CN110199219B - Monomer composition for contact lens, polymer for contact lens and preparation method thereof, and contact lens and preparation method thereof - Google Patents

Abstract

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

Description

Monomer composition for contact lens, polymer for contact lens and preparation method thereof, with and contact lenses and methods of making the same

technical field

The present invention relates to a monomer composition for contact lenses, a polymer of the composition and a method for producing the same, and a contact lens formed from a hydrate of the polymer and a method for producing the same.

Background technique

The conventional type of hydrogel contact lens has insufficient oxygen supply to the cornea of the eye, and has a problem in terms of safety when worn for a long time. A silicone hydrogel contact lens has been developed as a contact lens that solves this defect and improves safety.

However, silicone hydrogel contact lenses have a problem in that it is difficult to make the lens surface hydrophilic. In general, soft contact lenses are produced by a casting method, in which a mold made of polypropylene is often used. When a 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 surface of the mold. Therefore, the silicone portion is formed on the surface of the lens, and the hydrophilicity of the surface becomes low. When the hydrophilicity of the lens surface is insufficient, there is a possibility that lipids, proteins, etc. adhere to the lens, causing cloudiness of the lens or ocular diseases.

Therefore, it is proposed to perform coating on the lens surface with plasma gas or hydrophilic polymer or use hydrophilic monomer to form a surface graft polymer after the preparation of the silicone hydrogel contact lens. However, these surface treatments require many apparatuses and require complicated processes, so they are not expected in mass production.

For the purpose of improving the hydrophobicity of the surface 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 cannot be said to be sufficient.

Patent Document 1 discloses a method for producing a lens from a silicone hydrogel composition containing a (meth)acryloyl group-containing silicone monomer, a vinyl group-containing Hydrophilic monomer, crosslinkable monomer, and polymerization initiator whose half-life temperature is 70°C to 100°C for 10 hours. This method aims to improve the hydrophilicity of the lens surface by utilizing the difference in polymerizability of the raw material monomers, but satisfactory hydrophilicity is still not obtained.

Patent Document 2 discloses a contact lens monomer composition comprising a phosphorylcholine group-containing (meth)acrylate monomer, a hydroxyl group-containing (meth)acrylate silicone monomer, and a crosslinking agent. Patent Document 3 discloses a silicone hydrogel contact lens comprising 2-methacryloyloxyethylphosphorylcholine (MPC), dimethylacryloylsilicone macromonomer and (3). - a composition of methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane (SiGMA) was obtained. Patent Document 4 discloses a contact lens comprising a (meth)acrylate monomer containing a phosphorylcholine group or a carboxybetaine group, a (meth)acrylate silicone monomer having a secondary hydroxyl group , a composition of a (meth)acrylate cyclic silicone monomer having no hydroxyl group, a maleic acid or fumaric acid diester silicone monomer having a fluorinated alkyl group, and the like can be obtained. However, in the contact lenses of Patent Documents 2 to 4, although the hydrophilicity of the lens surface is improved, there is a problem that the oxygen permeability decreases.

Patent Document 5 discloses a composition containing a phosphorylcholine group-containing (meth)acrylate monomer, a (meth)acrylate silicone monomer having a hydroxyl group, and silicone (meth)acrylic acid ester, and it is described that this polymer can be utilized in contact lenses. Patent Document 6 discloses a composition containing a siloxane group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and describes that the polymer can be used in contact lenses. Patent Documents 5 and 6 have obtained favorable results in terms of the hydrophilicity and oxygen permeability of the lens surface.

prior art 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

SUMMARY OF THE INVENTION

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, their mechanical strength and wearing feeling are insufficient, and further improvement is considered 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 when produced using a hydrophobic mold formed 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 in 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 studies and found that all of the above can be achieved 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 object, thus completing the present invention.

According to one embodiment of the present invention, there is provided a monomer composition for a contact lens comprising: (A) a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1) (B) selected from hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethylacrylamide, ethylene glycol monovinyl ether and diethyl ether One or more hydroxyl-containing monomers in the group consisting of glycol monovinyl ethers; (C) a siloxane group-containing itaconic acid diester monomer represented by the following formula (2); (D) under A siloxane group-containing (meth)acrylate represented by the formula (3); and (E) a crosslinking agent. 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 of (C) component is 100 mass % in total of all monomer components in the composition. The content ratio is 30 to 70 mass %, the content ratio of the (D) component is 5 to 40 mass %, and the content ratio of the (E) component is 0.1 to 10 mass %.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

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 embodiment of the present invention, there are provided a polymer for a contact lens formed from the polymer of the above-mentioned monomer composition for a contact lens, and a method for producing the same.

According to yet another embodiment of the present invention, there is provided a contact lens formed from the hydrate of the above-mentioned polymer for contact lens, and a method for producing the same.

Invention effect

The monomer composition for contact lenses of this invention contains (A) - (E) component as an essential component. 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. Further, according to the method for producing a polymer for a contact lens and the method for producing a contact lens of the present invention, a silicone hydrogel soft contact lens having the above-mentioned excellent properties can be produced.

Detailed ways

The monomer composition for contact lenses of this invention is a uniform transparent liquid, It contains (A)-(E) component mentioned later as an essential component, and may further contain (F) component as an optional component. The polymer for a contact lens of the present invention is formed from the polymer of the monomer composition for a contact lens, and the contact lens of the present invention is formed from 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 this invention is abbreviated as a polymer.

(A) Component: Phosphorylcholine group-containing methacrylate monomer

The component (A) is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1), specifically, 2-methacryloyloxyethylphosphorylcholine (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.

[Chemical formula 4]

In the composition of this invention, the content rate of (A) component is 5-20 mass %, Preferably it is 8-20 mass %, when the sum total of all monomer components is made into 100 mass %. When the content rate of (A) component 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, and 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 group-containing monomer

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

Specific examples of (B) component include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, polyethylene glycol monomethacrylate, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl)acrylamide, Ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, etc. The component (B) may be any one of these monomers, or may be a mixture of two or more.

Since the solubility of the component (A) is 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, particularly 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, the content rate of (B) component is 5-25 mass %, when the sum total of all monomer components is made into 100 mass %. When the content rate of the component (B) is less than 5 mass %, there is a possibility that the composition of the present invention is difficult to become 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: Siloxane group-containing itaconic acid diester monomer

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

[Chemical formula 5]

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

In the above-mentioned esterification reaction, a by-product of a structural isomer represented by the following formula (2') may be produced in 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 siloxane group-containing itaconic acid diester monomer represented by the formula (2)" includes not only the monomer of the formula (2) but also the monomer of the formula (2). A part of isomers of formula (2') are also included.

[Chemical formula 6]

In the composition of this invention, the content rate of (C)component is 30-70 mass %, Preferably it is 30-60 mass %, when the sum total of all monomer components is made into 100 mass %. If the content rate of (C)component is less than 30 mass %, there exists a possibility that it may become difficult to melt|dissolve in the composition of this invention (A) component, or the produced polymer for contact lenses may become cloudy. 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 group-containing (meth)acrylate

The component (D) is a siloxane group-containing (meth)acrylate represented by the following formula (3). The component (D) contributes to improving the oxygen permeability and adjusting the mechanical strength of the contact lens. The component (D) can be prepared by the method disclosed in Japanese Patent Application Laid-Open No. 2014-031338 or the like, and may be a commercially available product.

[Chemical formula 7]

In formula (3), R ¹ is a hydrogen atom or a methyl group. m represents the number of vinyloxy groups and is 0 or 1. n is the number of repetitions of the dimethylsiloxane moiety, and is 10 to 20. The component (D) may be a mixture of a plurality of compounds having different numbers of repetitions n. At this time, n is the average value in the number average molecular weight, and it exists in the range of 10-20. When n is less than 10, the oxygen permeability decreases, which is not preferable. 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, it is preferable that (D)component is a siloxane group-containing (meth)acrylate represented by following formula (4). In addition, R ¹ and n in formula (4) are the same as R ¹ and n in formula (3).

[Chemical formula 8]

In the composition of this invention, the content rate of (D)component is 5-40 mass %, when the sum total of all monomer components is made into 100 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.

Moreover, in the composition of this invention, when the sum total of all monomer components is made into 100 mass %, the total content ratio of (C)component and (D) component becomes like this. Preferably it is 40-75 mass %, More preferably, it is 60 mass % -65 mass %. By making this total content ratio 40 mass % or more, it becomes easy to obtain the composition of this invention which is a uniform transparent liquid. On the other hand, by setting it as 75 mass % or less, a contact lens can be prevented from becoming too hard.

(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 this invention contains a predetermined amount of (E) component, since the polymer of this invention has a crosslinked structure, the contact lens of this invention shows excellent solvent resistance.

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

[Chemical formula 9]

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 in the number average molecular weight, and it 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 other than the silicone dimethacrylate of the above formula (5). ether, methylenebisacrylamide, allyl methacrylate, (2-allyloxy) ethyl methacrylate, 2-(2-vinyloxyethoxy) ethyl acrylate and 2-( 2-vinyloxyethoxy) ethyl methacrylate, etc. (E) Component may be any one of these crosslinking agents, or may be a mixture of two or more.

In the composition of this invention, the content rate of (E) component is 0.1-10 mass %, when the sum total of all monomer components is made into 100 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 is brittle, and a breakage may arise, 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 or the like.

As (F) component, the monomer which has 1 or more types of functional groups chosen from an amide group, a carboxyl group, and an ester group can be illustrated. Specific examples of the monomer having an amide group include N-vinylpyrrolidone, N-vinylpiperidin-2-one, N-vinyl-ε-caprolactam, N-vinyl-3-methyl- 2-Caprolactam, N,N-Dimethacrylamide, N,N-Diethylacrylamide, Acrylamide, N-Isopropylacrylamide, Acryloylmorpholine, N-Vinyl-N-Methyl Acrylamide amide, N-vinylacetamide, N-vinylformamide, etc. Specific examples of the monomer having a carboxyl group include (meth)acrylic acid, mono[2-[(2-meth-acryloyl)oxy]ethyl] succinate, 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. (F) component may be any one of these monomers, and may be a mixture of two or more.

When the composition of the present invention contains the (F) component, the content of the (F) component is preferably 25% by mass or less when the total of all monomer components is set to 100% by mass. When it is 25 mass % or less, the solubility in a composition of (A) component will become favorable, and the surface hydrophilicity of a contact lens will also become 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 preferable. 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 melt|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, 2-methyl alcohol -2-butanol, 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. From the viewpoint of the solubility of the component (A) and the pH stability of the composition, it is particularly preferable that the solvent consists 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, the content of the solvent is preferably 25 parts by mass or less when the total of all monomer components in the composition is 100 parts by mass. 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 other than the said (A)-(F) component. The polymerization initiator may be a known polymerization initiator, and is preferably a thermal polymerization initiator. When a thermal polymerization initiator is used, the copolymerizability of each monomer component is easily changed due to the temperature change during the polymerization. Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile, dimethyl azobisisobutyrate, 2,2'-azobis[2-(2-imidazoline- 2-yl)propane] hydrochloride, 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 -pyrrolidinyl-2-methylpropane) dihydrochloride, azodimethyl N-bismethylolhydroxyethyl propionamide, 2,2'-azo[2-methyl-N-(2 -Hydroxyethyl) propionamide], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azo[2-methyl-N-(2-hydroxyethyl) Azo-based polymerization initiators such as phenyl) propionamide], or benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, tert-butyl peroxycaproate (tert-butyl peroxycaproyl) -butyl peroxy hexanoate), bis(3,5,5-trimethylhexanoyl) peroxide and other peroxide-based polymerization initiators. These polymerization initiators may be used alone or in combination of two or more. Among them, from the viewpoint of safety and availability, azo-based polymerization initiators are preferred, and from the viewpoint of reactivity, 2,2'-azobisisobutyronitrile and dimethyl azobisisobutyrate are particularly preferred and 2,2'-azobis(2,4-dimethylvaleronitrile).

The amount of the polymerization initiator to be added is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, particularly preferably 0.2 to 1 part by mass, when the total of all monomer components in the composition is 100 parts 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 parts, 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 for contact lenses and manufacturing a contact lens.

The composition of the present invention may contain additives such as a polymerizable ultraviolet absorber and a polymerizable dye (colorant) in addition to the above-mentioned (A) to (F) components, as long as the object of the present invention is not inhibited. By blending an ultraviolet absorber, it is possible to reduce the burden on the eyes from ultraviolet rays such as sunlight. In addition, by blending pigments, colored contact lenses can be produced.

The preparation method of the composition of the present invention is not particularly limited. For example, it can be prepared by adding the components to a stirring (mixing) device in any order or together, and stirring (mixing) at a temperature of 10°C to 50°C until uniform. Among them, 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. It is preferable to add and mix other components after mixing and dissolving the three components (A), (B), and (C) components from the viewpoint of improving the solubility of the (A) component.

The polymer of the present invention is formed from 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 this production method.

The polymer of the present invention can be prepared by filling a mold with the composition of the present invention and carrying out a polymerization reaction. As the mold, a mold having a hydrophobic surface formed of polypropylene or the like can be used.

The polymerization reaction can be carried out, for example, by 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 accordance with the decomposition temperature of the polymerization initiator to be used. The polymerization method of two or more stages in the polymerization step 2 is carried out. 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 step 1]

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

The polymerization temperature in the polymerization step 1 is preferably 50°C to 70°C, and more preferably 55°C to 70°C. When the polymerization temperature of the polymerization step 1 is 45° C. to 75° C., a polymer having favorable physical properties such as surface hydrophilicity can be stably obtained.

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

[Polymerization step 2]

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

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

The polymerization time in the polymerization step 2 is preferably 1 hour or more and 10 hours or less. When the polymerization time of the polymerization step 2 is 1 to 10 hours, a polymer having favorable physical properties such as surface hydrophilicity can be obtained efficiently.

The atmosphere in which the polymerization steps 1 and 2 are performed is not particularly limited, but it is preferable to perform both the polymerization steps 1 and 2 in an inert gas atmosphere such as nitrogen or argon from the viewpoint of increasing the polymerization rate. At this point, an inert gas can be passed through the composition or this makes the composition filling site of the mold an inert gas atmosphere.

The pressure in the mold can be from atmospheric pressure to slightly positive pressure. 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 formed from 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 part in a polymer. Since the composition of the present invention contains components (C) and (D) as silicone-containing monomers, the polymer has a silicone moiety, and by hydrating (containing water), a silicone hydrogel can be formed.

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, and more preferably 35% by mass or more and 50% by mass or less. When the moisture content is 35 to 60 mass %, the balance with oxygen permeability can be made excellent.

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 the production method.

After the above-described polymerization reaction, the polymer may be in a state of a mixture with unreacted monomer components (unreacted materials), residues of the components, by-products, residual solvents, and the like. Although such a mixture can be directly used for the hydration treatment, it is preferable to use a purification solvent to purify the polymer before the hydration treatment.

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

The contact lens of the present invention can be obtained by immersing the polymer in physiological saline and hydrating it so that it has a predetermined moisture content. The physiological saline can be boric acid buffered physiological saline, phosphate buffered physiological saline, or the like. Moreover, you may immerse in the care solution for soft contact lenses containing physiological saline. From the viewpoint of hydration, the osmotic pressure of the physiological saline is preferably 250 to 400 mOms/kg.

The lens surface of the contact lens of the present invention has good hydrophilicity, is not easy to adhere to dirt such as lipids, is easy to wash and remove even when attached, and is excellent in mechanical strength, so it can be used for about one month in a normal use form according to needs. . It is of course also possible to replace 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 by these Examples and Comparative Examples. First, components used in Examples and Comparative Examples are shown below.

(A) Component (phosphorylcholine-containing methacrylate monomer)

MPC: (2-methacryloyloxyethyl)phosphorylcholine

(B) Component (hydroxyl group-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 and 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: Compound of formula (2) as product of the esterification reaction of itaconic acid monoethylene glycol with 3-iodopropyl[tris(trimethylsiloxy)]silane

(D) Component (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) ethyl acrylate

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 hours half-life temperature 65℃)

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

The following items were evaluated for the compositions, polymers, and contact lenses of Examples and Comparative Examples. Hereinafter, "composition", "polymer", and "contact lens" in each evaluation item and each table include not only the "composition", "polymer", and "contact lens" of each example, but also comparative examples. "Composition", "Polymer" and "Contact Lens".

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 evaluated by the naked eye according to the following criteria.

○: solid

×: Liquid (including viscous liquid)

Transparency of polymers

The transparency of the polymer was evaluated by the naked eye according to the following criteria.

○: Transparent

△: Slightly cloudy

×: cloudy

Transparency of Contact Lenses

After the polymer was purified, it was immersed in physiological saline described in ISO-18369-3 and swollen to obtain a hydrogel (contact lens). The hydrogel (contact lens) was evaluated by the naked eye according to the following criteria. ) transparency.

○: Transparent

△: Slightly cloudy

×: cloudy

Surface Hydrophilicity of Contact Lenses (WBUT)

The surface hydrophilicity of contact lenses was evaluated by WBUT (water film break up time). Specifically, the contact lens was immersed in ISO physiological saline overnight, the outer periphery was pulled out from the water surface with tweezers, and the time until the water film on the lens surface disappeared from the water surface (water film retention time) was measured. The state of disappearance of the water film was judged by the naked eye. This measurement was performed three times, the average value thereof was obtained, and it was determined that the surface hydrophilicity was good when it was 30 seconds or longer.

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 [MPa] of the contact lens was measured according to JIS-K7127, and the mechanical strength was evaluated. In detail, using the contact lens cut out to a width of 2 mm, a 200 gf load cell was used, and the interval between clamps was set to 6 mm, and the modulus was measured at a speed of 1 mm/sec. When the modulus was 0.2 MPa or more and less than 0.7 MPa, it was determined that the mechanical strength was good.

Oxygen permeability of contact lenses

According to the measuring method based on the polarographic method described in ISO 18369-4, the oxygen permeability coefficient of the sample which overlapped 2-4 contact lenses was measured. In the measurement, O ₂ Permeometer Model 201T from Createch/Rehder-dev Co. was used. The thickness of the lens was plotted on the x-axis and the t/Dk value obtained by the measurement on the y-axis, and the reciprocal 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. Polymacon and omafilcon A were used as standard contact lenses for evaluation. The lubricity of polymacon was set to 2, and the lubricity of omafilcon A was set to 8, and the evaluation was performed in ten steps of 1 to 10. When the evaluation score was 6 points or more, it was judged that the surface lubricity was good, and when the evaluation score was 5 points or less, it was judged that the surface lubricity was poor.

Example 1

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 in a container and stirred at room temperature until 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, and the mixture was heated at room temperature. Stir until homogeneous to obtain a composition. The composition was evaluated as described above.

0.3 g of the above composition was injected into a 25 mm × 70 mm × 0.2 mm spacer sandwiched between two polypropylene plates with a polyethylene terephthalate sheet having a thickness of 0.1 mm as a spacer. in a cell and placed in an oven. After the inside of the oven was replaced with nitrogen, the temperature was raised to 65°C and maintained at that temperature 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 cell and evaluated as described above.

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 perform purification. Furthermore, the polymer was immersed in the physiological saline described in ISO-18369-3, and it was made to swell (hydrate), and it was set as a contact lens. The contact lens was processed into a sample having a 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, the polymerization conditions, and each evaluation result.

Examples 2 to 27

The compositions, polymers, and contact lenses of Examples 2 to 27 were prepared/manufactured in the same manner as in Example 1, except that the content ratio of each component and the polymerization conditions were changed to those shown in Tables 1 to 4, and an evaluation test was performed. The results are shown in Tables 1 to 4.

Comparative Example 1

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 in a container 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, and the mixture was heated at room temperature. The mixture was stirred until uniform, and the composition of Comparative Example 1 was obtained. The composition was evaluated as described above.

0.3 g of the above composition was injected into a cell of 25 mm × 70 mm × 0.2 mm sandwiched between two polypropylene plates with a polyethylene terephthalate sheet with a thickness of 0.1 mm as a gasket, and Place in oven. After nitrogen-substituting the inside of the oven, the temperature was raised to 65° C. and maintained at that temperature for 3 hours, and then the temperature was further raised to 120° C. and maintained for 2 hours to polymerize the composition to obtain the polymer of Comparative Example 1. The polymer was removed from the cell and evaluated as described above.

The polymer of Comparative Example 1 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 materials 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 of the comparative example 1 was produced. The contact lens was processed into a sample having a 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 0 seconds, which was a poor result, other evaluations were not performed.

Comparative Examples 2 to 5

The compositions, polymers, and contact lenses of Comparative Examples 2 to 5 were prepared/manufactured 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 an evaluation test was performed. The results are shown in Table 5. In Comparative Example 5, as in Comparative Example 1, since the WBUT was 0 seconds, which was a poor result, other evaluations were not performed. In Comparative Examples 2 and 3, the polymerization was not performed due to the uneven composition. Therefore, the polymers and contact lenses of Comparative Examples 2 and 3 could not be prepared/manufactured, and their evaluation 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]

*1 (A) to (F) component blending amount: the content ratio relative to the total 100 mass % of all monomer components in the composition

*2 Blending amount of other components: Content ratio relative to the total of 100 parts by mass of all monomer components in the composition

※3 Contact lenses

[Table 2]

*1 (A) to (F) component blending amount: the content ratio relative to the total 100 mass % of all monomer components in the composition

*2 Blending amount of other components: Content ratio relative to the total of 100 parts by mass of all monomer components in the composition

※3 Contact lenses

[table 3]

*1 (A) to (F) component blending amount: the content ratio relative to the total 100 mass % of all monomer components in the composition

*2 Blending amount of other components: Content ratio relative to the total of 100 parts by mass of all monomer components in the composition

※3 Contact lenses

[Table 4]

*1 (A) to (F) component blending amount: the content ratio relative to the total 100 mass % of all monomer components in the composition

*2 Blending amount of other components: Content ratio relative to the total of 100 parts by mass of all monomer components in the composition

※3 Contact lenses

*4 After 7 hours at 55°C, 5 hours at 75°C

[table 5]

*1 (A) to (F) component blending amount: the content ratio relative to the total 100 mass % of all monomer components in the composition

*2 Blending amount of other components: Content ratio relative to the total of 100 parts by mass of all monomer components in the composition

※3 Contact lenses

Claims (7)

1. A monomer composition for a contact lens, comprising a component A, a component B, a component C, a component D and a component E:

the component A is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1);

the component B is more than one hydroxyl-containing monomer selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether;

the component C is an itaconic acid diester monomer containing a siloxane group represented by the following formula (2);

the component D is a siloxane group-containing (meth) acrylate represented by the following formula (3); and

the component E is a cross-linking agent,

the content of the component A is 5-20 mass%, the content of the component B is 5-25 mass%, the content of the component C is 30-70 mass%, the content of the component D is 5-40 mass%, and the content of the component E is 0.1-10 mass% based on 100 mass% of the total of all monomer components in the composition,

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the formula (3), R¹Is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10 to 20.

2. The monomer composition for a contact lens according to claim 1, wherein,

the composition further comprises a component F: the content of the component F is 25% by mass or less based on 100% by mass of the total of all monomer components in the composition.

3. The monomer composition for a contact lens according to claim 1 or 2, wherein,

the composition further contains a solvent having a hydroxyl group, and the content of the solvent is 25 parts by mass or less based on 100 parts by mass of the total of all monomer components in the composition.

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

5. A method for producing the polymer for a contact lens according to claim 4, comprising:

a polymerization step 1 of adding a polymerization initiator to the monomer composition for a contact lens according to any one of claims 1 to 3, and maintaining the mixture at a temperature of 45 to 75 ℃ for 1 hour or more to carry out polymerization; and

and a polymerization step 2 in which the mixture is maintained at 90 to 140 ℃ for 1 hour or more after the polymerization step 1 to carry out polymerization.

6. A contact lens formed from a hydrate of the polymer for a contact lens of claim 4.

7. A method of manufacturing a contact lens, comprising:

mixing the polymer for a contact lens according to claim 4 with at least one solvent selected from the group consisting of water, methanol, ethanol, 1-propanol and 2-propanol, and immersing the polymer in the solvent at a temperature of 10 to 40 ℃ for 10 minutes to 5 hours to purify the polymer; and

and a step of immersing the purified polymer in physiological saline having an osmotic pressure of 250 to 400mOms/kg, and hydrating the polymer so that the water content of the obtained contact lens is 35 to 60 mass%.