JPH04175316A - Production of oxygen-permeable polymer - Google Patents

Abstract

PURPOSE:To produce the title polymer improved in oxygen permeability, processability and mechanical strengths by copolymerizing a specified muconic acid (ester) with a vinyl monomer. CONSTITUTION:10-90wt.% muconic acid (ester) of formula I (wherein R<1> and R<2> are each H, alkyl or a group of any one of formulas II-VI; X<1> is fluoroalkyl; X<2> and X<4> are each an organosiloxane residue; X<3> and X<5> are each a fluoroorganosiloxane residue; Y<1> is a bivalent hydrocarbon group; and Y<2> is a bivalent hydroxyhydrocarbon group) is copolymerized with 90-10wt.% vinyl monomer (e.g. pentamethyldisiloxanylmethyl methacrylate) and at most 30wt.% polyfunctional monomer (e.g. diethylene glycol diacrylate) at 40-120 deg.C for 5-72hr in the presence of a thermal polymerization initiator (e.g. benzoyl peroxide).

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing oxygen permeable polymers.

More specifically, it relates to a method for producing an oxygen-permeable polymer that is extremely useful as a material for ophthalmic components such as contact lenses and intraocular lenses (prior art). Various plastic materials, particularly polymethyl methacrylate, are used as materials for the parts. However, these materials have low oxygen permeability, and dirt components in lachrymal fluid and intraocular fluid tend to stick to them, so there is a problem that they cannot be worn for long periods of time, especially when used as contact lenses.

Poly(N-vinyl-2-
Highly water-containing soft contact lenses, whose main ingredient is pyrrolidone, were revolutionary because they could be worn for long periods of time; It had the disadvantage of being extremely complicated to handle.

Furthermore, recently, a polymer material made by copolymerizing siloxanyl mono(meth)acrylate and fluoro(meth)acrylate has been proposed as a material for ophthalmic components that overcomes these drawbacks.

However, this polymeric material exhibits properties that vary greatly depending on the copolymerization ratio of the monomers.

In other words, increasing the copolymerization ratio of siloxanyl mono(meth)acrylate improves oxygen permeability, but on the other hand, adsorption or adhesion of dirt components increases significantly, and the material becomes too soft despite being brittle.
Conversely, when the copolymerization ratio of fluoro(meth)acrylate increases, it becomes difficult to adsorb and fix dirt components;
On the other hand, it has been difficult to form a material with a good balance of desirable properties such as reduced oxygen permeability.

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel method for producing an oxygen-permeable polymer.

An object of the present invention is to provide a method for producing a novel polymer material that has excellent oxygen permeability, excellent processability, and mechanical strength and is suitable as a material for ophthalmic components such as contact lenses and intraocular lenses. It is about providing.

Still another object of the present invention is to provide a novel polymer material that has high oxygen permeability and has very little adsorption or adhesion of dirt components in lacrimal fluid or intraocular fluid.

Further objects and advantages of the invention will become apparent from the description below.

(Means for Solving the Problems) According to the present invention, the above objects and advantages of the present invention are as follows: (A) The following formula (I) R100C-CH=CH-CH=CH-COOR2
...... (I) Here, R1 and R) are the same or different, and are a hydrogen atom, an alkyl group, a group represented by the following formula (I)-a, a group represented by the following formula (I)-b , a group represented by the following formula (1)-c, a group represented by the following formula (1)
)-d or a group represented by the following formula (I)-f, x+-yt-, (t)-a X-Yl-, (1)-b X Knee Y'-,,,, (1) -c X4-Y knee (1)
-aX5-Y'-,,,(I)-f (wherein, Xl represents a fluoroalkyl group, X2 and X4 represent organosiloxane residues, x3 and X5 represent fluoroorganosiloxane residues, Yl represents a divalent hydrocarbon group, and Y: represents a divalent hydrocarbon group having a hydroxyl group.) at least one first polymerizable monomer selected from muconic acid and its ester; and (B) a vinyl monomer that is a second polymerizable monomer that can be copolymerized with the first polymerizable monomer. achieved by law.

As mentioned above, the polymerizable monomer used in the method of the present invention is muconic acid or its ester represented by formula (I) (
It consists of a vinyl monomer (first polymerizable monomer) and a vinyl monomer (second polymerizable monomer).

In the above formula (I), R1 and R2 are the same or different, and are a hydrogen atom, an alkyl group, a group represented by the above formula (I)-a, a group represented by the above formula (1)-b, and a group represented by the above formula (1)-b. A group represented by I)-c, a group represented by the above formula (I)-d, or a group represented by the above formula (I)-f.

Here, the alkyl group in formula (I) may be linear or branched, and preferably has 1 to 20 carbon atoms.
, especially 1 to 12 alkyl groups, such as 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,
Examples include octyl group, 2-engineered tylhekynyl group, nonyl group, denyl group, dodecyl group, and undecyl group.

Further, the fluoroalkyl group represented by XI in formula (I)-a may be linear or branched, and preferably has 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms. For example, -CH, -CFyu, -C
H(CF,,)CF Yu.

-CH, CF2CF3H, -CH2CF, CF2CF3
．． -CH-, CF, CFHCF Yu.

-CH, CF, CF2CF yo, -CH, CF Yu CF Eng C
FYCF:.

-CI(2CH2CF5.-CH,CHYuCF:CF Engineering.

-C1j2CH2CF2CF:CF8. -CH Yu CH Yu CF2 CF, CF, CF, .

-CH2CH0CF2CF, CF, CF, CF engineering CF,
Examples include CF2CF2.

In formula (I)-b and formula (r)-d, X: and
Organosiloxane residues represented by 4 and formula (1
)-c and formula (I)-f, the fluoroorganosiloxane residues represented by X3 and
Preferably an alkyl group having 1 to 20 carbon atoms, especially 1 to 12 carbon atoms, a fluoroalkyl group, preferably a fluoroalkyl group having 2 to 20 carbon atoms, especially 2 to 12 carbon atoms, a phenyl group, a vinyl group, or the following formula % formula % () Here, R+8 and RI9 are the same or different,
A hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 12 carbon atoms, and a fluoroalkyl group, preferably having 2 to 20 carbon atoms. In particular, it is a 2 to 12 fluoroalkyl group, a phenyl group or a vinyl group, and X3 is a divalent hydrocarbon group, preferably having 1 to 10 carbon atoms,
In particular, it is a 2-4 divalent hydrocarbon group, B2 is a hydrogen atom or an unsaturated polymerizable group, and n is a number of 0-100, preferably 1-4, And m is a number of O to 100, preferably O to 50. It can also represent a group represented by the following. Of the groups represented by formula (a), the group containing at least one fluoroalkyl group is, of course, a fluoroorganosiloxane residue, and the group not containing a fluoroalkyl group is an organosiloxane residue.

Also, formula (I)-a, formula (I)-b and formula (r)-c
As the divalent hydrocarbon group represented by Yl in,
For example, preferred examples include alkylene groups having 1 to 4 carbon atoms such as methylene, ethylene, trimethylene, and tetramethylene.

In addition, the divalent hydrocarbon group having a hydroxyl group represented by yx in formula (I)-d and formula (I)-f is,
For example, -CH:CH(OH)CH2-, etc. can be mentioned.

Furthermore, in the above formula (a), the alkyl group and fluoroalkyl group in the definitions of RIE to R17 and the definition of RIS%R'' are the same as the alkyl group and fluoroalkyl group in the definitions of R1 and R2. I can do it.

X3 in formula (a)' is a divalent hydrocarbon group having 1 to 10 carbon atoms, such as a methylene group, ethylene group, trimethylene group, or tetramethylene group. Particularly preferred are two to three alkylene groups.

Further, as the unsaturated polymerizable group defined by B2 in formula (A), for example, vinyl group (CH, =CH-),
(meth)acryloxy group, acrylamide group (CH-, = CH-C0NH-), styryl group (CH-C,,H4-), acrylonitrile group (CH-C(CN)-) and 2-cyanoacryloxy group (CH-C(CN)Coo-) ) etc. can be mentioned as suitable ones.

Specific examples of muconic acid and its ester represented by the above formula (I) include HOOC-CH=CH-CH=CH-COOH.

HOOC-CH=CH-CH=CH-COOCH,,H
BCOOC-CH=CH-CH=CH-COOCH3,
HOOC-CH=CH-CH=CH-COOC:H,,
, H5(,0OC-CH=CH-CH=CH-COOC
2H,,,HOOC-CH=CH-CH=CH-COO
C2H7, H7C300C-CH=CH-CH=CH-
COOC3H,, cl H3HOOC-CH=CH-CH=CH-COOC-CH-
CH-: , CH, City HOOC-CH=CH-CH=CH-COOC4CH,
,,H,,C400C-CH=CH-CH=CH-CO
OC4H,,,HOOC-CH=CH-CH=CH-C
OOC8CH, □, HI 7 Ca 0OC-CH=
CH-CH=CH-COOC,= Hl 7 , HO
OC-CH=CH-CH=CH-COOCH CF3
, F3CH2COOC-CH=CH-CH=CH-CO
OCH2CF3, HOOC-CH=CH-CH=C
H-COOC2H4C4F, ,F,,C4H4(,
0OC-CH=CH-CH=CH-COOC:H4C4
F, ..., CF3 HOOC-CH=CH-CH=CH-COOCH CF3, can be mentioned.

The compound of formula (I) above can be produced by a method known per se.

Muconic acid, for example, is published in Fermentation Engineering, Vol. 55, p. 95 (1977).
It can be produced microbially from benzoic acid according to the method disclosed in J. Org. Chem, Vol. 45, p. 2737 (1980).
)) can be produced by oxidizing phenol with acetic acid peroxide.

Further, dimethyl muconate can be obtained by adding an ether solution of diazomethane to a tetrahydrofuran solution of muconic acid, stirring overnight, distilling off the solvent, and recrystallizing the product from methanol.

Furthermore, muconic acid was added to 50-60% with an excess of thionyl chloride.
After the reaction, thionyl chloride is distilled off, dichloromethane is added, and an alcohol corresponding to the ester, such as tridecafluorooctyl alcohol, is added dropwise in the presence of triethylamine. can get.

These first polymerizable monomers can be used alone or in combination of two or more.

In the present invention, the vinyl monomer that is the second polymerizable monomer is copolymerizable with the first polymerizable monomer, and the first polymerizable monomer is It dissolves.

Such vinyl monomers include, for example, the following formula (II), where A is an unsaturated polymerizable group, and Xl is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 3 carbon atoms. and RE, R4, R5, R(, R7 and Ro are the same or different, hydrogen atom, alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, especially 1 to 12 carbon atoms, a fluoroalkyl group, preferably carbon number 2~20
, especially 2 to 12 fluoroalkyl groups, phenyl groups, vinyl groups or the following formula (II)-a, where R'] and RI C are the same or different, and are hydrogen atoms, alkyl groups, preferably having 1 to 1 carbon atoms. 20,
In particular, an alkyl group, a fluoroalkyl group having 1 to 12 carbon atoms, preferably a fluoroalkyl group having 2 to 20 carbon atoms, especially a fluoroalkyl group having 2 to 12 carbon atoms, a phenyl group or a vinyl group, X2 is defined the same as Xl, and B1 is a hydrogen atom. or an unsaturated polymerizable group, and λ is a number of O to 20, preferably 1 to 4, and Z is an alkyl group, preferably having 1 to 20 carbon atoms, especially 1 to 4 carbon atoms.
12 alkyl group, fluoroalkyl group, preferably a fluoroalkyl group having 2 to 20 carbon atoms, especially 2 to 12 carbon atoms, or a group represented by (II)-a above, and k is 0 to 100. Preferably a number from 0 to 50, or a compound represented by the following formula (I[I) CH2=C-Co-R12...
... (III) Here, Rl is a hydrogen atom,
A fluorine atom, a methyl group or a trifluoromethyl group, and R12 is an alkyl group, preferably a C1-C20, especially a C1-12 alkyl group or a fluoroalkyl group, preferably a C2-C20, especially a C2-C Preferred examples include compounds represented by the following, which are 12 fluoroalkyl groups.

In the above formula (II), A is an unsaturated polymerizable group.

Specific examples of such unsaturated polymerizable groups include the above formula (a)
The same unsaturated polymerizable groups as those exemplified in B2 can be mentioned.

XI in formula (n) is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples of such hydrocarbon groups include the above formula (
A) The same divalent hydrocarbon groups as those exemplified for X3 in ° can be mentioned.

R2, R4, R5, Rζ, R7 and R' in formula (II) are the same or different and are represented by a hydrogen atom, an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group or the above formula (If)-a It is the basis. Such alkyl groups and fluoroalkyl groups include R1 and R
The same examples as those exemplified in : can be mentioned as specific examples.

Further, specific examples of R', R1, X2 and 131 groups in the above (II) -a include specific examples of R1 di, R1; I can name the same thing.

Further, Z in formula (II) is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a group represented by the above formula (II) -a. Examples of such alkyl groups and fluoroalkyl groups include the same specific examples of R1 and R2 in formula (I) above.

Examples of the compound represented by formula (n) include pentamethyldisiloxanyl methyl methacrylate, pentamethyldisiloxanyl methyl acrylate, pentamethyldisiloxanyl propyl methacrylate, and pentamethyldisiloxa. Nylpropyl acrylate, Methylbis(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)silylpropylglycerol acrylate, Mono(methylbis(trimethylsiloxy)siloxy)bis(trimethylsiloxy)silylpropylglycerol methacrylate, Mono Siloxanyl mono(meth)acrylates such as (methylbis(trimethylsiloxy)siloxy)bis(trimethylsiloxy)silylpropylglycerol acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglycerol methacrylate, trimethylsilylethyltetramethyldisiloxanylbropylglycerol acrylate; (3,3,3-trifluoropropyldimethylsiloxy)bis(trimethylsiloxy)silylmethylmethacrylate, (3,3,3-trifluoropropyldimethylsiloxy)bis(trimethylsiloxy)silylmethylacrylate, (3,3,4 , 4,5,5,5-hebutafluoropentyldimethylsiloxy) (methylbis(tritylsiloxy)siloxy)trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-hebutafluoropentyl dimethylsiloxy)(methylbis(trimethylsiloxy)siloxy)trimethylsiloxysilylprobyl acrylate, (3,3,4,4,5,5,
Fluorosiloxanyl mono(
Preferred examples include siloxanyl cy(meth)acrylates represented by meth)acrylate; and the like.

Among the compounds represented by formula (n), pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylpropyl methacrylate, methylbis(trimethylsiloxy)silylpropyl methacrylate, tris(trimethylsiloxy)silylpropyl methacrylate Siloxanyl mono (meth)acrylates such as; (3,3,3-)lifluoropropyldimethylsiloxy)bis(trimethylsiloxy)silylmethylmethacrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethyl siloxy)(methylbis(trimethylsiloxy)siloxy)trimethylsiloxysilylpropyl methacrylate, (3,3,4,4゜5.5.5-heptafluoropentyldimethylsiloxy)(pentamethyldisiloxanyloxy)trimethylsiloxysilyl methacrylate Fluorosiloxanyl monomethacrylates such as; and siloxanyl dimethacrylates may be mentioned as preferred.

Further, in the above formula (III), R1+ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Furthermore, R12 is an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms. Specific examples of such alkyl groups and fluoroalkyl groups include those exemplified for R1 and R: in the formula (I) above.

Examples of the compound represented by the formula (II[) include 2.2.2-trifluoroethyl methacrylate, 2.2.2-)lifluoroethyl acrylate, and 2.2-trifluoroethyl methacrylate.
．． 2-trifluoroethyl-α-fluoroacrylate, 2.2.2-trifluoroethyl-α-trifluoromethyl methacrylate, 2.2.3.3-tetrafluoropropyl methacrylate, 2.2,3.3-tetra Fluoropropyl acrylate, 2.2,3.3.3-pentafluoropropyl methacrylate, 2.2,3.3.3-pentafluoropropyl acrylate, 2.2.2.2°, 2', 2'-to Hexafluoroisopropyl methacrylate, 2.2.2.2', 2°, 2°-Δ, 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-dodecafluorohebutyl methacrylate, 2.2,3,3,4,4,5,5 , 6,6,7.7-dodecafluorohebutyl 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-Octafluoro-1,1-dimethylpentyl acrylate: and methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, isobyl acrylate, butyl a5-alkyl (meth) such as methacrylate, butyl acrylate-1, tert-butyl methacrylate, tert-butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, benzyl methacrylate, benzyl acrylate, inbornyl methacrylate, isobornyl acrylate, etc. Mention may be made of acrylates.

Among these compounds represented by formula (III), preferred are: 2.2.2-) Lifluoroethyl methacrylate, 2.2.2-) Lifluoroethyl-α-fluoroacrylate, 2.2. 2-trifluoroethyl-α-trifluoromethyl 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-
Dodecafluorohebutyl 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, 2.2.3.3.4.4.5.5-octafluoro -1
, 1-dimethylpentyl methacrylate; and acrylic methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and tert-butyl methacrylate.

The second polymerizable monomers represented by formulas (n) and (III) above can be used alone or in combination of two or more.

In the present invention, the ratio of the first polymerizable monomer to the second polymerizable monomer is determined based on the total weight of the first polymerizable monomer and the second polymerizable monomer.
The content of the polymerizable monomer is preferably 10 to 90% by weight, and the content of the second polymerizable monomer is preferably 90 to 10% by weight. More preferably, the first polymerizable monomer is 10 to 70% by weight and the second polymerizable monomer is 10 to 70% by weight.
90 to 30% by weight of the first polymerizable monomer, particularly preferably 15 to 60% by weight of the first polymerizable monomer, and 85 to 40% by weight of the second polymerizable monomer. .

The first polymerizable monomer, particularly in formula (I), R+ and R2 are alkyl groups or formula (1)-a, formula (I)-b,
By using a muconate ester which is a group represented by formula (I)-c, formula (■)-d or formula (I)-f, the compatibility with the second polymerizable monomer can be further improved. However, so-called striae do not occur in the polymer after copolymerization,
The processability of the polymer can be improved while maintaining high oxygen permeability, and adsorption or adhesion of dirt and the like can be prevented.

In the present invention, in addition to the first and second polymerizable monomers described above, other polymerizable monomers may be used as appropriate without departing from the purpose of the present invention.

For example, polyfunctional monomers are used to increase the hardness of the resulting polymer and improve processability such as machinability and polishability.

Examples of such polyfunctional monomers include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and tetraethylene glycol. Diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1
．． Examples include 4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate.

Such polyfunctional monomers can be used alone or in combination of two or more. It is believed that such polyfunctional monomers create crosslinked structures in the resulting polymer. Such polyfunctional monomers are preferably used in a proportion of 30% by weight or less, more preferably 20% by weight or less, based on the total weight of all monomers used. If it exceeds 30% by weight, the brittleness of the resulting polymer increases and the oxygen permeability tends to decrease.

In addition, for example, in order to impart hydrophilicity to the obtained polymer, for example, acrylic acid, methacrylic acid, N-vinyl-2
- It is also possible to copolymerize hydrophilic monomers such as pyrrolidone and 2-hydroxyethyl methacrylate. Such hydrophilic monomers are preferably used in an amount of 20% by weight or less, more preferably 15% by weight or less, based on the total weight of all monomers used.

If the copolymerization ratio of these hydrophilic monomers is too high, the oxygen permeability of the resulting polymer will be impaired.

Copolymerization in the present invention can be carried out by a normal radical polymerization reaction. For example, polymerization is carried out by raising the temperature stepwise in the presence of a thermal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile, or by ultraviolet rays in the presence of a photopolymerization initiator such as benzoin, benzophenone, or Michler's ketone. It can be carried out by a method of irradiating and polymerizing.

The polymerization temperature of thermal polymerization is preferably 40 to 120°C, for example,
It is best to raise the temperature in stages.

Moreover, the polymerization time of thermal polymerization is advantageously 5 to 72 hours.

Further, the polymerization temperature for photopolymerization is preferably, for example, 10 to 100°C, and it is preferable to raise the temperature in steps. Further, the intensity of ultraviolet rays for photopolymerization is preferably 10 to 200 μW/cm, and the irradiation time is usually 4 to 72 hours.

The thermal polymerization initiator or photopolymerization initiator is generally used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of all monomers used.

The polymer obtained by the above production method of the present invention exhibits the same machinability and abrasiveness as conventional hard contact lenses made of polymethyl methacrylate, and is also tougher and has excellent oxygen permeability and stain resistance. be.

In addition, when the polymer obtained by the present invention is used for applications that require compatibility with lachrymal fluid or intraocular fluid, such as contact lenses or intraocular lenses, the material may be added to contact lenses or intraocular lenses as necessary. After processing into the shape of an intraocular lens, surface treatment is performed, for example, by alkali treatment, plasma treatment with oxygen or nitrogen, plasma polymerization with a compound containing a hydrophilic group, vapor deposition of an inorganic oxide, sputtering, or ion blasting. By doing so, the surface can be made hydrophilic.

[Examples] The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, the evaluation criteria for workability and the test methods of various tests in the following Examples and Comparative Examples are as follows.

■ Workability evaluation criteria Machinability A: The cutting surface is glossy. B: The cut surface is glossy, but it is a little dull. transparent, C: The cut surface becomes rough and white. Abrasiveness A: The cut surface has good gloss. B: Uneven polishing occurs. C: The polished surface becomes rough and white.

■ Test method for oxygen permeability coefficient Using the obtained contact lens, using Rika Seiki Kogyo Seikaken type film oxygen permeability meter,
Measurement was performed in 0.9% physiological saline at 5°C.

■ Visible light transmittance test method Using the obtained disk, measure 500 to 60 with a double beam spectrophotometer 200-20 model manufactured by Hitachi, Ltd.
Transmittance at 0 nm was measured.

■ Stain resistance test method Using the obtained disc, immerse it in a dirt solution for 30 days, then wash it with a contact lens cleaner (-Always Cleaner manufactured by Ricky Contact Lens Co., Ltd.) to remove dirt adhering to the surface. , expressed as the rate of change in visible light transmittance when the visible light transmittance before immersion is taken as 100.

The stain solution used was a mixed solution consisting of 01 parts by weight of egg albumin, 0.1 parts by weight of egg white lysozyme, 0.1 parts by weight of bovine gastric mucosal mucin, 0.1 parts by weight of egg yolk lecithin, and 100 parts by weight of purified water. Replaced with fresh stain solution every 2-3 days.

Example 1 35 parts by weight of muconic acid dibutyl ester, 35 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 20 parts by weight of methyl methacrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of ethylene glycol dimethacrylate.
parts by weight and 0.1 parts by weight of benzoin methyl ether as a polymerization initiator were thoroughly mixed at room temperature, the mixed solution was poured into a polyethylene polymerization container, and the mixture was irradiated with ultraviolet rays for 16 hours at room temperature under a nitrogen atmosphere. Polymerized.

After copolymerization, the obtained bulk polymer was cut and polished to form a contact lens and a disc with a thickness of 02 mm and a diameter of 15 mm to evaluate workability, and then various tests were conducted.

The results are shown in Table 1.

Example 2 40 parts by weight of muconic acid dinonafluorohexyl ester,
30 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 20 parts by weight of methyl methacrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of ethylene glycol dimethacrylate, and 01 parts by weight of benzoin methyl ether as a polymerization initiator were thoroughly mixed at room temperature, This mixed solution was poured into a polyethylene polymerization container, and copolymerized by irradiating ultraviolet rays at room temperature in a nitrogen atmosphere for 16 hours.

After the copolymerization, the obtained bulk polymer was cut and polished to form a contact lens and a disk with a thickness of 0.2 mm and a diameter of 15 mm to evaluate workability, and then various tests were conducted.

The results are shown in Table 1.

Comparative Example 1 50 parts by weight of tris(trimethylsiloxy)silylpropyl methacrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of ethylene glycol dimethacrylate, and 1 part by weight of benzoin methyl ether as a polymerization initiator were thoroughly mixed at room temperature, and this mixed solution was prepared. was poured into a polyethylene polymerization container, and copolymerized by irradiating with ultraviolet rays at room temperature in a nitrogen atmosphere for 16 hours.

After the copolymerization, the obtained bulk polymer was cut and polished to form a contact lens and a disk with a thickness of 0.2 mm and a diameter of 15 mm to evaluate workability, and then various tests were conducted.

The results are shown in Table 1.

Table 1 (Effects of the Invention) The oxygen permeable polymer produced according to the present invention has extremely high oxygen permeability, and is free from stains caused by dirt components in lacrimal fluid and intraocular fluid and various usage environments. It has an excellent feature of being difficult to adsorb or stick to. Moreover, machinability,
It has good workability such as polishability and excellent mechanical strength. Therefore, the oxygen permeable polymer produced according to the present invention is suitably used as ophthalmic components such as contact lenses and intraocular lenses.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Patent attorney Agent: Masataka Oshima

Claims (1)

[Claims] 1. (A), the following formula (I) R^1OOC-CH=CH-CH=CH-COOR^2
......(I) Here, R^1 and R^2 are the same or different, and represent a hydrogen atom, an alkyl group, a hydrogen atom, an alkyl group, a
)-a, a group represented by the following formula (I)-b, a group represented by the following formula (I)-c, a group represented by the following formula (I)-c, a group represented by the following formula (I)-c, a group represented by the following formula (I)-b, a group represented by the following formula (I)-c,
)-d or a group represented by the following formula (I)-f, X^1-Y^1-...(I)-a X^2-Y^1-...・(I)-b X^3-Y^1-...(I)-c X^4-Y^2-...(I)-d X^5-Y^2-... ...(I)-f (wherein, X^1 represents a fluoroalkyl group, and X^2
and X^4 represents an organosiloxane residue,
3 and X^5 represent fluoroorganosiloxane residues, Y^1 represents a divalent hydrocarbon group, and Y^2 represents a divalent hydrocarbon group having a hydroxyl group. ); and (B) a second polymerizable monomer copolymerizable with the first polymerizable monomer. 1. A method for producing an oxygen permeable polymer, which comprises copolymerizing a vinyl monomer.