JPH11326848A - Production of polymer for ocular lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to have high oxygen permeability and to obtain excellent water wettability of a surface by bringing a polymer contg. a monomer having a siloxanyl group as an essential polymn. component into contact with an inorg. acid soln of a specific concn. SOLUTION: An ocular lens polymer consists of a copolymer contg. the monomer having the siloxanyl group as the essential polymn. component. The siloxanyl group refers to a group having at least one Si-O-Si bond. A compd. having the siloxanyl group and a carbon-carbon unsatd. bond is usable as such a monomer having the siloxanyl group. The ocular lens polymer is brought into contact with the inorg. acid soln. of a concn. 5 to 100 wt.%. While the usable inorg. acid is not particularly limited, oxygen acid contg. sulfur atoms, oxygen acid contg. nitrogen atoms and oxygen acid contg. phosphor atoms, are adequate in terms of easy obtaining of a high reforming effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polymer suitably used for ophthalmic lenses such as contact lenses, intraocular lenses and artificial cornea.

[0002]

2. Description of the Related Art In recent years, polymers having a siloxanyl group, such as tris (trimethylsiloxy) silylpropyl methacrylate, and polymers containing a modified polysiloxane as one component have been developed as ophthalmic lens polymers having high oxygen permeability. (See, for example, JP-A-60-142324 and JP-A-54-24).
No. 047).

However, polymers composed of these monomers or macromers have poor water wettability on the surface due to the effect of siloxanyl groups or polysiloxane components introduced for the purpose of improving oxygen permeability. Was not preferred.

In order to improve the water wettability,
In the case of a polymer obtained by copolymerizing a monomer having high water absorption such as (meth) acrylic acid (or a metal salt thereof) with the monomer or macromer, the water content is extremely increased, and as a result, the oxygen permeability is reduced. Had the disadvantage of doing so.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and is intended to obtain a polymer for an ophthalmic lens having a high oxygen permeability and a good surface wettability. It is an object of the present invention to provide a method for producing a polymer for an ophthalmic lens.

[0006]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have conducted intensive studies and as a result, by producing a polymer for an ophthalmic lens having excellent oxygen permeability by a specific method, the oxygen permeability has been improved. It has been found that high water wettability can be imparted to the surface without significantly impairing the properties, and the present invention has been achieved.

That is, in the method for producing a polymer for an ophthalmic lens according to the present invention, a polymer containing a monomer having a siloxanyl group as an essential polymerization component is contained in a concentration of 5% by weight to 10% by weight.
A method for producing a polymer for an ophthalmic lens, comprising contacting the polymer with a 0% by weight inorganic acid solution.

The present invention includes the following preferred embodiments.

(A) The concentration of the inorganic acid solution is 30% by weight or less.
100% by weight.

(B) The inorganic acid is at least one selected from an oxygen acid containing a sulfur atom, an oxygen acid containing a nitrogen atom, and an oxygen acid containing a phosphorus atom.

(C) The inorganic acid is at least one selected from oxygen acids containing a sulfur atom.

(D) The inorganic acid is sulfuric acid.

(E) The contact time between the polymer and the inorganic acid is within 10 minutes.

(F) contacting the polymer with an inorganic acid solution and then treating it under basic conditions; (g) The monomer having a siloxanyl group is a monomer represented by the following formula (a) or (b).

[0015]

Embedded image [In the formulas (a) and (b), A represents a substituent represented by the following formula (A). X represents a group having a carbon-carbon unsaturated bond. Y represents a substituent selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group and an optionally substituted aryl group. n represents an integer of 1 to 10. ]

Embedded image [In the formula (A), A ^{1 to} A ¹¹ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. k represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where k = a = b = c = 0 is excluded. ]

[0016]

Embodiments of the present invention will be described below.

The method for producing a polymer for an ophthalmic lens of the present invention is applicable to a polymer for an ophthalmic lens comprising a copolymer containing a monomer having a siloxanyl group as an essential polymerization component.

In the present invention, the siloxanyl group means a group having at least one Si—O—Si bond. As the monomer having a siloxanyl group, a compound having a siloxanyl group and a carbon-carbon unsaturated bond can be used.

As the monomer having a siloxanyl group, a monomer represented by the following formula (a) or (b) is preferably used.

[0020]

Embedded image [In the formulas (a) and (b), A represents a substituent represented by the following formula (A). X represents a group having a carbon-carbon unsaturated bond. Y represents a substituent selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group and an optionally substituted aryl group. n represents an integer of 1 to 10. ]

Embedded image [In the formula (A), A ^{1 to} A ¹¹ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. k represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where k = a = b = c = 0 is excluded. In the formulas (a) and (b), X represents a group having a carbon-carbon unsaturated bond. Preferred examples thereof include substitution represented by the following formulas (x1) to (x6). A group of which the formula (x
The substituent represented by the formula (x1) and the formula (x5) are preferred because they can impart high water wettability.

[0021]

Embedded image [In the formulas (x1) to (x6), R ¹ represents a hydrogen atom or a methyl group. In formula (a), Y represents a substituent selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, and an optionally substituted aryl group.

The alkyl group which may be substituted is not particularly limited whether it is linear or branched, but is preferably an alkyl group having 1 to 20 carbon atoms. Specifically, a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2,3-dihydroxypropyl group,
Hydroxybutyl group, 4-hydroxybutyl group, 2-hydroxypentyl group, 5-hydroxypentyl group, 2-
Hydroxyhexyl group, 6-hydroxyhexyl group, 3
Examples include -methoxy-2-hydroxypropyl group, 3-ethoxy-2-hydroxypropyl group, and substituents represented by the following formulas (y1) and (y2).

[0023]

Embedded image [In the formulas (y1) and (y2), R ^{2 to} R ⁴ are each independently a substituent selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group and an optionally substituted aryl group. Represents a group. R ³ and R ⁴ are bonded to each other to form N
A ring containing an atom may be formed. If the substituents represented by the formulas (y1) and (y2) are more specifically exemplified, the following formulas (y1-1) to (y1-
14) and substituents represented by the following formulas (y2-1) to (y2-15).

[0024]

Embedded image

Embedded image

Embedded image [In the formulas (y1-10) and (y1-13), i is 3
Represents an integer of ８8. Here, the aryl group which may be substituted is not particularly limited, but preferably has 6 to 20 carbon atoms, and specifically includes a 4-hydroxyphenyl group, a 2-hydroxyphenyl group and the like. No.

In the formulas (a) and (b), n is 1-10
Represents an integer of 1 to 5, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and most preferably 3.

In the formula (A), A ^{1 to} A ¹¹ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. Examples include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include an alkyl group such as a sec-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, and an octyl group, and an aryl group such as a phenyl group and a naphthyl group.

In the formula (A), k is an integer of 0 to 200, preferably 0 to 50, more preferably 0 to 200.
It is 10. A, b, and c are each independently an integer of 0 to 20, preferably a, b, and c are each independently an integer of 0 to 5. When k = 0, preferably a = b = c = 1 or a = b = 1 and c = 0.

Further, among the substituents represented by the formula (A), those which are particularly preferable because they can be obtained industrially at relatively low cost include a tris (trimethylsiloxy) silyl group and a bis (trimethylsiloxy) methylsilyl group. , A polydimethylsiloxane group, a polymethylsiloxane group, and a poly-co-methylsiloxane-dimethylsiloxane group.

The polymer for an ophthalmic lens applicable to the present invention may further contain another monomer as a copolymer component. The copolymerization component in that case is not particularly limited as long as copolymerization is possible, and is a monomer having a (meth) acryloyl group, a styryl group, an allyl group, a vinyl group and other copolymerizable carbon-carbon unsaturated bonds. Etc. can be used.

Hereinafter, some examples will be given, but the present invention is not limited to these examples. Alkyl such as methyl (meth) acrylate and ethyl (meth) acrylate
(Meth) acrylates, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol monoalkyl ether (meth) acrylate, polyalkylene glycol bis (meth) acrylate, trimethylolpropane tris (meth) acrylate, pentaerythritol tetrakis (meth) Acrylates, polyfunctional (meth) acrylates such as siloxane macromers having carbon-carbon unsaturated bonds at both ends, trifluoroethyl
(Meth) acrylate, halogenated alkyl (meth) acrylates such as hexafluoroisopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyalkyl having a hydroxyl group such as 2,3-dihydroxypropyl (meth) acrylate ( (Meth) acrylates, N, N-dimethylacrylamide, N, N-
Diethylacrylamide, N, N-di-n-propylacrylamide, N, N-diisopropylacrylamide,
(Meth) acrylamides such as N, N-di-n-butylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, N-acryloylpyrrolidine, N-methyl (meth) acrylamide, styrene, α-
Examples include aromatic vinyl monomers such as methylstyrene, vinylpyridine, and divinylbenzene; maleimides; and heterocyclic vinyl monomers such as N-vinylpyrrolidone.

The polymer for an ophthalmic lens applicable to the method for producing the polymer for an ophthalmic lens according to the present invention comprises, as a copolymer component, a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule. It is preferred to include. When the production method of the present invention is applied, the surface of the polymer for an ophthalmic lens may be roughened and the transparency may be impaired, but a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule may be used. By including it as a copolymer component, the surface roughness can be reduced or prevented. In order to reduce or prevent surface roughness, it is preferable that a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule be contained in an amount of 0.5% by weight or more as a copolymerization component, and 3% by weight. % Or more, more preferably 5% by weight or more.

In the polymer for ophthalmic lenses applicable to the present invention, the copolymerization ratio of the monomer having a siloxanyl group is preferably 30% by weight or more, from the viewpoint of ensuring high oxygen permeability. It is preferably at least 50% by weight, most preferably at least 60% by weight.

The polymer for an ophthalmic lens applicable to the present invention may contain an ultraviolet absorber, a dye, a colorant, and the like. Further, an ultraviolet absorber having a polymerizable group, a dye, a colorant, and the like may be contained in a copolymerized form.

As a polymerization method and a molding method of the polymer for an ophthalmic lens applicable to the present invention, known methods can be used. For example, there is a method in which an ophthalmic lens polymer is once polymerized and shaped into a round bar or a plate, and then processed into a desired shape by cutting or the like, a mold polymerization method, a spin cast polymerization method, or the like.

The process for producing a polymer for an ophthalmic lens according to the present invention comprises the steps of: preparing a polymer for an ophthalmic lens comprising a copolymer containing a monomer having a siloxanyl group as an essential polymerization component;
It is characterized by contacting with an inorganic acid solution having a concentration of 5% by weight to 100% by weight.

The inorganic acid that can be used in the present invention is not particularly limited, but oxygen acids containing a sulfur atom (eg, sulfuric acid, sulfurous acid, dithionous acid, etc.), nitrogen atom And oxyacids containing phosphorus atoms (eg, phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid, metaphosphoric acid, diphosphorous acid, phosphorous acid) , Hypophosphorous acid and the like) are preferable, and among them, an oxygen acid containing a sulfur atom is preferable, and sulfuric acid is most preferable. Inorganic acids can be used as a mixture of two or more kinds.

As the solvent for the inorganic acid solution, various inorganic and organic solvents can be used. For example, various alcohols such as water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and glycerin, and various aromatic carbons such as benzene, toluene and xylene. Hydrogen, hexane, heptane, octane, decane, petroleum ether, kerosene, ligroin, various aliphatic hydrocarbons such as paraffin, various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl benzoate, phthalate Various esters such as dioctyl acid, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether Tel,
Various ethers such as triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, hexamethylphosphoric triamide, dimethyl sulfoxide And various aprotic polar solvents such as methylene chloride, chloroform, dichloroethane, trichloroethane, and trichloroethylene;

Among them, water is most preferable in terms of economy, simplicity of handling, and chemical stability. As the solvent, a mixture of two or more substances can be used. However, the solvent is not essential.

The concentration of the inorganic acid solution is from 5% by weight to 100% by weight, and from 30% by weight to
00% by weight is preferred, and 50% to 100% by weight is most preferred. When the concentration of the inorganic acid solution is 50% by weight to 100% by weight, a large modifying effect can be obtained even if the treatment time is as short as 10 minutes or less.

The inorganic acid solution used in the present invention comprises:
It may contain components other than the inorganic acid and the solvent. Particularly preferred as components other than the inorganic acid and the solvent are oxidizing agents such as hydrogen peroxide and reducing agents. By using an oxidizing agent or a reducing agent together, a greater reforming effect may be obtained.

In the method for producing the polymer for an ophthalmic lens of the present invention, the method for bringing the polymer for an ophthalmic lens into contact with an inorganic acid solution is not particularly limited. Method for dipping polymer for ophthalmic use, method for spraying inorganic acid solution on polymer for ophthalmic lens, method for applying inorganic acid solution to polymer for ophthalmic lens with spatula, brush, etc. Examples thereof include a method of applying by a spin coating method or a dip coating method.

In the present invention, the temperature at which the polymer for an ophthalmic lens is brought into contact with an inorganic acid solution is not particularly limited, but is usually within a temperature range of about -50 ° C to 300 ° C. In consideration of workability, the temperature range is preferably -10C to 150C, and most preferably -5C to 60C.

In the present invention, the time for bringing the polymer for ophthalmic lenses into contact with the inorganic acid solution varies depending on the concentration and temperature of the inorganic acid solution, but is generally within 10 minutes, preferably within 1 minute. Is more preferred.
If the contact time is too long, not only the workability and the productivity will deteriorate, but also the surface of the polymer for ophthalmic lenses will be roughened and the transparency may be impaired.

In the present invention, it is preferable that the polymer for an ophthalmic lens is brought into contact with an inorganic acid solution and then the inorganic acid is removed by washing.

Various inorganic and organic solvents can be used as the washing solvent. For example, water, methanol, ethanol,
Various alcohols such as propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and glycerin, various aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, octane, Decane, petroleum ether,
Kerosene, ligroin, various aliphatic hydrocarbons such as paraffin, acetone, methyl ethyl ketone, various ketones such as methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl benzoate, various esters such as dioctyl phthalate, diethyl ether, tetrahydrofuran, Various ethers such as dioxane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidy Various aprotic polarities such as non-, hexamethylphosphoric triamide, dimethyl sulfoxide Medium, methylene chloride, chloroform,
Halogen solvents such as dichloroethane, trichloroethane, and trichloroethylene, and chlorofluorocarbon solvents.

As a washing solvent, a mixture of two or more solvents can be used. The washing solvent may contain components other than the solvent, for example, inorganic salts, a surfactant, and a detergent.

In the present invention, after the polymer for an ophthalmic lens is brought into contact with an inorganic acid solution, it can be further treated under basic conditions. Further water wettability can be imparted by treating under basic conditions.

Examples of the treatment under basic conditions include a method in which the ophthalmic lens polymer is brought into contact with a basic solution, a method in which the ophthalmic lens polymer is brought into contact with a basic gas, and the like. The simplest method of obtaining a large modifying effect is to immerse the ophthalmic lens polymer in a basic solution, particularly an aqueous solution of a basic inorganic substance.

Examples of the aqueous solution of a basic inorganic substance include aqueous solutions of typical basic inorganic substances such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonia and ammonium salts. Needless to say, a pH buffer having a pH of more than 7 can also be preferably used.

In the present invention, the temperature at the time of treatment under basic conditions is not particularly limited, but is usually -50 ° C to 300 ° C.
It is performed within a temperature range of about ° C. Considering workability-
A temperature range of 10 ° C to 150 ° C is more preferable, and -5 ° C to
60 ° C. is most preferred.

The treatment under the basic condition may also serve as the treatment for removing the inorganic acid by the above-mentioned washing.

Further, as a preservative solution for an ophthalmic lens, a pH of 7
A pH buffer solution of ８8 may be used. In this case, storage in this storage solution can also serve as the treatment under the above basic conditions.

The treatment time under the basic conditions of the present invention is not particularly limited, but is generally preferably within 100 hours, more preferably within 50 hours. If the processing time is too long, the workability and productivity deteriorate, which is not preferable. However, as described above, this is not limited to the case where the storage of the ophthalmic lens in the storage solution also serves as the treatment under the basic condition.

The polymer for an ophthalmic lens obtained by the present invention has a water wettability having a dynamic contact angle with pure water (at the time of advance,
The immersion speed (0.1 mm / sec) is preferably 90 ° or less, more preferably 70 ° or less, and most preferably 65 ° or less. The oxygen permeability is determined by the oxygen permeability coefficient [ml (ST
P) cm · cm ^-2 · sec ^-1 · mmHg ^-1 ] is 55 × 1
0 ^-11 or more is preferable, 75 x 10 ^-11 or more is more preferable, and 85 x 10 ^-11 or more is most preferable.

When the application of the polymer for an ophthalmic lens is a soft contact lens, the tensile modulus of the polymer for an ophthalmic lens obtained by the present invention is from 0.01 to 0.01.
30 MPa is preferable, 0.1 to 7 MPa is more preferable, and 0.4 to 1.5 MPa is most preferable.

The polymer for ophthalmic lenses of the present invention is suitable for ophthalmic lenses such as contact lenses, intraocular lenses and artificial cornea.

[0057]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

[Measurement Methods] Various measurements in this example were performed by the following methods.

(1) Proton nuclear magnetic resonance spectrum Measured using EX270 manufactured by JEOL Ltd. Chloroform-d was used as a solvent.

(2) A dynamic contact angle sample having a film size of about 5 mm × 10 mm × 0.2 mm was used.
The dynamic contact angle during forward movement was measured using a T-6000 model. Immersion speed is 0.1mm / sec, immersion depth is 7mm
And

(3) Oxygen Permeability Coefficient The oxygen permeability coefficient of a film sample was measured in water at 35 ° C. using a Kakenhi type film oxygen permeability system manufactured by Rika Seiki Kogyo.

[Synthesis Example 1] Compound represented by formula (M1)
Synthesis of Monomer Containing Substance as Main Component In a 100 ml eggplant type flask, glycidyl methacrylate (12.1 g, 0.085 mol) and 3-aminopropyltris (trimethylsiloxy) silane (30.0 g,
0.085 mol), and the mixture was stirred at 60 ° C for 8 hours. The proton nuclear magnetic resonance spectrum of this reaction product was measured and analyzed. As a result, it was confirmed that the reaction product was a monomer containing a compound represented by the following formula (M1) as a main component.

[0063]

Embedded image Synthesis Example 2 Synthesis of Compound Represented by Formula (M8) In a 1 L eggplant-shaped flask, 2-hydroxyethyl acrylate (65.0 g, 0.56 mol) and 3-aminopropyltris (trimethylsiloxy) silane (200 g) were placed. ,
0.56 mol) and ethyl acetate (250 ml), and the mixture was stirred at room temperature for 7 days. After completion of the reaction, the solvent was removed using a rotary vacuum evaporator, and then vacuum distillation was performed to obtain a transparent liquid. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of this liquid, it was confirmed that the liquid was a compound represented by the formula (M8).

[0064]

Embedded image [Synthesis Example 3] A compound represented by Formula (M9) as a main component
Synthesis of Monomer A compound (94.0 g, 0.20 mol) of formula (M8) and glycidyl methacrylate (29.9 g, 0.21 mol) were added to a 200 ml eggplant-shaped flask, and the mixture was added to a flask.
Stirred at C for 18 hours. After completion of the reaction, volatile components were removed at 60 ° C. for 5 hours under reduced pressure. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, it was confirmed that the liquid was a monomer containing the compound represented by the formula (M9) as a main component.

[0065]

Embedded image [Polymerization Example 1] A monomer having the compound represented by the formula (M1) as a main component (85 parts by weight, Synthesis Example 1), N, N-dimethylacrylamide (15 parts by weight), and triethylene glycol dimethacrylate (1 part by weight) Parts), 2,2′-azobis- (2,4-
After addition of dimethylvaleronitrile) (0.1 parts by weight), the monomer mixture was degassed under an argon atmosphere, poured between glass plates and sealed. First, polymerization was carried out at 100 ° C. for 4 hours, and then the temperature was lowered from 100 ° C. to 40 ° C. over 3.5 hours, and then kept at 40 ° C. for 2 hours or more to obtain a film sample of a polymer for an ophthalmic lens.

[Polymerization Example 2] A monomer having a compound represented by the formula (M1) as a main component (85 parts by weight, Synthesis Example 1),
N, N-dimethylacrylamide (15 parts by weight) and triethylene glycol dimethacrylate (5 parts by weight)
Was uniformly mixed, and 2,2′-azobis- (2,4-dimethylvaleronitrile) (0.1 part by weight) was added as a polymerization initiator. Then, the monomer mixture was degassed under an argon atmosphere. Poured between glass plates and sealed. First 10
Polymerization was carried out at 0 ° C. for 4 hours, followed by cooling from 100 ° C. to 40 ° C. over 3.5 hours, followed by holding at 40 ° C. for 2 hours or more to obtain a film sample of a polymer for ophthalmic lenses.

[Polymerization Example 3] Instead of a monomer (85 parts by weight, Synthesis Example 1) containing a compound represented by Formula (M1) as a main component, a compound represented by Formula (M9) is used as a main component. A film sample of a polymer for an ophthalmic lens was obtained in the same manner as in Polymerization Example 2 except that the monomer (85 parts by weight, Synthesis Example 3) was used.

[Polymerization Example 4] Instead of a monomer (85 parts by weight, Synthesis Example 1) containing a compound represented by the formula (M1) as a main component, tris (trimethylsiloxy) silylpropyl methacrylate (85 parts by weight, Shin-Etsu) Except for using Chemical Industry Co., Ltd., was performed in the same manner as in Polymerization Example 2 to obtain a film sample of the polymer for ophthalmic lenses.

[Polymerization Example 5] Instead of a monomer (85 parts by weight, Synthesis Example 1) containing a compound represented by the formula (M1) as a main component, N- [tris (trimethylsiloxy) silylpropyl] acrylamide (85 (Parts by weight) in the same manner as in Polymerization Example 2 to obtain a film sample of the polymer for ophthalmic lenses.

Example 1 A film-shaped sample of the polymer for an ophthalmic lens obtained in Polymerization Example 1 was immersed in concentrated sulfuric acid (96% by weight) for 3 seconds, immediately immersed in pure water, and further purified. Rinse with water. This was immersed in a 1 M aqueous sodium hydroxide solution at 40 ° C. for 60 minutes. Next, it was immersed in pure water and washed twice (5 minutes) by an ultrasonic cleaner. Pure water was replaced every time washing was completed.

The obtained sample was immersed in a boric acid / sodium borate system pH 7.2 buffer (hereinafter abbreviated as “buffer A”) and left at room temperature for 24 hours. The dynamic contact angle and oxygen permeability coefficient of this sample with respect to pure water were measured. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

Example 2 The procedure was carried out except that the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 2 was used instead of the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 1. The procedure was the same as in Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

Example 3 The procedure was performed except that the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 3 was used instead of the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 1. The procedure was the same as in Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

Example 4 The procedure was performed except that the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 4 was used instead of the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 1. The procedure was the same as in Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

Example 5 The procedure was carried out except that the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 5 was used instead of the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 1. The procedure was the same as in Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

Example 6 A film sample of the polymer for an ophthalmic lens obtained in Polymerization Example 2 was immersed in a 50% by weight aqueous sulfuric acid solution for 15 seconds, immediately immersed in pure water, and further rinsed with pure water. did. It was immersed in a 1 M aqueous sodium hydroxide solution at 40 ° C. for 60 minutes. Next, it was immersed in pure water, and washed twice with an ultrasonic cleaner (for 5 minutes). Pure water was replaced every time washing was completed.

The obtained sample was immersed in buffer A and left at room temperature for 24 hours. Then, the dynamic contact angle and oxygen permeability coefficient of this sample with respect to pure water were measured. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.

[Comparative Examples 1 to 5] Film-shaped samples of the polymer for ophthalmic lenses obtained in Polymerization Examples 1 to 5 were immersed in buffer A without any special treatment, and left at room temperature for 24 hours. .

For each of these samples, the dynamic contact angle with pure water and the oxygen permeability coefficient were measured. These samples had high oxygen permeability, but poor surface wettability. The results are shown in Table 1.

[0080]

[Table 1]

[0081]

According to the present invention, by producing a polymer for an ophthalmic lens having excellent oxygen permeability by a specific method, it is possible to impart high water wettability to the surface without greatly impairing the oxygen permeability. it can. The polymer for an ophthalmic lens produced by the production method of the present invention is suitably used for an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.

Claims (8)

[Claims] 1. A method for producing a polymer for an ophthalmic lens, comprising contacting a polymer containing a monomer having a siloxanyl group as an essential polymerization component with a 5% to 100% by weight inorganic acid solution. 2. The concentration of the inorganic acid solution is 30% by weight to 1%.
The method for producing a polymer for an ophthalmic lens according to claim 1, wherein the amount is 00% by weight. 3. The method according to claim 2, wherein the inorganic acid is an oxygen acid containing a sulfur atom,
3. The method for producing a polymer for an ophthalmic lens according to claim 1, wherein the polymer is at least one selected from an oxygen acid containing a nitrogen atom and an oxygen acid containing a phosphorus atom. 4. The method for producing a polymer for an ophthalmic lens according to claim 1, wherein the inorganic acid is at least one selected from oxygen acids containing a sulfur atom. 5. The method for producing a polymer for an ophthalmic lens according to claim 4, wherein the inorganic acid is sulfuric acid. 6. The method for producing an ophthalmic lens polymer according to claim 1, wherein a contact time between the polymer and the inorganic acid is 10 minutes or less. 7. The method for producing an ophthalmic lens polymer according to claim 1, wherein the polymer is brought into contact with the inorganic acid solution and then treated under a basic condition. 8. The ophthalmic lens according to claim 1, wherein the monomer having a siloxanyl group is a monomer represented by the following formula (a) or (b). Of manufacturing polymer for medical use. Embedded image [In the formulas (a) and (b), A represents a substituent represented by the following formula (A). X represents a group having a carbon-carbon unsaturated bond. Y represents a substituent selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group and an optionally substituted aryl group. n represents an integer of 1 to 10. ] [In the formula (A), A ^{1 to} A ¹¹ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. k represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where k = a = b = c = 0 is excluded. ]