KR100214747B1 - Contact lens and method of producing a contact lens - Google Patents

Abstract

The present invention relates to a surface graft treated contact lens which improves the wettability of the lens surface by graft polymerizing a hydrophilic monomer on the contact lens base surface, and a method of manufacturing the same. It obtains contact lens with oxygen permeability, crosslinks the graft polymer and stores the lens base in the protective fixing member during polymerization, and gives the polymerization container a rocking motion to increase the adhesive strength between the graft polymer and the lens base and to provide excellent wear resistance. The contact lens is obtained, and further, by specifying the graft lens base, the graft state is improved, the yield is improved, and the cost is reduced.

Description

[Name of invention]

Contact Lenses and Manufacturing Method Thereof

Detailed description of the invention

[Technical Field]

TECHNICAL FIELD The present invention relates to a contact lens, and more particularly, to a hard contact lens having excellent wettability and wearing comfort.

[Background]

Although methacrylate (silicone and no fluorine) is generally used as the contact lens base material, in addition, siloxanyl methacrylate (free of fluorine), fumarate and fluorine-based contact lens base materials generally have oxygen permeability. It is known as an excellent contact lens. For example, it is known that the contact lens base material containing the fluoroalkyl methacrylate described in Japanese Patent Laid-Open No. 62-294201 is a material which is particularly excellent in oxygen permeability. However, this contact lens having excellent oxygen permeability has a drawback in that the wettability of the surface of the base material is poor and the feeling of wearing is poor because it feels dry when worn.

It is important to improve the affinity between the cornea and the lens surface in order to reduce the foreign body feeling when contact lenses are worn, thereby improving the fit. As a specific method, the wettability of the lens surface is improved by graft-polymerizing a hydrophilic monomer on the contact lens surface. After discharging the conventional lens surface under normal pressure or reduced pressure, graft polymerization was performed by contacting only the hydrophilic monomer with the contact lens substrate. However, such a conventional polymerization method has a drawback that the adhesion force between the graft polymer and the lens substrate is weak, and the graft polymer introduced by rubbing with a finger or the like falls back relatively easily before graft, which falls off relatively easily.

Therefore, the present invention solves this problem, the main object of the present invention is to provide a contact lens having a good fit and excellent oxygen permeability, and a high wear resistance contact lens to improve the adhesion strength between the lens substrate and the graft polymer And a method for producing the same.

In addition, the present invention provides a method for resolving the problem newly generated by the means used to improve the adhesion strength between the lens substrate and the graft polymer.

[Initiation of invention]

In order to solve the above problems, the contact lens of the present invention is a siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula.

Provided that 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 of R ¹ = C ₁ -C ₆ , cyclohexyl phenyl; R ² = C ₁ -C ₆ alkyl, cyclohexyl phenyl; R ³ = C ₁ -C ₆ alkyl, cyclohexyl phenyl; 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 (

Provided that R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group; ), Polyfluoroalkylsiloxy substituted esters of acrylic acid or methacrylic acid represented by the following general formula (

Provided that R = CH ₃ or H; Fluoroalkyl groups of R _f = C ₁ -C ₄ ; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3) and acryl (methacryl) oxyalkylsilanol represented by the following general formula (

Provided that R = CH ₃ or H; Alkyl _{X, Y = C 1 ~C 6} ; 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 ; Alkyl, cyclohexyl or phenyl of R ³ = C ₁ -C ₆ ; ), Polyacryl (methacryl) oxyalkyl pulleysiloxane represented by the following general formula (

Provided that R = CH ₃ or H; m = 0 to 3; n = 1 to 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 to} C ₆ ), and a fluorine-containing siloxanyl methacrylate represented by the following general formula (

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 = 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; An alkyl group which may contain a fluorine atom or an oxygen atom of R ² = C ₁ -C ₃₀ ; ), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

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; An alkyl group which may contain a fluorine atom or an oxygen atom of R ² = C _{1 to} C ₃₀ ), a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula (

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

A = H, F or an alkyl group; B = H, F or an alkyl group; C = H, F or an alkyl group; A C _{1 to} C ₃₀ fluoroalkyl group which may contain D = F or an oxygen atom bonded to at least one fluorine atom; In the fluorine-containing contact lens base material selected from the group consisting of an ester compound of acrylic acid or methacrylic acid which is a copolymer containing at least one of n = 0, 1 or 2), a hydrophilic monomer is graphed on the surface of the lens base material. It is characterized by the above-mentioned.

In addition, in the contact lens obtained by graft polymerization of a hydrophilic monomer on the lens surface, the graft polymer chain is introduced to be crosslinked.

In addition, a crosslinking agent is used as the crosslinking method between the polymer chains.

In addition, a hydrogen bond is used as a crosslinking method between the polymer chains.

In addition, the said crosslinking agent consists of N, N'-methylenebisacrylamide, The said N, N in the said hydrophilic monomer aqueous solution rather consisting of at least acrylamide, N, N'-methylenebisacrylamide, and water. The concentration of '-methylenebisacrylamide is 10 wt% or less.

In addition, the graft polymer is composed of acrylamide and N, N'-methylene bisacrylamide and the formation of hydrogen bond is composed of acrylic acid.

In addition, the siloxy substituted ester of acrylic acid or methacrylic acid in which the lens base material is represented by the following general formula (

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

Provided that R = CH ₃ or H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group; ), Polyfluoroalkylsiloxy substituted esters of acrylic acid or methacrylic acid represented by the following general formula (

Provided that R = CH ₃ or H; Fluoroalkyl groups of R _f = C ₁ -C ₄ ; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3; ) And acryl (methacryl) oxy alkylsilanol represented by the following general formula (

Provided that R = CH ₃ or H; Alkyl _{X, Y = C 1 ~C 6} ; 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) oxyalkyl pulleysiloxane represented by the following general formula (

Provided that R = CH ₃ or H; m = 1 to 3; n = 1 to 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 (

1 = 1 to 3; m = 0 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 = 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; An alkyl group which may contain a fluorine atom or an oxygen atom of R ² = C ₁ -C ₃₀ ; ), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

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; An alkyl group which may contain a fluorine atom or an oxygen atom of R ² = C ₁ -C ₃₀ ; ), A fluorine-containing acrylate or dimethacrylate monomer represented by the following general formula (

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

A = H, F or an alkyl group; B = H, F or an alkyl group; C = H, F or an alkyl group; A C _{1 to} C ₃₀ fluoroalkyl group which may contain D = F or an oxygen atom bonded to at least one fluorine atom; In the fluorine-containing contact lens substrate selected from the group consisting of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of n = 0, 1, or 2), a hydrophilic monomer is formed on the surface of the lens substrate. It is characterized by graft polymerization.

In addition, the lens base material is at least alkyl methacrylate, alkyl fumarate pullurooalkyl 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

Wherein X and Y are selected from the group consisting of C ₁ to C ₆ alkyl groups and Z groups, and Z is a structural formula

And B represents a C ₁ to C ₆ alkyl group. k, l, m, and n represent an integer of 0 or +.) A polymer of methacrylic acid and an ester compound of fumaric acid, which is a public product, is used as a raw material.

In addition, the graft polymerization is carried out while imparting fluctuations to the polymerization system, and the contact lens substrate is housed in a protective fixing member, and the graft polymerization is stored in a polymerization vessel, followed by graft polymerization. The surface hardness of the member is smaller than the surface hardness of the substrate.

Moreover, the following are mentioned as a typical compound represented by the said general formula.

Fluorobutylhexamethyltrisiloxanyl methacrylate

Trifluoroethyl methacrylate

Trifluoropropyltetramethyldisiloxanylmethylmethacrylate

Moreover, the following are mentioned as a typical ester compound of fumaric acid.

Dimethyl fumarate

Bis (pentamethyldisiloxanylmethyl) fumarate

Bis (trifluoroethyl) fumarate

As mentioned above, although the indication of the invention was described, it demonstrates below with the effect about the effect expressed by this.

In general, contact lenses having excellent oxygen permeability lack surface wettability. Therefore, by graft polymerization of a hydrophilic monomer on the surface of the lens base, a contact lens having excellent oxygen permeability, being easy to be friendly to the eyes, and having a comfortable fit appears.

In addition, contact lenses having excellent water permeability and low oxygen permeability, especially fluorine-containing lenses, have a weaker adhesive strength than hydrophilic graft polymers. As described above, by adding a crosslinking agent to the monomer solution, the graft polymer grafted on the surface of the substrate takes the form of a bridge between adjacent polymers. When mechanical stress is applied to the graft surface from the outside, the stress resistance can be improved because the external stress is dispersed between the polymer chains through the leg-shaped structure. However, the addition of a crosslinking agent or the like to the monomer solution during the graft polymerization treatment means that the composition of the solution is composed of multiple components. At this time, as shown in the present invention, since the homogeneity of the solution components can be improved by not causing the polymerization system to shake, the graft surface thus obtained can have a structure with a uniform leg shape. Therefore, when it comes to wear resistance, the uniformity in the inner surface of the adhesive strength of the graft film on the substrate surface is good. In addition, there is optically no refractive error region and the surface treatment state is excellent in transmittance.

When the polymerization system is shaken, since the substrate moves randomly in the container, defects or scratches may occur in the substrate when the substrate and the container wall come into contact with each other. In particular, substrates requiring a long graft polymerization time are likely to be scratched because of the increased number of times of contact with the container walls. Therefore, when the base material is stored in the protective fixing member as in the present invention, since the range of motion of the base material during the polymerization treatment is limited to a narrow area, contact between the base material and the container wall can be prevented, and thus no defects or scratches of the base material occur. . In addition, the same effect can be obtained by selecting a specific base material. For example, graft polymerization is initiated by decomposing a peroxide produced on a substrate surface by a discharge treatment in a monomer solution, and the graft polymerization rate is as fast as the amount of peroxide produced on the substrate surface is large. On the other hand, the peroxide production amount is characteristic according to the composition of the substrate. Therefore, the polymerization time can be shortened by selecting a lens substrate such as a large amount of peroxide as the graft substrate. In this case, since the number of times of contact between the lens and the container wall during polymerization decreases, the problem such as scratches of the substrate is solved. In addition, the short polymerization time is effective in that thermal deformation and deterioration of the substrate can be prevented when the polymerization is carried out by heating.

[Brief Description of Drawings]

1 is a view showing a contact lens base protective fixing member of the present invention.

2 is a cross-sectional view of the fixed protective fixing member of the present invention.

* Explanation of symbols for main parts of the drawings

1: Protective fixing member 2: Contact lens base material

3: polymerization vessel 4: 0 ring

Best Mode for Carrying Out the Invention

In order to describe the present invention in more detail, this will be explained according to the following examples.

Example 1

γ ... methacryloxypropyl-tris (trimethylsiloxy) silane 48wt%, 2,2,2-trifluoroethyl methacrylate 19wt, 1,3-bis (γ-methacryloxypropyl) -1, 1,3,3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, methyl methacrylate 1wt%, ethylene Glycol dimethacrylate 7wt%, 2,2'-azobis (2,4-isobutyronitrile) (but as a polymerization initiator) 0.25wt% of the copolymer, and cut to a lens shape The processed contact lens base material (diameter about 8 mm, thickness about 0.1 mm) was prepared.

The lens substrate was installed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), and after glow discharge treatment for 5 seconds in an argon atmosphere of 0.04 Torr, the lens substrate was left in the air for a while and placed in a test tube.

Acrylamide and N, N'-methylenebisacrylamide were dissolved in water to make a monomer aqueous solution. At that time, according to Table 1, six types of aqueous solution which changed the weight ratio of each component were prepared. 3.0 ml of each aqueous solution was aliquoted into a test tube so that the entire lens substrate was immersed in the aqueous monomer solution. After nitrogen gas substitution, the pressure reduction was sealed. The test tube was placed in an incubator at 80 ° C. for 60 minutes, and the monomer was graft-polymerized on the lens base surface (Table 1, Sample Nos. 1 to 6). Moreover, the sample using 40 wt% acrylamide monomer aqueous solution without crosslinking agent was produced for the comparison with the conventional method (Table 1, Comparative Examples 1-6). The polymerization conditions at this time are Table 1, Sample No. Same as the case of 1-6.

The transmittance | permeability in visible light (480 nm) was measured about the lens after a graft process, and the cloudy state of the lens was evaluated. The results are shown in Table 1.

* AAm: Acrylamide

MBAAm: N, N'-methylenebisacrylamide

Subsequently, the test which confirmed the wear resistance was performed about the lens without a turbidity with a high transmittance | permeability (the same thing as Table 1, Sample No. 1-4).

First of all, it was rubbed and washed 1000 times in the palm with detergent. Next, the peeling state of the graft polymer was evaluated by measuring the contact angle of the lens surface after rubbing and seeing the difference with the previously recorded contact angle before rubbing.

For comparison, the graft treatment foam (the same as Table 1, Comparative Examples 1 to 6) in 40 wt% acrylamide aqueous solution system without crosslinking agent was added. The same operation as 1 to 4 was performed.

In addition, the contact angle was measured by droplet contact and the solvent used water. The results of this are shown in Table 2.

Example 2

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydropa-fluorobutyl 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% , 2,2'-azobis (2,4-isobutylnitrile) (except as a polymerization initiator) 0.25 wt% of copolymer and processed into lens by cutting polishing method (diameter About 8 mm, thickness about 0.1 mm) was prepared.

The lens substrate was placed in a space made of spacer pieces having a thickness of 1.5 mm between electrodes of a corona discharge treatment apparatus having an electrode diameter of 70 nm, an inter-electrode voltage of 15 kilovolts, and a frequency of 60 hertz, and the discharge treatment was performed. In addition, discharge processing was performed for 40 seconds on both sides of each engraving surface.

Next, 3.0 ml of each monomer aqueous solution which changed the component ratio similarly to Example 1 was prepared in the test tube, and 0.047g of molar salts (ferrous ammonium sulfate) were added as a redox catalyst, and it stirred and dissolved in each. The discharged lens base material was put therein, and it was pressure-sealed after nitrogen gas substitution. The test tube was placed in a 35 degreeC thermostat for 20 minutes, and the monomer was graft-polymerized on the lens base surface (Table 3, sample No. 1-6).

In addition, the sample using the 40 wt% acrylamide monomer aqueous solution which does not add a crosslinking agent was prepared for comparison (Table 3, Comparative Examples 1-6). The polymerization conditions at this time are Table 3, Sample No. Same as the case of 1-6.

The transmittance | permeability in visible light (480 nm) was measured about the lens after a graft process, and the cloudy state of the lens was evaluated. The results are shown in Table 3.

* AAm: Acrylamide

MBAAm: N, N'-methylenebisacrylamide

Subsequently, the test which confirmed abrasion resistance was performed about the lens without a turbidity with a high transmittance | permeability (the same thing as Table 3, Sample No. 1-4).

First of all, it was rubbed and washed 1000 times in the palm with detergent. Next, the peeling state of the graft polymer was evaluated by measuring the contact angle of the lens surface after rubbing and seeing the difference with the contact angle before rubbing previously recorded.

For comparison, the graft treatment foam (the same as in Table 3 and Comparative Examples 1 to 6) in 40 wt% acrylamide aqueous solution system without crosslinking agent was added. The same operation as 1 to 4 was performed.

In addition, the contact angle was measured by droplet contact and the solvent used water. The results of this are shown in Table 4.

As is apparent from Table 1 and Table 3, the graft polymer contains at least 10 wt% of N, N'-methylenebisacrylamide in a polymerization solution composed of acrylamide, N, N'-methylenebisacrylamide and water ( Tables 1 and 3 and Samples 1 to 4) were excellent in the transmission of visible light, and no whitening of the lens surface was observed. In addition, the value of the transmittance | permeability at this time was not lower than the polymer (Table 1, Table 3, Comparative Examples 1-6) in 40 wt% acrylamide aqueous solution system, and was a value satisfactory enough as transparency of a contact lens. On the other hand, when the N, N'-methylenebisacrylamide exceeded 10 wt% (Table 1 and Table 3, Sample Nos. 5 and 6), the lens surface became cloudy and its transmittance was greatly reduced.

In addition, as shown in Tables 2 and 4, the increase in the contact angle after rubbing was significantly suppressed with respect to the addition of the crosslinking agent (Tables 2 and 4, Sample Nos. 1 to 4), and the water wettability of the lens surface was maintained. As a result, the acrylamide graft polymer was crosslinked by N, N'-methylenebisacrylamide, and the adhesion strength between the lens substrate and the graft polymer was increased by graft polymerization by adding a crosslinking agent to an aqueous hydrophilic monomer solution. It shows that the wear resistance of the lens surface can be improved. It was also confirmed that the durability of the graft contact lens having no turbidity of 10 wt% or less of the crosslinking agent addition amount was sufficiently large, and practically no problem occurred.

As described above, a graft contact lens having abundant durability and no cloudiness on the lens surface could be manufactured.

Example 3

A monomer aqueous solution was prepared by dissolving in 10 g of acrylamide, 0.266 g of N, N'-methylenebisacrylamide (as a crosslinking agent), and 100 ml of water.

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 , 3, 3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, methyl methacrylate 1wt%, ethylene glycol Dimethacrylate 7wt%, 2,2'-azobis (2,4-isobutyronitrile) (0.25 wt% copolymer) (as a polymerization initiator) consisting of a lens, by a cutting polishing method The processed contact lens base material (diameter about 8 mm, thickness about 0.1 mm) was prepared.

The lens substrate was placed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), and after 5 hours of glow discharge treatment in an argon atmosphere of 0.04 Torr, the lens substrate was left in the air for a while.

3 ml of the aqueous solution of the crosslinked additive acrylamide monomer was added to the test tube, the lens base material after the discharge treatment was inserted therein, and the whole substrate was immersed in the solution. The test tube was placed in an incubator at 80 ° C. for 60 minutes, and acrylamide was graft-polymerized on the lens substrate surface.

Subsequently, 5 g of acrylic acid, 0.133 g of N, N'-methylenebisacrylamide (as a crosslinking agent) and 40 mg of ammonium persulfate (as a polymerization initiator) were prepared by dissolving in 100 ml of water. The above-described surface graft treated contact lens was placed in this aqueous solution, and the graft polymer was sufficiently swollen. Then, the resultant was heated to 60 ° C. to carry out a polymerization reaction of acrylic acid (Table 5, Sample Nos. 1 to 6). Moreover, the sample which performed only the graft superposition | polymerization process was produced, without performing the polymerization process of acrylic acid for the comparison with the conventional method (Table 5, Comparative Examples 1-6). The polymerization conditions at this time performed the same operation as said sample.

In addition, the lens after the treatment was rubbed and washed in a palm coated with detergent 1000 times, and then subjected to an abrasion resistance test. The peeling evaluation of the graft polymer was examined by the change of the contact angle of the lens surface before and after rubbing. The contact angle was measured by the droplet method, and water was used as the solvent. The results of this are shown in Table 5.

Example 4

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1, 1-dihydropa-fluorobutyl 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% , 2,2'-azobis (2,4-isobutylnitrile), a contact lens substrate (diameter of about 8) consisting of a 0.25 wt% copolymer and processed into a lens by a cutting method Mm and thickness of about 0.1 mm) were prepared.

This lens base material was installed in a space made of a spacer having a thickness of 1.5 mm between the electrodes of the electrode distance 10 mm, the electrode voltage 15 kilovolts, and the frequency 60 hertz corona discharge treatment apparatus, and the discharge treatment was performed. In addition, discharge processing was performed for 40 seconds on both sides of each engraving surface. A test tube was prepared, and 2.7 ml of the crosslinking agent addition acrylamide monomer aqueous solution (10 g of acrylamide and 0.266 g of N, N'-methylenebisacrylamide / 100 ml of water) similar to Example 3 prepared in advance was added thereto. As a redox catalyst, 0.3 ml of a solution (0.158 g / 10 ml) in which ferrous ammonium sulfate (molten salt) was previously dissolved in water was injected.

Next, the discharged lens substrate was placed in a test tube, so that the whole substrate was immersed in the solution, and after nitrogen gas replacement, the pressure-sensitive sealing tube was carried out. The test tube was placed in a 35 degreeC thermostat for 60 minutes, and the acrylamide was graft-polymerized on the lens base surface.

Subsequently, 5 g of acrylic acid, 0.133 g of N, N'-methylenebisacrylamide (as a crosslinking agent) and 40 mg of ammonium persulfate (as a polymerization initiator) were prepared by dissolving in 100 ml of water. The above-mentioned surface-grafted contact lens was put in this aqueous solution, and the graft polymer was fully swollen, and it heated at 60 degreeC and performed the polymerization reaction of acrylic acid (Table 6, sample No. 1-6).

Moreover, the sample which performed only the graft superposition | polymerization process was produced, without performing the polymerization process of acrylic acid for the comparison with the conventional method (Table 6, Comparative Examples 1-6). In this case, polymerization conditions were performed in exactly the same manner as in the above sample.

In addition, the lens after the treatment was rubbed and washed in a palm coated with detergent 1000 times, and then subjected to an abrasion resistance test. The peeling evaluation of the graft polymer was examined by the change of the contact angle of the lens surface before and after rubbing. The contact angle was measured by the droplet method, and water was used as the solvent. The results of this are shown in Table 6.

As can be seen from Tables 5 and 6, the increase in the contact angle after rubbing was greatly suppressed by introducing the acrylic acid polymerization step, and the water wettability of the lens surface was maintained. This phenomenon can be explained as follows. When entangled polyacrylic acid in the molecular chain of acrylamide polymer introduced on the contact lens surface is networked, a hydrogen bond is formed between the amide group of the polyacrylamide and the carboxyl group of the polyacrylic acid, and thus the graft polymer chain is similarly crosslinked (see the figure below). As a result, the stress of the rubbing is dispersed per graft polymer chain, the adhesion strength between the lens substrate and the graft polymer is increased, and the wear resistance of the graft-treated lens surface is improved.

Example 5

35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as a crosslinking agent) were dissolved in 60 g of water 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 , 3, 3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, methyl methacrylate 1wt%, ethylene glycol Dimethacrylate 7wt%, 2, 2'-azobis (2,4-isobutyronitrile) (0.25 wt%) copolymer (as a polymerization initiator), and formed into a lens by cutting One contact lens base material (diameter about 8 mm, thickness about 0.1 mm) was prepared.

The lens substrate was placed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), glow discharged for 5 seconds in an argon atmosphere of 0.04 Torr, and the lens substrate was left in the air for a while. The discharged lens substrate was placed in a test tube and 3.0 ml of the monomer aqueous solution was added. This was connected to a vacuum system, the tube was degassed, and the vacuum sealing tube was performed as it was. In this state, the test tube was inserted into a reciprocating vibrator (EP-1, manufactured by Ocean Service Center Co., Ltd.) and subjected to graft polymerization to the substrate surface for 60 minutes at a constant temperature of 80 ° C. After the completion of the polymerization, the presence or absence of turbidity on the treated surface was evaluated by an optical microscope. In addition, the rocking conditions (swing cycle and amplitude) of the reciprocating oscillator were set as shown in Table 7, and the six samples (Tables 7 and 1 to 6) were examined.

On the other hand, for the remarks, the surface graft polymerization treatment was conducted without causing fluctuations as before (Table 7, Comparative Examples 1 to 6).

As can be seen from Table 7, all surface conditions were good and there was no turbidity in the case of the rocking during the graft polymerization (Table 7, Sample Nos. 1 to 6). On the other hand, the thing which does not give fluctuation at the time of superposition | polymerization (Table 7, Comparative Examples 1-6) was observed under the optical microscope, and it turned out that it was a cloudy part over part or the whole surface of the surface.

From the above results, it was clarified that the uniformity of the concentration of the monomer solution was ensured by giving fluctuations during the graft polymerization, and this was very effective in making the surface graft state satisfactory.

○ Good surface condition (no cloudy)

× Poor surface condition (with cloudy)

Example 6

35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as crosslinking agent) were dissolved in 60 g of water to prepare a monomer aqueous solution.

The graft polymerization process was performed as follows.

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydropa-fluorobutyl 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% And a contact lens substrate composed of a 0.25 wt% copolymer of 2,2'-azobis (2,4-isobutylnitrile).

The lens substrate 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. In addition, discharge processing was performed for 40 seconds on both sides of each engraving surface. Next, the discharged lens substrate was placed in a test tube, and the monomer aqueous solution was added in an amount so that the lens substrate was sufficiently submerged. This was connected to a vacuum system, the inside of the tube was degassed, and the vacuum sealing tube was performed as it was. In this state, the test tube was inserted into a reciprocating vibrator (EP-1, manufactured by Ocean Service Center Co., Ltd.) and subjected to graft polymerization to the substrate surface for 60 minutes at a constant temperature of 80 ° C. After the completion of the polymerization, the presence or absence of turbidity on the treated surface was evaluated by an optical microscope. The oscillation conditions (oscillation period, amplitude) of the reciprocating oscillator were set as shown in Table 8, and the six samples (Table 8, Sample Nos. 1 to 6) were examined.

On the other hand, for comparison, the surface graft polymerization treatment was performed without causing fluctuations as before (Table 8, Comparative Examples 1 to 6).

As can be seen from Table 8, all of the surface conditions were good, and there was no turbidity for the rocking during the graft polymerization (Table 8, Sample Nos. 1 to 6). On the other hand, the thing which does not give oscillation at the time of superposition | polymerization (Table 8, Comparative Examples 1-6) was observed under the optical microscope, and it turned out that it was a cloudy part over part or the whole surface of the surface.

From the above results, it was proved that the uniformity of the concentration of the monomer solution was ensured by giving fluctuations during the graft polymerization, which was very effective in making the surface graft state satisfactory.

○ Good surface condition (no cloudy)

× Poor surface condition (with cloudy)

Example 7

It dissolved in 35 g of acrylamide, 5 g of N, N'-methylenebisacrylamide (as a crosslinking agent), and 60 g of water, and prepared the 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 Dimethacrylate 7wt%, 2,2'-azobis (2,4-isobutyronitrile) (0.25 wt% copolymer) as a polymerization initiator, formed into a lens by cutting polishing One contact lens base material (diameter about 8 mm, thickness about 0.1 mm) was prepared.

The lens substrate was placed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), glow discharged for 5 seconds in an argon atmosphere of 0.04 Torr, and the lens substrate was left in the air for a while. 3 ml of the above-mentioned crosslinking agent-added acrylamide monomer solution was added to a glass polymerization container, and as shown in FIG. 1, a protective member 1 made of silicon-laver fitted with a contact lens substrate 2 was inserted therein. After decomposing nitrogen gas by substituting the whole substrate in the solution, a decompression sealing tube was carried out.

The test tube was placed in an incubator at 80 ° C for 30 minutes, and acrylamide was graft-polymerized on the lens base surface. Six samples (Table 9, Sample Nos. 1 to 6) which performed the same operation as described above were prepared.

For comparison with the conventional method, a sample in which graft polymerization was carried out by inserting a contact lens substrate which was not stored in the protective fixing member 1 into a glass polymerization vessel was prepared (Table 9, Comparative Examples 1 to 6). The discharge conditions at this time, the polymerization temperature and the polymerization time were set in the same manner as the samples (Table 9, Sample Nos. 1 to 6) when stored in the protective fixing member 1.

Then, the presence or absence of the defect of the edge part of a contact lens and surface damage after a graft process was observed and evaluated by the optical microscope. The results are shown in Table 9.

○: no crack or deformation

×: crack and deformation

Example 8

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 1, 1-dihydropa-fluorobutyl 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% , 2,2'-azobis (2,4-isobutylnitrile) (wherein, as a polymerization initiator) a contact lens substrate (0.25 in diameter) formed into a lens shape by a cutting polishing method 8 mm, thickness of about 0.1 mm) was prepared.

The lens base material was installed in a space made of a spacer having a thickness of 1.5 mm between electrodes of a corona discharge treatment apparatus having a distance of 70 mm between electrodes, a voltage of 15 kilovolts between electrodes, and a frequency of 60 hertz, and the discharge treatment was performed. In addition, discharge processing was performed for 40 seconds on both sides of each engraving surface.

After the discharge of the contact lens substrate as shown in FIG. 2, it is housed in a fixed protective fixing member 1 made of a bottom cover and a base material holder-integrated silicon-lab, and screwed into a glass polymerization container 3 Fixed. To the polymerization vessel, 2.7 ml of a monomer aqueous solution prepared by dissolving 35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as a crosslinking agent) in 50 g of water was densified. As a redox catalyst, 0.3 ml of a solution of ferrous ammonium sulfate (molten salt) previously dissolved in water (1.56 g / 10 g of water) was injected, and the entire base material was immersed in a solution, followed by sealing under reduced pressure. The test tube was placed in a 350 DEG C incubator for 50 minutes and graft polymerized acrylamide on the lens substrate surface. Thus, all were created in six samples (Table 10, sample No. 1-6) which performed the same operation.

For comparison with the conventional method, a sample in which graft polymerization was carried out by inserting a contact lens base material not stored in the protective fixing member 1 into a glass polymerization vessel was prepared (Table 10, Comparative Examples 1 to 6). The discharge conditions, the polymerization temperature and the polymerization time at this time were set completely as in the samples (Table 10, Sample Nos. 1 to 6) when stored in the protective fixing member 1.

Then, the presence or absence of the defect of the edge part of a contact lens and surface damage after a graft process was observed and evaluated by the optical microscope. The results are shown in Table 10.

○: no crack or deformation

×: crack and deformation

As can be seen from Table 9 and Table 10, when the prior art, i.e., the protection fixing member is not mounted, damage to the edges and laceration of the surface could not completely prevent this. On the other hand, when the protective fixing member according to the present invention is mounted, there is no damage to the edge portion or damage to the surface.

Example 9

35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as crosslinking agent) were dissolved in 60 g of water 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 , 3, 3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, methyl methacrylate 1wt%, ethylene glycol Dimethacrylate 7wt%, 2, 2'-azobis (2,4-isobutylnitrile) 0.25wt% of copolymer (as a polymerization initiator) and processed into a lens shape by cutting polishing A contact lens base (diameter about 8 mm, thickness about 0.1 mm, beakers hardness about 8.0) was prepared.

The lens substrate was installed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), and glow discharged for 5 seconds in an argon atmosphere of 0.04 Torr, and the lens substrate was then left in the air for a while. 3 ml of the above-mentioned crosslinking agent-added acrylamide monomer solution was added to a glass polymerization container, and as shown in FIG. 1, the protection of a silicon lab product (Beakers hardness: about 5.5) equipped with the contact lens base material 2 The fixed member 1 was inserted, and the whole substrate was immersed in the solution, and after the nitrogen gas replacement, the pressure reduction sealing tube was carried out.

The test tube was placed in an incubator at 80 ° C. for 30 minutes, and acrylamide was graft-polymerized on the lens substrate surface. Thus, 6 samples (Table 11, Sample No. 1-6) which performed the same operation completely were created.

For comparison with the conventional method, the contact lens substrate housed in the protective fixing member 1 made of a copolymer (beakers hardness of about 20) mainly composed of dimethacrylate and styrene of brittle bisphenol A was added to a glass polymerization container. The sample which inserted and performed graft polymerization was prepared (Table 11, Comparative Examples 1-6). The discharge conditions, the polymerization temperature and the polymerization time at this time were set completely as in the samples (Table 11, Sample Nos. 1 to 6) when attached to the protective fixing member 1 made of silicon lab.

Then, the presence or absence of the defect of the edge part of a contact lens and surface damage after a graft process was observed and evaluated by the optical microscope. The results are shown in Table 11.

○: no crack or deformation

×: crack and deformation

As can be seen from Table 11, in the case of using a protective fixing member having a beaker's hardness larger than that of the lens base material, edge damage and surface cracking could not be completely prevented. On the other hand, when the beakers were housed in a protective material made of silicon labber, which is a material that is softer than that of the lens base material, there were no defects in the edges and damage to the surface.

Example 10

γ-methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2, 2, 2-trifluoroethyl methacrylate 19 wt%, 1, 3-bis (γ-methacryloxypropyl) -1, 1 , 3, 3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, methyl methacrylate 1wt%, ethylene glycol Dimethacrylate 7wt%, 2, 2'-azobis (2,4-isobutylnitrile) 0.25wt% of copolymer (as a polymerization initiator) and processed into a lens shape by cutting polishing A contact lens substrate (diameter about 8 mm, thickness about 0.1 mm) was prepared. This is hereinafter referred to as CL1.

A contact made of a copolymer of methyl methacrylate 60 wt%, tris (trimethylsiloxy) silylpropyl methacrylate 35 wt%, 2-hydroxyethyl methacrylate 5 wt% and processed into a lens shape by cutting and polishing A lens substrate (diameter about 8 mm, thickness about 0.1 mm) was prepared. This is hereinafter referred to as CL2.

CL1 was installed 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 diameter of 70 mm, an interelectrode voltage of 15 kilovolts, and a frequency of 60 hertz, and the discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds on both sides of each piece.

The contact lens base material after discharge was put into the test tube, 35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as a crosslinking agent) were dissolved in 50 g of water, and 2.7 ml of a monomer aqueous solution prepared in advance was added. As a redox catalyst, 0.3 ml of a solution of ferrous ammonium sulfate (molten salt) dissolved in water (1.568 g / 10 g of water) in advance was injected, and the entire base material was immersed in a solution, followed by sealing under reduced pressure. The test tube was placed in a 350 ° C. thermostatic bath, and acrylamide was graft-polymerized on the lens substrate surface. Moreover, polymerization time was as showing in Table 12 and Sample No. 1-6.

Subsequently, the surface wettability of the lens after graft polymerization was evaluated by measuring the contact angle. The contact angle was measured by the droplet method and the solvent was water.

Moreover, for comparison with the conventional method, the sample which performed the same process using CL2 was produced (Table 12, Comparative Examples 1-6). Table 12 and Sample No. of the polymerization time at this time. It changed as in 1-6. These results are shown in Table 12.

○ Good surface condition (no cloudy)

× Poor surface condition (with cloudy)

As can be seen from Table 12, CL2 was found to require more time to complete graft polymerization compared to CL1. Therefore, it became clear that the lens base material containing CL1, or fluoroalkyl methacrylate, was very effective in that the manufacturing cost was lower than that of the conventional siloxanyl methacrylate-based lens base material.

Example 11

Contact lens base material consisting of a copolymer of alkyl fumarate, siloxanyl fumarate, fluoroalkyl fumarate and methyl methacrylate and processed into a lens shape by a cutting polishing method (diameter about 8 mm, thickness about 0.1 mm) Prepared. This is referred to as CL3 below. In addition, a siloxanyl methacrylate-based lens base material and CL2 similar to those in Example 10 were prepared. CL3 was installed 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 diameter of 70 mm, an interelectrode voltage of 15 kilovolts, and a frequency of 60 hertz, and the discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds on both sides of each piece.

The contact lens base material after discharge was put into the test tube, 35 g of acrylamide and 5 g of N, N'-methylenebisacrylamide (as a crosslinking agent) were dissolved in 50 g of water, and 2.7 ml of a monomer aqueous solution prepared in advance was added. As a redox catalyst, 0.3 ml of a solution of ferrous ammonium sulfate (molten salt) dissolved in water (1.568 g / 10 g of water) in advance was injected, and the entire base material was immersed in a solution, followed by sealing under reduced pressure. The test tube was placed in a 35 degreeC thermostat, and acrylamide was graft-polymerized on the lens base material surface. Moreover, polymerization time was as showing in Table 13 and Sample No. 1-6.

Subsequently, the surface wettability of the lens after graft polymerization was evaluated by measuring the contact angle. The contact angle was measured by the droplet method and the solvent was water.

Moreover, for comparison with the conventional method, the sample which performed the same process using CL2 was produced (Table 13, Comparative Examples 1-6). Table 13 and sample No. of the polymerization time at this time. It changed as in 1-6. These results are shown in Table 13.

○ Good surface condition (no cloudy)

× Poor surface condition (with cloudy)

As can be seen from Table 13, CL2 requires more time to complete graft polymerization than CL3. Therefore, it can be seen that CL3, that is, the fumarate lens base material is very effective in that the manufacturing cost is lower than that of the conventional siloxanyl methacrylate lens base material.

As described above, according to the present invention, the graft polymer capable of adding a crosslinking agent such as N, N'-methylenebisacrylamide to a polymerization system made of a hydrophilic monomer aqueous solution such as acrylamide forms a crosslinked structure and forms a lens base material. Adhesion strength with was increased and wear resistance improved dramatically. This has the effect of maintaining the water wettability of the contact lens for a long time. In addition, by limiting the amount of N, N'-methylenebisacrylamide added as described in the claims, the wear resistance of the graft chain can be improved to maintain high wettability over a long period of time, and do not produce surface turbidity, Did not deteriorate the properties.

In addition, as the polyacrylic acid is entangled within the chains of hydrophilic polymers such as acrylamide grafted on the contact lens surface, the polymer chains form hydrogen bonds with each other, and the graft polymers thus formed have increased adhesion strength with the lens base material. Abrasion resistance was remarkably improved. This has the effect of maintaining the water wettability of the contact lens for a long time. In addition, since the uniformity of the concentration of the monomer solution is ensured by rocking during the graft polymerization, the surface graft state is found to be very effective.

In addition, by attaching a protective fixing member, the contact lens base material collides with the inner wall of the polymerization vessel during degassing or polymerization, thereby preventing the edge portion from being damaged or the surface being damaged. In addition, by limiting the material of the protection fixing member to a material having a smaller surface hardness of the lens base material, the surface damage during polymerization could be prevented as much as possible. Therefore, in view of protecting the contact lens base material, the present invention can be said to be a very effective method, and the other effect is great.

In addition, the lens base material containing fluoroalkyl methacrylate and the fumarate lens base material have a relatively short time required for graft polymerization, and thus have a lower manufacturing cost than conventional siloxanyl methacrylate lens base materials. It turned out to be very effective at.

Example 12

Copolymer A based on methyl methacrylate (containing no silicon or fluorine), siloxanyl methacrylate (containing no fluorine) copolymer B, fumarate copolymer C and fluorine-containing system (γ) -Methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, ethyl methacrylate 1wt%, ethylene glycol di Methacrylate 7wt%, 2,2'-azobis (2,4-isobutyronitrile) (but consisting of 0.25wt% of copolymer) as a copolymerization initiator The contact lens base material A, the base material B, the base material C, and the base material D (about 8 mm in diameter, thickness about 0.1 mm each) were prepared for the shape. The lens substrate was installed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), glow discharged for 5 seconds in an argon atmosphere of 0.04 Torr, and then the lens substrate was left in the air for a while and placed in a test tube. .

A test tube was prepared, and 2.7 ml of the previously prepared cross-linking acrylamide monomer aqueous solution (105 g of acrylamide and 15 g of N, N'-methylenebisacrylamide dissolved in 150 g of water) was added thereto. As a redox catalyst, 0.3 ml of a solution (0.158 g / 10 ml) previously dissolved in ferrous ammonium sulfate (molten salt) in water was injected.

Next, the discharged lens substrate was placed in a test tube so that the entire substrate was immersed in the solution, and after the nitrogen gas replacement, the pressure-sensitive sealing tube was carried out. The test tube was placed in a 35 degreeC thermostat for 60 minutes, and the acrylamide was graft-polymerized on each lens base surface.

Let graft lenses be A ', B', C 'and D', respectively. Each lens was evaluated for surface wettability and nitrogen permeability. The wettability was evaluated by the contact angle by the droplet method, and water was used as the solvent. Oxygen permeability was evaluated by measuring the oxygen permeability coefficient in physiological saline at 35 ° C. using 0.92% by Zadex Inc., and obtaining the DK value (CC · cm / cm 2 · sec · mmHg).

The results are shown in Table 14.

As can be seen from Table 14, the graft lens D 'has high oxygen permeability and excellent surface wettability. However, for other graft lenses, the wettability is high but the oxygen permeability is relatively small. Accordingly, by graft polymerizing a hydrophilic polymer on the surface of the fluorine-containing contact lens base material, a very excellent contact lens having good surface wettability and high oxygen permeability was obtained.

Example 13

Copolymer A based on methyl methacrylate (containing no silicon or fluorine), siloxanyl methacrylate (containing no fluorine) copolymer B, fumarate copolymer C and fluorine-containing system (γ) -Methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, ethyl methacrylate 1wt%, ethylene glycol di 7 wt% methacrylate and 2,2'-azobis (2,4-isobutylnitrile) (but consisting of 0.25 wt% of copolymer as a polymerization initiator). Contact lens base material A, base material B, base material C and base material D (about 8 mm in diameter and about 0.1 mm in thickness) were prepared.

This lens base material was installed in a space made of a spacer of 1.5 mm thickness between the electrodes of 3.5 cm between electrodes and a voltage of 15 kilovolts between electrodes, a frequency of 60 Hertz corona discharge treatment apparatus, and the discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds on both sides of each piece. Next, the discharged lens base material was placed in a test tube and 3.0 ml of a pre-prepared crosslinking agent-added acrylamide monomer solution (105 g of acrylamide and 15 g of N, N'-methylenebisacrylamide dissolved in 180 g of water) was added thereto.

This is an amount sufficient for the monomer solution to immerse the lens base material. The test tube was connected to a vacuum system, the tube was degassed, and the vacuum sealing tube was performed as it was. In this state, the test tube was inserted into a reciprocating vibrator (EP-1, manufactured by Ocean Service Center Co., Ltd.) and subjected to graft polymerization treatment on the surface of the base material for a predetermined time at a constant temperature of 80 ° C. Let graft lenses be A ', B', C 'and D', respectively. After completion of the polymerization, the nature of the graft polymerization was evaluated according to the contact angle. The contact angle uses the droplet method (water) (Table 15). In addition, the presence or absence of damage on the graft lens surface and edges was evaluated by an optical microscope.

In addition, the base curve (BC) of the lens before and after the graft polymerization was measured to calculate the rate of change (Table 16). The swinging conditions (swinging period and amplitude) of the reciprocating vibrator were carried out at a swinging cycle of 160 cycles and a swinging amplitude of 30 mm.

○ No surface damage, edge damage

× surface scratches, edge damage

In Table 15, it can be seen that the lens required for the graft polymerization of less than 20 minutes is the base material D only. In addition, in Table 16, the polymerization time is 20 minutes or more, and the surface state and damage or base curve change occur. Therefore, the graft polymerization treatment using the fluorine-containing contact lens base material is very effective in that the wound and the lens shape do not change.

Example 16

Copolymer A based on methyl methacrylate (containing no silicon or fluorine), siloxanyl methacrylate (containing no fluorine) copolymer B, fumarate copolymer C and fluorine-containing system (γ) -Methacryloxypropyl-tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl methacrylate 19 wt%, 1,3-bis (γ-methacryloxypropyl) -1,1, 3,3-tetrakis (trimethylsiloxy) disiloxane 8wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7wt%, methacrylic acid 10wt%, ethyl methacrylate 1wt%, ethylene glycol di 7 wt% methacrylate and 2,2'-azobis (2,4-isobutylnitrile) (but consisting of 0.25 wt% of copolymer as a polymerization initiator). Contact lens base material A, base material B, base material C and base material D (about 8 mm in diameter and about 0.1 mm in thickness) were prepared. The lens substrate was installed in a discharge device (600 mm between electrodes, 270 volts between electrodes, frequency 60 hertz), glow discharged for 5 seconds in an argon atmosphere of 0.04 Torr, and then the lens substrate was left in the air for a while and placed in a test tube. .

A test tube was prepared, and 2.7 ml of the previously prepared cross-linking acrylamide monomer aqueous solution (105 g of acrylamide and 15 g of N, N'-methylenebisacrylamide dissolved in 150 g of water) was added thereto. As a redox catalyst, 0.3 ml of a solution (0.158 g / 10 ml) previously dissolved in ferrous ammonium sulfate (molten salt) in water was injected.

Next, the discharged lens substrate was placed in a test tube so that the entire substrate was immersed in the solution, and after the nitrogen gas replacement, the pressure-sensitive sealing tube was carried out. The test tube was placed in a 35 degreeC thermostat for 60 minutes, and the acrylamide was graft-polymerized on each lens base surface. Let graft lenses be A ', B', C 'and D', respectively.

Each test was then carried out to confirm the wear resistance. First of all, I did the laundry with 200 round trips in the palm with detergent. Next, the contact angle of the lens surface after rubbing was measured, and the peeling state of the graft polymer was evaluated by looking at the difference with the contact angle before rubbing previously recorded.

For comparison, the same procedure as in Table 17 and Samples A 'to D' was performed on the graft treated product in a 40 wt% acrylamide aqueous solution system without adding a crosslinking agent.

In addition, the contact angle was measured by the droplet method and the solvent used water. These results are shown in Table 17.

Sample: using cross-linking additive monomer solution

Comparative Example: Crosslinking agent-free monomer solution (using acrylamide 40wt% aqueous solution)

In Table 17, in the case of the comparative example, that is, without the crosslinking agent, the wettability is worsened by rubbing for all the graft lenses. In particular, the contact angle change before and after rubbing of the graft treatment foam of the D ', fluorine-containing lens, is remarkably large, indicating that the adhesion strength between the graft layer and the lens base material is very weak. By the way, in the case of addition of a crosslinking agent (Table 17, sample A'-D '), there is little change of contact angle, and the difference by the kind of base material in the adhesive strength with the base material of a graft layer is not recognized. Therefore, it can be said that the base material D is significantly more effective in improving the adhesion strength due to the crosslinking agent than the other base materials A ', B' and C '. In other words, by supplying a fluorine-containing contact lens as the base material to be graft, the effect of improving the scratch resistance of the graft polymer is increased. According to the above, this invention can be said to be a very effective method regarding the contact lens which is excellent in a wearing feeling, and its manufacture.

[Industry availability]

Embodiments of the present invention have been described with respect to a contact lens base material consisting of a fluoroalkyl-containing contact lens base material and a copolymer of alkyl fumarate, siloxanyl fumarate, fluoroalkyl fumarate, methyl methacrylate, but not limited thereto. The same effect is also obtained for other composition hard contact lenses and soft contact lenses such as silicon lab. The same effect was obtained for the surface treatment of polyethylene film, polypropylene, polyvinyl chloride, polyvinylidene chloride, acetate, polyester, polyvinyl alcohol, polystyrene, polycarbonate, and various other polymer materials.

In the examples of the present invention, for example, acrylamide N, N'-methylenebisacrylamide and acrylic acid are described as hydrophilic monomers, but the present invention is not limited thereto, and other hydrophilic monomers, 2-hydroxyethyl methacrylate, polyvinyl alcohol, N-vinylpyrrolidone, polyethylene oxido, and acrylate-based ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, such as glycerol diacrylate and trimethyl propane triacrylate as bifunctional monomers, N-ethyl acrylamide, N-methyl acrylamide, N-cyclopropyl acrylamide which are methacrylate type or N substituted acrylamide monomers, such as a triethylene glycol dimethacrylate and 1, 3- butanediol dimethacrylate Even if alkylacrylamide, dialkylacrylamides, such as N, N'- dimethyl acrylamide and N-methyl-N-ethyl acrylamide, etc. are used, it is the same. Made sure to get the effect. In addition, the graft polymer is entangled with polyacrylic acid and is networked. Therefore, the graft polymer has a thermosensitive characteristic. Therefore, the graft polymer can be applied to applications such as suppression of enzyme reaction by desorption and adsorption of enzyme, recovery of enzyme and sensor for micromachine. have. In addition, it can be applied to medical products such as various packaging materials, agricultural maintenance agents or artificial organs.

Claims (18)

(a) a contact lens substrate surface activation process for activating the 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 crosslinking agent. Method of manufacturing a lens. The method of manufacturing a contact lens according to claim 1, wherein acrylamide is used as said hydrophilic monomer. The method of manufacturing a contact lens according to claim 2, wherein N, N'-methylenebisacrylamide is used as the crosslinking agent. The method of manufacturing a contact lens according to claim 3, wherein the graft polymerization step is performed while the contact lens substrate is immersed in a solution containing acrylamide, N, N'-methylenebisacrylamide and water. . 5. A contact lens according to claim 4, wherein N, N'-methylenebisacrylamide is contained in a solution containing acrylamide, N, N'-methylenebisacrylamide and water in an amount of 10% by weight or less. Way. (a) a contact lens substrate surface activation process for activating a contact lens substrate surface, (b) a graft polymerization process for graft polymerizing a hydrophilic monomer on the contact lens substrate surface, and (c) between the graft polymerized polymer chains A method of manufacturing a contact lens, characterized in that it is configured in the order of a pseudo crosslinking step of pseudocrosslinking using hydrogen bonding. The method of manufacturing a contact lens according to claim 6, wherein acrylamide is used as said hydrophilic monomer. The method of manufacturing a contact lens according to claim 7, wherein acrylic acid is used as a reagent for performing the pseudo crosslinking process. The graft polymerization process according to claim 8, wherein (b) the graft polymerization step is carried out while the contact lens substrate is immersed in a solution containing acrylamide, and (c) acrylic acid, N, N'-methylenebisacrylamide and water are A contact lens base material is immersed in a solution to contain, and said pseudo crosslinking process is performed, The manufacturing method of a contact lens characterized by the above-mentioned. (a) (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 ~C ₆ alkyl, cyclohexyl or phenyl; Alkyl, cyclohexyl, or phenyl of R 2 = C ₁ -C ₆ ; R3 = C ₁ ~C ₆ alkyl, cyclohexyl or phenyl; R4 = C ₁ ~C ₆ alkyl, cyclohexyl or 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 is H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group (C) polyfluoroalkyl siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula; (Wherein, R = CH ₃ or H; R _f = C _{1 to} C ₄ fluoroalkyl group; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3) (D) acryl (methacryl) oxyalkyl silanol represented by the following general 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 alkyl, cyclohexyl or phenyl) (E) 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 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 alkyl, cyclohexyl or phenyl) (F) fluorine-containing siloxanyl methacrylate represented by the following general formula; (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 = 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 oxygen atom Alkyl group which may contain (H) 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 oxygen atom Alkyl group which may contain (I) a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula; And (Wherein R 1, R 2 = CH ₃ or H; 1 = 2-4; p, q = 1 or 2; m and n are each an integer whose sum is in the range of 1-20) (J) Fluorine-containing cyclic olefin represented by the following 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; a contact lens substrate surface activation process for activating a contact lens substrate surface using a copolymer of an ester compound of acrylic acid or methacrylic acid containing at least one selected from n = 0, 1 or 2) and (b) a graft polymerization step of graft polymerizing a hydrophilic monomer on the surface of the contact lens base material. (a) a contact lens substrate surface activation step of activating a contact lens substrate surface mainly comprising a copolymer of an ester compound of acrylic acid or methacrylic acid and an ester compound of fumaric acid; and (b) a hydrophilic monomer on the surface of the contact lens substrate. A method for manufacturing a contact lens, characterized in that it is configured in the order of a graft polymerization step of graft polymerization. (a) a contact lens substrate surface activation process for activating the contact lens substrate surface and (b) a graft polymerization process for graft polymerizing a hydrophilic monomer on the contact lens substrate surface while giving a fluctuation; Method of manufacturing a lens. (a) a contact lens substrate surface activation step for activating a contact lens substrate surface; and (b) a graft polymerization step of graft polymerizing a hydrophilic monomer on the contact lens substrate surface in a state where the contact lens substrate is housed in a protective jig. Method for manufacturing a contact lens, characterized in that configured in order. The method of manufacturing a contact lens according to claim 13, wherein a protective jig having a surface hardness lower than that of the contact lens substrate is used. Preparation of a contact lens, characterized in that the hydrophilic monomer is graft-polymerized on the surface of the contact lens base material using a copolymer of an ester compound of acrylic acid or methacrylic acid containing at least one selected from the following as the contact lens base material. Way. (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 ~C ₆ alkyl, cyclohexyl or phenyl; Alkyl, cyclohexyl, or phenyl of R 2 = C ₁ -C ₆ ; R3 = C ₁ ~C ₆ alkyl, cyclohexyl or phenyl; R4 = C ₁ ~C ₆ alkyl, cyclohexyl or 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 is H; A = H cyclohexyl, phenyl or R _f ; R _f = polyfluoroalkyl group or pentafluorophenyl group (C) polyfluoroalkyl siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula; (Wherein, R = CH ₃ or H; R _f = C _{1 to} C ₄ fluoroalkyl group; 1 = 1 to 4; m = 0, 1 or 2; n = 1 to 3) (D) acryl (methacryl) oxyalkyl silanol represented by the following general 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 alkyl, cyclohexyl or phenyl) (E) 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 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 alkyl, cyclohexyl or phenyl) (F) Fluorine-containing siloxanyl methacrylate represented by the following general formula (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 = 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 oxygen atom Alkyl group which may contain (H) 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 oxygen atom Alkyl group which may contain) (I) a fluorine-containing diacrylate or dimethacrylate monomer represented by the following general formula; And (Wherein R 1, R 2 = CH ₃ or H; 1 = 2-4; p, q = 1 or 2; m and n are each an integer whose sum is in the range of 1-20) (J) fluorine-containing cyclic olefins represented by the following 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) Fluoroalkyl group; n = 0, 1 or 2) A method for producing a contact lens, characterized in that a hydrophilic monomer is graft-polymerized on the surface of a contact lens base material mainly comprising a copolymer of an ester compound of acrylic acid or methacrylic acid and an ester compound of fumaric acid. The method of manufacturing a contact lens according to claim 15 or 16, wherein the graft polymer is crosslinked. The method of manufacturing a contact lens according to claim 15 or 16, wherein the contact lens is pseudo-crosslinked by hydrogen bonding between graft polymer chains.