharide solution in which an oligosaccharide in a weight average molecular weight (Mw) ranges from 1,000 to 20,000. Characterized in that the modification of the contact lens comprising a.

The oligosaccharide used as a modifier of the present invention has excellent wettability and additional hydrophilic groups are bonded as necessary, so that modified contact lenses have a large amount of hydrophilic groups on the surface of the lens to facilitate moisture supply, thereby improving lens fit. It works.

The solvent used to dissolve the oligosaccharide according to the present invention has the effect of eliminating cytotoxicity to the eye by removing residual monomers and side reaction intermediates present on the IPN internal structure and surface.

The contact lens subjected to the reforming method of the present invention has an effect of increasing the surface pore size to facilitate the supply of oxygen to increase the lens fit.

The contact lens substrate applied to the modification method according to the present invention is a conventional acrylate or silicone acrylate hydrogel contact lens having an IPN internal structure, and may be a transparent contact lens or a color contact lens with a pigment added thereto. .

As the monomer used in the preparation of the hydrogel contact lens, an acrylic monomer may be representatively used. Such acrylic monomers include acrylic acid; Methacrylic acid; Acrylamide; C ₁ -C ₁₅ saturated or unsaturated alkyl acrylates or methacrylates; C ₁ -C ₁₅ hydroxyalkyl acrylates or methacrylates having 1 to 3 hydroxy groups substituted; And one, two or more selected from N, N-di (C ₁ -C ₁₅ saturated or unsaturated alkyl) acrylamides. More specifically, acrylic acid (AA), methacrylic acid (MA), 2-hydroxyethyl methacrylate (HEMA), fluoroethyl methacrylate (FMA), 2-ethoxyethyl methacrylate (EOEMA), Lauryl methacrylate (LMA), glycerol monomethacrylate (GMMA), neopentyl glycol dimethacrylate, acrylamide, N, N-dimethylacrylamide (DMA) and the like. In addition, the silicone acryl-based monomer may typically include a polydimethylsiloxane compound and the like. In addition, N-vinyl-2-pyrrolidone (NVP), N-methylpyrrolidone (NMP), tris (3-methacryloxypropyl) silane, 2- (trimethylsilyloxy) ethyl methacrylate, 3- Hydrophilic monomers such as tris (trimethylsilyloxy) silylpropyl methacrylate, 3-methacryloxypropyl tris (trimethylsilyl) silane (MPTS), 4-methacryloxybutyl terminated polydimethylsiloxane can be used.

A crosslinking agent is used to polymerize the monomer to form a composite film having an internal structure of an interpenetrating polymer network (IPN). As the crosslinking agent, diethylene glycol methacrylate (DGMA), ethylene glycol dimethacrylate (EDMA), divinylbenzene, trimethylolpropane trimethacrylate (TMPTMA) and the like can be used. As polymerization initiators, benzoin methyl ether (BME), 2,5-dimethyl-2,5-di- (2-ethylhexanoylperoxy) hexane, 2,2'-azobisisobutyronitrile, Darocur1173, etc. This can be used.

After the crosslinking and polymerization of the monomer, the crosslinking agent and the polymerization initiator at room temperature to 200 ° C, a contact lens substrate is prepared by molding into a film with a thickness of 0.04 to 2.0 mm. In the case of color contact lenses, a gel polymer obtained by adding a pigment such as phthalocyanate copper salt, titanium dioxide, and phthalocyanine green to a hydrophilic monomer is coated on the surface of the above contact lens substrate to prepare a color contact lens substrate. It may be.

The contact lens substrate manufactured through the crosslinking polymerization has an IPN internal structure, and gas and liquid may be transferred using pores constituting the IPN internal structure as a transfer passage. In the present invention, by modifying the pore size and pore distribution of the internal structure of the IPN through the reforming to supply oxygen more smoothly and the presence of a large amount of hydrophilic groups on the surface of the moisture to easily combine the eye health by supplying moisture You can get the effect of adjusting the In addition, in the present invention, by removing the foreign substances such as unreacted monomers, side reaction intermediates, and other additives remaining in the IPN internal structure and the lens surface through reforming, fundamentally solve the cytotoxic effect on the eye, and also clean the lens surface It also helps to mitigate protein and mineral deposits that may occur later.

The modification method of the contact lens characterized by the present invention will be described in more detail as follows.

First, the contact lens substrate is swollen. The swelling in the present invention is immersed for 5 to 120 minutes at a temperature of 20 ℃ to 60 ℃ in a swelling medium selected from alcohols having 1 to 6 carbon atoms, aqueous solution of 0.1 to 1.0% by weight concentration, and mixtures thereof. And, the swelling rate can be calculated by the following equation 1, so that the swelling rate is 10 to 50%.

[Equation 1]

The swelled contact lens substrate is then immersed in an oligosaccharide solution for surface modification.

The oligosaccharide used as the modifier is an oligomer in which two or more monosaccharides form glycosidic bonds, and has a weight average molecular weight (Mw) in the range of 100 to 200,000. Such oligosaccharides may be natural oligosaccharides present in plants or the like, or oligosaccharides prepared by partially degrading polysaccharides. Most of natural oligosaccharides include disaccharides such as sucrose, maltose (maltose), lactose (lactose) and the like, and glycoproteins and glycolipids are mostly included in oligosaccharides. In addition, oligosaccharides are hydrolysis using starch, cellulose, glycogen, chitin, pectin, hyaluronic acid, caronin sulfate, algin, carrageic acid, glycosaminoglycan and other polysaccharides using an appropriate acid or alkali, or ozone ( The oligomer having a viscosity controlled to a specific range can be prepared by chemically cutting the molecular structure by O ₃ ) treatment or physically cutting the molecular structure. The method for cleaving the molecular structure of such polysaccharides is a method known in the art, and the present invention does not place any particular limitation on its method selection. Specific examples of the oligosaccharides used in the present invention include sucrose oligosaccharides, maltose oligosaccharides, lactose oligosaccharides, glucose oligosaccharides, glucosamine oligosaccharides, N-acetylglucosamine oligosaccharides, glucopyranoside oligosaccharides, glucosaminoglycan oligosaccharides (eg, Chondroitin or salts thereof, dermatan or salts thereof, keratan or salts thereof, heparan or salts thereof, hyaluronic acid, heparin), galacturonic acid oligosaccharides, cellobiose oligosaccharides, algin oligosaccharides.

Oligosaccharides can be expected to sufficiently improve the wettability of the lens by itself, but in the present invention, in order to maximize the wettability of the lens, oligosaccharides in which a hydrophilic reactor is substituted through ion exchange or the like can be used. 5? Based on the total weight of oligosaccharides 100 wt%, preferably 20? 100% by weight. Examples of the hydrophilic reactor that may be substituted with an oligosaccharide through ion exchange may include, for example, a hydroxyl group (-OH), a carboxylic acid group (-COOH), and a carboxylate group (-COOR, R = C _1-6 alkyl). , Ketone group (-CO-), aldehyde group (-COH), amide group (-NHCO-), alkanoate group (RCOO-, R = C _1-6 alkyl), hydroxymethyl group (-CH ₂ OH) The hydrophilic group selected from may be substituted or unsubstituted.

As the solvent for dissolving the above oligosaccharide, in the present invention, a single solvent or a mixed solvent selected from a solvent system having a solvent polarity index provided by Burdick & Jackson of 3 or more, preferably 3 to 7, is used. do. Organic solvents having a polarity index of 3 to 7 are typically acetic acid, acetone, acetonitrile, butyl acetate, chloroform, dichloroethane, dichloromethane, dimethylformamide, dioxane, ethyl alcohol, ethyl acetate, methanol, 2- Butanone, n-propanol, isopropyl alcohol, dichloromethane, dichloroethane, propanol, isopropyl alcohol, butyl alcohol, trichloroethylene, chloroform, ethyl acetate, gamma butyrolactone, butyl acetate, tetrahydrofuran and the like. have. More preferably, dichloromethane, isopropyl alcohol, ethyl acetate, gamma butyrolactone and butyl acetate are used as the solvent. By selecting and using a solvent having a specific polarity, the hydrophilic groups are concentrated on the surface of the contact lens substrate, thereby improving the surface properties of the lens and remaining in the internal structure without destroying the internal structure of the IPN (Interpenetrating Polymer Network). By extracting and removing foreign matter, the effect of resolving the cytotoxicity of the lens can be obtained.

However, using a solvent with a solvent polarity index above 7 may result in inefficiency or loss of contact lens components. Highly polar organic solvents having a polarity index greater than 7 may typically include dimethyl sulfoxide and the like.

In addition, the oligosaccharide solution used for surface modification is preferably used in a concentration range of 0.001 to 1% by weight. If the concentration of the oligosaccharide solution used as the modifier is less than 0.001% by weight, foreign substances remaining on the IPN internal structure and the lens surface of the contact lens substrate may be sufficiently removed to solve the cytotoxic problem, but the oligosaccharide film is not formed on the contact lens substrate surface. It is difficult to efficiently control deposition of proteins, minerals, etc. during lens wearing or storage. In addition, if the concentration of the oligosaccharide solution is maintained at a high concentration of more than 1% by weight, it is not easy to remove foreign substances remaining on the IPN internal structure and the lens surface of the contact lens substrate, but rather it may act as a foreign substance and affect the lens refractive index. have.

In the present invention, there is no particular limitation on the reforming conditions, it is usually to maintain a range of 10 to 100 rpm, the stirring time is to maintain a range of 1 to 60 minutes. In addition, the modification temperature is approximately 20 ° C to 200 ° C temperature range, although the modification effect can be sufficiently obtained at room temperature, the heating of the solvent boiling point may be more easily formed of the oligosaccharide film. According to the experiments of the present inventors, when heated to a temperature of 90 ° C to 200 ° C, the hydrophilic group ion-bonded to the oligosaccharide forms a chemical bond with a residue (for example, a hydroxyl group, a carboxylic acid group, and a siloxane group) present on the contact lens surface, thereby forming a strong oligosaccharide. A film can be formed. It is also possible to introduce ultrasonic, vibration, and microwave during the modification if necessary.

When the modification process as described above is completed, the modified contact lens is washed with water, ethanol or a mixed solution thereof, and treated at a temperature of 80 to 150 ° C. for sterilization.

The contact lens modified according to the present invention has a surface contact angle of 15? 30 °, tensile strength 3? 15 kg / cm ² , Modulus of elasticity 0.3? As 1.6 MPa, it can be seen that the wettability and mechanical properties are greatly improved compared to the contact lens substrate before modification.

Such a present invention will be described in more detail based on the following Preparation Examples and Examples, but the present invention is not limited thereto.

The physical properties of the contact lenses prepared in Preparation Examples and Examples of the present invention were evaluated by the following method.

[Measurement of physical properties]

1) Contact angle (°): Measured by a fixed bubble array method using the DSA100.

2) Water content (%): measured by the drying loss method.

3) Tensile strength: measured according to JIS K7113: 1995.

4) Elastic modulus (MPa): measured by Young's Modulus method.

5) Cytotoxicity: Measured by the Food and Drug Administration Notice No. 2008-41, Proliferation Inhibition Test of Cultured Cells of Medical Device Standard.

[Manufacturing Example]

Representative manufacturing method of the contact lens substrate applied to the modification process according to the present invention is shown as the following preparation example, which is only some embodiments for showing a specific example of the present invention. Therefore, the contact lens substrate applied to the modification process of the present invention is not limited to the contact lens substrate prepared in the following Preparation Example.

Preparation Example 1 Preparation of Acrylate-based Contact Lens Substrate

The monomers as shown in Table 1 were mixed, and 0.4 g of azodiisobutylonitrile was added as a crosslinking agent to 100 g of the total amount of the monomers, followed by stirring to prepare a monomer mixture solution. To prepare an acrylate-based contact lens substrate. The moisture content, the wetting angle, the tensile strength, and the elastic modulus of the prepared acrylate-based contact lens substrates were measured and shown in Table 1 below.

Preparation Example 2 Preparation of Silicon acrylate Contact Lens Base

The monomers as shown in Table 1 were mixed, and 0.4 g of azodiisobutylonitrile was added as a crosslinking agent to 100 g of the total amount of the monomers, followed by stirring to prepare a monomer mixture solution. To prepare a silicone acrylate-based contact lens substrate. The water content, the wetting angle, the tensile strength, and the elastic modulus of the prepared silicon acrylate-based contact lens substrates were measured and shown in Table 1 below.

Preparation Example 3 Preparation of Color Contact Lens Base

To 100 g of 2-hydroxyethyl methacrylate (HEMA), add 50 g of cyclopentanone as a polymerization solvent, 0.4 g of ethylene glycol as a crosslinking agent, and 0.4 g of 2,2'-azobisisobutyronitrile as a polymerization initiator and stir. To prepare a monomer mixture. The monomer mixture prepared above was injected into a contact lens mold and thermally polymerized at a temperature of 80 to 100 ° C.

Then, 30 g of 2-hydroxyethyl methacrylate (HEMA), 2.5 g of methacrylic acid (MA), 2 g of fluoroethyl methacrylate (FMA), and 5 g of 2-ethoxyethyl methacrylate (EOEMA) , 4 g of N-vinyl-2-pyrrolidone (NVP), 45 g of cyclopentanone, 2 g of 2-mercaptoethanol, 0.4 g of ethylene glycol as a crosslinking agent, and 2,2'-azobisisobutyine as a polymerization initiator 0.4 g of ronitrile were mixed to prepare a gel polymer.

Then, 1 part by weight of the prepared gel polymer, 1 part by weight of phthalocyanate copper salt, and 1 part by weight of ethyl lactate were mixed, and the surface of the thermal polymer was printed by a pad (PAD) printing method. Contact lenses were prepared. The water content, the wetting angle, the tensile strength, and the elastic modulus of the prepared color contact lens substrates were measured and shown in Table 1 below.

division Monomer composition
(Usage, g) Properties of Contact Lens Bases The tensile strength
(kg / cm ² ) Moisture content
(%) Wetting angle
(°) Modulus
(MPa) Preparation Example 1 HEMA (100 g) 4.4 38 42 1.2 Production Example 2 HEMA (98 g), DMA (1 g), Acrylmer (1 g) 3.6 40 44 1.4 Production Example 3 HEMA (97.5 g), MA (2.5 g) 4.2 55 40 1.0 HEMA: hydroxyethyl methacrylate
DMA: N, N-dimethylacrylamide
Acrylmer: Acrylmer ™ -SiHy843, silicone acrylate

[Example]

Example 1 Preparation of Modified Acrylate-based Contact Lenses

The acrylate-based contact lens substrate prepared in Preparation Example 1 was swollen at 30 ° C. for 2 hours in an aqueous ethanol solution containing 0.2% by weight of sodium bicarbonate. Then, the swelled contact lens substrate was immersed in 10 mL of the modified solution having the composition shown in Table 2 below, followed by surface modification by stirring for 5 minutes at a stirring speed of 20 rpm. When the modification was completed, washed with a mixture of deionized water and ethanol (7: 3, volume ratio), sterilized at 120 ℃ temperature and dried to obtain a modified acrylate-based contact lens. The results of measuring contact lens properties before and after modification are shown in Table 2 below.

division Reforming solution (weight ratio) Properties Wetting angle
(°) The tensile strength
(kg / cm ² ) Modulus
(MPa) Cytotoxicity
(%) Preparation Example 1 Before reforming 42 4.4 1.2 27.0 Example 1-1 Dichloroethane (50), hyaluronic acid (Mw 50,000) (1) 26 6.5 0.8 16.8 Examples 1-2 Dichloromethane (50), Glucosamine (Mw 25,000) (1) 30 6.0 0.9 18.2 Example 1-3 Ethyl Acetate (30), Alginic Acid (Mw 50,000) (1) 25 6.5 0.7 19.5 Example 1-4 Gamma Butyrolactone (10), Isopropanol (40) Hyaluronic Acid (Mw 50,000) (1) 28 6.4 0.6 16.3 Examples 1-5 Chloroform (30), Glucosamine (Mw 25,000) (1) 29 6.3 0.8 18.5 Examples 1-6 Tetrahydrofuran (50), Glucosamine (Mw 25,000) (1) 29 6.5 0.9 16.2 Example 1-7 Isopropanol (20), Dimethoxyethanol (30), Glucosamine (Mw 25,000) (1) 28 6.4 0.8 15.3 Examples 1-8 Dichloromethane (30), n-butanol (20), hyaluronic acid (Mw 50,000) (1) 20 6.9 0.7 18.5 Example 1-9 Dimethylacetamide (5), ethyl acetate (35), hyaluronic acid (Mw 50,000) (1) 22 6.8 0.6 16.6 Example 1-10 Methyl ethyl ketone (10), methanol (40), glucosamine (Mw 25,000) (1) 21 6.9 0.5 17.8

1 is a SEM photograph of contact lens surfaces before and after modification using the modifier of Example 1-1, and it can be seen that the contact lens surfaces after modification are evenly distributed.

Example 2 Preparation of Modified Silicone Acrylate-based Contact Lenses

The silicon acrylate-based contact lens substrate prepared in Preparation Example 2 was swollen at a temperature of 20 ° C. for 6 hours in an aqueous ethanol solution containing 0.2% by weight of sodium bicarbonate. Then, the swelled contact lens substrate was immersed in 10 mL of the reforming solution having the composition shown in Table 3 below, followed by surface modification by stirring for 5 minutes at a stirring speed of 20 rpm. When the modification was completed, washed with a mixture of deionized water and ethanol (7: 3, volume ratio), sterilized at 120 ℃ temperature and dried to obtain a modified silicone acrylate-based contact lens. The results of measuring contact lens properties before and after modification are shown in Table 3 below.

division Reforming solution (weight ratio) Properties Wetting angle
(°) The tensile strength
(kg / cm ² ) Modulus
(MPa) Cytotoxicity
(%) Production Example 2 - 44 3.6 1.4 29.2 Example 2-1 Dichloromethane (50), Glucosamine (Mw 25,000) (1) 28 7.0 0.7 16.8 Example 2-2 Ethyl Acetate (30), Alginic Acid (Mw 50,000) (1) 20 6.8 0.8 18.5 Example 2-3 Gamma Butyrolactone (5), Methanol (45) Hyaluronic Acid (Mw 50,000) (1) 15 6.9 0.5 15.5 Examples 2-4 Chloroform (30), Glucosamine (Mw 25,000) (1) 19 6.9 0.7 16.9 Example 2-5 Tetrahydrofuran (50), Glucosamine (Mw 25,000) (1) 20 6.6 0.8 18.8

Example 3 Preparation of Modified Color Contact Lenses

The color contact lens substrate prepared in Preparation Example 3 was swollen at 30 ° C. for 2 hours in an aqueous ethanol solution containing 0.2% by weight of sodium bicarbonate. Then, the swelled contact lens substrate was immersed in 10 mL of the reforming solution having the composition shown in Table 4 below, followed by surface modification by stirring for 5 minutes at a stirring speed of 20 rpm. When the modification was completed, washed with a mixed solution of deionized water and ethanol (7: 3, volume ratio), sterilized at 120 ℃ temperature and dried to obtain a modified color contact lens. Physical properties of the color contact lenses before and after modification are shown in Table 4 below.

division Reforming solution (weight ratio) Properties Wetting angle
(°) The tensile strength
(kg / cm ² ) Modulus
(MPa) Cytotoxicity
(%) Production Example 3 - 40 4.2 1.0 88.0 Example 3-1 Dichloromethane (50), Glucosamine (Mw 25,000) (1) 25 6.2 0.9 19.8 Example 3-2 Ethyl Acetate (30), Alginic Acid (Mw 50,000) (1) 16 6.5 0.7 17.6 Example 3-3 Gamma Butyrolactone (50), Hyaluronic Acid (Mw 50,000) (1) 15 6.6 0.6 16.7 Example 3-4 Chloroform (30), Glucosamine (Mw 25,000) (1) 28 6.5 0.9 16.8 Example 3-5 Tetrahydrofuran (50), Glucosamine (Mw 25,000) (1) 20 6.4 0.7 17.2 Examples 3-6 Dimethylformamide (20), Dimethylacetamide (30), Glucosamine (Mw 25,000) (1) 16 6.9 0.9 16.8 Example 3-7 Dichloromethane (30), ethanol (20), hyaluronic acid (Mw 50,000) (1) 21 6.9 0.8 17.6 Examples 3-8 Gamma Butyrolactone (5), Ethyl Acetate (35), Hyaluronic Acid (Mw 50,000) (1) 22 7.0 0.7 17.3 Example 3-9 Acetonitrile (10), methanol (40), glucosamine (Mw 25,000) (1) 18 6.8 0.7 16.9

Example 4 Preparation of Modified Silicone Acrylate Contact Lenses

The silicon acrylate-based contact lens substrate prepared in Preparation Example 2 was swollen at 40 ° C. for 2 hours in an aqueous ethanol solution containing 0.2% by weight of sodium bicarbonate. Then, the swelled contact lens substrate was immersed and modified in 10 mL of a modified solution in which gamma butyrolactone and hyaluronic acid (Mw 50,000) were mixed at a weight ratio of 50: 1. However, the surface was modified by stirring for 5 minutes at a stirring speed of 20 rpm while changing the temperature of the reforming solution as shown in Table 5 below. When the modification was completed, washed with a mixture of deionized water and ethanol (7: 3, volume ratio), sterilized at 120 ℃ temperature and dried to obtain a modified silicone acrylate-based contact lens. The results of measuring contact lens properties before and after modification are shown in Table 5 below.

division Reforming temperature (℃) Properties Wetting angle
(°) The tensile strength
(kg / cm ² ) Modulus
(MPa) Cytotoxicity
(%) Production Example 2 - 44 3.6 1.4 29.2 Example 4-1 20 36 6.9 0.9 16.9 Example 4-2 50 35 6.8 0.9 16.8 Example 4-3 100 30 6.9 0.8 15.5 Example 4-4 150 28 7.0 0.7 16.0 Example 4-5 200 28 6.9 0.8 15.5

Claims (11)

Swelling the contact lens substrate in a swelling ratio of 10 to 50%; And
Modifying the lens surface by immersing the swollen contact lens substrate in an oligosaccharide solution in which oligosaccharides in a weight average molecular weight (Mw) range from 100 to 200,000 are dissolved;
Method of manufacturing a modified contact lens comprising a.
The method according to claim 1,
And said swelling using a swelling medium selected from alcohols having 1 to 6 carbon atoms, aqueous sodium bicarbonate solution at a concentration of 0.1 to 1.0% by weight, and mixtures thereof.
The method according to claim 1,
The oligosaccharide solution is a method for producing a modified contact lens, characterized in that the oligosaccharides are dissolved in a solvent concentration of 0.001 to 1% by weight in a solvent polarity index (3-7 range) provided from Burdick & Jackson.
The method according to claim 3,
The solvent in which the oligosaccharide is dissolved is acetic acid, acetone, acetonitrile, butyl acetate, chloroform, dichloroethane, dichloromethane, dimethylformamide, dioxane, ethyl alcohol, ethyl acetate, methanol, 2-butanone, n-propanol, iso One or more solvents selected from propyl alcohol, dichloromethane, dichloroethane, propanol, isopropyl alcohol, butyl alcohol, trichloroethylene, chloroform, ethyl acetate, gamma butyrolactone, butyl acetate, and tetrahydrofuran A method of manufacturing a modified contact lens, characterized in that.
The method according to claim 1,
The oligosaccharide is a natural oligosaccharide, or a method for producing a modified contact lens, characterized in that the oligosaccharide prepared by partially decomposing a polysaccharide (polysaccharide).
The method according to claim 1,
The oligosaccharides are hydroxyl group (-OH), carboxylic acid group (-COOH), carboxylate group (-COOR, R = C _1-6 alkyl), ketone group (-CO-), aldehyde group (-COH), amide Preparation of a modified contact lens characterized in that a hydrophilic group selected from a group (-NHCO-), an alkanoate group (RCOO-, R = C _1-6 alkyl), and a hydroxymethyl group (-CH ₂ OH) is substituted Way.
The method according to claim 1,
The modification is a method of manufacturing a modified contact lens, characterized in that carried out under stirring conditions at a speed of 10 to 100 rpm.
The method according to claim 1,
The modification is a method of manufacturing a modified contact lens, characterized in that carried out under heating conditions of 90 ℃ to 150 ℃.
The method according to claim 1,
The modification is a method of manufacturing a modified contact lens, characterized in that performed under conditions that irradiate ultrasonic (ultrasonic), vibration (vibration), or microwave (microwave).
The method according to claim 1,
The contact lens substrate is a method of manufacturing a modified contact lens, characterized in that the hydrogel contact lens made of acrylate or silicone acrylate.
The compound according to any one of claims 1 to 10,
The surface contact angle of the modified contact lens is 15? 30 °, the method of manufacturing a modified contact lens.