JP2012017285A - Silicone monomer, method of producing the same, monomer composition and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a silicone monomer that has large silicone content, shows high transparency and high oxygen transmission rate when the monomer is copolymerized with a polymerizable monomer such as (meth)acrylic monomer and is suitable for human eyes; a method of producing the same; and a monomer composition and polymer using the monomer.SOLUTION: One example of the silicone monomer is listed in the following. The monomer is suitable for producing a device for eyes such as contact lens.

Description

  The present invention relates to a polymerizable silicone monomer that can be used for manufacturing ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas, a manufacturing method thereof, and a monomer composition using the silicone monomer. And a polymer.

Various articles including a biological device are formed from, for example, an organic silicon compound-containing material. One organosilicon compound material useful for biomedical devices such as soft contact lenses is a silicon-containing hydrogel material. In general, silicon-based materials have higher oxygen permeability than water, and therefore, articles having higher oxygen permeability can be provided.
Organosilicon compound materials conventionally used for hard contact lenses are highly oxygen permeable, but are harder than materials used for soft contact lenses. Also, since such organosilicon compound materials are hydrophobic, manufacturing lenses using them requires additional processing to provide a hydrophilic surface.
For example, the following TRIS (3- [tris (trimethylsiloxy) silyl] propyl methacrylate) is known as an ophthalmic silicone monomer used in ophthalmic devices (Patent Document 1).

Since TRIS is also a hydrophobic monomer, when used as an ophthalmic lens material, for example, it may be copolymerized with a hydrophilic monomer. However, TRIS has poor compatibility with hydrophilic monomers such as HEMA (2-hydroxyethyl methacrylate). When copolymerized with such hydrophilic monomers, a transparent polymer cannot be obtained and used as a lens material. There is a disadvantage that it can not. In addition, many combinations with other hydrophilic monomers such as N-vinylpyrrolidone and N, N-dimethylacrylamide have a strong water repellency when containing water, so TRIS may be difficult to use as a soft contact lens material. Are known.
For the purpose of improving this, Patent Document 2 and Patent Document 3 propose SiGMA (dimethyldi (trimethylsiloxy) silylpropylglycerol methacrylate), which is used as a compatibilizer monomer in silicone hydrogel contact lens applications. Since SiGMA has an appropriate oxygen permeation performance, it also plays a role as an oxygen permeation preparation. Since this SiGMA has a hydroxyl group, it is known to express good hydrophilicity.

  As a method for reducing oligomer crosslinking components that adversely affect the wearing feeling of the lens, Patent Document 4 proposes a new method for producing the monomer. However, when the mass ratio of the siloxanyl group in one monomer molecule is defined as the silicone content, the SiGMA has a silicone content of 52.4% (the total atomic weight of each atom constituting the siloxanyl group in one molecule of SiGMA is 221). Since the molecular weight of SiGMA is 422, the silicone content at this time can be calculated as 221/422 × 100 = 52.4%.) Compared with the silicone content of TRIS of 72%, the silicon content Therefore, it was difficult to obtain sufficient oxygen permeability.

Patent Document 5 proposes a silicone monomer TMSAA represented by the following formula having an amide bond in the molecule. Since the silicone monomer has an amide group, the hydrophilicity is improved as compared with TRIS.
However, sufficient hydrophilicity has not been obtained, and when a soft contact lens is prepared using this, the lens surface becomes hydrophobic, and it is necessary to perform a hydrophilic treatment on the surface. Therefore, there has been a problem that the manufacturing process becomes complicated.

  Patent Document 6 proposes a new monomer obtained by a reaction between a methacrylic acid halide and an oligoethylene glycol-modified linear silicone. Oligoethylene glycol has a large free hydroxyl group at the end together with the ether group in the molecule and contributes to hydrophilicity. However, the hydroxyl group of the monomer does not function sufficiently because it forms an ester bond, and in order to obtain hydrophilicity It is necessary to increase the number of repeating units having an ether structure. For this reason, the silicone content in the monomer tends to decrease, and it has been difficult to satisfy both the surface hydrophilicity and oxygen permeability of the lens.

Patent Document 7 proposes a silicone monomer having a quaternary ammonium in the molecule represented by the formula (3), which is obtained by a reaction between a tertiary amine and an alkyl halide. This monomer achieves the hydrophilicity of the lens surface by polymerization, but the silicone content is 295/587 = 50.3%, which is similar to SiGMA, and it is difficult to satisfy oxygen permeability. Further, since the monomer is cationic, there is a concern that the lens surface using the monomer may cause white turbid contamination on the lens surface such as protein adsorption.

  From the above circumstances, in the field of ophthalmic silicone monomers used in ophthalmic devices, it is a silicone monomer having a hydrophilicity with a new molecular structure, which is easy to manufacture and is inexpensive for daily disposable lenses. There is a need to develop a silicone monomer that can be used and has a large proportion (silicone content) of siloxanyl groups in one monomer molecule.

US Pat. No. 3,808,178 JP 54-0661126 A Japanese Patent Application Laid-Open No. 11-310613 JP 2008-510817 A U.S. Pat. No. 4,711,943 JP 2008-202060 A JP 2009-521546 A

  An object of the present invention is a silicone suitable for application to the eye, which has a high silicone content and is assumed to have high transparency and high oxygen permeability when copolymerized with a polymerizable monomer such as a (meth) acrylic monomer. It is providing the monomer, its manufacturing method, the monomer composition and polymer using this silicone monomer.

(式（１）中、Ｒは水素原子又はメチル基を示す。Ｘは式(２a)〜式(２f)から選ばれる基を示す。ｎは０または１を表す。)

According to the present invention, a silicone monomer represented by the formula (1) is provided.

(In formula (1), R represents a hydrogen atom or a methyl group. X represents a group selected from formulas (2a) to (2f). N represents 0 or 1)

Further, according to the present invention, the silicone monomer represented by the above formula (1) comprising a step of reacting an N- (meth) acryloylamino acid obtained by reacting an amino acid and (meth) acrylic acid with an alkyl halide-modified silicone. A manufacturing method is provided.
Furthermore, according to the present invention, the silicone monomer is selected from the group consisting of 20 to 60% by mass and 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide or a mixture of two or more of these. A monomer composition containing 40 to 80% by mass of a hydrophilic monomer is provided.
Furthermore, according to the present invention, there is provided a polymer obtained by polymerizing the monomer composition.

  The silicone monomer of the present invention has a high silicone content, and since it has an amide group or an ester group derived from a hydrophilic amino acid in the molecule, it is highly hydrophilic, and other polymerizable monomers such as (meth) acrylic monomers Because of its high compatibility, when used for the purpose of copolymerization, it is considered that both transparency and oxygen permeability are satisfied at the same time, and it is useful as a silicone monomer used as a raw material for ophthalmic devices. In addition, since the monomer composition and polymer of the present invention utilize the silicone monomer of the present invention, they are useful for the production of ophthalmic devices such as contact lenses that satisfy both transparency and oxygen permeability.

2 is a chart showing ¹ H-NMR spectrum of the monomer prepared in Example 1. FIG. 2 is a chart showing the IR spectrum of the monomer prepared in Example 1. FIG. 2 is a chart showing ¹ H-NMR spectrum of the monomer prepared in Example 2. FIG. 6 is a chart showing an IR spectrum of the monomer prepared in Example 2. 4 is a chart showing ¹ H-NMR spectrum of a monomer prepared in Example 3. FIG. 4 is a chart showing an IR spectrum of a monomer prepared in Example 3. 6 is a chart showing ¹ H-NMR spectrum of the monomer prepared in Example 4. FIG. 6 is a chart showing an IR spectrum of a monomer prepared in Example 4. 6 is a chart showing ¹ H-NMR spectrum of the monomer prepared in Example 5. FIG. 6 is a chart showing an IR spectrum of a monomer prepared in Example 5. 6 is a chart showing ¹ H-NMR spectrum of the monomer prepared in Example 6. FIG. 6 is a chart showing an IR spectrum of a monomer prepared in Example 6.

Hereinafter, the present invention will be described in more detail.
The silicone monomer of the present invention is a silicone monomer of an amino acid derivative represented by the above formula (1). Here, the amino acid means an organic compound having both amino group and carboxyl group functional groups. Specifically, the monomer is a monomer in which an unsaturated polymerizable group and a siloxanyl group are chemically bonded via an amide group and an ester group by an amine and a carboxylic acid of an amino acid.
In the formula (1), R represents a hydrogen atom or a methyl group. n represents 0 or 1.

In formula (1), X represents a group selected from the above formulas (2a) to (2f).
In the silicone monomer of the present invention, it is preferable that the ratio of the siloxanyl group in one molecule is as large as possible. From this viewpoint, for example, in the formula (1), X is the formula (2a), in the formula (1) Particularly preferred are compounds wherein X is the formula (2c) and compounds wherein X is the formula (2d) in the formula (1).
In the formula (1), X is the formula (2a), R is a methyl group, and the compound represented by n = 1 is represented by the formula (4a).

式（４ａ）で表されるモノマーの分子量は４９３であり、シロキサニル基を構成する各原子の原子量の合計は２９５であることから、このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。

Since the molecular weight of the monomer represented by the formula (4a) is 493 and the total atomic weight of each atom constituting the siloxanyl group is 295, the silicone content of this monomer is 295/493 × 100 = 59.8%. It is.

式（４ｂ）で表されるモノマーの分子量は４９３であり、シロキサニル基を構成する各原子の原子量の合計は２９５であることから、このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。 In the formula (1), X is the formula (2d), R is a hydrogen atom, and the compound represented by n = 1 is represented by the formula (4b).

Since the molecular weight of the monomer represented by the formula (4b) is 493 and the total atomic weight of each atom constituting the siloxanyl group is 295, the silicone content of this monomer is 295/493 × 100 = 59.8%. It is.

  The silicone monomer of formula (4a) or formula (4b) has a high proportion of silicone content in the monomer of about 60%, which is considered to effectively increase the oxygen permeability of the resulting copolymer. Among them, it can be expected to be used as a silicone monomer for contact lenses.

The silicone monomer of the present invention includes an N- (meth) acryloyl amino acid (derivative) obtained by reacting an amino acid and a (meth) acrylic acid halide, for example, (meth) acrylic acid chloride, and a halogenated alkyl-modified silicone, for example, It can be obtained by the production method of the present invention in which 3-iodopropyl [tris (trimethyl) siloxy] silane is reacted.
Specifically, in the formula (5) (in the formula (5), R represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 6 carbon atoms which may contain an oxygen atom or a nitrogen atom. And (meth) acryloylamino acid represented by formula (6) (in formula (6), Y is halogen, preferably Br or I. n represents 0 or 1) Is a halogen, preferably Br or I.).

In the reaction, for example, a silicone compound represented by the formula (6) is represented by the formula (5) in an organic solvent containing 5 to 60% by mass of the (meth) acryloyl amino acid represented by the formula (5). It is preferable to mix 10 mol%-100 mol% with respect to the carboxylic acid of acryloyl amino acid, and to carry out at the temperature of 20-100 degreeC in a thermostat.
Preferred examples of the organic solvent include aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile.

The (meth) acryloyl amino acid represented by the above formula (5) is obtained by a known method. For example, it can be synthesized by dropping (meth) acryloyl chloride into an aqueous sodium salt solution of an amino acid under ice cooling (Journal of Applied Polymer Science, 24, 1551, 1979, US Pat. No. 4,172,934).
Since the silicone compound represented by the above formula (6) affects the purity of the resulting silicone monomer, it is preferably a high-purity product, for example, see Dokl. Akad. Nauk, SSSR, 1976, 227, 607-610; Organomet. Chem. , 1988, 340, 31-36, JP-A-2002-68930, can be obtained from trialkoxysilane or trichlorosilane and hexamethyldisiloxane, and can be purified by extraction or distillation purification. it can.

The above reaction is preferably performed in the presence of a base in order to increase the reaction rate. Preferred bases include, for example, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU). A base. More preferably, potassium carbonate and triethylamine are mentioned.
The usage-amount of the said base is about 1 mol-3 mol with respect to 1 mol of silicone compounds shown by Formula (6).

  In the reaction, it is preferable to use a polymerization inhibitor so that the (meth) acrylic group is not polymerized. Examples of the polymerization inhibitor include hydroquinone monomethyl ether, 1,4-dihydroxybenzene, dibutylhydroxytoluene and the like. The inhibitor is preferably added to the reaction solution at 100 ppm to 10000 ppm.

Since the silicone monomer obtained after the reaction is a liquid having a high boiling point and it is difficult to use recrystallization or distillation operation, purification by liquid separation washing, adsorbent treatment or the like is desirable.
When purifying by washing, a solution (hydrophobic phase) obtained by dissolving the reaction solution in a hydrocarbon such as n-hexane, cyclohexane, heptane, octane, etc., ion-exchanged water, aqueous alkali solution, aqueous alcohol solution, etc. (hydrophilic phase) It is desirable to wash with. The alkali used at this time is preferably sodium hydroxide, sodium carbonate, or sodium bicarbonate. As the alcohol used in the aqueous alcohol solution, it is desirable to use a mixture selected from methanol, ethanol, 1-propanol, 2-propanol having high polarity or a mixture thereof with water in order to form a liquid separation state.
In order to form the hydrophobic phase, it is preferable to add 0.5 to 3 times the amount of hydrocarbon by mass ratio to the reaction solution. If it is less than 0.5 times, it is difficult to separate the liquid, and if it exceeds 3 times, it is economically disadvantageous. The amount of the cleaning liquid used is preferably about the same as that of hydrocarbon.

  After the washing, using a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, a small amount of water contained in the reaction solution is dehydrated, and after filtering off the solid, the solvent is removed using, for example, an evaporator. Thus, the target product can be obtained. It is desirable to remove the solvent at about 50 ° C. or less and for about 1 hour with a vacuum pump at 10 mmHg or less.

The silicone monomer of the present invention can be used, for example, as a raw material for polymers that form ophthalmic devices. In order to produce an ophthalmic device using the silicone monomer, for example, a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a styryl group, an allyl group, or a vinyl group, which can be copolymerized with the silicone monomer of the present invention. It can be obtained by mixing and polymerizing with other monomers having a hydrophilic group such as a hydroxyl group, amide group, zwitterion, etc., in which sufficient hydrophilicity of the obtained polymer surface is further improved. it can.
The amount of the silicone monomer of the present invention used for producing an ophthalmic device varies depending on the type of other monomers used, but in order to improve the surface hydrophilicity of the obtained ophthalmic device and to control flexibility, the raw material monomer 10-80 mass% is preferable.

The monomer composition of the present invention includes the above-described silicone monomer of the present invention and, for example, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, 2- (methacryloyloxyethyl)- It contains a hydrophilic monomer selected from the group consisting of 2- (trimethylammonioethyl) phosphate or a mixture of two or more of these, and can be used as a composition for polymerization of ophthalmic devices such as contact lenses.
In the monomer composition of the present invention, the content of the silicone monomer of the present invention is 20 to 60% by mass based on the total amount of the composition, and the total content of the hydrophilic monomers is 40 based on the total amount of the composition. -80 mass%. If the content of the silicone monomer of the present invention is less than 20% by mass, the polymer obtained by polymerization may have low oxygen permeability, and if it exceeds 60% by mass, the surface wettability of the polymer obtained by polymerization May be reduced.

In the monomer composition, other monomers can be appropriately contained as required within a range not impairing the above-described properties of the silicone monomer of the present invention. Examples of other monomers include 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. Nonionic monomers such as (meth) acrylic acid, (meth) acryloyloxyethyl succinic acid, styrene sulfonic acid, (meth) acryloyloxyphosphonic acid and other anionic monomers; 2-hydroxy -Cationic monomer containing amino group or ammonium group such as 3- (meth) acryloyloxypropyltrimethylammonium chloride, aminoethyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate; N-methacryloyloxyethyl Zwitterionic monomers such as -N, N-dimethylammonium-α-N-methylcarboxybetaine, 3-[[2- (methacryloyloxy) ethyl] (dimethyl) ammonio] -1-propanesulfonate, and the like. 1 type (s) or 2 or more types can be used.
The content ratio in the case of using the other monomer can be appropriately determined within the range not impairing the desired effect of the present invention, but the total amount is usually 40% by mass based on the total amount of the monomer composition. Hereinafter, it is preferably 30% by mass or less.

The polymer of the present invention is obtained by polymerizing the monomer composition of the present invention, and can be used, for example, for the production of ophthalmic devices such as contact lenses.
The said polymerization can be performed according to well-known conditions and methods using arbitrary polymerization methods, such as thermal polymerization, photopolymerization, mold polymerization, for example. At this time, a known polymerization initiator can be appropriately used depending on the polymerization method.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In addition, each measurement in an example was performed using the following apparatuses.
1) Silicone monomer purity measurement method (GC method)
Gas chromatograph: GC system 7890A manufactured by Agilent,
Capillary column: J & W company HP-1 (0.53 mm, 30 m, 2.65 μm),
Inlet temperature: 250 ° C
Temperature rising program: 80 ° C. (0 minutes) → 20 ° C./minute→250° C. (20 minutes)
Detector: FID, 250 ° C., carrier gas: helium (5 ml / min), split ratio: 5: 1, injection volume: 2 μl.
2) ¹ H-NMR measurement method JNM-AL400 manufactured by JEOL Ltd., solvent; CDCl ₃ or CD ₃ OD (TMS standard).
3) Infrared absorption (IR) measurement method Measurement method: liquid film method, integration number: 16 times 4) Mass measurement method (LC-MS method)
LC Department: Waters 2695 Separations Module,
MS department; Waters 2695 Q-micro,
LC eluent conditions: acetonitrile / 50 mM ammonium acetate aqueous solution (9/1).

Example 1-1
Synthesis of MAglyS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloyl glycinate) (silicone content 59.8%)
In a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.4 g (0.387 mol) of methacryloylglycine and 0.35 g of p-methoxyphenol (hereinafter referred to as MQ) were added and stirred, and then 35.7 g (0 .258 mol) was added and the reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 350 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, 800 g of methanol was mixed with the heptane phase and extracted into the methanol phase, and methanol was removed under reduced pressure to obtain 101.8 g of a transparent liquid (yield 82%). The purity of the silicone compound obtained by GC was 94%. Each measurement result is shown below and in FIG.1 and FIG.2.

¹ H-NMR measurement CH ₂ ═C—: 5.78 ppm (1H), 5.43 ppm (1H), —CH ₂ —: 4.92 ppm (2H), 4.00 ppm (2H), 1.70 ppm (2H) 0.50ppm (2H)
_{-CH 3: 1.96ppm (3H),} 0.10ppm (27H).
IR measurement results 3345 cm ⁻¹ , 3090 cm ⁻¹ , 2960 cm ⁻¹ , 1745 cm ⁻¹ , 1670 cm ⁻¹ , 1625 cm ⁻¹ , 1455 cm ⁻¹ , 1255 cm ⁻¹ , 1065 cm ⁻¹ , 840 cm ⁻¹ .
As a result of measuring the molecular weight by LC-MS, the molecular weight was 493. Thus, it was identified as the compound (MAglyS) represented by the above formula (4a). The silicone content of this monomer is 295/493 × 100 = 59.8%.

Example 1-2
Synthesis of MalaS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloylalaninate) (silicone content 58.2%)
In a 1 L eggplant flask, 701.7 g of N, N-dimethylformamide, 60.87 g (0.387 mol) of methacryloylalanine and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added. The reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 108.0 g of Mala S (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below and in FIG.3 and FIG.4.

−ＣＨ₂−：４．０９ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、−ＣＨ₃：１．９６ｐｐｍ（３Ｈ）、１．４４ｐｐｍ（３Ｈ）、０．１３ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３３３５ｃｍ^-1、３０９０ｃｍ^-1、２９６０ｃｍ^-1、１７４０ｃｍ^-1、１６６０ｃｍ^-1、１６２５ｃｍ^-1、１５５０ｃｍ^-1、１２５５ｃｍ^-1、１０６５ｃｍ^-1、８４０ｃｍ^-1。
ＬＣ−ＭＳによる分子量測定の結果、分子量５０７であることから、ＭａｌａＳは、式（７）で表されることが特定された。このモノマーのシリコーン含量は２９５／５０７×１００＝５８．２％である。 ¹ H-NMR measurement CH ₂ ═C—: 5.75 ppm (1H), 5.43 ppm (1H),

_{-CH 2 -: 4.09ppm (2H)} , 1.71ppm (2H), 0.51ppm (2H), - CH 3: 1.96ppm (3H), 1.44ppm (3H), 0.13ppm (27H) .
IR measurements ^{3335cm -1, 3090cm -1, 2960cm -1} , 1740cm -1, 1660cm -1, 1625cm -1, 1550cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507, so that it was specified that MalaS was represented by the formula (7). The silicone content of this monomer is 295/507 × 100 = 58.2%.

Example 1-3
Synthesis of AbalS (3- [Tris (trimethylsiloxy) silyl] propyl-N-acryloyl-β-alaninate) (silicone content 59.8%)
To a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.43 g (0.387 mol) of acryloyl-β-alanine, and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added and reacted. The liquid was heated to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 105.5 g of AbalS (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below, and in FIG.5 and FIG.6.

¹ H-NMR measurement result CH ₂ ═CH—: 6.21 ppm (2H), 5.63 ppm (1H), —CH ₂ —: 4.04 ppm (2H), 3.51 ppm (2H), 2.58 ppm (2H) ), 1.67ppm (2H), 0.48ppm (2H), - CH 3: 0.11ppm (27H).
IR measurement result ^{3290cm -1, 3075cm -1, 2955cm -1} , 1740cm -1, 1680cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1065cm -1, 840cm -1
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507, and thus the compound (AbalS) represented by the above formula (4b) was specified. The silicone content of this monomer is 295/493 × 100 = 59.8%.

Example 1-4
Synthesis of AglylyS (N- [3-tris (trimethylsiloxy) silylpropyl] acryloylglycylglycine) (silicone content 56.5%)
In a 300 mL eggplant flask, 65.6 g of dimethyl sulfoxide, 6.41 g (0.0344 mol) of N- (N-acryloylglycyl) glycine and 0.082 g of MQ were added and stirred, and then 2.97 g (0.0215 mol) of potassium carbonate. ), And the temperature of the reaction solution was raised to 40 ° C. Further, 10.0 g (0.0215 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 65.6 g of heptane, and the heptane phase was diluted with 65.6 g of 1% sodium bicarbonate water followed by 65.6 g of 30% ethanol (w / w) aqueous solution. Washed. After washing, the heptane phase was removed under reduced pressure to obtain 6.8 g of a white solid (yield 60%). The purity of the silicone compound by GC was 82%. Each measurement result is shown below and in FIG.7 and FIG.8.

¹ H-NMR measurement CH ₂ ═CH—: 6.28 ppm (2H), 5.69 ppm (1H), —CH ₂ —: 4.08 ppm (2H), 3.97 ppm (4H), 1.69 ppm (2H) , 0.49ppm (2H), - CH 3: 0.11ppm (27H).
IR measurements ^{3295cm -1, 3080cm -1, 2960cm -1} , 1745cm -1, 1665cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1052cm -1, 840cm -1.
As a result of the structure identification by LC-MS, the molecular weight was 507, and thus it was identified as AglylyS represented by the formula (8). The silicone content of this monomer is 295/522 × 100 = 56.5%.

Example 1-5
Synthesis of MAserS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloylserine) (silicone content 58.0%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 8.38 g (0.0484 mol) of N-methacryloylserine and 0.012 g of MQ were added and stirred, and then 4.46 g (0.0323 mol) of potassium carbonate was added and the reaction solution was added. The temperature was raised to 40 ° C. Further, 15.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 120 g of heptane, and the heptane phase was washed with 120 g of 1% aqueous sodium bicarbonate followed by 120 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 13.2 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 90%. Each measurement result is shown below, and in FIG.9 and FIG.10.

¹ H-NMR measurement CH ₂ ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH ₂ —: 4. 11ppm (2H), 1.71ppm (2H ), 0.51ppm (2H), - CH 3: 1.99ppm (3H), 1.20ppm (3H), 0.11ppm (27H).
IR measurements ^{3435cm -1, 3090cm -1, 2955cm -1} , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1060cm -1, 840cm -1.
As a result of the structure identification by LC-MS, the molecular weight was 509, so that it was identified as MAserS represented by the formula (9). The silicone content of this monomer is 295/509 × 100 = 58.0%.

Example 1-6
Synthesis of MAthrS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloyl threonine) (silicone content 56.4%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 9.06 g (0.0484 mol) of methacryloyl-DL-threonine and 0.012 g of MQ were added and stirred, and then 4.46 g (0.0323 mol) of potassium carbonate was added and reacted. The liquid was heated to 40 ° C. Further, 120.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel and diluted with 96 g of heptane. After washing, the heptane phase was removed under reduced pressure to obtain 13.5 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 92%. Each measurement result is shown below, and in FIG.11 and FIG.12.

¹ H-NMR measurement CH ₂ ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH ₂ —: 4. 11ppm (2H), 1.71ppm (2H ), 0.51ppm (2H), - CH 3: 1.99ppm (3H), 1.20ppm (3H), 0.11ppm (27H).
IR measurements ^{3440cm -1, 3085cm -1, 2960cm -1} , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of structure identification by LC-MS, the molecular weight was 523, and therefore, it was identified as MAthrS represented by the formula (10). The silicone content of this monomer is 295/523 × 100 = 56.4%.

Example 2-1
60 parts by mass of hydroxyethyl methacrylate (HEMA), 40 parts by mass of the compound represented by the formula (4a) prepared in Example 1-1 (MAGlyS), 0.27 parts by mass of ethylene glycol dimethacrylate (EDMA), azobis 0.04 parts by mass of isobutyronitrile (AIBN) was mixed and dissolved uniformly. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. The following evaluation and measurement were performed on the obtained polymer. The results are shown in Table 1.

[Method of confirming uniformity of compound]
The mixture before polymerization was put into a colorless and transparent container and visually confirmed according to the following evaluation criteria.
○: Transparent, x: cloudiness or precipitation.
[Transparency evaluation method]
The transparency of the gel-like polymer obtained by swelling was visually confirmed according to the following evaluation criteria.
○: Transparent, Δ: Slightly turbid, ×: White turbidity.
[Surface wettability]
The gel-like polymer obtained by swelling was pulled up from the physiological saline, and the time until the water film on the surface was cut was measured. Judgment criteria are shown below.
○: 30 seconds or more, ×: less than 30 seconds.
[Oxygen permeability measurement method]
An oxygen transmission coefficient (Dk) was measured by a method defined in ISO18369-4 (FATT method) using a planar electrode cell of an oxygen transmission rate measuring apparatus (201T, Rehder).

Examples 2-2 to 2-5
It polymerized by the method similar to Example 2-1, and the transparent gel-like polymer was obtained by being immersed in the physiological saline. Table 1 shows the blending ratio of each monomer.

Comparative Example 1
30 parts by mass of hydroxyethyl methacrylate (HEMA), 70 parts by mass of a compound represented by the formula (4a) (MAGlyS), 0.27 parts by mass of ethylene glycol dimethacrylate (EDMA), 0. azobisisobutyronitrile (AIBN) 04 parts by mass were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. This polymer could not obtain sufficient surface hydrophilicity.

Comparative Example 2
90 parts by mass of N-vinylpyrrolidone (Vp) and 90 parts by mass of the compound represented by the formula (4a) (MAGlyS), 0.04 parts by mass of ethylene glycol dimethacrylate (EDMA), 0 of azobisisobutyronitrile (AIBN) .04 parts by mass were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. Although the obtained polymer was immersed in physiological saline and swollen, the obtained gel polymer was cloudy.

Comparative Example 3
A monomer was mixed in the same manner as in Example 2-1 except that 3- [tris (trimethylsiloxy) silyl] propyl methacrylate was used instead of the compound represented by the formula (4a) (MAGlyS), but it was not uniformly dissolved. It was.

ＭＡｇｌｙＳ：式（４ａ）で表される化合物、
ＴＲＩＳ：３−［トリス（トリメチルシロキシ）シリル］プロピルメタクリレート、
ＤＭＡ：Ｎ，Ｎ−ジメチルアクリルアミド、
ＨＥＡ：ヒドロキシエチルアクリレート、
Ｖｐ：Ｎ−ビニルピロリドン、
ＥＤＭＡ：エチレングリコールジメタクリレート、
ＡＩＢＮ：α,α'‐アゾビスイソブチロニトリル、
DK：酸素透過係数（単位は、×10^-11 (cm²/sec)・(mlO₂/ml×mmHg)）。

MAglyS: a compound represented by the formula (4a),
TRIS: 3- [Tris (trimethylsiloxy) silyl] propyl methacrylate,
DMA: N, N-dimethylacrylamide,
HEA: hydroxyethyl acrylate,
Vp: N-vinylpyrrolidone,
EDMA: ethylene glycol dimethacrylate,
AIBN: α, α′-azobisisobutyronitrile,
DK: Oxygen permeability coefficient (unit: × 10 ^-11 (cm ² / sec) · (mlO ₂ / ml × mmHg)).

  The silicone monomer, monomer composition and polymer of the present invention are suitably used for the production of ophthalmic devices such as contact lenses.

Claims (4)

A silicone monomer represented by the formula (1).

(In Formula (1), R represents a hydrogen atom or a methyl group. X represents a group selected from Formula (2a) to Formula (2f). N represents 0 or 1)

  The production of a silicone monomer represented by formula (1) according to claim 1, comprising a step of reacting an N- (meth) acryloylamino acid obtained by reacting an amino acid and (meth) acrylic acid chloride with an alkyl halide-modified silicone. Method.   20 to 60% by mass of the silicone monomer according to claim 1, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, 2- (methacryloyloxyethyl) -2- (trimethylammonio) A monomer composition comprising 40-80% by weight of a hydrophilic monomer selected from the group consisting of ethyl) phosphate or a mixture of two or more of these.   A polymer obtained by polymerizing the monomer composition according to claim 3.

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