Polysiloxane compound and its manufacturing method

Abstract

To provide a polysiloxane compound preferred to a medical material, and a production method of the same.SOLUTION: The polysiloxane compound is a polysiloxane compound including one 8-20C cyclic aliphatic hydrocarbon group in a molecule which has a (meth)acryloxy group, and a tertiary hydroxy group on an aliphatic ring of the cyclic aliphatic hydrocarbon group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polysiloxane compound and a method for producing the same. [Background technology]

[0002] Conventionally, siloxane-containing monomers have been known as compounds used in medical materials, including ophthalmic devices. For example, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) is widely used as a monomer for ophthalmic devices. Polymers obtained by copolymerizing this TRIS with hydrophilic monomers N,N-dimethylacrylamide and N-vinyl-2-pyrrolidone have the beneficial feature of being highly oxygen permeable. However, highly hydrophobic siloxane monomers are not highly compatible with these hydrophilic monomers, and there is a problem that phase separation occurs when hydrogels that are used as medical materials are prepared, resulting in cloudiness.

[0003] Patent Document 1 describes siloxanes having glycerol methacrylate represented by the following formulas (a) and (a'). [ka] Furthermore, Patent Document 2 describes siloxanes having glycerol methacrylate represented by the following formulas (b) and (b'). [ka] Furthermore, Patent Document 3 describes a siloxane having an alicyclic methacrylate represented by the following formula (c). [ka] These compounds have good hydrophilicity due to the presence of hydroxyl groups in the molecule, and therefore have the advantage of being highly compatible with hydrophilic monomers.

[0004] However, when preparing a hydrogel using a compound having a primary hydroxyl group or a secondary hydroxyl group in the linking group between the (poly)siloxane and the polymerizable group as described above, these highly reactive hydroxyl groups may cause undesirable results. For example, radicals may be added to the hydroxyl groups, forming a crosslinked structure due to hydroxyl radicals. This causes an unexpected increase in hardness and a decrease in flexibility. Therefore, conventional siloxane compounds cannot provide medical materials with beneficial hydrophilicity and sufficient strength. Therefore, there is still a demand for compounds and compositions that overcome these drawbacks. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2005-170827 A [Patent Document 2] JP 2013-231046 A [Patent Document 3] Special Publication No. 2018-510946 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a polysiloxane compound suitable for use in medical materials and a method for producing the same. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides a polysiloxane compound containing one cyclic aliphatic hydrocarbon group having 8 to 20 carbon atoms in one molecule, the polysiloxane compound having a (meth)acryloxy group and a tertiary hydroxyl group on the aliphatic ring of the cyclic aliphatic hydrocarbon group.

[0008] Such a polysiloxane compound can be suitably used as a medical material.

[0009] In the present invention, the polysiloxane compound is preferably a compound represented by the following formula (1). [ka] (In formula (1), R 1 is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3). [ka] [ka] (In the formula (2), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 200. The dashed line represents a bond. In the formula (3), R is as defined above, a is an integer of 0 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed line represents a bond.)

[0010] Such a polysiloxane compound can be suitably used as a medical material.

[0011] In the present invention, it is preferable that in the formula (1), A is represented by the formula (2) and n is an integer of 4 to 100.

[0012] Such a polysiloxane compound can be more suitably used as a medical material.

[0013] In the present invention, it is also preferable that in the formula (1), A is represented by the formula (3), a is 1, b is 1 and c is 0.

[0014] Such a polysiloxane compound can be more suitably used as a medical material.

[0015] In the present invention, in the formula (1), R 1 is preferably a methyl group.

[0016] The polysiloxane compound of the present invention is preferably such a compound.

[0017] In the present invention, in the formula (2) or (3), R is preferably, independently of each other, a methyl group or a butyl group.

[0018] The polysiloxane compound of the present invention is more preferably such a compound.

[0019] The present invention also provides a polymer that contains repeating units derived from polymerization of the (meth)acryloxy groups of the above-described polysiloxane compound.

[0020] Such a polymer has good compatibility with other compounds having a polymerizable group such as a (meth)acryloxy group.

[0021] In this case, the mass proportion of the repeating unit is preferably 10 mass % or more based on the total mass of the polymer.

[0022] Such a polymer is likely to exhibit the properties of the polysiloxane compound.

[0023] The present invention also provides a hydrogel or a medical material that contains the above-described polymer.

[0024] The polymer of the present invention can be suitably used for such applications.

[0025] The present invention also provides a method for producing a polysiloxane compound represented by the following formula (1): [ka] (In formula (1), R 1 is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3). [ka] [ka] (In the formula (2), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 200. The dashed line represents a bond. In the formula (3), R is as defined above, a is an integer of 0 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed line represents a bond.) A compound having an unsaturated group at a terminal, represented by the following formula (4): [ka] (R 1 is as above.) A hydrogen siloxane compound represented by the following formula (5) or (6): [ka] [ka] (R, n, a, b, and c are as defined above.) and subjecting the resulting compound to a hydrosilylation reaction to obtain a polysiloxane compound represented by formula (1).

[0026] Such a method for producing a polysiloxane compound makes it possible to obtain a polysiloxane compound with high purity. Effect of the Invention

[0027] The polysiloxane compound of the present invention has a cyclic aliphatic hydrocarbon group substituted with a tertiary hydroxyl group, and therefore has excellent compatibility with hydrophilic monomers, and does not cause unexpected increase in hardness or decrease in flexibility when used as a medical material. Furthermore, (co)polymers containing repeating units derived from polymerization of the (meth)acryloxy groups of the polysiloxane compound of the present invention have favorable strength. The polysiloxane compound of the present invention is useful as a monomer for medical materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] As described above, there has been a demand for the development of a polysiloxane compound suitable for use in medical materials and a method for producing the same.

[0029] The present inventors have conducted extensive research to solve the above problems and have found that a polysiloxane compound having a cyclic aliphatic hydrocarbon group substituted with a tertiary hydroxyl group has excellent compatibility with other hydrophilic monomers, and further that a (co)polymer of the (poly)siloxane compound and a hydrophilic monomer has excellent flexibility.

[0030] That is, the present invention relates to a polysiloxane compound containing one cyclic aliphatic hydrocarbon group having 8 to 20 carbon atoms in one molecule, the polysiloxane compound having a (meth)acryloxy group and a tertiary hydroxyl group on the aliphatic ring of the cyclic aliphatic hydrocarbon group, and in particular to a polysiloxane compound represented by the following formula (1): [ka] (In formula (1), R 1 is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3). [ka] [ka] (In the formula (2), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 200. The dashed line represents a bond. In the formula (3), R is as defined above, a is an integer of 0 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed line represents a bond.) The present invention further provides a method for producing the polysiloxane compound, a polymer containing a repeating unit derived from the compound, and a medical material, particularly an ophthalmic device, containing the polymer.

[0031] The present invention will be described in detail below, but the present invention is not limited thereto.

[0032] [Polysiloxane compounds] The present invention relates to a polysiloxane compound containing one cyclic aliphatic hydrocarbon group having 8 to 20 carbon atoms in one molecule, the polysiloxane compound having a (meth)acryloxy group and a tertiary hydroxyl group on the aliphatic ring of the cyclic aliphatic hydrocarbon group.

[0033] The alicyclic hydrocarbon group having a (meth)acryloxy group and a tertiary hydroxyl group on the aliphatic ring is not particularly limited as long as it has 8 to 20 carbon atoms, but is preferably a alicyclic hydrocarbon group as shown in the following formula. [ka] (In the above formula, * represents a free radical bonded to a silicon atom of polysiloxane.)

[0034] In particular, the polysiloxane compound is preferably a polysiloxane compound represented by the following formula (1). [ka] (In formula (1), R 1 is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3). [ka] [ka] (In the formula (2), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 200. The dashed line represents a bond. In the formula (3), R is as defined above, a is an integer of 0 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed line represents a bond.)

[0035] The compound has a polysiloxane structure, and the linking group between the polysiloxane and the (meth)acryloxy group, which is a polymerizable group, contains a cyclic aliphatic hydrocarbon group substituted with a tertiary hydroxyl group. In the polysiloxane compound of the present invention, the tertiary hydroxyl group becomes a hydrophilic group, which has a steric restriction. This suppresses side reactions during the reaction, and it is presumed that a strong hydrogen bond due to the directionality of the hydrogen bond is generated in a polymer ((co)polymer) containing a repeating unit derived from the polymerization of the (meth)acryloxy group of the polysiloxane compound of the present invention, and high strength is obtained. That is, the polysiloxane compound of the present invention has high compatibility with hydrophilic monomers, and can provide a preferable strength in the derived (co)polymer, and further, no unexpected increase in hardness or decrease in flexibility occurs.

[0036] In the above formula (1), R 1 is a methyl group or a hydrogen atom, and is preferably a methyl group.

[0037] A is a group represented by the above formula (2) or (3), and n is an integer of 1 to 200, preferably an integer of 4 to 100, and more preferably an integer of 4 to 30. a is an integer of 0 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10, with the proviso that a+b+c is 2 or more. In formula (3), it is preferable that a is 1, b is 1, and c is 0.

[0038] In the above formula (2) or (3), R is, independently of each other, a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl. R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or a butyl group.

[0039] [Method for producing polysiloxane compound] A method for producing the polysiloxane compound represented by the above formula (1) will now be described. The method for producing a polysiloxane compound of the present invention includes the steps of: [ka] (R 1 is as above.) A hydrogen siloxane compound represented by the following formula (5) or (6): [ka] [ka] (R, n, a, b, and c are as defined above.) and reacting the above with each other in the presence of a catalyst to obtain a compound represented by formula (1).

[0040] The method for producing a polysiloxane compound of the present invention is characterized by using a compound (formula (4)) having an unsaturated bond at the end and a cyclic aliphatic hydrocarbon group substituted with a tertiary hydroxyl group as a raw material. In the method for producing a polysiloxane compound of the present invention, the hydroxyl group of the raw material compound represented by the above formula (4) is a tertiary hydroxyl group present on a cyclohexane ring, so that the hydroxyl group can be prevented from causing an undesirable side reaction in the hydrosilylation reaction. This makes it possible to obtain the polysiloxane compound of the present invention with high purity.

[0041] The hydrosilylation reaction may be carried out according to a conventional method. In the present invention, the unsaturated compound represented by formula (4) may be added, for example, in an amount of 1 molar equivalent or more to the hydrogensiloxane compound represented by formula (5) or formula (6) and reacted. The reaction temperature is not particularly limited, but a temperature not exceeding the boiling point of the solvent used is preferred. For example, the reaction may be carried out at a temperature of about 0°C to about 120°C. The hydrosilylation reaction may be carried out in the presence of a solvent, a hydrosilylation catalyst, or a stabilizer. The solvent, hydrosilylation catalyst, and stabilizer may be conventionally known and are not particularly limited.

[0042] In the above hydrosilylation reaction, the unsaturated compound is preferably added in an amount of 1 molar equivalent or more relative to the hydrogensiloxane compound. More preferably, it is 1.0 to 3.0 molar equivalents, even more preferably, it is 1.1 to 2.0 molar equivalents, and particularly preferably, it is 1.2 to 1.5 molar equivalents. By adding 1 molar equivalent or more of the unsaturated compound relative to the hydrogensiloxane compound, it is possible to suppress the remaining hydrogensiloxane compound and side reactions. In addition, although there is no upper limit, it is preferable that the amount is 3.0 molar equivalents or less in terms of yield and economic efficiency.

[0043] (Hydrosilylation catalyst) The hydrosilylation catalyst is preferably, for example, a noble metal catalyst, particularly a platinum catalyst derived from chloroplatinic acid. In particular, it is preferable to completely neutralize the hydrogen ions of chloroplatinic acid with sodium bicarbonate to improve the stability of the platinum catalyst. For example, a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and sodium bicarbonate neutralized chloroplatinic acid (Karstead catalyst) is more preferable.

[0044] The amount of the hydrosilylation catalyst added may be a catalytic amount sufficient to promote the hydrosilylation reaction, for example, a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and chloroplatinic acid neutralized with sodium bicarbonate may be used in an amount equivalent to 1 ppm to 80 ppm of platinum relative to the mass of the hydrogensiloxane compound represented by formula (5) or (6).

[0045] (solvent) Examples of the solvent include glycol ether solvents such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, and methyl benzoate; aliphatic hydrocarbon solvents such as linear hexane, linear heptane, and linear octane; alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and petroleum solvents; and alcohol solvents such as methyl alcohol, ethyl alcohol, linear propyl alcohol, isopropyl alcohol, linear butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. The above solvents may be used alone or in combination of two or more.

[0046] (Stabilizer) Examples of the stabilizer include phenol-based antioxidants, phosphorus-based antioxidants, amine-based antioxidants, and sulfur-based antioxidants. Examples of the phenol-based antioxidant include, but are not limited to, compounds selected from the group consisting of p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenol resins, and cresol resins. Examples of phosphorus-based antioxidants include, but are not limited to, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-ditert-butyl-6-methylphenyl)phosphite. Examples of amine-based antioxidants include, but are not limited to, tri- or tetra-C1-3 alkylpiperidine or a derivative thereof, bis(2,2,6,6-tetramethyl-4-piperidyl)o tree Examples of the sulfur-based antioxidant include, but are not limited to, dilauryl thiodipropionate, distearyl thiodipropionate, etc. The stabilizers may be used alone or in combination of two or more.

[0047] In the above hydrosilylation reaction, the end point of the reaction can be confirmed by a conventionally known method, for example, by the disappearance of the peak of the raw material compound by thin layer chromatography (TLC), high performance liquid chromatography (HPLC), gas chromatography (GC), or the like. After the reaction is completed, the product may be purified according to a conventional method. For example, the organic layer may be washed with water and then the solvent may be removed to isolate the product. Alternatively, reduced pressure distillation or activated carbon treatment may be used.

[0048] As an example of the method for producing the polysiloxane compound of the present invention, 1 molar equivalent of the hydrogensiloxane compound represented by formula (5) or formula (6), 1.3 molar equivalent of the unsaturated compound represented by the above formula (4), a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5 wt%) is added in an amount of 10 ppm in terms of platinum relative to the mass of the polysiloxane compound, and toluene is added at 100 mass% relative to the hydrogensiloxane compound, and the mixture is heated and stirred at 80°C under a nitrogen atmosphere. The reaction is completed by reacting for about 2 hours. The progress of the reaction can be confirmed by monitoring the unsaturated compound or the compound produced during the reaction by GC measurement or the like. After the reaction is completed, 100 mass% of n-hexane is added relative to the hydrogensiloxane compound, the organic layer is washed with methanol water (methanol:water = 4:1), and the solvent and unreacted raw materials present in the organic layer are distilled off under reduced pressure to obtain the polysiloxane compound represented by the above formula (1).

[0049] [polymer] The polysiloxane compound of the present invention can give a polymer containing a repeating unit derived from the (meth)acryloxy group of the polysiloxane compound (addition) polymerization. The polysiloxane compound of the present invention has good compatibility with other compounds having a polymerizable group such as a (meth)acryloxy group (hereinafter referred to as a polymerizable monomer or a hydrophilic monomer). Therefore, a colorless and transparent copolymer can be obtained by copolymerizing with a polymerizable monomer. It is also possible to polymerize it alone.

[0050] In the production of a copolymer containing a repeating unit derived from the polymerization of the polysiloxane compound of the present invention and another polymerizable (hydrophilic) monomer, the blending ratio of the polysiloxane compound of the present invention is preferably such that the mass ratio of the repeating unit derived from the polysiloxane compound of the present invention is 10 mass% or more relative to the total mass of the polymer. More specifically, the repeating unit derived from the (addition) polymerization of the (meth)acryloxy group of the polysiloxane compound of the present invention is preferably 10 to 80 mass parts, more preferably 10 to 60 mass parts, relative to 100 mass parts in total of the polysiloxane compound of the present invention and the polymerizable (hydrophilic) monomer. If the mass ratio of the repeating unit is 10 mass% or more, the properties of the polysiloxane compound of the present invention are easily exhibited.

[0051] 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, 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 N-vinylpyrrolidone, for example, crotonic acid, cinnamic acid, and vinylbenzoic acid; and siloxane monomers having a polymerizable group such as a (meth)acrylic group. These may be used alone or in combination of two or more.

[0052] The copolymerization of the polysiloxane compound of the present invention with the other polymerizable monomers may be carried out by a conventionally known method. For example, known polymerization initiators such as thermal polymerization initiators and photopolymerization initiators may be used. Examples of the polymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and 2,2'-azobis(2-methylpropionamidine) dihydrochloride. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the polymerization components.

[0053] The polymer containing the repeating unit derived from the polymerization of the (meth)acryloxy group of the polysiloxane compound of the present invention has excellent hydrophilicity. In addition, the hydrogel obtained from the polymer has high transparency and strength. In addition, medical materials can be obtained from the polymer. Therefore, the polysiloxane compound of the present invention is suitable for producing medical materials, such as ophthalmic devices, contact lenses, intraocular lenses, and artificial corneas. The method for producing medical materials using the polymer is not particularly limited, and may follow the conventionally known method for producing medical materials. For example, when forming into the shape of a lens such as a contact lens or an intraocular lens, a cutting method or a casting method can be used. EXAMPLES

[0054] 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. In the following examples: 1 H-NMR analysis was carried out using a JEOL ECS400 and deuterated chloroform as the measurement solvent. In addition, all gas chromatographic (GC) measurements were carried out under the following conditions. Measurement equipment: Agilent gas chromatography (FID detector) Capillary column: Agilent J&W HP-5ms (Inner diameter: 0.25 mm x length: 30 m x film thickness: 0.25 μm) Heating program: 50℃ (5 min) → 10℃ / min → 250℃ (hold) Inlet temperature: 250℃ Detector temperature: FID 300℃ Carrier gas: Helium (1.0 ml / min) Split ratio: 50:1 Injection volume: 1μL

[0055] The compounds used in the following Examples and Comparative Examples are as follows. MHMVCH: ​​a compound represented by formula (7) [ka] AHPM: isomeric mixture of compounds represented by formula (8A) and (8B) [ka] C-SiGMA: isomeric mixture of compounds represented by formulas (9A) and (9B) [ka]

[0056] Synthesis Example 1 In a 300mL three-necked flask equipped with a Dimroth and thermometer, 50.0g of the hydrogensiloxane compound represented by the following formula (10), 42.6g of MHMVCH (molar ratio of unsaturated compounds to hydrogensiloxane compound = 1.3), 50.0g of toluene, and 0.03g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5wt%) were added under a nitrogen atmosphere, and the mixture was heated to 80℃ and aged for 4 hours. After the reaction, 50.0g of n-hexane was added, washed five times with an aqueous methanol solution (methanol:water = 4:1), and the solvent and unreacted raw materials were distilled off under reduced pressure at an internal temperature of 80℃ to obtain a colorless transparent liquid. Yield 72.5g. 1It was confirmed by H-NMR that the compound was the compound represented by formula (10A). GC measurement was performed, and the purity of the target compound was calculated from the area % to be 92.3%. [ka] [ka] Below 1 H-NMR data is shown. -0.10-0.20ppm(21H), 0.30ppm(1H), 0.54ppm(1H), 0.88ppm(3H), 1.17ppm(2.5H), 1.30-1.80ppm(9H), 1.90-2 .00ppm(3H), 2.20-2.30ppm(0.5H), 4.08ppm(0.4H), 4.84ppm(0.6H), 5.48-5.58ppm(1H), 6.05-6.12ppm(1H).

[0057] Synthesis Example 2 A colorless, transparent liquid was obtained in the same manner as in Synthesis Example 1, except that the hydrogensiloxane compound represented by formula (10) in Synthesis Example 1 was replaced with 50.0 g of a hydrogensiloxane compound represented by the following formula (11) and 17.5 g of MHVCH (molar ratio of unsaturated compound to hydrogensiloxane compound=1.3). Yield: 61.2 g. 1 It was confirmed by 1 H-NMR that the compound was the compound represented by the following formula (11A). GC measurement was performed, and the purity of the target product was calculated from the area % to be 93.2%. [ka] [ka] Below 1 H-NMR data is shown. -0.10-0.20ppm(33H), 0.30ppm(1H), 0.54ppm(1H), 0.88ppm(3H), 1.17ppm(2.5H), 1.30-1.80ppm(9H), 1.90-2 .00ppm(3H), 2.20-2.30ppm(0.5H), 4.08ppm(0.4H), 4.84ppm(0.6H), 5.48-5.58ppm(1H), 6.05-6.12ppm(1H).

[0058] Synthesis Example 3 A colorless, transparent liquid was obtained in the same manner as in Synthesis Example 1, except that the hydrogensiloxane compound represented by formula (10) in Synthesis Example 1 was replaced with 50.0 g of a hydrogensiloxane compound represented by the following formula (12) and 10.5 g of MHVCH (molar ratio of unsaturated compound to hydrogensiloxane compound=1.3). Yield: 48.8 g. 1 H-NMR confirmed that the compound was the compound represented by the following formula (12A). [ka] [ka] Below 1 H-NMR data is shown. -0.10-0.20ppm(132H), 0.30ppm(1H), 0.40ppm(2H), 0.54ppm(1H), 0.88ppm(6H), 1.17ppm(2.5H), 1.30-1.80ppm(13H) , 1.90-2.00ppm(3H), 2.20-2.30ppm(0.5H), 4.08ppm(0.4H), 4.84ppm(0.6H), 5.48-5.58ppm(1H), 6.05-6.12ppm(1H).

[0059] Comparative synthesis example 1 A colorless, transparent liquid was obtained in the same manner as in Synthesis Example 1, except that MHMVCH in Synthesis Example 2 was replaced with 40.8 g of AHPM (molar ratio of unsaturated compound to hydrogensiloxane compound=1.3). Yield: 72.5 g. 1It was confirmed by H-NMR that the product was an isomer mixture of the compounds represented by the following formulae (13A) and (13B). GC measurement was performed, and the purity of the target product was calculated from the area % to be 89.3%. [ka]

[0060] As shown in Synthesis Example 2 and Comparative Synthesis Example 1, an unsaturated group-containing compound containing a tertiary hydroxyl group present on a cyclohexane ring (MHMVCH) suppresses side reactions during the hydrosilylation reaction in the addition reaction with hydrogensiloxane, and therefore it is possible to produce a polysiloxane compound with higher purity than an unsaturated group-containing compound having primary and secondary hydroxyl groups (AHPM).

[0061] [Examples 1 to 4 and Comparative Examples 1 to 3] Hydrogel manufacturing example The compounds obtained in the above Synthesis Examples 1 to 3, the compounds obtained in the above Comparative Synthesis Example 1, C-SiGMA represented by the above formula, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) represented by the following formula, 2-hydroxyethyl methacrylate (HEMA), N,N-dimethylacrylamide (DMA), ethylene glycol dimethacrylate (EGDMA), and Irgacure 1173 (IRG1173) were mixed in the compositions and blending ratios shown in Tables 1 or 2, and stirred until a uniform solution was obtained. After stirring, N2 was bubbled for 5 minutes to thoroughly degas the mixture, and the mixture was sealed in a polypropylene mold. UV irradiation was performed using a high-pressure mercury lamp to cure the mixture. After curing, the mixture was washed by immersing it in isopropanol, a 50% isopropanol aqueous solution, and deionized water in that order for several seconds, to obtain a hydrogel film. The physical properties of the obtained film were measured according to the methods shown below. The results are shown in Tables 1 and 2. TRIS: 3-[tris(trimethylsiloxy)silyl]propyl methacrylate [ka]

[0062] [Equilibrium moisture content] The film was immersed in deionized water at 25°C for 48 hours, the surface water was wiped off, and the mass of the hydrated film was measured. The hydrated film was then dried in an oven at 50°C for 48 hours and at 25°C for 24 hours, and the mass of the dry film was measured. The equilibrium moisture content was calculated using the following formula. Equilibrium moisture content (%) = 100 × (mass of hydrated film - mass of dry film) / mass of hydrated film

[0063] [Transparency] The film was immersed in deionized water at 25° C. for 48 hours, and then the water on the surface was wiped off to prepare a hydrated film. The appearance of the film was visually observed and evaluated according to the following criteria. A: Uniform and transparent B: Uneven or cloudy

[0064] [Elastic modulus (Young's modulus) and elongation] The film was immersed in deionized water at 25°C for 48 hours, and then the surface moisture was wiped off to prepare a hydrated film. The Young's modulus of the hydrated film was measured using an Instron 5943. The film was cut to 0.8cm x 4.0cm and measured with a 50N load cell and a head speed of 1cm / min. The initial (linear) slope of the stress-strain curve, with the vertical axis representing the stress and the horizontal axis representing the strain, was calculated and used as the Young's modulus of elasticity (MPa). The elongation at which the film broke was used as the maximum elongation (%).

[0065] [Table 1]

[0066] [Table 2]

[0067] As shown in Table 2, the hydrogel using TRIS as a comparative compound has problems with transparency (Comparative Example 1). Also, the hydrogels using formulas (13A) and (13B) and C-SiGMA as comparative compounds have a high elastic modulus and a low maximum elongation (Comparative Examples 2 and 3). On the other hand, as shown in Table 1, the hydrogel using the polysiloxane compound of the present invention has excellent transparency, elastic modulus and maximum elongation. In other words, the hydrogel using the polysiloxane compound of the present invention provides a medical material having beneficial hydrophilicity and sufficient strength and flexibility.

[0068] [Industrial Applicability] The polysiloxane compound of the present invention provides a hydrogel having excellent hydrophilicity and strength. The polysiloxane compound of the present invention is useful as a monomer for producing medical materials, such as ophthalmic devices, contact lenses, intraocular lenses, artificial corneas, and eyeglass lenses.

[0069] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A polysiloxane compound containing one cyclic aliphatic hydrocarbon group having 8 to 20 carbon atoms in one molecule, the polysiloxane compound having a (meth)acryloxy group and a tertiary hydroxyl group on the aliphatic ring of the cyclic aliphatic hydrocarbon group.

2. 2. The polysiloxane compound according to claim 1, which is a compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), R １ is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3): 【Chemistry 2】 【Chemistry 3】 (In the formula (2), R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 200. The dashed lines represent bonds. In the formula (3), R is as defined above, a is an integer from 0 to 10, b is an integer from 0 to 10, and c is an integer from 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed lines represent bonds.)

3. The polysiloxane compound according to claim 2, wherein in the formula (1), A is represented by the formula (2), and n is an integer of 4 to 100.

4. 3. The polysiloxane compound according to claim 2, wherein in the formula (1), A is represented by the formula (3), a is 1, b is 1, and c is 0.

5. In the formula (1), R １ The polysiloxane compound according to any one of claims 2 to 4, characterized in that: is a methyl group.

6. 6. The polysiloxane compound according to claim 2, wherein in the formula (2) or (3), R's are each independently a methyl group or a butyl group.

7. A polymer comprising a repeating unit derived from polymerization of a (meth)acryloxy group of the polysiloxane compound according to any one of claims 1 to 6.

8. The polymer according to claim 7, wherein the mass proportion of the repeating unit is 10 mass % or more based on the total mass of the polymer.

9. A hydrogel comprising the polymer according to claim 7 or 8.

10. A medical material comprising the polymer according to claim 7 or 8.

11. A method for producing a polysiloxane compound represented by the following formula (1), 【Chemistry 4】 (In formula (1), R １ is a methyl group or a hydrogen atom, and A is a group represented by the following formula (2) or (3): 【Chemistry 5】 【Chemistry 6】 (In the formula (2), R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 200. The dashed lines represent bonds. In the formula (3), R is as defined above, a is an integer from 0 to 10, b is an integer from 0 to 10, and c is an integer from 0 to 10, with the proviso that a+b+c is 2 or greater. The dashed lines represent bonds.) A compound having an unsaturated group at a terminal, represented by the following formula (4): 【Chemistry 7】 (R １ is as stated above.) A hydrogen siloxane compound represented by the following formula (5) or (6): 【Chemistry 8】 【Chemistry 9】 (R, n, a, b, and c are as defined above.) and subjecting the resulting compound to a hydrosilylation reaction to obtain a polysiloxane compound represented by formula (1).

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