JP2000191667A - Monomer for lens for eye, polymer for lens for eye, and contact lens using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound excellent in compatibility with a hydrophilic monomer such as hydroxyethyl methacrylate and useful for lens for eye such as contact lens having high oxygen permeability, high hydrophilic property and low elastic modulus. SOLUTION: This compound is represented by formula I [R1 is H or methyl; R2 to R4 are each H, a (substituted) alkyl or a (substituted) aryl; (a) is 0-3 when R1 is H or 0-1 when R1 is methyl; (k) is 0-20], e.g. a compound of formula II (Me is methyl). The compound of formula I, e.g. a compound of formula II is obtained by reacting 3-glycidoxypropyldimethylethoxy-silane with methoxytrimethylsilane in water at room temperature and reacting the resultant compound with methacrylic acid in the presence of hydroquinone and potassium hydroxide. This polymer is obtained from the compound. The polymer is useful as lens for eye, artificial cornea, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a monomer for an ophthalmic lens and a polymer for an ophthalmic lens. The monomer for an ophthalmic lens and the polymer for an ophthalmic lens are 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. But 3- [Tris
(Trimethylsiloxy) silyl] propyl methacrylate is inferior in compatibility with hydrophilic monomers such as 2-hydroxyethyl methacrylate, and when copolymerized therewith, there is a drawback that a transparent polymer cannot be obtained.

For example, Japanese Patent Publication Nos. 56-39450 and 56-40324 describe monomers represented by the following formulas (b1) and (b2).

[0005]

Embedded image These monomers have excellent compatibility with a hydrophilic monomer such as 2-hydroxyethyl methacrylate, and have a feature that a polymer obtained by polymerizing the monomer has high oxygen permeability and high hydrophilicity.

However, the polymer obtained by polymerizing these monomers has a high elastic modulus, and has a drawback that, for example, when used as a soft contact lens, the feeling of wearing is poor.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an ophthalmic lens polymer which is excellent in compatibility with a hydrophilic monomer such as 2-hydroxyethyl methacrylate, and is obtained by polymerizing the polymer. An object of the present invention is to provide an ophthalmic lens monomer having high hydrophilicity and low elastic modulus.

[0008]

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

"(1) A monomer for an ophthalmic lens represented by the following general formula (a):

[0010]

Embedded image [R ¹ represents H or a methyl group.

R ^{2 to} R ⁴ each independently represent H, a substituent selected from an optionally substituted alkyl group and an optionally substituted aryl group.

A represents an integer of 0 to 3 when R ¹ is H;
When R ¹ is a methyl group, it represents an integer of 0 to ¹ .

K represents an integer of 0 to 20. (2) A polymer for an ophthalmic lens, comprising the monomer for an ophthalmic lens according to the above (1) as a polymerization component.

(3) A contact lens using the polymer described in the above item (2). "

[0015]

Embodiments of the present invention will be described below.

The monomer for an ophthalmic lens of the present invention has the following constitution.

"A monomer for an ophthalmic lens represented by the following general formula (a):

[0018]

Embedded image [R ¹ represents H or a methyl group.

R ^{2 to} R ⁴ each independently represent H, a substituent selected from an optionally substituted alkyl group and an optionally substituted aryl group.

A represents an integer of 0 to 3 when R ¹ is H;
When R ¹ is a methyl group, it represents an integer of 0 to ¹ .

K represents an integer of 0 to 20. ]] Hereinafter, each substituent in the formula (a) will be described.

R ¹ represents H or a methyl group.

R ^{2 to} R ⁴ each independently represent H, a substituent selected from an optionally substituted alkyl group and an optionally substituted aryl group, and preferred examples thereof include H, methyl Group, ethyl group, propyl group, butyl group,
Pentyl, hexyl, 2-ethylhexyl, octyl, decyl, undecyl, dodecyl, octadecyl, cyclohexyl, benzyl, phenyl, naphthyl and the like. Among them, H, a methyl group, an ethyl group and a phenyl group are preferred, and a methyl group is most preferred.

A represents an integer of 0 to 3 when R ¹ is H;
When R ¹ is a methyl group, it represents an integer of 0 to 1. In order to provide high oxygen permeability, preferably, when R ¹ is H, 1
Represents an integer of ¹ to 3, and represents ¹ when R ¹ is a methyl group.

K represents an integer of 0 to 20, and is preferably 0 or 1 in order to provide high oxygen permeability.
Most preferably, it is 0.

Among the monomers represented by the general formula (a), those preferable in terms of balance between oxygen permeability, hydrophilicity and elastic modulus are monomers represented by the following formulas (M1) to (M8). The most preferred are the monomers represented by the formulas (M1) to (M4).

[0027]

Embedded image The monomer for an ophthalmic lens of the present invention has a hydrophobic silicon group, a hydrophilic hydroxyl group and an ether bond in its molecule. This silicon group has a function of improving the oxygen permeability of the obtained copolymer.
However, those having a silicon group, especially those having no hydrophilic group in the molecule, have extremely strong water repellency and are difficult to use as polymers for ophthalmic lenses without copolymerization with a hydrophilic monomer. . However, a hydrophobic monomer having no hydrophilic group has poor copolymerizability with the hydrophilic monomer, and when the amount of the hydrophilic monomer is increased, the obtained copolymer becomes opaque. (In order to increase oxygen permeability, the number of silicon groups must be increased correspondingly. However, since doing so increases the water repellency, it is necessary to copolymerize more hydrophilic monomers.) However, the monomer for an ophthalmic lens of the present invention,
Since it has a hydroxyl group and an ether bond that are hydrophilic in the molecular structure, it is compatible with the hydrophilic monomer at an arbitrary ratio and has good copolymerizability, so that the obtained copolymer is colorless and transparent even when containing water. It becomes.

The polymer for an ophthalmic lens of the present invention can be obtained by polymerizing the monomer for an ophthalmic lens represented by the general formula (a) alone or by copolymerizing with another monomer. is there. The copolymerizable monomer when copolymerized with another monomer is not particularly limited as long as copolymerization is possible, and may be a (meth) acryloyl group, a styryl group, an allyl group, a vinyl group, or another copolymerizable carbon carbon. Monomers having unsaturated bonds can be used.

Hereinafter, some examples will be given, but the present invention is not limited to these examples. (Meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinylbenzoic acid, methyl
Alkyl (meth) acrylates such as (meth) acrylate and ethyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol monoalkyl ether (meth) acrylate, polyalkylene glycol bis (meth) acrylate, trimethylol Multifunctional (meth) acrylates such as propane tris (meth) acrylate, pentaerythritol tetrakis (meth) acrylate, siloxane macromer having a carbon-carbon unsaturated bond at both terminals, trifluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) ) Halogenated alkyl (meth) such as acrylate
Hydroxyalkyl (meth) acrylates having a hydroxyl group such as acrylates, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, N, N-dimethylacrylamide, N, N
-Diethylacrylamide, N, N-di-n-propylacrylamide, N, N-diisopropylacrylamide, N, N-din-butylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, N
(Meth) acrylamides such as -acryloylpyrrolidine, N-methyl (meth) acrylamide, styrene,
aromatic vinyl monomers such as α-methylstyrene and vinylpyridine; maleimides; heterocyclic vinyl monomers such as N-vinylpyrrolidone; 3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylate;
-[Bis (trimethylsiloxy) methylsilyl] propyl (meth) acrylate, 3-[(trimethylsiloxy) dimethylsilyl] propyl (meth) acrylate,
3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylamide, 3- [bis (trimethylsiloxy) methylsilyl] propyl (meth) acrylamide, 3-[(trimethylsiloxy) dimethylsilyl] propyl (meth) acrylamide, [Tris (Trimethylsiloxy) silyl] methyl (meth) acrylate, [bis (trimethylsiloxy) methylsilyl] methyl (meth) acrylate, [(trimethylsiloxy) dimethylsilyl] methyl (meth) acrylate, [tris (trimethylsiloxy) silyl] methyl ( (Meth) acrylamide, [bis (trimethylsiloxy) methylsilyl] methyl (meth) acrylamide, [(trimethylsiloxy)
[Dimethylsilyl] methyl (meth) acrylamide, [tris (trimethylsiloxy) silyl] styrene, [bis (trimethylsiloxy) methylsilyl] styrene,
[(Trimethylsiloxy) dimethylsilyl] styrene,
And compounds of the following formulas (c1) to (c20).

[0030]

Embedded image

Embedded image

Embedded image

Embedded image [In the formulas (c1) to (c20), R ¹¹ represents H or a methyl group. R ¹² represents a substituent selected from H, an optionally substituted alkyl group and an optionally substituted aryl group. R ¹³ and R ¹⁴ each independently represent a substituent selected from H, an optionally substituted alkyl group and an optionally substituted aryl group, and R ¹³ and R ¹⁴ are bonded to each other to contain N It may form a ring. Hereinafter, specific examples of each substituent in formulas (c1) to (c20) will be described.

R ¹¹ represents H or a methyl group.

R ¹² represents a substituent selected from H, an optionally substituted alkyl group and an optionally substituted aryl group. Preferred examples thereof include a methyl group, an ethyl group and a propyl group. , Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, undecyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl Group, benzyl group, hydroxymethyl group, 2-hydroxyethyl group,
2-hydroxypropyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxybutyl group, 4-hydroxybutyl group, 2-hydroxypentyl group, 5-hydroxypentyl group, 2-hydroxyhexyl group, 6-hydroxyhexyl group, 3-methoxy-2-hydroxypropyl group, 3-ethoxy-2-hydroxypropyl group, phenyl group, 4-hydroxyphenyl group, 2-hydroxyphenyl group, 4-methoxyphenyl group, 2-methoxy A phenyl group and the following formulas (d1) to
And a substituent represented by (d10).

[0033]

Embedded image [In the formulas (d1) to (d10), m represents an integer of 2 to 20. R ¹³ and R ¹⁴ each independently represent H, a substituent selected from an optionally substituted alkyl group and an optionally substituted aryl group, and R ¹³ and R ¹⁴ are bonded to each other to form N A preferred example of the substituent may be the same as the above-mentioned preferred example of R ¹² . When R ¹³ and R ¹⁴ are bonded to each other to form a ring containing N, specific examples of the portion represented by the following structure (e) include:

Embedded image The following formulas (e1) to (e7) can be exemplified.

[0034]

Embedded image In the polymer for ophthalmic lenses of the present invention, two or more copolymerizable carbon-carbon unsaturated molecules in one molecule means that good mechanical properties can be obtained and good resistance to disinfectants and cleaning solutions can be obtained. It is preferable to use a monomer having a bond 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 (co) polymerization ratio of the monomer for an ophthalmic lens represented by the general formula (a) in the polymer for an ophthalmic lens of the present invention is such that high oxygen permeability and high hydrophilicity are compatible. Is 30% by weight to 100% by weight, more preferably 50% by weight to 99% by weight, and most preferably 60% by weight when other silicon group-containing monomer is not copolymerized.
When copolymerizing another silicon group-containing monomer, the total of the ophthalmic lens monomer represented by the general formula (a) and the other silicon group-containing monomer is 30% by weight or more.
100% by weight, more preferably 50% to 99% by weight, most preferably 60% to 95% by weight.

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

When the polymer for an ophthalmic lens of the present invention is obtained by (co) polymerization, a thermal polymerization initiator represented by a peroxide or an azo compound or a photopolymerization initiator is added to facilitate polymerization. Is preferred. In the case of performing the thermal polymerization, a material having an optimum decomposition characteristic for a desired reaction temperature is selected and used. Generally, the 10-hour half-life temperature is 40
Azo initiators and peroxide initiators at -120 ° C are preferred. 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 for an ophthalmic lens of the present invention is obtained by (co) 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, methyl alcohol, ethyl alcohol, normal propyl alcohol,
Isopropyl alcohol, normal butyl alcohol,
Alcohol solvents such as isobutyl alcohol and tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, glycol ether solvents such as triethylene glycol dimethyl ether, ethyl acetate, Ester solvents such as butyl acetate, amyl acetate, ethyl lactate and methyl benzoate; aliphatic hydrocarbon solvents such as normal hexane, normal heptane and normal octane; alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane. Solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene System solvent, are those of petroleum solvents such as various, it can be used alone or in combination.

As the polymerization method and the molding method of the polymer for an ophthalmic lens of the present invention, known methods can be used. For example, there are a method of once polymerizing and shaping into a round bar or a plate shape, and processing this into a desired shape by cutting or the like, a mold polymerization method, a spin cast polymerization method, and the like.

An example in which a monomer composition containing the monomer for an ophthalmic lens of the present invention is polymerized by a mold polymerization method to obtain an ophthalmic lens will be described below.

The monomer composition is filled into the space between two molds having a predetermined shape. Then, photopolymerization or thermal polymerization is performed to shape the mold. The mold is
It 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 for an ophthalmic lens, in many cases, a void is formed by two opposing molds, and the void is filled with the monomer composition, but depending on the shape of the mold and the properties of the monomer. May be used in combination with a gasket having a purpose of giving a certain thickness to the ophthalmic lens and preventing 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 heated in an oven or a liquid tank to be polymerized. There may be a method in which heat polymerization is performed after the photopolymerization, or conversely, a method in which both photopolymerization is performed after the heat polymerization is used. 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 raised from around room temperature, and the temperature is raised to 60 ° C to 20 ° C over several hours to several tens of hours.
The condition of increasing the temperature to 0 ° C. is preferred in order to maintain the optical uniformity and quality of the ophthalmic lens and to enhance the reproducibility.

The polymer for an ophthalmic lens of the present invention has a water wettability based on a dynamic contact angle with pure water (at the time of advance, when the immersion rate is 0.1
mm / sec) is preferably 130 ° or less, more preferably 120 ° or less, and most preferably 100 ° or less. The water content is preferably 3% to 50%, more preferably 5% to 50%, and most preferably 7% to 50%. The oxygen permeability is determined by the oxygen permeability coefficient [ml (STP) cm · cm ⁻² · sec ^-1 ·
mmHg ^-1 ] 60 × 10 ^-11 or more, preferably 70 × 1 ^-11
It is more preferably 0 ^-11 or more, most preferably 80 × 10 ^-11 or more. The tensile modulus is preferably 0.01 to 30 MPa, more preferably 0.1 to 7 MPa.

The polymer for an ophthalmic lens of the present invention is particularly suitable as an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.

[0044]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto.

[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) Dynamic Contact Angle A film-like sample having a size of about 5 mm × 10 mm × 0.2 mm was used as a sample, and was manufactured by Resca WE
The dynamic contact angle at the time of advance with respect to pure water was measured using Model T-6000. The immersion speed was 0.1 mm / sec, and the immersion depth was 7 mm.

(3) Oxygen Permeability Coefficient The oxygen permeability coefficient of a film sample was measured in water at 35 ° C. using a Kakenhi type film oxygen permeability system manufactured by Rika Seiki Kogyo.

(4) Tensile modulus As a sample, 19.5 mm × 15 mm × 0.2 mm
It was measured using a film-shaped material of about the size and using Tensilon RTM-100 manufactured by Orientec. The tensile speed was 100 mm / min, and the distance between grips was 5 mm.

(5) Moisture Content A film having a size of about 10 mm × 10 mm × 0.2 mm was used as a sample. The sample was dried in a vacuum dryer at 40 ° C. for 16 hours, and the weight of the sample (W
d) was measured. Then, the sample was immersed in pure water and kept in a constant temperature bath at 40 ° C. for one night or more to contain water. Then, the surface water was wiped off with a Kimwipe and the weight (Ww) was measured. The water content was determined by the following equation.

Water content (%) = 100 × (Ww−Wd) / Ww Reference Synthesis Example 1 (1) Methyl acrylate (4
8.0 g), 3-aminopropyltris (trimethylsiloxy) silane (200.0 g), ethyl acetate (250 g)
ml) and stirred at room temperature for 7 days. After completion of the reaction, the solvent was removed using a rotary vacuum evaporator, and then vacuum distillation was performed to obtain a transparent liquid. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of this liquid, it was found that it was around 0.1 ppm (27H), around 0.4 ppm (2H), around 1.5 ppm (3H), around 2.6 ppm (4H), 2.9 ppm. Near (2H) and 3.7p
Since a peak was detected near pm (3H), it was confirmed that the compound was represented by the formula (K).

[0052]

Embedded image (2) In a 200 ml eggplant-shaped flask, a compound of the formula (K) (88.0 g) and glycidyl methacrylate (2
9.9 g) and stirred at 60 ° C. for 18 hours. After completion of the reaction, volatile components were removed at 60 ° C. for 5 hours under reduced pressure. The proton nuclear magnetic resonance spectrum of the obtained liquid was measured and analyzed.
Around 4 ppm (2H), around 1.5 ppm (2H),
Around 1.9 ppm (3H), around 2.3 to 4.3 ppm (15H), around 5.6 ppm (1H) and 6.1p
pm (1H), the equation (L
It was confirmed that the monomer was a compound represented by 1) as a main component.

[0053]

Embedded image Example 1 Synthesis of Monomer for Ophthalmic Lens-1 (1) Water (500 g) and 3-glycidoxypropyldimethylethoxysilane (50.0) were placed in a 1 L Erlenmeyer flask.
g) and methoxytrimethylsilane (72.0 g) were added, and the mixture was stirred at room temperature for 10 hours using a magnetic stirrer, and then allowed to stand overnight. Since the reaction solution was separated into an organic layer and an aqueous layer, they were separated, and the aqueous layer was further extracted with ethyl ether. The organic layer and the ethyl ether extract were mixed, and anhydrous sodium sulfate was added to perform dehydration. Then, sodium sulfate was removed by filtration, and the solvent was distilled off using a rotary vacuum evaporator. Separation and purification were performed by distillation under reduced pressure to obtain a colorless transparent liquid (41.8 g). As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of this liquid, it was found that it was around 0.1 ppm (15H), around 0.5 ppm (2H), around 1.6 ppm (2H), around 2.6 ppm (1H), 2.8 ppm. Around (1H), 3.2 ppm
Around (1H), around 3.5 ppm (3H) and 3.7
Since a peak was detected near ppm (1H), it was confirmed that the compound was represented by the following formula (J1).

[0054]

Embedded image (2) 20 equipped with a cooling pipe, a stirrer, and a dropping funnel
In a 0 ml three-necked flask, the compound of the formula (J1) (20.
0g), hydroquinone (0.06 g) and potassium hydroxide (0.50 g), and methacrylic acid (13.12 g) was added thereto under stirring at room temperature under a nitrogen atmosphere.
It was added dropwise over 0 minutes. After completion of dropping, 100
Reaction was carried out at 8 ° C for 8 hours. After standing overnight, hexane (50 ml) was added and the mixture was stirred at room temperature for 2 hours. The precipitate was removed by filtration, and the hexane solution was washed several times with 0.5 M sodium hydroxide, and further washed three times with a saturated saline solution. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Furthermore, at 60 ° C under reduced pressure
The volatile components were removed over time, and a colorless transparent liquid (20.0
g) was obtained. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum, it was found that the concentration was around 0.1 ppm (15H), 0.5 pp.
m (2H), 1.6 ppm (2H), 1.9p
pm (3H), 2.6 ppm (1H), 3.3
About 4.3 ppm (7H), about 5.6 ppm (1
H) and peaks were detected around 6.1 ppm (1H), and it was confirmed that the mixture was a mixture containing the monomer for an ophthalmic lens represented by the formula (M1) as a main component.

[0055]

Embedded image Example 2 Synthesis of Ophthalmic Lens Monomer-2 (1) 20 equipped with a cooling tube, a stirrer, and a dropping funnel
In a 0 ml three-necked flask, toluene (50 ml), allyl glycidyl ether (60.0 g), chloroplatinic acid · 6
Hydrate (5 mg) and 2,6-di-tert-butyl-4-methylphenol (25 mg) were charged. To this, tris (trimethylsiloxy) silane (29.67 g) was added dropwise over 40 minutes while stirring at 70 ° C. After completion of the dropwise addition, the reaction was carried out at 100 ° C. for 50 hours with stirring. After the completion of the reaction, the solvent was removed using a rotary vacuum evaporator, and the mixture was distilled under reduced pressure to obtain a colorless transparent liquid (25.8 g). As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of this liquid, 0.1 p
pm (27H), 0.4 ppm (2H),
Around 6 ppm (2H), around 2.6 ppm (1H),
Around 2.8 ppm (1H), around 3.2 ppm (1H)
H) Since peaks were detected at around 3.4 ppm (3H) and around 3.7 ppm (1H), the following formula (J
2)

Embedded image It was confirmed that the compound was represented by the following formula:

(2) A compound of the formula (J2) (10.23 g) and hydroquinone (0.03 g) were placed in a 200 ml three-necked flask equipped with a condenser, a stirrer and a dropping funnel.
And potassium hydroxide (0.19 g) were added thereto, and acrylic acid (3.59) was added thereto while stirring at room temperature under a nitrogen atmosphere.
g) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction was carried out at 100 ° C. for 8 hours while stirring. After leaving overnight,
Hexane (50 ml) was added and the mixture was stirred at room temperature for 2 hours.
The precipitate was removed by filtration, and the hexane solution was washed several times with 0.5 M sodium hydroxide, and further washed three times with a saturated saline solution. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Further under reduced pressure 6
Volatile components were removed at 0 ° C. for 4 hours to obtain a colorless transparent liquid (9.8 g). As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum, a value around 0.1 ppm (27H),
Around 0.5 ppm (2H), around 1.6 ppm (2H)
H) around 2.6 ppm (1H), 3.3 to 4.3 pp
m (7H), 5.8 ppm (1H), 6.1p
Since peaks were detected at around pm (1H) and around 6.4 ppm (1H), it was confirmed that the mixture was mainly composed of the monomer for ophthalmic lenses represented by the formula (M2).

[0057]

Embedded image [Example 3] Synthesis of monomer for ophthalmic lens-3 300 ml equipped with cooling tube, stirrer, and dropping funnel
In a three-necked flask, a compound of the formula (J3) (50.0 g, manufactured by Shin-Etsu Chemical Co., Ltd.)

Embedded image Hydroquinone (0.12 g) and potassium hydroxide (0.97 g) were added, and acrylic acid (21.48 g) was added dropwise thereto over about 30 minutes while stirring at room temperature under a nitrogen atmosphere. After completion of the dropwise addition, the reaction was carried out at 100 ° C. for 8 hours while stirring. After leaving overnight, hexane (85m
l) was added and the mixture was stirred at room temperature for 2 hours. The precipitate was removed by filtration, and the hexane solution was washed several times with 0.5 M sodium hydroxide, and further washed three times with a saturated saline solution. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Further, volatile components were removed under reduced pressure at 60 ° C. for 4 hours to obtain a colorless transparent liquid (35.0 g). As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum, around 0.1 ppm (21H), around 0.4 ppm (2H), around 1.6 ppm (2H), around 2.6 ppm (1H), 3.3-4. 4. around 3 ppm (7H);
Since peaks were detected at around 8 ppm (1H), around 6.1 ppm (1H), and around 6.4 ppm (1H), the mixture was mainly composed of the monomer for an ophthalmic lens represented by the formula (M3). It was confirmed.

[0058]

Embedded image Example 4 Synthesis of Monomer for Ophthalmic Lens-4 200 ml provided with a cooling tube, a stirrer, and a dropping funnel
In a three-necked flask, the formula (J1) obtained in Example 1- (1) was added.
Compound (20.0 g), hydroquinone (0.06
g) and potassium hydroxide (0.50 g) were added, and acrylic acid (1 g) was added thereto while stirring at room temperature under a nitrogen atmosphere.
0.98 g) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction was carried out at 100 ° C. for 8 hours while stirring. After standing overnight, hexane (85 ml) was added and the mixture was stirred at room temperature for 2 hours. The precipitate is removed by filtration, and the hexane solution is
After washing several times with sodium hydroxide, it is further washed with saturated saline solution.
Washed twice. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Further, volatile components were removed at 60 ° C. for 4 hours under reduced pressure to obtain a colorless transparent liquid (17.1 g). The proton nuclear magnetic resonance spectrum was measured and analyzed.
H), around 0.4 ppm (2H), around 1.6 ppm (2H), around 2.8 ppm (1H), 3.3 to 4.3.
around ppm (7H), around 5.8 ppm (1H), 6.
Around 1 ppm (1H) and around 6.4 ppm (1H)
Since the peak was detected in the above, it was confirmed that the mixture was mainly composed of the monomer for an ophthalmic lens represented by the formula (M4).

[0059]

Embedded image [Example 5] Synthesis of monomer for ophthalmic lens -5 200 ml equipped with cooling tube, stirrer, and dropping funnel
In a three-necked flask, 2-hydroxyethyl acrylate (2.32 g), hydroquinone (8 mg) and triethylamine (0.14 g) were put, and the mixture was obtained in Example 2- (1) while stirring at room temperature under a nitrogen atmosphere. The formula (J
The compound of (2) (8.21 g) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction was carried out at 85 ° C. for 8 hours while stirring. After standing overnight, it was dissolved in hexane (300 ml). The precipitate was removed by filtration, and the hexane solution was washed several times with 0.5 M sodium hydroxide, and further washed three times with a saturated saline solution. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Further, volatile components were removed under reduced pressure at 60 ° C. for 4 hours to obtain a transparent liquid. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum, around 0.1 ppm (27H), around 0.5 ppm (2H), around 1.6 ppm (2H), 2.6 ppm
Around (1H), around 3.3 to 4.3 ppm (11H),
Around 5.8 ppm (1H), Around 6.1 ppm (1H)
And a peak was detected at around 6.4 ppm (1H). Thus, it was confirmed that the mixture was mainly composed of the monomer for ophthalmic lenses represented by the formula (M6).

[0060]

Embedded image [Example 6] Synthesis of monomer for ophthalmic lens-6 200 ml equipped with a cooling tube, a stirrer, and a dropping funnel
In a three-necked flask, 2-hydroxyethyl acrylate (11.6 g), hydroquinone (0.04 g) and triethylamine (0.70 g) were placed, and the compound of the formula (J3) was stirred under a nitrogen atmosphere at room temperature while stirring. (See Example 3, 33.6 g, Shin-Etsu Chemical Co., Ltd.) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction was carried out at 85 ° C. for 8 hours while stirring. After leaving overnight, hexane (300m
l). The precipitate was removed by filtration, and the hexane solution was washed several times with 0.5 M sodium hydroxide, and further washed three times with a saturated saline solution. After dehydration by adding anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Further, volatile components were removed under reduced pressure at 60 ° C. for 4 hours to obtain a transparent liquid. As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum, a value around 0.1 ppm (21H),
Around 0.4 ppm (2H), around 1.6 ppm (2H)
H) around 2.6 ppm (1H), 3.3 to 4.3 pp
m (11H), 5.8 ppm (1H), 6.1
Since peaks were detected at around 1 ppm (1H) and around 6.4 ppm (1H), it was confirmed that the mixture was mainly composed of the monomer for ophthalmic lenses represented by the formula (M7).

[0061]

Embedded image Example 7 A mixture (21.3 parts by weight) containing the monomer for an ophthalmic lens of Formula (M1) obtained in Example 1 as a main component, and a compound of Formula (L1) obtained in Reference Synthesis Example 1 were mainly used. A mixture (63.7 parts by weight), N, N-dimethylacrylamide (7 parts by weight), acrylamide (7 parts by weight), acrylic acid (1 part by weight), triethylene glycol dimethacrylate (1 part by weight), Diethylene glycol dimethyl ether (25 parts by weight) is uniformly mixed as a solvent, and azobisisobutyronitrile (0.3 parts by weight) is added as a polymerization initiator. Then, the monomer mixture is degassed under an argon atmosphere. Poured between plates and sealed. First, polymerization was carried out at 100 ° C. for 4 hours.
From 40 to 40 ° C over 3.5 hours, then to 40 ° C
For 2 hours or more to obtain a film sample of the polymer for ophthalmic lenses.

The sample was transparent and free of turbidity. After this sample film was immersed in water at room temperature for 24 hours, various physical properties were measured. The results are shown in Table 1. The polymer for ophthalmic lenses showed high oxygen permeability, high hydrophilicity, and low elastic modulus.

Examples 8 to 10 The formula (M) obtained in Example 1
The mixture (2) containing the monomer for ophthalmic lens of 1) as a main component
(1.3 parts by weight) instead of the formula (M) obtained in Examples 2 to 4.
2) to (M4), a film-like sample of an ophthalmic lens polymer was obtained in the same manner as in Example 7, except that mixtures (21.3 parts by weight) each containing an ophthalmic lens monomer as a main component were used. .

Each sample was transparent and free from turbidity. After immersing each sample film in water at room temperature all day and night, various physical properties were measured. The results are shown in Table 1. Each ophthalmic lens polymer exhibited high oxygen permeability, high hydrophilicity, and low elastic modulus.

Comparative Example 1 A mixture (21.3) containing the monomer for an ophthalmic lens of the formula (M1) obtained in Example 1 as a main component
(Parts by weight) instead of using a mixture (21.3 parts by weight) containing a compound of the following formula (b1) as a main component in the same manner as in Example 7 to obtain a film sample of a polymer for an ophthalmic lens. Was.

[0066]

Embedded image The sample was clear and free of turbidity. After immersing the sample film in water at room temperature all day and night, various physical properties were measured. The results are shown in Table 1. Each ophthalmic lens polymer exhibited high oxygen permeability and high hydrophilicity, but had a high elastic modulus.

[0067]

[Table 1] [Examples 11 to 12] Instead of the mixture (21.3 parts by weight) containing the monomer for an ophthalmic lens of formula (M1) obtained in Example 1 (21.3 parts by weight), the formulas obtained in Examples 5 to 6 ( M6) to (M
The mixture (2) containing the monomer for ophthalmic lens of 7) as a main component
(1.3 parts by weight), and a film sample of the polymer for ophthalmic lenses was obtained in the same manner as in Example 7 except that each was used.

Each sample was transparent and free from turbidity. After immersing each sample film in water at room temperature all day and night, various physical properties were measured. The results are shown in Table 2. Each ophthalmic lens polymer exhibited high oxygen permeability, high hydrophilicity, and low elastic modulus.

Comparative Example 2 A mixture (21.3) containing the monomer for an ophthalmic lens of the formula (M1) obtained in Example 1 as a main component
(Parts by weight) instead of using a mixture (21.3 parts by weight) containing a compound of the following formula (b2) as a main component, in the same manner as in Example 7, to obtain a film sample of a polymer for an ophthalmic lens. Was.

[0070]

Embedded image The sample was clear and free of turbidity. After immersing the sample film in water at room temperature all day and night, various physical properties were measured. The results are shown in Table 1. Each ophthalmic lens polymer exhibited high oxygen permeability and high hydrophilicity, but had a high elastic modulus.

[0071]

[Table 2] Example 13 A mixture (60 parts by weight) containing the monomer for an ophthalmic lens of the formula (M1) obtained in Example 1 as a main component, 2-
Hydroxyethyl methacrylate (40 parts by weight) and triethylene glycol dimethacrylate (1 part by weight)
And Darocur 1173 (CI
(BA company, 0.5 parts by weight), the monomer mixture was degassed under an argon atmosphere, and a transparent resin (TPX) was added.
Into a contact lens mold. The sample was polymerized by light irradiation (6 J / cm ² ) using an insect lamp to obtain a polymer sample for an ophthalmic lens. The sample was clear and free of turbidity.

[Examples 14 to 18] Instead of the mixture (60 parts by weight) containing the monomer for an ophthalmic lens of the formula (M1) obtained in Example 1 (60 parts by weight), the formulas obtained in Examples 2 to 6 ( M
2) An ophthalmic solution was prepared in the same manner as in Example 13 except that a mixture (60 parts by weight) containing (M3), (M4), (M6) and (M7) as the main components of the monomer for ophthalmic lens was used. A sample of the lens polymer was obtained. All samples were clear and free of turbidity.

Comparative Example 3 Instead of the mixture (60 parts by weight) containing the monomer for the ophthalmic lens of the formula (M1) obtained in Example 1 (60 parts by weight), 3- [tris (trimethylsiloxy) silyl] propyl methacrylate was used. Example 13 except that
A polymer sample was obtained in the same manner as described above. The sample was cloudy and was unsuitable as an ophthalmic lens.

[0074]

Industrial Applicability According to the present invention, a polymer for an ophthalmic lens having excellent compatibility with a hydrophilic monomer such as 2-hydroxyethyl methacrylate and obtained by polymerizing the same has high oxygen permeability, high hydrophilicity and A monomer for an ophthalmic lens having a low elastic modulus could be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H006 BB06 4C081 AB21 AB22 AB23 BB01 BB02 BB07 CA032 CA072 CA081 CA082 CA102 CA271 CC01 CC05 DA01 DA02 DC12 EA03 EA05 4H049 VN01 VP02 VP03 VP04 VQ30 VQ78 VR21 VR23 VR40

Claims (4)

[Claims] 1. A monomer for an ophthalmic lens represented by the following general formula (a). Embedded image [R ¹ represents H or a methyl group. R ^{2 to} R ⁴ each independently represent H, a substituent selected from an optionally substituted alkyl group and an optionally substituted aryl group. a represents an integer of 0 to 3 when R ¹ is H, and represents an integer of 0 to ¹ when R ¹ is a methyl group. k represents an integer of 0 to 20. ] 2. In the general formula (a), R ^{2 to} R ⁴ each represent a methyl group, a represents an integer of 1 to 3 when R ¹ is H, and 1 when R ¹ is a methyl group. , K is 0 or 1
The monomer for an ophthalmic lens according to claim 1, wherein 3. A polymer for an ophthalmic lens comprising the monomer for an ophthalmic lens according to claim 1 as a polymerization component. 4. A contact lens using the polymer according to claim 3.