WO2008023604A1 - composé pour modification de surface et procédé de modification de surface l'utilisant - Google Patents

composé pour modification de surface et procédé de modification de surface l'utilisant Download PDF

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Publication number
WO2008023604A1
WO2008023604A1 PCT/JP2007/065839 JP2007065839W WO2008023604A1 WO 2008023604 A1 WO2008023604 A1 WO 2008023604A1 JP 2007065839 W JP2007065839 W JP 2007065839W WO 2008023604 A1 WO2008023604 A1 WO 2008023604A1
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Prior art keywords
compound
surface modification
hydrophobic substrate
structural unit
modifying compound
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PCT/JP2007/065839
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English (en)
Japanese (ja)
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Yasuhiko Iwasaki
Kazuhiko Ishihara
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National University Corporation, Tokyo Medical And Dental University
The University Of Tokyo
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Priority to JP2008530864A priority Critical patent/JPWO2008023604A1/ja
Publication of WO2008023604A1 publication Critical patent/WO2008023604A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment

Definitions

  • the present invention relates to a surface modification compound suitable for use in modifying the surface of a hydrophobic substrate such as silicone and a surface modification method using the same.
  • the artificial joint is subject to wear because friction occurs at the sliding portion due to the operation of daily life.
  • the wear powder generated by the wear has an adverse effect on the human body, and when the wear progresses! / So-called loose looseness, the function as an artificial joint becomes difficult to fully function.
  • Patent Document 1 describes that the sliding surface of the artificial joint is made of a polymer having a phosphorylcholine group, for example, a heavy polymer composed of 2-methacryloyloxychetyl phosphorylcholine.
  • a method of forming a coalescence (called MPC polymer) is described! /.
  • MPC polymer the material to be treated made of ultra high molecular weight polyethylene is immersed in an acetone solution containing benzophenone, further immersed in an aqueous solution containing MPC, and then irradiated with ultraviolet light.
  • MPC polymer is synthesized on the surface of the workpiece.
  • Patent Document 2 A medical member made of a polymer material is immersed in a solution containing a diisocyanate compound, and further immersed in a solution containing a mixture of a polyalkylene oxide and a polyurethane prepolymer, whereby the surface of the medical device is lubricated. A method for imparting is described.
  • Patent Document 1 JP 2003-310649 A
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-287845
  • Patent Document 2 the method described in Patent Document 2 described above requires a coating of a diisocyanate compound and then a mixture of a polyalkylene oxide and a polyurethane prepolymer, which is favorable in terms of operability.
  • a functional group such as a hydroxyl group that reacts with a diisocyanate compound be present on the surface of the medical member, it is not suitable for surface modification of a hydrophobic substrate.
  • the present invention has been proposed in view of the problems as described above, and is suitable for use in modifying the surface of a hydrophobic substrate such as silicone to impart lubricity. It is an object of the present invention to provide a medical compound, a surface modification method using the same, and a surface-modified hydrophobic substrate and a medical member.
  • a polymer (B) composed of a hydrophilic monomer capable of radical polymerization is polymerized via a chain transfer agent or an alkyl halide initiator on a polysiloxane compound (A) having a bur group in the side chain.
  • Compound for surface modification is a polymer (B) composed of a hydrophilic monomer capable of radical polymerization.
  • the hydrophobic substrate after surface modification is suitable for surface modification of medical members because non-specific adsorption of biological substances and the like is suppressed.
  • the polymer (B) is polymerized at both ends of the polysiloxane compound (A)! /,
  • the polymer (B) at both ends is polymerized after the surface modification. It is arranged in a cilia-like manner on the surface of the hydrophobic substrate. Therefore, the lubricity of the hydrophobic substrate surface can be further enhanced.
  • the polysiloxane compound (A) contains in its structure a copolymer of a structural unit (al) derived from dimethylsiloxane and a structural unit (a2) derived from a butylmethylsiloxane force.
  • the surface modifying compound according to (1) or (2) is a copolymer of a structural unit (al) derived from dimethylsiloxane and a structural unit (a2) derived from a butylmethylsiloxane force.
  • the polysiloxane compound (A) is a copolymer of the structural unit ( a 1) derived from 1S dimethylsiloxane and the structural unit ( a 2) derived from butylmethylsiloxane. Is included in the structure, and therefore, the force S is bonded to the surface of the hydrophobic substrate via the bull group of the structural unit (a2).
  • the polymer (B) is composed of the structural unit (b) induced by the 2-methacryloyloxychetyl phosphorylcholine force, and is therefore excellent in biocompatibility. Therefore, it is particularly suitable for surface modification of medical members.
  • the surface modifying compound according to (3), wherein the polysiloxane compound (A) is represented by the following general formula (1).
  • R 2 independently represents an alkylene group having 1 to 4 carbon atoms, and 1 and m represent the number of polymerizations of the structural unit (al) and the structural unit (a2), respectively.
  • the polysiloxane compound (A) since the polysiloxane compound (A) has a structure represented by the general formula (1), it is particularly preferable as the structure of the surface modifying compound.
  • the molar ratio of the structural unit (al) to the structural unit (a2) is in the above range, it can be stably bonded to the surface of the hydrophobic substrate.
  • the surface is stably bonded to the surface of the hydrophobic substrate.
  • it can provide sufficient lubricity.
  • the force S is preferably used for surface modification.
  • a hydrophilic monomer is polymerized into a living radical polymerization (reversible addition-fragmentation chain transfer (RAFT) polymerization or atom transfer radical polymerization (ATR)) to the polysiloxane compound (A). Since it is polymerized by P)), it can be suitably used for surface modification with a narrow molecular weight distribution.
  • RAFT reversible addition-fragmentation chain transfer
  • ATR atom transfer radical polymerization
  • the surface of a hydrophobic substrate having a Si-H group or having a Si-H group introduced therein particularly a substrate made of silicone or ceramics Suitable for use in reforming.
  • a surface modification method comprising: a treatment step; and a step of heating the hydrophobic substrate treated with a solution containing the surface modification compound.
  • the surface of the hydrophobic substrate is hydrosilylated in advance as necessary, and the bull group is formed by treating with a solution containing the surface modifying compound.
  • the surface modifying compound can be bonded to the surface of the hydrophobic substrate.
  • the compound for surface modification has a polymer (B) composed of a hydrophilic monomer, it can impart lubricity to the surface of the hydrophobic substrate after the surface modification.
  • the polymer (B) is arranged in a cilia-like manner on the surface of the hydrophobic substrate. Therefore, the cilia-like polymer (B) retains the liquid and maintains the lubricity.
  • the surface of the hydrophobic substrate after surface modification is suitable for surface modification of medical members because nonspecific adsorption of biological substances and the like is suppressed.
  • a surface modification method comprising a step of coating the surface of a hydrophobic substrate with the surface modification compound according to any one of (1) to (11) by a plasma polymerization method.
  • the compound for surface modification can be bonded to the surface of the hydrophobic substrate.
  • the coalesced (B) is arranged in the form of cilia on the surface of the hydrophobic substrate, the ciliary polymer (B) retains the liquid and maintains the lubricity.
  • non-specific adsorption of biological substances and the like is suppressed on the surface of the hydrophobic substrate after surface modification.
  • lubricity can be imparted to the surface of a hydrophobic substrate by modifying the surface of a hydrophobic substrate such as silicone using the surface modifying compound of the present invention.
  • a hydrophobic substrate such as silicone
  • the surface modifying compound of the present invention by performing surface modification of the hydrophobic substrate using the surface modifying compound of the present invention, nonspecific adsorption of biological substances or the like on the surface of the hydrophobic substrate can be suppressed.
  • FIG. 1 is a graph showing the relationship between polymerization time and MPC concentration.
  • FIG. 2 is a graph showing the relationship between the polymerization time and the molecular weight of the surface modifying compound.
  • FIG. 3 is a diagram showing a procedure for applying surface modification to a test piece.
  • FIG. 4 is a graph showing the surface analysis results of a test piece after surface modification.
  • FIG. 5 is a graph showing a comparison of the coefficient of friction of test pieces with and without surface modification.
  • FIG. 6 is a diagram showing non-specific adhesion of platelets with and without surface modification.
  • the compound for surface modification of the present invention is a polysiloxane compound having a bur group in the side chain (A).
  • a polymer (B) composed of a hydrophilic monomer capable of radical polymerization is polymerized via a chain transfer agent or a halogenated alkyl initiator.
  • the polysiloxane compound (A) is not particularly limited as long as it has a bull group in the side chain. This polysiloxane compound (A) is hydrophobic and can be bonded to the surface of the hydrophobic substrate via a vinyl group as described later.
  • polysiloxane compounds (A) those having a hydroxyl group at one or both ends for introducing a chain transfer agent or a halogenated alkyl initiator are preferred.
  • the polymer (B) By introducing a chain transfer agent or an alkyl halide initiator through this hydroxyl group, the polymer (B) can be polymerized at one or both ends of the polysiloxane compound (A).
  • the polysiloxane compound (A) is preferable because it can polymerize the polymer (B) at both ends, and the effect of surface modification can be further enhanced.
  • polysiloxane compounds (A) those containing a copolymer of a structural unit (al) derived from dimethylsiloxane and a structural unit (a2) derived from butylmethylsiloxane force in the structure.
  • a2 structural unit derived from dimethylsiloxane
  • a2 structural unit derived from butylmethylsiloxane force in the structure.
  • Those having a structure represented by the following general formula (1) are more preferable.
  • R 2 independently represents an alkylene group having 1 to 4 carbon atoms, and 1 and m represent the number of polymerizations of the structural unit (al) and the structural unit (a2), respectively.
  • Each R 2 independently represents an alkylene group having 1 to 4 carbon atoms.
  • Examples of the alkylene group having a carbon number of! To 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like, and a group from which one hydrogen atom has been removed.
  • 1 and m represent the number of polymerization of the structural unit (a 1) and the structural unit (a2), respectively.
  • the molar ratio of the structural unit (al) to the structural unit (a2) is preferably 1: 9 to 9: 1. More preferably, it is 3: 7 to 7: 3.
  • the surface modifying compound can be stably bonded to the surface of the hydrophobic substrate.
  • the polymer (B) can be used without particular limitation as long as it is composed of a radically polymerizable hydrophilic monomer, such as acrylamide, N-butylpyrrolidone, and polyethylene glycol methacrylate. This polymer (B) is hydrophilic and can impart lubricity to the surface of the hydrophobic substrate.
  • a radically polymerizable hydrophilic monomer such as acrylamide, N-butylpyrrolidone, and polyethylene glycol methacrylate.
  • This polymer (B) is hydrophilic and can impart lubricity to the surface of the hydrophobic substrate.
  • polymers (B) a polymer obtained by polymerizing a structural unit (b) derived from 2 methacryloyloxyphosphorylcholine shown in the following structural formula (2). Particularly preferred for modification.
  • 2-Methacryloyloxychetylphosphorylcholine is known to have the same polarity as the phospholipid molecules constituting the biological membrane and is excellent in biocompatibility.
  • CH 2 C 1 C— O— CH 2 — CH 2 — 0— P— 0—CH 2 — CH 2 — N + — CH 3
  • the molar ratio of the structural units (al) and (a2) to the structural unit (b) Is preferably 1: 9 to 9: 1. More preferably, it is 3: 7 to 7: 3.
  • the surface modifying compound can be controlled with a force S that imparts sufficient lubricity while stably bonding to the surface of the hydrophobic substrate.
  • the polymer (B) is obtained by polymerizing the polysiloxane compound (A) with a hydrophilic monomer by living radical polymerization (reversible addition-fragmentation chain transfer (RAFT) polymerization or atom transfer radical polymerization (ATRP)).
  • RAFT reversible addition-fragmentation chain transfer
  • ATRP atom transfer radical polymerization
  • A) is polymerized via a chain transfer agent or an alkyl halide initiator.
  • the chain transfer agent used in the case of reversible addition-cleavage chain transfer polymerization is not particularly limited, but includes 4 cyanopentanoic acid dithiobenzoate, acetic acid dithiobenzoate, butanoic acid dithiobenzoate, 4 toluic acid dithiol. Examples include benzoate.
  • the halogenated alkyl initiator used in the case of atom transfer radical polymerization is not particularly limited, 2-bromoisobutyryl bromide, 2-chloroisobutyryl chloride, bromoacetyl bromide, bromoacetyl And chloride.
  • the surface modifying compound of the present invention preferably has a mass average molecular weight of 1000 to 1000000. More preferably, it is 10,000 to 500,000. By setting the content in the above range, the surface modifying compound of the present invention can be suitably used for surface modification of a hydrophobic substrate.
  • the surface modifying compound of the present invention synthesizes a polysiloxane compound (A), introduces a chain transfer agent into the polysiloxane compound (A), and performs chain transfer to the polysiloxane compound (A) by living radical polymerization. It can be synthesized by polymerizing the polymer (B) via an agent or an alkyl halide initiator.
  • the polymer (B) may be synthesized at one end or at both ends of the polysiloxane compound (A) . In the following, as an example, the polymer (B) is synthesized at both ends of the polysiloxane compound (A). Explain how to synthesize!
  • the polysiloxane compound (A) is synthesized.
  • This polysiloxane compound (A) is, for example, a hydroxyl group or a hydroxyl group-terminated functional group bonded to both ends (dimethylsiloxane) as a starting material, and otamethylcyclotetrasiloxane and tetramethyltetrabule. Synthesized by adding ring-opening polymerization reaction by adding cyclotetrasiloxane in a desired ratio.
  • a chain transfer agent or an alkyl halide initiator is introduced into the polysiloxane compound (A).
  • This chain transfer agent or alkyl halide initiator is reacted, for example, by adding a dicyclohexyl carpositimide solution dropwise into a solution in which the polysiloxane compound (A) and the chain transfer agent or alkyl halide initiator are dissolved. Can be introduced.
  • the polymer (B) is polymerized to the polysiloxane compound (A) via a chain transfer agent or a halogenated alkyl initiator by living radical polymerization.
  • This polymerization reaction is reversible
  • the polysiloxane compound (A) having a chain binder introduced therein and a hydrophilic monomer are dissolved in a predetermined solvent, a polymerization initiator is added, and the mixture is added at 50 to 80 ° C. Performed by heating for ⁇ 48 hours.
  • the solvent used in the polymerization reaction is not particularly limited, but water, methanol, ethanol, propanol, tert-butanol, benzene, toluene, dimethylformamide, tetrahydrofuran, chloroform, or a mixture thereof can be used. Can be mentioned.
  • the polymerization initiator is not particularly limited, but 2,2'-azobisisoptyronitrile, benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy 2-ethino hexanoate, tert-butyl olepenoleoxy Pivalate, t-butinolepenoleoxydiisoptylate, persulfate, persulfate bisulfite, and the like can be used.
  • the transition metal complex is not particularly limited, and complexes such as monovalent copper and divalent ruthenium can be used.
  • the first surface modification method of the present invention comprises a step of treating the surface of a hydrophobic substrate having Si—H groups or having Si—H groups introduced therein with a solution containing the surface modification compound of the present invention. And heating the hydrophobic substrate treated with the solution containing the surface modifying compound.
  • the surface of the hydrophobic substrate may be hydrosilylated to further include a step of introducing Si-H groups.
  • This hydrosilation can be achieved by known methods such as immersing the hydrophobic substrate in a poly (hydromethylsiloxane) solution, for example.
  • the surface of the hydrophobic substrate having Si—H groups or having Si—H groups introduced therein is treated with a solution containing the surface modifying compound of the present invention.
  • a solution containing the surface modifying compound of the present invention may be applied by a known coating method such as a spin coating method in which a hydrophobic substrate may be immersed in a solution containing a surface modifying compound.
  • the solvent of the solution containing the surface modifying compound is not particularly limited, but methanol, ethanol, isopropanol, or a mixed solution thereof can be used.
  • the compound for surface modification is dissolved in this solvent at a concentration of 0.0;
  • the solution contains a catalyst such as a Pt catalyst.
  • the surface modifying compound is bonded to the surface of the hydrophobic substrate by heating the hydrophobic substrate treated with the solution containing the surface modifying compound.
  • the heating temperature is preferably 35 to 80 ° C.
  • the Si—H group of the hydrophobic substrate is bonded to the bull group of the polysiloxane (A) of the surface modifying compound. Note that the time required for bonding can be shortened by increasing the heating temperature.
  • the polysiloxane compound (A) is fixed via a vinyl group, and the polymer (B) is arranged in a cilia shape. Accordingly, the liquid is held by the ciliated polymer (B) and the lubricity is maintained. In addition, non-specific adsorption of biological substances and the like is suppressed on the surface of the hydrophobic substrate after surface modification.
  • the second surface modification method of the present invention includes a step of coating the surface of the hydrophobic substrate with the surface modification compound of the present invention by a plasma polymerization method.
  • the surface modification compound can be bonded to the surface of the hydrophobic substrate.
  • the polymer (B) is arranged in a cilia shape on the surface of the hydrophobic substrate, so that the liquid is retained by the ciliated polymer (B) and the lubricity is maintained.
  • non-specific adsorption of biological substances and the like is suppressed on the surface of the hydrophobic substrate after surface modification.
  • the hydrophobic substrate of the present invention has been modified with the surface modifying compound of the present invention.
  • the hydrophobic substrate include silicone, ceramics, glass, metal, and semiconductor nanoparticles. Among these, silicone and ceramics are preferable.
  • the medical member of the present invention has been modified using the surface modifying compound of the present invention.
  • This medical member is manufactured using a hydrophobic base material that has been surface-modified in advance, even if it has been surface-modified to a medical member that has already been manufactured.
  • Medical members include artificial joints, catheters, balloon force tables Examples include treatment machine instruments such as drills and guide wires, inspection instrument instruments such as fiberscope endoscopes, and ophthalmic members such as contour lenses.
  • Tetrasiloxane (Me SiO) (manufactured by Shin-Etsu Chemical Co., Ltd.) and tetramethyltetraburushiku
  • PD V MS was synthesized by causing a ring-opening polymerization reaction.
  • the molecular weight (Mw) and dispersity (Mw / Mn) are shown in Table 1.
  • the apparent molecular weight was measured by gel filtration chromatography (GPC), and the absolute molecular weight was measured by a multi-angle light scattering detector (MALL S).
  • V m S-CTA 4 Cyananopentanoic acid dithiobenzoate was used as the chain transfer agent and this was added to McC Synthesized according to the method of ormic et al. (Mitsukami, Y .; Donovan, MS; Lowe, AB; McCormick, CL Macromolecules 2001, 34, 2248). Di-solubilized a given amount of PD V MS and a 4-fold molar amount of 4-cyanopentanoic acid dithiobenzoate
  • Chloromethane (in CH CI UOOmL, dicyclohexyl dissolved in lOOmL of dichloromethane)
  • Lucal positive imide (manufactured by Kanto Chemical Co., Inc.) was added dropwise and stirred at 40 ° C for 20 hours. Thereafter, insoluble matters were removed by filtration through a filter. Next, the dichloromethane was distilled off, and the reaction product was washed with methanol until the methanol was no longer colored, and then dissolved in chloroform. Then, after washing three times with saturated saline, the water was removed with magnesium sulfide and concentrated.
  • DCC Lucal positive imide
  • Methacryloyloxetyl phosphorylcholine was polymerized to synthesize PMPC -PD V MS -PMPC, a surface modification compound.
  • Fig. 1 shows the relationship between the polymerization time and the MPC concentration when the molar amounts of MPC, CTA, and AIBN as raw materials are 15 mmol, 0.05 mmol, and 0.025 mmol, respectively.
  • M represents the initial concentration of MPC
  • M represents the MPC concentration at a certain time point.
  • Figure 2 shows the relationship between the polymerization time and the molecular weight of PMPC -PD V MS -PMPC.
  • the MPC polymerization reaction in the present invention is a living radical reaction, the rate of decrease in MPC concentration is almost constant as shown in Fig. 1, and the molecule of PMPC -PD V MS -PMPC
  • V MS -PMPC The molecular weight of V MS -PMPC is shown in Table 2.
  • PDMS prepolymer (Silpotl8 4, Dow 'Koyungu Co.) and 1 0 of the crosslinking catalyst: 1 and stirred well a mixture of (w / w), was added dropwise a Teflon plate. That Thereafter, it was deaerated and cured by heating at 100 ° C. for 2 hours. The cured film was peeled off from the plate and processed into a disk shape with a diameter of 15 mm. The obtained disc-shaped test piece was washed with hexane and acetone and dried at room temperature under reduced pressure for 1 day.
  • Pt catalyst platinum dibule tetramethyldisiloxane complex
  • Figure 4 shows the ratio (P / C) of the phosphorus atom signal to the carbon atom signal.
  • XPS X-ray photoelectron spectrometer
  • FIG. 5B is an enlarged view of a portion surrounded by a broken line in FIG.
  • the coefficient of static friction of the test piece surface-modified with the surface modifying compound of the present invention is higher than that of the test piece not surface-modified. Both the dynamic friction coefficients are significantly reduced. This is presumably because water as a lubricating liquid was retained by the polymer (B) of the surface modifying compound.
  • Platelet rich plasma was prepared by centrifuging human whole blood with 1/10 volume of 8% sodium citrate added to blood at 12000 rpm for 15 minutes and collecting the supernatant. The sample was fixed to a 24-well culture plate with a silicon ring, and 1 ml of phosphate buffered saline was added to equilibrate. Thereafter, 1 ml of PRP was added to each well and allowed to stand at room temperature for 180 minutes.
  • Figure 6 shows the results of surface observation with a scanning electron microscope (SEM).
  • the surface modifying compound of the present invention is suitable for surface modification of a medical member that comes into contact with a biological substance or the like.
  • the surface modifying compound of the present invention has been described focusing on the effect of imparting lubricity, but the surface modifying compound of the present invention is as shown in FIG.
  • the biosensor can be suitably used for applications that require less non-specific adsorption rather than lubricity, such as biochips.

Abstract

La présente invention concerne un composé pour modification de surface qui peut modifier la surface d'une base hydrophobe, qui est composé de silicone ou analogue, pour apporter un pouvoir lubrifiant à celle-ci. L'invention concerne également un procédé de modification de surface utilisant un tel composé pour modifier une surface, une base hydrophobe à surface modifiée et un élément médical à surface modifiée. L'invention concerne en particulier un composé pour une modification de surface que l'on obtient par la polymérisation d'un polymère (B) composé d'un monomère hydrophile à polymérisation radicalaire avec un composé polysiloxane (A) comportant un groupe vinylique dans une chaîne latérale au moyen d'un agent de transfert de chaîne ou d'un initiateur alkylique halogéné. Lors de la modification de la surface, la surface d'une base hydrophobe peut être hydrosylilée le cas échéant, puis traitée avec une solution contenant le composé pour modification de surface. En variante, la surface d'une base hydrophobe est revêtue du composé pour modification de surface par polymérisation plasma.
PCT/JP2007/065839 2006-08-21 2007-08-14 composé pour modification de surface et procédé de modification de surface l'utilisant WO2008023604A1 (fr)

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JP2010505993A (ja) * 2006-10-03 2010-02-25 センター ナショナル ド ラ ルシェルシュ サイエンティフィーク Ｓｉ−Ｈ基を含有する表面を処理する方法
WO2010122817A1 (fr) * 2009-04-24 2010-10-28 株式会社ネクスト２１ Produit à base de résine à usage médical et tube d'assistance respiratoire
JPWO2010122817A1 (ja) * 2009-04-24 2012-10-25 株式会社ネクスト２１ 医療用樹脂製製品及び呼吸補助チューブ
US8957173B2 (en) 2009-04-24 2015-02-17 Next21 K.K. Resin product for medical use and respiration-assisting tube
WO2010147779A3 (fr) * 2009-06-15 2011-02-17 Dsm Ip Assets B.V. Silicones amphiphiles à base de phosphorylcholine pour applications médicales
EP2444448A1 (fr) * 2009-06-15 2012-04-25 DSM IP Assets B.V. Silicones amphiphiles à base de phosphorylcholine pour applications médicales
CN102803350A (zh) * 2009-06-15 2012-11-28 帝斯曼知识产权资产管理有限公司 用于医疗应用的磷酸胆碱基两亲性硅酮
JP2012530052A (ja) * 2009-06-15 2012-11-29 ディーエスエム アイピー アセッツ ビー．ブイ． ホスロリルコリンをベースにする医療用両親媒性シリコーン
US9181401B2 (en) 2009-06-15 2015-11-10 Dsm Ip Assets B.V. Phosphorylcholine-based amphiphilic silicones for medical applications
US10647829B2 (en) 2013-06-20 2020-05-12 Sumitomo Rubber Industries, Ltd. Surface modification method and surface modification body
WO2015060129A1 (fr) * 2013-10-21 2015-04-30 住友ゴム工業株式会社 Dispositif médical métallique ayant une lubricité et des caractéristiques de faible adsorption de protéines et/ou des caractéristiques de faible adsorption de cellules, et son procédé de production
EP2992909A1 (fr) * 2014-09-02 2016-03-09 Sumitomo Rubber Industries, Ltd. Dispositif médical métallique
US10092680B2 (en) 2014-09-02 2018-10-09 Sumitomo Rubber Industries, Ltd. Metal medical device
US10759918B2 (en) 2015-08-03 2020-09-01 Sumitomo Rubber Industries, Ltd. Surface modification method and surface-modified elastic body
WO2018212209A1 (fr) * 2017-05-17 2018-11-22 国立大学法人九州大学 Matériau polymère médical ayant une excellente propriété de liaison osseuse
JPWO2018212209A1 (ja) * 2017-05-17 2020-03-19 国立大学法人九州大学 骨結合性に優れる医療用高分子材料
JP7157458B2 (ja) 2017-05-17 2022-10-20 国立大学法人九州大学 骨結合性に優れる医療用高分子材料
US11542367B2 (en) 2017-05-17 2023-01-03 Kyushu University, National University Corporation Medical polymer material having excellent bone-bonding property
KR20190103728A (ko) * 2018-02-28 2019-09-05 인하대학교 산학협력단 폴리메틸하이드로실록산 표면 도포 기법을 이용한 폴리디메틸실록산의 표면 개질 방법 및 이로 제조된 폴리디메틸실록산
KR102050715B1 (ko) * 2018-02-28 2020-01-08 인하대학교 산학협력단 폴리메틸하이드로실록산 표면 도포 기법을 이용한 폴리디메틸실록산의 표면 개질 방법 및 이로 제조된 폴리디메틸실록산
WO2019194264A1 (fr) 2018-04-05 2019-10-10 日油株式会社 Monomère de polysiloxane contenant un groupe phosphorylcholine
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