Carboxybetaine group-containing polysiloxane compound, method for producing same, polymer, hydrogel, and medical material

Abstract

The present invention pertains to a carboxybetaine group-containing polysiloxane compound represented by formula (1). As a result, provided are: a carboxybetaine group-containing polysiloxane compound suitable for medical materials; and a method for producing the same. (In the formula, L represents a divalent hydrocarbon group having 1-20 carbon atoms and optionally including at least one ether bond or urethane bond, R1 represents a hydrogen atom or a methyl group, each R independently represents a monovalent hydrocarbon group having 1-6 carbon atoms, Y represents a group represented by formula (2), Z represents a group represented by formula (3), n represents an integer of 1-200, m represents an integer of 1-50, p represents an integer of 0-49, and m+p is an integer of 1-50.)

Description

Carboxybetaine group-containing polysiloxane compound, its production method, polymer, hydrogel, and medical material

[0001] The present invention relates to a carboxybetaine group-containing polysiloxane compound, a method for producing the same, a polymer, a hydrogel, and a medical material.

[0002] Silicone hydrogels have been used in medical devices, including ophthalmic devices. While they have good oxygen permeability and can reduce the burden on the human body, including the eyes, their low surface wettability and lubricity, derived from highly hydrophobic polysiloxanes, present challenges. Currently, various studies are being conducted to improve wettability, including the introduction of zwitterionic groups into the material.

[0003] Patent Documents 1 and 2 disclose polysiloxane compounds in which zwitterionic groups have been introduced at one or both ends of the silicone chain. These compounds can improve compatibility with hydrophilic monomers and produce transparent silicone hydrogels, but because zwitterions are introduced into the main chain, they are not sufficient to improve surface wettability or lubricity.

[0004] Patent Document 3 discloses a polysiloxane compound in which a phosphorylcholine group, a type of zwitterionic group, is introduced into the side chain of the silicone chain. Because the zwitterionic group is present in the side chain, which allows for a high degree of freedom of molecular movement, this compound is expected to improve surface wettability and lubricity. However, the compound alone does not improve surface wettability or lubricity. This is thought to be due to the aggregation of the zwitterionic groups introduced into the polysiloxane compound within the material, preventing the zwitterionic groups from being exposed to the surface of the material. Furthermore, the compound is a gel, which also supports the aggregation of the zwitterionic groups. In other words, although a polysiloxane compound in which a zwitterionic group has been introduced is disclosed, the improvement in the surface wettability and lubricity of the material cannot be said to be sufficient.

[0005] JP 2012-530052 A JP 2014-505067 A WO2019-194264 A

[0006] In the prior art, materials used in medical applications, which are derived from highly hydrophobic polysiloxanes, have had problems with poor surface wettability and lubricity.

[0007] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a carboxybetaine group-containing polysiloxane compound suitable for medical materials, a method for producing the same, a polymer, a hydrogel, and a medical material.

[0008] As a result of intensive research to solve the above problems, the present inventors discovered that surface wettability and lubricity can be improved in hydrogels using polysiloxane compounds in which carboxybetaine groups have been introduced into the side chains of silicone chains, leading to the completion of the present invention.

[0009] That is, the present invention provides a carboxybetaine group-containing polysiloxane compound, which is a polysiloxane compound having a carboxybetaine group in a side chain of the silicone chain, a method for producing the same, a polymer, a hydrogel, and a medical material, as described in detail below.

[0010] The present invention provides a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.)

[0011] Such carboxybetaine group-containing polysiloxane compounds have excellent compatibility with hydrophilic monomers. Furthermore, polymers derived from these compounds have excellent surface wettability and lubricity, making them useful as monomers for medical materials. In this specification, the bonding order of the siloxane units in the parenthesized polysiloxane compounds may be block or random.

[0012] In this case, it is preferable that L in the formula (1) is a propylene group.

[0013] Such a carboxybetaine group-containing polysiloxane compound is preferred.

[0014] In the formulas (2) and (3), L １ is a propylene group, and two R ２ are preferably all methyl groups.

[0015] Such a carboxybetaine group-containing polysiloxane compound is preferred.

[0016] In the formula (1), it is preferred that n is an integer of 1 to 100, m is an integer of 1 to 15, and p is an integer of 0 to 10.

[0017] Such a carboxybetaine group-containing polysiloxane compound is preferred.

[0018] In the formula (1), the ratio of n to m, n:m, is preferably 5:1 to 15:1.

[0019] When the ratio of n is 5 or more, the properties of siloxane are fully exhibited, and when the ratio of n is 15 or less, the properties of carboxybetaine are fully exhibited.

[0020] Furthermore, the present invention provides a polymer containing repeating units derived from polymerization of the (meth)acryloxy groups of the above-described carboxybetaine group-containing polysiloxane compound.

[0021] Such a polymer has good compatibility with other compounds having a polymerizable group such as a (meth)acryloxy group.

[0022] In this case, the mass proportion of the repeating unit is preferably 10 mass % or more relative to the total mass of the polymer.

[0023] Such a polymer is likely to exhibit the properties of the carboxybetaine group-containing polysiloxane compound of the present invention.

[0024] The present invention also provides a hydrogel comprising the above-described polymer.

[0025] The polymer of the present invention can be suitably used for such applications.

[0026] The present invention also provides a medical material containing the above-described polymer.

[0027] The polymer of the present invention has excellent surface wettability and lubricity, and can therefore be suitably used for such applications.

[0028] Furthermore, there is provided a method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to silicon atoms.) Sodium chloroacetate, and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １, R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0029] Such a method for producing a polysiloxane compound makes it possible to obtain the above-described carboxybetaine group-containing polysiloxane compound with high purity.

[0030] Also, there is provided a method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) Propiolactone and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0031] Such a method for producing a polysiloxane compound makes it possible to obtain the above-described carboxybetaine group-containing polysiloxane compound with high purity.

[0032] As described above, the carboxybetaine group-containing polysiloxane compound of the present invention has excellent compatibility with hydrophilic monomers due to the presence of a carboxybetaine group in the side chain of the silicone chain. Furthermore, (co)polymers containing repeating units derived from polymerization of the (meth)acryloxy groups of the polysiloxane compound of the present invention have excellent surface wettability and lubricity. The carboxybetaine group-containing polysiloxane compound of the present invention is useful as a monomer for medical materials.

[0033] As described above, there has been a need for the development of a carboxybetaine group-containing polysiloxane compound suitable for medical materials, a method for producing the same, a polymer, a hydrogel, and a medical material.

[0034] The present inventors have conducted extensive research to solve the above problems and have found that polysiloxane compounds having carboxybetaine groups in the side chains of silicone chains have excellent compatibility with other hydrophilic monomers. They have also found that (co)polymers of the (poly)siloxane compounds and hydrophilic monomers have excellent surface wettability and lubricity, leading to the completion of the present invention.

[0035] That is, the carboxybetaine group-containing polysiloxane compound of the present invention is a compound represented by the following formula (1). (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.)

[0036] Furthermore, the present invention provides a method for producing a carboxybetaine group-containing polysiloxane compound represented by the above formula (1), which comprises the steps of: (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to silicon atoms.) Sodium chloroacetate, and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above) to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0037] Furthermore, the present invention provides a method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) Propiolactone and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0038] The present invention will be described in detail below, but the present invention is not limited thereto.

[0039] [Carboxybetaine Group-Containing Polysiloxane Compound] The carboxybetaine group-containing polysiloxane compound of the present invention (sometimes simply referred to as a polysiloxane compound in this specification) is a compound represented by the following formula (1). (In formula (1), L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more ether bonds or urethane bonds, and R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. The bonding of each siloxane unit bounded by m, n, and p may be block or random. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.)

[0040] In the formula (1), R １ is a hydrogen atom or a methyl group, and a methyl group is particularly preferred.

[0041] In the formula (1), L is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more ether bonds or urethane bonds, and is preferably an alkylene group having 3 to 10 carbon atoms, an oxyalkylene group having 3 to 10 carbon atoms, or an oxyalkylene group having 3 to 10 carbon atoms and containing one or more urethane bonds in the functional group chain. Examples include groups represented by the following formula: (In the formula, the site indicated by * is the site of bonding to the silicon atom in formula (1), and the site indicated by ** is the site of bonding to the oxygen atom in formula (1). The dashed lines represent bonds.)

[0042] In this case, it is preferable that L in the formula (1) is a propylene group.

[0043] In the formula (1), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, 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 particularly preferably a methyl group.

[0044] In the formula (1), n ​​is an integer of 1 to 200, m is an integer of 1 to 50, and p is an integer of 0 to 49. Preferably, n is an integer of 1 to 100, m is an integer of 1 to 15, and p is an integer of 0 to 10. Also preferably, the ratio of n to m, n:m, is 5:1 to 15:1. When the ratio of n is 5 or more, the properties of siloxane are fully exhibited, and when the ratio of n is 15 or less, the properties of carboxybetaine are fully exhibited.

[0045] The siloxane units bound by m, n, and p may be bonded in either a block or random fashion.

[0046] In the formula (1), Y is a group represented by the formula (2), and in the formula (2), L １is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.

[0047] In the formula (1), Z is a group represented by the formula (3), and in the formula (3), L １ and R ２ is L shown in the above formula (2) １ and R ２ The dashed lines represent bonds to the silicon atom.

[0048] In the formula (2), L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms. Examples include a methylene group, an ethylene group, a 1,3-propylene group, a 1-methylpropylene group, a 1,1-dimethylpropylene group, a 2-methylpropylene group, a 1,2-dimethylpropylene group, a 1,4-butylene group, a 2-methyl-1,4-butylene group, a 3-methyl-1,4-butylene group, a 1,5-pentylene group, and a 1,6-hexanylene group. Preferred are a 1,3-propylene group, a 2-methylpropylene group, and a 1,4-butylene group. In the formula (3), L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, specifically a methylene group or an ethylene group.

[0049] In the formula (2), R ２ are independently monovalent hydrocarbon groups having 1 to 3 carbon atoms, and are preferably methyl or ethyl groups. ２ is the two R ２ can be bonded to form a ring structure having 4 to 6 carbon atoms. ２ are bonded to form a five-membered ring structure that becomes a butylene group, i.e., a pyrrolidine ring structure.

[0050] In this case, in the formulas (2) and (3), L １ is a propylene group, and two R ２ are preferably all methyl groups.

[0051] [Method for producing a carboxybetaine group-containing polysiloxane compound] The present invention provides a method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to silicon atoms.) Sodium chloroacetate, and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0052] The present invention also provides a method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) Propiolactone and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above) to obtain the carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0053] Such a method for producing a polysiloxane compound makes it possible to obtain a carboxybetaine group-containing polysiloxane compound with high purity.

[0054] The method for producing a polysiloxane compound of the present invention is characterized by using an amino-modified polysiloxane compound represented by formula (4) as a raw material. In the method for producing a polysiloxane compound of the present invention, the amount of carboxybetaine groups introduced can be controlled by the molar ratio of sodium chloroacetate or propiolactone reacted with the amino groups. In addition, the carboxybetaine groups can be introduced without using a hydrosilylation reaction with a compound having an ionic group, thereby preventing undesirable side reactions. This allows the carboxybetaine group-containing polysiloxane compound of the present invention to be obtained with high purity.

[0055] The above reaction may be carried out according to a conventionally known method. In the present invention, sodium chloroacetate or propiolactone may be added to the amino-modified polysiloxane compound represented by formula (4) in the amount desired to be introduced, followed by reaction. 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 reaction may be carried out in the presence of a solvent or stabilizer. The solvent and stabilizer may be conventionally known and are not particularly limited.

[0056] (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-based solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, and methyl benzoate; aliphatic hydrocarbon-based solvents such as linear hexane, linear heptane, and linear octane; alicyclic hydrocarbon-based solvents such as cyclohexane and ethylcyclohexane; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and petroleum-based solvents; and alcohol-based 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; and water. The solvents may be used alone or in combination of two or more. For the reaction with sodium chloroacetate, alcohol solvents such as linear propyl alcohol, isopropyl alcohol, linear butyl alcohol, isobutyl alcohol, and tert-butyl alcohol, and water are preferred, and for the reaction with propiolactone, aliphatic hydrocarbon solvents such as linear hexane, linear heptane, and linear octane, alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and petroleum solvents are preferred.

[0057] (Stabilizer) Examples of the stabilizer include phenolic antioxidants, phosphorus-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, etc. Examples of the phenolic antioxidant include, but are not limited to, 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 ethylbis(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 derivatives thereof, bis(2,2,6,6-tetramethyl-4-piperidyl)oxalate, 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, phenylnaphthylamine, N,N'-diphenyl-1,4-phenylenediamine, and N-phenyl-N'-cyclohexyl-1,4-phenylenediamine. Examples of sulfur-based antioxidants include, but are not limited to, dilauryl thiodipropionate and distearyl thiodipropionate. The stabilizers may be used alone or in combination of two or more.

[0058] In the above reaction, the reaction end point can be confirmed by a conventionally known method. For example, １This can be confirmed by the disappearance of the peaks of the raw material compounds by H-NMR or the like. After the reaction is complete, the product can be purified according to a conventionally known method. For example, the organic layer can be washed with water, and then the solvent can be removed to isolate the product. Alternatively, vacuum distillation or activated carbon treatment may be used.

[0059] In one example of the method for producing the polysiloxane compound of the present invention, 1 molar equivalent of the amino-modified polysiloxane compound represented by formula (4), 1.0 molar equivalent of sodium chloroacetate, 200% by mass of isopropyl alcohol (IPA) based on the amino-modified polysiloxane compound, and 50% by mass of water based on the amino-modified polysiloxane compound are added, and the mixture is heated and stirred at 80°C under a nitrogen atmosphere. The reaction is completed after about 15 hours of reaction. In addition, the amino-modified polysiloxane compound or the compound produced during this reaction is １ The progress of the reaction can be confirmed by monitoring with H-NMR, etc. After completion of the reaction, the solvent is distilled off under reduced pressure, and then 200% by mass of ethyl acetate relative to the amino-modified polysiloxane compound is added, the organic layer is washed with water, and the solvent present in the organic layer is distilled off under reduced pressure, thereby obtaining the polysiloxane compound represented by the above formula (1).

[0060] In one example of the method for producing the polysiloxane compound of the present invention, 1 molar equivalent of the amino-modified polysiloxane compound represented by formula (4), 1.0 molar equivalent of propiolactone, and toluene are added in an amount of 100% by mass relative to the amino-modified polysiloxane compound, and the mixture is heated and stirred at 80°C under a nitrogen atmosphere. The reaction is completed after about 8 hours of reaction. In addition, the amino-modified polysiloxane compound or the compound produced during this reaction is １ The progress of the reaction can be confirmed by monitoring with H-NMR, etc. After completion of the reaction, the solvent and remaining propiolactone are distilled off under reduced pressure, thereby obtaining the polysiloxane compound represented by the above formula (1).

[0061] [Polymer] The polysiloxane compound of the present invention can produce a polymer containing repeating units derived from the (addition) polymerization of the (meth)acryloxy groups of a carboxybetaine group-containing polysiloxane compound. The polysiloxane compound of the present invention has good compatibility with other compounds having polymerizable groups such as (meth)acryloxy groups (hereinafter referred to as polymerizable monomers or hydrophilic monomers). Therefore, copolymerization with a polymerizable monomer can produce a colorless and transparent copolymer. It can also be polymerized alone.

[0062] In the production of a copolymer containing repeating units derived from the polymerization of the polysiloxane compound of the present invention with other polymerizable (hydrophilic) monomers, the proportion of the polysiloxane compound of the present invention is preferably such that the mass proportion of the repeating units 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 amount of the repeating units derived from the (addition) polymerization of the (meth)acryloxy groups of the polysiloxane compound of the present invention is preferably 10 to 80 mass parts, more preferably 10 to 60 mass parts, per 100 mass parts of the total of the polysiloxane compound of the present invention and the polymerizable (hydrophilic) monomer. When the mass proportion of the repeating units is 10 mass% or more, the properties of the polysiloxane compound of the present invention are easily exhibited.

[0063] Examples of polymerizable monomers 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.

[0064] Copolymerization of the polysiloxane compound 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, 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 polymerization initiator added is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total polymerization components.

[0065] Polymers containing repeating units derived from polymerization of (meth)acryloxy groups in the polysiloxane compound of the present invention have excellent hydrophilicity. Furthermore, hydrogels obtained from the polymers have high transparency. Furthermore, medical materials can also be obtained from the polymers. Therefore, the polysiloxane compounds of the present invention are suitable for producing medical materials, such as ophthalmic devices, contact lenses, intraocular lenses, and artificial corneas. The method for producing medical materials using the polymers is not particularly limited, and may follow conventional methods for producing medical materials. For example, cutting methods, molding methods, and the like can be used to form lenses such as contact lenses and intraocular lenses.

[0066] 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.

[0067] In the following examples: １ H-NMR analysis was carried out using a JEOL ECS400 and deuterated chloroform as the measurement solvent. All gas chromatograph (GC) measurements were carried out under the following conditions. Measurement device: Agilent gas chromatograph (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°C (5 min) → 10°C / min → 250°C (hold) Injection port temperature: 250°C Detector temperature: FID 300°C Carrier gas: Helium (1.0 ml / min) Split ratio: 50:1 Injection volume: 1 μL

[0068] The compounds used in the following Examples and Comparative Examples are as follows: DMAACB: a compound represented by formula (5) HDM1: Hydrogensiloxane compound represented by formula (6) (n'=80, m'=6) HDM2: Hydrogensiloxane compound represented by formula (6) (n'=150, m'=15)

[0069] Synthesis Example 1: In a 500 mL three-necked recovery flask equipped with a Dimroth thermometer, 200.0 g of HDM1, 20.4 g of dimethylallylamine (molar ratio of unsaturated compound to hydrogensiloxane compound = 1.3), and 4.0 g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5 wt%) were added under a nitrogen atmosphere, heated to 80°C, and aged for 4 hours. １ H-NMR was used to confirm that the peaks derived from hydrogensiloxane had disappeared. After the reaction, unreacted raw materials were distilled off under reduced pressure at an internal temperature of 80°C, yielding a yellow, transparent liquid. Yield: 210.3 g １ H-NMR confirmed that the compound was the compound represented by formula (7) (n'=80, m'=6).

[0070] Synthesis Example 2: A yellow, transparent liquid was obtained in the same manner as in Synthesis Example 1, except that HDM1 in Synthesis Example 1 was replaced with 200.0 g of the hydrogensiloxane compound HDM2 and 26.7 g of dimethylallylamine (molar ratio of unsaturated compound to hydrogensiloxane compound = 1.3). Yield: 205.0 g. １ H-NMR confirmed that the compound was the compound represented by the following formula (8): (n'=150, m'=15)

[0071] Example 1 In a 500 mL three-necked flask equipped with a Dimroth thermometer, 50.0 g of (7), 10.9 g of sodium chloroacetate (molar ratio to amino groups = 2.0), 125 g of isopropanol, and 25 g of water were added under a nitrogen atmosphere, and the mixture was heated to 80°C and aged for 15 hours. １ H-NMR was used to track the reaction, and it was confirmed that the peak derived from the dimethylamino group had shifted. After the reaction, the solvent and unreacted raw materials were distilled off under reduced pressure at an internal temperature of 80°C, 100.0 g of ethyl acetate was added, and the mixture was washed three times with 50 g of water. The solvent and other ingredients were distilled off under reduced pressure at an internal temperature of 80°C, yielding a yellow, transparent liquid. Yield: 50.4 g. １ H-NMR confirmed that the compound was the compound represented by formula (9) (n=80, m=6, p=0).

[0072] Example 2 A yellow transparent liquid was obtained in the same manner as in Example 1, except that (7) was replaced with 50.0 g of compound (8) and 14.2 g of sodium chloroacetate (molar ratio to amino group=2.0). Yield: 53.4 g. １ H-NMR confirmed that the compound was the compound represented by formula (10A) (n=150, m=15, p=0).

[0073] Example 3 A yellow, transparent liquid was obtained in the same manner as in Example 2, except that 7.1 g of sodium chloroacetate (molar ratio to amino groups=1.0) was used instead. Yield: 49.5 g. １ H-NMR confirmed that the compound was the compound represented by formula (10B) (n=150, m=10, p=5).

[0074] Example 4: 20.0 g of (7) and 2.0 g of propiolactone (molar ratio relative to amino groups = 1.5) were added to a 100 mL three-necked flask equipped with a Dimroth thermometer under a nitrogen atmosphere, heated to 80°C, and aged for 4 hours. The reaction was monitored by 1H-NMR, and a shift in the peak attributable to the dimethylamino group was confirmed. After the reaction, unreacted raw materials were distilled off under reduced pressure at an internal temperature of 80°C, yielding a yellow, transparent liquid. Yield: 18.7 g. １ H-NMR confirmed that the compound was the compound represented by formula (11) (n=80, m=6, p=0).

[0075] Comparative Example 1 In Synthesis Example 1, dimethylallylamine was replaced with 42.7 g of DMAACB (molar ratio of unsaturated compound to hydrogensiloxane compound = 1.3) of formula (5), and the reaction was carried out in the same manner, but the reaction did not proceed. Therefore, 200 g of isopropanol was used as a solvent, and 16.0 g of a toluene solution of chloroplatinic acid sodium bicarbonate / vinylsiloxane complex (platinum content 0.5 wt%) was added, heated to 80 ° C, and aged for a further 8 hours. After confirming the progress of the reaction, 800.0 g of ethyl acetate was added, washed three times with 300 g of water, and the solvent was distilled off under reduced pressure at an internal temperature of 80 ° C to obtain a slightly cloudy brown liquid. Yield: 66.5 g. １H-NMR revealed that some of the methacryl groups were saturated and some of the hydrogen siloxane was dehydrogenated (n=80, m=5.5, p=0.5). (Z = Z １ +Z ２ , Z １ = 1.4, Z ２ = 0.6)

[0076] As shown in Examples 1 to 4 and Comparative Example 1, when an unsaturated group-containing compound (DMAACB) containing a carboxybetaine group is reacted with a hydrogensiloxane, a side reaction occurs during the hydrosilylation reaction, making it impossible to obtain the target product. On the other hand, a polysiloxane compound containing a carboxybetaine group can be produced by reacting an amino-modified polysiloxane compound with sodium chloroacetate or propiolactone.

[0077] [Examples 5 to 8 and Comparative Example 2] Hydrogel Production Examples The compounds obtained in Examples 1 to 4 above, the compound obtained in Comparative Example 1 above, Me-SiGMA represented by the following formula, 2-hydroxyethyl methacrylate (HEMA), N,N-dimethylacrylamide (DMA), Irgacure 1173 (IRG1173), and 1-propanol were mixed in the compositions and blending ratios shown in Table 1, and stirred until a uniform solution was obtained. ２ The mixture was bubbled with HCl for 5 minutes, thoroughly degassed, and then sealed in a polypropylene mold. It was then cured by UV irradiation using a high-pressure mercury lamp. After curing, the mixture was washed by immersing it in isopropanol, a 50% aqueous isopropanol solution, and deionized water, successively, for several seconds each, to obtain a hydrogel film. The physical properties of the resulting film were measured according to the methods described below. The results are shown in Table 1.

[0078] [Equilibrium Moisture Content] After immersing the film in deionized water at 25°C for 48 hours, the surface moisture 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 then in an oven 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 x (mass of hydrated film - mass of dry film) / mass of hydrated film

[0079] [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 was visually observed and evaluated according to the following criteria: A: Uniform and transparent B: Non-uniform or cloudy

[0080] [Water Drainage Test] A hydrated film was prepared by immersing the film in deionized water at 25° C. for 48 hours. The film was then removed from the water, and the time until the water on the surface was drained was measured to evaluate the water wettability of the film.

[0081] (In the table, the numerical values ​​for items other than the evaluation results are in parts by weight.)

[0082] As shown in Table 1, the hydrogel using the comparative compound (12) (Comparative Example 2) has poor transparency and poor water wettability. On the other hand, as shown in Table 1, the hydrogels using the polysiloxane compounds of the present invention (Examples 5 to 8) have excellent transparency and excellent water wettability. In other words, the hydrogels using the polysiloxane compounds of the present invention provide medical materials with useful transparency and hydrophilicity.

[0083] The present specification includes the following aspects: [1] A carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) [2] The carboxybetaine group-containing polysiloxane compound according to [1], wherein in the formula (1), L is a propylene group. [3] In the formulas (2) and (3), L １ is a propylene group, and two R ２ and m are all methyl groups. [4] The carboxybetaine group-containing polysiloxane compound according to any one of [1] to [3], wherein in formula (1), n ​​is an integer of 1 to 100, m is an integer of 1 to 15, and p is an integer of 0 to 10. [5] The carboxybetaine group-containing polysiloxane compound according to any one of [1] to [4], wherein in formula (1), the ratio of n to m, n:m, is 5:1 to 15:1. [6] A polymer comprising a repeating unit derived from polymerization of a (meth)acryloxy group of the carboxybetaine group-containing polysiloxane compound according to any one of [1] to [5]. [7] The polymer according to [6], wherein the mass proportion of the repeating unit is 10 mass% or more relative to the total mass of the polymer. [8] A hydrogel comprising the polymer according to [6] or [7]. [9] A medical material comprising the polymer according to [6] or [7].

[10] A method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1), comprising: (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to silicon atoms.) Sodium chloroacetate, and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[11] A method for producing a carboxybetaine group-containing polysiloxane compound represented by formula (1) below, comprising: (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) Propiolactone and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

[0084] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) 2. The carboxybetaine group-containing polysiloxane compound according to claim 1, characterized in that in formula (1), L is a propylene group.

3. In the formulas (2) and (3), L １ is a propylene group, and two R ２ The carboxybetaine group-containing polysiloxane compound according to claim 1, characterized in that each of the groups is a methyl group.

4. The carboxybetaine group-containing polysiloxane compound according to claim 1, characterized in that in formula (1), n ​​is an integer of 1 to 100, m is an integer of 1 to 15, and p is an integer of 0 to 10.

5. The carboxybetaine group-containing polysiloxane compound according to claim 1, characterized in that in the formula (1), the ratio of n to m is 5:1 to 15:

1.

6. A polymer characterized by containing repeating units derived from polymerization of (meth)acryloxy groups of the carboxybetaine group-containing polysiloxane compound according to any one of claims 1 to 5.

7. The polymer according to claim 6, wherein the mass proportion of the repeating unit is 10 mass % or more based on the total mass of the polymer.

8. A hydrogel comprising the polymer of claim 6.

9. A medical material comprising the polymer according to claim 6.

10. A method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to silicon atoms.) Sodium chloroacetate, and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

11. A method for producing a carboxybetaine group-containing polysiloxane compound represented by the following formula (1): (wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one of an ether bond and a urethane bond; R １ is a hydrogen atom or a methyl group, R are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a group represented by the following formula (2), Z is a group represented by the following formula (3), n is an integer of 1 to 200, m is an integer of 1 to 50, p is an integer of 0 to 49, and m+p is an integer of 1 to 50. (In the formula, L １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and L ２ is a divalent hydrocarbon group having 1 to 2 carbon atoms, and R ２ are independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, or two R ２ are bonded to form a ring structure having 4 to 6 carbon atoms. The dashed lines represent bonds to the silicon atom.) Propiolactone and an amino-modified polysiloxane compound represented by the following formula (4), (wherein m' is an integer of 1 to 50, and L, R １ , R, Y, and n are as defined above), to obtain a carboxybetaine group-containing polysiloxane compound represented by formula (1).

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