Monomer composition for contact lenses, polymer thereof, contact lenses and method for manufacturing the same

Abstract

Provided are: a monomer composition for contact lenses, in which a silicone compound having a small molecular weight is used and which enables the production of a contact lens having satisfactory oxygen permeability, mechanical strength, transparency and durability and an excellent feeling during wearing; a polymer of the composition; and a contact lens produced using the polymer. More specifically, provided are: a composition comprising (A) a methacrylic ester monomer containing a phosphocholine group, (B) an itaconic acid diester monomer containing a siloxanyl group, (C) a specific hydrophilic monomer, (D) a (meth)acrylate containing a siloxanyl group, and (E) a specific crosslinking agent at a specified content ratio; a polymer of the composition; and a contact lens produced using the polymer.

Description

[Technical Field]

[0001] The present invention relates to a monomer composition for contact lenses, a polymer thereof, and a contact lens containing the polymer, which has high transparency and durability and therefore provides a comfortable wearing experience, and a method for producing the same. [Background technology]

[0002] Conventional hydrogel contact lenses have an insufficient supply of oxygen to the cornea, posing safety concerns when worn for extended periods of time. Silicone hydrogel contact lenses have been developed to address this drawback and improve safety. However, the manufacturing process for silicone hydrogel contact lenses poses a problem: it is difficult to render the surface of a silicone hydrogel contact lens hydrophilic. Specifically, when silicone hydrogel contact lenses are manufactured using the cast molding method, a common soft contact lens manufacturing method, in which polypropylene is used as a mold, the raw material silicone monomer is polymerized in a state oriented at the interface with the mold because polypropylene is hydrophobic. As a result, silicone polymer moieties are present on the lens surface, reducing the hydrophilicity of the lens surface.

[0003] If the hydrophilicity of the soft contact lens surface is insufficient, there is a risk of the lens becoming cloudy due to the adhesion of lipids and proteins, and of eye diseases due to the adhesions. For this reason, silicone hydrogel contact lenses with insufficient hydrophilicity are subjected to surface coating with plasma gas or hydrophilic polymers after lens formation, or to the formation of surface graft polymers using hydrophilic monomers. However, these surface treatments require many more devices and processes to produce soft contact lenses than those that do not require surface treatment, making them undesirable for mass production.

[0004] Patent Document 1 discloses a method for producing lenses from a silicone hydrogel composition containing a silicone monomer having a (meth)acryloyl group, a hydrophilic monomer having a vinyl group, a crosslinkable monomer, and a polymerization initiator having 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 difference in polymerizability of the raw material monomers, but still fails to achieve satisfactory hydrophilicity.

[0005] Patent Document 2 discloses a silicone hydrogel contact lens obtained from a composition containing 2-methacryloyloxyethyl phosphorylcholine (MPC), dimethacryloyl silicone macromer, and (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane. However, although the contact lens disclosed in Patent Document 2 shows improved hydrophilicity of the lens surface, it suffers from the problem of reduced oxygen permeability.

[0006] Patent Documents 3 and 4 disclose compositions containing a siloxanyl group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and state that the polymer can be used for contact lenses. The contact lens disclosed in Patent Document 3 exhibits good results in terms of lens surface hydrophilicity and oxygen permeability, and the contact lens disclosed in Patent Document 4 also exhibits good results in terms of breaking elongation and peelability. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2015 / 001811 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-089477 [Patent Document 3] International Publication No. 2018 / 135421 [Patent Document 4] International Publication No. 2020 / 054711 Summary of the Invention [Problem to be solved by the invention]

[0008] However, although the contact lenses disclosed in Patent Documents 3 and 4 have good hydrophilicity and oxygen permeability on the lens surface, they contain a large amount of highly hydrophobic silicone compounds, which raises concerns about reduced transparency when thick contact lenses used for high-power vision correction are produced. While a method for improving transparency can be used to use a silicone compound with a lower molecular weight, this method alone raises concerns about reduced comfort due to poor oxygen permeability and mechanical strength. Furthermore, silicone hydrogel contact lenses are generally known to be susceptible to hydrolysis and to a decrease in mechanical strength after long-term storage. Thick contact lenses are susceptible to this effect, raising concerns about a deterioration in comfort when wearing contact lenses after long-term storage.

[0009] Therefore, an object of the present invention is to provide a monomer composition for contact lenses using a silicone compound with a low molecular weight, which can be used to produce contact lenses that have good oxygen permeability, mechanical strength, transparency, and durability and that are comfortable to wear. It is also an object of the present invention to provide a polymer for contact lenses obtained by polymerizing the composition. It is also an object of the present invention to provide a contact lens using the polymer and a method for producing the same. [Means for solving the problem]

[0010] As a result of extensive research, the present inventors have discovered that all of the above-mentioned objects can be achieved by using, as a raw material for contact lenses, a monomer composition containing two types of hydrophilic monomers, a siloxanyl group-containing itaconic acid diester monomer, a siloxanyl group-containing silicone monomer of a specific molecular weight, and a specific crosslinking agent, and by adjusting these monomers to a specific compositional ratio, thereby completing the present invention.

[0011] That is, according to the present invention, there is provided a polymerizable composition comprising (A) a phosphorylcholine group-containing methacrylic acid ester monomer represented by formula (1), (B) a siloxanyl group-containing itaconic acid diester monomer represented by formula (2), (C) one or more hydrophilic monomers 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, (D) a siloxanyl group-containing (meth)acrylate represented by formula (3), and (E) ethylene glycol dimethacrylate, and one or more crosslinking agents selected from the group consisting of diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and a siloxanyl group-containing dimethacrylate represented by formula (4), wherein the content of component (A) in the composition is 5 to 25 mass%, the content of component (B) is 5 to 30 mass%, the content of component (C) is 15 to 45 mass%, the content of component (D) is 15 to 40 mass%, and the content of component (E) is 0.2 to 2.5 mass%, relative to 100 mass% total of components (A) to (E).

[0012] [ka]

[0013] [ka]

[0014] [ka] [In formula (3), R 1 is hydrogen or a methyl group, m is 0 or 1, and n is 3 to 9.

[0015] [ka] [In formula (4), p and r are 0 or 1, and q is 5 to 20.]

[0016] According to another aspect of the present invention, there is provided a polymer for contact lenses, which is a polymer of the monomer composition for contact lenses of the present invention.

[0017] Furthermore, according to another aspect of the present invention, there are provided contact lenses containing the hydrates of the contact lens polymers of the present invention, and methods for producing the same. [Effects of the Invention]

[0018] The monomer composition for contact lenses of the present invention essentially contains components (A) to (E) in specific proportions, and by using the polymer, it is possible to obtain contact lenses that have high transparency and durability and are comfortable to wear. Furthermore, the method for producing contact lenses of the present invention makes it possible to produce contact lenses with the above-mentioned excellent performance. The contact lenses of the present invention are silicone hydrogel soft contact lenses. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in further detail below. The monomer composition for contact lenses of the present invention is a composition containing, in specific proportions, (A) a phosphorylcholine group-containing methacrylic acid ester monomer represented by formula (1) [component (A)], (B) a siloxanyl group-containing itaconic acid diester monomer represented by formula (2) [component (B)], (C) one or more hydrophilic monomers selected from N-vinylpyrrolidone, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether [component (C)], (D) a siloxanyl group-containing (meth)acrylate represented by formula (3) [component (D)], and (E) one or more crosslinking agents selected from ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and siloxanyl group-containing dimethacrylate represented by formula (4) [component (E)]. Hereinafter, the monomer composition for contact lenses of the present invention may be simply referred to as the composition of the present invention.

[0020] The composition of the present invention may further contain a specific amount of one or more components selected from (F) a monomer other than the above (A) to (E) [component (F)] and (G) a solvent having a hydroxyl group [component (G)]. The composition of the present invention may also contain (H) a polymerization initiator [component (H)].

[0021] 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.

[0022] Component (A): Phosphorylcholine group-containing methacrylic acid ester monomer Component (A) is a phosphorylcholine group-containing methacrylic acid ester monomer represented by formula (1), specifically 2-methacryloyloxyethyl phosphorylcholine (MPC). By including component (A), the hydrophilicity and lubricity of the surface of a contact lens produced from the polymer of the composition of the present invention can be improved. [ka]

[0023] The content of component (A) in the composition of the present invention is 5 to 25% by mass, preferably 8 to 20% by mass, and more preferably 8 to 18% by mass, based on 100% by mass of the total of components (A) to (E). If it is less than 5% by mass, the contact lens surface will not be sufficiently hydrophilic. If it exceeds 25% by mass, it will be difficult to dissolve component (A) in the composition, and there is a concern that the oxygen permeability of the contact lens will decrease.

[0024] Component (B): Siloxanyl group-containing itaconic acid diester monomer Component (B) is a siloxanyl group-containing itaconic acid diester monomer represented by formula (2): Component (B) is a component that improves the oxygen permeability and transparency of the contact lens of the present invention. [ka]

[0025] The content of component (B) is 5 to 30% by mass, preferably 5 to 25% by mass, and more preferably 10 to 25% by mass, relative to 100% by mass of the total of components (A) to (E) in the composition of the present invention. If it is less than 5% by mass, it may be difficult to dissolve component (A) in the composition, and the transparency of the contact lens may decrease. If it exceeds 30% by mass, the mechanical strength of the contact lens may decrease.

[0026] Component (C): Hydrophilic monomer Component (C) is one or more hydrophilic monomers 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. Component (C) is a component that improves the mechanical strength of the contact lens of the present invention and the hydrophilicity of the contact lens surface.

[0027] Specific examples of component (C) include N-vinylpyrrolidone, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (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 of them.

[0028] In this specification, the terms "(meth)acrylate" and "(meth)acrylic acid ester" mean acrylate and / or methacrylate, and acrylic acid ester and / or methacrylic acid ester, respectively.

[0029] 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, based on 100% by mass of the total of components (A) to (E) in the composition of the present invention. If it is less than 15% by mass, there is a concern that the hydrophilicity of the contact lens surface will be insufficient, and if it exceeds 45% by mass, there is a concern that the mechanical strength of the contact lens will be reduced.

[0030] Component (D): Siloxanyl group-containing (meth)acrylate Component (D) is a siloxanyl group-containing (meth)acrylate represented by formula (3): Component (D) is a component that improves the transparency of the contact lens of the present invention. [ka] [In formula (3), R 1 is hydrogen or a methyl group, m is 0 or 1, and n is 3 to 9.

[0031] 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, based on 100% by mass of the total of components (A) to (E) in the composition of the present invention. If it is less than 15% by mass, there is a concern that the oxygen permeability of the contact lens will decrease, and if it exceeds 40% by mass, there is a concern that the modulus of the contact lens will increase beyond the allowable range during long-term storage.

[0032] The siloxanyl group-containing (meth)acrylate represented by formula (3) may be a commercially available product, or may be produced by the method disclosed in, for example, JP-A-2014-031338.

[0033] Component (E): Crosslinking agent Component (E) is one or more crosslinking agents selected from ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and a siloxanyl group-containing dimethacrylate represented by formula (4). Component (E) is a component that improves the oxygen permeability and transparency of the contact lens of the present invention. [ka] [In formula (4), p and r are each 0 or 1, and q is 5 to 20.]

[0034] The content of component (E) is 0.2 to 2.5% by mass, preferably 0.2 to 2.2% by mass, and more preferably 0.5 to 2.2% by mass, relative to 100% by mass of the total amount of components (A) to (E) in the composition of the present invention. If it is less than 0.2% by mass, the transparency and oxygen permeability of the contact lens may be insufficient, and if it exceeds 2.5% by mass, the durability of the contact lens may be insufficient.

[0035] The content ratio of component (D) to component (E), expressed as a mass ratio [(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 adjusting this mass ratio to 0.01 to 0.06, the transparency and durability of the contact lens of the present invention may be improved.

[0036] Component (F): Monomer other than (A) to (E) Component (F) is a monomer other than (A) to (E). Component (F) is an optional component that can be added for the purpose of adjusting the physical properties of the contact lens of the present invention.

[0037] Examples of component (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, acryloylmorpholine, N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinylformamide, (meth)acrylic acid, 2-methacryloyloxyethylsuccinic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methoxypolyethylene glycol methacrylate, (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, and (3-methacryloxypropyl)trimethoxysilane. Examples of component (F) also include crosslinking agents (monomers) such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, methylenebisacrylamide, allyl methacrylate, (2-allyloxy)ethyl methacrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, and divinylbenzene. Component (F) may be any one of these, or a mixture of two or more.

[0038] When component (F) is contained, it 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, per 100 parts by mass of the total of components (A) to (E) in the composition of the present invention. When component (F) contains the above-mentioned crosslinking agent, the content of the crosslinking agent is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, per 100 parts by mass of the total of components (A) to (E). If the content of component (F) exceeds 20 parts by mass, the transparency and durability of the contact lens may be reduced.

[0039] (G) Component: Solvent Component (G) is a solvent containing a hydroxyl group. Component (G) is an optional component and may be added to improve the solubility of component (A) in the composition of the present invention. Specifically, the inclusion of component (G) has the advantage of increasing the dissolution rate of component (A) in the composition of the present invention, facilitating its dissolution. 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-amyl alcohol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol. Examples of carboxylic acids include glycolic acid, lactic acid, and acetic acid. Component (G) may be any one of these solvents or a mixture of two or more of them. In terms of improving the dissolution rate of component (A) and the pH stability of the composition of the present invention, it is preferable to incorporate one or more selected from ethanol, 1-propanol, 2-propanol, and 1-hexanol as component (G).

[0040] When component (G) is contained, its content is not particularly limited, but 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, per 100 parts by mass of the total 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.

[0041] The composition of the present invention may also contain a polymerization initiator (H) [component (H)]. When component (H) is contained, care must be taken when storing the composition of the present invention, but the composition has the advantage that the polymer for contact lenses of the present invention can be easily obtained with stable quality by simply heating the composition of the present invention. Component (H) is not particularly limited, but known thermal polymerization initiators and photopolymerization initiators can be used.

[0042] Examples of the thermal polymerization initiator 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-dimethylvaleronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]dihydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropionamidine), Examples of suitable thermal polymerization initiators include azo polymerization initiators such as 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-methylpropionamidine) dihydrochloride, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and peroxide polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyhexanoate, and 3,5,5-trimethylhexanoyl peroxide. As component (H), any one of these thermal polymerization initiators may be blended alone, or two or more may be blended.

[0043] Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-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, benzoin methyl ester, camphorquinone, and ethyl-4-(N,N-dimethylamino)benzoate. Examples of photopolymerization initiators represented by trade names include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850, Darocur 1173, and Darocur 2959. As the component (H), any one of these photopolymerization initiators may be blended, or two or more may be blended.

[0044] When component (H) is contained, its content is preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of components (A) to (E) in the composition of the present invention. If the content is less than 0.1 part by mass, the polymerizability of the monomers in the composition may be insufficient, and the benefits of incorporating component (H) may not be obtained. If the content exceeds 3 parts by mass, when the contact lens polymer obtained by polymerization is washed to produce a contact lens, the reaction decomposition products of component (H) may not be sufficiently extracted and removed.

[0045] The method for producing the composition of the present invention is not particularly limited, and the composition can be produced by adding the components in any order or all at once to a stirring (mixing) device and stirring and mixing the components at 40°C or below until they become uniform. However, when component (H) is included, in order to avoid initiation of a polymerization reaction during mixing, if component (H) is a thermal polymerization initiator, mixing is preferably carried out at 40°C or below and at a temperature 10°C or more lower than the 10-hour half-life temperature of the initiator, and if component (H) is a photopolymerization initiator, mixing is preferably carried out in the dark.

[0046] The composition of the present invention may contain components other than those described above, provided that the purpose of the present invention is not impaired. Examples of other components include polymerizable ultraviolet absorbers and polymerizable dyes as colorants. By incorporating an ultraviolet absorber, the contact lenses of the present invention can reduce eye strain caused by ultraviolet light, such as sunlight. Furthermore, by incorporating a dye, 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, per 100 parts by mass of the total amount of components (A) to (E) in the composition of the present invention.

[0047] Next, an embodiment of the method for producing a contact lens polymer of the present invention will be described. Note that the production method described below is one embodiment for obtaining a contact lens polymer of the present invention, and the contact lens polymer of the present invention is not limited to the polymer obtained by this production method. Hereinafter, unless otherwise specified, the term "composition" refers to the composition of the present invention, and the term "polymer" refers to the contact lens polymer of the present invention.

[0048] The polymer is produced by using a mold (metal mold) having a hydrophobic surface made of polypropylene or the like, filling the mold with the composition, and polymerizing it. In the case of a composition that does not contain component (H), a polymerization initiator similar to that used for component (H) is added to the composition in an amount approximately equal to that of component (H), and then filling the mold.

[0049] When polymerizing with a thermal polymerization initiator, the reaction is carried out for at least one hour at a temperature between 45 and 140°C that is appropriate for the thermal polymerization initiator contained. When polymerizing with a photopolymerization initiator, the reaction is carried out by irradiating ultraviolet light of a wavelength appropriate for the photopolymerization initiator contained at 0.3 mW / cm. 2 The reaction is carried out for 5 minutes or more at the above irradiance. After the polymerization is completed, the produced polymer is removed from the mold.

[0050] Although the polymerization atmosphere is not particularly limited, an inert gas atmosphere such as nitrogen or argon is preferred in terms of improving the polymerization rate. Examples of a method for creating such an inert gas atmosphere include a method of passing an inert gas through the composition or a method of creating such an atmosphere at the location where the composition is filled into a mold.

[0051] The pressure inside the mold can be atmospheric pressure to slight pressure, and when polymerizing in an inert gas atmosphere, the gauge pressure should be 1 kgf / cm. 2 The following pressure is preferred:

[0052] The contact lenses of the present invention are silicone hydrogel contact lenses, which are hydrates of the above-mentioned polymers. Here, "hydrate" means that the polymer contains water, and the contact lenses of the present invention are those in a hydrogel form due to the hydration of the polymer, i.e., silicone hydrogel contact lenses of the present invention. Because the polymer contains unreacted substances, by-products, and optionally (G) solvent, the polymer is purified by washing or the like before hydration.

[0053] As used herein, the term "silicone hydrogel" refers to a hydrogel containing silicone moieties (siloxane bonds) within the polymer. Because the composition of the present invention contains components (B) and (D), which are siloxanyl group-containing monomers, the polymer contains silicone moieties within the polymer and can form a silicone hydrogel upon hydration (water absorption).

[0054] Next, an embodiment of a method for manufacturing a contact lens of the present invention will be described. Note that the manufacturing method described below is one embodiment for obtaining a 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, when referring to a "contact lens," it refers to the contact lens of the present invention.

[0055] The polymer removed from the mold is purified by washing with a solvent to remove unreacted materials such as unreacted monomers and other impurities. Examples of solvents that can be used include water, methanol, ethanol, 1-propanol, 2-propanol, and mixtures thereof. Washing can be performed, for example, by immersing the polymer in the above-mentioned alcohol for 10 minutes to 5 hours at 10 to 40°C, followed by immersion in water for 10 minutes to 5 hours. Between the alcohol wash and the water wash, the polymer may be immersed in a hydrous alcohol with an alcohol concentration of 20 to 50 wt% for 10 minutes to 5 hours. As the water, pure water such as distilled water, ion-exchanged water, or RO water is preferred.

[0056] The polymer purified by washing is immersed in physiological saline and hydrated to a predetermined water content to obtain a contact lens. As the physiological saline, borate buffered saline or phosphate buffered saline may be used. These physiological saline solutions are used in storage solutions for soft contact lenses, so the polymer may be immersed in the storage solution for soft contact lenses to hydrate it. From the viewpoint of hydration, it is preferable that the osmotic pressure of these physiological saline solutions is 250 to 400 mOms / kg. [Example]

[0057] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0058] The components constituting the compositions of the Examples and Comparative Examples are shown below. (A): Phosphorylcholine group-containing methacrylate ester monomer MPC: (2-methacryloyloxyethyl)phosphorylcholine

[0059] (B): Siloxanyl group-containing itaconic acid diester monomer ETS: a compound of formula (2)

[0060] (C): Hydrophilic monomer NVP: N-vinylpyrrolidone HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate EGMV: Ethylene glycol monovinyl ether ·DEGMV: Diethylene glycol monovinyl ether

[0061] (D): Siloxanyl group-containing methacrylate mPDMS3-9: Compound of formula (3) (R 1 is a methyl group, m=0, n=8, Mn=800)

[0062] (E): Crosslinking agent EGDMA: Ethylene glycol dimethacrylate 2EGDMA: Diethylene glycol dimethacrylate 3EGDMA: Triethylene glycol dimethacrylate 4EGDMA: Tetraethylene glycol dimethacrylate dmPDMS5-20: Compound of formula (4) (p=r=0, q=10, Mn=1000)

[0063] (F): Monomers other than (A) to (E) SiGMA: (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane mPDMS15-20: Compound of formula (5) (m = 0, n = 17, Mn = 1500) [ka] MMA: Methyl methacrylate TEGDV: Triethylene glycol divinyl ether

[0064] (G); Solvent NPA: 1-propanol (normal propanol) HeOH: 1-hexanol (normal hexanol)

[0065] (H): Polymerization initiator AIBN: 2,2'-azobis(isobutyronitrile) I-819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

[0066] Next, the evaluation items and the preparation of contact lenses, etc. will be explained. The compositions, polymers, contact lenses, and plate-shaped silicone hydrogels of each comparative example, which are outside the scope of the present invention, as well as the plate-shaped silicone hydrogels described below, will be simply referred to as the composition, polymer, contact lens, and plate-shaped silicone hydrogel, as in the examples. The plate-shaped silicone hydrogels are prepared by polymerizing the compositions using a specific cell instead of a contact lens mold, and then purifying the polymers. That is, the plate-shaped silicone hydrogels were prepared so that only the shape differed from that of the corresponding contact lenses, in order to obtain a shape suitable for the following a. modulus and d. durability evaluations. b. oxygen permeability coefficient and c. transparency were evaluated using contact lenses.

[0067] [a.Modulus] The modulus of plate-shaped silicone hydrogel (hereinafter sometimes abbreviated as SG) was measured in accordance with JIS-K7127 using a Yamaden BAS-3305(W) breaking strength analyzer. A 2N load cell was used. SG cut to a width of 2 mm was used as the measurement sample, and the specimen was pulled at a rate of 1 mm / s with a clamp distance of 6 mm, and the modulus was measured from the initial stress.

[0068] [b. Oxygen permeability coefficient] The oxygen permeability coefficient of contact lenses was measured according to the method described in ISO 18369-4. Contact lenses with an oxygen permeability coefficient of 70 or higher were considered to be good.

[0069] [c. Transparency] The thickness of the resulting polymer was changed, and contact lenses were fabricated so that the thickness after swelling was 100±20 μm, 200±20 μm, and 300±20 μm. Light scattering was evaluated visually using the following criteria. ◎: All thicknesses of contact lenses are transparent ○: Light scattering is confirmed with contact lenses with a thickness of 300±20μm △: Light scattering is confirmed for contact lenses with thicknesses of 200±20μm and 300±20μm. ×: Light scattering was confirmed for all thicknesses of contact lenses.

[0070] [d.Durability] The SG was heated 10 times in an autoclave at 121°C for 20 minutes to prepare a long-term storage SG. The modulus of the long-term storage SG was measured in the same manner as above, and the modulus increase rate was calculated using the following formula. The modulus increase rate was evaluated according to the following criteria. [Modulus increase rate] = [Modulus of long-term stored SG] / [Modulus of SG] ◎: 0.8 or more, less than 1.3 〇: 1.3 or more, less than 1.5 △: 1.5 or more, less than 2.0 ×: Less than 0.8 or 2.0 or more

[0071] [Example 1] 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 in a container and stirred at room temperature until the MPC was dissolved. 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 the mixture was homogenous to obtain a composition. A portion of the composition was filled into a lens mold. A portion of the composition was filled into a 25 mm x 70 mm x 0.2 mm cell sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer. The lens mold and cell filled with the composition were placed in an oven, and the oven's atmosphere was replaced with nitrogen. The oven was then heated to 80°C and maintained at 80°C for 12 hours to polymerize the composition and obtain a polymer. Each polymer was removed from the lens mold and cell, yielding two different polymer shapes. Both polymers were immersed in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchanged water for 4 hours to remove unreacted materials and for purification. After purification, both polymers were immersed in physiological saline according to ISO-18369-3 and allowed to swell (hydrate) to prepare contact lenses and silicone hydrogel plates (SGs), which differ only in shape from the contact lenses. The contact lenses and SGs were then cut into sizes and shapes appropriate for the above evaluations, and each evaluation was performed. Table 1 shows the blending ratio of each component in the composition, polymerization conditions, and evaluation results.

[0072] [Examples 2 to 5] The contact lenses and SGs of each example were prepared in the same manner as in Example 1, except that the blending ratios of each component in the composition and the polymerization conditions were as shown in Table 1. In Example 5, polymerization was carried out in two stages, with the first stage being at a temperature of 55°C for 7 hours and the second stage being at a temperature of 120°C for 2 hours. The contact lenses and SGs of each example were also evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0073] [Example 6] 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 in a container and stirred at room temperature until the MPC was dissolved. Additionally, 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 a composition. A portion of the composition was filled into a lens mold. A portion of the composition was filled into a 25mm x 70mm x 0.2mm cell sandwiched between two polypropylene plates using a 0.1mm thick polyethylene terephthalate sheet as a spacer. The lens mold and cell filled with the composition were placed in a UV-LED irradiator (irradiation wavelength 405nm) and irradiated at room temperature with an irradiance of 1.5mW / cm. 2 The composition was polymerized by irradiating UV light at 400 K for 30 minutes to obtain a polymer. Each polymer was removed from the lens mold and cell to obtain two different polymer shapes. Both polymers were immersed in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchanged water for 4 hours to remove unreacted materials and purify them. After purification, both purified polymers were immersed in physiological saline according to ISO-18369-3 to swell (hydrate) them, preparing contact lenses and SGs, which differ only in shape from contact lenses. The contact lenses and SGs were divided into sizes and shapes appropriate for each of the above evaluations, and each evaluation was performed. The blending ratios of each component in the composition, polymerization conditions, and evaluation results are shown in Table 1.

[0074] [Examples 7 and 8] The contact lenses and SGs of each Example were prepared in the same manner as in Example 6, except that the blending ratios of each component in the composition and the polymerization conditions were as shown in Table 1. The contact lenses and SGs of each Example were also evaluated in the same manner as in Example 6. The results are shown in Table 1.

[0075] [Comparative Example 1] 0.50 g (10.0 wt%) of MPC, 1.25 g (25.0 wt%) of ETS, 0.50 g (10.0 wt%) of HBMA, and 1.25 g (25.0 parts by mass) of HeOH were mixed in a container and stirred at room temperature until the MPC was dissolved. 1.25 g (25.0 wt%) of NVP, 1.50 g (30.0 wt%) 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 then added to the container and stirred at room temperature until a uniform mixture was obtained. A portion of the composition was filled into a lens mold. A portion of the composition was also filled into a 25 mm x 70 mm x 0.2 mm cell sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer. The lens mold and cell filled with the composition were placed in an oven, and the oven was purged with nitrogen. The oven was then heated to 80°C and maintained at 80°C for 12 hours to polymerize the composition and obtain a polymer. Each polymer was removed from the lens mold and cell, yielding two different polymer shapes. Both polymers were immersed in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchanged water for 4 hours to remove unreacted materials and purify them. After purification, both purified polymers were immersed in physiological saline according to ISO-18369-3 to swell (hydrate) them and prepare contact lenses and SGs, which differ only in shape from the contact lenses. The contact lenses and SGs were divided into sizes and shapes appropriate for each of the above evaluations, and each evaluation was performed. The blending ratios of each component in the composition, polymerization conditions, and evaluation results are shown in Table 2. The contact lenses and SGs of Comparative Example 1 had poorer oxygen permeability, transparency, and durability than the contact lenses and SGs of each Example.

[0076] Comparative Example 2 A contact lens and SG were prepared in the same manner as in Comparative Example 1, except that the blending ratio of each component in the composition and the polymerization conditions were as shown in Table 2. The contact lens and SG of Comparative Example 2 were also evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2. The SG (plate-shaped silicone hydrogel) of Comparative Example 2 was significantly inferior in durability compared to the SGs of each Example.

[0077] Comparative Example 3 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 mass) of HeOH were mixed in a container and stirred at room temperature until the MPC was dissolved. 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 mass) of mPDMS15-20, and 0.010 g (0.2 parts by mass) of I-819 were added to the container and stirred at room temperature until homogeneous to obtain a composition. A portion of the composition was filled into a lens mold. A portion of the composition was filled into a 25mm x 70mm x 0.2mm cell sandwiched between two polypropylene plates using a 0.1mm thick polyethylene terephthalate sheet as a spacer. The lens mold and cell filled with the composition were placed in a UV-LED irradiator (irradiation wavelength 405nm) and irradiated at room temperature with an irradiance of 1.5mW / cm. 2 The composition was polymerized by irradiating UV light at 400 K for 30 minutes at 400 K for 30 minutes to obtain a polymer. Each polymer was removed from the lens mold and cell to obtain two different polymer shapes. Both polymers were immersed in 100 mL of 50 vol% 2-propanol aqueous solution for 4 hours, followed by immersion in 100 mL of ion-exchanged water for 4 hours to remove unreacted materials and purify them. After purification, both purified polymers were immersed in physiological saline according to ISO-18369-3 to swell (hydrate) them, thereby preparing contact lenses and SGs, which differed only in shape from the contact lenses. The contact lenses and SGs were divided into sizes and shapes appropriate for each of the above evaluations, and each evaluation was performed. The blending ratios of each component in the composition, polymerization conditions, and evaluation results are shown in Table 2. The contact lens and SG of Comparative Example 3 had poorer transparency and significantly inferior durability compared to the contact lenses of each Example.

[0078] Comparative Example 4 A contact lens and SG were prepared in the same manner as in Comparative Example 3, except that the blending ratio of each component in the composition and the polymerization conditions were as shown in Table 2. The contact lens and SG of Comparative Example 4 were also evaluated in the same manner as in Comparative Example 3. The results are shown in Table 2. The contact lens and SG of Comparative Example 4 were significantly inferior in transparency and durability compared to the contact lenses and SG of each Example.

[0079] [Table 1]

[0080] [Table 2]

Claims

1. (A) a phosphorylcholine group-containing methacrylic acid ester monomer represented by the following formula (1), 【Chemistry 1】 (B) a siloxanyl group-containing itaconic acid diester monomer represented by the following formula (2), 【Chemistry 2】 (C) one or more hydrophilic monomers 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; (D) a siloxanyl group-containing (meth)acrylate represented by formula (3), 【Transformation 3】 [In formula (3), R1 is hydrogen or a methyl group, m is 0 or 1, and n is 3 to 9.] (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 a siloxanyl group-containing dimethacrylate represented by the following formula (4): 【Chemistry 4】 [In formula (4), p and r are 0 or 1, and q is 5 to 20.] the content of the component (A) is 5 to 25 mass%, the content of the component (B) is 5 to 30 mass%, the content of the component (C) is 15 to 45 mass%, the content of the component (D) is 15 to 40 mass%, and the content of the component (E) is 0.2 to 2.5 mass%, relative to 100 mass% of the total of the components (A) to (E) in the composition; the content ratio of the component (D) to the component (E) in the composition is a mass ratio [(E) / (D)] of 0.01 to 0.06; Monomer composition for contact lenses.

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

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

4. A polymer of the monomer composition for contact lenses according to any one of claims 1 to 3. Polymers for contact lenses.

5. A composition comprising the hydrate of the polymer for contact lenses according to claim 4. Contact lenses.

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

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