CN-116133861-B - Calcium phosphate powder

Abstract

The purpose of the present invention is to provide a calcium phosphate powder which can produce a slurry for laminated modeling that has excellent dispersion stability in laminated modeling, and can produce a high-strength three-dimensional laminated modeling product. A calcium phosphate powder having an average particle diameter (D 50 ) of 0.1 to 5.0 [ mu ] m and a mesopore volume (pore diameter of 2 to 50 nm) of 0.01 to 0.06cc/g as measured by a gas adsorption method is excellent in dispersion stability in a slurry for laminated molding, and a three-dimensional laminated molded article having high strength useful for an implant such as an artificial bone can be produced by laminated molding using the slurry for laminated molding containing the calcium phosphate.

Inventors

• Guimu Yangping
• Board Dongming
• Qiao Benwang
• KITAMURA NAOYUKI

Assignees

• 富田制药株式会社

Dates

Publication Date

20260508

Application Date

20210716

Priority Date

20200730

Claims (12)

1. 1. A laminate molding material comprising a calcium phosphate powder having an average particle diameter D 50 to 5.0 [ mu ] m, The calcium phosphate powder has a mesopore volume of 0.01-0.06 cc/g, as measured by a gas adsorption method, of mesopores having a pore diameter of 2-50 nm, The calcium phosphate powder has a pore volume of 0.02-0.10 cc/g as measured by a gas adsorption method and a pore diameter of 50-200 nm The calcium phosphate powder has a D 10 of 1.0 [ mu ] m or less as measured by a laser diffraction/scattering particle size distribution measuring device.
2. 2. The material for laminated molding according to claim 1, wherein the calcium phosphate comprises at least 1 of hydroxyapatite, tricalcium phosphate, α -TCP, calcium deficient hydroxyapatite, and β -TCP.
3. 3. The material for laminated molding according to claim 1 or 2, wherein the calcium phosphate powder has a BET specific surface area of 0.1 to 20m 2 /g.
4. 4. The material for laminated molding according to claim 1 or 2, wherein the calcium phosphate powder has a pore volume of 0.02 to 0.09cc/g as measured by a gas adsorption method, wherein the pore volume is 50 to 200 nm.
5. 5. The laminated molding material according to claim 1 or 2, wherein the calcium phosphate powder has a D 10 of 0.1 to 0.9 μm as measured by a laser diffraction/scattering particle size distribution measuring device.
6. 6. The laminated molding material according to claim 1 or 2, wherein the calcium phosphate powder has a D 10 of 0.2 to 0.8 μm as measured by a laser diffraction/scattering particle size distribution measuring device.
7. 7. The material for laminated molding according to claim 1 or 2, which is used for light molding.
8. 8. The material for laminated modeling according to claim 1 or 2, which is used for manufacturing an implant.
9. 9. A slurry for laminated molding comprising a calcium phosphate powder and a photocurable resin, The average particle diameter D 50 of the calcium phosphate powder is 0.1-5.0 mu m, The calcium phosphate powder has a mesopore volume of 0.01-0.06 cc/g, as measured by a gas adsorption method, of mesopores having a pore diameter of 2-50 nm, The calcium phosphate powder has a pore volume of 0.02-0.10 cc/g as measured by a gas adsorption method and a pore diameter of 50-200 nm The calcium phosphate powder has a D 10 of 1.0 [ mu ] m or less as measured by a laser diffraction/scattering particle size distribution measuring device.
10. 10. A method for producing a three-dimensional laminated molded article, comprising the steps (1) to (4), (1) A step of forming a slurry layer using the slurry for laminated molding according to claim 9; (2) A step of irradiating the slurry layer with a laser beam in a predetermined pattern shape to cure the slurry layer; (3) And (2) repeating the steps (1) and (2) to form a three-dimensional laminated cured product, and (4) And removing the uncured resin and the cured resin from the three-dimensional laminated cured product.
11. 11. The method of manufacturing a three-dimensional laminate molding of claim 10, wherein the three-dimensional laminate molding is an implant.
12. 12. The use of a calcium phosphate powder as a material for laminated molding, The average particle diameter D 50 of the calcium phosphate powder is 0.1-5.0 mu m, The calcium phosphate powder has a mesopore volume of 0.01-0.06 cc/g, as measured by a gas adsorption method, of mesopores having a pore diameter of 2-50 nm, The calcium phosphate powder has a pore volume of 0.02-0.10 cc/g as measured by a gas adsorption method and a pore diameter of 50-200 nm The calcium phosphate powder has a D 10 of 1.0 [ mu ] m or less as measured by a laser diffraction/scattering particle size distribution measuring device.

Description

Calcium phosphate powder Technical Field The present invention relates to a calcium phosphate powder which can produce a slurry for laminated molding having excellent dispersion stability in laminated molding (LAMINATE SHAPING) and can produce a three-dimensional laminated molded article having high strength. Background In recent years, artificial bones (ARTIFICIAL BONE) have been used as a substitute for human bones in bone defect parts for the treatment of bone diseases such as fractures. As a raw material of the artificial bone, a metal, a ceramic, a polymer material, or the like is used. Ceramics have a lower mechanical strength than metals and polymer materials, but have excellent biocompatibility and are useful as a raw material for artificial bones. Among ceramics, calcium phosphates such as Hydroxyapatite (HAP) and β -tricalcium phosphate (β -TCP) have a composition equivalent to that of human bone, and are excellent in osteoinductive properties, and therefore, are directly bonded to bone or become a component of bone formation, and thus, many studies on artificial bone formed from calcium phosphate have been made. However, since an artificial bone made of calcium phosphate has a composition equivalent to that of bone, but the treatment rate is inferior to that of autogenous bone, a block-shaped or granular artificial bone having a porous body and communication holes has been developed so that the artificial bone made of calcium phosphate has a structure equivalent to that of autogenous bone, but the treatment rate is inferior to that of autogenous bone, and further, it is necessary to mold the artificial bone in accordance with a defect site at the time of surgery. In order to solve such a problem, in the formation of an artificial bone based on calcium phosphate, attempts have been made to produce an artificial bone that not only matches the shape of a defect site but also reproduces the internal structure of the bone using a lamination modeling technique (3D printer). In a 3D printer applied to artificial bones, a molding method (powder lamination molding method) in which a curing liquid is injected into a powder to cure the powder, a molding method (photo molding (photo fabrication)) in which a slurry for lamination molding (molding paste) obtained by kneading a ceramic raw material and a photo-curable resin is irradiated with ultraviolet rays to cure the slurry, and the resin is removed from the obtained cured product, and the like are known. Non-patent document 1 discloses that an artificial bone is produced by powder lamination molding using a powder containing α -tricalcium phosphate, tetracalcium phosphate, dicalcium phosphate and HAP, but the compressive strength of the obtained artificial bone is limited to about 27 MPa. In addition, non-patent document 2 discloses that an artificial bone is produced by a photodefinable method using HAP having a particle diameter of 12 μm, but the compressive strength of the obtained artificial bone is only about 15 MPa. Thus, the artificial bone produced by the lamination technique using calcium phosphate in the related art has a disadvantage that it has low compressive strength and cannot be applied to a portion (femur or the like) to which a strong load is applied. Patent document 1 discloses alumina, zirconia, and the like as ceramic raw materials used in the lamination modeling technique, but these raw materials can give a three-dimensional lamination modeling product having a certain strength, but have a problem of poor osteoinductive properties. In addition, the manufactured artificial bone is required to have reproducibility (molding accuracy) of the bone to such an extent that molding is not required during the operation. In order to improve the molding accuracy in the photolithography, it is effective to reduce the particle size of the calcium phosphate powder, but if the average particle size of the calcium phosphate powder is reduced to 1 μm or less, the calcium phosphate powder tends to agglomerate in the slurry and tends to be not uniformly dispersed. Against the background of such conventional techniques, it has been desired to develop a calcium phosphate powder which can prepare a slurry for laminated molding having excellent dispersion stability and can produce a high-strength three-dimensional laminated molded article by using a laminated molding technique. Prior art literature Non-patent literature Non-patent document 1 proposes an artificial bone molding method using a powder laminate molding method-porous molded bone-biomedical engineering 47 (2): 142-147,2009 Non-patent literature 2：Additive manufacturing of hydroxyapatite bone scaffolds via digital lightprocessing and in vitro compatibility(Ceramics InternationalVolume 45,Issue 81 June 2019Pages 11079-11086) Patent literature Patent document 1 International publication No. 2016/147681 Disclosure of Invention Problems to be solved by the invention The purpose of the present invention