JP2865746B2 - Oxygen permeable contact lens - Google Patents

Description

The present invention relates to an oxygen-permeable contact lens. More specifically, the present invention relates to an oxygen-permeable contact lens made of a copolymer containing a specific structural unit as one component.

[Prior art] Conventionally, as contact lenses, a water-containing contact lens containing 2-hydroxyethyl methacrylate or vinylpyrrolidone as a main component, and methyl methacrylate (MMA), an alkyl fluoride methacrylate or a silicone methacrylate as a main component. Non-hydrated contact lenses are commercially available.

However, the above-mentioned conventional water-containing soft contact lenses are difficult to wear for a long time due to low oxygen permeability, or have low strength and are hard to withstand use.

In addition, conventional non-water-containing hard contact lenses containing MMA as a main component have a major drawback in that it is difficult to continuously wear them for a long period of time on corneal physiology because they have almost no oxygen permeability. Conventional silicone methacrylate-based hard contact lenses have better oxygen permeability than those based on MMA, but are still insufficient for continuous wear and have poor water wettability. It is inferior and has a disadvantage that it is easily contaminated by lipids and the like.

In recent years, for the purpose of solving the above-mentioned problems, there have been proposed ones in which the content of silicone methacrylate is increased or in which a fluorine atom is contained. For example, Japanese Patent Publication 62-876
No. 9 and JP-A-59-28127 propose an oxygen-permeable rigid contact lens comprising an alkyl fluoride (meth) acrylate and a siloxanylalkyl (glycerol) (meth) acrylate. Also, JP-A-60-131518, JP-A-61-57612, JP-A-6
1-281116, JP-A-61-281216, JP-A-61-28
Japanese Patent Application Laid-Open No. 5426 and Japanese Patent Application Laid-Open No. 62-54220 propose an oxygen-permeable rigid contact lens comprising siloxanyl propyloxy ethoxy (meth) acrylate and alkyl (meth) acrylate or alkyl itaconate. JP-A-61-87102 and JP-A-62-38419
The specification discloses an oxygen-permeable rigid contact lens made of alkylsiloxanyl fluoride (glycerol) (meth) acrylate.

[Problems to be Solved by the Invention] However, oxygen permeability is increased in any of the above-mentioned silicone methacrylate content-increased and fluorine atom-containing ones, and even those containing both silicone methacrylate and fluorine atoms. When it is increased, water wettability decreases, and there is a relationship that the lens becomes cloudy during wearing and is easily contaminated by lipids, etc., while maintaining oxygen permeability and water wettability, oxygen permeation that also has contamination resistance The emergence of sexually rigid contact lenses is expected.

Accordingly, an object of the present invention is to provide a contact lens having both oxygen permeability, water wettability, and stain resistance.

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and have obtained a contact lens made of a copolymer containing a specific compound as one constitutional unit having high oxygen permeability and good water. The inventors have found that they have wettability and stain resistance, and have reached the present invention.

That is, the present invention provides a compound of formula (I): Is an oxygen-permeable contact lens made of a copolymer having the unit represented by (1) as one constitutional unit (however, excluding one obtained by reacting an ethylenically unsaturated isocyanate). Here, R ¹ represents a methyl group or a hydrogen atom, and R ² represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms or a hydrocarbon group having 1 to 15 carbon atoms, which is partially or entirely fluorinated;
R ³ is a partially or wholly fluorinated hydrocarbon group having 1 to 15 carbon atoms (excluding those in which when R ² represents a hydrogen atom, the number of fluorine atoms contained in R ³ is 2 or less) ). Among them, R ¹ is preferably a methyl group in terms of hardness and oxygen permeability.

The copolymer according to the present invention has the formula (I ′): (Wherein R ¹ , R ² and R ³ are the same as above) in an amount of at least 10% by weight, preferably 30-80% by weight, of various known monomers (however, ethylenically unsaturated isocyanates). 90% by weight or less, preferably 20-70%
% By weight.

Specific examples of the monomer (I ′) include N- (2,2,2
-Trifluoroethyl) methacrylamide, N- (2,2,2
-Trifluoroethyl) acrylamide, N- (2,2,3,3,
3-pentafluoropropyl) methacrylamide, N-
(2,2,3,3,3-pentafluoropropyl) acrylamide, N- (2,2,3,3,4,4,4-heptafluorobutyl) methacrylamide, N- (2,2,3, 3,4,4,4-heptafluorobutyl) acrylamide, N- (1H, 1H-pentadecafluorooctyl) methacrylamide, N- (1H, 1H-pentadecafluorooctyl) acrylamide, N, N-bis (tri (Fluoroethyl) methacrylamide, N, N-bis (trifluoroethyl) acrylamide, N, N-bis (pentafluoropropyl) methacrylamide, N, N-bis (pentafluoropropyl) acrylamide, N, N-bis (hepta) Fluorobutyl) methacrylamide, N, N-, bis (heptafluorobutyl) acrylamide, N, N-bis (pentadecafluorooctyl) methacrylamide, N, N-bis (pentadecafluorooctyl) acrylamide, N-
(Trifluorophenyl) methacrylamide, N- (trifluorophenyl) acrylamide, N- (tetrafluorophenyl) methacrylamide, N- (tetrafluorophenyl) acrylamide, N- (pentafluorophenyl)
Methacrylamide, N- (pentafluorophenyl) acrylamide, N- (trifluoromethylphenyl) methacrylamide, N- (trifluoromethylphenyl) acrylamide, N- (trifluoromethylbenzyl) methacrylamide, N- (trifluoromethyl) Benzyl) acrylamide, N- [di (trifluoromethyl) phenyl] methacrylamide, N- [di (trifluoromethyl) phenyl] acrylamide, N- [di (trifluoromethyl) benzyl] methacrylamide, N- [di ( Trifluoromethyl) benzyl] acrylamide, N- (heptafluoronaphthyl) methacrylamide, N- (heptafluoronaphthyl) acrylamide and the like.

Among these compounds, methacrylamide-based compounds are more preferable in terms of oxygen permeability and hardness, and N- (2,
2,2-trifluoroethyl) methacrylamide and N, N-
Bis (trifluoroethyl) methacrylamide is more preferred. These compounds may be used alone or
Two or more kinds may be used as a mixture.

These compounds can be obtained, for example, by reacting the corresponding fluorinated amine with (meth) acrylic acid chloride.

These compounds have a high oxygen permeability because they have a fluorine-containing group at the molecular end, and can be copolymerized with other unsaturated bond monomers because they have a double bond at the other end. It is. Since the compound further has a hydrophilic amide bond in the molecule, it has compatibility with the hydrophilic monomer, and the hydrophilicity of the copolymer obtained by polymerization tends to be larger than that of the known silicone compound. There is.

Examples of known monomers include alkyl (meth) acrylates, silicone (meth) acrylates, fluorinated alkyl (meth) acrylates, organic acid vinyls, styrene compounds, allyl compounds, and the like. . Among them, copolymers with alkyl methacrylates having 1 to 15 carbon atoms and silicone-containing methacrylates are particularly preferred in view of oxygen permeability, strength, water wettability and stain resistance.

Examples of alkyl (meth) acrylates include, for example:
Methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, isopropyl acrylate, t-butyl methacrylate, t-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, t-amyl methacrylate, t-amyl acrylate, 2-ethylhexyl methacrylate, 2 -Ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate,
Examples include cyclohexyl methacrylate and cyclohexyl acrylate. Among them, methyl methacrylate and cyclohexyl methacrylate having 1 to 6 carbon atoms are preferable. These compounds may be used alone or in a combination of two or more.

Examples of silicone (meth) acrylates include
Trimethylsilylmethyl methacrylate, trimethylsilylmethyl acrylate, trimethylsilylpropyl methacrylate, trimethylsilylpropyl acrylate, pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylmethyl acrylate,
Pentamethyldisiloxanylpropyl methacrylate,
Pentamethyldisiloxanylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, methylbis (trimethylsiloxy) silylpropyl acrylate, tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate, mono [methylbis (trimethyl) (Siloxy) siloxy] bis (trimethylsiloxy) silylpropyl methacrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl methacrylate, tris [methylbis (trimethylsiloxy) ) Siloxy] silylpropyl acrylate, methylbis (trime (Siloxy) silylpropylglycerol methacrylate, methylbis (trimethylsiloxy) silylpropylglycerol acrylate, tris (trimethylsiloxy) silylpropylglycerol methacrylate, tris (trimethylsiloxy) silylpropylglycerol acrylate, heptamethylcyclotetrasiloxanylpropyl methacrylate, heptamethylcyclo Tetrasiloxanyl propyl acrylate,
Acryloxyethoxypropyl (trimethylsiloxy)
Silane, methacryloxyethoxypropyl (trimethylsiloxy) silane, N- [tris (trimethylsiloxy) silyl] propylacrylamide, N- [tris (trimethylsiloxy) silyl] propyl methacrylamide, N-methyl-N- [tris (trimethylsiloxy) ) Silyl] propylacrylamide, N-methyl-N
-[Tris (trimethylsiloxy) silyl] propyl methacrylamide, N- [methylbis (trimethylsiloxy) silyl] propylacrylamide, N- [methylbis (trimethylsiloxy) silyl] propyl methacrylamide, N-methyl-N- [methylbis (trimethyl) (Siloxy) silyl] propylacrylamide, N-methyl-N- [methylbis (trimethylsiloxy) silyl] propylmethacrylamide, N- [tris (pentamethyldisiloxy) silyl] propylacrylamide, N-
[Tris (pentamethyldisiloxy) silyl] propyl methacrylamide, N-methyl-N- [tris (pentamethyldisiloxy) silyl] propylacrylamide,
N-methyl-N- [tris (pentamethyldisiloxy)
[Silyl] propyl methacrylamide, N- [bis (trimethylsiloxy) mono (pentamethyldisiloxy) silyl] propylacrylamide, N- [bis (trimethylsiloxy) mono (pentamethyldisiloxy) silyl] propylmethacrylamide, N-methyl -N- [bis (trimethylsiloxy) mono (pentamethyldisiloxy) silyl] propylacrylamide, N-methyl-N- [bis (trimethylsiloxy) mono (pentamethyldisiloxy) silyl] propylmethacrylamide, N- [mono (Trimethylsiloxy) bis (pentamethyldisiloxy) silyl] propylacrylamide, N- [mono (trimethylsiloxy) bis (pentamethyldisiloxy) silyl] propylmethacrylamide, N-methyl-N-
[Mono (trimethylsiloxy) bis (pentamethyldisiloxy) silyl] propylacrylamide; N-methyl-N- [mono (trimethylsiloxy) bis (pentamethyldisiloxy) silyl] propyl methacrylamide; Among these compounds, methacrylic compounds are more preferable in terms of oxygen permeability and hardness. Further, among these, trimethylsilylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate, N- [tris (trimethylsiloxy) silyl] propyl methacrylamide, N-methyl-N- [tris ( Trimethylsiloxy) silyl] propyl methacrylamide is practical and more preferred.
These compounds may be used alone or in a combination of two or more.

In order to further improve water wettability, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, a hydrophilic monomer such as dimethylacrylamide, or ethylene glycol dimethacrylate, ethylene glycol A crosslinking agent such as diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, allyl acrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate may be added.

If necessary, a dye can be added to a mixture of the compound represented by the formula (I) and these monomers to obtain a polymer by a known polymerization method.

When using a polymerization catalyst as a polymerization method, for example,
Benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobismethylisobutyrate,
Catalysts such as 2,2'-azobisdimethylvaleronitrile and t-butylperoxy-2-ethylhexanoate can be used. The addition ratio of the polymerization catalyst is 0.01 to
5% by weight is preferred.

In addition, polymerization methods such as photopolymerization and radiation polymerization may be employed.

To obtain a contact lens, a lens may be manufactured by cutting and polishing from the above polymer, or a lens may be manufactured by directly polymerizing a mixture of the above monomers in a mold. By these methods, it is possible to obtain an oxygen-permeable hard contact lens having high oxygen permeability, sufficient water wettability, and less likely to be contaminated by lipids and the like.

[Examples] Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

In the examples, "parts" means "parts by weight", and physical properties were measured using the following measuring devices.

Oxygen Permeability Coefficient: Rika Seiki Kogyo Co., Ltd. Kaken Lab Film Oxygen Permeability Meter Vickers Hardness: Akashi Seisakusho Co., Ltd. Micro Hardness Tester (Model MVP-F) Contact Angle: Elma Optical Co., Ltd. Gonio Meter-type contact angle measuring device (GI type) The numerical value of the contact angle is a measure of water wettability, and the smaller the numerical value, the better the water wettability.

Stain resistance: A test piece having a diameter of 13 mm and a thickness of 1 mm collected from the copolymer was immersed in physiological saline containing 0.1% by weight of lysozyme (manufactured by Wako Pure Chemical, chicken egg white) at room temperature for 48 days, Thereafter, it was taken out and air-dried. The transmittance of the test piece before and after immersion in visible light (wavelength 400 nm) was measured with a double beam spectrophotometer 228A manufactured by Hitachi, Ltd. The lower the transmittance decrease rate, the less the contamination.

Reference Example Synthesis of N- (2,2,2-trifluoroethyl) methacrylamide 300 ml of ethyl ether, 24 g of pyridine and 30 g of trifluoroethylamine were added to a 1000 ml Erlenmeyer flask, and cooled to 10 ° C. or lower in an ice bath with stirring. did.

Separately, methacrylic acid chloride 3 in 300 ml of ethyl ether
The solution in which 1.5 g was dissolved was put into a 500-ml separating funnel.

While the content of the 1000 ml Erlenmeyer flask was kept at 10 ° C. or lower while stirring, the content of the separating funnel was dropped. After the addition, the mixture was stirred at room temperature for 16 hours, washed with water to remove water-soluble substances, and the ether layer was concentrated. This concentrate was distilled under reduced pressure to obtain 27.3 g of a fraction having a boiling point of 110 ° C. (20 mmHg). This had a parent peak at m / e = 167 as a result of mass spectrometry, and N-
(2,2,2-trifluoroethyl) methacrylamide was confirmed.

Synthesis of N- (pentafluorophenyl) methacrylamide 200 ml of ethyl ether, 16 g of pyridine and 36.6 g of pentafluoroaniline were added to a 1000 ml Erlenmeyer flask, and cooled to 10 ° C. or lower in an ice bath with stirring.

Separately, methacrylic acid chloride 2 in 150 ml of ethyl ether
The solution in which 0.9 g was dissolved was placed in a 300 ml separating funnel.

While the content of the 1000 ml Erlenmeyer flask was kept at 10 ° C. or lower while stirring, the content of the separating funnel was dropped. After the addition, the mixture was stirred at room temperature for 16 hours, washed with water to remove water-soluble substances, and the ether layer was concentrated. The concentrate was distilled under reduced pressure to obtain 16.1 g of a fraction having a boiling point of 132 ° C. (2.5 mmHg). This had a parent peak at m / e = 251 as a result of mass spectrometry, and N-
It was confirmed to be (pentafluorophenyl) methacrylamide.

Example 1 40 parts of N- (2,2,2-trifluoroethyl) methacrylamide and 20 parts of methyl methacrylate obtained in Reference Example
Part, 3-methacryloxypropyltris (trimethylsiloxy) silane (35 parts) and ethylene glycol dimethacrylate (5 parts) were mixed, and 2,2'-
0.2 parts of azobisdimethylvaleronitrile was added. This mixture was placed in a 20-ml polypropylene test tube, the gas phase was replaced with nitrogen, and then sealed.

Put this in a circulating water bath at 65 ° C for 65 hours and at 40 ° C.
The polymerization was carried out at 50 ° C. for 5 hours for 24 hours. Further, the test tube was transferred to a circulating drier and subjected to heat polymerization at 80 ° C. for 2 hours, at 100 ° C. for 1 hour, and finally at 110 ° C. for 1 hour.

The obtained polymer was colorless and transparent. A hard contact lens was obtained from the polymer by cutting and polishing.

 Table 1 shows the physical property values of this polymer.

Example 2 40 parts of N- (pentafluorophenyl) methacrylamide, 20 parts of methyl methacrylate,
Methacryloxypropyl tris (trimethylsiloxy)
35 parts of silane and 5 parts of ethylene glycol dimethacrylate were mixed, and 0.2 part of t-butylperoxy-2-ethylhexanoate as a polymerization catalyst was added to the mixture, and the mixture was placed in a polypropylene test tube and purged with nitrogen. The test tube was heated at 60 ° C. for 64 hours, then at 80 ° C. for 5 hours, at 100 ° C. for 2 hours, and at 120 ° C. for 1 hour for polymerization. A hard contact lens was obtained from the polymer by a cutting and polishing method. The physical properties of this lens are as shown in Table 1.

Examples 3 to 5 Mixed liquids having the compositions shown in Table 1 were prepared, and a polymer was obtained by the same polymerization procedure as in Example 1. Table 1 shows the physical properties of this polymer.

Comparative Example 1 30 parts of 3-methacryloxypropyltris (trimethylsiloxy) silane, 10 parts of methyl methacrylate, 50 parts of trifluoroethyl methacrylate and 10 parts of ethylene glycol dimethacrylate were mixed and operated in the same manner as in Example 1. The physical properties of the obtained lens are as shown in Table 1.

From the above examples, it is clear that the contact lens of the present invention is excellent in oxygen permeability, water leakage and stain resistance.

[Effects of the Invention] The oxygen-permeable contact lens of the present invention has good oxygen permeability, water wettability and stain resistance, and is therefore suitable for continuous wearing, and the present invention has a large practical significance.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G02C 1/00-13/00 C08F 20/00-20/70 C08F 120/00-120/70 C08F 220/00-220 / 70

Claims (1)

(57) [Claims] (1) Chemical formula (I): [In the formula, R ¹ represents a methyl group or a hydrogen atom, R ² represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms partially or wholly fluorinated. , R ³ is a carbon number partially or completely fluorinated 1-15
Hydrocarbon group (provided that when R ² represents a hydrogen atom, R ³
Excluding those having 2 or less fluorine atoms). ] An oxygen-permeable contact lens comprising a copolymer having the unit represented by the formula (1) as a constituent unit (however, excluding one obtained by reacting an ethylenically unsaturated isocyanate).