JPH04130109A - Material for soft contact lens - Google Patents

Abstract

PURPOSE:To obtain the title material excellent in oxygen diffusibility, hydrophilicity, staining resistance and biocompatibility by copolymerizing a specified hydrophilic monomer with a specified methacrylic acid derivative and a fluoro urethane dimethacrylate ester. CONSTITUTION:At least one hydrophilic monomer selected from among 2- hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, methacrylic acid, dimethylacrylamide and N-vinylpyrrolidone is copolymerized with at least one methacrylic acid derivative selected from among ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, pentaerythritol tetramethacrylate and allyl methacrylate and a fluoro urethane dimethacrylate ester of the formula (wherein R1 and R2 are each 1-4C alkyl; and (n)is 1-10).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a soft contact lens material made of a fluorine-containing polymer that has excellent oxygen permeability, wear comfort, durability, and stain resistance.

(Prior art) Polymethyl methacrylate (denoted as PMMA) has conventionally been used as a material for hard contact lenses (denoted as HCL).
is widely used due to its excellent optical properties and machinability. However, since it is a material with low oxygen permeability, sufficient oxygen cannot be supplied to the cornea, and by wearing HCL,
A barrier to oxygen forms, which can result in hyperemia, edema, and other corneal damage. Since PMMA-based HCL has low oxygen permeability as described above, various materials with high oxygen permeability have been studied in recent years. Among them, there are materials such as siloxanyl methacrylate-based materials, which have improved oxygen permeability by introducing a siloxane bond into the ester part of a methacrylic acid ester, fumarate resin-based materials, and styryl-based materials having siloxane bonds.

Products containing these materials have higher oxygen permeability than conventional PMMA-based HCL, but their low hardness makes contact lenses easy to break, and the surface of contact lenses has poor hydrophilicity. , dirt such as lipids adheres,
It has the disadvantage that it sticks. In addition, soft contact lenses whose main component is 2-hydroxyethyl methacrylate swell with water to form a hydrogel, and are flexible and comfortable to wear, and have good oxygen permeability.
It has disadvantages such as poor dimensional stability and mechanical strength, and because it contains a large amount of water, it is susceptible to contamination with mold, bacteria, and tear fluid components (proteins, lipids, mucin, etc.) and is complicated to handle. On the other hand, fluorine-containing polymers are corrosion resistant, stain resistant (and gas permeable). Taking advantage of these properties, soft contact lenses that are resistant to stains are manufactured from copolymers of fluorine-containing monomers. Although a method has been found, it is not sufficient in terms of dimensional stability and mechanical strength because it is necessary to reduce the thickness of the contact lens in order to further improve the oxygen permeability of the contact lens.

(Problems to be Solved by the Present Invention) As mentioned above, the present invention eliminates the drawbacks of conventional contact lenses, is resistant to dirt, reduces lens thickness, and improves oxygen permeability. The object of the present invention is to provide a soft contact lens material for manufacturing soft contact lenses, which has high dimensional stability and mechanical strength.

(Means and effects for solving the problem) In order to achieve the above object, as a result of various studies, the general formula (■): (In the formula, R and Rz are alkyl having 1 to 4 carbon atoms, respectively)I4
, n is an integer from 1 to 10. ) In particular, a fluorine-containing polymer prepared from a fluorine-containing urethane dimethacrylate ester represented by 0.05 to 5.0% by weight of a fluorine-containing urethane dimethacrylate ester, 80 to 95% by weight of a hydrophilic monomer, and a methacrylic acid derivative 0.1~1
It has been found that when producing soft contact lenses from copolymers obtained by copolymerizing 0% by weight, the above objects are achieved in the product.

The fluorine-containing urethane dimethacrylate ester compound represented by the general formula (1), which is a raw material used in the present invention, is mainly involved in the oxygen permeability of the soft contact lens produced, and when used as a material for soft contact lenses, R1 and R2 must be a lower alkyl group, n must be a compound in the range of 1 to IO, R5 in other ranges,
The use of a fluorine-containing urethane dimethacrylate ester compound having Rz and n is undesirable because it adversely affects the oxygen permeability and hardness of the resulting copolymer.

The hydrophilic monomers used are mainly responsible for the hydrophilicity of the produced soft contact lenses and are selected from 2-hydroxyethyl methacrylate, polyethylene glycol monomethacrylate, methacrylic acid, dimethylacrylamide and N-vinylpyrrolidone. Methacrylic acid derivatives are mainly involved in the plasticity and mechanical strength of soft contact lenses produced together with hydrophilic monomers, and include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, and Selected from pentaerythritol tetramethacrylate. These three components are copolymerized under heating by a conventional method in the presence of at least one type of polymerization initiator selected from radical polymerization initiators commonly used for polymerization of unsaturated hydrocarbon compounds. to obtain the desired copolymer. In order to use the produced copolymer as a material for soft contact lenses, 0.005 to 5.0% by weight of fluorine-containing urethane dimethacrylate ester and 8% of hydrophilic monomer are required.
It is necessary to copolymerize a composition of 0 to 95% by weight and 0.1 to 10% by weight of a methacrylic acid derivative in the presence of a polymerization initiator of 0.03 to 0.07% by weight (based on the weight of the ML initial product). .

The fluorine-containing urethane dimethacrylate copolymer thus obtained has superior hydrophilicity and stain resistance, as well as strong mechanical strength, compared to conventional copolymers, allowing lenses to be made thinner and with even higher oxygen permeability. It can be improved.

EXAMPLES The present invention will be specifically described below with reference to Examples.

(Example-1) Adding 0.05% by weight of fluorine-containing dimethacrylate to a monomer mixture of 80% by weight of 2-hydroxyethyl methacrylate, 17% of hydroxypropyl methacrylate, and 3% by weight of ethylene glycol dimethacrylate. Then, 0.07% by weight of the initiator azobisisobutyronitrile was mixed, and the mixture was dispensed into polypropylene test tubes and the water temperature was 6.
A copolymer was obtained by standing in a constant temperature water bath at 0°C. A lens obtained from this copolymer by cutting and polishing has an oxygen permeability of 1
2X10-'', tensile strength of 23 kg/cm'', and stretch layer of 280%, and no stains were observed in the artificial tear fluid stain test.

(Example-2) 3.0% by weight of fluorine-containing urethane dimethacrylate was added to a monomer mixture of 70% by weight of N-vinylpyrrolidone, 20% by weight of 2-hydroxyethyl methacrylate, and 7% by weight of triethylene glycol dimethacrylate. Further, 0.04% by weight of initiator azobisisobutyronitrile was mixed, and the mixture was dispensed into polypropylene test tubes and left standing in a constant temperature water bath at a water temperature of 45°C to obtain a copolymer. A lens obtained from this copolymer by cutting and polishing has an oxygen permeability of 24×10
Tensile strength 30 kg/ctx”, stretch layer 320%
No stains were detected in the stain test for tear artificial tears.

(Example-3) 5.0% by weight of fluorine-containing urethane dimethacrylate was added to a mixed monomer of 9511% 2-hydroxyethyl methacrylate and 5% by weight allyl methacrylate, and further an initiator azobisisobutyronitrile was added. 0.06% by weight was mixed, dispensed into polypropylene test tubes, and left to stand in a constant temperature water bath at a water temperature of 60°C to obtain a copolymer. A lens obtained from this copolymer by cutting and polishing has an oxygen permeability of 15×10-”,
It has a tensile strength of 28 kg/cm'' and a stretch layer of 260%, and no stains were observed in the artificial tear fluid stain test.

(Example 4) The fluorine-containing urethane dimethacrylate ester used in Examples 1 to 3 was synthesized by the following method.

3.4,5.6-perfluorooctanediol 400
g (1,3793 mol) and dibutyltin dilaurate 0.21 g, hydroquinone monomethyl ether 0.0
8g for 2! Pour into a Mitsuro flask and stir thoroughly for 30 minutes.

Thereafter, the internal temperature was raised to 60°C, and 428 g (2,7586 mol) of 2-isocyanate ethyl methacrylate was evenly added dropwise over 4 hours. During this time, the internal temperature was 60°
Control the temperature to C.

After the completion of the dropwise addition, the reaction was further carried out at 60″C for 14 hours,
When the isocyanate content in the reaction system was measured, it was found to be 0.
．． Since the amount was less than 0.01% by weight, the reaction was stopped and the desired urethane methacrylate product was obtained.

(Effects of the Invention) Soft contact lenses manufactured from the soft contact lens material according to the present invention have superior oxygen permeability, hydrophilicity, and stain resistance to tear components, and are biocompatible, compared to conventional soft contact lenses. Because of its excellent properties, it can be worn for long periods of time.

Agent: Patent Attorney Hideaki Kuwahara (Volunteer) Proceedings (Jukosho, October 13, 1990)

Claims (6)

[Claims] (1) At least one hydrophilic monomer selected from the group consisting of 2-hydroxyethylene methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, methacrylic acid, dimethylacrylamide, and N-vinylpyrrolidone; ethylene glycol dimethacrylate , at least one methacrylic acid derivative selected from the group consisting of diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and allyl methacrylate, and a fluorine-containing compound represented by the general formula (I). Fluorine-containing soft contact lens material obtained by copolymerizing urethane dimethacrylate ester ▲Mathematical formula, chemical formula,
There are tables, etc.▼(I) (In the formula, R_1 and R_2 are each an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10.) (2) 0.05-5.0% by weight of fluorine-containing urethane dimethacrylate ester of general formula (I); 80-95% by weight of hydrophilic monomer and 0.1-10% of methacrylic acid derivative
The soft contact lens material according to claim 1, which is obtained by copolymerizing % by weight. (3) the hydrophilic monomers are 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate,
The soft contact lens material according to claim 2, wherein the methacrylic acid derivative is ethylene glycol dimethacrylate. (4) The soft contact lens material according to claim (2), wherein the hydrophilic monomers are N-vinylpyrrolidone and 2-hydroxyethyl methacrylate, and are a methacrylic acid derivative or triethylene glycol dimethacrylate. (5) The soft contact lens material according to claim (2), wherein the hydrophilic monomer is 2-hydroxyethyl methacrylate and the methacrylic acid derivative is allyl methacrylate. (6) At least one polymerization initiator selected from radical polymerization initiators used in the polymerization of unsaturated hydrocarbon compounds is used in a proportion of 0.03 to 0.07% by weight based on the polymerization material. The soft contact lens material according to claim (2), which is polymerized.