TW201350432A - Using shell as raw material to form calcium phosphate material and the method of making calcium phosphate material - Google Patents

Abstract

The present invention provide shells as raw material to form calcium phosphate material, the shells is species one of the Veneroida, otherwise, it also provide a method to form calcium phosphate material, wherein the method at least includes steps of (a) grinding shells to be a shell powder; (b) adding phosphate to the shell powder to form a mixture; and (c) forming calcium phosphate material by a heating procedure.

Description

Calcium phosphate material prepared by using shell as a base material and manufacturing the calcium phosphate Material method

The present invention relates to a calcium phosphate material and a method for producing the calcium phosphate material, and more particularly to a method for synthesizing calcium phosphate by using calcium carbonate formed by biomineralization as a base material and using the calcium carbonate.

With the increase of bone tumor patients and the gradual aging of the population, when bone defects occur in a large range of bone defects, due to the decreased or insufficient ability of the body to repair itself, it is necessary to help repair through bone transplantation, making bone transplantation a world. The second largest organ transplant surgery, with the increase in the number of bone grafts, the demand for bone graft materials is also increasing.

The general bone graft materials can be divided into four types, including (1) autogenous graft: taking out the bone graft of the patient's own body to the required site; (2) allogenic graft: the patient accepts Transplantation of bone tissue from others; (3) Heterogenous graft: transplantation of bone or bone marrow tissue from animals such as cattle and pigs to humans; (4) Cancellous bone substitutes: chemically synthesized osteoids Or treated coral skeleton or sea urchin skeleton as a filling for bone defects. Since the amount of bone available for autologous transplantation is not large, allogeneic bone grafts and allografts need to avoid disease or organ rejection, and the use of artificial substitutes as bone substitute materials is currently the most beneficial and safe. the way.

Among them, artificial substitutes need good biocompatibility as a bone substitute material, and hydroxyapatite is one of them. In recent years, calcium phosphate such as hydroxyapatite (HA) and α/β- Synthetic bone substitute materials such as α/β-tricalcium phosphate (β-TCP) have been widely used in dental and bone grafting. However, due to the lack of network structure of chemically synthesized calcium phosphate materials The connected voids are more unfavorable to the attachment and proliferation of cells, and delay the recovery rate after bone transplantation. The natural hydroxyapatite transformed with natural materials has a natural network structure and connected voids. Many kinds of calcium carbonate (such as coral skeleton, nacre, sea urchin, cuttlefish bone, etc.) formed by biomineralization have been used as raw materials to synthesize calcium phosphate, and then the bone tissue scaffold material has been synthesized.

Because natural biosynthetic derivatives are weak in antigenicity and have good tissue affinity and binding, their natural pore structure is beneficial to the attachment and proliferation of osteoblasts, but it is known that the basic raw materials such as corals are biomineralized. Bone, because of its small number, can not be obtained in large quantities, or such as sea urchin bones and sea urchin needles, due to its high magnesium ion content, its structure is relatively hard, when used to manufacture calcium phosphate materials, the energy consumption is more High, and its manufacturing method is more time-consuming; it is to find a ubiquitous and environmentally-based biomineralization of the basic raw materials and the appropriate calcium phosphate manufacturing method, which is one of the technical issues to be solved in this case.

On the other hand, fluorescent powder materials used in conventional light emitting diodes (LEDs) are mostly chemically synthesized products. If an alternative product with higher luminous efficiency and reduced usage is found, this is also the case. Another technical issue to be solved.

The present invention provides a calcium phosphate material synthesized using shells as a base material.

The present invention further provides a method for synthesizing calcium phosphate materials of different crystal phases by using shells as a base material.

The present invention further provides a method of using a shell as a base material to form a bone substitute material.

The present invention further provides a method of using a shell as a base material to form a phosphor powder material for a light-emitting diode.

In a preferred embodiment of the present invention, a calcium phosphate material is provided which is based on a shell as a base material, wherein the shell comprises at least one of the species of Veeroroida.

In the above preferred embodiment, the method for manufacturing the calcium phosphate material comprises the steps of: (a) providing the shell; wherein the shell is a shell of aragonite; (b) heating the shell of the aragonite, Converting it into a shell of a calcite phase; and (c) processing the shell of the calcite phase to form the calcium phosphate material.

In the above preferred embodiment, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell.

In the above preferred embodiment, wherein in the step (a1), the interface is alive. The agent is accompanied by ultrasonic vibration to remove impurities attached to the surface of the shell; or, in the step (a2), the shell is dried at room temperature.

In the above preferred embodiment, in the step (b), the shell of the aragonite phase is heated under the conditions of a temperature of 400 ° C to 500 ° C and a constant temperature of 2 hours or more.

In the above preferred embodiment, wherein the step (c) comprises the steps of: (c1) processing the shell of the calcite phase to form a shell powder; (c2) adding a phosphate to the shell powder to form a shell powder mixture; and (c3) processing the shell powder mixture to form the calcium phosphate material.

In the above preferred embodiment, in the step (c1), the shell of the calcite phase is ground by a grinding rod.

In the above preferred embodiment, in the step (c2), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (c3), the temperature is 900 ° C. At ~1300 ° C, and under constant temperature sintering for 2 hours or more, a solid state diffusion reaction procedure is performed on the shell powder mixture to form the calcium phosphate material.

In the above preferred embodiment, wherein the phosphate powder has a weight of 0.6 to 1.0 times the weight of the shell powder in the step (c2); and wherein, in the step (c3), the calcium phosphate material is It is a β-tricalcium phosphate (β-TCP).

In the above preferred embodiment, wherein in the step (c2), an aqueous solution of phosphate is added to the shell powder to form the shell powder mixture; and wherein In the step (c3), the shell powder mixture is subjected to a hydrothermal reaction at a temperature of 100 ° C to 180 ° C under a constant temperature for 4 hours or more to form the calcium phosphate material.

In the above preferred embodiment, wherein the concentration of the aqueous phosphate solution is 0.1 g mL ^-1 in the step (c2); and wherein, in the step (c3), the calcium phosphate material is monohydroxyl Apatite (HA).

In the above preferred embodiment, the hydroxyapatite (HA) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure.

In the above preferred embodiment, the heating procedure is to heat the hydroxyapatite enthalpy under the conditions of a temperature of 800 ° C to 1000 ° C and a constant temperature of 3 days or more.

In the above preferred embodiment, in the step (c2), a metal may be added to the shell powder mixture; and wherein, in the step (c3), the calcium phosphate material is used as a phosphor material.

In the above preferred embodiment, the method for producing the calcium phosphate material comprises the steps of: (d) providing the shell; wherein the shell is a shell of aragonite; and (e) processing the shell of the aragonite To form the calcium phosphate material.

In the above preferred embodiment, wherein the step (d) comprises the steps of: (d1) washing the shell; and (d2) drying the shell.

In the above preferred embodiment, in the step (d1), the surfactant attached to the surface of the shell is removed by ultrasonic vibration accompanied by ultrasonic wave oscillating; and, in the step (d2), The shells were dried at room temperature.

In the above preferred embodiment, wherein the step (e) comprises the steps of: (e1) processing the shell of the aragonite phase to form a shell powder; (e2) adding a phosphate to the shell powder to cause Forming a shell powder mixture; and (e3) processing the shell powder mixture to form the calcium phosphate material.

In the above preferred embodiment, in the step (e1), the shell of the aragonite phase is ground by a grinding rod.

In the above preferred embodiment, in the step (e2), an aqueous solution of a phosphate solution is added to the shell powder to form the shell powder mixture; and wherein, in the step (e3), the temperature is 100 ° C. The mixture of the shell powder was subjected to a hydrothermal process to form the calcium phosphate material at ~180 ° C and under constant temperature for 4 hours or more.

In the above preferred embodiment, wherein in the step (e2), the concentration of the aqueous phosphate solution is 0.1 g mL ^-1 ; and wherein, in the step (e3), the calcium phosphate material is composed of a β-three --tricalcium phosphate (β-TCP) is composed of hydroxyapatite (HA).

In the above preferred embodiment, the calcium phosphate material obtained in the step (e3) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure.

In the above preferred embodiment, the heating procedure is performed by heating the calcium phosphate material at a temperature of 800 ° C to 1000 ° C and a constant temperature heating for 3 days or more.

In the above preferred embodiment, in the step (e2), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (e3), the temperature is 900 ° C. At ~1300 ° C, and under constant temperature sintering for 2 hours or more, a solid state diffusion reaction procedure is performed on the shell powder mixture to form the calcium phosphate material.

In the above preferred embodiment, wherein the phosphate powder has a weight of 0.6 to 1.0 times the weight of the shell powder in the step (e2); and wherein, in the step (e3), the calcium phosphate material is It is a β-tricalcium phosphate (β-TCP).

In the above preferred embodiment, in the step (e2), a metal may be added to the shell powder mixture; and, in the step (e3), the calcium phosphate material may serve as a phosphor material.

In the above preferred embodiment, the phosphate system is any one of hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ) and dihydrogen phosphate ((NH ₄ )H ₂ PO ₄ ). .

In the above preferred embodiment, the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal.

Another preferred method of the present invention relates to a method for producing a calcium phosphate material, which comprises a shell as a base material, and the shell comprises at least any one of Veenoroida, wherein the calcium phosphate material The manufacturing method comprises the following steps: (a) providing the shell, wherein the shell is a shell of aragonite; (b) heating the shell of the aragonite phase to convert it into a shell of a calcite phase; (c) processing the shell of the calcite phase to form a shell powder; (d) adding a phosphate to the shell powder Forming a shell powder mixture; and (e) heating the shell powder mixture to form a calcium phosphate material.

In the above preferred embodiment, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell.

In the above preferred embodiment, in the step (a1), an interface surfactant is used to remove impurities attached to the surface of the shell with ultrasonic vibration; or, in the step (a2), The shells were dried at room temperature.

In the above preferred embodiment, in the step (b), the shell of the aragonite phase is heated under the conditions of a temperature of 400 ° C to 500 ° C and a constant temperature of 2 hours or more.

In the above preferred embodiment, in the step (c), the shell of the calcite phase is ground by a grinding rod.

In the above preferred embodiment, wherein in the step (d), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (e), the temperature is 900 ° C. At ~1300 ° C, and under constant temperature sintering for 2 hours or more, a solid state diffusion reaction procedure is performed on the shell powder mixture to form the calcium phosphate material.

In the above preferred embodiment, wherein in the step (d), the phosphate powder is heavy The amount of the shell powder is 0.6 to 1.0 times; and, in the step (e), the calcium phosphate material is β-tricalcium phosphate (β-TCP).

In the above preferred embodiment, wherein in the step (d), an aqueous solution of phosphate is added to the shell powder to form the shell powder mixture; and wherein, in the step (e), the temperature is 100 ° C. The mixture of the shell powder was subjected to a hydrothermal process at ~180 ° C under a constant temperature for 4 hours or more to form the calcium phosphate material.

In the above preferred embodiment, wherein the concentration of the aqueous phosphate solution is 0.1 g mL ^-1 in the step (d); and wherein, in the step (e), the calcium phosphate material is monohydroxyl Apatite (HA).

In the above preferred embodiment, the hydroxyapatite (HA) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure.

In the above preferred embodiment, the heating procedure is performed by heating the hydroxyapatite (HA) under the conditions of a temperature of 800 ° C to 1000 ° C and a constant temperature of 3 days or more.

In the above preferred embodiment, in the step (d), a metal may be added to the shell powder mixture; and wherein, in the step (e), the calcium phosphate material is used as a phosphor material.

Another preferred method of the present invention relates to a method for producing another calcium phosphate material, which comprises a shell as a base material, and the shell comprises at least any one of the species of Veneroida, wherein the calcium phosphate The method of manufacturing the material includes the following steps: (a) providing the shell, wherein the shell is a shell of aragonite; (b) processing the shell of the aragonite phase to form a shell powder; (c) adding a phosphate to the shell powder, Forming a shell powder mixture; and (d) heating the shell powder mixture to form a calcium phosphate material.

In the above preferred embodiment, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell.

In the above preferred embodiment, in the step (a1), an interface surfactant is used to remove impurities attached to the surface of the shell with ultrasonic vibration; or, in the step (a2), The shells were dried at room temperature.

In the above preferred embodiment, in the step (b), the shell of the aragonite phase is ground by a grinding rod.

In the above preferred embodiment, wherein in the step (c), an aqueous solution of phosphate is added to the shell powder to form the shell powder mixture; and wherein, in the step (d), the temperature is 100 ° C. The shell powder mixture was subjected to a hydrothermal process to form the calcium phosphate material at ~180 ° C and under constant temperature for 4 hours or more.

In the above preferred embodiment, wherein in the step (c), the concentration of the aqueous phosphate solution is 0.1 g mL ^-1 ; and wherein, in the step (d), the calcium phosphate material is composed of a β-three --tricalcium phosphate (β-TCP) is composed of hydroxyapatite (HA).

In the above preferred embodiment, the calcium phosphate material obtained in the step (d) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure.

In the above preferred embodiment, the heating procedure is performed by heating the calcium phosphate material at a temperature of 800 ° C to 1000 ° C and a constant temperature heating for 3 days or more.

In the above preferred embodiment, wherein in the step (c), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (d), the temperature is 900 ° C. The mixture of the shell powder is subjected to a solid state diffusion reaction process to form the calcium phosphate material at ~1300 ° C and under constant temperature sintering for 2 hours or more.

In the above preferred embodiment, wherein in the step (c), the phosphate powder has a weight of 0.6 to 1.0 times the weight of the shell powder; and wherein, in the step (d), the calcium phosphate material is It is a β-tricalcium phosphate (β-TCP).

In the above preferred embodiment, in the step (c), a metal may be added to the shell powder mixture; and wherein, in the step (d), the calcium phosphate material is used as a phosphor material.

In the above preferred embodiment, the phosphate system is any one of hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ) and dihydrogen phosphate ((NH ₄ )H ₂ PO ₄ ). .

In the above preferred embodiment, the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal.

In a preferred practice of the present invention, a calcium phosphate material is provided which is a shell The base material, the shell comprising at least one of the species of Venerodia; wherein the calcium phosphate material is applied as any one of a bone substitute material or a phosphor powder material.

In the above preferred embodiment, the crystalline phase of the calcium phosphate material comprises: hydroxyapatite (HA), β-tricalcium phosphate (β-TCP). At least one.

In the above preferred embodiment, the phosphor material is added with a metal during the synthesis.

In the above preferred embodiment, the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal.

In daily life, the shell left by the cockroaches or cockroaches after eating is often not used effectively and can only be discarded. However, the present invention applies the characteristics of the shell component of bismuth or bismuth, especially to calcium calcium phosphate. Production of materials.

The biomineralized calcium carbonate described in the present invention preferably refers to a shell of any species of the family Veeniroida, and may also be a crystalline phase of calcium carbonate, an aragonite phase, a calcite phase or an aragonite phase. Convert to any of the three types of calcite.

The basic raw materials and the synthesized calcium phosphate materials in this case can be analyzed by X-ray powder diffractometer to obtain the relationship between the diffraction angle (2θ) and the intensity (intensity). 1; where the x-axis represents the diffraction angle (2θ), y The axis represents the intensity (intensity), 11 is the crystal phase analysis chart of the shell provided by the case without any treatment, and 10 represents the standard relationship diagram of the aragonite phase lattice (JCPDS: 05-0453); After the pattern represented by 11, the shell provided in this case can be determined, and the crystal lattice type is a stone phase.

Please refer to FIG. 2 , wherein 20 is a schematic diagram of the manufacturing process of the first preferred calcium phosphate material. In other words, first collect the clam shell or clam shell (of course, this is only an example, and it can also be changed to any type of shell of the curtain), as shown in Figure 1, the clam shell or clam shell without any treatment, Its crystalline phase is an aragonite phase. To synthesize the calcium phosphate material, the impurities are first removed (step S21), wherein the process of removing the impurities (step S21) includes: first cleaning and removing the shell by means of clear water, diluted bleach or surfactant accompanied by ultrasonic oscillation Surface impurities or organic substances.

Then, drying is performed (step S22), and the process of drying (step S22) includes: drying the washed casing at room temperature, or drying by using a dryer to 100 ° C, thereby obtaining a text Stone shells (of course, other crystal phases can also be directly supplied to the aragonite phase of calcium carbonate, not limited to this).

Then, grinding is performed (step S23), and grinding (step S23) is to grind the shell of the aragonite phase with a grinding rod to form a powder of a shell of aragonite phase; after the grinding is completed, phosphate powder is added (step S24), and phosphoric acid is added. The process of the salt powder (step S24) comprises: weighing 1 g of a powder of a shell of aragonite phase, followed by adding 0.893 g of hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ) powder or 0.7778 g of dihydrogen phosphate (( NH ₄ )H ₂ PO ₄ ) powder, the mixture of the aragonite shell powder was placed in a grinding glass or a ball mill for 30 minutes to fully mix the powder of the shell with the phosphate powder.

After being fully mixed, the sintering is performed (step S25), and the sintering process (step S25) is a mixture of the shell powder at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more. A solid state diffusion reaction procedure was performed to form the calcium phosphate material, and it was found by an X-ray powder diffraction apparatus that the crystal phase of the obtained calcium phosphate material was a powdery pure phase of β-tricalcium phosphate. Salt (β-tricalcium phosphate, β-TCP).

3, 31 is an analytical chart of the crystalline phase of the product obtained in the first preferred embodiment of the present invention, and 30 represents a standard relationship diagram of β-tricalcium phosphate (β-TCP) crystal lattice. (JCPDS: 09-0169), after comparing the patterns represented by the above symbols 30 and 31, it was confirmed that the obtained calcium phosphate material was β-tricalcium phosphate (β-TCP).

Please refer to FIG. 4, wherein 40 is a schematic diagram of the manufacturing process of a second preferred calcium phosphate material. The steps S41 to S43 are the same as the steps S21 to S23 of FIG. 2, and details are not described herein.

Further, after the grinding is completed (step S43), a phosphate aqueous solution is subsequently added (step S44), wherein the addition of the aqueous phosphate solution (step S44) includes: weighing 0.4 g of aragonite shell powder and placing it in iron In the Fluorine cup, 3.3 mL of a phosphate aqueous solution having a concentration of 0.1 g mL ^-1 is added, and the phosphate aqueous solution includes: an aqueous solution of hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ) or dihydrogen phosphate ( Either (NH ₄ )H ₂ PO ₄ ) aqueous solution, and thoroughly mixed.

After the powder of the acacia phase shell is thoroughly mixed with the phosphate aqueous solution, a water heat (step S45) procedure is performed, wherein the water heat (step S45) procedure comprises: loading the shell The Teflon cup of the shell powder and the phosphate mixed aqueous solution is sealed in a stainless steel reactor, and the stainless steel reactor is placed in a high temperature reaction furnace; the temperature is 100 ° C to 180 ° C, and the temperature is heated for 4 hours or more. A hydrothermal process, after the reaction is completed, it is cooled at room temperature, and then filtered to obtain an off-white precipitate. The off-white precipitate is dried at 100 ° C for 12 hours to obtain the phosphoric acid. Calcium material, analyzed by X-ray powder diffractometer, found that the calcium phosphate material is a two-phase mixed calcium phosphate (BCP), which is composed of β-tricalcium phosphate (β-TCP) and hydroxyl groups. Apatite (HA) is composed of apatite.

Therefore, please refer to FIG. 5; wherein 52 is an analytical chart of the crystalline phase of the product obtained in the second preferred embodiment of the present invention, and 50 represents a standard relationship diagram of the hydroxylapatite (HA) crystal lattice (JCPDS). :09-0432), 51 represents the standard relationship diagram of β-tricalcium phosphate (β-TCP) crystal lattice (JCPDS: 09-0169). After comparison, the obtained calcium phosphate material is determined by Hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) are a two-phase mixed calcium phosphate material (HA/beta-TCP, BCP); Of course, in Fig. 5, the symbol H represents the peak of hydroxyapatite (HA), and the symbol β represents the peak of β-tricalcium phosphate (β-TCP).

In addition, in this case, in addition to using the shell of aragonite phase to make calcium phosphate material, the shell of the aragonite phase can be heated at a temperature of 400 ° C ~ 500 ° C, and heated at a constant temperature for more than 2 hours, so that the crystal phase is aragonite. The phase is converted into a calcite phase.

Please refer to the analysis chart of the crystal phase of Fig. 6, wherein 61 is the crystal phase relationship diagram of the shell after the above heating process, and 60 represents the standard of the calcite phase lattice. Diagram (JCPDS: 05-0586); after comparing the patterns represented by the above symbols 60, 61, it can be determined that the shell of the aragonite phase is converted by the aragonite phase by the heating process. Calcite phase.

Please refer to FIG. 7 and FIG. 70 is a schematic flow chart showing the manufacturing process of a third preferred calcium phosphate material. The steps S71 to S72 are the same as the steps S21 to S22 in FIG. 2 and the steps S41 to S42 in FIG. 4, and are not described here.

Further, after the drying (step S72) is completed, the heating (step S73) is performed, wherein the heating (step S73) is performed at a temperature of 400 ° C to 500 ° C and a constant temperature heating for 2 hours or more. The shell of the aragonite phase is heated, and the shell of the aragonite phase is converted into a shell of a calcite phase (the calcium carbonate of the calcite phase can also be directly supplied).

Next, grinding is performed (step S74), and the grinding (step S74) is to grind the shell of the calcite phase with a grinding rod to form a powder of a shell of the calcite phase, and after the grinding is completed, the phosphate powder is added (step S75). The procedure of adding the phosphate powder (step S75) comprises: weighing 1 g of the powder of the shell of the calcite phase, followed by adding 0.893 g of hydrogen phosphate diamine powder or 0.7778 g of dihydrogen phosphate powder, and placing the mixture of the calcite shell powder Into the grinding crucible or a ball mill for 30 minutes, the shell powder is mixed with the phosphate powder.

After the powder of the shell is fully mixed with the phosphate powder, a sintering (step S76) procedure is performed, wherein the sintering (step S76) is performed at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more. The solid state diffusion reaction process is performed on the mixture of the calcite shell powder to form the phosphoric acid The calcium material was analyzed by X-ray powder diffraction. The crystal phase of the obtained calcium phosphate material was a powdery pure phase of β-tricalcium phosphate (β-TCP).

It should be noted that the calcium phosphate material obtained in the third preferred embodiment of the present invention has the same crystal phase as the crystalline phase of the product obtained in the first preferred embodiment of the present invention, and is indeed a powdery pure phase. The β-tricalcium phosphate (β-TCP), which confirms the alignment method, is similar to that shown in Fig. 3 and will not be further described herein.

Please refer to FIG. 8 , which is a schematic diagram of the manufacturing process of the fourth preferred calcium phosphate material. The steps S81 to S84 are the same as the steps S71 to S74 in FIG. 7, and are not described here.

To be stated, after the grinding (step S84) is completed, an aqueous phosphate solution is added (step S85), wherein the procedure of adding the aqueous phosphate solution (step S85) comprises: weighing 0.4 g of the calcite phase of the shell powder, placing it In the Teflon cup, 3.3 mL of a phosphate aqueous solution having a concentration of 0.1 g mL ^-1 is subsequently added; the phosphate aqueous solution includes any one of an aqueous solution of hydrogen phosphate diamine or an aqueous solution of dihydrogenamine phosphate, and It is fully mixed.

After the phosphate aqueous solution is sufficiently mixed with the shell powder, a water heat step (step S86) is performed, and the procedure of the water heat (step S86) is: placing the Teflon cup containing the shell powder and the phosphate mixed aqueous solution The stainless steel reactor is sealed in a stainless steel reactor, and the stainless steel reactor is placed in a high temperature reaction furnace at a temperature of 100 ° C to 180 ° C and heated at a constant temperature for 4 hours or more, and a hydrothermal reaction is carried out. After the reaction is completed, The mixture was cooled at room temperature, and then filtered to obtain an off-white precipitate. The pale-white precipitate was dried at 100 ° C for 12 hours to obtain the calcium phosphate material, which was analyzed by X-ray powder diffraction. The calcium phosphate material is composed of a pure phase of hydroxyapatite (hydroxyapatite, HA) composition.

Please refer to FIG. 9 , wherein 91 is an analytical chart of the crystalline phase of the product obtained in the fourth preferred embodiment of the present invention, and 90 represents a standard relationship diagram of the hydroxylapatite (HA) crystal lattice (JCPDS: 09- 0432), after comparing the patterns represented by the above symbols 90, 91, it is determined that the obtained calcium phosphate material is hydroxyapatite (HA).

In this case, the pure phase of hydroxyapatite (HA) or the two-phase mixed calcium phosphate (BCP) may be subjected to a heat treatment to convert it into a pure phase of β-tricalcium phosphate (β-tricalcium). Phosphate, β-TCP).

Please refer to FIG. 10, a schematic diagram of a process flow for manufacturing a fifth preferred calcium phosphate material in the present invention, the steps comprising: providing a pure phase of hydroxyapatite (HA) or a two-phase mixed calcium phosphate ( BCP) (step S101), followed by a heating (step S102) program, the heating (step S102) program is based on the temperature of 800 ° C ~ 1000 ° C, and constant temperature heating for more than 3 days, the supply of calcium phosphate The material is heated and the resulting product is a powdery pure phase of β-tricalcium phosphate (β-TCP).

It is to be noted that the calcium phosphate material obtained in the fifth preferred embodiment of the present invention has the same crystal phase as that of the product obtained in the first preferred embodiment or the third preferred embodiment of the present invention. It is indeed a powdery pure phase of β-tricalcium phosphate (β-TCP), and the method for confirming the alignment is similar to that shown in Fig. 3, and will not be further described herein.

The calcium phosphate material synthesized by the above method in this case can be applied to bone substitute materials. The material is formed; of course, in the present case, at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal may be added during the process of mixing the phosphate, and the calcium phosphate material synthesized by adding the metal may be used as the fluorite. Light powder material.

Please refer to FIG. 11 , which is a schematic diagram of the manufacturing process of the first preferred phosphor material of the present invention. Steps S111 to S113 and S115 are the same as steps S21 to S23 and S25 in FIG. 2 . In the step S114, a phosphate powder and a metal powder are added. Preferably, 0.893 g of hydrogen phosphate diamine powder or 0.7778 g of dihydrogen phosphate powder may be added in step S114, and 0.033 g of Eu is added. ₂ O _{3 was} mixed, and the obtained phosphor powder material was analyzed by X-ray powder diffractometer to find that the crystal phase was β-tricalcium phosphate (β-TCP).

Referring to FIG. 12, 121 is an analysis chart of the crystal phase of the product obtained in the first preferred embodiment of the phosphor powder material synthesis, wherein 120 represents β-tricalcium phosphate (β-TCP). The standard relationship diagram of the crystal lattice (JCPDS: 09-0169), after comparison, determines that the obtained phosphor material is a β-tricalcium phosphate (β-TCP).

Referring to FIG. 13, 130 is a schematic flow chart of manufacturing a second preferred phosphor material of the present invention, wherein steps S121 to S123 and step S125 are the same as steps S31 to S33 and S35 of FIG. 3, and the difference lies in In step S124, an aqueous solution of a monophosphate solution and a metal solution are added. Preferably, in step S124, 3.3 mL of a phosphate aqueous solution having a concentration of 0.1 g mL ^-1 and 600 μL of Eu(NO ₃ ) _{3 (aq)} or 200 μL of Gd(NO ₃ ) _{3 (aq)} , the obtained phosphor powder material was analyzed by X-ray powder diffractometer and found to be β-tricalcium phosphate (β-TCP) and hydroxyl group. Apatite (HA) is composed of apatite.

Please refer to FIG. 14 , wherein 142 is an analysis chart of the crystal phase of the product obtained in the second preferred embodiment of the phosphor powder material synthesis, and 140 represents the standard relationship of the hydroxyl apatite (HA) crystal lattice. Figure (JCPDS: 09-0432), 141 represents the standard relationship diagram of β-tricalcium phosphate (β-TCP) crystal lattice (JCPDS: 09-0169). After comparison, the obtained firefly is determined. The light powder material is composed of hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP), which is a two-phase mixed calcium phosphate material (HA/beta-TCP). , BCP), in addition, the symbol H represents the peak of hydroxyapatite (HA), and the symbol β represents the peak of β-tricalcium phosphate (β-TCP).

Please refer to FIG. 15, which is a schematic flow chart of the manufacturing process of a third preferred phosphor material of the present invention. Steps S151 to S154 and S156 are the same as steps S71 to S74 and S76 in FIG. In step S155, a phosphate powder and a metal powder are added. Preferably, 0.893 g of hydrogen phosphate diamine powder or 0.7778 g of dihydrogen phosphate powder may be added in step S155, and 0.033 g of Eu is added. ₂ O _{3 was} mixed, and the obtained phosphor powder material was analyzed by X-ray powder diffractometer to find that the crystal phase was β-tricalcium phosphate (β-TCP).

It is to be noted that the phosphor powder material obtained in the third preferred embodiment of the present invention has the same crystal phase as the crystal phase of the product obtained in the first preferred embodiment of the phosphor powder material synthesis of the present invention. It is a powdery pure phase of β-tricalcium phosphate (β-TCP), and the method for confirming the alignment is similar to that shown in Fig. 12, and will not be further described herein.

Please refer to FIG. 16, which is a schematic diagram of the manufacturing process of a fourth preferred phosphor material of the present invention. Steps S161 to S164 and S166 are the same as steps S81 to S84 and S86 in FIG. In step S165, an aqueous solution of a monophosphate solution and a metal solution are added. Preferably, in step S145, 3.3 mL of a phosphate aqueous solution having a concentration of 0.1 g mL ^-1 and 600 μL of Eu(NO ₃ ) _{3 (aq) may be added. )} or 200μL of _{Gd (NO 3) 3 (aq} ), the resulting phosphor material was found by analysis of X-ray powder diffractometer, Department of hydroxyapatite (hydroxyapatite, HA) is composed.

Please refer to FIG. 17, wherein 171 is an analysis chart of the crystalline phase of the product obtained in the fourth preferred embodiment of the phosphor powder material synthesis, and 170 represents the standard relationship of the hydroxyapatite (HA) crystal lattice. Figure (JCPDS: 09-0432), after comparison, determined that the resulting phosphor material is hydroxyapatite (HA).

In this case, the phosphor powder material having a crystal phase of hydroxyapatite (HA) or a phosphor powder material having a crystal phase of two-phase mixed calcium phosphate (BCP) may be converted into a heat treatment to convert it into a The crystal phase is a phosphor powder material of β-tricalcium phosphate (β-TCP).

Please refer to FIG. 18, a schematic diagram of a process flow for manufacturing a fifth preferred phosphor material in the present invention, the steps comprising: providing a crystalline phase of hydroxyapatite (HA) or a two-phase mixed calcium phosphate ( BCP) phosphor powder (step S181), followed by a heating (step S182) program, the heating (step S182) program is carried out at a temperature of 800 ° C ~ 1000 ° C, and a constant temperature heating for more than 3 days, The provided fluorescent powder was heated, and the heat-treated product was analyzed by X-ray powder diffraction to find that the crystal phase was β-tricalcium phosphate (β-TCP).

It is to be noted that the phosphor powder material obtained in the fifth preferred embodiment of the present invention has the same crystal phase as that of the first preferred embodiment or the third preferred embodiment of the phosphor powder material synthesis of the present invention. The crystalline phase of the product is indeed a powdery pure phase of β-tricalcium phosphate (β-TCP), which confirms that the alignment method is similar to that shown in Figure 12, and is no longer given here. Narration.

The phosphor powder material synthesized by the basic materials and methods provided by the present invention has higher light absorption capacity and photoexcitation intensity than the chemically synthesized phosphor powder material due to its natural structure.

As shown in FIG. 19, the phosphor powder material synthesized by chemical synthesis and shell-and-sinter synthesis is Ca ₃ (PO ₄ ) ₂ -Eu ³⁺ , and the molar percentage of the mole is equal to 2, wherein The x-axis represents the wavelength (wavelength (nm)), the y-axis represents the intensity (intensity), 191 represents the light absorptivity of the shell-formed phosphor material, 192 represents the light absorptivity of the chemically synthesized phosphor material; 193 represents the shell The photoexcitation intensity of the synthesized phosphor material, and 194 represents the photoexcitation intensity of the chemically synthesized phosphor material.

The results show that under the same concentration conditions, the light absorption rate and photoexcitation intensity of the phosphor powder material synthesized by the shell are much higher than that of the chemically synthesized phosphor powder material. In addition, due to different biomineralization The relationship between the concentration of metal in calcium carbonate and the phosphor powder synthesized by the shell of Veneroida is better than that of sea urchin needle or coral. Powder material.

Furthermore, the hydroxyapatite (HA) synthesized in this case was observed by an electron microscope, and its structure was arranged and the hydroxyapatite synthesized by the sea urchin needle or coral (hydroxyapatite) was observed. , HA) distinctly different, these knots When applied to bone substitute materials, a good distinction can be made between materials that are otherwise mineralized or chemically synthesized.

In summary, the calcium phosphate material (which can be directly used as a bone substitute material) or the phosphor powder material synthesized from the shell provided by the present case is more applicable than the other biomineralized calcium carbonate and chemical synthesis. Calcium phosphate material (bone material) or phosphor powder; on the other hand, compared with the prior art, the present invention also provides a synthesis method with lower energy consumption and shorter time, which can greatly enhance the calcium phosphate. The efficiency of synthesis; therefore, this case is actually a very industrial value.

This case has been modified by people who are familiar with the art, and is not intended to be protected as intended.

S21~S25‧‧‧Steps

S41~S45‧‧‧Steps

S71~S76‧‧‧Steps

S81~S86‧‧‧ steps

S101~102‧‧‧Steps

S111~S115‧‧‧Steps

S131~S135‧‧‧Steps

S151~S156‧‧‧Steps

S161~S166‧‧‧Steps

S181~S182‧‧‧Steps

Figure 1: It is an X-ray powder diffraction pattern of untreated anthraquinone shells provided in this case.

Figure 2 is a schematic flow chart showing the first preferred embodiment of the synthetic calcium phosphate material provided in the present invention.

Figure 3: X-ray powder diffraction diagram of β-tricalcium phosphate (β-TCP), a calcium phosphate material synthesized in the present invention.

Figure 4 is a schematic flow chart of a second preferred embodiment of the synthetic calcium phosphate material provided herein.

Figure 5: X-ray powder diffraction diagram of the calcium phosphate material synthesized in this case - two-phase mixing (HA/beta-TCP, BCP).

Figure 6: It is a diffraction diagram of X-ray powder after heat treatment of the shells provided in this case.

Figure 7 is a schematic flow chart of a third preferred embodiment of the synthetic calcium phosphate material provided in the present invention.

Figure 8 is a schematic flow chart of a fourth preferred embodiment of the synthetic calcium phosphate material provided herein.

Figure 9: X-ray powder diffraction diagram of the calcium phosphate material - hydroxyapatite (HA) synthesized in this case.

Figure 10 is a schematic flow chart showing a fifth preferred embodiment of the synthetic calcium phosphate material provided in the present invention.

Figure 11 is a flow chart showing the first preferred embodiment of the synthetic phosphor material provided in the present invention.

Fig. 12 is a diffraction diagram of X-ray powder of β-tricalcium phosphate (β-TCP), which is a phosphor material synthesized in the present invention.

Figure 13 is a schematic flow chart showing a second preferred embodiment of the synthetic phosphor material provided in the present invention.

Figure 14: X-ray powder diffraction diagram of the phosphor powder material synthesized in this case - two-phase mixing (HA/beta-TCP, BCP).

Figure 15 is a flow chart showing a third preferred embodiment of the synthetic phosphor material provided in the present invention.

Figure 16 is a flow chart showing a fourth preferred embodiment of the synthetic phosphor material provided in the present invention.

Figure 17 is a diagram showing the X-ray powder diffraction relationship of the phosphor powder material hydroxyapatite (HA) synthesized in the present invention.

Figure 18 is a flow chart showing the fifth preferred embodiment of the synthetic phosphor material provided in the present invention.

Figure 19 is a graph showing the light absorptivity and photoexcitation intensity of the phosphor material synthesized in this case.

Claims (57)

A calcium phosphate material comprising a shell as a base material, wherein the shell comprises at least one of the species of Veerroida. The calcium phosphate material according to claim 1, wherein the method for producing the calcium phosphate material comprises the steps of: (a) providing the shell; wherein the shell is a shell of aragonite; (b) heating the shell The shell of the aragonite phase converts it into a shell of a calcite phase; and (c) processes the shell of the calcite phase to form the calcium phosphate material. The calcium phosphate material of claim 2, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell. The calcium phosphate material according to claim 3, wherein in the step (a1), a surfactant is accompanied by ultrasonic vibration to remove impurities attached to the surface of the shell; or, wherein, in the step (a2) In the case, the shell is dried at room temperature. The calcium phosphate material according to the second aspect of the patent application, wherein in the step (b), the shell of the aragonite phase is heated under the conditions of a temperature of 400 ° C to 500 ° C and a constant temperature heating for 2 hours or more. The calcium phosphate material as described in claim 2, wherein the step (c) comprises the following steps: (c1) processing the shell of the calcite phase to form a shell powder; (c2) adding a monophosphate to the shell powder to form a shell powder mixture; and (c3) processing the shell powder mixture to The calcium phosphate material is formed. The calcium phosphate material according to claim 6, wherein in the step (c1), the shell of the calcite phase is ground by a grinding rod. The calcium phosphate material according to the sixth aspect of the invention, wherein in the step (c2), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (c3) The solid state diffusion reaction procedure is carried out on the mixture of the shell powder at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more to form the calcium phosphate material. The calcium phosphate material according to claim 8, wherein in the step (c2), the phosphate powder has a weight of 0.6 to 1.0 times the weight of the shell powder; and wherein, in the step (c3) The calcium phosphate material is a β-tricalcium phosphate (β-TCP). The calcium phosphate material according to the sixth aspect of the invention, wherein in the step (c2), an aqueous solution of a phosphate solution is added to the shell powder to form the shell powder mixture; and wherein, in the step (c3) The mixture of the shell powder is subjected to a hydrothermal process at a temperature of 100 ° C to 180 ° C and heated at a constant temperature for 4 hours or more to form the calcium phosphate material. The calcium phosphate material according to claim 10, wherein in the step (c2), the aqueous phosphate solution has a concentration of 0.1 g mL ^-1 ; and wherein, in the step (c3), the calcium phosphate material It is a hydroxyapatite (HA). The calcium phosphate material according to claim 11, wherein the hydroxyapatite (HA) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure. . The calcium phosphate material according to claim 12, wherein the heating procedure is a heating procedure of the hydroxyapatite enthalpy under the conditions of a temperature of 800 ° C to 1000 ° C and a constant temperature of 3 days or more. The calcium phosphate material according to claim 6, wherein in the step (c2), a metal may be added to the shell powder mixture; and wherein, in the step (c3), the calcium phosphate material is used as A phosphor powder material. The calcium phosphate material according to claim 1, wherein the method for producing the calcium phosphate material comprises the steps of: (d) providing the shell; wherein the shell is a shell of aragonite; and (e) processing The shell of the aragonite phase forms the calcium phosphate material. The calcium phosphate material of claim 15, wherein the step (d) comprises the steps of: (d1) washing the shell; and (d2) drying the shell. The calcium phosphate material according to claim 16, wherein in the step (d1), an interfacial activator is accompanied by ultrasonic vibration to remove impurities attached to the surface of the shell; and wherein, in the step (d2) In the case, the shell is dried at room temperature. A calcium phosphate material as described in claim 15 wherein the step (e) comprises The following steps: (e1) processing the shell of the aragonite phase to form a shell powder; (e2) adding a phosphate to the shell powder to form a shell powder mixture; and (e3) processing the shell powder The mixture is allowed to form the calcium phosphate material. The calcium phosphate material according to claim 18, wherein in the step (e1), the shell of the aragonite phase is ground by a grinding rod. The calcium phosphate material according to claim 18, wherein in the step (e2), an aqueous solution of phosphate is added to the shell powder to form a mixture of the shell powder; and wherein, in the step (e3) In the case, the mixture of the shell powder is subjected to a hydrothermal reaction at a temperature of 100 ° C to 180 ° C and a constant temperature of 4 hours or more to form the calcium phosphate material. The calcium phosphate material according to claim 18, wherein in the step (e2), the aqueous phosphate solution has a concentration of 0.1 g mL ^-1 ; and wherein, in the step (e3), the calcium phosphate material It consists of a β-tricalcium phosphate (β-TCP) and a hydroxyapatite (HA). The calcium phosphate material according to claim 21, wherein the calcium phosphate material obtained in the step (e3) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure. The calcium phosphate material according to claim 22, wherein the heating procedure is a heating procedure of the calcium phosphate material at a temperature of 800 ° C to 1000 ° C and a constant temperature heating for 3 days or more. The calcium phosphate material according to claim 18, wherein in the step (e2), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step (e3) The solid state diffusion reaction procedure is carried out on the mixture of the shell powder at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more to form the calcium phosphate material. The calcium phosphate material according to claim 24, wherein in the step (e2), the phosphate powder has a weight of 0.6 to 1.0 times the weight of the shell powder; and wherein, in the step (e3) The calcium phosphate material is a β-tricalcium phosphate (β-TCP). The calcium phosphate material according to claim 18, wherein in the step (e2), a metal may be added to the shell powder mixture; and wherein, in the step (e3), the calcium phosphate material is used as A phosphor powder material. The calcium phosphate material according to any one of claims 6 to 18, wherein the phosphate system is: hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ), dihydrogen phosphate Any of ((NH ₄ )H ₂ PO ₄ ). The calcium phosphate material according to any one of claims 14 to 26, wherein the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal. A method for producing a calcium phosphate material, which comprises a shell as a base material, wherein the shell comprises at least one of the species of Velenoida; wherein the method for producing the calcium phosphate material comprises the following steps: (a Providing the shell; wherein the shell is a shell of aragonite; (b) heating the shell of the aragonite phase to convert it into a shell of a calcite phase; (c) processing the shell of the calcite phase to form a shell powder; (d) adding a phosphate to the shell powder Forming a shell powder mixture; and (e) heating the shell powder mixture to form a calcium phosphate material. The method for producing a calcium phosphate material according to claim 29, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell. The method for producing a calcium phosphate material according to claim 30, wherein in the step (a1), a surfactant is accompanied by ultrasonic vibration to remove impurities attached to the surface of the shell; or In the step (a2), the shell is dried at room temperature. The method for producing a calcium phosphate material according to claim 29, wherein in the step (b), the acacia phase shell is heated at a temperature of 400 ° C to 500 ° C and at a constant temperature for 2 hours or more. It is heated. The method for producing a calcium phosphate material according to claim 29, wherein in the step (c), the shell of the calcite phase is ground by a grinding rod. The method for producing a calcium phosphate material according to claim 29, wherein in the step (d), a phosphate powder is added to the shell powder to form a mixture of the shell powder; and wherein In the step (e), the mixture of the shell powder is subjected to a solid state expansion at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more. A solid state diffusion reaction procedure is performed to form the calcium phosphate material. The method for producing a calcium phosphate material according to claim 34, wherein in the step (d), the weight of the phosphate powder is 0.6 to 1.0 times the weight of the shell powder; and wherein, in the step ( In e), the calcium phosphate material is a β-tricalcium phosphate (β-TCP). The method for producing a calcium phosphate material according to claim 29, wherein in the step (d), an aqueous solution of an aqueous phosphate is added to the shell powder to form the shell powder mixture; and wherein the step is In (e), the shell powder mixture is subjected to a hydrothermal reaction at a temperature of 100 ° C to 180 ° C for 4 hours or more to form the calcium phosphate material. The method for producing a calcium phosphate material according to claim 36, wherein in the step (d), the concentration of the aqueous phosphate solution is 0.1 g mL ^-1 ; and wherein, in the step (e), the The calcium phosphate material is hydroxyapatite (HA). The method for producing a calcium phosphate material according to claim 37, wherein the hydroxyapatite (HA) can be converted into a β-tricalcium phosphate (β-) by a heating procedure. -TCP). The method for producing a calcium phosphate material according to claim 38, wherein the heating procedure is performed at a temperature of 800 ° C to 1000 ° C and at a constant temperature for 3 days or more, the hydroxyapatite ( Hydroxypatite, HA) 遂 heating procedure. The method for producing a calcium phosphate material according to claim 29, wherein in the step (d), a metal is added to the shell powder mixture; and wherein, in the step (e), the calcium phosphate is The material can be used as a phosphor material. A method for producing a calcium phosphate material, which comprises a shell as a base material, wherein the shell comprises at least one of the species of Velenoida; wherein the method for producing the calcium phosphate material comprises the following steps: (a Providing the shell; wherein the shell is a shell of aragonite; (b) processing the shell of the aragonite phase to form a shell powder; (c) adding a phosphate to the shell powder to cause Forming a shell powder mixture; and (d) heating the shell powder mixture to form a calcium phosphate material. The method for producing a calcium phosphate material according to claim 41, wherein the step (a) comprises the steps of: (a1) washing the shell; and (a2) drying the shell. The method for producing a calcium phosphate material according to the invention of claim 42, wherein in the step (a1), a surfactant is accompanied by ultrasonic vibration to remove impurities attached to the surface of the shell; or In the step (a2), the shell is dried at room temperature. The method for producing a calcium phosphate material according to claim 41, wherein in the step (b), the shell of the aragonite phase is ground by a grinding rod. The method for producing a calcium phosphate material according to claim 41, wherein in the step (c), an aqueous solution of a phosphate solution is added to the shell powder to form the shell powder mixture; and wherein, in the step In (d), the shell powder mixture is hydrothermally reacted at a temperature of 100 ° C to 180 ° C and a constant temperature of 4 hours or more. (hydrothermal) procedure to form the calcium phosphate material. The method for producing a calcium phosphate material according to claim 45, wherein in the step (c), the aqueous phosphate solution has a concentration of 0.1 g mL ^-1 ; and wherein, in the step (d), the The calcium phosphate material is composed of a β-tricalcium phosphate (β-TCP) and a hydroxyapatite (HA). The calcium phosphate material according to claim 46, wherein the calcium phosphate material obtained in the step (d) can be converted into a β-tricalcium phosphate (β-TCP) via a heating procedure. The method for producing a calcium phosphate material according to claim 47, wherein the heating procedure is a heating procedure of the calcium phosphate material under the conditions of a temperature of 800 ° C to 1000 ° C and a constant temperature heating for 3 days or more. The method for producing a calcium phosphate material according to claim 41, wherein in the step (c), a phosphate powder is added to the shell powder to form the shell powder mixture; and wherein, in the step In (d), a mixture of the shell powder is subjected to a solid state diffusion reaction process at a temperature of 900 ° C to 1300 ° C and a constant temperature sintering for 2 hours or more to form the calcium phosphate material. The method for producing a calcium phosphate material according to claim 49, wherein in the step (c), the weight of the phosphate powder is 0.6 to 1.0 times the weight of the shell powder; and wherein, in the step ( In d), the calcium phosphate material is a β-tricalcium phosphate (β-TCP). The method for producing a calcium phosphate material according to claim 49, wherein in the step (c), a metal may be added to the shell powder mixture; and wherein, in the step In (d), the calcium phosphate material can be used as a phosphor material. The method for producing a calcium phosphate material according to any one of the preceding claims, wherein the phosphate system is: hydrogen phosphate diamine ((NH ₄ ) ₂ HPO ₄ ), phosphoric acid Any of dihydrogenamines ((NH ₄ )H ₂ PO ₄ ). The method for producing a calcium phosphate material according to any one of the preceding claims, wherein the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal. A calcium phosphate material comprising a shell as a base material, the shell comprising at least one of Veenoroida; wherein the calcium phosphate material is applied as a bone substitute material or a phosphor powder Any of the materials. The calcium phosphate material according to claim 54, wherein the calcium phosphate material comprises: a hydroxyl apatite (HA), a β-tricalcium phosphate (β-tricalcium phosphate, At least one of β-TCP). A calcium phosphate material as described in claim 54 wherein the phosphor material is added to the metal during the synthesis. The calcium phosphate material according to claim 56, wherein the metal comprises at least one of a lanthanide metal, an alkali metal, an alkaline earth metal, and a transition metal.