WO2018168474A1 - Composition de ciment de phosphate de calcium, kit de ciment de phosphate de calcium et procédé de production de corps en ciment de phosphate de calcium durci - Google Patents

Composition de ciment de phosphate de calcium, kit de ciment de phosphate de calcium et procédé de production de corps en ciment de phosphate de calcium durci Download PDF

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WO2018168474A1
WO2018168474A1 PCT/JP2018/007579 JP2018007579W WO2018168474A1 WO 2018168474 A1 WO2018168474 A1 WO 2018168474A1 JP 2018007579 W JP2018007579 W JP 2018007579W WO 2018168474 A1 WO2018168474 A1 WO 2018168474A1
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calcium phosphate
component
phosphate
calcium
powder
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PCT/JP2018/007579
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English (en)
Japanese (ja)
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由華 宇野
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オリンパステルモバイオマテリアル株式会社
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/02—Phosphate cements

Definitions

  • the present invention relates to a calcium phosphate cement composition, a calcium phosphate cement kit, and a method for producing a hardened calcium phosphate cement.
  • cement for bone implants based on brushite (calcium hydrogen phosphate dihydrate, CaHPO 4 .2H 2 O, DCPD) is known (for example, see Patent Document 1).
  • Brushite is characterized by its high solubility in water compared to other calcium phosphate compounds.
  • the degradation rate of the cement hardened body is controlled by adding particles having a particle size larger than that of the raw material for the brushite to the brushite matrix and decomposing more slowly than the brushite. is doing.
  • Patent Document 1 does not focus on the bone forming ability of the cured body in vivo, and there is a problem that sufficient bone forming ability cannot be expected.
  • the present invention has been made in view of the above-described circumstances, and is capable of enhancing the bone forming ability of the cured body while controlling the decomposition rate of the cured body, the calcium phosphate cement kit, and the calcium phosphate cement hardening. It aims at providing the manufacturing method of a body.
  • a first aspect of the present invention is a hydraulic calcium phosphate cement composition that hardens by reaction with water, and is a powdered calcium phosphate component, a powder or liquid phosphate component, and particles larger than the calcium phosphate component
  • a calcium phosphate cement composition comprising a hollow sphere having a diameter and a calcium phosphate granule having a particle diameter of 50 ⁇ m or more and 150 ⁇ m or less.
  • a powdery calcium phosphate component, a powdered or liquid phosphate component, and a calcium phosphate granule are added with a liquid containing water, and the mixture is kneaded to produce a paste having fluidity. Then, by curing the produced paste, a hardened body is produced in which the cement component produced by the reaction of the calcium phosphate component, the phosphoric acid component and water is used as a base material.
  • the hardened body mainly composed of calcium phosphate can be used as a bone implant to be transplanted into a bone defect portion in a living body.
  • the decomposition rate of the hardened body in vivo can be controlled by the calcium phosphate granules mixed in the hardened body and having a different decomposition speed in vivo from the cement component. Further, pores composed of hollow spherical calcium phosphate granules are formed in the cured body. When such a cured body is transplanted into the body, osteoblasts responsible for bone formation enter into the pores of the cured body, thereby promoting the induction of osteoblasts from the surrounding tissue to the cured body. Thereby, the bone formation ability of a hardening body can be improved.
  • the calcium phosphate component may be ⁇ tricalcium phosphate, and the phosphate component may be calcium dihydrogen phosphate.
  • a particle diameter of the calcium phosphate granule may be 50 ⁇ m or more and 150 ⁇ m or less.
  • the function of calcium phosphate granules as a scaffold for osteogenesis by osteoblasts can be further enhanced to further improve the bone-forming ability of the cured body, and the fluidity of the paste can be improved by the addition of granules.
  • the effect can be further enhanced.
  • molding die with a paste using a small diameter needle it can prevent clogging with a paste inside a needle.
  • the thickness of the spherical shell of the calcium phosphate granule may be 15 ⁇ m or more.
  • a ratio of the mass of the calcium phosphate granule to the mass of the cement component generated from the calcium phosphate component and the phosphate component may be 0.1 or more and 2.0 or less.
  • a primary particle diameter of the calcium phosphate component may be 0.2 ⁇ m or more, and a total particle diameter of the calcium phosphate component may be 10 ⁇ m or less.
  • the phosphoric acid component may be a powder having an average particle size of 15 ⁇ m or more and 400 ⁇ m or less.
  • the calcium phosphate component and the phosphate component may be included as main components.
  • the hardening body which has as a main component the cement component produced
  • Hollow spherical calcium phosphate granules have a lower compressive strength than dense cement components. Therefore, by using the cement component as the main component of the cured body, it is possible to prevent an excessive decrease in the compressive strength of the cured body due to the mixing of ⁇ -TCP granules.
  • mixing the said calcium-phosphate component, the said phosphate-type component, the said calcium-phosphate granule, and water may have a compressive strength of 10 Mpa or more.
  • a cured body having a compressive strength higher than the compressive strength (3 MPa to 5 MPa) of cancellous bone has a compressive strength capable of withstanding the load for a period until bone is formed after being transplanted to a bone defect. You can continue to have
  • the calcium phosphate granule comprises ⁇ -tricalcium phosphate ( ⁇ -TCP), hydroxyapatite, carbonate apatite, dicalcium phosphate, ⁇ -tricalcium phosphate ( ⁇ -TCP), quaternary calcium phosphate, Or the granule of a calcium metaphosphate may be sufficient.
  • ⁇ -TCP ⁇ -tricalcium phosphate
  • ⁇ -TCP ⁇ -tricalcium phosphate
  • ⁇ -TCP quaternary calcium phosphate
  • 2nd aspect of this invention is a calcium-phosphate cement kit provided with the calcium-phosphate cement composition in any one of the said, and the liquid agent containing water.
  • the ratio of the total mass (g) of the calcium phosphate component, the phosphate component, and the calcium phosphate granule to the volume (mL) of the solution is 3.5 or more and 5.0 or less. May be.
  • the solution may be a citric acid-sodium citrate buffer.
  • a citric acid-sodium citrate buffer that acts as a retarder that delays the curing rate of the paste, the curing rate of the paste can be suppressed and the operation time of the paste can be secured.
  • a citric acid-sodium citrate buffer as the liquid agent, the amount of the liquid agent added to the solid agent can be minimized, and the strength of the cured body can be prevented from being reduced due to the addition of the retarder.
  • a third aspect of the present invention is a calcium phosphate granule having a powdery calcium phosphate component, a powdered phosphate component, and a hollow sphere having a particle size larger than that of the calcium phosphate component, wherein the particle size is 50 ⁇ m or more and 150 ⁇ m or less. And water are kneaded, and the produced paste is hardened, and a method for producing a hardened calcium phosphate cement.
  • the bone forming ability of the cured body can be enhanced while controlling the decomposition rate of the cured body.
  • FIG. 2 is a scanning electron micrograph of ⁇ -TCP granules contained in a calcium phosphate cement composition.
  • 4 is a chart showing production conditions for a cured body in Example 1.
  • FIG. 2 is an optical micrograph of a cured body transplanted in vivo in Example 1 for 12 weeks.
  • 10 is a chart showing test results of Example 2.
  • 10 is a chart showing test results of Example 3.
  • 4 is a scanning electron micrograph of MCPM powder used for Sample 15 in Example 4.
  • FIG. 4 is a scanning electron micrograph of MCPM powder used for Sample 16 in Example 4.
  • FIG. 4 is a scanning electron micrograph of MCPM powder used for Sample 17 in Example 4.
  • FIG. 4 is a scanning electron micrograph of MCPM powder used for Sample 18 in Example 4.
  • FIG. 10 is a chart showing test results of Example 4.
  • 10 is a chart showing test results of Example 5.
  • the calcium phosphate cement kit according to the present embodiment is for generating a hardened body suitable for a bone implant, and as shown in FIG. 1, is added to a solid agent composed of a calcium phosphate cement composition and the solid agent. And liquid.
  • the cured body can be produced by kneading the solid agent and the liquid agent to produce a paste and curing the produced paste.
  • the solid agent and the liquid agent are stored separately and mixed when the paste is produced.
  • the solid agent is composed of a first component composed of ⁇ -TCP ( ⁇ tricalcium phosphate) powder (calcium phosphate component) and calcium dihydrogen phosphate powder (phosphate component), ⁇ -TCP powder and calcium dihydrogen phosphate powder. And a second component composed of ⁇ -TCP granules (calcium phosphate granules) having a larger particle diameter.
  • the main component in the solid agent is the first component, and the second component is contained in a mass equal to or less than that of the first component.
  • the solid agent may contain various solid additive substances (for example, drugs such as a curing rate adjusting agent and antibiotics).
  • the primary particle diameter of ⁇ -TCP powder is 0.2 ⁇ m or more, and the total particle diameter of ⁇ -TCP powder is 10 ⁇ m or less.
  • ⁇ -TCP powder exists in a state where a plurality of powders are aggregated.
  • the primary particle size is the particle size of each powder, and the total particle size is the particle size of an agglomerate composed of a plurality of powders.
  • ⁇ -TCP powder having a primary particle size of 0.2 ⁇ m or more the curing rate of the paste can be suppressed so as to ensure the operation time of the paste.
  • the primary particle diameter of ⁇ -TCP powder is less than 0.2 ⁇ m, the paste may be difficult to manipulate with a needle due to rapid hardening of the paste.
  • the larger the total particle size of the ⁇ -TCP powder the lower the paste fluidity and the compressive strength of the cured body.
  • ⁇ -TCP powder having a total particle size of 10 ⁇ m or less both high paste fluidity and high compression strength of the cured product can be achieved.
  • the total particle size of the ⁇ -TCP powder is larger than 10 ⁇ m, the fluidity of the paste is lowered and the compressive strength of the cured product is lowered.
  • Calcium dihydrogen phosphate is a hydrate (calcium dihydrogen phosphate monohydrate, MCPM) or an anhydride (anhydrous calcium dihydrogen phosphate, MCPA).
  • MCPM calcium dihydrogen phosphate monohydrate
  • MCPA anhydrous calcium dihydrogen phosphate
  • the average particle size of the MCPM / MCPA powder is 15 ⁇ m or more and 400 ⁇ m or less.
  • MCPM / MCPA powder having an average particle size of 15 ⁇ m or more and 400 ⁇ m or less a cured product with high compressive strength can be obtained while suppressing the curing rate of the paste.
  • the average particle size of the MCPM / MCPA powder is less than 15 ⁇ m, the paste may be difficult to manipulate with a needle due to rapid hardening of the paste.
  • the average particle diameter of MCPM / MCPA powder is larger than 400 ⁇ m, there is a possibility that the desired compression strength of the cured body cannot be obtained.
  • the first component ⁇ -TCP powder (Ca 3 (PO 4 ) 2 ) and MCPM / MCPA powder (Ca (H 2 PO 4 ) 2 .H 2 O) react with water contained in the liquid as follows.
  • brushite (CaHPO 4 ⁇ H 2 O) is generated.
  • the first component preferably contains ⁇ -TCP powder and MCPM / MCPA powder so that ⁇ -TCP and MCPM / MCPA are equimolar.
  • the ⁇ -TCP granule is a hollow spherical granule composed of a spherical shell having a substantially spherical cavity inside as shown in FIG.
  • Such hollow spherical ⁇ -TCP granules are coated, for example, by coating the outer surface of a bead of resin (eg, polymethyl methacrylate resin) having a diameter approximately equal to the diameter of the cavity with ⁇ -TCP powder. It is manufactured by evaporating the resin by heating the beads at a high temperature.
  • resin eg, polymethyl methacrylate resin
  • the particle diameter of ⁇ -TCP granules is 50 ⁇ m or more and 150 ⁇ m or less. Thereby, a paste with high fluidity can be generated.
  • ⁇ -TCP granules having a particle size of 50 ⁇ m or more and 150 ⁇ m or less promote bone remodeling by osteoblasts and osteoclasts in the body. By mixing such ⁇ -TCP granules in the cured body, the bone forming ability of the cured body can be enhanced.
  • the particle diameter of ⁇ -TCP granules is larger than 150 ⁇ m, the surface area of the entire ⁇ -TCP granules in the cured body decreases, so that the dissolution of ⁇ -TCP granules in the body is suppressed and bone remodeling The promotion effect is reduced.
  • a fine needle having an inner diameter of 3 mm or less is used, but ⁇ -TCP granules having a large particle diameter may cause clogging in the needle. .
  • ⁇ -TCP granules when the particle diameter of ⁇ -TCP granules is less than 50 ⁇ m, the difference in particle diameter between ⁇ -TCP granules and ⁇ -TCP powder becomes small, and the effect of the granules cannot be expected. That is, ⁇ -TCP granules are also easily consumed in the reaction to generate brushite and the reaction rate increases, and the viscosity of the paste increases and the operability of the paste decreases.
  • the cavity of ⁇ -TCP granule exerts an effect of promoting osteogenesis when osteoblasts enter the cavity. When the particle size is less than 50 ⁇ m, osteoblasts can enter. It is difficult to form a cavity having a size, and the function as a scaffold for bone formation may not be obtained.
  • the thickness of the spherical shell of ⁇ -TCP granules is 15 ⁇ m or more.
  • the compressive strength specifically 10 MPa or more
  • the thickness of the spherical shell is less than 15 ⁇ m, there is a possibility that a compressive strength of 10 MPa or more cannot be obtained.
  • the mass ratio between the first component and the second component is the mass ratio of ⁇ -TCP granule to the cement component brushite (DCPD) produced by the reaction between the first component and water ( ⁇ -TCP granule / DCPD) is determined to be 0.1 or more and 2.0 or less.
  • the ⁇ -TCP granule / DCPD mass ratio is calculated from the following equation. In the following formula, 310.18 [g / mol] is the molecular weight of ⁇ -TCP, and 18 [g / mol] is the molecular weight of H 2 O.
  • the solution is a citric acid-sodium citrate buffer.
  • Citric acid and sodium citrate have the effect of delaying the cure rate of the paste. Therefore, by using the citric acid-sodium citrate buffer at the time of producing the paste, the time during which the paste can be operated can be extended.
  • a liquid agent is added to a solid agent, and a mixture of the solid agent and the liquid agent is kneaded to produce a paste.
  • brushite is generated by the reaction of ⁇ -TCP, MCPM / MCPA and water.
  • the amount of the liquid agent added to the solid agent is adjusted so that water is approximately 1 equivalent to the ⁇ -TCP powder and the MCPM / MCPA powder.
  • the ratio (powder-liquid ratio) of the total mass (g) of the solid agent (first component and second component) to the volume (mL) of the liquid agent is 3.5 or more and 5.0 or less.
  • the volume of the liquid agent is determined with respect to the mass of the solid agent.
  • powdery ⁇ -TCP is preferentially consumed in the brushite production reaction.
  • the liquid agent and the granule hardly react. Therefore, ⁇ -TCP granules remain in the paste as they are with little involvement in the brushite formation reaction.
  • the amount of the liquid agent is related to the fluidity and curing time of the paste and the strength of the cured body.
  • the powder / liquid ratio may be provided in a state of being contained in a container or the like in such an amount that the powder-liquid ratio is in the above range so that the measurement of the solid agent and the liquid agent is not required at the time of producing the paste.
  • the produced paste is filled into a syringe, the paste is filled into a molding die via a needle connected to the syringe, and the paste is cured until the paste is cured, whereby a cured body mainly composed of brushite. Is obtained.
  • a solid agent in which the particle diameter of the powder and granules, the thickness of the spherical shell, and the mass ratio are controlled in the above range, and mixing the solid agent and the liquid agent in a powder / liquid ratio in the above range.
  • a cured product having a compressive strength of 10 MPa or more can be obtained.
  • the produced cured body is taken out from the mold and then transplanted into a bone defect portion in a living body.
  • the paste may be directly filled into a bone defect part in a living body and cured in the bone defect part.
  • the hardened body is gradually decomposed by dissolving the brushite in the hardened body by contact with the body fluid of the surrounding tissue.
  • bone remodeling is performed on the ⁇ -TCP granules by osteoblasts and osteoclasts that have migrated from the surrounding tissue to the sclerosis. That is, osteoblasts enter into the pores of the cured body to form bone inside the cured body, and osteoclasts dissolve and absorb ⁇ -TCP granules.
  • the decomposition of the cured body and the formation of new bone proceed simultaneously, so that the cured body transplanted to the bone defect portion is gradually replaced with bone.
  • the hollow spherical ⁇ -TCP granules are mixed in the hardened body to form pores in the hardened body, and thus the bone forming ability of the hardened body can be improved.
  • the bone forming ability of the hardened body can be improved.
  • ⁇ -TCP granules having a particle size of 50 ⁇ m or more and 150 ⁇ m or less there is an advantage that the bone forming ability of the cured body can be further enhanced.
  • ⁇ -TCP granules having a particle size larger than that of the first component powder are contained in the paste, the paste fluidity is improved, so an extra liquid agent is solidified for the purpose of improving the paste fluidity. There is no need to add to the agent.
  • the amount of the liquid agent added to the solid agent is sufficient as the minimum amount required for the production of brushite.
  • the hardening body which has high compressive strength of 10 Mpa or more can be obtained by raising a powder-liquid ratio.
  • ⁇ -TCP granules having a particle size larger than the powder of the first component are mixed in the paste, thereby increasing the powder-liquid ratio and generating a fine brushite.
  • melt dissolution of brushite in a hardening body can be suppressed and precipitation of HA can also be suppressed and biodegradation of the whole hardening body can be achieved.
  • the delay in absorption of the cured body in the body due to suppression of dissolution of the brushite is compensated by the effect of promoting bone remodeling by the ⁇ -TCP granules, so that the absorbability of the cured body is not impaired.
  • ⁇ -TCP granules are used, but the components of the hollow spherical granules are hydroxyapatite, carbonate apatite, dicalcium phosphate (DCPA or brushite), ⁇ -TCP, quaternary calcium phosphate.
  • Other calcium phosphate ceramics such as (TeCP) and calcium metaphosphate may be used.
  • ⁇ -TCP powder and MCPM / MCPA powder are used as components for generating brushite, but instead, ⁇ -TCP powder or hydroxyapatite is used as the calcium phosphate component, A phosphoric acid solution may be used as the phosphoric acid component.
  • a combination of calcium powders may be employed.
  • Example 1 The inhibitory effect of HA precipitation by hollow spherical ⁇ -TCP granules was evaluated by the following procedure. (1) A columnar bone defect having a diameter of 4 mm and a height of 7 mm was formed at the femoral shaft end of a rabbit. (2) A solid agent ( ⁇ -TCP granule, ⁇ -TCP powder, MCPM powder) and a liquid agent (citrate-sodium citrate buffer) are kneaded, and the resulting paste is columnar with a diameter of 4 mm and a height of 7 mm. Filled the mold.
  • the conditions of the solid agent and the liquid agent in this example are as shown in FIG. (3) Ten minutes after the start of kneading, the cured product was taken out of the mold and transplanted into the bone defect part of the rabbit. (4) Twelve weeks after transplantation, the cured body and its surrounding tissues were removed from the body and evaluated.
  • FIG. 4 shows an optical micrograph of the extracted cured body and the surrounding tissue. As shown in FIG. 4, precipitation of HA crystals was not observed on the surface of the cured body. In addition, one layer of bone formation was observed on the entire surface of the cured body, and formation of bone and bone marrow was observed in the cured body. Moreover, the hardening body was couple
  • Example 2 The relationship between the thickness of the spherical shell of the hollow spherical ⁇ -TCP granule, the fluidity of the paste and the compressive strength of the cured product was examined by the following procedure.
  • a solid agent ⁇ -TCP granule 4.0 g, ⁇ -TCP powder 2.2 g, MCPM powder 1.8 g
  • a volume of liquid agent citrate-sodium citrate buffer corresponding to a powder-liquid ratio of 4.2
  • Fig. 5 shows the test results of samples 1 to 3. As shown in FIG. 5, all the pastes of Samples 1 to 3 were able to be injected from the needle. Further, the compression strengths of the cured bodies of all the samples 1 to 3 exceeded 10 MPa.
  • Example 3 The relationship between the mass ratio of ⁇ -TCP granule to brushite ( ⁇ -TCP granule / DCPD mass ratio), the fluidity of the paste and the compressive strength of the cured product was examined by the following procedure.
  • Liquid agent citric acid-citric acid
  • solid agent ⁇ -TCP granules 0.8-6.0 g, ⁇ -TCP powder 1.1-4.0 g, MCPM or MCPA powder 0.9-3.2 g
  • Sodium buffer was added and kneaded for 1 minute to produce a paste.
  • 11 types of samples 4 to 14 having different ⁇ -TCP granule / DCPD mass ratio and powder-liquid ratio were prepared.
  • Example 4 The relationship between the particle diameter of ⁇ -TCP powder, the fluidity of the paste, and the compressive strength of the cured body was examined by the following procedure. (1) To a solid agent ( ⁇ -TCP granule 4.0 g, ⁇ -TCP powder 2.2 g, MCPM powder 1.8 g), add a solution (citric acid-sodium citrate buffer), knead for 1 minute, and paste Was generated.
  • a solution citric acid-sodium citrate buffer
  • the total particle size of ⁇ -TCP powder was 10 ⁇ m or less in all samples 15 to 18, and ⁇ -TCP powder having the same total particle size was used in samples 15 to 18.
  • the cured product was allowed to stand in a constant temperature bath at 37 ° C. for 24 hours, and then subjected to a compressive strength test (loading rate: 0.5 mm / min).
  • FIGS. 7A to 7D Scanning electron micrographs of the used ⁇ -TCP powder are shown in FIGS. 7A to 7D, and the conditions and test results of Samples 15 to 18 are shown in FIG.
  • the pastes of all samples 15 to 18 were able to be injected from the needle.
  • the compressive strengths of the cured bodies of all the samples 15 to 18 exceeded 10 MPa.
  • the larger the primary particle size of the ⁇ -TCP powder the greater the compressive strength of the cured body. This is because the larger the primary particle size, the slower the dissolution and reaction rate of ⁇ -TCP powder, thereby suppressing the formation of brushite crystal nuclei, resulting in the formation of large and strong brushite crystals. This is thought to be because the entanglement between crystals becomes stronger.
  • it is considered that the amount of the liquid agent is reduced due to the delay of the curing of the paste.
  • Example 5 The relationship between the average particle diameter of MCPM / MCPA powder, the fluidity of the paste, and the compressive strength of the cured body was examined by the following procedure.
  • a solid agent ⁇ -TCP granule 3.8 g, ⁇ -TCP powder 2.31 g, MCPM powder 1.89 g
  • a liquid agent citrate-sodium citrate buffer corresponding to a powder-to-liquid ratio 3.6
  • Fig. 9 shows the test results of samples 19 to 24. As shown in FIG. 9, all of the pastes of samples 19 to 24 could be ejected from the needle. Further, the compression strength of the cured bodies of Samples 19 to 23 having an average particle diameter of 15 ⁇ m or more and 411 ⁇ m or less exceeded 10 MPa, but the compression strength of Sample 24 having an average particle diameter of 700 ⁇ m was lower than 10 MPa. Thus, a correlation was confirmed between the average particle size of MCPM powder and the compressive strength, in which the larger the average particle size, the lower the compressive strength. From this test result, it was confirmed that a cured product having a compressive strength of 10 MPa or more can be produced by using MCPM powder having an average particle size of 15 ⁇ m or more and 400 ⁇ m or less.

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Abstract

L'invention concerne une composition de ciment de phosphate de calcium hydraulique qui contient un constituant phosphate de calcium pulvérulent, un constituant à base d'acide phosphorique pulvérulent ou liquide, et des granules de phosphate de calcium qui ont une forme sphérique creuse avec une taille de particule supérieure à celle d'une poudre de phosphate β-tricalcique et ont une taille de particule de 50 à 150 µm.
PCT/JP2018/007579 2017-03-16 2018-02-28 Composition de ciment de phosphate de calcium, kit de ciment de phosphate de calcium et procédé de production de corps en ciment de phosphate de calcium durci WO2018168474A1 (fr)

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JP2017051123A JP6993783B2 (ja) 2017-03-16 2017-03-16 リン酸カルシウムセメント組成物、リン酸カルシウムセメントキットおよびリン酸カルシウムセメント硬化体の製造方法

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CN109125804A (zh) * 2018-10-18 2019-01-04 暨南大学 一种适用于磷酸钙基骨水泥的固化液及其制备方法与应用
CN109125804B (zh) * 2018-10-18 2021-03-19 暨南大学 一种适用于磷酸钙基骨水泥的固化液及其制备方法与应用

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