JP3021685B2 - Fluorine-containing crosslinked copolymer and oxygen permeable body comprising the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing crosslinked copolymer excellent in oxygen permeability, water swelling property, feeling of wearing, stain resistance and boiling disinfection resistance, and a fluorine-containing crosslinked copolymer. It relates to an oxygen permeable body. More specifically, the present invention, when used as a medical oxygen permeable body such as a soft contact lens, is excellent in biocompatibility, enables long-time wearing, and exhibits excellent performance and a fluorine-containing crosslinked copolymer and It relates to an oxygen permeable body made of such a copolymer.

[0002]

2. Description of the Related Art Since the cornea of the eye is a tissue without blood vessels, oxygen required for its respiratory metabolism is obtained by diffusion from the eyelid conjunctiva and aqueous humor when the eyelid is closed, and when the eyelid is opened. We take in from the atmosphere. Therefore, wearing a contact lens, whether a hard contact lens or a soft contact lens, on the eyeball tends to cause oxygen metabolism disorders in the cornea, especially when worn for a long time, congestion, Often causes edema and other corneal disorders. Therefore, the materials for contact lenses must have not only excellent optical properties, chemical properties, physical properties, mechanical properties, etc., but also excellent oxygen permeability and excellent water swelling properties. In addition, it is essential to have excellent biocompatibility.

Further, materials for contact lenses, especially soft contact lenses, have excellent resistance to contamination of proteins, lipids, mucins, etc., which are tear components, and to bacteria and fungi. It is also required to have excellent durability against boiling disinfection for preventing the propagation of bacteria and fungi. Conventionally, as a material for such a contact lens, polymethyl methacrylate and polymers of various methacrylate monomers have been widely used. Although these materials have excellent optical properties,
Most have poor oxygen permeability, and contact lenses made of these cannot withstand prolonged wearing.

Therefore, in order to improve the oxygen permeability of a methacrylate polymer, for example, Japanese Patent Publication No. Sho 52-3
No. 3502 proposes a siliconized methacrylate polymer in which a siloxane bond is introduced into a methacrylate molecule, and is disclosed in JP-A-57-51705 and JP-A-61-111308. A contact lens using an oxygen-permeable polymer mainly composed of cellulose acetate butyrate or a fluorine-containing methacrylate polymer has been proposed.

[0005] However, such a polymer has a somewhat improved oxygen permeability as compared with the above-mentioned polymethyl methacrylate or methacrylate ester-based polymer, but is still not sufficiently satisfactory. There is a need for a polymer having further improved properties. Further, these polymers are not yet satisfactory in performance such as stain resistance, hydrophilicity, water swelling property, and feeling of wearing.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in conventional oxygen-permeable bodies, particularly, oxygen-permeable polymers as materials for contact lenses, especially soft contact lenses. To provide a fluorine-containing copolymer excellent in oxygen permeability, hydrophilicity, water swelling property, wearing feeling, stain resistance, boiling disinfection resistance and the like, and an oxygen permeable body comprising such a copolymer. With the goal.

[0007]

The fluorine-containing copolymer according to the present invention comprises:

(A) General formula

Embedded image

Wherein Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and k is an average number in the range of 10 to 20,000. One molecule of the monomer of the functional (meth) acrylate monomer has one or more fluorine-substituted hydrocarbon groups having 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. (B) 10 to 99% by weight of a first fluorine-containing bifunctional (meth) acrylate-based monomer component unit in which at least one is graft-bonded
At least three fluorine atoms are contained in the carbon atom of the alkylene group in the main chain of the trifunctional or higher polyfunctional (meth) acrylate ester-based monomer composed of poly (meth) acrylate of polyoxyalkylene glycol having a branched structure. Trifunctional or more than three functional fluorine-containing polyfunctional (meth) acrylate-based monomer component units in which at least one fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms bonded thereto is graft-bonded per one molecule of the monomer. ~ 90% by weight,

(C) General formula

Embedded image

(Where Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and r represents 1 to
Indicates an integer of 9. ), A fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to the carbon atom of the alkylene group in the main chain of the bifunctional (meth) acrylate monomer. 1 to 10% by weight of a second fluorine-containing bifunctional (meth) acrylate-based monomer component unit having at least one graft-bonded per monomer molecule;

(D) General formula

Embedded image

(In the formula, Rc represents a hydrogen atom or a methyl group, and Rd represents a hydrogen atom, a methyl group or an ethyl group.

Represents a group, and Re is

Embedded image

(Wherein, Rf, Rg and Rh represent a hydrogen atom or a methyl group), and q represents 1
Represents an integer of from 5 to 5. 1) to 50% by weight of a nitrogen-containing (meth) acrylate monomer component represented by

(E) General formula

Embedded image

(In the formula, Ri represents a hydrogen atom or a methyl group, and Rj represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms to which at least three fluorine atoms are bonded.) It is characterized by comprising 1 to 50% by weight of the contained (meth) acrylate monomer component.

The oxygen permeable material according to the present invention is characterized by comprising such a fluorine-containing copolymer. In the bifunctional (meth) acrylate monomer represented by the general formula (Formula 1), Ra is a hydrogen atom or a methyl group, Rb is a hydrogen atom or a lower alkyl group, preferably a hydrogen atom Or a methyl group, particularly preferably a hydrogen atom. k is a number in the range of 10 to 20,000 on average, preferably 15 to 15000, particularly preferably 20 to 10000.

Specific examples of such a bifunctional (meth) acrylate monomer include, for example,

[0020]

Embedded image

And the like. Further, a trifunctional or higher polyfunctional (meth) composed of a bifunctional (meth) acrylate monomer represented by the general formula (Formula 1) or a poly (alkyl) glycol poly (meth) acrylate having a branched structure. The fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms to which at least three fluorine atoms are bonded to the carbon atom of the alkylene group in the main chain of the acrylate monomer is preferably a fluorine-substituted saturated alkyl. Group or a fluorine-substituted cyclo optionally having a fused or bridged ring

It is an alkyl group. Therefore, as a specific example, for example,

Embedded image

A fluorine-substituted saturated alkyl group such as

Embedded image

And the like. Among the above, a C2-C20 fluorine-substituted alkyl group having at least three fluorine atoms is particularly preferred. Such a fluorine-substituted hydrocarbon group is a trifunctional or higher functional group consisting of a poly (alkylene glycol) having a (meth) acrylate monomer represented by the general formula (1) or a polyoxyalkylene glycol having a branched structure. Polyfunctional (meta)
The graft ratio of the fluorinated hydrocarbon group to the carbon atom of the alkylene group of the oxyalkylene group in the main chain of the acrylate monomer is the same as that of the (meth) acrylate monomer. At least one, preferably 1 to 400, per main chain of the molecule. As a result, the resulting fluorine-containing (meth) acrylate-based monomer usually has a fluorine atom per main chain of the molecule. 3
It has from 10,000 to 10,000, preferably from 3 to 5,000.

Therefore, the first fluorine-containing difunctional (meth) acrylate monomer

Specific examples of the component unit (a) include, for example,

Embedded image

Here, m + n is an integer of 1 to 20,000. In the above equation,

Embedded image

Are randomly arranged. Hereinafter, the same applies.

Embedded image

And the like. Further, a trifunctional or higher polyfunctional (meth) acrylate-based monomer comprising the poly (alkylene glycol) polyoxyalkylene glycol having the branched structure

As a specific example, for example,

Embedded image

Here, Ra represents a hydrogen atom or a methyl group, and l + m represents an integer of 1 to 20,000.

Next, In the above equation,

Embedded image

Are randomly arranged. Hereinafter, the same applies.

Embedded image

Here, l '+ m' indicates an integer of 1 to 20,000. The same applies hereinafter.

Embedded image

Here,

Embedded image

Are randomly arranged. The same applies hereinafter.

Embedded image

And the like. In addition, a fluorine-containing polyfunctional (meth) acrylate monomer having three or more functional groups is used.

As the minute unit (b), specifically,

Embedded image

Here, Ra represents a hydrogen atom or a methyl group, and l + 1 '+ m and n + n' represent 1 to 200.

Indicates an integer of 00. Also,

Embedded image

Are randomly arranged. The same applies hereinafter.

Embedded image

Here, Rb represents a hydrogen atom or a lower alkyl group.

Embedded image

Here, l + l '+ m, n + n' + n "and p +
p 'represents an integer of 1 to 20,000. Bifunctional Fluorine-Containing (Meth) Forming Fluorine-Containing Cross-Linked Copolymers According to the Invention
The first fluorine-containing difunctional (meth) acrylate monomer unit (a) is contained in a mixture of an acrylate monomer and a trifunctional or more fluorine-containing (meth) acrylate monomer. ) From 10 to 99% by weight, preferably 15
From 95 to 95% by weight, particularly preferably from 30 to 90% by weight, and from 1 to 9 of the above-mentioned trifunctional or higher functional bifunctional (meth) acrylate monomer unit (b).
The content may be 0% by weight, preferably 5 to 85% by weight, particularly preferably 10 to 70% by weight.

The fluorine-containing difunctional (meth) acrylate ester represented by the general formula (Formula 2)

As the monomer unit (c), specifically,

Embedded image

And the like. Also, a nitrogen-containing (meth) acrylate represented by the general formula (Formula 3)

As the system monomer component unit (d), specifically,

Embedded image

And the like. Further, the fluorine-containing monofunctional (meth) acrylic compound represented by the general formula (Formula 5)

As the acrylate ester monomer unit (e), specifically,

Embedded image

The fluorine-containing crosslinked copolymer according to the present invention comprises
It can be produced by a general copolymerization method. For example, by polymerizing a mixture comprising the above-mentioned monomer components (a) to (e) and a polymerization initiator in a polymerization mold, a fluorine-containing crosslinked copolymer having a desired shape can be obtained. . As the polymerization initiator, any of a thermal polymerization initiator and a photopolymerization initiator can be used. Examples of the thermal polymerization initiator include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, and t-butyl. Hydroperoxide and the like can be mentioned.
Also, photopolymerization

As the initiator, for example, a compound represented by the general formula

Embedded image

(Wherein, R represents an isopropyl group, an isobutyl group, etc.);
In addition, benzophenones such as benzophenone and benzoate, xanthones such as xanthone and thioxanthone,

[0053]

Embedded image

And the like. The reaction temperature of the thermal polymerization is usually 40 to 200 ° C, preferably 45 to 120 ° C.
° C, and the time required for the polymerization is usually 0.5 to 5
000 minutes, preferably 30 to 2000 minutes. On the other hand,
In the case of photopolymerization, the polymerization time is different depending on the type and amount of the monomer and the photopolymerization initiator used, and further, depending on the type of the light source used.

Then, as described above

Embedded image

In the case of using a copolymer, a copolymer having practically sufficient strength can be obtained by irradiation with ultraviolet rays in a time period ranging from several seconds to several minutes. In order to obtain a contact lens comprising the fluorine-containing crosslinked copolymer according to the present invention, polymerization may be performed in a polymerization type of the contact lens. When used for other purposes and uses, polymerization may be performed in a polymerization type according to each purpose and use.

The fluorine-containing crosslinked copolymer according to the present invention comprises
By immersing in water, a hydrophilic and water-swellable gel can be obtained. The water content is usually 30 to 90
%, Preferably 30 to 70%. The water content of the hydrogel of such a fluorine-containing crosslinked copolymer is measured as follows. First, the specimen is kept at 37 ° C. in a desiccator containing anhydrous calcium sulfate, taken out of the desiccator every 24 hours, and weighed (mg) to one significant digit after the decimal point. Weight change is 0 for 24 hours.
When the weight is 5 mg or less, the test specimen is immersed in a physiological saline solution at 37 ° C., taken out with tweezers every 24 hours, wiped with clean gauze for 30 seconds, shaken in the air for 15 seconds, and then weighed (mg) to the decimal point. Request up to the following. When the weight change becomes 0.5 mg or less, the water content is calculated according to the following (Formula 1).

Calculate the rate.

(Equation 1)

Further, the fluorine-containing crosslinked copolymer according to the present invention has excellent oxygen permeability,

The oxygen permeability coefficient

(Equation 2)

Is generally in the range of 20 to 2000, preferably 30 to 2000, particularly preferably 50 to 2000. Here, the oxygen permeability coefficient was measured using a film oxygen permeability meter manufactured by Kakenh. In order to exclude the influence of the potassium chloride solution on the electrode portion, the hydrous gel was sandwiched between two poly (4-methyl-1-pentene) films having a known oxygen permeability coefficient and having a thickness of 50 μm. Make a three-layer sample,

The measurements were taken. The oxygen permeability coefficient of the hydrogel is

(Equation 3)

Was obtained based on here,

(Equation 4)

Is as follows. Further, the copolymer according to the present invention is
Excellent resistance to boiling disinfection. The boiling disinfection resistance was evaluated as follows. After heating to about 90 ° C in 30 minutes,
Using a boiling tester that automatically repeats a pattern of cooling to room temperature in 0 minutes, 600 repeated boiling tests corresponding to three years of practical use were performed. In the meantime, it was taken out every 50 times and examined for cloudiness and dimensional stability. The white turbidity was measured by using a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. to measure the ratio of light transmittance to scattered light ratio (scattered light ratio / total transmitted light ratio). In addition, the diameter was measured with a caliper, and the dimensional change was examined. The copolymer according to the invention withstands more than 600 boil-resistant disinfections.

[0065]

As described above, the fluorine-containing crosslinked copolymer according to the present invention is excellent in oxygen permeability, hydrophilicity, water swellability and stain resistance, and is very useful as an oxygen permeable material. Moreover, since it has high biocompatibility and excellent boiling disinfection resistance, it can be preferably used as a contact lens material.

Such a contact lens has not only excellent oxygen permeability but also excellent feeling of wearing, resistance to contamination with tear components, and excellent biocompatibility as compared with conventional ones, so that it can be used for a long time. Is possible.

[0067]

EXAMPLES Hereinafter, a production example of a monomer for producing a fluorine-containing crosslinked copolymer according to the present invention will be described as a reference example.
Next, production of the fluorine-containing crosslinked copolymer according to the present invention and physical properties thereof will be described as examples. However, the present invention
It is not limited to these examples. Reference Example 1 The general operation of a monomer for producing a fluorine-containing crosslinked copolymer according to the present invention is as follows.

A polyoxyalkylene glycol such as polyethylene glycol is dissolved in a solvent such as chlorobenzene, and a fluorine-containing reactive monomer such as hexafluoropropylene is grafted under pressure using benzoyl peroxide or the like as an initiator. Fluorine polyoxyalkylene glycol is obtained. This is dissolved in chloroform and reacted with a large excess of methacrylic acid chloride using pyridine as a catalyst to obtain a fluorinated polyoxyalkylene glycol polymethacrylate monomer.

Next, the results of analysis of monomers for the obtained fluorine-containing crosslinked copolymer will be shown. FIG. 1 shows an average molecular weight of 60.
The GPC pattern in the process of obtaining a fluorinated polyethylene glycol polymethacrylate monomer by the method described above using polyethylene glycol of 00 (GPC, polystyrene equivalent) as a raw material is shown. In FIG. 1, (a) is the GPC pattern of the starting polyethylene glycol, and the peak A
Indicates it. (b) is a pattern after the grafting of hexafluoropropylene. New peak A on high molecular weight side
Is observed. (c) is the pattern after methacrylate formation.

The high molecular weight compound belonging to the peak A on the high molecular weight side was fractionated by a GPC column and purified.

As a result of the Roton NMR and 13 C-NMR analysis,

Embedded image

It was confirmed that the following bond was formed,
Thus, it was found that a coupling reaction between polyethylene glycols occurred in the graft reaction, and trifunctional or higher polyfunctional polyethylene glycol was generated. Further, from the peak area ratio and average molecular weight of A and B, bifunctional fluorine-containing polyethylene glycol dimethacrylate monomer (hereinafter, abbreviated as F-based PEGDM) and trifunctional or more fluorine-containing polyethylene glycol polymethacrylate monomer The ratio of the PEGPM (hereinafter, abbreviated as F-type 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 method described in Reference Example 1, the average molecular weight was 15,000.
50% by weight of F-type PEGDM and 50% by weight of F-type PEGPM using polyethylene glycol and hexafluoropropylene
Monomer (hereinafter referred to as F type PEGDM / F type)
Abbreviated as PEGPM monomer. ) Got. The average molecular weight of this monomer was 21,400 in terms of polystyrene.

N, N-Diethylaminoethyl methacrylate (hereinafter referred to as DEAM) 1 was added to 57 parts by weight of this monomer.
0 parts by weight, hexafluoropropyl (HFP) group-containing trie

Tylene glycol dimethacrylate

Embedded image

(Hereinafter referred to as 3G-Rf) 3 parts by weight and hexafluorobutyl methacrylate (hereinafter referred to as HFB)
It is called M. ) 30 parts by weight were kneaded by adding, further, t- butyl peroxypivalate 0.5 part by weight was added and sufficiently kneaded. This kneaded material was charged under nitrogen atmosphere between two polyester films using a 100 μm aluminum plate as a spacer, fixed with fasteners, and then placed in a thermostat.
Vacuum degassed at 0 ° C. for 5 minutes. Then, the mixture was heated at 90 ° C. for 16 hours to be polymerized.

After the completion of the polymerization, the obtained film was peeled off from the polyester film and immersed in a physiological saline solution to obtain a transparent hydrogel film containing water. Table 1 shows the oxygen permeation coefficient and the water content of this film together with the evaluation of boiling disinfection resistance. Comparative Example 1 30 parts by weight of the same hexafluoropropyl group-containing triethylene glycol dimethacrylate as described above was added to 70 parts by weight of the same F-based PEGDM / F-based PEGPM monomer as in Example 1 and kneaded. Similarly, a hydrated hydrogel film was obtained. Table 1 shows the oxygen permeation coefficient and the water content of this film together with the evaluation of boiling disinfection resistance. Comparative Example 2 N, N-diethylaminoethyl methacrylate (30 parts by weight) was added to 70 parts by weight of the same F-based PEGDM / F-based PEGPM monomer as in Example 1, and kneaded. A gel film was obtained. Table 1 shows the oxygen permeation coefficient and the water content of this film together with the evaluation of boiling disinfection resistance. Comparative Example 3 N, N-diethylaminoethyl methacrylate (25 parts by weight) and the same hexafluoropropyl group-containing triethylene glycol dimethacrylate (5 parts by weight) were added to the same F-type PEGDM / F-type PEGPM monomer ( 70 parts by weight) as in Example 1. In addition, the mixture was kneaded, and a hydrogel film containing water was obtained in the same manner as in Example 1. Table 1 shows the oxygen permeation coefficient and the water content of this film together with the evaluation of boiling disinfection resistance. Comparative Example 4 For polyhydroxyethyl methacrylate (hereinafter, referred to as p-HEMA), which is a material for a commercially available soft contact lens, the oxygen permeability coefficient and the water content are similarly shown in Table 1 together with the evaluation of boiling disinfection resistance.

[0077]

[Table 1]

[Brief description of the drawings]

FIG. 1 shows a gel permeation chromatography (GPC) pattern (a) of polyethylene glycol used as a raw material in Reference Example 1 and trifunctional or higher functional groups obtained by performing a graft reaction of hexafluoropropylene on the polyethylene glycol. The gel permeation chromatography pattern (b) of the graft mixture of the polyfunctional polyethylene glycol and the raw material bifunctional polyethylene glycol, and the methacrylate of the polyethylene glycol graft mixture (polymethacrylate of polyfunctional polyethylene glycol and dimethacrylate of bifunctional polyethylene glycol) 2 is a gel permeation chromatography pattern (c) of the mixture of Example 1.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-2-138315 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 20/00-20/70 C08F 120 / 00-120/70 C08F 220/00-220/70 C08F 290/00-290/14

Claims (2)

(57) [Claims] (1) (a) a general formula: (Wherein, Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and k is 10 to 10 on average.
It is a number in the range of 20,000. ), A fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to the carbon atom of the alkylene group in the main chain of the bifunctional (meth) acrylate monomer. (B) a polyoxyalkylene glycol having a branched structure having 10 to 99% by weight of a first fluorine-containing bifunctional (meth) acrylate-based monomer component unit having at least one graft-bonded per molecule of the monomer; A poly (meth) acrylate having at least three fluorine atoms bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylic acid ester-based monomer having 1 to 30 carbon atoms; Trifunctional or higher-functional fluorine-containing polyfunctional (meth) acrylic acid ester monomer having at least one fluorine-substituted hydrocarbon group grafted per molecule of the monomer 1 to 90% by weight of body component unit, (c) general formula (Wherein, Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and r represents an integer of 1 to 9). 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 the body
Second fluorine-containing difunctional (meth) acrylate-based monomer component units having at least one fluorine-substituted hydrocarbon group graft-bonded per molecule of the monomer.
% By weight, (d) general formula (Wherein, Rc represents a hydrogen atom or a methyl group, Rd represents a hydrogen atom, a methyl group or an ethyl group, and Re represents (Wherein, Rf, Rg and Rh represent a hydrogen atom or a methyl group), and q represents an integer of 1 to 5. 1) to 50% by weight of a nitrogen-containing (meth) acrylate-based monomer component represented by the following formula: and (e) a general formula: (In the formula, Ri represents a hydrogen atom or a methyl group, and Rj represents a carbon atom having 1 to 30 carbon atoms to which at least three fluorine atoms are bonded.)
Represents a fluorine-substituted hydrocarbon group. ) Monofunctional fluorine-containing (meth) acrylate monomer component 1 represented by
A fluorine-containing crosslinked copolymer, characterized in that it comprises from 50 to 50% by weight. (2) (a) a general formula (Wherein, Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and k is 10 to 10 on average.
It is a number in the range of 20,000. ), A fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms in which at least three fluorine atoms are bonded to the carbon atom of the alkylene group in the main chain of the bifunctional (meth) acrylate monomer. (B) a polyoxyalkylene glycol having a branched structure having 10 to 99% by weight of a first fluorine-containing bifunctional (meth) acrylate-based monomer component unit having at least one graft-bonded per molecule of the monomer; A poly (meth) acrylate having at least three fluorine atoms bonded to carbon atoms of an alkylene group in the main chain of a trifunctional or higher polyfunctional (meth) acrylic acid ester-based monomer having 1 to 30 carbon atoms; Trifunctional or higher-functional fluorine-containing polyfunctional (meth) acrylic acid ester monomer having at least one fluorine-substituted hydrocarbon group grafted per molecule of the monomer 1 to 90% by weight of body component unit, (c) general formula (Wherein, Ra represents a hydrogen atom or a methyl group, Rb represents a hydrogen atom or a lower alkyl group, and r represents an integer of 1 to 9). 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 the body
Second fluorine-containing difunctional (meth) acrylate monomer unit 1 to 10 in which at least one fluorine-substituted hydrocarbon group is graft-bonded per one molecule of the monomer.
% By weight, (d) general formula (Wherein, Rc represents a hydrogen atom or a methyl group, Rd represents a hydrogen atom, a methyl group or an ethyl group, and Re represents (Wherein, Rf, Rg and Rh represent a hydrogen atom or a methyl group), and q represents an integer of 1 to 5. 1) to 50% by weight of a nitrogen-containing (meth) acrylate-based monomer component represented by the following formula: and (e) a general formula: (In the formula, Ri represents a hydrogen atom or a methyl group, and Rj represents a carbon atom having 1 to 30 carbon atoms to which at least three fluorine atoms are bonded.)
Represents a fluorine-substituted hydrocarbon group. ) Monofunctional fluorine-containing (meth) acrylate monomer component 1 represented by
An oxygen permeable material, comprising a fluorine-containing crosslinked copolymer of from 50 to 50% by weight.