TW201827892A - 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

Provided is a contact lens monomer composition useful for manufacturing a contact lens having excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wear comfort. Furthermore provided are a contact lens polymer obtained from the composition, and a contact lens. The composition contains specific amounts of: (A) a methacrylate monomer having a phosphorylcholine group; (B) one or more types of hydroxyl-group-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) an itaconic acid diester monomer containing a siloxanyl group; (D) a siloxanyl-group-containing (meth)acrylate; and (E) a crosslinking agent.

Description

Monomer composition for contact lens, polymer for contact lens, preparation method thereof, contact lens and manufacturing method thereof

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

In the past, hydrogel contact lenses have insufficient oxygen supply to the cornea, and there is a problem in safety when worn for a long period of time. As a contact lens that solves this drawback and improves safety, a silicone hydrogel contact lens has been developed.

However, an anthrone ketone hydrogel contact lens has a problem that it is difficult to impart hydrophilicity to the surface of the lens. Generally, soft contact lenses are manufactured by a cast mold method in which a polypropylene mold is often used. When the fluorenone hydrogel contact lens is produced by this method, since the polypropylene is hydrophobic, the fluorenone monomer is polymerized in a state of being oriented on the surface of the mold. Therefore, the anthrone component is formed on the surface of the lens, and the hydrophilicity of the surface is lowered. When the hydrophilicity of the surface of the lens is insufficient, lipids, proteins, and the like may adhere to the lens, which may cause white turbidity or eye diseases of the lens.

Therefore, proposals have been made to form a coating based on a plasma gas or a hydrophilic polymer or a surface graft polymer based on a hydrophilic monomer on the surface of the lens after the manufacture of the fluorenone hydrogel contact lens. However, these surface treatments require many devices and the process is complicated, so it is not ideal in mass production.

In order to improve the hydrophobicity of the surface of a soft contact lens using an anthrone-containing copolymer, it has been proposed to N,N-dimethylpropenamide, N-vinyl-2-pyrrolidone, N-methyl- A method of using a vinyl group-containing hydrophilic monomer such as N-vinylacetamide or N-vinylpyrrolidone for a monomer composition. However, even if such a hydrophilic monomer is used, the hydrophilicity of the surface of the lens is not sufficient.

Patent Document 1 discloses a method for producing a lens from a composition for an anthrone hydrogel, which comprises: an anthrone monomer having a (meth)acrylinyl group, and a vinyl group; A hydrophilic monomer, a crosslinkable monomer, and a polymerization initiator having a 10-hour half-life temperature of 70 ° C to 100 ° C. Although this method aims to improve the hydrophilicity of the surface of the lens by utilizing the difference in polymerizability of the raw material monomers, satisfactory hydrophilicity is not obtained.

Patent Document 2 discloses a monomer composition for a contact lens comprising: a (meth) acrylate monomer containing a phosphatiline base, a (meth) acrylate fluorenone monomer having a hydroxyl group, and Crosslinker. Patent Document 3 discloses a method comprising a 2-methylpropenyloxyethylphosphonium choline (MPC), a dimethyl propylene fluorenone macromonomer, and (3-methacryloxyloxy-2). An anthrone hydrogel contact lens obtained from a composition of -hydroxypropyloxy)propylbis(trimethyldecyloxy)methylnonane (SiGMA). Patent Document 4 discloses a (meth) acrylate monomer containing a phosphonium base or a carboxy betsulfonyl group, a (meth) acrylate fluorenone monomer having a secondary hydroxyl group, and having no hydroxyl group ( A contact lens obtained from a composition of a methyl acrylate cyclic fluorenone monomer, a maleic acid or a fumaric acid diester fluorenone monomer having a fluorinated alkyl group. However, although the hydrophilicity of the lens surface of the contact lenses of Patent Documents 2 to 4 is improved, there is a problem that the oxygen permeability is lowered.

Patent Document 5 discloses a composition comprising a (meth) acrylate monomer containing a phosphorus choline base, a (meth) acrylate fluorenone monomer having a hydroxyl group, and an anthrone (meth) acrylate. It is also disclosed that its polymer can be used in contact lenses. Patent Document 6 discloses a composition containing a decyloxy group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and discloses that the polymer thereof can be used for a contact lens. Patent Documents 5 and 6 gave good results in terms of hydrophilicity and oxygen permeability of the lens surface.

Conventional technical literature

Patent literature

Patent Document 1: International Publication No. 2015/001811

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

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

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

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

Patent Document 6: International Publication No. 2010/104000

Technical problem to be solved by the present invention

However, the contact lenses of Patent Documents 5 and 6 are considered to be excellent in terms of hydrophilicity and oxygen permeability of the lens surface, but mechanical strength and wearing feeling are not sufficient, and further improvement is required.

A 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 it is manufactured using a hydrophobic mold formed of polypropylene or the like. In addition, "excellent surface hydrophilicity" means a characteristic that the water film holding 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 which are applicable to obtain the above contact lens.

Another technical problem of the present invention is to provide a method for producing the above polymer and contact lens.

Technical means to solve technical problems

The inventors of the present application conducted intensive studies and found that a monomer composition containing two kinds of hydrophilic monomers and two fluorenyl group-containing fluorenone monomers can be used as a raw material for contact lenses. All of the above objects have been made, thereby completing the present invention.

According to an embodiment of the present invention, there is provided a monomer composition for a contact lens, wherein the composition contains: (A) a component, which is a phosphorus-containing choline group represented by the following formula (1) The acrylate monomer and the component (B) are selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, and ethylene One or more hydroxyl group-containing monomers in the group consisting of alcohol monovinyl ether and diethylene glycol monovinyl ether, and (C) component, which is a nonoxyalkyl group represented by the following formula (2) The itaconic acid diester monomer and the component (D) are a methoxyalkyl group-containing (meth) acrylate represented by the following formula (3) and a component (E), which is a crosslinking agent. The total content of all the monomer components in the composition is 100% by mass, the content of the component (A) is 5 to 20% by mass, the content of the component (B) is 5 to 25% by mass, and the content of the component (C) is 30 to 70% by mass, the content of the component (D) is 5 to 40% by mass, and the content of the component (E) is 0.1 to 10% by mass. In the formula (3), R ¹ is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10 to 20.

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

According to another aspect of the present invention, a contact lens comprising the hydrate of a polymer for a contact lens described above and a method of manufacturing the same are provided.

Effect of the invention

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. 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, an fluorenone hydrogel soft contact lens excellent in the above properties can be produced.

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 further containing the component (F) as an optional component. The polymer for contact lenses of the present invention is composed of the polymer of the monomer composition for contact lenses, and the contact lens of the present invention is composed of the hydrate of the polymer for contact lenses. Hereinafter, the monomer composition for a contact lens of the present invention is simply referred to as a composition. Further, the polymer for a contact lens of the present invention is simply referred to as a polymer.

(A) component: methacrylate monomer containing phosphorus choline base

The component (A) is a phosphatidyl group-containing methacrylate monomer represented by the following formula (1), specifically, 2-methylpropenyloxyethylphosphonium choline (MPC). By containing the component (A), the hydrophilicity and lubricity of the surface of the contact lens produced from the polymer of the composition of the present invention can be improved.

In the composition of the present invention, when the total amount of all the monomer components is 100% by mass, the content of the component (A) is 5 to 20% by mass, preferably 8 to 20% by mass. When the content ratio of the component (A) is less than 5% by mass, sufficient surface hydrophilicity cannot be obtained. On the other hand, when it exceeds 20% by mass, the component (A) is hardly dissolved in the composition, or the mechanical strength of the contact lens may be lowered. Further, in the present invention, the "monomer component" means the components (A) to (F).

(B) component: hydroxyl-containing monomer

The component (B) is selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, and More than one hydroxyl-containing monomer in the group consisting of ethylene glycol monovinyl ether. The component (B) is dissolved in the composition of the present invention by containing the component (B) in a predetermined amount. In view of the solubility of the component (A), the hydroxyl group of the component (B) is preferably a primary hydroxyl group. Further, in the present invention, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acrylic" 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 (meth)acrylic acid-4- Hydroxybutyl ester, 2-hydroxybutyl (meth)acrylate, polyethylene glycol monomethacrylate, N-(2-hydroxyethyl) acrylamide, N-methyl-N-(2-hydroxyl Ethyl) acrylamide, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, and the like. The component (B) may be any of these monomers, or a mixture of two or more kinds.

In view of making the solubility of the component (A) more favorable, it is preferably 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 the present invention, when the total amount of all the monomer components is 100% by mass, the content of the component (B) is 5 to 25% by mass. When the content ratio of the component (B) is less than 5% by 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% by mass, there is a possibility that the oxygen permeability of the contact lens is lowered.

(C) component: itaconic acid diester monomer containing a decyloxyalkyl group

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

The monomer of the formula (2) is obtained by an esterification reaction of monoethylene glycol itaconate with 3-iodopropyl [tris(trimethyldecyloxy)]decane. Itaconic acid monoethylene glycol ester is obtained, for example, by reacting itaconic anhydride with ethylene glycol as described in Patent Document 6. Further, a commercially available product can be used for 3-iodopropyl [tris(trimethylphosphonio)]decane, but in order to increase the purity of the obtained fluorenone monomer of the present invention, a high-purity product is preferably used.

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

In the composition of the present invention, when the total amount of all the monomer components is 100% by mass, the content of the component (C) is from 30 to 70% by mass, preferably from 30 to 60% by mass. When the content ratio 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 be difficult, or the polymer used for the contact lens may be cloudy. possibility. On the other hand, when it exceeds 70 mass%, the surface hydrophilicity of a contact lens may become inadequate.

(D) component: (meth) acrylate containing a decyloxy group

The component (D) is a methoxyalkyl group-containing (meth) acrylate represented by the following formula (3). The component (D) contributes to the improvement of the oxygen permeability of the contact lens and the adjustment of the mechanical strength. The component (D) can be produced by the method disclosed in JP-A-2014-031338, or a commercially available product.

In the 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 dimethyloxane moiety, which is 10-20. The component (D) may be a mixture of a plurality of compounds having different numbers of repeats 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 is lowered, so that it is not excellent. Further, when n is greater than 20, the surface hydrophilicity or mechanical strength of the contact lens is lowered.

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

In the composition of the present invention, when the total amount of all the monomer components is 100% by mass, the content of the component (D) is 5 to 40% by mass. When the content ratio of the component (D) is less than 5% by mass, the mechanical strength of the contact lens becomes excessively large, and the 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 the monomer components is 100% by mass, the total content ratio of the component (C) to the component (D) is preferably 40 to 75% by mass, more preferably The ground is 60 to 65 mass%. By setting the total content ratio to 40% by mass or more, the composition of the present invention which is a uniform transparent liquid can be easily obtained. On the other hand, by setting it as 75 mass % or less, it can prevent that a contact lens is hardened excessively.

(E) component: crosslinker

The component (E) functions as a crosslinking agent in the polymerization reaction of the monomers of the components (A) to (D). 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 crosslinked structure, and thus the contact lens of the present invention exhibits excellent solvent resistance.

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

In the formula (5), p and r are equal to each other and are 0 or 1. q represents the number of repetitions of the dimethyloxane moiety, and is 10 to 70. The fluorenone dimethacrylate represented by the formula (5) may be a mixture of a plurality of compounds having a different number of repetitions 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, in addition to the fluorenone dimethacrylate of the above formula (5), ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol II. Vinyl ether, methylene bis acrylamide, allyl methacrylate, (2-allyloxy) ethyl methacrylate, 2-(2-vinyloxyethoxy) A acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, and the like. The component (E) may be any of these crosslinking agents, or a mixture of two or more kinds.

In the composition of the present invention, when the total amount of all the monomer components is 100% by mass, the content of the component (E) is 0.1 to 10% by mass. When the content ratio of the component (E) is less than 0.1% by mass, the solvent resistance of the contact lens is lowered. On the other hand, when it exceeds 10% by mass, the contact lens may become brittle and may be damaged, and the mechanical strength may become too high to deteriorate the wearing feeling of the contact lens.

(F) component: a monomer other than the components (A) to (E)

The component (F) is a monomer other than the components (A) to (E). The component (F) is an optional component and can be used for the purpose of adjusting the moisture content of the contact lens or the like.

As the component (F), a monomer having one or more functional groups selected from the group consisting of a guanamine group, a carboxyl group, and an ester group can be exemplified. Specific examples of the monomer having a guanamine group include N-vinylpyrrolidone, N-vinyl acridine-2-one, N-vinyl-ε-caprolactam, and N-vinyl-3. -methyl-2-caprolactam, N,N-dimethyl decylamine, N,N-diethyl acrylamide, acrylamide, N-isopropyl acrylamide, propylene morpholine N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinylformamide, and the like. Specific examples of the monomer having a carboxyl group include (meth)acrylic acid, 2-methylacryloxyethyl succinic acid, and the like. Specific examples of the monomer having an ester group include alkyl (meth)acrylate or methoxy group such as methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. Polyethylene glycol methacrylate and the like. The component (F) may be any of these monomers, or a mixture of two or more kinds.

In the case where the composition of the present invention contains the component (F), when the total amount of all the monomer components is 100% by mass, the content of the component (F) is preferably 25% by mass or less. When it is 25% by mass or less, the solubility in the composition of the component (A) is good, and the surface hydrophilicity of the contact lens is also good.

The composition of the present invention may contain a solvent in addition to the above components (A) to (F). The solvent is not particularly limited as long as it can improve the solubility of each component in the composition, but is preferably a solvent having a hydroxyl group. By using a solvent having a hydroxyl group, the dissolution rate of the component (A) in the composition of the present invention becomes high, and dissolution thereof becomes easy.

The solvent having a hydroxyl group may be an alcohol or a carboxylic acid. Specific examples of the alcohol include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, and tert-amyl alcohol. 1-hexanol, 1-octanol, 1-nonanol, 1-dodecyl alcohol, and the like. Specific examples of the carboxylic acid include glycolic acid, lactic acid, acetic acid, and the like. The solvent may be any one of these solvents, or a mixture of two or more kinds. In view of the solubility of the component (A) and the pH stability of the composition, the solvent is preferably composed of one or more selected from the group consisting of ethanol, 1-propanol and 2-propanol.

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

The composition of the present invention may contain a polymerization initiator in addition to the above components (A) to (F). The polymerization initiator may be a conventional polymerization initiator, preferably a thermal polymerization initiator. When a thermal polymerization initiator is used, it is easy to change the copolymerization property of each monomer component based on the temperature change in the middle of a polymerization. Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2-azobis(2-methylpropionic acid) dimethyl ester, and 2,2'-azodiene. [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-methylpropylguanidine) dihydrochloride, 2,2'-azodi [N-(2-carboxyethyl)-2-methylpropyl hydrazine] 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-di (hydroxymethyl)-2-hydroxyethyl}propanamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'- Azo polymerization initiated by azobis(2-methylpropylguanidine) dihydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide Agent, or benzamidine peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauryl peroxide, t-butyl peroxyhexanoate, 3,5,5-trimethylhexanide Peroxide peroxide-based polymerization initiators. These polymerization initiators may be used singly or in combination of two or more. Among these initiators, in view of safety and availability, an azo polymerization initiator is preferred, and in view of reactivity, it is more preferably 2,2'-azobisisobutyronitrile. 2,2'-azobis(2-methylpropionic acid) dimethyl ester and 2,2'-azobis(2,4-dimethylvaleronitrile).

When the total amount of all the monomer components in the composition is 100 parts by mass, 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, still more preferably 0.2 to 1 part by mass. When the amount 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 the polymerization initiator is not obtained. When the polymer for contact lenses is washed and the contact lens is produced at more than 3 masses, there is a possibility that the extraction removal of the polymerization initiator decomposition product becomes insufficient.

The composition of the present invention may contain an additive such as a polymerizable ultraviolet absorber or a polymerizable dye (colorant) in addition to the above components (A) to (F), insofar as the object of the present invention is not impaired. By blending the ultraviolet absorber, the burden on the eyes caused by ultraviolet rays such as sunlight can be reduced. In addition, colored contact lenses can be made by blending pigments.

The preparation method of the composition of the present invention is not particularly limited, and for example, it can be prepared by adding the components in any order or simultaneously to a stirring (mixing) apparatus, and stirring at a temperature of 10 ° C to 50 ° C. (mixed) until uniform. However, when the composition contains a polymerization initiator, it is noted that the polymerization is not initiated at the time of mixing, and it is preferably mixed at 40 ° C or lower. In view of the fact that the solubility of the component (A) is improved, it is preferred to add and mix the other components after mixing the three components (A), (B) and (C).

The polymer of the present invention is composed of the polymer of the above composition of the present invention. Hereinafter, a method for producing the polymer of the present invention will be described. The preparation 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 be obtained by the production method.

The polymer of the present invention can be prepared by filling the composition of the present invention into a mold and performing a polymerization reaction. As the mold, a mold having a hydrophobic surface made 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 from 45 ° C to 140 ° C for 1 hour or more by blending the decomposition temperature of the polymerization initiator to be used, but preferably by including the following The polymerization process 1 and the polymerization process 2 are carried out by two or more polymerization processes. At this time, the hydrophilicity of the surface of the contact lens can be further improved. After the completion of the polymerization, for example, it can be cooled to 60 ° C or lower, and the polymer is taken out from the mold.

[Polymerization Process 1]

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

The polymerization temperature of the polymerization process 1 is preferably from 50 ° C to 70 ° C, more preferably from 55 ° C to 70 ° C. When the polymerization temperature of the polymerization process 1 is 45 to 75 ° C, a polymer having 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. When 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 efficiently obtained.

[Polymerization Process 2]

The polymerization process 2 is a process which is carried out after the polymerization process 1 and which is subjected to a polymerization reaction at a temperature higher than the polymerization process 1, that is, from 90 ° C to 140 ° C.

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

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

The environment in which the polymerization processes 1 and 2 are carried out is not particularly limited, but in view of increasing the polymerization rate, the preferred polymerization processes 1 and 2 are carried out in an inert gas atmosphere such as nitrogen or argon. At this time, an inert gas may be introduced into the composition, or the place where the composition of the mold is filled may be set to an inert gas atmosphere.

The pressure in the mold can be from atmospheric pressure to micro-pressurization. When the polymerization is carried out in an inert gas atmosphere, it is preferably 1 kgf/cm ² or less in terms of gauge pressure.

The contact lens of the present invention is an indolone hydrogel contact lens composed of a hydrate of the above polymer. That is, the contact lens of the present invention is obtained by hydrating the polymer of the present invention and hydrating it to form a hydrogel. Further, in the present specification, "anthrone hydrogel" means a hydrogel having an anthrone component in a polymer. Since the composition of the present invention contains the components (C) and (D) as the fluorenone-containing monomer, the polymer has an anthrone component, and an oxime ketone hydrogel can be formed by hydrating (aqueous).

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

Next, a method of manufacturing the contact lens of the present invention will be described. The manufacturing method shown below is only one embodiment of the method of obtaining the contact lens of the present invention, and the contact lens of the present invention is not limited to being obtained by the manufacturing method.

After the polymerization reaction, the polymer may be in a state of a mixture of an unreacted monomer component (unreacted product), a residue of each component, a by-product, and a residual solvent. Although such a mixture can be directly supplied to the hydration treatment, it is preferred to purify the polymer using a solvent for purification before the hydration treatment.

Examples of the solvent for purification include water, methanol, ethanol, 1-propanol, 2-propanol, and a mixture of these solvents. Purification can be carried out, for example, by 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 in water for 10 minutes to 5 hours. Further, after immersing in an alcohol solvent, it may be immersed in an aqueous alcohol having an alcohol concentration of 20 to 50% by weight for 10 minutes to 5 hours, and further immersed in water. As water, it is preferably pure water or ion-exchanged water.

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

The surface of the lens of the contact lens of the present invention has good hydrophilicity, is less likely to adhere to dirt such as lipids, and is easily cleaned and removed even if adhesion occurs, and is excellent in mechanical strength. Therefore, it can be used in a normal use form for about one month. Of course, it is also possible to exchange in a period shorter than one month.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. First, the components used in the examples and comparative examples are shown below.

(A) component (methacrylate monomer containing phosphorus choline base)

MPC: (2-methacryloxyethyl) phosphonium choline

(B) component (hydroxyl-containing monomer)

HEA: 2-hydroxyethyl acrylate

HEMA: 2-hydroxyethyl methacrylate

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

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

HPA: 2-hydroxypropyl acrylate (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester mixture, 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 (the itaconic acid diester monomer containing a decyloxy group)

ES: a compound of the formula (2) as an esterification reaction of itaconic acid monoethylene glycol ester with 3-iodopropyl [tris(trimethyldecyloxy)]decane

(D) component (methacrylate containing decyloxy group)

FM-0711: a compound represented by the 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: a compound represented by the formula (5) (p=r=0, number average molecular weight Mn=about 1,000)

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

TEGDMA: Tetraethylene glycol divinyl ether

(F) component (monomer other than (A) to (E))

NVP: N-vinylpyrrolidone

DMAA: N,N-dimethyl methacrylate

NIPA: N-isopropyl acrylamide

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 temperature is 65 °C)

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

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

Composition uniformity and transparency

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

○: Uniform transparency

×: There is white turbidity or precipitation

Polymer morphology

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

○: solid

×: liquid (including viscous liquid)

Polymer transparency

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

○: transparent

△: slightly turbid

×: white turbid

Contact lens transparency

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

○: transparent

△: slightly turbid

×: white turbid

Surface hydrophilicity of contact lenses (WBUT)

The surface hydrophilicity of the contact lens was evaluated according to WBUT (water film break up time). Specifically, the contact lens was immersed in ISO physiological saline for one night, and the outer peripheral portion was sandwiched by tweezers, and the time from the surface of the water surface to the break of the water film on the surface of the lens (water film holding time) was measured from the water surface. The state of the water film fracture was judged by visual observation. The measurement was performed three times, and the average value was determined. When the measurement was performed for 30 seconds or more, it was determined that the surface hydrophilicity was good.

Water content of contact lenses

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

Mechanical strength of contact lenses

The mechanical strength was evaluated by measuring the modulus [MPa] of the contact lens according to JIS-K7127 using a BAS-3305 (W) breaking strength analyzer manufactured by YAMADEN Co., Ltd. Specifically, the contact lens was cut into a sample having a width of 2 mm, and a 200 gf load cell was used, and the jig between the jigs was set to 6 mm and stretched at a speed of 1 mm/sec, and the modulus was measured. 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

According to the polarographic method based on ISO 18369-4, the oxygen permeability coefficient of a sample obtained by laminating two to four contact lenses was measured. The O2 Permeometer Model 201T from Rehder Development Company was used for the measurement. The thickness of the lens was plotted on the x-axis, and the t/Dk value obtained by the measurement was plotted as the y-axis, and the reciprocal of the slope of the regression line was taken 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 a standard contact lens for evaluation, polymacon and omafilcon A were used. The lubricity of the polymacon was set to 2, the lubricity of the omafilcon A was set to 8, and it was evaluated in the order of 1 to 10 levels. When the evaluation score was 6 or more, it was determined that the surface lubricity was good, and when it was 5 or less, it was determined that the surface lubricity was poor.

Example 1

0.5 g (5.0% by mass) of MPC, 1.0 g (10.0% by mass) of HEA, 4.0 g (40.0% by mass) of ES, and 0.5 g (5 parts by mass) of EtOH were mixed in a vessel, and stirred at room temperature. Dissolve to MPC. Further, 1.9 g (19.0% by mass) of FM-0711, 0.1 g (1.0% by mass) of TEGDV, 2.5 g (25.0% by mass) of NVP, and 0.05 g (0.5 parts by mass) of AIBN were added to the vessel. The mixture was stirred until homogeneous to obtain a composition. The above evaluation was carried out on the composition.

A polyethylene terephthalate sheet having a thickness of 0.1 mm as a separator was sandwiched between 25 mm × 70 mm × 0.2 mm boxes between two polypropylene sheets, and 0.3 g of the above composition was injected. Place in the oven. After the inside of the oven was purged with nitrogen, the temperature was raised to 65 ° C, and the temperature was maintained at the above temperature for 3 hours. Thereafter, the temperature was further raised to 120 ° C for 2 hours, and the composition was polymerized to obtain a polymer. The above evaluation was carried out by taking the polymer out of the box.

The 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 materials and the like, and purified. Further, the polymer was immersed in physiological saline described in ISO-18369-3 and swelled (hydrated) to prepare a contact lens. The contact lenses were processed into samples suitable for the size and shape of each evaluation test, and each evaluation was performed. The blending ratio, polymerization conditions, and evaluation results of the respective components in the composition are shown in Table 1.

Example 2~27

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. Evaluation test. 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% by mass) of ES, and 0.5 g (5 parts by mass) 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 part by mass) of AIBN were added to the vessel. The mixture was stirred until homogeneous, and the composition of Comparative Example 1 was obtained. The above evaluation was carried out on the composition.

A polyethylene terephthalate sheet having a thickness of 0.1 mm as a separator was sandwiched between 25 mm × 70 mm × 0.2 mm boxes between two polypropylene sheets, and 0.3 g of the above composition was injected. Place in the oven. After the inside of the oven was purged with nitrogen, the temperature was raised to 65 ° C, and the temperature was maintained at the above temperature for 3 hours, and then the temperature was further raised to 120 ° C for 2 hours to polymerize the composition, whereby the polymer of Comparative Example 1 was obtained. The above evaluation was carried out by taking the polymer out of the box.

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 purified. Further, the polymer was immersed in physiological saline described in ISO-18369-3 and swelled (hydrated) to prepare a contact lens of Comparative Example 1. The contact lenses were processed into samples suitable for the size and shape of each evaluation test, and each evaluation was performed. The blending ratio, polymerization conditions, and evaluation results of the respective components in the composition of Comparative Example 1 are shown in Table 5. In the evaluation of the surface hydrophilicity, since the WBUT was a poor result of 0 seconds, evaluations other than the above were not performed.

Comparative example 2~5

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 carried out. . The results are shown in Table 5. Since Comparative Example 5 was the same as Comparative Example 1, and the WBUT was a result of 0 seconds, no evaluation other than this was performed. In Comparative Examples 2 and 3, since the composition was not uniform, polymerization was not carried out. Therefore, the polymers and contact lenses of Comparative Examples 2 and 3 could not be produced, and the evaluation was not carried out. The surface of the contact lens of Comparative Example 4 was excellent in hydrophilicity, but the mechanical strength was 0.9 MPa, and the oxygen permeability was 67, which was inferior to the examples.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

no

no

Claims (7)

A monomer composition for a contact lens comprising: (A) a component, a phosphatidyl group-containing methacrylate monomer represented by the following formula (1); (B) a component selected 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: the (C) component is a decyloxyalkyl group-containing itaconate diester monomer represented by the following formula (2); a methoxyalkyl group-containing (meth) acrylate represented by the following formula (3); and (E) a component, a crosslinking agent, based on the total amount of all monomer components in the monomer composition 100% by mass, the content of the component (A) is 5 to 20% by mass, the content of the component (B) is 5 to 25% by mass, and the content of the component (C) is 30 to 70% by mass, and the component (D) The content ratio is 5 to 40% by mass, and the content of the component (E) is 0.1 to 10% by mass. In the formula (3), R ¹ is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10 to 20. The monomer composition for contact lenses according to claim 1, further comprising a component (F) which is a monomer other than the components (A) to (E), relative to the single The total amount of all the monomer components in the bulk composition is 100% by mass, and the content of the component (F) is 25% by mass or less. The monomer composition for contact lenses according to claim 1 or 2, further comprising a solvent having a hydroxyl group, relative to 100 parts by mass of the total of all monomer components in the monomer composition, The content ratio of the solvent is 25 parts by mass or less. A polymer for a contact lens comprising a polymer of a monomer composition for a contact lens according to any one of claims 1 to 3. A method for producing a polymer for a contact lens according to the invention of claim 4, comprising: a polymerization process: the use of the contact lens according to any one of claims 1 to 3 The monomer composition is maintained at a temperature of 45 ° C to 75 ° C for 1 hour or more to carry out polymerization; Polymerization Process 2: After the polymerization process 1, the polymerization is carried out at a temperature of 90 ° C to 140 ° C for 1 hour or more. A contact lens comprising a hydrate of a polymer for a contact lens as described in claim 4 of the patent application. A method for producing a contact lens, comprising: a polymer for a contact lens according to item 4 of claim 4, and a group selected from the group consisting of water, methanol, ethanol, 1-propanol and 2-propanol A process in which one or more solvents in the group are mixed, the polymer used for the contact lens is purified, and the polymer used for the contact lens is immersed in physiological saline to be subjected to a hydration process.