KR102508234B1 - Method For Preparing Whitlockite by Temporal Separation - Google Patents

Abstract

This application relates to a method for producing witrockite.

Description

Method for preparing whitlockite by temporal separation {Method For Preparing Whitlockite by Temporal Separation}

According to the present application, a method for preparing a calcium phosphate compound is disclosed. More specifically, a method for producing witrockite is disclosed.

Currently, calcium phosphate compounds are widely used as biocompatible inorganic materials. The calcium phosphate compound is used as a raw material for products such as artificial bone, dental restorative materials, bone cement, oral compositions, and fillers inserted into the body for regeneration or treatment of human tissue.

))와 β-트리칼슘 포스페이트(tricalcium phosphate, TCP: (

))가 있다. As a representative calcium phosphate compound, hydroxyapatite (HAp (

)) and β-tricalcium phosphate (TCP: (

)).

Artificially synthesized HAp has excellent biocompatibility and has almost the same chemical properties as bone, but has a disadvantage in that it is not degraded in vivo and cannot replace natural bone because its crystallinity is too large.

Since β-TCP is degraded in vivo and induces natural bone growth, many studies have been conducted on single-phase β-TCP or biphasic calcium phosphate (BCP) in which β-TCP and HAp are mixed. However, conventional techniques have difficulties in synthesizing nano-sized β-TCP in large quantities, and thus there is a limit to the application of β-TCP to various fields.

In order to solve this problem, recently, whitlockite, which is a calcium phosphate compound similar to HAp and β-TCP, but whose chemical structure, components, and crystal structure are different from each other, has been studied.

)는 어린 나이의 몸과 생체미네랄화의 초기 단계에 높은 비율로 존재한다. 이는 휘트록카이트가 경조직의 발달에 중요한 역할을 수행함을 의미한다는 것은 간접적으로 나타낸다. 특히, 휘트록카이트에 포함된 마그네슘이 인체 내에서 주변 골 조직의 골 형성을 촉진하는 역할을 수행한다고 알려져 있다. 이러한 휘트록카이트가 경조직으로의 발달에 있어 중요한 역할을 한다는 점에 기초하여, 기존의 하이드록시아파타이트와 베타-트리칼슘포스페이트(β-tricalciumphosphate, β-TCP)를 대체하는 생체 적합성 무기 재료로서 휘트록카이트에 대한 관심이 증가되고 있는 실정이다. 다만, 하이드록시아파타이트와 베타 트리칼슘포스페이트에 대하여는 활발히 연구되어 왔으나, 휘트록카이트에 대하여는 연구가 많이 이루어지지 않아, 휘트록카이트의 역할, 합성 메커니즘을 규명하기 위한 연구에 대한 필요성이 증대되고 있고 있다.Whitrockite (WH,

) is present in high proportions in the body at a young age and in the early stages of biomineralization. This indirectly indicates that whitrockite plays an important role in the development of hard tissue. In particular, it is known that magnesium contained in whitlockite plays a role in promoting bone formation of surrounding bone tissue in the human body. Based on the fact that whitrockite plays an important role in the development of hard tissue, whitrock as a biocompatible inorganic material that replaces existing hydroxyapatite and beta-tricalciumphosphate (β-TCP) Interest in kites is increasing. However, although hydroxyapatite and beta-tricalcium phosphate have been actively studied, not much research has been done on whitrockite, and the need for research to identify the role and synthesis mechanism of whitrockite is increasing. .

However, compared to HAp and β-TCP, whitlockite has a more complicated production process, so much research has not been conducted academically, and it is difficult to find industrially applied examples.

In order to solve the problem that it is difficult to synthesize whitrockite, a method for producing whitrockite has been proposed by a conventional patent (Korean Patent Registration No. 10-1423982 (July 22, 2014)).

However, the conventional method for producing witlockite requires a lot of manufacturing cost due to a long manufacturing time, and in order to form a target intermediate product in the intermediate process and to form high-purity witlockite, the pH of the aqueous solution must be precisely adjusted. There is a problem that the manufacturing method is complicated because it needs to be controlled.

In order to solve the above problems, the present application is a wheat that allows the process of reacting calcium ions with phosphate ions and the process of reacting cations other than calcium ions constituting witlockite with phosphate ions to proceed independently of each other. A method for producing rockite is provided.

The present application provides a manufacturing method of witrockite that can easily control process conditions while reducing manufacturing time compared to the conventional manufacturing method of witrockite.

According to one aspect provided by the present application, a method for producing witrockite by spatial separation is disclosed.

According to another aspect provided by the present application, a method for producing witrockite by temporal separation is disclosed.

Disclosed in the present application According to an embodiment of the method for producing witrockite disclosed in the present application, a first solution containing calcium ions and a second solution containing a first amount of phosphate ions are mixed for a first time. Process-A second process of forming a first mixed solution in which the product of the first process is reacted for a second time to form a first phosphate material-The terminal point of the second time is later than the terminal point of the first time located at the point; A third process of mixing a third solution containing cations other than calcium ions and a fourth solution containing phosphate ions in a second amount with the first mixed solution for a third time—the initial point of the third time located later than the terminal point of the first time; A fourth process in which the product of the third process is reacted for a fourth time to form a second phosphate material to form a second mixed solution - the terminal point of the fourth time is later than the terminal point of the third time positioned; A fifth process in which a fifth solution containing a third amount of phosphate ions is mixed with the second mixed solution for a fifth time - the initial point of the fifth time is located later than the terminal point of the third time ; and a sixth process of aging the product of the fifth process for a sixth time - the terminal point of the sixth time is located later than the terminal point of the fifth time; Including, the ratio of the first amount, the second amount, and the third amount may be 0.44 (±0.05): 0.26 (±0.05): 0.30 (±0.05).

According to an embodiment of the method for producing witrockite disclosed in the present application, at least a part of the first time and at least a part of the second time overlap, and at least a part of the third time and at least a part of the fourth time is overlapped, and at least a portion of the fifth time and at least a portion of the sixth time may overlap.

According to an embodiment of the method for producing witrockite disclosed in the present application, the ratio of the amount of phosphate ions contained in the fifth solution to the sum of the amounts of phosphate ions contained in the second solution and the fourth solution is It may be in the range of 0.3 or more and 0.55 or less.

According to an embodiment of the method for producing witrockite disclosed in the present application, the phosphate ion is selected from phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate and phosphate. It may be supplied by a phosphate ion feed material comprising one or more.

According to an embodiment of the method for producing witlockite disclosed in the present application, the calcium ion is selected from among calcium hydroxide, calcium carbonate, calcium nitrate and calcium acetate. It may be supplied by a calcium ion supplying material comprising one or more selected ones.

According to an embodiment of the method for producing witrockite disclosed in the present application, the cation other than the calcium ion is a magnesium ion, and the magnesium ion is magnesium hydroxide, magnesium carbonate, magnesium nitrate It can be supplied by a magnesium ion supplying material containing at least one selected from (Magnesium nitrate) and Magnesium acetate.

According to an embodiment of the method for producing witrockite disclosed in the present application, a seventh process of mixing an oxidizing agent for a seventh time is further included, wherein the initial point of the seventh time is earlier than the initial point of the first time or may overlap with at least a part of the first to sixth times.

According to an embodiment of the method for producing witrockite disclosed in the present application, the oxidizing agent may be hydrogen peroxide.

According to an embodiment of the method for producing witrockite disclosed in the present application, the cation other than the calcium ion is a magnesium ion, and the second solution for the amount of calcium ions contained in the first solution in the first step The ratio of the amount of phosphate ions contained in is in the range of 0.6 or more and 1.4 or less, and the ratio of the amount of phosphate ions contained in the fourth solution to the amount of magnesium ions contained in the third solution in the third step may be in the range of 0.6 or more and 5 or less.

According to an embodiment of the method for producing witrockite disclosed in the present application, the first mixed solution includes a solid first phosphate material, and the second mixed solution includes a solid first phosphate material and a solid second phosphate material. Including all materials, the second mixed solution may be formed as the third solution and the fourth solution are additionally added to the first mixed solution after the first mixed solution is formed.

According to an embodiment of the method for producing witlockite disclosed in the present application, the first phosphate material is hydroxyapatite, brushite, and dicalcium phosphate dehydrate (DCPD) or any of these It may be a substance containing a combination.

), 디마그네슘 포스페이트(Dimagnesium phosphate,

), 뉴베리아이트(Newberyite), 트리마그네슘 포스페이트(Trimagnesium phosphate,

) 및이들의 조합을 포함하는 물질일 수 있다. According to one embodiment of the method for producing witrockite disclosed in the present application, the second phosphate material is monomagnesium phosphate (Monomagnesium phosphate,

), Dimagnesium phosphate,

), Newberyite, Trimagnesium phosphate,

) and combinations thereof.

According to an embodiment of the method for producing witrockite disclosed in the present application, at least one process in the first to sixth processes may be performed at a temperature of 50° C. or more and 95° C. or less.

According to the embodiments according to the present application, a method for manufacturing witrockite that significantly reduces manufacturing time can be provided.

According to the embodiments according to the present application, a method for producing witrockite that can significantly reduce the cost of operating the process can be provided.

According to the embodiments according to the present application, a manufacturing method capable of manufacturing witrockite simply and intuitively can be provided.

According to the embodiments according to the present application, a manufacturing method capable of manufacturing high-purity witrockite can be provided.

1 is a flowchart schematically showing a conventional method for producing witrockite.
2 is a timeline schematically showing steps of a conventional method for producing witrockite on a time axis.
3 is a flowchart schematically showing an embodiment of a method for producing witrockite by spatial separation disclosed in the present application.
FIG. 4 is a flow chart showing a step (S10) of forming a mixed solution including the first phosphate material of FIG. 3 in subdivided form.
FIG. 5 is a flow chart showing a step (S20) of forming a mixed solution including the second phosphate material of FIG. 3 in subdivided form.
FIG. 6 is a flowchart showing a process (S40) of aging a mixed solution including the first phosphate material and the second phosphate material of FIG. 3 in subdivided form.
7 is a timeline schematically showing an embodiment of a method for producing witrockite by spatial separation disclosed in the present application on the time axis.
FIG. 8 is a timeline schematically illustrating the time and timing of each process of FIG. 7 .
9 is SEM DATA of the resultant formed according to an embodiment of the method for manufacturing witrockite by spatial separation disclosed in the present application.
10 is a graph showing the results of XRD DATA of a product formed according to an embodiment of a method for producing witrockite by spatial separation disclosed in the present application.
11 is a flowchart schematically illustrating an embodiment of a method for producing witrockite by temporal separation disclosed in the present application.
FIG. 12 is a flow chart showing a step (S100) of forming a mixed solution including the first phosphate material of FIG. 11 in subdivided form.
FIG. 13 is a flow chart showing a process (S200) of forming a mixed solution including the second phosphate material of FIG. 11 in subdivided form.
FIG. 14 is a flowchart showing a process (S300) of aging a mixed solution including a first phosphate material and a second phosphate material of FIG. 11 in subdivided form.
15 is a timeline schematically showing an embodiment of a method for producing whitrockite by temporal separation disclosed in the present application on the time axis.
FIG. 16 is a timeline schematically illustrating the time and timing of each process of FIG. 15 .
17 is SEM DATA of the result formed according to an embodiment of the method for producing witrockite by temporal separation disclosed in the present application.
18 is a graph showing the results of XRD DATA of a product formed according to an embodiment of a method for producing witrockite by temporal separation disclosed in the present application.
19 is SEM DATA of the resultant formed according to the second experiment of the method for producing witrockite by temporal separation disclosed in the present application.
20 is XRD DATA of the resultant formed according to the second experiment of the method for producing witrockite by temporal separation disclosed in the present application.
21 is a graph showing the results of XRD DATA of the product formed according to the second experiment of the method for producing witrockite by temporal separation disclosed in the present application.
22 is SEM DATA of the resultant formed according to the third experiment of the method for producing witrockite by temporal separation disclosed in the present application.
23 is a graph showing the results of XRD DATA of the product formed according to the third experiment of the method for producing witrockite by temporal separation disclosed in the present application.
24 is SEM DATA of the result obtained according to the fourth experiment of the method for producing witrockite by temporal separation disclosed in the present application.
25 is XRD DATA of the resultant formed according to the fourth experiment of the method for producing witrockite by temporal separation disclosed in the present application.
26 is a graph showing the results of XRD DATA of the product formed according to the fourth experiment of the method for producing witrockite by temporal separation disclosed in the present application.

The foregoing objects, features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings. However, the present invention can apply various changes and can have various embodiments. Hereinafter, specific embodiments will be illustrated in the drawings and described in detail.

Like reference numerals designate essentially like elements throughout the specification. In addition, components having the same function within the scope of the same idea appearing in the drawings of each embodiment are described using the same reference numerals.

If it is determined that a detailed description of a known function or configuration related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, numbers (eg, first, second, etc.) used in the description process of this specification are only identifiers for distinguishing one component from another component.

1. Conventional method for producing witrockite

Referring to FIGS. 1 and 2, in the conventional method for producing witrockite (Korean Patent Registration No. 10-1423982 (July 22, 2014)), an aqueous cation solution is prepared by adding a calcium ion supplying material and a cation supplying material to water. Forming (S1), adding a phosphoric acid feed material to the aqueous cation solution (dropwise method) and aging (S2), and drying the aged aqueous solution to form witrockite powder (S3).

The conventional method for producing witrockite has a fatal disadvantage in that the production time is long.

The reason is firstly, in the step of forming an aqueous cation solution by adding a calcium ion supplying material and a cation supplying material to water (S1), a calcium ion supplying material and a cation supplying material other than calcium are added 'simultaneously' to water. is in Although the first reaction condition required for calcium ion to react with phosphate ion and the second reaction condition required for cation other than calcium to react with phosphate ion are different, the calcium ion supplying material and the other cation supplying material other than calcium are different. By adding 'at the same time', the first reaction condition and the second reaction condition cannot be provided differently, so the preparation time increases.

The second reason is that the phosphoric acid feed material is added slowly and dropwise. Referring to FIG. 2, it can be confirmed that the phosphoric acid supply material is added (S21) in a dropwise manner until aging (S22). Therefore, it takes a long time to add all of the phosphate ions required to form witlockite, which results in a long manufacturing time.

In addition, the conventional method for producing witrockite has a problem that the manufacturing method is complicated.

Since the conventional method for producing witrockite depends on the thermodynamic stability of the first phosphate and the second phosphate according to the pH, the pH must be precisely controlled to form witrockite. In order to precisely control the pH, the phosphoric acid feed material was added dropwise, and the production method was complicated because the addition rate and amount of the phosphoric acid feed material according to the dropwise method had to be accurately set.

In order to solve these problems, there is an increasing need for a method for manufacturing witrockite that is simpler and has a shorter manufacturing time.

2. Manufacturing method of witrockite by spatial separation (first embodiment)

Hereinafter, a method for manufacturing witrockite according to an embodiment of the present application will be described with reference to FIGS. 3 to 8 .

Referring to FIG. 3, the manufacturing method of witrockite according to an embodiment of the present application includes a process of preparing a mixed solution including a first phosphate material (S10) and a process of preparing a mixed solution including a second phosphate material (S10). S20), combining the first phosphate material and the second phosphate material into one mixed solution to make a mixed solution (S30), aging the mixed solution containing both the first phosphate material and the second phosphate material It includes a step (S40) of doing. At this time, in the method for producing witrockite according to the present application, the step of making a mixed solution containing the first phosphate material (S10) and the step of making a mixed solution containing the second phosphate material (S20) are carried out in separate containers. can

In other words, if the process of making a mixed solution containing the first phosphate material is performed in the first container, the process of making the mixed solution containing the second phosphate material is performed in a second container separate from the first container. can

According to the method for producing witrockite disclosed in the present application, mixing and reaction may preferably be performed in the same container, but mixing and reaction do not necessarily have to be performed in the same container.

In other words, according to the present application, if the mixed solution containing the first phosphate material is made in the first container and the mixed solution containing the second phosphate material is made in a second container separate from the first container, this is sufficient. The purpose of the application can be achieved.

Preferably, through such spatial separation, the step of making a mixed solution including the first phosphate material (S10) and the process of making a mixed solution including the second phosphate material (S20) partially overlap on the time axis. Can proceed. That is, the time during which the process of preparing the mixed solution containing the first phosphate material (S10) proceeds and the time during which the process of preparing the mixed solution containing the second phosphate material (S20) proceeds partially overlapped. It can be. For example, the process of preparing a mixed solution including the first phosphate material (S10) and the process of preparing a mixed solution including the second phosphate material (S20) may be performed simultaneously. Through spatial separation, the two processes can be performed simultaneously, and thus the total manufacturing time for making whitrockite can be significantly reduced.

Since the process of preparing a mixed solution including the first phosphate material (S10) and the process of preparing a mixed solution including the second phosphate material (S20) are carried out in separate containers, the first phosphate material and the second phosphate material are In order to make a mixed solution containing all of the substances, a step of combining the first phosphate material and the second phosphate material contained in each container into one mixed solution (S30) may be included. Through the step of combining the first phosphate material and the second phosphate material into one mixed solution (S30), a mixed solution including both the first phosphate material and the second phosphate material may be formed.

After the mixed solution containing both the first phosphate material and the second phosphate material is formed, an aging process (S40) is performed.

In step S40 of aging the solution including the first phosphate material and the second phosphate material, a solution containing phosphate ions may be additionally added.

As described above, in the conventional method for producing witrockite, phosphate ions are added dropwise throughout the entire process to finely adjust the pH to gradually change the pH condition from a basic condition to an acidic condition. However, since the phosphate ion is added dropwise, there is a fatal disadvantage that the preparation time is long. For example, a first pH condition required for producing stabilized calcium phosphate by reacting calcium ions with phosphate ions and a second pH condition required for producing stabilized magnesium phosphate by reacting magnesium ions with phosphate ions. The pH conditions may be different from each other, but according to the dropping method, an inevitable time is required to change from the first pH condition to the second pH condition. The inevitable time required to change the pH conditions serves as one of the causes of lengthening the manufacturing time of witrockite.

In addition, the pH must be precisely controlled from the beginning of the reaction throughout the aging process, and the addition rate and amount of the phosphate ion supplying material must be accurately set according to the dropping method, so there is a problem that the manufacturing method of witlockite is complicated. .

In contrast, the method for producing witrockite disclosed in the present application has the following advantages over the conventional method for producing witrockite.

The method for producing whitlockite according to a preferred embodiment of the present invention includes a first reaction condition required for calcium ions to react with phosphate ions through spatial separation and a second reaction condition required for cations other than calcium to react with phosphate ions. Different reaction conditions can be provided, and the manufacturing time can be shortened because the phosphate ion supplying material is added in a 'one time' method (Pouring method) rather than a dropwise method. . Reaction conditions may be provided in consideration of pH or amount of phosphoric acid.

In addition, since only a specific amount of phosphate ion needs to be added without the need to complexly adjust the pH, it is possible to produce whitrockite simply and intuitively.

Hereinafter, with reference to FIGS. 3 to 8, each process will be described in more detail.

In the process of preparing a mixed solution containing the first phosphate material (S10), a solution containing calcium ions and a solution containing phosphate ions are mixed and reacted to form a solid first phosphate material in a first container for a first time. includes doing

The first phosphate material is a phosphate material containing calcium ions. That is, it is a calcium phosphate substance. For example, it may be a material comprising hydroxyapatite, which is a calcium phosphate material, dicalcium phosphate dehydrate (DCPD), brushite, monetite, or a combination thereof. there is. However, it is not limited to the exemplified materials, and any material in which calcium ions and phosphate ions are combined can be regarded as a calcium phosphate material. Preferably, the first phosphate material may be hydroxyapatite.

The first time means a time from when the solution containing calcium ions and the solution containing phosphate ions start mixing to the time when the reaction of forming the first phosphate material is completed. However, if the reaction of forming the first phosphate material is not completely completed until the process of combining into one mixed solution (S30) begins, the first time is to mix the solution containing calcium ions and the solution containing phosphate ions. It may be the time from the start of the process to the start of the process of combining into one mixed solution (S30) to be described later.

A solution containing calcium ions can be prepared by dissolving in water a substance that contains calcium atoms and is easily ionized when dissolved in water. That is, the calcium ion-containing solution may be prepared by dissolving a calcium ion donor (or calcium ion donor) in water. The calcium ion donor material may include calcium hydroxide, calcium carbonate, calcium nitrate, and calcium acetate.

As described above, the step of forming the mixed solution containing the first phosphate material (S10) has been described as mixing a solution containing phosphate ions and a solution containing calcium ions, but the phosphate ions and calcium ions are mixed with each other. If a solution coexisting in the solution can be prepared, the calcium ion donating material is directly mixed with the phosphate ion donating material (or phosphate ion donating material) described later, or the phosphate ion donating material and the calcium ion donating material are mixed together in water. Mixing may also be performed.

At this time, although it has been described that a solution containing phosphate ions and a solution containing calcium ions are mixed with each other, the phosphate ions and calcium ions are mixed together in water, such as by mixing the phosphate ion supplying material and the calcium ion supplying material at once. In the case of preparing a solution coexisting in the first time, the calcium ion and phosphate ion coexist in the aqueous solution by mixing the calcium ion supply material and the phosphate ion supply material for the first time from the time when calcium ions and phosphate ions start to coexist. It may mean up to the point at which the reaction of ions is completed.

Referring to FIGS. 3 and 4 , in this process (S10), a solution containing calcium ions and a solution containing phosphate ions are mixed and reacted for a first time. According to a preferred embodiment of the present application, in the process (S10), a solution containing calcium ions and a solution containing phosphate ions are mixed (S11) for a second time, and a solution containing calcium ions is mixed for a third time. A mixed solution containing the first phosphate material is formed by reacting the solution with a solution containing phosphate ions (S12).

Referring to FIGS. 7 and 8, the second time is, more specifically, from the point at which the solution containing calcium ions and the solution containing phosphate ions start to mix, the solution containing calcium ions and the phosphate ions It means the time until the mixing of the containing solution is completed.

The third time is the earlier of the time when calcium ions and phosphate ions start to react to generate the first phosphate, when the reaction is completed, or when the process of combining into one mixed solution (S30) starts. means the time until

The first time is the sum of the second time and the third time, but means a time excluding the overlapping time.

At least part of the second time period and at least part of the third time period may overlap on the time axis. That is, at least part of the mixing process (S11) and at least part of the reaction (S12) may occur simultaneously.

For example, as soon as a solution containing calcium ions and a solution containing phosphate ions are mixed, a reaction of forming a first phosphate material may occur. In this case, the first time may have the same value as the time of the third time.

According to an embodiment of the present application, at the terminal point of the second time, when the 'mixing' process (S11) of the solution containing calcium ions and the solution containing phosphate ions is completed, calcium ions and phosphate ions are mixed with the solution. may be included in However, since the mixing process ( S11 ) and the reaction process ( S12 , which will be described later) may partly occur simultaneously, a calcium phosphate material, which is the first phosphate material, may be further included at the terminal point of the second time.

In the step of 'reacting' the solution containing calcium ions and the solution containing phosphate ions (S12), calcium phosphate material, which is a solid first phosphate material formed by reacting calcium ions with phosphate ions, may be included in the mixed solution. Therefore, at the time when the reaction process (S12) is completed, that is, at the terminal point of the third time, the solid calcium phosphate material may be included in the mixed solution.

According to one embodiment of the present application, the process of reacting the solution containing at least calcium ions with the solution containing phosphate ions (S12) may be performed at 50° C. or more and 100° C. or less. The process of mixing the solution containing calcium ions and the solution containing phosphate ions (S11) may also be carried out at 50 ° C or more and 100 ° C or less, but the reaction step (S12) to form the first phosphate is 50 ° C or more and 100 ° C or less. If proceeded in, the object of the present application can be achieved.

Referring back to FIG. 3, in the process of preparing a mixed solution containing the second phosphate material (S20), the second cation (or other than calcium ion) is formed in the second container for a fourth time to form a solid second phosphate material. cations) and a solution containing phosphate ions are mixed and reacted.

The second cation is a cation other than a calcium ion, and for example, at least one or more of Mg, Co, Sb, Fe, Mn, Y, Eu, Cd, Nd, Na, La, Sr, Pb, Ba, and K It may be in ionic form. Preferably, the second cation may be a magnesium ion.

The fourth time refers to a time from when the solution containing cations other than calcium ions starts mixing the solution containing phosphate ions to the time when the reaction of forming the second phosphate material is completed. However, if the reaction of forming the second phosphate material is not completely completed until the process of combining into one mixed solution (S30) begins, the fourth time includes a solution containing cations other than calcium ions and phosphate ions. It may be the time from the time of starting to mix the solution to the time of starting the step of combining into one mixed solution (S30) to be described later.

), 디마그네슘 포스페이트(Dimagnesium phosphate,

), 뉴베리아이트(Newberyite), 트리마그네슘 포스페이트(Trimagnesium phosphate,

) 또는 이들의 조합을 포함하는 물질일 수 있다. 다만, 예시된 물질로 제한되지 않으며, 마그네슘 이온과 인산 이온이 결합된 물질이라면 마그네슘 포스페이트 물질로 볼 수 있을 것이다. The second phosphate material is a phosphate material containing the second cation. That is, the second phosphate material may be regarded as a material in which a second cation and a phosphate ion are combined. For example, if the second cation is a magnesium ion, the second phosphate material is a magnesium phosphate material, and monomagnesium phosphate (Monomagnesium phosphate,

), Dimagnesium phosphate,

), Newberyite, Trimagnesium phosphate,

) or a material comprising a combination thereof. However, it is not limited to the exemplified materials, and any material in which magnesium ions and phosphate ions are combined can be regarded as a magnesium phosphate material.

)일 수 있다.In addition, if the second cation is a cobalt ion, the second phosphate material is cobalt (II) phosphate hydrate (Cobalt (II) phosphate hydrate,

) can be.

), 아이언(III) 포스페이트 테트라하이드레이트(Iron(III) phosphate tetrahydrate,

) 또는 이들의 조합을 포함하는 물질일 수 있다.In addition, if the second cation is iron ion, the second phosphate material is iron (III) phosphate dihydrate (Iron (III) phosphate dihydrate,

), iron (III) phosphate tetrahydrate,

) or a material comprising a combination thereof.

)일 수 있다.In addition, if the second cation is sodium ion, the second phosphate material is sodium phosphate (Sodium phosphate,

) can be.

)일 수 있다.In addition, if the second cation is a potassium ion, the second phosphate material is potassium phosphate tribasic (Potassium phosphate tribasic,

) can be.

)일 수 있다.In addition, if the second cation is a strontium ion, the second phosphate material is strontium phosphate (Strontium phosphate,

) can be.

)일 수 있다.In addition, if the second cation is a barium ion, the second phosphate material is barium phosphate (Barium phosphate,

) can be.

However, the second phosphate material is not limited to the exemplified material, and any material that can exist in an aqueous solution by combining the above-described second cation and phosphate ion will be regarded as the second phosphate material.

The solution containing the second cation may be prepared by dissolving in water a material that has the atomic form (X) of the second cation and is easily ionized when dissolved in water. That is, the solution containing the second cation may be prepared by dissolving the second cation-providing material (or the second cation-providing material) in water. The second cation-providing material may be X hydroxide, X carbonate, X nitrate, X acetate, and the like.

For example, if the second cation is magnesium ion, the solution containing the second cation dissolves magnesium hydroxide or magnesium carbonate, magnesium nitrate, magnesium acetate, etc. containing magnesium atom form, which is a magnesium ion supply material, in water It can be produced by

However, according to the foregoing, the step of forming the mixed solution containing the second phosphate material (S20) has been described as mixing the solution containing the phosphate ion and the solution containing the second cation, but the phosphate ion and the second cation If a solution in which two cations coexist in a solution can be prepared, a method of directly mixing the phosphate ion donor material with the second cation donor material or mixing the phosphate ion donor material and the second cation donor material with water at once. may also be performed.

For example, if the second cation is a magnesium ion, a solution containing the second cation may be prepared by dissolving magnesium hydroxide in a solid state in water, and may be mixed with a solution containing phosphate ion. In addition, it may be performed by directly mixing the magnesium hydroxide material in a solid state with a solution containing phosphate ions, or by simultaneously mixing the phosphate providing material and magnesium hydroxide with water.

At this time, although it has been described that the solution containing phosphate ions and the solution containing the second cation are mixed with each other, the phosphate ion and the second cation providing material are mixed together in water, such as mixing the phosphate ion donor material and the second cation donor material together. In the case of preparing a solution in which cations coexist in the solution, the fourth time is to coexist in the aqueous solution by mixing the second cation supply material and the phosphate ion supply material from the time point at which the second cation and phosphate ion start to coexist. It may mean up to the time when the reaction between the second cation and the phosphate ion is completed.

3 and 5, in the process of forming a mixed solution containing a second phosphate material (S20), a solution containing a second cation other than calcium ions and a solution containing phosphate ions are prepared in a fourth step. Mix and react for an hour. According to a preferred embodiment of the present application, in the process of forming a mixed solution containing the second phosphate material (S20), the solution containing the second cation and the solution containing the phosphate ion are mixed for a fifth time (S21) and a step of reacting the solution containing the second cation with the solution containing the phosphate ion for a sixth time to form a mixed solution containing the second phosphate material (S22).

7 and 8, the fifth time is, more specifically, the solution containing the second cation from the point at which the solution containing the second cation and the solution containing the phosphate ion start to mix. and the time until mixing of the solution containing the phosphate ion is completed.

The sixth time is the earliest of the time from when the second cation and phosphate ion start to react to generate the second phosphate, when the reaction is completed, or when the process of combining into one mixed solution (S30) starts. refers to the time to the point in time.

The fourth time is the sum of the fifth time and the sixth time, but means a time excluding the overlapping time.

At least a part of the fifth time period and at least a part of the sixth time period may overlap on a time axis. That is, at least part of the mixing process (S21) and at least part of the reaction process (S22) may occur simultaneously.

For example, as soon as a solution containing magnesium ions and a solution containing phosphate ions are mixed, a reaction of forming a second phosphate material may proceed. In this case, the fourth time period may be substantially equal to the value of the sixth time period.

In addition, according to an embodiment of the present application, the time when the 'mixing' process (S21) of the solution containing a cation other than the second cation, calcium ion, and the solution containing phosphate ion is completed, that is, the terminal of the fifth time. At a point, the second cation and phosphate ion may be included in the aqueous solution. However, since the mixing process (S21) and the reaction process (S22, which will be described later) may partly occur simultaneously, a second phosphate material, for example, a magnesium phosphate material may be further included at the terminal point of the fifth time.

However, since the step of making the mixed solution containing the second phosphate material (S20) is performed in a separate container from the process of making the mixed solution containing the first phosphate material (S10), mixing at the terminal point of the fifth time The solution may not contain a solid calcium phosphate material.

In the step of 'reacting' the solution containing the second cation with the solution containing the phosphate ion (S22), a mixed solution containing the solid second phosphate material formed by reacting the second cation with the phosphate ion may be formed. Therefore, at the time when the reaction process (S22) is completed, that is, at the terminal point of the sixth time, the solid second phosphate material may be included in the mixed solution.

According to one embodiment of the present application, the step (S22) of reacting a solution containing cations other than calcium ions with a solution containing phosphate ions may be performed at a temperature of 50° C. or more and 100° C. or less. The process of mixing a solution containing cations other than calcium ions and a solution containing phosphate ions (S21) may also be performed at 50 ° C or more and 100 ° C or less, but the reaction step (S22) to form the second phosphate is 50 ° C. The object of the present application can be achieved if it is carried out at 100 ° C or less.

7 and 8, since the process of making a mixed solution containing the first phosphate material (S10) and the process of making a mixed solution containing the second phosphate material (S20) can be performed in separate containers, The process of preparing a mixed solution containing the first phosphate material (S10) and the process of preparing a mixed solution containing the second phosphate material (S20) may be performed simultaneously. That is, at least a part of the first time and at least a part of the fourth time may overlap on the time axis.

Also, the initial point and terminal point of the second time may be independently located independently of the initial point and terminal point of the fourth and fifth time.

Also, the initial point and terminal point of the third time may be independently located independently of the initial point and terminal point of the fourth and fifth time.

In other words, since they are spatially separated, the process of preparing a mixed solution containing the first phosphate material (S10) and the process of preparing a mixed solution containing the second phosphate material (S20) can proceed independently.

In the case of the conventional Whitlockite manufacturing method, a solution containing phosphate ions is added dropwise to a solution containing both calcium ions and second cations in one container to form the first phosphate material, and then It sequentially forms a substance of the second phosphate. Thereafter, by gradually lowering the pH to form an acidic condition, some atoms of the first phosphate material are replaced with some atoms of the second phosphate material or ions included in the aqueous solution, thereby changing the crystal structure to form witlockite. As such, the conventional witrockite manufacturing method forms a second phosphate material 'after' the first phosphate material, and the manufacturing time is long in that phosphate ions are added through a dropwise method. .

In the method for producing witrockite according to the present application, the first phosphate material and the second phosphate material can be simultaneously formed through spatial separation, and the reaction conditions in each container to form a target intermediate product from the beginning, for example, phosphoric acid The amount and pH of may be appropriately provided, and in order to create different reaction environments in each container, the amount and pH of added phosphate ions may be provided differently. In other words, the first reaction conditions required to form the first phosphate material and the second reaction conditions required to form the second phosphate material may be different from each other.

At this time, according to the conventional method for producing witrockite, the first reaction condition and the second reaction condition cannot be provided at the same time, and at the first time, the first reaction condition is given to the reaction vessel, and as the reaction proceeds, Accordingly, at the second time point, the process time could not be shortened because the second reaction condition was designed to be given to the reaction vessel.

However, in the method for producing witrockite according to the present application, the first reaction condition can be directly applied to the first container and the second reaction condition can be directly applied to the second container at the same time. While the first phosphate material can be produced immediately, it is possible to simultaneously produce the second phosphate material in the second container. In other words, it is possible to set the reaction conditions in each container differently from the beginning so that the reactions in the first container and the second container proceed simultaneously through spatial separation, so that the manufacturing time is longer than that of the conventional manufacturing method in synthesizing witrockite. can be significantly shortened.

In addition, the fact that phosphate ions can be added by pouring rather than dropwise also contributes to significantly shortening the manufacturing time of witrockite. The pouring method will be described later in detail. As the manufacturing time is shortened, there is also an effect that the operating cost of the process can be reduced.

Referring again to FIG. 3, in order to make a mixed solution containing both the first phosphate material and the second phosphate material, the first phosphate material contained in the first container and the second phosphate material contained in the second container are combined into one It may include a step (S30) of combining with a mixed solution of. When combining into one mixed solution, the mixed solution may be combined into either the first container or the second container, or may be combined into a third container.

According to a preferred embodiment of the present application, the first phosphate material and the second phosphate material are formed by combining the mixed solution containing the first phosphate material and the mixed solution containing the second phosphate material into one mixed solution (S30). A mixed solution containing all of the phosphate materials is formed. For example, the product of this process (S30) may include both hydroxyapatite and dimagnesium phosphate.

Referring again to FIGS. 7 and 8, a process of combining the mixed solution in the first container containing the first phosphate material and the mixed solution in the second container containing the second phosphate material into one mixed solution (S30) This starting initial point may be located later than the terminal point of the second time or the terminal point of the fifth time.

That is, the present process (S30) may be started after the completion of the mixing process (S11) of the process of making the mixed solution including the first phosphate material (terminal point of the second time).

Similarly, this process (S30) may be started after the time (terminal point of the fifth time) of the mixing process (S21) of the process of making the mixed solution containing the second phosphate material is completed.

In addition, the initial point of the step (S30) of combining the mixed solution of the first container containing the first phosphate material and the mixed solution of the second container containing the second phosphate material into one mixed solution is the terminal of the third time It can be located at a later point in time rather than a point. In other words, according to the method for producing witrockite disclosed in the present application, after the reaction step (S12) of the process of making a mixed solution containing the first phosphate material is completed, the process of combining into one mixed solution ( S30) does not have to be started, but preferably, this process (S30) can be started after the reaction process (S12) of the process of making the mixed solution containing the first phosphate material is completed.

Referring again to FIG. 3 , after the mixed solution containing both the first phosphate material and the second phosphate material is formed, a process of mixing and aging the solution containing phosphate ions for a seventh time (S40) proceeds. At this time, conditions may be provided for sufficient phase transformation to form witlockite from the mixed solution including the first phosphate material and the second phosphate material.

See Figures 3 and 6. According to a preferred embodiment of the present application, the process of aging the mixed solution containing both the first phosphate material and the second phosphate material (S40) is a mixture containing the first phosphate material and the second phosphate material for an 8 hr. A step of mixing a solution containing phosphate ions with a solution (S41) and a step of aging for a ninth hour to change the crystal structure of a first phosphate material in which some atoms are substituted with different atoms to form witlockite (S42). can do.

Referring again to FIGS. 7 and 8 , the eighth time period is from the time when mixing of the solution containing phosphate ions with the mixed solution containing the first phosphate material and the second phosphate material starts to the time when mixing is completed. is the time of

The ninth time refers to the time from the start of aging the mixed solution including the first phosphate material and the second phosphate material to form witlockite to the completion of aging.

The seventh time is the sum of the eighth time and the ninth time, but excluding the overlapping time.

At least part of the eighth time period and at least part of the ninth time period may overlap on the time axis. That is, the mixing process (S41) and the aging process (S42) of the solution containing phosphate ions and the mixed solution containing the first phosphate material and the second phosphate material may occur simultaneously.

For example, as soon as a solution containing phosphate ions is mixed with a mixed solution containing hydroxyapatite and dimagnesium phosphate, the mixed solution containing hydroxyapatite and magnesium phosphate may be aged. In this case, the seventh time may be substantially the same as the value of the ninth time.

According to one embodiment of the present application, the terminal point at the time when the 'mixing' process (S41) of the mixed solution including the first phosphate material and the second phosphate material and the solution containing phosphate ions is completed, that is, at the terminal point of the 8th time. In , the first phosphate material, the second phosphate material, and phosphate ions may be included in the mixed solution. However, since the mixing process (S41) and the aging process (S42, which will be described later) may partly occur simultaneously, witrockite may be further included at the terminal point of the eighth hour.

In the 'aging' process (S42) of the mixed solution containing the first phosphate material, the second phosphate material, and phosphate ions, aging is performed for a ninth time, and witrockite is formed while the crystal structure of the first phosphate material changes. can Therefore, at the terminal point of the ninth hour, the mixed solution may contain solid witrockite.

According to one embodiment of the present application, the 'aging' process (S42) of the mixed solution including the first phosphate material, the second phosphate material, and phosphate ions may be performed at 50 °C or more and 100 °C or less. The 'mixing' process (S41) of the mixed solution including the first phosphate material and the second phosphate material and the solution containing the phosphate ion may also be performed at 50 ° C. or more and 100 ° C. or less, but the first phosphate material and the second phosphate material The object of the present application can be achieved if the 'aging' process (S42) of the mixed solution containing phosphate ions is performed at a temperature of 50°C or more and 100°C or less.

A step of forming a mixed solution including a first phosphate material (S10), a step of forming a mixed solution including a second phosphate material (S20), and aging the solution including the first phosphate material and the second phosphate material In step S40, a solution containing phosphate ions is mixed.

를 의미한다고 볼 수 있으나, 이에 제한되지는 않으며, 수용액 상에서 인산(Phosphoric acid)가 존재할 수 있는 형태를 모두 포함할 수 있다. 예를 들어,

,

,

,

모두 상기 인산 이온으로 볼 수 있다.The phosphate ion may include all forms of phosphoric acid that may exist depending on the pH of the aqueous solution. In general, when referring to phosphate ion,

It can be seen to mean, but is not limited thereto, and may include all forms in which phosphoric acid may exist in an aqueous solution. for example,

,

,

,

All can be regarded as the above phosphate ions.

The phosphate ion may be supplied by a phosphate ion supply material containing at least one selected from phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate and phosphate, Preferably it can be supplied by phosphoric acid.

The solution containing the phosphate ion may be prepared by dissolving a phosphate ion-providing material (eg, diammonium phosphate, ammonium phosphate, phosphate) existing as a solid at room temperature in water or an aqueous solution. Alternatively, the phosphate ion donor material such as phosphoric acid may contain water as a solvent so that the phosphate ion donor itself contains phosphate ions.

For example, when mixing a solution containing calcium ions and a solution containing phosphate ions in the step of forming a mixed solution containing the first phosphate material (S10), an aqueous solution obtained by dissolving solid diammonium phosphate in water may be mixed with a solution containing calcium ions, or an aqueous solution of phosphoric acid containing water as a solvent in the phosphate ion providing material itself may be mixed with a solution containing calcium ions.

In addition, a process of forming a mixed solution containing a solution containing phosphate ions and a first phosphate material (S10), a process of forming a mixed solution containing a second phosphate material (S20), and the first phosphate material and the second In the process of aging the solution containing the phosphate material (S40), when the solution containing the phosphate ion is mixed, it may be mixed by a pouring method. The pouring method is different from the dropwise method, and means a method of adding all the volume of the solution to be added in a substantially very short time at once. For example, in the conventional method for producing witrockite, a solution containing phosphate ions was continuously mixed dropwise at a volume flow rate of 12.5 ml/min. On the other hand, according to one embodiment of the method for manufacturing Whitlockite disclosed in this application, the solution containing phosphate ions can be mixed at once at a volume flow rate of 2ml/sec (120ml/min) to 130ml/sec (7800ml/min) . The mixing time of the solution containing the phosphate ion is shortened, and thus the manufacturing time of whitlockite can be shortened.

That is, the second time, the fifth time, or the eighth time may be a substantially very short time (eg, within about 1 second). However, even in the pouring method, the second, fifth, or eighth time may be extended from several seconds to several tens of seconds depending on the volume of the solution containing the phosphate ion to be added.

The volume of the solution containing phosphate ions mixed in the process of forming a mixed solution containing the first phosphate material (S10) and the process of forming a mixed solution containing the second phosphate material (S20) It can be determined by considering the stoichiometric ratio for forming the phosphate material and the pH of the mixed solution.

For example, in the first container, a phosphate ion supply material including an amount of phosphate ions in consideration of a stoichiometric ratio for mixing and reacting with calcium ions to form hydroxyapatite, which is one of the first phosphate materials, can be mixed. In addition, a phosphate ion supply material including phosphate ions may be added in consideration of the pH of the mixed solution for stably forming the first phosphate material and maintaining a stable state. For example, when phosphoric acid (Phosphate acid) is used as a phosphate ion supply material, it is necessary to provide the amount (mole) of phosphate ion to stably generate hydroxyapatite and the pH at which hydroxyapatite can be stably maintained. The first amount (Volume) of phosphoric acid may be mixed in consideration of the amount (mole) of hydrogen ions for Alternatively, when phosphoric acid (Phosphate acid) is used as a phosphate ion supply material, after adding the amount (Volume) of phosphoric acid in consideration of the amount (Mole) of phosphate ion for stably generating hydroxyapatite, hydroxyapatite A material other than phosphoric acid may be additionally mixed to provide (or adjust) a pH that can be stably maintained.

At this time, preferably, the ratio of the amount (mole) of phosphate ion to the amount (mole) of calcium ion mixed in the step of forming the mixed solution containing the first phosphate material (S10) is in the range of 0.6 or more and 1.4 or less. may apply. In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

Similarly, in the second container, a phosphate ion feed material containing phosphate ions is mixed and reacted with magnesium ions in consideration of a stoichiometric ratio to form a second phosphate material, preferably dimagnesium phosphate (MgHPO4) can be added. In addition, in order to stably generate the second phosphate material and maintain a stable state, a phosphate ion providing material including phosphate ions may be mixed in consideration of the pH of the mixed solution. For example, the amount (mole) of phosphate ion to stably generate dimagnesium phosphate from magnesium ion and phosphate ion and the amount (mole) of hydrogen ion to provide a pH at which dimagnesium phosphate can be stably maintained Considering this, a second volume of phosphoric acid may be mixed. Alternatively, when phosphoric acid (Phosphate acid) is used as a phosphate ion supply material, after adding the amount (Volume) of phosphoric acid in consideration of the amount (Mole) of phosphate ion for stably generating dimagnesium phosphate, dimagnesium phosphate A material other than phosphoric acid may be additionally mixed to provide (or adjust) a pH that can be stably maintained.

At this time, preferably, the ratio of the amount (mole) of phosphate ion to the amount (mole) of magnesium ion mixed in the step (S20) of forming the mixed solution including the second phosphate material is in the range of 0.6 or more and 5 or less. may apply. In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

In this case, the first volume of phosphoric acid and the second volume of phosphoric acid may be the same, but preferably, the first volume and the second volume may be different.

In the step of aging the solution including the first phosphate material and the second phosphate material (S40), the volume of the solution containing the phosphate ion mixed is a mixture of wheat from the first phosphate material and the second phosphate material. The pH condition under which rockite can be produced or the target amount of whitrockite produced may be considered and determined. For example, the amount of the solution containing the phosphate ion may be determined in consideration of pH conditions for producing witrockite through ion exchange between the hydroxyapatite and the magnesium phosphate. However, since substances other than phosphoric acid for pH adjustment may be mixed, phosphoric acid is mixed to supply phosphate ions in consideration of the target witrockite production amount, and substances other than phosphoric acid for pH adjustment may be additionally mixed. can

If a feed material other than phosphoric acid (e.g., diammonium hydrogen phosphate, ammonium phosphate, and phosphate) is used as the phosphate ion feed material, Along with the solution, a solution containing hydrogen ions for adjusting the pH may be further added. For example, when solid diammonium hydrogen phosphate is dissolved to form a solution containing phosphate ions and added to a mixed solution containing a first phosphate material and a second phosphate material, whitrock A solution containing hydrogen ions (or a solution for adjusting the pH) may be additionally added so that the mixed solution is aged at a pH for stably generating kites.

In addition, the volume of the solution containing phosphate ions mixed in the process of aging the solution containing the first phosphate material and the second phosphate material (S40) is the total amount of cations mixed to form witlockite. It can be mixed in consideration of the ratio of the total sum of and anions.

For example, in the step of forming a mixed solution containing the first phosphate material (S10), the volume of the phosphoric acid solution containing phosphate ions required to form a certain amount of witrockite is the third volume. When the amount (Volume) of the phosphoric acid solution to be is the first amount and the amount (Volume) of the phosphoric acid solution mixed in the step of forming the mixed solution including the second phosphate material (S20) is the second amount, the first phosphate material And the volume of the phosphoric acid solution mixed in the aging process (S40) of the mixed solution containing both the second phosphate material can be seen as the amount obtained by subtracting the sum of the first and second amounts from the third amount. there is.

Preferably, the ratio of the amount of the phosphoric acid solution mixed in the process of aging the mixed solution containing both the first phosphate material and the second phosphate material to the sum of the first amount and the second amount (S40) is 0.3 or more. It may be in the range of 0.55 or less. In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

According to one embodiment disclosed in the present application, since whitrockite can be prepared by adding a predetermined amount of phosphate ions three times without the need to finely control the pH, it is much simpler and , has the advantage of being able to prepare witrockite in an intuitive and clear way.

Again, referring to FIGS. 7 and 8 , as the solutions containing phosphate ions are mixed by pouring, the terminal point of the third time may be located later than the terminal point of the second time.

In other words, the process of mixing the solution containing calcium ions and the solution containing phosphate ions (S11) is completed prior to the point at which the reaction to form the first phosphate material is completed (terminal point of the third time). For example, when mixing of a solution containing phosphate ions and a solution containing calcium ions is completed within a short time within 1 second by the pouring method, the first phosphate material is added even after the point at which the mixing is completed (terminal point of the second time). reactions can proceed.

Similarly, the terminal point of the sixth time may be located later than the terminal point of the fifth time. In other words, the process of mixing the solution containing the second cation and the solution containing the phosphate ion (S21) is completed before the reaction to form the second phosphate material is completed (terminal point of the sixth time). For example, when a solution containing phosphate ions and a solution containing second cations are mixed within 1 second by the pouring method, the second phosphate material is produced even after the mixing is completed (terminal point of the fifth time) reaction can proceed.

Similarly, the terminal point of the ninth time may be located later than the terminal point of the eighth time. In other words, the mixing process (S41) of the mixed solution including the first phosphate material and the second phosphate material and the solution including phosphate ions is completed when the aging process to form witrockite is completed (terminal point of the ninth time) may be completed earlier. For example, when mixing is completed within 1 second by pouring a solution containing phosphate ions into a mixed solution containing a first phosphate material and a second phosphate material, the point at which mixing is completed (terminal point of the 8th time) Even after that, a process of aging to form whitlockite may proceed.

In addition, according to an embodiment of the present application, a step of forming a mixed solution including a first phosphate material (S10), a step of forming a mixed solution including a second phosphate material (S20), and a first phosphate material And in the step of aging the solution containing the second phosphate material (S40), the solution containing phosphate ions is mixed.

At this time, the solution containing phosphate ions may be mixed three times at predetermined time intervals.

In other words, the initial point of the eighth time may be located later than the terminal point of the second time and the terminal point of the fifth time. For example, after a predetermined time has elapsed from the point at which the process of mixing the solution containing calcium ions and the solution containing phosphate ions (S11) is completed (terminal point of the second time), the first phosphate material and the second A process ( S41 ) of mixing a solution containing a phosphate material and a solution containing phosphate ions may be started.

In addition, after a predetermined time has elapsed from the time when the step (S21) of mixing the solution containing the second cation and the solution containing the phosphate ion is completed (the terminal point of the fifth time), the first phosphate material and the second phosphate A process ( S41 ) of mixing a solution containing a material and a solution containing phosphate ions may be started.

However, the process of mixing the solution containing calcium ions and the solution containing phosphate ions (S11) and the process of mixing the solution containing the second cation and the solution containing phosphate ions (S21) may proceed simultaneously on the time axis. Therefore, the terminal point of the second time and the terminal point of the fifth time may be the same regardless of their order on the time axis, and may be completely the same on the time axis.

In the step of aging the solution including the first phosphate material and the second phosphate material (S42), the second cation contained in the liquid phase of the mixed solution or the second cation derived from the solid second phosphate material is added to the first phosphate material. Some atoms of are substituted and bonded in atomic form, and some atoms substituted in the first phosphate material may be in the form of ions in the liquid phase. At this time, as the first phosphate material in which the second cation is partially substituted is aged, the crystal structure is changed through a phase transition to form witlockite.

For example, the crystal structure of hydroxyapatite before some calcium atoms of hydroxyapatite are replaced with magnesium atoms is a hexagonal structure. As some calcium atoms are replaced with magnesium atoms and aged, the structure of hydroxyapatite is changed to a rhombohedral structure, so that witrockite can be formed. In other words, hydroxyapatite has a Hexagonal structure, and Whitlockite has a Rhombohedral structure, which is a different structure. As hydroxyapatite in which some calcium atoms are replaced with magnesium atoms is matured, the crystal structure changes through phase transition, forming Whitlockite. It can be.

According to a preferred embodiment of the present invention, a step of forming a mixed solution including a first phosphate material (S10), a step of forming a mixed solution including a second phosphate material (S20), and combining into one mixed solution At least one process of the process (S30) and the process (S40) of aging the solution including the first phosphate material and the second phosphate material may be performed at 50°C or more and 95°C or less.

According to one embodiment disclosed by the present application, the method for producing witrockite includes forming a mixed solution including the above-described first phosphate material (S10), and forming a mixed solution including the second phosphate material In at least one or more processes of the process (S20), the process of combining into one mixed solution (S30), and the process of aging the solution containing the first phosphate material and the second phosphate material (S40), an oxidizing agent is additionally added ( or mixed). For example, in the process of forming a mixed solution containing the first phosphate material (S10), in the process of mixing the solution containing the first cation and the solution containing the phosphate ion (S11), an oxidizing agent may be added together. there is.

Alternatively, the oxidizing agent may be added prior to the initial point of the first time, which is the starting point of the process of forming the mixed solution including the first phosphate material (S10). For example, an oxidizing agent may be added to the first vessel before the process of forming the mixed solution including the first phosphate material (S10) starts.

Alternatively, the oxidizing agent may be added at a time earlier than the initial point of the fourth time, which is the starting point of the process of forming the mixed solution including the second phosphate material (S20). For example, an oxidizing agent may be added to the second vessel before the process of forming the mixed solution including the second phosphate material (S20) starts.

In other words, the method for producing witrockite by spatial separation according to the present application further includes a fifth step of mixing an oxidizing agent for the 10th time, wherein the initial point of the 10th time is the first or fourth time. It may be located at a point in time prior to the initial point, or may overlap at least a part of the first to ninth times on the time axis.

By adding an oxidizing agent, it is possible to shorten the production time required to prepare witlockite crystals.

Preferably, the oxidizing agent may be hydrogen peroxide.

In order to additionally prepare whitrockite, filtering, washing, oven drying, ball milling, and sieving processes may be further included.

Whitlockite produced according to the present manufacturing method can be used as a raw material for products such as artificial bone, dental restorative material, bone cement, oral composition, and filler inserted into the body for regeneration or treatment of human tissue.

2.1 Experimental example

In the experiment (first experiment) related to the method for producing whitlockite by spatial separation (Example 1), the content of magnesium ions was set to about 26 mol% with respect to total cations, and the molar ratio of total phosphate ions to total cations was Whitrockite was synthesized by aging at about 1 at 80°C.

6.85g(약 0.0924mol)을 증류수(125ml)에 용해시켜, 칼슘 이온을 포함하는 용액(0.74M

수용액 125mL)을 제조하고, 인산 이온을 포함하는 85% 인산용액(

) 3.81mL(107.19ml DW, 즉 0.5M

수용액 111mL)과 혼합하였다. 이후 80℃ 에서 1시간 동안 스터링(stirring)하여 칼슘 포스페이트 물질을 형성하도록 반응시켰다. In the first container, solid calcium hydroxide

6.85 g (about 0.0924 mol) was dissolved in distilled water (125 ml), and a solution containing calcium ions (0.74 M

125 mL of aqueous solution) was prepared, and an 85% phosphoric acid solution containing phosphate ions (

) 3.81mL (107.19ml DW i.e. 0.5M

111 mL of aqueous solution). Thereafter, the mixture was reacted to form a calcium phosphate material by stirring at 80° C. for 1 hour.

) 1.90g(약 0.032579mol)을 증류수(125ml)에 용해시켜, 마그네슘 이온을 포함하는 용액(0.26M

수용액 125mL)을 제조하고, 인산 이온을 포함하는 85% 인산용액(

) 2.23mL(62.77ml DW, 즉 0.5M

수용액 65mL)과 혼합하였다. 이후 80℃ 에서 1시간 동안 스터링(stirring)하여 마그네슘 포스페이트 물질을 형성하도록 반응시켰다. 이 때, 마그네슘 이온의 몰 수는 마그네슘 이온과 칼슘 이온의 몰 수의 합인 전체 양이온의 몰 수의 26몰%이다. 제1 용기와 제2 용기에서 혼합되는 각각의 인산 이온의 양(mole) 또는 인산 이온을 포함하는 인산 용액의 양(Volume)은 1.7:1의 비율로 상이하게 혼합하였다. In the second container, solid magnesium hydroxide (

) 1.90 g (about 0.032579 mol) was dissolved in distilled water (125 ml), and a solution containing magnesium ions (0.26 M

125 mL of aqueous solution) was prepared, and an 85% phosphoric acid solution containing phosphate ions (

) 2.23mL (62.77ml DW i.e. 0.5M

65 mL of aqueous solution). Thereafter, the mixture was stirred at 80° C. for 1 hour to form a magnesium phosphate material. At this time, the number of moles of magnesium ions is 26 mol% of the total number of moles of cations, which is the sum of the number of moles of magnesium ions and calcium ions. The amount (mole) of each phosphate ion or the amount (volume) of the phosphoric acid solution containing phosphate ion mixed in the first container and the second container was mixed at a ratio of 1.7:1.

Thereafter, the mixed solution in the first container and the mixed solution in the second container were combined into one mixed solution to form a mixed solution containing a calcium phosphate material and a magnesium phosphate material.

) 2.54mL(71.46 ml DW, 즉 0.5M

수용액 74mL)을 혼합하였다. 이후 80℃ 에서 23시간 동안 스터링(stirring)하여 숙성시켰다. 이 때 인산 이온이 포함된 용액이 첨가될 때, 적하 방식(Dropwise)이 아니라 세 번에 걸쳐 각각 해당하는 양의 인산을 한꺼번에 첨가하는 Pouring 방식을 이용하여 첨가하였다. Then, an 85% phosphoric acid solution containing phosphate ions in a mixed solution containing a calcium phosphate material and a magnesium phosphate material (

) 2.54 mL (71.46 ml DW, i.e. 0.5M

74 mL of aqueous solution) were mixed. Thereafter, the mixture was aged by stirring at 80° C. for 23 hours. At this time, when a solution containing phosphate ions was added, it was added using a pouring method in which a corresponding amount of phosphoric acid was added at once in three steps rather than a dropwise method.

After aging the mixed solution for 23 hours, the mixed solution was filtered, washed, oven dried, ball milled, and sieved to prepare a dried powder.

Then, the synthesized powder was analyzed through SEM and XRD, and referring to FIGS. 9 and 10, it can be confirmed that high-purity whitlockite having various shapes and fine sizes was synthesized through this experiment. The SEM Data in FIG. 9 is data magnified by 50000 times the manufactured crystal.

3. Manufacturing method of witrockite by temporal separation (Example 2)

Referring to FIG. 11, the manufacturing method of witrockite according to an embodiment of the present application includes a process of preparing a mixed solution including a first phosphate material (S100) and a process of preparing a mixed solution including a second phosphate material (S100). S200), and aging the mixed solution including both the first phosphate material and the second phosphate material (S300).

3 and 11, the manufacturing method of witrockite according to an embodiment of the present application, unlike the above-described first embodiment, includes a step of making a mixed solution including a first phosphate material (S100) and a second step. The process of making a mixed solution containing 2 phosphate materials (S200) is performed in the same container. However, unlike the first embodiment in which the manufacturing time of whitrockite was significantly reduced compared to the prior art through spatial separation, the present embodiment can shorten the manufacturing time of whitrockite compared to the prior art through temporal separation.

See Figures 11 and 12. According to one embodiment of the present application, the process of making a mixed solution containing the first phosphate material (S100) is a process of mixing a solution containing calcium ions and a solution containing phosphate ions for a first time (hereinafter, 1 process S101) and a process of forming a mixed solution by reacting the product of the first process for a second time to form a first phosphate material (hereinafter referred to as a second process S102).

After the process of preparing the mixed solution including the first phosphate material (S100) is performed, the process of preparing the mixed solution including the second phosphate material (S200) may proceed sequentially.

Referring to FIGS. 11 and 13, the process of making a mixed solution containing a second phosphate material (S200) is a process of mixing a solution containing a cation other than calcium ion, which is a second cation, and a phosphate ion for a third time. (hereinafter, a third process, S201) and a process in which the product of the third process is reacted for a fourth time to form a second phosphate material to form a mixed solution (hereinafter, a fourth process, S202).

According to the method for producing witrockite disclosed in the present application, the mixing in the first step (S101) and the reaction in the second step (S102) may preferably be performed in the same container, but they must be in the same container. It does not have to proceed from courage.

Similarly, the mixing of the third step (S201) and the reaction of the fourth step (S202) may preferably be performed in the same container, but do not necessarily have to be performed in the same container.

In other words, according to the present application, if the mixed solution containing the first phosphate material is made in a first container and the mixed solution containing the second phosphate material is also made in the same first container, the object of the present application can be sufficiently achieved. there will be

Unlike the first embodiment, since the process of making a mixed solution containing a first phosphate material (S100) and the process of making a mixed solution containing a second phosphate material (S200) can occur sequentially in one container, The mixed solution of the product of the fourth process may include both the first phosphate material and the second phosphate material.

In addition, there is a difference from the first embodiment in that a mixed solution including both the first phosphate material and the second phosphate material can be formed without a process of combining into one mixed solution (S30 in FIG. 3).

After the process of preparing the mixed solution including the second phosphate material (S200) proceeds, a process of aging the mixed solution including both the first phosphate material and the second phosphate material (S300) may proceed sequentially.

11 and 14, the process of aging the mixed solution including both the first phosphate material and the second phosphate material (S300) includes both the first phosphate material and the second phosphate material as a result of the fourth process. A process of mixing a solution containing phosphate ions with a mixed solution for a fifth time (hereinafter, a fifth process, S301) and a process of aging the result of the fifth process for a sixth time (hereinafter, a sixth process, S302) can do.

In the conventional method for producing whitlockite, calcium ions and second cations are mixed together from the beginning, and the reaction proceeds by adding a phosphoric acid supply material to an aqueous solution in which the two cations coexist, and the first phosphate and second phosphate produced Whitlockite was prepared by relying on the thermodynamic stability of phosphate as a function of pH.

However, in the conventional method for producing whitlockite, phosphate ions must be supplied dropwise to precisely control the pH, and the supply rate and amount of phosphate ions must be precisely controlled. There was a problem that it was extended and the manufacturing method was complicated.

According to a preferred embodiment of the present application, the process of forming the mixed solution including the first phosphate material (S100) and the process of forming the mixed solution including the second phosphate material (S200) may be temporally separated.

Separation in time means that after applying the first reaction condition for preparing a mixed solution containing the first phosphate material, and after a predetermined time interval has elapsed, the second reaction for preparing a mixed solution containing the second phosphate material It can mean that the condition is applied.

For example, in the step of forming a mixed solution including the first phosphate material (S100), a solution containing calcium ions and a solution containing a first amount of phosphate ions are mixed and reacted to generate a first phosphate material. can After a predetermined time has elapsed, in the step of forming a mixed solution containing a second phosphate material (S200), a solution containing a second cation and a solution containing a second amount of phosphate ions are mixed to form a second phosphate material. You can react by mixing.

Through this temporal separation, desired intermediates can be formed in each process, and whitrockite can be produced simply and intuitively without complicated control of pH to form desired intermediates.

In addition, since it is not necessary to precisely control the pH, the phosphate ion supply material can be added in a pouring manner rather than a dropwise manner, so that the manufacturing time of witrockite can be significantly reduced. In other words, according to the method for manufacturing witrockite disclosed in the present application, a method for manufacturing high-purity witrockite that takes a short manufacturing time and is simple and intuitive can be provided.

Hereinafter, with reference to FIGS. 11 to 16, each process will be described in more detail.

According to one embodiment of the present application, the process of making a mixed solution containing the first phosphate material (S100) is a process of mixing a solution containing calcium ions and a solution containing phosphate ions for a first time (first step). , S101) and a process of forming a mixed solution by reacting the product of the first process for a second time to form the first phosphate material (second process, S102).

The first phosphate material may be a phosphate material containing calcium ions. That is, it may be a calcium phosphate material. For example, it may be a material comprising hydroxyapatite, which is a calcium phosphate material, dicalcium phosphate dehydrate (DCPD), brushite, monetite, or a combination thereof. there is. However, it is not limited to the exemplified materials, and any material in which calcium ions and phosphate ions are combined can be regarded as a calcium phosphate material. Preferably, the first phosphate material may be hydroxyapatite and may exist in a solid state in the mixed solution.

The solution containing calcium ions can be prepared by dissolving in water a material containing calcium atoms and ionizing well when dissolved in water. That is, the solution containing the first cation may be prepared by dissolving a calcium ion providing material in water. The calcium ion donating material may include calcium hydroxide, calcium carbonate, calcium nitrate, and calcium acetate.

As described above, the step of forming the mixed solution containing the first phosphate material (S100) has been described as including mixing a solution containing phosphate ions and a solution containing calcium ions, but phosphate ions and calcium If a solution in which ions coexist in the solution can be prepared, the calcium ion donor may be directly mixed with the phosphate ion donor material, or the phosphate ion donor material and the calcium ion donor may be mixed together in water. will be able to be carried out

Referring to FIGS. 15 and 16, the first time means a time from the time when the solution containing calcium ions and the solution containing phosphate ions start to mix to the time when the mixing is completed, and the second time means the time from when the solution containing calcium ions starts to react with the solution containing phosphate ions to the time when the reaction is completed.

At least a portion of the first time period and at least a portion of the second time period may overlap on a time axis. That is, the reaction (S102) of generating the first phosphate material of the second process may proceed simultaneously with the mixing process (S101) of the first process. For example, as soon as mixing of a solution containing calcium ions and a solution containing phosphate ions starts, a reaction of generating a first phosphate material may occur.

According to one embodiment of the present application, at the terminal point of the first time, when the mixing process (first process) of the solution containing calcium ions and the solution containing phosphate ions is completed, calcium ions and phosphate ions are dissolved in an aqueous solution. may be included in However, since the first process (S101) and the second process (S102, which will be described below) may partly occur simultaneously, a calcium phosphate material, which is the first phosphate material, may be further included at the terminal point of the first time.

According to a preferred embodiment of the present application, in the second process (S102), a mixed solution containing a calcium phosphate material, which is a solid first phosphate material formed by reacting calcium ions with phosphate ions, may be formed. Accordingly, when the second process is completed, that is, at the terminal point of the second time, the solid calcium phosphate material may be included in the mixed solution.

According to one embodiment of the present application, the process of reacting the solution containing at least the calcium ion with the solution containing phosphate ion (S102) may be performed at 50°C or more and 100°C or less. The step of mixing the solution containing calcium ions and the solution containing phosphate ions (S101) may also be carried out at 50° C. or more and 100° C. or less, but the reaction step of forming the first phosphate (S102) is 50° C. or more and 100° C. or less. If proceeded in, the object of the present application can be achieved.

According to one embodiment of the present application, after the process of preparing a mixed solution including the first phosphate material (S100) is performed, the process of preparing a mixed solution including the second phosphate material (S200) is sequentially performed.

In the process of preparing a mixed solution containing a second phosphate material (S200), a solution containing a second cation (or a cation other than calcium ions) and a solution containing phosphate ions are mixed with the product of the second process for a third time. It may include a process of mixing during the process (third process, S201) and a process of forming a mixed solution by reacting the product of the third process for a fourth time to form a second phosphate material (fourth process, S202).

The second cation is a cation other than a calcium ion, and for example, at least one or more of Mg, Co, Sb, Fe, Mn, Y, Eu, Cd, Nd, Na, La, Sr, Pb, Ba, and K It may be in ionic form. Preferably, the second cation may be a magnesium ion.

The second phosphate material is a phosphate material containing the second cation. That is, the second phosphate material may be regarded as a material in which a second cation and a phosphate ion are combined.

), 디마그네슘 포스페이트(Dimagnesium phosphate,

), 뉴베리아이트(Newberyite), 트리마그네슘 포스페이트(Trimagnesium phosphate,

) 또는 이들의 조합을 포함하는 물질로 볼 수 있다. 다만, 예시된 물질로 제한되지 않으며, 마그네슘 이온과 인산 이온이 결합된 물질이라면 마그네슘 포스페이트 물질로 볼 수 있을 것이다. For example, if the second cation is a magnesium ion, the second phosphate material is a magnesium phosphate material, and monomagnesium phosphate (Monomagnesium phosphate,

), Dimagnesium phosphate,

), Newberyite, Trimagnesium phosphate,

) or a material containing a combination thereof. However, it is not limited to the exemplified materials, and any material in which magnesium ions and phosphate ions are combined can be regarded as a magnesium phosphate material.

)일 수 있다.In addition, if the second cation is a cobalt ion, the second phosphate material is cobalt (II) phosphate hydrate (Cobalt (II) phosphate hydrate,

) can be.

), 아이언(III) 포스페이트 테트라하이드레이트(Iron(III) phosphate tetrahydrate,

) 또는 이들의 조합을 포함하는 물질일 수 있다.In addition, if the second cation is iron ion, the second phosphate material is iron (III) phosphate dihydrate (Iron (III) phosphate dihydrate,

), iron (III) phosphate tetrahydrate,

) or a material comprising a combination thereof.

)일 수 있다.In addition, if the second cation is sodium ion, the second phosphate material is sodium phosphate (Sodium phosphate,

) can be.

)일 수 있다.In addition, if the second cation is a potassium ion, the second phosphate material is potassium phosphate tribasic (Potassium phosphate tribasic,

) can be.

)일 수 있다.In addition, if the second cation is a strontium ion, the second phosphate material is strontium phosphate (Strontium phosphate,

) can be.

)일 수 있다.In addition, if the second cation is a barium ion, the second phosphate material is barium phosphate (Barium phosphate,

) can be.

However, the second phosphate material is not limited to the exemplified material, and any material that can exist in an aqueous solution by combining the above-described second cation and phosphate ion will be regarded as the second phosphate material.

The solution containing the second cation may be prepared by dissolving in water a material that has the atomic form (X) of the second cation and is easily ionized when dissolved in water. That is, the solution containing the second cation may be prepared by dissolving the second cation providing material in water. The second cation-providing material may be X hydroxide, X carbonate, X nitrate, X acetate, and the like.

For example, when the second cation is a magnesium ion, a magnesium ion containing at least one selected from magnesium hydroxide, magnesium carbonate, magnesium nitrate, and magnesium acetate It may be supplied by a feed material, preferably by magnesium hydroxide.

As described above, the process of forming a mixed solution containing the second phosphate material (S200) has been described as mixing a solution containing a phosphate ion and a solution containing a second cation with the product of the second process, If a solution in which phosphate ions and second cations can coexist in a mixed solution can be prepared, the second cation donor may be directly mixed with the phosphate ion donor material and mixed with the product of the second process, or It may also be performed by mixing the phosphate ion-providing material and the second cation-providing material at once with the product of the second process.

For example, if the second cation is a magnesium ion, a solution containing the second cation may be prepared by dissolving solid magnesium hydroxide in water, which is mixed with a solution containing phosphate ion and the result of the second process. can be mixed. Alternatively, the solid state magnesium hydroxide material may be directly mixed with the phosphate ion donor material and then mixed with the product of the second process, or the phosphate ion donor material and magnesium hydroxide may be mixed together with the product of the second process. There will be

Referring to FIGS. 15 and 16, the third time means a time from the time when the mixing in the third process (S201) starts to the time when the mixing is completed, and the fourth time means the time in the fourth process (S201). S202) means the time from the start of the reaction to the completion of the reaction.

According to a preferred embodiment of the present application, at least a portion of the third time period and at least a portion of the fourth time period may overlap on the time axis. That is, the reaction (S202) of generating the second phosphate material of the fourth process may proceed simultaneously with the mixing process (S201) of the third process. For example, as soon as mixing between the solution containing magnesium ions and the solution containing phosphate ions and the product of the second process starts, a reaction of forming the second phosphate material may proceed.

According to one embodiment of the present application, since the mixed solution of the resultant product of the second process contains a solid calcium phosphate material, a solution containing a cation other than calcium ion, which is the second cation, and a phosphate ion are included. When the solution is completely mixed with the product of the second process, that is, at the terminal point of the third time, the calcium phosphate material, the second cation, and the phosphate ion may be included in the mixed solution. However, since the third process (S201) and the fourth process (S202, which will be described below) may partly occur simultaneously, a second phosphate material may be further included at the terminal point of the third time.

According to an embodiment of the present application, in the fourth process ( S202 ), a mixed solution including a solid second phosphate material generated by reacting the second cation with the phosphate ion may be formed. Therefore, at the time when the fourth process is completed, that is, at the terminal point of the fourth time, the mixed solution may contain the solid second phosphate material.

In addition, since the solid first phosphate material formed in the second process remains in the fourth process, the mixed solution at the terminal point of the fourth time, when the fourth process is completed, may further include the first phosphate material. there is. In other words, the mixed solution at the terminal point of the fourth time may include the first phosphate material and the second phosphate material.

According to one embodiment of the present application, at least the process of reacting a solution containing a cation other than the calcium ion with a solution containing a phosphate ion (S202) may be performed at 50°C or more and 100°C or less. The process of mixing a solution containing cations other than calcium ions and a solution containing phosphate ions (S201) may also be performed at 50 ° C or more and 100 ° C or less, but the reaction step (S202) to form the second phosphate is 50 ° C. The object of the present application can be achieved if it is carried out at 100 ° C or less.

According to a preferred embodiment according to the present application, after the mixed solution containing the solid calcium phosphate material is preferentially formed in the second process (S102), the fourth process (S202) in which the second phosphate material is formed proceeds It is characterized in that a mixed solution containing both the solid calcium phosphate material and the solid second phosphate material can be formed only from the initial point of the fourth process.

There is a difference from the first embodiment in that a mixed solution including both the first phosphate material and the second phosphate material is formed without a process of combining into one mixed solution (S30 in FIG. 3).

After the mixed solution including both the first phosphate material and the second phosphate material is formed by the fourth process, a process of sequentially aging the mixed solution including both the first phosphate material and the second phosphate material (S300) proceeds. do. At this time, conditions may be provided for sufficient phase transformation (Transform) to form witlockite from the mixed solution containing the first phosphate material and the second phosphate material.

According to one embodiment of the present application, in the step of aging the mixed solution containing both the first phosphate material and the second phosphate material (S300), the first phosphate material and the second phosphate material as a result of the fourth process are A step of mixing a solution containing phosphate ions with a mixed solution containing all of them for a fifth time (5th step, S301) and a step of aging the result of the 5th step for a 6th time (6th step, S302) can do.

15 and 16, the fifth time period is from the time when mixing of the solution containing phosphate ions with the mixed solution containing the first phosphate material and the second phosphate material starts to the time when mixing is completed. means time.

The sixth time refers to the time from the start of aging the mixed solution including the first phosphate material and the second phosphate material to form witlockite to the completion of aging.

At least part of the fifth time period and at least part of the sixth time period may overlap on the time axis. That is, the aging process (S302) of the sixth process may proceed at the same time as the mixing process (S301) of the fifth process.

For example, as soon as the solution containing phosphate ions starts to be mixed with the mixed solution containing hydroxyapatite and dimagnesium phosphate, the mixed solution containing hydroxyapatite and dimagnesium phosphate may be aged.

According to one embodiment of the present application, the mixing process (fifth process, S301) of the mixed solution containing the first phosphate material and the second phosphate material and the solution containing phosphate ions is completed, that is, at the fifth time At the terminal point, the first phosphate material, the second phosphate material, and phosphate ions may be included in the mixed solution. However, since the fifth process and the aging process (sixth process, S302) to be described below may partly occur simultaneously, whitrockite may be further included at the terminal point of the fifth time.

According to an embodiment of the present application, in the 'aging' process (sixth process, S302) of the mixed solution containing the first phosphate material and the second phosphate material and the solution containing phosphate ions, aging is performed for a sixth time. It goes on. In this step (S302), the second cations included in the liquid phase of the mixed solution or the second cations derived from the second phosphate material in the solid phase are substituted with some atoms of the first phosphate material and bonded in atomic form, Some of the atoms displaced in the phosphate material may be in the form of ions in the liquid phase. At this time, as the first phosphate material in which the second cation is partially substituted is aged, the crystal structure is changed through a phase transition to form witlockite.

For example, the crystal structure of hydroxyapatite before some calcium atoms of hydroxyapatite are replaced with magnesium atoms is a hexagonal structure. As some calcium atoms are replaced with magnesium atoms or matured, the structure of hydroxyapatite is changed to a rhombohedral structure, so that witlockite can be formed. In other words, calcium phosphate material, preferably hydroxyapatite, has a Hexagonal structure, Whitlockite has a Rhombohedral structure, which is a different structure. Whitlockite can be formed while changing.

Accordingly, at the terminal point of the sixth hour, the mixed solution may contain solid witrockite.

According to an embodiment of the present application, the 'aging' process (S302) of the mixed solution including the first phosphate material, the second phosphate material, and phosphate ions may be performed at 50°C or more and 100°C or less. The 'mixing' process (S301) of the mixed solution including the first phosphate material and the second phosphate material and the solution containing the phosphate ion may also be performed at 50 ° C. or more and 100 ° C. or less, but the first phosphate material and the second phosphate material The object of the present application can be achieved if the 'aging' process (S302) of the mixed solution containing phosphate ions is performed at a temperature of 50°C or more and 100°C or less.

According to one embodiment of the present application, a step of forming a mixed solution including a first phosphate material (S100), a step of forming a mixed solution including a second phosphate material (S200), and a first phosphate material and a second 2 In the step of aging the solution containing the phosphate material (S300), the solution containing the phosphate ion is mixed.

를 의미한다고 볼 수 있으나, 이에 제한되지는 않으며, 수용액 상에서 인산(Phosphoric acid)가 존재할 수 있는 형태를 모두 포함할 수 있다. 예를 들어,

,

,

,

모두 상기 인산 이온으로 볼 수 있다.The phosphate ion may include all types of phosphate ions that may exist depending on the pH of the aqueous solution. In general, when referring to phosphate ion,

It can be seen to mean, but is not limited thereto, and may include all forms in which phosphoric acid may exist in an aqueous solution. for example,

,

,

,

All can be regarded as the above phosphate ions.

The phosphate ion may be supplied by a phosphate feed material containing at least one selected from phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate and phosphate, preferably Preferably it can be supplied by phosphoric acid.

The solution containing the phosphate ion may be prepared by dissolving a phosphate ion-providing material (eg, diammonium phosphate, ammonium phosphate, phosphate) existing as a solid at room temperature in water or an aqueous solution. Alternatively, the phosphate ion donor material such as phosphoric acid may contain water as a solvent so that the phosphate ion donor itself contains phosphate ions.

For example, when mixing a solution containing calcium ions and a solution containing phosphate ions in the step of forming a mixed solution containing the first phosphate material (S100), an aqueous solution obtained by dissolving solid diammonium phosphate in water may be mixed with a solution containing calcium ions, or an aqueous solution of phosphoric acid containing water as a solvent in the phosphate ion providing material itself may be mixed with a solution containing calcium ions.

In addition, a process of forming a mixed solution containing a solution containing phosphate ions and a first phosphate material (S100), a process of forming a mixed solution containing a second phosphate material (S200), the first phosphate material and the second phosphate material In the step of aging the solution containing the phosphate material (S300), when the solution containing the phosphate ion is mixed, it may be mixed by a pouring method. The pouring method is different from the dropwise method, and means a method of adding all the solutions to be added in a substantially very short time at once. For example, in the conventional method for producing witrockite, a solution containing phosphate ions was continuously mixed dropwise at a volume flow rate of 12.5 ml/min. On the other hand, according to one embodiment of the method for manufacturing Whitlockite disclosed in this application, the solution containing phosphate ions can be mixed at once at a volume flow rate of 2ml/sec (120ml/min) to 130ml/sec (7800ml/min) . The mixing time of the solution containing the phosphate ion can be shortened, thereby reducing the manufacturing time of whitlockite.

That is, the first time, the third time, or the fifth time may be a substantially very short time (eg, within about 1 second). However, even in the pouring method, the first time, the third time, or the fifth time may increase from several seconds to several tens of seconds depending on the volume of the solution containing the phosphate ion to be added.

In the step of forming a mixed solution including the first phosphate material (S100) and the step of forming the mixed solution including the second phosphate material (S200), the amount (Volumne) of the solution containing the phosphate ion mixed is desired It can be determined by considering the stoichiometric ratio for forming the phosphate material and the pH of the mixed solution.

For example, in the step of forming a mixed solution including the first phosphate material (S100), the stoichiometric ratio for forming the first phosphate material, hydroxyapatite, by mixing and reacting with calcium ions is considered Phosphate ion feedstock containing one mole of phosphate ion may be mixed. In addition, a phosphate ion supply material including phosphate ions may be added in consideration of the pH of the mixed solution for stably forming the first phosphate material and maintaining a stable state. For example, in the case of using phosphoric acid (Phosphate acid) as a phosphate ion supply material, the amount of phosphate ion for stable generation of hydroxyapatite and the pH condition for stable generation and maintenance of hydroxyapatite are required. The first volume of phosphoric acid may be mixed in consideration of the amount of hydrogen ions for Alternatively, when phosphoric acid (Phosphate acid) is used as a phosphate ion supply material, after adding the amount (Volume) of phosphoric acid in consideration of the amount (Mole) of phosphate ion for stably generating hydroxyapatite, hydroxyapatite A material other than phosphoric acid may be additionally mixed to provide (or adjust) a pH that can be stably maintained. At this time, preferably, the ratio of the amount (mole) of phosphate ion to the amount (mole) of calcium ion mixed in the step of forming the mixed solution including the first phosphate material (S100) is in the range of 0.6 or more and 1.4 or less. may apply. In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

In addition, in the step of forming a mixed solution including the second phosphate material (S200), the second phosphate material, preferably dimagnesium phosphate (Dimagnesium phosphate, MgHPO4) is mixed and reacted with magnesium ions to form a stoichiometric Phosphate ion feedstock containing a proportionate amount (moles) of phosphate ions may be added. In addition, in order to stably generate the second phosphate material and maintain a stable state, a phosphate ion feed material including phosphate ions may be mixed in consideration of the pH of the mixed solution. For example, considering the amount of phosphate ions to stably generate dimagnesium phosphate from magnesium ions and phosphate ions and the amount of hydrogen ions to provide pH conditions in which dimagnesium phosphate can be stably generated and maintained, phosphoric acid The second volume (Volume) of can be mixed. Alternatively, when phosphoric acid (Phosphate acid) is used as a phosphate ion supply material, after adding the amount (Volume) of phosphoric acid in consideration of the amount (Mole) of phosphate ion for stably generating dimagnesium phosphate, dimagnesium phosphate A material other than phosphoric acid may be additionally mixed to provide (or adjust) a pH that can be stably maintained.

At this time, preferably, the ratio of the amount of phosphate ions to the amount of magnesium ions (mole) mixed in the step of forming the mixed solution including the second phosphate material (S200) may fall within the range of 0.6 or more and 5 or less. there is. In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

In the step of aging the solution including the first phosphate material and the second phosphate material (S300), the volume of the solution containing the phosphate ion mixed is a mixture of wheat from the first phosphate material and the second phosphate material. The pH conditions under which rockite can be produced or the target production amount of whitrockite may be considered and determined. For example, the volume of a phosphoric acid solution containing phosphate ions may be determined in consideration of pH conditions for producing witlockite through ion exchange between the hydroxyapatite and the magnesium phosphate. However, in the case of mixing phosphoric acid in consideration of pH conditions, substances other than phosphoric acid for pH control may be mixed, so phosphoric acid is mixed to supply phosphate ions in consideration of the target witlocite production amount, and pH Substances other than phosphoric acid for adjustment may be further mixed.

If a feed material other than phosphoric acid (e.g., diammonium hydrogen phosphate, ammonium phosphate, and phosphate) is used as the phosphate ion feed material, Along with the solution, a solution containing hydrogen ions for adjusting the pH may be further added. For example, when solid diammonium hydrogen phosphate is dissolved to form a solution containing phosphate ions and added to a mixed solution containing a first phosphate material and a second phosphate material, whitrock A solution containing hydrogen ions (or a solution for adjusting the pH) may be additionally added so that the mixed solution is aged at a pH at which kites can be stably produced.

In addition, the volume of the solution containing phosphate ions mixed in the process of aging the solution containing the first phosphate material and the second phosphate material (S300) is the total amount of cations mixed to form witlockite. It can be determined by considering the ratio of the total sum of the anion and

For example, the amount of the phosphoric acid solution required to form a certain amount of witlockite is the third volume, and the amount of the phosphoric acid solution mixed in the step of forming the mixed solution including the first phosphate material (S100) When this is the first volume and the amount of the phosphoric acid solution mixed in the step of forming the mixed solution including the second phosphate material (S200) is the second volume, the first phosphate material and the second phosphate The volume of the phosphoric acid solution mixed in the step of aging the mixed solution containing all substances (S300) can be seen as an amount obtained by subtracting the sum of the first and second amounts from the third volume.

Preferably, the amount of the phosphoric acid solution mixed in the step of aging the mixed solution containing both the first phosphate material and the second phosphate material with respect to the sum of the first amount and the second amount (S300) is 0.3 or more and 0.55 or less. range can be In the case of a ratio outside this range, substances other than witrockite may be formed in the resultant.

Also, preferably, the ratio of the first amount, the second amount, and the third amount may be 0.44 (±0.05): 0.26 (±0.05): 0.30 (±0.05).

According to one embodiment disclosed in the present application, since witrockite can be prepared by adding a predetermined amount of solution containing phosphate ions three times without the need to finely control the pH, the conventional witlockite manufacturing method It has the advantage of being able to manufacture whitlockite in a much simpler, more intuitive, and clear way.

Again, referring to FIGS. 15 and 16 , as the solutions containing phosphate ions are mixed by pouring, the terminal point of the second time may be located later than the terminal point of the first time. In other words, the process of mixing the solution containing calcium ions and the solution containing phosphate ions (S101) is completed before the time point at which the reaction to form the first phosphate material is completed (terminal point of the second time). For example, when a solution containing phosphate ions and a solution containing calcium ions are mixed within 1 second by the pouring method, a reaction for generating a first phosphate material even after the mixing is completed (terminal point of the first time) this can proceed.

Similarly, the terminal point of the fourth time may be located later than the terminal point of the third time. In other words, the process of mixing the solution containing the second cation and the solution containing the phosphate ion ( S201 ) may be completed before the reaction to form the second phosphate material is completed (terminal point of the fourth time). For example, when a solution containing phosphate ions and a solution containing second cations are mixed within 1 second by the pouring method, the second phosphate material is produced even after the mixing is completed (terminal point of the third time) reaction can proceed.

Similarly, the terminal point of the sixth time may be located later than the terminal point of the fifth time. In other words, the mixing process of the mixed solution including the first phosphate material and the second phosphate material and the solution including phosphate ions (S301) is completed when the aging process to form witrockite is completed (terminal point of the sixth time) may be completed earlier. For example, when mixing is completed within 1 second by pouring a solution containing phosphate ions into a mixed solution containing a first phosphate material and a second phosphate material, the point at which mixing is completed (terminal point of the 5th time) Even after that, a process of aging to form whitlockite may proceed.

As described above, while the solution containing phosphate ions is mixed in a substantially short time in the pouring method, the time for preparing witrockite can be significantly reduced.

In addition, according to an embodiment of the present application, a step of forming a mixed solution including a first phosphate material (S100), a step of forming a mixed solution including a second phosphate material (S200), and a first phosphate material And the solution containing the phosphate ion may be mixed three times in the step of aging the solution containing the second phosphate material (S300).

At this time, the solution containing phosphate ions may be mixed three times at predetermined time intervals.

In other words, the initial point of the fifth time may be located later than the terminal point of the first time and the terminal point of the third time. Also, the initial point of the third time may be located later than the terminal point of the first time.

For example, after a predetermined amount of time has elapsed from the point at which the process of mixing the solution containing calcium ions and the solution containing phosphate ions (S101) is completed (terminal point of the first time), to form a second phosphate material , a process of mixing a solution containing phosphate ions with a mixed solution containing a solution containing cations other than calcium ions and a first phosphate material (S201) may be started.

In addition, after a predetermined time has elapsed from the time when the step of mixing the solution containing the second cation and the solution containing the phosphate ion (S201) is completed (the terminal point of the third time), the first phosphate material and the second phosphate A process of mixing a solution containing a substance and a solution containing phosphate ions ( S301 ) may start.

In summary, the initial point of the fifth time may be located later than the terminal point of the third time, and the terminal point of the third time may be located later than the terminal point of the first time. In other words, the solution containing phosphate ions may be mixed three times with a predetermined time interval.

As described above, as a solution containing phosphate ions is mixed three times in a specific amount, it is possible to prepare whitrockite without the need to finely control the pH, which is much simpler than the conventional method for producing whitrockite. and can produce witrockite in an intuitive and clear way.

According to a preferred embodiment of the present application, at least one process in the first process to the sixth process may be performed at 50°C or more and 95°C or less.

According to an embodiment disclosed by the present application, the method for producing witrockite includes forming a mixed solution including the above-described first phosphate material (S100), and forming a mixed solution including a second phosphate material In at least one process of the process (S200) and the process (S300) of aging the solution including the first phosphate material and the second phosphate material, an oxidizing agent may be additionally added (or mixed). For example, in the process of forming a mixed solution containing the first phosphate material (S100), in the process of mixing the solution containing the first cation and the solution containing the phosphate ion (S101), an oxidizing agent may be added together. can

Alternatively, the oxidizing agent may be added prior to the initial point of the first time, which is the starting point of the process of forming the mixed solution including the first phosphate material (S100). For example, an oxidizing agent may be first added before the process of forming the mixed solution including the first phosphate material (S100) starts.

In other words, the method for producing witrockite by temporal separation disclosed by the present application further includes a seventh step of mixing an oxidizing agent for a seventh time, wherein the initial point of the seventh time is the initial point of the first time It may be located at an earlier time point or overlap with at least a portion of the first to sixth times on the time axis.

By adding an oxidizing agent, it is possible to shorten the production time required to prepare witlockite crystals.

Preferably, the oxidizing agent may be hydrogen peroxide.

In order to additionally prepare whitrockite, filtering, washing, oven drying, ball milling, and sieving processes may be further included.

Whitlockite produced according to the present manufacturing method can be used as a raw material for products such as artificial bone, dental restorative material, bone cement, oral composition, and filler inserted into the body for regeneration or treatment of human tissue.

3.1 Experimental example

In an experiment related to the method for preparing whitlockite by temporal separation (Example 2) (hereinafter, Experiment 1), the content of magnesium ions was set to 26 mol% with respect to total cations, and the molar ratio of total phosphate ions to total cations was Whitrockite was synthesized by aging at about 1 at 80°C.

)을 6.85g(약 0.0924mol)을 증류수(112.5ml)에 용해시켜, 칼슘 이온을 포함하는 용액(0.74M

수용액 125mL)을 제조하고, 인산 이온을 포함하는 85% 인산용액(

) 3.81mL(107.19ml DW, 즉 0.5M

111mL)과 혼합하였다. 이후 80℃에서 제1 반응시간 동안 스터링(stirring)하여 칼슘 포스페이트 물질을 형성하도록 반응시켰다. 제1 실험에서는 상기 제1 반응시간은 1h로 실험하였다. 30% aqueous hydrogen peroxide solution (25 ml) and solid calcium hydroxide (

) was dissolved in 6.85 g (about 0.0924 mol) of distilled water (112.5 ml), and a solution containing calcium ions (0.74 M

125 mL of aqueous solution) was prepared, and an 85% phosphoric acid solution containing phosphate ions (

) 3.81mL (107.19ml DW i.e. 0.5M

111 mL). Thereafter, the mixture was stirred at 80° C. for a first reaction time to form a calcium phosphate material. In the first experiment, the first reaction time was 1 h.

) 1.90g(약 0.032579mol)을 증류수(112.5ml)에 용해시켜, 마그네슘 이온을 포함하는 용액(0.26M

수용액 125mL)을 제조하여, 인산 이온을 포함하는 85% 인산용액(

) 2.23mL(62.77ml DW, 즉 0.5M

65mL)과 함께 상기 칼슘 포스페이트 물질이 포함된 혼합용액에 혼합하였다. 이후 80℃에서 제2 반응시간 동안 스터링(stirring)하여 마그네슘 포스페이트 물질을 형성하도록 반응시켰다. 제1 실험에서는 상기 제2 반응시간은 1h로 진행하였다. Sequentially solid magnesium hydroxide (

) 1.90 g (about 0.032579 mol) was dissolved in distilled water (112.5 ml), and a solution containing magnesium ions (0.26 M

125mL of aqueous solution) was prepared, and an 85% phosphoric acid solution containing phosphate ions (

) 2.23mL (62.77ml DW i.e. 0.5M

65mL) was mixed with the mixed solution containing the calcium phosphate material. Thereafter, stirring was performed at 80° C. for a second reaction time to form a magnesium phosphate material. In the first experiment, the second reaction time was 1 h.

) 2.54mL(71.46 ml DW, 즉 0.5M

수용액 74mL)을 혼합하였다. 이후 80℃에서 제3 숙성시간 동안 스터링(stirring)하여 숙성시켰다. 제1 실험에서는 상기 제3 숙성시간은 5h로 진행하였다. 85% phosphoric acid solution containing phosphate ions in a mixed solution containing calcium phosphate material and magnesium phosphate material in sequence (

) 2.54 mL (71.46 ml DW, i.e. 0.5M

74 mL of aqueous solution) were mixed. Thereafter, the mixture was aged by stirring at 80° C. for a third aging time. In the first experiment, the third aging time was 5 h.

At this time, when a solution containing phosphate ions was added, it was added using a pouring method in which a corresponding amount of phosphoric acid was added at once in three steps rather than a dropwise method.

The ratio of the moles of phosphate ions added three times or the ratio of the volumes of the phosphoric acid solution containing phosphate ions was mixed at a ratio of 0.444:0.260:0.296.

After aging the mixed solution for 5 h, the mixed solution was filtered, washed, oven dried, ball milled, and sieved to prepare a dried powder.

Then, the synthesized powder was analyzed through SEM and XRD, and referring to FIGS. 17 and 18, it was confirmed that high-purity whitrockite having various shapes was synthesized through the first experiment. SEM Data in FIG. 17 is data obtained by magnifying the manufactured crystal 5000 times.

In the first modified experiment of the first experiment (hereinafter referred to as the second experiment or the first modified example), the third aging time was fixed to 5 hours, and then the experiment was conducted with the first reaction time as a variable. Experiments were conducted while changing the first reaction time to 5min, 15min, 30min, and 60min, and the other experimental conditions were carried out in the same manner as in the first experiment to prepare whitlockite powder. Then, the synthesized powder was confirmed through SEM and XRD, and referring to FIGS. 19 to 21, it was confirmed that high-purity witrockite was synthesized by significantly reducing the manufacturing time to less than 7 hours through the second experiment. The SEM Data in FIG. 19 is data magnified by 10,000 times the prepared crystal. In (a) of FIG. 19, the first reaction time is 5 min, (b) is the first reaction time is 15 min, and (c) is the first reaction time. 1 reaction time is 30 min, (d) is SEM Data when the first reaction time is 60 min. 20 (a) shows that the first reaction time is 5 min, (b) shows that the first reaction time is 15 min, (c) shows that the first reaction time is 30 min, and (d) shows that the first reaction time is 60 min. It is XRD Data in case of .

In the second modified experiment of the first experiment (hereinafter referred to as the third experiment or the second modified example), the first reaction time was fixed to 60 min, and the experiment was conducted with the third aging time as a variable. Experiments were conducted while changing the third aging time to 5 h and 10 h, and the other experimental conditions were carried out in the same manner as in the first experiment to prepare whitrockite powder.

Then, the synthesized powder was analyzed through SEM and XRD, and referring to FIGS. 22 and 23, it was confirmed that high-purity witrockite was synthesized by significantly reducing the manufacturing time to less than 12 hours through the third experiment. The SEM Data in FIG. 22 is data magnified by 50000 times the manufactured crystal. 22 (a) is SEM data when the third aging time is 5 h, and (b) is 10 h.

In the third modified experiment of the first experiment (hereinafter referred to as the fourth experiment or the third modified example), the first reaction time was fixed at 15 min, and the experiment was conducted with the third aging time as a variable. Experiments were conducted while changing the third aging time to 30min, 1h, 3h, and 5h, and other experimental conditions were carried out in the same manner as in the first experiment to prepare whitlockite powder.

Then, the synthesized powder was analyzed through SEM and XRD, and referring to FIGS. 24 to 26, it can be confirmed that high-purity witrockite was synthesized even within 6 hours, particularly within 2 hours, through the fourth experiment. Therefore, it was confirmed that the manufacturing time of Whitrockite was considerably shortened. The SEM Data in FIG. 24 is data magnified by 10000 times of the manufactured crystal, and FIG. 3 The aging time is 1h, (d) is SEM data when the third aging time is 30min. In (a) of FIG. 25, the third aging time is 5 h, (b) is the third aging time is 3 h, (c) is the third aging time is 1 h, and (d) is the third aging time is 30 min. It is XRD Data in case of .

In the above, the configuration and characteristics of the present invention have been described based on the embodiments and drawings according to the present invention, but the present invention is not limited thereto, and various changes or modifications can be made within the spirit and scope of the present invention. It is apparent to those skilled in the art to which it pertains, and therefore such changes or modifications are intended to fall within the scope of the appended claims.

Claims (22)

A method for producing witrockite comprising the following steps:
A first process comprising: adding a first solution containing calcium ions and a second solution containing phosphate ions to a first container, or adding a third solution containing calcium ions and phosphate ions;
At this time, the amount of phosphate ions added in the first step is the first amount,
At this time, the first process is performed for a first time;
A second process comprising: reacting the material in the first vessel after the initial point of the first time to form a first phosphate material;
At this time, the second process is performed for a second time, and the terminal point of the second time is located later than the terminal point of the first time;
A third process comprising: adding a fourth solution comprising a first cation and a fifth solution comprising a phosphate ion to the first container, or adding a sixth solution comprising the first cation and phosphate ion added,
At this time, the first cation is a cation other than calcium ion,
At this time, the amount of phosphate ions added in the third step is the second amount,
At this time, the third process is performed for a third time, and the initial point of the third time is located at a point later than the terminal point of the first time;
A fourth process comprising: reacting the material in the first vessel after the initial point of the third time to form a second phosphate material;
At this time, the fourth process is performed for a fourth time, and the terminal point of the fourth time is located at a point later than the terminal point of the third time;
A fifth process comprising: adding a seventh solution containing phosphate ions to the first vessel;
At this time, the fifth process includes a mixing process of mixing the materials in the first container,
At this time, the amount of phosphate ions added in the fifth step is the third amount,
In this case, the fifth process is performed for a fifth time, and the initial point of the fifth time is located later than the terminal point of the third time; and
A sixth process comprising: aging the material in the first vessel after the initial point of the fifth hour;
At this time, the sixth process is performed for a sixth time, and the terminal point of the sixth time is located later than the terminal point of the fifth time.
According to claim 1,
The first process further comprises a mixing process of mixing the materials in the first container,
A method for producing whitrockite.
According to claim 1,
The third process further comprises a mixing process of mixing the materials in the first container,
A method for producing whitrockite.
According to claim 1,
At least part of the first time and at least part of the second time overlap,
At least part of the third time and at least part of the fourth time overlap,
At least part of the fifth time and at least part of the sixth time overlap,
A method for producing whitrockite.
According to claim 1,
Characterized in that the phosphate ion is supplied by a phosphate ion supply material containing at least one selected from phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate, and phosphate. to do,
A method for producing whitrockite.
According to claim 1,
The calcium ions are supplied by a calcium ion supply material containing at least one selected from calcium hydroxide, calcium carbonate, calcium nitrate, and calcium acetate. to do,
A method for producing whitrockite.
According to claim 1,
The first cation is a magnesium ion, and the magnesium ion is magnesium including at least one selected from magnesium hydroxide, magnesium carbonate, magnesium nitrate, and magnesium acetate. Characterized in that supplied by an ion supply material,
A method for producing whitrockite.
According to claim 1,
Whitrockite production method further comprising a seventh process including:
Adding an oxidizing agent to the first vessel.
According to claim 8,
The seventh process includes a mixing process of mixing materials in the first container,
At this time, the seventh process is performed for a seventh time,
At this time, the initial point of the seventh time is located at a time point earlier than the initial point of the first time, is located at any time point between the initial point of the first time and the terminal point of the sixth time, or the sixth time which is located at a point later than the terminal point of
A method for producing whitrockite.
According to claim 1,
The ratio of the third amount to the sum of the first amount and the second amount (third amount / (first amount + second amount)) is 0.3 or more and 0.55 or less,
Method for producing whitrockite.
According to claim 1,
The amount of the first cation added in the third step is the fourth amount,
The ratio of the second amount to the fourth amount (second amount / fourth amount) is 0.6 or more and 5 or less,
A method for producing whitrockite.
According to claim 1,
The first phosphate material is a material including hydroxyapatite, dicalcium phosphate dehydrate (DCPD), brushite, monetite, or a combination thereof,
A method for producing whitrockite.
The method of claim 1, wherein the second phosphate material is monomagnesium phosphate (Mg(H ₂ PO ₄ ) ₂ ), dimagnesium phosphate (MgHPO ₄ ), newberyite, trimagnesium phosphate (trimagnesium phosphate, Mg ₃ (PO ₄ ) _2- ) or a material containing a combination thereof,
A method for producing whitrockite.
According to claim 1,
At least one or more of the first to sixth processes are carried out at 50 ° C or more and 95 ° C or less,
A method for producing whitrockite.
According to claim 1,
A method for producing whitlockite, further comprising an eighth step including at least one of filtering, washing, oven drying, ball milling, and sieving.
According to claim 15,
The eighth process is performed after the sixth process,
A method for producing whitrockite.
According to claim 1,
Any one or more of the first solution to the seventh solution is added to the first container by a pouring method,
A method for producing whitrockite.
According to claim 1,
Any one or more of the first solution to the seventh solution is added to the first container at a volume flow rate of 2 ml / sec or more,
A method for producing whitrockite.
According to claim 1,
Wherein the first step further comprises adding the first cation to the first vessel.
According to claim 1,
At the terminal point of the second hour, the solution in the first container comprises the first phosphate material.
A method for producing whitrockite.
According to claim 1,
At the terminal point of the fourth hour, the solution in the first vessel comprises the second phosphate material.
A method for producing whitrockite.
According to claim 1,
At the terminal point of the fourth hour, the solution in the first container comprises the first phosphate material and the second phosphate material.
A method for producing whitrockite.

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