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

Abstract

To provide a polymerizable silicone monomer which gives a polymer excellent in transparency, surface hydrophilicity, durability and stain resistance, a method for producing the monomer, a curable composition containing the monomer, a polymer of the composition, and an ophthalmic device using the polymer.SOLUTION: The polymerizable silicone monomer is represented by the following formula (1). (In the formula, each R1 is independently a C1-4 monovalent hydrocarbon group; each R2 is independently a C1-10 alkyl group or a C6-10 aryl group; R3 is a hydrogen atom or a methyl group; A1 is a single bond or a C1-20 divalent hydrocarbon group; Q is a divalent group selected from -A2-O-A3- and -O-A4-O-; A2 and A3 are each independently a single bond or an optionally branched C1-3 divalent hydrocarbon group, wherein at least one hydrogen atom bonded to a carbon atom of the divalent hydrocarbon group may be substituted with a C1-4 alkoxy group; and n is an integer of 1-3.)SELECTED DRAWING: None

Description

[Technical field]

[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. [Background technology]

[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 problem 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, and describe that the composition gives a polymer excellent in transparency, water absorption, and toughness. The polymerizable compound has the property of undergoing cyclic polymerization by a radical polymerization mechanism. The polymer of the composition containing the polymerizable compound has superior transparency, water absorption, and toughness compared to those containing conventional polymerizable compounds. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2011-074068 A [Patent Document 2] JP 2011-137123 A

[0005] Silicone monomers having acryloyl or methacryloyl groups are known as silicone monomers having 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 properties. Summary of the Invention [Problem to be solved by the invention]

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

[0007] As a result of intensive research into achieving the above-mentioned object, the inventors have 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 has excellent transparency, surface hydrophilicity, durability, and stain resistance, thereby completing the present invention.

[0008] That is, the present invention provides [1] Provided is a polymerizable silicone monomer represented by the following formula (1): [ka] (In the formula, R 1 are each independently a monovalent hydrocarbon group 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, A 1 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Q is -A 2 -OA 3 - and -OA 4 A is a divalent group selected from -O-, 2 and A 3are 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, A 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.

[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): [ka] (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 is a group selected from the following: [ka] [4]A 2 and A 3 The polymerizable silicone monomer according to any one of the above [1] to [3], wherein one of the following is a single bond and the other is a group selected from the following: [ka] [5]A 2 , A 3 , and A 4The polymerizable silicone monomer according to any one of the above [1] to [4], wherein is a methylene group.

[0010] Further, the present invention relates to [6] A polymerizable silicone monomer represented by the following formula (1): [ka] (In the formula, R 1 are each independently a monovalent hydrocarbon group 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, A 1 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Q is -A 2 -OA 3 - and -OA 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, A 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. The method comprises the steps of: [ka] and a carboxylate metal salt compound represented by the following formula (3): [ka] (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, which further has at least one of the following configurations [7] to

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

[10] A 2 , A 3 , and A 4 The method according to any one of the above [6] to [9], wherein is a methylene group.

[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 above formula (2) to the carboxylate metal salt compound represented by the above formula (3) is 1.0:0.3 to 1.0:3.0 in terms of molar ratio.

[0012] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of:

[12] A polymerizable silicone monomer represented by the following formula (1): [ka] (In the formula, R1 are each independently a monovalent hydrocarbon group 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, A 1 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Q is -A 2 -OA 3 - and -OA 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, A 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. A method for producing An organosilicon compound represented by the following formula (4), [ka] A hydrolyzable organosilicon compound represented by the following formula (5) and / or a disiloxane compound represented by the following formula (6): [ka] (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, a bromine atom, or an iodine atom. and a step of subjecting the above to a hydrolysis and condensation reaction in the presence of an acid to obtain a polymerizable silicone monomer represented by the above formula (1).

[0013] The present invention further provides the above-mentioned production method, which further has at least one of the following configurations

[13] to

[19] .

[13] The method according to the above

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

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

[15] A 2 and A 3 wherein one of the above is a single bond, and the other is a group selected from the following: [ka]

[16] A 2 , A 3 , and A 4 The method according to any one of the above

[12] to

[15] , wherein is a methylene group.

[17] The organosilicon compound represented by the above formula (4) and the hydrolyzable organosilicon compound represented by the above formula (5) are subjected to OR 4 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 group is from 1:1 to 1:10.

[18] An organosilicon compound represented by the above formula (4) and a disiloxane compound represented by the following formula (6) are combined with an OR having the organosilicon compound represented by the above formula (4). 4 R in the disiloxane represented by formula (6) above relative to the number of moles of the group 1 3The 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 the above formula (4).

[0014] The present invention further provides a curable composition comprising 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 comprising the polymer.

[0015] That is,

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

[21] The curable composition according to

[14] above, wherein the curable composition contains the polymerizable silicone monomer according to any one of [1] to [5] above 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. to provide. Furthermore, the present invention provides an ophthalmic device having at least one of the following configurations

[24] to

[28] .

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

[25] The ophthalmic device according to the above

[24] , wherein the content of the polymerizable silicone monomer represented by the formula (1) is 10 to 80 parts by mass per 100 parts by mass 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 acrylic monomers, acrylic acid derivatives, crotonic acid, cinnamic acid, vinyl benzoic acid, and silicone monomers 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 a polymerization initiator, an antioxidant, a colorant, a lubricant, an internal wetting agent, and a strengthening agent.

[28] The ophthalmic device according to any one of

[24] to

[27] above, which is selected from 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 stain resistance, and can therefore be suitably used in applications such as ophthalmic devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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). [ka]

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

[0020] R 2are 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 of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, and cyclohexyl groups. Examples of the aryl group 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, and 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 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 of the alkylene groups 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, and preferably 2 or 3.

[0024] Q is -A 2 -OA 3 - and -OA 4 A is a divalent group selected from -O-. 2 and A3 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 Neither of are single bonds. A 4 is a divalent hydrocarbon group having 1 to 3 carbon atoms which may have a branch, and 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.

[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, and are preferably a methylene group.

[0026] The polymerizable silicone monomer of the present invention is preferably represented by the following formula: [ka] (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.

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

[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: [ka]

[0029] Above A 2 , A 3 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). [ka] (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). [ka] (wherein Me represents a methyl group).

[0033] [Manufacturing 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 carboxylate metal salt compound represented by the following formula (3). [ka] (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] The alkali metal for M includes sodium, potassium, and the like.

[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. [ka] A 2 , A 3 and A 4 is as described above, and is preferably a group selected from the following. In another preferred embodiment, A 2 and A 3 One of the groups is a single bond, and the other is a group selected from the following: [ka] Most preferably A 2 , A 3 and A 4 is a methylene group.

[0037] Examples of the carboxylate 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 the formula (2) and the metal carboxylate compound represented by the 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 necessary. Examples of the phase transfer catalyst 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, its amount is not particularly limited, but from the standpoint of reactivity and productivity, it is preferable to use 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 of the catalyst per 100 parts by mass of the halogen-containing organosilicon compound represented by the above formula (2).

[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, decane, etc., ether solvents such as diethyl ether, tetrahydrofuran, etc., aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc. 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 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] [Manufacturing method 2] The polymerizable silicone monomer of the present invention can be obtained by subjecting an organosilicon compound represented by formula (4) below to a hydrolysis condensation reaction with a hydrolyzable organosilicon compound represented by formula (5) below and / or a disiloxane compound represented by formula (6) below in the presence of an acid. [ka] [ka] (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. Among these, a methyl group and an ethyl group are more preferable.

[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. [ka] A 2 , A 3 and A 4 is as described above, and is preferably a group selected from the following structures. In another preferred embodiment, A 2 and A 3 One of the groups is a single bond, and the other is a group selected from the following formulas: [ka] 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). [ka] (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 above formula (4) and the hydrolyzable organosilicon compound represented by the above formula (5) are, in terms of molar ratio, OR in the organosilicon compound. 4 The reaction is preferably carried out in a ratio of group:hydrolyzable organosilicon compound=1:1 to 1:10, particularly preferably 1:2 to 1:5.

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

[0057] The hydrolyzable organosilicon compound represented by the above formula (5) and the disiloxane represented by the above formula (6) may be mixed with the organosilicon compound represented by the above formula (4) in such a ratio that the above-mentioned ratio is satisfied.

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

[0059] During the hydrolysis and condensation reaction, a solvent may be used as necessary. For example, an alcohol solvent such as methanol, ethanol, 1-propanol, or 2-propanol may be used. 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 adding sulfuric acid, the organosilicon compound represented by formula (4) above, and water in that order to a mixture of a disiloxane compound represented by formula (6) above and a solvent.

[0061] The reaction temperature in the above 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] The reaction liquid after the above hydrolysis and condensation reaction 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, and purified by distillation under reduced pressure to obtain the polymerizable silicone monomer of the present invention.

[0064] When producing the polymerizable silicone monomer of the present invention, it is preferable to add a polymerization inhibitor, and it is more preferable to make 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] As the polymerization inhibitor, a polymerization inhibitor for radical polymerizable monomers can be used. For example, phenol-based 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 can be mentioned. Among these, phenol-based inhibitors are preferred in terms of low coloration and polymerization inhibition ability, and p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 6-t-butyl-2,4-xylenol, and 2,6-di-t-butylphenol are preferred in terms of availability and economy. These polymerization inhibitors may be used alone or in combination of two or more types. The amount of the 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 the above formula (3) or the organosilicon compound represented by the above formula (4).

[0066] According to the production method of the present invention, a compound represented by the above formula (1) having a specific n, 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-mentioned specific structure in high purity. High purity means that the one type having the above-mentioned specific structure constitutes more than 95 mass %, preferably 97 mass % or more, and more preferably 99 mass % or more of the total mass of the compound. In the present invention, the purity is determined by gas chromatography (hereinafter referred to as "GC") analysis. Detailed conditions will be described later. When the compound has the above-mentioned 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% by mass, more preferably 20 to 70% by mass. In addition, when the composition contains a solvent, the content refers to the non-volatile 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 polymerizable with the polymerizable silicone monomer represented by the above formula (1). 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 vinyl benzoic 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] The copolymerization of the polymerizable silicone monomer of the present invention with the other polymerizable monomers may be carried out by a conventionally known method. For example, it may be carried out using a known polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator. Examples of the polymerization initiator 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 the polymerization initiator is 0.001 to 2 parts by mass, preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total of the polymerization components. The polymerization reaction may be carried out under conventionally known reaction conditions. For example, there is a method of photopolymerization by irradiating light containing ultraviolet rays using a mercury lamp or an ultraviolet lamp for, for example, within 1 hour, or a method of thermal polymerization at a temperature of, for example, 60°C to 200°C for, for example, 0.1 hour to several hours.

[0070] [Ophthalmic Devices] The present invention preferably provides an ophthalmic device made of a copolymer of a monomer mixture containing the polymerizable silicone monomer of the present invention and the other polymerizable monomer. The content ratio 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 the range that does not impair the object and effect 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 stain resistance.Therefore, it is suitable for manufacturing ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas.The manufacturing method of the ophthalmic device using the polymer is not particularly limited, and may follow the manufacturing method of the conventionally known ophthalmic device.For example, when forming into the shape of a lens such as a contact lens or an intraocular lens, cutting processing method or casting (mold) method can be used. EXAMPLES

[0072] 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. In the following, the purity of the compounds was measured by gas chromatography (GC) under the following conditions. Gas chromatography (GC) measurement conditions Gas chromatograph: Agilent Technologies Detector: FID, temperature 300℃ Capillary column: J&W HP-5MS (0.25mm x 30m x 0.25μm) Heating program: 50℃ (5 min) → 10℃ / min → 250℃ (hold) Inlet temperature: 250℃ Carrier gas: Helium (1.0 ml / min) Split ratio: 50:1 Injection volume: 1μl

[0074] [Example 1] Synthesis of Silicone Compound 1 (Production Method 1) In a 1L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 150.0g (0.833 mol) of potassium 2-(allyloxymethyl)acrylate, 75g of toluene, 0.56g of 2,6-di-t-butyl-p-cresol and 5.2g of tetrabutylammonium bromide were placed, and 295.6g (0.793 mol) of 3-chloropropyltris(trimethylsiloxy)silane was added dropwise at an internal temperature of 95-105°C over 1 hour. After stirring at 100°C for 3 hours, the disappearance of 3-chloropropyltris(trimethylsiloxy)silane was confirmed by analysis using gas chromatography. The resulting solution was purified by distillation under conditions of 7mmHg and 150°C to obtain 183.6g of a colorless and transparent liquid (silicone compound 1) with a purity of 98.7%. 1 1 H-NMR measurement 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). [ka]

[0075] [Example 2] Synthesis of Silicone Compound 1 (Production Method 2) In a 2L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 115.1g of 35% hydrochloric acid, 115.1g of water, and 230.3g of 2-propanol were placed, and 171.2g (0.563 mol) of an organosilicon compound represented by the following formula (12) and 550.0g (5.069 mol) of trimethylchlorosilane were added dropwise at an internal temperature of -3 to 15°C over 1 hour, and then stirred at 25°C for 2 hours. 115.1g of water was added, and the mixture was allowed to stand, after which the lower layer of hydrochloric acid was separated and removed by washing with water five times. 0.23g of 2,6-di-t-butyl-p-cresol was added to the obtained upper layer solution, and then distillation purification was performed under conditions of 7mmHg and 150°C to obtain 120.0g of a colorless and transparent liquid (silicone compound 1) with a purity of 98.4%. [ka] 1 1 H-NMR measurement 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 in Example 1, to obtain 155.3 g of a colorless, transparent liquid (silicone compound 2) with a purity of 98.5%. 1 By 1 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). [ka]

[0077] Preparation of the 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 in the same manner and with the same composition as in Example 4, except that the silicone compound 1 was replaced with the silicone compound 2.

[0079] [Comparative Example 1] In Comparative Example 1, a monomer mixture 3 was prepared with the same composition and by the same 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. A mixture in which the silicone compound and other (meth)acrylic compounds have good compatibility was colorless and transparent, but a mixture in which the compatibility was poor was cloudy. The results are shown in Table 1 below.

[0081] (2) Appearance of the film (polymer) The monomer mixtures 1 to 3 obtained above were each 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 about 0.3 mm. The appearance of the film was visually observed. The results are shown in Table 1 below.

[0082] (3) Hydrophilic surface 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 type (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(-) was incubated in a known artificial lipid liquid at 37°C ± 2°C for 8 hours. It was then 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, one of which was wiped to remove surface moisture and then immersed in 37°C phosphate buffer solution (PBS(-)) for 24 hours. Each film before and after immersion in PBS(-) was cut into a dumbbell shape with a width of 2.0 mm, and the upper and lower ends of the test sample were clamped with a jig and the breaking strength and breaking elongation when pulled at a constant speed were measured using a breaking tester AGS-50NJ (manufactured by Shimadzu Corporation). If the breaking strength and breaking elongation before and after immersion in PBS(-) each changed by within 10%, they were marked as ○, and if a decrease of more than 10% was observed in either one, they were marked as ×. The results are shown in Table 1 below.

[0085] [Table 1]

[0086] As shown in Comparative Example 1, silicone compound 3 has poor compatibility with other (meth)acrylic monomer compounds, and a transparent polymer cannot be obtained. In addition, the obtained polymer has poor surface hydrophilicity and stain resistance, and furthermore, the mechanical strength is reduced by immersion 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 furthermore, the mechanical strength of the polymer does not decrease even when immersed in a phosphate buffer solution. [Industrial Applicability]

[0087] The polymerizable silicone monomer of the present invention is colorless and transparent, and provides a polymer with excellent surface hydrophilicity and stain resistance. Furthermore, the polymer containing the repeating unit derived from the polymerizable silicone monomer of the present invention does not lose mechanical strength even when immersed in a phosphate buffer solution, and has excellent durability. In addition, the production method of the present invention can provide a compound consisting of one type of compound having a specific structure with high purity. Therefore, the polymerizable silicone monomer of the present invention and the production method of the polymerizable silicone monomer are useful for the production of 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): 【Chemistry 1】 (In the formula, R １ are each independently a monovalent hydrocarbon group 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, A 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, A 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): 【Chemistry 2】 (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: 【Chemistry 3】

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: 【Chemistry 4】

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): 【Chemistry 5】 (In the formula, R １ are each independently a monovalent hydrocarbon group 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, A 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, A 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. The present invention relates to a method for producing a halogen-containing organosilicon compound represented by the following formula (2): 【Chemistry 6】 and a carboxylate metal salt compound represented by the following formula (3): 【Chemistry 7】 (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: 【Chemistry 8】

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: 【Chemistry 9】

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): 【Chemistry 10】 (In the formula, R １ are each independently a monovalent hydrocarbon group 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, A 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, A 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. A method for producing An organosilicon compound represented by the following formula (4): 【Chemistry 11】 A hydrolyzable organosilicon compound represented by the following formula (5) and / or a disiloxane compound represented by the following formula (6): 【Chemistry 12】 (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. and reacting the above with each other by hydrolysis and condensation 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: 【Chemistry 13】

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: 【Chemistry 14】

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

14. 6. A curable composition comprising the polymerizable silicone monomer according to claim 1 and another polymerizable monomer having a group that polymerizes with the 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 mass %.

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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