JPS63123854A - Hardenable material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a curable material having self-hardening properties upon hydration, and more particularly to a curable material that forms a hardened apatite body and is useful as a biomaterial, particularly an oral cavity material. .

(Prior art) Calcium-phosphorus apatite, which is a type of calcium phosphate, has the theoretical formula Ca (PO) Y = (1) (Y represents an anion such as OH'-, CfV, F-, etc.) . Here, the gram atom ratio of Ca/P is theoretically lo/cs', t, a7, but in reality it is C
It is said that it is possible to form an apatite structure with an a/P ratio in the range of 1.3 to 2.0. Therefore, various general formulas have been proposed.1For example, Ca(HP O) (P
O4) 6-Xy 2-x・-(2)10-x
4 x (Y has the same meaning as above, and 0≦X≦2).

This calcium-phosphorus apatite is the same as the main mineral component of teeth and bones.

Therefore, it has excellent in-vivo compatibility and is easily assimilated into living hard tissue, a property not found in other biomaterials, so it is widely used as biomaterials such as artificial tooth roots and filling materials for bone defects. is being studied.

Calcium-phosphorus apatite, which has such excellent properties, has been used as a biomaterial in the past 2. For example, after molding apatite powder using a method such as mold press molding or casting molding, it is fired to form a ceramic material. Generally, attempts have been made to obtain a desired molded article.

However, with this molding method, it is extremely difficult to precisely mold biomaterials with desired dimensions and complex shapes, and this is true when individual treatments require molded bodies with different shapes and dimensions. It was impossible to do anything about it.

As a method to solve this problem, a method has been proposed in which an apatite molded body is obtained by curing a slurry or paste-like substance containing an apatite precursor at near biological temperature (Japanese Patent Application Laid-Open No. 88351/1989, Kaisho 59-18
Publication No. 2263 and Gypsum and Lime No. 188% 19
84).

According to the technology disclosed in the above-mentioned publications and documents, apatite hardens within a relatively short period of time at around biological temperature by adding an organic or inorganic acid or a readily aqueous solution of halide to tricalcium phosphate. It is possible to generate a body.

(Problems to be Solved by the Invention) However, according to the studies of the present inventors, in order to actually use the hardened apatite body obtained by the techniques disclosed in the above-mentioned publications and documents as a biomaterial, the following steps must be taken. It is clear that there are still problems that need to be resolved.9
Ta.

That is, in the above method, (1) the hardness of the obtained cured product is low, and only a Knoop hardness of about 6 kg/mm1 can be obtained.

(2) The generated cured product easily disintegrates in water.

(3) The shrinkage rate during curing is large, and the obtained cured product lacks dimensional accuracy, making it difficult to fit it to the affected area.

(Means for Solving the Problem) Therefore, the present inventors further investigated the curable material made of the above-mentioned calcium-phosphorus apatite precursor, and found that a curable material made of calcium phosphate, acids, and water was developed. By combining one or more compounds containing metal atoms that can form divalent or trivalent ions other than calcium, a cured product with higher hardness and even better stability in water and prevention of shrinkage during curing can be obtained. The present invention was completed based on the discovery that the following can be obtained.

That is, the present invention provides a hydrated self-hardening calcium phosphate containing calcium and phosphorus in a gram atom ratio of Ca/P = 1.3 to 2.0, and a metal ion may be contained in the calcium phosphate. , metal atoms that can become divalent or trivalent ions other than calcium (hereinafter referred to as
The object of the present invention is to provide a curable material characterized by comprising a compound (hereinafter simply referred to as a dissimilar metal compound) of a dissimilar metal (hereinafter simply referred to as a dissimilar metal compound) and an acid.

The present invention will be explained in detail below.

The hydrated self-hardening calcium phosphate used in the present invention is 1
For example, calcium diphosphate and calcium carbonate
/P ratio is mixed at a desired ratio, and the mixture is baked at 700 to 1400°C for about 1 to 6 hours. In addition, calcium diphosphate was heated to 500 to 600℃.
Calcium phosphate with good curing reactivity can be obtained by calcining it at a temperature of 700 to 1400℃ for about 1 to 4 hours after converting it to -H calcium pyrophosphate, adding calcium carbonate, adjusting the desired Ca/P ratio, and then calcining it again at 700 to 1400℃ for about 1 to 4 hours. This is particularly preferable because it provides the following.

It is not preferable to use calcium phosphate whose firing temperature is outside the above range because the rate of conversion into hardened apatite will be slow.

Note that the Ca/P gram atom ratio in calcium phosphate is 1.3 to 2. O1 is preferably in the range of 1.4 to L,S. If calcium phosphate outside this composition range is used, the difference from the Ca/P gram atom ratio of the theoretical composition of apatite is too large, so even if hardening accelerators such as acids are added and kneaded, it will not convert to an apatite structure. It is difficult to obtain a good cured product.

The dissimilar metals constituting the dissimilar metal compound used in the hardening material of the present invention include Fe, Co, and Ni.

Those that can be divalent or trivalent ions, such as Zn, Mg, AfL%Sr, Y, Mn, and Sn, are effective. These different metal compounds are oxides, water oxides, or salts of inorganic or organic acids such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, citric acid, oxalic acid, and acetic acid. Note that among these different metal compounds, those that are soluble in water may be added in the form of an aqueous solution.

By adding water to an uninvented curable material and kneading and curing them, the dissimilar metal in the dissimilar metal compound replaces a part of Ca in the apatite, but in the present invention, this dissimilar metal is may be used as a different metal-containing calcium phosphate.

The method for preparing this different metal-containing calcium phosphate is 1. For example, calcium diphosphate is mixed with a predetermined amount of a different metal compound, calcined at 500 to 600°C for 1 to 4 hours, calcium carbonate is added to this powder, and further heated to 700 to 1400°C. It can be prepared by baking for 1 to 4 hours. It can also be prepared by mixing a predetermined amount of a different metal compound and calcium carbonate and firing the mixture at 700 to 1400°C for 1 to 6 hours.

In the present invention, acids are used as curing accelerators. Examples of acids used in the present invention include lower-basic fatty acids such as formic acid, acetic acid, and propionic acid; malic acid, glycolic acid;
Hydroxycarboxylic acids such as lactic acid, citric acid, sugar acid, and ascorbic acid; Acidic amino acids such as glutamic acid and aspartic acid; Oxalic acid, malonic acid, succinic acid, geltaric acid, adipic acid, maleic acid, fumaric acid, muconic acid, etc. Dibasic acids; keto acids such as pyruvic acid, acetoacetic acid, and levulinic acid; salicylic acid, benzoic acid, and cinnamic acid.

Aromatic carboxylic acids such as phthalic acid; inorganic acids such as diphosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid; and salts such as alkali metal, alkaline earth metal, or ammonium salts of these acids; and carboxylic acid groups can be easily converted by hydrolysis. There are derivatives of the above-mentioned organic acids that are generated, such as acid anhydrides and acid chlorides.

Examples of inorganic acids include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and their salts such as alkali metal, alkaline earth metal, or ammonium salts.

Among these, organic acids are particularly preferred.

These acids have the effect of shortening curing time and increasing hardness. When these acids are used as curing accelerators, the pH of the aqueous solution is preferably 2.5 to 6.0 from the viewpoint of curing speed and physical properties of the cured product. 0 range, more preferably 3.0~
It is in the range of 5.0゛.

The curable material of the present invention preferably contains a fluoride in addition to the above components. That is, by adding calcium phosphate, a different metal compound, an acid, and water and kneading and hardening these, an apatite having a composition in which a part of Ca is replaced with a different metal in the general formula (2) of the apatite and Y is substantially OH is obtained. A cured product is obtained, and by using a fluoride in addition to the above components, a cured product of fluoroapatite containing different metals, in which part or most of Y is F, can be obtained.

Such preferably used fluorides include alkali metal salts of hydrofluoric acid such as sodium fluoride, lithium fluoride, potassium fluoride, cesium fluoride, and rubidium fluoride, ammonium fluoride, acidic ammonium fluoride,
Examples include calcium fluoride, titanium fluoride, and tin fluoride.

Furthermore, fluorides of different metals are also preferably used.

The hardened apatite body obtained from the curable material of the present invention containing a different metal has a higher hardness than the hardened apatite body that does not contain the different metal. Furthermore, the effect is increased by using a fluorine compound in combination. That is, it is thought that by using a fluorine compound in combination, the foreign metal and fluorine are quickly incorporated into the calcium phosphate of the apatite precursor, resulting in a physically and chemically stable hardened body of fluoroapatite containing a different metal.

Further, the curable material of the present invention is mixed with water in order to advance the curing reaction. The amount of water is theoretically required to be at least 1/3 mole per P (1 mole as PO4) for the curing reaction. However, in consideration of kneading properties, workability, etc., an appropriate amount of water can be used, but usually H20/PO4
The molar ratio is preferably about 1/3 to 50.

The curable material of the present invention refers to an uncured or uncured material made of a combination of the above-mentioned components.The method of use thereof is to prepare each component separately and knead it with water before use. The desired hardened product may be obtained by curing, but for example, the following powder components and liquid components (water or aqueous solution) may be used.
That is, it is preferable to prepare a powder part and a liquid part separately, and knead and harden them before use to obtain the desired cured product.

For example, (i) the powder component is composed of calcium phosphate, a different metal compound, and an acid (e.g., an organic acid), and the power source component is water, and (if) the powder component is calcium phosphate and a different metal compound.

- When the power source body part is an acid aqueous solution; (iii) When the powder component is calcium phosphate; - When the power source body component is an aqueous solution of a different metal compound and an acid. In these cases, when fluoride is used as described above, it can be added to the powder part and/or liquid part of each of the above combinations. As a modification of the above cases (i) and (ii), powdered calcium phosphate containing a different metal may be used.
These are typical usage modes of the curable material of the present invention, but of course the usage is not limited thereto.

In the curable material of the present invention, the powder component and the liquid component are preferably used in a weight ratio of 10.0:2.0 to 10.0:5.0. The fluidity of the kneaded mixture of the body component and the liquid component is insufficient and it is difficult to form it into the desired shape. Both are undesirable.

The amount of the different metal compound used in the curable material of the present invention is determined by the gram atom ratio M of the different metal atoms (herein, the different metal atoms are expressed as Me) to the phosphorus content in calcium phosphate.
Preferable as a/P (f2.5x10-4 or more, kt) Good! b〈is used at 5.0x10-4 or more. The amount of different metal compound is 2.5xlO as the above molar ratio
If the value is less than -', the effect of the present invention is unlikely to appear; on the other hand,
The upper limit of the content of the different metal compound is not particularly limited, but is preferably 3XIO-3 or less, and the above M e / P gram atom ratio is 6X10-
Even if it is used in an amount larger than 3, the effects of the present invention will not particularly increase.

Further, the amount of acids used in the curable material of the present invention is 2X10-5■ol/g to 1.2x relative to calcium phosphate.
The acid content is preferably in the range of 10-31 of/g; if the acid content is less than this lower limit, it will take a long time to cure, and if it exceeds the upper limit, the curing rate will be too fast and the operability will deteriorate.

When fluoride is used in the curable material of the present invention, the molar ratio F/Po4 with PO4 in calcium phosphate is 0. O
It is preferable that the range is 2N2.33. If the content is less than this lower limit, the effect of adding fluoride will not be exhibited. On the other hand, if it exceeds 0.33, the theoretical formula (1) Ca
As is clear from 1o (P 04 )6Y2, only excess fluoride remains in the cured apatite body,
No further improvement in the effect of containing fluoride was observed.

(Function of the invention) In the present invention, it is important to use calcium phosphate containing a different metal in the curable material, or to use calcium phosphate and the above-mentioned different metal compound together. The resulting hardened apatite body has a higher hardness than one that does not contain a different metal. Although the reason for this is not yet clear, it is presumed as follows. That is, when calcium phosphate having a Ca/P gram atom ratio of 1.3 to 2.0 as an apatite precursor is kneaded with an aqueous solution of acids, it is converted to apatite, which is the most stable among various calcium phosphates.
A hardened body is formed, but at this time gold (different from Ca) i! One possible reason is that the inclusion of an appropriate amount of atoms (different metals) makes it easier for the apatite precursor to transition from calcium phosphate to apatite. Therefore, it is preferable that the calcium phosphate precursor and the different metal compound are mixed as uniformly as possible, and it is more effective to include the different metal compound when preparing the calcium phosphate, and also from the viewpoint of workability during use. Considering this, it is preferable because the number of types of powder components to be blended is reduced and it is simple.

(Effects of the Invention) The curable material of the present invention is mixed in the presence of a predetermined amount of water, kneaded, and left to stand to give a hardened material made of apatite with excellent hardness.

In order to use a curable material as a biomaterial, if the time required for self-curing of the curable material is too long or too short, clinical operations become difficult. Preferably, the time required for curing can be easily controlled depending on the intended use.

According to the curable material of the present invention, by adjusting the amount of acid added and the pH of the acid aqueous solution, it is possible to change the curing time within a range of about 5 minutes to several hours at a relatively low temperature near the biological temperature. .

In addition, the cured product made of the curable material of the present invention hardly shrinks during the curing process, so when it is filled into a living body, no gap is created at the interface between the living body and the filler.
Therefore, the filling material has excellent compatibility with the living body.

Two basic functions are required of biomaterials. One of these is its functional strength as a material, and the other is its biocompatibility. Mechanical strength includes hardness, compressive strength, bending strength, etc., and in order to maintain these at a constant level, it is necessary that the cured product is sufficiently cured. In order to see whether the cured product continues to function as a cured product, which is the basic function when applied to living organisms, the cured product made of the curable material of the present invention was stored in water and observed whether it disintegrated or not. As a result, the cured product did not collapse and continued to maintain its shape. Further, when the hardness, which expresses the physical properties of the cured products, was measured, all of the cured products had Knoop hardness values of 22 to 29. Moreover, it is noteworthy that when the cured product was stored in artificial saliva instead of water, the surface hardness increased over time, and some were observed to reach a Knoop hardness of about 65. Therefore, it is shown that the cured product obtained from the curable material of the present invention has improved mechanical strength and physical properties.

It can be said that it is an excellent biomaterial. Furthermore, in order to examine the biocompatibility of the cured product based on the present invention, defects were created in the alveolar bone of pegle dogs and filled with the mixture, and the subsequent progress was observed, and it was confirmed that it is excellent as an oral filling material. .

In addition, in many cases, the hardened cement material, which is composed of an inorganic powder and a liquid component containing a water-soluble mechanical polymer, has a consistency derived from the water-soluble organic polymer, which makes it difficult to perform kneading operations or treatments. It was creating difficulties. However, since the cured product of the curable material of the present invention does not use an organic polymer as a component, it does not have the problems of viscosity or stringiness as described above, and is easy to operate. is also a feature.

(Examples) Next, the present invention will be described in more detail based on Examples. Note that the percentages below indicate weight percentages unless otherwise specified.

Example I Ca HP O4235, 01g and Fe(P
O) 0.41 g was thoroughly mixed and fired in an electric furnace at 550° C. for 2 hours. 367-29 g of Ca CO was added to 170 g of the above calcined powder cooled to room temperature, thoroughly mixed, calcined again in an electric furnace at 1200° C. for 2.5 hours, and then cooled to obtain Fe-containing calcium phosphate. Chemical analysis of this calcium phosphate was carried out to reveal CaO54.1%, P
Results were obtained of 2O44B, 1%, and Fe471ppm.

4. Fe-containing calcium phosphate obtained by the above procedure.
0g to 1M citric acid solution (however, the pH is adjusted with ammonia water)
1.01i (adjusted to 4.5) was added and thoroughly kneaded. This kneaded product was poured into a mold with an inner diameter of 12mm and a height of 5mm, which was a combination of an acrylic resin ring and a glass plate at the bottom. was measured. The curing time was defined as the time required until no trace of the Vigor needle was left. the result.

Setting time was 5 minutes and curing time was 19 minutes. The hardness after 24 hours of curing was 24 on the Knoop hardness.

Further, this cured product was stored in artificial saliva having the following composition kept at 37° C., and changes in Knoop hardness were observed. Result 1
25 kg/mm” after 60 days, and 40.0 kg after 60 days.
/mm''. The results are summarized in Table 1.

Liquid A; Ammonium chloride (NH, C) 0.466g
Potassium chloride (C1) 2j24g Potassium monophosphate (K12PO4) Q, 7B8gN
a3(C,H2O7)' 2H200,0206g2
06g phosphorus Ha2HPO40,750g urine
Add 346 g of elementary (NH2)2C00 and dissolve the above components to make 14 u.

Solution B: Calcium chloride dihydrate (CaC12・2H□0) 0.4
20g Magnesium chloride CMgC12) Add 0.04g water to dissolve the above components and make 11.

When used, liquid A and liquid B are mixed at a volume ratio of 1:1.

Example 2 Fe-containing calcium phosphate was prepared in exactly the same manner except that the Fe content was changed. Its chemical analysis value is Ca0 5
3.8%, P2O 545.4%, and Fal 180 ppm. This Fe-containing calcium phosphate was kneaded with the same 1M citric acid solution (pH 4, 5) used in Example 1 at the same powder/liquid ratio, and an evaluation test was conducted in the same manner as in Example 1. The results are summarized in Table 1.

Example 3 A powder obtained by sufficiently mixing 4 g of Fe-containing calcium phosphate prepared in Example 1 and 0.1339 g of calcium fluoride was mixed with a 1M aqueous citric acid solution (however, the pH was adjusted with aqueous ammonia).
Adjusted to 4, 5) 1. Od was added and thoroughly kneaded. Evaluation experiments were conducted in the same manner as in Example 1.

The results are summarized in Table 1.

Examples 4 to 7 Various dissimilar metal compounds (n) were thoroughly mixed with Ca HP 04 (I) in the proportions shown in Table 1 below, and this was sintered in an electric furnace at 550''C for 2 hours. Ca CO was added to the calcined powder (In) obtained by cooling to room temperature.
3(Pi) was added in the proportions shown in Table 1 below, thoroughly mixed, fired again in an electric furnace at 1200° C. for 2.5 hours, and then cooled to obtain calcium phosphate containing different metals. Chemical analysis of this calcium phosphate was conducted. The results are shown in Table 1.

1 sol of 1M citric acid aqueous solution (adjusted to pH 4.5 with aqueous ammonia) was added to the powder obtained by sufficiently mixing 4 g of the above-mentioned dissimilar metal-containing calcium phosphate and 0.1339 g of calcium fluoride, and thoroughly kneaded. Example 1 below
An evaluation test was conducted in the same manner.

Example 8 041000 g of Ca HP was calcined in an electric furnace at 550° C. for 2 hours. The above fired powder 65 cooled to room temperature
8 g of Ca CO:l 259 was added to 0 g, thoroughly mixed, fired again in an electric furnace at 1200° C. for 2.5 hours, and then cooled to obtain tribasic calcium phosphate. Chemical analysis of this calcium phosphate was carried out and found that Ca054.1% and P2O
A result of 545.5% was obtained.

4g of the above tricalcium phosphate and calcium fluoride (
After thoroughly mixing 11,339 g of magnesium chloride and 1 mg of magnesium chloride, a 1M aqueous citric acid solution (
(However, the pH was adjusted to 4.5 with aqueous ammonia) was added to the mixture and thoroughly kneaded. Evaluation tests were conducted in the same manner as in Example 1. The results are summarized in Table 1.

Comparative Example 1 The same 1M citric acid solution (pH 4,5) as that used in Example 1 using the tribasic calcium phosphate synthesized in Example 8
were kneaded at the same powder/liquid ratio as in Example 1, and an evaluation test was conducted in the same manner as in Example 1. The results are summarized in Table 1.

Reference Example 1 The same 1M citric acid aqueous solution (p
1 m of H4,5) was added and thoroughly kneaded. An evaluation test was then conducted in the same manner as in Example 1. The result is the first
They are summarized in the table.

Application example 3.0 g of calcium fluoride mixed powder of 7.0 g of α-tertiary calcium phosphate and 3.5 g of β-tertiary calcium phosphate
g, 3 mg of magnesium chloride, and 3 ml of an aqueous citric acid solution having a pH of 4.0 were added and kneaded to obtain a miscible kneaded product.

Next, a biocompatibility test was conducted on this material. The left and right molars of the upper and lower jaws of a 12-month-old male peagle dog, which had completed its permanent dentition, were used as experimental subjects.

Prior to the experiment, the gingival periosteal flap was peeled off under infiltration anesthesia with xylocaine, an intramuscular injection of Ketaral 50 (0,3 g/kg) and an intravenous injection of Nembutal (0, J1 g/kg), and the gingival periosteum flap was removed using an air turbine (1 x 3 x 2 mm). ) A bone defect cavity was formed. The bone defect cavity was filled with the above mixed mixture, and the gingival-periosteal flap was sutured with braided thread. A fluorescent labeling agent was administered every 4 weeks, and after 18 months, the jawbone was delaminated, the extracted jawbone was divided into sections with a saw, fixed in 10% neutral formalin, a portion was decalcified, dehydrated in an ethanol series, and embedded in paraffin. went. Slice this into approximately 4 cm pieces, add hemato, xylin,
Eosin (H, E) staining etc. were applied and microscopic examination was performed.

Furthermore, other parts were used as samples for non-deashing, and were dehydrated with an ethanol series, transparentized with styrene, embedded in resin, and sliced into polished specimens, which were observed using fluorescence microscopy, microradiography, polarized light microscopy, etc. On the other hand, bone formation was observed by XMA opacity in X-ray radiography.

According to fluorescence microscopy, the orange color of TetraCycling's fluorescent labeling agent indicated that the alveolar bone in the defect was new bone. However, a layer of soft tissue was observed at the boundary with the cementum, and polarized light microscopy revealed it to be a regular fibrous material. Furthermore, microradiography and X-ray radiography also confirmed this, and there was a clear alveolar hard line (a whitish, clearly outlined line in which the bone material is arranged very densely and has high X-ray absorption) in the regenerated alveolar bone. Admitted.

In addition, microscopic examination using H, E staining, Van Gieson staining, etc. of decalcified thin sections revealed that a layer of soft tissue perpendicular to the cementum was periodontal ligament fibers. In other words, it was suggested that when filled into the alveolar bone, it had a buffering effect (against occlusal pressure) and could also act as a periodontal ligament-shaped J& (promoting) agent.

As is clear from Table 1, which summarizes the experimental results of Examples and Comparative Examples, the initial surface hardness of the cured products obtained in Examples 1 to 8 containing different metals was 22 to 29 as Knoop hardness.
The value of kg/mrn' is shown. Furthermore, the surface hardness in artificial saliva increased over time and reached a high value of 45 to 63 after 65 days.

Among these, the increase in hardness was particularly large when a different metal and a fluorine compound were used together.

In all of the examples, the fluidity of the kneaded body was good,
The hardened material is removed from the molding ring (in which the kneaded material is poured).
〈It was suggested that the shrinkage rate during curing was extremely small.
When the dimensional change over time of the cured product immersed in artificial saliva was actually measured, no dimensional change was observed even after 65 days.

On the other hand, as shown in Comparative Example 1, when neither a different metal nor a fluoride was contained, the initial surface hardness of the cured product was an extremely low Knoop hardness of 6 kg/mrn'.

Furthermore, as is clear from the results of an application example in which the curable material of the present invention was used to fill a bone defect cavity formed in the jawbone of a peagle dog, the curable material of the present invention has excellent biocompatibility, and the filling cured material The formation of regular fibrillar material was observed at the interface between the tooth and the alveolar bone, suggesting that it also serves as a material for (promoting) periodontal ligament formation. Therefore, the curable material according to the present invention is extremely useful as a biomaterial.

Claims (1)

[Claims] 1. Calcium and phosphorus as gram atom ratio Ca/P
= hydrated self-hardening calcium phosphate contained in a ratio of 1.3 to 2.0, and a divalent or trivalent compound other than calcium that may be contained as a metal ion in the calcium phosphate.
A curable material characterized by being composed of a compound of metal atoms that can become valent ions and an acid. 2. The content of metal atoms (Me) that can become divalent or trivalent ions other than calcium is Me/P = 2.5 × as a gram atom ratio to the phosphorus content in calcium phosphate.
The curable material according to claim 1, which has a hardness of 10^-^4 or more. 3. The content of metal atoms (Me) that can become divalent or trivalent ions other than calcium is Me/P = 2.5 × as a gram atom ratio to the phosphorus content in calcium phosphate.
10^-^4 to 6 x 10^-^3, the curable material according to claim 1 or 2. 4. Metal atoms that can become divalent or trivalent ions other than calcium include Fe, Co, Ni, Zn, Mg, Al,
The curable material according to claim 1, which is at least one selected from the group consisting of Sr, Y, Mn, and Sn. 5. The curable material according to claim 1, wherein the hydrated self-hardening calcium phosphate contains a metal atom other than calcium that can be divalent or trivalent. 6. The curable material according to claim 1, wherein the curable material contains a fluoride. 7. The content of fluoride is 0.01 to 0.0 as the molar ratio F/PO_4 to the phosphate group in calcium phosphate.
6. The curable material of claim 6, which is No. 33.