JP2530323B2 - Method of manufacturing ophthalmic lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a stable surface hydrophilicity especially for a long period of time among ophthalmic lenses prescribed in ophthalmology, such as contact lenses, intraocular lenses and artificial corneas. The present invention relates to a method for manufacturing an ophthalmic lens that requires

[Prior Art] In recent years, mainly silicone-based materials have been used for contact lenses having good oxygen permeability and flexible intraocular lens materials. However, although silicone-based materials generally exhibit hydrophobicity, the surface thereof exhibits water repellency, and thus is unsuitable as a lens material as it is in direct contact with a living body (eye tissue).

In order to impart hydrophilicity to the surface, various improvements have been proposed, such as subjecting the silicone material to discharge treatment or copolymerizing a silicone monomer and a hydrophilic monomer.

However, when the surface is hydrophilized by the discharge treatment as described above, there is a problem that the hydrophilicity is lowered during use. When a silicone-based monomer and a hydrophilic monomer are copolymerized, the compatibility between the silicone-based monomer and the hydrophilic monomer is poor,
In particular, it is extremely difficult to uniformly mix a high molecular weight monomer having strong hydrophobicity such as polyorganosiloxane with a considerable amount of hydrophilic monomer that imparts sufficient hydrophilicity to the obtained ophthalmic lens. There was a problem. If the mixture is polymerized in a non-uniform manner, only an opaque copolymer can be obtained and it cannot be used as an ophthalmic lens. Therefore, in order to solve the above problems, a method of introducing a hydrophilic group into a silicone-based monomer and polymerizing it with another monomer has been proposed, but fundamentally, the hydrophobicity of the material is improved. Has not arrived.

Therefore, the inventors of the present invention, as already disclosed in JP-A-61-138613, copolymerize a polyorganosiloxane having a polymerizable group and a hydrophilic group in the same molecular side chain with another monomer. At this time, by using a monomer in which a hydroxyl group of a hydrophilic monomer having a hydroxyl group is protected with a trimethylsilyl group, the compatibility between the polyorganosiloxane having a polymerizable group and a hydrophilic group in the same molecular side chain and the hydrophilic monomer is improved. Microscopically, "sea-bird" composed of a hydrophobic domain and a hydrophilic domain, which is obtained by improving and copolymerizing and then subjecting to desilylation (hydrolysis treatment).
We have proposed a material for oxygen-permeable soft contact lenses that has a structure but is macroscopically uniform and transparent.

On the other hand, a material mainly composed of polyorganosiloxane is usually soft at room temperature (room temperature) and difficult or impossible to process by a normal cutting method. Therefore, a molding method using a mold is the most effective manufacturing method. Is believed to be.

[Problems to be Solved by the Invention] However, a polyorganosiloxane having a polymerizable group and a monomer having a hydroxyl group protected by a trimethylsilyl group are used together with a template having a hydrophobic surface such as a polypropylene template. When polymerized, there is a problem that the surface remains hydrophobic even if hydrolyzed and hydrophilicity is not imparted.

The reason for this is that, particularly in a monomer having a hydroxyl group having an ester bond such as hydroxyalkyl (meth) acrylate, when the protective group (protective group) is weaker in hydrophobicity than an ester bond such as a trimethylsilyl group, the protective group is protected. The hydrophilicity of the ester bond acts more strongly than the hydrophobicity of the group, and even though it is protected by the hydrophobic group, the hydrophilic monomer protected by the protecting group has a hydrophobic mold surface such as a polypropylene mold. It is possible to obtain a copolymer molded product in which a polyorganosiloxane having strong hydrophobicity is located close to the surface of the hydrophobic mold, and as a result, even if the molded product is hydrolyzed, the surface of the copolymer has a hydrophobic surface. It is thought that only lenses for use can be obtained.

On the other hand, a hydrophobic mold made of synthetic resin such as polypropylene is easy to make into a desired shape by injection molding, and a mold forming surface that gives the surface with high precision required for an ophthalmic lens. However, it has many advantages that it can be manufactured with high precision and is easily available, and it was difficult to throw away as a mold for ophthalmic lenses.

Therefore, the present inventors tried to obtain an ophthalmic lens having good surface hydrophilicity by surface-modifying the surface of the hydrophobic template to hydrophilicity by plasma irradiation or the like. There is a problem that a strong affinity such as hydrogen bond increases with the surface of the mold, making it difficult to release from the mold, and if the mold is forcibly released, the molded product will be damaged. It was Further, when electron beam irradiation or plasma irradiation is applied to the mold, the precision of the molding surface of the mold deteriorates, and there is a disadvantage that a molded product having a good surface shape as an ophthalmic lens cannot be obtained.

Therefore, as a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventors have found a manufacturing method capable of solving all of these problems, and completed the present invention.

That is, the object of the present invention is to produce a ophthalmic lens containing a polyorganosiloxane or the like as a main component by means of a mold, which has good surface wettability and is stable in hydrophilicity over a long period of time. An object of the present invention is to provide a method for producing an ophthalmic lens which does not impair good physical properties such as oxygen permeability, mechanical strength and flexibility.

It is also an object of the present invention to provide a method for producing an ophthalmic lens, which has good releasability when the lens is released from the mold, and there is almost no risk of damage to the ophthalmic lens due to the release.

[Means for Solving Problems] That is, according to the present invention, a polyorganosiloxane having a polymerizable group and a general formula (III) having an affinity with a hydrophobic template surface: (In the formula, R ₄ , R ₅ and R ₆ may be the same or different, and may have an alkyl group having 1 or more carbon atoms, an optionally substituted phenyl group, or a silicon number of 1 or more. Represents an optionally substituted organosiloxy group, provided that a silyl-containing monomer having a hydroxyl group protected by a hydrophobic silyl group represented by R ₄ , R ₅ and R ₆ is not a methyl group at the same time). Characterized by desilylating a copolymer molded product obtained by copolymerizing a monomer composition containing a monomer having a modified hydroxyl group as a main component in a mold having a hydrophobic surface made of synthetic resin. The present invention relates to a method for manufacturing an ophthalmic lens.

[Operation] According to the present invention, a template having a hydrophobic surface made of a synthetic resin and a monomer having a hydroxyl group protected by a hydrophobic silyl group having affinity with the hydrophobic surface of the template have good affinity. ,
Copolymerization is carried out in a state where the hydrophobic silyl group of the monomer is close to the template surface, and a copolymer molded product having many hydrophobic silyl groups on the surface is obtained. When the molded product is hydrolyzed and desilylated, hydroxyl groups are generated on the surface of the molded product, and an ophthalmic lens having a hydrophilic surface and good water wettability can be obtained. Further, in the thus obtained ophthalmic lens, since the hydrophilic portion is generated and exists not only on the surface but also inside thereof by desilylation, it is not necessary to perform the hydrophilic treatment by electron beam or plasma. Different,
There is no concern about deterioration of the surface hydrophilicity due to wear during use of the ophthalmic lens, and stable hydrophilicity can be maintained for a long period of time.

Moreover, as a result, other good physical properties of the ophthalmic lens, such as oxygen permeability, mechanical strength, and flexibility, are not impaired.

In addition, since both the mold surface and the surface of the molded product are hydrophobic, a strong affinity (bond) such as a hydrogen bond does not occur between them, so that the mold releasability is good and the mold release The risk of breakage of the molded product of the copolymer is extremely low.

[Example] In the present invention, a polyorganosiloxane having a polymerizable group and a monomer having a silylated hydroxyl group containing a monomer having a hydroxyl group protected by a hydrophobic silyl group having affinity with the template surface are used as monomer compositions. Used as the main component.

The polyorganosiloxane having a polymerizable group (hereinafter, referred to as polyorganosiloxane (A)) is particularly useful as a component for obtaining an ophthalmic lens having good oxygen permeability or an ophthalmic lens having good flexibility, Examples of the polyorganosiloxane (A) include those represented by the general formula (I): (Wherein R ₁ , R ₂ and R ₃ are the same or different C _{1 to} C ₄ alkyl groups, groups selected from trimethylsiloxane groups and phenyl groups, A is a polymerizable group, p and q are polymerizable groups. It is a number to express the content rate of the group A polysiloxane having a structural unit represented by:

The average molecular weight of the polyorganosiloxane having polymerizable groups is preferably between about 5,000 and 200,000.
If the molecular weight is lower than this range, polyorganosiloxane that does not contain a polymerizable group will also be mixed,
Since it becomes difficult (or impossible) to polymerize or crosslink, the moldability becomes poor (molding as an ophthalmic lens becomes difficult). Therefore, if the number of polymerizable groups is increased while the molecular weight is small, the obtained ophthalmic lens loses its flexibility and becomes brittle. On the other hand, if the molecular weight is too large than the above range, the viscosity of the polyorganosiloxane becomes high, and it is difficult to uniformly mix the monomer having a single hydroxyl group and other monomers, which is a disadvantage in handling. Will occur.

Since the polyorganosiloxane (A) has at least one polymerizable group in the side chain of the molecule, it can be copolymerized with various other monomers, and has a physical property suitable for a desired ophthalmic lens. Polymer moldings can be obtained. When the molecular side chain of the polyorganosiloxane (A) has at least two polymerizable groups, the copolymer itself has the ability to crosslink (crosslinking performance), and the crosslinkage causes It is possible to improve the mechanical (mechanical) strength, shape stability, durability, etc. of the united body itself.

In order to improve the compatibility with other monomers and obtain a macroscopically transparent and homogeneous ophthalmic lens, the polyorganosiloxane (A) has the general formula (II): (In the formula, R ₁ , R ₂ , R ₃ , p, q, and A are the same as above,
X represents a hydrophilic group-containing portion), and a polysiloxane having a structural unit represented by

Examples of the hydrophilic group-containing portion include those represented by the formula: A portion having a hydroxyl group or an ether bond such as, or an amino group, a carboxyl group, a sulfonic acid group, an amide bond,
A portion containing a urea bond, a urethane bond, a sulfonyl group, a lactam ring, etc. is considered.

Examples include polyorganosiloxane (specifically preferably polydimethylsiloxane) into which a functional group containing a polymerizable unsaturated double bond such as a (meth) acryloyl group, a vinyl group, an allyl group is inserted as a polymerizable group. To be
Particularly, as the polyorganosiloxane (A) having a structural unit represented by the general formula (II), for example, a polyorganosiloxane having at least one epoxy group (preferably glycidyl group) in a molecular side chain (hereinafter referred to as polyorganosiloxane (B)) and a polymerizable group-containing compound (unsaturated group-containing compound such as unsaturated double bond, for example, (meth) acrylic acid) can be mentioned, and more specifically, The following structural units: And the like.

In the monomer having a silylated hydroxyl group containing a monomer whose hydroxyl group is protected by a hydrophobic silyl group exhibiting an affinity for the hydrophobic template surface, particularly, the hydroxyl group is protected by a hydrophobic silyl group exhibiting an affinity for the template surface. The above-mentioned monomer is used because the affinity between the template having a hydrophobic surface made of synthetic resin and the monomer whose hydroxyl group is protected by the hydrophobic silyl group exhibiting affinity with the template surface is improved, and the hydrophobicity of the monomer is increased. This is because the copolymerization is carried out in a state where the hydrophobic silyl group is close to the template surface, and a molded copolymer product having many hydrophobic silyl groups on the surface can be obtained. Then, by subjecting the molded product to a hydrolysis treatment and desilylation, hydroxyl groups are generated on the surface of the molded product, and an ophthalmic lens having a hydrophilic surface and good wettability can be obtained. Moreover, as a result, other good physical properties of the ophthalmic lens, such as oxygen permeability,
Mechanical strength and flexibility are not impaired. Furthermore, the surface of the mold and the surface of the molded product exhibit hydrophobicity, and neither has a strong affinity (bonding force) such as hydrogen bonding,
Good releasability and less risk of breakage of the ophthalmic lens due to releasability.

The hydrophobic silyl group having an affinity with the template surface has the general formula (III): (In the formula, R ₄ , R ₅ and R ₆ may be the same or different, and an optionally substituted alkyl group having a urea number of 1 or more, an optionally substituted phenyl group or a silicon number of 1 or more. Represents an optionally substituted organosiloxy group, provided that a hydrophobic silyl group having a larger molecular weight than a trimethylsilyl group such as that represented by R ₄ , R ₅ and R ₆ is a methyl group at the same time). Specific examples of such a hydrophobic silyl group include a triethylsilyl group and t-
Examples thereof include a butyldimethylsilyl group, an n-octyldimethylsilyl group, a phenyldimethylsilyl group and a trimethylsiloxydimethylsilyl group.

A monomer having a hydroxyl group protected by a hydrophobic silyl group as described above can be obtained by introducing the hydrophobic silyl group into a hydroxyl group-containing hydrophilic monomer.

That is, the monomer in which the hydroxyl group is protected by the hydrophobic silyl group is a hydroxyl group-containing hydrophilic monomer in a non-polar solvent having no hydroxyl group such as acetone, toluene, xylene, and represented by the general formula (IV): (In the formula, Y is a halogen atom, R _4, R ₅ and R ₆ are R _4, the same as R ₅ and R ₆ in the general formula (III)) triorganosilyl halide represented by or, hexaorganodisilazane It can be obtained by reacting with.

Specific examples of the hydroxyl group-containing hydrophilic monomer include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; 2,3-dihydroxy-2- Dihydroxyalkyl (meth) acrylates such as methylpropyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate; 2-dihydroxy-3- (meth)
Hydroxyaryl (meth) acrylates such as acryloyloxynaphthalene; hydroxy (poly) alkylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate; di (Poly) glycerol mono (meth) acrylate such as glycerol mono (meth) acrylate; alkoxy (poly) glycerol mono (meth) acrylate such as 2-ethylhexoxyglycerol mono (meth) acrylate, phenoxyglycerol mono (meth) acrylate, etc. Aryloxy (poly) glycerol mono (meth) acrylate of formula; (In the formula, R ₇ is a hydrogen atom or a methyl group) and examples thereof include a hydroxyl group-containing (meth) acrylate represented by a monomer and the like, and an unsaturated carboxylic acid such as (meth) acrylic acid.

A monomer having a silylated hydroxyl group other than the monomer having a hydroxyl group protected by a hydrophobic silyl group having an affinity for the template surface desilylates (hydrolyzes) a copolymer molded article.
Is added in order to improve the surface hydrophilicity (water wettability) of the ophthalmic lens after being treated and to maintain the transparency in water, but when the monomer is added, the mechanical properties of the ophthalmic lens ( (Mechanical) strength can be improved. The monomer is obtained by reacting the hydroxyl group-containing hydrophilic monomer with a trialkylsilyl halide such as trimethylchlorosilane in the solvent used for obtaining the monomer having the hydroxyl group protected by the hydrophobic silyl group. .

The silylation of hydroxyl groups in the hydroxyl group-containing aqueous monomer proceeds according to the following reaction formula (VI).

(In the formula, R is the same as any of R _{4 to} R ₆ or a methyl group).

The monomer having a silylated hydroxyl group may be a monomer having a hydroxyl group protected by a hydrophobic silyl group having an affinity with all of the hydrophobic template surfaces, and a hydrophobic silyl group having an affinity with the template surface. You may use together the monomer which protected the hydroxyl group by and the other monomer which has a silylated hydroxyl group. However, when used in combination, with respect to 100 parts by weight of the monomer having a fully silylated hydroxyl group, 10 parts by weight or more of a monomer having a hydroxyl group protected by a hydrophobic silyl group having affinity with the template surface, preferably 20 to It is recommended to use 70 parts by weight. Polyorgano that exhibits strong hydrophobicity when it comes into contact with a template having a hydrophobic surface made of synthetic resin when the proportion of the monomer whose hydroxyl group is protected by a hydrophobic silyl group that is compatible with the template surface is less than 10 parts by weight. A large amount of siloxane collects, and even if desilylated (hydrolyzed), an ophthalmic lens having a hydrophilic surface cannot be obtained.

The use ratio of the polyorganosiloxane having a polymerizable group and the monomer having a silylated hydroxyl group (polyorganosiloxane having a polymerizable group / monomer having a silylated hydroxyl group) is 50/50 to 95/5 by weight ratio, 70/30 to 90/10 is preferable. When the use ratio of the polyorganosiloxane having the polymerizable group is less than 50 parts by weight, it becomes impossible to obtain an ophthalmic lens having sufficient oxygen permeability or flexibility and non-hydrous or low hydrous is not maintained. , If it has a water content equivalent to that of a normal water-containing ophthalmic lens (for example, a polymer composed of hydroxyethyl methacrylate as a main component), it must be sterilized by boiling if necessary. Like Further, when the use ratio of the polyorganosiloxane having the polymerizable group is more than 95 parts by weight, the use ratio of the monomer having a relatively silylated hydroxyl group is correspondingly decreased, and as a result, the surface becomes hydrophilic. It is difficult to get an ophthalmic lens.

In addition to the polyorganosiloxane having a polymerizable group and the silylated monomer having water acidity, if necessary, for example, alkylstyrene such as styrene, α-methylstyrene, t-butylstyrene, isopropylstyrene, or benzyl methacrylate, or the like. Hydrophobic monomer having aromatic ring, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (Meth) acrylate, optionally substituted alkyl (meth) acrylate such as dodecyl (meth) acrylate; methoxydiethylene glycol (meth) acrylate, ethoxytripropylene glycol (meth Alkoxy (poly) alkylene glycol (meth) acrylates such as acrylates; Alkyl itaconates such as dimethyl itaconate and diethyl itaconate; Alkyl crotonates such as propyl crotonate; N, N-dimethyl (meth) acrylamide, N-vinylpyrrolidone Etc. may be added.

The amount of the above-mentioned other monomers used is 0 to 25 parts by weight based on 100 parts by weight of all the monomer components, and it is desirable to contain at least 5 parts by weight from the viewpoint of improving strength.

Among these monomers, when a hydrophobic monomer having an aromatic ring is used in addition to the above-mentioned polymerizable polyorganosiloxane (A) and a monomer having a silylated hydroxyl group, especially, a monomer having a silylated hydroxyl group and an aromatic ring are used. When used together with a hydrophobic monomer having, the synergistic effect can dramatically improve the strength of the material.

Further, in particular, when a hydrophobic monomer having an aromatic ring is used, in order to fully exert the effect of the monomer, the ratio of the silylated monomer and the hydrophobic monomer having an aromatic ring (the silylated hydroxyl group is The weight ratio of (monomer having / perhydrophilic monomer having aromatic ring) is 1/1 to 3/1
It is desirable to be in the range of.

The polymerization molding method of the monomer composition comprising the polyorganosiloxane having a polymerizable group, the monomer having a silylated hydroxyl group, and optionally the other monomer is performed by an ordinary molding method. That is, the monomer composition is mixed, a polymerization initiator is added thereto, and the mixture is uniformly mixed and gently poured into the concave mold,
Properly tighten the concave and convex molds by placing the convex mold on the concave mold and sandwiching it with a clamp or placing a weight on the mold.
The mixture is polymerized by putting the mold in a suitable polymerization container and heating or irradiating an electromagnetic wave. When heating, it may be heated at about 40 to 90 ° C for several hours to several tens of hours to polymerize (if the temperature is higher than about 90 ° C, the synthetic resin mold may be deformed. However, if necessary, the temperature may be raised stepwise to carry out the polymerization. In order to satisfactorily complete the polymerization, for example, an oxygen scavenger may be placed in the polymerization vessel and the polymerization may be performed under reduced pressure. After the polymerization is completed, the mold is cooled and the concave mold and the convex mold are separated,
The lens-shaped copolymer molded product is peeled from the mold. In this case, the copolymer molded product may be removed from the casting in a solvent such as alcohol or acetone which does not adversely affect the copolymer molded product, if necessary.

As the template, a template having a hydrophobic surface made of synthetic resin is used, and examples of the material thereof include polypropylene, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polytrifluoroethylene chloride and the like. Among these, polypropylene is preferable. The hydrophobic mold made of a synthetic resin such as polypropylene is easy to injection-mold into a mold shape, and it is possible to accurately manufacture a mold that gives an accurate surface required for an ophthalmic lens. It has various advantages that it is easily available, and is very useful as a mold for ophthalmic lenses. The mold has a molding surface of a standard (radius of curvature, diameter, thickness, etc.) whose inner surface can obtain a target ophthalmic lens, and is manufactured by, for example, injection molding or the like with one set of concave and convex molds To be done.

The copolymer molding thus obtained is then subjected to desilylation.

Desilylation (hydrolysis treatment) is carried out by heating the obtained copolymer molded product in an ordinary alcohol aqueous solution. Further, the ophthalmic lens is heated in an aqueous alcohol solution using an extractor to extract and remove unreacted substances in the polymerization reaction and unnecessary reaction products generated by desilylation. By removing the silyl group and generating a hydroxyl group by this treatment, it is possible to impart long-term stable surface hydrophilicity (water wettability) to the ophthalmic lens.

Examples of the alcohol used in the desilylation reaction include methanol, ethanol, propanol and the like,
In particular, isopropanol and the like, which have the closest properties to the nonpolar solvent, are preferable. The aqueous alcohol solution is an alcohol containing about 1 to 40% of water, and the reason why the aqueous alcohol solution is used is that the aqueous alcohol solution has a good affinity with a hydrophobic polyorganosiloxane or a hydrophobic silyl group, Moreover, since the copolymer molding is swollen to some extent, desilylation can be efficiently proceeded to the inside of the copolymer molding, and unreacted products of important reaction and unnecessary products due to desilylation are formed. This is because extraction and removal can be done easily.

Subsequently, the obtained ophthalmic lens is dried by removing the solvent used in the extraction treatment and then stored by being immersed in an aqueous solution such as physiological saline.

Next, the method for manufacturing an ophthalmic lens of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. (Synthesis of Monomer Having Hydroxyl Group Protected by Hydrophobic Silyl Group Having Affinity with Template Surface) Synthesis Example 1 2-hydroxyethyl methacrylate 33 g, triethylamine 25 g, and acetone 500 ml were weighed in an Erlenmeyer flask. Continue to stir while cooling the flask with ice, and
A solution prepared by dissolving 38 g of butyldimethylchlorosilane in 50 ml of acetone was added dropwise, and the reaction was allowed to proceed for about 3 hours while maintaining the temperature below 10 ° C.

After removing the reaction product (CH ₃ CH ₂ ) ₃ N · HCl from the reaction solution, the solvent was further removed, and distilled to distill t-butyldimethylsilylated 2-hydroxyethyl methacrylate 17.9 g (62 ° C / 0.15mmHg) was obtained. It was confirmed by infrared absorption spectrum analysis that it was t-butyldimethylsilylated 2-hydroxyethyl methacrylate. When analyzed by gas chromatography, its purity was 98.1%.

Synthesis Example 2 33 g of 2-hydroxyethyl methacrylate, 25 g of triethylamine and 500 ml of acetone were weighed in an Erlenmeyer flask. While the flask was cooled with ice, stirring was continued, 52 g of octyldimethylchlorosilane was added dropwise thereto, and the reaction was allowed to proceed for about 3 hours while maintaining the temperature below 10 ° C.

In the same manner as in Reference Example 1, 25.5 g (109 ° C.) of octyldimethylsilylated 2-hydroxyethyl methacrylate
/0.2mmHg). It was confirmed to be octyldimethylsilylated 2-hydroxyethyl methacrylate by infrared absorption spectrum analysis and the like. When analyzed by gas chromatography, its purity was 97.4%.

Synthesis Example 3 In the same manner as in Reference Example 1, triethylchlorosilane 50 g
By reacting with 44 g of 2-hydroxyethyl methacrylate, 38.0 g (purity 98.4%) of triethylsilylated 2-hydroxyethyl methacrylate was obtained.

(Production of Polyorganosiloxane Having Polymerizability) Synthesis Example 4 A polyorganosiloxane having a glycidyl group in a molecular side chain having a molecular weight of about 70,000 in a three-necked flask (content of glycidyl group: 0.4%, Shin-Etsu Chemical Co., Ltd.) 60 g, methacrylic acid 120 g, and hydroquinone monomethyl ether 0.3 g as a polymerization inhibitor were added, and the mixture was reacted at 123 to 131 ° C. for 90 minutes.

Then, n-hexane 4.5 was added to the obtained reaction solution,
It was washed with a 1% aqueous sodium hydroxide solution 5. After further washing with water 5, anhydrous magnesium sulfate was added and dried, magnesium sulfate was filtered off, and n-hexane was removed under reduced pressure to obtain 57.2 g of a synthetic product (polyorganosiloxane having a polymerizing group).

The obtained compound is a viscous pale yellow transparent liquid (hereinafter referred to as Si
was called).

Example 1 A concave lens mold and a convex lens mold having a predetermined shape (shape giving a contact lens having a base curve of 8.4 mm and a diameter of 13.5 mm) were produced by injection molding using polypropylene resin.

70 parts by weight of Sil obtained in Synthesis Example 4, 20 parts by weight of t-butyldimethylsilylated 2-hydroxyethyl methacrylate obtained in Synthesis Example 1, 10 parts by weight of styrene, and 2,2'-azobis (as a polymerization initiator 0.4 parts by weight of (2,4-dimethylvaleronitrile) were mixed, and a few drops of the mixed solution were gently dropped into the concave mold for molding in the same manner as air bubbles.
Then put a convex mold on it and then put the mold in a container for polymerization, put a weight on it, put about 10 g of an oxygen scavenger into the container to reduce the pressure, After heating in a hot air circulation dryer at 50 ° C for 8.5 hours, the temperature was raised stepwise to 90 ° C at a rate of 10 ° C / 90 minutes, and heating was performed for about 15 hours for copolymerization.

After the method was cooled, the convex mold and the concave mold were separated from each other, and the copolymer molded product was peeled from the mold. Peeling of the copolymer molded product from the mold was very easy, and there was no need to immerse it in a solvent such as alcohol for peeling, and the releasability was good. The cured state of the copolymer molded product due to polymerization was also good, and it had a desired lens shape.

Next, the copolymer molded product was boiled in a 90% isopropanol aqueous solution and subjected to a hydrolysis treatment to eliminate the silyl group. Furthermore, the copolymer molded product was boiled in a 90% isopropanol aqueous solution using a Soxhlet extractor to extract and remove unreacted products and unnecessary products due to desilylation, and then the obtained lenses were dried, A contact lens was obtained by immersing the lens in physiological saline.

The obtained contact lens is colorless and transparent, has good shape stability, and has sufficient restoring force against bending,
The water wettability (surface hydrophilicity) of the lens was also good.

Contact angle of the contact lens obtained, punching load,
Table 1 shows the results obtained by measuring the elongation, the thickness of the central portion, and the oxygen permeability.

The various physical properties of the obtained ophthalmic lens were measured according to the following methods.

(Releasability) Whether or not the copolymer molded product was easily peeled from the mold release was determined. When the peeling was so easy that it was not necessary to immerse it in a solvent such as alcohol for peeling, the mold releasability was considered to be good. If there is something that needs to be soaked in a solvent such as alcohol and peeled off, it is said that the releasability is almost good, and peeling is difficult or impossible even if soaked in a solvent such as alcohol. In that case, the releasability was determined to be poor.

(Cured state) The cured state (whether or not the polymerization proceeded satisfactorily) of the released molded copolymer was visually observed.

(Shape) The shape of the lens when immersed in physiological saline was visually observed.

(Water wettability) A lens immersed in physiological saline was taken out of the physiological saline, and the wet state of the lens surface was visually observed.

(Contact Angle) The contact angle (wettability) of the lens surface with water was measured by the bubble method.

(Transparency) The transparency of the lens when immersed in physiological saline was visually observed.

(Punching Load) A 1 / 16-inch diameter pressing needle was applied to the approximate center of a lens fixed in a physiological saline solution by an Instron type compression tester, and the load at break was measured.

(Elongation rate) The elongation rate with respect to the original length at the time of breakage of the lens when the punching load was measured was measured.

(Oxygen permeability coefficient) Seikaken film oxygen permeability meter (Riken Seiki Kogyo Co., Ltd.)
Manufactured) at 35 ° C. in physiological saline.

Examples 2 to 3 Various components were blended as shown in Table 1 and contact lenses were prepared in the same manner as in Example 1.

However, as the mold used in Example 3, a standard polypropylene mold designed to obtain a contact lens having a base curve of 7.18 mm and a diameter of 12.05 mm was used.

After cooling, the convex and concave molds were separated from each other and the copolymer molded product was peeled from the mold, but it was very easy to peel the copolymer molded product from the cast iron, and it was immersed in a solvent such as alcohol. There was no need to peel it off and the releasability was good.
The cured state of the copolymer molded product due to polymerization was also good, and it had a desired lens shape.

The contact lenses obtained by desilylation are all colorless and transparent, have good shape stability, have sufficient restoring force against bending, and have good lens wettability (surface hydrophilicity). there were.

Contact angle of the contact lens obtained, punching load,
Table 1 shows the results obtained by measuring the elongation, the thickness of the substantially central portion, the oxygen permeability, and the like in the same manner as in Example 1.

Examples 4 to 13 Contact lenses were produced in the same manner as in Example 1 by mixing various components as shown in Table 2.

However, as the mold used in Examples 11 to 13, a standard polypropylene mold designed to obtain a contact lens having a base curve of 7.18 mm and a diameter of 12.05 mm was used.

After allowing to cool, the convex and concave molds of the mold were pulled apart to peel the copolymer molded product from the mold, but peeling of the copolymer molded product from the mold was very easy, and it was immersed in a solvent such as alcohol. There was no need for peeling, and the releasability was good. The cured state of the copolymer molded product due to polymerization was also good, and it had a desired lens shape.

The contact lenses obtained by desilylation are all colorless and transparent, have good shape stability, have sufficient restoring force against bending, and have good lens wettability (surface hydrophilicity). there were.

Contact angle of the obtained contactor lens, punching load,
Table 2 shows the results obtained by measuring the elongation rate, the thickness of the approximately central portion, the oxygen permeability and the like in the same manner as in Example 1.

Comparative Examples 1 to 4 Various components were blended as shown in Table 3 and copolymerized in the same manner as in Example 1.

However, the mold used in Comparative Examples 2 to 4 was a standard polypropylene mold designed to obtain a contact lens having a base curve of 7.18 mm and a diameter of 12.05 mm.

After allowing to cool, the convex mold and the concave mold of the mold were separated from each other to separate the copolymer molded product from the mold. Although peeling of the copolymer molded product from the mold was almost easy, some of them needed to be immersed in a solvent such as alcohol for peeling. The cured state of the copolymer molded product due to polymerization was also good, and all had desired lens shapes.

Then, the molded product of the copolymer was boiled in a 90% aqueous solution of isopropanol and subjected to a hydrolysis treatment to eliminate the silyl group. Furthermore, the copolymer molded product was boiled in a 90% isopropanol aqueous solution using a Soxhlet extractor to extract and remove unreacted products and unnecessary products due to desilylation, and then the obtained lenses were dried, A contact lens was obtained by immersing the lens in physiological saline.

Contact angle of the contact lens obtained, punching load,
Table 3 shows the results obtained by measuring the elongation, the thickness of the substantially central portion, the oxygen permeability and the like in the same manner as in Example 1.

As described above, when manufacturing an ophthalmic lens with a mold having a hydrophobic surface made of a synthetic resin such as a polypropylene mold, a monomer whose hydroxyl group is protected by a hydrophobic silyl group having affinity with the mold surface is used. It is clear that the surface hydrophilicity (water wettability) becomes poor unless it is done. Further, it is apparent in Comparative Example 4 that the surface becomes even less hydrophilic unless even a hydrophilic monomer having a trimethylsilylated hydroxyl group is used.

Comparative Example 5 A standard polypropylene mold designed to obtain a contact lens with a base curve of 8.4 mm and a diameter of 13.5 mm was prepared by subjecting the mold surface to hydrophilic treatment by plasma treatment.

73 parts by weight of Sil, 18 parts by weight of trimethylsilylated 2-hydroxyethyl methacrylate, 9 parts by weight of styrene and 0.4 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed, and the mixed solution was poured into the above mold. A few drops were gently dropped so as not to entrap the air bubbles. Hereinafter, Example 1
Was copolymerized in the same manner as in.

After allowing to cool, the convex and concave molds of the mold were separated from each other to try to peel the copolymer molded product from the mold, but it could not be easily peeled, and the copolymer molded product was torn when forcedly peeled. . Although it was attempted to peel it by immersing it in a solvent such as alcohol, peeling was difficult, and many of the copolymer moldings were damaged.

As described above, when an attempt is made to manufacture an ophthalmic lens using a mold in which the mold surface is subjected to plasma treatment to make it hydrophilic, a strong affinity occurs between the copolymer molded product and the mold surface, It is clear that the peelability is very poor.

[Effects of the Invention] According to the method for manufacturing an ophthalmic lens of the present invention, an ophthalmic lens having a hydrophilic surface and good wettability can be obtained. Moreover, since the obtained ophthalmic lens has a hydrophilic portion up to the inside thereof, there is no concern of deterioration of hydrophilicity of the lens surface, and stable hydrophilicity can be maintained for a long period of time. The obtained ophthalmic lens has good oxygen permeability, good mechanical strength, and excellent flexibility.

Furthermore, since the vertical surface and the surface of the molded product both exhibit hydrophobicity, a strong affinity such as hydrogen bond does not occur between them, so that the mold releasability is good and There is almost no risk of damage to polymer moldings.

Therefore, the manufacturing method of the present invention is useful for manufacturing, for example, a contact lens, an intraocular lens, an artificial cornea and the like, and can be particularly preferably applied to manufacturing of a contact lens.

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Claims (3)

(57) [Claims] 1. A polyorganosiloxane having a polymerizable group, and a general formula (II) having an affinity with a hydrophobic template surface.
I): (In the formula, R ₄ , R ₅ and R ₆ may be the same or different, and the optionally substituted alkyl group having 1 or more carbon atoms is an optionally substituted phenyl group or has 1 silicon atom. The above represents an optionally substituted organosiloxy group, provided that it contains a monomer whose hydroxyl group is protected by a hydrophobic silyl group represented by R ₄ , R ₅ and R ₆ (excluding the case where R ₄ , R ₅ and R ₆ are simultaneously methyl groups). It is possible to desilylate a copolymer molded product obtained by copolymerizing a monomer composition having a silylated hydroxyl group-containing monomer as a main component in a template having a synthetic resin hydrophobic surface. A method for manufacturing a characteristic ophthalmic lens. 2. The method for producing an ophthalmic lens according to claim 1, wherein the polyorganosiloxane having a polymerizable group has an unsaturated double bond. 3. A monomer having a silylated hydroxyl group containing a monomer having a hydroxyl group protected by a hydrophobic silyl group having an affinity for the template surface, relative to 100 parts by weight of the monomer having a silylated hydroxyl group, The method for producing an ophthalmic lens according to claim 1, wherein 10 parts by weight or more of a monomer having a hydroxyl group protected by a hydrophobic silyl group having an affinity for the template surface is added.