JP7014185B2 - Monomer composition for contact lenses, polymers for contact lenses and methods for producing them, and contact lenses and methods for producing them. - Google Patents

Description

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 comprising a hydrate of the polymer and a method for producing the same.

Conventional hydrogel contact lenses have insufficient oxygen supply to the cornea of the eye, and have a problem in safety when worn for a long time. Silicone hydrogel contact lenses have been developed as contact lenses that solve this drawback and improve safety.

However, the silicone hydrogel contact lens has a problem that it is difficult to make the lens surface hydrophilic. Generally, soft contact lenses are manufactured by a cast molding method, in which a polypropylene mold is often used. When the silicone hydrogel contact lens is manufactured by this method, since polypropylene is hydrophobic, the silicone monomer is polymerized in a state of being oriented on the mold surface. Therefore, a silicone portion is formed on the lens surface, and the hydrophilicity of the surface becomes low. If the hydrophilicity of the lens surface is not sufficient, lipids, proteins, etc. may adhere to the lens surface, causing cloudiness of the lens and eye diseases.

Therefore, after preparing a silicone hydrogel contact lens, it has been proposed to coat the lens surface with plasma gas or a hydrophilic polymer, or to form a surface graft polymer with a hydrophilic monomer. However, these surface treatments require a large number of devices and complicate the process, which is not desirable in mass production.

N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-methyl-N-vinylacetamide, N-vinyl for the purpose of improving the hydrophobicity of the surface of soft contact lenses using silicone-containing copolymers. A method of using a hydrophilic monomer having a vinyl group such as pyrrolidinone in a monomer composition has been proposed. However, even if such a hydrophilic monomer is used, the hydrophilicity of the lens surface cannot be said to be sufficient.

Patent Document 1 is a composition for a silicone hydrogel containing a silicone monomer having a (meth) acryloyl group, a hydrophilic monomer having a vinyl group, a crosslinkable monomer, and a polymerization initiator having a 10-hour half-life temperature of 70 ° C to 100 ° C. Discloses a method of manufacturing a lens from. This method aims to improve the hydrophilicity of the lens surface by utilizing the difference in the polymerizable property of the raw material monomers, but the hydrophilicity is still not satisfactory.

Patent Document 2 discloses a monomer composition for contact lenses containing a phosphorylcholine group-containing (meth) acrylic ester monomer, a (meth) acrylic ester silicone monomer having a hydroxyl group, and a cross-linking agent. Patent Document 3 is obtained from a composition containing 2-methacryloyloxyethyl phosphorylcholine (MPC), dimethacryloylsilicone macromer, and (3-methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane (SiGMA). Silicone hydrogel contact lenses are disclosed. Patent Document 4 describes a (meth) acrylic ester monomer containing a phosphorylcholine group or a carboxybetaine group, a (meth) acrylic ester silicone monomer having a secondary hydroxyl group, a (meth) acrylic ester cyclic silicone monomer having no hydroxyl group, and an alkyl fluoride. A contact lens obtained from a composition containing a maleic acid having a group, a fumaric acid diester silicone monomer, or the like is disclosed. However, the contact lenses according to Patent Documents 2 to 4 have a problem that oxygen permeability is lowered, although the hydrophilicity of the lens surface is improved.

Patent Document 5 discloses a composition containing a phosphorylcholine group-containing (meth) acrylic ester monomer, a (meth) acrylic ester silicone monomer having a hydroxyl group, and a silicone (meth) acrylate, and the polymer thereof is used as a contact lens. It is stated that it can be used. Patent Document 6 discloses a composition containing a siloxanyl group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and describes that the polymer can be used for contact lenses. In Patent Documents 5 and 6, good results are obtained in terms of hydrophilicity and oxygen permeability of the lens surface.

International Publication No. 2015/001811 Japanese Unexamined Patent Publication No. 2007-909060 Japanese Unexamined Patent Publication No. 2014-089477 Japanese Unexamined Patent Publication No. 2007-0562220 JP-A-2007-197513 International Publication No. 2010/104000

However, although the contact lenses according to Patent Documents 5 and 6 are good in terms of hydrophilicity and oxygen permeability of the lens surface, they do not have sufficient mechanical strength and wearing feeling, and further improvement is considered necessary.

An object of the present invention is to provide a contact lens capable of exhibiting excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wearing feeling even when manufactured using a hydrophobic mold made of polypropylene or the like. That is. 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 object of the present invention is to provide a composition and a polymer that can be suitably used for obtaining the above contact lens.

A further object of the present invention is to provide a production method for obtaining the above-mentioned polymer and contact lens.

As a result of diligent research, the present inventors can achieve all the above-mentioned objects by using a monomer composition containing two kinds of hydrophilic monomers and two kinds of siroxanyl group-containing silicone monomers as raw materials for contact lenses. The present invention was completed.

According to one embodiment of the present invention, (A) a phosphorylcholine group-containing methacrylic ester monomer represented by the following formula (1), (B) hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth). ) One or more hydroxyl group-containing monomers selected from the group consisting of acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether, and (C) siroxanyl group-containing itaconic acid diester represented by the following formula (2). A composition containing a monomer, (D) a siroxanyl group-containing (meth) acrylate represented by the following formula (3), and (E) a cross-linking agent, and a total of 100 of all the monomer components in the composition. The content ratio of the component (A) is 5 to 20% by mass, the content ratio of the component (B) is 5 to 25% by mass, and the content ratio of the component (C) is 30 to 70% by mass with respect to the mass%. %, The content ratio of the component (D) is 5 to 40% by mass, and the content ratio of the component (E) is 0.1 to 10% by mass, and a monomer composition for a contact lens is provided.

In 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 embodiment of the present invention, there is provided a contact lens polymer composed of a polymer of the above contact lens monomer composition, and a method for producing the same.

According to a further embodiment of the present invention, there is provided a contact lens made of a hydrate of the polymer for contact lenses, and a method for producing the same.

The monomer composition for contact lenses of the present invention contains the components (A) to (E) 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 contact lenses and the method for producing a contact lens of the present invention, it is possible to produce a silicone hydrogel soft contact lens having the above-mentioned excellent performance.

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

Component (A): Phosphorylcholine group-containing methacrylic ester monomer (A) The component (A) is a phosphorylcholine group-containing methacrylic ester monomer represented by the following formula (1), specifically 2-methacryloyloxyethylphosphorylcholine (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 of all the monomer components is 100% by mass, the content ratio of the component (A) is 5 to 20% by mass, preferably 8 to 20% by mass. If the content of the component (A) is less than 5% by mass, sufficient surface hydrophilicity cannot be obtained. On the other hand, if it exceeds 20% by mass, it becomes difficult to dissolve the component (A) in the composition, and there is a concern that the mechanical strength of the contact lens is lowered. In the present invention, the "monomer component" refers to the components (A) to (F).

Component (B): Hydroxyl-containing monomer The component (B) comprises hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. One or more hydroxyl group-containing monomers selected from the group. By containing the component (B) in a predetermined amount, the dissolution of the component (A) in the composition of the present invention becomes good. In terms of the solubility of the component (A), the hydroxyl group of the component (B) is preferably a primary hydroxyl group. In the present invention, "(meth) acrylate" means "acrylate and / or methacrylate", and "(meth) acrylic" means "acrylic and / or methacrylic".

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

2-Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide in terms of better solubility of the component (A). , Ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether are preferred, especially 2-hydroxyethyl acrylate, N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, and ethylene glycol monovinyl ether. preferable.

In the composition of the present invention, when the total of all the monomer components is 100% by mass, the content ratio of the component (B) is 5 to 25% by mass. If the content of the component (B) is less than 5% by mass, there is a concern that the composition of the present invention may not be a uniform transparent liquid. On the other hand, if it exceeds 25% by mass, there is a concern that the oxygen permeability of the contact lens may decrease.

Component (C): Itaconic acid diester monomer containing siroxanyl group The component (C) is an itaconic acid diester monomer containing siroxanyl group 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 formula (2) is obtained by an esterification reaction of itaconic acid monoethylene glycol ester with 3-iodopropyl [tris (trimethylsiloxy)] silane. The itaconic acid monoethylene glycol ester is obtained, for example, by reacting anhydrous itaconic acid with ethylene glycol as described in Patent Document 6. Further, although a commercially available product may be used for 3-iodopropyl [tris (trimethylsiloxy)] silane, it is preferable to use a high-purity product in order to increase the purity of the obtained silicone monomer of the present invention.

In the above esterification reaction, a small amount of the structural isomer represented by the following formula (2') may be produced as a by-product. In the present invention, a mixture of the monomer of the formula (2) and a small amount of the monomer of the formula (2') may be used as the component (C). That is, in the present invention, the "siloxanyl group-containing itaconic acid diester monomer represented by the formula (2)" is not only the monomer of the formula (2) alone, but also the monomer of the formula (2') other than the monomer of the formula (2). It also includes those containing some isomers.

In the composition of the present invention, when the total of all the monomer components is 100% by mass, the content ratio of the component (C) is 30 to 70% by mass, preferably 30 to 60% by mass. If the content of the component (C) is less than 30% by mass, it may be difficult to dissolve the component (A) in the composition of the present invention, or the polymer for contact lenses to be produced may become cloudy. There is sex. On the other hand, if it exceeds 70% by mass, there is a concern that the surface hydrophilicity of the contact lens becomes insufficient.

Component (D): Siroxanyl group-containing (meth) acrylate The component (D) is a siroxanyl group-containing (meth) acrylate represented by the following formula (3). The component (D) contributes to the improvement of oxygen permeability of the contact lens and the adjustment of the mechanical strength. The component (D) can be prepared by the method disclosed in Japanese Patent Application Laid-Open No. 2014-301338, or may be a commercially available product.

In formula (3), R ¹ is a hydrogen atom or a methyl group. m represents the number of ethyleneoxy groups and is 0 or 1. n represents the number of repetitions of the dimethylsiloxane portion and is 10 to 20. The component (D) may be a mixture of a plurality of compounds having different repetition numbers n. In this case, n is an average value in the number average molecular weight and is in the range of 10 to 20. If n is less than 10, oxygen permeability is lowered, which is not preferable. Further, when n is larger than 20, the surface hydrophilicity and mechanical strength of the contact lens are lowered.

It is preferable that m in the formula (3) is 0. That is, the component (D) is preferably a siroxanyl group-containing (meth) acrylate represented by the following formula (4). In addition, ^R1 and n in the formula (4) are synonymous with those in the formula (3).

In the composition of the present invention, when the total of all the monomer components is 100% by mass, the content ratio of the component (D) is 5 to 40% by mass. If the content of the component (D) is less than 5% by mass, the mechanical strength of the contact lens becomes too large, and there is a concern that the wearing feeling is not excellent. On the other hand, if it exceeds 40% by mass, there is a concern that the surface hydrophilicity of the contact lens may decrease.

Further, in the composition of the present invention, when the total of all the monomer components is 100% by mass, the total content ratio of the component (C) and the component (D) is preferably 40 to 75% by mass, which is more preferable. Is 60 to 65% by mass. By setting the total content to 40% by mass or more, the composition of the present invention in a uniform transparent liquid can be easily obtained. On the other hand, when it is 75% by mass or less, it is possible to prevent the contact lens from becoming excessively hard.

Component (E): Cross-linking agent The component (E) acts as a cross-linking agent during 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 therefore the contact lens of the present invention exhibits excellent solvent resistance.

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

In equation (5), p and r are equal to each other and are 0 or 1. q represents the number of repetitions of the dimethylsiloxane portion and is 10 to 70. The silicone dimethacrylate represented by the 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 terms of number average molecular weight, and is in the range of 10 to 70 in terms of availability.

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

In the composition of the present invention, when the total of all the monomer components is 100% by mass, the content ratio 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, if it exceeds 10% by mass, the contact lens may be brittle and may be damaged, and the mechanical strength may become too high to deteriorate the wearing feeling of the contact lens.

Component (F): 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 is used for the purpose of adjusting the water content of the contact lens and the like.

As the component (F), a monomer having one or more functional groups selected from an amide group, a carboxyl group, and an ester group can be exemplified. Specific examples of the monomer having an amide group include N-vinylpyrrolidone, N-vinylpiperidin-2-one, N-vinyl-ε-caprolactam, N-vinyl-3-methyl-2-caprolactam, N, N-dimethyl. Examples thereof include acrylamide, N, N-diethylacrylamide, acrylamide, N-isopropylacrylamide, acryloylmorpholine, N-vinyl-N-methylacetamide, N-vinylacetamide, and N-vinylformamide. Specific examples of the monomer having a carboxyl group include (meth) acrylic acid, 2-methacryloyloxyethyl succinic acid and the like. Specific examples of the monomer having an ester group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, and methoxypolyethylene glycol methacrylate. The component (F) may be any one of these monomers or a mixture of two or more.

When the composition of the present invention contains the component (F), the content ratio of the component (F) is preferably 25% by mass or less when the total of all the monomer components is 100% by mass. When it is 25% by mass or less, the solubility of the component (A) in the composition 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-mentioned 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 a solvent having a hydroxyl group is preferable. By using a solvent having a hydroxyl group, the dissolution rate of the component (A) in the composition of the present invention is increased, and the dissolution is facilitated.

The solvent having a hydroxyl group may be alcohols or carboxylic acids. Specific examples of alcohols include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, tert-amyl alcohol, 1-hexanol, 1 -Hexanol, 1-decanol, 1-dodecanol and the like can be mentioned. Specific examples of carboxylic acids include glycolic acid, lactic acid, acetic acid and the like. The solvent may be any one of these or a mixture of two or more. In terms of the solubility of the component (A) and the pH stability of the composition, the solvent is particularly preferably composed of one or more selected from ethanol, 1-propanol, and 2-propanol.

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

The composition of the present invention may contain a polymerization initiator in addition to the above-mentioned components (A) to (F). The polymerization initiator may be a known one, and is preferably a thermal polymerization initiator. When a thermal polymerization initiator is used, it is easy to change the copolymerizability of each monomer component due to a temperature change during polymerization. Examples of thermal polymerization initiators are 2,2'-azobisisobutyronitrile, dimethyl 2,2-azobis (2-methylpropionate), 2,2'-azobis [2- (2-imidazolin-). 2-yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihide Rate, 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] dihydrate, 2,2'-azobis [2 -(2-Imidazorin-2-yl) propane], 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis [2-methyl-N- { 1,1-bis (hydroxymethyl) -2-hydroxyethyl} propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2) -Azo-based polymerization initiators such as methylpropion amidine) dihydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], benzoyl peroxide, t-butyl hydroperoxide, etc. Examples thereof include peroxide-based polymerization initiators such as cumenehydroperoxide, lauroyl peroxide, t-butylperoxyhexanoate, and 3,5,5-trimethylhexanoyl peroxide. These polymerization initiators may be used alone or in combination of two or more. Of these, azo-based polymerization initiators are preferable in terms of safety and availability, and 2,2'-azobisisobutyronitrile and dimethyl 2,2-azobis (2-methylpropionate) are preferable in terms of reactivity. ), And 2,2'-azobis (2,4-dimethylvaleronitrile) are particularly preferred.

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, when the total of all the monomer components in the composition is 100 parts by mass. Yes, particularly preferably 0.2 to 1 part by mass. If it is less than 0.1 part by mass, the polymerizable property of the composition is insufficient, and the advantage of blending the polymerization initiator may not be obtained. If it exceeds 3 parts by mass, the extraction and removal of the polymerization initiator decomposition product may be insufficient when the polymer for contact lenses is washed to produce contact lenses.

The composition of the present invention contains, in addition to the above-mentioned components (A) to (F), additives such as a polymerizable ultraviolet absorber and a polymerizable dye (coloring agent) as long as the object of the present invention is not impaired. You may. By blending an ultraviolet absorber, the burden on the eyes due to ultraviolet rays such as sunlight can be reduced. Further, by blending a dye, a color contact lens can be obtained.

The method for producing the composition of the present invention is not particularly limited, and for example, each component is put into a stirring (mixing) device in any order or collectively, and stirred at a temperature of 10 ° C to 50 ° C until uniform. Can be manufactured by mixing). However, when the composition contains a polymerization initiator, care must be taken not to start the polymerization reaction at the time of mixing, and it is preferable to mix at 40 ° C. or lower. In terms of improving the solubility of the component (A), it is preferable to mix and dissolve the three components (A), (B), and (C), and then add and mix the other components.

The polymer of the present invention comprises the polymer of the above-mentioned composition of the present invention. Hereinafter, the method for producing 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 that obtained by the production method.

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

The polymerization reaction may be carried out by, for example, a one-step polymerization method in which the composition is maintained at a temperature of 45 ° C. to 140 ° C. for 1 hour or more according to the decomposition temperature of the polymerization initiator used. It is preferable to carry out by a polymerization method of two or more steps including the polymerization step 2. In this case, the hydrophilicity of the surface of the contact lens can be further improved. After completion of the polymerization, the polymer may be removed from the mold by cooling to, for example, 60 ° C. or lower.

[Polymerization step 1]
In the polymerization step 1, if necessary, the above-mentioned polymerization initiator is added to the composition, 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., more preferably 55 ° C. to 70 ° C. When the polymerization temperature in the polymerization step 1 is 45 ° C to 75 ° C, a polymer having good physical properties such as surface hydrophilicity can be stably obtained.

The polymerization time of 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 good physical properties such as surface hydrophilicity can be efficiently obtained.

[Polymerization step 2]
The polymerization step 2 is carried out after the polymerization step 1 and is a step of carrying out the polymerization reaction at a temperature higher than that of the polymerization step 1 of 90 ° C to 140 ° C.

The polymerization temperature of 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 good physical properties such as surface hydrophilicity can be stably obtained, and the polymer can be efficiently produced without deforming a mold made of polypropylene or the like. You can get it well.

The polymerization time of 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 good physical properties such as surface hydrophilicity can be efficiently obtained.

The atmosphere in which the polymerization steps 1 and 2 are carried out is not particularly limited, but it is preferable to carry out both the polymerization steps 1 and 2 in an atmosphere of an inert gas such as nitrogen or argon in terms of improving the polymerization rate. In this case, the composition may be ventilated with an inert gas, or the composition filling location of the mold may be an inert gas atmosphere.

The pressure in the mold may be atmospheric pressure to slight pressure. When polymerizing in an atmosphere of an inert gas, the gauge pressure is preferably 1 kgf / cm ² or less.

The contact lens of the present invention is a silicone hydrogel contact lens made of the hydrate of the above polymer. That is, the contact lens of the present invention can be obtained by hydrating the polymer of the present invention and water-containing the polymer to form a hydrogel. In addition, in this specification, "silicone hydrogel" means a hydrogel which has a silicone part in a polymer. Since the composition of the present invention contains the components (C) and (D) which are silicone-containing monomers, the polymer thereof has a silicone portion, and a silicone hydrogel can be formed by hydration (water content).

The water content of the contact lens (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 water content is 35 to 60% by mass, the balance with oxygen permeability can be excellent.

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

After the above polymerization reaction, the polymer may be in a state of a mixture with an unreacted monomer component (unreacted product), a residue of each component, a by-product, a remaining solvent and the like. Although such a mixture can be directly subjected to the hydration treatment, it is preferable to purify the polymer with a purification solvent before the hydration treatment.

Examples of the purification solvent include water, methanol, ethanol, 1-propanol, 2-propanol, and a mixture thereof. 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, then in water for 10 minutes to 5 hours, and the like. Further, it may be immersed in an alcohol solvent, then immersed in a hydrous alcohol having an alcohol concentration of 20 to 50% by weight for 10 minutes to 5 hours, and further immersed in water. As the 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 as to have a predetermined water content. The physiological saline solution may be boric acid buffered saline solution, phosphate buffered saline solution, or the like. Further, it may be immersed in a preservative solution for soft contact lenses containing physiological saline. The osmotic pressure of the physiological saline solution is preferably 250 to 400 mOms / kg in terms of hydration.

The contact lens of the present invention has good hydrophilicity on the lens surface, is hard to adhere to stains such as lipids, is easy to clean and remove even if it adheres, and has excellent mechanical strength. It can be used for about one month in the usage pattern of. Of course, it may be replaced in a shorter period of time.

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

Component (A) (Methacrylic ester monomer containing phosphorylcholine group)
MPC: (2-methacryloyloxyethyl) phosphorylcholine

(B) Component (hydroxyl group-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 Catalyst)
HBMA: 2-Hydroxybutyl methacrylate (2-hydroxybutyl ester, 2-hydroxy-1-ethylethyl ester mixture, manufactured by Sigma-Aldrich)
HPA: 2-Hydroxypropyl acrylate (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester mixture, manufactured by Tokyo Kasei)
HBA: 4-Hydroxybutyl Acrylate HEAA: Hydroxyethylacrylamide EMV: Ethylene Glycol Monovinyl Ether MEMVE: Diethylene Glycol Monovinyl Ether

Component (C) (Itaconic acid diester monomer containing siroxanyl group)
ES: Compound of formula (2) which is an esterification reaction product of itaconic acid monoethylene glycol ester and 3-iodopropyl [tris (trimethylsiloxy)] silane.

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

(E) Ingredient (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 the formula (5) (p = r = 0) , Number average molecular weight Mn = about 1,000)
FM-7721: Compound represented by the formula (5) (p = r = 0, number average molecular weight Mn = about 5,000)
TEGDMA: Tetra Ethylene Glycol Divinyl Ether

Component (F) (monomer other than components (A) to (E))
NVP: N-vinylpyrrolidone DMAA: N, N-dimethylacrylamide NIPA: N-isopropylacrylamide VMA: N-vinyl-N-methylacetamide VFA: N-vinylformamide MA: Methacrylate MMA: Methyl methacrylate

Solvent EtOH: Ethanol NPA: 1-propanol (normal propyl alcohol)
IPA: 2-propanol (isopropyl alcohol)

Polymerization Initiator AIBN: 2,2'-azobis (isobutyronitrile) (10-hour half-life temperature 65 ° C.)
ADVN: 2,2'-azobis (2,4-dimethylvaleronitrile) (10-hour half-life temperature 51 ° C.)

The following items were evaluated for the compositions, polymers, and contact lenses of Examples and Comparative Examples. Hereinafter, the “composition”, “polymer” and “contact lens” in each evaluation item and each table include not only those of Examples but also those relating to Comparative Examples.

Uniformity and Transparency of Composition The composition was placed in a colorless and transparent container, and the state of the composition was visually evaluated according to the following criteria.
◯: Uniformly transparent ×: White turbidity or precipitation

Polymer morphology The polymer morphology was visually evaluated according to the following criteria.
◯: Solid ×: Liquid (including viscous liquid)

Transparency of Polymer The transparency of the polymer was visually evaluated according to the following criteria.
○: Transparent △: Slightly turbid ×: White turbidity

Transparency of contact lenses The transparency of the hydrogel (contact lens) obtained by purifying the polymer and then immersing it in the physiological saline solution described in ISO-18369-3 and swelling it was visually evaluated according to the following criteria.
○: Transparent △: Slightly turbid ×: White turbidity

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 is immersed in ISO physiological saline overnight, the outer periphery is pinched with tweezers and pulled up from the water surface, and the time from when the contact lens is pulled up from the water surface until the water film on the lens surface breaks (water film retention time). It was measured. The state in which the water film was cut was visually determined. This measurement was performed three times, the average value was calculated, and the case of 30 seconds or more was judged to have good surface hydrophilicity.

Moisture content of contact lenses The water content was measured by the method described in ISO-18369-4.

Mechanical Strength of Contact Lenses The modulus [MPa] of contact lenses was measured according to JIS-K7127 using a BAS-3305 (W) breaking strength analyzer manufactured by Yamaden Co., Ltd., and the mechanical strength was evaluated. Specifically, a sample obtained by cutting a contact lens to a width of 2 mm was used, a load cell of 200 gf was used, and the clamps were pulled at a speed of 1 mm / sec with a distance of 6 mm, 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 The oxygen permeability coefficient of a sample in which 2 to 4 contact lenses were superposed was measured according to the measurement method by the polarography method described in ISO 18369-4. For the measurement, O ₂ Permeometer Model 201T manufactured by Rehder Development Company was used. The thickness of the lens was plotted on the x-axis, the t / Dk value obtained by measurement was plotted on the y-axis, and the reciprocal of the slope of the regression line was defined 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 with fingertips. Polymacon and omafilcon A were used as standard contact lenses for evaluation. The lubricity of polymacon was 2 and the lubricity of omafilcon A was 8, and the evaluation was made on a scale of 1 to 10. When the evaluation score was 6 or more, it was judged that the expressed lubricity was good, and when it was 5 or less, it was judged that the surface lubricity was poor.

Example 1
0.5 g (5.0% by weight) MPC, 1.0 g (10.0% by weight) HEA, 4.0 g (40.0% by weight) ES, and 0.5 g (5 parts by weight) EtOH. Was mixed in a container and stirred at room temperature until the MPC was dissolved. 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 was added to the vessel and stirred at room temperature until uniform to obtain a composition. The above evaluation was performed on this composition.

0.3 g of the above composition was poured into a 25 mm × 70 mm × 0.2 mm cell sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer, and placed in an oven. After performing nitrogen substitution in the oven, the temperature was raised to 65 ° C. and maintained at the 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 taken out of the cell and evaluated as described above.

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 substances and the like for purification. Further, the polymer was immersed in the physiological saline solution described in ISO-18369-3 and swollen (hydrated) to prepare contact lenses. This contact lens was processed into a sample of 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 the evaluation results.

Examples 2-27
The compositions, polymers, and contact lenses of Examples 2 to 27 were prepared and evaluated 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. Was done. The results are shown in Tables 1 to 4.

Comparative Example 1
1.98 g (19.8% by mass) HEA, 4.95 g (49.5% by mass) ES, and 0.5 g (5 parts by mass) EtOH were mixed in a container and stirred at room temperature. Further, 1.98 g (19.8% by mass) FM-071, 0.1 g (1.0% by mass) TEGDV, 0.99 g (9.9% by mass) DMAA, and 0.1 g (1. AIBN (0 part by mass) was added to the container and stirred at room temperature until uniform to obtain the composition of Comparative Example 1. The above evaluation was performed on this composition.

0.3 g of the above composition was poured into a 25 mm × 70 mm × 0.2 mm cell sandwiched between two polypropylene plates using a 0.1 mm thick polyethylene terephthalate sheet as a spacer, and placed in an oven. After performing nitrogen substitution in the oven, the temperature was raised to 65 ° C. and maintained at the temperature for 3 hours, then the temperature was further raised to 120 ° C. and maintained for 2 hours, and the composition was polymerized to polymerize the polymer of Comparative Example 1. Got The polymer was taken out of 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 substances and the like for purification. Further, the polymer was immersed in the physiological saline solution described in ISO-18369-3 and swollen (hydrated) to prepare a contact lens of Comparative Example 1. This contact lens was processed into a sample of 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, the polymerization conditions, and the evaluation results. Since the WBUT was a bad result of 0 seconds in the evaluation of surface hydrophilicity, no other evaluation was carried out.

Comparative Examples 2-5
The compositions, polymers, and contact lenses of Comparative Examples 2 to 5 were prepared and evaluated 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. rice field. The results are shown in Table 5. Similar to Comparative Example 1, Comparative Example 5 had a bad result of WBUT of 0 seconds, so no other evaluation was performed. In Comparative Examples 2 and 3, the composition was not uniform, so polymerization was not carried out. Therefore, the polymers and contact lenses of Comparative Examples 2 and 3 could not be prepared and their evaluation could not be carried out. In Comparative Example 4, the surface hydrophilicity of the contact lens was good, but the mechanical strength was 0.9 MPa and the oxygen permeability was 67, which were inferior to those of the examples.

Claims (7)

(A) The following formula (1):

Phosphorylcholine group-containing methacrylic ester monomer represented by
(B) Containing one or more hydroxyl groups 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. Monomer and
(C) The following formula (2):

The siroxanyl group-containing itaconic acid diester monomer of the compound represented by the above, or the siroxanyl group-containing itaconic acid containing the compound of the formula (2) and the compound of the following formula (2') which is a by-product of the compound of the formula (2). With any of the diester monomers,

(D) The following formula (3):

[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. ] With the siroxanyl group-containing (meth) acrylate represented by
(E) A composition containing a cross-linking agent.
The content ratio of the component (A) is 5 to 20% by mass, and the content ratio of the component (B) is 5 to 25% by mass with respect to the total 100% by mass of all the monomer components in the composition. As for the content ratio of the component (C), the total amount of the compounds of the formula (2) and the formula (2') is 30 to 70% by mass, the content ratio of the component (D) is 5 to 40% by mass, and (E) The content ratio of the component is 0.1 to 10% by mass.
Monomer composition for contact lenses. The composition further contains (F) monomers other than the components (A) to (E), and the content ratio of the component (F) is 100% by mass of the total of all the monomer components in the composition. 25% by mass or less,
The monomer composition for a contact lens according to claim 1. The composition further contains a solvent having a hydroxyl group, and the content ratio of the solvent is 25 parts by mass or less with respect to a total of 100 parts by mass of all the monomer components in the composition.
The monomer composition for contact lenses according to claim 1 or 2. A polymer of the monomer composition for contact lenses according to any one of claims 1 to 3.
Polymers for contact lenses. The polymerization step 1 in which the monomer composition for contact lenses according to any one of claims 1 to 3 is maintained at a temperature of 45 ° C. to 75 ° C. for 1 hour or more to carry out polymerization.
After the polymerization step 1, the polymerization step 2 of maintaining the polymerization at a temperature of 90 ° C. to 140 ° C. for 1 hour or more is included.
The method for producing a polymer for contact lenses according to claim 4. The hydrate of the polymer for contact lenses according to claim 4.
contact lens. The polymer for contact lenses according to claim 4 is mixed with one or more solvents selected from the group consisting of water, methanol, ethanol, 1-propanol, and 2-propanol, and the polymer is purified. Process and
The present invention comprises a step of immersing the polymer in physiological saline to hydrate the polymer.
How to make contact lenses.