TWI753090B - Monomer composition for contact lens, polymer for contact lens and method for preparing the same, as well as contact lens and method for producing the same - Google Patents

Abstract

The present invention provides a monomer composition for contact lenses useful in producing contact lenses having excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wearing feel. Further, a polymer and a contact lens for contact lenses obtained from the composition are provided. The composition contains: a specific amount of (A) a phosphorochoyl group-containing methacrylate monomer, (B) selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylate base) one or more hydroxyl-containing monomers selected from the group consisting of hydroxybutyl acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether, (C) silicon-containing monomers Itaconic acid diester monomer of oxyalkyl group, (D) siloxane group-containing (meth)acrylate and (E) crosslinking agent.

Description

Monomer composition for contact lens, polymer for contact lens and method of making the same, and contact lens and method of making the same

The present invention relates to a monomer composition for contact lenses, a polymer of the composition and a method for preparing the same, and a contact lens composed of a hydrate of the polymer and a method for manufacturing the same.

The conventional hydrogel contact lenses do not provide sufficient oxygen to the cornea, and therefore have safety problems when worn for a long time. As a contact lens that solves this defect and improves safety, a silicone hydrogel contact lens has been developed.

However, silicone hydrogel contact lenses have a problem in that it is difficult to impart hydrophilicity to the lens surface. In general, soft contact lenses are produced by a cast mold method, in which a polypropylene mold is often used. When the silicone hydrogel contact lens is produced by this method, since polypropylene is hydrophobic, the silicone monomer is polymerized in a state of being oriented on the mold surface. Therefore, the silicone component is formed on the surface of the lens, and the hydrophilicity of the surface is reduced. When the hydrophilicity of the lens surface is insufficient, lipids, proteins, etc. adhere to the lens, which may cause cloudiness of the lens or eye disease.

Therefore, it has been proposed to form a coating based on plasma gas or a hydrophilic polymer, or a surface-grafted polymer based on a hydrophilic monomer on the surface of the lens after manufacturing the silicone hydrogel contact lens. However, these surface treatments require many devices and complicated manufacturing processes, so they are not ideal for mass production.

For the purpose of improving the surface hydrophobicity of soft contact lenses using silicone-containing copolymers, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-methyl- A method in which a hydrophilic monomer having a vinyl group such as N-vinylacetamide and N-vinylpyrrolidone is used in a monomer composition. However, even if such a hydrophilic monomer is used, the hydrophilicity of the lens surface is not sufficient.

Patent Document 1 discloses a method for producing a lens from a composition for a silicone hydrogel comprising: a silicone monomer having a (meth)acryloyl group, a vinyl Hydrophilic monomer, cross-linkable monomer and polymerization initiator with a half-life temperature of 70°C to 100°C for 10 hours. Although this method aims at improving the hydrophilicity of the lens surface by utilizing the difference in polymerizability of the raw material monomers, satisfactory hydrophilicity cannot be obtained.

Patent Document 2 discloses a monomer composition for contact lenses comprising: a phosphorocholine group-containing (meth)acrylate monomer, a (meth)acrylate silicone monomer having a hydroxyl group, and crosslinking agent. Patent Document 3 discloses a compound containing 2-methacryloyloxyethylphosphorylcholine (MPC), dimethylacrylosilicone macromonomer and (3-methacryloyloxy-2 -Hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (SiGMA) composition to obtain silicone hydrogel contact lenses. Patent Document 4 discloses a (meth)acrylate silicone monomer containing a (meth)acrylate monomer containing a phosphorocholine group or a carboxybetaine group, a (meth)acrylate silicone monomer having a secondary hydroxyl group, and a (meth)acrylate silicone monomer having no hydroxyl group. A contact lens obtained from a composition of a meth)acrylate cyclic silicone monomer, a maleic acid or fumaric acid diester silicone monomer having a fluorinated alkyl group, and the like. However, although the hydrophilicity of the lens surface of the contact lens of patent documents 2-4 is improved, there exists a problem that oxygen permeability falls.

Patent Document 5 discloses a composition comprising a phosphorochoyl group-containing (meth)acrylate monomer, a (meth)acrylate silicone monomer having a hydroxyl group, and a silicone (meth)acrylate, And disclosed that its polymer can be used in contact lenses. Patent Document 6 discloses a composition containing a siloxyl group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and discloses that the polymer thereof can be used for contact lenses. Patent Documents 5 and 6 have obtained favorable results in terms of the hydrophilicity and oxygen permeability of the lens surface.

Known technical literature

Patent Literature

Patent Document 1: International Publication No. 2015/001811

Patent Document 2: Japanese Patent Laid-Open No. 2007-009060

Patent Document 3: Japanese Patent Laid-Open No. 2014-089477

Patent Document 4: Japanese Patent Laid-Open No. 2007-056220

Patent Document 5: Japanese Patent Laid-Open No. 2007-197513

Patent Document 6: International Publication No. 2010/104000

The technical problem to be solved by the present invention

However, although the contact lenses of Patent Documents 5 and 6 are good in terms of the hydrophilicity and oxygen permeability of the lens surface, the mechanical strength and wearing feeling are insufficient, and further improvement is considered to be necessary.

The technical problem of the present invention is to provide a contact lens which can exhibit excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wearing feeling even if it is produced using a hydrophobic mold made of polypropylene or the like. In addition, "excellent surface hydrophilicity" refers to the characteristic that the water film retention time is 30 seconds or more under the WBUT (water film break up time) evaluation described in detail in the Examples.

Another technical problem of the present invention is to provide a composition and a polymer suitable for obtaining the above-mentioned contact lens.

Another technical problem of the present invention is to provide a manufacturing method for obtaining the above-mentioned polymer and contact lens.

technical means to solve technical problems

The inventors of the present application have conducted intensive research, and as a result found that, by using a monomer composition containing two types of hydrophilic monomers and two types of siloxane group-containing silicone monomers as a raw material for contact lenses, it is possible to achieve All the above-mentioned objects have been completed, thereby completing the present invention.

式（3）中，R¹ 為氫原子或甲基，m為0或1，n為10~20。According to one embodiment of the present invention, there is provided a monomer composition for a contact lens, wherein the composition contains: (A) component, which is a phosphorocholine-containing methyl group represented by the following formula (1). Base acrylate monomer and (B) component selected from hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene diacrylate One or more hydroxyl-containing monomers and (C) components in the group consisting of alcohol monovinyl ether and diethylene glycol monovinyl ether are siloxane-containing groups represented by the following formula (2). Itaconic acid diester monomer, (D) component, is a siloxane group-containing (meth)acrylate represented by the following formula (3), and (E) component, is a crosslinking agent, relative to the above The total amount of all monomer components in the composition is 100 mass %, the content ratio of (A) component is 5 to 20 mass %, the content ratio of (B) component is 5 to 25 mass %, and the content ratio of (C) component is 30-70 mass %, the content ratio of (D)component is 5-40 mass %, and the content ratio of (E) component is 0.1-10 mass %.

In formula (3), R ¹ is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10-20.

According to another aspect of the present invention, there is provided a polymer for a contact lens composed of the polymer of the above-mentioned monomer composition for a contact lens, and a method for producing the same.

According to another aspect of this invention, the contact lens which consists of the hydrate of the said polymer for contact lenses, and its manufacturing method are provided.

Invention effect

The monomer composition for contact lenses of the present invention contains (A) to (E) components as essential components. Therefore, the contact lens of the present invention obtained by using the polymer of the composition can exhibit excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wearing feeling. In addition, according to the method for preparing a polymer for a contact lens and the method for manufacturing a contact lens of the present invention, the above-mentioned silicone hydrogel soft contact lens with excellent performance can be manufactured.

The monomer composition for contact lenses of the present invention is a uniform transparent liquid containing the components (A) to (E) described later as essential components, and may further contain the component (F) as an optional component. The polymer for a contact lens of the present invention is composed of a polymer of the monomer composition for a contact lens, and the contact lens of the present invention is composed of a hydrate of the polymer for a contact lens. Hereinafter, the monomer composition for contact lenses of the present invention is simply referred to as a composition. In addition, the polymer for contact lenses of the present invention is simply referred to as a polymer.

(A) Component: Phosphocholine-containing methacrylate monomer

The component (A) is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1), specifically, 2-methacryloyloxyethyl phosphorylcholine (MPC). By containing (A) component, the hydrophilicity and lubricity of the surface of the contact lens manufactured from the polymer of the composition of this invention can be made favorable.

In the composition of this invention, when the total amount of all monomer components is made into 100 mass %, the content rate of (A) component is 5-20 mass %, Preferably it is 8-20 mass %. When the content ratio of the component (A) is less than 5 mass %, sufficient surface hydrophilicity cannot be obtained. On the other hand, when it exceeds 20 mass %, (A) component becomes difficult to melt|dissolve in a composition, or there exists a possibility that the mechanical strength of a contact lens may fall. In addition, in this invention, "monomer component" means (A) - (F) component.

(B) Component: Hydroxyl-containing monomer

(B) Component is selected from hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethyl ether. One or more hydroxyl-containing monomers in the group consisting of ethylene glycol monovinyl ether. By containing the (B) component in a predetermined amount, the dissolution of the (A) component in the composition of the present invention becomes favorable. In consideration of the solubility of the component (A), the hydroxyl group of the component (B) is preferably a primary hydroxyl group. In addition, in this invention, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

Specific examples of the component (B) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxypropyl (meth)acrylate. Hydroxybutyl, (meth)acrylate-2-hydroxybutyl, polyethylene glycol monomethacrylate, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxy ethyl) acrylamide, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, etc. The component (B) may be any one of these monomers, or a mixture of two or more of them may be used.

In view of making the solubility of the component (A) more favorable, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl) acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether, more preferably 2-hydroxyethyl acrylate, N-( 2-Hydroxyethyl) acrylamide, N-methyl-N-(2-hydroxyethyl) acrylamide and ethylene glycol monovinyl ether.

In the composition of this invention, when the total amount of all monomer components is made into 100 mass %, the content rate of (B) component is 5-25 mass %. If the content ratio of the component (B) is less than 5 mass %, there is a possibility that the composition of the present invention cannot be a uniform transparent liquid. On the other hand, when it exceeds 25 mass %, there exists a possibility that the oxygen permeability of a contact lens may fall.

(C) Component: Itaconic acid diester monomer containing siloxane group

The component (C) is a siloxyl group-containing itaconic acid diester monomer represented by the following formula (2). The component (C) contributes to improving the oxygen permeability and transparency of the contact lens.

The monomer of formula (2) is obtained by esterification of itaconic acid monoethylene glycol ester with 3-iodopropyl[tris(trimethylsiloxy)]silane. Itaconic acid monoethylene glycol is obtained by reacting itaconic acid anhydride with ethylene glycol as described in Patent Document 6, for example. In addition, a commercial product can be used for 3-iodopropyl[tris(trimethylsiloxy)]silane, but a high-purity product is preferably used in order to improve the purity of the obtained silicone monomer of the present invention.

In the above-mentioned esterification reaction, the structural isomer represented by the following formula (2') may be produced by a small amount. In the present invention, a mixture of the monomer of the formula (2) and a small amount of the monomer of the formula (2′) can be used as the component (C). That is, in the present invention, "the siloxyl group-containing itaconic acid diester monomer represented by the formula (2)" includes not only the monomer of the formula (2) but also the monomer containing the formula (2). In addition to the monomer, a part of the monomer of the isomer of the formula (2') is contained.

In the composition of this invention, when the total amount of all monomer components is made into 100 mass %, the content rate of (C)component is 30-70 mass %, Preferably it is 30-60 mass %. If the content of the component (C) is less than 30% by mass, there is a possibility that the dissolution of the component (A) in the composition of the present invention may become difficult, or the produced polymer for contact lenses may become cloudy. possibility. On the other hand, when it exceeds 70 mass %, there exists a possibility that the surface hydrophilicity of a contact lens may become inadequate.

(D) Component: Siloxane-containing (meth)acrylate

The component (D) is a siloxane group-containing (meth)acrylate represented by the following formula (3). The component (D) contributes to the improvement of the oxygen permeability and the adjustment of the mechanical strength of the contact lens. (D) Component can be prepared by the method etc. disclosed in Unexamined-Japanese-Patent No. 2014-031338, or may be a commercial item.

In formula (3), R ¹ is a hydrogen atom or a methyl group. m represents the number of ethyleneoxy groups, which is 0 or 1. n represents the number of repetitions of the dimethylsiloxane moiety, which is 10 to 20. The component (D) may be a mixture of a plurality of compounds having different repetition numbers n. At this time, n is an average value based on the number average molecular weight, which is in the range of 10 to 20. When n is less than 10, the oxygen permeability decreases, so it is not excellent. In addition, when n is greater than 20, the surface hydrophilicity or mechanical strength of the contact lens decreases.

m in formula (3) is preferably 0. That is, the (D) component is preferably a siloxane group-containing (meth)acrylate represented by the following formula (4). In addition, R ¹ and n in formula (4) are synonymous with R ¹ and n in formula (3).

In the composition of this invention, when the total amount of all monomer components is made into 100 mass %, the content rate of (D)component is 5-40 mass %. When the content ratio of (D)component is less than 5 mass %, the mechanical strength of a contact lens will become large too much, and there exists a possibility that wearing feeling may not be excellent. On the other hand, when it exceeds 40 mass %, there exists a possibility that the surface hydrophilicity of a contact lens may fall.

Further, in the composition of the present invention, when the total amount of all monomer components is set to 100% by mass, the total content ratio of the (C) component and the (D) component is preferably 40 to 75% by mass, more preferably The ground is 60 to 65 mass %. By making the said total content ratio into 40 mass % or more, the composition of this invention which is a uniform transparent liquid can be obtained easily. On the other hand, by setting it as 75 mass % or less, a contact lens can be prevented from becoming hard too much.

(E) Component: Cross-linking agent

(E) Component functions as a crosslinking agent at the time of the polymerization reaction of the monomers of (A) to (D) components. The component (E) usually has two or more polymerizable unsaturated groups. Since the composition of the present invention contains a predetermined amount of the component (E), the polymer of the present invention has a cross-linked structure, and thus the contact lens of the present invention exhibits excellent solvent resistance.

For example, the component (E) may be silicone dimethacrylate represented by the following formula (5).

In formula (5), p and r are equal to each other and are 0 or 1. q represents the number of repetitions of the dimethylsiloxane moiety, and is 10 to 70. The silicone dimethacrylate represented by formula (5) may be a mixture of a plurality of compounds having different repetition numbers q. In this case, q is an average value based on the number average molecular weight, and is in the range of 10 to 70 from the viewpoint of availability.

Specific examples of the component (E) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether in addition to the silicone dimethacrylate of the above formula (5). Vinyl ether, methylenebisacrylamide, allyl methacrylate, (2-allyloxy)ethyl methacrylate, 2-(2-vinyloxyethoxy)ethyl Ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate, etc. The component (E) may be any one of these crosslinking agents, or a mixture of two or more of them may be used.

In the composition of this invention, when the total amount of all monomer components is made into 100 mass %, the content rate of (E) component is 0.1-10 mass %. The solvent resistance of a contact lens will fall that the content rate of (E) component is less than 0.1 mass %. On the other hand, when it exceeds 10 mass %, there exists a possibility that a contact lens becomes brittle and may be damaged, and there exists a possibility that a mechanical strength may become too high and the wearing feeling of a contact lens may deteriorate.

(F) Component: Monomers other than (A) to (E) components

(F) component is a monomer other than (A)-(E) component. (F) component is an arbitrary component, and can be used for the purpose of adjusting the moisture content of a contact lens, etc.

As the (F) component, a monomer having one or more functional groups selected from the group consisting of an amide group, a carboxyl group, and an ester group can be exemplified. Specific examples of the monomer having an amide group include N-vinylpyrrolidone, N-vinylpyridin-2-one, N-vinyl-ε-caprolactam, and N-vinyl-3 -Methyl-2-caprolactamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylamide, N-isopropylacrylamide, acrylmorpholine , N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinylformamide, etc. Specific examples of the monomer having a carboxyl group include (meth)acrylic acid, 2-methacryloyloxyethylsuccinic acid, and the like. Specific examples of the monomer having an ester group include alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, or methoxyl groups. polyethylene glycol methacrylate, etc. The component (F) may be any one of these monomers, or a mixture of two or more of them may be used.

When the composition of this invention contains (F) component, when the total amount of all monomer components is made into 100 mass %, the content rate of (F) component becomes like this. Preferably it is 25 mass % or less. If it is 25 mass % or less, the solubility in the composition of (A) component will be favorable, and the surface hydrophilicity of a contact lens will also be favorable.

The composition of this invention may contain a solvent other than the said (A)-(F) component. The solvent is not particularly limited as long as the solubility of each component in the composition can be improved, but a solvent having a hydroxyl group is preferred. By using the solvent which has a hydroxyl group, the dissolution rate of (A) component in the composition of this invention becomes high, and the dissolution becomes easy.

The solvent having a hydroxyl group may be alcohol or carboxylic acid. Specific 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, 1-dodecanol, etc. Specific examples of carboxylic acids include glycolic acid, lactic acid, and acetic acid. The solvent may be any one of these solvents, or may be a mixture of two or more. In consideration of the solubility of the component (A) and the pH stability of the composition, the solvent is preferably composed of at least one selected from the group consisting of ethanol, 1-propanol, and 2-propanol.

When the composition of the present invention contains a solvent, when the total amount of all monomer components in the composition is 100 parts by mass, the content ratio of the solvent is preferably 25 parts by mass or less. The mechanical strength of a contact lens is favorable as it is 25 mass parts or less.

The composition of this invention may contain a polymerization initiator in addition to the said (A)-(F) component. The polymerization initiator may be a conventional polymerization initiator, preferably a thermal polymerization initiator. When a thermal polymerization initiator is used, the change of the copolymerizability of each monomer component based on the temperature change in the middle of the polymerization is easy. Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2-azobis(2-methylpropionic acid)dimethylester, 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-methylpropylamidine)dihydrochloride, 2,2'-azobis [N-(2-Carboxyethyl)-2-methylpropylamidine] dihydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2 '-Azobis(1-imino-1-pyrrolidinyl-2-methylpropane) dihydrochloride, 2,2'-azobis[2-methyl-N-{1,1-dihydrochloride] (Hydroxymethyl)-2-hydroxyethyl}propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'- Azo-based polymerization initiators such as azobis(2-methylpropylamidine)dihydrochloride and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] agent, or benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, lauryl peroxide, tert-butyl peroxycaproate, 3,5,5-trimethylhexanoyl Peroxide-based polymerization initiators such as peroxides, etc. These polymerization initiators may be used alone, or two or more of them may be used in combination. Among these initiators, in view of safety and availability, azo-based polymerization initiators are preferred, and in view of reactivity, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl ester and 2,2'-azobis(2,4-dimethylvaleronitrile).

When the total amount of all monomer components in the composition is set as 100 parts by mass, the amount of the polymerization initiator added is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.1 to 3 parts by mass. 0.2 to 1 part by mass. When it is less than 0.1 part by mass, the polymerizability of the composition is insufficient, and there is a possibility that the advantage of blending a polymerization initiator cannot be obtained. When it exceeds 3 mass, there exists a possibility that extraction and removal of a decomposition|disassembly product of a polymerization initiator may become inadequate at the time of washing|cleaning the polymer used for a contact lens and manufacturing a contact lens.

In the range which does not impair the objective of this invention, the composition of this invention may contain additives, such as a polymerizable ultraviolet absorber and a polymerizable dye (coloring agent), in addition to the said (A)-(F) component. By incorporating an ultraviolet absorber, the burden on the eyes caused by ultraviolet rays such as sunlight can be reduced. In addition, by blending pigments, colored contact lenses can be made.

The preparation method of the composition of the present invention is not particularly limited, for example, it can be prepared by the following method: adding the ingredients in any order or adding them together into a stirring (mixing) device, stirring at a temperature of 10°C to 50°C (mix) until homogeneous. However, when the composition contains a polymerization initiator, care should be taken not to initiate a polymerization reaction during mixing, and mixing is preferably performed at 40° C. or lower. In consideration of improving the solubility of the component (A), after mixing and dissolving the three components (A), (B), and (C), the other components are preferably added and mixed.

The polymer of the present invention consists of the polymer of the composition of the present invention described above. Hereinafter, the production method of the polymer of the present invention will be described. The production method shown below is only one embodiment of the method for obtaining the polymer, and the polymer of the present invention is not limited to being obtained by the production method.

The polymer of the present invention can be produced by filling a mold with the composition of the present invention and conducting a polymerization reaction. As the mold, a mold made of polypropylene or the like and having a hydrophobic surface can be used.

The polymerization reaction can be carried out by, for example, a one-stage polymerization method in which the composition is maintained at a temperature of 45° C. to 140° C. for 1 hour or more in combination with the decomposition temperature of the polymerization initiator used, but it is preferably carried out by including the following The polymerization process 1 and the polymerization process 2 are implemented in two or more stages of polymerization. In this case, the hydrophilicity of the surface of the contact lens can be further improved. After the completion of the polymerization, the polymer can be taken out from the mold, for example, by cooling to 60° C. or lower.

[Polymerization process 1]

In the polymerization process 1, the above-mentioned polymerization initiator is added to the composition as needed, and the polymerization is carried out at a temperature of 45° C. to 75° C. for more than 1 hour.

The polymerization temperature of the polymerization process 1 is preferably 50°C to 70°C, more preferably 55°C to 70°C. If the polymerization temperature of the polymerization process 1 is 45° C. to 75° C., a polymer with good physical properties such as surface hydrophilicity can be stably obtained.

The polymerization time of the polymerization process 1 is preferably 2 hours or more and 12 hours or less. If the polymerization time of the polymerization process 1 is 1 to 12 hours, a polymer having good physical properties such as surface hydrophilicity can be obtained efficiently.

[Polymerization process 2]

The polymerization process 2 is a process performed after the polymerization process 1, and the polymerization reaction is performed at a temperature higher than that of the polymerization process 1, ie, 90° C. to 140° C.

The polymerization temperature of the polymerization process 2 is preferably 100°C to 120°C. When the polymerization temperature in the polymerization process 2 is 90°C to 140°C, a polymer with good physical properties such as surface hydrophilicity can be stably obtained, and the polymer can be obtained efficiently without deforming a mold made of polypropylene or the like.

The polymerization time of the polymerization process 2 is preferably 1 hour or more and 10 hours or less. If the polymerization time of the polymerization process 2 is 1 to 10 hours, a polymer with good physical properties such as surface hydrophilicity can be obtained efficiently.

The environment in which the polymerization processes 1 and 2 are performed is not particularly limited, but in consideration of improving the polymerization rate, it is preferable to perform the polymerization processes 1 and 2 in an inert gas environment such as nitrogen or argon. At this time, an inert gas may be passed through the composition, or the composition filling place of the mold may be set to an inert gas environment.

The pressure in the mold can be atmospheric pressure ~ slightly pressurized. When the polymerization is carried out in an inert gas atmosphere, the gauge pressure is preferably 1 kgf/cm ² or less.

The contact lens of the present invention is a silicone hydrogel contact lens composed of a hydrate of the above-mentioned polymer. That is, the contact lens of this invention is obtained by hydrating the polymer of this invention, making it water-containing, and making it into a hydrogel state. In addition, in this specification, "silicone hydrogel" means the hydrogel which has a silicone component in a polymer. Since the composition of the present invention contains components (C) and (D) as silicone-containing monomers, the polymer has a silicone component, and a silicone hydrogel can be formed by hydrating (water-containing).

The moisture content of the contact lens (the ratio of water to the total mass of the contact lens) is preferably 35% by mass or more and 60% by mass or less, more preferably 35% by mass or more and 50% by mass or less. When the moisture content is 35 to 60 mass %, it can be excellent in balance with oxygen permeability.

Next, the manufacturing method of the contact lens of this invention is demonstrated. The production method shown below is only one embodiment of the method for obtaining the contact lens of the present invention, and the contact lens of the present invention is not limited to being obtained by this production method.

After the above-mentioned polymerization reaction, the polymer may be in a state of a mixture of unreacted monomer components (unreacted products), residues of the components, by-products, residual solvents, and the like. Although such a mixture may be directly supplied to the hydration treatment, the polymer is preferably purified using a purification solvent before the hydration treatment.

Examples of the purification solvent include water, methanol, ethanol, 1-propanol, 2-propanol, a mixture of these solvents, and the like. Purification can be performed by, for example, immersing the polymer in an alcohol solvent at a temperature of 10° C. to 40° C. for 10 minutes to 5 hours, and then immersing the polymer in water for 10 minutes to 5 hours. Moreover, after immersing in an alcohol solvent, you may immerse in water for 10 minutes - 5 hours in the water-containing alcohol whose alcohol density|concentration is 20 to 50weight%, and you may immerse in water further. As water, pure water and ion-exchanged water are preferable.

The contact lens of the present invention is obtained by immersing the polymer in physiological saline and hydrating it so as to have a predetermined water content. The physiological saline can be boric acid buffered physiological saline, phosphate buffered physiological saline, or the like. In addition, it may be immersed in a preservation solution for soft contact lenses containing physiological saline. In consideration of hydration, the osmotic pressure of physiological saline is preferably 250 to 400 mOms/kg.

The lens surface of the contact lens of the present invention has good hydrophilicity, does not easily adhere to contaminants such as lipids, is easy to wash and remove even if it does adhere, and is excellent in mechanical strength, so that it can be used for about a month in a normal usage form as required. It is of course also possible to exchange within a period shorter than one month.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. First, components used in Examples and Comparative Examples are shown below.

(A) Component (phosphocholine group-containing methacrylate monomer)

MPC: (2-methacryloyloxyethyl)phosphocholine

(B) Component (hydroxyl-containing monomer)

HEA: 2-hydroxyethyl acrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 2-hydroxypropyl methacrylate (mixture of 2-hydroxypropyl ester and 2-hydroxy-1-methylethyl ester, manufactured by Nippon Shokubai Co., Ltd.)

HBMA: 2-hydroxybutyl methacrylate (mixture of 2-hydroxybutyl ester, 2-hydroxy-1-ethylethyl ester, manufactured by Sigma-Aldrich Co. LLC.)

HPA: 2-hydroxypropyl acrylate (mixture of 2-hydroxypropyl ester and 2-hydroxy-1-methylethyl ester, manufactured by Tokyo Chemical Industry Co., Ltd.)

HBA: 4-hydroxybutyl acrylate

HEAA: Hydroxyethyl acrylamide

EMVE: Ethylene Glycol Monovinyl Ether

DEMVE: Diethylene glycol monovinyl ether

(C) Component (siloxane group-containing itaconic acid diester monomer)

ES: Compounds of formula (2) as esterification reactants of monoethylene glycol itaconic acid with 3-iodopropyl[tris(trimethylsiloxy)]silane

(D) Ingredient (siloxane group-containing methacrylate)

FM-0711: Compound represented by formula (3) (R ¹ =methyl group, m=0, n=11, number average molecular weight Mn=about 1000)

(E) Component (crosslinking agent)

TEGDV: triethylene glycol divinyl ether

DEGDV: Diethylene glycol divinyl ether

EGDV: Ethylene Glycol Divinyl Ether

VEEA: 2-(2-Vinyloxyethoxy)ethylacrylate

FM-7711: Compound represented by formula (5) (p=r=0, number average molecular weight Mn=about 1,000)

FM-7721: Compound represented by formula (5) (p=r=0, number average molecular weight Mn=about 5,000)

TEGDMA: Tetraethylene glycol divinyl ether

(F) Component (monomers other than (A) to (E) components)

NVP: N-Vinylpyrrolidone

DMAA: N,N-Dimethacrylamide

NIPA: N-isopropylacrylamide

VMA: N-vinyl-N-methylacetamide

VFA: N-Vinylformamide

MA: methacrylic acid

MMA: methyl methacrylate

solvent

EtOH: Ethanol

NPA: 1-Propanol (n-Propanol)

IPA: 2-Propanol (Isopropanol)

polymerization initiator

AIBN: 2,2'-azobis(isobutyronitrile) (10-hour half-life at 65°C)

ADVN: 2,2'-azobis(2,4-dimethylvaleronitrile) (10 hours half-life temperature 51°C)

The following items were evaluated for the compositions, polymers, and contact lenses of Examples and Comparative Examples. In the following description, "composition", "polymer", and "contact lens" in each evaluation item and each table include not only the respective examples but also the aforementioned substances in the comparative examples.

Composition homogeneity and transparency

The composition was put into a colorless and transparent container, and the state of the composition was visually evaluated according to the following criteria.

○: uniform and transparent

×: There is cloudiness or precipitation

Morphology of the polymer

The morphology of the polymer was visually evaluated according to the following criteria.

○: solid

×: Liquid (including viscous liquid)

Transparency of polymers

The transparency of the polymer was evaluated visually according to the following criteria

○: Transparent

△: Slightly cloudy

×: cloudy

Transparency of Contact Lenses

After the polymer was purified, it was immersed in the physiological saline described in ISO-18369-3 to swell to obtain a hydrogel (contact lens), and the hydrogel (contact lens) was visually evaluated according to the following criteria. glasses) transparency.

○: Transparent

△: Slightly cloudy

×: cloudy

Surface Hydrophilicity of Contact Lenses (WBUT)

The surface hydrophilicity of the contact lenses was evaluated according to WBUT (water film break up time). Specifically, the contact lens was immersed in ISO physiological saline overnight, the outer peripheral portion was clamped with tweezers, and the contact lens was lifted from the water surface, and the time (water film retention time) from the time when the contact lens was lifted from the water surface until the water film on the lens surface was broken was measured. The state of water film rupture was determined by visual observation. The measurement was performed three times, and the average value was obtained. When the time was 30 seconds or longer, it was determined that the surface hydrophilicity was good.

Moisture content of contact lenses

The moisture content was measured by the method described in ISO-18369-4.

Mechanical strength of contact lenses

Using the BAS-3305(W) breaking strength analyzer manufactured by YAMADEN Co., Ltd., the modulus (modulus) [MPa] of the contact lens was measured according to JIS-K7127, and the mechanical strength was evaluated. Specifically, the contact lens was cut into a sample having a width of 2 mm, and a 200 gf load cell was used to measure the modulus by setting the gap between the jigs to 6 mm and pulling at a speed of 1 mm/sec. When the modulus was 0.2 MPa or more and less than 0.7 MPa, it was judged that the mechanical strength was good.

Oxygen permeability of contact lenses

The oxygen permeability coefficient of a sample in which 2 to 4 contact lenses were stacked was measured according to the polarographic measurement method described in ISO 18369-4. For the measurement, O2 Permeometer Model 201T from Rehder Development Company was used. The thickness of the lens was plotted on the x-axis, the t/Dk value obtained by the measurement was plotted on the y-axis, and the inverse of the slope of the regression line was used as the oxygen permeability coefficient. The larger the oxygen permeability coefficient, the better the oxygen permeability.

Surface lubricity of contact lenses

Lubricity was evaluated by sensory evaluation of fingertips. As standard contact lenses for evaluation, polymacon and omafilcon A were used. The lubricity of polymacon was set to 2, and the lubricity of omafilcon A was set to 8, and the evaluation was performed on ten scales of 1 to 10. When the evaluation score was 6 or more, it was judged that the surface lubricity was good, and when it was 5 or less, it was judged that the surface lubricity was poor.

Example 1

In a container, 0.5 g (5.0 mass %) of MPC, 1.0 g (10.0 mass %) of HEA, 4.0 g (40.0 mass %) of ES, and 0.5 g (5 mass parts) of EtOH were mixed and stirred at room temperature until the MPC dissolves. Further, 1.9 g (19.0 mass %) of FM-0711, 0.1 g (1.0 mass %) of TEGDV, 2.5 g (25.0 mass %) of NVP, and 0.05 g (0.5 mass part) of AIBN were added to the container, The mixture was stirred at a temperature until uniform, and a composition was obtained. The compositions were evaluated as described above.

Into a box of 25 mm x 70 mm x 0.2 mm in which a polyethylene terephthalate sheet having a thickness of 0.1 mm as a spacer was sandwiched between two polypropylene plates, 0.3 g of the above composition was injected, and Place in oven. After nitrogen-substituting the inside of the oven, the temperature was raised to 65°C, the temperature was maintained for 3 hours, and then the temperature was further raised to 120°C and maintained for 2 hours to polymerize the composition to obtain a polymer. The polymer was removed from the box and the above evaluation was performed.

The above-mentioned polymer was immersed in 40 g of 2-propanol for 4 hours, and then immersed in 50 g of ion-exchanged water for 4 hours to remove unreacted substances and the like, and then purified. Furthermore, the polymer was immersed in the physiological saline described in ISO-18369-3, and it was made to swell (hydrate), and the contact lens was produced. The said contact lens was processed into the sample of the size and shape suitable for each evaluation test, and each evaluation was performed. Table 1 shows the blending ratio of each component in the composition, polymerization conditions, and each evaluation result.

Embodiments 2 to 27

The compositions, polymers, and contact lenses of Examples 2 to 27 were produced in the same manner as in Example 1, except that the content ratio of each component and the polymerization conditions were changed as shown in Tables 1 to 4, and the Evaluation test. The results are shown in Tables 1 to 4.

Comparative Example 1

In a container, 1.98 g (19.8 mass %) of HEA, 4.95 g (49.5 mass %) of ES, and 0.5 g (5 mass parts) of EtOH were mixed and stirred at room temperature. Further, 1.98 g (19.8 mass %) of FM-0711, 0.1 g (1.0 mass %) of TEGDV, 0.99 g (9.9 mass %) of DMAA and 0.1 g (1.0 mass parts) of AIBN were added to the container, The mixture was stirred at a temperature until uniform, and the composition of Comparative Example 1 was obtained. The compositions were evaluated as described above.

Into a box of 25 mm x 70 mm x 0.2 mm in which a polyethylene terephthalate sheet having a thickness of 0.1 mm as a spacer was sandwiched between two polypropylene plates, 0.3 g of the above composition was injected, and Place in oven. After the inside of the oven was replaced with nitrogen, the temperature was raised to 65°C, the temperature was maintained for 3 hours, and then the temperature was further raised to 120°C and maintained for 2 hours to polymerize the composition, thereby obtaining the polymer of Comparative Example 1. The polymer was removed from the box and the above evaluation was performed.

After the polymer of Comparative Example 1 was immersed 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 substances and the like, and purified. Furthermore, the polymer was immersed in the physiological saline described in ISO-18369-3, and it was made to swell (hydrate), and the contact lens of the comparative example 1 was produced. The said contact lens was processed into the sample of the size and shape suitable for each evaluation test, and each evaluation was performed. Table 5 shows the blending ratio of each component in the composition of Comparative Example 1, polymerization conditions, and each evaluation result. In the evaluation of the surface hydrophilicity, since the WBUT was an unsatisfactory result of 0 seconds, other evaluations were not performed.

Comparative Examples 2 to 5

The compositions, polymers, and contact lenses of Comparative Examples 2 to 5 were produced in the same manner as in Comparative Example 1, except that the content ratio of each component and the polymerization conditions were changed as shown in Table 5, and evaluation tests were performed. . The results are shown in Table 5. Since the comparative example 5 was the same as the comparative example 1, and the WBUT was the unsatisfactory result of 0 second, other evaluations were not implemented. In Comparative Examples 2 and 3, since the composition was not uniform, polymerization was not performed. Therefore, the polymers and contact lenses of Comparative Examples 2 and 3 could not be produced, and the evaluation thereof could not be carried out. Although the surface hydrophilicity of the contact lens of the comparative example 4 was favorable, the mechanical strength was 0.9 MPa, and the oxygen permeability was 67, which was inferior to the Example.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

none

none

Claims (7)

A monomer composition for contact lenses, comprising: (A) component, which is a phosphorocholine-containing methacrylate monomer represented by the following formula (1); (B) component, which is selected from Free hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, and diethylene glycol monoethylene One or more hydroxyl group-containing monomers in the group consisting of base ethers; (C) component is a siloxyl group-containing itaconic acid diester monomer represented by the following formula (2); (D) component , is a siloxane group-containing (meth)acrylate represented by the following formula (3); and (E) component is a crosslinking agent, relative to the total amount of all monomer components in the monomer composition 100 mass %, the content ratio of (A) component is 5~20 mass %, the content ratio of (B) component is 5~25 mass %, the content ratio of (C) component is 30~70 mass %, (D) component The content ratio of 5 to 40 mass %, and the content ratio of (E) component is 0.1 to 10 mass %,

In formula (3), R ¹ is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10-20. The monomer composition for contact lenses according to claim 1, further comprising (F) component, which is a monomer other than the above (A) to (E) components, relative to the monomer composition The total amount of all monomer components is 100 mass %, and the content ratio of (F) component is 25 mass % or less. The monomer composition for contact lenses according to claim 1 or 2, further comprising a solvent having a hydroxyl group, the amount of the solvent is 100 parts by mass relative to the total amount of all monomer components in the monomer composition. The content ratio is 25 parts by mass or less. A polymer for contact lenses, which is composed of the polymer of the monomer composition for contact lenses according to any one of claims 1 to 3. A method for preparing a polymer for contact lenses as claimed in claim 4, comprising: a polymerization process 1: adding the monomer composition for contact lenses as described in any one of claims 1 to 3 in 45 The temperature is maintained at a temperature of ℃~75℃ for more than 1 hour, and the polymerization is carried out; Polymerization process 2: After the polymerization process 1, the temperature is maintained at a temperature of 90° C. to 140° C. for more than 1 hour to perform polymerization. A contact lens consisting of a hydrate of the polymer for contact lenses as claimed in claim 4. A method for manufacturing contact lenses, comprising: immersing the polymer for contact lenses as described in claim 4 in monoalcohol for 10 minutes to 5 hours at a temperature of 10° C. to 40° C., and then immersing the polymer in water for 10 minutes to 5 hours. minutes to 5 hours, or the polymer for contact lenses as claimed in claim 4 is immersed in the alcohol for 10 minutes to 5 hours at a temperature of 10°C to 40°C, and the alcohol concentration is 20 to 50% by weight % water-containing alcohol for 10 minutes to 5 hours, then immersed in water for 10 minutes to 5 hours to purify the polymer for contact lenses, wherein the alcohol is selected from methanol, ethanol, 1-propanol and at least one of 2-propanol; and the process of immersing the purified polymer in a physiological saline to make it perform hydration, wherein the osmotic pressure of the physiological saline is 250-400 mOms/kg.