JPH11326849A - 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 org. acid or org. acid soln. 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 org. acid or org. acid soln. While the usable org. acid is not particularly limited, 1-20C org. carboxylic acid and 1-20C org. sulfonic acid are adequate in terms of easy availability and ease of obtaining a high reforming effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer for an ophthalmic lens suitably used for an ophthalmic lens such as a contact lens, an intraocular lens and an artificial cornea.

[0002]

2. Description of the Related Art In recent years, polymers having a siloxanyl group-containing methacrylate such as tris (trimethylsiloxy) silylpropyl methacrylate or a modified polysiloxane as one component have been developed and used as polymers for ophthalmic lenses having high oxygen permeability. (Japanese Patent Laid-Open No. 60-1423)
No. 24 and JP-A-54-24047).

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.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a process for producing a polymer for an ophthalmic lens having high oxygen permeability and excellent surface wettability. The purpose is to provide.

[0005]

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, the process for producing a polymer for an ophthalmic lens according to the present invention comprises contacting a polymer containing a monomer having a siloxanyl group as an essential polymerization component with an organic acid or an organic acid solution. It is a method for producing a polymer for use. In the present invention, it is preferable that the polymer produced in such a manner is treated under basic conditions and further treated with heated water, if necessary.

In the present invention, the organic acid solution is preferably an organic acid aqueous solution or an organic acid alcohol solution, and the organic acid is an organic carboxylic acid having 1 to 20 carbon atoms and an organic carboxylic acid having 1 to 20 carbon atoms. It is preferable that at least one selected from organic sulfonic acids is used. Furthermore, in the method for producing a polymer for an ophthalmic lens of the present invention, it is included as a preferable embodiment that the monomer having a siloxanyl group is a monomer represented by the following formula (a) or (b). .

[0008]

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. ]

[0009]

Embodiments of the present invention will be described below.

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.

[0013]

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.

[0014]

Embedded image [In the formulas (x1) to (x6), R ¹ represents a hydrogen atom or a methyl group. In the formulas (a) and (b), 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 preferably has 1 to 20 carbon atoms, specifically hydroxymethyl Group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxybutyl group, 4-hydroxybutyl group, 2-hydroxypentyl group, 5-hydroxypentyl Group, 2-hydroxyhexyl group, 6-hydroxyhexyl group, 3-methoxy-2-hydroxypropyl group, 3-ethoxy-2-hydroxypropyl group, and substituents represented by the following formulas (y1) and (y2) Can be mentioned.

[0015]

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).

[0016]

Embedded image

Embedded image

Embedded image [In the formulas (y1-10) and (y1-13), i is 3
Represents an integer of ８8. The aryl group which may be substituted is not particularly limited, but preferably has 6 to 20 carbon atoms, and particularly preferable groups are a 4-hydroxyphenyl group and a 2-hydroxy group. And a phenyl group.

In the formulas (a) and (b), n is 1 to 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, and more preferably 0 to 10. a, b, and c each independently represent an integer of 0 to 20; preferably, a, b, and c each independently represent an integer of 0 to 5; When k = 0, preferably a = b = c = 1 or a = b = 1 and c = 0.

Among the substituents represented by the formula (A), those which are particularly preferable because they are commercially available at relatively low cost,
A tris (trimethylsiloxy) silyl group, 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 copolymerization component. The copolymerization component in that case is not particularly limited as long as it is copolymerizable, and may be a (meth) acryloyl group, a styryl group, an allyl group, a vinyl group, or another monomer having a copolymerizable carbon-carbon unsaturated bond. 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-
Aromatic vinyl monomers such as methylstyrene, vinylpyridine, divinylbenzene, maleimides, and N-
And heterocyclic vinyl monomers such as vinylpyrrolidone.

The polymer for ophthalmic lenses applicable to the present invention preferably contains, as a copolymerization component, a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule. When the production method of the present invention is applied, the mechanical properties of the polymer for an ophthalmic lens may be reduced. In such a case, two or more copolymerizable carbon-carbon unsaturated bonds are contained in one molecule. By including the monomer as a copolymer component, a decrease in mechanical properties can be reduced or prevented. In order to reduce or prevent mechanical property deterioration,
It is preferred that the copolymer component contains at least 0.5% by weight or more of a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule, more preferably 3% by weight or more, and 5% by weight or more.
% By weight or more is more preferable.

In the polymer for an ophthalmic lens 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, a dye, and a colorant having a polymerizable group 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 are 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 present invention is characterized in that a polymer for an ophthalmic lens comprising a copolymer containing a monomer having a siloxanyl group as an essential polymerization component is brought into contact with an organic acid or an organic acid solution.

The organic acid which can be used in the present invention is not particularly limited. However, the organic acid having 1 to 20 carbon atoms and the organic carboxylic acid having 1 carbon atom are preferable in that they are easily available and a large modifying effect is easily obtained. -20 organic sulfonic acids are preferred.

Preferred examples of the organic carboxylic acid having 1 to 20 carbon atoms include various amino acids, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, (meth) acrylic acid, crotonic acid, Isocrotonic acid, itaconic acid, benzoic acid, phthalic acid, isophthalic acid,
Terephthalic acid, trimellitic acid, vinylbenzoic acid, cinnamic acid, salicylic acid, maleic acid, fumaric acid, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphoric acid, naphthoic acid, toluic acid, furic acid, tenic acid, nicotinic acid, isonicotinic acid, glycolic acid, lactic acid Glyceric acid, tartronic acid, malic acid, tartaric acid, tropic acid, anisic acid, vanillic acid, veratric acid, protocatechuic acid and gallic acid. In addition, carbon number 1-20
Preferred examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid,
Trifluoromethanesulfonic acid, benzenesulfonic acid,
p-Toluenesulfonic acid, dodecylbenzenesulfonic acid and the like. Organic acids can be used as a mixture of two or more.

In the present invention, when an organic acid solution is used, various inorganic and organic solvents can be used as the solvent. 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, 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. Among these, water and various alcohols are preferable because the mechanical properties of the polymer for ophthalmic lenses are not easily reduced. A mixture of two or more substances can be used as the solvent.

The concentration of the organic acid solution is preferably 0.1% by weight or more, more preferably 1% by weight or more, and most preferably 5% by weight or more from the viewpoint of the effect of the modifying effect. If the concentration of the organic acid solution is less than 0.1% by weight, the resulting modifying effect is not sufficient, which is not preferable.

The organic acid or organic acid solution used in the present invention may contain components other than the organic acid and the solvent. In particular, when a basic compound is contained, a large modifying effect may be obtained. In that case, it is preferable to use water or alcohol as a solvent from the viewpoint of solubility. Preferred examples of the basic compound include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, various amines, and the like. be able to. Among these, compounds having strong basicity are preferred, and lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, ammonia, tetraalkylammonium hydroxide, 1,8-diazabicyclo [5.4.0] undecene are preferred. -7,1,5-diazabicyclo [4.3.0] nonene-
5,1,2-dimethyl-1,4,5,6-tetrahydropyrimidine and the like are most preferred.

In the present invention, the method of contacting the polymer for an ophthalmic lens with an organic acid or an organic acid solution is not particularly limited. For example, the method for contacting the polymer for an ophthalmic lens with an organic acid or an organic acid solution may be used. Immersion method, method of spraying organic acid or organic acid solution to polymer for ophthalmic lens, method of applying organic acid or organic acid solution to polymer for ophthalmic lens with spatula, brush, etc., organic method for polymer for ophthalmic lens A method of applying an acid or organic acid solution by a spin coating method or a dip coating method can be used.

In the present invention, the temperature at which the polymer for an ophthalmic lens is brought into contact with an organic acid or an organic acid solution is not particularly limited, but it is usually carried out within a temperature range of about -50 ° C. to 300 ° C. -10 ℃ ~ 150 ℃
Is more preferable, and -5 ° C to 60 ° C is most preferable.

In the present invention, the optimal time for contacting the polymer for ophthalmic lenses with an organic acid or an organic acid solution varies depending on the concentration and temperature of the organic acid or the organic acid solution, but generally 100 hours. Within 24 hours, more preferably within 24 hours, most preferably within 12 hours. If the contact time is too long, not only the workability and productivity will deteriorate, but also adverse effects such as a decrease in oxygen permeability and a decrease in mechanical properties may be caused.

In the present invention, the polymer for an ophthalmic lens is preferably removed from the polymer by contact with an organic acid or an organic acid solution and then washing the polymer.

As the washing solvent, 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; A mixture of two or more solvents can be used as the washing solvent.

The washing solvent may contain components other than the solvent, for example, inorganic salts, surfactants and detergents.

In the present invention, after the polymer for an ophthalmic lens is brought into contact with an organic acid or an organic 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 the basic conditions include a method of bringing an ophthalmic lens polymer treated with an organic acid or an organic acid solution into contact with a basic solution, and a method of bringing the polymer into contact with a basic gas. Can be The simplest method of obtaining a large modifying effect is to immerse the ophthalmic lens polymer in a basic compound solution. Preferred examples of the basic compound include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, various amines, and the like. be able to. As the solvent for the basic compound solution, water and alcohols are preferable. As the basic compound solution, a pH buffer having a pH of more than 7 can also be preferably used.

The temperature at the time of the treatment under the basic conditions is not particularly limited, but it is usually carried out within a temperature range of about -50 ° C to 300 ° C.
C. is more preferable, and -5.degree. C. to 60.degree. C. is most preferable.

The treatment under such basic conditions may also serve as the treatment for removing the organic acid by the above-mentioned washing.

Further, as a preservation solution for an ophthalmic lens, a pH of 7
A pH buffer of ｐＨ8 may be used. In this case, preservation in this preservation solution can also serve as the treatment under the above basic conditions.

The treatment time under basic conditions 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.

In the present invention, a further greater reforming effect can be obtained by further performing a heating water treatment. In the present invention, the heated water treatment means a treatment in which heated water molecules are brought into contact. Specifically, a method of immersing the polymer for ophthalmic lens in water and heating or a method of exposing the polymer for ophthalmic lens to heated steam can be applied. The heating temperature in this case is selected from the range of 50C to 300C. If the heating temperature exceeds 100 ° C,
Heated water treatment should be performed in a pressure vessel. The time of the heating water treatment is preferably about 1 minute to 24 hours,
A period of about minutes to 12 hours is more preferable.

The polymer for an ophthalmic lens obtained by the present invention has a water wettability based on 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 polymer for an ophthalmic lens is used as a soft contact lens, the polymer for an ophthalmic lens obtained by the present invention has a tensile modulus of 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.

[0049]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

[Measurement Methods] The measurement of various characteristic values in each of Examples and Comparative Examples was performed by the following methods.

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

(2) A dynamic contact angle sample was used as a sample having a film size of about 5 mm × 10 mm × 0.2 mm. Was measured. Immersion speed is 0.1mm / sec, immersion depth is 7m
m.

(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 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.

[0055]

Embedded image Synthesis Example 2 Synthesis of Compound Represented by Formula (M2) In a 1 L eggplant-shaped flask, methyl acrylate (48.
2g, 0.56mol), 3-aminopropyltris
(Trimethylsiloxy) silane (200g, 0.56mo
l) and ethyl acetate (250 ml) were added 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 (M2).

[0056]

Embedded image [Synthesis Example 3] A compound represented by Formula (M3) as a main component
Synthesis of Monomer to a Compound A compound of formula (M2) (88.0 g, 0.20 mol) and glycidyl methacrylate (29.9 g, 0.21 mol) were added to a 200 ml eggplant-shaped flask, and the mixture was stirred at 60 ° C. for 18 hours. After the completion of the reaction,
Volatile components were removed at 5 ° C. for 5 hours. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid,
It was confirmed that the monomer represented by the formula (M3) was a main component.

[0057]

Embedded image Synthesis Example 4 Synthesis of Compound Represented by Formula (M4) In a 1 L eggplant-shaped flask, butyl acrylate (71.
8 g, 0.56 mol), 3-aminopropyl tris
(Trimethylsiloxy) silane (200g, 0.56mo
l) and ethyl acetate (250 ml) were added 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 (M4).

[0058]

Embedded image [Synthesis Example 5] A compound represented by Formula (M5) as a main component
A compound of formula (M4) (96.4 g, 0.20 mol) and glycidyl methacrylate (29.9 g, 0.21 mol) were added to a 200 ml eggplant-shaped flask, followed by stirring at 60 ° C. for 18 hours. After the completion of the reaction,
Volatile components were removed at 5 ° C. for 5 hours. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid,
It was confirmed that the compound was a monomer containing the compound represented by the formula (M5) as a main component.

[0059]

Embedded image [Polymerization Example 1] A monomer having the compound represented by the formula (M1) as a main component (100 parts by weight, Synthesis Example 1) and triethylene glycol dimethacrylate (5 parts by weight) are uniformly mixed, and used as a polymerization initiator. 2,2'-azobis-
(2,4-dimethylvaleronitrile) (0.1 parts by weight)
After the addition of, the monomer mixture was degassed under an argon atmosphere, poured between glass plates and sealed. First 100 ℃
For 4 hours, followed by 100 ° C to 40 ° C.
After the temperature was lowered over 5 hours, the temperature was kept at 40 ° C. for 2 hours or more to obtain a film sample of the polymer for ophthalmic lenses.

[Polymerization Example 2] A monomer having a compound represented by Formula (M3) as a main component (85 parts by weight, Synthesis Example 3),
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] A monomer containing a compound represented by the formula (M5) as a main component instead of a monomer containing a compound represented by the formula (M3) as a main component (85 parts by weight, Synthesis Example 3) (85 parts by weight, Synthesis Example 5) Except that Polymerization Example 2 was used, a film sample of an ophthalmic lens polymer was obtained.

[Polymerization Example 4] Tris (trimethylsiloxy) silylpropyl methacrylate (60 parts by weight)
N, N-dimethylacrylamide (40 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 5] Polymerization Example 4 was repeated except that N- [tris (trimethylsiloxy) silylpropyl] acrylamide (60 parts by weight) was used instead of tris (trimethylsiloxy) silylpropyl methacrylate (60 parts by weight). In the same manner, a film sample of the polymer for an ophthalmic lens was obtained.

Example 1 A film sample of the polymer for an ophthalmic lens obtained in Polymerization Example 1 was prepared using acrylic acid
It was immersed in a 0% by weight aqueous solution at room temperature for 24 hours. Then, it was immersed in pure water and rinsed with pure water. It was immersed in a 1 M aqueous sodium hydroxide solution at 40 ° C. for 15 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 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 the obtained sample 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 of Example 1 was repeated, except that a 50% by weight aqueous solution of propionic acid was used instead of the 50% by weight aqueous solution of acrylic acid. 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 4 was used instead of the film sample of the polymer for ophthalmic lenses obtained in Polymerization Example 1. It carried out like 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 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 5 A film sample of the polymer for an ophthalmic lens obtained in Polymerization Example 2 was mixed with acrylic acid and a 0.1 M aqueous sodium hydroxide solution (weight ratio 1 /
1) was immersed at room temperature for 24 hours. Then immerse in pure water,
Rinse with pure water. It was immersed in pure water and heated in an autoclave at 120 ° C. for 30 minutes.

The obtained sample was immersed in buffer A and left at room temperature for 24 hours. The dynamic contact angle and oxygen permeability coefficient of the obtained sample 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 6 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 2. The procedure was as in Example 5. 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 allowed to stand at room temperature for 24 hours. .

The dynamic contact angles of these samples with respect to 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.

[0074]

[Table 1]

[0075]

According to the present invention, it is possible to obtain an ophthalmic lens polymer having high oxygen permeability and good surface wettability.

Claims (6)

[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 an organic acid or an organic acid solution. 2. The organic acid solution according to claim 1, wherein the organic acid solution is an organic acid aqueous solution or an organic acid alcohol solution.
A method for producing the polymer for ophthalmic lenses according to the above. 3. The method for producing a polymer for an ophthalmic lens according to claim 1, wherein the polymer is further treated under a basic condition. 4. The method for producing a polymer for an ophthalmic lens according to claim 1, wherein the polymer is further treated with heated water. 5. The organic acid according to claim 1, wherein the organic acid is at least one selected from organic carboxylic acids having 1 to 20 carbon atoms and organic sulfonic acids having 1 to 20 carbon atoms.
5. The method for producing a polymer for an ophthalmic lens according to any one of items 1 to 4. 6. 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 polymer production for 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. ]