JPH05310837A - Production of oxygen-permeable polymeric material - Google Patents

Abstract

PURPOSE:To obtain a polymeric material having excellent oxygen permeability and good processability by subjecting a mixture of a specified polymerizable monomer with a miscible bolatile organic solvent to polymerization while removing the substantial portion of the solvent. CONSTITUTION:An oxygen-permeable polymeric material is produced by subjecting a mixture of a monomer component comprising a polymerizable monomer of formula I [wherein A is a polymerizable unsaturation; X is a bivalent hydrocarbon group; R<1> to R<6> are each alkyl, fluoroalkyl, phenyl, vinyl, H or a group of formula II (wherein Y<1>, Y<2> and Y<3> are each alkyl, fluoroalkyl, phenyl, vinyl or H) ; Z is alkyl, fluoroalkyl or H; and k is 0-100[ and/or a polymerizable monomer of formula III (wherein R<7> is alkyl, fluoroalkyl, F or H; and R is alkyl or fluoroalkylalkylene) and a cross-linking monomer with a miscible volatile organic solvent while removing the substantial portion of the solvent from the polymerization system.

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 an oxygen permeable polymer material which is particularly useful as an ophthalmic material such as a contact lens and an intraocular lens.

[0002]

2. Description of the Related Art Conventionally, various plastic materials such as polymethylmethacrylate have been used for ophthalmic materials such as contact lenses and intraocular lenses. However, conventional ophthalmic materials have low oxygen permeability, In addition, since stain components in tear fluid or intraocular fluid tend to adhere, there is a problem that contact lenses cannot be continuously worn for a long time, for example. Therefore, a highly water-containing soft contact lens containing poly (N-vinyl-2-pyrrolidone) as a main component, which can be worn for a long time, has been developed. This also has a high mechanical strength because of its high water content. It was not sufficient, and when it was used as a contact lens, it had to be disinfected each time, and handling was extremely complicated. On the other hand, as an ophthalmic material without such a defect, a non-water-containing ophthalmic material made of a copolymer of siloxanyl monoacrylate or siloxanyl monomethacrylate and fluoroacrylate or fluoromethacrylate has recently been attracting attention. However, the disadvantage of this material is that its properties vary greatly depending on the copolymerization ratio of siloxanyl monoacrylate or siloxanyl monomethacrylate and fluoroacrylate or fluoromethacrylate. For example, if the copolymerization ratio of siloxanyl monoacrylate or siloxanyl monomethacrylate is increased, the oxygen permeability is improved, but the adsorption or adhesion of dirt components becomes remarkable, and it is brittle and too soft, which makes handling complicated in another sense. On the contrary, when the copolymerization ratio of fluoroacrylate or fluoromethacrylate is increased, the dirt component becomes difficult to be adsorbed or fixed, but there is a problem that oxygen permeability is lowered. Further, Japanese Patent Laid-Open No. 1-225913 discloses, as a method for obtaining a contact lens having good oxygen permeability,
There has been proposed a method in which a monomer component and a solvent compatible with the monomer component are mixed by casting polymerization, and then the solvent is removed from the polymerized molded product. However,
Since this method removes the entire amount of the solvent after the polymerization is completed, when cast polymerization is performed in the lens shape from the beginning, the predetermined lens shape cannot be maintained in the solvent removal step, and the rod-shaped , It is difficult to maintain the original shape of the polymerization as it is even when it is polymerized into a block or the like, so that machining such as cutting after the polymerization becomes difficult, and the step of removing the solvent after the polymerization is completed. Therefore, there is a problem in workability and economical efficiency.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved method for producing an oxygen permeable polymer material which is excellent in oxygen permeability and also machinability.

In order to solve the above-mentioned problems, the present inventors have proposed a method for producing an ophthalmic polymer material composed of siloxanyl monoacrylate, siloxanyl monomethacrylate, etc. and fluoroacrylate, fluoromethacrylate, etc. As a result of diligent study on the relationship with the characteristics of the molecular material, by removing a substantial part of the volatile organic solvent in the process of polymerizing the monomer component in the presence of a volatile organic solvent compatible with it. It was found that an oxygen-permeable polymer material having excellent oxygen permeability and good processability can be obtained, and the present invention has been completed. That is, the present invention is one or more polymerizable monomers represented by the following general formula (1) and / or one or more polymerizable monomers represented by the following general formula (2) and one or more. A monomer component containing a crosslinkable monomer of (1) is mixed with a compatible volatile organic solvent, and then polymerization is performed while removing a substantial part of the volatile organic solvent from the polymerization system. And a method for producing an oxygen-permeable polymer material.

[In the formula, A represents a polymerizable unsaturated group, X represents a divalent hydrocarbon group (preferably having 1 to 10 carbon atoms, and
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and are an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group, a hydrogen atom (provided that R ¹ and R ² And R ³
And R ⁴ or R ⁵ and R ⁶ are not hydrogen atoms at the same time. ) Or expression

Embedded image {wherein Y ¹ , Y ² and Y ³ may be the same or different from each other, and are an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group or a hydrogen atom (provided that Y ¹ , Y ² and Y ³ If it is any one of hydrogen atoms of the Y ^3, the other Y ¹ to Y ³ is not a hydrogen atom.). }, Z is an alkyl group, a fluoroalkyl group or a hydrogen atom, and k is 0 to 100 (preferably 0 to 2).
0) is an integer. ]

[In the formula, R ⁷ represents an alkyl group, a fluoroalkyl group, a fluorine atom or a hydrogen atom, and R ⁸ represents an alkyl group (preferably having 1 to 20 carbon atoms) or a divalent hydrocarbon group (preferably A fluoroalkyl group (preferably having 1 to 20 carbon atoms) bonded through a carbon number of 1 to 4) is shown. ]

The present invention will be described in detail below, which will clarify the purpose, constitution and effect of the present invention. In the polymerizable monomer represented by the general formula (1) used in the present invention, as the polymerizable unsaturated bond of A, for example, a vinyl group represented by the formula CH ₂ = CH-, a formula CH ₂ = C (R)
COO- (wherein R is a methyl group, a fluoromethyl group, a fluorine atom or a hydrogen atom), an acryloxy group or a methacryloxy group, an acrylamide group represented by the formula CH ₂ = CHCONH-, a formula CH ₂ = CHC ₆ H ₄ - styryl group represented by the formula CH ₂ = C (CN) - acrylonitrile group represented by the formula CH ₂ = C (CN) 2- cyanoacryloxy represented by COO- Groups and the like.

Further, as X in the general formula (1), for example, methylene group, ethylene group, propylene group, butylene group,
Examples thereof include a pentylene group, a hexylene group, a heptylene group, an octylene group, and examples of the divalent hydrocarbon group represented by R ⁸ in the general formula (2) include a methylene group, an ethylene group, a propylene group and a butylene group. Be done.

Further, R ¹ to R ⁶ and Y ^{1 to} Y ^{3 of the} general formula (1) are
And Z and R ⁷ and R ⁸ in the general formula (2),
Examples of the alkyl group include a methyl group, an ethyl group and n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group Group, an undecyl group, a linear or branched alkyl group such as a dodecyl group, and the fluoroalkyl group,
For example, trifluoromethyl group, trifluoroethyl group,
Examples thereof include linear or branched fluoroalkyl groups such as trifluoropropyl group, pentafluorobutyl group, heptafluoropentyl group and nonafluorohexyl group. R ^{1 to} R ⁶ or Y ^{1 to} Y ^{3 in} the general formula (1), and R ⁷ and R ^{8 in} the general formula (2) may be the same or different from each other, and also in the general formula (1). k is 2 to 1
When it is 00, a plurality of groups -Si (R ³ ) (R ⁴ ) -O- may be the same or different.

Specific examples of the polymerizable monomer represented by the general formula (1) include pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, Pentamethyldisiloxanylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy)
Silylpropyl acrylate, tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl glycerol methacrylate, methylbis (trimethylsiloxy) silylpropyl glycerol acrylate, tris (trimethylsiloxy) silylpropyl glycerol Methacrylate, tris (trimethylsiloxy) silylpropyl glycerol acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy)
Siloxy such as silylpropyl glycerol methacrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl glycerol acrylate, trimethylsilylethyl tetramethyldisiloxanylpropyl glycerol methacrylate, trimethylsilylethyl tetramethyldisiloxanylpropyl glycerol acrylate Sanyl monomethacrylate or siloxanyl monoacrylate; (3,3,
3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate,
(3,3,3-Trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl acrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) ) Trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl acrylate, (3,3,4,4) , 5,
5,5-heptafluoropentyldimethylsiloxy)
(Pentamethyldisiloxanyloxy) trimethylsiloxysilyl methacrylate, (3,3,4,4,5,
5,5-heptafluoropentyldimethylsiloxy)
Examples include fluorosiloxanyl monomethacrylate or fluorosiloxanyl monoacrylate such as (pentamethyldisiloxanyloxy) trimethylsiloxysilyl acrylate.

Next, specific examples of the polymerizable monomer represented by the general formula (2) include 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate and 2,2. 2,2-trifluoroethyl-α-fluoroacrylate, 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
-Dodecafluoroheptylmethacrylate, 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, 3,3,4,4,4
5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 3,3,4,5,5,5
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
Fluoromethacrylate or fluoroacrylate such as 5,5-octafluoro-1,1-dimethylpentyl acrylate; methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate, n-butyl acrylate, alkyl methacrylates or alkyl acrylates such as t-butyl methacrylate, t-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-trifluoro) Propyl) acrylate, (alpha-
Α-alkylacrylic acid such as nonafluorohexyl) acrylic acid or α-fluoroalkylacrylic 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-hydroxypropyl- (α-butyl) acrylate DOO, diethylaminoethyl - (alpha-butyl) acrylate - DOO, glycidyl - (alpha-
Butyl) acrylate and other alkyl (α-alkyl) acrylates; 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-trifluoro Propyl) acrylate, butyl- (α-trifluoropropyl) acrylate, methyl- (α-nonafluorohexyl) acrylate, ethyl- (α-nonafluorohexyl) acrylate, propyl- (α- Nonafluorohexyl) acrylate, butyl- (α-nonafluorohexyl) acrylate, and other alkyl (α- Fluoroalkyl) 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
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, 3,3,4,4,5,5,5
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,
3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl- (α-nonafluorohexyl) acrylate, 2,2,3,3-tetrafluoro −
1-methylpropyl- (α-nonafluorohexyl) 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-pentafluoropropyl-
Examples thereof include fluoroalkyl (α-fluoroalkyl) acrylates such as (α-pentadecafluorononyl) acrylate.

Of the polymerizable monomers represented by the general formula (1) or (2), preferred monomers are pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylmethyl acrylate and pentamethyl. Disiloxanylpropyl methacrylate, pentamethyldisiloxanylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl acrylate,
Siloxanyl monomethacrylate or siloxanyl monoacrylate such as tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate; (3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate , (3,3,3
-Trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl acrylate, (3,
3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (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 Fluorosiloxanyl methacrylate or fluorosiloxani such as methacrylate, (3.3.4,4,5,5,5-heptafluoropentyldimethylsiloxy) (pentamethyldisiloxanyloxy) trimethylsiloxysilylacrylate Acrylate; 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl-α-fluoroacrylate, 2,2,2-trifluoroethyl-α-trifluoromethyl acrylate, 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, 2,2
Fluoromethacrylate or fluoroacrylate such as 3,3,4,4,5,5-octafluoro-1,1-dimethylpentylmethacrylate; methylmethacrylate, methylacrylate, ethylmethacrylate, ethylacrylate, isopropylmethacrylate, isopropylacrylate, n- Butyl methacrylate, n-
Butyl acrylate, t-butyl methacrylate, t-
Butyl acrylate, cyclohexyl methacrylate,
Alkyl methacrylates or alkyl acrylates such as cyclohexyl acrylate, benzyl methacrylate, benzyl acrylate, isobornyl methacrylate, isobornyl acrylate and the like.

The crosslinkable monomer in the present invention contains a large amount of two or more polymerizable unsaturated groups copolymerizable with the polymerizable monomer represented by the general formula (1) or (2). It is a functional compound. However, this crosslinkable monomer does not include a compound having a vinyl group bonded to a Si atom among the polymerizable monomers represented by the general formula (1).

Specific examples of the crosslinkable monomer 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 trimethacrylate, trimethylolpropane triacrylate A polyfunctional methacrylate or polyfunctional acrylate containing or not containing a fluorine atom such as acrylate, bisphenol A dimethacrylate, bisphenol A diacrylate, bistrifluoromethyl bisphenol A dimethacrylate, bistrifluoromethyl bisphenol A diacrylate; Examples include the silicone-based polyfunctional compounds represented.

[Chemical 4] ,

[Chemical 5] ,

[Chemical 6] ,

[Chemical 7] Siloxanyl dimethacrylate, etc .;

[Chemical 8] Such as fluorosiloxanyl dimethacrylate;

[Chemical 9] Cyclic siloxane group-containing dimethacrylate such as;

[Chemical 10] Siloxanyl dimethacrylate containing bisphenol A ether group such as.

Of the above-mentioned crosslinkable monomers, preferred monomers are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane. Polyfunctional methacrylates such as trimethacrylate and bisphenol A dimethacrylate;

[Chemical 4],

[Chemical 5],

And siloxanyl dimethacrylate.

The copolymerization ratio of the polymerizable monomer represented by the general formula (1) and / or (2) and the crosslinkable monomer in the present invention is usually 99.5 / 0. 5-5 / 9
5, and preferably 99/1 to 10/90. However, when the polymerizable monomer represented by the general formula (1) is used and the monomer has a vinyl group bonded to a Si atom, the vinyl group can also be polymerized, It is desirable to adjust the copolymerization ratio of the crosslinkable monomer according to the desired degree of crosslinking of the polymer material obtained.

Further, in the present invention, if desired,
A polymerizable monomer other than the above may be used in combination. In this case, for example, by copolymerizing a hydrophilic monomer such as acrylic acid, methacrylic acid, vinylpyridine, N-vinyl-2-pyrrolidone, and 2-hydroxyethylmethacrylate, the surface of the polymer material obtained is made hydrophilic. Can be expressed.

The volatile organic solvent in the present invention is an organic solvent which does not substantially inhibit the polymerization reaction and has compatibility. Here, having compatibility means that both the monomer component and the produced copolymer are compatible. As such an organic solvent, one having a boiling point of 150 ° C. or lower is preferable. Specific examples of the volatile organic solvent include n
Saturated hydrocarbons such as -pentane, n-hexane, n-heptane, 2-methylhexane, 2,4-dimethylpentane, cyclopentane and methylcyclopentane; 1-hexene, 1-heptene, cyclohexene, benzene, toluene, etc. Unsaturated hydrocarbons; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, hexafluorobenzene; diethyl ether, diisopropyl ether, ethyl vinyl ether,
Ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate, n-propyl acetate and n-butyl acetate. The volatile organic solvent in the present invention is used alone or in combination of two or more.

The amount of the volatile organic solvent used in the present invention is usually 5 to 20 with respect to 100 parts by weight of all the monomer components.
It is 0 part by weight, preferably 5 to 100 parts by weight. If the amount of the volatile organic solvent used is less than 5 parts by weight, the oxygen permeability of the polymer material obtained may not be sufficiently improved, and if it exceeds 200 parts by weight, the polymer material obtained by polymerization may shrink and deform. There is a risk that it will be easier and the workability will be reduced.

The polymerization in the present invention is usually carried out by radical polymerization, in which a thermal polymerization initiator such as penzoyl peroxide or azobisisobutyronityryl is used, for example, per 100 parts by weight of all the monomer components. 0.01 to 5 parts by weight, and optionally a step of increasing the polymerization temperature to perform polymerization, and a photopolymerization initiator such as benzoin, benzophenone, Michler's ketone, etc., for example, 0 per 100 parts by weight of all monomer components. 0.01 to 5 parts by weight, irradiating with ultraviolet rays, and optionally a method of increasing the polymerization temperature stepwise to perform polymerization, using a thermal polymerization initiator and a photopolymerization initiator in combination, under the irradiation of ultraviolet rays, Depending on the case, a method such as a method of increasing the polymerization temperature stepwise, a method of performing polymerization under irradiation of radiation, and the like can be adopted. When the polymerization temperature is raised stepwise in the presence of a thermal polymerization initiator to perform polymerization, two or more types of thermal polymerization initiators having different decomposition temperatures can be used in combination. In the present invention, it is preferable to use a thermal polymerization initiator and a photopolymerization initiator-containing agent in combination, to irradiate ultraviolet rays in an atmosphere of an inert gas such as nitrogen to increase the polymerization temperature stepwise to perform polymerization. ..

In the present invention, "polymerizing while removing a substantial part of the volatile organic solvent from the polymerization system" means at least 70% by weight, preferably 80% by weight, of the solvent mixed with the monomer component before the initiation of the polymerization. The above means that it is removed during the polymerization. The solvent still remaining after the polymerization can be almost completely removed by an appropriate method such as a method of volatilizing under reduced pressure or a method of evaporating by heating. When removing a substantial part of the volatile organic solvent from the polymerization system, (a)
A method of continuously removing the solvent during the polymerization, a method of (b) removing the solvent stepwise during the polymerization, and the like can be adopted. Further, in the case of (a), the solvent removal rate can be made uniform, or the solvent removal rate can be gradually increased or decreased. In the case of (b), the solvent removal rate can be the same at each stage. The removal rate can be increased or decreased sequentially in each stage, or the removal rate can be the highest or lowest in the intermediate stage of the polymerization in each stage. The method for removing these volatile organic solvents is appropriately selected and carried out in consideration of the monomer composition, the desired size and distribution of pores in the resulting polymer material, the type and amount of the solvent used, and the like. It

In the present invention, a polymerization vessel or a polymerization apparatus which can remove the volatile organic solvent during the polymerization must be used. As such a polymerization vessel or a polymerization apparatus, there is, for example, one having a gap in which the organic solvent can be volatilized during the polymerization or capable of changing from a closed state to an open state at an appropriate stage of the polymerization.

The method of polymerizing while removing the volatile organic solvent has heretofore been performed as one of the methods for controlling the polymerization temperature in general solution polymerization, precipitation polymerization and the like using an organic solvent. However, in the production of oxygen-permeable polymer materials such as ophthalmic materials that require precision processing, this is a technique that has never been attempted. In the present invention, as will be shown in Examples and Comparative Examples described later, by polymerizing while removing a substantial portion of the volatile organic solvent, not only oxygen permeability is significantly improved, but also contact lenses. It is possible to obtain a polymer material excellent in machinability and polishability, which is indispensable for processing a precision molded product such as an intraocular lens. Also,
Since the removal of the volatile organic solvent is mainly performed from the monomer stage to the prepolymer stage (that is, the partial polymerization stage), the generation of strain of the polymer material due to the removal of the solvent is suppressed, and moreover, after the polymerization, Does not require a solvent removal step,
Alternatively, the process can be simplified and the production process of the oxygen-permeable polymer material can be remarkably rationalized.

The polymerization in the present invention is carried out by, for example, polymerizing a mixture of a monomer component and a volatile organic solvent while removing a substantial part of the volatile organic solvent to produce a block copolymer. Can be done by. In this case, the obtained block-shaped copolymer is cut and polished into a predetermined shape such as a contact lens or an intraocular lens.

Since the polymer material obtained by the present invention exhibits the same cutting property and polishing property as a hard lens made of conventional polymethylmethacrylate, it can be molded into a predetermined shape (such as a contact lens or an intraocular lens). It can be easily processed, is tough, and has extremely excellent oxygen permeability.

Furthermore, when the polymer material obtained by the present invention is used in applications such as contact lenses, intraocular lenses, etc., which require familiarity with tear fluid or intraocular fluid, it is preferably processed into a predetermined shape. To impart hydrophilicity to the surface by treating with alkali, plasma treatment with oxygen or nitrogen, plasma polymerization treatment with hydrophilic group-containing compound, vapor deposition of inorganic oxide, sputtering or ion plating treatment. You can also

[0025]

EXAMPLES The specific modes and effects of the present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The tests of oxygen transmittance, visible light transmittance and processability in these Examples and Comparative Examples were carried out as follows. Oxygen transmission rate: Polymer material is processed into contact lens,
Using a Rika Seiki Seikaken film oxygen permeation meter, 3
It was measured in 0.9% by weight physiological saline at 5 ° C. Visible light transmittance: disk made of polymer material (thickness 0.2
mm × diameter 15 mm), using a Hitachi Double Beam Spectrophotometer Model 200-20, a wavelength of 500-
It was measured at 600 nm. Processability: albeit glossy cutting surface, becomes slightly opaque × - - machinability ○ - Shiny the cutting surface △ abrasive cutting surface is rough whitening ○ - polished surface excellent gloss △ - polishing unevenness X-The polished surface becomes rough and whiten.

Example 1 Formula

35 parts by weight of siloxanyl dimethacrylate of
20 parts by weight of 2,2,2-trifluoroethyl methacrylate, 30 parts by weight of methyl methacrylate, 50 parts by weight of n-hexane, and 0.1 part by weight of benzoin methyl ether and 0.1 of azobisisobutyronitrile as a polymerization initiator. A polyethylene polymerization container with an open upper surface (radius 2 cm x height 4 cm) by mixing well parts by weight at room temperature
Injected. This polymerization vessel was placed in another polymerization vessel capable of introducing nitrogen (internal volume: 500 cm ³ ), irradiated with ultraviolet rays at room temperature for 16 hours while flowing nitrogen at a flow rate of 1 liter / minute, and then at 40 ° C. for 8 hours. , 8 hours at 80 ° C, 12
Polymerization was carried out at 0 ° C for 12 hours. During this polymerization process, almost all of n-hexane was volatilized along with the nitrogen flow. After the completion of the polymerization, the obtained copolymer was cut and polished to be processed into a contact lens and a disc, and the respective tests were conducted. The test 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 30 parts by weight, ethylene glycol dimethacrylate 5 parts by weight Parts, ethyl (α-nonafluorohexyl) acrylate 10 parts by weight, methacrylic acid 5 parts by weight,
80 parts by weight of fluorobenzene, 0.1 part by weight of benzoin methyl ether as a polymerization initiator and 0.1 part by weight of azobisisobutyronitrile were mixed well at room temperature, and then the mixture was polymerized in the same manner as in Example 1 to complete the polymerization. After that, the copolymer was cut and polished to be processed into a contact lens and a disk, and a test was conducted. The test results are shown in Table 1.

Comparative Example 1 Formula

35 parts by weight of siloxanyl dimethacrylate of
20 parts by weight of 2,2,2-trifluoroethyl methacrylate, 30 parts by weight of methyl methacrylate, 0.1 parts by weight of benzoin methyl ether and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator are mixed well at room temperature. After that, polymerization was carried out in the same manner as in Example 1, and after the completion of the polymerization, the copolymer was cut and polished to be processed into a contact lens and a disk, and a test was conducted. The test results are shown in Table 1.

Comparative Example 2 A reaction mixture having the same composition as in Example 1 was injected into a glass tube, the atmosphere was replaced with nitrogen, and then polymerization was performed in the same manner as in Example 1 except that n-hexane was not removed during the polymerization. A copolymer block was obtained. Then, the copolymer block is added to 120
The n-hexane was removed by vacuum drying at ° C for 48 hours. The copolymer block after removal of n-hexane was greatly deformed and could not maintain a columnar shape, and it was impossible to mount it on a lathe for cutting.

[0030]

[Table 1]

[0031]

The oxygen-permeable polymer material obtained by the method of the present invention has extremely high oxygen permeability and is excellent in machinability and polishability. Moreover, the method of the present invention is
Since a substantial part of the volatile organic solvent is removed during the polymerization, the solvent removal step after the polymerization is not required or the solvent removal step can be simplified. Therefore, the oxygen-permeable polymer material obtained by the present invention is extremely useful as an ophthalmic material that requires precision processing such as a contact lens and an intraocular lens, and the present invention is extremely rational for such an ophthalmic material. Can be manufactured.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G02B 1/04 7132-2K G02C 7/04

Claims (1)

[Claims] 1. One or more kinds of polymerizable monomers represented by the following general formula (1) and / or one or more kinds of polymerizable monomers represented by the following general formula (2) and one or more kinds. A monomer component containing a crosslinkable monomer of (1) is mixed with a compatible volatile organic solvent, and then polymerization is performed while removing a substantial part of the volatile organic solvent from the polymerization system. And a method for producing an oxygen-permeable polymer material. [Chemical 1] [In the formula, A represents a polymerizable unsaturated group, X represents a divalent hydrocarbon group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other. Well, alkyl group, fluoroalkyl group, phenyl group, vinyl group, hydrogen atom (provided that R ¹ and
R ² and R ³ and R ⁴ or R ⁵ and R ⁶ are not hydrogen atoms at the same time. ) Or the formula: {Here, Y ¹ , Y ² and Y ³ may be the same or different from each other, and are an alkyl group or a fluoroalkyl group, a phenyl group, a vinyl group or a hydrogen atom (provided that Y ¹ , Y ² and Y ³
When any one of Y ³ is a hydrogen atom,
Y ^{1 to} Y ³ never become hydrogen atoms. ). } Is shown, Z is an alkyl group, a fluoroalkyl group or a hydrogen atom, and k is an integer of 0-100. ] [Chemical 3] [In the formula, R ⁷ represents an alkyl group, a fluoroalkyl group, a fluorine atom or a hydrogen atom, and R ⁸ represents an alkyl group or a fluoroalkyl group bonded via a divalent hydrocarbon group. ]