JPH0830761B2 - Soft contact lens - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a soft contact lens formed of a fluorine-containing polymer having excellent oxygen permeability, water swelling property and stain resistance.

More specifically, the present invention relates to a soft contact lens that has excellent biocompatibility, can be worn for a long time, and can exhibit excellent performance.

[Conventional technology]

Since the cornea of the eyelid is a tissue without blood vessels, oxygen required for its respiratory metabolism is obtained by diffusion from the eyelid conjunctiva and aqueous humor during sleep, but from the atmosphere when awake. I am incorporating it. Therefore, wearing a contact lens, whether it is a hard contact lens or a soft contact lens, is likely to impair oxygen supply, and long-term wearing often causes hyperemia, 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, the material for contact lenses, especially soft contact lenses, is excellent in stain resistance against tear fluid components such as proteins, lipids and mucins, and against bacteria and fungi. It is required to have excellent water swellability and biocompatibility.

Conventionally, polymethylmethacrylate (PMMA) and polymers of various methacrylic acid ester-based monomers have been widely used as materials for contact lenses, but most of them have poor oxygen permeability and are worn for a long time. I couldn't stand it.

In order to improve the oxygen permeability of conventional methacrylic acid ester-based polymers, a silicone-methacrylate-based polymer in which a siloxane bond is introduced into the methacrylic acid ester molecule (Japanese Patent Publication No. 52-33502) and cellulose acetate butyrate are mainly used. Oxygen-permeable polymer and fluorine-containing methacrylate-based polymer (Japanese Patent Application Laid-Open No. 57-51705 and Japanese Patent Application Laid-Open No.
A contact lens using, for example, Japanese Patent Laid-Open No. 1-111308) has been proposed. However, these polymers are
Compared to methacrylic acid ester-based polymers such as PMMA, oxygen permeability is improved, but it is not yet sufficient, and there is a demand for a polymer with improved oxygen permeability. Further, these polymers are not satisfactory in performance such as stain resistance, hydrophilicity and water swelling property.

[Problems to be solved by the invention]

The present inventors have recognized that the prior art of conventional oxygen permeators, particularly contact lenses, especially soft contact lenses, is in the above-mentioned situation, and oxygen permeability, hydrophilicity,
As a result of intensive studies on an oxygen permeation material excellent in water swelling property and stain resistance, the present inventors have found that a specific fluorine-containing polymer satisfies the above-mentioned object, and arrived at the present invention.

[Means for solving problems]

According to the present invention, the following general formula [I] or general formula [I
I] [In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a methyl group, and R ⁴ represents an oxygen atom having 1 to 30 carbon atoms or a hydrocarbon group which may contain a fluorine atom, m
And n each represent an integer of 1 to 1000], wherein the alkylene group carbon in the main chain of the (meth) acrylic acid ester monomer has at least 3 fluorine atoms and is substituted with fluorine having 1 to 30 carbon atoms. Oxygen-permeable water-swellable gel obtained by polymerizing and molding a fluorine-containing (meth) acrylic acid ester monomer having a molecular structure in which at least one hydrocarbon group is bonded per molecule of the monomer. Provided is a soft contact lens comprising a crosslinked polymer.

The polymer forming the soft contact lens of the present invention has the general formula [I] or the general formula [II] [In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a methyl group, and R ⁴ represents an oxygen atom having 1 to 30 carbon atoms or a hydrocarbon group which may contain a fluorine atom, m
And n each represents an integer of 1 to 1000], and the alkylene group in the main chain of the (meth) acrylic acid ester monomer represented by the following formula has at least 3 fluorine atoms and is substituted with fluorine having 1 to 30 carbon atoms. A water-swellable gel-like cross-linked polymer obtained by polymerizing, as a main component, a fluorine-containing (meth) acrylic acid ester-based monomer in which at least one hydrocarbon group is bonded per molecule of the monomer, In addition to a homopolymer of a fluorine-containing (meth) acrylic acid ester-based monomer, a copolymer of the fluorine-containing (meth) acrylic acid ester-based monomer and another copolymerizable monomer Good.

R ⁴ constituting the (meth) acrylic acid ester monomer represented by the general formula [I] may contain an oxygen atom or a fluorine atom having 1 to 30, preferably 0 to 61 carbon atoms. Indicates a hydrocarbon group, more specifically -CH
_{3, -C 2 H 5, -C} 4 H 9, -C 6 H 12, -C 10 H 21, -C 12 H 25, -C
₂₀ H ₄₁ , -CH (CH ₃ ) ₂ , CF ₂ CFH (CF ₂ ) ₆ H, -COCF ₃ , -COC ₂ F
_{5, -COCH (CF 3) 2} , -COC 7 F 15, -COC 10 F 21, -COCH 2 CH 2 C 6
F _{13 and the} like can be specifically exemplified, and among these, —CH ₃ , —C ₂ H ₅ , —COCF ₃ , —COC ₂ F ₅ , —COC ₇ F _{15 and the} like are preferable. Further, in the general formula [I] or the general formula [II], m and n are 1 to 1000, preferably 3 to 70.
It is 0, particularly preferably in the range of 3 to 500.

Specifically as the (meth) acrylic acid ester monomer represented by the general formula [I], Etc. and mixtures thereof can be exemplified. Further, as the (meth) acrylic acid ester monomer represented by the general formula [I], specifically, Etc. and mixtures thereof can be exemplified.

Further, the number of carbon atoms having at least 3 fluorine atoms bonded to the alkylene group carbon in the main chain of the (meth) acrylic acid ester monomer represented by the above general formula [I] or [II] is 1 to specific examples 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 these, at least 3 carbon atoms bonded with fluorine atoms have 2 to 20 carbon atoms.
Fluorine-substituted alkyl groups are preferred.

The fluorine-substituted hydrocarbon group is bonded to the alkylene group carbon of the oxyalkylene group in the main chain of the (meth) acrylic acid ester monomer represented by the general formula [I] or the general formula [II], The bonding ratio of the fluorine-substituted hydrocarbon group is at least 1, preferably 1 to 20 per molecule of the (meth) acrylic acid ester monomer, and the resulting fluorine-containing (meth) acrylic acid ester-based monomer The monomer usually contains 3 to 400, preferably 3 to 200, fluorine atoms per molecule.

Specifically as the fluorine-containing (meth) acrylic acid ester-based monomer, for example, Here, m + n is 1 to 1000.

Indicates that they are randomly arranged. The same applies hereinafter.) And the like.

As a method for producing such a monomer, for example, a fluorine-substituted hydrocarbon group is bound to a compound forming a main chain structure such as polyethylene glycol or triethylene glycol monomethyl ester, and then reacted with methacrylic acid chloride to form a molecule. A method of (meth) creating a terminal can be exemplified.

Further, in the fluorine-containing polymer forming the soft contact lens of the present invention, specifically as a copolymerizable monomer that may be copolymerized with the fluorine-containing (meth) acrylic acid ester-based monomer, Hydrocarbon-based methacrylates and acrylates such as Hydroxyalkyl methacrylate and acrylate, such as Fluorine-based methacrylates and acrylates such as And so on Aminomethacrylate and acrylate, such as Acrylamide and methacrylamide, such as N-vinyl lactam, such as Polyethylene glycol monomethacrylate and acrylate or polypropylene glycol monomethacrylate and acrylate, such as Bifunctional methacrylate, including polyethylene glycol dimethacrylate and acrylate, etc. Polyfunctional methacrylates and the like can be exemplified, among these copolymerizable monomers Polyethylene glycol (mono or di) methacrylate, polypropylene glycol (mono or di) methacrylate and the like are preferable. As a method for producing the fluorine-containing polymer, a mixture of the fluorine-containing (meth) acrylic acid ester-based monomer and, if necessary, the copolymerizable monomer and a polymerization initiator is used. A fluorine-containing polymer having a desired shape can be obtained by polymerizing in a polymerization mold. Among the polymerization initiators, specifically, as radical polymerization initiators, radical initiators for thermal polymerization are azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile. , Benzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide and the like can be exemplified. R = benzoin ethers such as isopropyl and isobutyl, 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 varies depending on the type and amount of the monomer and photopolymerization initiator used, and also depending on the type of light source used, for example, When used, a polymer having a practically sufficient strength can be obtained by UV irradiation for a time in the range of several seconds to several minutes.

Polymerization of the contact lens of the present invention is carried out in a polymerization mold of the contact lens and is polymerized and molded.

The fluorine-containing polymer forming the contact lens of the present invention may be a homopolymer of the fluorine-containing (meth) acrylic acid ester-based monomer, or may be a fluorine-containing (meth) polymer.
It may be a copolymer of an acrylic acid ester-based monomer and the copolymerizable monomer, but in the latter case as well, it contains the fluorine-containing (meth) acrylic acid ester-based monomer component. The content is usually 20 mol% or more, preferably 40 mol% or more, particularly preferably 50 to 90 mol%.

The fluorine-containing polymer is a hydrophilic gel-like cross-linked polymer and has water swelling property. The water content of the fluorine-containing polymer is usually 30 to 90%, preferably 30 to 70%.
Here, the water content of the fluorine-containing polymer was measured by the following method. First, put the test sample in a desiccator containing anhydrous calcium sulfate, keep it at 37 ° C, take it out of the desiccator every 24 hours, and weigh the weight (mg) to one digit below the decimal point of the effective figure. , If it is within 0.5 mg, dip the test body in 37 ° C physiological saline,
Take out with forceps every hour, wipe with clean gauze for 30 seconds, shake in air for 15 seconds, and then calculate the weight (mg) to the right of the decimal point. When the weight change was within 0.5 mg, the water content was calculated by the following formula.

Further, the fluorine-containing polymer has excellent oxygen permeability,
Its oxygen permeability coefficient (DK value × 10 ^-11 cc (STP) cm / cm ² · sec
・ MmHg) is usually 20 to 2000, preferably 30 to 200
It is in the range of 0, particularly preferably 50 to 2000. Here, the oxygen permeability coefficient of the fluorine-containing polymer was measured using a film oxygen permeability meter of Seikaken type. In the case of a water-containing sample, in order to exclude the effect of the KC1 solution in the electrode part, TPX (poly-4-methyl-1-
A three-layer sample in which the hydrogel was sandwiched between two pieces of penten film was prepared and measured. The oxygen permeability coefficient of the hydrous gel was calculated from the following formula.

The fluorine-containing polymer has excellent stain resistance to tear components such as proteins, lipids and mucins.

The soft contact lens made of the fluorine-containing polymer of the present invention is superior in oxygen permeability, hydrophilicity, water swelling property, stain resistance, particularly stain resistance against tear components, and is biocompatible as compared with conventional ones. Since it is excellent, there is an advantage that it can be worn for a long time.

EXAMPLES Next, the present invention will be specifically described with reference to examples.

Example 1 Polyethylene glycol having an average molecular weight of 6000 was dissolved in chlorobenzene, and perfluoropropylene (hereinafter abbreviated as PFP) was bonded thereto under pressure using benzoyl peroxide as an initiator to obtain a fluorinated polyethylene glycol. This was dissolved in chloroform and reacted with a large excess of methacrylic acid chloride using pyridine as a catalyst to obtain fluorine-based polyethylene glycol dimethacrylate (hereinafter abbreviated as F-based PEGDM). F content by elemental analysis is 1
6wt%, average molecular weight by GPC is 6500 in terms of polystyrene
Met.

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 keeping this solution at 50 ° C., pour it into a space between two glass plates using a 200 μm Teflon packing as a spacer under a nitrogen atmosphere,
After fixing with fasteners, put in an electric furnace, 60 ℃ for 24 hours, 70 ℃,
Polymerization was carried out by heating at 80 ° C. and 90 ° C. for 2 hours each.

After completion of the polymerization, the produced film was peeled from the glass plate and immersed in physiological saline to obtain a water-containing transparent hydrogel film, and the oxygen permeability coefficient and water content were measured. The results are shown in Table 1.

Examples 2 to 5 As in Example 1, various F-based PEGDM compounds were polymerized in the same manner as in Example 1 by using polyethylene glycols having different average molecular weights and fluorine-containing olefins bound as raw materials. The results of the hydrous hydrogel film obtained are shown in Table 1.

Example 6 In the same manner as in Example 1, triethylene glycol monomethyl ester was used as a raw material, one molecule of PFP was bonded, and it was methacrylated to synthesize fluorine-based triethylene glycol monomethyl monomethacrylate (hereinafter abbreviated as F-based TEGMM). 50 parts of this compound and the F-based PEGDM5 synthesized in Example 2
A mixture of 0 parts became a viscous solution at room temperature. This solution 100
0.5 parts to azobisisobutyronitrile,
After sufficiently stirring and mixing, deaeration was carried out at room temperature, and a hydrous hydrogel film was obtained by the same operation as in Example 1 at room temperature. As a result, although the water content was lower than that in Example 2, high oxygen permeability was maintained. Table 2 shows the results.

Example 7 Under the same conditions as in Example 6, except that 8-monohydroperfluoro-1-octene [CF ₂ ═CF (CF ₂ ) ₆ H] was used instead of PFP and two molecules were bonded. F type TEGMM was synthesized, and a hydrous hydrogel was obtained by the same operation as in Example 6.
Table 2 shows the results.

Example 8 F-based TEGMM synthesized in Example 6 and 50 parts of polyethylene glycol dimethacrylate having an average molecular weight of 6000 containing no fluorine functional group were mixed in an amount of 50 parts by the same procedure as in Example 6.
A hydrogel having a content of 9% was obtained. The water content of this film is 33% and the oxygen permeability coefficient is 32 × 10 ^-11 ml (STP) cm / cm ²
・ It was sec ・ mmHg.

Examples 9 to 11 The F-based PEGDM used in Example 4 (the oxygen permeation coefficient of the hydrogel film is 33 × 10 ⁻¹¹ ml (STP) cm / cm ² · sec · m
mHg), N-vinylpyrrolidone (hereinafter abbreviated as NVP) hexafluoroisopropyl methacrylate (hereinafter abbreviated as HFIM), 2-hydroxyethyl methacrylate (hereinafter abbreviated)
Abbreviated as HEMA. Using a solution prepared by mixing 50 parts of each of the compounds), a hydrogel film was obtained in the same manner as in Example 6, and the water content and oxygen permeability coefficient were measured.
The results are shown in Table 3.

Comparative Example 1 Using a solution prepared by mixing 100 parts of HEMA and 5 parts of diethylene glycol dimethacrylate (hereinafter abbreviated as 2G) as a cross-linking agent in the same manner as in Example 6, a hydrous hydrogel film was obtained to obtain a water content, The oxygen permeability coefficient was measured.
The results are shown in Table 4.

Comparative Example 2 NVP, methyl methacrylate (hereinafter abbreviated as MMA), 2G
A hydrous hydrogel film was obtained in the same manner as in Example 6 using the solution mixed in the proportions of 70 parts, 30 parts and 5 parts, and the water content and oxygen permeability coefficient were measured. The results are shown in Table 4.

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Claims (1)

[Claims] 1. The following general formula [I] or general formula [II] (In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom or a fluorine atom, m
And n each represents an integer of 1 to 1000), wherein the alkylene group carbon in the main chain of the (meth) acrylic acid ester monomer has at least 3 fluorine atoms and is substituted with fluorine having 1 to 30 carbon atoms. Oxygen-permeable water-swellable gel obtained by polymerizing and molding a fluorine-containing (meth) acrylic acid ester monomer having a molecular structure in which at least one hydrocarbon group is bonded per molecule of the monomer. Soft contact lens made of linear cross-linked polymer.