JPH0813864B2 - Oxygen permeators and contact lenses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in biocompatibility and long-lasting when used as an oxygen permeation body comprising a fluorine-containing crosslinked polymer having excellent oxygen permeability, particularly as a medical oxygen permeation body. The present invention relates to an oxygen permeable body and a contact lens which can be worn for a long time and can exhibit excellent performance.

[Conventional technology]

Since the cornea of the eye is a tissue without blood vessels, the oxygen required for its respiratory metabolism is obtained by diffusion from the palpebral conjunctiva and aqueous humor when the eyelid is closed, but it is taken from the atmosphere when the eyelid is opened. There is. Therefore, wearing contact lenses is likely to hinder oxygen supply, and if worn for a long time, hyperemia,
Often cause edema and other corneal disorders. Therefore, materials for contact lenses are required to have excellent oxygen permeability in addition to excellent optical properties, chemical properties, physical properties, and mechanical properties. In addition to being excellent in stain resistance to tear fluid components such as proteins, lipids, mucins, etc. and bacteria and fungi, the material for contact lenses also has excellent wearing comfort and biocompatibility. Required to be present.

As materials for conventional contact lenses, polymethylmethacrylate (PMMA) and polymers of various methacrylic acid ester-based monomers are widely used, but most of them have poor oxygen permeability and can be used for a long time. It wasn't worth wearing. In order to improve the oxygen permeability of such a conventional methacrylic acid ester-based polymer, a silicone methacrylate-based polymer having a siloxane bond introduced in the methacrylic acid ester molecule (Japanese Patent Laid-Open No. 52-33502), butyric acid acetate Oxygen-permeable polymers based on cellulose and methacrylate polymers containing fluorine (Japanese Patent Laid-Open No. 57-57
-51705 publication) and the like have been proposed.

However, although these polymers have improved oxygen permeability as compared with conventional methacrylic acid ester-based polymers such as PMMA, they are not yet sufficient, and polymers with further improved oxygen permeability are required. ing. Further, there is a problem that these polymers are not satisfactory in performance such as stain resistance and wearing feeling.

[Problems to be Solved by the Invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a transparent oxygen permeation body and a contact lens which are excellent in oxygen permeability, wearing feeling and stain resistance.

[Means for solving the problem]

In the present invention, the siloxanyl (meth) acrylate monomer component (a) is 20 to 90% by weight, and the (meth) acrylate monomer component (b) is 10 to 50% by weight.
% By weight, 2 to 20% by weight of the polyalkylene glycol di (meth) acrylate monomer component (c), and the general formula [I] [In the formula, A ¹ is an oxyalkylene group having 2 to 4 carbon atoms, R ¹ is a hydrogen atom or a methyl group, and h is 1 to 20.
Indicates an integer of 000. ] The carbon atom of the oxyalkylene group in the main chain of the bifunctional (meth) acrylic acid ester-based monomer represented by
30 fluorine-substituted hydrocarbon groups are bonded to at least one fluorine-containing difunctional (meth) acrylic acid ester-based monomer component (d) per molecule of this monomer, and the fluorine-containing cross-linked polymer is 1 to 10% by weight. It is an oxygen permeable body and a contact lens which are composed.

Siloxanyl (meth) acrylate monomer component (a)
As the following general formula [II] [In the formula, R ² is a hydrogen atom or a methyl group, and X ¹ , X ² , and X ³ are independently And X ⁴ and X ⁵ are independent Represents P is an integer of 1 to 5 and q is 0 to 3
And r is an integer of 0 to 2. ] There is a thing represented by. In particular, And the like, and these can be used alone or in admixture of two or more. The amount of the siloxanyl (meth) acrylate monomer component (a) used is 20 to 90% by weight, preferably 40 to 70% by weight.

The (meth) acrylate monomer component (b) has the following general formula [III] [In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents 1 carbon atom.
4 to 4 alkyl groups are shown. ] There is a thing represented by. In particular, And the like, and these can be used alone or in admixture of two or more. The amount of the (meth) acrylate monomer component (b) used is 10 to
It is 50% by weight, preferably 15 to 40% by weight.

The polyalkylene glycol di (meth) acrylate monomer component (c) has the following general formula [IV]: [In the formula, R ⁷ is a hydrogen atom or a methyl group, and A ² is a carbon atom of 2
To oxyalkylene groups, and j is an integer of 1 to 4. ] There is a thing represented by. In particular, And the like, and these can be used alone or in admixture of two or more. The amount of the polyalkylene glycol di (meth) acrylate monomer component (c) used is 2 to 20% by weight, preferably 3 to 10% by weight.

The fluorine-containing bifunctional (meth) acrylic acid ester-based monomer component (d) is an oxyalkylene group in the main chain of the bifunctional (meth) acrylic acid ester-based monomer represented by the general formula [I]. At least 1 fluorine-containing oxyalkylene group in which at least 3 fluorine atoms are bonded at random to a C 1-30 fluorine-substituted hydrocarbon group having at least 3 fluorine atoms bonded thereto, per molecule of this monomer.
It is a bifunctional (meth) acrylic acid ester-based monomer that contains one individual.

In the general formula [I], the average value of h is 1 to 20000,
Preferably 3 to 15000, particularly preferably 9 to 1
It is in the range of 0000.

In addition, as the bifunctional (meth) acrylic acid ester-based monomer represented by the general formula [I], specifically, [In the formula, k and k + 1 represent integers of 1 to 20000. ] Etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

Fluorine having 1 to 30 carbon atoms having at least three fluorine atoms graft-bonded to the oxyalkylene group in the main chain of the bifunctional (meth) acrylic acid ester-based monomer represented by the general formula [I] Specific examples of the substituted hydrocarbon group include -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, the number of carbon atoms to which at least 3 fluorine atoms are bonded is 2 to 20.
Fluorine-substituted alkyl groups are preferred.

The fluorine-substituted hydrocarbon group is randomly graft-bonded to the alkylene group of the oxyalkylene group in the main chain of the bifunctional (meth) acrylic acid ester-based monomer represented by the general formula [I].

Specifically, as the fluorine-containing bifunctional (meth) acrylic acid ester-based monomer component (d) having such a fluorine-substituted hydrocarbon group kraft-bonded, (In the above formulas, m + n is an integer of 1 to 20000,
It shows that the oxyalkylene group in the main chain and the oxyalkylene group to which the fluorine-substituted hydrocarbon group is bonded are randomly arranged. ) And the like, and these can be used alone or in admixture of two or more.

The fluorine content as the fluorine-containing bifunctional (meth) acrylic acid ester-based monomer component (d) is 4 to 70% by weight, preferably 10 to 50% by weight. The amount used is 1 to 10% by weight, preferably 2 to 7% by weight.

Further, various additives such as various stabilizers, pigments and thickeners can be added to the fluorine-containing crosslinked polymer of the present invention before or after the polymerization in an arbitrary ratio.

As a method for producing the fluorine-containing crosslinked polymer of the present invention, a general polymerization method can be applied, and the siloxanyl (meth) acrylate monomer, (meth) acrylate monomer, polyalkylene glycol di (meth) acrylate can be used. Examples thereof include a method of reacting a mixture of a monomer and a monomer mixture of a fluorine-containing bifunctional (meth) acrylic acid ester-based monomer with a polymerization initiator. Of the polymerization initiators used at this time, specific examples of the radical initiator for thermal polymerization include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile and benzoylperoxide. Oxide, di-t-butyl peroxide,
Examples of the photopolymerization initiator among the polymerization initiators include t-butyl hydroperoxide and the like. (In the formula, R ⁸ represents an alkyl group.), Benzoin ethers such as benzophenone and benzoate, xanthone,
Examples thereof include xanthones such as thioxanthone and para-hydroxyisobutyrylisopropylbenzene. The temperature during the thermal polymerization is usually 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 varies depending on the type and amount of the monomer and photopolymerization initiator used, and the type of light source used.For example, para-hydroxyisobutyrylisopropylbenzene is used. When used, a fluorine-containing crosslinked polymer having a practically sufficient strength can be obtained by irradiating with ultraviolet rays within a time period of several seconds to several minutes.

The fluorine-containing crosslinked polymer produced in this manner has excellent oxygen permeability, and its oxygen permeability coefficient (DK value × 10
^-11 cc (STP) cm / cm ² · sec · mmHg) is usually 10 or more, and it is used as the oxygen permeation body of the present invention. Here, the oxygen permeability coefficient is measured using a Seikaken film oxygen permeability meter.

Furthermore, this fluorine-containing crosslinked polymer is also excellent in resistance to tear components such as proteins, lipids and mucins and bacteria such as bacteria and fungi.

The oxygen permeation body comprising the fluorine-containing crosslinked polymer of the present invention having such characteristics is suitable for use as a biological oxygen permeation body, and is particularly used as a contact lens in the present invention.

As a method for producing the contact lens of the present invention,
By cutting and polishing the fluorine-containing cross-linked polymer obtained by polymerizing a mixture of the monomer mixture, optionally other additives and a polymerization initiator in a polymerization mold, or a desired shape. A contact lens having a desired shape can be obtained by a usual molding method such as polymerization molding using a contact lens molding die that has this.

The contact lens of the present invention produced in this manner has excellent oxygen permeability, wearing sensation, anti-staining property against tear fluid components, and excellent biocompatibility as compared with conventional ones, and therefore, is worn for a long time. Is possible.

〔The invention's effect〕

As described above, the oxygen permeation body and the contact lens made of the fluorine-containing cross-linked polymer of the present invention have a siloxanyl (meth) acrylate monomer component (a), a (meth) acrylate monomer component (b), and a polyalkylene glycol. Since it is obtained by polymerizing the di (meth) acrylate monomer component (c) and the fluorine-containing difunctional (meth) acrylic acid ester monomer component (d), it is transparent and has excellent oxygen permeability and wearability. In addition to being excellent, it has excellent resistance to tear components such as proteins, lipids and mucins, and bacteria such as bacteria and fungi.

〔Example〕

 Examples of the present invention will be described below.

Example 1 Polypropylene glycol (number average molecular weight 3000) was dissolved in a chlorobenzene solvent, and hexafluoropropylene (hereinafter abbreviated as HFP) fluorine-containing reactivity under pressure using di-t-butyl peroxide as a polymerization initiator. The monomer was graft-polymerized to obtain a fluorine-containing polyoxyalkylene glycol. This is dissolved in a mixed solvent of tetrahydrofuran and hexane, in the presence of triethylamine,
Fluorine-containing polypropylene glycol dimethacrylate (hereinafter referred to as F
(Abbreviated as PPGDM) was obtained. The number average molecular weight of this monomer was 4,400 in terms of polystyrene. Next, siloxanyl methacrylate (hereinafter abbreviated as SiMA) 90 parts by weight (hereinafter abbreviated as “part”), methyl methacrylate (hereinafter abbreviated as MMA) 40
Part, 5 parts of ethylene glycol dimethacrylate (hereinafter abbreviated as ED), 3 parts of F-based PPGDM, and 0.5 part of azobisisobutyronitrile to 100 parts of this monomer mixture, at 50 ° C. Mix thoroughly for 1 to 5 minutes with stirring.
Vacuum degassed at ℃ for 10 minutes. While keeping this solution at 50 ° C, pour between two polyester films using a 200 μm aluminum plate as a spacer in a nitrogen atmosphere, fix it with fasteners, put it in a constant temperature bath, and keep it at 60 ° C for 24 hours, 70, 80,
Polymerization was carried out by heating at 90 ° C. for 2 hours each.

After completion of the polymerization, the produced film was peeled from the polyester film to prepare a sample. Then, the oxygen permeability coefficient and hardness of the sample were measured. The results are shown in Tables 1 and 2.

 At this time, the hardness was measured with a Vickers hardness meter.

Further, using aluminum plates having different thicknesses as spacers, copolymers having various film thicknesses were produced by the same method, and the relationship between the film thickness of the copolymer and the oxygen permeability coefficient was determined. The results are shown in Tables 1 and 2. From this, the oxygen permeation coefficient at infinite film thickness (hereinafter abbreviated as DKg value) was calculated.
It was 120 × 10 ^-11 cc (STP) cm / cm ² · sec · mmHg.

Example 2 The same procedure as in Example 1 was carried out using a polymer prepared by the same method as in Example 1 except that the fluorine-containing polybutylene glycol dimethacrylate synthesized in the same manner as in Example 1 was used. Was measured. Table 2 shows the results.

Comparative Example The measurement was carried out in the same manner as in Example 1 using as a sample a polymer obtained by polymerizing 90 parts of siloxanyl methacrylate, 40 parts of methyl methacrylate and 5 parts of ethylene glycol dimethacrylate in the same manner as in Example 1. Table 2 shows the results.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hideo Mitsuyama 2-248 Mitsuhashi, Omiya City, Saitama Prefecture

Claims (2)

[Claims] 1. A siloxanyl (meth) acrylate monomer component (a) of 20 to 90% by weight, a (meth) acrylate monomer component (b) of 10 to 50% by weight, and a polyalkylene glycol di (meth) acrylate. 2 to 20% by weight of the monomer component (c), and the general formula [I] [In the formula, A ¹ is an oxyalkylene group having 2 to 4 carbon atoms, R ¹ is a hydrogen atom or a methyl group, and h is 1 to 20.
Indicates an integer of 000. ] The carbon atom of the oxyalkylene group in the main chain of the bifunctional (meth) acrylic acid ester-based monomer represented by
30 fluorine-substituted hydrocarbon groups are bonded to at least one fluorine-containing difunctional (meth) acrylic acid ester-based monomer component (d) per molecule of this monomer, and the fluorine-containing cross-linked polymer is 1 to 10% by weight. An oxygen permeation body consisting of a united body. 2. A contact lens comprising the oxygen permeation body according to claim 1.