Polymerizable silicone monomer, method for producing same, curable composition, polymer thereof, and ophthalmic device using same

Abstract

[Problem] To provide: a polymerizable silicone monomer providing a polymer excellent in transparency, surface hydrophilicity, durability, and stain resistance; a method for producing same; a curable composition including the monomer; a polymer obtained by polymerizing the composition; and an ophthalmic device using the polymer. [Solution] This polymerizable silicone monomer is represented by formula (1) (in the formula, each R1 is independently a monovalent hydrocarbon having 1-4 carbon atoms; each R2 is independently an alkyl group having 1-10 carbon atoms or an aryl group having 6-10 carbon atoms; R3 is a hydrogen atom or a methyl group; A1 is a single bond or a divalent hydrocarbon group having 1-20 carbon atoms; Q is a divalent group selected from-A2-O-A3- and -O-A4-O -; A2 and A3 are each independently a single bond or a divalent hydrocarbon group which may have a branch of 1-3 carbon atoms, wherein at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1-4 carbon atoms, provided that A2 and A3 are not a single bond, A4 is a divalent hydrocarbon group which may have a branch of 1-3 carbon atoms, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1-4 carbon atoms; and n is an integer of 1-3).

Description

Polymerizable silicone monomer, its manufacturing method, curable composition, polymer thereof, and ophthalmic device using the same

[0001] The present invention relates to a polymerizable silicone monomer having an alkenyl ether moiety and an acryloyl group in the same molecule, a method for producing the same, a curable composition containing the monomer, a polymer obtained by polymerizing the composition, and an ophthalmic device using the polymer.

[0002] Polymerizable silicone monomers are used as resin modifiers for (meth)acrylic resins, copolymerized with other hydrophilic monomers for ophthalmic devices, etc. However, polymers obtained from conventional polymerizable silicone monomers have the drawback of being poor in transparency, water absorption, toughness, and oxygen permeability.

[0003] Patent Documents 1 and 2 describe a polymerizable compound having an allyl ether moiety and an acryloyl group in the same molecule, and a composition containing the polymerizable compound, which is described as providing a polymer with excellent transparency, water absorbency, and toughness. The polymerizable compound has the property of undergoing cyclopolymerization via a radical polymerization mechanism. The polymer of the composition containing the polymerizable compound has superior transparency, water absorbency, and toughness compared to those containing conventional polymerizable compounds.

[0004] JP 2011-074068 A JP 2011-137123 A

[0005] Silicone monomers with acryloyl or methacryloyl groups are known as silicone monomers with polymerizable groups, but there are few examples of silicone monomers with different α-substituents. In particular, there have been no reports of polymerizable silicone monomers that have an alkenyl ether moiety and an acryloyl group in the same molecule and exhibit cyclopolymerization.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a polymerizable silicone monomer that gives a polymer with excellent transparency, surface hydrophilicity, durability, and stain resistance, and a method for producing the same, as well as a curable composition containing the polymerizable silicone monomer, a polymer obtained by polymerizing the composition, and an ophthalmic device using the polymer.

[0007] As a result of extensive research into achieving the above-mentioned object, the present inventors synthesized a polymerizable silicone monomer having an alkenyl ether moiety and an acryloyl group in the same molecule, and discovered that a curable composition containing this polymerizable silicone monomer gives a polymer that exhibits excellent transparency, surface hydrophilicity, durability, and stain resistance, thereby completing the present invention.

[0008] That is, the present invention provides: [1] a polymerizable silicone monomer represented by the following formula (1): (In the formula, R １ are each independently a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ３ is a hydrogen atom or a methyl group, １ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Q represents -A ２ -O-A ３ -, and -O-A ４ is a divalent group selected from —O—, and A ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, and A ４ is a divalent hydrocarbon group having 1 to 3 carbon atoms, which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.

[0009] The present invention further provides the above polymerizable silicone monomer, which further has at least one of the following structures [2] to [5]: [2] The polymerizable silicone monomer according to the above [1], which is represented by the following formula (a) or (b): In the formula, R １ , R ２ , R ３ , A ２ , A３ , A ４ and n are as defined above, and m is an integer from 1 to 10. [3] A ２ , A ３ , and A ４ is a group selected from the following: [4] A ２ and A ３ The polymerizable silicone monomer according to any one of [1] to [3] above, wherein one of the following is a single bond and the other is a group selected from the following: [5] A ２ , A ３ , and A ４ is a methylene group.

[0010] Furthermore, the present invention provides: [6] a polymerizable silicone monomer represented by the following formula (1): (In the formula, R １ are each independently a monovalent hydrocarbon having 1 to 4 carbon atoms, and R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ３ is a hydrogen atom or a methyl group, １ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Q represents -A ２ -O-A ３ -, and -O-A ４ is a divalent group selected from —O—, and A ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, and A ４is a divalent hydrocarbon group having 1 to 3 carbon atoms, which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3), and a carboxylate metal salt compound represented by the following formula (3): (In the formula, R １ , R ２ , R ３ , A １ , Q and n are as defined above, X is a chlorine atom, a bromine atom, or an iodine atom, and M is an alkali metal ion) to obtain a polymerizable silicone monomer represented by formula (1).

[0011] The present invention further provides the above-mentioned production method further having at least one of the following features [7] to

[11] . [7] The production method according to the above-mentioned [6], wherein the polymerizable silicone monomer represented by the formula (1) is represented by the above-mentioned formula (a) or (b). [8] A ２ , A ３ , and A ４ is a group selected from the following: [9] A ２ and A ３ The method according to the above [6] or [7], wherein one of the following is a single bond and the other is a group selected from the following:

[10] A ２ , A ３ , and A ４

[11] The method according to any one of the above [6] to

[10] , wherein the compounding ratio of the halogen-containing organosilicon compound represented by the formula (2) to the carboxylic acid metal salt compound represented by the formula (3) is 1.0:0.3 to 1.0:3.0 in terms of molar ratio.

[0012]

[12] A polymerizable silicone monomer represented by the following formula (1): (In the formula, R １are each independently a monovalent hydrocarbon having 1 to 4 carbon atoms, and R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ３ is a hydrogen atom or a methyl group, １ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Q represents -A ２ -O-A ３ -, and -O-A ４ is a divalent group selected from —O—, and A ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, and A ４ is a divalent hydrocarbon group having 1 to 3 carbon atoms, which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3), which comprises reacting an organosilicon compound represented by the following formula (4): A hydrolyzable organosilicon compound represented by the following formula (5) and / or a disiloxane compound represented by the following formula (6): (In the formula, R １ , R ２ , R ３ , A １ , Q and n are the same as above, and R ４ is an alkyl group having 1 to 4 carbon atoms, and Y is a chlorine atom, bromine atom, or iodine atom) in the presence of an acid to obtain a polymerizable silicone monomer represented by formula (1).

[0013] The present invention further provides the above-mentioned production method further having at least one of the following features

[13] to

[19] .

[13] The production method according to the above-mentioned

[12] , wherein the polymerizable silicone monomer represented by the formula (1) is represented by the above-mentioned formula (a) or (b).

[14] A ２ , A ３, and A ４ is a group selected from the following:

[15] A ２ and A ３ The method according to the above

[12] or

[13] , wherein one of the following is a single bond, and the other is a group selected from the following:

[16] A ２ , A ３ , and A ４

[17] The method according to any one of the above

[12] to

[15] , wherein the OR group of the organosilicon compound represented by the formula (4) is a methylene group. ４

[18] The method according to any one of the above

[12] to

[16] , wherein the molar ratio of the hydrolyzable organosilicon compound represented by the above formula (5) to the number of moles of the OR group contained in the organosilicon compound represented by the above formula (4) is 1:1 to 1:10. ４ R in the disiloxane represented by formula (6) above relative to the number of moles of the group １ ３ The method according to any one of the above

[12] to

[16] , wherein the reaction is carried out in a compounding ratio such that the molar ratio of Si groups is 1:1 to 1:10.

[19] The method according to any one of the above

[12] to

[18] , wherein the amount of the acid is 0.1 to 50 moles per mole of the organosilicon compound represented by formula (4).

[0014] The present invention further provides a curable composition containing the polymerizable silicone monomer and another polymerizable monomer having a group that polymerizes with the polymerizable silicone monomer, a polymer obtained by polymerizing the curable composition, and an ophthalmic device using the polymer.

[0015]

[20] A curable composition comprising the polymerizable silicone monomer according to any one of [1] to [5] above and another polymerizable monomer having a group polymerizable with the polymerizable silicone monomer;

[21] The curable composition according to

[14] above, wherein the polymerizable silicone monomer according to any one of [1] to [5] above is contained in the curable composition in an amount of 10 to 80 mass %;

[22] A polymer obtained by polymerizing the curable composition according to

[20] or

[21] above; and

[23] An ophthalmic device comprising the polymer according to

[22] above. Further provided is an ophthalmic device having at least one of the following structures

[24] to

[28] .

[24] An ophthalmic device comprising a polymer of a monomer mixture comprising the polymerizable silicone monomer according to any one of [1] to [5] above and another polymerizable monomer having a group polymerizable with the polymerizable silicone monomer.

[25] The ophthalmic device according to

[24] above, wherein the content of the polymerizable silicone monomer represented by formula (1) is 10 to 80 mass parts per 100 mass parts of the monomer mixture.

[26] The ophthalmic device according to

[24] or

[25] above, wherein the other polymerizable monomer is at least one selected from the group consisting of an acrylic monomer, an acrylic acid derivative, crotonic acid, cinnamic acid, vinyl benzoic acid, and a silicone monomer having a polymerizable group.

[27] The ophthalmic device according to any one of

[24] to

[26] above, wherein the monomer mixture further contains at least one additive selected from the group consisting of a polymerization initiator, an antioxidant, a colorant, a lubricant, an internal wetting agent, and a reinforcing agent.

[28] The ophthalmic device according to any one of

[24] to

[27] above, wherein the ophthalmic device is selected from the group consisting of a contact lens, an intraocular lens, and an artificial cornea.

[0016] The polymer obtained by polymerizing the curable composition containing the polymerizable silicone monomer of the present invention has excellent transparency, surface hydrophilicity, durability, and contamination resistance, and is therefore suitable for use in applications such as ophthalmic devices.

[0017] The present invention will now be described in more detail.

[0018] [Polymerizable Silicone Monomer] The polymerizable silicone monomer of the present invention is represented by the following formula (1).

[0019] R １ are each independently a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Of these, a methyl group or an ethyl group is preferred.

[0020] R ２ are each independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, and cyclohexyl groups. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl groups. Among these, R ２ is preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group, more preferably a methyl group, an ethyl group, and a phenyl group.

[0021] R ３ is a hydrogen atom or a methyl group.

[0022] A １ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group may be linear, branched, or cyclic. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an aralkylene group having 7 to 10 carbon atoms. More specifically, examples thereof include alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene groups; cycloalkylene groups such as cyclohexylene groups; alkenylene groups such as vinylene and propenylene groups; arylene groups such as phenylene, tolylene, xylylene, and naphthylene groups; and aralkylene groups such as benzylene, phenylethylene, and phenylpropylene groups.

[0023] n is an integer of 1 to 3, preferably 2 or 3.

[0024] Q is -A ２ -O-A ３ -, and -O-A ４ A is a divalent group selected from —O—. ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds. ４ is a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms.

[0025] Examples of the divalent hydrocarbon group having 1 to 3 carbon atoms, which may have a branch, include alkylidene groups having 1 to 3 carbon atoms, such as methylene, ethylidene, propylidene, and isopropylidene groups, with a methylene group being preferred.

[0026] The polymerizable silicone monomer of the present invention is preferably represented by the following formula: In the formula, R １ , R ２ , R ３ , A ２ , A ３ , A ４ and n is as described above, and m is an integer from 1 to 10.

[0027] Preferably, A ２ , A ３ and A ４ is a group selected from the following structures:

[0028] Another preferred embodiment is A ２ and A ３ One of the groups is a single bond, and the other is a group selected from the following formulas:

[0029] Above A ２ , A３ and A ４ is preferably a methylene group.

[0030] m is an integer of 1 to 10, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6.

[0031] The polymerizable silicone monomer of the present invention is more preferably represented by the following formula (8): In the formula, R １ , R ２ , m and n are as defined above.

[0032] Examples of the polymerizable silicone monomer include compounds represented by the following formulas (9) to (11). In the formula, Me represents a methyl group.

[0033] [Production Method 1] The polymerizable silicone monomer of the present invention can be obtained, for example, by reacting a halogen-containing organosilicon compound represented by the following formula (2) with a carboxylic acid metal salt compound represented by the following formula (3). In the formula, R １ , R ２ , R ３ , Q and n are as defined above, X is a chlorine atom, a bromine atom or an iodine atom, and M is an alkali metal ion.

[0034] Examples of the alkali metal represented by M include sodium and potassium.

[0035] Examples of the halogen-containing organosilicon compound represented by the above formula (2) include 3-chloropropyltris(trimethylsiloxy)silane, 3-chloropropylmethylbis(trimethylsiloxy)silane, and 3-chloropropyldimethyl(trimethylsiloxy)silane.

[0036] The carboxylate metal salt compound represented by the above formula (3) is more specifically represented by the following structure. A ２ , A ３ and A ４ is as described above, and is preferably a group selected from the following: ２ and A３ One of the groups is a single bond, and the other is a group selected from the following: Most preferably A ２ , A ３ and A ４ is a methylene group.

[0037] Examples of the carboxylic acid metal salt compound represented by the above formula (3) include sodium 2-(allyloxymethyl)acrylate and potassium 2-(allyloxymethyl)acrylate.

[0038] The halogen-containing organosilicon compound represented by formula (2) and the metal carboxylate compound represented by formula (3) are preferably reacted in a molar ratio of halogen-containing organosilicon compound:metal carboxylate compound=1.0:0.3 to 1.0:3.0, particularly 1:0.8 to 1:1.2.

[0039] When producing the polymerizable silicone monomer of the present invention, a catalyst such as a phase transfer catalyst may be used as needed. Examples of phase transfer catalysts include quaternary phosphonium salts and quaternary ammonium salts.

[0040] Examples of the quaternary phosphonium salts include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetrabutylphosphonium bromide, triphenylbenzylphosphonium bromide, and tetraphenylphosphonium bromide.

[0041] Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, trimethylphenylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, N-benzylpicolinium chloride, N-lauryl 4-picolinium chloride, N-laurylpicolinium chloride, tricaprylmethylammonium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, and tetrabutylammonium hydrogen sulfate.

[0042] When a catalyst is used, the amount used is not particularly limited, but from the standpoint of reactivity and productivity, the amount of catalyst used is preferably 0.1 to 10.0 parts by mass, more preferably 1.0 to 5.0 parts by mass, and even more preferably 2.0 to 4.0 parts by mass per 100 parts by mass of the halogen-containing organosilicon compound represented by formula (2) above.

[0043] A solvent may be used, if necessary, during the production of the polymerizable silicone monomer of the present invention. There are no particular restrictions on the solvent, so long as it is non-reactive with the halogen-containing organosilicon compound and metal salt compound that are the raw materials.

[0044] Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and decane; ether solvents such as diethyl ether and tetrahydrofuran; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. These solvents may be used alone or in combination of two or more.

[0045] The reaction temperature in the above reaction is not particularly limited, and the reaction can be carried out at a temperature from 0° C. under heating, preferably 0 to 200° C. In order to obtain an appropriate reaction rate, the reaction is preferably carried out under heating, and from this viewpoint, the reaction temperature is more preferably 40 to 110° C., and even more preferably 40 to 90° C.

[0046] The reaction time is not particularly limited, and is usually about 1 to 30 hours, preferably 1 to 20 hours, and more preferably 1 to 10 hours.

[0047] The alkali metal halide generated during the production of the polymerizable silicone monomer of the present invention can be separated from the target polymerizable silicone monomer by known methods such as filtration. The polymerizable silicone monomer of the present invention can be further purified by known methods such as reduced pressure distillation and liquid column chromatography.

[0048] [Production Method 2] The polymerizable silicone monomer of the present invention can be obtained by subjecting an organosilicon compound represented by the following formula (4) to a hydrolysis condensation reaction with a hydrolyzable organosilicon compound represented by the following formula (5) and / or a disiloxane compound represented by the following formula (6) in the presence of an acid. R １ , R ２ , R ３ , A １ , Q and n are as defined above.

[0049] In the above formula (4), R ４ are each independently an alkyl group having 1 to 4 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Of these, a methyl group and an ethyl group are more preferred.

[0050] Y is a chlorine atom, a bromine atom, or an iodine atom.

[0051] The carboxylate metal salt compound represented by the above formula (4) is more specifically represented by the following structure. A ２ , A ３ and A ４is as described above, and is preferably a group selected from the following structures. ２ and A ３ One of the groups is a single bond, and the other is a group selected from the following formulas: Most preferably A ２ , A ３ and A ４ is a methylene group.

[0052] Examples of the organosilicon compound represented by the above formula (4) include those represented by the following formulas (12) to (17). In the formula, Me represents a methyl group, and Et represents an ethyl group.

[0053] Examples of the hydrolyzable organosilicon compound represented by the above formula (5) include trimethylchlorosilane, triethylchlorosilane, trimethylbromosilane, triethylbromosilane, trimethyliodosilane, and triethyliodosilane.

[0054] Examples of the disiloxane compound represented by the above formula (6) include hexamethyldisiloxane and hexaethyldisiloxane.

[0055] The organosilicon compound represented by the formula (4) and the hydrolyzable organosilicon compound represented by the formula (5) are mixed in a molar ratio of OR in the organosilicon compound. ４ The reaction is preferably carried out at a ratio of group:hydrolyzable organosilicon compound=1:1 to 1:10, particularly 1:2 to 1:5.

[0056] The organosilicon compound represented by the formula (4) and the disiloxane represented by the formula (6) are mixed in a molar ratio of OR ４ Group: R in disiloxane １ ３ It is preferable to carry out the reaction at a ratio of Si group=1:1 to 1:10, particularly 1:2 to 1:5.

[0057] The hydrolyzable organosilicon compound represented by the formula (5) and the disiloxane represented by the formula (6) may be mixed with the organosilicon compound represented by the formula (4) in the above proportions as described above.

[0058] Examples of the acid include hydrochloric acid, sulfuric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, acetic anhydride, and trifluoroacetic acid, with hydrochloric acid and sulfuric acid being particularly preferred. The amount of the acid used is preferably 0.1 to 50 moles, and more preferably 1 to 10 moles, per mole of the organosilicon compound represented by formula (4).

[0059] A solvent may be used in the hydrolysis and condensation reaction, if necessary. Examples of the solvent include alcoholic solvents such as methanol, ethanol, 1-propanol, and 2-propanol. These solvents may be used alone or in combination of two or more.

[0060] The hydrolysis and condensation reaction can be carried out, for example, by adding the organosilicon compound represented by formula (4) above and the hydrolyzable organosilicon compound represented by formula (5) above to a mixture of aqueous hydrochloric acid and a solvent, or by sequentially adding sulfuric acid, the organosilicon compound represented by formula (4) above, and water to a mixture of a disiloxane compound represented by formula (6) above and a solvent.

[0061] The reaction temperature in the hydrolysis condensation reaction is preferably −10 to 50° C., particularly preferably −5 to 30° C. The reaction time is not particularly limited and is usually about 1 to 30 hours, preferably 1 to 20 hours, and more preferably 1 to 10 hours.

[0062] The acid used is preferable because the layer containing the acid can be removed by liquid separation.

[0063] After the hydrolysis and condensation reaction, the reaction liquid is washed with water, aqueous sodium bicarbonate, aqueous sodium sulfate, or the like, and then dehydrated with anhydrous sodium sulfate, calcium chloride, or the like, followed by purification by distillation under reduced pressure to obtain the polymerizable silicone monomer of the present invention.

[0064] During the production of the polymerizable silicone monomer of the present invention, it is preferable to add a polymerization inhibitor, and it is more preferable to have a molecular oxygen-containing gas coexist with the polymerization inhibitor. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used, and is blown into the handling equipment.

[0065] The polymerization inhibitor may be a polymerization inhibitor for radically polymerizable monomers. Examples include phenolic inhibitors such as hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, and 2,2'-methylenebis(4-methyl-6-t-butylphenol); organic acid copper salts; and phenothiazine. Among these, phenolic inhibitors are preferred in terms of low coloration and polymerization-inhibiting ability, and p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 6-t-butyl-2,4-xylenol, and 2,6-di-t-butylphenol are particularly preferred in terms of availability and economy. These polymerization inhibitors may be used alone or in combination of two or more. The amount of polymerization inhibitor to be added is not particularly limited, but is about 100 to 100,000 ppm based on the mass of the metal salt compound represented by formula (3) above or the organosilicon compound represented by formula (4) above.

[0066] According to the manufacturing method of the present invention, a compound represented by the above formula (1) having a specific n and A １ , Q, R １ , R ２ and R ３ It is possible to provide a compound having one type of compound having the above specific structure in high purity. High purity means that the one type having the specific structure accounts for more than 95% by mass, preferably 97% by mass or more, and more preferably 99% by mass or more of the total mass of the compound. In the present invention, purity is determined by gas chromatography (hereinafter referred to as "GC") analysis. Detailed conditions will be described later. When the compound has the above high purity, a more transparent polymer can be obtained.

[0067] [Curable Composition] The curable composition of the present invention contains a polymerizable silicone monomer represented by the above formula (1). The content of the polymerizable silicone monomer in the composition is not particularly limited, but is preferably 10 to 80 mass %, more preferably 20 to 70 mass %. Note that when the composition contains a solvent, the content refers to the nonvolatile content excluding the solvent.

[0068] The curable composition of the present invention preferably contains another compound (hereinafter referred to as a polymerizable monomer) having a group that polymerizes with the polymerizable silicone monomer represented by formula (1) above. Examples of the polymerizable monomer include acrylic monomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (poly)ethylene glycol dimethacrylate, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol monoalkyl ether (meth)acrylate, trifluoroethyl (meth)acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate; acrylic acid derivatives such as N,N-dimethylacrylamide, N,N-diethylacrylamide, N-acryloylmorpholine, and N-methyl(meth)acrylamide; other unsaturated aliphatic or aromatic compounds such as crotonic acid, cinnamic acid, and vinylbenzoic acid; and silicone monomers having a polymerizable group such as a (meth)acrylic group. These may be used alone or in combination of two or more.

[0069] [Polymer] Copolymerization of the polymerizable silicone monomer of the present invention with the other polymerizable monomers described above may be carried out by conventionally known methods. For example, known polymerization initiators such as thermal polymerization initiators and photopolymerization initiators may be used. Examples of such polymerization initiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide. These polymerization initiators may be used alone or in combination of two or more. The amount of polymerization initiator added is 0.001 to 2 parts by mass, preferably 0.01 to 1 part by mass, per 100 parts by mass of the total polymerization components. The polymerization reaction may be carried out under conventionally known reaction conditions. For example, photopolymerization may be carried out by irradiating the polymer with ultraviolet light using a mercury lamp or ultraviolet lamp for, for example, one hour or less, or thermal polymerization may be carried out at a temperature of, for example, 60°C to 200°C for, for example, 0.1 hour to several hours.

[0070] [Ophthalmic Device] The present invention preferably provides an ophthalmic device comprising a copolymer of a monomer mixture containing the polymerizable silicone monomer of the present invention and the other polymerizable monomer described above. The content of the polymerizable silicone monomer of the present invention in the monomer mixture is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, per 100 parts by mass of the monomer mixture. The monomer mixture may further contain known additives such as antioxidants, colorants, lubricants, internal wetting agents, and reinforcing agents, as necessary and within limits that do not impair the objects and effects of the present invention.

[0071] The polymer containing the polymerizable silicone monomer of the present invention as a polymerization component has excellent transparency, surface hydrophilicity, durability, and contamination resistance. Therefore, it is suitable for producing ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas. The method for producing ophthalmic devices using the polymer is not particularly limited, and may follow conventional methods for producing ophthalmic devices. For example, when molding into the shape of lenses such as contact lenses and intraocular lenses, cutting methods and molding methods can be used.

[0072] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0073] In the following examples: １ H-NMR analysis was carried out using a JNM-ECP500 (manufactured by JEOL Ltd.) and deuterated chloroform as the measurement solvent. The purity of the compounds below was measured by gas chromatography (GC) under the following conditions. Gas chromatography (GC) measurement conditions Gas chromatograph: manufactured by Agilent Technologies Inc. Detector: FID, temperature 300°C Capillary column: J&W HP-5MS (0.25 mm x 30 m x 0.25 μm) Heating program: 50°C (5 min) → 10°C / min → 250°C (hold) Injection port temperature: 250°C Carrier gas: helium (1.0 ml / min) Split ratio: 50:1 Injection volume: 1 μl

[0074] Example 1 Synthesis of Silicone Compound 1 (Production Method 1) 150.0 g (0.833 mol) of potassium 2-(allyloxymethyl)acrylate, 75 g of toluene, 0.56 g of 2,6-di-t-butyl-p-cresol, and 5.2 g of tetrabutylammonium bromide were placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 295.6 g (0.793 mol) of 3-chloropropyltris(trimethylsiloxy)silane was added dropwise over 1 hour at an internal temperature of 95 to 105°C. The mixture was then stirred at 100°C for 3 hours, and analysis by gas chromatography confirmed the disappearance of 3-chloropropyltris(trimethylsiloxy)silane. The resulting solution was purified by distillation under conditions of 7 mmHg and 150°C, yielding 183.6 g of a colorless, transparent liquid (Silicone Compound 1) with a purity of 98.7%. １ By H-NMR measurement, it was confirmed that the obtained silicone compound 1 had a structure represented by the following formula (9). １ H-NMR (CDCl ３, 500MHz) δ: 0.1 (s, 27H), 0.5 (t, 2H), 2.7 (m, 2H), 4.05 (d, 2H), 4.15 (t, 2H ), 4.2 (s, 2H), 5.15-5.25 (m, 2H), 5.7 (s, 1H), 5.7-6.0 (m, 1H), 6.3 (s, 1H).

[0075] Example 2 Synthesis of Silicone Compound 1 (Production Method 2) 115.1 g of 35% aqueous hydrochloric acid, 115.1 g of water, and 230.3 g of 2-propanol were placed in a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 171.2 g (0.563 mol) of an organosilicon compound represented by the following formula (12) and 550.0 g (5.069 mol) of trimethylchlorosilane were added dropwise over 1 hour at an internal temperature of −3 to 15° C., followed by stirring for 2 hours at 25° C. 115.1 g of water was added, and the mixture was allowed to stand, after which washing with water was repeated five times to remove the lower layer of hydrochloric acid by separation. To the resulting upper layer solution, 0.23 g of 2,6-di-t-butyl-p-cresol was added, and the mixture was purified by distillation under conditions of 7 mmHg and 150°C, yielding 120.0 g of a colorless, transparent liquid (silicone compound 1) with a purity of 98.4%. １ By H-NMR measurement, it was confirmed that the obtained silicone compound 1 had a structure represented by the above formula (9). １ H-NMR (CDCl ３ , 500MHz) δ: 0.1 (s, 27H), 0.5 (t, 2H), 2.7 (m, 2H), 4.05 (d, 2H), 4.15 (t, 2H ), 4.2 (s, 2H), 5.15-5.25 (m, 2H), 5.7 (s, 1H), 5.7-6.0 (m, 1H), 6.3 (s, 1H).

[0076] Example 3 Synthesis of Silicone Compound 2 The steps of Example 1 were repeated, except that 250.0 g (0.793 mol) of 3-chloropropylmethylbis(trimethylsiloxy)silane was used instead of 3-chloropropyltris(trimethylsiloxy)silane, to obtain 155.3 g of a colorless, transparent liquid (silicone compound 2) with a purity of 98.5%. １ ​By H-NMR measurement, it was confirmed that the obtained silicone compound 2 had a structure represented by the following formula (10). １ H-NMR (CDCl ３ , 500MHz) δ: 0.1 (s, 21H), 0.5 (t, 2H), 2.7 (m, 2H), 4.05 (d, 2H), 4.15 (t, 2H ), 4.2 (s, 2H), 5.15-5.25 (m, 2H), 5.7 (s, 1H), 5.7-6.0 (m, 1H), 6.3 (s, 1H).

[0077] Preparation of Monomer Mixture [Example 4] The silicone compound 1 (60 parts by mass) obtained in Example 1, N,N-dimethylacrylamide (35 parts by mass), triethylene glycol dimethacrylate (1 part by mass), trifluoroethyl (meth)acrylate (5 parts by mass), and Darocur 1173 (manufactured by Ciba Specialty Chemicals, 0.5 parts by mass) were mixed and stirred to obtain a monomer mixture 1.

[0078] Example 5 In Example 5, a monomer mixture 2 was prepared using the same composition and method as in Example 4, except that silicone compound 1 was replaced with silicone compound 2.

[0079] Comparative Example 1 In Comparative Example 1, a monomer mixture 3 was prepared using the same composition and method as in Example 4, except that silicone compound 1 was replaced with silicone compound 3 (3-[tris(trimethylsiloxy)silyl]propyl methacrylate, manufactured by Gelest).

[0080] [Evaluation Test] (1) Compatibility with Other Polymerizable Monomers The appearance of the monomer mixtures 1 to 3 obtained above was visually observed. Mixtures in which the silicone compound and other (meth)acrylic compounds have good compatibility were colorless and transparent, while mixtures in which compatibility was poor were cloudy. The results are shown in Table 1 below.

[0081] (2) Appearance of Film (Polymer) Each of the monomer mixtures 1 to 3 obtained above was degassed under an argon atmosphere. The mixture was poured into a mold sandwiched between two quartz glass plates and irradiated with an ultra-high pressure mercury lamp for 1 hour to obtain a film with a thickness of approximately 0.3 mm. The appearance of the film was visually observed. The results are shown in Table 1 below.

[0082] (3) Surface Hydrophilicity of Film (Polymer) The water contact angle (°) of the film produced in (2) above was measured by the drop method using a contact angle meter CA-D model (manufactured by Kyowa Interface Science Co., Ltd.) The results are shown in Table 1 below.

[0083] (4) Stain resistance of film (polymer) The film produced in (2) above was immersed in 37°C phosphate buffer solution (PBS(-)) for 24 hours. Each film before and after immersion in PBS(-) for 24 hours was incubated in a known artificial lipid solution at 37°C ± 2°C for 8 hours. Thereafter, the film was rinsed with PBS(-) and immersed in a 0.1% Sudan Black-sesame oil solution. A mark of ○ was given when no difference in the staining state was observed before and after immersion, and a mark of × was given when staining from colorless to black was observed. The results are shown in Table 1 below.

[0084] (5) Durability of Film (Polymer) Two films were prepared according to (2) above, and after wiping off the surface moisture from one of them, it was immersed in phosphate buffer solution (PBS(-)) at 37°C for 24 hours. Each of the films before and after immersion in PBS(-) for 24 hours was cut into a dumbbell shape with a width of 2.0 mm. The upper and lower ends of the test sample were clamped with jigs, and the breaking strength and breaking elongation when continuously pulled at a constant speed were measured using a breaking tester AGS-50NJ (manufactured by Shimadzu Corporation). When the breaking strength and breaking elongation before and after immersion in PBS(-) each changed by 10% or less, they were marked with a circle, and when a decrease of more than 10% was observed in either one, they were marked with an ×. The results are shown in Table 1 below.

[0085]

[0086] As shown in Comparative Example 1, silicone compound 3 has poor compatibility with other (meth)acrylic monomer compounds, making it impossible to obtain a transparent polymer. Furthermore, the resulting polymer has poor surface hydrophilicity and stain resistance, and its mechanical strength decreases when immersed in a phosphate buffer solution. In contrast, the polymerizable silicone monomer of the present invention has good compatibility with other (meth)acrylic monomers, is colorless and transparent, and can provide a polymer with excellent surface hydrophilicity and stain resistance, and the mechanical strength of the polymer does not decrease even when immersed in a phosphate buffer solution.

[0087] The polymerizable silicone monomer of the present invention provides a colorless, transparent polymer with excellent surface hydrophilicity and contamination resistance. Furthermore, polymers containing repeating units derived from the polymerizable silicone monomer of the present invention exhibit excellent durability, without loss of mechanical strength even when immersed in a phosphate buffer solution. Furthermore, the production method of the present invention can provide a compound consisting of a single compound with a specific structure in high purity. Therefore, the polymerizable silicone monomer of the present invention and the method for producing the polymerizable silicone monomer are useful for producing ophthalmic devices such as contact lens materials, intraocular lens materials, and artificial cornea materials.

Claims

1. A polymerizable silicone monomer represented by the following formula (1): (In the formula, R １ are each independently a monovalent hydrocarbon having 1 to 4 carbon atoms; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; R ３ is a hydrogen atom or a methyl group; １ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; Q is -A ２ -O-A ３ -, and -O-A ４ A is a divalent group selected from -O-; ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, ４ is an optionally branched divalent hydrocarbon group having 1 to 3 carbon atoms, at least one of the hydrogen atoms bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.

2. The polymerizable silicone monomer according to claim 1, which is represented by the following formula (a) or (b): (In the formula, R １ , R ２ , R ３ , A ２ , A ３ , A ４ and n is as defined above and m is an integer from 1 to 10.

3. A ２ , A ３ , and A ４ 2. The polymerizable silicone monomer of claim 1, wherein is a group selected from the following:

4. A ２ and A ３ 2. The polymerizable silicone monomer according to claim 1, wherein one of the following is a single bond and the other is a group selected from the following:

5. A ２ , A ３ , and A ４ The polymerizable silicone monomer of claim 1 , wherein is a methylene group.

6. A polymerizable silicone monomer represented by the following formula (1): (In the formula, R １ are each independently a monovalent hydrocarbon having 1 to 4 carbon atoms; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; R ３ is a hydrogen atom or a methyl group; １ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; Q is -A ２ -O-A ３ -, and -O-A ４ A is a divalent group selected from -O-; ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, ４ is a divalent hydrocarbon group having 1 to 3 carbon atoms which may be branched, at least one of the hydrogen atoms bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3), and a carboxylate metal salt compound represented by the following formula (3): (In the formula, R １ , R ２ , R ３ , A １ , Q and n are as defined above, X is a chlorine atom, a bromine atom or an iodine atom, and M is an alkali metal ion) to obtain a polymerizable silicone monomer represented by formula (1).

7. A ２ , A ３ , and A ４ The method according to claim 6, wherein is a group selected from the following:

8. A ２ and A ３ The method according to claim 6, wherein one of the above is a single bond and the other is a group selected from the following:

9. A ２ , A ３ , and A ４ The method according to claim 6, wherein is a methylene group.

10. A polymerizable silicone monomer represented by the following formula (1): (In the formula, R １ are each independently a monovalent hydrocarbon having 1 to 4 carbon atoms; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; R ３ is a hydrogen atom or a methyl group; １ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; Q is -A ２ -O-A ３ -, and -O-A ４ A is a divalent group selected from -O-; ２ and A ３ are each independently a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, with the proviso that A ２ and A ３ are not single bonds, ４ is a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3, comprising an organosilicon compound represented by the following formula (4): A hydrolyzable organosilicon compound represented by the following formula (5) and / or a disiloxane compound represented by the following formula (6): (In the formula, R １ , R ２ , R ３ , A １ , Q and n are the same as above, R ４ is an alkyl group having 1 to 4 carbon atoms, and Y is a chlorine atom, a bromine atom, or an iodine atom) in the presence of an acid to obtain a polymerizable silicone monomer represented by formula (1).

11. A ２ , A ３ , and A ４ The method according to claim 10, wherein is a group selected from the following:

12. A ２ and A ３ The method according to claim 10, wherein one of the above is a single bond and the other is a group selected from the following:

13. A ２ , A ３ , and A ４ The method according to claim 10, wherein is a methylene group.

14. A curable composition comprising the polymerizable silicone monomer according to any one of claims 1 to 5 and another polymerizable monomer having a group that polymerizes with said polymerizable silicone monomer.

15. The curable composition according to claim 14, wherein the polymerizable silicone monomer according to any one of claims 1 to 5 is contained in the curable composition in an amount of 10 to 80% by weight.

16. A polymer obtained by polymerizing the curable composition according to claim 15.

17. An ophthalmic device comprising the polymer according to claim 16.

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