JPH0312410A - Fluorine-containing copolymer and contact lens made thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having excellent biocompatibility, oxygen-permeability and contamination resistance and useful for contact lens, etc., by grafting a hydrocarbon group containing plural fluorine atoms to a silicone (meth)acrylic acid ester and copolymerizing the grafted ester with a comonomer. CONSTITUTION:The objective copolymer can he produced by copolymerizing (A) 3-95wt.% of a monomer component produced by grafting a fluorine- substituted 2-30C hydrocarbon group having >=3 fluorine atoms to a carbon atom of an alkylene group in the main chain of a silicone (meth)acrylic acid ester compound of formula I [R<1> is H or methyl; R<2> is group of formula II (i is 0-300; j is 1-30); R<3> is 1-30C alkyl, alkoxy or group of formula III (R<4> is H or methyl; l is 0-300; k is 1-30); X is group of formula IV (R<5> is 1-30C alkyl or 6-12C aryl; m is 0-10); h is 0-1,000] and (B) 95wt.% of a monofunctional or polyfunctional (meth)acrylic acid ester monomer component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluorine-containing copolymer and a contact lens made of the same, and more particularly, to a fluorine-containing copolymer useful as an oxygen permeable material with excellent biocompatibility. The present invention relates to a copolymer and a contact lens made of such a fluorine-containing copolymer and which can be worn for a long time.

Conventionally, the cornea of the q-technical eye is a tissue without blood vessels, so the oxygen necessary for its respiratory metabolism is obtained by diffusion from the palpebral conjunctiva and aqueous humor when the eyelids are closed, and from the atmosphere when the eyelids are open. I am incorporating it. 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. It is.

Conventionally, polymethyl methacrylate and various methacrylate ester copolymers 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, and furthermore, they have poor stain resistance. Also, in terms of wearability,
There is room for improvement.

The present invention was made in order to solve the above-mentioned problems in oxygen permeable polymers as materials for medical oxygen permeable materials, particularly contact lenses, etc. The present invention aims to provide a fluorine-containing copolymer that is useful as a novel oxygen-permeable polymer for medical use, and a contact lens made of such a fluorine-containing polymer.

The fluorine-containing copolymer according to the present invention for f
CIl□cogo) i (CH2) j-, R
3 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or 4-(CL)k(QC)Itch) L-OCOC=
C) It represents a hydrogen atom or a methyl group; group or a C6 to C12 group, and h4! O~1000S i and!
are respectively 0 to 300, j and k are each 1 to 30, m
represents an integer from 0 to 10. ) A fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is attached to the carbon atom of the alkylene group in the main chain of the silicone (meth)acrylic acid ester compound represented by the above silicone (meth)acrylic acid. 3 to 95% by weight of at least one fluorine-containing silicone (meth)acrylic ester monomer component graft-bonded per molecule of the ester compound, and (b) mono- and polyfunctional (meth) acrylic ester monomer components. Mass component 1-95
% by weight.

The contact lens according to the present invention is characterized by being made of such a fluorine-containing copolymer.

In the fluorine-containing copolymer according to the present invention, the first monomer component has the formula (1) (1) (wherein R1 is a hydrogen atom and represents a methyl group, and R2 is -
(00□C1], 0) i (CH□), -, R
3 is an alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group, or -(CH*(OCHzC
) lx) L -0COC= CHz, R4 represents a hydrogen atom or a methyl group, X each independently represents an alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, or It represents an alkoxy group or a C6 to C12 atomyl group, preferably a phenyl group, h is O to 1000, preferably O to 500, i
and l are each O~3001, preferably 0~30X
j and k are each 1 to 30. Preferably 1-24, m
represents an integer from 0 to 10. ) In the carbon atom of the alkylene group in the main chain of the silicone (meth)acrylic acid ester compound, a fluorine-substituted hydrocarbon group having at least three fluorine atoms and having a carbon number of 2 to 30 is added to the above siloxanyl (meth)acrylic acid. It is a fluorine-containing silicone (meth)acrylic ester having at least one graft bond per molecule of the ester compound.

First, the production of the fluorine-containing silicone (meth)acrylic ester used as a monomer component in the present invention will be explained.

Such a fluorine-containing silicone (meth)acrylate monomer has the formula -a (II) (II) (wherein, R2 is -(C)12CH20) i (C)It) j-, and R3 is carbon represents an alkyl group, alkoxy group or -(CHffi)a(OCToCHz)t-OH having 1 to 30 atoms, preferably 110 atoms, each X independently represents 1 to 30 carbon atoms, R5 each independently represents 1 to 30 carbon atoms, Preferably, it represents an alkyl group or alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a phenyl group, and h is O to 1000, preferably 0 to 500,
i and l are each 0 to 300, preferably 0 to 30
, j and k are each 1 to 30, preferably 1 to 24,
m represents an integer from O to IO. ) is reacted with a fluorine-containing olefin in the presence of a radical generator to add at least three fluorine atoms to the carbon atoms of the alkylene group in the main chain in the general formula (rV). A fluorine-containing hydroxy silicone compound in which at least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms is graft-bonded per molecule of the hydroxy silicone compound is obtained, and then the fluorine-containing hydroxy silicone compound is treated with a solvent and In the presence of basic compounds (meth)
It can be obtained by reacting acrylic acid or (meth)acrylic acid ester.

Specific examples of the hydroxysilicone compound represented by the above general formula (I) include the following.

The above-mentioned fluorine-containing hydroxy silicone compound has the above-mentioned -
A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having a carbon number of 2 to 30 is attached to the carbon atom of the alkylene group in the main chain of the hydroxysilicone compound represented by formula (rV) per molecule of the hydroxysilicone compound. At least one of them is grafted.

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, -CFICFllC
F3, -CFICFHC2h, -ChCFHC*Fw,
-ChCFHCaF I :1, -ChCFHC+. F
-ChCFHCll, -ChCFH(CFz)
gl[1-CFzCFH(CFz)44! , -CFz
CFH(CFz)a)I, -CPzCFII-(CF
z) J, -ChCFH(CFz)! , -CFzCP
H(Ch)J, -ChCFH(Ch)r. H, -CH
2CHICF3, -(JIzCHzCzFs, -CHz
Cl(t(Ch)J, -CFzCFHCL:C(CF3
)s, -CF, CFI(-CFtC)I(CzFs), and fluorine-substituted saturated alkyl groups, and the like.

Among the above, particularly preferred are alkyl groups having 2 to 20 carbon atoms and having at least three fluorine atoms.

In the fluorine-containing hydroxysilicone compound, the fluorine-substituted hydrocarbon group has the formula (II
) is grafted to the carbon atom of the alkylene group in the main chain of the hydroxysilicone compound, and the proportion of grafted fluorine-substituted hydrocarbon groups per molecule of the hydroxysilicone compound is small (both one or more, Preferably, the number is 1 to 10, and therefore, the fluorine-containing hydroxy silicone compound usually contains 1 to 10 in one molecule.
It has 3 to 200 fluorine atoms, preferably 3 to 100 fluorine atoms.

When a plurality of fluorine-substituted hydrocarbon groups are graft-bonded to the fluorine-containing hydroxysilicone compound, each of these fluorine-substituted hydrocarbon groups is usually graft-bonded to different carbon atoms.

Therefore, as a specific example of such a fluorine-containing hydroxy silicone compound, for example, CR3 ■ CH3 OC1]3 HO-CH-Si-(OCF+3) 2CFsuCIIP
CF! shir2t, flt'La'3 shiH3 CH3 Hs CFZC) IPCF3 O CH3 (JI3-3t-CH3 CH3 Q CH3 L CH3 (wherein, h represents an integer from 0 to 100.

) etc. can be mentioned.

The fluorine-containing hydroxysilicone compound as described above can be obtained by reacting the hydroxysilicone compound represented by formula (n) with a fluorine-containing olefin in the presence of a radical generator.

Examples of the above-mentioned fluorine-containing olefin include CF, CFCl2, C
F! ff1CFC*HsXCFt=ICFC4)1w,
Ch-CFCbH+s, CF! -CF-C7゜H2iC
F2・CFCF3, CF!・CFCh41. CFz・
CF (CFt) 2H.

CFZ-CF(CFri,)l, CF! =CF(CF,
)&H,CF, -CF(CF,)? H.

CFt=CF(CFg)at(, CFz・CF(CF,
)9H, CFt・CF (CF z) r. HlCHl
CHCFs, CH2・CHCzF CL・CI (CFri !H1CFz-CFCPzC(Ch) !, CFz-
CFCFzCF! (CJs) t, CFtlICF-C
FllCFtl and the like can be mentioned.

The reaction between the fluorine-containing olefin and the hydroxysilicone compound represented by formula (IV) is preferably carried out in a solvent in the presence of a radical generator. Although the radical generator is not particularly limited, it usually includes, for example, isobutyryl peroxide.
1-hexyl peroxyneohexanoate, 2,4-
Dichlorobenzoyl peroxide, octanoyl peroxide, cumyl peroxyoctoate, m-) lylver oxide, benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxybenzoate% t-butyl cumyl peroxide, di- t
-butyl peroxide, t-butyl hydroperoxide and the like.

Such radical generators are usually present in the reaction mixture.
0.1 v++ol/1 to 10mol/j! , preferably 10 mmol/1 to IIIIof/
Used in the range 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, pencitrifluoride, chloropencitrifluoride,
Xylene hexafluoride, etc. are used.

The reaction between the hydroxy silicone compound and the fluorine-containing olefin is usually carried out at 20 to 300°C, preferably at 5°C.
It is usually carried out at a temperature in the range of 0 to 200°C for 0.2 to 5 hours.

After the reaction is completed, the unreacted fluorinated olefin and the solvent are separated and removed from the resulting reaction mixture under reduced pressure to obtain the fluorinated alicyclic alcohol of the present invention, and if necessary, distillation is performed. It can be purified by

Next, it can be obtained by reacting such a fluorine-containing silicone compound with (meth)acrylic acid or (meth)acrylic acid halide in the presence of a solvent and a basic compound.

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 and hydrogen carbonates such as potassium hydrogen carbonate are 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 and the like are preferably used, such as hexane, pentane, benzene, toluene, cyclohexane, acetone, methyl isobutyl ketone, diethyl ethyl, diisopropyl ether, tetrahydrofuran and the like.

(Meta) of the above fluorine-containing hydroxy silicone compound
The acrylic acid esterification reaction is usually carried out at a temperature of 0 to 150°C, preferably 10 to 80°C. The reaction time is usually about 0.2 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.
If the filtrate is concentrated and the basic compound that has not reacted with the solvent and the (meth)acrylic acid ester by-produced in the above decomposition operation are removed, for example by distillation, the fluorine-containing siloxanyl (meth)acrylic acid according to the present invention can be obtained. Ester compounds can be obtained.

Therefore, in the fluorine-containing copolymer according to the present invention, specific examples of the fluorine-containing siloxanyl (meth)acrylate compound used as the first monomer component include:
For example;11. .

111υ Mu CH3-5t-CH3 C)13 In the fluorine-containing copolymer according to the present invention, the fluorine-containing silicone (meth)acrylate monomer component may be used alone or in a mixture of two or more. As, 3~
It is used in an amount of 95% by weight, preferably 20 to 80% by weight.

In the fluorine-containing copolymer of the present invention, specific examples of mono- and polyfunctional (meth)acrylic acid esters that are the second monomer component include acrylic acid, methacrylic acid, methyl acrylate, Ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, etc.
In addition to meth)acrylic acid alkyl esters, HI CH! -CCOOCToCHgCFHCF3, CH3 1 CHg-C(:00CHgC)It(CFx)sCF:
+II Cfh = CC00CH,CHg (CF,) 7c
F3, CI(.

CHg=CC00CH2CHz(Ch)ttch, CH
z”(JICOOCHgCH20C4HwCL=C)I
COO(CToCHzO)zczHsCHz = CF
ICOO(Cll□CHzO)zcHsCHz=CHC
OO(CHzCl(0)zcH3CI(z""CHCO
OCToCHx-0-P-OtlH CH3 chi -C-C00CH2CH! -N (C1+I2
H3 CHz=C-COOCHzCHt-N(CHzCI(3
)zC)Is CH2=C-COOCHzCHCH2 =C-C00CHzCH! 2CH20HCHI=C
HCOOC) IzC) Ic) IsH C) 13 CFlt 工C-C00CEIzCHCtbCHzH CL-CHCOOCl(zcHgO)1Ha C1b-C1(COOCHzcF!z-OCOCHzC
FIz-, C0OHH3 CHz-C-COO-CHzCHx-OCO-CJ(J
lzCOO1+ CHzC-COO-CH2Cl, -0-P-OH■ 11 CJ-CHCOO-CToCHg-0-P-01 (0H CIlx = C-COO-(CHgCHgO) !-
CO-C= CH2CH2= CHCOO(CIri 6
-OCO-CIl = CHzC)13Cl(z = (JCOO-C1(z-C-CHz-O
CO-CI = CH2113 CH3 Cll! -C-C0O-CHzCHCH*-0CO
-CI=CHzH CH2=C-Coo-CToCToCHzCHz-O
CO-C-C)ItCHl CH:+CHzC[CJ-OCO-C-C)Izl 3
113 Hz=C-Coo-CHzCH-CIl, etc. can be mentioned.

Such mono- and polyfunctional (meth)acrylic acid ester monomers may be used alone or as a mixture of two or more. In the fluorine-containing copolymer according to the present invention, the polyfunctional (meth)acrylic acid ester monomer contains 1 to
It is used in an amount of 95% by weight, preferably 5 to 70% by weight.

The fluorine-containing copolymer according to the present invention can be produced by a common 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 abbisisobutyronitrile, azobiscyclohexanecarbonitrile, phenyl azobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, t-butyl hydro Peroxide etc. can be mentioned. In addition, examples of the photopolymerization initiator include benzoin ethers represented by the following formula (wherein R9 represents an alkyl group), benzophenones such as benzophenone and benzoate, xanthone, thioxanthone, etc. Examples include xanthone L 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 in the range of 0.5 to 5000 minutes, preferably 30 to 200 minutes.
It is 0 minutes.

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 isobutyryl isopropylbenzene 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 D
K is CDK value X 10-”-(STP)1:11/cI
A・sec・mHg) is usually 42 or more.

Here, the oxygen permeability coefficient is measured using a film oxygen permeability meter manufactured by Seikan.

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 can be used as an oxygen permeable body 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 into a desired shape and cutting and polishing.

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.

Rehabilitation effect As described above, the fluorine-containing copolymer according to the present invention has (
It consists of the fluorine-containing siloxanyl (meth)acrylic ester monomer component and (kl) the polyfunctional (meth)acrylic ester monomer component, and has excellent optical properties and oxygen permeability, and when used as a contact lens. In addition to being comfortable to wear, it also has excellent stain resistance against tear fluid components such as proteins, lipids, and mucin, as well as against bacteria, fungi, and the like.

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

Reference Example 1 (Manufacture of hexafluoropropyl silicone diol) Silicone diol represented by the following formula and having an average molecular weight of 1000 (XC-22-160As manufactured by Shin-Etsu Chemical Co., Ltd.)
was used as the raw material.

Characteristic absorption wavelength (cm-') of its infrared absorption spectrum
is as follows.

3450 (shi0-h), 2960.2900.14
40.1405.1260°1100-1000.86
0.800.700゜54g of the above silicone diol and 11 g of di-t-butyl peroxide as a radical generator
．． Then, 27 g of hexafluoropropylene was press-fitted into the autoclave made of stainless steel with an internal volume of 100 ml, and the autoclave was sealed, followed by a grafting reaction at 130° C. for 7 hours with stirring.

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

The reaction mixture was concentrated under reduced pressure, and unreacted hexafluoropropylene, the radical generator, its decomposition products, etc. were distilled off to obtain 61 g of hexafluoropropyl silicone diol in which hexafluoropropylene was graft-bonded to the silicone diol. Obtained.

In addition, the characteristic absorption wavelength (am
” ') is as follows.

3450 (C0-H), 2960. 2900.
1440. 1410-1380゜1280, 126
0. 1205-1180 (C-F), 110
0-1000° 860, 800.700° (Manufacture of fluorine-containing siloxanyl dimethacrylate ester) Next, 52 g of the above hexafluoropropyl silicone diol was added to a 50011 capacity 4 tube equipped with a stirrer under a nitrogen stream.
Put it in a two-flask and add 150 g of tetrahydrofuran to it.
m1 was added and stirred to dissolve.

Add 22 g of methacrylic acid chloride to this solution under a nitrogen stream.
was added, and while cooling the flask in a water bath, a solution of 31 g of triethylamine dissolved in 50 ml of tetrahydrofuran was added dropwise over 1.5 hours while stirring, and then stirred at room temperature for 2 hours. I reacted below.

Next, the flask was cooled in a water bath, and 10 ml of methanol was gradually added dropwise to the resulting reaction mixture under a nitrogen stream to decompose excess methacrylic acid chloride.
The mixture was further stirred at room temperature for 1 hour.

After the reaction was completed, the reaction mixture was filtered under a nitrogen stream. The resulting filtrate was concentrated under reduced pressure at 40°C to remove the solvent and volatiles. Hexane was added to this concentrated solution to precipitate a trace amount of salt dissolved in the reaction mixture, which was filtered off, and the filtrate was again concentrated under reduced pressure at 40° C. to distill off the hexane. Thereafter, volatile components were distilled off to obtain 56 g of fluorine-containing silicone acrylic ester as a pale yellow homogeneous transparent liquid.

The amount of fluorine determined by ion chromatography was 8.6% by weight. Moreover, the infrared absorption spectrum is shown in FIG.

In the infrared absorption spectrum of fluorine-containing siloxanyl meccrylic acid ester, 3450 cm-(shi0-■
) absorption completely disappeared, confirming that it had been converted into a methacrylic acid ester.

Further, the number average molecular weight Mn in terms of styrene determined by gel permeation chromatography was 1200.

Reference Example 2 In the same manner as in Reference Example 1, as shown in Table 1, silicone diols having various average molecular weights were reacted with fluorine-containing olefins to obtain fluorine-containing silicone diols, and then fluorine-containing silicone diols were obtained. ) Acrylic acid chloride was reacted to obtain a fluorine-containing siloxanyl (meth)acrylic ester.

Table 1 shows the amount of fluorine in the obtained fluorine-containing siloxanyl (meth)acrylic ester.

Example 1 Abbisisobutylene was added to 100 parts by weight of a monomer mixture consisting of 90 parts by weight of fluorine-containing siloxanyl methacrylate ester, 40 parts by weight of methyl methacrylate, and 5 parts by weight of ethylene glycol dimethacrylate prepared in Reference Example 1. Add 0.5 parts by weight of lonitrile and heat at 50°C for 1 to 5 minutes.
The mixture was thoroughly stirred and mixed and vacuum degassed at 50°C for 10 minutes.

The solution was heated at 50°C for 2 hours under a nitrogen atmosphere.
After pouring a 00μm aluminum plate between two polyester films as a spacer and fixing it with a fastener,
The mixture was placed in a constant temperature bath and heated at 60°C for 24 hours, 70°C, 180°C, and 90°C for 2 hours each to polymerize.

After completion of polymerization, the obtained film was peeled off from the polyester film and used as a sample, and its oxygen permeability coefficient (DK value
10-”cJ (STP) cm/cal-sec-mmHg)
was measured using a Seikaken film oxygen permeability meter. The results are shown in Table 2.

Various fluorine-containing siloxanyl (meth) shown in Table 1
A polymer film was obtained in the same manner as in Example 1 using an acrylic ester. The oxygen permeability coefficients of these films are shown in Table 2.

Example 2 80 parts by weight of the fluorine-containing siloxanyl methacrylate obtained in Reference Example 1 and 1, obtained in Reference Example 3.

23.3.3-Hexafluoropropylcyclohexane-1,3-diol A mixture consisting of 20 parts by weight of dimethacrylate and 0.5 parts by weight of azobisisobutyronitrile was polymerized in the same manner as in Example 1, and the film thickness was A 222 μm film was obtained. Oxygen permeability coefficient (DK value
I Q-1lc (STP) Cm/c/sec/mmHg
) was 42.

Comparative Example 1 0.5 parts by weight of azobisisobutyronitrile was added to 100 parts by weight of a mixture consisting of 90 parts by weight of 3-tris(trimethylsilyloxy)silylpropyl methacrylate, 40 parts by weight of methyl methacrylate, and 5 parts by weight of ethylene glycol dimethacrylate. In addition, a film was obtained in the same manner as in Example 1. The oxygen permeability coefficient of this film is shown in Table 2.

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of an example of a fluorine-containing siloxanyl (meth)acrylate ester used as a monomer component in the polymer according to the present invention.

Claims (2)

[Claims] (1) (a) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2
represents -(CH_2CH_2O)_i(CH_2)_j-, R^3 represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or ▲a numerical formula, chemical formula, table, etc.▼, and R^4 represents a hydrogen atom or a methyl group, each X independently represents ▲a mathematical formula, a chemical formula, a table, etc.▼, and R^5 each independently represents an alkyl group or alkoxy group having 1 to 30 carbon atoms, or an alkyl group or alkoxy group having 6 to 12 carbon atoms. represents an aryl group, h is 0 to 1000, i and l are each 0 to 300, j
and k each represent an integer of 1 to 30, and m represents an integer of 0 to 10. ) A fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is attached to the carbon atom of the alkylene group in the main chain of the silicone (meth)acrylic acid ester compound represented by the above silicone (meth)acrylic acid. 3 to 95% by weight of at least one fluorine-containing silicone (meth)acrylic ester monomer component graft-bonded per molecule of the ester compound, and (b) mono- and polyfunctional (meth) acrylic ester monomer components. A fluorine-containing copolymer comprising 95% by weight of a fluorine-containing copolymer. (2) (a) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2
represents -(CH_2CH_2O)_i(CH_2)_j-, R^3 represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or ▲a numerical formula, chemical formula, table, etc.▼, and R^4 represents a hydrogen atom or a methyl group, each X independently represents ▲a mathematical formula, a chemical formula, a table, etc.▼, and R^5 each independently represents an alkyl group or alkoxy group having 1 to 30 carbon atoms, or an alkyl group or alkoxy group having 6 to 12 carbon atoms. represents an aryl group, h is 0 to 1000, i and l are each 0 to 300, j
and k each represent an integer of 1 to 30, and m represents an integer of 0 to 10. ) A fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is attached to the carbon atom of the alkylene group in the main chain of the silicone (meth)acrylic acid ester compound represented by the above silicone (meth)acrylic acid. 3 to 95% by weight of at least one fluorine-containing silicone (meth)acrylic ester monomer component graft-bonded per molecule of the ester compound, and (b) mono- and polyfunctional (meth) acrylic ester monomer components. A contact lens comprising a fluorine-containing copolymer comprising 1 to 95% by weight of mercury components.