JPH05107511A - Soft contact lens with high water content - Google Patents

Abstract

PURPOSE:To supply oxygen necessary for cornea physiology and to improve antifouling property and mechanical strength of a lens so that the lens can be continuously mounted for a long time by forming the lens from a resin containing a compd. having a phospholipid-like structure expressed by specified formula as the structural component. CONSTITUTION:The lens consists of a resin containing a compd. having a phospholipid-like structure expressed by formula I as the structural component. In formula I, X is expressed by formulae II, III, etc., R1 is hydrogen atom or methyl group, Y is expressed by formula IV, V, etc., n is an integer 1-20, and R2-R4 are same or different groups of alkyl groups or hydroxyalkyl groups having 1-8 carbon number. Polymers with n>20 is not preferable since hydrophilicity largely decreases. R2-R4 are alkyl groups of 1-8 carbon number, and if the carbon number exceeds 8, it is not preferable since hydrophilicity decreases or polymerizing property of monomers decreases. Thereby, antifouling property and mechanical strength of the lens can be improved so that the lens can be continuously mounted for a long time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly water-containing soft contact lens which has a high water content, is excellent in transparency, and can prevent the adhesion of dirt.

[0002]

2. Description of the Related Art A highly hydrous soft contact lens is worn on the eye as compared with a non-hydrous hard contact lens containing methyl methacrylate, siloxanyl alkyl methacrylate (Japanese Patent Publication No. 52-33502), etc. as a main monomer component. The feature is that there is little discomfort when doing and it is excellent in wearing feeling. For hydrous soft contact lenses,
When 2-hydroxyethyl methacrylate was the main component, the water content was low, so the amount of oxygen supplied to the eye was small, and the feeling of wearing was insufficient. Therefore, recently, in order to increase the water content, a contact lens has been proposed in which N-vinylpyrrolidone is copolymerized with methyl methacrylate, 2-hydroxyethyl methacrylate or methacrylic acid. However, the contact lens has drawbacks that stains are more likely to adhere to the contact lens, its strength is reduced, and further yellowing occurs when heat treatment for sterilization is repeated.

[0003]

An object of the present invention is to provide a high water content soft contact which has a high water content of 40% or more in water content, is excellent in mechanical strength and antifouling property, and can be worn continuously for a long period of time. To provide a lens.

[0004]

According to the present invention, the following general formula

[0005]

[Chemical 3]

R ₁ represents a hydrogen atom or a methyl group. Also Y is

[0007]

[Chemical 4]

Either of the above is shown. n shows the integer of 1-20. R ₂ , R ₃ and R ₄ are the same or different and represent an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group. The present invention provides a highly hydrous soft contact lens comprising a resin containing as a constituent a compound having a phospholipid-like structure represented by the formula (1).

The present invention will be specifically described below. In the highly hydrous soft contact lens of the present invention, the compound having a phospholipid-like structure used as an essential constituent component is the monomer represented by the general formula (1). n is represented by an integer of 1 to 20, and the polymer obtained when n is 20 or more is not preferable because the hydrophilicity is remarkably lowered. Also R
_{In 2 to} R ₄ , the number of carbon atoms of the alkyl group is an integer of 1 to 8, and if it exceeds 8, the hydrophilicity is remarkably lowered and the polymerizability of the monomer is lowered, so that it becomes unsuitable for use.

As the monomer represented by the general formula (1), 2- (methacryloyloxy) ethyl 2'-
(Trimethylammonio) ethyl phosphate, 3- (methacryloyloxy) propyl 2 ′-(trimethylammonio) ethyl phosphate, 4- (methacryloyloxy) butyl 2 ′-(trimethylammonio) ethyl phosphate,
5- (methacryloyloxy) pentyl 2 '-(trimethylammonio) ethyl phosphate, 6- (methacryloyloxy) ethyl 2'-(trimethylammonio) ethyl phosphate,

2- (methacryloyloxy) ethyl
2 '-(N-methyl-N, N-diethylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl
2 '-(N, N-dimethylethylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl 2'-
(Triethylammonio) ethyl phosphoric acid, 2- (methacryloyloxy) ethyl 2 '-(N, N-dimethylpropylammonio) ethyl phosphoric acid, 2- (methacryloyloxy) ethyl 2'-(N, N-dipropylN-methyl) Ammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl 2 '-(tributylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl 2'
-(Tricyclohexylammonio) ethyl phosphate, 2
-(Vinyloxy) ethyl 2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxy) 2'-
(Trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl 2 '-(trimethylammonio)
Ethyl phosphoric acid, 2- (vinylbenzoyloxy) ethyl 2 '-(trimethylammonio) ethyl phosphoric acid,

2- (styryloxy) ethyl 2'-
(Trimethylammonio) ethyl phosphoric acid, 2- (allyloxycarbonyl) ethyl 2 ′-(trimethylammonio) ethyl phosphoric acid, 2- (vinyloxycarbonyl)
Ethyl 2 '-(trimethylammonio) ethyl phosphate,
2- (acryloylamino) ethyl 2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonylamino) ethyl 2'-(trimethylammonio)
Ethyl phosphoric acid, (methacryloyloxy) methyloxy 2 '-(trimethylammonio) ethyl phosphoric acid, 2-
(Methacryloyloxy) ethyloxy 2 '-(trimethylammonio) ethylphosphoric acid, 3- (methacryloyloxy) propyloxy 2'-(trimethylammonio) ethylphosphoric acid, 2- (methacryloyloxy) isopropyloxy 2 '-(trimethylammonio) ) Ethyl phosphoric acid, 4- (methacryloyloxy) butyloxy 2 '-(trimethylammonio) ethyl phosphoric acid, etc. can be mentioned, and they can be used in a mixture of 1 type or 2 types, and the resulting contact lens has high water content. ,
Antifouling property and strength can be imparted.

To prepare the above monomers, for example,
By reacting hydroxyalkyl (meth) acrylate with 2-chloro-2-oxo-1,3,2-dioxaphosphorane in the presence of triethylamine and then reacting with trialkylamine, the target monomer can be easily prepared. Can be obtained. The product obtained is preferably purified by a known method such as recrystallization.

In the present invention, other than the above-mentioned monomers, copolymerizable monomers which can be used as raw material monomers, such as styrene,
α-methylstyrene, methyl nucleus-substituted styrene, chloro nucleus-substituted styrene, vinyl acetate, vinyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid, (meth ) Acrylamide, N, N-dimethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethyl vinyl ether, n-butyl vinyl ether, N-vinyl pyrrolidone, vinyl pyridine, diethyl itaconate, di-n-butyl itaconate, etc. Can be mentioned.

Further, for example, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diallyl. Polyfunctional monomers such as phthalate, diethylene glycol bisallyl carbonate, divinylbenzene, methylenebisacrylamide, triallyl trimellitate, triallyl cyanurate can also be used.

The monomer component represented by the general formula (1) can be used alone or as a mixture when used. In addition, in order to improve the heat resistance, processability, and shape stability of the resulting highly hydrous soft contact lens, it is preferable to use at least one or more polyfunctional monomers. In this case, the other monomer component is preferably used in an amount of 10,000 to 5 parts by weight, particularly 1000 to 100 parts by weight, relative to 100 parts by weight of the monomer having the phospholipid-like structure represented by the general formula (1). It is preferably used within the range of parts. When the other monomer component exceeds 10,000 parts by weight, the water content of the resulting water-containing soft contact lens,
Antifouling property decreases, and if less than 5 parts by weight, processability,
The shape stability is reduced.

In the present invention, in order to polymerize the above-mentioned raw material monomer to prepare a contact lens, it can be easily obtained by radical polymerization in the presence of the above radical polymerization initiator. Examples of the radical polymerization agent include benzoyl peroxide, lauroyl peroxide, diisopropyloxydicarbonate, t-butylperoxypivalate-t-butylperoxydiisobutyrate, azobisisobutyronitrile, azobis-2,4-dimethylvalero. A thermal polymerization initiator such as nitrile and a photopolymerization initiator such as benzoin methyl ether or benzoin ethyl ether can be preferably used. The amount of the radical polymerization initiator used is preferably 10 parts by weight or less based on 100 parts by weight of the raw material monomer,
It is more preferably 5 parts by weight or less.

In order to carry out the radical polymerization, it is preferable that the polymerization system is replaced with an inert gas such as nitrogen, carbon dioxide, helium or the like or under an atmosphere. The polymerization conditions are
In thermal polymerization, the polymerization temperature is in the range of 20 to 140 ° C., and the polymerization time is about 6 to 120 hours. UV light in photopolymerization,
It can be performed by irradiating with visible light for 1 minute to 20 hours. It is also possible to carry out thermal polymerization and photopolymerization in combination, if necessary.

Further, in the present invention, if necessary, a colorant such as a dye and an additive such as an ultraviolet absorber may be added to the raw material monomer. To produce the hydrous contact lens of the present invention, based on the radical polymerization conditions, for example, the raw material monomers are copolymerized in a suitable container such as a test tube to obtain a round bar or block, and then cut. , A method of machining such as polishing, a method of injecting the raw material monomer and a polymerization initiator into a desired mold, a method of directly forming a contact lens by template polymerization, a method of casting while performing heating or light irradiation, or It can be obtained by a method in which a polymer is produced in advance by a radical polymerization method or the like, then the polymer is dissolved in an appropriate solvent, and the solvent is removed by a casting method.

The water content of the high water content soft contact lens of the present invention is preferably 30% or more, particularly preferably 60% or more. When the water content is less than 30%, the cornea is affected, which is not preferable.

[0021]

The highly water-containing soft contact lens of the present invention is a contact lens obtained by polymerizing a raw material monomer containing a monomer having a phospholipid-like structure having a specific structure, and has a high water content and a corneal physiology. It can supply necessary and sufficient oxygen and is also excellent in preventing dirt from adhering to proteins and lipids.

[0022]

The present invention will be described in more detail below, but the present invention is not limited thereto. Example 1 Raw material monomers shown in Table 1, that is, 20 parts by weight of 2- (methacryloyloxy) ethyl 2 '-(trimethylammonio) ethyl phosphate, 80 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of allyl methacrylate, azobis 0.2 parts by weight of isobutyronitrile was poured into a test tubular glass mold, and after nitrogen substitution and deaeration in the system were repeated, the system was sealed and heat-cured. Heating is 50-100 in a constant temperature bath.
The temperature was raised to 50 ° C. over 50 hours. When the cured product was taken out of the mold after the completion of the polymerization, the obtained polymer was colorless and transparent. By the usual processing method for the obtained polymer,
Cutting and polishing were performed to prepare a test piece having a predetermined shape, and the following physical properties were evaluated. The results are shown in Table 2. (1) Moisture content 0.9% by weight After immersing in physiological saline to make a saturated water content, the weight was measured and calculated by the following formula.

Moisture content (% by weight) = (W ₁ −W ₂ ) / W ₁ × 100 W ₁ : Weight at saturated water content W ₂ : Initial film weight (2) Oxygen permeability coefficient Using 35 ℃, 0.
The oxygen permeation coefficient in 9 wt% saline was measured. (3) Tensile strength An array-shaped flat plate with a constricted center was used as a test piece, and the temperature was 20 ° C.
It was immersed in 0.9% by weight of physiological saline to bring it to a saturated water content state, and then tested at a pulling speed of 60 mm / min. (4) Antifouling property Albumin 0.39% (w / v), lysozyme 0.17% (w / v)
v), immersing the contact lens in a physiological saline solution containing 0.105% γ-globulin (w / v) (2 weeks, 35 ° C)
Then, it was washed with physiological saline, the protein was peeled from the contact lens with a surfactant, a reagent for protein quantification was injected into the solution, and the amount of protein adsorbed on the contact lens was measured.

Examples 2 to 10 Polymerization was carried out in the same manner as in Example 1 except that the raw material monomers shown in Table 1 were used, and the physical properties were measured. The results are shown in Table 2. Comparative Examples 1 to 3 Polymerization was performed in the same manner as in Example 1 except that the raw material monomers shown in Table 1 were used, and the physical properties were measured. The results are shown in Table 2.

[0025]

[Table 1] The abbreviations in the table indicate the following compounds.

HEMA: 2-hydroxyethyl methacrylate METMAEP: 2- (methacryloyloxy) ethyl 2 '-(trimethylammonio) ethyl phosphate DEGMA: diethylene glycol dimethacrylate AMA: allyl methacrylate MMA: methyl methacrylate METMAEP: 3- (methacryloyloxy) Propyl 2 '-(trimethylammonio) ethyl phosphate METEAEP: 2- (methacryloyloxy) ethyl 2'-(triethylammonio) ethyl phosphate NVP: N-vinylpyrrolidone

[0027]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinji Nakata 2-26-2 Kasuga, Tsukuba, Ibaraki Prefecture (72) Inventor Takeo Matsumoto 2-14-9, East, Tsukuba, Ibaraki Prefecture (72) Inventor Yasumi Koinuma Tsukuba, Ibaraki Prefecture 32-16-1-102 Higashiarai, Ichi

Claims (1)

[Claims] 1. A general formula: R ₁ represents a hydrogen atom or a methyl group. Also, Y is Indicates either n shows the integer of 1-20. R ₂ , R ₃ and R ₄ are the same or different and represent an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group. ) A highly hydrous soft contact lens comprising a resin containing a compound having a phospholipid-like structure represented by the formula (1) as a constituent.