JP2551603B2 - contact lens - Google Patents

Description

TECHNICAL FIELD The present invention relates to a contact lens which has excellent oxygen permeability and stain resistance and can be worn safely and for a long period of time.

[Prior Art] Polymethylmethacrylate (hereinafter abbreviated as PMMA) as a main component has been widely known as a material for contact lenses, but these have low oxygen permeability and wear time is restricted. There was a desire for improvement. As a result, a copolymer using a silicone compound and a fluorine-containing compound as a monomer has come to be used as a contact lens (see, for example, JP-A-58-194014). Further, polydimethylsiloxane has a high oxygen permeability, for example, as shown in JP-A-58-58519,
Silicone rubber lenses to which this is applied are also being researched. On the other hand, there are soft contact lenses made of hydrous gels obtained from monomers such as 2-hydroxyethyl methacrylate and N-vinyl-2-pyrrolidone, and these have been studied for high water content in order to enhance oxygen permeability. ing. An example thereof is that described in JP-A-57-8521. Also, in recent years there have been attempts to improve oxygen permeability by using polyfluorinated monomers,
For example, Japanese Examined Patent Publication (Kokoku) No. 62-33573 discloses a contact lens made of a polymer having 2,3,4,5,6-pentafluorostyrene as a monomer in which all hydrogen atoms on the benzene ring are substituted with fluorine. There is. Further, for example, JP-A-58-127914 also discloses a contact lens made of a polymer in which a macromonomer having a perfluoropolyether is used as a monomer.

[Problems to be Solved by the Invention] However, a copolymer using a silicone compound and a fluorine-containing compound as a monomer, as described in JP-A-58-194014, is compared with a copolymer using PMMA as a material. Then, although the oxygen permeability is improved, if the oxygen permeability is further improved to further improve the safety, the mechanical strength is remarkably lowered, which is a practical problem. Further, although the silicone rubber lens described in JP-A-58-58519 has excellent oxygen permeability, it easily causes eye damage and has not been sufficiently spread. Further, a soft contact lens made of a hydrogel as described in JP-A-57-8521 has to have a high water content in order to enhance oxygen permeability, but if so, scratches and breakage are likely to occur and stains are likely to occur. Durability and safety problems such as easy adhesion are accompanied. See also
In the contact lens using a polyfluorinated monomer described in JP-A-33573 or JP-A-58-127914, oxygen permeability generally improves as the number of fluorine atoms increases, but it becomes sufficient. I haven't arrived.

Therefore, an object of the present invention is to solve the above-mentioned drawbacks of conventional contact lenses, to provide a contact lens which has excellent oxygen permeability and stain resistance and which can be worn safely and for a long period of time.

[Means for Solving the Problem] The present invention has been made to solve the above-described object, and the contact lens of the present invention is a compound represented by the following general formula [I] and / or a general formula [II] below. ] It consists of the polymer which makes the compound shown by these into an essential monomer component.

In the general formulas [I] and [II], Rf is a bulky perfluoroalkyl group or a perfluoroalkenyl group, and the latter perfluoroalkenyl group is particularly preferable, and such a perfluoroalkenyl group has the following structure. Formula [III],
Representative examples include those represented by [IV] and [V], but the invention is not limited to these.

That is, the above-mentioned monomer [I] or [II] which gives the contact lens of the present invention has a bulky fluoroalkyl ether group or fluoroalkenyl ether group introduced at the para-position of styrene or 2,3,5,6-tetrafluorostyrene. It is characterized by being.

 Hereinafter, the present invention will be described more specifically.

The material constituting the contact lens of the present invention is a polymer containing the monomer represented by the general formula [I] and / or the monomer represented by the general formula [II] as an essential monomer component. The term "polymer" as used herein means a monomer of the general formula [I] or a homopolymer of the monomer of the general formula [II];
Copolymer of monomers of formula [II] Copolymer of monomers of formula [II]; Monomer of formula [I] and formula [II]
A copolymer of the monomer of formula [I] and the monomer of formula [II] with another monomer for copolymer (a specific example of which will be described later). Combined: a mixture of at least one monomer selected from the monomer of the general formula [I] and the monomer of the general formula [II] and another monomer for copolymer (a specific example will be described later) is a hydrophilic monomer and / or It means a copolymer or the like obtained by copolymerizing with a polyfunctional monomer (a specific example of which will be described later) as a crosslinking component.

As the above-mentioned other monomers for copolymers, styrene derivatives other than the styrene derivatives of the general formulas [I] and [II], 2,3,4,5,6-pentafluorostyrene and their para-substituted derivatives, Acrylic acid or methacrylic acid ester is used, and specific examples thereof include styrene, p-methylstyrene, p-chlorostyrene, p-trifluoromethylstyrene, 2,3,4,5,6-pentafluorostyrene, and 2,3. ,
5,6-Tetrafluoro-4- (2,2,2-trifluoroethyl)
Styrene, methyl acrylate, n-butyl acrylate, methyl methacrylate, isopropyl methacrylate, 4-t-butylcyclohexyl methacrylate, 2,
2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate and the like can be mentioned.

Further, as the hydrophilic monomer in the present invention, an acrylic acid ester or a methacrylic acid ester having an alcoholic hydroxyl group is used, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glyceryl methacrylate and the like. Further, other than the above, copolymerization with N-vinyl-2-pyrrolidone or an unsaturated carboxylic acid such as acrylic acid or methacrylic acid is also possible.

As the polyfunctional monomer as a crosslinking component, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, divinylbenzene, etc. Can be mentioned.

These monomer components are appropriately used in order to obtain desired physical properties such as processability, mechanical properties, optical properties and hydrophilicity of the material.

The polymer for a highly oxygen permeable contact lens of the present invention has, as the monomer component, a polymerization initiator that generates a usual free radical, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxide, diisopropyloxydicarbonate, and azobisisocarbonate. It can be obtained by mixing butyronitrile, azobisdimethylvaleronitrile, etc. and heating and polymerizing. It is also possible to polymerize by photopolymerization in the presence of an ultraviolet initiator.

The thus obtained polymer having a required shape such as a plate shape, a disk shape or a bar shape is cut and polished according to a usual method to obtain a predetermined contact lens shape. Alternatively, the contact lens can be directly molded by cast polymerization using a mold having a predetermined radius of curvature.

The contact lens produced in this manner has a feature of high oxygen permeability, which is a para-bulky perfluoroalkyl ether or styrene or 2,3,5,6-tetrafluorostyrene. This is because a monomer having a perfluoroalkenyl ether group introduced therein is used.
That is, this high oxygen permeability is a remarkable technical effect that cannot be obtained by the contact lens of the prior art obtained by polymerizing a monomer in which hydrogen on the benzene ring of styrene is replaced by fluorine. Further, the contact lens of the present invention not only has excellent oxygen permeability, but also has a property of less dirt adhering to tear fluid during wearing, and thus has a higher safety than contact lenses of the prior art. Have sex.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A polymerization initiator (azobisdimethylvaleronitrile) was added to 100 parts by weight of PFTFST-3 (see the abbreviation table) corresponding to the fluorine-containing monomer of the formula [II] (Rf = perfluoroalkenyl group of the formula [V]). Add 0.1 parts by weight, inject 2 ml of this product into a polypropylene polymerization container, and seal the top, then at 35 ° C.
For 20 hours, 45 ° C. for 10 hours, 60 ° C. for 8 hours, and 110 ° C. for 10 hours in a hot air circulation type thermostat to polymerize and cure. A contact lens was obtained by cutting and polishing this polymer into a predetermined shape. The oxygen permeability coefficient of this contact lens was measured using a Seikaken film oxygen permeability meter manufactured by Rika Seiki Kogyo Co., Ltd. at 35 ° C. in 0.9% physiological saline, and as shown in Table 1, it was 80 ×. 10 ^-11 cm
³ (STP) · cm / cm ² · sec · mmHg, showing excellent oxygen permeability. Further, as shown in Table-1, the machinability and the stain resistance were also good.

Example 2 PFST-2 corresponding to the fluorine-containing monomer of the formula [I] (Rf = perfluoroalkenyl group of the formula [IV]) (see the abbreviation table)
90 parts by weight, 1H, 1H, 2H, 2H perfluorohexyl methacrylate 10 parts by weight, 2 ml of a monomer mixture consisting of 0.1 part by weight of benzoyl peroxide was injected into a polypropylene polymerization container, and the top was sealed, then 40 Polymerization and curing were carried out by heating in a hot air circulation type thermostat for 20 hours at 50 ° C, 10 hours at 50 ° C, 10 hours at 60 ° C, 10 hours at 80 ° C, 13 hours at 120 ° C. A contact lens was obtained by cutting and polishing this polymer into a predetermined shape. When the oxygen permeability coefficient of this contact lens was measured under the same conditions as in Example 1, it was 62 × 10 ^-11 cm ^{3 as} shown in Table 1.
(STP) · cm / cm ² · sec · mmHg, showing high oxygen permeability. Further, as shown in Table-1, the machinability and the stain resistance were also good.

Examples 3 to 8 According to the method of Examples 1 and 2, a mixture of various monomers shown in Table 1 was poured into an appropriate mold, and polymerization was performed under the conditions of a temperature of 30 to 150 ° C. and a heating time of 5 to 72 hours. Cured. The obtained polymer was machined into a contact lens, and the oxygen permeability coefficient was measured in the same manner as in Example 1. The machinability and stain resistance were also investigated. As a result, as shown in Table-1, the contact lenses of Examples 3 to 8 were also excellent in oxygen permeability, machinability and stain resistance.

Comparative Example 1 Polymerization was carried out according to the method of Example 1 by adding 0.1 part by weight of a polymerization initiator (azobisdimethylvaleronitrile) to 100 parts by weight of 2,3,4,5,6-pentafluorostyrene. Table-1
As shown in Figure 4, the machinability and stain resistance of this polymer were good, but the oxygen permeability coefficient was 9.0 × 10 ^-11 cm ³ (STP)
It was cm / cm ² · sec · mmHg, and sufficient oxygen permeability was not obtained.

Comparative Example 2 2,3,4,5,6-pentafluorostyrene 90 parts by weight and 1H, 1
A monomer mixture consisting of 10 parts by weight of H, 2H, 2H perfluorohexyl methacrylate and 0.1 part by weight of benzoyl peroxide was polymerized according to the method of Example 2.
As shown in Table 1, the stain resistance of this polymer was good, but the machinability was poor, and the oxygen permeability coefficient was 21 × 10 ^-11 c.
It was m ³ (STP) · cm / cm ² · sec · mmHg, and although a slight improvement was obtained, the oxygen permeability was still low.

Comparative Example 3 2,3,4,5,6-pentafluorostyrene 80 parts by weight and 2,2,2
A monomer mixture consisting of 20 parts by weight of trifluoroethyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate and 0.2 parts by weight of azobisisobutyronitrile was polymerized according to the method of Example 2. As shown in Table-1, the machinability and stain resistance of this polymer were good, but the oxygen permeability coefficient was 8.8 × 10 ^-11 cm ³ (STP) · cm.
/ cm ² · sec · mmHg, which was far lower than the oxygen permeability of Example 3.

Comparative Example 4 20 parts by weight of trifluoroethyl methacrylate, 74 parts by weight of tris (trimethylsiloxy) silyl methacrylate, 6 parts by weight of ethylene glycol dimethacrylate,
A monomer mixture consisting of 0.5 part by weight of azobisdimethylvaleronitrile was polymerized according to the method of Example 2. As shown in Table-1, the oxygen permeability coefficient of this polymer was 74 × 10 ^-11 cm ³ (STP) · cm / cm ² · sec · mmHg, which was a high value, but it was difficult to machine. Yes, and it was terribly contaminated.

(Abbreviation table) TMSPMA: Tris (trimethylsiloxy) silylpropyl methacrylate MMA: Methyl methacrylate PFST: 2,3,4,5,6-pentafluorostyrene 6FMA: Hexafluoroisopropyl methacrylate 9FMA: 1H, 1H, 2H, 2H Perfluorohexyl methacrylate TFEMA: 2,2,2-Trifluoroethylmethacrylate NVP: N-vinyl-2-pyrrolidone HEMA: 2-hydroxyethylmethacrylate 1G: ethylene glycol dimethacrylate 2G: diethylene glycol dimethacrylate DVB: divinylbenzene AIBN: azobisisobutyro Nitrile ADVN: Azobisdimethylvaleronitrile BPO: Benzoyl peroxide [Effect of the invention] The contact lens of the present invention has high oxygen permeability and stain resistance, is safe and can be worn for a long time, and has good machinability. Is also excellent. These effects are obtained by using a polymer having a bulky perfluoroalkyl ether or perfluoroalkenyl ether group at the para position as a styrene or 2,3,5,6-tetrafluorostyrene monomer as an essential monomer component. It is realized for the first time and is an effect peculiar to the present invention.

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula [I] and / or
Alternatively, a contact lens comprising a polymer containing a compound represented by the following general formula [II] as an essential monomer component. (In the formula, Rf is a bulky perfluoroalkyl or perfluoroalkenyl group)