JPH039909A - Fluorinated copolymer and contact lens produced therefrom - Google Patents

Abstract

PURPOSE:To obtain a copolymer with excellent oxygen permeability by copolymerizing siloxanyl (meth)acrylate, (meth)acrylate, a fluorinated styrenic monomer and a fluorinated alicyclic (meth)acrylate. CONSTITUTION:A fluorinated copolymer consisting of 10wt.% or more siloxanyl (meth)acrylate monomer, 30wt.% or less (meth)acrylate monomer, 3wt.% or more fluorinated styrenic monomer and 1wt.% or more fluorinated alicyclic (meth)acrylate monomer wherein at least one 1-30C fluorinated hydrocarbon group with at least 3 F atom is grafted onto a satd. carbon atom of an alicyclic (meth)acrylate of formula I based on one molecule of said alicyclic (meth) acrylate. In the formula I, R<1> is H, OH, a group of formula II (wherein R<2> is H or a methyl); x and y are each 0-30; m is 0-10; n is 1-12; m+n is 1-22.

Description

[Detailed Description of the Invention] The present invention provides a fluorine-containing copolymer with excellent oxygen permeability,
The present invention also relates to a contact lens made of such a fluorine-containing copolymer, which has excellent biocompatibility and can be worn for a long period of time.

Since the cornea of the Ibaramai eye is a tissue without blood vessels, the oxygen necessary for its respiratory metabolism is obtained by diffusion from the palpebral conjunctiva and aqueous humor when the eyelids are closed, and is obtained from the atmosphere when the eyelids are open. It is taken from. Therefore, wearing a contact lens on the eyeball causes a disturbance in oxygen metabolism in the cornea, and especially when the contact lens is worn for a long period of time, it often causes hyperemia, edema, and other corneal damage. Therefore, materials for contact lenses must not only have excellent optical properties, chemical properties, physical properties, etc., but also excellent oxygen permeability. Furthermore, it is important that materials for contact lenses have excellent stain resistance against proteins, lipids, mucin, etc. that are components of tear fluid, stain resistance against bacteria and fungi, comfortable wear, and biocompatibility. be.

Conventionally, polymethyl methacrylate and various methacrylate ester polymers have been widely used as materials for such contact lenses.

Although these materials have satisfactory optical properties, they do not have sufficient oxygen permeability, and contact lenses made of these materials cannot withstand long-term wear.

Therefore, in order to improve the oxygen permeability of methacrylic ester polymers, for example, Japanese Patent Publication No. 52-33502 proposed a siliconized methacrylic ester polymer in which siloxane bonds were introduced into the methacrylic ester molecules. JP-A-57-51705, JP-A-61-111308, etc. use an oxygen-permeable polymer mainly composed of cellulose acetate butyrate or a fluorine-containing methacrylate ester polymer. Contact lenses have been proposed.

However, although such polymers have somewhat improved oxygen permeability compared to the aforementioned polymethyl methacrylate and methacrylate ester polymers, they are still far from being sufficient (in addition, they have poor stain resistance). In terms of gender and wearability,
There is room for improvement.

The present invention has been made in order to solve the above-mentioned problems in oxygen permeable polymers used as materials for medical oxygen permeable materials, particularly contact lenses and the like. An object of the present invention is to provide a fluorine-containing copolymer that is useful as a new medical oxygen-permeable polymer, and a contact lens made of such a fluorine-containing polymer.

The fluorine-containing copolymer according to the present invention for preparing the amount of
0% by weight or more, (b) 30% by weight or less of a (meth)acrylate monomer component, (c) 3% by weight or more of a fluorine-containing styrenic monomer component,
and (d)-maximum (1) (1) (wherein RI represents a hydrogen atom, a hydroxyl group or a group, X and y are each an integer of 0 to 30, m is an integer of O to 10,
n represents an integer of 1 to 12, and m+n is 1 to 22.

) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by It is characterized by comprising 1% by weight or more of a fluorine-containing alicyclic (meth)acrylic acid ester monomer component, which is characterized by having at least one graft bonded per molecule.

Further, the contact lens according to the present invention is characterized by being made of the above-mentioned fluorine-containing copolymer.

First, a siloxanyl (meth)acrylate monomer component (a) is used as the monomer component of the fluorine-containing copolymer according to the present invention.

In the present invention, as the siloxanyl (meth)acrylate monomer component (a), - maximum () () (wherein R3 represents a hydrogen atom or a methyl group, and XI represents C
1h The amount xt each independently represents -(0-Si)-CHs,
A siloxanyl (meth)acrylate monomer represented by CHp is an integer of 1 to 5, q is an integer of 1 to 3, and r is an integer of 0 to 2 is preferably used.

Specific examples of such siloxanyl (meth)acrylate monomers include, for example, CHg = CHCOOCHz-5i (OSi (C
Hs) s) sco.

(Jlt = CC00CHtCHt-Si [OSi
(CJs) sl sH3 CHg = CCOOCHgCIbCC00CH[OS
i (CHri sl sCHg-CCOOCHtCHz
CHz-5tLO5i (CHsJ3JzCH1 TomiCHC
OOCHzCHtCToCHt-5i [OSi (C
J? ) z) s etc. These may be used alone or as a mixture of two or more.

In the fluorine-containing copolymer according to the present invention, the siloxanyl (meth)acrylate monomer component is contained in an amount of 10% by weight or more.

In addition, as the (meth)acrylate monomer component (b), -maximum (III) 4 CHz = C-C0OR' (III) (wherein, R4 represents a hydrogen atom or a methyl group, and H% represents hydrogen represents an atom, an alkyl group having 1 to 14 carbon atoms, or a fluorine-substituted alkyl group.) Those represented by the following are preferably used.

Specific examples of such (meth)acrylate monomer components include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, etc. ) In addition to acrylic acid alkyl ester, CH3 C1h=CCOOCHgCToCFHCh, CHg 薯CHg -CCC00CIbC11(Ch) SOF2
, CH2 CH! UecOOcHzcHz (Ch) MaCF! , C.H.
3 GHz-CCOOCHzCHz (Ch)ttcF3,C
I.

CHz-CCOOCHgCFzCFHCFs,? Hs C8z = CC00CHgcF (CF 5) CFH
CF (CF RiiH3 GHz = CC00C(CHs) zcF gcFH
(CF z) J rate monomers can also be used alone or as a mixture of two or more.

In the fluorine-containing copolymer according to the present invention, such (
The meth)acrylate monomer component is contained in a range of 30% by weight or less.

Further, the fluorine-containing styrenic monomer component preferably has -maximum (IV) (IV) (wherein X3 is each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and (one or more represents a fluorine atom or a fluoroalkyl group).Specific examples of such fluorine-containing styrenic monomer components include the following.These (meth)acrylates, etc. I can do it.

The fluorine-containing styrenic monomer component may also be used alone or in combination with
It is used as a mixture of more than one species, and is contained in a range of 3% by weight or more in the fluorine-containing copolymer according to the present invention.

In addition to the above, the fluorine-containing copolymer according to the present invention has at least three fluorine atoms in the saturated carbon atoms of the alicyclic (meth)acrylic ester represented by the above-mentioned maximum (I). It contains a fluorine-containing (meth)acrylic ester component in which at least one 30 fluorinated hydrocarbon groups are grafted to each molecule of the alicyclic (meth)acrylic ester.

In the present invention, in the above-mentioned maximum (1), X and y are each an integer of 0 to 30, preferably an integer of O or l, and m is an integer of θ to 10, preferably θ to 4
n is an integer of 1 to 12, preferably 3 to 12, and n is an integer of 1 to 12, preferably 3 to
Indicates an integer of 8.

Therefore, examples of (meth)acrylic acid esters having a cyclic structure represented by (I) above include (2).

The fluorine-containing (meth)acrylic ester used as a monomer component in the present invention preferably has at least 3 carbon atoms forming the cyclic structure of the alicyclic (meth)acrylic ester having the cyclic structure. This is a compound in which at least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having 1 fluorine atom is graft-bonded to each molecule of the alicyclic (meth)acrylic acid ester.

The fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having a fluorine atom is preferably a fluorine-substituted saturated alkyl group or a fluorine-substituted cycloalkyl group which may have a condensed ring or a bridged ring.

Therefore, as a specific example, for example, -ChCFHCFs
, -CPtCFHCtFs, -CFICFHC4F9,
-CFtCFHCaFts, -ChCFHCt. F□,
-CFtCFHCFtHl-CFtCFI ((CFt)
J.

-ChCFH(CFt)J, -CFtCFHCCFt
)hH, -CFtCFH-(Ch)Jl-CFt(:F
H(CFt)sH, -CFtCFH(Ch)J.

-CFgCFH(CFt)+J, -CHzCHzCh,
-CHzCHzCzFs, -CHgCIlz(CPg)
J--ChCFHCPoc(CFs)s, -CF,CF
H-ChCH(CzFs)z, -CF(CFs)CF
Examples include fluorine-substituted saturated alkyl groups such as HCF(CFs)z, and the like.

Among the above, particularly preferred are alkyl groups having 2 to 20 carbon atoms and having at least three fluorine atoms.These fluorine-substituted hydrocarbon groups form the cyclic structure of the (meth)acrylic acid ester having the cyclic structure. Randomly grafted onto carbon atoms.

Therefore, the fluorine-containing (meth) used in the present invention
Specific examples of the acrylic ester component include CFzCFHCPs.

These fluorine-containing (meth)acrylic acid ester components also
It can be used alone or as a mixture of two or more.

The above fluorine-containing (meth)acrylic acid ester is -maximum (V) (V) (wherein, R6 represents a hydrogen atom or a hydroxyl group, X and y are each an integer of 0 to 30, and m is an integer of 0 to 10. , n is 1
Indicates an integer of ~12, and m+n is 1-22. ) is reacted with a fluorine-containing olefin in the presence of a radical generator to form a fluorine-containing alicyclic alcohol having at least three fluorine atoms and having 2 to 30 carbon atoms in the carbon atoms forming the alicyclic alcohol. At least 1 substituted hydrocarbon group per molecule of the alicyclic alcohol
The fluorine-containing alicyclic alcohol is then grafted with (meth)acrylic acid or (meth)acrylic acid halide in a solvent in the presence of a basic compound. It can be obtained by reacting.

Examples of the alicyclic alcohol represented by the maximum (V) above include cyclopropylmethanol, cyclobutanol, cyclopenkune-1,3-diol, cyclopentylmethanol, cyclopentanol, 3-cyclopentyl-1-propatol, and cyclohexyl. methanol,
Cyclohexane-1゜6-simethanol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexanol, 4-cyclohexyl-1-butanol, cyclohexylethyl carbinol, 1 -cyclohexyl-
2-ethanol, cycloheptane-1,2-diol,
Cycloheptylmethanol, cycloheptatool, cyclooctane-1,2-diol, cyclooctane-1,
Examples include 4-diol and cyclooctatool.

In the above-mentioned fluorine-containing alicyclic alcohol, the above-mentioned fluorine-substituted hydrocarbon group is graft-bonded to the carbon atom in the saturated hydrocarbon chain of the alicyclic alcohol represented by -maximum (V). The grafting ratio of fluorine-substituted hydrocarbon groups is at least one or more, preferably 1 to 4, per molecule of alicyclic alcohol. Therefore, the above-mentioned fluorine-containing alicyclic alcohol usually contains , 3-1
It has 20, preferably 3 to 60 fluorine atoms.

When a plurality of fluorine-substituted hydrocarbon groups are graft-bonded to the above-mentioned fluorine-containing alicyclic alcohol, these fluorine-substituted hydrocarbon groups are usually graft-bonded to different carbon atoms.

Therefore, as specific examples of the above-mentioned fluorine-containing alicyclic alcohol, for example, CHg=ICICF+, CHt=CHCgFs, CH
t=CI(Ch)i■, CFz=CFCFzC(CF3
) x, CFg=CPCFzCH(CtFs)t, C
h=lCF−CF=CF! , etc.

The above-mentioned fluorine-containing olefins include, for example, Ch.CFCl2, Ch.
=CFC*)Is, CF*=CFCJw, CFg=CF
CiH+ s, CFz・CF-C1 (lHll, CFt
=CFCF3, CFPCFCF! H,CFt=CF(C
Ft) J.

CFz-CF(CFt)J, CFz=CF(CPg)
aHS CFz・CF(CFri)■, CFg=CF(C
Fg)J, CFz・CF(CFz)J, CFt
=CF(CFz)ton.

etc. can be mentioned.

The reaction between the fluorine-containing olefin and the alicyclic alcohol is preferably carried out in a solvent in the presence of a radical generator. The radical generator is not particularly limited, but typically includes, for example, isobutyryl peroxide, 1-hexyl oxyneohexanoate), 2,4-dichlorobenzoyl peroxide, octanoyl peroxide, Cumyl peroxyoctoate, m-tolyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl cumyl peroxide, di-t-butyl peroxide, t-butyl hydroper Oxide etc. can be mentioned.

Such radical generators are usually present in the reaction mixture.
It is used in a range of 0.1 mmol/1 to 10 sol/jl, preferably 10 mmol/1 to 1 sol/1.

As the reaction solvent, aromatic hydrocarbons and halogenated aromatic hydrocarbons, particularly chlorinated or fluorinated alkyl aromatic hydrocarbons, are preferably used. For example, benzene, xylene, toluene, chlorobenzene, dichlorobenzene, pensitrifluoride, Chlorobenzytrifluoride,
Xylene hexafluoride, etc. are used.

The reaction between the alicyclic alcohol and the fluorine-containing olefin is usually carried out at a temperature of 20 to 300°C, preferably 50 to 200°C.
It is usually carried out at a temperature in the range of 0.2 to 5 hours.

After completion of the reaction, the unreacted fluorinated olefin and solvent are separated and removed from the resulting reaction mixture under reduced pressure to obtain the fluorinated alicyclic alcohol, and if necessary, by distillation, Can be purified.

Furthermore, (meth)acrylic acid or (meth)acrylic acid is added to the fluorine-containing alicyclic alcohol in the presence of a basic compound in a solvent.
The fluorine-containing (meth)acrylic ester can be obtained by reacting acrylic acid halide.

As the (meth)acrylic acid halide, (meth)acrylic acid chloride is preferably used.

Both inorganic and organic bases can be used as the basic compound, and examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. , alkali metal carbonates such as potassium hydrogen carbonate, and charcoal #
I urea salt is used. Further, as the organic base, an amine compound is preferable, and for example, triethylamine, methyldiethylamine, triisopropylamine, pyridine, etc. are used.

As the reaction solvent, hydrocarbons, ketones, ethers, etc. are preferably used, and for example, hexane, pentane, benzene, toluene, cyclohexane, acetone, ethyl isobutyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, etc. are used.

The (meth)acrylic acid esterification reaction of the alicyclic fluorine-containing alcohol is usually carried out at 0 to 150°C, preferably at 10°C.
It is carried out at a temperature of ~80°C. The reaction time is usually 0.
It takes about 2 to 50 hours.

After completion of the reaction, excess or unreacted (meth)acrylic acid halide remaining in the reaction mixture is decomposed using an alcohol such as methanol as necessary, and solid matter is filtered.
By concentrating the filtrate and removing unreacted basic compounds with the solvent and (meth)acrylic acid esters produced by the above decomposition operation, for example, by distilling them off, the fluorine-containing alicyclic (meth)acrylic acid can be obtained. Esters can be obtained.

The fluorine-containing copolymer according to the present invention can be produced by a conventional copolymerization method. For example, the monomer components described above may be polymerized in the presence of a polymerization initiator. If desired, various stabilizers, pigments, thickeners, etc. can be added to the reaction mixture before or after polymerization.

As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator can be used. Examples of the thermal polymerization initiator include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenyl azobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, t-butyl hydro Peroxide etc. can be mentioned. In addition, as a photopolymerization initiator, for example, -max (in the formula, l?
represents an alkyl group. ), benzophenones such as benzophenone and benzoate, xanthone such as xanthone and thioxanthone, and p-hydroxyisobutyrylisopropylbenzene.

The reaction temperature for thermal polymerization is usually in the range of 40 to 200°C, preferably 45 to 120°C, and the time required for polymerization is
Usually 0.5 to 5000 minutes, preferably 30 to 2000 minutes
It's a minute.

On the other hand, in the case of photopolymerization, the polymerization time varies depending on the type and amount of monomers and photopolymerization initiators used, as well as the type of light source used. When isobutyrylisopropylbenzene is used, a copolymer having sufficient strength for practical use can be obtained by irradiation with ultraviolet light in a time range of several seconds to several minutes.

The fluorine-containing copolymer of the present invention thus obtained has excellent oxygen permeability, and its oxygen permeability coefficient is CD K g X 10-" cc (STP) am/
d·sec·m Hg) is usually 159 or more. Here, the oxygen permeability coefficient is determined by preparing copolymers with various film thicknesses using aluminum plates of different thicknesses as spacers, determining the relationship between the film thickness of the copolymer and the oxygen permeability coefficient, and calculating the relationship between the film thickness of the copolymer and the oxygen permeability coefficient. Oxygen permeability coefficient at infinity (DK g x 10-” c
c (STP)as/cd・sec・NHg).

Furthermore, the copolymer according to the present invention has excellent stain resistance against proteins, lipids, mucins, and the like.

Therefore, the fluorine-containing copolymer according to the present invention is useful as an oxygen permeable material for living organisms, and is particularly suitable as a material for contact lenses.

In the contact lens according to the present invention, the above-mentioned monomer components and a polymerization initiator are injected into a predetermined mold together with other additives as necessary and polymerized to obtain a copolymer. It can be obtained by cutting and polishing into the desired shape. It can also be obtained by a method such as polymerization using a contact lens mold having a predetermined shape.

The contact lenses of the present invention obtained in this manner not only have superior oxygen permeability, but also superior wearability, resistance to tear fluid components, and excellent biocompatibility compared to conventional lenses. , can be worn for long periods of time.

As described above, the fluorine-containing copolymer of the present invention contains a siloxanyl (meth)acrylate component, a (meth)acrylate component,
Consisting of an acrylic ester component, a fluorine-containing styrenic monomer component, and a fluorine-containing (meth)acrylic ester component, it has excellent optical properties and oxygen permeability, and when used as a contact lens, it provides excellent wearing comfort. It has excellent stain resistance against tear fluid components such as proteins, lipids, and mucin, as well as against bacteria, fungi, and the like.

Hereinafter, the present invention will be explained with reference to examples showing the production of fluorine-containing (meth)acrylic acid ester used as a comonomer in the present invention. It is not limited in any way.

Reference Example 1 (Production of 1-hexafluoropropyl-1,3-cyclohexanediol) 65 g of cyclohexane-1,3-diol, 3.5 g of di-t-butyl peroxide as a radical generator, and 250 ml of chlorobenzene as a solvent. 500m
1 in a stainless steel autoclave, then
110 g of hexafluoropropylene was press-fitted into the flask, the flask was sealed, and the flask was reacted at 120° C. for 7 hours with stirring.

After the reaction is complete, the contents of the autoclave are cooled to room temperature,
After slowly purging the gas inside, the autoclave was opened and the reaction mixture was taken out.

After concentrating the reaction mixture under reduced pressure and distilling off the solvent,
Extraction with diethyl ether and washing of this extract with water were repeated.

The ether layer was then concentrated to isolate a crude product with a purity of 96% (by gas chromatography).

Furthermore, this was subjected to vacuum distillation to obtain 135 g of 1-hexafluoropropyl-1,3-cyclohexanediol represented by the following formula with a purity of 99% (as determined by gas chromatography). The infrared absorption spectrum is shown in FIG.

The yield based on hexafluoropropylene was 69%, and the yield based on cyclohexane-1,3-diol was 90%.

Shi O-H3600ca+-' (37,3350cm
+-' (S, br,).

C-H2920cm-' (s), 2850cm-
'δC-H1440cm-' C-F 1200cm-' GC-MS analysis El m/e=266, 416 (very weak")
(M”)”C-NMR (solvent CDCl!, reference value 77.
0 ppm (C”DCI) Boiling point 121-b Elemental analysis HF Actual value 38.9 4.1 44.1 Calculated value 40.6 4,5 42.9 (The calculated value is
Calculated value as a 1:1 adduct of cyclohexane-1,3-diol and hexafluoropropylene. ) Attribution peak number of each peak in the infrared absorption spectrum (1) Chemical shift (δppm) ? 4.59.76.01 (divided into 8 pieces each) JF"F~C+ #2O-30Hz 34.43.34.65.37.81゜66.89.6
7.12.67.30゜27.65.27.87.28
．． 25°14.42.14.78.18.60°38.
26 67.31 28.65 18.78 (8) (9) 29.30. 29.50. 30.2. 32.11
1? , 2. Jyy~C7#258Hz.

JFII~Cyζ19.5Hz 82.96. Jys~C*#196)1z.

JF9. JFt～Cs”=26Hz 121.2. Jr*~C*#282Hz.

JFI~C9#25.8H2 From the above analysis results, the reaction product is 1 shown by the following formula.
, 1-hexafluoropropyl-1,3-cyclohexanediol containing trace amounts of 3-bis(hexafluoropropyl)-1,3-cyclohexanediol.

(Production of 1-hexafluoropropyl-1-cyclohexanol-3-methacrylate) Next, 77 g of the above 1-hexafluoropropyl-1,3-cyclohexanediol 1 9 g of methacrylic acid chloride
0 g and 300 ml of tetrahydrofuran were charged, and 105 g of triethylamine was added dropwise thereto over 2 hours under a nitrogen atmosphere while cooling in a water bath. Then, the mixture was reacted at 40° C. for 3 hours with stirring.

After the reaction was completed, methanol was added dropwise to the resulting reaction mixture to decompose excess methacrylic acid chloride, and then
The reaction mixture was filtered. The resulting filtrate was concentrated under reduced pressure to obtain the crude product. Ether was added to this, filtered again, and the ether was distilled off from the filtrate under reduced pressure to obtain a purity of 97.
92 g of 1-hexafluoropropyl-1-cyclohexanol-3-methacrylate expressed in % (by gas chromatography) was obtained.

Elemental analysis HF Actual value 45.8 4,6 33.6 Calculated value 46.7 4.8 34.1 Infrared absorption spectrum 0-H3550cm-'C-H2950cm-',2870cm-'νC
=0 1720cm-'νC=C1640cm-' C-F 1200cm-' GC-MS analysis El at/e=334 (M")"C-NMR
(Solvent CDCl!, standard value 77.0 ppm (C”D
CI) 69.2. 69.6. 69.7. 70.2
25.3-29.0 15.0. 15.11. 18.3. 18.602
8.0-30.6 117.6. Jv,~Cq #258Hz.

83.21L Jrs~Ca#196Hz.

JF Q * JF? ~Cs #27Hz (9
) 123.0. Jrq～Cq#2B2H
z.

JFI~C9″426H2 (10) 125.27 (11) 136.5 (12) 17.6-18.0 (13)
166.91 Attribution peak number of each peak (1) (2) Chemical shift (δpp■) 75.63 (split into 4), 74.0 (split into 5) JF? ~C1"v 20-3082 30.8.30.6.34.2.35.1 Example 1 90 parts by weight of siloxanyl methacrylate (hereinafter abbreviated as parts), 8 parts of methacrylic acid, 10 parts of pentafluorostyrene
and 3 parts of 1-hexafluoropropyl-1-cyclohexanol-3-methacrylate, 0.5 parts of azobisisobutyronitrile
After stirring and mixing thoroughly at 50°C for 1 to 5 minutes, the mixture was vacuum degassed at 50°C for 10 minutes. This solution was heated to 50°C.
A 200 μm aluminum plate was poured between two polyester films as a spacer under a nitrogen atmosphere, fixed with a fastener, and then placed in a thermostatic oven for 6 hours.
Polymerization was carried out by heating at 0°C for 24 hours and at 70°C, 80°C, and 90°C for 2 hours each.

After the polymerization was completed, the resulting film was peeled off from the polyester film and used as a sample. The oxygen permeability coefficient and Vickers hardness of the sample were measured.

In addition, using aluminum plates of different thicknesses as spacers, copolymers with various thicknesses were prepared in the same manner, and the relationship between the film thickness and oxygen permeability coefficient of the copolymers was determined. Oxygen permeability coefficient at infinity (hereinafter abbreviated as DKg value).

), D K g −182X 10 ”
cc (STP) cm/cm”・sec・+u+Hg.

Table 1 shows the oxygen permeability coefficient and Vickers hardness of the fluorine-containing copolymer thus obtained.

Examples 2 to 9 Fluorine-containing copolymers were obtained in the same manner as in Example 1, except that the monomer composition was changed as shown in Table 1. The oxygen permeability coefficient and Vickers hardness are shown in Table 1.

Comparative Examples 1 and 2 As shown in Table 2, except for using a monomer composition that did not use a fluorine-containing (meth)acrylic acid ester monomer component,
A fluorine-containing copolymer was obtained in the same manner as in Example 1. The oxygen permeability coefficient and Vickers hardness are shown in Table 2.

[Brief explanation of drawings]

Figure 1 shows an infrared absorption spectrum of an example of a fluorine-containing alicyclic alcohol, and Figure 2 shows an infrared absorption spectrum of an example of a fluorine-containing (meth)acrylic acid ester used as a monomer component in the present invention. .

Claims (4)

[Claims] (1) (a) Siloxanyl (meth)acrylate monomer component 10% by weight or more, (b) (meth)acrylate monomer component 30% by weight or less, (c) Fluorine-containing styrenic monomer component 3% by weight that's all,
and (d) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom, hydroxyl group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates a thyl group , x and y are each integers of 0 to 30, m
is an integer of 0 to 10, n is an integer of 1 to 12, m+n
is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by A fluorine-containing copolymer comprising 1% by weight or more of a fluorine-containing alicyclic (meth)acrylic acid ester monomer component, which is graft-bonded at least one per molecule. (2) (a) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^3 represents a hydrogen atom or a methyl group, and X^1
each independently represents the group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X^2 each independently represent the group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, p is an integer from 1 to 5, and q is 1 An integer of ~3, r is 0
Indicates an integer between ~2. ) 10% by weight or more of the siloxanyl (meth)acrylate monomer component represented by (b) General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (In the formula, R^4 is a hydrogen atom or Indicates a methyl group, R^5
represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or a fluorine-substituted alkyl group. ) 30% by weight or less of the (meth)acrylate monomer component represented by (c) General formula (IV) ▲ Numerical formulas, chemical formulas, tables, etc. 3% by weight of a fluorine-containing styrenic monomer component represented by a fluorine atom, a fluorine atom, or a fluoroalkyl group, at least one of which is a fluorine atom or a fluoroalkyl group.
Above, and (d) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom, hydroxyl group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Chill group , x and y are each an integer of 0 to 30, m
is an integer of 0 to 10, n is an integer of 1 to 12, m+n
is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by A fluorine-containing copolymer comprising 1% by weight or more of a fluorine-containing alicyclic (meth)acrylic acid ester monomer component, which is graft-bonded at least one per molecule. (3) (a) Siloxanyl (meth)acrylate monomer component 10% by weight or more, (b) (meth)acrylate monomer component 30% by weight or less, (C) Fluorine-containing styrenic monomer component 3% by weight that's all,
and (d) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom, hydroxyl group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates a thyl group , x and y are each integers of 0 to 30, m
is an integer of 0 to 10, n is an integer of 1 to 12, m+n
is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by It is characterized by being formed from a fluorine-containing copolymer consisting of 1% by weight or more of a fluorine-containing alicyclic (meth)acrylic acid ester monomer component, which is characterized by having at least one graft bond per molecule. contact lenses. (4) (a) General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^3 represents a hydrogen atom or a methyl group, and X^1 is each independently a group ▲ Numerical formula, There are chemical formulas, tables, etc. ▼ , X^2 is each independently a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , p is an integer from 1 to 5, q is an integer from 1 to 3, r is 0
Indicates an integer between ~2. ) 10% by weight or more of the siloxanyl (meth)acrylate monomer component represented by (b) General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (In the formula, R^4 is a hydrogen atom or Indicates a methyl group, R^5
represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or a fluorine-substituted alkyl group. ) 30% by weight or less of the (meth)acrylate monomer component expressed by 3% by weight of a fluorine-containing styrenic monomer component represented by a fluorine atom, a fluorine atom, or a fluoroalkyl group, at least one of which is a fluorine atom or a fluoroalkyl group.
Above, and (d) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom, hydroxyl group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , R^2 represents a hydrogen atom or a methyl group, and x and y are each 0-
m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by It is characterized by being formed from a fluorine-containing copolymer comprising 1% by weight or less of a fluorine-containing alicyclic (meth)acrylic acid ester monomer component, which is characterized by having at least one graft bond per molecule. contact lenses.