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EP-4310131-B1 - SILOXANE COMPOUND AND METHOD FOR PRODUCING SAME

EP4310131B1EP 4310131 B1EP4310131 B1EP 4310131B1EP-4310131-B1

Inventors

  • OKAMURA KAORU

Dates

Publication Date
20260506
Application Date
20220316

Claims (16)

  1. A siloxane compound represented by the following formula (1), having at least two groups represented by the following formula (2) in one molecule: wherein R is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 1 is, independently of each other, a group defined for R or a group represented by the following formula (2) or (3), R 2 is, independently of each other, a group represented by said formula (2) or (3), p is an integer of 0 to 500, q is an integer of 0 to 50, provided that said formula (1) has at least two groups represented by said formula (2), the bonding order of the siloxane units is not limited and may form a block structure or a random bonding, wherein R 3 is a hydrogen atom or a methyl group, R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, L 1 is a divalent hydrocarbon group having 1 to 5 carbon atoms, L 2 is a divalent hydrocarbon group having 2 to 10 carbon atoms and which may contain an ether bond, and the site marked with * is a binding position to the silicon atom in the formula (1), wherein R 4 , L 1 and L 2 are as described above, and the site marked with ** is a binding position to the silicon atom in the formula (1).
  2. The siloxane compound according to claim 1, wherein R 3 is a methyl group.
  3. The siloxane compound according to claim 1 or 2, comprising 2 to 50 groups represented by said formula (2) in one molecule.
  4. The siloxane compound according to any one of claims 1 to 3, wherein p is an integer of 0 to 200 and q is 0 or an integer of 1 to 20.
  5. The siloxane compound according to claim 4, wherein p is an integer of 10 to 100 and q is 0 or an integer of 3 to 10.
  6. The siloxane compound according to any one of claims 1 to 5, wherein q is 0 and R 1 is the group represented by the said formula (2).
  7. The siloxane compound according to any one of claims 1 to 6, wherein R is a methyl group.
  8. A polymer derived by polymerization of the siloxane compound according to any one of claims 1 to 7.
  9. A copolymer derived by polymerization of the siloxane compound according to any one of claims 1 to 7 with other polymerizable monomer(s).
  10. The copolymer according to claim 9, wherein a mass proportion of the repeating units derived from the siloxane compound is 10 mass% or more to 80 mass%, relative to the mass of the copolymer.
  11. The copolymer according to claim 9 or 10, wherein at least one of the other polymerizable monomer(s) is a (meth)acrylic monomer other than a siloxane compound, and a total mass proportion of the repeating units derived from the siloxane compound and the repeating units derived from the (meth)acrylic monomer is 50 mass% or more, relative to the mass of the copolymer.
  12. A hydrogel comprising the polymer according to claim 8 or the copolymer according to any one of claims 9 to 11.
  13. A medical material comprising the polymer according to claim 8 or the copolymer according to any one of claims 9 to 11.
  14. A method for preparing the siloxane compound represented by the following formula (1), having at least two groups represented by the following formula (2) in one molecule: wherein R is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 1 is, independently of each other, a group defined for R or a group represented by the following formula (2) or (3), R 2 is, independently of each other, a group represented by the following formula (2) or (3), p is an integer of 0 to 500, q is an integer of 0 to 50, provided that said formula (1) has at least two groups represented by the following formula (2), the bonding order of the siloxane units is not limited and may form a block structure or a random bonding, wherein R 3 is a hydrogen atom or a methyl group, R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, L 1 is a divalent hydrocarbon group having 1 to 5 carbon atoms, L 2 is a divalent hydrocarbon group having 2 to 10 carbon atoms and which may contain an ether bond, and the site marked with * is a binding position to the silicon atom in formula (1), wherein R 4 , L 1 and L 2 are as described above, and the site marked with ** is a binding position to the silicon atom in formula (1), wherein the method comprises a step of reacting a siloxane compound having an amino group and represented by the following formula (5) with a lactone compound having 2 to 6 carbon atoms to obtain a compound represented by the following formula (4): wherein R 5 is, independently of each other, a group defined for the R or a group represented by the following formula (6), R 6 is, independently of each other, a group represented by the following formula (6), R, p and q are as described above, and said formula (5) has at least two groups represented by said formula (6) in one molecule, wherein R 4 and L 2 are as described above, and the site marked with *** is a binding position to the silicon atom in said formula (5), wherein R, p and q are as described above, R 1' is, independently of each other, the group defined for the R or the group represented by said formula (3), R 2' is, independently of each other, a group represented by said formula (3), and said formula (4) has at least two groups represented by said formula (3) in one molecule, and a step of reacting the compound represented by formula (4) with a (meth)acrylic acid halide to obtain the siloxane compound represented by said formula (1).
  15. The method according to claim 14, wherein the lactone compound is selected from the group consisting of α-acetolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone.
  16. The method according to claim 14 or 15, wherein the (meth)acrylic acid halide is methacrylic acid chloride, acrylic acid chloride, methacrylic acid bromide or acrylic acid bromide.

Description

TECHNICAL FIELD The present invention relates to a siloxane compound and a method for preparing the same. Specifically, the present invention provides a siloxane compound suitable for medical materials. BACKGROUND ART Conventionally, monomers having siloxanes are known as a compound used for preparing medical materials including ophthalmic devices. For example, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) is widely used as a monomer for medical materials. A polymer obtained by the copolymerization of TRIS with a hydrophilic monomer, such as 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, and N-vinyl-2-pyrrolidone, has beneficial characteristics such as high oxygen permeability. However, highly hydrophobic siloxane monomers do not have sufficient compatibility with such a hydrophilic monomer and, accordingly, in the preparation of a hydrogel prepared therefrom for medical materials, there is a problem in that phase separation occurs, causing the hydrogel to be cloudy. Therefore, attempts to improve compatibility have been performed by introducing a hydrophilic group in a siloxane monomer molecule. Patent Literatures 1, 2, and 3 disclose a siloxane compound, which is methyl bis(trimethylsiloxy)silyl propyl glycerol methacrylate (SiGMA), having glycerol methacrylate represented by the following formula (a) or (a'). SiGMA is a monomer with a hydroxyl group in the molecule and formed by an addition reaction between methacrylic acid and an epoxy-modified siloxane compound, therefore it expresses satisfactory hydrophilicity. However, with SiGMA, a side reaction in an addition reaction of carboxylic acid with the epoxy-modified siloxane compound cannot be prevented, and there is a problem in that a purity of the intended siloxane compound decreases, thus SiGMA is not desirable as a raw material for medical materials. Patent Literatures 4 and 5 disclose a siloxane compound having a (meth)acrylamide group. Since the compound has an (meth)acrylamide in the molecule, it expresses satisfactory hydrophilicity and has well reactively with other (meth)acrylamide monomer(s). Patent Literature 6 discloses carbosiloxane vinylic monomers useful for making silicon hydrogel ophthalmic lenses (in particular contact lenses) having relatively-long thermal stability and to such ophthalmic lenses (in particular contact lenses). PRIOR LITERATURES Patent Literature 1: Japanese Patent Application Laid-Open No. Sho 54-55455(1979)Patent Literature 2: Japanese Patent Application Laid-Open No. Sho 56-22325(1981)Patent Literature 3: Japanese Patent Application Laid-Open No. 2004-182724Patent Literature 4: Japanese Patent Application Laid-Open No. Hei 5-17577(1993)Patent Literature 5: Japanese National Phase Publication No. 2017-517585Patent Literature 6: US 9 329 306 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Most other monomers for medical materials that are polymerized with siloxane compounds have (meth)acrylates. The siloxane compound having a (meth)acrylamide group disclosed in Patent Literatures 4 and 5 is inferior in terms of reactivity with monomer compounds having a (meth)acrylate group, has poor reactivity with compound having a (meth)acrylate group and causes phase separation during polymerization, which may make the obtained materials non-uniformity. As described above, while a siloxane compound having a hydrophilic group has compatibility with hydrophilic monomers, it has problems with reactivity and purity. Therefore, the siloxane compound not desirable as a raw material of (meth)acrylic resins, particularly a raw material for medical materials. Consequently, providing a material having beneficial hydrophilicity, transparency, and strength is difficult with conventional siloxane compounds. Therefore, demand still exists for compounds and compositions that will overcome these drawbacks. The present invention has been made in view of the above circumstances, and one of the purposes of the present invention is to provide a siloxane compound having an amide bond and a (meth)acrylate group. Further, other purpose of the present invention is to provide a method for preparing a siloxane compound having beneficial purity as a medical material. SOLUTIONS TO THE PROBLEMS As a result of serious examination to solve the above-described problems, the present inventor found that a compound having a siloxane unit and a (meth)acrylate group, and having an amide bond at a linking group portion thereof, has excellent compatibility with other monomers including hydrophilic monomers, and further, has satisfactory reactivity. Further, the present inventor found that the siloxane compound obtained from a siloxane compound having an amino group, a lactone compound, and a (meth)acrylic acid halide has a high purity and, therefore, the siloxane compound is preferred as a raw material of a (meth)acrylic resin serving as a medical material. That is, the present invention provides a siloxane compound represented by