WO2008053865A1 - Agent de dispersion pour particules céramiques et procédé de préparation d'une suspension de monomère - Google Patents
Agent de dispersion pour particules céramiques et procédé de préparation d'une suspension de monomère Download PDFInfo
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- WO2008053865A1 WO2008053865A1 PCT/JP2007/071073 JP2007071073W WO2008053865A1 WO 2008053865 A1 WO2008053865 A1 WO 2008053865A1 JP 2007071073 W JP2007071073 W JP 2007071073W WO 2008053865 A1 WO2008053865 A1 WO 2008053865A1
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- WIPO (PCT)
- Prior art keywords
- hydroxyapatite
- suspension
- mold
- particles
- composite material
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 74
- 239000000725 suspension Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000178 monomer Substances 0.000 title claims abstract description 36
- 239000000919 ceramic Substances 0.000 title abstract description 9
- 239000002270 dispersing agent Substances 0.000 title description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 106
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 106
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- -1 nitrogen-containing cyclic compound Chemical class 0.000 claims abstract description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 16
- 239000001506 calcium phosphate Substances 0.000 claims description 14
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 14
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 14
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000013461 design Methods 0.000 claims description 12
- 238000005242 forging Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 150000001923 cyclic compounds Chemical class 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- NMGPHUOPSWFUEB-UHFFFAOYSA-N 2-(butylamino)ethyl 2-methylprop-2-enoate Chemical compound CCCCNCCOC(=O)C(C)=C NMGPHUOPSWFUEB-UHFFFAOYSA-N 0.000 claims description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000316 bone substitute Substances 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract 2
- 230000008569 process Effects 0.000 description 16
- 239000011148 porous material Substances 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- 239000004621 biodegradable polymer Substances 0.000 description 7
- 229920002988 biodegradable polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002591 computed tomography Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011960 computer-aided design Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
- C04B2235/3212—Calcium phosphates, e.g. hydroxyapatite
Definitions
- Dispersant for ceramic particles and method for preparing monomer suspension Dispersant for ceramic particles and method for preparing monomer suspension
- the present invention relates to a composite material and a method for preparing a monomer suspension that can be used as a dispersant for dispersing ceramic particles, particularly hydroxyapatite particles, in an organic solvent with good fluidity and stability.
- Hydroxyapatite has a very high affinity with living organisms and is widely used as a bone defect filler. Considering this affinity with the living body, it is preferable to be porous so that cells can enter and form new bone.
- a molded body having a uniform structure composed of hydroxyapatite particles is obtained by coating the surface of hydroxyapatite particles in an aqueous solution with a polymer to prevent aggregation of particles due to intermolecular forces.
- the process of obtaining is known. Also, by using such a process, the dispersibility of the hydroxyapatite particles is improved, and the morphology control and pore control can be performed relatively easily. In particular, by using such a process, the fluidity of the nodyl and adroxyapatite particle suspension is improved, and it becomes easy to inject into a saddle type having a specific structure. Shape control and hole control can be performed relatively easily.
- aqueous dispersions of polymers and fine inorganic particles are generally known. This is a liquid system in which a polymer coil composed of a plurality of twisted polymer chains and fine inorganic particles are dispersed as a dispersed phase in an aqueous dispersion medium.
- Aqueous dispersions of inorganic particles have the potential to form modified polymer coatings containing fine inorganic particles, eg for compositions covering paints or leather, paper or plastic films.
- the particle powder obtained from the aqueous dispersion of inorganic particles is used as an additive for plastics and as a component of toner preparations, and further as an additive for electrophotography (for example, patent documents;! To 3). See).
- hydroxyapatite particles are polar and often aggregate in a solution.
- a dispersant for obtaining a molded article having a uniform structure composed of hydroxyapatite particles by coating the surface of the hydroxyapatite particles with a polymer and preventing aggregation of particles due to intermolecular force There was nothing commercially appropriate.
- Patent Document 1 US Pat. No. 3,544,500
- Patent Document 2 U.S. Pat.No. 4,421,660
- Patent Document 3 European Patent No. 104498
- the ceramic particle dispersant and monomer suspension preparation method according to the present invention which meets the above-mentioned problems and needs, is suitable for dispersion stability and suspension of ceramic particles, particularly hydroxyapatite particles.
- the purpose is to obtain a liquid.
- a dispersant for obtaining a molded article having a uniform structure composed of hydroxyapatite particles by coating the surface of hydroxyapatite particles with a polymer and preventing aggregation of particles due to intermolecular repulsion is to provide.
- a basic polymer having a nitrogen atom is a hydroxyapatite (HAP), tricalcium phosphate (/ 3-TCP), or a mixture thereof.
- HAP hydroxyapatite
- / 3-TCP tricalcium phosphate
- a composite material comprising coating the surface of a particle made of material.
- the inventors of the present invention made a hydroxyapatite monomer suspension in the process of producing a bone filling material (skihold) made of a hydroxyapatite artificial bone and a bioabsorbable polymer that has undergone a forging process! By injecting a suspension and conducting a polymerization reaction in the cage, It was necessary to obtain a notite compact.
- the hydroxyapatite molded body is not only an artificial bone product itself, but also a scaffold type made of a bioabsorbable polymer.
- the basic polymer having a nitrogen atom is a basic polymer obtained by a polymerization reaction of a polymer having an amino group or a cyclic compound containing nitrogen with a monomer that can be copolymerized. I like it.
- Basic copolymer strength By covering the surface of particles made of hydroxyapatite particles, tricalcium phosphate (/ 3-TCP), or composite materials of these, the surface area with polarity is reduced and the dispersibility of the particles is increased. To increase.
- the polymer having an amino group includes dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate, jetylaminoethyl methacrylate, jetylaminoethyl acrylate, butylaminoethyl methacrylate.
- DMAEMA dimethylaminoethyl methacrylate
- jetylaminoethyl methacrylate jetylaminoethyl methacrylate
- jetylaminoethyl acrylate jetylaminoethyl acrylate
- butylaminoethyl methacrylate butylaminoethyl methacrylate.
- at least one selected from the group consisting of rate, dimethylaminopropylmethacrylamide, and chitosan is used.
- the cyclic compound containing nitrogen is selected from at least one of pyridine and pyrrolidone.
- the copolymerizable monomer is preferably selected from any one of an acrylic compound, a methacrylic compound, and a styrene compound.
- an acrylic compound a methacrylic compound
- a styrene compound a styrene compound
- isobornyl acrylate (IBA) can be used as an acrylic compound.
- the ratio of the amino group-containing polymer or nitrogen-containing cyclic compound to the copolymerizable monomer is preferably 3: 7 to 1: 9 by weight.
- the composition ratio of the basic monomer (polymer having amino group or cyclic compound containing nitrogen) in the copolymer, that is, the setting of the polymerization ratio is the key to improving the suspendability.
- the composite material according to the first aspect is polymerized or crosslinked.
- a suspension is provided which is added to the bridging monomer.
- the suspension according to the second aspect is poured into a forging wax (WAX) mold, sintered after the polymerization reaction, and used to produce a molded article.
- WAX forging wax
- the crosslinkable monomer is preferably one having two or more polymerizable unsaturated groups, for example, divinylbenzene! /.
- a copolymer of an amino group-containing polymer or a nitrogen-containing cyclic product and a monomer copolymerizable with hydroxyapatite (HA), phosphorus there is provided a copolymer of an amino group-containing polymer or a nitrogen-containing cyclic product and a monomer copolymerizable with hydroxyapatite (HA), phosphorus.
- the above suspension preparation method includes dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate, jetylaminoethyl methacrylate, jetylaminoethyl acrylate, butylaminoethyl methacrylate.
- DMAEMA dimethylaminoethyl methacrylate
- Copolymer of a compound selected from at least one of tallylate, dimethylaminopropylmethacrylamide, and chitosan and one selected from an acrylic compound, a methacrylic compound, and a styrene compound In Hydroxyapatite (HA), Tricalcium Phosphate (/ 3-TCP) or their composites
- a method for preparing a bone filling material using a three-dimensional shape-designed saddle having a communicating hole structure the method for preparing a monomer suspension of the present invention described above.
- a method for producing a bone filling material including a step of sintering.
- the monomer suspension prepared by using the suspension preparation method according to the fourth aspect of the present invention is polymerized and cured in a mold, and the mold is incinerated and removed by the designer.
- Shape control as intended 'Porosity-controlled compacts hydroxyapatite, tricalcium phosphate or composites of these materials
- Such a molded body is expected to be used as a custom-made artificial bone adapted to the shape of the bone defect.
- the mold is made using a 3D CAD (Computer Aided Design) by a designer and using a wax for fabrication (WAX) resin.
- WAX wax for fabrication
- the bone prosthetic material manufacturing method according to the fifth aspect of the present invention is a bone prosthetic material manufacturing method using a three-dimensional shape-designed saddle shape having a communicating hole structure.
- the step of solidifying and the step of removing the second saddle mold with a predetermined solvent are characterized in that it is characterized in that it is structured.
- the shape controlled and pore controlled molded body as designed by the designer molded body of hydroxyapatite, tricalcium phosphate or a composite material of these
- the molded body obtained in the previous forging process is used again as a mold, and the resin is injected and solidified to remove the mold.
- the target bone substitute material is obtained.
- a bioabsorbable bone grafting material can be obtained by using a bioabsorbable polymer such as polylactic acid as the resin.
- the method further comprises a step of dissolving the cage with an organic solvent, It is preferable to go through a step of sintering the mold.
- a wax (WAX) type the wax type is dissolved and removed with acetone or the like.
- the upper edge of the saddle is removed as a pretreatment in the step of injecting the monomer suspension into the saddle.
- Monomer suspension Is obtained after sintering due to the difference in shrinkage rate due to the presence or absence of pores in the upper part of the mold. Cracks of the molded body such as hydroxyapatite occur.
- the reason for removing the upper edge of the saddle type as a pretreatment is to avoid the occurrence of cracks in the molded body.
- the hole shape of the communicating hole in the saddle type having a communicating hole structure and having a three-dimensional shape design is a substantially cylindrical shape.
- the pore shape is a simple rectangle (for example, a square shape)
- cracks tend to occur from the corners of the pore shape of a molded article such as hydroxyapatite obtained after sintering.
- An agent can be obtained.
- the suspension prepared by using the suspension preparation method of the present invention is injected into a cage having a three-dimensional shape having a communicating hole structure, and a polymerization reaction is performed in the cage. Then, the hydroxyapatite molded body having a shape control as controlled by the designer as intended by the designer can be obtained by curing the hydrated xanthite particles and then sintering the mold. Further, a hydroxyapatite molded body with force, shape control and pore control can be used for a scaffold type artificial bone product or a scaffold made of a bioabsorbable polymer.
- Figure 1 shows a particle made of hydroxyapatite particles coated with a polymer and intermolecular force. The image figure which prevents aggregation of each other is shown.
- Fig. 1 (a) when hydroxyapatite particles 1 are present in an organic solvent 2 such as acrylic or methacrylic, the surfaces of the hydroxyapatite particles 1 are polar, so the particles It coalesces and aggregates, resulting in poor dispersibility.
- an organic solvent 2 such as acrylic or methacrylic
- the surface of the hydroxyapatite particle 1 is coated with the basic copolymer 3 to prevent the particles from aggregating due to the attractive force acting between the polar molecules, and the dispersion stability is good even in an organic solvent! /, A suspension is obtained.
- Dimethylaminoethyl methacrylate (HDMAEMA) 0.754g, Isobornyl acrylate (IBA) 20.0g, and toluene 20mL (milliliter) were mixed, shaken at 70 ° C, by radical polymerization reaction.
- DMAEMA IBA copolymer is obtained.
- Hydroxyapatite particles adsorbed with polymer by methylisobutyl ketone (MIBK) are washed, and 5g of hydroxyapatite particles are mixed with 1.92mL of IBA, 0.48mL of crosslinker (dibutylbenzene), and polymerization initiator. By doing this, it is possible to produce 4 mL of a monomer suspension with high fluidity and a hydroxyapatite content of about 40 vol%.
- MIBK methylisobutyl ketone
- the surface of the particles is coated with a basic copolymer, and the basic and non-treated hydroxyapatite particles are used.
- the filling rate when using the coalesced was examined.
- untreated and idroxyapatite particles it was possible to produce a monomer suspension having a hydroxyapatite content of 16.7 vol%.
- a non-basic polymer for example, polymethyl methacrylate
- a monomer suspension having a hydroxyapatite content of 17.6 vol% could be produced.
- the hydroxyapatite particle content is about 40 vol%, which is the highest filling rate. It can be said that there is an advantage that a monomer suspension having the most fluidity can be produced.
- FIG. 2 shows the result of the sedimentation test of the suspension prepared by the method of Preparation Example 1.
- a plot of the results showing the dispersibility of silane-treated hydroxyapatite and untreated hydroxyapatite is shown!
- Various types and idoxyapatite are suspended in methyl methacrylate (10 vol%), and the sedimentation rate of hydroxyapatite is measured.
- Silane-treated hydroxyapatite is prepared by suspending 10 g of hydroxyapatite particles in 75 mL of isopropyl alcohol solution containing 3.1 g of ⁇ -methacryloxypropyltrimethoxysilane and stirring at 60 ° C. Is.
- Untreated hydroxyapatite is a commercially available natural apatite ceramic (Exera Corporation, fine powder type).
- the suspension produced by the method of Production Example 1 can be dispersed significantly more stably than the dispersibility of silane-treated hydroxyapatite and untreated hydroxyapatite. Accordingly, it will be understood that the copolymer of dimethylaminoethyl methacrylate (DMAEMA) and isobornylacrylic acid functions as a dispersant that can prevent aggregation of hydroxyapatite particles.
- DMAEMA dimethylaminoethyl methacrylate
- isobornylacrylic acid functions as a dispersant that can prevent aggregation of hydroxyapatite particles.
- Example 2 a method for producing a bone prosthetic material using a hydroxyapatite suspension (HA suspension) produced by the method of Production Example 1 described above will be described.
- HA suspension hydroxyapatite suspension
- Fig. 3 shows a schematic diagram of the bone prosthesis preparation protocol that goes through a two-step forging process. 2 steps
- the bone prosthesis preparation protocol through the forging process of (1) to (4) consists of the former forging process of steps (1) to (4) and the forging process of the latter stage of procedures (5) to (6).
- the steps (1) to (6) are explained below in order.
- Procedure (1) is a phase in which the first saddle-shaped 3D shape model design is performed using 3D CAD.
- a 3D CAD is used to frame the saddle and convert 3D data into slice data.
- step (2) is a phase in which the first saddle shape is obtained by performing three-dimensional additive manufacturing using the slice data and wax (WAX) resin.
- step (3) is a phase in which the HA suspension prepared by the method of Preparation Example 1 described above is poured into a first saddle mold and a polymerization reaction is performed to cure the suspension.
- isobornyl acrylate is added.
- Isobornyl acrylate is an acrylic compound.
- methacrylic compounds and styrene compounds can also be used as additives for carrying out the polymerization reaction.
- the procedure (4) is a phase in which the first mold into which the HA suspension is injected is sintered and at the same time the wax (WAX) is pyrolyzed and removed. As a result, a hydroxyapatite molded body (HA molded body) is obtained. The size of the HA compact is reduced by sintering compared to the size of the WAX type (first saddle type).
- the HA compact obtained in the above procedure (4) can be used as it is as a hydroxyapatite artificial bone product.
- step (5) is a phase in which the obtained HA molded body is used as a mold (second mold) and a biodegradable polymer is injected into the second mold.
- the method for injecting the biodegradable polymer into the second mold is to immerse the second mold in the molten biodegradable polymer for a sufficient time. In the case of a vertical type with complex holes (communication holes) inside, it should be sufficiently impregnated by applying pressure from the outside. Then, after sufficiently injecting the biodegradable polymer into the second bowl, it is cooled to solidify the biodegradable polymer. At this time, the biodegradable polymer protruding from the second bowl is wiped away, and the outer shape is shaped along the bowl.
- a hydoxy oxide composition is removed by treatment with a solvent such as an acid or a decalcification solution to obtain a molded body (target bone filling material) composed only of a biodegradable polymer. Hue It is.
- the first mold into which the HA suspension has been injected is sintered, and at the same time the wax (WAX) is pyrolyzed and removed! Cracks due to thermal shrinkage during the sintering process ⁇
- the design of the WAX type (the first saddle type) was improved to improve the side warp (see Fig. 4), and the produced HA compact was used as a CT (Computed Tomography) fault. Evaluation was performed using images.
- Fig. 5 (1) shows a schematic diagram (before and after removal of the upper edge) before and after improvement of the saddle type structural design.
- Fig. 5 (2) shows CT cross-sectional images that show the effects before and after the structural design improvement.
- the HA suspension is filled in the upper edge, which is essentially redundant, so that the shrinkage rate due to the presence or absence of pores
- the upper warp due to thermal shrinkage is improved and the cracks associated therewith are improved. It can be confirmed that the occurrence of this is improved.
- FIG. 6 (1) shows a schematic diagram (change of hole shape) before and after the improvement of the saddle-type structure design.
- Fig. 6 (2) shows CT cross-sectional images showing the effects before and after the structural design improvement.
- the HA suspension was injected.
- the wax mold (WAX) is decomposed and removed as a pretreatment (step (4) above) by dissolving and removing the first mold of the wax mold with aceton.
- the hydroxyapatite suspension prepared using the method for preparing a monomer suspension of the present invention is injected into a cage having a three-dimensional shape design, and a polymerization reaction is performed in the cage.
- the hydroxyapatite particles are cured by curing the hydroxyapatite particles and then sintering the mold to control the shape as designed by the designer. Can be obtained.
- the hydroxyapatite suspension prepared using the method for preparing a monomer suspension of the present invention has excellent dispersion stability and can form a hydroxyapatite molded product having a uniform structure. This is very beneficial for obtaining a hydroxyabatite compact that requires complex shape control and pore control. This has the effect of improving the mechanical properties of the target products, hydroxyapatite artificial bone products and scaffolds made of bioabsorbable polymers.
- the method for preparing a ceramic particle dispersant and monomer suspension of the present invention can be used for preparing a dispersant and a suspension of hydrated xanthite or 13-TCP.
- FIG.1 Image of hydroxyapatite particles coated with a polymer to prevent aggregation between particles due to intermolecular forces
- FIG. 2 is a graph showing the result of a sedimentation test of a suspension prepared by the method of Preparation Example 1.
- FIG. 5 CT cross section image showing improvement of vertical structure design (removal of upper edge) and its effect
- FIG. 6 Improvement of vertical structure design (changing hole shape) and its effect CT cross section image
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Abstract
Cette invention propose d'obtenir une suspension de particules céramiques, en particulier, de particules d'hydroxyapatite qui a une stabilité élevée de dispersion. L'invention concerne un procédé de préparation d'une suspension d'un monomère d'hydroxyapatite qui peut être facilement versée dans un moule de coulée au cours de la fabrication d'une matière de substitution de l'os (un échafaudage) comportant un os artificiel d'hydroxyapatite et un polymère bioabsorbable par une étape de coulée, les particules artificielles d'hydroxyapatite étant enrobées d'un copolymère basique. Ainsi, la force cohésive des particules d'hydroxyapatite est abaissée et les particules sont stabilisées pour améliorer de cette façon la dispersibilité. Le copolymère basique tel que décrit ci-dessus est un copolymère d'un composé de masse moléculaire élevée ayant un groupe amino ou un composé cyclique contenant de l'azote avec un monomère copolymérisable. Par un contrôle approprié du rapport de composition du monomère basique (c'est-à-dire le composé de masse moléculaire élevée ayant un groupe amino ou le composé cyclique contenant de l'azote) dans ce copolymère, à savoir le rapport de polymérisation, les propriétés de mise en suspension peuvent être améliorées.
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JP2014529456A (ja) * | 2011-09-06 | 2014-11-13 | ヴィタ ツァーンファブリーク ハー. ラオテル ゲーエムベーハー ウント コー カーゲー | 医療用セラミックインプラントを作製するためのプロセス |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000302567A (ja) * | 1999-04-13 | 2000-10-31 | Toshiba Ceramics Co Ltd | リン酸カルシウム系多孔質焼結体およびその製造方法 |
JP2002121088A (ja) * | 2000-10-13 | 2002-04-23 | Toshiba Ceramics Co Ltd | リン酸カルシウム系多孔質焼結体およびその製造方法 |
JP2003159321A (ja) * | 2001-11-27 | 2003-06-03 | Takiron Co Ltd | 有機−無機複合多孔体及びその製造方法 |
WO2003075975A1 (fr) * | 2002-03-14 | 2003-09-18 | Degradable Solutions Ag | Matiere pour implant biocompatible poreuse et procede pour sa fabrication |
JP2004026653A (ja) * | 2002-03-04 | 2004-01-29 | Mitsuru Akashi | ハイドロキシアパタイト−ポリマー複合材料の止血用組成物 |
-
2007
- 2007-10-30 WO PCT/JP2007/071073 patent/WO2008053865A1/fr active Search and Examination
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000302567A (ja) * | 1999-04-13 | 2000-10-31 | Toshiba Ceramics Co Ltd | リン酸カルシウム系多孔質焼結体およびその製造方法 |
JP2002121088A (ja) * | 2000-10-13 | 2002-04-23 | Toshiba Ceramics Co Ltd | リン酸カルシウム系多孔質焼結体およびその製造方法 |
JP2003159321A (ja) * | 2001-11-27 | 2003-06-03 | Takiron Co Ltd | 有機−無機複合多孔体及びその製造方法 |
JP2004026653A (ja) * | 2002-03-04 | 2004-01-29 | Mitsuru Akashi | ハイドロキシアパタイト−ポリマー複合材料の止血用組成物 |
WO2003075975A1 (fr) * | 2002-03-14 | 2003-09-18 | Degradable Solutions Ag | Matiere pour implant biocompatible poreuse et procede pour sa fabrication |
Non-Patent Citations (3)
Title |
---|
HIGUCHI Y. ET AL.: "Hone Saiseiyo Porous Scaffold-gata no Zokei Process no Kento", BIO FRONTIER KOENKAI KOEN RONBUNSHU, vol. 15TH, 4 November 2004 (2004-11-04), pages 57 - 58, XP003022605 * |
KATO K. ET AL.: "In situ hydroapatite crystallization for the formation of hydroxyapatite/polymer composites", JOURNAL OF MATERIALS SCIENCE, vol. 32, no. 20, 1997, pages 5533 - 5543, XP000722390 * |
TABOAS J.M. ET AL.: "Indirect solid free form fabrication of local and global porous, biomimetic and composite 3D polymer-ceramic scaffolds", BIOMATERIALS, vol. 24, no. 1, 2003, pages 181 - 194, XP004390634 * |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2014529456A (ja) * | 2011-09-06 | 2014-11-13 | ヴィタ ツァーンファブリーク ハー. ラオテル ゲーエムベーハー ウント コー カーゲー | 医療用セラミックインプラントを作製するためのプロセス |
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