JP5234538B2 - Cement composition, cement kit, cement, and method for producing cement - Google Patents

Description

  The present invention relates to a cement composition, a cement kit, a cement, and a method for producing the cement.

Calcium phosphate is a group of bioactive materials having almost the same composition and structure as inorganic substances found in hard tissues such as vertebrate bones and teeth, and exhibiting biocompatibility.
Above all, hydroxyapatite does not cause rejection of the living body or necrosis even when implanted in the living body, and has the property of being easily assimilated and joined to living hard tissue, so it is expected as a repair material for bone defects and bone voids. Yes. The material forms of hydroxyapatite include dense bodies, porous bodies, granules, cement, and the like, but apatite cement that can be molded into an arbitrary shape is a material that is expected to develop in the future.

Patent Document 1 discloses that apatite has a chemical composition of Ca _10-x (H, Na) _x (PO ₄ ) ₆ (OH) _2-x · nH ₂ O (provided that 0.05 <x <0.4). , N = 2x), hydroxyapatite is disclosed.

Patent Document 2 discloses a powder characterized in that it contains hydrated and hardened calcium phosphate as a main component and contains granules that are crushed with a load of 200 g or less. It is described that a water-soluble polymer such as a polysaccharide can be contained from the viewpoints of maintaining the viscosity of the calcium phosphate paste, improving the form-imparting property of the calcium phosphate paste, and suppressing disintegration in vivo. Examples are dextran or dextran sulfate.
However, since the conventional apatite cement is accompanied by an acid / base reaction when cured, there is a problem in that local pH fluctuation occurs before curing in vivo and an inflammatory reaction is induced.
As a means for solving this problem, there is a method of Patent Document 3. Patent Document 3 discloses a cement material characterized by containing microcrystals in which inositol phosphate, phytic acid, or a salt thereof is adsorbed on the surface of a calcium compound.

Japanese Patent Laid-Open No. 5-229807 JP 2006-130122 A JP 2005-95346 A

  The problem to be solved by the present invention is to prepare a cement composition that is excellent in curability, cures without changing pH at the time of curing, and can adjust the solid-liquid ratio according to the application, and the cement composition In addition to providing a cement kit, it is to provide a cement excellent in biocompatibility and compressive strength and a method for producing the cement.

The above object of the present invention has been achieved by the following means.
<1> A cement composition obtained by kneading a cement material containing a calcium salt powder having inositol phosphate adsorbed on a surface thereof and a kneading liquid containing a polysaccharide, inositol phosphate and a solvent. ,
<2> The cement composition according to <1>, wherein the polysaccharide is a polysaccharide having an acidic group.
<3> The cement composition according to <1>, wherein the polysaccharide is dextran sulfate.
<4> The cement composition according to any one of <1> to <3>, wherein the inositol phosphate contained in the kneading liquid is phytic acid,
<5> The cement composition according to any one of <1> to <4>, wherein the calcium salt is hydroxyapatite,
<6> The cement according to any one of <1> to <5>, wherein the calcium salt powder having inositol phosphate adsorbed on its surface is a calcium salt powder having phytic acid adsorbed on its surface. Composition,
<7> Cement material containing calcium salt powder having inositol phosphate adsorbed on its surface, cement kit containing polysaccharide, inositol phosphate and solvent, wherein the cement material and solvent are packaged separately Cement kit, characterized by
<8><1> to <6> Cement characterized by curing the cement composition according to any one of
<9> Cement material preparation step of preparing a cement material containing calcium salt powder having inositol phosphate adsorbed on its surface, a kneading solution preparation step of preparing a kneading solution containing polysaccharide, inositol phosphate and solvent, A method for producing cement, comprising: a cement composition preparing step for kneading the cement material and the kneading liquid; and a curing step for curing the cement composition.

ADVANTAGE OF THE INVENTION According to this invention, it provides the cement kit which is excellent in sclerosis | hardenability, hardens | cures without a pH change at the time of hardening, and can adjust fluidity | liquidity according to a use, and the said cement composition. be able to.
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a cement excellent in biocompatibility and compressive strength and cement can be provided.

I. Cement composition The cement composition of the present invention was obtained by kneading a cement material containing calcium salt powder having inositol phosphate adsorbed on the surface thereof and a kneading liquid containing polysaccharide, inositol phosphate and solvent. It is characterized by that.
Hereinafter, the present invention will be described in detail.

1. Cement Material In the present invention, the cement material includes calcium salt powder having inositol phosphate adsorbed on its surface. In the present invention, the term “inositol phosphate” includes a salt thereof and is synonymous with “inositol phosphate and / or a salt thereof” unless otherwise specified.
(1) Inositol Phosphate Inositol phosphate used in the present invention includes inositol monophosphate, inositol diphosphate, inositol triphosphate, inositol tetraphosphate, inositol pentaphosphate, and phytic acid (inositol hexaphosphate). Can be mentioned.
The salt of inositol phosphate is preferably an alkali metal salt or an alkaline earth metal salt, such as sodium salt, potassium salt, magnesium salt, calcium salt and barium salt.
Among these, a mode in which phytic acid, phytic acid sodium salt or phytic acid potassium salt is used alone or in combination of two or more thereof is preferable. When using phytic acid, it is preferable to adjust the pH to 6 to 11 with sodium hydroxide or potassium hydroxide and use it as sodium phytate or potassium phytate.
There are several types of sodium phytate having different crystal water contents, such as sodium phytate 38 hydrate, sodium phytate 47 hydrate, sodium phytate 12 hydrate, and the like. However, any of them can be preferably used.

  In the present invention, the method for producing phytic acid or phytic acid alkali metal salt is not particularly limited, and any method may be used. For example, phytic acid sodium salt is extracted from diluted defatted plant seed powder with dilute hydrochloric acid, precipitated into insoluble copper salt, iron salt, etc., purified and then converted to sodium salt and added with alcohol to precipitate. Can be obtained.

(2) Calcium salt <Calcium salt>
As the calcium salt, calcium phosphate, calcium carbonate and the like are preferably used. These may be used alone or in combination of two. When one kind is used alone, it is preferable to use calcium phosphate.

  As the calcium phosphate, hydroxyapatite, α-tricalcium phosphate, β-tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, and amorphous calcium phosphate are preferable. Apatite, α-tricalcium phosphate, and β-tricalcium phosphate are more preferable, and hydroxyapatite is particularly preferable. These may be used alone or in combination of two or more.

<Specific surface area>
In the present invention, the specific surface area of the powder of the calcium salt was adsorbed inositol phosphate on the surface is preferably from 60~150m ² / g, more preferably 80~130m ² / g, 90~120m More preferably, it is ² / g. Within the above numerical range, the inositol phosphate is sufficiently adsorbed on the surface of the calcium salt powder, so that a sufficient chelate site is obtained, and when used as a cement material, a cement having a sufficient compressive strength is obtained. can get.

The specific surface area (SPA) of the powder can be measured by the BET method using a micromeritics automatic specific surface area measuring apparatus Flowsorb III2305 (manufactured by Shimadzu Corporation). Liquid nitrogen was used as the refrigerant. The saturated adsorption amount correction value was calculated using the following equation.
S = (273.2 / temperature (° C.)) × (atmospheric pressure (mmHg) / 760) × ((6.023 × 10 ²³ × 16.2 × 10 ⁻²⁰ ) / (22.414 × 10)) × ( 1- (ratio of nitrogen (%) × atmospheric pressure (mmHg)) / 775)
The amount of gas adsorbed on the powder when the sample was cooled with the refrigerant (adsorption data) and the amount of gas released from the powder when the sample was taken out of the refrigerant (desorption data) were measured. Desorption data was adopted as experimental values.

<Half-width by X-ray diffraction>
In the present invention, the half width of the diffraction line on the (002) plane of the hydroxyapatite powder by X-ray diffraction is preferably 0.30 to 0.45 °, and preferably 0.32 to 0.45 °. More preferably, it is 0.35-0.45 degree.
Cement having sufficient compressive strength is obtained when the value is within the above range.

The orientation of crystallites such as hydroxyapatite, determination of crystal structure and identification of constituent crystal components, evaluation of crystallinity, and evaluation of the three-dimensional texture of crystallites can be performed together by X-ray diffraction.
Above all, the crystallinity is evaluated by measuring the half width of each diffraction line. The half width of the (002) plane of the hydroxyapatite powder can be calculated based on a diffraction peak having a Bragg angle (2θ) of 25.6 °. The half width is the width of the diffraction peak at a position where the intensity is halved, and the unit is an angle. When this half-value width increases, it means that the crystallinity is low. The crystallinity is determined by the crystallite size and the lattice strain, and the crystallinity is lowered when the crystallite is small and the lattice strain is large. Therefore, in the present invention, a calcium salt powder having a large half width and low crystallinity is preferable.

<Method for producing calcium salt powder>
There are no particular limitations on the method for producing the calcium salt powder used in the cement material, and any method may be used. Examples of the method for producing the calcium salt powder include a dry method, a semi-dry method, and a wet method, and the wet method is preferable. With the wet method, high-purity calcium salt powder with low crystallinity and a large specific surface area can be mass-produced efficiently.

(3) Cement material manufacturing method 1
<Manufacture of calcium salt powder by wet method>
The case where the calcium salt powder used in the present invention is produced by a wet method will be described.
In the present invention, the method for producing a calcium salt powder comprises (Step 1) a step of obtaining a precipitate by mixing a solution containing calcium ions adjusted to be alkaline and a solution containing phosphate ions (Step 2). Preferably, the method includes a step of aging the system containing the precipitate while obtaining alkalinity to obtain a calcium salt powder, and (step 3) a step of recovering and drying the calcium salt powder.

(Step 1) and (Step 2) will be described.
(Step 1) In the step of obtaining a precipitate by mixing a solution containing calcium ions adjusted to alkalinity and a solution containing phosphate ions, the method of mixing is not limited. For example, the simultaneous mixing method, one side Any of a mixing method or a combination thereof may be used.
The simultaneous mixing method is a method in which a solution containing calcium ions adjusted to alkalinity and a solution containing phosphate ions are simultaneously injected into a precipitation tank for forming calcium phosphate, and as one example, a solution in which precipitation of calcium salt is generated. Examples include a method of maintaining a constant ratio between the calcium ion concentration and the phosphate ion concentration in the phase, that is, a so-called controlled double jet method.
The one-side mixing method is a method of forming a calcium salt precipitate by adding a solution containing phosphate ions (or calcium ions) to a calcium ion excess (or phosphate ion excess) solution adjusted to be alkaline. The one-side mixing method will be described below by taking as an example the synthesis of hydroxyapatite as a calcium salt.
When a solution containing phosphate ions is added dropwise to a solution containing calcium ions such as calcium hydroxide that has been adjusted to be alkaline in advance, and the system containing the resulting precipitate is aged while keeping it alkaline, a hydroxyapatite powder is obtained. It is done. As an alkaline substance for adjusting the pH of the solution, ammonia is preferably used. The pH in the reaction solution is preferably 7 to 12, and more preferably 10 to 11.
The concentration of the solution containing calcium ions is preferably 0.5 to 2.0M, more preferably 0.7 to 1.5M, and still more preferably 0.9 to 1.1M. Moreover, it is preferable that the density | concentration of the solution containing a phosphate ion is 0.3-1.2M, It is more preferable that it is 0.42-0.9M, It is further that it is 0.54-0.66M preferable.

When the calcium salt is hydroxyapatite, the ratio of Ca element to P element contained in the hydroxyapatite powder is preferably Ca element / P element = 1.60 to 1.70, 1.63 to 1 More preferred is .69. Adjustment of the ratio of Ca element and P element is performed by adjusting the concentration ratio of the solution containing calcium ions and the solution containing phosphate ions. For example, by setting the ratio of the molar concentration of the solution containing calcium ions to the molar concentration of the phosphoric acid aqueous solution to 5: 3, the ratio of Ca element to P element in the solution can be about 1.67.
When the ratio of Ca element to P element is within the above numerical range, hydroxyapatite powder can be efficiently obtained. Further, when hydroxyapatite in the above range is used as a cement material, a cement having excellent compressive strength can be obtained.

  In (Step 1), the temperature of the reaction vessel is generally 20 to 70 ° C., preferably 30 to 50 ° C., particularly preferably 30 to 40 ° C. Within the above numerical range, an apatite crystal having a high specific surface area can be easily prepared.

  In order to prevent carbon dioxide in the air from being taken into the calcium salt powder, the series of operations is preferably performed in an inert gas atmosphere such as nitrogen gas. In this method, the purity of the material used is reflected in the purity of the calcium salt powder obtained. Therefore, if a high-purity material is used, a high-purity calcium salt powder can be obtained.

(Step 3) The step of recovering and drying the calcium salt powder will be described.
The step of collecting and drying the calcium salt powder is preferably freeze drying or heat drying at 50 to 150 ° C., more preferably freeze drying. When freeze-dried, a calcium salt powder having a large specific surface area can be obtained.
When the step of collecting and drying the calcium salt powder is freeze drying, the drying temperature is preferably −150 to 0 ° C., more preferably −80 to −10 ° C., and −50 to − More preferably, it is 30 ° C. The drying time is preferably 1 to 48 hours.
When the step of collecting and drying the calcium salt powder is heat drying, the drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and 90 More preferably, it is -120 degreeC. The drying time is preferably 1 to 48 hours.
Conventionally, organic components and the like have been removed from calcium salt powder by heat treatment, immersion in an acidic solution, or the like in order to reduce rejection from living organisms to be applied. In the case of heat treatment, organic components and the like can be removed by heat treatment at 300 to 700 ° C. for 1 to 1,000 hours.
Furthermore, the calcium salt powder from which the organic component was removed was calcined at 600 to 1,400 ° C. to adjust the crystal grain size, porosity, orientation, and mechanical properties of the calcium phosphate material.
The calcium salt used for the cement material produced by the wet method does not contain a substance that causes rejection from the living body. Therefore, it is not necessary to remove organic components by heat treatment. Further, a calcium salt powder having a low crystallinity and a large specific surface area can be obtained by freeze drying or heat drying in the range of 50 to 150 ° C. without calcining at 600 to 1,400 ° C.

<Median diameter>
The median diameter of the calcium salt powder used for the cement material is preferably in the range of 3 to 50 μm, more preferably 5 to 20 μm. A powder having a large specific surface area can be obtained within the above numerical range, so that a cement having excellent compressive strength can be obtained. The median diameter of the powder can be calculated using, for example, a laser diffraction / scattering particle size distribution analyzer LA-300 (manufactured by Horiba, Ltd.).

<Particle size distribution>
The particle size distribution of the calcium salt powder is such that the ratio (volume%) of the powder having a particle diameter of 3 to 50 μm is preferably 60% or more of the whole, more preferably 80% or more of the whole. .
This ratio is, for example, plotted from the measurement results using a laser diffraction / scattering particle size distribution measuring apparatus LA-300 (manufactured by Horiba, Ltd.), and the relationship between the particle diameter and frequency integration is plotted in the range of 3 to 50 μm. It can be obtained from the frequency integration amount.

<Crusher>
In the present invention, in order to increase the specific surface area of the calcium salt, it is preferable to further include a step of mechanically pulverizing the calcium salt powder. Mechanical pulverization can not only increase the specific surface area but also efficiently reduce the crystallinity.
As a method of mechanically pulverizing calcium salt powder, various pulverizers can be used. As the pulverizer, a known one can be used as long as the specific surface area and particle diameter of the powder can be within a desired range, and the pulverizer is not limited, but specifically, a vertical roller Examples thereof include a mill, a high-speed rotation mill, a container drive medium mill, a medium stirring mill, and the like. Among these, a container drive medium mill is preferable.
A container drive medium mill is a fine pulverizer in which a pulverization medium such as steel balls, ceramic balls, cobblestones, steel rods, pebble or beads is filled in a cylindrical mill container and pulverized by driving the mill container. Machine. Depending on the motion mode of the mill, it is roughly classified into a rolling mill, a vibration mill and a planetary mill, and a planetary mill can be preferably used. Further, the type of grinding medium is classified into a ball mill, a pebble mill, a rod mill and the like, and a ball mill is preferable. Accordingly, a planetary ball mill can be preferably used in the present invention.
The planetary ball mill is of a type that revolves around the center axis of the mill parallel to the rotation axis while the cylindrical crushing vessel rotates, and as a specific example, planetary ball mills P-4, P-5, P-6 and P-7 (made by FRITSCH) can be mentioned.

The planetary ball mill may use any conventionally known grinding media, and is not limited to steel balls (SWRM, SUJ ₂ , SUS440, chrome steel), ceramics (high alumina, steatite, zirconia (oxidized). Zirconium), silicon carbide, silicon nitride), glass (general soda glass, non-alkali glass, high bee), super hard sphere (tungsten carbide), natural stone (flint SiO ₂ ), plastic polyamide, etc. can be exemplified, among which zirconia ( Zirconium oxide) can be preferably used.
The Mohs hardness of the grinding medium is preferably 8.0 to 9.0. Within the above numerical range, the medium can be used repeatedly without being worn or damaged. The Mohs hardness of zirconia is 8.5. The diameter of the grinding medium is preferably 2 to 40 mm, and more preferably 10 to 20 mm.

In the present invention, the pulverization is preferably wet pulverization.
Generally, wet pulverization is more suitable for producing fine powder than dry pulverization. This is a synergistic effect of reducing the surface energy of the particles by wetting the particle surface (Rehinder effect) and maintaining the dispersed state of the crushed material in the mill by suppressing the cohesive action between the particles. This is probably due to the effect. Further, when fine pulverization is performed in a dry process, fine particles are coated with a pulverizing medium to cause a cushioning phenomenon and reduce the pulverization efficiency.

<Adsorption of inositol phosphate>
In order to adsorb the inositol phosphate on the surface of the calcium salt powder, the calcium salt powder is preferably immersed in a dilute solution of inositol phosphate. Inositol phosphate is considered to be chemically adsorbed on the surface of calcium salt powder by dipping treatment.

  After the calcium salt powder is mixed with an inositol phosphate aqueous solution and adsorbed on the powder surface, the powder is separated and dried to adsorb the inositol phosphate on the surface. Can be obtained.

  When using an aqueous solution of inositol phosphate, an aqueous alkaline solution is preferably added to the aqueous solution in advance to adjust the pH to 6 to 11, and more preferably to pH 6 to 8. The aqueous alkali solution used for adjusting the pH is not particularly limited, and examples thereof include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution.

The concentration of the inositol phosphate aqueous solution is preferably 1,000 to 10,000 ppm, more preferably 1,000 to 5,000 ppm, and still more preferably 1,000 to 2,500 ppm.
The molar ratio of inositol phosphate and calcium salt is preferably 0.001 to 0.1, and more preferably 0.001 to 0.05.

There is no particular limitation on the method of adsorption, and a method of separating the target powder after immersing the calcium salt powder in an aqueous solution of inositol phosphoric acid and completing the adsorption while stirring or shaking appropriately can be exemplified. .
The mixing temperature is preferably 20 to 60 ° C, and more preferably 20 to 40 ° C. The mixing time is preferably 2 to 24 hours, and more preferably 2 to 10 hours.

  The drying temperature of the powder adsorbed with inositol phosphate is preferably freeze-dried or heat-dried at 50 to 150 ° C., and is freeze-dried, as in the step of collecting and drying the calcium salt powder. More preferred. The drying time is preferably 12 to 48 hours, more preferably 12 to 24 hours.

  The cement material prepared by the above method is composed of a powder in which inositol phosphate or the like is adsorbed on the surface of a calcium salt powder. In particular, adsorption of inositol phosphates and the like on calcium salt powder can be approximated to uniform adsorption of a monolayer from a Langmuir plot of the adsorption isotherm.

(4) Cement material manufacturing method 2
The following method can also be adopted as a method for producing a cement material.
Specifically, a step of obtaining a precipitate by mixing a solution containing calcium ions adjusted to alkalinity, a solution containing phosphate ions, and a solution containing inositol phosphate, and a system containing the precipitate A cement material production method characterized by comprising a step of aging while maintaining alkalinity to obtain a powder of calcium salt having inositol phosphate can be adopted.
That is, unlike the production method in which inositol phosphate is adsorbed on the calcium salt powder, a solution containing inositol phosphate is added simultaneously when the calcium salt is synthesized. The method for mixing the solution is not limited to the above-described method for producing the cement material, but any one of the one-side mixing method, the simultaneous mixing method, or a combination thereof may be used.

2. Kneading liquid The kneading liquid contains a polysaccharide, inositol phosphate and a solvent.

(1) Polysaccharides Polysaccharides known in the art can be used, but are not limited, polysaccharides extracted and isolated from plants, animals, etc., polysaccharides produced by microorganisms modified by genetic engineering techniques, Polysaccharides obtained by chemical synthesis can be used.

In the present invention, the polysaccharide is preferably a water-soluble polysaccharide.
Specific examples of water-soluble polysaccharides that can be used in the present invention include microorganism-derived polysaccharides, plant-derived polysaccharides, seaweed-derived polysaccharides, and mammal-derived polysaccharides.
More specifically, polysaccharides derived from microorganisms such as dextran, curdlan, pullulan and xanthan, polysaccharides derived from plants such as hemicellulose, pectin, sap (gum), starch and cellulose, alginic acid, polyuronic acid salt and sulfated galactan ( And polysaccharides derived from seaweed such as agar, porphyran, carrageenan) and polysaccharides derived from mammals such as glycogen, chitin and proteoglycan (chondroitin sulfate, dermatan sulfate). In addition to the above polysaccharides, bacterial polysaccharides, complex carbohydrates, glycoproteins, glycolipids and the like can be mentioned.

The polysaccharide that can be used in the present invention is preferably a polysaccharide having an acidic group. In the present invention, unless otherwise specified, “polysaccharide having an acidic group” is synonymous with “polysaccharide having an acidic group and / or a salt thereof”. A polysaccharide having an acidic group has a high solubility in water and can easily enjoy the effects of the present invention.
In the present invention, polysaccharides having acidic groups include those obtained by chemically introducing acidic groups to known polysaccharides, polysaccharides having naturally derived acidic groups, and those obtained by further chemically introducing acidic groups.
Examples of the acidic group include a carboxy group (—COOH), a sulfuric acid group (—OSO ₃ H), a phosphoric acid group (—OPO ₃ H ₂ ), and among them, a carboxy group and a sulfuric acid group are preferable.
Examples of the salt of polysaccharide having an acidic group include salts with alkali metals such as sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt and calcium salt, etc. Among them, sodium salt, potassium salt and the like Alkali metal salts are preferred.

Specific examples of the polysaccharide having an acidic group that can be used in the present invention include dextran sulfate, heparin, carrageenan, chondroitin sulfate, sulfated lentinan, fucoidan, xylofuran sulfate, ribofuran sulfate, cellulose sulfate, curdlan sulfate, keratan sulfate, Examples include dermatan sulfate, heparan sulfate, hyaluronic acid, carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, carboxymethyl starch, xanthan gum, alginic acid, pectin, and salts thereof. The said polysaccharide which has an acidic group can be used 1 type or in combination of 2 or more types.
In the present invention, the polysaccharide having an acidic group is preferably a polysaccharide having a sulfate group and / or a carboxy group, more preferably dextran sulfate, alginic acid and salts thereof, and further preferably dextran sulfate.

In the present invention, a known polysaccharide having a sulfate group introduced may be used.
As a method for introducing a sulfate group into a polysaccharide, a known method can be used. For example, 10 to 30 ml of an ice-cooled solvent is prepared for 1 g of the raw material polysaccharide, and a sulfating agent is added 2 to 6 times to 1 g of the raw material polysaccharide. A sulfate group can be introduced by adding 1 g of the raw material polysaccharide to this solvent and reacting at 0 to 100 ° C. for 1 to 10 hours.
As the sulfating agent, any known sulfating agent can be used as long as it is used for sulfation of saccharides, and examples thereof include, but are not limited to, sulfur trioxide-pyridine complex, sulfur trioxide-trimethylamine complex, chloro Examples thereof include a sulfonic acid-pyridine complex and dicyclohexylcarbodiimide-sulfuric acid.
As a solvent to be used, pyridine, N, N-dimethylformaldehyde, N, N-dialkylacrylamide and the like can be used.

  The produced polysaccharide can be purified by purification operations commonly used in the production of various modified polysaccharides. For example, neutralization, desalting by dialysis, an operation for recovering a precipitate by addition of an organic solvent, a recovery operation by lyophilization, and the like can be mentioned.

  The molecular weight of the polysaccharide is not particularly limited, and those having a molecular weight of about 5,000 to 2,000,000 can be preferably used. Within the above numerical range, it is easy to adjust the fluidity of the cement composition while maintaining excellent compressive strength, and a cement composition having excellent handling properties can be provided.

  The concentration of the polysaccharide contained in the kneaded liquid is preferably 1 to 40% by weight, more preferably 10 to 40% by weight, and still more preferably 20 to 30% by weight. Within the range of the above numerical values, the viscosity of the kneaded liquid is appropriate, so that the produced cement composition is excellent in handling properties and the resulting cement is excellent in compressive strength.

(2) Inositol phosphate In the present invention, the kneading liquid contains inositol phosphate. Unless otherwise specified, the term “inositol phosphate” is synonymous with “inositol phosphate and / or a salt thereof”.
Examples of inositol phosphates that can be used in the present invention include inositol monophosphate, inositol diphosphate, inositol triphosphate, inositol tetraphosphate, inositol pentaphosphate, phytic acid (inositol hexaphosphate), Of these, phytic acid is preferred.
The salt of inositol phosphate is preferably an alkali metal salt or an alkaline earth metal salt, such as sodium salt, potassium salt, magnesium salt, calcium salt, barium salt, etc. Among them, sodium salt and potassium salt are preferable.
When using phytic acid, it is preferable to adjust the pH to 6-8 with sodium hydroxide or potassium hydroxide and use it as sodium phytate or potassium phytate.
There are several types of sodium phytate having different crystal water contents, such as sodium phytate 38 hydrate, sodium phytate 47 hydrate, sodium phytate 12 hydrate, and the like. However, any of them can be preferably used.

  In the present invention, the method for producing phytic acid or phytic acid alkali metal salt is not particularly limited, and any method may be used. For example, phytic acid sodium salt is extracted from diluted defatted plant seed powder with dilute hydrochloric acid, precipitated into insoluble copper salt, iron salt, etc., purified and then converted to sodium salt and added with alcohol to precipitate. Can be obtained.

  The kneading liquid used in the present invention may contain a plurality of the above inositol phosphates, but preferably contains phytic acid alone.

  The kneaded liquid preferably contains 5,000 to 20,000 ppm of inositol phosphate, more preferably 7,000 to 15,000 ppm, and even more preferably 8,000 to 12,000 ppm. Within the above numerical range, the cement composition has excellent handling properties, and the resulting cement has excellent compressive strength.

(3) Solvent Examples of the solvent contained in the kneaded liquid include water and a mixture of water and an aqueous organic solvent such as ethanol. In the present invention, water is preferable.

(4) Additives In addition to the polysaccharide and inositol phosphate, additives can be added to the kneading liquid as necessary. Examples of the additive include water-soluble polymers, and well-known ones can be used, but proteins such as collagen, gelatin and derivatives thereof can be used.
Depending on the disease to be applied, physiologically active substances such as anti-rheumatic therapeutic agents, anti-inflammatory agents, antibiotics, antitumor agents, osteoinductive factors, retinoic acid, retinoic acid derivatives, etc. may be added.

(5) Property of kneaded liquid The pH of the kneaded liquid is preferably pH 6.0 to 8.0, and more preferably pH 6.0 to 7.5. A cement composition having excellent biocompatibility is obtained when the value is within the above range.

3. Cement composition The cement composition of the present invention is obtained by kneading the cement material and the kneading liquid. In the cement composition of the present invention, the fluidity can be adjusted according to the use by appropriately adjusting the solid-liquid ratio representing the amount (volume) of the kneading liquid used per unit weight of the cement material. is there.
Examples of the use of the cement composition include a case where a cement composition having high fluidity is preferable, for example, when a cement composition is injected into a bone defect using a syringe. Moreover, when filling a bone defect part with a cement composition with a spatula etc., or when producing the molded article applied to a bone defect part etc., the case where the cement composition which has low fluidity is preferable is mentioned. The fluidity of the cement composition of the present invention can be adjusted by adjusting the solid-liquid ratio, and in any case, a cement having excellent compressive strength can be provided.

The solid-liquid ratio (weight of calcium salt powder (g) / volume of kneading liquid (ml)) representing the amount (volume) of the kneading liquid used per unit weight of the cement material is 1 / 0.30-1 /1.00 is preferable, and 1 / 0.35 to 1 / 0.80 is more preferable. Cement excellent in compressive strength is obtained as it is in the above-mentioned numerical range.
When the cement composition is injected with a syringe or the like, such as when a filling site such as a bone defect is narrow, the solid-liquid ratio is preferably 1 / 0.70 to 1 / 1.00, and 1 / 0.0. More preferably, it is 70-1 / 0.80. Within the above numerical value range, even when filling a defective part having a complicated shape, it is possible to fill every corner and to provide a cement having excellent compressive strength.
Moreover, when filling a bone defect part with a cement composition with a spatula etc., or when producing a molded article, 1 / 0.30 / 1 / 0.50 is preferable, and 1 / 0.30 is preferable. 1 / 0.40 is more preferable. Cement excellent in compressive strength can be obtained as it is in the range of the above-mentioned numerical value.

  The pH of the cement composition is preferably pH 6.0 to 8.0, and more preferably pH 6.0 to 7.5. A cement composition having excellent biocompatibility is obtained when the value is within the above range.

II. Cement kit The cement kit of the present invention is a kit containing a cement material containing a calcium salt powder having inositol phosphate adsorbed on its surface, a polysaccharide, inositol phosphate, and a solvent, and at least the cement material and the solvent And is packaged separately. The cement material, polysaccharide, inositol phosphate and solvent contained in the cement kit of the present invention are the same as the cement material, polysaccharide, inositol phosphate and solvent that can be used in the cement composition, and preferred embodiments Is the same.
Furthermore, the cement kit of the present invention is preferably one in which the cement material and a kneading liquid containing a polysaccharide, inositol phosphate and a solvent are separately packaged. The kneading liquid contained in the cement kit is the same as the kneading liquid used for the preparation of the cement composition, and the preferred embodiment is also the same. Hereinafter, the cement kit of the present invention will be described.

Long-term storability is achieved by separately packaging the cement material and the solvent that react and harden when brought into contact with each other among the cement material, polysaccharide, inositol phosphate and solvent contained in the cement kit of the present invention. An excellent cement kit can be provided. By using the cement kit of the present invention, a kneading liquid is prepared at a necessary place when necessary, and further, the cement composition of the present invention can be prepared by kneading the cement material and the kneading liquid.
Those that do not react by contact are preferably packaged and stored and transported. For example, a kit in which the cement material and a kneaded liquid prepared in advance are packaged separately is convenient to carry. Since it is not necessary to prepare a kneading liquid at the time of use, it is preferable because a cement composition can be quickly prepared.
A preferred embodiment of the cement kit according to the present invention includes the cement kit according to <7>, wherein the cement material and a kneaded solution in which a polysaccharide and inositol phosphate are dissolved in water are separately packaged. The polysaccharide is preferably dextran sulfate, and the inositol phosphate is preferably phytic acid. Moreover, the range of the amount (solid-liquid ratio) of the kneading liquid used for the cement material contained in the cement kit of the present invention is the same as the range of the solid-liquid ratio in the cement composition, and the preferred range is also the same.

The cement kit of the present invention may be provided with a delivery device such as a syringe for feeding the cement composition to a target site when the cement composition is used, and the cement material and the kneading liquid are kneaded immediately before use. A container, a tool such as a rubber spatula, etc. may be attached.
Further, the kit of the present invention may contain the above-mentioned additives.

III. Cement and Cement Production Method The cement of the present invention is characterized by curing the cement composition of the present invention.
Further, the method for producing a cement of the present invention includes a cement material preparation step for preparing a cement material containing a calcium salt powder having inositol phosphate adsorbed on its surface, a kneading liquid containing a polysaccharide, inositol phosphate and a solvent. A kneading liquid preparing step for preparing the cement material, a cement composition preparing step for kneading the cement material and the kneading liquid, and a curing step for curing the cement composition. The cement material preparation step, the kneading liquid preparation step, and the cement composition preparation step are as described above.

A curing process for curing the cement composition will be described.
When the affected area such as a bone defect is filled with the cement composition of the present invention, it begins to harden in 1 to 5 minutes after kneading, and hardens to become cement within 20 minutes. Furthermore, the compressive strength becomes maximum 5 to 10 hours after kneading. Since the cement composition of the present invention has a short setting time, the treatment time can be shortened, and the patient's pain can be reduced.

  Unlike the conventional apatite cement, the cement of the present invention does not cause an acid / base reaction at the time of curing, so there is no pH change before and after curing. Furthermore, pH fluctuations are suppressed by the buffering action of inositol phosphate contained in the kneaded liquid. Therefore, the cement of the present invention is less likely to cause an inflammatory reaction. In addition, new bone is easily generated and easily integrated with a hard tissue of a living body.

According to the present invention, it is possible to provide a cement having excellent compressive strength even when the solid-liquid ratio is low (the amount of the kneading liquid is large) as compared with the conventional cement described in Patent Document 3. It was possible, and it became possible to adjust the fluidity | liquidity of a cement composition according to a use.
Therefore, it can be preferably used for the mode of injection with a syringe or the like, and even when the filling part such as a bone defect part is narrow or when filling a defect part having a complicated shape, the cement composition can be filled to every corner. It is.

  The compressive strength of the cement of the present invention is preferably 22 MPa or more, more preferably 25 MPa or more, and further preferably 30 MPa or more. The compressive strength of the cement obtained so far in the present invention is 22 to 34 MPa, and it can be applied to a part such as a waist part where a relatively load is applied.

  With the advent of an aging society, it is self-evident that treatment related to “compressed fractures” peculiar to the elderly will increase, and the “high-strength chelate-curing bone repair cement” provided by the present invention is injected with a syringe or the like. By applying this technique to a compression fracture of the spine, it is possible to construct a clinically minimally invasive treatment method (with less burden and influence on the body). This new cement treatment method promises to improve QOL (quality of life) from a global perspective. The cement of the present invention can be used for treatment of fractures, osteoporosis, rheumatoid arthritis and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to an Example.
In the following examples, “hydroxyapatite” is “HAp”, “phytic acid” is “IP ₆ ”, and “hydroxyapatite powder having phytic acid adsorbed on the surface” is “HAp / IP ₆ powder”. Also referred to as “body”.

1. Preparation of wet synthetic HAp powder and wet synthetic HAp / IP ₆ powder (1) Preparation of wet synthetic HAp powder A 0.5 M calcium hydroxide suspension 500 cm ³ was prepared and 0.3 M phosphoric acid aqueous solution was prepared. 500 cm ³ was dropped (dropping rate: 17 ml / min). The concentrations of calcium hydroxide and phosphoric acid were adjusted to be Ca / P = 1.67 (molar ratio). Further, pH of the reaction tank was adjusted at 10 <pH <11 become as pH adjusting agents (25% NH ₄ OH). After completion of the dropwise addition of the phosphoric acid aqueous solution, the mixture was further stirred for 1 hour, and then left to stand in an incubator set at 37 ° C. for 24 hours for aging. After aging, the HAp slurry was collected by suction filtration and frozen overnight in a -80 ° C freezer. The frozen HAp slurry was dried for 24 hours using a freeze dryer Free Zone (trademark) (manufactured by LABCONCO).
The obtained HAp powder was pulverized under the following conditions using a P-6 planetary ball mill (manufactured by FRITSCH). In a zirconia pot, 10.0 g of HAp powder, 50 φ10 mm zirconia balls and 40 ml of purified water were placed, and wet pulverized for 5 minutes at 300 rpm. After pulverization, the sample was collected so as to be washed out of the container using purified water, and the pulverized HAp slurry was collected by suction filtration. The recovered slurry was frozen at −80 ° C. overnight, and then dried for 24 hours using a freeze dryer Free Zone (trademark) (manufactured by LABCONCO) to obtain a wet synthetic HAp powder.

(2) Preparation of wet synthetic HAp / IP ₆ powder 1.00 g of 50 wt% IP ₆ aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was accurately weighed and diluted to about 300 cm ^{3 with} purified water, and then hydroxylated. The pH was adjusted to 7.3 using an aqueous sodium solution and hydrochloric acid, and an IP ₆ aqueous solution with a concentration of 1,000 ppm was prepared by measuring up to 500 cm ³ using a measuring flask.
10.0 g of wet synthetic HAp powder was suspended in 200 cm ³ of an IP ₆ aqueous solution having a concentration of 1,000 ppm, and stirred for 5 hours at 37 ° C. and a stirring speed of 400 rpm. This was subjected to suction filtration, and the resulting slurry was washed with purified water and then frozen at −80 ° C. overnight. The frozen HAp / IP ₆ slurry was dried for 24 hours using a freeze dryer Free Zone (trademark) (manufactured by LABCONCO) to obtain a wet synthetic HAp / IP ₆ powder.
The obtained wet synthetic HAp / IP ₆ powder had a median diameter of 7.9 μm and a specific surface area of 98.5 m ² / g.

2. Preparation of kneading liquid (1) Screening of polysaccharide (Example 1)
Dextran sulfate Na (molecular weight 5,000) shown in Table 1 was added to an IP ₆ aqueous solution (pH 7.3) having a concentration of 10,000 ppm at a concentration shown in Table 1 to prepare a kneaded liquid.

(Cement production)
₆₀ to 160 μl of the kneaded liquid is added to 0.2 g of the wet synthetic HAp / IP ₆ powder (1 / 0.30 to 1 / 0.80 in solid-liquid ratio (powder g / ml of kneaded liquid)). In addition, a cement composition was prepared by kneading using a rubber spatula.
Cement test specimens were prepared by filling the cement composition in a φ5 mm mold molding machine and uniaxially pressing with a molding pressure of 2 kN. The molded cement specimen was dried in air for 24 hours. The size of the cement test piece was φ4.5 to 5 mm, height 6 to 8 mm, and weight 0.2 g.

(Mechanical property evaluation of cement)
All mechanical properties of cement were evaluated by compressive strength test. As the tester, AUTOGRAPH AGS-J manufactured by SHIMADZU was used. The measurement conditions are shown below.
Crosshead speed: 0.5 mm · s ^-1
Set load: 5kN
AUTO STOP: ON
The compressive strength of the cement produced using the kneading liquid shown in Table 1 was measured.

(Examples 2 to 4 and Comparative Examples 1 to 4)
Except for preparing the kneading liquid having the composition shown in Table 1, the cements of Examples 2 to 4 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, and the mechanical properties of the cement were measured in the same manner as in Example 1. did.

The results of Example 1 and Comparative Example 1 are shown in FIG. 1, the results of Example 2 and Comparative Example 2 are shown in FIG. 2, the results of Example 3 and Comparative Example 3 are shown in FIG. 3, and the results of Example 4 and Comparative Example 4 are shown. The results are shown in FIG.
Table 1 shows the maximum compressive strength of the cements obtained in Examples 1 to 4 and Comparative Examples 1 to 4 and the solid-liquid ratio at which the maximum compressive strength was obtained.

When Example 1 and Comparative Example 1 are compared, the cement (Example 1) prepared by using a kneading liquid containing IP ₆ in the range of the solid / liquid ratio around 1 / 0.4 to around 1 / 0.6. However, compared with the cement produced using the kneading liquid not containing IP ₆ (Comparative Example 1), it showed high compressive strength. In particular, excellent compressive strength was shown in the range of the solid-liquid ratio of around 1 / 0.3 to around 1 / 0.4.
In Example 2 (Na of dextran sulfate, molecular weight 500,000), a kneaded liquid containing IP ₆ in a wider solid-liquid ratio range from 1 / 0.3 to 1 / 0.8 as compared with Example 1. The compressive strength of the cement produced using No. ₆ was higher than that of the cement produced using the kneading liquid not containing IP ₆ (Comparative Example 2). In particular, an excellent compressive strength was exhibited in the range of the solid / liquid ratio around 1 / 0.4 to 1 / 0.8. By using the kneading liquid of Example 2, it was possible to obtain a cement excellent in compressive strength in a wider solid-liquid ratio range as compared with Example 1. Therefore, by using a kneading liquid containing dextran sulfate Na having a molecular weight of 500,000 and IP ₆ , it was possible to provide a cement composition that can be more easily adjusted in fluidity and excellent in handling properties.
In Example 3 and Example 4, kneading without IP ₆ at a solid-liquid ratio of about 1 / 0.45 to about 1 / 0.8 and a solid-liquid ratio of about 1 / 0.7 to about 1 / 0.8, respectively. The compressive strength of the cement was higher than when the liquid was used (Comparative Examples 3 and 4 respectively), and the effect of adding IP ₆ was recognized (FIGS. 3 and 4).

3. Surface modification of calcium salt powder (Comparative Example 5)
Cement was prepared in the same manner as in Example 2 except that the wet synthetic HAp powder (which was not surface-modified with IP ₆ ) was used as the cement material, and the compressive strength was measured in the same manner as in Example 1. did. The results are shown in FIG. 5 together with the results of Example 2.
From FIG. 5, a higher compressive strength is obtained when the calcium powder surface-modified with IP ₆ (wet synthetic HAp / IP ₆ powder) is used at a solid-liquid ratio of about 1 / 4.40 to about 1 / 0.80. I understand that

4). About concentration of polysaccharide (Examples 5 to 7)
Except that the concentration of dextran sulfate Na (molecular weight 500,000) was 10% by weight (Example 5), 20% by weight (Example 6) and 30% by weight (Example 7), it was the same as Example 2. Cement was prepared and the compressive strength was measured in the same manner as in Example 1. The results are shown in FIG. 6 together with the results of Example 2.

(Comparative Example 6)
The compressive strength was measured in the same manner as in Example 2 except that the concentration of dextran sulfate Na (molecular weight 500,000) was 0% by weight. The results are shown in FIG.
It can be seen from FIG. 6 that when the concentration of dextran sulfate Na having a molecular weight of 500,000 is 20% by weight, excellent compressive strength is exhibited, and when it is 25-30% by weight, particularly excellent compressive strength is exhibited. In Comparative Example 6 where the kneaded liquid did not contain dextran sulfate Na, not only the IP ₆ addition effect of the kneaded liquid was not recognized, but also cement could not be molded in the vicinity of the solid-liquid ratio of 1 / 0.8.

5. Concentration of IP ₆ in the kneading liquid (Examples 8 to 9)
Compressed in the same manner as in Example 2 (IP ₆ agricultural concentration: 10,000 ppm) except that the concentration of IP ₆ contained in the kneaded liquid was 5,000 ppm (Example 8) and 20,000 ppm (Example 9). The strength was measured. The results of Example 2, Example 8, and Example 9 are shown in FIG. 7 together with the result of Comparative Example 2 (IP ₆ concentration 0 ppm).
By adding IP ₆ to the kneading liquid, the compressive strength was improved, and the compressive strength was greatly improved at an IP ₆ concentration of 5,000 to 10,000 ppm.

6). About composition of kneading liquid (Example 2, Comparative Examples 7-9)
An object of the present invention is to simultaneously improve the compressive strength and handling property by adding a polysaccharide and IP ₆ to water as a kneading liquid. However, since IP ₆ has a buffering action, it is considered that the strength is improved due to the constant pH during kneading.
Therefore, a solute (Tris-HCl; concentration: 0.05 M (Comparative Example 7) or phosphate buffer; concentration: 0.5 to 2.0% by weight (Comparative Example 8)) having a buffering action instead of IP ₆ is used. The added kneading liquid and the kneading liquid (Comparative Example 9) obtained by neutralizing the polysaccharide with NaOH without adding IP ₆ or the buffering solute were used as control kneading liquids, and the cement sample pieces were used. The sample was prepared under the same conditions as in Example 2 and compared with the compressive strength of the cement sample piece of Example 2.
The result is shown in FIG. Although the cement sample piece of Example 2 maintained a high compressive strength of about 34 MPa even when the solid-liquid ratio decreased (even when the amount of the kneaded liquid increased), in Comparative Examples 7 to 9, the solid-liquid ratio decreased ( Their compressive strength decreased with increasing amount of kneading liquid. In particular, there is a marked difference in compressive strength when the solid-liquid ratio is 1 / 0.8 with a large amount of kneading liquid, and the effect of adding the polysaccharide and IP ₆ is clear, and IP ₆ acts as a simple buffer. I can understand that it is not only to do.

7). Evaluation of maximum strength arrival time and curing time (Bicker needle test) (Example 10)
Wet synthetic HAp / IP ₆ powder is used as the cement material, and an aqueous solution containing 25% by weight of dextran sulfate Na (molecular weight 500,000) and 10,000 ppm of IP ₆ is used as the kneading liquid. .7 cement composition was prepared, and the maximum strength reaching time and the setting time (Vicat needle test) were evaluated.

(Maximum strength arrival time)
The change over time in the compressive strength after kneading was measured, and the maximum strength arrival time was measured.
After measuring the compressive strength within 5 minutes immediately after kneading, the cement is allowed to stand at room temperature, and after 30 minutes, 1 hour, 2 hours, 3 hours, 6 hours, 8 hours, 10 hours and 24 hours have elapsed since the kneading. The compressive strength was measured in the same manner as in Example 1. The results are shown in FIG.

(Evaluation of curing time (Bicker needle test))
The curing time was measured by a Vicat needle method according to a dental zinc phosphate cement measuring method (JIS T6602). Specifically, the cement composition is kneaded, and after 5 minutes, the cement composition is transferred to a thermostat having a temperature of 37 ° C. and a relative humidity of about 100%, and a 200 g Vicat needle is gently dropped on the surface of the kneaded product. Then, it is checked whether or not needle marks are formed, and the time when no needle marks remain is counted from the start of kneading as the curing time.
The measurement was further performed after 10 minutes, 30 minutes, 60 minutes, 120 minutes and 180 minutes. The results of the Vicat needle test are shown in FIG.
(Comparative Example 10)
The change over time in the compressive strength after kneading was measured in the same manner as in Example 10 except that the wet synthetic HAp powder was used as the cement material. The results are shown in FIG.
In addition, a Vicat needle test was performed using a cement similarly produced. The results are shown in FIG.

From FIG. 9, in the present invention (Example 10) using the wet synthetic HAp / IP ₆ powder as the cement material, the maximum strength became about 32 MPa in about 10 hours after kneading. In Comparative Example 10 using wet synthetic HAp powder, the compressive strength is as low as about 16 MPa and does not reach the maximum value even after 24 hours from kneading.
Further, in FIG. 10 to Example 10, curing was completed in about 50 minutes after kneading (the Vicat needle was not penetrated), whereas in Comparative Example 10, curing was not completed even after 180 minutes (the Vicat needle was penetrated). )

Manufacturers and product names of the polysaccharides listed in Table 1 are as follows.
Dextran sulfate Na (molecular weight 5,000); manufactured by Wako Pure Chemical Industries, Ltd., dextran sodium sulfate 5,000
Dextran sulfate Na (molecular weight 500,000); manufactured by Wako Pure Chemical Industries, Ltd., dextran sodium sulfate 500,000
Alginic acid Na (low viscosity): MP Biomedicals, ALGINIC ACID SODIUM SALT
Na-alginate (high viscosity); Wako Pure Chemical Industries, Ltd., sodium alginate 80-120 cP

(Comparative Example 6 and Comparative Example 11)
Comparative Example 6 and Comparative Example 11 are cases where no polysaccharide is added to the kneaded liquid. Comparative Example 6 is a cement sample piece prepared by adding an IP ₆ aqueous solution to a wet synthetic HAp / IP ₆ powder and kneading. On the other hand, Comparative Example 11 is a cement test piece prepared by kneading wet synthetic HAp / IP ₆ powder with pure water to which neither polysaccharide nor IP ₆ is added. It can be understood that these results are inferior to those of Example 2 in which the highest maximum compressive strength and excellent handling properties are obtained this time.

Kneading liquid is a diagram illustrating the effect of which contains the and IP ₆ dextran sulfate Na (molecular weight 5,000). Kneading liquid is a diagram illustrating the effect of which contains the and IP ₆ dextran sulfate Na (molecular weight 500,000). Kneading liquid, it shows the effects that contain alginate Na (low viscosity) and IP _6. Kneading liquid, it shows the effects that contain alginate Na (high viscosity) and the IP _6. With wet synthesis HAp / IP ₆ powder as a material for cement, shows that the cement compressive strength superior can be obtained than with wet synthesis HAp powder. Using wet synthetic HAp / IP ₆ powder as a cement material and using a kneaded liquid containing dextran sulfate Na (molecular weight 500,000) and IP ₆ , the relationship between the concentration of dextran sulfate Na and the compressive strength of cement FIG. Using a wet synthetic HAp / IP ₆ powder as a material for cement, it is a diagram illustrating IP ₆ concentration the relationship between the compressive strength when using a kneading liquid containing IP ₆ dextran sulfate Na (molecular weight 500,000) . Using a wet synthetic HAp / IP ₆ powder as a material for cement, the case of using the solute or NaOH with a pH stabilizing effect as the kneading liquid component, it shows a comparison of the case of using the IP _6. For maximum compressive strength arrival time of the cement is a diagram in which the comparison with the case of using the case of using a wet synthesis HAp / IP ₆ powder and wet synthesis HAp powder as a material for cement. The setting time of the cement (Vicat needle test) is a diagram in which the comparison with the case of using the case with wet synthesis HAp / IP ₆ powder and wet synthesis HAp powder as a material for cement.

Claims (6)

A cement material comprising calcium salt powder having inositol phosphate adsorbed on the surface;
It is obtained by kneading a kneading liquid containing polysaccharide, inositol phosphate and solvent ,
The polysaccharide is a polysaccharide having an acidic group;
Inositol phosphate contained in the kneading liquid is phytic acid,
A cement composition, wherein the calcium salt powder having inositol phosphate adsorbed on the surface thereof is a calcium phosphate hydroxyapatite powder having phytic acid adsorbed on the surface .   The cement composition according to claim 1, wherein the polysaccharide is dextran sulfate. A cement kit comprising a calcium salt powder having inositol phosphate adsorbed on its surface, a cement kit comprising a polysaccharide, inositol phosphate and a solvent,
The cement material and the solvent are separately packaged ,
The polysaccharide is a polysaccharide having an acidic group;
Inositol phosphate contained in the kneading liquid is phytic acid,
The cement kit, wherein the calcium salt powder having the inositol phosphate adsorbed on the surface thereof is a calcium apatite hydroxyapatite powder having phytic acid adsorbed on the surface . Cement, characterized in that curing the cement composition according to claim 1 or 2. A cement material preparation process for preparing a cement material containing calcium salt powder having inositol phosphate adsorbed on its surface;
A kneading liquid preparation step for preparing a kneading liquid containing a polysaccharide, inositol phosphate and a solvent;
Cement composition preparation step of kneading the cement material and the kneading liquid, and
Look including a curing step of curing the cement composition,
The polysaccharide is a polysaccharide having an acidic group;
Inositol phosphate contained in the kneading liquid is phytic acid,
A method for producing a cement, wherein the calcium salt powder having the inositol phosphate adsorbed on the surface thereof is a calcium phosphate phosphate hydroxyapatite powder having the surface adsorbed phytic acid .   As the cement material preparation step, (step 1) a step of obtaining a precipitate by mixing a solution containing calcium ions adjusted to alkalinity and a solution containing phosphate ions, (step 2) a system containing the precipitate 6. A method for producing cement according to claim 5, comprising: a step of aging to maintain a calcium salt powder to obtain a calcium salt powder; and (step 3) a step of recovering and freeze-drying the calcium salt powder. .

Images