JP5402934B2 - Silicone monomer, its production method and use - Google Patents

Description

  The present invention relates to a novel silicone monomer that is compatible with a hydrophilic monomer, a method for producing the same, and a polymerizable composition using the monomer.

Silicones are used in various applications such as mold release agents, fiber treatment agents, lubricants, polishes, water repellents, cosmetic additives and the like. In recent years, silicone monomers have been used as lens raw materials for the purpose of reducing the burden on the eyes of ophthalmic lenses (Patent Documents 1 and 2). As described above, when silicone is added to the lens raw material, the lens surface becomes hydrophobic and there is a concern about eye damage. Therefore, it is necessary to make the lens surface hydrophilic.
Conventionally, as a method of obtaining a polymer such as a lens having a hydrophilic surface, a method of obtaining a copolymer by compatibilizing a hydrophilic monomer with a silicone monomer is known. As a silicone monomer compatible with the hydrophilic monomer, for example, methyldi (trimethylsiloxy) silylpropylglycerol methacrylate (abbreviated as SiGMA) (Patent Documents 3 and 4) is known, and hydrophilic such as N, N-dimethylacrylamide is known. The surface can be hydrophilized by compatibilizing with the functional monomer.
SiGMA is not sufficiently compatible with more hydrophilic monomers such as 2-methacryloyloxyethyl-2-trimethylammonioethyl phosphate (abbreviated as MPC). There is a problem that it cannot be contained (Patent Document 5).
Therefore, a new surface hydrophilization technique such as plasma treatment has been developed in order to impart sufficient hydrophilicity to the polymer surface (Patent Documents 6 and 7).

JP-A-11-119169 JP 2001-311917 A JP 54-0661126 A Japanese Patent Application Laid-Open No. 11-310613 JP 2007-197513 A JP 2002-513948 A JP 2007-070405 A

  The object of the present invention is to make hydrophilic monomers such as MPC compatible with a wider range of mixed compositions and to uniformly copolymerize them, and to fully demonstrate the high hydrophilicity and the performance of silicone monomers Another object of the present invention is to provide a silicone monomer useful for the production of such a copolymer, a method for producing the same, and a composition for polymerization.

  The present inventors diligently studied to solve the above problems. It is known that conventional silicone monomers can easily compatibilize hydrophilic monomers by having a hydroxyl group in the molecule. However, since a strong hydrogen bond is formed in the silicone phase between the hydroxyl groups, the orientation to the hydrophilic monomer is not sufficient, and it is difficult to blend a sufficient amount of the hydrophilic monomer. In view of this, in the molecular structure of the silicone monomer, it is surprising that conventional hydrophilicity is obtained by containing 2 to 4, preferably 3 ester groups which are hydrophilic groups having weak hydrogen bonding properties in the vicinity of hydroxyl groups having strong hydrogen bonding properties. It has been found that the compatibility of hydrophilic monomers such as MPC and silicone monomers can be significantly improved compared to silicone monomers that have been used for compatibility with monomers. The present invention was completed by successfully producing a silicone monomer.

(式(１)中、Xはエステル基を１又は２有していてよい炭素数１〜１２の有機基、Ｒは水素原子またはメチル基を表す。Y¹〜Y⁹はそれぞれが互いに独立に水素原子、炭素数１〜４のアルキル基または炭素数６〜１０のアリール基を表す。ｎは０〜３の整数を表す。ａ、ｂ及びｃはそれぞれが互いに独立に０〜３の整数を表す。ただしａ＋ｂ＋ｃ≧１である。)
また本発明によれば、式(３)で表されるカルボン酸と式(４)で表されるエポキシ基含有シロキサンとを反応させることを特徴とする上記式(１)で表されるシリコーンモノマーの製造方法が提供される。According to the present invention, a silicone monomer represented by the formula (1) is provided.

(In the formula (1), X represents an organic group having 1 to 12 carbon atoms which may have 1 or 2 ester groups, R represents a hydrogen atom or a methyl group. Y ¹ to Y ⁹ are each independently of each other. Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, n represents an integer of 0 to 3. a, b and c each independently represents an integer of 0 to 3; (Where a + b + c ≧ 1)
Further, according to the present invention, the silicone monomer represented by the above formula (1) is produced by reacting the carboxylic acid represented by the formula (3) with the epoxy group-containing siloxane represented by the formula (4). A manufacturing method is provided.

(式(３)中、Xはエステル基を１又は２有していてよい炭素数１〜１２の有機基、Ｒは水素原子またはメチル基を表す。式(４)中、Y¹〜Y⁹はそれぞれが互いに独立に水素原子、炭素数１〜４のアルキル基または炭素数６〜１０のアリール基を表す。ｎは０〜３の整数を表す。ａ、ｂ及びｃはそれぞれが互いに独立に０〜３の整数を表す。ただしａ＋ｂ＋ｃ≧１である。)
更に本発明によれば、上記式(１)で表されるシリコーンモノマーと、MPCとを含む重合用組成物が提供される。

(In Formula (3), X represents an organic group having 1 to 12 carbon atoms which may have 1 or 2 ester groups, and R represents a hydrogen atom or a methyl group. In Formula (4), Y ^{1 to} Y ^9. Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, n represents an integer of 0 to 3, and a, b and c are each independently independent of each other. Represents an integer of 0 to 3, provided that a + b + c ≧ 1.)
Furthermore, according to the present invention, there is provided a polymerization composition comprising a silicone monomer represented by the above formula (1) and MPC.

  Since the silicone monomer of the present invention has a structure represented by the above formula (1), hydrophilic monomers such as MPC can be compatibilized in a wide range of mixed compositions. For this reason, the composition for polymerization comprising the silicone monomer and the hydrophilic monomer of the present invention can be uniformly copolymerized in a wide range of compositions, and sufficiently exerted the high hydrophilicity and the performance of the silicone monomer. A copolymer having excellent transparency can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
The silicone monomer of the present invention is represented by the above formula (1).
In formula (1), R represents a hydrogen atom or a methyl group. X represents an organic group having 1 to 12 carbon atoms which may have 1 or 2 ester groups. X is preferably a group represented by the formula (2) or the formulas (5a) to (5c) because the raw materials are easily available.

式(２)中、Ｚは炭素数１〜６の二価の炭化水素基又は炭素数６〜１０の二価の環状炭化水素基を表す。

In formula (2), Z represents a C1-C6 bivalent hydrocarbon group or a C6-C10 bivalent cyclic hydrocarbon group.

In Z in the formula (2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group. Preferably, an ethylene group is used from the viewpoint of stability and availability of raw materials.
Examples of the divalent cyclic hydrocarbon group having 6 to 10 carbon atoms include 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,2-phenylene group, 1 , 3-phenylene group, 1,4-phenylene group, 1,2-naphthalene group, 1,3-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group, 1,6-naphthalene group, 1, Examples include 7-naphthalene group, 1,8-naphthalene group, 2,3-naphthalene group, and 2,6-naphthalene group, and preferably 1,2-cyclohexylene group and 1,2-phenylene group for reasons of availability. Is mentioned.

More specific examples of the group represented by the formula (2) include groups represented by the formulas (6a) to (6e), and preferably the formula (6b) and the formula And a group represented by (6d).

In formula (1), n represents an integer of 0 to 3. Preferably, n = 2 or 3 because of high stability.
In formula (1), Y ^{1 to} Y ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a phenylethyl group, and a naphthyl group. Most preferred as Y ^{1 to} Y ⁹ is a methyl group because the raw materials are easily available.

  In the formula (1), a, b and c each independently represent an integer of 0 to 3, preferably 0 to 2. However, a + b + c ≧ 1. Preferred a, b and c combinations are a = b = c = 1, a = b = 1 and c = 0, and a = 1 and b = c = 0 because the raw materials are easily available .

  Preferred examples of the silicone monomer represented by the formula (1) include silicone monomers having structures represented by the formulas (7a) to (7d). Among these, the most preferable one is a compound represented by the formula (7a) which is particularly excellent in compatibility with a hydrophilic monomer and can be easily dissolved with other silicone monomers.

As a preferable method for producing the silicone monomer represented by the formula (1), for example, a method of reacting the carboxylic acid represented by the above formula (3) with the epoxy group-containing siloxane represented by the above formula (4). The desired silicone monomer can be obtained by separating and purifying the resulting product.
X and R in the above formula (3), Y ¹ to Y ⁹ , n, a, b and c in the above formula (4) correspond to the above formula (1). Specific examples are given.

  A commercially available carboxylic acid represented by the formula (3) can be used. Preferably, the carboxylic acid is not compatible with a hydrophilic monomer or has a low compatibility with other silicone monomers and hydrophilic monomers. For the reason that it is high, a carboxylic acid represented by the formula (5) containing three ester groups can be mentioned.

式(５)中、Ｚは炭素数１〜６の二価の炭化水素基または炭素数６〜１０の二価の環状炭化水素基を示す。Ｒは水素原子またはメチル基を示す。尚、式(５)中のＺの具体例は、前記式(２)のＺと同一のものが挙げられる。

In the formula (5), Z represents a divalent hydrocarbon group having 1 to 6 carbon atoms or a divalent cyclic hydrocarbon group having 6 to 10 carbon atoms. R represents a hydrogen atom or a methyl group. Specific examples of Z in formula (5) include the same as Z in formula (2).

  Most preferred examples of the carboxylic acid represented by the formula (5) include, for example, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl, because the raw materials are easily available. Hexahydrophthalic acid is mentioned.

  As the epoxy group-containing siloxane represented by the above formula (4), commercially available ones can be used. However, since the raw materials are easily available, those represented by the formulas (8a) to (8c) are preferably exemplified. More preferred are those shown in 8b).

  The reaction of the carboxylic acid represented by the formula (3) and the epoxy group-containing siloxane represented by the formula (4) can be performed, for example, without a solvent or in an aprotic solvent. The reaction temperature is usually 70 to 150 ° C., preferably 70 to 100 ° C. at which side decomposition reaction hardly occurs, and the reaction time is usually 6 to 48 hours, preferably 12 to 24 hours.

In the reaction, a catalyst can be used to accelerate the reaction. Examples of the catalyst include potassium hydroxide, sodium ethoxide, 1,8-diazabicyclo [5,4,0] undec-7-ene, trimethylbenzylammonium chloride, trimethylbenzylammonium chloride, and triethylamine. Particularly preferred catalysts include 1,8-diazabicyclo [5,4,0] undec-7-ene, triethylamine and sodium ethoxide because of their low nucleophilicity.
The amount of the catalyst used is preferably 0.03 to 0.24 molar ratio with respect to the carboxylic acid represented by the formula (3).

In the reaction, it is preferable to use a polymerization inhibitor so that carboxylic acid or the like is not polymerized. Examples of the polymerization inhibitor include hydroquinone monomethyl ether, 1,4-dihydroxybenzene, and 4-methoxyphenol, and 1,4-dihydroxybenzene can be easily removed by base washing after the completion of the reaction. Or the use of 4-methoxyphenol is preferred.
The amount of the polymerization inhibitor used is usually about 100 to 1000 ppm in the reaction solution.

  In the reaction, the charge ratio of the carboxylic acid represented by the formula (3) and the epoxy group-containing siloxane represented by the formula (4) is such that the epoxy group-containing siloxane in the reaction system is reacted by 99% or more. The carboxylic acid is preferably in a ratio of 1.5 to 3 moles with respect to 1 mole of the epoxy group-containing siloxane.

The silicone monomer obtained after the reaction is a liquid having a high boiling point and polymerizability, and it is difficult to use it for recrystallization or distillation operation.
The washing can be performed, for example, by dissolving the obtained reaction solution in n-hexane and using a sodium hydroxide aqueous solution or an organic base acetonitrile solution as the washing solution. Examples of the organic base include triethylamine, ammonia, triethanolamine, diethanolamine, and ethanolamine.
The amount of n-hexane used is preferably about 9 times the volume of the reaction solution because the oil phase and the aqueous phase can be easily separated during purification. Moreover, the usage-amount of the said washing | cleaning liquid is about the same volume as n-hexane normally.

By such washing, excess carboxylic acid remaining after the reaction can be removed. Since the carboxylic acid is extracted into the cleaning liquid as a salt with the base in the cleaning liquid (lower phase), the cleaning liquid is removed using a separatory funnel, and this cleaning is repeated until the cleaning liquid becomes basic. It is preferable.
On the other hand, since a small amount of base is mixed in the n-hexane phase, it is preferable to further wash with water or saline to remove the alkali. This operation is desirably repeated until the washed saline becomes neutral.

After the washing, using a dehydrating agent such as anhydrous sodium sulfate, dehydrating a small amount of water contained in the reaction solution, and after filtration, for example, by distilling off n-hexane using an evaporator, The desired silicone monomer is obtained.
The distillation of n-hexane is preferably performed at about 60 ° C. or less, and is performed by an operation of reducing the pressure to 5 to 10 mmHg using a vacuum pump and suctioning for about 1 hour.

式(１')中、Ｒ、Ｘ、Y¹〜Y⁹、ｎ、ａ、ｂ及びｃは、式(１)のものと同様である。The product after the purification is usually obtained as a mixture of the target silicone monomer represented by the formula (1) and the silicone monomer represented by the formula (1 ′).

In the formula (1 ′), R, X, Y ^{1 to} Y ⁹ , n, a, b and c are the same as those in the formula (1).

  The mixture can be used as it is for the polymerization composition of the present invention described later, but the content ratio of the silicone monomer represented by the formula (1) and the silicone monomer represented by the formula (1 ′) in the mixture is: The mass ratio is usually 2/1 to 8/1, preferably 3/1 to 5/1. When the ratio of the silicone monomer represented by the formula (1) is less than 2/1, the compatibilizing ability of the hydrophilic monomer may be lowered.

  The silicone monomer of the present invention can be used, for example, as a lens material. In particular, since the silicone monomer of the present invention is compatible with a highly hydrophilic monomer such as MPC, for example, the polymerization composition of the present invention containing the silicone monomer of the present invention and MPC can be used. .

In the polymerization composition of the present invention, the content of MPC is usually based on 100 parts by mass of the silicone monomer of the present invention or a mixture of the silicone monomer of the present invention and the silicone monomer represented by the above formula (1 ′). It is 10-70 mass parts, Preferably it is 20-50 mass parts. If the MPC content is less than 10 parts by mass, the hydrophilicity of the surface of the resulting polymer may be reduced, and if it is more than 70 parts by mass, the oxygen permeability of the resulting polymer may be reduced.
The polymerization composition of the present invention can contain other copolymerizable monomers as necessary. The content of the other copolymerizable monomer is usually 0 to 150 parts by mass, preferably 0 to 100 parts by mass with respect to 100 parts by mass of the silicone monomer of the present invention.

  Other copolymerizable monomers are not limited as long as they can be copolymerized, and monomers having (meth) acryloyl group, styryl group, allyl group, vinyl group and other copolymerizable carbon-carbon unsaturated bonds are used. can do.

  Other copolymer monomers include, for example, alkyl (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, phosphorylcholine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and the like ( (Meth) acrylates; polyalkylene glycol mono (meth) acrylate, polyalkylene glycol monoalkyl ether (meth) acrylate, polyalkylene glycol bis (meth) acrylate, trimethylolpropane tris (meth) acrylate, pentaerythritol tetrakis (meth) acrylate Polyfunctional (meth) acrylates such as siloxane macromers having carbon-carbon unsaturated bonds at both ends; alkyl halides such as trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate (meth) ) Acrylates; hydroxyalkyl (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, glycerol (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-acryloylpyrrolidine, N (Meth) acrylamides such as methyl (meth) acrylamide; Aromatic vinyl monomers such as styrene, α-methylstyrene and vinylpyridine; Maleimides; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazolidone Heterocyclic vinyl monomers such as 1-vinylimidazole, N-vinylcarbazole, vinylpyridine, and vinylpyrazine; N-vinylcarboxamides such as N-vinylformamide, N-vinylacetamide, and N-methyl-N-vinylacetamide; vinyl acetate Vinyl esters such as 3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylate, 3- [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) Acrylic net [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 (trimethyl) Siloxy) methylsilyl] styrene, [(trimethylsiloxy) dimethylsilyl] styrene, N- [3- [tris (trimethylsiloxy) silyl] propyl] vinyl carbamate, N- [3- [bis (trimethylsiloxy) methylsilyl] propyl] Cal Examples thereof include siloxane-containing monomers such as vinyl bamate and N- [3-[(trimethylsiloxy) dimethylsilyl] propyl] carbamate, and (meth) acrylates are preferable because they have good copolymerizability.

When polymerizing the polymerization composition of the present invention, it is preferable to use a thermal polymerization initiator typified by a peroxide or an azo compound or a photopolymerization initiator in order to facilitate the polymerization.
In the case of performing thermal polymerization, one having an optimum decomposition characteristic for a desired reaction temperature can be selected and used. In general, an azo initiator or a peroxide initiator having a 10-hour half-life temperature of 40 to 120 ° C. is suitable.
Examples of the photopolymerization initiator include carbonyl compounds, peroxides, azo compounds, sulfur compounds, halogen compounds, and metal salts.
These polymerization initiators are used alone or in combination, and the amount used is approximately 1 part by mass or less with respect to 100 parts by mass of the polymerization composition.
The composition for polymerization of the present invention can be suitably used as a raw material for silicone hydrogel contact lenses and the like.

Hereinafter, the present invention will be described specifically by way of examples.
Various measurements in this example were performed by the following methods.
〔Measuring method〕
(1) Proton nuclear magnetic resonance spectrum The proton nuclear magnetic resonance spectrum was measured using AL400 type manufactured by JEOL. Chloroform-d was used as the solvent, and the peak of chloroform was used as an internal standard (7.26 ppm).
(2) High performance liquid chromatography A high performance liquid chromatography system (LC-8020 manufactured by Tosoh Corporation) was used. The effluent from the high performance liquid chromatography column was detected using a UV detector and an RI detector. A mixture of 90% by volume of acetonitrile and 10% by volume of 0.05M ammonium acetate aqueous solution was used as an eluent, and a sample was dissolved in this eluent at a concentration of 0.5% by volume and subjected to analysis. The high performance liquid chromatography conditions are as follows.
C ₁₈ (octadecylated silica) column (15 mm × 4.6 mm).
(3) Mass spectrometry Using Q-micro (Waters, ESI ionization method), the sample was dissolved in methanol for analysis.
(4) Infrared absorption spectrum analysis Using FT / IR-6100 (manufactured by JASCO Corp.), the sample was absorbed into a polyethylene film and measured.

Example 1
In a 300 ml three-necked flask equipped with a condenser, a stirrer, and a dropping funnel, 36.6 g of the compound represented by the above formula (8b) (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 g of 1,4-dihydroxybenzene and 0.66 g of triethylamine Then, 50.0 g of a compound represented by the formula (9) (manufactured by Kyoeisha Chemical Co., Ltd.) was added dropwise over about 30 minutes while stirring at room temperature under a nitrogen atmosphere.

Reaction was performed at 85 degreeC for 24 hours, stirring after completion | finish of dripping. After leaving overnight, 170 ml of hexane was added and stirred at room temperature for 2 hours. The precipitate was removed by filtration, and the hexane solution was washed several times with 5% by mass sodium bicarbonate and further washed with saturated brine until neutral. After anhydrous sodium sulfate was added for dehydration, 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. under reduced pressure for 4 hours to obtain 50.0 g of a colorless transparent liquid. The obtained liquid was separated and purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 1/1 (v / v)) to obtain a colorless transparent liquid.
As a result of measuring and analyzing the obtained liquid by proton nuclear magnetic resonance spectrum, peaks derived from methacryloyl groups were observed at around 6.1 ppm (1H), 5.8 ppm (1H), and 1.9 ppm (3H). A peak derived from O—CH ₂ —CH ₂ —O around 4 ppm (4H), a peak derived from C (═O) —CH ₂ —CH ₂ —C═O around 1.6 ppm (4H), 1.6 ppm A peak derived from C—CH ₂ —C was observed in the vicinity (2H), a peak derived from —CH ₂ —Si was observed in the vicinity of 0.5 ppm (2H), and a peak derived from Si—CH ₃ was observed in the vicinity of 0 ppm (21H). . Peaks characteristic of the compound of formula (10) were observed in the vicinity of 3.7 to 3.9 ppm and 5.0 ppm. Further, a peak derived from the compound represented by the formula (7a) was confirmed in the vicinity of 4.0 to 4.2 ppm. From this area ratio, it was found that the mass ratio of the silicone monomer represented by the formula (7a) and the compound represented by the formula (10) was about 4/1.

Further, as a result of infrared absorption spectrum analysis, a peak derived from a hydroxyl group was 3510 cm ⁻¹ , a peak derived from a double bond was 1640 cm ⁻¹ , a peak derived from a methacrylic ester bond was 1730 cm ⁻¹ , and succinic acid the peak 1740 cm ^-1 derived from an ester, the peak 1040 cm ^-1 derived from Si-O-Si bond, peak 2960 cm ^-1 derived from a methyl group, 1410 cm ^-1, the 1300 cm ^-1, attached to the siloxane A peak derived from a methyl group was detected at 845 cm ⁻¹ . Furthermore, peaks derived from the epoxy group of the 910 cm ^-1, a peak derived from a carboxylic acid of 1715 cm ^-1 was detected.
Next, when analyzed by high performance liquid chromatography, a single peak was observed. The purity was about 90%. When ESI-mass spectrometry was performed, the molecular weights of the two compounds were both 566.

Example 2
In a 300 ml three-necked flask equipped with a condenser, a stirrer and a dropping funnel, 36.6 g of the compound represented by the above formula (8b) (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 g of 1,4-dihydroxybenzene, 0.66 g of triethylamine And 61.8 g of a compound represented by the formula (11) (manufactured by Kyoeisha Chemical Co., Ltd.) was added and dissolved while stirring. Thereafter, the reaction was carried out at 85 ° C. for 24 hours with stirring.

After leaving overnight, 170 ml of hexane was added and stirred at room temperature for 2 hours. The precipitate was removed by filtration, and the hexane solution was washed several times with an acetonitrile solution in which 2% by mass of triethylamine was dissolved. After anhydrous magnesium sulfate was added and dehydration was performed from the hexane phase, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary vacuum evaporator. Furthermore, volatile components were removed at 60 ° C. under reduced pressure for 4 hours to obtain 35.0 g of a colorless transparent liquid. The obtained liquid was separated and purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 2/1 (v / v)) to obtain a colorless transparent liquid.
As a result of measuring and analyzing the proton nuclear magnetic resonance spectrum of the obtained liquid, a peak derived from a methacryloyl group was observed at around 6.1 ppm (1H), around 5.6 ppm (1H), and around 1.9 ppm (3H). A peak derived from O—CH ₂ —CH ₂ —O around 2 ppm (4H), a peak derived from C (═O) —CH ₂ —CH ₂ —C═O around 2.6 ppm (4H), from 1.5 A peak derived from C—CH ₂ —C around 1.9 ppm (10H), a peak derived from —CH ₂ —Si around 0.5 ppm (2H), a peak derived from Si—CH ₃ around 0 ppm (21H), and the like. Observed. In addition, a peak derived from the compound represented by the formula (7b) was confirmed near 3.9 to 4.1 ppm, and a peak derived from the compound represented by the formula (12) was confirmed from 3.6 to 3.7 ppm. It was. From this area ratio, it was found that the mixture was an about 4/1 mixture of the compound of formula (7b) and the compound represented by the following formula.
According to mass spectrometry, the molecular weights of the two compounds were both 620.

Example 3
37.0 parts by mass of a compound represented by the formula (7a) and a compound represented by the formula (10) obtained in Example 1, 37.0 parts by mass, 37.5 parts by mass of tris (trimethylsiloxy) silylpropyl methacrylate, MPC 15 parts by mass, 10 parts by mass of ethanol and 0.5 parts by mass of azobisisobutyronitrile were mixed and dissolved, and then allowed to stand at 100 ° C. for 5 hours for polymerization. After the polymerization, a transparent solid was obtained.

Comparative Example 1
Methyldi (trimethylsiloxy) silylpropylglycerol methacrylate (SiGMA) 37.0 parts by mass, tris (trimethylsiloxy) silylpropyl methacrylate 37.5 parts by mass, MPC 15 parts by mass, ethanol 10 parts by mass, azobisisobutyronitrile 0.5 After mixing a mass part and making it compatible, it superposed | polymerized by leaving to stand at 100 degreeC for 5 hours. After the polymerization, a cloudy solid was obtained.

Example 4
60.0 parts by mass of the compound represented by the formula (7a) and the compound represented by the formula (10) obtained in Example 1 and 40 parts by mass of MPC dissolved in 10 parts by mass of ethanol were mixed. When they were stirred, they were compatible.

Example 5
60.0 parts by mass of the compound represented by the formula (7a) obtained in Example 1 and the compound represented by the formula (10), 60.0 parts by mass, 8 parts by mass of ethanol, and 20 parts by mass of MPC were mixed and stirred. However, it was compatible.

Comparative Example 2
When 60.0 parts by mass of methyldi (trimethylsiloxy) silylpropylglycerol methacrylate (SiGMA), 8 parts by mass of ethanol and 20 parts by mass of MPC were mixed and stirred, a precipitate was observed.

Claims (3)

A silicone monomer represented by the formula (1).

(In the formula (1), X represents a group represented by the formula (2) , R represents a hydrogen atom or a methyl group. Y ¹ to Y ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. Or an aryl group having 6 to 10 carbon atoms, n represents an integer of 0 to 3. a, b and c each independently represent an integer of 0 to 3, provided that a + b + c ≧ 1.

(In formula (2), Z represents a C1-C6 divalent hydrocarbon group or a C6-C10 divalent cyclic hydrocarbon group.) The method for producing a silicone monomer according to claim 1, wherein the carboxylic acid represented by the formula (3) is reacted with the epoxy group-containing siloxane represented by the formula (4).

(In the formula (3), X represents a group represented by the formula (2) according to claim 1 , R represents a hydrogen atom or a methyl group. In the formula (4), Y ^{1 to} Y ⁹ are each independently of each other. Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, n represents an integer of 0 to 3. a, b and c each independently represents an integer of 0 to 3; (Where a + b + c ≧ 1)   A composition for polymerization comprising the silicone monomer of claim 1 and 2-methacryloyloxyethyl-2-trimethylammonioethyl phosphate.