JPH05105727A - Method for producing oxygen passable polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having high oxygen passability, less sticking of dirt such as tear and excellent processability by copolymerizing a polymerizable monomer such as a pentene with a polymerizable monomer selected from specific compounds. CONSTITUTION:(A) One or more polymerizable monomers (e.g. 2-methyl-1- pentene) selected from 6-10C alkenes containing one double bond and one methyl one the side chain is radically polymerized with (B) a polymerizable monomer comprising a compound of formula I [A is unsaturated polymerizable groups; X is 1-10C bifunctional hydrocarbon; R<1> to R<6> are (F-substituted) alkyl, phenyl, H, etc., with the proviso that R<1> and R<2>, R<3> and R<4>, and R<4> and R<6> are not H at the same time; Z is XB (B is unsaturated polymerizable group or H) or fluoroalkyl; K is 0-100; when plural groups of formula II exist in the formula, the groups may be the same] or formula III [R<7> is H, F, etc.; R<8> is H, 1-20C alkyl, etc.; when R<8> is H, R<7> is (F-substituted)alkyl] to give the objective polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an oxygen permeable polymer. For more details, contact lenses,
The present invention relates to a method for producing an oxygen-permeable polymer which is extremely useful as an ophthalmic material such as an intraocular lens.

[0002]

2. Description of the Related Art Conventionally, various plastic materials such as polymethylmethacrylate have been used as ophthalmic materials such as contact lenses and intraocular lenses. Such a conventional ophthalmic material has low oxygen permeability, and since stain components in tear fluid or intraocular fluid are easily fixed, there is a problem that it cannot be worn for a long time when used as a contact lens, for example. ..

In such a situation, poly (N-vinyl-), which can be worn for a long time as a contact lens, is used.
2-pyrrolidone) as a main component, a highly hydrous soft contact lens was developed, but it also has a low mechanical strength due to its high hydrous content, and boiling disinfection is required for use as a contact lens. However, there is a problem that handling is extremely complicated.

In recent years, as an ophthalmic material that overcomes such drawbacks, a polymer material obtained by copolymerizing siloxanyl mono (meth) acrylate and fluoro (meth) acrylate has been proposed.

[0005]

However, the above-mentioned polymeric material has the following problem due to the copolymerization ratio of siloxanyl mono (meth) acrylate and fluoro (meth) acrylate.
The nature is very different. That is, when the copolymerization ratio of siloxanyl mono (meth) acrylate is increased, the oxygen permeability is improved, but the adsorption or fixation of dirt components becomes remarkable, and the material becomes brittle and too soft. Conversely, the copolymerization ratio of fluoro (meth) acrylate is increased. If the value is increased, dirt components will not easily be adsorbed or adhered, but
There is a problem that oxygen permeability is lowered.

Therefore, an object of the present invention is to provide a method for producing an oxygen permeable polymer. Another object of the present invention is to solve the above problems and to have extremely high oxygen permeability,
The oxygen permeable polymer is suitable for use as an ophthalmic material such as a contact lens or an intraocular lens, which does not become soiled by adhering or adhering dirt components in tear fluid or intraocular fluid and has excellent processability. It is to provide a manufacturing method. Further objects and advantages of the present invention will be apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention include (1) having one double bond,
And at least one first polymerizable monomer selected from the group consisting of C6-10 alkenes having one methyl group in the side chain, and (2) the following general formula (I)

[0008]

[Chemical 3]

And the following general formula (II)

[0010]

[Chemical 4]

This is accomplished by a method of making an oxygen permeable polymer which is characterized by copolymerizing at least one second polymerizable monomer selected from the group consisting of compounds represented by:

The first polymerizable monomer used in the present invention is an alkene having one double bond and one methyl group in the side chain. Examples of such a first polymerizable monomer include 2-methyl-1-pentene and 2
-Methyl-2-pentene, 3-methyl-1-pentene,
3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene, 2-methyl-1-hexene, 2-methyl-2-hexene, 3-methyl-1-hexene, 3- Methyl-2-hexene, 3-methyl-3-
Hexene, 4-methyl-1-hexene, 4-methyl-2
-Hexene, 5-methyl-1-hexene, 5-methyl-
2-hexene, 2-methyl-1-heptene, 3-methyl-2-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene, 2-methyl-1-nonene, 2-methyl-1- Examples thereof include octene, and preferably 4-methyl-1-pentene and 4-methyl-2-pentene. These may be used alone or in combination with each other. The second polymerizable monomer is a compound represented by the general formula (I) or the general formula (II).

In the general formula (I), A represents an unsaturated polymerizable group. Examples of the unsaturated polymerizable group include vinyl group, CH
₂ = C (R) COO- (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a fluoromethyl group) represented by (fluoro) (meth) acryloxy group, CH ₂ = C
Acrylamide group represented by HCONH-, CH ₂ = C
HC ₆ H ₄ - styryl group represented by, CH ₂ = C (CN)
- vinyl cyanide groups represented _{by, CH 2 = C (CN)} C
A preferable example is a 2-cyanoacryloxy group represented by OO-.

In the general formula (I), R ¹ , R ² , R ³ ,
Examples of the alkyl group represented by R ⁴ , R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, i-Pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, undecyl group, or other linear or branched carbon number 1-20, especially carbon number 1- Twelve alkyl groups may be mentioned as preferred. As the alkyl group substituted with a fluorine atom, for example, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a pentafluorobutyl group, a heptafluoropentyl group, a nonafluorohexyl group or the like having 1 to 20 carbon atoms, A fluoroalkyl group having 3 to 8 carbon atoms is particularly preferable.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can also be phenyl, vinyl or Q. Here, in the Q group, Y ¹ , Y ² and Y ³ are an alkyl group which may be substituted with fluorine, a phenyl group, a vinyl group or a hydrogen atom. In addition, as the alkyl group which may be substituted with fluorine, the same groups as those exemplified for R ^{1 to} R ⁶ can be exemplified.

In the general formula (I), X has 1 to 10 carbon atoms.
Is a divalent hydrocarbon group. 2 with 1 to 10 carbon atoms
As the valent hydrocarbon group, those having 1 to 4 carbon atoms such as methylene group, ethylene group and propylene group are preferable.

Further, in the general formula (I), Z is a group —X—B, X is a divalent hydrocarbon group of 1 to 10 as described above, and B is an unsaturated polymerizable group or a hydrogen atom. is there. In addition,
As the unsaturated polymerizable group for B, the same as those exemplified for A can be exemplified. k is a number of 0 to 100, preferably 1 to 20. When k is 2 or more, R ³ and R ⁴ may be the same or different.

Examples of the compound represented by the general formula (I) include (fluoro) siloxanyl mono (meth) acrylate and (fluoro) siloxanyl di (meth) acrylate. As a specific example,
Pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, pentamethyldisiloxanylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) Silylpropyl acrylate, tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy)
Siloxanyl mono (meth) acrylates such as silylpropyl acrylate;

(3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate, (3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl acrylate, (3,3 3,4,4,5,5,5-heptafluoropentyl dimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyl Dimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl acrylate, (3,3,4,4,5,5,5
-Heptafluoropentyldimethylsiloxy) (pentamethyldisiloxanyloxy) trimethylsiloxysilyl methacrylate and other fluorosiloxanyl mono (meth) acrylates;

[0020]

[Chemical 5]

Siloxanyl di (meth) acrylate represented by:

[0022]

[Chemical 6] ,

The following formula

[0024]

[Chemical 7]

A fluorosiloxanyl di (meth) acrylate represented by, for example, can be mentioned.

Further, in the general formula (II), R ⁷ represents a hydrogen atom, a fluorine atom or an alkyl group which may be substituted with a fluorine atom. Examples of the alkyl group which may be substituted with a fluorine atom are the same as those exemplified for R ^{1 to} R ⁶ .

R ⁸ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a linear or branched fluoroalkyl group having 1 to 20 carbon atoms bonded through a divalent hydrocarbon group having 1 to 4 carbon atoms. Indicates a group. Specific examples of these groups will be apparent from the example of the divalent fluoroalkyl group for the hydrocarbon group and R ¹ to R ⁶ of the alkyl group, X for R ¹ to R ^6. When R ⁸ is a hydrogen atom, R ⁷ is limited to an alkyl group which may be substituted with a fluorine atom.

Examples of such a compound represented by the general formula (II) include 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate and 2,2,2-trifluoroethyl. -Α-fluoro acrylate, 2,2,2-trifluoroethyl-α-trifluoromethyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2 , 2,3,3,3-Pentafluoropropyl methacrylate, 2,2,3,3,3-
Pentafluoropropyl acrylate, 2,2,2,2,
2,2-hexafluoroisopropyl methacrylate,
2,2,2,2,2,2-hexafluoroisopropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4,
4,5,5-octafluoropentyl acrylate, 2,
2,3,3,4,4,5,5,6,6,7,7-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,
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl acrylate, 3,3,4,4,5,5,5,6,6,
7,7,8,8,8-Tridecafluorooctyl methacrylate, 3,3,4,4,5,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 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
Fluoroalkyl (meth) acrylates such as 5-octafluoro-1,1-dimethylpentyl acrylate;

Methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, isopropyl acrylate,
n-butyl methacrylate, n-butyl acrylate,
Alkyl (meth) acrylates such as tert-butyl methacrylate, tert-butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, benzyl methacrylate, benzyl acrylate, isobornyl methacrylate, isobornyl acrylate;

(Α-Ethyl) acrylic acid, (α-butyl) acrylic acid, (α-trifluoroethyl) acrylic acid, (α-trifluoropropyl) acrylic acid, (α-
Nonafluorohexyl) α-alkyl or α-fluoroalkyl acrylic acid such as acrylic acid;

Methyl- (α-ethyl) acrylate, ethyl- (α-ethyl) acrylate, propyl- (α-
Ethyl) acrylate, butyl- (α-ethyl) acrylate, 2-hydroxyethyl- (α-ethyl) acrylate, 2-hydroxypropyl- (α-ethyl) acrylate, diethylaminoethyl- (α-ethyl) acrylate, glycidyl- ( α-ethyl) acrylate,
Methyl- (α-butyl) acrylate, ethyl- (α-
Butyl) acrylate, propyl- (α-butyl) acrylate, butyl- (α-butyl) acrylate, 2-
Hydroxyethyl- (α-butyl) acrylate, 2-
Alkyl (α-alkyl) acrylates such as hydroxypropyl- (α-butyl) acrylate, diethylaminoethyl- (α-butyl) acrylate, glycidyl- (α-butyl) acrylate;

Methyl- (α-trifluoroethyl) acrylate, ethyl- (α-trifluoroethyl) acrylate, propyl- (α-trifluoroethyl) acrylate, butyl- (α-trifluoroethyl) acrylate, methyl- ( α-trifluoropropyl) acrylate, ethyl- (α-trifluoropropyl) acrylate, propyl- (α-trifluoropropyl) acrylate, butyl- (α-trifluoropropyl) acrylate, methyl- (α-nonafluorohexyl) Alkyl (α-fluoroalkyl) acrylates such as acrylate, ethyl- (α-nonafluorohexyl) acrylate, propyl- (α-nonafluorohexyl) acrylate, butyl- (α-nonafluorohexyl) acrylate;

2,2,2-Trifluoroethyl- (α-trifluoroethyl) acrylate, 2,2,3,3-tetrafluoropropyl- (α-trifluoroethyl) acrylate, 2,2,3,3 , 3-Pentafluoropropyl-
(Α-trifluoroethyl) acrylate, 2,2,2,
2,2,2-hexafluoroisopropyl- (α-trifluoroethyl) acrylate, 2,2,3,4,4,4-hexafluorobutyl- (α-trifluoroethyl) acrylate, 2,2,3, 3,4,5,5-octafluoropentyl- (α-trifluoroethyl) acrylate,
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl- (α-trifluoroethyl) acrylate, 2,2,3,3,4,4,5 , 5,6,6,7,7,8,8,9,
9-hexadecafluorononyl- (α-trifluoroethyl) acrylate, 3,3,4,4,5,5,6,6,7,7,
8,8,8-Tridecafluorooctyl- (α-trifluoroethyl) acrylate, 2,2,3,3-tetrafluoro-1-methylpropyl- (α-trifluoroethyl) acrylate, 2,2,3 , 3-tetrafluoro-1,
1-dimethylpropyl- (α-trifluoroethyl) acrylate, 2,2,3,3,4,4,5,5-octafluoro-1,1-dimethylpentyl- (α-trifluoroethyl) acrylate, 2 , 2,2-trifluoroethyl-
(Α-Nonafluorohexyl) acrylate, 2,2,
3,3,3-Pentafluoropropyl- (α-nonafluorohexyl) acrylate, 2,2,2,2,2,2-hexafluoroisopropyl- (α-nonafluorohexyl) acrylate, 2,2,3, 4,4,4-hexafluorobutyl- (α-nonafluorohexyl) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl- (α-nonafluorohexyl) acrylate, 2,
2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl- (α-nonafluorohexyl) acrylate,
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-
Hexadecafluorononyl- (α-nonafluorohexyl) acrylate, 3,3,4,4,5,5,5,6,6,7,7,
8,8,8-Tridecafluorooctyl- (α-nonafluorohexyl) acrylate, 2,2,3,3-tetrafluoro-1-methylpropyl- (α-nonafluorohexylethyl) acrylate, 2,2, 3,3-Tetrafluoro-1,1-dimethylpropyl- (α-nonafluorohexyl) acrylate, 2,2,3,3,4,4,5,5-
Octafluoro-1,1-dimethylpentyl- (α-nonafluorohexyl) acrylate, 2,2,2-trifluoroethyl- (α-pentadecafluorononyl) acrylate, 2,2,3,3,3-penta Fluoropropyl-
A fluoroalkyl- (α-fluoroalkyl) acrylate such as (α-pentadecafluorononyl) acrylate; and

2,2,2-Trifluoroethyl (α-ethyl) acrylate, 2,2,3,3-tetrafluoropropyl (α-ethyl) acrylate, 2,2,3,3,3-pentafluoropropyl (Α-ethyl) acrylate,
2,2,2,2 ', 2', 2'-hexafluoroisopropyl (α-ethyl) acrylate, 2,2,3,4,4,4-
Hexafluorobutyl (α-ethyl) acrylate,
2,2,3,3,4,4,5,5-octafluoropentyl (α-ethyl) acrylate, 2,2,3,3,4,4,5
5,6,6,7,7-dodecafluoroheptyl (α-ethyl) acrylate, 2,2,2-trifluoroethyl (α
-Butyl) acrylate, 2,2,3,3-tetrafluoropropyl (α-butyl) acrylate, 2,2,3,3,
3-pentafluoropropyl (α-butyl) acrylate, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl (α-butyl) acrylate, 2,2,3,4,4,
4-hexafluorobutyl (α-butyl) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (α-butyl) acrylate, 2,2,3,3,4,4,
Mention may be made of fluoroalkyl (α-alkyl) acrylates such as 5,5,6,6,7,7-dodecafluoroheptyl (α-butyl) acrylate.

Among the second polymerizable monomers represented by the general formula (I) or (II), those which are particularly preferably used in the present invention are pentamethyldisiloxanylmethyl methacrylate and pentamethyl. Siloxanyl mono (meth) acrylates such as disiloxanylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate;

(3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (methylbis (trimethyl Siloxy) siloxy) trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (pentamethyldisiloxanyloxy) trimethylsiloxysilylmethacrylate and other fluorosiloxanyl monomethacrylates (Meth) acrylate;

2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,2,2 ' , 2 ', 2'-Hexafluoroisopropyl 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, 3,3,4,4, 5, 5,
6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 2,2,3,3-tetrafluoro-1-methylpropyl methacrylate, 2,2,3,3-tetrafluoro-1, 1-dimethylpropyl methacrylate, 2,
Fluoroalkyl (meth) acrylates such as 2,3,3,4,4,5,5-octafluoro-1,1-dimethylpentylmethacrylate;

Alkyl (meth) acrylates such as methylmethacrylate, ethylmethacrylate, isopropylmethacrylate, n-butylmethacrylate, tert-butylmethacrylate, cyclohexylmethacrylate, benzylmethacrylate, isobornylmethacrylate; methyl (α-butyl) acrylate, ethyl ( Alkyl (α-alkyl) acrylate such as α-butyl) acrylate; Alkyl (α-such as methyl (α-nonafluorohexyl) acrylate, ethyl (α-nonafluorohexyl) acrylate, butyl (α-nonafluorohexyl) acrylate Fluoroalkyl) acrylate; and the following formula

[0039]

[Chemical 8]

It is a siloxanyl dimethacrylate represented by

These second polymerizable monomers are, by themselves,
Alternatively, two or more kinds can be combined and copolymerized with the first polymerizable monomer. Here, the copolymerization ratio of the first polymerizable monomer and the second polymerizable monomer is preferably 5 to 80% by weight of the first polymerizable monomer and the second polymerizable monomer. The amount of the monomer is 20 to 95% by weight, more preferably 10 to 60% by weight of the first polymerizable monomer, and 40 to 90% by weight of the second polymerizable monomer.

Further, in the present invention, in addition to the first polymerizable monomer and the second polymerizable monomer, other monomers are copolymerized within a range that does not impair the effects of the present invention. It can be polymerized.

Examples of such other monomers include ethylene glycol dimethacrylate, ethylene glycol diacrylate, 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 Such as trimethacrylate and trimethylolpropane triacrylate It can be mentioned functional crosslinking monomer. One or more of these polyfunctional crosslinkable monomers can be used.

These polyfunctional crosslinkable monomers are used to increase the hardness of the resulting polymer and improve the processability such as machinability and polishing property, and the copolymerization ratio thereof is
Usually, it is 30% by weight or less, preferably 20% by weight or less. If the copolymerization ratio exceeds 30% by weight, the resulting material may become brittle or may have low oxygen permeability.

In order to express the hydrophilicity of the surface of the obtained polymer, for example, acrylic acid, methacrylic acid, N-
Hydrophilic monomers such as vinyl-2-pyrrolidone and 2-hydroxyethyl methacrylate can also be copolymerized. Since increasing the copolymerization ratio of these hydrophilic monomers may impair the oxygen permeability of the resulting material, the copolymerization ratio is usually 20% by weight or less, preferably 15% by weight or less.

The copolymerization in the present invention can be carried out by an ordinary radical polymerization reaction, for example, by gradually raising the temperature in the presence of a thermal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile to carry out the polymerization. It can be carried out by a method or a method of polymerizing by irradiating with ultraviolet rays in the presence of a photopolymerization initiator such as benzoin, benzophenone or Michler's ketone. Here, the thermal polymerization initiator or the photopolymerization initiator is usually used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the monomer mixture.

When the polymer obtained according to the present invention is used in a contact lens, an intraocular lens, or any other application that requires compatibility with tear fluid or intraocular fluid, the polymer is further used as a contact lens or an eye lens. After processing into a shape such as an inner lens, surface treatment with alkali, surface treatment with plasma such as oxygen or nitrogen, surface treatment with plasma polymerization of compound containing hydrophilic group or vapor deposition of inorganic oxide, sputtering or ion plating By performing the surface treatment, the surface can be rendered hydrophilic.

[0048]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The processability evaluation criteria and test methods for various tests in the following examples and comparative examples are as follows.

(1) Machinability Evaluation Criteria A: Cutting surface has gloss, B: Cutting surface has gloss, but becomes slightly opaque, C: Cutting surface becomes rough and white, and polishing property A : Polished surface has good gloss. B: Polishing unevenness occurs. C: Polished surface is rough and white.

(2) Oxygen Permeability Coefficient Testing Method Using the obtained contact lens, Rika Seiki Co., Ltd.
Seikaken Film Oxygen Permeability Meter was used at 35 ℃ 0.9
% Measured in physiological saline.

(3) Visible Light Transmittance Test Method Using the obtained disk, the transmittance at 500 to 600 nm was measured with a double beam spectrophotometer Model 200-20 manufactured by Hitachi, Ltd.

(4) Test method for stain resistance Using the obtained disc, the disc was immersed in a stain solution for 30 days, and then washed with a contact lens cleaner (all-way cleaner manufactured by Ricky Contact Lens Co., Ltd.) to obtain a surface. The stain adhering to was removed, and the change in visible light transmittance when the visible light transmittance before immersion was set to 100 was expressed. The stain solution was 0.1 parts by weight of albumen albumin, 0.1 parts by weight of egg white lysozyme, 0.1 parts of mucous membrane of cattle stomach.
Parts by weight, egg yolk lecithin 0.1 parts by weight and purified water 100
A mixture of 1 part by weight was used and replaced with fresh soil solution every 2-3 days.

Example 1 The following formula:

[0054]

[Chemical 9]

35 parts by weight of siloxanyl dimethacrylate represented by: 20 parts by weight of 2,2,2-trifluoroethyl methacrylate, 20 parts by weight of methyl methacrylate, 4
-Methyl-1-pentene (25 parts by weight) and benzoin methyl ether (0.1 part by weight) as a polymerization initiator were mixed well at room temperature, and the mixture was poured into a polyethylene polymerization container, which was then irradiated with UV light at room temperature under a nitrogen atmosphere. Was irradiated for 16 hours for copolymerization.

After the copolymerization, the obtained block copolymer was cut and polished to form a contact lens and a disc having a thickness of 0.2 mm and a diameter of 15 mm to evaluate the workability,
Then, various tests were conducted. The results are shown in Table 1.

Example 2 Tris (trimethylsiloxy) silylpropyl methacrylate 40 parts by weight 2,2,2,2,2,2-hexafluoroisopropyl methacrylate 5 parts by weight, methyl methacrylate 20 parts by weight, 4-methyl-1- 20 parts by weight of pentene, 10 parts by weight of ethyl (α-nonafluorohexyl) acrylate, 5 parts by weight of methacrylic acid and 0.1 part by weight of benzoin methyl ether as a polymerization initiator were mixed well at room temperature, and this mixture was polymerized by polyethylene. The mixture was poured into a container and irradiated with ultraviolet rays for 16 hours at room temperature under a nitrogen atmosphere to cause copolymerization.

After the copolymerization, the obtained block copolymer was cut and polished to form a contact lens and a disc having a thickness of 0.2 mm and a diameter of 15 mm to evaluate workability,
Then, various tests were conducted. The results are shown in Table 1.

Example 3 40 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 25 parts by weight of methyl methacrylate,
20 parts by weight of 4-methyl-2-pentene, 10 parts by weight of methyl (α-nonafluorohexyl) acrylate, 5 parts by weight of ethylene glycol dimethacrylate and 0.1 part by weight of benzoin methyl ether as a polymerization initiator were mixed well at room temperature. Then, this mixed solution was poured into a polyethylene polymerization container, and UV rays were irradiated for 16 hours at room temperature under a nitrogen atmosphere to carry out copolymerization.

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

Comparative Example 1 Tris (trimethylsiloxy) silylpropyl methacrylate 35 parts by weight 2,2,2-trifluoroethyl methacrylate 45 parts by weight, methyl methacrylate 15 parts by weight, ethylene glycol dimethacrylate 5 parts by weight and as a polymerization initiator 0.1 part by weight of benzoin methyl ether was mixed well at room temperature, the mixture was poured into a polyethylene polymerization container, and ultraviolet rays were irradiated for 16 hours at room temperature under a nitrogen atmosphere to carry out copolymerization.

After the copolymerization, the obtained block copolymer was cut and polished to form a contact lens and a disc having a thickness of 0.2 mm and a diameter of 15 mm to evaluate the workability,
Then, various tests were conducted. The results are shown in Table 1.

[0063]

[Table 1]

[0064]

The oxygen-permeable high-molecular polymer produced according to the present invention has excellent characteristics that it has extremely high oxygen permeability and that stain components in tear fluid or intraocular fluid are not easily absorbed or fixed. In addition, it has good workability such as machinability and polishability. Therefore, the oxygen-permeable polymer produced by the present invention is suitably used as an ophthalmic material such as a contact lens and an intraocular lens.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 230/08 MNU 7242-4J 299/08 MRY 7442-4J C08G 77/20 NUG 8319-4J NUH 8319 -4J G02C 7/04 8807-2K

Claims (1)

[Claims] (1) At least one first group selected from the group consisting of alkenes having 6 to 10 carbon atoms having one double bond and having one methyl group in the side chain. A polymerizable monomer, and (2) the following general formula (I): And the following general formula (II): A method for producing an oxygen-permeable polymer, which comprises copolymerizing at least one second polymerizable monomer selected from the group consisting of compounds represented by: