# US 2019/0167841 A1 · Method for producing calcium phosphate molded article, calcium phosphate molded article, and material for transplantation

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- Number: US 2019/0167841 A1
- Document ID: US20190167841A1
- Status: Published application
- Kind: A1
- Application number: 16/204,987
- Filed: 2018-11-29
- Published: 2019-06-06
- Earliest claimed: 2016-05-30
- Assignees: FUJIFILM Corporation
- Applicants: FUJIFILM Corporation
- Inventors: Hiroshi OTA; Manabu KATSUMURA; Kazuya KAWASAKI; Yoshio ISHII; Hideo FUSHIMI; Takahiro HIRATSUKA; Ai OKAMURA; Mamoru NISHITANI; Masayuki EZUMI
- Web page: https://patentgrep.com/patent/US20190167841A1

## CPC

- A61L 27/12: Phosphorus-containing materials, e.g. apatite
- A61L 27/222: {Gelatin}
- A61L 27/34: Macromolecular materials
- A61L 27/427: {of other specific inorganic materials not covered by A61L27/422 or A61L27/425}
- A61L 27/58: Materials at least partially resorbable by the body
- B28B 1/001: {Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00)}
- B28B 1/30: by applying the material on to a core or other moulding surface to form a layer thereon (to form a permanent layer B28B19/00)
- B29C 67/00: Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- C04B 35/447: based on phosphates {, e.g. hydroxyapatite}
- C07K 14/78: Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin or cold insoluble globulin [CIG]
- A61L 2430/02: for reconstruction of bones; weight-bearing implants
- A61L 2430/04: for mammary reconstruction
- A61L 2430/06: for cartilage reconstruction, e.g. meniscus
- A61L 2430/38: for reconstruction of the spine, vertebrae or intervertebral discs
- B33Y 80/00: Products made by additive manufacturing
- 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 (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- B28B: SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER (foundry moulding B22C; working stone or stone-like material B28D; shaping of substances in a plastic state, in general B29C; making layered products not composed wholly of these substances B32B)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C07K: PEPTIDES (peptides in foodstuffs A23; obtaining protein compositions for foodstuffs, working-up proteins for foodstuffs A23J; preparations for medicinal purposes A61K; peptides containing beta-lactam rings C07D; cyclic dipeptides not having in their molecule any other peptide link than those which form their ring, e.g. piperazine-2,5-diones, C07D; ergot alkaloids of the cyclic peptide type C07D519/02; macromolecular compounds having statistically distributed amino acid units in their molecules, i.e. when the preparation does not provide for a specific; but for a random sequence of the amino acid units, homopolyamides and block copolyamides derived from amino acids C08G69/00; macromolecular products derived from proteins C08H1/00; preparation of glue or gelatine C09H; single cell proteins, enzymes C12N; genetic engineering processes for obtaining peptides C12N15/00; compositions for measuring or testing processes involving enzymes C12Q; investigation or analysis of biological material G01N33/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING

## Abstract

Provided are a method for rapidly producing a calcium phosphate molded article having high strength with high shaping precision, a calcium phosphate molded article produced by the method, and a material for transplantation. Disclosed is a method for producing a calcium phosphate molded article, the method including: step (a) of forming a layer containing a calcium phosphate powder having a ratio of the numbers of atoms of Ca/P of 1.4 to 1.8 on a substrate; and step (b) of producing a calcium phosphate molded article by jetting an organic acid solution having a pH of 3.5 or lower and including an organic acid whose calcium salt has a solubility in water of 1 g/100 mL or less, through a nozzle unit into a liquid droplet state, thereby dropping the organic acid solution onto the layer containing a calcium phosphate powder formed in step (a).

## Claims

### Claim 1

A calcium phosphate molded article formed from calcium phosphate,
the molded article having holes communicating with the external space, having a specific gravity of 0.7 g/mL or higher and/or a porosity according to a mercury infusion method of 75% or lower, and having a water absorption infiltration rate of 0.05 mm/second or higher:
provided that the water absorption infiltration rate is measured under the following conditions: an experiment system is established, in which one end of a plastic cylinder having an inner diameter of 2 mm is connected to a calcium phosphate molded article having a diameter of 8 mm and a height of 20 mm, the other end of the plastic cylinder is connected to one end of a tube having a length of 100 mm, and the other end of the tube is connected to a 10-mL syringe; under the conditions regulated such that the height at which the calcium phosphate molded article is contacted with the plastic cylinder, and the height of the level of ink contained in the syringe are maintained equal from the initiation to the completion of water absorption and infiltration, the ink in the syringe is subjected to absorption and infiltration into the calcium phosphate molded article; in a case in which the height of the region infiltrated by the ink in the calcium phosphate molded article reaches 15 mm within 5 minutes, a value obtained by dividing 15 mm by the time required for infiltration is defined as the water absorption infiltration rate; and in a case in which the height of the region infiltrated by the ink in the calcium phosphate molded article does not reach 15 mm within 5 minutes, a value obtained by dividing the height of the region infiltrated by the ink in the calcium phosphate molded article at the time point of 5 minutes, by 5 minutes, which is the time required for infiltration, is defined as the water absorption infiltration rate.

### Claim 2 (depends on 1)

The calcium phosphate molded article according to claim 1, wherein the calcium phosphate has a ratio of the numbers of atoms of Ca/P of 1.4 to 1.8.

### Claim 3 (depends on 1)

The calcium phosphate molded article according to claim 1, having a structure in which a relatively compact layer and a relatively sparse layer as distinguished by an analysis by nanofocus X-ray CT or microfocus X-ray CT are alternately laminated.

### Claim 4 (depends on 3)

The calcium phosphate molded article according to claim 3, wherein at least five or more layers of the relatively compact layer and at least five or more layers of the relatively sparse layer are alternately laminated.

### Claim 5 (depends on 3)

The calcium phosphate molded article according to claim 3, wherein the pitch between a first relatively compact layer and a second relatively compact layer next to the first relatively compact layer is 50 to 300 μm.

### Claim 6 (depends on 1)

The calcium phosphate molded article according to claim 1, wherein in a waveform chart based on a nanofocus X-ray CT image of the calcium phosphate molded article, with the horizontal axis representing the distance in one direction of the molded article and the vertical axis representing the relative CT intensity, peaks and troughs exist alternately.

### Claim 7 (depends on 6)

The calcium phosphate molded article according to claim 6, having at least five or more peaks.

### Claim 8 (depends on 6)

The calcium phosphate molded article according to claim 6, wherein the pitch between a first peak and a second peak next to the first peak is 50 to 300 μm.

### Claim 9

A material for transplantation, comprising a calcium phosphate molded article having a surface partially or entirely coated with a recombinant gelatin.

### Claim 10 (depends on 9)

The material for transplantation according to claim 9, wherein the calcium phosphate has a ratio of the numbers of atoms of Ca/P of 1.4 to 1.8.

### Claim 11 (depends on 9)

The material for transplantation according to claim 9, wherein the recombinant gelatin is thermally crosslinked or chemically crosslinked.

### Claim 12 (depends on 9)

The material for transplantation according to claim 9, wherein the surface of the calcium phosphate molded article coated with recombinant gelatin exists on the surface and in the interior of the material for transplantation.

### Claim 13 (depends on 9)

The material for transplantation according to claim 9, wherein the calcium phosphate molded article is block-shaped.

### Claim 14 (depends on 9)

The material for transplantation according to claim 9, wherein the calcium phosphate molded article is granular.