JPH10177152A - Moisture-containing soft contact lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-containing soft contact lens that has a high moisture content and high oxygen permeability, is safely produced and used, is capable of suppressing the adhesion of stains, etc., and maintains the strength to some extent. SOLUTION: This soft contact lens contains a polymerized material obtd. by polymerizing a raw material contg. 1 to 70wt.% polymer (A) contg. the phosphoryl choline-contg. (meth)acrylate expressed by the formula (R<1> : H, CH2 , n=1 to 10) as a constitutional unit and 99 to 39wt.% vinyl monomer (B), which is liquid at ordinary temp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrous soft contact lens. More specifically, the present invention relates to a water-containing soft contact lens excellent in water content, oxygen permeability, antifouling property and mechanical strength.

[0002]

2. Description of the Related Art A water-containing soft contact lens is compared with a non-water-containing hard contact lens containing a monomer such as methyl methacrylate or siloxanyl alkyl methacrylate (Japanese Patent Publication No. 52-23502).
It is known that it has a feeling of being worn easily on the eyes and having an excellent feeling of wearing, that is, a state without discomfort when worn on the eyes. Generally, 2-hydroxyethyl methacrylate (hereinafter abbreviated as "HEMA") is used as a main raw material as a hydrous soft contact lens, and as a hydrous soft contact lens, it has excellent mechanical strength and workability. There are features. However, since these conventional soft contact lenses have a low water content of 35% or less, they are not sufficient for long-time continuous wearing. Therefore, in order to improve this, it has been proposed to increase the water content of the lens material to obtain a water-containing soft contact lens having a more comfortable wearing feeling. For example, a highly water-containing soft contact lens made of a polymer obtained by copolymerizing methyl methacrylate, 2-hydroxyethyl methacrylate, or the like with N-vinylpyrrolidone and methacrylic acid as copolymer components has been proposed (Japanese Patent Publication No. Sho 54). -4269).

On the other hand, a high water content gives an excellent feeling of wearing. However, in a high water content soft contact lens using N-vinylpyrrolidone and methacrylic acid, dirt easily adheres, strength is reduced, and yellowness due to repeated sterilization is reduced. Various drawbacks such as strangeness occur.

In all cases, the hydrous soft contact lenses generally have disadvantages such as adhesion of proteins and lipids, hygiene problems such as propagation of bacteria, and decrease in mechanical strength due to high water content. In order to solve these problems, Japanese Patent Application Laid-Open No. Hei 5-107511 discloses a contact lens mainly composed of a (meth) acrylate monomer containing a phosphorylcholine group for the purpose of preventing adhesion of dirt. However, the phosphorylcholine group-containing (meth) acrylate monomer has a problem that heat generation at the time of polymerization is large and it is difficult to control the polymerization, resulting in a decrease in mechanical strength of the lens.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-containing material having a high water content and high oxygen permeability, which can be manufactured and used safely, and which can suppress the adhesion of dirt and the like, and has a certain strength. It is to provide a soft contact lens.

[0006]

According to the present invention, the present invention is represented by the following general formula (1), wherein R ¹ represents a hydrogen atom or a methyl group, and n represents a number of 1 to 10. A raw material containing 1 to 70% by weight of a polymer (A) containing a phosphorylcholine group-containing (meth) acrylic acid ester as a constituent unit and 99 to 30% by weight of a vinyl monomer (B) liquid at room temperature is polymerized. The present invention provides a hydrous soft contact lens containing the polymer material obtained by the above method.

[0007]

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The water-containing soft contact lens of the present invention comprises a polymer (A) containing a specific phosphorylcholine group-containing (meth) acrylate represented by the above formula (1) as a constitutional unit, It includes a polymerized material obtained by polymerizing a raw material containing a vinyl monomer which is liquid at room temperature.
The physical properties of the water-containing soft contact lens of the present invention are preferably 40 to 80% by weight, particularly 40 to 75% by weight, and oxygen permeability of 8 to 50 × 10 ⁻¹¹ ml / cm ² · sec.
・ MmHg, especially 10 to 40 × 10 ^-11 ml / cm ²・ s
ec · mmHg is desirable. In the above formula (1), when n exceeds 10, the strength and processability of the obtained polymer material decrease.

The specific phosphorylcholine group-containing (meth) acrylic acid ester monomer (hereinafter abbreviated as “PC monomer”) used in the present invention includes, for example, 2-PC
(Meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxypropyl-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 and the like are mentioned. Can be.

The polymer (A) used as a raw material in the present invention may be a polymer of one or more kinds of PC monomers. May be a copolymer with the above monomer. Examples of other copolymerizable monomers include (meth) acrylic esters other than PC monomers, (meth) acrylic amides, and styrenes. These other copolymerizable monomers can be used so as to be 95% by weight or less in the polymer (A). The blending ratio of the polymer (A) in the raw materials is 1 to 70% by weight, preferably 5 to 50% by weight. If it exceeds 70% by weight, the resulting polymer material cannot be sufficiently imparted with hydrophilicity and biocompatibility. If it is less than 1% by weight, the effect of the polymer (A) cannot be expected. The polymer (A) is a vinyl monomer (B) which is liquid at room temperature as described below.
It is preferable to carry out the polymerization in a state in which the vinyl monomer (B) is dissolved. Therefore, the blending ratio is particularly preferably equal to or less than the blending amount of the vinyl monomer (B). The number average molecular weight of the polymer (A) is 20
The range of 00 to 200,000 is desirable. The polymer (A) can impart high water content, high oxygen permeability and antifouling property to the obtained contact lens.

To prepare the polymer (A), for example, P
Only a C monomer, or a PC monomer and another monomer, by a known radical polymerization method, preferably a solution polymerization method, etc.
It can be prepared by radical polymerization in the presence or absence of a chain transfer agent.

The vinyl monomer (B) at room temperature which is used as a raw material in the present invention is, for example, styrene, nucleus-substituted styrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid. -N-butyl, -N, N-dimethyl (meth) acrylamide (meth) acrylate, 2-hydroxyethyl (meth) acrylate, fluoroalkyl (meth) acrylate, (meth) acrylate
Silylalkyl acrylate, N-vinylpyrrolidone, N
-Vinylpyridine and the like, and can be used alone or as a mixture when used. Preferably, by using at least one water-soluble vinyl monomer, the water content, mechanical strength, and the like of the obtained contact lens can be adjusted. The compounding ratio of the vinyl monomer (B) in the raw material is 99 to 30% by weight, preferably 95 to 50% by weight, and particularly preferably the compounding amount of the polymer (A) or more.

In the present invention, in order to further improve the heat resistance, processability, shape stability and the like of the obtained contact lens, if necessary, for example, (meth)
Allyl acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate
Crosslinkable polyfunctional monomers such as acrylates, 1,4-butanediol di (meth) acrylate, divinylbenzene, diallyl phthalate, and divinyl adipate can also be used. The mixing ratio of the raw materials that can be used as required is preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the raw materials.

In the present invention, to polymerize the raw materials, nitrogen, helium,
It can be carried out under a substitution or atmosphere with an inert gas such as argon. Specifically, the raw material and the polymerization initiator are injected and sealed in a desired shape such as metal, glass, plastic, or the like, for example, a test tube, a lens-shaped mold, or the like, and heated or irradiated with light. Can be. The polymerized material obtained by this polymerization is formed into a lens by cutting, polishing or the like, and a water-containing soft contact lens can be produced by a known method of swelling by hydration. The lens can also be formed by a method of directly forming a lens by a known casting polymerization method, a method of performing casting while irradiating light, or the like. Upon polymerization, a coloring agent such as a dye,
An ultraviolet absorber or a monomer having these functions may be added.

Examples of the radical polymerization initiator include, but are not limited to, benzoyl peroxide, diisopropylperoxycarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butyl. Preferred are peroxydiisobutyrate, lauroyl peroxide, azobisisobutyronitrile (hereinafter abbreviated as “AIBN”), azobis-2,4-dimethylvaleronitrile, benzoin methyl ether, benzoin ethyl ether and the like. The amount of the polymerization initiator to be charged is preferably 10% by weight or less, particularly preferably 5% by weight or less based on 100 parts by weight of the raw materials.

The polymerization temperature at the time of polymerizing the raw materials is as follows:
Although it depends on the type of the polymerization initiator, the polymerization temperature is preferably from 20 to 140C, and the polymerization time is preferably from 6 to 120 hours.

[0017]

The water-containing soft contact lens of the present invention comprises a raw material comprising a polymer (A) containing a phosphorylcholine group-containing (meth) acrylate as a constitutional unit and a vinyl monomer (B) as essential components. Since it contains a polymerized polymer material, it has a high water content and high oxygen permeability, and is also excellent in wearing feeling. Furthermore, adhesion of dirt such as proteins and lipids can be suppressed, uniform production of the lens is possible, and safety in use can be ensured.

[0018]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

Synthesis Example 1 20 g (0.072 mol) of 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate (hereinafter abbreviated as “MPC”), and AIBN 0.2
g and 80 g of ethanol, a stirrer,
200 ml 4 equipped with thermometer, reflux condenser and nitrogen inlet tube
The mixture was charged in a one-necked flask and polymerized by heating at 50 ° C. for 10 hours in a thermostat. After the polymerization, the polymerization solution was poured into a large amount of diisopropyl ether to precipitate a polymer, which was separated by filtration and dried in vacuo to obtain a white powder polymer (A-1). The yield of the polymer (A-1) was 92%, and the number average molecular weight measured by GPC (using polyethylene glycol as a standard) was 55,800.

Synthesis Example 2 The composition of the mixed solution was changed to 10 g (0.036 mol) of MPC.
, HEMA10g (0.078mol), AIBN
Polymerization was performed in the same manner as in Synthesis Example 1 except that 0.2 g and 80 g of ethanol were used, and a polymer (A-2) as a white powder was obtained.
I got The yield of the polymer (A-2) was 85%, and the number average molecular weight measured in the same manner as in Example 1 was 63,700. The weight ratio of the charged MPC and HEMA was 50/50.
In contrast, the weight ratio of the copolymer was 50/50.

Synthesis Example 3 0.02 g of ethanediol as a chain transfer agent was added to the mixture.
Polymerization was carried out in the same manner as in Synthesis Example 1 except that was added, to obtain a white powder polymer (A-3). The yield of the polymer (A-3) was 74%, and the number average molecular weight measured in the same manner as in Example 1 was 28,500.

Example 1 A mixed solution comprising 4 g of the polymer (A-1) obtained in Synthesis Example 1, 16 g of 2-hydroxyethyl methacrylate, and 0.4 g of ethylene glycol di (meth) acrylate. Was poured into a test tubular glass mold, the system was purged with nitrogen, degassed, sealed, and then heated and polymerized. Heating is 30 ° C
For 10 hours, the temperature was raised to 30 to 80 ° C. over 24 hours,
After the polymerization, the cured product was removed from the mold. The cured product is cut and polished by a normal processing method, hydrated and swelled, and has a diameter of 13 m.
m, a hydrous soft contact lens having a thickness of 0.2 mm was prepared. The water content, oxygen permeability, tensile test and antifouling property of this contact lens were measured according to the following measuring methods. Table 1 shows the results.

1. Moisture content: The contact lens was immersed in physiological saline and determined by weight change before and after immersion (moisture content (%) = {(water content-dry weight) / water content} × 10
0). 2. Oxygen Permeability Coefficient: Measured in physiological saline at 35 ° C. using a film oxygen permeation measuring device manufactured by Seikaken Co., Ltd. (model 316). 3. Tensile test: manufactured by Yamaden Co., Ltd. (Model Leona RE-330
The contact lens was measured at a tensile speed of 1 mm / sec by applying a load of 20 g to the contact lens using the tensile tester of 5). 4. Antifouling property: containing 0.39% by weight of albumin, 0.17% by weight of lysodium and 0.105% by weight of globulin 3
After immersing the contact lens in physiological saline at 5 ° C. for 2 weeks, the contact lens was washed with physiological saline and the protein was separated from the contact lens with a surfactant. The separated proteins were injected with a reagent for protein quantification and quantified by UV measurement.

Examples 2 to 5 Except that the raw materials shown in Table 1 were used, water-containing soft contact lenses were prepared in the same manner as in Example 1, and various measurements were made. Table 1 shows the results.

Comparative Examples 1-4 A water-containing soft contact lens was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used, and various measurements were made. Table 2 shows the results.

From the results shown in Tables 1 and 2, it can be seen that the water-containing soft contact lens of the present invention has a higher water content, oxygen permeability and strength, a smaller amount of adsorbed protein and a better balance than the comparative example.

The symbols used in the table are as follows:
The unit of oxygen permeability is × 10 ⁻¹¹ ml / cm ² · sec.
mmHg. HEMA: 2-hydroxyethyl methacrylate (2-
Hydroxyethyl methacrylate), EGMA: ethylene glycol dimethacrylate, MA: methacrylic acid, NVP: N-vinylpyrrolidone, MPC: 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate.

[0028]

[Table 1]

[0029]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasumi Koinuma 32-16 Higashiarai, Tsukuba, Ibaraki Prefecture (72) Inventor Kiyoshi 27-1-1, Kasuga, Tsukuba, Ibaraki Prefecture (72) Inventor Norio Nakabayashi Matsudo, Chiba Prefecture (72) Inventor Kazuhiko Ishihara 3-16-37, Josuihoncho, Kodaira-shi, Tokyo

Claims (1)

[Claims] 1. A phosphorylcholine group-containing (meth) acrylate represented by the following general formula (1), wherein R ¹ represents a hydrogen atom or a methyl group, and n represents a number of 1 to 10. Containing a polymer material obtained by polymerizing a raw material containing 1 to 70% by weight of a polymer (A) containing as a structural unit and 99 to 30% by weight of a vinyl monomer (B) which is liquid at room temperature. Soft contact lenses. Embedded image