JP3014408B2 - Method for producing oxygen-permeable polymer material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Field of the Invention The present invention has particularly good stain resistance and oxygen permeability,
The present invention relates to a method for producing an oxygen-permeable polymer material which is extremely useful as an ophthalmic material such as a contact lens and an intraocular lens.

b. Conventional technology Various plastic materials, for example, polymethyl methacrylate, have been used as ophthalmic materials such as contact lenses and intraocular lenses, but these materials have low oxygen permeability, and tear fluid and intraocular fluid are used. There is a problem that the components cannot be worn for a long time because the components inside are fixed and stained.

In such a situation, a soft contact lens having high water content containing poly (N-vinyl-2-pyrrolidone) as a main component was developed to enable wearing for a long time. There is a problem that handling is complicated, for example, the target strength is low, and it needs to be disinfected by boiling when worn to contain water.

In recent years, as a contact lens material that overcomes these drawbacks, an oxygen-permeable polymer combining siloxanyl (meth) acrylate and fluoro (meth) acrylate has been proposed.

c. Problems to be Solved by the Invention However, in the above-mentioned oxygen-permeable polymer, if siloxanyl (meth) acrylate is added in order to increase oxygen permeability, the adhesion of dirt is remarkable and the material becomes brittle and soft. Increasing the amount of (meth) acrylate makes it difficult to fix dirt, but has a problem that oxygen permeability decreases.

An object of the present invention is to solve the above problems and have high oxygen permeability, and furthermore, it is suitable as an ophthalmic material such as a contact lens, an intraocular lens, etc., in which components of tears and intraocular fluid do not adhere and become dirty. It is an object of the present invention to provide a method for producing an oxygen-permeable polymer material used for the above.

d. Means for Solving the Problems The present invention provides (A) the following general formula (I): [Wherein, R represents a hydrogen atom or a methyl group, and Rf is
A fluoroalkyl group having 1 to 8 carbon atoms is shown, a and b are integers of 1 to 3, and n is an integer of 1 to 20. 30 to 90% by weight of siloxanyl di (meth) acrylate (hereinafter referred to as "monomer (A)") and (B) siloxanyl mono (meth) acrylate (hereinafter referred to as "monomer (B)") A method for producing an oxygen-permeable polymer material characterized by copolymerizing 50% by weight; and (C) the following general formula (II): [Wherein, R represents the above-mentioned meaning, and R ¹ and R ² each represent an alkyl group or a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, which may be the same or different from each other. Often, b is an integer from 1 to 3 and m is an integer from 1 to 20. Siloxanyl di (meth) acrylate (hereinafter referred to as "monomer (C)")
(D) a fluoroalkyl mono (meth) acrylate having a hydrogen atom-containing fluoroalkyl group (hereinafter referred to as "monomer (D)") in an amount of 10 to 70% by weight. A method for producing an oxygen-permeable polymer material characterized by comprising:

As described above, there are two types of the method for producing the oxygen-permeable polymer material of the present invention, and the present invention will be described below for each of these types.

First Type The first type of production method involves copolymerizing the monomer (A) and the monomer (B) as described above.

Monomer (A): The monomer (A) is represented by the general formula (I): Is represented by

Here, R is a hydrogen atom or a methyl group, and
Rf _{is, CF 3 -, C 2 F} 5 -, C 3 F 7 -, C 4 F 9 -, C 6 F 13 -, C 8 F
₁₇ - is a fluoroalkyl group having 1 to 8 carbon atoms, such as.

A and b are integers of 1 to 3, and n is 1 to 20.
N is preferably an integer of 9 or less in order to obtain a hard material.

Specific examples of the monomer (A) include the following.

These monomers (A) can be used alone or in combination of two or more.

In the first type of production method of the present invention, the monomer (A) is copolymerized at a ratio of 30 to 90% by weight, preferably 40 to 80% by weight. If the copolymerization amount is less than 30% by weight, the obtained material does not show sufficient stain resistance and oxygen permeability, and if it exceeds 90% by weight, the obtained material has insufficient strength and is brittle. .

Monomer (B): Specific examples of the monomer (B) include the following.

Pentamethyldisiloxanylmethyl methacrylate,
Pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, pentamethyldicycloxanylpropyl acrylate, methyl bis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl acrylate, tris (trimethylsiloxy) Silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl methacrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl acrylate, Tris (Methyl bis (trimethylsiloxy) siloxy) silylpropyl methacrylate Tris (methylbis (trimethylsiloxy) siloxy) silylpropyl acrylate, methylbis (trimethylsiloxy) silylpropylglycerol methacrylate, methylbis (trimethylsiloxy) silylpropylglycerol acrylate, tris (trimethylsiloxy) silylpropylglycerol methacrylate, tris (trimethylsiloxy) silylpropyl Glycerol acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglycerol methacrylate,
Mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglycerol acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglycerol methacrylate, trimethylsilylethyltetramethyldisiloxanylpropylglycerol acrylate, trimethylsilylmethyl methacrylate, trimethylsilylmethyl acrylate , Trimethylsilylpropyl methacrylate, trimethylsilylpropyl acrylate, trimethylsilylpropyl glycerol methacrylate, trimethylsilylpropyl glycerol acrylate, pentamethyldisiloxanylpropyl glycerol methacrylate, pentamethyldisiloxanylpropyl glycerol acrylate, methyl bis Trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl methacrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl methacrylate, tetramethyltriisopropylcyclotetrasiloxa Nylpropyl acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl methacrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl acrylate.

These monomers (B) can be used alone or in combination of two or more.

Monomer (B) particularly preferably used in the present invention
Are pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy), silylpropyl methacrylate, mono (methylbis (trimethylsiloxy) siloxy) bis ( Trimethylsiloxy)
Silylpropyl methacrylate, tris (methylbis (trimethylsiloxy) siloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl methacrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl methacrylate, tetramethyltriisopropylcyclo And tetrasiloxybis (trimethylsiloxy) silylpropyl methacrylate.

The copolymerization amount of these monomers (B) is 10 to 50% by weight, preferably 15 to 45% by weight. 10% by weight of this copolymer
If it is less than 50%, the obtained material does not show sufficient oxygen permeability, and if it exceeds 50% by weight, the obtained material is unsatisfactory in strength and becomes brittle.

Other Monomers; The first type of the production method of the present invention is characterized in that, besides the monomers (A) and (B) described above, the copolymerization amount of these monomers is within the range specified above. To some extent, other monomers can be copolymerized.

For example, since the monomer (A) is a bifunctional monomer, a crosslinkable monomer is not particularly essential, but a crosslinkable monomer is used in terms of increasing the hardness of the material and improving the processability. It is desirable to copolymerize the body.

As such a crosslinkable monomer, a bifunctional monomer other than the monomer (A) can be used. Examples thereof include ethylene glycol dimethacrylate, ethylene glycol diacrylate, and diethylene glycol dimethacrylate. , Diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1, 4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate , Trimethylolpropane triacrylate, tetramethyldisiloxanylbis (methylmethacrylate), tetramethyldisiloxanylbis (methylacrylate), hexamethyltrisiloxanylbis (methylmethacrylate), hexamethyltrisiloxanylbis (methylacrylate) , Tetramethyldisiloxanylbis (ethyl methacrylate), tetramethyldisiloxanylbis (ethyl acrylate),
Hexamethyltrisiloxanyl bis (ethyl methacrylate), hexamethyl trisiloxanyl bis (ethyl acrylate), tetramethyl disiloxanyl bis (propyl methacrylate), tetramethyl disiloxanyl bis (propyl acrylate), hexamethyl trisiloxanyl bis (Propyl methacrylate), hexamethyltrisiloxanyl bis (propyl acrylate) and the like. One or more of these crosslinkable monomers can be used.

If the copolymerization amount of these crosslinkable monomers is too large, the obtained material becomes brittle or the oxygen permeability becomes low. Therefore, it is desirable to copolymerize in a range of 60% by weight or less. In particular, when siloxanyl bis (alkyl (meth) acrylate) such as tetramethyldisiloxanyl bis (methyl methacrylate) is used, the content may be up to 60% by weight, but alkylene glycol dialkyl such as ethylene glycol dimethacrylate may be contained. When (meth) acrylate is used, the copolymerization amount is preferably 20% by weight or less.

Further, for example, (fluoro) alkyl mono (meth) acrylate or the like may be copolymerized in order to improve the material strength, improve the workability, or improve the stain resistance.

The copolymerization amount of these (fluoro) alkyl mono (meth) acrylates is desirably in the range of 50% by weight or less, and if it exceeds 50% by weight, the resulting material may be reduced in oxygen permeability. .

These (fluoro) alkyl mono (meth) acrylates include 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,
3,3-pentafluoropropyl methacrylate, 2,2,3,
3,3-pentafluoropropyl acrylate, 2,2,3,4,
4,4-hexafluorobutyl methacrylate, 2,2,3,4,
4,4-hexafluorobutyl acrylate, 2,2,2,2 ',
2 ', 2'-hexafluoroisopropyl methacrylate, 2,2,2,2', 2 ', 2'-hexafluoroisopropyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, isopropyl acrylate, butyl Examples thereof include methacrylate, butyl acrylate, tertiary butyl methacrylate, tertiary butyl acrylate, cyclohexyl methacrylate, and cyclohexyl acrylate, and one or more of these can be used.

Further, in order to express the hydrophilicity of the material surface, a hydrophilic monomer such as N-vinyl-2-pyrrolidone and 2-hydroxyethyl methacrylate can be copolymerized, but copolymerization with these monomers can be obtained. Since the oxygen permeability of the material is reduced, the copolymerization amount is preferably kept to a minimum, and usually 20% by weight or less.

Second Type As described above, the second type of production method involves copolymerizing the monomer (C) and the monomer (D).

Monomer (C): The monomer (C) is represented by the general formula (II): Is represented by

Here, R is a hydrogen atom or a methyl group as in the general formula (I), and R ¹ and R ² are CH ₃ — and C
_{2 H 5 -, C 3 H} 7 -, C 4 H 9 -, C 5 H 11 -, C 8 H 17 -, CF 3 -, C 2
1 carbon atom such as F _5- , C ₃ F _7- , C ₄ F _9- , C ₆ F _13-, etc.
The resulting material is an alkyl group or a fluoroalkyl group, or a phenyl group, wherein at least one of R ¹ and R ² is a fluoroalkyl group, particularly a fluoroalkyl group having 1 to 6 carbon atoms. Is suitable for expressing sufficient stain resistance. B is 1 to 3
And m is an integer of 1 to 20, and m is preferably an integer of 9 or less in order to obtain a hard material.

The monomer (C) partially overlaps the monomer (A), and specific examples thereof include the following.

These monomers (C) can be used alone or in combination of two or more.

In the second type of the production method of the present invention, the monomer (C) is copolymerized at a ratio of 10 to 90% by weight, preferably 30 to 80% by weight. If the copolymerization amount is less than 10% by weight, the obtained material does not show sufficient stain resistance and oxygen permeability, and if it exceeds 90% by weight, the obtained material has insufficient strength and is brittle.

Monomer (D): The production method of the second type of the present invention is, for example, the following general formula (III): [Wherein, R represents a hydrogen atom or a methyl group, and Rg is
A fluoroalkyl group containing one or more hydrogen atoms, b
Is an integer of 1 to 3. It is important that the monomer (D) represented by the following formula is copolymerized. For example, in the case where the fluoroalkyl group in the monomer (D) is a compound in which no hydrogen atom is bonded to a carbon atom such as a perfluoropropyl group, the resulting material does not have high hardness. Is generated.

Preferred monomers (D) include 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,4,4-hexafluoro Butyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4 , 4,5,5-octafluoropentyl acrylate, 2,2,3,3,4,4,5,5,5
6,6,7,7-dodecafluoroheptyl methacrylate, 2,
2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7 , 8,8,9,9-Hexadecafluorononyl methacrylate, 2,2,3,3,4,4,5,5,5
6,6,7,7,8,8,9,9-hexadecafluorononyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8 9,9,10,10,11,11
-Eicosafluoroundecyl methacrylate, 2,2,3,
4,4,4-hexafluorobutyl methacrylate, 2,2,3,
4,4,4-hexafluorobutyl acrylate, 3,3,4,4,
5,5,6,6,7,7,8,8-dodecafluorooctyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,1
0-hexadedecafluorodecyl methacrylate, 3,
3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadedecafluorodecyl acrylate, 2,2,3,3,4,4,5, 5,6,6,7,7,
8,8,9,9,10,10,11,11-eicosafluoroundecyl acrylate, 2,2,3,3-tetrafluoro-1-methylpropyl methacrylate, 2,2,3,3-tetrafluoro -1
-Methylpropyl acrylate, 2,2,3,3-tetrafluoro-1,1-dimethylpropyl methacrylate, 2,2,3,3
-Tetrafluoro-1,1-dimethylpropyl acrylate, 2,2,3,3,4,4,5,5-octafluoro-1,1-dimethylpentyl methacrylate, 2,2,3,3,4,4 , 5,5-octafluoro-1,1-dimethylpentyl acrylate and the like, among which particularly preferred are 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3 , 3,4,4-hexafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 2,2,3,3-tetrafluoro-
1-methylpropyl methacrylate, 2,2,3,3-tetrafluoro-1,1-dimethylpropyl methacrylate, 2,
2,3,3,4,4,5,5-octafluoro-1,1-dimethylpentyl methacrylate and the like can be mentioned.

These monomers (D) can be used alone or in combination of two or more, and the copolymerization amount of the monomer (D) is 10 to 70% by weight, preferably 20 to 60% by weight. Range. When the copolymerization amount of the monomer (D) is less than 10% by weight, the obtained material becomes soft and does not show sufficient stain resistance. The permeability decreases.

Other monomers; The second type of production method of the present invention is the same as the first type of production method, except that the above-mentioned monomer (C) and monomer (D)
In addition, other monomers can be copolymerized as long as the copolymerization amount is within the range specified above.

For example, as in the case of the first type of production method, since the monomer (C) is a bifunctional monomer, a crosslinkable monomer is not particularly essential. It is desirable to copolymerize a crosslinkable monomer from the viewpoint of improving the properties.

As such a crosslinkable monomer, a bifunctional monomer other than the monomer (A) can be used. Examples thereof include ethylene glycol dimethacrylate, ethylene glycol diacrylate, and diethylene glycol dimethacrylate. , Diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1, 4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate Alkylene glycols such as trimethylol propane triacrylate di (meth)
Among acrylates and siloxanyl di (meth) acrylates represented by the general formula (I), those having n of 5 or less can be mentioned, and one or more of these can be used.

If the copolymerization amount of these crosslinkable monomers is too large, the obtained material becomes brittle or the oxygen permeability becomes low, so that it is generally 60% by weight or less, preferably 30% by weight.
The content is particularly preferably not more than 20% by weight.

Further, the monomer (B) or the alkyl (meth) acrylate of the first type of production method can be used as another monomer, and the alkyl (meth) acrylate is the same as that of the first type of production method. Alkyl (meth) acrylates among those listed as (fluoro) alkyl (meth) acrylates in other monomers can be suitably used. The copolymerization amount of the monomer (B) and the alkyl (meth) acrylate is desirably within a range of 50% by weight or less. This results in a decrease in soiling.

Furthermore, a hydrophilic monomer can be used as another monomer, but the copolymerization amount is preferably kept to a minimum in order to prevent a decrease in oxygen permeability of the obtained material,
Usually, it is 20% by weight or less.

The copolymerization method in the above-described first and second types of production methods of the present invention is not particularly limited,
For example, a method in which a monomer mixture is polymerized by gradually increasing the temperature in the presence of a peroxide or an azo compound such as benzoyl peroxide as a thermal polymerization initiator, azobisisobutyronitrile, Benzoin, benzophenone, a method of polymerizing by irradiating ultraviolet rays in the presence of a photopolymerization initiator such as Michler's ketone can be used.The polymerization initiator is usually used per 100 parts by weight of the monomer mixture.
0.01 to 1 part by weight is used.

The material obtained by the production method of the present invention described above exhibits cutting and polishing properties similar to conventional hard contact lenses made of polymethyl methacrylate, and is tough, excellent in oxygen permeability, and excellent in stain resistance. Is desirable.

The material obtained by the production method of the present invention can be processed by an ordinary processing method for an optical material such as cutting and polishing, whereby the material can be molded and used according to the intended use.

In addition, when used for applications that require familiarity with tear fluid or intraocular fluid such as contact lenses and intraocular lenses, alkali treatment, plasma treatment with oxygen, nitrogen, etc., plasma with hydrophilic monomers or compounds containing oxygen, etc. The surface of a contact lens or an intraocular lens can be made hydrophilic by polymerization, surface treatment such as vapor deposition of an inorganic oxide or the like, sputtering, or ion plating.

e. Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Examples 1 and 2 are examples of the first type manufacturing method, and Examples 3 and 4 are examples of the second type.

Example 1 The following formula: Siloxanyl dimethacrylate 60 parts by weight Tris (trimethylsiloxy) silylpropyl methacrylate 35 parts by weight Ethylene glycol dimethacrylate 5 parts by weight and benzoin methyl ether (photopolymerization initiator) 0.1 part by weight are mixed well at room temperature. The mixture was poured into a polyethylene polymerization vessel, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours to copolymerize.

After copolymerization, the obtained block copolymer was cut and polished to form a contact lens and a disk having a thickness of 0.2 mm and a diameter of 15 mm.The following workability was evaluated, and then the following various tests were performed. Was. The results are shown in Table 1.

The workability was evaluated based on the following criteria.

Criteria for machinability A: Gloss on the cut surface B: Gloss on the cut surface, but slightly opaque C: Cut surface becomes rough and white Abrasive standard A: Polished surface is good gloss B: Polished surface C: The polished surface becomes rough and white. The oxygen permeability coefficient was measured using a contact lens and a Rika Seiki Co., Ltd. Kaken type film oxygen permeation meter.
Measured in 0.9% physiological saline at ℃.

Visible light transmittance was measured using a disk, Hitachi, Ltd.
The transmittance at 500 to 600 nm was measured with a double beam spectrophotometer 200-20 manufactured by FUJIFILM Corporation.

Stain properties are obtained by immersing the disk in the stain solution for 30 days,
It was washed with a contact lens cleaner (all-way cleaner manufactured by Ricky Contact Lens Co., Ltd.) to remove dirt adhering to the surface, and determined from the change in visible light transmittance before and after immersion in the dirt solution. Visible light transmittance before immersion is 10
It was expressed as a change rate when it was set to 0.

In addition, as a stain liquid, 0.1 parts by weight of ovalbumin,
0.1 parts by weight of egg white lysozyme, 0.1 part by weight of mucin of bovine gastric mucosa,
Using a mixed solution consisting of 0.1 part by weight of egg yolk lecithin and 100 parts by weight of purified water, the mixture was replaced with a new stain every 2-3 days.

Example 2 The following formula: Siloxanyl dimethacrylate 60 parts by weight Methyl bis (trimethylsiloxy) silylpropyl methacrylate 15 parts by weight 2,2,2-trifluoroethyl methacrylate 20 parts by weight Ethylene glycol dimethacrylate 5 parts by weight and benzoin methyl ether 0.1 part by weight The mixture was mixed well at room temperature, and the mixture was poured into a polyethylene polymerization vessel, and was irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours to copolymerize.

After the copolymerization, the obtained block copolymer was cut and polished to obtain a contact lens and a disk having a thickness of 0.2 mm and a diameter of 15 mm. Then, various tests were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Tris (trimethylsiloxy) silylpropyl methacrylate 45 parts by weight 2,2,2-trifluoroethyl methacrylate 50 parts by weight Ethylene glycol dimethacrylate 5 parts by weight and benzoin methyl ether 0.1 part by weight were thoroughly mixed at room temperature. The mixture was poured into a polyethylene polymerization vessel, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours to copolymerize.

After the copolymerization, the obtained block copolymer was cut and polished to obtain a contact lens and a disk having a thickness of 0.2 mm and a diameter of 15 mm. Then, various tests were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 3 The following formula: Siloxanyl dimethacrylate 60 parts by weight 2,2,3,3,4,4-hexafluorobutyl methacrylate 25 parts by weight Tris (trimethylsiloxy) silylpropyl methacrylate 10 parts by weight The following formula: 5 parts by weight of siloxanyl dimethacrylate and 0.1 parts by weight of benzoin methyl ether are well mixed at room temperature, and the mixture is poured into a polyethylene polymerization vessel, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours. And copolymerized.

After the copolymerization, the obtained block copolymer was cut and polished to obtain a contact lens and a disc having a thickness of 0.2 mm and a diameter of 15 mm. Then, various tests were carried out in the same manner as in Example 1, and the following was further performed. A strength test was performed. The results are shown in Table-2.

Strength test is 0.15mm thick, 8.5mm diameter, 9mm base curve
Was prepared and placed on a test table with the front curve surface facing upward, a steel ball weighing 6.0 g was dropped, and the breaking strength of the contact lens was determined from the broken height.

Example 4 The following formula: Siloxanyl dimethacrylate 60 parts by weight 2,2,3,3-tetrafluoropropyl methacrylate 35 parts by weight Ethylene glycol dimethacrylate 5 parts by weight and benzoin methyl ether 0.1 part by weight are mixed well at room temperature, and this mixed liquid Was injected into a polyethylene polymerization container, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours to carry out copolymerization.

After the copolymerization, the obtained block copolymer was cut and polished to obtain a contact lens and a disk having a thickness of 0.2 mm and a diameter of 15 mm. Then, various tests were performed in the same manner as in Example 3. The results are shown in Table-2.

Comparative Example 2 Tris (trimethylsiloxy) silylpropyl methacrylate 35 parts by weight 2,2,2,2 ', 2', 2'-hexafluoroisopropylyl methacrylate 60 parts by weight Ethylene glycol dimethacrylate 5 parts by weight and benzoin methyl ether 0.1 part by weight was mixed well at room temperature, and this mixed solution was poured into a polyethylene polymerization vessel, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours to carry out copolymerization.

After the copolymerization, the obtained block copolymer was cut and polished to obtain a contact lens and a disk having a thickness of 0.2 mm and a diameter of 15 mm. Then, various tests were performed in the same manner as in Example 3. The results are shown in Table-2.

Comparative Example 3 100 parts by weight of methyl methacrylate and 0.1 part by weight of benzoin methyl ether were mixed well at room temperature, and the mixture was poured into a polyethylene polymerization vessel, and irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours. Polymerized.

After the polymerization, a strength test was performed in the same manner as in Example 3. The results are shown in Table-2.

f. Effects of the Invention According to the production method of the present invention, as an ophthalmic material such as a contact lens or an intraocular lens which has high oxygen permeability and does not become dirty due to fixation of components of tears and intraocular fluid. It is possible to obtain a suitably used oxygen permeable material.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kenji Yasuda 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-249508 (JP, A) JP-A JP-A-3-257421 (JP, A) JP-A-3-257420 (JP, A) JP-A-3-223321 (JP, A) JP-A-3-43711 (JP, A) A) JP-A-2-304093 (JP, A) JP-A-3-228014 (JP, A) JP-A-54-115590 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name ) C08F 290/00-290/14 G02C 7/04 A61L 27/00 C08F 30/00-30/10 C08F 230/00-230/10

Claims (2)

(57) [Claims] (A) The following general formula (I): [Wherein, R represents a hydrogen atom or a methyl group, and Rf is
A fluoroalkyl group having 1 to 8 carbon atoms is shown, a and b are integers of 1 to 3, and n is an integer of 1 to 20. Siloxanyl di (meth) acrylate represented by the formula:
90% by weight, (B) 10 to 50% by weight of siloxanyl mono (meth) acrylate, and up to 60% by weight of another copolymerizable monomer so that the monomer content is 100% by weight. A method for producing an oxygen-permeable polymer material. (C) The following general formula (II): [Wherein, R represents the above-mentioned meaning, and R ¹ and R ² each represent an alkyl group having 4 to 8 carbon atoms or 1 to 8 carbon atoms, excluding a 2- (trifluoromethyl) ethyl group.
Which may be the same or different from each other, b is an integer of 1 to 3,
Is an integer of 1 to 20. Siloxanyl di (meth) acrylate represented by the formula:
90% by weight, (D) 10 to 70% by weight of a fluoroalkyl mono (meth) acrylate having a fluoroalkyl group containing a hydrogen atom,
And a method for producing an oxygen-permeable polymer material, comprising copolymerizing up to 60% by weight of another copolymerizable monomer so that the total amount of monomers is 100% by weight.