TW202140584A - Monomer composition for contact lens and polymer for contact lens - Google Patents

Abstract

A monomer composition for a contact lens according to the present invention contains: (A) a phosphorylcholine group-containing methacrylic ester monomer represented by formula (1); (B) at least one hydroxyl group-containing monomer selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, tetera methylene glycol monovinyl ether, and diethylene glycol monovinyl ether; (C) a itaconic acid diester monomer containing a specific siloxanyl group; (D) a (meth)acrylate containing a specific siloxanyl group; (E) N-vinylpyrrolidone; and (F) a photopolymerization initiator, wherein the composition contains 2-40 mass% of component (A), 5-45 mass% of component (B), 7-35 mass% of component (C), 7-55 mass% of component (D), 0.5-35 mass% of component (E), and 0.1-10 mass% of component (F) when the sum of the monomer components in the composition is 100 mass%. The present invention can provide a monomer composition for a contact lens from which a contact lens can be formed which is capable of relieving discomfort in a user by alleviating pollinosis symptoms, and also has excellent oxygen permeability.

Description

Monomer composition for contact lens and polymer for contact lens

The present invention relates to a monomer composition for contact lenses, a polymer for contact lenses, and contact lenses composed of a hydrate of the polymer.

Since soft contact lenses are simple, portable and convenient to use, the number of users has increased sharply. There are more than 10 million soft contact lens wearers in Japan, and they wear them for a long time each day. In addition, it is estimated that the prevalence of hay fever in Japan is as high as 1/3 of that of Japanese nationals (Non-Patent Document 1), and the number is considered to be as high as 30 million. Therefore, it can be considered that most soft contact lens wearers also have hay fever.

Hay fever is caused by allergic reactions. For example, pollen scattered from cedar or pollen protein released from such pollen adheres and adsorbs on the surface of the cornea or the surface of soft contact lenses, resulting in symptoms. As a representative symptom of hay fever, a runny nose or watery nose can be cited. In order to treat, alleviate, and prevent the allergic symptoms caused by hay fever, as a pharmaceutical/chemical method, it is known to use medicines or eye drops formulated with anti-allergic drugs for treatment and relief (Patent Document 1). As a physical method, it is known to wear glasses or eye masks to prevent pollen or pollen protein from contacting the surface of the cornea or the surface of soft contact lenses from the source (Patent Document 2 and Patent Document 3).

At the same time, it is known that although pharmacological/chemical methods exhibit high effectiveness, they have side effects such as inducing drowsiness. In addition, with regard to physical methods, if pollen or pollen protein adheres to and adsorbs on the surface of the cornea or the surface of soft contact lenses, it is known that This method is effective. Once pollen or pollen protein adheres to and adsorbs on the surface of the cornea or the surface of soft contact lenses, the effectiveness will be lost. Furthermore, there is also the following concern: once pollen or pollen protein adheres during the wearing process of soft contact lenses, it will be difficult to wash away with tears or artificial tears and other eye drops, eye washes, etc., resulting in long-lasting allergic symptoms time. In addition, since the wearing time per day is long, it is also necessary to impart high oxygen permeability to the contact lens. Therefore, it is required to develop a technology that can alleviate and alleviate the symptoms and discomfort of hay fever by inhibiting the adhesion of pollen or pollen protein and adsorbing on the surface of soft contact lenses or the surface of the cornea. However, the technology development for these needs is insufficient. Lack of effective methods. Prior art literature Non-patent literature

Non-Patent Document 1: Ministry of the Environment, Hay fever Environmental Health Guide-Revised Edition in January 2014- Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2018-203791 Patent Document 2: Japanese Patent Laid-Open No. 2017-134100 Patent Document 3: Japanese Patent Laid-Open No. 2014-111147

[The problem to be solved by the invention]

The subject of the present invention is to provide a monomer composition for contact lenses, which can form contact lenses with the following characteristics: can alleviate the symptoms of hay fever by inhibiting the adsorption of pollen and/or pollen protein on the surface of the contact lens, thereby improving Discomfort, and excellent oxygen permeability. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research in order to solve the above-mentioned problems. As a result, it was found that by using a monomer composition for contact lenses that contains 3 types of hydrophilic monomers, 2 types of siloxane group-containing monomers, and further contains a photopolymerization initiator, a pollen and/or pollen inhibitor can be formed. A contact lens with protein adsorption and excellent oxygen permeability. The contact lens can alleviate the symptoms of hay fever, thereby improving discomfort. That is, the present invention is as follows.

[化2]

[化3]

(式(3)中，R₁ 為氫原子或甲基，n為1～15)。 [2]一種隱形眼鏡用聚合物，其係使如上述[1]之隱形眼鏡用單體組合物進行聚合而獲得。 [3]一種隱形眼鏡，其係使如上述[2]之隱形眼鏡用聚合物進行水合而獲得。 [4]如上述[3]之隱形眼鏡，其用於抑制花粉及/或花粉蛋白之吸附。 [發明之效果][1] A monomer composition for contact lenses, which is a composition containing the following components: (A) a phosphocholine group-containing methacrylate monomer represented by formula (1); (B) is selected from ( Hydroxyethyl meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, And one or more hydroxyl-containing monomers in the group consisting of diethylene glycol monovinyl ether; (C) a siloxyalkyl-containing itaconic acid diester monomer represented by formula (2); (D) The siloxane group-containing (meth)acrylate represented by formula (3); (E) N-vinylpyrrolidone; and (F) photopolymerization initiator; When the monomer in the above composition When the total of the components is 100% by mass, the composition contains 2-40% by mass (A) component, 5-45% by mass (B) component, 7-35% by mass (C) component, and 7-55 Mass% (D) component, 0.5-35% by mass (E) component, and 0.1-10% by mass (F) component, [Chemical 1]

[化2]

[化3]

(In formula (3), R ₁ is a hydrogen atom or a methyl group, and n is 1 to 15). [2] A polymer for contact lenses obtained by polymerizing the monomer composition for contact lenses as described in [1] above. [3] A contact lens obtained by hydrating the polymer for contact lenses as described in [2] above. [4] The contact lens of [3] above, which is used to inhibit the adsorption of pollen and/or pollen protein. [Effects of the invention]

By using the monomer composition for contact lenses of the present invention, a contact lens with the following characteristics can be formed: it can inhibit the adsorption of pollen and the adsorption of pollen protein, thereby alleviating and alleviating the symptoms of hay fever and improving discomfort. . In addition, the monomer composition for contact lenses of the present invention can form contact lenses with excellent oxygen permeability.

[Monomer composition for contact lenses] The monomer composition for contact lenses of the present invention is a composition containing the components (A) to (F) as essential components, and is preferably a uniform transparent liquid. The polymer for contact lenses of the present invention is obtained by polymerizing the monomer composition for contact lenses, and the contact lens of the present invention is obtained by hydrating the polymer for contact lenses.

In this specification, when a preferable numerical range (for example, a range of a concentration or a weight average molecular weight, etc.) is described step by step, each lower limit and upper limit can be combined independently. For example, in the description of "preferably 10 or more, more preferably 20 or more, and preferably 100 or less, and more preferably 90 or less", "preferably lower limit: 10" and "better upper limit" Value: 90" is combined into "10 above 90". For example, in the description of "preferably 10 to 100, more preferably 20 to 90", it may be similarly made to "10 to 90".

In the present invention, "(meth)acrylic acid" means acrylic acid or methacrylic acid (Methacryl), "(meth)acryloyl group" means acrylic acid group or methacryloyl group (Methacryloyl), "(former "Acrylate" means acrylate or methacrylate.

<Component (A): Methacrylate monomer containing phosphorylcholine> The component (A) in the present invention is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1), specifically, 2-methacryloxyethyl phosphorylcholine (MPC) ). By containing the component (A) in a specific amount, the contact lens, which is the polymer of the monomer composition for contact lenses of the present invention, can impart the adsorption inhibitory effect of pollen and pollen protein.

[化4]

In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the component (A) is 2-40% by mass. From the viewpoint of imparting pollen and pollen protein adsorption inhibitory effects to contact lenses, the content of component (A) is preferably 5-40% by mass, more preferably 10-30% by mass, and still more preferably 15-30 quality%. If the content of (A) component is less than 2% by mass, there is a risk that the contact lens will not be able to obtain sufficient pollen and pollen protein adsorption inhibitory effect. If it is more than 40% by mass, it may be difficult to dissolve (A) component in In the monomer composition for contact lenses, there is a risk that the mechanical strength of the contact lens itself is reduced, and the production of the contact lens becomes difficult. In addition, in this specification, the term "monomer component" means a compound having a polymerizable unsaturated group such as a (meth)acrylate group and a vinyl group. Therefore, the term "monomer component" means excluding the (A) component, (B) component, (C) component, (D) component, and (E) component as essential components contained in the contact lens monomer composition , Component (G) that can be formulated as an optional component.

＜Component (B): Hydroxyl-containing monomer＞ The component (B) in the present invention is selected from hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monoethylene One or more hydroxyl-containing monomers in the group consisting of ether, tetramethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. By containing the component (B) in a specific amount, the dissolution of the component (A) in the monomer composition for contact lenses of the present invention is improved.

Specific examples of the component (B) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl) Base) acrylamide, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether and the like. (B) As long as the component is any one of these monomers, it may be a mixture of two or more types.

In terms of further improving the solubility of component (A), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether.

In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the component (B) is 5 to 45% by mass. From the viewpoint of improving the solubility of component (A) in the monomer composition for contact lenses, the content ratio of component (B) is preferably 5-40% by mass, more preferably 7-38% by mass, and more Preferably, it is 10 to 35% by mass. If the content ratio of the component (B) is less than 5% by mass, there is a risk that the composition of the present invention will not become a uniform transparent liquid. On the other hand, if it exceeds 45% by mass, it is difficult to further improve the solubility of the component (A).

＜(C)Component: Iconic acid diester monomer containing siloxane group＞ The component (C) in the present invention is a siloxane group-containing itaconic acid diester monomer represented by the following formula (2). By containing the component (C) in a specific amount, it is possible to impart excellent oxygen permeability to contact lenses obtained by polymerizing the monomer composition for contact lenses of the present invention.

[化5]

The single system of formula (2) is obtained by the esterification reaction of monoethylene glycol itaconic acid and 3-iodopropyl[tris(trimethylsilyloxy)]silane. Iconate monoethylene glycol ester is obtained, for example, by the method described in WO2010/104000. In this esterification reaction, the structural isomer represented by the following formula (2') is produced by-product. In the present invention, a mixture of the monomer of formula (2) and the monomer of formula (2') can be used as the component (C). That is, in the present invention, "the siloxyalkyl-containing itaconic acid diester monomer represented by the formula (2)" includes not only the monomer of the formula (2) alone, but also the monomer of the formula (2) In addition to the isomers, a part of the isomers of formula (2') is also included.

[化6]

In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the component (C) is 7 to 35% by mass. From the viewpoint of imparting oxygen permeability to contact lenses, the content of the component (C) is preferably 10 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 10 to 20% by mass. If the content of (C) component is less than 7% by mass, there is a risk that the manufactured contact lens polymer will appear cloudy. On the other hand, if it is more than 35% by mass, there is a risk that the mechanical strength of the contact lens will decrease, making it difficult to manufacture the contact lens.

＜(D)Component: (meth)acrylate containing siloxane group＞ The component (D) in the present invention is a siloxane group-containing (meth)acrylate represented by the following formula (3). By containing the component (D) in a specific amount, it is possible to impart oxygen permeability to the contact lens obtained by polymerizing the monomer composition for contact lens of the present invention.

式(3)中，R₁ 為氫原子或甲基。n表示二甲基矽氧烷部之重複數，為1～15。(D)成分可為重複數n不同之複數個化合物之混合物，於此情形時，n為數量平均分子量中之平均值，處於1～15之範圍，較佳為3～9之範圍。當n為3以上時，能夠賦予充分之透氧性，當n為9以下時，易獲得均勻地溶解之隱形眼鏡用單體組合物。[化7]

In the formula (3), R ₁ is a hydrogen atom or a methyl group. n represents the number of repetitions of the dimethylsiloxane moiety, and is 1-15. (D) The component may be a mixture of multiple compounds with different repeating numbers n. In this case, n is the average value of the number average molecular weight, in the range of 1-15, preferably 3-9. When n is 3 or more, sufficient oxygen permeability can be imparted, and when n is 9 or less, it is easy to obtain a uniformly dissolved monomer composition for contact lenses.

In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the component (D) is 7 to 55% by mass. From the viewpoint of imparting oxygen permeability to the contact lens, the content ratio of the component (D) is preferably 10 to 50% by mass, more preferably 13 to 45% by mass, and still more preferably 13 to 35% by mass. If the content of (D) component is less than 7% by mass, there is a risk that the manufactured contact lens polymer will appear cloudy. On the other hand, if it is more than 55% by mass, there is a risk that the mechanical strength of the contact lens will decrease, making it difficult to manufacture the contact lens.

＜(E) Component: N-vinylpyrrolidone＞ The component (E) in the present invention is N-vinylpyrrolidone. By containing the component (E) in a specific amount, the contact lens obtained by polymerizing the monomer composition for contact lenses of the present invention can impart the adsorption inhibitory effect of pollen and pollen protein. In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the (E) component is 0.5 to 35% by mass. From the viewpoint of the pollen and pollen protein adsorption inhibitory effect of the contact lens, the content of the component (E) is preferably 0.5-30% by mass, more preferably 1-25% by mass, and still more preferably 1-10% by mass %, particularly preferably 1 to 5 mass%. If the content of (E) component is less than 0.5% by mass, there is a risk that the adsorption inhibitory effect of the pollen and pollen protein of the contact lens will become insufficient. On the other hand, if it is more than 35% by mass, it is difficult to improve the adsorption inhibitory effect of pollen and pollen protein of the contact lens. Furthermore, from the viewpoint of the pollen and pollen protein adsorption inhibitory effect of the contact lens, the mass ratio (A)/(E) of the component (A) to the component (E) is preferably 0.1-20, more preferably 2～ 15, more preferably 3-10, particularly preferably 5-10.

<Component (F): Photopolymerization initiator> The component (F) in the present invention is a photopolymerization initiator. By blending a specific amount of component (F), not only the monomer composition for contact lenses of the present invention can be polymerized to produce contact lenses with excellent transparency and yield, but also component (A) can be uniformly dissolved It is used in contact lenses and hardened, so it can be made into contact lenses with excellent pollen and pollen protein adsorption inhibitory effect. (F) The component is not particularly limited, and examples include phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl -1-Phenyl-propan-1-one, bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6- Trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, Benzoin methyl ester, camphorquinone, and ethyl 4-(N,N-dimethylamino)benzoate, etc. (F) The component may be one type or a mixture of two or more types.

In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the component (F) is 0.1-10% by mass. From the viewpoint of polymerizability to contact lenses, it is preferably 0.5 to 5% by mass, and more preferably 0.5 to 4% by mass. If the content of (F) component is less than 0.1% by mass, there is a risk of incomplete polymerization and failure to produce contact lenses. On the other hand, when it is more than 10% by mass, there is a risk of incomplete polymerization and failure to produce contact lenses.

<(G) component: monomers other than (A) component-(F) component, etc.> The (G) component of the present invention is a monomer other than the (A) component to (F) component. The component (G) is optional and can be formulated for the purpose of adjusting the mechanical strength and moisture content of the contact lens. As (G) component, the monomer which has an amide group, the monomer which has a carboxyl group, and the monomer which has an ester group can be illustrated. Examples of monomers having an amide group include N-vinylpiperidin-2-one, N-vinyl-ε-caprolactam, and N-vinyl-3-methyl-2-caprolactone. Amine, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylamide, N-isopropylacrylamide, acrylamide, N-vinyl-N-methyl Acetamide, N-vinylacetamide, N-vinylformamide, etc. Examples of the monomer having a carboxyl group include (meth)acrylic acid, 2-methacryloxyethyl succinic acid, and the like. Examples of monomers having ester groups include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, and methoxy polyethylene Diol methacrylate etc. The component (G) can be used regardless of whether it is any one of these monomers or a mixture of two or more of them. When the monomer composition for contact lenses of the present invention contains the (G) component, when the total of all the monomer components is 100% by mass, the content of the (G) component is preferably 25% by mass or less.

In addition to the above-mentioned (A) component to (G) component, the monomer composition for contact lenses of the present invention may contain a solvent. The solvent is not particularly limited, as long as it can improve the solubility of each component in the composition. As the solvent, for example, an alcohol-based solvent or a carboxylic acid-based solvent can be exemplified. Examples of alcohol solvents include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 2-pentanol, and tertiary amino alcohol. , 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, etc. Examples of carboxylic acid solvents include glycolic acid, lactic acid, acetic acid, and the like. Either one of these solvents or a mixture of two or more of them can be used. From the viewpoint of the manufacturability of the contact lens polymer, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1- Octanol, 1-decanol. When the monomer composition for contact lenses of the present invention contains a solvent, when the total of all monomer components is 100% by mass, the content of the solvent is preferably 25% by mass or less.

In addition to the above-mentioned (A) component to (G) component, the monomer composition for contact lenses of the present invention may contain a crosslinking agent. The crosslinking agent usually has two or more polymerizable unsaturated groups, and a known crosslinking agent can be used. As the crosslinking agent, for example, in addition to silicone dimethacrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and ethylene glycol dimethacrylate can also be cited. , Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, methylene bisacrylamide, allyl methacrylate, methacrylic acid (2 -Allyloxy) ethyl, 2-(2-vinyloxyethoxy) ethyl acrylate, 2-(2-vinyloxyethoxy) ethyl methacrylate, etc. The crosslinking agent can be used regardless of whether it is any one of them or a mixture of two or more. In the monomer composition for contact lenses of the present invention, when the total of all monomer components is 100% by mass, the content ratio of the crosslinking agent is preferably 0.1-10% by mass.

In addition to the above-mentioned (A) component to (G) component, the monomer composition for contact lenses of the present invention may contain additives such as ultraviolet absorbers and colorants within a range that does not hinder the purpose of the present invention.

[Polymers for contact lenses, contact lenses] The polymer for contact lenses of the present invention is obtained by polymerizing the above-mentioned monomer composition for contact lenses. Specifically, the monomer composition for contact lenses of the present invention is mixed and uniformly dissolved, dispensed into a mold for contact lenses, and polymerized by irradiating visible light or UV (Ultraviolet) light within a specific period of time. Thus, a polymer for contact lenses can be obtained.

The polymerization reaction can be carried out in the atmosphere, but in order to increase the polymerization rate of the monomers, it can also be carried out in an inert gas atmosphere such as nitrogen or argon. When performing polymerization in an inert gas atmosphere, it is preferable to set the pressure in the polymerization system to 1 kgf/cm ² or less. After the polymerization, a known method can be used to release the mold from the mold, and the polymer for contact lenses can be taken out in a dry state. In addition, the polymer for contact lenses and the mold can be immersed in a solvent (for example, water, methanol, ethanol, 1-propanol, 2-propanol, and mixed solutions of these) to swell the polymer for contact lenses , So as to make it demould. Furthermore, it is repeatedly immersed in these solvents etc. for washing, and the residues, residues, by-products, etc. of each component are removed, and a contact lens can be manufactured.

As the solvent used for washing, water, methanol, ethanol, 1-propanol, 2-propanol, mixtures of these, and the like can be mentioned. For washing, for example, the polymer can be immersed in an alcohol solvent at a temperature of 10°C to 40°C for 10 minutes to 10 hours. Moreover, after washing in an alcohol-based solvent, it may be immersed in an aqueous solution having an alcohol concentration of 20 to 50% by mass for 10 minutes to 10 hours for washing. Any solvent can be used for the cleaning solvent, as long as it has the quality for medicine, quasi-drug, and medical equipment.

The contact lens of the present invention is obtained by hydrating the above-mentioned polymer for contact lens. Specifically, the cleaned contact lens polymer is immersed in physiological saline to hydrate it in a manner to achieve a specific moisture content, thereby obtaining the contact lens of the present invention. As the physiological saline, physiological saline containing a boric acid buffer or physiological saline containing a phosphate buffer can be used.

The contact lens of the present invention is obtained by the monomer composition for contact lens with the above-mentioned specific composition, which can inhibit the adsorption of pollen and pollen protein on the surface of the contact lens. That is, the contact lens of the present invention can be preferably used to inhibit the adsorption of pollen and/or pollen protein. [Example]

Hereinafter, the present invention will be described in more detail with examples and comparative examples, but the present invention is not limited to these examples and comparative examples. Hereinafter, the compounds used in the present examples and comparative examples are shown.

(A) Ingredient MPC: 2-Methacryloxyethyl Phosphate Choline

(B) Ingredients HEA: Hydroxyethyl acrylate HEAA: Hydroxyethyl acrylamide HEMA: Hydroxyethyl methacrylate HPMA: Hydroxypropyl methacrylate HBMA: hydroxybutyl methacrylate EGMV: Ethylene glycol monovinyl ether DGMV: Diethylene glycol monovinyl ether TGMV: Tetraethylene glycol monovinyl ether

(C) Ingredients ETS: The esterification reactant of monoethylene glycol itaconic acid and 3-iodopropyl [tris(trimethylsilyloxy)] silane is the compound of formula (2) (D) Ingredients MCR-M07: compound of formula (3) [R1: methyl, n: 6, number average molecular weight: 600-800]

(E) Ingredients NVP: N-vinylpyrrolidone (F) Ingredients I-819: Phenylbis(2,4,6-trimethylbenzyl) phosphine oxide

(G) Ingredients MMA: methyl methacrylate Other ingredients HeOH: 1-hexanol TEGDMA: Tetraethylene glycol dimethacrylate TEGDV: Triethylene glycol divinyl ether

The monomer composition for contact lenses, the polymer for contact lenses, and the contact lenses produced in the examples and comparative examples were evaluated by the following methods.

＜The uniformity and solubility of the composition＞ The composition was put into a colorless and transparent container, and the evaluation was performed by visual inspection using the following criteria. 〇: Uniform and transparent ×: Inhomogeneous, with white turbidity or sediment, etc.

＜Form of polymer＞ The morphology of the polymer for contact lenses was evaluated visually and using the following criteria. 〇: Solid ×: Liquid (including viscous liquid)

<Oxygen Permeability> The oxygen permeability of contact lenses was evaluated by measuring the oxygen permeability coefficient as follows. Use samples with different thicknesses to determine the oxygen permeability coefficient according to the polarographic method described in ISO 18369-4. _{The O 2} Permeometer Model 201T of Rehder Development Company (Rehder Development Company) was used in the measurement. The thickness of the lens is taken as the x-axis, and the t/Dk value obtained by the measurement is plotted on the y-axis, and the reciprocal of the slope of the regression line is set as the oxygen permeability coefficient. The larger the oxygen permeability coefficient, the higher the oxygen permeability. The case where the oxygen permeability coefficient is 60 or more is judged as the pass criterion or higher, and the case where the oxygen permeability coefficient is 80 or more is judged as good.

<Pollen adsorption test, pollen protein adsorption test> In the following pollen adsorption test and pollen protein adsorption test, a phosphate buffer solution (hereinafter referred to as "PBS") was used. PBS (composition: potassium chloride 0.02 w/v%, potassium dihydrogen phosphate 0.02 w/v%, sodium chloride 0.8 w/v%, disodium hydrogen phosphate 0.115 w/v%) is based on Sigma-Aldrich (Sigma -Aldrich) products.

(Pollen adsorption test) In the following order, a pollen adsorption test was performed using the contact lenses of each example and each comparative example. (1) Take out a piece of contact lens, rinse it with 10 mL of PBS, and then soak it in 2 mL of PBS overnight. (2) Using Japanese cedar pollen (manufactured by Biostir) and PBS, a solution (hereinafter referred to as "pollen solution") was prepared so that the concentration of Japanese cedar pollen was 3 mg/mL. (3) Prepare a new 24-well plate, put 1.5 mL of pollen solution in it, and then immerse the contact lens prepared in (1) in the pollen solution. After that, in order to fully absorb the pollen on both sides of the contact lens, the contact lens was turned over every about 1 hour. (4) Take out the soft contact lens 5 hours after the start of immersion, and wash it thoroughly with 10 mL of PBS. (5) Prepare a new 24-well plate, put the washed contact lenses and 2 mL of PBS into it, and shake it for 5 minutes. (6) Use a microscope to measure the pollen adsorbed on the contact lens. In addition, regarding the pollen adsorption test, the following criteria were used to determine the pollen adsorption inhibitory effect of contact lenses. Based on Comparative Example 1-5, the pollen adsorption inhibition rate was calculated using the following formula to determine whether there is a pollen adsorption inhibition effect. Pollen adsorption inhibition rate={1－[(pollen adsorption amount of each example or each comparative example)/(pollen adsorption amount of comparative example 1-5)]}×100 "Criteria of Judgment" Pollen adsorption inhibition rate is more than 70%: pollen adsorption inhibition effect is extremely excellent Pollen adsorption inhibition rate is more than 50% and less than 70%: excellent pollen adsorption inhibition effect Pollen adsorption inhibition rate is more than 30% and less than 50%: it has pollen adsorption inhibition effect Pollen adsorption inhibition rate is less than 30%: no pollen adsorption inhibition effect

(Pollen protein adsorption test) In accordance with the following sequence, the pollen protein adsorption test was performed on the contact lenses in each example and each comparative example. (1) Move the contact lenses of each example and each comparative example after the pollen adsorption test to a new 24-well plate, put 2 mL of PBS and let it stand for 30 minutes. (2) In addition, the peroxidase-labeled anti-Cryj1 antibody was diluted 1000 times with PBS. (3) Put 1 mL of the solution prepared in (2) into the sample bag, and then immerse the contact lens prepared in (1) in it, and shake at room temperature for 3 hours. (4) After standing still, take out the immersed contact lenses, rinse them thoroughly with 20 mL of PBS, and put them in a new 24-well plate. (5) Add 2 mL of PBS and wash for 10 minutes. In order to wash it sufficiently, this washing operation is performed again. (6) Using DAB Substrate Kit (manufactured by SK-4100, Vector), prepare DAB (Diaminobenzidine) coloring solution, and add 1.2 mL to the 24-well plate. (7) Put the cleaned contact lens in (5) into the 24-well plate of (6) and let it react for at least 2 hours. After that, wash with purified water and measure the absorbance at 450 nm to measure the amount of pollen protein adsorbed on the contact lens (because the amount of pollen protein adsorbed is dependent on the absorbance, the pollen protein adsorbed by the lower absorbance is judged Less amount).

[Example 1-1] 8.6 g of MPC, 8.7 g of HBMA, 17.4 g of EGMV, 13.1 g of ETS, 30.5 g of MCR-M07, 8.7 g of NVP, 13.0 g of MMA, 1.0 g of TEGDMA, 2.5 g of TEGDV and 10.0 g of HeOH were mixed and dissolved uniformly to obtain a composition. The composition was evaluated for the homogeneity and solubility of the above-mentioned composition. Table 1 shows the content ratio of each component and the evaluation result. 1.0 g of I-819 was added to the above composition to prepare a monomer composition for contact lenses, and the composition was allowed to flow. A polyethylene terephthalate sheet with a thickness of 0.1 mm was sandwiched between two polypropylene plates as a spacer. Place it in the UV irradiation device (manufactured by CCS Co., Ltd.). In a UV irradiation device, 405 nm, 1.5 mW/cm ² UV light was irradiated for 30 minutes to polymerize the composition to obtain a polymer for contact lenses. The polymer was taken out of the tank, and the above evaluation was performed. Table 1 shows the polymerization conditions and evaluation results.

After immersing the above polymer in 40 g of 2-propanol for 4 hours, it was immersed in 50 g of ion-exchanged water for 4 hours to remove unreacted materials and the like, thereby purifying it. The purified polymer is immersed in the physiological saline described in ISO18369-3 and swelled (hydrated) to prepare a hydrate. The hydrate is processed in a shape suitable for each evaluation to prepare contact lenses for evaluation. The results of each evaluation are shown in Table 1.

[Example 1-2 to Example 1-8, Comparative Example 1-1 to Comparative Example 1-5] According to the ingredients and amounts described in Table 1, the operation was carried out in the same manner as in Example 1-1 to prepare Examples 1-2 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-5. Contact lenses for evaluation. The results of each evaluation are shown in Table 1.

[Table 1] Table 1 Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 Example 1-7 Example 1-8 combination Ingredients (mass%) (A) Ingredient MPC 8.6 13.0 15.7 5.0 25.0 13.0 5.0 9.0 (B) Ingredients HEA HEAA 4.0 HEMA 6.0 HPMA 12.0 HBMA 8.7 8.7 8.7 20.0 5.0 EGMV 17.4 17.4 17.4 3.0 20.0 5.0 DGMV 20.0 TGMV 6.0 (C) Ingredients ETS 13.1 13.1 13.1 13.1 30.0 30.0 10.0 20.0 (D) Ingredients MCR-M07 30.5 30.5 30.5 30.5 13.6 30.5 10.0 50.0 (E) Ingredients NVP 8.7 4.4 1.6 4.4 4.4 4.5 30.0 6.0 (F) Ingredients I-819 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Other ingredients (mass%) (G) Ingredients MMA 13.0 13.0 13.0 15.0 15.0 15.0 5.0 5.0 Other ingredients HeOH 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 TEGDMA 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 TEGDV 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (A)/(E) 1.0 3.0 9.8 1.1 5.7 2.9 0.2 1.5 Total of (A), (B), (C), (D), (E), (G) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Polymerization conditions Wavelength (nm) 405 405 405 405 405 405 405 405 Irradiation intensity (mW/cm ² ) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Time (min.) 30 30 30 30 30 30 30 30 evaluate Uniformity and solubility of the composition 〇 〇 〇 〇 〇 〇 〇 〇 Polymer form 〇 〇 〇 〇 〇 〇 〇 〇 Oxygen Permeability of Contact Lenses (DK) 81 82 80 81 83 97 64 102 Pollen adsorption inhibition rate 90% 95% 98% 84% 99% 91% 87% 85% Pollen protein adsorption inhibitory effect (absorbance) 0.15 0.12 0.10 0.18 0.07 0.16 0.19 0.20

[Table 2] Table 2 Comparative example 1-1 Comparative example 1-2 Comparative example 1-3 Comparative example 1-4 Comparative example 1-5 combination Ingredients (mass%) (A) Ingredient MPC 25.0 20.0 20.0 (B) Ingredients HEA HEAA HEMA 20.0 HPMA HBMA 8.7 1.5 20.0 8.5 EGMV 17.4 1.5 20.0 8.5 DGMV TGMV (C) Ingredients ETS 13.1 15.0 5.0 15.0 50.0 (D) Ingredients MCR-M07 30.5 35.0 5.0 35.0 (E) Ingredients NVP 17.3 9.0 17.0 30.0 (F) Ingredients I-819 1.0 1.0 1.0 1.0 1.0 Other ingredients (mass%) (G) Ingredients MMA 13.0 13.0 13.0 13.0 Other ingredients HeOH 10.0 10.0 10.0 10.0 10.0 TEGDMA 1.0 1.0 1.0 1.0 1.0 TEGDV 2.5 2.5 2.5 2.5 2.5 (A)/(E) 0.0 2.8 1.2 - 0.0 Total of (A), (B), (C), (D), (E), (G) 100.0 100.0 100.0 100.0 100.0 Polymerization conditions Wavelength (nm) 405 405 405 405 405 Irradiation intensity (mW/cm ² ) 1.5 1.5 1.5 1.5 1.5 Time (min.) 30 30 30 30 30 evaluate Uniformity and solubility of the composition 〇 X 〇 〇 - ^＊ Polymer form 〇 X X X - ^＊ Oxygen Permeability of Contact Lenses (DK) 79 - ^＊＊ 34 83 - ^＊ Pollen adsorption inhibition rate 13% - ^＊＊ 63% 58% - ^＊ Pollen protein adsorption inhibitory effect (absorbance) 0.45 - ^＊＊ 0.33 0.38 - ^＊ *: Since this comparative example serves as a reference, no evaluation was performed. **: Since a uniform monomer composition for contact lenses was not obtained, polymerization or the like was not performed.

[Example 2-1] Using the contact lens of Example 1-1, the pollen as the test object was changed from Japanese cedar pollen to the cypress pollen described in Table 3, and the pollen adsorption test and the pollen protein adsorption test were carried out. The results are shown in Table 3.

[Example 2-2 to Example 2-8] Using the contact lenses of the examples described in Table 3 and various pollens, the pollen adsorption test and the pollen protein adsorption test were carried out. The results are shown in Table 3.

[table 3] table 3 Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 Example 2-7 Example 2-8 Evaluation of the contact lenses used Example 1-1 Example 1-1 Example 1-1 Example 1-1 Example 1-1 Example 1-1 Example 1-2 Example 1-3 Assess the type of pollen used Hinoki Pollen Hogweed pollen Rice pollen Ginkgo Pollen Wormwood Pollen Pollen of Goldenrod Hinoki Pollen Hogweed pollen evaluation result Pollen adsorption inhibition rate 87% 84% 81% 82% 78% 77% 90% 91% Pollen protein adsorption inhibitory effect (absorbance) 0.15 0.19 0.20 0.20 0.22 0.24 0.13 0.15

In the contact lenses of Examples 1-1 to 1-8, the pollen adsorption inhibition rate was 84% to 99%. In the contact lenses of Comparative Example 1-1, the pollen adsorption inhibition rate was 13%. The examples show It has an excellent pollen adsorption inhibitory effect. In the contact lenses of Comparative Example 1-2 to Comparative Example 1-4, although the pollen adsorption inhibitory effect was exhibited, the polymer had a poor morphology and was not suitable as a contact lens. Similarly, it can be seen that the pollen protein adsorption inhibitory effect of the contact lenses of each example is more excellent than that of the comparative example. Regarding these pollen adsorption inhibitory effects and pollen protein adsorption inhibitory effects, it can be seen that the contact lenses of Examples 2-1 to 2-8 in which the types of pollen are changed also exhibit excellent effects. [Industrial availability]

By using the contact lens of the present invention, the adsorption of pollen and pollen protein on the surface of the contact lens can be suppressed, so that many symptoms of hay fever can be alleviated and reduced, and discomfort can be reduced. Therefore, it can be a contact lens with excellent wearing feeling.

Claims (4)

A monomer composition for contact lenses, which is a composition containing the following components: (A) a phosphorylcholine group-containing methacrylate monomer represented by formula (1); (B) selected from (methyl) Hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, and diethyl One or more hydroxyl-containing monomers in the group consisting of glycol monovinyl ether; (C) the siloxyalkyl-containing itaconic acid diester monomer represented by the formula (2); (D) the formula (3) (Meth) acrylate containing siloxy group represented by ); (E) N-vinylpyrrolidone; and (F) photopolymerization initiator; When the sum of the monomer components in the above composition When it is set to 100% by mass, the composition contains 2-40% by mass (A) component, 5-45% by mass (B) component, 7-35% by mass (C) component, and 7-55% by mass (D) component, 0.5-35% by mass (E) component, and 0.1-10% by mass (F) component, [Chemical 1]

[化2]

[化3]

(In formula (3), R ₁ is a hydrogen atom or a methyl group, and n is 1 to 15). A polymer for contact lenses, which is obtained by polymerizing the monomer composition for contact lenses according to claim 1. A contact lens obtained by hydrating the polymer for contact lenses as in Claim 2. Such as the contact lens of claim 3, which is used to inhibit the adsorption of pollen and/or pollen protein.