JP3400510B2 - Hydrous soft contact lens - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-containing soft contact lens, and more particularly to a water-containing soft contact lens excellent in water content, oxygen permeability and stain resistance.

[0002]

2. Description of the Related Art Hydrous soft contact lenses are compared with non-hydrous hard contact lenses (Japanese Examined Patent Publication No. 52-23502) which contain monomers such as methyl methacrylate and siloxanyl alkyl methacrylate as a main component, It is known that it is easy to fit in and has an excellent wearing feeling. Conventionally, as a hydrous soft contact lens, a soft contact lens containing 2-hydroxyethyl methacrylate as a main component and having excellent mechanical strength and processability has been used. However, since the soft contact lens has a low water content of 40% or less, there is a problem that it is not suitable for continuous wear for a long time.

Therefore, recently, there has been a demand for a water-containing soft contact lens which enables continuous wear by further increasing the water content of the lens material. For example, there has been proposed a water-containing soft contact lens made of a polymer obtained by copolymerizing N-vinylpyrrolidone as a main component with methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid and the like. However, water-containing soft contact lenses containing N-vinylpyrrolidone as a main component tend to be stained with dirt, have reduced strength, are difficult to process by cutting and polishing, and require repeated sterilization treatment, which is essential for soft contact lenses. There are various problems such as yellowing. Further, the water-containing soft contact lens containing 2-hydroxyethyl methacrylate as a main component does not have the above-mentioned problems, but the water content is low, so that it takes a long time for the water content to be saturated and the water content varies. There is a problem in production. In general, hydrous soft contact lenses have the ability to attach proteins, lipids, etc.
There are various problems such as hygiene such as bacterial growth and mechanical strength of the lens that decreases when the water content is increased.Therefore, it is usually necessary to use hygiene management using care products such as boiling sterilization, disinfectant, cleaning solution, etc. is necessary.

In order to solve these problems, Japanese Unexamined Patent Publication No.
Japanese Patent No. 107511 discloses a contact lens containing a (meth) acrylate monomer having a phosphorylcholine group as a component for the purpose of preventing adhesion of dirt. However, since the (meth) acrylate monomer having a phosphorylcholine group is a solid, the polymerization method is limited, and there is a problem that the amount used is also limited in copolymerization.

[0005]

The object of the present invention is to have a high water content, a high oxygen permeability, an excellent wearing feeling, a reduced effect on the eyes, and further to prevent the adhesion and deposition of proteins and lipids. An object of the present invention is to provide a hydrous soft contact lens which can be suppressed and can be worn continuously for a long period of time.

[0006]

According to the present invention, a (meth) acrylic acid ester represented by the following general formula 3 (hereinafter referred to as a (meth) acrylic acid ester A) and a general formula 4 below. A water-containing soft contact lens is provided which comprises a polymer obtained by copolymerizing a polymerization component containing itaconic acid diester (hereinafter referred to as itaconic acid diester B).

[0007]

[Chemical 3]

[0008]

[Chemical 4]

The present invention will be described in more detail below.

The hydrous soft contact lens of the present invention contains a polymer obtained by copolymerizing a polymerization component containing a specific (meth) acrylic acid ester and a specific itaconic acid diester. The specific (meth) acrylic acid ester is the (meth) acrylic acid ester A represented by the general formula ³ above, and when R ³ has 9 or more carbon atoms and n is 9 or more, it is obtained. The hydrophilicity and antifouling property of the obtained polymer are lowered. On the other hand, the specific itaconic acid diester is the itaconic acid diester B represented by the general formula 4, and when m is 7 or more in the formula, the production is difficult.

Examples of the (meth) acrylic ester A include 2- (meth) acryloyloxyethyl-
2 '-(trimethylammonio) ethyl phosphate,
2- (meth) acryloyloxypropoxyethyl-
2 '-(trimethylammonio) ethyl phosphate,
4- (meth) acryloyloxybutyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth)
Acryloyloxyethoxyethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxydiethoxyethyl-2'-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxytriethoxyethyl-2 '-(Trimethylammonio) ethyl phosphate, 6- (meth) acryloyloxyhexyl-2'-(trimethylammonio) ethyl phosphate, 3- (meth) acryloyloxypropyl-2 '-(triethylammonio) ethyl phosphate, 4- (meth) acryloyloxybutyl-2 '-(triethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2'-
(Tributylammonio) ethyl phosphate, 2-
Examples thereof include (meth) acryloyloxyethyl-2 ′-(2 ″ -trihydroxyethylammonio) ethyl phosphate. Such (meth) acrylic acid ester A is used for the water content and oxygen of the contact lens obtained. Permeability can be improved and at the same time proteins,
It is possible to impart antifouling property to lipids and the like.

To prepare the (meth) acrylic ester A, for example, a method in which a hydroxyalkyl (meth) acrylate is reacted with phosphorus oxytrichloride and choline chloride in the presence or absence of an amine, or hydroxyalkyl is used. It can be prepared by a method of reacting (meth) acrylate with 2-bromoethylphosphoryl dichloride and then reacting with a predetermined tertiary amine. (Meth) acrylic acid ester A thus obtained
Is preferably purified by a known method such as recrystallization before being subjected to polymerization.

Examples of the itaconic acid diester B include di- (2-hydroxyethyl) itaconate and di- (2-hydroxyethyl) itaconate.
(2-hydroxyethoxyethyl) itaconate, di (triethyleneglycol) itaconate, di (ethyleneglycol) itaconate, di- (2-hydroxypropyl) itaconate, di- (4-hydroxybutyl)
Examples thereof include itaconate and diglyceroyl itaconate. Such itaconic acid diester B is
Excellent solubility with the (meth) acrylic ester A,
High water content can be imparted to the polymer.

To prepare the itaconic acid diester B, for example, itaconic acid and the corresponding mono- or polyethylene glycol, propylene glycol, 1,4-butanediol or diol such as glycerin are esterified in the presence of an acid catalyst. It can be prepared by a known method such as a chemical reaction.

When the (meth) acrylic acid ester A and the itaconic acid diester B are copolymerized, the charging ratio is 1: 0.1 to 99, and particularly 1: 0.2 to the weight ratio.
It is preferably 90. The itaconic acid diester B
If the charging ratio exceeds 99% by weight, the antifouling property decreases, while if less than 0.1% by weight, the strength decreases, which is not preferable.

In the hydrous soft contact lens of the present invention, the (meth) acrylic acid ester A and the itaconic acid diester B, which are essential components, are further copolymerizable with a vinyl monomer and / or a crosslinkable polyfunctional monomer. It can also be contained as a polymerization component.

Examples of the copolymerizable vinyl monomer include styrene, methylstyrene, methyl nucleus-substituted styrene, chloro nucleus-substituted styrene, methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth).
Acrylate, (meth) acrylic acid, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2
-Hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyl propionate, vinyl pivalate, methyl vinyl ether,
Examples thereof include ethyl vinyl ether, n-butyl vinyl ether, diethyl itaconate and di-n-butyl itaconate. The copolymerizable vinyl monomer can control the water content, mechanical strength, and the like of the water-containing soft contact lens.

Further, as the crosslinkable polyfunctional monomer,
Allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, divinylbenzene, diallyl phthalate, diethylene glycol bisallyl carbonate, methylenebisacrylamide, triallyl trimellitate, triallyl cyanurate, divinyl adipate, etc. may be mentioned. The crosslinkable polyfunctional monomer can improve the heat resistance, processability, shape stability and the like of the hydrous soft contact lens.

When the copolymerizable vinyl monomer and / or the crosslinkable polyfunctional monomer is used as a polymerization component for copolymerization, the charged amount is 100 parts by weight of the (meth) acrylic acid ester A and the itaconic acid diester B. On the other hand, 2000 to 0.1 parts by weight is preferable, and 100 is particularly preferable.
0 to 1 part by weight is desirable. When the charged amount exceeds 2000 parts by weight, the water content and heat resistance of the resulting hydrous soft contact lens are remarkably lowered, while when it is less than 1 part by weight, the effect of the copolymerization is not sufficient, which is not preferable.

The polymer constituting the hydrous soft contact lens of the present invention is a method of substituting each of the above-mentioned polymerization components with an inert gas such as nitrogen, helium or argon in the presence of a polymerization initiator or polymerizing in an atmosphere. Can be prepared by Specifically, in order to polymerize to obtain a water-containing soft contact lens, the polymerization component and the polymerization initiator are poured into a desired shape made of metal, glass, or plastic, for example, a test tube, a lens-shaped mold is sealed and heated. Alternatively, it can be polymerized by irradiation with light, and then, for example, a desired soft contact lens can be produced by a method such as cutting and polishing the obtained polymer to form a lens and hydrating and swelling. It can be obtained by a method of directly forming a lens by a mold polymerization method, a method of casting while irradiating with light, or the like.

The above-mentioned polymerization initiator is not particularly limited as long as it is an ordinary radical polymerization initiator, but for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethyl hexanoate, Preferable examples include t-butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobis-2,4-dimethylvaleronitrile, benzoin methyl ether, and benzoin ethyl ether.

The charged amount of the above-mentioned polymerization initiator is the polymerization component 1
It is preferably 10 parts by weight or less, especially 5
Less than or equal to parts by weight is desirable. The polymerization temperature varies depending on the type of the polymerization initiator, but is preferably 20 to 140 ° C., and the polymerization time is preferably 6 to 120 hours. Furthermore, in the above-mentioned polymerization, a coloring agent such as a dye, an ultraviolet absorber, or a monomer having such a function may be added.

The water content of the hydrous soft contact lens of the present invention is preferably 10 to 80%. When the water content is less than 10%, the wearing feeling deteriorates, and when it exceeds 80%, the strength decreases, which is not preferable.

[0024]

The hydrous soft contact lens of the present invention contains a (meth) acrylic acid ester A having a phospholipid-like polar group and an itaconic acid diester B having a hydroxyl group, and thus has a high water content and a high oxygen content. It is transparent and can be worn on the eyes. Furthermore, since adhesion and deposition of stains such as proteins and lipids can be suppressed, lens denaturation prevention and eye safety can be improved.

[0025]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

[0026]

Example 1 2-methacryloyloxyethyl-2'-
9 g of (trimethylammonio) ethyl phosphate,
10 g of di- (2-hydroxyethyl) itaconate,
A mixture consisting of 1 g of ethylene glycol dimethacrylate and 0.02 g of t-butylperoxypivalate was injected into a test tube-shaped glass mold, and the system was sufficiently deaerated with nitrogen, and the mold was sealed and then heated. Polymerized. For heating, the temperature was raised to 40 to 120 ° C. in a constant temperature chamber over 50 hours, and after completion of the polymerization, a colorless cured product was taken out from the mold. The obtained cured product is cut and polished by an ordinary processing method to obtain a contact lens and a thickness of 13 mm × 0.2 mm.
A test piece having a shape was prepared, and the water content, oxygen permeability, and stain resistance were measured by the following methods. The measurement results are shown in Table 1.

Moisture content: After being immersed in 0.9% physiological saline and swollen, the water content was determined by weight change. Moisture content (% by weight) = [ (W1-W2) / W1 ] x 100 W1: Weight when saturated water content W2: Weight when dehydrating and drying lens Oxygen permeability coefficient; Seikaken film oxygen permeation meter (Rika Seiki Kogyo) (Trade name, "K-316IPI type" manufactured by Co., Ltd.)
Was measured at 35 ° C. in 0.9% physiological saline.

Antifouling property: After immersing the contact lens in a physiological saline solution containing 0.39% by weight of albumin, 0.17% by weight of lysozyme and 0.105% by weight of globulin at 35 ° C. for 2 weeks, After washing with physiological saline, proteins were separated from the contact lenses with a surfactant.
A reagent for protein quantification was injected into the separated solution, and the amount of protein adsorbed on the contact lens was measured.

[0029]

Examples 2 to 8 and Comparative Examples 1 and 2 A contact lens and a test piece were prepared in accordance with Example 1 except that the polymerization components were changed to have the compositions and blending ratios shown in Table 1, and each measurement was performed. went. The results are shown in Table 1.

[0030]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08F 299/02 C08F 299/02 (72) Inventor Nobuo Nakabayashi 5-6-20 Koganehara, Matsudo City, Chiba Prefecture (72) Invention Kazuhiko Ishihara 6-5-9-201, 6-5-9-201, Kamimizumoto, Kodaira-shi, Tokyo (56) Reference JP-A-6-43400 (JP, A) JP-A-6-313865 (JP, A) JP-A-9-20814 (JP, A) JP 5-107511 (JP, A) JP 6-43401 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02C 7/04

Claims (2)

(57) [Claims] 1. A polymer obtained by copolymerizing a polymerization component containing a (meth) acrylic acid ester represented by the following general formula 1 and an itaconic acid diester represented by the following general formula 2. A unique hydrous soft contact lens. [Chemical 1] [Chemical 2] 2. The hydrous soft contact lens according to claim 1, wherein the polymerization component further contains a copolymerizable vinyl monomer and / or a crosslinkable polyfunctional monomer.