WO2003042265A1

WO2003042265A1 - Polymer and ophthalmic lenses made by using the same

Info

Publication number: WO2003042265A1
Application number: PCT/JP2002/011776
Authority: WO
Inventors: Kazuhiko Fujisawa; Naoki Shimoyama; Mitsuru Yokota
Original assignee: Toray Industries, Inc.
Priority date: 2001-11-13
Filing date: 2002-11-12
Publication date: 2003-05-22

Abstract

The invention aims at providing a transparent polymer exhibiting a proper modulus of elasticity, a proper breaking extension and good form recovery properties, and ophthalmic lenses made by using the same. This aim is attained by a polymer comprising as monomer components a siloxanyl monomer (A) having a hydroxyl group, a polydimethylsiloxane (B) having a poly- merizable substituent at one end, and a hydrophilic monomer (C) with proviso that the total content of the monomers (A) and (B) and the content of the monomer (C) are 30 to 95 parts by weight and 5 to 70 parts by weight respectively per 100 parts by weight of the total of the monomers (A), (B), and (C).

Description

TECHNICAL FIELD Polymer and ophthalmic lens using the same

The present invention relates to polymers. The polymer is suitably used as an ophthalmic lens such as a contact lens, an intraocular lens, and a human cornea. Background art

Polymers for ophthalmic lenses are required to balance various properties such as transparency, oxygen permeability, hydrophilicity, and mechanical properties (such as resistance to breakage). Among these, various materials using silicone components have been studied as polymers focusing on oxygen permeability, hydrophilicity, and elasticity.

For example, a siloxanyl monomer represented by the following formula (a)

And a polymer obtained by copolymerizing N, N-dimethylacrylamide, which is a hydrophilic monomer, with N, N-dimethylacrylamide. Although this polymer has high transparency, it has a drawback that shape recovery is poor.

Also, the polymer obtained by polymerizing polydimethylsiloxane having a methacrylic group at one end has the characteristics of rubber elasticity and good shape recovery properties, but such as N, N-dimethylacrylamide. When the copolymerization is attempted with a hydrophilic monomer, the compatibility is low. For example, when used as a contact lens, there is a disadvantage that the obtained lens becomes cloudy. Disclosure of the invention

The present invention is transparent, has an appropriate modulus of elasticity and elongation at break, and has good shape recovery. An object of the present invention is to provide a reversible polymer and an ophthalmic lens using the same.

In order to achieve the above object, the present invention has the following configuration.

As a monomer component,

Siloxanyl monomer having a hydroxyl group (monomer component (A)),

Polydimethylsiloxane having a polymerizable substituent at one end (monomer component (B)), and '

Hydrophilic monomer (monomer component (C))

And the total amount of the monomer components (A), (B) and (C) is 100 parts by mass, and the total content of the monomer components (A) and (B) is 30 to 50 parts by mass. 95 parts by weight, a polymer having a monomer component (C) content of 5 to 70 parts by weight. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

The polymer of the present invention needs to have excellent transparency so that it can be suitably used for an ophthalmic lens. If the transparency is poor, the field of view becomes large when used as an ophthalmic lens, and sufficient visual acuity cannot be obtained.

Shape recovery is extremely important especially when the polymer of the present invention is used as a soft contact lens. In other words, the soft contact lens is supported by the upper and lower eyelids so that it does not fall off the cornea of the eyeball when worn, and is constantly receiving forces from various directions from the eyelids. For example, when blinking, the upper eyelid exerts a force that pushes down the lens in the downward direction, and the lower eyelid exerts a resistance to it, and then when the eyelid rises, a force in the opposite direction acts. . If the shape of the soft contact lens changes while repeatedly receiving such a force, the soft contact lens will gradually adhere to the cornea. Then, the metabolic waste of the cornea accumulated under the lens cannot be discharged by the movement of the lens, causing damage to the cornea and the propagation of bacteria in the air into the waste, thereby causing infectious diseases and other diseases. May cause ulcers and other complications.

In addition, because the cornea has no blood vessels in its tissues, oxygen required for metabolism is dissolved in tears. Existing oxygen is used. Especially in the case of contact lenses, the lens floats on the tears, which hinders the dissolution of oxygen from the air into the tears. Also, because the eyelids are closed during bedtime, the dissolution of oxygen from the air into the tears is limited, and oxygen is supplied from the capillaries behind the eyelids, but the lens is still connected to the oxygen supply route. Is an obstacle. Therefore, high oxygen permeability is important in order not to disturb the corneal metabolic system.

In the polymer of the present invention, a siloxanyl monomer having a hydroxyl group (hereinafter, referred to as a monomer component (A)) is added to one end to obtain high oxygen permeability while achieving both transparency and shape recovery. It is essential to contain two types of silicon-containing components, ie, polydimethylsiloxane having a polymerizable substituent (hereinafter, referred to as a monomer component (B)). If only one of the components is contained, problems such as poor transparency and poor shape recovery occur.

In the polymer of the present invention, the monomer component (A) is used for permeating oxygen by the action of siloxanyl groups and ensuring compatibility with water contained in the polymer by the action of hydroxyl groups. Some examples are as follows.

Here, R ³ and R ⁴ each represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ represents an alkyl group respectively substituted by a hydroxyl group. A represents an organosiloxane group, p represents an integer from 0 to 200, and k represents an integer from 1 to 20.

Among these siloxanyl monomers having a hydroxyl group, a monomer represented by the following general formula (1) can be most preferably used.

In the formula, II represents an integer of 1 to 3.

In the present invention, it is essential that the monomer component (A) has a hydroxyl group. By having both siloxanyl and hydroxyl groups in one molecule, the monomer component

(A) has compatibility with both polydimethylsiloxane (monomer component (B)) and hydrophilic monomer (monomer component (C) described below), and has an effect of increasing transparency. In addition, having a hydroxyl group has an effect of enhancing shape recovery of the polymer by hydrogen bonding. In other words, if there is no hydroxyl group, the compatibility with the hydrophilic monomer (monomer component (C)) is reduced, so that the transparency is lowered. Properties, especially shape recovery, are degraded.

The polymer's shape recovery is such that when the sample is repeatedly pulled with the rheometer, the sample changes shape, resulting in zero stress between the pull and the next pull. It can be expressed in time (hereinafter referred to as “zero stress time”). The method of measuring the zero stress time will be described later. The zero stress time of the polymer of the present invention is preferably 3 seconds or less.

In addition, in the formula (1), when n is large, the elastic modulus is high, and when n is small, the elastic modulus is low. Therefore, it is possible to obtain a polymer having a desired elastic modulus by mixing them and using them. . When n = 2, a polymer having desirable mechanical properties is easily obtained.

In the monomer component (B) of the present invention, the polymerizable substituent includes a monomer component

There is no particular limitation as long as it is copolymerizable with the polymerizable group of (A), and (meth) acrylyl, styryl, aryl, butyl, and other polymerizable carbon-carbon unsaturated bonds are used. be able to. It is essential that the monomer component (B) of the present invention has a polymerizable substituent only at one end. Here, having a polymerizable substituent at one end means having only one polymerizable substituent in one molecule. In other words, when the polymerizable substituents are present at both ends, although the compatibility with the monomer component (A) is good, it is easy to form a phase containing only the siloxane component in the polymer, and the hydrophilic monomer

Phase separation with (monomer component (C)) is likely to occur. Furthermore, when polymerizable substituents are present at both ends, the polydimethylsiloxane chain is fixed to the main chain of other components at both ends, resulting in an excessively high modulus of elasticity or a decrease in elongation at break. However, the mechanical properties deteriorate, which is not preferable. When no polymerizable substituent is present at any of the terminals, copolymerization cannot be performed, and a polymer having desired properties cannot be obtained. The elastic modulus is extremely important when the polymer of the present invention is used especially as a soft contact lens. If the elastic modulus is too high, the feeling of foreign matter when worn is too strong. In particular, when performing continuous wearing while sleeping, complications such as arcuate scratches on the cornea may occur. On the other hand, if the elastic modulus is too low, the self-holding property of the lens shape is deteriorated, and it becomes difficult to insert the lens into the eye when wearing. Therefore, the elastic modulus of the polymer of the present invention is preferably in the range of 0.34 to 1.03 MPa, and preferably in the range of 0.41 to 0.75 MPa. More preferably, it is even more preferably in the range of 0.44 to 0.69 MPa.

Further, the elongation at break has a close relationship with breakage during handling of the lens. Softcon Tact lenses are so soft that they deform significantly during handling. However, if the breaking elongation is small, they cannot withstand this deformation and may be damaged. If the elongation at break is too large, the shape recovery tends to be poor. Therefore, the elongation at break is preferably from 200% to 600%, more preferably from 250% to 500%.

The molecular weight of the monomer component (B) affects the transparency of the obtained polymer. In other words, the higher the molecular weight, the more other components, especially hydrophilic monomers (monomer components)

The compatibility with (C)) is degraded and the phase tends to separate. If the molecular weight is too small, the oxygen permeability coefficient tends to decrease. In order to have sufficient transparency and oxygen permeability, the molecular weight of the monomer component (B) is preferably in the range of 200 to 100,000. The molecular weight of the monomer component (B) is more preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less. Further, the molecular weight of the monomer component (B) is more preferably 500 or more.

The hydrophilic monomer used in the polymer of the present invention (hereinafter referred to as a monomer component

(Referred to as (C)) can be any hydrophilic monomer as used for ordinary contact lenses. An example is 2—Hydroxyshetil

(Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene dalicol Mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, dipropylene glycol ( (Meth) acrylates having a hydroxyl group such as (meth) acrylate, unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid and maleic acid, (meth) acrylamide, N-methyl (meth) ) Acrylamide, N-ethyl (meth) atarylamide, N, N-dimethyl (meth) acrylyl amide, N, N-getyl (meth) atarylamide, N, N-di-n-propyl

(Meth) atarylamide, N, N-diisopropyl (meth) atarylamide,, N-di-n-butyl (meta) atalinoleamide, N-atarylonyremorpholine, N, N-methylethyl (meta) (Meta) acrylamides such as acrylamide, -Bi-N-pyrrolidone, N-vininoleviperidone, N-vinyl diprolactam, ビ -buractams such as vinylcaprylactam, aminoethyl (meth) acrylate, Ν-methylaminoethyl (meth) acrylate, ,, Ν —Aminoalkyl (meth) atalylates such as dimethylaminoethyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, methoxethyl (meth) acrylate, ethoxyxethyl (meth) acrylate, methoxydiethylene glycol Examples include (meth) acrylates containing alkoxy groups such as (meth) atalylate and methoxypolyethylene dalichol (meth) acrylate. Among them, from the viewpoints of solubility, intermolecular interaction, and water absorption, acrylates having a hydroxyl group, methacrylates having a hydroxyl group, acrylamides, methacrylamides, and One or more monomers selected from the group consisting of burlactams can be preferably used. Among them, one or two or more monomers selected from the group consisting of ,, Ν-dimethylaquinoleamide, 2-hydroxyshethyl methacrylate, and Ν-bulpyrrolidone can be most preferably used.

The monomer component (C) used in the present invention is used to give the polymer of the present invention water absorption and water content. The polymer of the present invention becomes flexible by being hydrated, and can be suitably used, for example, as a soft contact lens.

In order for the obtained polymer to have sufficient oxygen permeability and water content, the monomer component (Α), the monomer component (Β) and the monomer component (C) in a total of 100 parts by weight, total 3 0-9 5 parts by weight of the content of Alpha) and (beta), and the monomer component (C) the content is for 5-7 0 parts by weight is preferred _c in this case, the monomer component (a ) Is preferably 5 to 90 parts by weight, and the content of the monomer component (B) is preferably 5 to 90 parts by weight. When the content of the monomer component (A) increases, the modulus of elasticity increases and the elongation at break tends to decrease, whereas when the content of the monomer component (B) increases, The elastic modulus tends to decrease and the elongation at break tends to increase. The monomer component (A) is contained in an amount of 5 to 75 parts by weight, based on the total of 100 parts by weight of the monomer component (A), the monomer component (B) and the monomer component (C), and the monomer component (B). Content of 5 to 75 parts by weight, monomer component More preferably, the total content of (A) and (B) is 40 to 80 parts by weight, and the content of the hydrophilic monomer (C) is 20 to 60 parts by weight. Further, the content of the monomer component (A) is 5 to 60 parts by weight, the content of the monomer component (B) is 5 to 60 parts by weight, and the total content of the monomer components (A) and (B) is 50%. It is more preferable that the content of the monomer component (C) is 25 to 50 parts by weight.

In the polymer of the present invention, a monomer having two or more polymerizable substituents in one molecule (hereinafter, referred to as a monomer) in order to obtain good mechanical properties and good resistance to a disinfecting solution and a cleaning solution. Component D) is preferably used as a copolymerization component. The polymerizable substituent is not particularly limited as long as it is copolymerizable with other monomer components, and may be a (meth) acrylic group, a styryl group, an aryl group, a vinyl group, or another polymerizable carbon-carbon unsaturated group. Bonding can be used. The monomer component (D) is not particularly limited as long as it has two or more polymerizable substituents in one molecule, and is the same as the monomer components (A), (B) and (C). Excluding Examples of such monomers include ethylenedial glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Polyethylene glycol di (meth) acrylate, biel (meth) acrylate, aryl (meth) acrylate, stilbene, polydimethylsiloxane having (meth) acrylyl groups at both ends, and the like. No. The copolymerization ratio of the monomer component (D) is preferably at least 0.1 part by weight, more preferably at least 0.3 part by weight, based on 100 parts by weight of the total of the monomer components (A), (B) and (C). And more preferably 0.5 part by weight or more. The copolymerization ratio of the monomer component (D) is

The total amount of (A), (B) and (C) is preferably 100 parts by weight or less based on 100 parts by weight.

The polymer of the present invention may contain an ultraviolet absorber, a dye, a colorant, and the like. Further, an ultraviolet absorber, a dye, or a colorant having a polymerizable group may be contained by copolymerization.

When the polymer of the present invention is obtained by polymerization, a peroxide may be used to facilitate the polymerization. It is preferable to add a thermal polymerization initiator represented by a diazo compound or a photopolymerization initiator. In the case of performing thermal polymerization, those having the optimum decomposition characteristics for the desired reaction temperature are selected and used. In general, azo initiators and peroxide initiators having a 10-hour half-life temperature of 40 ° C. to 120 ° C. are suitable. Examples of the photopolymerization initiator include a carbonyl compound, a peroxide, an azo compound, a sulfur compound, a halogen compound, and a metal salt. These polymerization initiators are used alone or as a mixture, and are used in an amount of up to about 1 part by weight.

When the polymer of the present invention is obtained by polymerization, a polymerization solvent can be used. Various organic and inorganic solvents can be used as the solvent, and there is no particular limitation. Examples include water, various alcoholic solvents such as methanol, ethanol, propanol, 2-propanol, butanol, and tert-butanol, various aromatic hydrocarbon solvents such as benzene, toluene, and xylene, hexane, heptane, octane. , Decane, petroleum ether, kerosene, rig mouth, paraffin and other aliphatic hydrocarbon solvents, acetone, methylethyl ketone, methylisobutyl ketone and other ketone solvents, ethyl acetate, butyl acetate, Various ester solvents such as methyl benzoate and dioctyl phthalate, getyl ether, tetrahydrofuran, dioxane, ethylene glycol diol resin alkyl ether, diethylene glycol dianol alkyl ether, triethylene glycol dianol alkyl ether Tetraethylene glycol di § Lucino les ether Honoré is various da recall ether solvents such as polyethylene glycidyl Kono register alkyl ether. These can be used alone or as a mixture.

As the polymerization method and the molding method of the polymer of the present invention, ordinary methods can be used. For example, there is a method in which the material is once formed into a round bar or a plate shape and then processed into a desired shape by cutting or the like, a mold polymerization method, a spin casting method, or the like. —As an example, the case where the polymer of the present invention is obtained by a mold polymerization method will be described below.

The monomer composition is filled into the space between two molds having a certain shape. Then, photopolymerization or thermal polymerization is performed to shape the mold. The mold is made of resin, glass, ceramic, metal, etc. An optically transparent material such as glass is used. In the production of polymers, voids are often formed by two opposing molds, and the voids are filled with the monomer composition, but depending on the shape of the mold and the nature of the monomer, the polymer A gasket may be used in combination with a gasket having a predetermined thickness to prevent leakage of the filled monomer composition. The mold filled with the monomer composition in the voids is subsequently irradiated with an actinic ray such as ultraviolet light, or is heated by being opened or placed in a liquid tank and polymerized. There may be a method in which both are used in combination, such as heat polymerization after photopolymerization or photopolymerization after heat polymerization. In the case of photopolymerization, for example, it is common to irradiate light containing a large amount of ultraviolet light from a mercury lamp or insect trap as a light source for a short time (usually 1 hour or less). In the case of thermal polymerization, the condition is to gradually raise the temperature from around room temperature and raise it to a temperature of 60 ° C to 200 ° C over several hours to several tens of hours. Preferred for maintaining uniformity, quality, and improving reproducibility. The polymer of the present invention can be modified by various methods. In order to improve the surface wettability, it is preferable to perform the modification treatment.

Specific methods for modifying the polymer include electromagnetic wave (including light) irradiation, plasma irradiation, chemical vapor deposition such as evaporation and sputtering, heating, base treatment, acid treatment, and other suitable surface treatment agents. Use, and combinations thereof. Of these reforming means, simple and preferred are a base treatment and an acid treatment.

Examples of the base treatment or the acid treatment include a method of contacting a molded article comprising the polymer of the present invention with a basic or acidic solution, a method of contacting a molded article with a basic or acidic gas, and the like. More specific methods include, for example, a method of dipping a molded article in a basic or acidic solution, a method of spraying a basic or acidic solution on a molded article, a method of spraying a basic or acidic gas on a molded article, Examples thereof include a method of applying a basic or acidic solution to a molded article with a spatula or a brush, and a method of applying a basic or acidic solution to a molded article by a spin coating method or a dip coating method. The simplest and most effective method for obtaining a large reforming effect is to immerse the molded article in a basic or acidic solution.

The temperature at which the molded article is immersed in a basic or acidic solution is not particularly limited. It is usually performed within a temperature range of about 50 ° C. to 300 ° C. From the viewpoint of workability, the temperature range is more preferably from 10 ° C to 150 ° C, and most preferably from −5 ° C to 60 ° C.

The time for immersing the molded article in a basic or acidic solution varies depending on the temperature, but is generally preferably within 100 hours, more preferably within 24 hours, most preferably within 12 hours. preferable. If the contact time is too long, not only will workability and productivity deteriorate, but also adverse effects such as a decrease in oxygen permeability and a decrease in mechanical properties may occur.

Bases include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, various amines, and polyethyleneimine, polybutylamine, etc. High molecular weight bases can be used. Among these, alkali metal hydroxides are most preferred because of their low cost and great treatment effect.

As the acid, various inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, various organic acids such as acetic acid, formic acid, benzoic acid, and phenol, and various high molecular weight acids such as polyacrylic acid and polystyrene sulfonate can be used. is there. Of these, high molecular weight acids are most preferred because of their high treatment effect and little adverse effect on other physical properties.

Various inorganic or organic solvents can be used as the solvent for the basic or acidic solution. For example, various alcohols such as water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and glycerin, benzene, Various aromatic hydrocarbons such as toluene and xylene, hexane, heptane, octane, decane, petroleum ether, various aliphatic hydrocarbons such as kerosene, lignin, paraffin, acetone, methyl ethyl ketone, methyl isobutyl ketone Various esters such as ketones, ethyl acetate, butyl acetate, methyl benzoate, dioctyl phthalate, getyl ether, tetrahydrofuran, furan, dioxane, ethylene glycolone resin Various ethers such as tenole, diethylene glycol cornole resin alkyl ether, triethylene glycol corn resin alkyl ether, tetraethylene glycol monoresinole alkyl ether, polyethylene glycol dialkyl ether, etc., dimethinole honole amide , Dimethylacetami , N-methyl-2-pyrrolidone, dimethylimidazolidinone, hexamethylphosphoric triamide, dimethylsulfoxide, and other non-protonic polar solvents, methylene chloride, methylene chloride, chlorophonolem, dichloroethane, trichloroethane, trichloroethane Mouth: Halogen solvents such as ethylene, and chlorofluorocarbon solvents. Among them, water is most preferable in terms of economy, simplicity of handling, and chemical stability. As the solvent, a mixture of two or more substances can be used.

The basic or acidic solution used in the present invention may contain components other than the basic or acidic substance and the solvent.

In the present invention, the molded article can be subjected to a base treatment or an acid treatment, and then a basic or acidic substance can be removed by washing.

Various inorganic or organic solvents can be used as the washing solvent. For example, various alcohols such as water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, etc. Benzene, toluene, xylene, etc., various aromatic hydrocarbons, hexane, heptane, octane, decane, petroleum ether, kerosene, lignin, paraffin, etc., various aliphatic hydrocarbons, acetone, methyl ethyl ketone, Various ketones such as methylisobutyl ketone, various esters such as ethyl acetate, butyl acetate, methyl benzoate, and dioctyl phthalate, getyl ether, tetrahydrofuran, dioxane, ethylene glycol resin alkylene Ether, diethylene glycol diolequine oleate ^^, triethylene glycol dianolequinoleate ethere, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and other ethers, dimethylformamide , Non-protonic polar solvents such as dimethylacetoamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, hexamethylphosphoric triamide, dimethylsulfoxide, methylene chloride, chlorophonolem, dichloroethane, Examples of such solvents include nitrogen-based solvents such as trichloroethane and trichloroethylene, and chlorofluorocarbon-based solvents.

As the washing solvent, a mixture of two or more solvents can be used. The cleaning solvent contains components other than the solvent, for example, inorganic salts, surfactants, or cleaning agents. You may.

The modification treatment may be performed on the entire molded article, or may be performed only on a part of the molded article such as the surface. When only the surface is modified, it is possible to improve only the water wettability of the surface without greatly changing the properties of the entire polymer forming the molded article.

The polymer of the present invention can be suitably used for an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea. Among them, it is particularly suitable for contact lenses.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. , <Measurement method>

The measurement of the “zero stress time” in this example was performed as follows. Using a Rheometer R D-300 manufactured by Sun Science Co., Ltd., the distance between the chucks was set to 5 mm, and the measurement sample was gripped. The measurement sample was pulled at 10 Oram at a speed of 100 OmZmin, and then returned at a speed of 100 Oram / min. Then, the same operation was repeated twice. If the shape recovery of the sample is poor, the length of the sample is longer than the original length even after performing the first pulling and returning operations and then performing the second pulling operation. Therefore, in the early stage of the second pull, the stress remains zero, and the stress is detected only when the pulling distance is increased. Furthermore, during the third pulling operation, which is performed after the second pulling and returning operation, the time during which the stress remains zero becomes longer, and only if the pulling distance is longer than the second pulling operation. Stress is detected. In this measurement, the time from the start of the third pulling until the start of stress detection was measured, and this was defined as “zero stress time”.

The measurement of the elastic modulus and elongation at break was performed as follows. As a sample, a polymer molded product having a size of about 15 mm × 10 mm × 0.1 mm was used, and the measurement was performed using a Tensilon RTM-100 model manufactured by Toyo Boldwin Co., Ltd. The pulling speed was 100 mm / min and the distance between grips was 5 mm.

<Example 1> 30 parts by weight of a siloxanyl monomer represented by the following formula (a), 30 parts by weight of a polydimethylsiloxane having a methacryl group at one end and having a molecular weight of about 10000 (manufactured by Chisso, FM0771), N, N-dimethyl Acrylamide (hereinafter referred to as DMAA) 40 parts by weight, polydimethylsiloxane with a molecular weight of about 2,000 having methacrylic groups at both terminals (Shin-Etsu Chemical, X-22-164A) 4.98 parts by weight, butyl acetate 10 parts by weight were uniformly mixed, and 2-hydroxy-2-methylpropiophenone ("Darocure (registered trademark)" 1173, manufactured by CIBA) was added as a polymerization initiator. The monomer mixture was degassed under an argon atmosphere.

It was injected between plastic lens-shaped molds in a glove box under a nitrogen atmosphere and sealed. The polymerization was carried out by irradiating light (illuminance lmW / cm ² , 12 minutes) using a trap lamp. Thereafter, each mold was immersed in a mixed solution of purified isopropyl alcohol water = 50_ / 50 (parts by weight) at 60 ° C. for 16 hours and demolded to obtain a lens-shaped polymer molded product. The polymer molded product was immersed in a mixed solution of isopropyl alcohol purified water = 75/25 (parts by weight) at 60 ° C. for 16 hours to extract residual monomers. After that, the polymer molded article was washed with a mixed solution of isopropyl alcohol / purified water = 75 Z25 (parts by weight), and then immersed in a mixed solution of isopropyl alcohol purified water = 50 to 50 (parts by weight) for 30 minutes. Next, the polymer was immersed in a mixed solution of isopropyl alcohol / purified water = 25 to 75 (parts by weight) for 30 minutes, immersed in purified water for 16 hours, and allowed to stand completely to completely remove isopropyl alcohol from the polymer molded article. The polymer molded article was prepared as 1.2 wt% polyacrylic acid (average molecular weight:

(250, 000) at 23 ° C for 4 hours in an aqueous solution. Then, after sufficiently washing the polymer molded article with purified water, a borate buffer solution (pH 7.1 to 7.1.

3) and the vial was sealed. The vial was placed in an autocrepe and boiled at 120 ° C. for 30 minutes. After cooling, the polymer molded product is placed in a vial And immersed in borate buffer (PH 7.1 to 7.3). This polymer molded article was transparent and non-turbid, and had a stress-free time of 2.22 seconds.

Examples 2 to 8>

A polymer molded article was obtained in the same manner as in Example 1 except that the mixing ratio of the siloxanyl monomer represented by the formula (a), polydimethylsiloxane, and DMAA was changed as shown in Table 1. All of the obtained polymer molded articles were transparent and free from turbidity. The stress-free time [sec] of these samples is shown in Table 1, and all polymers were transparent and had good shape recovery properties.

Example 9>

A siloxanyl monomer having a hydroxyl group represented by the formula (b) instead of the siloxanyl monomer represented by the formula (a)

A polymer molded product was obtained in the same manner as in Example 1 except that 30 parts by weight was used. The obtained polymer molded product was transparent, and although the elastic modulus was slightly high, the stress-free time was short at 2.5 seconds, indicating good shape recovery.

A siloxanyl monomer having a hydroxyl group represented by the formula (c) instead of the siloxanyl monomer represented by the formula (a)

A polymer molded product was obtained in the same manner as in Example 1 except that 30 parts by weight was used. The obtained polymer molded article was transparent, and although the elastic modulus was slightly low, the stress-free time was short at 2.4 seconds, indicating good shape recovery.

<Comparative Example 1> '

A polymer molded article was obtained in the same manner as in Example 1, except that 65 parts by weight of the siloxanyl monomer ( _a ) and 35 parts by weight of DMAA were used without adding polydimethylsiloxane. Was. The stress-free time [sec] of the obtained polymer molded product was as shown in Table 1 below, and the shape recovery property was poor.

An attempt was made to polymerize in the same manner as in Example 1 using 65 parts by weight of polydimethylsiloxane and 35 parts by weight of DMAA without adding the siloxane monomer ( _a ). Phase separation occurred, and a lens-shaped product was not obtained.

30 parts by weight of a hydroxyl-free siloxal monomer represented by the formula (d),

A polymer molded article was obtained in the same manner as in Example 1 except that 30 parts by weight of polydimethylsiloxane having a polymerizable unsaturated group at one end and 40 parts by weight of N, N-dimethylacrylamide were used. The resulting polymer molded article had a short stress opening time of 2.2 seconds, which was good, but was cloudy and could not be used for ophthalmic lenses.

35 parts by weight of a siloxanyl monomer having a hydroxyl group represented by the formula (a), polydimethylsiloxane having a molecular weight of 500 and having an unsaturated double bond at both terminals (Shin-Etsu Chemical X—22-164 C) A polymer molded article was obtained in the same manner as in Example 1, except that 29 parts by weight and 35 parts by weight of N, N-dimethylacrylamide were used. Although the obtained polymer molded article was transparent, the elastic modulus was as high as 1.2 IMPa, the elongation at break was small, and the mechanical properties were inferior. .

Without adding the siloxanyl monomer ( _a ), polydimethylsiloxane having a molecular weight of 500,000 and having an unsaturated double bond at both ends (Shin-Etsu Chemical X—22-164C) 60 weight parts, A polymer molded article was obtained in the same manner as in Example 1, except that 40 parts by weight of N, N-dimethylacrylamide was used. The obtained polymer molded article became cloudy and had a high elastic modulus of 1.38 MPa and a low elongation at break of 50%, which was inferior in mechanical properties. Was. table 1

* 1 30 parts by weight of siloxanyl monomer containing no hydrophilic group

Industrial applicability

According to the present invention, there is provided a polymer which is transparent, has an appropriate elastic modulus and elongation at break, and has good shape recovery properties. The polymer of the present invention is useful for ophthalmic lenses, particularly for contact lenses.

Claims

The scope of the claims

1. As a monomer component,

Siloxanyl monomer having a hydroxyl group (monomer component (A)),

Polydimethylsiloxane having a polymerizable substituent at one end (monomer component (B)), and

Hydrophilic monomer (monomer component (C))

And the total content of the monomer components (A) and (B) is 30 to 95 with respect to 100 parts by weight of the total content of the monomer components (A), (B) and (C). A polymer in which the content of the monomer component (C) is 5 to 70 parts by weight.

2. The content of the monomer component (A) is 5 to 90 parts by weight, and the content of the monomer component (B) is 100 parts by weight of the total of the monomer components (A), (B) and (C). Is 5 to 90 parts by weight.

3. The monomer component (A) content is 5 to 60 parts by weight, and the monomer component (B) content is 100 parts by weight of the total of the monomer components (A), (B) and (C). Is 5 to 60 parts by weight, the content of the monomer component (C) is 25 to 50 parts by weight, and the total content of the monomer components (A) and (B) is 50 to 75 parts by weight. 3. The polymer according to claim 2, which is:

4. The polymer according to claim 1, wherein the monomer component (A) is a compound represented by the following general formula (1).

In the formula, n represents an integer of 1 to 3.

5. The polymer according to claim 4, wherein the monomer component (A) is a compound represented by n = 2 in the general formula (1).

6. The polymer according to claim 1, wherein the molecular weight of the monomer component (B) is in the range of 200 to 100,000.

7. Monomer component (c) One or more selected from the group consisting of i-acrylamides, methacrylamides, hydroxyl-containing atalylates, hydroxyl-containing methacrylates, and burlactams The polymer according to claim 1.

8. The claim that the monomer component (C) is one or more members selected from the group consisting of N, N-dimethylacrylamide, N-vinyl vinylidone, and 2-hydrogishethyl methacrylate. 8. The polymer according to item 7, wherein

9. A monomer having two or more polymerizable substituents in one molecule (monomer component D) is added to the monomer component (A), (B) and (C) in a total of 100 parts by weight, 2. The polymer according to claim 1, containing from! To 10 parts by weight.

10. The polymer according to claim 9, wherein the polymerizable substituent is a carbon-carbon double bond.

1 1. A polymer molded article obtained by subjecting a molded article made of the polymer according to claim 1 to surface modification by base treatment or acid treatment.

1 2. An ophthalmic lens using the polymer according to claim 1.

1 3. A contact lens using the polymer according to claim 1.