Contact lens monomer composition, polymer thereof, contact lens and method of making the same

Abstract

The present invention provides a contact lens monomer composition using a small molecular weight organosilicon compound, a polymer of the composition, and a contact lens using the polymer, which can produce a contact lens having excellent oxygen permeability, mechanical strength, transparency, durability, and wearing sensation. Specifically, a composition containing (A) a methacrylate monomer containing a phosphoryl choline group, (B) an itaconic acid diester monomer containing a siloxane group, (C) a specific hydrophilic monomer, (D) a (meth)acrylate containing a siloxane group, and (E) a specific crosslinking agent in specific proportions, a polymer thereof, and a contact lens using the polymer.

Description

Technical Field

[0001] This invention relates to a monomer composition for contact lenses, its polymer, contact lenses having the polymer and exhibiting good wearing comfort due to high transparency and durability, and a method for manufacturing the same. Background Technology

[0002] Traditional hydrogel contact lenses provide insufficient oxygen supply to the cornea, raising safety concerns during prolonged wear. To address these shortcomings and improve safety, silicone hydrogel contact lenses have been developed. However, a challenge exists in the manufacturing process of silicone hydrogel contact lenses: achieving a hydrophilic surface. Specifically, when using conventional methods for manufacturing soft contact lenses, such as the molding process using polypropylene molds, the silicone monomers in the raw material polymerize in an interfacially oriented state with the mold due to the hydrophobic nature of polypropylene. As a result, silicone polymer portions are present on the lens surface, reducing its hydrophilicity.

[0003] In the absence of sufficient hydrophilicity on the surface of soft contact lenses, lipid and protein adhesion can lead to lens opacity and eye diseases. Therefore, for silicone hydrogel contact lenses with insufficient hydrophilicity, a coating is formed on the surface after lens formation using plasma gas and hydrophilic polymers, and a surface-grafted polymer is formed using hydrophilic monomers. However, compared to the absence of surface treatment, these surface treatments require a large number of devices and processes for manufacturing soft contact lenses, making them less desirable for mass production.

[0004] Patent Document 1 discloses a method for manufacturing lenses from a silicone hydrogel composition comprising a silicone monomer having a (meth)acryloyl group, a hydrophilic monomer having a vinyl group, a crosslinking monomer, and a polymerization initiator with a 10-hour half-life temperature of 70°C to 100°C. Patent Document 1 aims to improve the hydrophilicity of the lens surface by utilizing the differences in the polymerizability of the raw material monomers, but it still fails to achieve satisfactory hydrophilicity.

[0005] Patent Document 2 discloses a silicone hydrogel contact lens, which is obtained from a composition comprising 2-methacryloyloxyethylphosphorylcholine (MPC), a dimethacryloyl silicone macromonomer, and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane. However, although the contact lens of Patent Document 2 has improved hydrophilicity of the lens surface, it suffers from reduced oxygen permeability.

[0006] Patent documents 3 and 4 disclose a composition comprising a siloxane-containing itaconic acid diester monomer with a primary hydroxyl group and MPC, and describe that the polymer can be used in contact lenses. The contact lens of patent document 3 achieves good results in terms of hydrophilicity and oxygen permeability of the lens surface, while the contact lens of patent document 4 also achieves good results in terms of elongation at break and peelability.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2015 / 001811

[0010] Patent Document 2: Japanese Patent Application Publication No. 2014-089477

[0011] Patent Document 3: International Publication No. 2018 / 135421

[0012] Patent Document 4: International Publication No. 2020 / 054711 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] However, while the contact lenses in Patent Documents 3 and 4 exhibit good hydrophilicity and oxygen permeability on the lens surface, they contain a large amount of highly hydrophobic silicone compounds. Therefore, when manufacturing thick contact lenses for high-prescription vision correction, transparency may be reduced. Methods using silicone compounds with lower molecular weights can be cited to improve transparency, but even with these methods alone, the wearing comfort may decrease due to reduced oxygen permeability and mechanical strength. Furthermore, it is known that silicone hydrogel contact lenses are generally susceptible to hydrolysis, and their mechanical strength decreases with prolonged storage. Thick contact lenses are particularly vulnerable to this effect, and the wearing comfort of contact lenses may deteriorate after long-term storage.

[0015] Therefore, the objective of this invention is to provide a monomer composition for contact lenses using an organosilicon compound with a low molecular weight, which can produce contact lenses with good oxygen permeability, mechanical strength, transparency, and durability, and excellent wearing comfort. It also aims to provide a polymer for contact lenses formed by polymerizing this composition. Furthermore, it aims to provide a contact lens using this polymer and a method for manufacturing the same.

[0016] Methods for solving problems

[0017] The inventors conducted in-depth research and found that by using a monomer composition containing two hydrophilic monomers, a siloxane-containing itaconic acid diester monomer, a siloxane-containing organosilicon monomer of a specific molecular weight, and a specific crosslinking agent as a raw material for contact lenses, and by making these monomers in a specific composition ratio, all the above-mentioned objectives can be achieved, thus completing the present invention.

[0018] That is, according to the present invention, a monomer composition for contact lenses is provided, the composition comprising: (A) a methacrylate monomer containing a phosphorylcholine group as shown in formula (1); (B) a siloxane-containing itaconic acid diester monomer as shown in formula (2); (C) one or more hydrophilic monomers selected from the group consisting of N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether; (D) a siloxane-containing (meth)acrylate as shown in formula (3); and (E) a ethylene glycol monomethacrylate monomer selected from the group consisting of N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether; One or more crosslinking agents from the group consisting of alcohol esters, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and siloxane-containing dimethacrylates as shown in formula (4), wherein, relative to 100% by mass of the total of components (A) to (E) in the composition, component (A) is present in a proportion of 5 to 25% by mass, component (B) in a proportion of 5 to 30% by mass, component (C) in a proportion of 15 to 45% by mass, component (D) in a proportion of 15 to 40% by mass, and component (E) in a proportion of 0.2 to 2.5% by mass.

[0019] [Chemical Formula 1]

[0020]

[0021] [Chemical Formula 2]

[0022]

[0023] [Chemical Formula 3]

[0024]

[0025] In equation (3), R 1 It can be hydrogen or methyl. m is 0 or 1, n is 3 to 9.

[0026] [Chemical Formula 4]

[0027]

[0028] [In equation (4), p and r are 0 or 1, and q is 5 to 20.]

[0029] In addition, according to another aspect of the present invention, a polymer of the monomer composition for contact lenses of the present invention is provided, namely, a polymer for contact lenses.

[0030] Furthermore, according to another aspect of the present invention, a contact lens having a hydrate of the polymer for contact lenses of the present invention and a method for manufacturing the same are provided.

[0031] Invention Effects

[0032] The monomer composition for contact lenses of the present invention contains components (A) to (E) as essential components in a specific ratio. Therefore, by using its polymer, contact lenses with high transparency and durability, and good wearing comfort, can be obtained. Furthermore, the contact lens manufacturing method according to the present invention can manufacture contact lenses with the above-mentioned excellent properties. The contact lens of the present invention is a silicone hydrogel soft contact lens. Detailed Implementation

[0033] The present invention will now be described in further detail.

[0034] The monomer composition for contact lenses of the present invention is a composition containing the following components in a specific proportion: (A) a phosphorylcholine-containing methacrylate monomer as shown in formula (1) [(A) component]; (B) a siloxane-containing itaconic acid diester monomer as shown in formula (2) [(B) component]; (C) one or more hydrophilic monomers selected from the group consisting of N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether [(C) component]; (D) a siloxane-containing (meth)acrylate as shown in formula (3) [(D) component]; and (E) one or more crosslinking agents selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and siloxane-containing dimethacrylate as shown in formula (4) [(E) component]. Hereinafter, the monomer composition for contact lenses of the present invention will sometimes be referred to simply as the composition of the present invention.

[0035] The compositions of the present invention may also contain a specific amount of one or more components selected from (F) monomers other than (A) to (E) above [(F) component] and (G) solvents having hydroxyl groups [(G) component]. In addition, the compositions of the present invention may also contain (H) polymerization initiator [(H) component].

[0036] The composition of the present invention is a homogeneous transparent liquid containing the above-mentioned components (A) to (E) as essential components and components (F) to (H) as optional components.

[0037] (A) Ingredients: Methacrylate monomers containing phosphorylcholine groups

[0038] Component (A) is a methacrylate monomer containing a phosphorylcholine group as shown in formula (1), specifically 2-methacryloyloxyethyl phosphorylcholine (MPC). By containing component (A), the surface of contact lenses made from the polymer of the composition of the present invention can be made to have good hydrophilicity and lubricity.

[0039] [Chemical Formula 5]

[0040]

[0041] Of 100% by mass of the total number of components (A) to (E) in the composition of the present invention, the content of component (A) is 5 to 25% by mass, preferably 8 to 20% by mass, and more preferably 8 to 18% by mass. At less than 5% by mass, sufficient hydrophilicity of the contact lens surface cannot be obtained. At more than 25% by mass, component (A) is difficult to dissolve in the composition, and may also reduce the oxygen permeability of the contact lens.

[0042] (B) Ingredients: Itaconic acid diester containing siloxane alkyl groups

[0043] (B) is a siloxane-containing itaconic acid diester monomer as shown in formula (2). (B) is the component that enables the contact lenses of the present invention to have good oxygen permeability and transparency.

[0044] [Chemical Formula 6]

[0045]

[0046] Relative to 100% by mass of the total of components (A) to (E) in the composition of the present invention, the content of component (B) is 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 10 to 25% by mass. When it is less than 5% by mass, there is a possibility that component (A) is difficult to dissolve in the composition, and there is a possibility that the transparency of the contact lens is reduced. When it exceeds 30% by mass, there is a possibility that the mechanical strength of the contact lens is reduced.

[0047] (C) Component: Hydrophilic monomer

[0048] (C) is a hydrophilic monomer selected from the group consisting of N-vinylpyrrolidone, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. (C) is a component that imparts good mechanical strength and hydrophilicity to the surface of the contact lens of the present invention.

[0049] Specific examples of component (C) include N-vinylpyrrolidone, hydroxyethyl 2-(meth)acrylate, hydroxypropyl 2-(meth)acrylate, hydroxybutyl 4-(meth)acrylate, hydroxybutyl 2-(meth)acrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. Component (C) may be any one of these monomers or a mixture of two or more.

[0050] In this specification, “(metha)acrylate” and “(metha)acrylic ester” refer to “acrylate and / or methacrylate” and “acrylic ester and / or methacrylic ester”, respectively.

[0051] Of the total mass of components (A) to (E) in the composition of the present invention, the content of component (C) is 15 to 45% by mass, preferably 20 to 40% by mass, and more preferably 20 to 35% by mass. When it is less than 15% by mass, the hydrophilicity of the contact lens surface may be insufficient, and when it is more than 45% by mass, the mechanical strength of the contact lens may be reduced.

[0052] (D) Ingredients: (meth)acrylates containing siloxanes

[0053] (D) is a siloxane-containing (meth)acrylate as shown in formula (3). (D) is the component that makes the contact lenses of the present invention have good transparency.

[0054] [Chemical Formula 7]

[0055]

[0056] In equation (3), R 1 It can be hydrogen or methyl. m is 0 or 1, n is 3 to 9.

[0057] Relative to 100% by mass of the total of components (A) to (E) in the composition of the present invention, the content of component (D) is 15 to 40% by mass, preferably 15 to 35% by mass, and more preferably 20 to 35% by mass. When it is less than 15% by mass, the oxygen permeability of the contact lens may decrease, and when it is more than 40% by mass, the increase in the modulus of the contact lens during long-term storage may exceed the permissible range.

[0058] The siloxane-containing (meth)acrylates shown in formula (3) can be commercially available. Alternatively, they can be manufactured and used, for example, by the method disclosed in Japanese Patent Application Publication No. 2014-031338.

[0059] (E) Component: Crosslinking agent

[0060] (E) is a crosslinking agent selected from ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and siloxane-containing dimethacrylates as shown in formula (4). (E) is a component that enables the contact lenses of the present invention to have good oxygen permeability and transparency.

[0061] [Chemical Formula 8]

[0062]

[0063] [In equation (4), p and r are 0 or 1 respectively. q is 5 to 20.]

[0064] Relative to 100% by mass of the total amount of components (A) to (E) in the composition of the present invention, the content of component (E) is 0.2 to 2.5% by mass, preferably 0.2 to 2.2% by mass, more preferably 0.5 to 2.2% by mass. When it is less than 0.2% by mass, the transparency and oxygen permeability of the contact lens may be insufficient, and when it exceeds 2.5% by mass, the durability of the contact lens may be insufficient.

[0065] The content ratio of component (D) to component (E) by mass [(E) / (D)] is preferably 0.01 to 0.06, more preferably 0.01 to 0.04, and even more preferably 0.02 to 0.04. By setting this mass ratio to 0.01 to 0.06, the transparency and durability of the contact lenses of the present invention are likely to be improved.

[0066] (F) Components: Monomers other than (A) to (E)

[0067] Component (F) is a monomer other than (A) to (E). Component (F) is any component that can be formulated for the purpose of adjusting the physical properties of the contact lenses of the present invention.

[0068] Examples of components (F) include monomers such as N-vinylpiperidin-2-one, N-vinyl-ε-caprolactam, N-vinyl-3-methyl-2-caprolactam, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylamide, N-isopropylacrylamide, acrylmorpholine, N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinylformamide, (meth)acrylic acid, 2-methacryloyloxyethylsuccinic acid, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, butyl acrylate, methoxy polyethylene glycol methacrylate, (3-methacryloyloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, and (3-methacryloyloxypropyl)trimethoxysilane. In addition, examples of component (F) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, methylene bisacrylamide, allyl methacrylate, (2-allyloxy)ethyl methacrylate, 2-(2-ethyleneoxyethoxy)ethyl acrylate, 2-(2-ethyleneoxyethoxy)ethyl methacrylate, divinylbenzene, and other crosslinking agents (monomers). Component (F) can be any one of these or a mixture of two or more.

[0069] When component (F) is present, the amount of crosslinking agent is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the total amount of components (A) to (E) in the composition of the present invention. When component (F) contains the above-described crosslinking agent, the amount of crosslinking agent is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, relative to 100 parts by mass of the total amount of components (A) to (E). If the amount of component (F) exceeds 20 parts by mass, the transparency and durability of the contact lens may decrease.

[0070] (G) Components: Solvent

[0071] Component (G) is a solvent containing hydroxyl groups. Component (G) can be any component and can be formulated to improve the solubility of component (A) in the composition of the present invention. Specifically, by formulating component (G), the dissolution rate of component (A) in the composition of the present invention is faster and its dissolution becomes easier. Examples of component (G) include alcohols and carboxylic acids. Examples of alcohols include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, tert-pentanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, etc. Examples of carboxylic acids include glycolic acid, lactic acid, acetic acid, etc. Component (G) can be any one of these solvents or a mixture of two or more. Regarding the improvement of the dissolution rate of component (A) and the pH stability of the composition of the present invention, it is preferable to formulate one or more selected from ethanol, 1-propanol, 2-propanol, and 1-hexanol as component (G).

[0072] When component (G) is present, its content is not particularly limited, but it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of components (A) to (E) in the composition of the present invention. If the content of component (G) exceeds 30 parts by mass, the oxygen permeability and mechanical strength of the contact lens may decrease.

[0073] The composition of the present invention can also be a composition containing a (H) polymerization initiator [(H) component]. While care must be taken regarding the storage of the composition of the present invention when containing the (H) component, it has the advantage that the polymer for contact lenses of the present invention can be easily obtained with stable quality simply by heating the composition. As for the (H) component, there are no particular limitations; known thermal polymerization initiators and photopolymerization initiators can be used.

[0074] Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile, dimethyl 2,2-azobis(2-methylpropionate), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfide dihydrate, 2,2'-azobis(2-methylpropamidinium) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropamidinium] dihydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropamidinium) dihydrate, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Azo polymerization initiators such as bis(1-imino-1-pyrrolyl-2-methylpropane) dihydrochloride, 2,2'-azobis[2-methyl-N-{1,1-bis(hydroxymethyl)-2-hydroxyethyl}propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropamidinium) dihydrochloride, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and peroxide polymerization initiators such as benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, tert-butyl peroxyhexanoate, and 3,5,5-trimethylhexanoyl peroxide, etc. As component (H), any one of these thermal polymerization initiators can be blended, or two or more can be blended.

[0075] Examples of photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl benzoate, camphorquinone, and ethyl-4-(N,N-dimethylamino)benzoate. Examples of photopolymerization initiators listed under trade names include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850, Darocur 1173, and Darocur 2959. As component (H), any one of these photopolymerization initiators can be mixed, or two or more can be mixed.

[0076] When containing component (H), its content is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the total amount of components (A) to (E) in the composition of the present invention. If it is less than 0.1 parts by mass, the polymerizability of the monomers in the composition may be insufficient, and the advantages of compounding component (H) may not be obtained. If it exceeds 3 parts by mass, the extraction and removal of reaction decomposition products of component (H) may become insufficient when washing the polymer obtained by polymerization to manufacture contact lenses.

[0077] The method for manufacturing the composition of the present invention is not particularly limited. It can be manufactured by adding the components in any order or all at once into a stirring (mixing) apparatus and stirring and mixing at a temperature below 40°C until the components become homogeneous. However, in the case of the (H) component, in order to avoid initiating a polymerization reaction during mixing, if the (H) component is a thermal polymerization initiator, it is preferable to mix at a temperature below 40°C and at least 10°C lower than the 10-hour half-life temperature of the initiator. If the (H) component is a photopolymerization initiator, it is preferable to perform the mixing while shielding from light.

[0078] The composition of the present invention may contain components other than those described above, without hindering the purpose of the present invention. Other components include polymerizable ultraviolet absorbers and polymerizable pigments as colorants. By incorporating ultraviolet absorbers, the contact lenses of the present invention can reduce eye strain caused by ultraviolet radiation such as sunlight. Furthermore, by incorporating pigments, the contact lenses of the present invention can be made into colored contact lenses. The content of other components in the composition of the present invention is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, relative to the total amount of components (A) to (E) in the composition of the present invention (100 parts by mass).

[0079] Next, an embodiment of the method for manufacturing the polymer for contact lenses of the present invention will be described. Furthermore, the manufacturing method shown below is one embodiment for obtaining the polymer for contact lenses of the present invention, and the polymer for contact lenses of the present invention is not limited to the polymer obtained by this manufacturing method. Hereinafter, unless otherwise specified, "composition" refers to the composition of the present invention, and "polymer" refers to the polymer for contact lenses of the present invention.

[0080] The polymer is manufactured by using a mold with a hydrophobic surface, such as polypropylene, and filling the mold with the composition to polymerize it. In the case of a composition that does not contain component (H), the same polymerization initiator as component (H) is added to the composition in the same manner as component (H) and then filled into the mold.

[0081] When polymerization is carried out using a thermal polymerization initiator, the reaction is carried out at a temperature suitable for the thermal polymerization initiator contained, between 45 and 140°C, for at least 1 hour. When polymerization is carried out using a photopolymerization initiator, the reaction is carried out under ultraviolet light of a wavelength suitable for the photopolymerization initiator contained, at a concentration of 0.3 mW / cm². 2 The reaction was carried out under the above irradiance for at least 5 minutes. After polymerization, the polymer was removed from the mold.

[0082] The polymerization atmosphere is not particularly limited, but setting it to an inert gas atmosphere such as nitrogen or argon is preferred in terms of improving the polymerization rate. As a method of setting such an inert gas atmosphere, examples include venting an inert gas into the composition and making the composition filling site in the mold the atmosphere.

[0083] The pressure inside the mold can range from atmospheric pressure to slightly pressurized. When polymerization is carried out in an inert gas atmosphere, a gauge pressure of 1 kgf / cm² is preferred. 2 The following pressure.

[0084] The contact lens of the present invention is a silicone hydrogel contact lens, which is a hydrate of the aforementioned polymer. Here, hydrate refers to a polymer containing water and exhibiting a hydrogel morphology, which is the contact lens of the present invention, i.e., the silicone hydrogel contact lens of the present invention. Since the polymer contains unreacted substances, byproducts, and optionally (G) solvent, the polymer is purified by washing or the like before hydration.

[0085] In this specification, "organosilicon hydrogel" refers to a hydrogel having an organosilicon portion (siloxane bond) in a polymer. The compositions of the present invention contain siloxane-containing monomers, namely components (B) and (D), and therefore the polymer has an organosilicon portion, which can be hydrated (containing water) to form an organosilicon hydrogel.

[0086] Next, an embodiment of the method for manufacturing the contact lens of the present invention will be described. Furthermore, the manufacturing method described below is one embodiment for obtaining the contact lens of the present invention, and the contact lens of the present invention is not limited to the contact lens obtained by this manufacturing method. Hereinafter, unless otherwise specified, "contact lens" refers to the contact lens of the present invention.

[0087] The polymer removed from the mold is purified by washing it with a solvent to remove unreacted monomers and other unreacted substances and impurities. Examples of solvents that can be used include water, methanol, ethanol, 1-propanol, 2-propanol, or mixtures thereof. The washing process can be performed, for example, by immersing the polymer in the aforementioned alcohol at 10–40°C for 10 minutes to 5 hours, followed by immersion in water for 10 minutes to 5 hours. Alternatively, a wash of immersion in an aqueous alcohol with an alcohol concentration of 20–50 wt% for 10 minutes to 5 hours can be added between the alcohol wash and the water wash. Distilled water, ion-exchange water, RO water, or other purified water is preferred.

[0088] The polymer, purified through washing, is impregnated with physiological saline to hydrate it to a specified water content, thereby obtaining contact lenses. Borate-buffered saline or phosphate-buffered saline can be used as the physiological saline. These saline solutions are used in storage solutions for soft contact lenses, and therefore the polymer can also be impregnated with such solutions to hydrate it. Regarding hydration, the osmotic pressure of these saline solutions is preferably 250–400 mmol / kg.

[0089] Example

[0090] The present invention will be specifically described below through embodiments, but the present invention is not limited to these embodiments.

[0091] The following shows the components of the compositions constituting the Examples and Comparative Examples.

[0092] (A): Methacrylate monomers containing phosphorylcholine groups

[0093] MPC: (2-Methacryloxyethyl)phosphocholine

[0094] (B): Itaconic acid diester containing siloxane alkyl groups

[0095] •ETS: Compound of formula (2)

[0096] (C) Hydrophilic monomers

[0097] • NVP: N-vinylpyrrolidone

[0098] HEMA: 2-Hydroxyethyl methacrylate

[0099] HPMA: 2-Hydroxypropyl Methacrylate

[0100] HBMA: 2-Hydroxybutyl Methacrylate

[0101] ·EGMV: Ethylene glycol monovinyl ether

[0102] DEGMV: Diethylene glycol monovinyl ether

[0103] (D): Siloxane-containing methacrylates

[0104] ·mPDMS3-9: Compound (R) of formula (3) 1 (Mn=800, m=0, n=8, Mn=800)

[0105] (E) Crosslinking agent

[0106] EGDMA: Ethylene dimethacrylate

[0107] ·2EGDMA: Diethylene glycol dimethacrylate

[0108] ·3EGDMA: Triethylene Dimethacrylate

[0109] 4EGDMA: Tetraethylene glycol dimethacrylate

[0110] ·dmPDMS5-20: Compounds of formula (4) (p=r=0, q=10, Mn=1000)

[0111] (F): Monomers other than (A) to (E)

[0112] SiGMA: (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane

[0113] ·mPDMS15-20: Compounds of formula (5) (m=0, n=17, Mn=1500)

[0114] [Chemical Formula 9]

[0115]

[0116] MMA: Methyl methacrylate

[0117] •TEGDV: Triethylene glycol divinyl ether

[0118] (G): Solvent

[0119] • NPA: 1-Propanol (n-Propanol)

[0120] HeOH: 1-Hexanol (n-Hexanol)

[0121] (H) Polymerization initiator

[0122] AIBN: 2,2'-azobis(isobutyronitrile)

[0123] I-819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

[0124] Next, the preparation of each evaluation item and contact lens, etc., will be described. The compositions, polymers, contact lenses, and plate-shaped silicone hydrogels described later in the comparative examples other than those of this invention will also be referred to as compositions, polymers, contact lenses, and plate-shaped silicone hydrogels, just as in the examples. The plate-shaped silicone hydrogel is prepared by purifying a polymer that is polymerized using a specific dish instead of a contact lens molding mold. That is, in order to achieve a shape suitable for the following evaluations: a. modulus and d. durability, the plate-shaped silicone hydrogel is prepared to differ from the corresponding contact lens only in shape. b. oxygen permeability and c. transparency are evaluated using contact lenses.

[0125] [a. modulus]

[0126] The modulus of the plate-shaped silicone hydrogel (hereinafter sometimes referred to as SG) was measured using a BAS-3305(W) fracture strength analyzer manufactured by Sangyo Electric Corporation, according to JIS-K7127. A 2N load cell was used. As the test specimen, a specimen cut from SG to a width of 2 mm was used, with a clamp spacing of 6 mm, and stretched at a speed of 1 mm / s. The modulus was determined based on the initial stress.

[0127] [b. Oxygen permeability coefficient]

[0128] The oxygen permeability of contact lenses is determined according to the method described in ISO 18369-4. Contact lenses with an oxygen permeability of 70 or higher are considered good.

[0129] [c. Transparency]

[0130] By varying the thickness of the obtained polymer and using contact lenses made with swollen thicknesses of 100±20μm, 200±20μm, and 300±20μm, the light scattering was evaluated visually according to the following criteria.

[0131] ◎: All thicknesses of contact lenses are transparent.

[0132] 〇: Light scattering can be confirmed using a contact lens with a thickness of 300±20μm.

[0133] △: Light scattering can be confirmed using contact lenses with thicknesses of 200±20μm and 300±20μm.

[0134] ×: Light scattering can be confirmed using contact lenses of all thicknesses.

[0135] [d. Durability]

[0136] Using an autoclave, SG was subjected to 10 heating treatments at 121°C for 20 minutes to prepare long-term storage SG. The modulus of the long-term storage SG was measured in the same manner as described above, and the rate of increase in modulus was calculated using the following formula. The value of the rate of increase in modulus was determined according to the following criteria.

[0137] [Rate of increase in modulus] = [Modulus of SG in long-term storage] / [Modulus of SG]

[0138] ◎: 0.8 or higher and less than 1.3

[0139] 〇: 1.3 or higher and less than 1.5

[0140] △: 1.5 or higher and less than 2.0

[0141] ×: Less than 0.8 or more than 2.0

[0142] [Example 1]

[0143] In a container, 0.70 g (10.0 wt%) of MPC, 1.00 g (14.3 wt%) of HPMA, 1.40 g (20.0 wt%) of ETS, and 1.05 g (15.0 parts by weight) of NPA were mixed and stirred at room temperature until the MPC dissolved. Then, 2.10 g (30.0 wt%) of NVP, 1.75 g (25.0 wt%) of mPDMS3-9, 0.049 g (0.7 wt%) of EGDMA, 0.042 g (0.6 parts by weight) of TEGDV, and 0.035 g (0.5 parts by weight) of AIBN were added to the container and stirred at room temperature until homogeneous to obtain the composition. A portion of the composition was filled into a lens molding die. Additionally, a portion of the composition was filled into a 25 mm × 70 mm × 0.2 mm dish sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer. The lens molding mold and dish filled with the composition were placed in an oven and purged with nitrogen. The oven temperature was then raised to 80°C and maintained at 80°C for 12 hours to polymerize the composition, yielding a polymer. The polymers were removed from the lens molding mold and dish, resulting in two polymer shapes. Both polymers were purified by immersing them in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of deionized water for 4 hours to remove unreacted substances. The purified polymers were then immersed in physiological saline as described in ISO-18369-3 to swell (hydrate), preparing contact lenses and plate-shaped silicone hydrogels (SG) that differ only in shape from the contact lenses. The contact lenses and SGs were cut into sizes and shapes suitable for the above evaluations and then evaluated. The mixing ratios of the components in the composition, polymerization conditions, and evaluation results are shown in Table 1.

[0144] [Examples 2-5]

[0145] Except that the mixing ratios and polymerization conditions of the components in the composition are as shown in Table 1, the contact lenses and SG of each embodiment were prepared in the same manner as in Example 1. In Example 5, polymerization was carried out in two stages: the first stage was carried out at a temperature of 55°C for 7 hours, and the second stage was carried out at a temperature of 120°C for 2 hours. Furthermore, the contact lenses and SG of each embodiment were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0146] [Example 6]

[0147] In a container, 0.90 g (18.0 wt%) of MPC, 1.00 g (20.0 wt%) of ETS, 0.79 g (15.8 wt%) of HBMA, and 1.00 g (20.0 parts by weight) of HeOH were mixed and stirred at room temperature until MPC dissolved. Then, 0.75 g (15.0 wt%) of NVP, 1.5 g (30.0 wt%) of mPDMS3-9, 0.060 g (1.2 wt%) of 4EGDMA, 0.030 g (0.6 parts by weight) of TEGDV, and 0.010 g (0.2 parts by weight) of I-819 were added to the container and stirred at room temperature until homogeneous to obtain the composition. A portion of the composition was filled into a lens molding die. Additionally, a portion of the composition was filled into a 25mm × 70mm × 0.2mm dish sandwiched between two polypropylene plates, with a 0.1mm thick polyethylene terephthalate sheet as a spacer. The lens molding die and dish filled with the composition were then placed in a UV-LED irradiator (irradiation wavelength 405nm) at room temperature with an intensity of 1.5mW / cm². 2 The composition was subjected to UV irradiation for 30 minutes to polymerize the material, yielding a polymer. The polymers were removed from the lens molding mold and dish, resulting in two polymer shapes. Both polymers were purified by immersing them in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchange water for 4 hours to remove unreacted substances. The purified polymers were then immersed in physiological saline as described in ISO-18369-3 to swell (hydrate), preparing contact lenses and SGs that differed from the contact lenses only in shape. The contact lenses and SGs were cut into sizes and shapes suitable for the above evaluations, and each evaluation was performed. The mixing ratios of the components in the composition, polymerization conditions, and evaluation results are shown in Table 1.

[0148] [Examples 7 and 8]

[0149] Except that the mixing ratios and polymerization conditions of the components in the composition are as shown in Table 1, the contact lenses and SG of each embodiment were prepared in the same manner as in Example 6. Furthermore, the contact lenses and SG of each embodiment were evaluated in the same manner as in Example 6. The results are shown in Table 1.

[0150] [Comparative Example 1]

[0151] In a container, 0.50 g (10.0% by mass) of MPC, 1.25 g (25.0% by mass) of ETS, 0.50 g (10.0% by mass) of HBMA, and 1.25 g (25.0 parts by mass) of HeOH were mixed and stirred at room temperature until MPC dissolved. Then, 1.25 g (25.0% by mass) of NVP, 1.50 g (30.0% by mass) of mPDMS3-9, 0.10 g (2.0 parts by mass) of TEGDV, and 0.025 g (0.5 parts by mass) of AIBN were added to the container and stirred at room temperature until homogeneous to obtain the composition. A portion of the composition was filled into a lens molding mold. Additionally, a portion of the composition was filled into a 25 mm × 70 mm × 0.2 mm dish sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer. The lens molding mold and dish filled with the composition were placed in an oven and purged with nitrogen. The oven temperature was then raised to 80°C and maintained at 80°C for 12 hours to polymerize the composition, yielding a polymer. The polymers were removed from the lens molding mold and dish, resulting in two polymer shapes. The two polymers were purified by immersing them in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of deionized water for 4 hours to remove unreacted substances. The purified polymers were then immersed in physiological saline as described in ISO-18369-3 to swell (hydrate), preparing contact lenses and SGs that differed from the contact lenses only in shape. The contact lenses and SGs were cut into sizes and shapes suitable for the above evaluations and evaluated. The mixing ratios of the components in the composition, polymerization conditions, and evaluation results are shown in Table 2. Compared to the contact lenses and SGs of the other examples, the contact lenses and SGs of Comparative Example 1 exhibited poorer oxygen permeability, transparency, and durability.

[0152] [Comparative Example 2]

[0153] Except that the mixing ratios and polymerization conditions of the components in the composition are as shown in Table 2, the contact lenses and SG were prepared in the same manner as in Comparative Example 1. Furthermore, the contact lenses and SG of Comparative Example 2 were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2. The SG (plate-like silicone hydrogel) of Comparative Example 2 exhibited significantly poorer durability compared to the SGs of the other examples.

[0154] [Comparative Example 3]

[0155] In a container, 0.75 g (15.0 wt%) of MPC, 1.50 g (30.0 wt%) of ETS, 1.20 g (24.0 wt%) of HBMA, and 1.25 g (25.0 parts by weight) of HeOH were mixed and stirred at room temperature until the MPC dissolved. Then, 1.00 g (20.0 wt%) of NVP, 0.5 g (10.0 wt%) of mPDMS3-9, 0.050 g (1.0 wt%) of 4EGDMA, 1.00 g (20.0 parts by weight) of mPDMS15-20, and 0.010 g (0.2 parts by weight) of I-819 were added to the container and stirred at room temperature until homogeneous to obtain the composition. A portion of the composition was filled into a lens molding die. Additionally, a portion of the composition was filled into a 25mm × 70mm × 0.2mm dish sandwiched between two polypropylene plates, with a 0.1mm thick polyethylene terephthalate sheet as a spacer. The lens molding die and dish filled with the composition were then placed in a UV-LED irradiator (irradiation wavelength 405nm) at room temperature with an intensity of 1.5mW / cm². 2 The composition was subjected to UV irradiation for 30 minutes to polymerize the material, yielding a polymer. The polymers were removed from the lens molding mold and dish, resulting in two polymer shapes. Both polymers were purified by immersing them in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchange water for 4 hours to remove unreacted substances. The purified polymers were then immersed in physiological saline as described in ISO-18369-3 to swell (hydrate), preparing a contact lens and an SG (similar in shape to the contact lens). The contact lenses and SG were cut into sizes and shapes suitable for the above evaluations, and each evaluation was performed. The mixing ratios of the components in the composition, polymerization conditions, and evaluation results are shown in Table 2. Compared to the contact lenses of the examples, the contact lenses and SG of Comparative Example 3 exhibited poorer transparency and significantly lower durability.

[0156] [Comparative Example 4]

[0157] Except that the mixing ratios and polymerization conditions of the components in the composition are as shown in Table 2, the contact lenses and SG were prepared in the same manner as in Comparative Example 3. Furthermore, the contact lenses and SG of Comparative Example 4 were evaluated in the same manner as in Comparative Example 3. The results are shown in Table 2. Compared with the contact lenses and SG of the other examples, the contact lenses and SG of Comparative Example 4 showed significantly poorer transparency and durability.

[0158] [Table 1]

[0159]

[0160] *1 Blending amount of any component: 100 parts by mass relative to the total amount of the necessary components (A~E)

[0161] *2 Irradiation wavelength: 405nm

[0162] *3 a. and d. were evaluated using SG, and b. and c. were evaluated using contact lenses (CL).

[0163] *4 SG: Plate-shaped silicone hydrogel

[0164] [Table 2]

[0165]

[0166] *1 Blending amount of any component: 100 parts by mass relative to the total amount of the necessary components (A~E)

[0167] *2 Irradiation wavelength: 405nm

[0168] *3 a. and d. were evaluated using SG, and b. and c. were evaluated using CL.

[0169] *4 SG: Plate-shaped silicone hydrogel.

Claims

1. A monomeric composition for contact lenses, the composition comprising: (A) The methacrylate monomer containing phosphorylcholine as shown in formula (1) below; [Chemical Formula 1] (B) The siloxane-containing itaconic acid diester monomer shown in formula (2) below; [Chemical Formula 2] (C) One or more hydrophilic monomers selected from the group consisting of N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether. (D) The siloxane-containing (meth)acrylate shown in formula (3); [Chemical Formula 3] In equation (3), R 1 It is hydrogen or methyl, m is 0 or 1, n is 3 to 9; And (E) is a crosslinking agent selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and siloxane-containing dimethacrylates as shown in formula (4) below. [Chemical Formula 4] In equation (4), p and r are 0 or 1, and q is 5 to 20; Relative to 100% by mass of the total of components (A) to (E) in the composition, component (A) contains 5 to 25% by mass, component (B) contains 5 to 30% by mass, component (C) contains 15 to 45% by mass, component (D) contains 15 to 40% by mass, and component (E) contains 0.2 to 2.5% by mass.

2. The monomer composition for contact lenses according to claim 1, wherein, The composition also contains monomer (F) other than (A) to (E), and the content of component (F) is 20 parts by mass or less relative to the total amount of components (A) to (E) in the composition of 100 parts by mass.

3. The monomer composition for contact lenses according to claim 1 or 2, wherein, The composition further contains a solvent having hydroxyl groups (G), and the content of component (G) is 30 parts by mass or less relative to the total amount of components (A) to (E) in the composition of 100 parts by mass.

4. A polymer for contact lenses, which is a polymer of the monomer composition for contact lenses according to any one of claims 1 to 3.

5. A contact lens comprising a hydrate of the polymer for contact lenses as claimed in claim 4.

6. A method for manufacturing a contact lens, comprising: The step of purifying the polymer for contact lenses according to claim 4 by mixing it with one or more solvents selected from the group consisting of water, methanol, ethanol, 1-propanol, and 2-propanol to obtain a purified polymer; and The process of hydrating the purified polymer by immersing it in physiological saline.

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