JP2002371116A - Monomer, polymer, ocular lens and contact lens each using the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer giving a polymer suitable ocular lens having high oxygen permeability and transparency. SOLUTION: This monomer is shown by the general formula (a) or (a') A is a siloxanyl group; R<1> is H or methyl; and R<2> is a substituent selected from the group consisting of (substituted) 1-20C alkyl, (substituted) 6-20C aryl and group of the formula (c) [where, R<3> is H or methyl; R<4> is a substituent selected from the group consisting of (substituted) 1-20C alkyl and (substituted) 6-20C aryl; and k is an integer of 0-200]}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a monomer and a polymer, and the monomer and the polymer are particularly suitably used as an ophthalmic lens such as a contact lens, an intraocular lens and an artificial cornea.

[0002]

2. Description of the Related Art Conventionally, monomers having a silicon group have been known as monomers for ophthalmic lenses.

[0003] For example, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate is widely used as a monomer for ophthalmic lenses. A polymer obtained by copolymerizing 3- [tris (trimethylsiloxy) silyl] propyl methacrylate with N, N-dimethylacrylamide as a hydrophilic monomer has a feature of being transparent and having high oxygen permeability. However, in order to obtain higher oxygen permeability and rubber elasticity, a ternary copolymer containing a silicone macromer such as polydimethylsiloxane having a methacrylic group at the end cannot provide sufficient compatibility. In some cases, the obtained lens became cloudy.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a monomer obtained by polymerizing the same and having a high oxygen permeability and a sufficient compatibility even in a three-component system of a silicone macromer / hydrophilic monomer. A polymer using
It is intended to provide an ophthalmic lens and a contact lens.

[0005]

In order to achieve the above object, the present invention has the following arrangement. "(1) a monomer having a polymerizable unsaturated double bond and a siloxanyl group and having a substituent having an ester group in a side chain, and (2) a monomer having an ester group having an ether bond and / or A monomer according to (1) having a polyalkylene glycol chain, (3) a monomer represented by the following general formula (a) or (a ′),

[0006]

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[A represents a siloxanyl group. R ¹ represents H or a methyl group. R ² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and the following formula (c)

[0008]

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Represents a substituent selected from the group consisting of In the formula (c), R ³ represents H or a methyl group, and R ⁴ comprises an optionally substituted alkyl group having 1 to 20 carbon atoms and an optionally substituted aryl group having 6 to 20 carbon atoms. Represents a substituent selected from the group, and k represents an integer of 0 to 200. And (4) the monomer according to (3), wherein in the general formula (a) or (a ′), the siloxanyl group (A) is a substituent represented by the following formula (b):

[0010]

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[In the formula (b), A ^{1 to} A ¹¹ each independently represent H, an alkyl group having 1 to 20 carbon atoms which may be substituted, or an alkyl group having 6 to 20 carbon atoms which may be substituted. Represents any of aryl groups. n represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ], (5) In general formula (a) or (a '),
Siloxanyl group (A) is tris (trimethylsiloxy)
The monomer according to (3), which is a substituent selected from a silyl group, a bis (trimethylsiloxy) methylsilyl group, and a trimethylsiloxydimethylsilyl group, (6) any of (1) to (5). (7) The polymer according to (6), wherein the ratio of the number of substituents having an ester group / the number of siloxanyl groups is 0.1 to 1, (8) the polymer of (1) to (5). A polymer which is a homopolymer of the monomer according to any of the above,
(9) A polymer containing the monomer according to any one of (1) to (5) as a polymerization component in a range of 10% to 80%,
(10) An ophthalmic lens using the polymer according to any one of (6) to (9). (11) A contact lens comprising the polymer according to any one of (6) to (9). "

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, each functional group in the present monomer will be described. The polymerizable unsaturated double bond may be any double bond capable of forming a polymer by radical polymerization, and examples thereof include a (meth) acryloyl group, a styryl group, a benzoyl group, and a vinyl group. be able to. Among them, a methacryloyl group can be preferably used from the viewpoint of ease of synthesis and polymerizability.

[0013] The siloxanyl group as used herein refers to a group having at least one Si-O-Si bond.
As the siloxanyl group, a substituent represented by the following formula (b) is preferably used in terms of availability of raw materials and ease of synthesis.

[0014]

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[In the formula (b), A ^{1 to} A ¹¹ are each independently H, an alkyl group having 1 to 20 carbon atoms which may be substituted, or an alkyl group having 6 to 20 carbon atoms which may be substituted. Represents any of aryl groups. n represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ]
The substituent having an ester group of the present invention is introduced to alleviate the water repellency of the monomer of the present invention and increase the hydrophilicity.In addition to a simple ester group, a polyalkylene glycol chain or an ether A substituent having a bond can be suitably used.

In order to explain the content of the present invention more clearly, each substituent in the general formula (a) or (a ') will be described more specifically below.

Formula (b) illustrating the siloxanyl group of A
Wherein A ¹ to A ¹¹ are each independently H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, hexyl, cyclohexyl, 2-hexyl, Examples include an alkyl group such as an ethylhexyl group and an octyl group, and an aryl group such as a phenyl group and a naphthyl group. Examples of further substituted alkyl and aryl groups include a 3-glycidoxypropyl group, a 2-hydroxyethoxypropyl group,
Examples include a hydroxypropyl group, a 3-aminopropyl group, and a fluorophenyl group. Most preferred among these are methyl groups.

In the formula (b), n is an integer of 0 to 200, preferably 0 to 50, and more preferably 0 to 10. a, b, and c each independently represent an integer of 0 to 20; preferably, a, b, and c each independently represent an integer of 0 to 5; When n = 0, preferred combinations of a, b, and c are a = b = c = 1, a = b = 1
And c = 0.

Among the substituents represented by the formula (b), particularly preferable ones which are industrially available at relatively low cost are tris (trimethylsiloxy) silyl, bis (trimethylsiloxy) methylsilyl and trimethylsiloxy. Examples include a dimethylsilyl group, a polydimethylsiloxane group, a polymethylsiloxane group, and a poly-co-methylsiloxane-dimethylsiloxane group.

In the formula (a) or (a ′), R ² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted and c)

[0021]

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Represents a substituent selected from the group consisting of
When R ² is selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms or an aryl group optionally having 6 to 20 carbon atoms, preferred examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, cyclohexyl group, benzyl group, phenyl group, naphthyl group and the like, among which preferable methyl group, ethyl group, phenyl group And most preferably a methyl group. When R ² is selected from the group consisting of a substituent of the type of formula (c), in formula (c), R ⁴ is an optionally substituted alkyl group having 1 to 20 carbon atoms and Represents a substituent selected from the group consisting of aryl groups having 6 to 20 carbon atoms, and preferable examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Heptyl group, octyl group, decyl group, cyclohexyl group, benzyl group, phenyl group, naphthyl group, etc.
Among them, preferred are a methyl group, an ethyl group and a phenyl group, and the most preferred is a methyl group.

In the formula (c), k represents an integer of 0 to 200. As k increases, hydrophilicity increases, but the balance with high oxygen permeability deteriorates. Is preferably 0 to 50, more preferably 0 to 20.

The polymer of the present invention can be obtained by polymerizing the monomer of the present invention alone or by copolymerizing with the other monomer. The other monomer in the case of copolymerization is not particularly limited as long as it can be copolymerized.
Acryloyl, styryl, allyl, vinyl, and other monomers having a polymerizable carbon-carbon unsaturated bond can be used.

Hereinafter, some examples will be given, but the present invention is not limited to these.

One group of examples is (meth) acrylic acid, itaconic acid, crotonic acid, vinylbenzoic acid,
A hydrophilic monomer group comprising (meth) acrylamides such as N, N-dimethylacrylamide and N-vinyllactams such as N-vinylpyrrolidone. Other examples include groups of hydrophobic monomers such as alkyl (meth) acrylates such as methyl (meth) acrylate and aromatic vinyl monomers such as styrene. Further, as monomers having oxygen permeability, there may be mentioned fluoroalkyl group-containing (meth) acrylates, silicone macromers such as polydimethylsiloxane having a (meth) acryloyl group at a terminal, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, etc. It is.

The (co) polymerization ratio of the monomer represented by the general formula (a) or (a ′) in the polymer of the present invention is as follows:
When no other monomer containing a silicon group is contained, from 30 to 10 to achieve both high oxygen permeability and high hydrophilicity.
0%, more preferably 40-99%, most preferably 50-95% by weight. In the copolymerization with an oxygen-permeable monomer, the total of the monomer of the present invention and another oxygen-permeable monomer is preferably within the above-mentioned copolymerization ratio. Further, in this case, if the ratio of siloxanyl groups is too high, it becomes difficult to secure a balance between water wettability and oxygen permeability. Therefore, the ratio of the number of substituents having ester groups / the number of siloxanyl groups in the polymer is not less than a certain value. It is important to That is, it is preferably in the range of 0.1 to 1, but particularly preferably in the range of 0.3 to 0.7.

The polymer of the present invention has two or more copolymerizable carbon-carbon unsaturated bonds per molecule in the sense that good mechanical properties can be obtained and good resistance to disinfectants and cleaning solutions can be obtained. Is preferably used as a copolymerization component. The copolymerization ratio of the monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and more preferably 0.5% by weight or more. Is more preferred.

The polymer of the present invention may contain an ultraviolet absorber, a dye, a colorant and the like. Further, an ultraviolet absorbent, a dye, and a colorant having a polymerizable group may be contained in a copolymerized form.

When the polymer of the present invention is obtained by polymerization,
To facilitate the polymerization, it is preferable to add a thermal polymerization initiator represented by a peroxide or an azo compound, or a photopolymerization initiator. In the case of performing the thermal polymerization, a material having an optimum decomposition characteristic for a desired reaction temperature is selected and used. In general, an azo initiator and a peroxide initiator 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 up to about 1% 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, methanol, ethanol, propanol, 2-propanol, butanol, tert-
Various alcohol solvents such as butanol, various aromatic hydrocarbon solvents such as benzene, toluene and xylene, hexane, heptane, octane, decane, petroleum ether,
Various aliphatic hydrocarbon solvents such as kerosene, ligroin, paraffin, various ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; various types such as ethyl acetate, butyl acetate, methyl benzoate, dioctyl phthalate, and ethylene glycol diacetate Ester solvents, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, various glycol ether solvents such as polyethylene glycol dialkyl 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, usual methods can be used. For example, there are a method in which the material is once formed into a round bar or a plate shape, and this is processed into a desired shape by cutting or the like, a mold polymerization method, a spin casting method, or the like. As an example, a case where the polymer of the present invention is obtained by a mold polymerization method will be described below.

The space between the two molds having a predetermined shape is filled with the monomer composition. Then, photopolymerization or thermal polymerization is performed to shape the mold. The mold is made of resin, glass, ceramics, metal or the like. In the case of photopolymerization, an optically transparent material is used, and usually, resin or glass is used. In the case of producing a polymer, a void is formed by two opposing molds in many cases, and the void is filled with the monomer composition. And a gasket having the purpose of preventing leakage of the filled monomer composition. Subsequently, the mold in which the voids are filled with the monomer composition is irradiated with an actinic ray such as ultraviolet rays, or is heated in an oven or a liquid tank to polymerize the monomers. 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, it is general to irradiate light containing a large amount of ultraviolet light from a mercury lamp or insect lamp for a short time (usually 1 hour or less). When performing thermal polymerization, the temperature is gradually increased from around room temperature, and the temperature is increased over several hours to several tens of hours.
Conditions for increasing the temperature to 0 ° C to 200 ° C are preferred in order to maintain the optical uniformity and quality of the polymer and to enhance the reproducibility.

A molded article using the polymer of the present invention is:
The reforming treatment can be performed by various methods. It is preferable to perform a modification treatment for improving the water wettability of the surface.

Specific examples of the modifying method include electromagnetic wave (including light) irradiation, plasma irradiation, chemical vapor deposition such as vapor deposition and sputtering, heating, base treatment, acid treatment, and use of other appropriate surface treatment agents. , And combinations thereof. Of these reforming means, simple and preferred are base and acid treatments.

Examples of the base treatment or acid treatment include a method of contacting a molded article 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 immersing a molded article in a basic or acidic solution, a method of spraying a basic or acidic solution or a basic or acidic gas on a molded article, and a method of spraying a basic or acidic solution on a molded article. Can be applied with a spatula, a brush, or the like, or a basic or acidic solution can be applied to a molded product by a spin coating method or a dip coating method.
The simplest way to obtain a large modifying 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 performed within a temperature range of about ° C. -1 considering workability
A temperature range of 0 ° C to 150 ° C is more preferable, and
0 ° C. is most preferred. The optimum 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, and most preferably within 12 hours.
If the contact time is too long, not only the workability and productivity will deteriorate, but also adverse effects such as a decrease in oxygen permeability and a decrease in mechanical properties may be caused.

Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, various amines, polyethyleneimine, polyvinylamine and the like. Can be used. Of 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 sulfonic acid are used. It is possible. Among these, a high molecular weight acid is most preferable because of its large processing effect and little adverse effect on other physical properties.

Various inorganic and organic solvents can be used as the solvent for the basic or acidic solution. For example, water, methanol, ethanol, propanol, 2-propanol,
Butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, various alcohols such as glycerin, various aromatic hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane, decane, petroleum ether, kerosene , Ligroin, various aliphatic hydrocarbons such as paraffin, acetone, methyl ethyl ketone, various ketones such as methyl isobutyl ketone, various esters such as ethyl acetate, butyl acetate, methyl benzoate, dioctyl phthalate, diethyl ether, tetrahydrofuran, dioxane , Ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol Lumpur dialkyl ether, various ethers such as polyethylene glycol dialkyl ethers, dimethylformamide, dimethylacetamide, N
-Various aprotic polar solvents such as -methyl-2-pyrrolidone, dimethylimidazolidinone, hexamethylphosphoric triamide, and dimethyl sulfoxide; halogen-based solvents such as methylene chloride, chloroform, dichloroethane, trichloroethane, and trichloroethylene; and freon-based solvents And so on. 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.

After the molded article is treated with a base or an acid, the basic or acidic substance can be removed by washing.

Various inorganic and organic solvents can be used as the washing solvent. For example, water, methanol, ethanol,
Propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, various alcohols such as glycerin, benzene, toluene, various aromatic hydrocarbons such as xylene, hexane, heptane, octane, Decane, petroleum ether,
Kerosene, ligroin, various aliphatic hydrocarbons such as paraffin, acetone, methyl ethyl ketone, various ketones such as methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl benzoate, various esters such as dioctyl phthalate, diethyl ether, tetrahydrofuran, Various ethers such as dioxane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidy Various aprotic polarities such as non-, hexamethylphosphoric triamide, dimethyl sulfoxide Medium, methylene chloride, chloroform,
Halogen solvents such as dichloroethane, trichloroethane and trichloroethylene, and chlorofluorocarbon solvents.

As the washing solvent, a mixture of two or more solvents can be used. The washing solvent may contain components other than the solvent, for example, inorganic salts, a surfactant, and a detergent.

The modification treatment may be performed on the entire molded product, or may be performed only on a part of the molded product, for example, only on the surface. When the modification treatment is performed only on the surface, only the water wettability of the surface can be improved without largely changing the properties of the whole molded article.

The oxygen permeability of the polymer of the present invention is preferably 70 × 10 ⁻¹¹ (cm ² / sec) mLO ₂ / (mL · hPa) or more.

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

[0048]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. <Measurement methods> Various measurements in this example were performed by the following methods. (1) Proton nuclear magnetic resonance spectrum Measured using EX270 type manufactured by JEOL Ltd. Chloroform-d was used as a solvent. (2) Gas chromatography (GC) A GC-18A type (detector: flame ionization detector) manufactured by Shimadzu Corporation was used for 1 minute at 100 ° C using a capillary column (TC-5HT) manufactured by GL Sciences. 340 ° C at a rate of 10 ° C / min.
The temperature was measured by a temperature raising program (inlet temperature: 340 ° C., detector temperature: 360 ° C.) for 5 minutes. Helium was used as the carrier gas. (3) Oxygen Permeability Coefficient The oxygen permeability coefficient of the contact lens-shaped sample was measured in water at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Kogyo.

Example 1 A 200-mL eggplant flask was reacted with methacrylic acid and 3-glycidoxypropylmethylbis (trimethylsiloxy) silane using sodium methacrylate as a catalyst described in JP-A-56-22325. The following formulas (d) and (d ') synthesized

[0050]

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Siloxanyl monomer mixture 4 represented by
0 g (95 mmol), 14.36 g of triethylamine
(142 mmol) and 80 ml of ethyl acetate.
While stirring with acetyl chloride 10.1 ml (142 mm
ol) was added dropwise. After the reaction solution was stirred at room temperature for 2 hours, the precipitate was removed by filtration, ethyl acetate was added, and the mixture was washed twice with a saturated aqueous solution of sodium hydrogen carbonate and once with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, and dried with an evaporator. Was distilled off. The obtained liquid was purified by distillation under reduced pressure to obtain a transparent liquid. In the GC of the obtained liquid, two peaks (peak area ratio 82/18) were observed. When the molecular weights of the compounds contained in these peaks were determined by GC-MS, the compounds contained in any of the peaks showed the same molecular weight. Therefore, it was confirmed that the compounds contained in these peaks were mutually isomers. did it. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of this liquid, it was found to be around 0 ppm (3H), around 0.1 ppm (18H), 0.4 ppm
Around (2H), around 1.5 ppm (2H), 1.9 pp
m (3H), 2.1 ppm (3H), 3.4p
pm (1H), 3.6 ppm (2H), 4.2
around ppm (1H), around 4.4 ppm (1H), 5.
Around 2 ppm (1H), around 5.6 ppm (1H),
Since a peak was detected at around 6.1 ppm (1H), it was considered to be a mixture of the compounds represented by the following formulas (M1) and (M1 ′).

[0052]

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Example 2 Methacrylic acid and 3-glycidoxypropyltris were prepared by using sodium methacrylate described in JP-A-56-22325 as a catalyst in place of the siloxanyl monomer mixtures (d) and (d '). The following formulas (e) and (e ') synthesized by a method of reacting (trimethylsiloxy) silane

[0054]

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The same synthesis as in Example 1 was carried out using the siloxanyl monomer mixture represented by As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid,
Around 0.1 ppm (27H), around 0.4 ppm (2
H), around 1.5 ppm (2H), around 1.9 ppm (3H), around 2.1 ppm (3H), around 3.4 ppm (1H), around 3.6 ppm (2H), 4.2 ppm.
Around (1H), around 4.4 ppm (1H), 5.2pp
m (1H), 5.6 ppm (1H), 6.1p
Since a peak was detected near pm (1H), it was considered to be a mixture of compounds represented by the following formulas (M2) and (M2 ′). The GC peak area ratio of this mixture was 87/13.

[0056]

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Example 3 The same synthesis as in Example 1 was carried out using propionyl chloride instead of acetyl chloride. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, it was found that it was around 0 ppm (3H), around 0.1 ppm (18H), 0.4 pp.
m (2H), 1.1 ppm (3H), 1.5p
pm (2H), 1.9 ppm (3H), 2.3
around ppm (2H), around 3.4 ppm (1H),
Around 3.6 ppm (2H), around 4.2 ppm (1
H) 4.4 ppm (1H), 5.2 ppm (1H), 5.6 ppm (1H), and 6.1 ppm (1H).
And a mixture of compounds represented by (M3 '). The GC peak area ratio of this mixture was 84/1.
It was 6.

[0058]

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Example 4 The same synthesis as in Example 2 was carried out using propionyl chloride instead of acetyl chloride. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, 0.1 pp
m (27H), around 0.4 ppm (2H), 1.1
around 1 ppm (3H), around 1.5 ppm (2H),
Around 9 ppm (3H), around 2.3 ppm (2H),
Around 3.4 ppm (1H), around 3.6 ppm (2
H) A peak was detected at around 4.2 ppm (1H), around 4.4 ppm (1H), around 5.2 ppm (1H), around 5.6 ppm (1H), and around 6.1 ppm (1H). It is considered to be a mixture of compounds represented by the following formulas (M4) and (M4 ′). G of this mixture
The peak area ratio of C was 86/14.

[0060]

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Example 5 Example 1 using butyryl chloride instead of acetyl chloride
The same synthesis as described above was performed. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, it was found to be about 0 ppm (3H), about 0.1 ppm (18H), 0.4 ppm
Around (2H), around 0.9 ppm (3H), 1.5pp
m (2H), 1.7 ppm (2H), 1.9p
pm (3H), 2.3 ppm (2H), 3.4
3. around ppm (1H), around 3.6 ppm (2H),
Around 2 ppm (1H), around 4.4 ppm (1H),
Around 5.2 ppm (1H), 5.6 ppm (1
H), a peak was detected at around 6.1 ppm (1H), and it is considered to be a mixture of compounds represented by the following formulas (M5) and (M5 ′). The GC peak area ratio of this mixture was 85/15.

[0062]

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Example 6 Example 2 using butyryl chloride instead of acetyl chloride
The same synthesis as described above was performed. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, it was found that it was around 0.1 ppm (27H), around 0.4 ppm (2H), 0.9 pp.
m (3H), 1.5 ppm (2H), 1.7p
pm (2H), 1.9 ppm (3H), 2.3
around ppm (2H), around 3.4 ppm (1H),
Around 6 ppm (2H), around 4.2 ppm (1H),
4.4 ppm (1H), 5.2 ppm (1
H) Since peaks were detected at around 5.6 ppm (1H) and around 6.1 ppm (1H), it was considered to be a mixture of compounds represented by the following formulas (M6) and (M6 ′). The GC peak area ratio of this mixture was 85/15.
Met.

[0064]

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Example 7 The same synthesis as in Example 1 was carried out using methoxyacetyl chloride instead of acetyl chloride. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, 0 pp
m (3H), around 0.1 ppm (18H), 0.4
around ppm (2H), around 1.5 ppm (2H), 1.
Around 9 ppm (3H), around 3.4 ppm (4H),
Around 3.6 ppm (2H), around 4.0 ppm (2H)
H) A peak was detected at around 4.2 ppm (1H), around 4.4 ppm (1H), around 5.2 ppm (1H), around 5.6 ppm (1H), and around 6.1 ppm (1H). It is considered to be a mixture of compounds represented by the following formulas (M7) and (M7 ′). G of this mixture
The peak area ratio of C was 83/17.

[0066]

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Example 8 The same synthesis as in Example 2 was carried out using methoxyacetyl chloride instead of acetyl chloride. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, 0.1
around ppm (27H), around 0.4 ppm (2H),
Around 1.5 ppm (2H), around 1.9 ppm (3
H) around 3.4 ppm (4H), around 3.6 ppm (2H), around 4.0 ppm (2H), around 4.2 ppm (1H), around 4.4 ppm (1H), 5.2 ppm.
Around (1H), around 5.6 ppm (1H), 6.1pp
m (1H), the following formula (M
It is considered to be a mixture of the compounds represented by 8) and (M8 '). The GC peak area ratio of this mixture was 87.
/ 13.

[0068]

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Example 9 Instead of the siloxanyl monomer mixtures (d) and (d '), methacrylic acid and 3-glycidoxypropylmethylbis were used by using sodium methacrylate as a catalyst described in JP-A-56-22325 as a catalyst. The following formulas (f) and (f ′) synthesized by reacting (trimethylsiloxy) silane using acrylic acid and sodium acrylate instead of methacrylic acid and sodium methacrylate

[0070]

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The same synthesis as in Example 1 was carried out using the siloxanyl monomer mixture represented by As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid,
Around 0.1 ppm (27H), around 0.4 ppm (2
H), around 1.5 ppm (2H), around 1.9 ppm (3H), around 2.1 ppm (3H), around 3.4 ppm (1H), around 3.6 ppm (2H), 4.2 ppm.
Around (1H), around 4.4 ppm (1H), 5.2pp
m (1H), 5.6 ppm (1H), 6.1p
Since peaks were detected at around pm (1H) and around 6.4 ppm (1H), it was considered to be a mixture of compounds represented by the following formulas (M9) and (M9 ′). The GC peak area ratio of this mixture was 85/15.

[0072]

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Example 10 A mixture (30 parts by weight) of the compounds of the formulas (M1) and (M1 ') obtained in Example 1, N, N-dimethylacrylamide (40 parts by weight), and a poly (methacrylate-terminated) Dimethyl siloxane (molecular weight about 1000, 30 parts by weight), triethylene glycol dimethacrylate (1 part by weight),
Darocur 1173 (CIBA, 0.2 parts by weight) was mixed and stirred. A homogeneous and clear monomer mixture was obtained. The monomer mixture was degassed under an argon atmosphere. Inject into a contact lens mold made of transparent resin (poly 4-methylpentene-1) in a glove box under a nitrogen atmosphere, and irradiate with light (1 mW / cm) using a trap lamp.
² , 10 minutes) and polymerized to obtain a contact lens-shaped sample.

After the obtained lenticular sample was hydrated, it was immersed in a 5% by weight aqueous solution of polyacrylic acid (molecular weight: about 150,000) and modified at 40 ° C. for 8 hours. After the modification treatment, the vial was sufficiently washed with purified water, immersed in a borate buffer (pH 7.1 to 7.3) in the vial, and the vial was sealed. The vial was placed in an autoclave and boiled at 120 ° C. for 30 minutes. After cooling, the lenticular sample was taken out of the vial, and the borate buffer (pH 7.1) was removed.
~ 7.3).

The obtained sample was transparent and free from turbidity. When this sample was subjected to a hydration treatment, the oxygen permeability coefficient was 79 × 10 ⁻¹¹ (cm ² / sec) mLO ₂ / (mL · hPa), indicating high transparency and high oxygen permeability.

Examples 11 to 18 Using the mixture of monomers obtained in Examples 2 to 9, contact lens-shaped samples were obtained in the same manner as in Example 10. All of the obtained samples were transparent and free from turbidity. The oxygen permeability coefficient [× 10 ⁻¹¹ (cm ² / sec) mLO ₂ / (mL · hPa)] of these samples after hydration treatment is as shown in the table below. Had the nature.

[0077]

[Table 1]

Comparative Example A monomer mixture was prepared using 3-tris (trimethylsiloxy) silylpropyl methacrylate in the same molar ratio as in Example 10, but the mixture was not sufficiently mixed and the phases were separated. This monomer mixture was irradiated with light and polymerized in the same manner as in Example 10, but no transparent contact lens-shaped sample was obtained.

[0079]

According to the present invention, there is provided a monomer which is obtained by polymerizing the polymer and has high oxygen permeability and transparency.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02C 7/04 G02C 7/04 4J100 F-term (Reference) 2H006 BB01 BB03 BB05 BB09 4C081 AB22 AB23 CA271 4C097 AA24 AA25 BB01 BB02 DD01 EE13 SA10 4H049 VN01 VP02 VQ03 VQ78 VR22 VR23 VR41 VR42 VU29 4J027 AC02 AC03 AC04 AC06 AC09 BA04 BA05 BA06 BA07 BA13 BA14 BA15 CB01 CB04 CB09 CB10 CC02 CC03 CC04 CD04 4J100 AJ02Q AJ08P ABA08 BAJ08A JA33 JA34

Claims (11)

[Claims] 1. A monomer having a polymerizable unsaturated double bond and a siloxanyl group and having a substituent having an ester group in a side chain. 2. The monomer according to claim 1, wherein the substituent having an ester group has an ether bond and / or a polyalkylene glycol chain. 3. A monomer represented by the following general formula (a) or (a '). Embedded image [A represents a siloxanyl group. R ¹ represents H or a methyl group. R ² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and the following formula (c): Represents a substituent selected from the group consisting of In the formula (c), R
³ represents H or a methyl group, and R ⁴ is a substituent selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms and an aryl group optionally having 6 to 20 carbon atoms. And k represents an integer of 0 to 200. ] 4. The monomer according to claim 3, wherein in the general formula (a) or (a ′), the siloxanyl group (A) is a substituent represented by the following formula (b). Embedded image [In the formula (b), A ^{1 to} A ¹¹ each independently represent H, an alkyl group having 1 to 20 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may be substituted. Indicates one of them. n represents an integer of 0 to 200;
b and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ] 5. In the general formula (a) or (a ′), the siloxanyl group (A) is a tris (trimethylsiloxy) silyl group, a bis (trimethylsiloxy) methylsilyl group,
The monomer according to claim 3, which is a substituent selected from a trimethylsiloxydimethylsilyl group. 6. A polymer comprising the monomer according to claim 1 as a polymerization component. 7. The polymer according to claim 6, wherein the ratio of the number of substituents having ester groups / the number of siloxanyl groups is in the range of 0.1 to 1. 8. A polymer which is a homopolymer of the monomer according to claim 1. 9. A polymer containing the monomer according to claim 1 as a polymerization component in a range of 10% to 80%. 10. An ophthalmic lens comprising the polymer according to claim 6. 11. A contact lens comprising the polymer according to claim 6.