JP2618238B2 - Fluorine-containing crosslinked copolymer and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluorine-containing crosslinked copolymer excellent in oxygen permeability, water swellability, wearing feeling and stain resistance, and a fluorine-containing crosslinked copolymer. It relates to the formed oxygen permeable body. More specifically, when used as a medical oxygen permeable material such as a soft contact lens, it is excellent in biocompatibility, can be worn for a long time, and can exhibit excellent performance. Oxygen permeable material.

[Conventional technology]

Since the cornea of the eye is a bloodless tissue, oxygen required for its respiratory metabolism is obtained by diffusion from the eyelid conjunctiva and aqueous humor when sleeping, but is taken in from the atmosphere when awake. ing. For this reason, wearing a contact lens, whether a hard contact lens or a soft contact lens, tends to be an obstacle to oxygen supply, and if worn for a long time, hyperemia, edema and other corneal disorders often occur. Accordingly, materials for contact lenses are required to be excellent in optical properties, chemical properties, physical properties, and mechanical properties, as well as excellent in oxygen permeability. In addition, materials for contact lenses, especially soft contact lenses, have excellent resistance to stains such as proteins, lipids, and mucins, which are tear components, and to bacteria and fungi.
It is required to be excellent in hydrophilicity and water swelling property and excellent in biocompatibility.

Conventionally, polymethyl methacrylate (PMMA) and polymers of various methacrylate monomers have been widely used as materials for contact lenses, but most of them have poor oxygen permeability and can be used for a long time. It was not endurable.

In order to improve the oxygen permeability of the conventional methacrylate polymer, a silicone methacrylate copolymer in which a siloxane bond is introduced into the methacrylate ester molecule (JP-B-52-33502), and cellulose acetate butyrate are mainly used. Oxygen permeable polymer and fluorine-containing methacrylate polymer (see JP-A-57-51705 and
-111308) has been proposed. However, these polymers are not
Compared to methacrylate polymer such as MA,
Although oxygen permeability is improved, it is not yet sufficient, and there is a need for a polymer having further improved oxygen permeability.
In addition, these polymers are stain resistant, hydrophilic, water swellable,
The performance such as wearing feeling is not satisfactory.

[Problems to be solved by the invention]

The present inventors have recognized that the prior art of conventional oxygen permeable bodies, especially contact lenses, especially soft contact lenses, is in the above situation, oxygen permeable, hydrophilic,
As a result of diligent studies on an oxygen permeable material having excellent water swellability, wearing feeling and stain resistance, the present inventors have found that a specific fluorine-containing crosslinked copolymer satisfies the above-mentioned object, and have reached the present invention.

[Means for solving the problem]

According to the present invention, general formula [I] [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a lower alkyl group, and the average value of k represents an integer of 1 to 20,000].
At least 3 fluorine atoms are bonded to carbon atoms of the alkylene group in the main chain of the acrylate monomer, and at least 3 fluorine-substituted hydrocarbon groups having 1 to 30 carbon atoms per molecule of the monomer are present. 10 to 99% by weight of a fluorine-containing bifunctional (meth) acrylate-based monomer component unit (a) having one graft bonded thereto, represented by the general formula [II]: [Wherein, R ¹ represents a hydrogen atom or a methyl group, l + m represents an integer of 1 to 20,000, n represents an integer of 1 to 20,000, and-(CH ₂ CH ₂ O)-and Are randomly arranged. Of polyoxyalkylene glycol having a branched structure represented by the following formula:
Fluorine substitution of 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylate monomer based on acrylate. 1 to 90% by weight of a trifunctional or higher functional fluorine-containing polyfunctional (meth) acrylate monomer unit (b) having at least one hydrocarbon group grafted per molecule of the monomer And a gelled fluorine-containing crosslinked copolymer obtained by polymerization. Further, according to the present invention, there is provided an oxygen permeable body formed from such a fluorine-containing crosslinked copolymer.

The fluorine-containing crosslinked polymer of the present invention has the general formula [I] [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a lower alkyl group, and the average value of k represents an integer of 1 to 20,000].
At least 3 fluorine atoms are bonded to carbon atoms of the alkylene group in the main chain of the acrylate monomer, and at least 3 fluorine-substituted hydrocarbon groups having 1 to 30 carbon atoms per molecule of the monomer are present. 10 to 99% by weight of a fluorine-containing bifunctional (meth) acrylate-based monomer component unit (a) having one graft bonded thereto, represented by the general formula [II]: [Wherein, R ¹ represents a hydrogen atom or a methyl group, l + m represents an integer of 1 to 20,000, n represents an integer of 1 to 20,000, and-(CH ₂ CH ₂ O)-and Are randomly arranged. Of polyoxyalkylene glycol having a branched structure represented by the following formula:
Fluorine substitution of 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylate monomer based on acrylate. 1 to 90% by weight of a trifunctional or higher functional fluorine-containing polyfunctional (meth) acrylate monomer unit (b) having at least one hydrocarbon group grafted per molecule of the monomer Is a water-swellable gel-like cross-linked copolymer obtained by polymerizing the fluorine-containing difunctional (meth) acrylate ester-based monomer component unit (a); In addition to the copolymer comprising the (meth) acrylic acid ester monomer component unit (b), the fluorine-containing difunctional (meth) acrylic acid ester monomer component unit (a); Containing polyfunctional (meth) acrylic Acid ester monomer component unit (b)
And a small amount of another copolymerizable monomer.

R ² constituting the (meth) acrylate monomer represented by the general formula [I] represents a hydrogen atom or a lower alkyl group, or may be a mixture thereof, preferably a hydrogen atom or methyl The radical is particularly preferably a hydrogen atom. In the general formula (I), the average value of k is in the range of 1 to 20,000, preferably 3 to 15,000, and particularly preferably 9 to 10,000.

Specific examples of the (meth) acrylate-based monomer represented by the general formula [I] include: And mixtures thereof.

Further, the bifunctional (meth) represented by the general formula [I]
Grafting to an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylate monomer composed of an acrylate monomer or a polyoxyalkylene glycol poly (meth) acrylate having a branched structure specific examples bound at least three C 1 -C fluorine atom is bonded to to 30 fluorine-substituted hydrocarbon _{group, -CF 2 CFHCF 3, -CF 2} CFHC 2 F 5, -CF 2 CFHC 4 F 9 , −CF ₂ CFHC ₆ F
₁₃ , -CF ₂ CFHC ₁₀ F ₂₁ , -CF ₂ CFHCF ₂ H, -CF ₂ CFH (CF ₂ ) ₂ H, -CF ₂ CFH (CF ₂ ) ₄ H, -CF ₂ CFH (CF ₂ ) ₆ H, −CF ₂ CFH (CF ₂ ) ₇ H, −CF ₂ CFH (CF ₂ ) ₈ H, −CF ₂ CFH (CF ₂ ) ₉ H, −CF ₂ CFH (CF ₂ ) ₁₀ H, −CH ₂ CH ₂ CF _{3, -CH 2 CH 2 C 2} F 5, -CH 2 CH 2 (CF 2) 6 H, -CF 2 CFHCF 2 C (CF 3) 3, -CF 2 CFHCF 2 CH (C 2 F 5) 2, And the like. Among them, carbon atoms having at least three fluorine atoms bonded thereto are 2 to 20 carbon atoms.
Is preferred.

The fluorine-substituted hydrocarbon group is a trifunctional or more polyfunctional (meth) acrylate monomer represented by the general formula (I) or a polyoxyalkylene glycol poly (meth) acrylate having a branched structure. The graft ratio of the fluorine-substituted hydrocarbon group to the alkylene group of the oxyalkylene group in the main chain of the (meth) acrylate monomer is 1%. At least one per main chain of the molecule
, Preferably 1 to 400, and the resulting fluorine-containing (meth) acrylate monomer generally has 3 to 1000, preferably 3 to 5,000 fluorine atoms per main chain of the molecule. It contains. The fluorine-containing bifunctional (meth) acrylate monomer unit (a)
Specifically, Here, m + n is an integer of 1 to 20,000.

Indicates that they are randomly arranged. The same applies hereinafter.) And mixtures thereof.

In the present invention, a trifunctional or higher-functional (meth) acrylate-based monomer composed of poly (alkylene glycol) of a polyoxyalkylene glycol having a branched structure,
General formula (II) [Wherein, R ¹ represents a hydrogen atom or a methyl group, l + m represents an integer of 1 to 20,000, n represents an integer of 1 to 20,000, and-(CH ₂ CH ₂ O)-and Are randomly arranged. ].

Specifically, such a trifunctional or higher-functional fluorine-containing polyfunctional (meth) acrylate-based monomer component unit (b) includes: [Where R ¹ represents a hydrogen atom or a methyl group, and l +
l '+ m, n + n' represents an integer of 1 to 20,000.

Indicates that they are randomly arranged. Hereinafter, the same applies. ] [Wherein R ² represents a hydrogen atom or a lower alkyl group. same as below. ] [Where l + l '+ m, n + n' + n ", p + p 'is 1
Or an integer of 20,000. And the like, and mixtures thereof.

Fluorine is contained in a mixture of a bifunctional fluorine-containing (meth) acrylate monomer and a tri- or higher-functional fluorine-containing (meth) acrylate monomer forming the fluorine-containing crosslinked copolymer of the present invention. 10 to 99% by weight, preferably 15 to 95% by weight, particularly preferably 30 to 90% by weight of the bifunctional (meth) acrylic acid ester monomer component unit (a) contained, and fluorine-containing trifunctional or higher. Multifunctional (meth) acrylic acid ester monomer component unit (b) is 1 to 90
%, Preferably 5 to 85% by weight, particularly preferably 10 to 70% by weight. The fluorine-containing cross-linked copolymer comprises the fluorine-containing bifunctional (meth) acrylate monomer unit (a) and the trifunctional or higher-functional fluorine-containing polyfunctional (meth) acrylate monomer unit. It may be composed of only the two components (b), or in addition to these essential two components, another copolymerization component may be copolymerized as long as the performance of the oxygen permeable body is not impaired.

For example, specifically as a copolymerizable monomer that may be copolymerized, Such as hydrocarbon methacrylates and acrylates, Hydroxyalkyl methacrylates and acrylates, such as Such as fluorine-based methacrylates and acrylates, Amino methacrylates and acrylates, such as CH ₂
Acrylamide and methacrylamide, such as ＝ CHCON (CH ₃ ) ₂ , CH ₂ CHCHCON (C ₂ H ₅ ) ₂ , N-vinyl lactam, such as Polyethylene glycol monomethacrylate and acrylate or polypropylene glycol monomethacrylate and acrylate, such as Bifunctional methacrylates, such as polyethylene glycol dimethacrylate or acrylate, etc. Polyfunctional methacrylates and the like can be exemplified, among these copolymerizable monomers Are preferred.

As a method for producing the fluorine-containing crosslinked copolymer, the fluorine-containing bifunctional (meth) acrylate-based monomer component unit (a) and the tri- or higher-functional fluorine-containing polyfunctional (meth) acrylate A fluorine-containing crosslink having a desired shape is obtained by polymerizing a mixture comprising a monomer comprising the copolymerizable monomer and, if necessary, a monomer comprising the copolymerizable monomer and a polymerization initiator in a polymerization mold. A copolymer can be obtained. Specifically, the radical initiator for thermal polymerization among the polymerization initiators is azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile , Benzoyl peroxide, di-
T-butyl peroxide, t-butyl hydroperoxide and the like can be exemplified, among the polymerization initiators specifically as a photopolymerization initiator, (R = isopropyl, isobutyl, etc.) benzoin ethers, benzophenones, such as benzophenone and benzoate, xanthones, such as xanthone and thioxanthone, And the like. The temperature during thermal polymerization is usually
It is in the range of 40 to 200 ° C., preferably 45 to 120 ° C., and the time required for the polymerization is usually 0.5 to 5000 minutes, preferably 30 to 2000 minutes.

In the case of photopolymerization, the time required for polymerization differs depending on the type and amount of the monomer and photopolymerization initiator used, and also differs depending on the type of light source used. When a polymer is used, a polymer having practically sufficient strength can be obtained by UV irradiation in a time period ranging from several seconds to several minutes.

When the fluorine-containing crosslinked copolymer of the present invention and the oxygen permeable body formed therefrom are contact lenses, the polymerization is carried out in the polymerization mold of the contact lens, and in other applications, the polymerization is carried out for each purpose. The polymerization is carried out in the desired polymerization mold.

The fluorine-containing crosslinked copolymer is a hydrophilic gel-like crosslinked polymer, and has water swellability. The water content of the fluorine-containing crosslinked copolymer is usually 30 to 90%, preferably 30 to 70%.
%. Here, the water content of the fluorine-containing crosslinked copolymer was measured by the following method. First, the specimen was placed in a desiccator containing anhydrous calcium sulfate, and kept at 37 ° C.
Take out of the desiccator every hour and weigh the weight (mg) to one decimal place. When the weight change is within 0.5 mg per 24 hours, the test specimen is immersed in physiological saline at 37 ° C, taken out with tweezers every 24 hours, wiped with clean gauze for 30 seconds, and shaken in the air for 15 seconds. , Weight (mg) to the decimal point. When the weight change was within 0.5 mg, the water content was calculated by the following equation.

Further, the fluorine-containing crosslinked copolymer has excellent oxygen permeability, and its oxygen permeability coefficient (DK value × 10 ⁻¹¹ cc (STP) cm / cm ²
(Sec · mmHg) is usually in the range of 20 to 2000, preferably 30 to 2000, particularly preferably 50 to 2000. Here, the oxygen permeability coefficient of the fluorine-containing crosslinked copolymer was measured using a film oxygen permeability meter manufactured by Kakenh. In the case of a sample containing water, in order to exclude the influence of the KCl solution on the electrode part, a 50 μm-thick TPX (poly-4
A three-layer sample in which the hydrogel was sandwiched between two pieces of -methyl-1-pentene) film was prepared and measured. The oxygen permeability coefficient of the hydrogel was calculated from the following equation.

In addition, the stain resistance is to stain a lens containing water with a standard protein (albumin), extract this protein,
The amount was evaluated based on the amount. A hydrated lens with a diameter of 1.7 cm and a thickness of 200μ was immersed in a 0.5% aqueous solution of albumin for 4 hours, and the amount of albumin was determined by Okamura, Iwata, Nikko Re, 2
3 , 10-14 (1981).

The fluorine-containing crosslinked copolymer is excellent in stain resistance to tear components such as protein, lipid and mucin.

The oxygen permeable body comprising the fluorine-containing crosslinked copolymer of the present invention is excellent in hydrophilicity, water swelling property, wearing feeling, and stain resistance, remarkably excellent in oxygen permeability, and excellent in biocompatibility. Therefore, it is suitable for applications such as an oxygen permeable material for a living body, such as a soft contact lens and various separation membranes.
In particular, when the oxygen permeable body of the present invention is used as a soft contact lens, it is excellent in oxygen permeability, hydrophilicity, water swelling property, stain resistance to tear components and wearing feeling as compared with conventional ones, and excellent in biocompatibility. Therefore, there is an advantage that it can be worn for a long time.

〔Example〕

Next, the fluorine-containing crosslinked copolymer of the present invention and the oxygen permeable body formed from the fluorine-containing crosslinked copolymer will be described in detail with reference to examples.

Reference Example 1 First, an outline of a method for producing a monomer for forming the fluorine-containing crosslinked copolymer of the present invention will be described. Polyoxyalkylene glycol such as polyethylene glycol is dissolved in a solvent such as chlorobenzene, and a fluorine-containing reactive monomer such as hexafluoropropylene (hereinafter abbreviated as HFP) is grafted under pressure using benzoyl peroxide or the like as an initiator. To obtain a fluorine-containing polyoxyalkylene glycol. This was dissolved in chloroform, and a large excess of methacrylic acid was reacted with chloride using pyridine as a catalyst to obtain a fluorine-containing polyoxyalkylene glycol polymethacrylate forming a fluorine-containing crosslinked copolymer of the present invention.

Next, the analysis results of the monomer for the obtained fluorine-containing crosslinked copolymer are shown.

FIG. 1 shows a GPC pattern in the process of obtaining a fluorine-based polyethylene glycol polymethacrylate by the above-mentioned method using polyethylene glycol having an average molecular weight of 6000 (GPC, polystyrene equivalent) as a raw material.

FIG. 1a shows a GPC pattern of a raw material polyethylene glycol. b shows a pattern after grafting of HFP, but a new peak A appeared on the high molecular weight side, and after methacrylate (c), there was no change. The high molecular weight compound belonging to the peak of A on the high molecular weight material side was fractionated by a GPC column, and the result of proton NMR and ¹³ C-MNR analysis showed that It can be seen that a bond has been formed, and during the grafting reaction,
It was found that a coupling reaction between the polyethylene glycols occurred and polyfunctional polyethylene glycols having three or more functional groups were formed. Further, based on the peak area ratio and the average molecular weight of A and B, bifunctional fluorine-based polyethylene glycol dimethacrylate (hereinafter abbreviated as F-based PEGDM)
The ratio of trifunctional or higher functional fluorine-based polyethylene glycol polymethacrylate (hereinafter abbreviated as F-based PEGPM) was 50 to 50 by weight. The amount of tri- or higher functionalized polyethylene glycol can be adjusted by controlling the graft reaction conditions such as the amount of the initiator and the reaction temperature.

Example 1 According to the production method shown in Reference Example 1, a monomer mixed at a ratio of 50% by weight of F-type FEGDM and 50% by weight of F-type FEGPM was obtained using polyethylene glycol having an average molecular weight of 15,000 and HFP. The average molecular weight of this monomer was 21,400 in terms of polystyrene.

To 100 parts of this compound, 0.5 parts of azobisisobutyronitrile was added, and the mixture was sufficiently stirred and mixed at 50 ° C. for 1 to 5 minutes, followed by vacuum degassing at 50 ° C. for 10 minutes. While maintaining this solution at 50 ° C, under a nitrogen atmosphere, it was poured between two polyester films each having a 200μ aluminum plate as a spacer, fixed with fasteners, and then placed in a thermostat at 60 ° C for 24 hours. , 70 ℃,
The polymerization was carried out by heating at 80 ° C. and 90 ° C. for 2 hours each.

After completion of the polymerization, the resulting film was peeled off from the polyester film, immersed in a physiological saline solution to obtain a transparent hydrogel film containing water, and the oxygen permeability coefficient, the water content and the amount of albumin adhered were measured. The attached amount of albumin indicates a relative ratio with the attached amount to poly-2-hydroxyethyl methacrylate (PHEMA) containing water being 100%.
Table 1 shows the results.

Examples 2 to 5 F-type FEGDM and F-type FEGPM synthesized according to the production method described in Reference Example 1 using polyester glycols having different average molecular weights and fluorine-containing graft substituents having different structures.
Table 1 shows the results of the hydrogel film containing water in the same manner as in Example 1 except that the mixture was used in various proportions.

Example 6 70 parts of a mixture of 50% by weight of F-based FEGDM and 50% by weight of F-based FEGPM used in Example 1, 2,2,3,4,4,4-hexafluorobutyl methacrylate Azobisisobutyronitrile 0.5 in 30 parts (abbreviated as HFBM)
The mixture was added, mixed well with stirring, and degassed under vacuum at 40 ° C. for 10 minutes. This solution was poured under a nitrogen atmosphere between two polyester films using a 200 μm aluminum plate as a spacer, fixed with fasteners, placed in a thermostat, and heated at 60 ° C. for 24 hours.
Heat polymerization was carried out 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, immersed in a physiological saline solution to obtain a transparent film containing water, and the oxygen permeability coefficient, the water content and the amount of albumin adhered were measured. Table 2 shows the results.

Example 7 In Example 6, F-type FEGDM50 weight% and F-type FEGPM50
A water-containing hydrogel film was obtained in the same manner as in Example 6, except that the mixing ratio of 50 parts by weight of the mixture with 50 parts by weight of HFBM was changed. Table 2 shows the results.

Examples 8 to 10 50% by weight of F type FEGDM and F type FEGPM50 used in Example 1
% By weight and 2,2,2-trifluoroethyl methacrylate (Abbreviated as TFEM) or HEMA The hydrogel film was obtained in the same manner as in Example 6 except that the mixing ratio was changed. Table 2 shows the results.

Comparative Example 1 Polyethylene glycol having an average molecular weight of 15,000 was dissolved in chloroform and reacted with a large excess of methacrylic acid chloride using pyridine as a catalyst to obtain an average molecular weight of 15200 (GPC
Polyethylene glycol dimethacrylate (polystyrene equivalent) (hereinafter abbreviated as PEGDM) was polymerized in the same manner as in Example 1, but the melt viscosity was too high to obtain a film suitable for measuring the oxygen permeability coefficient.

Comparative Example 2 PEGDM having an average molecular weight of 6100 (GPK, converted to polystyrene) was synthesized in the same manner as in Comparative Example 1, and a hydrogel was obtained in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 3 2-hydroxyethyl methacrylate (HEMA) Using a solution obtained by mixing 100 parts with 5 parts of diethylene glycol dimethacrylate (hereinafter abbreviated as 2G) as a cross-linking agent, a water-containing hydrogel film was obtained by the same operation as in Example 6, and the water content and oxygen permeability coefficient were obtained. And the amount of albumin attached was measured. Table 3 shows the results.

Comparative Example 4 N-vinyl-2-pyrrolidone (NVP) And methyl methacrylate (hereinafter abbreviated as MMA), 2G
Example 6 using a solution obtained by mixing parts, 30 parts and 5 parts
A water-containing hydrogel film was obtained in the same manner as described above, and the water content, the oxygen permeability coefficient, and the amount of albumin adhered were measured. Table 3 shows the results.

[Brief description of the drawings]

FIG. 1 shows a gel permeation chromatographic (GPC) pattern (a) of polyethylene glycol used as a raw material in Reference Example 1; trifunctional or higher functional groups obtained by performing a graft reaction of hexafluoropropylene on the above polyethylene glycol. Gel permeation chromatography (GP) of graft mixture of polyfunctional polyethylene glycol and raw material bifunctional polyethylene glycol
C) Pattern (b) and gel permeation chromatography (GPC) pattern (c) of a methacrylate of the above polyethylene glycol mixture (a mixture of polyfunctional polyethylene glycol polymethacrylate and bifunctional polyethylene glycol dimethacrylate).

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tokinori Ago 30 of 218, Ono-cho, Saeki-gun, Hiroshima Prefecture

Claims (2)

(57) [Claims] 1. A compound of the formula [I] [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a lower alkyl group, and the average value of k represents an integer of 1 to 20,000].
At least 3 fluorine atoms are bonded to carbon atoms of the alkylene group in the main chain of the acrylate monomer, and at least 3 fluorine-substituted hydrocarbon groups having 1 to 30 carbon atoms per molecule of the monomer are present. Fluorine-containing bifunctional (meth) acrylate monomer component (a) having one grafted bond
10 to 99% by weight, general formula [II] [Wherein, R ¹ represents a hydrogen atom or a methyl group, l + m represents an integer of 1 to 20,000, n represents an integer of 1 to 20,000, and-(CH ₂ CH ₂ O)-and Are randomly arranged. Of polyoxyalkylene glycol having a branched structure represented by the following formula:
Fluorine substitution of 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylate monomer based on acrylate. 1 to 90% by weight of a trifunctional or higher functional fluorine-containing polyfunctional (meth) acrylate monomer component (b) in which at least one hydrocarbon group is graft-bonded per one molecule of the monomer. Gelled fluorine-containing crosslinked copolymer obtained by polymerization. 2. Formula (I) [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a lower alkyl group, and the average value of k represents an integer of 1 to 20,000].
At least 3 fluorine atoms are bonded to carbon atoms of the alkylene group in the main chain of the acrylate monomer, and at least 3 fluorine-substituted hydrocarbon groups having 1 to 30 carbon atoms per molecule of the monomer are present. Fluorine-containing bifunctional (meth) acrylate monomer component (a) having one grafted bond
10 to 99% by weight, general formula [II] [Wherein, R ¹ represents a hydrogen atom or a methyl group, l + m represents an integer of 1 to 20,000, n represents an integer of 1 to 20,000, and-(CH ₂ CH ₂ O)-and Are randomly arranged. Of polyoxyalkylene glycol having a branched structure represented by the following formula:
Fluorine substitution of 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylate monomer based on acrylate. 1 to 90% by weight of a trifunctional or higher functional fluorine-containing polyfunctional (meth) acrylate monomer component (b) in which at least one hydrocarbon group is graft-bonded per one molecule of the monomer. An oxygen permeable material formed from a gelled fluorine-containing crosslinked copolymer obtained by polymerization.