KR100214748B1 - Contact lens and method of producing a contact lens - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method for producing a hard contact lens that maintains the wettability of a surface permanently and has excellent wear feeling. The present invention provides a discharge method by adding a reducing agent to a polymerization system in a graft polymerization process on a contact lens surface. Degradation of peroxide introduced into the surface of the contact lens material by the treatment at low temperature to generate radicals, and use of fluorine-containing material as the contact lens material prevents discoloration of the material during the treatment by shortening the treatment time. Dissolved oxygen removal is carried out by reducing the pressure while applying ultrasonic waves, or is characterized in that the surface graft polymerization is carried out at normal pressure by adding diammonium cerium nitrate (IV).

Description

[Name of invention]

Manufacturing Method of Contact Lens

Detailed description of the invention

[Technical Field]

The present invention relates to a method for producing a hard contact lens that maintains the wettability of the surface permanently and is excellent in wearing comfort.

[Background]

It is important to improve the affinity between the cornea and the lens in order to reduce the feeling of foreign matter when wearing contact lenses and to improve the fit. Optimization of the design of the size and shape of the lens is also an important factor, but moreover, the affinity with the chemical cornea (biological tissue) on the surface of the contact lens is indispensable for producing a contact lens excellent in wearing comfort. One typical example of a surface treatment method aimed at permanently adding corneal affinity to a contact lens surface is wettability (including water retention) and slippage of the lens surface by graft polymerization of a hydrophilic monomer such as acrylamide on the lens surface. It can improve the function, such as motility. In addition, in order to maintain wettability over a long period of time, there is a method of improving the wear resistance of the graft chain by crosslinking with N, N'-methylene bisacrylamide or the like.

There are two important factors for efficient surface graft reaction. The first is to generate radicals which are the starting point of polymerization on the surface of the target material, and the second is to remove the polymerization inhibitor which inhibits the graft polymerization reaction from the environment (solution). Growth begins). The first and second elements do not have optimal conditions independently of each other, but must find an optimal condition among the combinations of both. In addition, the surface graft polymerization reaction conditions vary depending on the target material, which should be considered. So far, the two elements described above have independent means, but the following briefly describes the conventional techniques for dealing with these two elements when grafting a hydrophilic monomer onto the contact lens material surface. .

First of all, a method of generating radicals on the surface of a contact lens material, which is the first element, is required to introduce a peroxide into the surface of a contact lens by discharge treatment or the like. It is only by chemical decomposition that radicals are produced on the surface of the material. Conventionally, thermal decomposition was carried out at a high temperature of 60-90 C to decompose the peroxide.

Next, the removal of the second factor, the polymerization inhibitor, is described. In general, the most important of the polymerization inhibitors in the solution system is the dissolved oxygen present in the solution. Therefore, if dissolved oxygen is removed in any way, the desired graft polymerization reaction can be initiated. Conventionally, as a method of sufficiently removing the dissolved oxygen, the container containing the monomer solution was removed by vacuum, and then knocked from the outside, and then, a series of steps were repeated several times, replacing the container with an inert gas such as nitrogen and then again evacuating it. .

However, the above-described prior art had a serious drawback pointed out below. First of all, decomposition of peroxide (radical generation) on the surface of the lens material by heating, which is the first element, requires 60-90 ° C in the prior art as described above. However, there is a drawback that the shape of the lens material mainly composed of acrylic resin, which is the mainstream, greatly changes or the optical characteristics deteriorate (change of lens power, change of transmittance in the visible region, etc.).

On the other hand, when describing the removal method of dissolved oxygen (polymerization inhibitory factor) necessary for causing the graft chain growth reaction at the start of polymerization, the above-mentioned conventional technique, that is, the container containing the solution is removed by vacuum and then In the method of repeating a series of steps of tapping from the outside and then replacing the inside of the container with an inert gas such as nitrogen and bleeding out again in a vacuum several times, the process is too complicated and is not a method for mass production. In addition, because the process management is difficult, dissolved oxygen in the solution cannot be removed uniformly, and the slight unevenness of the remaining oxygen causes variation in the graft polymerization conditions, unevenness of the graft surface state, and consequently the wear of the contact lens. Had the drawback.

In addition, as mentioned above, there are no examples of the method of connecting these two elements with optimum conditions, including the target material.

Accordingly, an object of the present invention is to solve various problems described above. In other words, it is an object of the present invention to provide a method for producing a contact lens that enables decomposition reaction of peroxide at a temperature sufficiently lower than the softening point of the contact lens material in terms of radical generation (first element). As for the removal of dissolved oxygen (second element), the dissolved oxygen removal operation at the time of surface graft polymerization is simplified, the process management is easy, and the mass production method is easy, It is an object of the present invention to provide a method for producing a contact lens which enables a high product rate surface graft polymerization treatment. One object of the present invention is to provide a manufacturing method that includes the target material and pays attention to the process compatibility of the first element and the second element and connects them optimally.

[Initiation of invention]

The method for producing a contact lens of the present invention relates to a contact lens material mainly containing a polymer of an ester compound of acrylic acid or methacrylic acid, or a contact lens mainly comprising a polymer which is a copolymer of an acrylic acid compound (a) (B) immersing the material in a hydrophilic monomer solution, (c) adding a reducing substance, and (d) the material surface at atmospheric pressure or reduced pressure. It is characterized by consisting of a step of graft polymerization of the hydrophilic monomer. In the method for manufacturing a contact lens of the present invention, the graft polymerization is initiated by heating. The method for producing a contact lens of the present invention is characterized in that the hydrophilic monomer is acrylamide or N, N'-methylene bisacrylamide. Moreover, the manufacturing method of the contact lens of this invention is siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula.

Wherein R = CH ₃ or H; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z;

R ¹ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ² = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ³ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ⁴ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; m = 1-3; n = 1-5; p = 1-3), a fluoroalkyl substituent of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula

(Wherein R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group), polyfluoric acid of acrylic acid or methacrylic acid represented by the following general formula Alkylsiloxy substituted ester

(Wherein R = CH ₃ or H; a fluoroalkyl group of R _f = C ₁ -C ₄ ;

l = 1-4; m = 0, 1 or 2; n = 1-3), acryl (methacryl) oxyalkyl silanol represented by the following general formula

In which R = CH ₃ or H; X, Y = C ₁ -C ₆ alkyl; phenyl or Z;

m = 1-3; n = 1-5; p = 1-3; R ¹ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ² = C ₁ -C ₆ 6 alkyl, cyclohexyl or phenyl; R ³ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl),

Polyacryl (methacryl) oxyalkyl polysiloxane represented by the following general formula

Wherein R = CH ₃ or H; m = 0-3; n = 1-5; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, Cyclohexyl, phenyl or Z;

P = 1-3; R ¹ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ² = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; R ³ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; Fluorine-containing siloxanyl methacrylate represented by the following general formula

(Wherein, l = 1-3; m = 1-10; n = 1-3; k = 1-3), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula

Wherein R _f = C ₁ to C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C ₁ to C ₃₀ fluorine atom or Alkyl group which may contain an oxygen atom), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula:

(Wherein R _f = C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C _{1 to} C ₃₀ fluorine atoms or Alkyl group which may contain an oxygen atom), a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula:

(Wherein R ¹ , R ² = CH ₃ or H; 1 = 2-4; p, q = 1 or 2; m, n are each an integer whose sum is in the range of 1-20) and the following general Fluorine-containing cyclic olefin represented by the formula

(Wherein A = H, F or alkyl group; B = H, F or alkyl group; C = H, F or alkyl group; D = F or C _{1 to} C _{30 which} may contain an oxygen atom bonded to at least one fluorine atom) A fluoroalkyl group of n = 0, 1 or 2), which relates to a contact lens material based on a polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of (a) the (B) immersing the material surface under normal pressure or reduced pressure; (b) immersing the material in a mixed monomer solution containing acrylamide and N, N'-methylenebisacrylamide as the main components, (c) ammonium nitrate ( IV) and a process for producing a contact lens comprising (d) graft polymerizing the mixed monomer on the surface of the material under normal pressure, wherein the amount of the diammonium cerium nitrate (IV) added is 1 g of mixed monomer. More than 0.01g per At the same time, it characterized in that not more than 1g. In addition, the method for producing a contact lens of the present invention is at least alkyl methacrylate, alkyl fumarate, fluoroalkyl fumarate and siloxanyl fumarate

Wherein A and A 'are selected from the group consisting of an alkyl group of C ₁ to C ₅ , or a D group, and D is a structural formula

It is group which has. Wherein X and Y are selected from the group consisting of C ₁ to C ₅ alkyl groups and Z groups, and Z is a structural formula

And B represents a C ₁ to C ₅ alkyl group.

k, l, m, n represents o or a positive integer) and a contact lens material based on a polymer of an ester compound of methacrylic acid and fumaric acid, which is a copolymer of (a) the material surface at atmospheric pressure, Or (b) immersing the material in a mixed monomer solution containing acrylamide and N, N'-methylenebisacrylamide as main components, and (c) adding ammonium diammonium nitrate (IV). And (d) graft polymerizing the mixed monomer on the surface of the material under normal pressure, wherein the amount of the addition of diammonium cerium (IV) is 0.01 g or more per 1 g of mixed monomer. At the same time, characterized in that less than 1g. Moreover, the manufacturing method of the contact lens of this invention is siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula.

Wherein R = CH ₃ or H; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z;

Alkyl, cyclohexyl or phenyl of R ¹ = C ₁ -C ₆ ; R ² = C ₁ -C ₆ alkyl, cyclohexyl or phenyl; Alkyl, cyclohexyl or phenyl of R ³ = C ₁ -C ₆ ; Alkyl, cyclohexyl or phenyl of R ⁴ = C ₁ -C ₆ ; m = 1 to 3; n = 1 to 5; p = 1 to 3), a fluoroalkyl substituent of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula

(Wherein, R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group), polyfluoric acid of acrylic acid or methacrylic acid represented by the following general formula Roalkyloxyoxysubstituted ester

(Wherein R = CH ₃ or H; a fluoroalkyl group of R _f = C _{1 to} C ₄ ; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3), represented by the following general formula Acryl (methacryl) oxy alkylsilanol

(Wherein R = CH ₃ or H; X, Y = C ₁ -C ₆ alkyl; phenyl or Z;

m = 1 to 3; n = 1 to 5; p = 1 to 3; Alkyl, cyclohexyl or phenyl of R ¹ = C ₁ -C ₆ ; Alkyl, cyclohexyl or phenyl of R ² ═C _{1 to} C ₆ ; R ³ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl), polyacryl (methacryl) oxyalkylpolysiloxane represented by the following general formula

Wherein R = CH ₃ or H; m = 0-3; n = 1-5; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, Cyclohexyl, phenyl or Z;

P = 1 to 3; Alkyl, cyclohexyl or phenyl of R ¹ = C ₁ -C ₆ ; Alkyl, cyclohexyl or phenyl of R ² ═C _{1 to} C ₆ ; Alkyl, cyclohexyl or phenyl of R ³ = C ₁ -C ₆ ), a fluorine-containing siloxanyl methacrylate represented by the following general formula:

(Wherein, 1 = 1 to 3; m = 1 to 10; n = 1 to 3; k = 1 to 3), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula

Wherein R _f is a C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C _{1 to} C ₃₀ fluorine atoms or Alkyl group which may contain an oxygen atom), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula:

Wherein R _f is a C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C _{1 to} C ₃₀ fluorine atoms or Alkyl group which may contain an oxygen atom), a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula:

(Wherein R ¹ , R ² = CH ₃ or H; 1 = 2 to 4; p, q = 1 or 2; m and n are each an integer whose sum is in the range of 1 to 20), and Fluorine-containing cyclic olefins represented by general formula

(Wherein A = H, F or alkyl group; B = H, F or alkyl group; C = H, F or alkyl group; D = F or C _{1 to} C _{30 which} may contain an oxygen atom bonded to at least one fluorine atom) A fluoroalkyl group, n = 0, 1 or 2), and a contact lens material made from a polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of (a) the material (B) immersing the material in a mixed monomer solution containing acrylamide and N, N'-methylenebisacrylamide as main components, (c) ferrous ammonium sulfate A method for producing a contact lens comprising a step of adding a (mol salt) and (d) graft polymerizing the mixed monomer on the surface of the material under reduced pressure, wherein the addition amount of ferrous ammonium sulfate (mol salt) is mixed. 0.02 g per 1 g The same time is characterized in that not more than 0.06g. In addition, the method for producing a contact lens of the present invention is at least alkyl methacrylate, alkyl fumarate, fluoroalkyl fumarate and siloxanyl fumarate

(Wherein A and A ′ are selected from the group consisting of C ₁ to C ₆ alkyl groups or D groups and D is a structural formula

It is group which has. Wherein X and Y are selected from the group consisting of C ₁ to C ₅ alkyl groups and Z groups, and Z is a structural formula

And B represents a C ₁ to C ₅ alkyl group. k, l, m, n represent o or a positive integer), and a contact lens material made from a polymer of an ester compound of methacrylic acid and fumaric acid, which is a copolymer of (a) the surface of the material (B) immersing the material in a mixed monomer solution containing acrylamide and N, N'-methylenebisacrylamide as main components, (c) ferrous ammonium sulfate ( Molten salt) and (d) a method for producing a contact lens comprising graft-polymerizing the mixed monomer on the surface of the material under reduced pressure, wherein the addition amount of ferrous ammonium sulfate (molten salt) is 1 g of mixed monomer. It is characterized in that more than 0.02g per sugar and less than 0.06g. Moreover, the manufacturing method of the contact lens of this invention is siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula.

Wherein R = CH ₃ or H; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z;

R ¹ = C ₁ -C ₆ alkyl, cyclohexyl, phenyl; R ² = C ₁ -C ₆ alkyl, cyclohexyl, phenyl; Alkyl, cyclohexyl, phenyl of R ³ = C ₁ -C ₆ ; R ⁴ = C ₁ -C ₆ alkyl, cyclohexyl, phenyl; m = 1 to 3; n = 1 to 5; p = 1 to 3), a fluoroalkyl substituent of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula

(Wherein, R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group), polyfluoric acid of acrylic acid or methacrylic acid represented by the following general formula Roalkylsiloxy substituted ester

(Wherein, R = CH ₃ or H; R _f = C _{1 to} C ₄ fluoroalkyl group; l = 1 to 4; m = 0, 1 or 2; n = 1 to 3), represented by the following general formula Acryl (methacryl) oxyalkyl silanol

Wherein R = CH ₃ or H; X, Y = C ₁ -C ₆ alkyl; phenyl or Z;

m = 1 to 3; n = 1 to 5; p = 1 to 3; Alkyl, cyclohexyl or phenyl of R ¹ = C ₁ -C ₆ ; Alkyl, cyclohexyl or phenyl of R ² ═C _{1 to} C ₆ ; R ³ = C ₁ -C ₆ alkyl, cyclohexyl or phenyl), polyacryl (methacryl) oxyalkylpolysiloxane represented by the following general formula

Wherein R = CH ₃ or H; m = 0-3; n = 1-5; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, cyclo Hexyl, phenyl or Z;

P = 1 to 3; Alkyl, cyclohexyl or phenyl of R ¹ = C ₁ -C ₆ ; Alkyl, cyclohexyl or phenyl of R ² ═C _{1 to} C ₆ ; Alkyl, cyclohexyl or phenyl of R ³ = C ₁ -C ₆ ), a fluorine-containing siloxanyl methacrylate represented by the following general formula:

(Wherein, l = 1 to 3; m = 1 to 10; n = 1 to 3; k = 1 to 3), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula

R _f = a C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C _{1 to} C ₃₀ fluorine atom or an alkyl group which may contain an oxygen atom), a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula

Wherein R _f = C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom bonded to at least three fluorine atoms; R ¹ = CH ₃ or H; R ² = C _{1 to} C ₃₀ fluorine atoms or Alkyl group which may contain an oxygen atom), a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula:

(Wherein R ¹ , R ² = CH ₃ or H; l = 2-4; p, q = 1 or 2; m and n are each an integer whose sum is in the range of 1-20), and Fluorine-containing cyclic olefins represented by general formula

(Wherein A = H, F or alkyl group; B = H, F or alkyl group; C = H, F or alkyl group; D = F or C _{1 to} C _{30 which} may contain an oxygen atom bonded to at least one fluorine atom) A fluoroalkyl group of n = 0, 1 or 2), and a contact lens material based on a polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of (a) its surface (B) a method of manufacturing a contact lens comprising the step of discharging at atmospheric pressure or under reduced pressure, and (b) graft polymerizing a hydrophilic monomer on the lens surface. It is characterized by applying. In addition, the manufacturing method of the contact lens of the present invention is characterized in that the output of the ultrasonic wave is 10 watts or more and the application time is 10 seconds or more and 10 minutes or less.

Although the above is the indication of this invention, the effect shown below is acquired by these methods of this invention.

The addition of a reducing agent (mol salt, cerium salt, etc.) to the polymerization system can cause a decrease in reaction temperature and reduce thermal load on the material by the catalysis. However, in the method of the present invention of the addition of a reducing agent, in particular, in a system using a molar salt, high precision control regarding the uniformity and dissolved oxygen amount of the concentration of the components in the system (including the concentration of the reducing agent), as compared with the conventional polymerization reaction by heating. Is required. In other words, if the balance of all these amounts is not appropriate, the graft chain may be excessively long to increase the viscosity of the system content (gelation) or, conversely, the polymerization reaction may not occur. In the former case, this is a case where the amount of dissolved oxygen in the system is extremely small or the monomer concentration is higher than the optimum condition, but the graft layer on the material surface becomes cloudy, resulting in a decrease in the transmittance in the visible region. The latter case (which corresponds to the case of high dissolved oxygen) means that the surface material cannot be formed. As shown in the present invention, when the dissolved oxygen is removed, the method of maintaining the system in a vacuum while applying ultrasonic waves, the uniformity and dissolved oxygen content of the concentration of the components (including the concentration of the reducing agent) in the system by the following action It is possible to control with high precision.

When ultrasonic waves are applied to the polymerization system, the wave energy is first converted into vibration energy of molecules in the system. The energy applied via this vibrational energy is converted into thermal energy, resulting in local temperature rise. At this time, the boiling point is uniformly determined by the degree of vacuum (pressure) in the system. If the temperature in the local part is higher than the boiling point, deoxygenation by boiling occurs there. Since the probability of locally occurring deoxygenation is proportional to the amount of dissolved oxygen at that moment, dissolved oxygen decreases exponentially and nonlinearly with respect to the ultrasonic application time. The time constant of the exponent part is determined by the size of the system, the output of the ultrasonic application device, and the like, which is obtained experimentally from the time change of the dissolved oxygen amount. On the other hand, the concentration of components in the system increases in proportion to time while being kept in a vacuum. This is because the solvent evaporates at a constant rate. This concentration rate is determined by the size of the system and the capacity of the exhaust pump used in the vacuum system.

By the above action, the dissolved oxygen amount and the component concentration in the system can be precisely controlled only by time management by optimizing the device parameter.

In addition, the dissolved oxygen removal by applying the ultrasonic wave has the advantage that it can escape from the complicated operation even when applied to the conventional graft polymerization process by heating. In the present invention, since the cerium salt as a reducing agent has a function of promoting the graft polymerization reaction even in the presence of dissolved oxygen, the object can be achieved by a very simple process.

As to the properties of the contact lens material, the fumarate material and the fluorine-containing material used in the present invention are methacrylate (silicon and fluorine-free) materials and siloxanyl methacrylate (fluorine-free). Since the peroxide generation efficiency on the material surface by the discharge treatment is higher than that of the system material, a high density polymerization start point can be introduced. In particular, fluorine-containing materials have the highest peroxide generation efficiency. The higher the density of the polymerization start point, the shorter the reaction time required for the surface graft polymerization treatment, and the following advantages are obtained for the fumarate-based material and the fluorine-containing material used in the present invention.

In the present invention, it is possible to lower the polymerization temperature by the addition of a reducing agent, but since the discoloration reaction occurs when the reducing agent is oxidized in the polymerization reaction (for example, in the case of molar salts, it is changed from transparent to yellow), which is required for the polymerization reaction. If the time is long, the original contact lens material also discolors. However, in the fumarate-based and fluorine-containing materials used in the present invention, since the polymerization reaction time is short for the reasons described above, discoloration of the material hardly occurs. In the case of the fluorine-containing material having the shortest reaction time, all discoloration by surface graft polymerization has no advantage.

[Best form for carrying out the invention]

In order to describe this invention in detail, it demonstrates in the following Example.

Example 1

5g of N, N'-methylenebisacrylamide, 48wt% of acryloxypropyl-tris (trimethylsiloxy) silane, 19wt% of 2,2,2-trifluoroethyl methacrylate, 1,3-bis (γ) Methacryloxypropyl) -1,1,3,3, -tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt% , A contact lens consisting of a copolymer of 1% by weight of methyl methacrylate, 7% by weight of ethylene glycol dimethacrylate, and 2,2'-azobis (2,4-isobutyronitrile) (0.25% by weight as a polymerization initiator) The material was prepared in the normal contact lens type.

A lens material was placed in a discharge device (6 cm between electrodes, 270 volts between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. The discharged lens material was exposed to air, placed in a test tube having a diameter of 18 mm, and 3 ml of the aqueous monomer solution was added. Then, 0.1 g of cerium diammonium nitrate (IV) was added thereto and dissolved by stirring. After the test tube was closed with a silicone stopper, surface graft reaction was performed for 60 minutes in a thermostat maintained at 50 ° C. After completion of the reaction, the lens was removed from the test tube and immersed in pure water at 50 ° C. for 20 hours to remove homopolymer or the like attached to the surface. It was determined by evaluating the wettability of the lens surface whether or not polyacrylamide (including N, N'-methylenebisacrylamide as a crosslinking agent) as a hydrophilic polymer was grafted on the contact lens surface obtained by the above operation. The contact angle of pure water was measured using a static contact angle meter (Kyogawa Kaimengaku, CA-D type), and the contact angle was 18 degrees. This value was the same as the contact angle of the contact lens surface obtained by a conventional manufacturing method, i.e., a method in which dissolved oxygen was removed under vacuum, followed by heating to about 80 ° C. to perform surface graft treatment. On the other hand, the contact angle was 90 degrees when the obtuse contact angle of the lens material without surface graft was measured for comparison.

As described above, according to the present invention, the addition of diammonium cerium nitrate (IV) as a reducing agent allowed the decomposition of peroxide introduced into the surface of the contact lens material by a discharge treatment at a low temperature of 50 ° C. to generate radicals which started the polymerization. In addition, the method of the present invention to which the diammonium nitrate (IV) is added makes it possible to perform the hydrophilization treatment by graft on the contact lens surface without removing the dissolved oxygen.

Example 2

5 g of N, N'-methylenebisacrylamide and 35 g of acrylamide as crosslinking agents were dissolved in distilled water to make 100 ml to prepare a monomer aqueous solution.

The graft polymerization treatment was performed as follows. γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 8 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 7 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 10 wt% of methacrylic acid, 1 wt% of methyl methacrylate, ethylene glycol Ten contact lens materials were prepared in the form of a conventional contact lens type consisting of a copolymer of 7 wt% dimethacrylate and 0.25 wt% 2,2'-azobis (2,4-isobutyronitrile) (as a polymerization initiator). Ready. A space made of a spacer having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 hertz, and the lens material was provided one by one, and discharge treatment was performed. Further, discharge treatment was performed on both sides for 40 seconds on one side. Next, the lens materials subjected to these discharge treatments were placed one by one in a test tube having a diameter of 18 mm, and each of 3 ml of the monomer aqueous solution was added, and then a predetermined amount (Table 1) of diammonium nitrate (IV) was added, followed by stirring sufficiently. Accordingly it was dissolved. After the test tube was closed with a silicone stopper, surface graft reaction was performed for 60 minutes in a thermostat maintained at 50 ° C. After completion of the reaction, the lens was taken out of the test tube and immersed in 50 ° C blunt water for 20 hours to remove homopolymer or the like attached to the surface. The polyacrylamide (containing N, N'-methylenebisacrylamide as a crosslinking agent) was grafted on the contact lens surface obtained by the above operation, and it was determined using the ninhydrin method. Polyacrylamide (including N, N'-methylenebisacrylamide as crosslinking agent) grafted on the surface is hydrolyzed with hydrochloric acid, and after neutralization, ninhydrin is added. The polyacrylamide (containing N, N'-methylenebisacrylamide as a crosslinking agent) is calculated | required at the time of coloration at that time.

Quantitative determination of polyacrylamide (including N, N'-methylenebisacrylamide as crosslinking agent) grafted on the lens surface by ninhydrin reaction to ten lenses subjected to graft polymerization (Samples 1 to 10) and The observation by the optical microscope of the surface state was performed. The results are shown in Table 1. In Table 1, when the amounts of samples 1 and 2, i.e., diammonium nitrate (IV), are less than 0.01 g per 1 g of monomers (N, N'-methylenebisacrylamide and acrylamide), polyacrylamide ( It can be seen that the N, N'-methylenebisacrylamide as a crosslinking agent) is not grafted. On the other hand, when the amount of diammonium cerium (IV) added is more than 1g per 1g of monomers (N, N'-methylenebisacrylamide and acrylamide) (Samples 9 and 10), it becomes cloudy on the lens surface by excessive graft. It was found to be inadequate as a treatment condition. Good surface graft treatment was possible for samples 3 to 8, i.e., 0.01 g or more and 1 g or less per 1 g of monomer (N, N'-methylenebisacrylamide and acrylamide) of the added amount of diammonium cerium (IV).

Example 3

5 g of N, N'-methylenebisacrylamide and 35 g of acrylamide which were Examples were dissolved in distilled water to make 100 ml, and the monomer prepared the aqueous solution. Graft polymerization was carried out as follows. Contact lens materials made of a copolymer of alkyl fumarate, siloxanyl fumarate, pullouroalkyl fumarate, and methyl methacrylate were prepared in a conventional contact lens type. The lens material was installed in a discharge device (6 cm between electrodes, 270 volts frequency between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. After the discharged lens material was exposed to air, it was placed in a test tube having a diameter of 18 mm, and the monomer was added to 3 ml of an aqueous solution, and 0.1 g of diammonium cerium (IV) nitrate was added thereto to dissolve it under sufficient stirring. After the test tube was sealed with a silicone stopper, surface graft reaction was performed for 60 minutes in a thermostat maintained at 50 ° C. After completion of the reaction, the lens was taken out of the test tube, and this was immersed in pure water at 50 ° C. for 20 hours to remove homopolymer or the like attached to the surface. It was determined by measuring the wettability of the lens surface whether or not polyacrylamide (including N, N'-methylenebisacrylamide as a crosslinking agent) as a hydrophilic polymer was grafted on the contact lens surface obtained by the above operation. The contact angle of pure water was measured using the static contact angle measuring device (type Kyowa Kaimengaku CA-D type), and the contact angle was 18 degrees. This value was the same as the contact angle of the contact lens surface obtained by the conventional manufacturing method, i.e., by removing the dissolved oxygen under vacuum and then heating to approximately 80 占 폚 to perform surface graft treatment. On the other hand, the contact angle of pure water of the lens material without surface graft was measured for comparison, and the contact angle was 90 degrees.

According to the present invention, by adding diammonium cerium nitrate (IV) as the reducing agent, the peroxide introduced into the contact lens material surface by the discharge treatment was decomposed at a low temperature of 50 deg. In addition, it has been found that the method of the present invention in which diammonium nitrate (IV) is added can be hydrophilized by graft onto a contact lens surface without removing dissolved oxygen.

Example 4

5 g of N, N'-methylenebisacrylamide and 35 g of acrylamide as additives were dissolved in distilled water to make 100 ml, and a monomer prepared an aqueous solution.

Graft polymerization was carried out as follows. Ten contact lens materials made of a copolymer of alkyl fumarate, siloxanyl fumarate, fluoroalkyl fumarate, and methyl methacrylate were prepared in a normal contact lens type.

A space made of spacers having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having a 3.5 cm electrode distance, 15 kilovolts between electrodes, and a frequency of 60 hertz. . Discharge treatment was carried out for 40 seconds on both sides on one side at all times. Next, the lens materials subjected to these discharge treatments were placed one by one in a test tube having a diameter of 18 mm, and 3 ml of the aqueous monomer solution was added. Then, a predetermined amount (Table 1) of diammonium nitrate (IV) was added and sufficiently stirred. Dissolved. After the test tube was covered with a silicon lid, a surface graft reaction was conducted for 60 minutes in a thermostat stored at 50 ° C. After completion of the reaction, the lens was taken out of the test tube, and this was immersed in pure water at 50 ° C. for 20 hours to remove homopolymer or the like adhering to the surface. Whether polyacrylamide (including N, N'-methylenebisacrylamide as a crosslinking agent) was grafted on the contact lens surface obtained by the above operation was determined using the ninhydrin method. Polyacrylamide (containing N, N'-methylenebisacrylamide as a crosslinking agent) grafted on the surface is hydrolyzed with hydrochloric acid, and after neutralization, nihydrin is added. The polyacrylamide (containing N, N'-methylenebisacrylamide as a crosslinking agent) can be obtained by the color shown at that time.

Quantitative determination of polyacrylamide (including N, N'-methylenebisacrylamide as a crosslinking agent) grafted on the lens surface according to the ninhydrin reaction for ten lenses subjected to graft polymerization (Samples 1 to 10) and Observation was carried out according to the optical microscope of the surface state. The results are shown in Table 2. In Table 2, when the amount of the samples 1 and 2, i.e., the diammonium nitrate (IV), is less than 0.01 g per 1 g of the monomers (N, N'-methylenebisacrylamide and acrylamide), the polyacrylamide ( It can be seen that the N, N'-methylenebisacrylamide as a crosslinking agent) is not grafted. On the other hand, if the amount of diammonium cerium (IV) added is more than 1g per 1g of monomers (N, N'-methylenebisacrylamide and acrylamide) (Samples 9 and 10), it will become cloudy on the lens surface by excessive graft. It was found to be inadequate as a treatment condition. When the addition amount of 8 in sample 3, ie, diammonium cerium (IV), was 0.01 g or more and 1 g or less per 1 g of monomers (N, N'-methylenebisacrylamide and acrylamide), good surface graft treatment was possible.

Example 5

Graft polymerization was performed as follows. γ-methacryloxypropyltris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 8 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 7 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 10 wt% of methacrylic acid, 1 wt% of methyl methacrylate, ethylene glycol di A contact lens material was prepared, consisting of copolymerization of 7 wt% of methacrylate and 0.5 wt% of 2,2'-azobis (2,4-isobutyronitrile) (as a polymerization initiator). The lens material was installed in a discharge device (6 cm between electrodes, 270 volts between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. The discharged lens material was exposed to air and placed in a test tube.

7 g of acrylamide and 1 g of N, N'-methylenebisacrylamide were dissolved in 12 g of pure water and made into a monomer aqueous solution. The monomer aqueous solution was separated into a 2.5 ml test tube, 0.0361 g of ferrous ammonium sulfate (molten salt) was added, stirred, and dissolved. The discharged lens was put there, and after nitrogen gas substitution, the tube was decompressed and sealed. The test tube was placed in a 45 degreeC thermostat for 15 minutes, and the monomer was graft-polymerized on the lens surface. In this manner, six samples (Samples 1 to 6) which were subjected to the same operation were produced.

Moreover, six samples using the monomer aqueous solution which did not add ferrous ammonium sulfate (molar salt) were prepared compared with the conventional method (Comparative Examples 1-6). At this time, the polymerization temperature was set at 80 ° C. and the polymerization time of 15 minutes, and the discharge conditions and the like were performed in the same manner as in the ferrous ammonium sulfate (molten salt) addition sample (samples 0.1 to 6). Subsequently, the curvature of the lens after the graft treatment was measured, and the amount of change from the curvature of the lens recorded beforehand was determined. Moreover, in order to evaluate the wettability of the lens surface, the contact angle was measured by the liquid crystal method. These results are shown in Table 3.

As can be seen from Table 3, the change in curvature of the lens was 5% or more in the conventional thermal polymerization method. On the other hand, any sample according to the method of the present invention subjected to low temperature treatment by adding ferrous ammonium sulfate (mol salt) was less than 1%. In addition, when the lens surface wettability was evaluated by the contact angle, it was found that there was no deterioration compared with the conventional thermal polymerization method, and the method of the present invention was able to perform a good surface graft treatment.

Example 6

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48wt%, 1,1-dihydroper-fluorobutylmethacrylate 19wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 7 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 8 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 11 wt% of methacrylic acid, 7 wt% of ethylene glycol dimethacrylate, A contact lens material consisting of a 0.25 wt% copolymer of 2,2'-azobis (2,4-isobutyronitrile) was prepared.

The lens material was placed in a space made of a spacer having a thickness of 1.5 mm between electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 hertz, and discharge treatment was performed. Further, discharge treatment was performed on both sides for 40 seconds on one side.

35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide were dissolved in 40 g of pure water to obtain a monomer aqueous solution. In addition, 1.568 g of ferrous ammonium sulfate hexahydrate (molar salt) was dissolved in 10 g of pure water, and this was made into a molar salt solution. 2.4 mL of monomer aqueous solutions, 0.3 mL of aqueous molar salts, and 0.3 mL of pure water were divided and stirred in a test tube. The discharged lens was put there, and after nitrogen gas replacement, the pressure reduction sealing pipe was carried out. The test tube was placed in a 35 ° C. thermostat for 5 to 60 minutes and graft polymerized on the lens surface. In this manner, six samples (Samples No. 1 to 6) which performed the same operation were prepared.

For comparison with the conventional method, six samples were prepared using an aqueous monomer solution without adding ferrous ammonium sulfate (mol salt) (Comparative Examples 1 to 6). The polymerization temperature at this time was set to 80 degreeC, and the polymerization time was 20 minutes, and discharge conditions etc. were performed similarly to the sample (sample No. 1-6) with the addition of ferrous ammonium sulfate (mol salt).

Subsequently, the curvature of the lens after the graft treatment was measured, and the amount of change from the curvature of the lens recorded beforehand was determined. Moreover, the contact angle for evaluating the wettability of the lens surface was measured by the liquid crystal method. These results are shown in Table 4.

As can be seen from Table 4, the change in the curvature of the lens was 5% or more in the case of the conventional thermal polymerization method. On the other hand, any sample according to the method of the present invention subjected to low temperature treatment by adding ferrous ammonium sulfate (mol salt) was stopped at 1% or less. In addition, when the wettability of the lens surface was evaluated by the contact angle, it was found that the method of the present invention can provide a good surface graft treatment without any inferiority to that of the conventional thermal polymerization method.

In the examples of the present invention, acrylamide is used as a hydrophilic monomer and N, N'-methylenebisacrylamide is used as an example of a crosslinking agent. However, the present invention is not limited thereto and 2-hydroxyethyl methacrylate, which is another hydrophilic monomer, It was confirmed that the same effect can be obtained even when using polyvinyl alcohol, N-vinylpyrrolidone, polyethylene oxide, dimethyl acrylamide, or the like. Moreover, as a crosslinking agent, acrylate type, such as glycerol diacrylate and a trimethol propane triacrylate, and ethylene glycol dimethacrylate, dimethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1, 3- butanediol di Similar effects were obtained even by using methacrylates such as methacrylate.

Example 7

Graft polymerization was performed as follows. γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 8 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 7 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 10 wt% of methacrylic acid, 1 wt% of methyl methacrylate, ethylene glycol A contact lens material was prepared consisting of a copolymer of 7 wt% dimethacrylate and 2,2'-azobis (2,4-isobutyronitrile) (0.25 wt% as a polymerization initiator). The lens material was installed in the discharge treatment (6 cm between electrodes, 270 volts between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. The discharged lens material was exposed in the air.

A monomer aqueous solution was prepared as follows. First, 35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide were weighed with a balance, dissolved in 40 g of water, and this was used as A solution. Ferrous ammonium sulfate hexahydrate was weighed with 1.568 g (0.04 mol) scale and dissolved in 10 g of water to obtain this solution as B solution.

2.4 mL of A solution and 0.15 mL of B solution were divided into test tubes, and 0.45 mL of water was added thereto to prepare a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, and about 0.025 g of ferrous ammonium sulfate (molten salt). That is, it is 0.02 wt% of the addition amount of a mole salt with respect to 1 wt% of monomer amounts (the sum total of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. The discharged lens was placed in a monomer aqueous solution in a test tube, and nitrogen gas replacement was carried out to reduce the pressure to seal the tube. The test tube was placed in a 35 degreeC thermostat for 20 minutes, and the monomer was graft-polymerized on the lens surface. Thus, two samples (sample Nos. 1 and 2) were prepared under these conditions.

2.4 mL of A solution and 0.3 mL of B solution were divided into test tubes, and 0.3 mL of water was added thereto to obtain a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, about 1.8 g of water, and about 0.05 g of ferrous ammonium sulfate (molten salt). That is, it is 0.04 wt% of the addition amount of a mole salt with respect to 1 wt% of monomer amounts (total of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. A discharged lens was placed in a monomer aqueous solution in a test tube, and the tube was sealed under reduced pressure after nitrogen gas replacement. The test tube was placed in a 35 degreeC thermostat for 20 minutes, and the monomer was graft-polymerized on the lens surface. Thus, two samples (sample Nos. 3 and 4) were prepared under these conditions. 2.4 mL of A solution and 0.45 mL of B solution were divided into test tubes, and 0.15 mL of water was added thereto to prepare a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, and about 0.075 g of ferrous ammonium sulfate (molten salt). That is, molar salt addition amount is 0.06 wt% with respect to 1 wt% of monomer amounts (total amount of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. The discharged lens was placed in a monomer aqueous solution in a test tube, and nitrogen gas was substituted, and the tube was sealed under reduced pressure. The test tube was placed in a 35 degreeC thermostat for 20 minutes, and the monomer was graft-polymerized on the lens surface. Thus, two samples (sample Nos. 5 and 6) were prepared under these conditions.

For comparison, four polymerization samples were prepared in a polymerization solution in which the mixture of B liquid and water was changed in addition to the above (Comparative Examples 1 to 4). The discharge conditions and polymerization temperature at this time performed the same operations as the above samples (sample Nos. 1 to 6).

Subsequently, the turbidity of the lens surface after the graft treatment was observed by an optical microscope. In order to confirm the completion of the graft polymerization treatment, the wettability of the contact lens surface was evaluated by the contact angle according to the liquid crystal method. These results are shown in Table 5.

As Table 5 shows, the sample No. 1-6 did not generate surface turbidity at all. In addition, the contact angle is less than 50 °, indicating that the graft polymerization proceeded without any problems.

On the other hand, in the case where the addition amount of the molar salt was small (Comparative Example 2), the contact angle was sufficiently lowered, and the graft polymerization treatment was completed. However, surface turbidity occurs and is not suitable for surface treatment. In addition, a large amount of molar salt addition (Comparative Examples 3 and 4) had a high contact angle, indicating that graft polymerization did not proceed. In addition, the polymerization does not proceed without mentioning that the molten salt is not added as in Comparative Example 1.

In the examples of the present invention, acrylamide is used as a hydrophilic monomer and N, N'-methylenebisacrylamide is used as an example of a crosslinking agent. However, the present invention is not limited thereto, and 2-hydroxyethyl methacrylate, which is another hydrophilic monomer, It was confirmed that the same result can be obtained by using polyvinyl alcohol, N-vinylpyrrolidone, polyethylene oxide, dimethyl acrylamide and the like. Moreover, as a crosslinking agent, acrylate type, such as glycerol diacrylate and a trimethol propane triacrylate, and ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1, 3- butanediol di Similar effects were obtained even by using methacrylates such as methacrylate.

Example 8

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydroperfluorobutyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 7wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 8wt%, methacrylic acid 11wt%, ethylene glycol dimethacrylate 7wt%, 2 A contact lens material consisting of a 0.25 wt% copolymer of 2'-azobis (2,4-isobutyronitrile) (as a single polymerization initiator) was prepared. A space made of a spacer having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 Hz, and the lens material was placed therein and discharged. Discharge treatment was carried out on both sides for 40 seconds on each side. The monomer aqueous solution was adjusted as follows. First, 35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide were measured with a balance, and dissolved in 40 g of water to obtain this as A solution. In addition, ferrous ammonium sulfate hexahydrate was measured by 1.568 g (0.04 mol) balance, and it melt | dissolved in 10 g of water, and this was made into B liquid. 2.4 mL of A solution and 0.15 mL of B solution were divided into test tubes, and 0.45 mL of water was added thereto to obtain a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, and about 0.025 g of ferrous ammonium sulfate (molten salt). That is, molar salt addition amount is 0.02 wt% with respect to 1 wt% of monomer amounts (total amount of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. The discharged lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was sealed under reduced pressure. The test tube was placed in a 35 degreeC thermostat for 10 minutes, and the monomer was graft-polymerized on the lens surface. Thus, two samples (sample Nos. 1 and 2) were prepared under these conditions.

2.4 mL of A solution and 0.3 mL of B solution were divided into test tubes, and 0.3 mL of water was added thereto to obtain a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, about 1.8 g of water, and about 0.05 g of ferrous ammonium sulfate (molten salt). That is, it is 0.04 wt% of the addition amount of a mole salt with respect to 1 wt% of monomer amounts (total of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. A discharged lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was sealed under reduced pressure. The test tube was placed in a 35 degreeC thermostat for 10 minutes, and the monomer was graft-polymerized on the lens surface. Thus, two samples (sample Nos. 3 and 4) were prepared under these conditions. 2.4 mL of A solution and 0.45 mL of B solution were divided into test tubes, and 0.15 mL of water was added thereto to obtain a polymerization solution. The composition of the polymerization aqueous solution at this time is about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide, and about 0.075 g of ferrous ammonium sulfate (molten salt). That is, it is 0.06 wt% of the addition amount of a mole salt with respect to 1 wt% of monomer amounts (the sum total of acrylamide and N, N'-methylenebisacrylamide) of a polymerization system. The discharged lens was placed in a monomer aqueous solution in a test tube, and nitrogen gas was substituted, and the tube was sealed under reduced pressure. The test tube was placed in a constant temperature bath at 35 ° C. for about 10 minutes and graft polymerized on the lens surface. Thus, two samples (sample Nos. 5 and 6) were prepared under these conditions.

For comparison, four graft polymerization samples were prepared in a polymerization solution in which the mixture of B liquid and water was changed in addition to the above (Comparative Examples 1 to 4). The discharge conditions and polymerization temperature at this time were carried out in exactly the same manner as the samples (Samples No. 1 to 6).

Then, the optical microscope was observed for the turbidity of the lens surface after a graft process. In order to confirm the completion of the graft polymerization treatment, the wettability of the contact lens surface was evaluated by the contact angle according to the liquid crystal method. These results are shown in Table 6.

As Table 6 shows, sample No. 1-6 did not generate surface turbidity at all. In addition, the contact angle is less than 50 °, indicating that the graft polymerization proceeded without any problems.

On the other hand, in the case where the addition amount of the molar salt was small (Comparative Example 2), the contact angle was sufficiently lowered, and the graft polymerization treatment was completed. However, surface turbidity occurs and is not suitable for surface treatment. In addition, a large amount of molar salt addition (Comparative Examples 3 and 4) had a high contact angle, indicating that graft polymerization did not proceed. In addition, the polymerization does not proceed without mentioning that the molten salt is not added as in Comparative Example 1.

In the examples of the present invention, acrylamide is used as a hydrophilic monomer and N, N'-methylenebisacrylamide is used as an example of a crosslinking agent. However, the present invention is not limited thereto, and 2-hydroxyethyl methacrylate, which is another hydrophilic monomer, It was confirmed that the same result can be obtained by using polyvinyl alcohol, N-vinylpyrrolidone, polyethylene oxide, dimethyl acrylamide and the like. Moreover, as a crosslinking agent, acrylate type, such as glycerol diacrylate and a trimethol propane triacrylate, and ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1, 3- butanediol di Similar effects were obtained even by using methacrylates such as methacrylate.

Example 9

Acrylamide was measured with a 10-g scale, and this was dissolved in distilled water to make 100 mL, to prepare a monomer aqueous solution.

Graft polymerization was performed as follows. γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 8 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 7 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 10 wt% of methacrylic acid, 1 wt% of methyl methacrylate, ethylene glycol A contact lens material was prepared, consisting of a copolymer of 7 wt% dimethacrylate and 2,2'-azobis (2,4-isobutyronitrile) (0.25 wt% as a polymerization initiator).

The lens material was installed in a discharge device (6 cm between electrodes, 270 volts between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. The discharged lens material was exposed to air, placed in a test tube, and the acrylamide monomer solution was added thereto, followed by addition of a molar salt to a vacuum system. Subsequently, the test tube was immersed in water filled in an ultrasonic vibrator. In this state, the inside of the tube was vacuumed for 1 minute with a rotary pump, and ultrasonic waves were applied at a predetermined output. After 1 minute elapsed, the test tube was vacuum sealed, and this was immersed in a constant temperature bath at 40 ° C. for 15 minutes to test graft polymerization onto the lens material surface. In addition, the output of the applied ultrasonic waves is shown in Table 7, and whether or not the surface graft polymerization under each application condition is also shown in Table 7.

As can be seen from Table 7, surface graft polymerization was possible when the applied ultrasonic power was more than 10 watts. On the other hand, when the applied output was less than 10 watts, dissolved oxygen in the aqueous monomer solution could not be sufficiently degassed and surface graft polymerization was impossible.

Apart from the above-mentioned examples, the conventional method of using ultrasonic waves during polymerization, i.e. removal of dissolved oxygen, removes the vessel containing the monomer solution into a vacuum, pulls it from the outside, and then replaces the vessel with nitrogen gas. A series of five re-vacuum processes were repeated. Then, regardless of the same operation for 10 lens materials, 3 sheets are not surface-grafted and 7 sheets are excessively subjected to surface graft polymerization, and the conventional method causes control of component concentration and dissolved oxygen in the system. I could not get good quality without it.

Example 10

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydroperfluorobutyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 7wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 8wt%, methacrylic acid 11wt%, ethylene glycol dimethacrylate 7wt%, 2 A contact lens material consisting of a 0.25 wt% copolymer of, 2'-azobis (2,4-isobutyronitrile) was prepared.

A space made of a spacer having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 Hz, and the lens material was placed therein and discharged. Discharge treatment was carried out on both sides for 40 seconds on each side. Next, the discharged lens material was placed in a test tube, and then the same treatment as in Example 9 was performed. The results are shown in Table 8.

When the output of the ultrasonic wave applied like Example 9 was 10 Watts or more, surface graft superposition | polymerization was possible. On the other hand, if the applied output was less than 10 watts, dissolved oxygen in the monomer solution could not be sufficiently degassed, and surface graft polymerization did not occur.

Apart from the above-mentioned example, the conventional method of not using ultrasonic waves during polymerization, that is, removal of dissolved oxygen, removes the container containing the monomer solution into a vacuum, pulls it from the outside, and then replaces the inside of the container with nitrogen gas. In this case, a series of five steps of re-vacuation was performed. Then, regardless of the same operation for 10 lens materials, 4 sheets are not surface-grafted and 6 sheets are excessively subjected to surface graft polymerization, so that the conventional method does not control the component concentration and dissolved oxygen amount of the system. I couldn't get quality goods without it.

Example 11

10 g of acrylamide was measured and dissolved in distilled water to make 100 mL, to prepare a monomer aqueous solution.

Graft polymerization was performed as follows. γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 8 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 7 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 10 wt% of methacrylic acid, 1 wt% of methyl methacrylate, ethylene glycol A contact lens material was prepared, consisting of a copolymer of 7 wt% dimethacrylate and 2,2'-azobis (2,4-isobutyronitrile) (0.25 wt% as a polymerization initiator).

The lens material was installed in a discharge device (6 cm between electrodes, 270 volts between electrodes, frequency 60 Hz), and glow discharge treatment was performed for 5 seconds in an argon atmosphere of 0.04 Torr. The discharged lens material was exposed to air, placed in a test tube, and the acrylamide monomer solution was added thereto, followed by addition of a molar salt to a vacuum system. Subsequently, the test tube was immersed in water filled in an ultrasonic vibrator. In this state, the inside of the tube was vacuumed for 1 minute with a rotary pump, and ultrasonic waves were applied at a predetermined output. After vacuuming for 1 minute, ultrasonic waves were applied. After the lapse of a predetermined time, the application of the ultrasonic wave was stopped, the test tube was vacuum sealed, and this was immersed in a constant temperature bath at 40 ° C. for 15 minutes, and the graft polymerization to the lens material surface was tested. In addition, the output and the application time of the applied ultrasonic waves are as shown in Tables 9 and 10.

As can be seen from Table 9, when the application time of the ultrasonic wave is less than 10 seconds, it was found that the dissolved oxygen in the monomer aqueous solution was not sufficiently removed and not polymerized.

In Table 10, when the ultrasonic application time was longer than 10 minutes, it became clear that the monomer solution was concentrated, and as a result, turbidity occurred over a part or the entire surface of the graft treatment surface. When the application time was 10 minutes or less, the state of the graft surface was good.

Apart from the above-mentioned example, the conventional method of not using ultrasonic waves during polymerization, that is, removal of dissolved oxygen, removes the container containing the monomer solution into a vacuum, pulls it from the outside, and then replaces the inside of the container with nitrogen gas. In this case, a series of five steps of re-vacuation was performed. Then, irrespective of the same operation for 10 lens materials, 3 sheets are not surface-grafted and 7 sheets are excessively subjected to surface graft polymerization, so that the conventional method does not control the component concentration and dissolved oxygen content of the system. I couldn't get a good one without it.

Example 12

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48wt%, 1,1-dihydroper-fluorobutylmethacrylate 19wt%, 1,3-bis (γ-methacryloxypropyl) -1,1 7 wt% of 3,3-tetrakis (trimethylsiloxy) disiloxane, 8 wt% of bis (trimethylsiloxy) -γ-methacryloxypropylsilanol, 11 wt% of methacrylic acid, 7 wt% of ethylene glycol dimethacrylate, A contact lens material consisting of a 0.25 wt% copolymer of 2,2'-azobis (2,4-isobutyronitrile) was prepared.

A space made of a spacer having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 Hz, and the lens material was placed therein and discharged. Discharge treatment was carried out on both sides for 40 seconds on each side. Next, the discharged lens material was placed in a test tube, and then the same treatment as in Example 11 was performed. The results are shown in Table 12.

When the output of ultrasonic waves applied in Example 11 was less than 10 seconds, dissolved oxygen in the monomer solution could not be sufficiently degassed and surface graft polymerization could not be performed. In addition, when the application time was longer than 10 minutes, it was found that turbidity occurred on the surface after the surface graft treatment. From the results in Table 11 and Table 12, it was found that a good surface graft state can be obtained only when the application time is 10 seconds or more or 10 minutes or less.

Apart from the above-mentioned example, the conventional method of not using ultrasonic waves during polymerization, that is, removal of dissolved oxygen, removes the container containing the monomer solution into a vacuum, pulls it from the outside, and then replaces the inside of the container with nitrogen gas. In this case, a series of five steps of re-vacuation was performed. Then, irrespective of the same operation for 10 lens materials, 4 sheets are not surface grafted and 6 sheets are excessively subjected to surface graft polymerization, so that the conventional method does not control the component concentration and dissolved oxygen content of the system. I couldn't get a good one without it.

Example 13

3 ml of pure water was put into the test tube of internal diameter 18mm, and this was connected to the vacuum gauge. Ultrasonic waves were applied to the test tube while evacuating the system with an exhaust pump having an exhaust capacity of 60 l / min. The time course change of dissolved oxygen in pure water was monitored by the dissolved oxygen meter. Dissolved oxygen amount I (t) after t minutes

I (t) = I (o) exp (-axt)

And p = 100 watts for the applied power p of the ultrasonic wave, and a = 8 for the time constant = 5 and p = 200 watts.

Example 14

3 ml of pure water was put into the test tube of internal diameter 18mm, and this was connected to the vacuum gauge. The test tube was pulled from the outside while the system was evacuated with an exhaust pump having an exhaust capacity of 60 l / min, and then, a series of processes were repeated five times, in which the inside of the vessel was replaced with nitrogen gas and the vacuum was removed again. The time-lapse change of the dissolved oxygen amount in the meantime was made into the monomer based on the dissolved oxygen system. When the experiment was repeated 10 times, all 10 times showed different time-lapse changes of dissolved oxygen amounts, and a function using the same time variable as that obtained in Example 13 could not be obtained.

Example 15

3 ml of 10% aqueous acrylamide solution was placed in a test tube having an internal diameter of 18 mm, and this was connected to a vacuum system. The change over time of the acrylamide concentration in aqueous solution when the ultrasonic wave of the output 100watt was applied to the test tube was exhausted in the system by the exhaust pump of 60 L / min of exhaust capacity.

Acrylamide concentration of (t5) after time t minutes

C (t) is C (t) = C (o) (1-0.06 × t)%

However, it changed according to C (o) = 10.

Example 16

3 ml of 10% acrylamide aqueous solution was put into the test tube of internal diameter 18mm, and this was connected to the vacuum system. The test tube was pulled from the outside while the system was evacuated with an exhaust pump having an exhaust capacity of 60 L / min, and then, the inside of the container was replaced with nitrogen gas, and the series of steps taken out by vacuum were repeated five times. In the meantime, the change of the acrylamide concentration in aqueous solution over time was investigated. When the experiment was repeated 10 times, all 10 times showed a change in the time-lapse of different acrylamide concentrations, and a function with time as a variable obtained in Example 15 was not obtained.

Example 17

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydroperfluorobutyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 7wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 8wt%, methacrylic acid 11wt%, ethylene glycol dimethacrylate 7wt%, 2 A fluorine-containing contact lens material consisting of a 0.25 wt% copolymer of 2'-azobis (2,4-isobutyronitrile) (as a polymerization initiator) was prepared. A space made of a spacer having a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment apparatus having an electrode distance of 3.5 cm, an electrode voltage of 15 kilovolts, and a frequency of 60 Hz, and the lens material was placed therein and discharged. Discharge treatment was carried out on both sides for 40 seconds on each side.

35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide were dissolved in 40 g of pure water to obtain a monomer aqueous solution. In addition, 1.568 g of ferrous ammonium sulfate hexahydrate (molar salt) was dissolved in 10 g of pure water, and this was made into a molar salt solution. 2.4 mL of aqueous monomer solutions, 0.3 mL of aqueous molar salts and 0.3 mL of pure water were added to a test tube and stirred. The discharged lens was put there and the tube was sealed under reduced pressure. The test tube was placed in a constant temperature bath at 35 deg. C, and the shortest time when the monomer was graft-polymerized was investigated. The polymerization time was 7 minutes. Similarly, 20 minutes and 50 minutes of the shortest polymerization time for the discharge-treated graft material and siloxanyl methacrylate (containing no fluorine) based material to the methacrylate (silicone and no fluorine) based material. It was minutes.

The transmittance was measured at a wavelength of 500 nm before the discharge treatment and immediately after the surface graft polymerization treatment at each shortest time. The results in Table 13 were obtained. As can be seen, the fluorine-containing material and the fumarate-based material hardly change the transmittance before and after the surface graft treatment. In particular, no change in transmittance occurred in the fluorine-containing material.

On the other hand, siloxanyl methacrylate (fluorine-free) -based materials and methacrylate (silicon-free, fluorine-based) materials are markedly discolored.

As mentioned above, the superiority of the fluorine-containing material which produces a polymerization process in a short time is clear. In addition, the fumalate-based material exhibited a favorable effect that is poor in fluorine-containing material but is hard to discolor.

As mentioned above, the manufacturing method of the contact lens of this invention is applied to the method for manufacturing the hard contact lens which maintains the wettability of the surface permanently and is excellent in a wearing feeling.

In the above embodiment, the fluorine-based methacrylate contact lens material has been mainly described. However, the present invention is not limited thereto, and other hard contact lenses, for example, a lens material made of a fumarate copolymer or silicone rubber are used. Similar results have been obtained for soft contact lenses. The same effect was obtained for the surface treatment of polyethylene film, polypropylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and various other polymer materials.

In addition, it can be applied to medical products such as various packaging materials, agricultural maintenance materials, or artificial organs using the materials described above.

Claims (22)

(a) a contact lens substrate surface activation process for activating a contact lens substrate surface and (b) a graft polymerization process for graft polymerizing a hydrophilic monomer on the contact lens substrate surface in the presence of a reducing material Manufacturing method. The method of manufacturing a contact lens according to claim 1, wherein diammonium cerium nitrate (IV) is used as the reducing material. The method of manufacturing a contact lens according to claim 2, wherein the diammonium cerium nitrate (IV) is used in an amount of 0.01 g or more or 1 g or less per 1 g of the hydrophilic monomer. The method of manufacturing a contact lens according to claim 1, wherein ferrous ammonium sulfate (molten salt) is used as the reducing material. The method of manufacturing a contact lens according to claim 4, wherein ferrous ammonium sulfate (mol salt) is used at a ratio of 0.02 g or more or 0.06 g or less per 1 g of the hydrophilic monomer. The method of manufacturing a contact lens according to claim 1, wherein the graft polymerization step is performed while the contact lens substrate is immersed in a solution containing a hydrophilic monomer and a reducing substance. The acrylamide, N, N'-methylenebisacrylamide, 2-hydroxyethyl methacrylate, polyvinyl alcohol, N-vinylpyrrolidone, polyethylene oxide or dimethyl acrylamide as said hydrophilic monomers. Method for producing a contact lens, characterized in that using. The method of manufacturing a contact lens according to claim 7, wherein acrylamide and N, N'-methylenebisacrylamide are used as main components of the hydrophilic monomer. The method of manufacturing a contact lens according to claim 1, wherein the graft polymerization step is accelerated by heating. The method of manufacturing a contact lens according to claim 6, wherein the solution containing the hydrophilic monomer and the reducing substance is subjected to the graft polymerization process under reduced pressure or normal pressure. The method of manufacturing a contact lens according to claim 10, wherein the graft polymerization process is performed after the solution containing the hydrophilic monomer and the reducing material is brought to a reduced pressure. The method of manufacturing a contact lens according to claim 11, wherein the solution containing the hydrophilic monomer and the reducing substance is brought into a reduced pressure while applying ultrasonic waves. The method of manufacturing a contact lens according to claim 12, wherein the output of the ultrasonic waves is 10 W or more and the application time of the ultrasonic waves is 10 seconds or more or 10 minutes or less. The method of manufacturing a contact lens according to claim 1, wherein as the contact lens base, a contact lens base composed mainly of a polymer of an ester compound of acrylic acid or methacrylic acid is used. 15. The method of manufacturing a contact lens according to claim 14, wherein a contact lens base material is used, which is a copolymer of an ester compound of acrylic acid or methacrylic acid containing at least one selected as the contact lens base material. . (A) siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula; (Wherein R = CH ₃ or H; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; R1 = C ₁ alkyl, cyclohexyl of ~C _6, phenyl; R2 = C ₁ ~C ₆ of alkyl, cyclohexyl, phenyl; R3 = C ₁ ~C ₆ of alkyl, cyclohexyl, phenyl; R4 = C ₁ ~C ₆ of alkyl, cyclohexyl, phenyl; m = 1 to 3; n = 1 to 5; p = 1 to 3) (B) fluoroalkyl substituents of acrylic acid or methacrylic acid having up to 20 fluorine atoms represented by the following general formula; (Wherein R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group), (C) acrylic acid or methacrylic acid represented by the following general formula Polyfluoroalkylsiloxy substituted esters of; (Wherein R = CH ₃ or H; a fluoroalkyl group of R _f = C _{1 to} C ₄ ; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3), (D) the following general Acrylic (methacryl) oxyalkyl silanol represented by a formula; Wherein R = CH ₃ or H; X, Y = C ₁ -C ₆ alkyl, phenyl or Z; m = 1 to 3; n = 1 to 5; p = 1 to 3; R1 = C ₁ ~C ₆ alkyl, cyclohexyl or phenyl; Alkyl, cyclohexyl, or phenyl of R 2 = C ₁ -C ₆ ; R3 = C ₁ ~C ₆ of alkyl, cyclohexyl or phenyl), (E) represented by formula to polyacrylic (methacrylic) oxyalkylene polysiloxane; Wherein R = CH ₃ or H; m = 0-3; n = 1-5; X = C ₁ -C ₆ alkyl, cyclohexyl, phenyl or Z; Y = C ₁ -C ₆ alkyl, Cyclohexyl, phenyl or Z; p = 1 to 3; R1 = C ₁ ~C ₆ alkyl, cyclohexyl or phenyl; Alkyl, cyclohexyl, or phenyl of R 2 = C ₁ -C ₆ ; R3 = a C ₁ ~C ₆ alkyl, cyclohexyl or phenyl), (F) to fluorine-containing siloxane sanil methacrylate represented by the general formula; (Wherein 1 = 1 to 3; m = 1 to 10; n = 1 to 3; k = 1 to 3), (G) a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula; Wherein R _f is a C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto; R 1 = CH ₃ or H; R 2 = C _{1 to} C ₃₀ fluorine atoms or oxygen atoms Alkyl group which may contain), (H) Fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula; Wherein R _f is a C _{1 to} C ₃₀ fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto; R 1 = CH ₃ or H; R 2 = C _{1 to} C ₃₀ fluorine atoms or oxygen atoms Alkyl group which may contain), (I) fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula; And (Wherein R 1, R 2 = CH ₃ or H; 1 = 2 to 4; p, q = 1 or 2; m and n are each an integer whose sum is in the range of 1 to 20), (J) Fluorine-containing cyclic olefins represented by general formula (Wherein A = H, F or alkyl group; B = H, F or alkyl group; C = H, F or alkyl group; D = F or C _{1 to} C _{30 which} may contain an oxygen atom bonded to at least one fluorine atom) A fluoroalkyl group of n = 0, 1 or 2). The method of manufacturing a contact lens according to claim 1, wherein as the contact lens substrate, a contact lens substrate comprising a copolymer of an ester compound of acrylic acid or methacrylic acid and an ester compound of fumaric acid is used. 17. The raw material according to claim 16, wherein as the contact lens base, a copolymer of (K) alkyl methacrylate, (L) alkyl fumarate, (M) fluoroalkyl fumarate and (N) siloxanyl fumarate is used as a raw material. A method for manufacturing a contact lens, comprising using a contact lens base. The method of manufacturing a contact lens according to claim 1, wherein the contact lens base surface activation step is performed by discharging the contact lens base surface under normal pressure or reduced pressure. (a) a contact lens substrate surface activation process for activating a contact lens substrate surface; and (b) a hydrophilic property on the surface of the contact lens substrate while the contact lens substrate is immersed in a solution containing a hydrophilic monomer and a reducing material and in a reduced pressure state. A method of manufacturing a contact lens, comprising a graft polymerization step of graft polymerization of monomers. The method of manufacturing a contact lens according to claim 19, wherein the solution containing the hydrophilic monomer and the reducing substance is reduced in pressure while applying ultrasonic waves. The method of manufacturing a contact lens according to claim 20, wherein the output of the ultrasonic waves is 10 W or more, and the application time of the ultrasonic waves is 10 seconds or more or 10 minutes or less. 22. The method of manufacturing a contact lens according to any one of claims 19 to 21, wherein the graft polymerization process is performed in the presence of ferrous ammonium sulfate (molten salt).