JP2954687B2 - Method for producing oxygen-permeable polymer material - Google Patents

Description

The present invention relates to a method for producing an oxygen-permeable polymer material, particularly an oxygen-permeable polymer material which is extremely useful as an ophthalmic material such as a contact lens or an intraocular lens. And a method for producing the same.

[Conventional technology]

Conventionally, various plastic materials, for example, polymethyl methacrylate, have been used as ophthalmic materials such as contact lenses and intraocular lenses. However, conventional ophthalmic materials have low oxygen permeability, and also have a problem that they cannot be worn for a long time when used as a contact lens, for example, because dirt components in tears and intraocular fluid are easily adsorbed or fixed. Was something.

Under such circumstances, 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 as a contact lens, has been developed. Due to its low mechanical strength, it is necessary to perform boiling disinfection in order to use it as a contact lens due to contamination by water.
There was a problem that handling was extremely complicated.

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

[Problems to be solved by the invention]

However, the properties of the above-mentioned polymer materials differ greatly depending on the copolymerization ratio of siloxanyl mono (meth) acrylate and fluoro (meth) acrylate. The oxygen permeability is improved by increasing the copolymerization ratio of siloxanyl mono (meth) acrylate. However, the adsorption or fixation of the dirt component becomes remarkable, and the material becomes brittle and too soft. Conversely, if the copolymerization ratio of fluoro (meth) acrylate is increased, the dirt component becomes difficult to be adsorbed or fixed, but the oxygen permeability However, there was a problem that was reduced.

Therefore, an object of the present invention is to solve the above-mentioned problems, have high oxygen permeability, do not adsorb or fix dirt components in tears or intraocular fluid, do not stain, and have excellent processing methods. An object of the present invention is to provide a method for producing an oxygen-permeable polymer material suitably used as an ophthalmic material such as a contact lens and an intraocular lens.

[Means for solving the problem]

The present invention provides the following general formula (I) Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ may be the same or different groups, and may be an alkyl group optionally substituted with a fluorine atom,
Represents a phenyl group, a vinyl group or a hydrogen atom, R ⁹ and
R ¹⁰ may be the same or different, and represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and A ¹ and A ² are unsaturated polymerizable groups. Represents a group or a hydrogen atom. However, both of A ¹ and A ² are not a hydrogen source simultaneously. m and n each represent a number from 0 to 100, preferably an integer from 1 to 20. Where the group When two or more are present, each group may be the same or different. An oxygen-permeable polymer material characterized by polymerizing or copolymerizing one or two or more polymerizable monomers having a bisphenylene ether represented by the following formula (hereinafter referred to as “monomer (A)”): Is provided.

In the general formula (I) showing the monomer (A) used in the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ ,
As the alkyl group among R ¹² , R ¹³ and R ¹⁴ , for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group, a pentyl group, Straight-chain or branched-chain alkyl groups such as isopentyl group, hexyl group, 2-methylbutyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group and undecyl group; Examples of the substituted alkyl group include a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a pentafluorobutyl group, a heptafluoropentyl group, a nonafluorohexyl group, and the like.
In the general formula (I), examples of the divalent hydrocarbon group having 1 to ¹⁰ carbon atoms of R ⁹ and R ¹⁰ include a methylene group, an ethylene group, and a propylene group.

Further, in the general formula (I), among the groups represented by A ¹ and A ² , examples of the unsaturated polymerizable group include a vinyl group and CH ₂ ＝
(Wherein, R represents a hydrogen atom, a fluorine atom, a methyl group or a fluoromethyl group) C (R) COO- represented by (fluoro) (meth) acryloxy group, an acrylamide group represented by CH ₂ = CHCONH- _{, CH 2 = CHC 6 H 4} - styryl group represented _{by, CH 2 = C (CN)} - acrylonitrile groups represented by, CH ₂ = and the like C (CN) 2-cyano acryloxy group represented by COO- be able to.

In addition, specific examples of the monomer (A) in the present invention include the following.

[Where MA is And Ak Is shown. These monomers (A) are, for example, After reacting The reacted, is prepared by reacting the like ^{_{CH 2 = CH-A 1,}} CH 2 = CHCH 2 -A 1 in Tsugitsu.

Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² and A ¹ have the same meaning as described above. The monomer (A) can be polymerized or copolymerized alone or in combination of two or more.

In the present invention, together with the monomer (A), (fluoro) siloxanyl mono (meth) acrylate, fluoro (meth) acrylate and / or siloxanyl di (meth) acrylate (hereinafter, these are referred to as “monomer (B)” ) Can produce an oxygen-permeable polymer material having further improved oxygen permeability and improved adsorption or fixation of dirt components.

Examples of the monomer (B) used here include the following.

Pentamethyldisiloxanylmethyl methacrylate,
Pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, pentamethyldisiloxanylpropyl acrylate, methyl bis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl acrylate, tris (trimethylsiloxy) Silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate, methylbis (trimethylsiloxy) silylpropylglycerol methacrylate, methylbis (trimethylsiloxy) silylpropylglycerol acrylate, tris (trimethylsiloxy) silylpropylglycerol methacrylate, tris (trimethylsiloxy) silylpropyl Glycerol acrylate, molybdenum (Methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglycerol methacrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglycerol acrylate, trimethylsilylethyltetramethyldisiloxanylpropyl glycerol methacrylate, trimethylsilyl Siloxanyl mono (meth) acrylates such as ethyltetramethyldisiloxanylpropylglycerol acrylate; (3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate, (3,3,3-trifluoropropyl Dimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentene) Dimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilyl Propyl acrylate, fluorosiloxanyl mono (meth) acrylate such as (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (pentamethyldisiloxanyloxy) trimethylsiloxysilyl methacrylate; 2,2-
Trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl-α-fluoroacrylate, 2,2,2-trifluoroethyl-α-trifluoromethyl methacrylate, 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-hexafluoro Butyl 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, 2,2,3,3,4,4,5,5,6,6,6
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,
6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-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, 2,2,3,3,4,4,5,5
Fluoro (meth) acrylates such as octafluoro-1,1-dimethylpentyl acrylate; And siloxanyl di (meth) acrylate.

Among these monomers (B), those particularly preferably used in the present invention include pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, Siloxanyl mono (meth) acrylates such as tris (trimethylsiloxy) silylpropyl methacrylate; (3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate, (3,3,4,4,5,5) ,
5-heptafluoropentyldimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5
Fluorosiloxanyl mono (meth) acrylates, such as 5-heptafluoropentyldimethylsiloxy) (pentamethyldiloxanyloxy) trimethylsiloxysilyl methacrylate; and 2,2,2-trifluoroethyl methacrylate, 2,2,2- Trifluoroethyl-α
-Fluoroacrylate, 2,2,2-trifluoroethyl-α-trifluoromethyl methacrylate, 2,2,3,3-
Tetrafluoropropyl methacrylate, 2,2,3,3-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 ,
It is a fluoro (meth) acrylate such as 3,3-tetrafluoro-1,1-dimethylpropyl methacrylate, 2,2,3,3,4,4,5,5-octafluoro-1,1-dimethylpentyl methacrylate. .

These monomers (B) can be copolymerized with the monomer (A) alone or in combination of two or more.

Here, the usage ratio of the monomer (A) and the monomer (B) is usually 10 to 100% by weight of the monomer (A) and 0 to 90% by weight of the monomer (B), Preferably monomer (A)
Is 10 to 90% by weight, the monomer (B) is 10 to 90% by weight, particularly preferably the monomer (A) is 30 to 80% by weight, and the monomer (B) is
20 to 70% by weight.

Further, in the production method of the present invention, other than the above-mentioned monomer (A) and monomer (B), other monomers may be copolymerized within a range not to impair the effects of the present invention. Can be.

Such other monomers include, for example, monomer (A)
Other than 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 di Crosslinkable monomers represented by polyfunctional monomers such as acrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimellilol propane trimethacrylate, trimellilol propane triacrylate, methyl methacrylate, methyl acrylate, ethyl Methacrylate, ethyl acrylate, isopropyl methacrylate, isopropyl acrylate,
Butyl methacrylate, butyl acrylate, tertiary butyl methacrylate, tertiary butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, benzyl methacrylate, benzyl acrylate, isobornyl methacrylate, alkyl mono (meth) acrylate represented by isobornyl acrylate, And hydrophilic monomers represented by N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate and the like.

The crosslinkable monomer is used to increase the hardness of the obtained material and to improve workability such as machinability and abrasiveness, and its copolymerization ratio is usually 30% by weight or less, preferably 20% by weight or less. If the copolymerization ratio exceeds 30% by weight, the obtained material may be brittle or the oxygen permeability may be low.

The alkyl mono (meth) acrylate is used to improve the strength, processability, etc. of the obtained material, and its copolymerization ratio is usually 50% by weight so as not to impair the oxygen permeability of the obtained material. %, Preferably 40% by weight or less.

In addition, the hydrophilic monomer is used when imparting hydrophilicity to the surface of the obtained material, but if the copolymerization ratio of the hydrophilic monomer is increased, the oxygen permeability of the obtained material is impaired. The copolymerization ratio is usually 20% by weight or less, preferably 15% by weight or less.

The polymerization or copolymerization in the present invention can be carried out by a usual radical polymerization reaction. Alternatively, the polymerization can be carried out by irradiating ultraviolet rays in the presence of a photopolymerization initiator such as benzoin, benzophenone, and Michler's ketone to carry out polymerization. Here, a photopolymerization initiator or a thermal polymerization initiator is usually used per 100 parts by weight of the monomer mixture.
0.01 to 5 parts by weight are used.

In addition, when the material obtained by the present invention is used for applications requiring familiarity with tears and intraocular fluid, such as contact lenses and intraocular lenses, the material is processed into the shape of contact lenses and intraocular lenses. After that, hydrophilicity is imparted to the surface by further performing alkali treatment, plasma treatment with oxygen or nitrogen, plasma polymerization with a compound containing a hydrophilic group, or surface treatment by vapor deposition, sputtering or ion plating of an inorganic oxide. can do.

〔Example〕

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The evaluation criteria of workability and the test methods of various tests in the following Examples and Comparative Examples are as follows.

Evaluation criteria for workability Machinability A: The cut surface is glossy B: The cut surface is glossy but slightly opaque C: The cut surface becomes rough and white Abrasive A: The polished surface is good gloss B: Polished Irregularity occurs C: Polished surface becomes rough and white Oxidation transmission coefficient test method Using the obtained contact lens, a Rika Seiki Co., Ltd. Kaken type film oxygen permeation meter is used at 35 ° C 0.9
% In normal saline.

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

Test method for dirtability The obtained disk was immersed in a dirt solution for 30 days, and then washed with a contact lens cleaner (all-way cleaner manufactured by Ricky Contact Lens Co., Ltd.) to remove dirt attached to the surface. It was expressed as a change rate of the visible light transmittance when the visible light transmittance before immersion was set to 100. The dirt solution was a mixture of 0.1 part by weight of ovalbumin, 0.1 part by weight of egg white lysozyme, 0.1 part by weight of bovine stomach mucosa mucin, 0.1 part by weight of egg yolk lecithin and 100 parts by weight of purified water. Replaced with fresh stain.

Example 1 The following formula: 55 parts by weight of siloxanyl dimethacrylate represented by
2,2,2-trifluoroethyl methacrylate 35 parts by weight,
10 parts by weight of methyl methacrylate, and 0.1 part by weight of benzoin methyl ether as a polymerization initiator are mixed well at room temperature, and the mixed solution is poured into a heavy container made of polyethylene,
Ultraviolet rays were irradiated at room temperature for 16 hours in 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 disk having a thickness of 0.2 mm and a diameter of 15 mm, thereby evaluating workability, and then performing various tests. The results are shown in Table 1.

Example 2 The following formula: Siloxanyl dimethacrylate represented by 40 parts by weight,
35 parts by weight of 2,2,2,2 ', 2', 2 ',-hexafluoroisopropyl methacrylate, 20 parts by weight of methyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate and 0.1 part by weight of benzoin methyl ether as a polymerization initiator at room temperature This mixture is poured into a polyethylene polymerization vessel and irradiated with ultraviolet light at room temperature under a nitrogen atmosphere.
Irradiated for hours to copolymerize.

After the 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, thereby evaluating workability, and then performing various tests. 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 polymerization parts, ethylene glycol dimethacrylate 5 parts by weight, and benzoin methyl ether as a polymerization initiator 0.1 part by weight was mixed well at room temperature, and the mixed solution was poured into a polyethylene polymerization co-container, and was irradiated with ultraviolet rays at room temperature under a nitrogen atmosphere for 16 hours for copolymerization.

After the 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, thereby evaluating workability, and then performing various tests. The results are shown in Table 1.

[Effects of the Invention] The oxygen-permeable polymer material produced according to the present invention has an extremely high oxygen permeability, and adsorbs dirt components in tears and intraocular fluid and dirt caused by various use environments. It has an excellent feature that it is hard to adhere, and also has good workability such as machinability and abrasiveness. Therefore, the oxygen-permeable polymer material produced by the present invention is suitably used as an ophthalmic material such as a contact lens and an intraocular lens.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI G02C 7/04 G02C 7/04 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 30/00-30/10 C08F 130/00-130/10 C08F 230/00-230/10 C08F 290/00-290/14 C08F 299/00-299/08 G02C 7/04 A61F 2/16 C08G 77/00-77/62

Claims (1)

(57) [Claims] 1. The following general formula (I) Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ may be the same or different groups, and may be an alkyl group optionally substituted with a fluorine atom,
Represents a phenyl group, a vinyl group or a hydrogen atom, R ⁹ and
R ¹⁰ may be the same or different, and represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and A ¹ and A ^{2 each} represent an unsaturated polymerizable group or a hydrogen atom. However, A ¹ and
Neither of A ² can be a hydrogen atom at the same time. m and n show the number of 0-100. Where the group When two or more are present, each group may be the same or different. ] A method for producing an oxygen-permeable polymer material, comprising polymerizing or copolymerizing one or more polymerizable monomers having a bisphenylene ether represented by the following formula: