WO2002068357A1 - Ciment de phosphate de calcium - Google Patents

Ciment de phosphate de calcium Download PDF

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Publication number
WO2002068357A1
WO2002068357A1 PCT/JP2001/004997 JP0104997W WO02068357A1 WO 2002068357 A1 WO2002068357 A1 WO 2002068357A1 JP 0104997 W JP0104997 W JP 0104997W WO 02068357 A1 WO02068357 A1 WO 02068357A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium phosphate
mass
cement
magnesium sulfate
quaternary
Prior art date
Application number
PCT/JP2001/004997
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Hirano
Hiroyasu Takeuchi
Nobuyuki Asaoka
Original Assignee
Mitsubishi Materials Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001054274A external-priority patent/JP4111421B2/ja
Priority claimed from JP2001054275A external-priority patent/JP2002255607A/ja
Priority claimed from JP2001054276A external-priority patent/JP4111422B2/ja
Application filed by Mitsubishi Materials Corporation filed Critical Mitsubishi Materials Corporation
Publication of WO2002068357A1 publication Critical patent/WO2002068357A1/fr

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/864—Phosphate cements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/876—Calcium oxide
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/02—Surgical adhesives or cements; Adhesives for colostomy devices containing inorganic materials
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications

Definitions

  • the present invention relates to a calcium phosphate cement which is used for augmentation treatment of a living body in a medical field including, for example, oral surgery and is capable of forming a high-strength hardened body.
  • a cement for living bone augmentation treatment includes: (1) a setting property of a slurry obtained by adding an aqueous solution for setting to the cement; and (2) a setting property of setting the slurry in the presence of moisture. (3) the strength of the hardened body is sufficient to allow the hardened body to move the therapeutic reinforcing bone; and (4) the ability of the hardened body to be absorbed into living bone and regenerated into living bone. It is required to have As cements having these properties, various types of cements for augmenting and treating biological bone have been proposed.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a calcium phosphate cement that can be used for augmentation treatment of a living body and can form a high-strength hardened body.
  • the present inventors have conducted studies to improve the strength of the hardened body formed by the calcium phosphate cement, and found that 0.03 to 2% by mass of magnesium sulfate; and 3 to 35% by mass of dibasic calcium phosphate Calcium phosphate containing at least one of quaternary calcium phosphate or model tribasic calcium phosphate and unavoidable impurities
  • cement the fluidity of the paste formed by adding a curable aqueous solution to this is further improved, and the entrapment of air bubbles in the paste is significantly reduced, and a dense cured body can be formed. It was found that the strength of the formed cured product was significantly improved, and the present invention was completed.
  • the calcium phosphate cement of the present invention comprises 0.03 to 2% by mass of magnesium sulfate; and 3 to 35% by mass of dibasic calcium phosphate, and the balance of quaternary calcium phosphate or ⁇ -type tribasic calcium phosphate is contained. Contains at least one and inevitable impurities.
  • the calcium phosphate cement according to a preferred embodiment of the present invention contains 0.03 to 1.5% by mass of magnesium sulfate and 3 to 25% by mass of dibasic calcium phosphate, and the balance is a mixture of tricalcium phosphate and inevitable impurities. It is composed of a composition.
  • a calcium phosphate cement according to another preferred embodiment of the present invention contains 0.03 to 2% by mass of magnesium sulfate and 5 to 35% by mass of dibasic calcium phosphate, with the balance being a quaternary phosphate calcium and inevitable impurities. It is composed of things.
  • Another preferred embodiment of the calcium phosphate cement of the present invention comprises: 0.33 to 0.5% by mass of magnesium sulfate, 3 to 10% by mass of dibasic calcium phosphate, and 10 to 25% by mass of quaternary calcium phosphate. It is composed of a mixed composition containing a tribasic calcium phosphate a and inevitable impurities.
  • Another preferred embodiment of the calcium phosphate cement according to the present invention comprises: 0.03 to 2.0% by mass of magnesium sulfate; 2 to 10% by mass of a hydration reaction product of dibasic calcium phosphate and tribasic calcium phosphate; It comprises 10 to 25% by mass of quaternary phosphoric acid and 10 to 25% by mass of quaternary phosphoric acid, and the balance is composed of a mixture of trichlorocalcium phosphate and inevitable impurities.
  • the calcium phosphate cement of the present invention contains 0.03 to 2% by weight of magnesium sulfate; and 3 to 35% by weight of dibasic calcium phosphate, and the remainder contains at least one of quaternary calcium phosphate or type tribasic calcium phosphate and inevitable impurities. Including. For example, It can be suitably used for reinforcement and treatment of living bone. However, the calcium phosphate cement of the present invention is not limited to this application, but can be used for other applications such as dental cement, gypsum substitutes such as dental gypsum, and cement for building materials.
  • the first embodiment of the calcium phosphate cement of the present invention contains 0.03 to 1.5% by mass of magnesium sulfate and 3 to 25% by mass of dibasic calcium phosphate, with the balance being ⁇ -type tribasic calcium phosphate and inevitable impurities. It is composed of a certain mixed composition.
  • magnesium sulfate By blending the magnesium sulfate, it is possible to improve the fluidity of a paste formed when a curable aqueous solution is added to the obtained cement, to significantly suppress the entrapment of bubbles in the paste, and to achieve a precise hardening. A body can be formed, and the strength of the cured body can be improved. In order to fully exert this effect, it is necessary to mix the remaining components, Q! -Type tribasic calcium phosphate, in a state where magnesium sulfate and dibasic calcium phosphate are kneaded in advance when preparing the calcium phosphate cement. is there.
  • the content of the magnesium sulfate in the calcium phosphate cement is preferably from 0.3 to 1.5% by mass, more preferably from 0.1 to 1.0% by mass, based on the total mass of the calcium phosphate cement. . If the content is less than 0.03% by mass, the desired effect of improving the strength of the cured product tends not to be obtained. If the content exceeds 1.5% by mass, the time required for curing the cured product increases rapidly. Tend to.
  • the content of the second calcium phosphate in the calcium phosphate cement is preferably 3 to 25% by mass, more preferably 6 to 20% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 3% by mass, the desired setting accelerating effect tends not to be obtained. If the content exceeds 25% by mass, the curing is remarkably accelerated, and the curing time is too short, so that the workability is reduced. Tends to be impaired.
  • curable aqueous solution used for producing the paste a curable aqueous solution that is usually used practically can be used.
  • a curable aqueous solution that is usually used practically can be used.
  • one or more of disodium succinate, sodium chondroitin sulfate, sodium lactate, sodium phosphate, sodium chloride, sodium bisulfite, and sodium pyrosulfite An aqueous solution containing a predetermined amount thereof, and distilled water.
  • the calcium phosphate cement of the first embodiment has a high-strength setting by mixing magnesium sulfate and dibasic calcium phosphate satisfying the above-mentioned contents in advance and mixing with the remaining component, mold tribasic calcium phosphate.
  • a calcium phosphate cement capable of forming a body can be prepared.
  • a second embodiment of the calcium phosphate cement of the present invention comprises a mixed composition containing 0.03 to 2% by mass of magnesium sulfate and 5 to 35% by mass of dibasic calcium phosphate, with the balance being quaternary calcium phosphate and unavoidable impurities. It is composed of things.
  • the content of magnesium sulfate in the calcium phosphate cement is preferably from 0.3 to 2% by mass, more preferably from 0.3 to 1.5% by mass, based on the total mass of the calcium phosphate cement. . If the content is less than 0.03% by mass, the desired effect of improving the strength of the cured product tends not to be obtained. If the content exceeds 2% by mass, the time required for curing the cured product tends to be drastically increased. It is in.
  • the content of the second calcium phosphate in the calcium phosphate cement is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 5% by mass, the desired setting accelerating effect tends not to be obtained. If the content exceeds 35% by mass, curing is remarkably accelerated and workability tends to be impaired.
  • the calcium phosphate cement of the second embodiment is obtained by mixing magnesium sulfate and dibasic calcium phosphate satisfying the above-mentioned contents in advance with kneading, and blending with the remaining component, quaternary calcium phosphate, to obtain a high-strength cured product.
  • a formable calcium phosphate cement can be prepared.
  • a third embodiment of the calcium phosphate cement of the present invention comprises: 0.33 to 0.5% by weight of magnesium sulfate, 3 to 10% by weight of dicalcium phosphate, and 10 to 25% by weight of quaternary calcium phosphate, with the balance being Is composed of a mixed composition which is a tribasic calcium phosphate and inevitable impurities.
  • the content of magnesium sulfate in the calcium phosphate cement is preferably from 0.3 to 0.5% by mass, more preferably from 0.1 to 0.3% by mass, based on the total mass of the calcium phosphate cement. It is. If the content is less than 0.03% by mass, the desired effect of improving the strength of the cured product tends not to be obtained. If the content exceeds 0.5% by mass, the time required for curing the cured product becomes longer. There is a tendency.
  • the content of dicalcium phosphate in the calcium phosphate cement is preferably 3 to 10% by mass, more preferably 4 to 8% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 3% by mass, the desired setting accelerating action tends not to be obtained, and if it exceeds 10% by mass, the curing is remarkably accelerated and the workability tends to be impaired.
  • the above-mentioned quaternary calcium phosphate has an action of promoting the absorption-substitution property of the hardened body to be regenerated into living bone.
  • the content of the quaternary calcium phosphate in the calcium phosphate cement is 10 to 25% by mass, and preferably 12 to 20% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 10% by mass, the effect of improving the absorption-substituting property tends not to be obtained, while if the content exceeds 25% by mass, the strength of the cured product tends to decrease.
  • the calcium phosphate cement of the third embodiment is prepared by mixing magnesium sulfate and dibasic calcium phosphate satisfying the above-mentioned contents in advance, and then blending the remaining components, ie, the fourth calcium phosphate and the third-class calcium triphosphate.
  • a calcium phosphate cement capable of forming a high-strength cured product can be prepared.
  • the fourth embodiment of the calcium phosphate cement of the present invention comprises: 0.03 to 2.0% by mass of magnesium sulfate, 2 to 10% by mass of a hydration reaction product of dibasic calcium phosphate and tribasic tribasic calcium phosphate, It comprises 3 to 10% by mass and 10 to 25% by mass of a quaternary calcium phosphate, and the balance is composed of a mixed composition of trichlorocalcium phosphate and inevitable impurities.
  • the content of magnesium sulfate in the calcium phosphate cement is preferably 0.03 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, based on the total mass of the calcium phosphate cement. It is.
  • the content is 0.03% by mass. If it is less than 0.5%, the desired effect of improving the strength of the cured product tends not to be obtained. If it exceeds 0.5% by mass, the time required for curing the cured product tends to be long.
  • the content of the second calcium phosphate in the calcium phosphate cement is preferably 3 to 10% by mass, more preferably 4 to 8% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 3% by mass, the desired setting accelerating action tends not to be obtained, and if it exceeds 10% by mass, the curing is remarkably accelerated and the workability tends to be impaired.
  • the above-mentioned quaternary calcium phosphate has an action of promoting the absorption-substitution property of the hardened body to be regenerated into living bone.
  • the content of the quaternary calcium phosphate in the calcium phosphate cement is 10 to 25% by mass, and preferably 12 to 20% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 10% by mass, the effect of improving the absorption-substituting property tends not to be obtained, while if the content exceeds 25% by mass, the strength of the cured product tends to decrease.
  • the hydration reaction product of the dibasic calcium phosphate and ⁇ ; type tribasic calcium phosphate (hereinafter referred to as the hydration reaction product) is dispersed in a slurry formed by adding a hardening aqueous solution to the obtained cement. Exists and acts as a starting point for the curing reaction. For this reason, by blending the hydration reaction product, a curing reaction is caused at a plurality of points in the slurry formed by adding a curable aqueous solution to the obtained cement, and the curing reaction is caused by the hydration reaction. The curing reaction proceeds simultaneously from the product. Thereby, the strength of the obtained cured product can be significantly improved.
  • the content of the hydration reaction product in the calcium phosphate cement is 2 to 10% by mass, and preferably 3 to 6% by mass, based on the total mass of the calcium phosphate cement. If the content is less than 2% by mass, the desired strength-improving effect tends not to be obtained. On the other hand, if the content exceeds 10% by mass, the fluidity of the slurry tends to decrease and the workability tends to be impaired.
  • the mixture was mixed at a mixing ratio of 10 to 1:20, and water was added to the obtained mixture.
  • It can be prepared by adding hydration at a ratio of 3: 1 to 0.4 and then pulverizing to a particle size of about 1 to 300 m.
  • the calcium phosphate cement of the fourth embodiment can be adjusted by the following method.
  • the obtained calcined product is pulverized and sieved to have a sieve size of 88 or less (average particle size: 6.5 rn), thereby being substantially quaternary calcium phosphate (content ratio: 90-5%).
  • the kneaded powder and the other raw material powders were blended at the blending ratios shown in Tables 2 to 5 and mixed, and the cement of the present invention 1 to 59 according to the embodiment of the present invention and the conventional cement according to the conventional embodiment were mixed.
  • each cement contains 5% sodium chondroitin sulfate, 15% disodium succinate hexahydrate, and 0.3% sodium hydrogen sulfite, and the balance is water, and the balance is water.
  • Cement: aqueous solution for hardening 3: 1 ratio was added and kneaded to obtain a slurry. This slurry was coagulated to form a columnar solid having dimensions of 6 mm in diameter and 12 mm in length.
  • each cement contains 5% sodium chondroitin sulfate, 15% cono, disodium oxalate hexahydrate, and the rest is water.
  • the mass ratio of cement: aqueous solution 3: Add at a ratio of 1 And made a slurry.
  • This slurry was coagulated to form a columnar solidified body having a diameter of 7 mm and a length of 14 mm.
  • the solidified body Na +: 142.
  • the calcium phosphate cement of the present invention enables the formation of a hardened body having high strength, and greatly contributes to the improvement of the strength of the bone for treatment reinforcement, and can reduce the use amount of the hardened body. It has useful properties.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Structural Engineering (AREA)
  • Transplantation (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Surgery (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)

Abstract

L'invention concerne un ciment de phosphate de calcium comprenant 0,03 à 2 % en masse de sulfate de magnésium, 3 à 35 % en masse de phosphate secondaire de calcium, et au moins un élément choisi dans le groupe contenant du phosphate quaternaire de calcium et du phosphate tertiaire de calcium de type α, ainsi que d'inévitables impuretés. Ce ciment de phosphate de calcium peut former des produits durcis possédant une résistance élevée.
PCT/JP2001/004997 2001-02-28 2001-06-13 Ciment de phosphate de calcium WO2002068357A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2001054274A JP4111421B2 (ja) 2001-02-28 2001-02-28 高強度硬化体の形成が可能な生体骨補強治療用リン酸カルシウムセメント
JP2001-54275 2001-02-28
JP2001054275A JP2002255607A (ja) 2001-02-28 2001-02-28 高強度硬化体の形成が可能な生体骨補強治療用リン酸カルシウムセメント
JP2001054276A JP4111422B2 (ja) 2001-02-28 2001-02-28 高強度硬化体の形成が可能な生体骨補強治療用リン酸カルシウムセメント
JP2001-54276 2001-02-28
JP2001-54274 2001-02-28

Publications (1)

Publication Number Publication Date
WO2002068357A1 true WO2002068357A1 (fr) 2002-09-06

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Application Number Title Priority Date Filing Date
PCT/JP2001/004997 WO2002068357A1 (fr) 2001-02-28 2001-06-13 Ciment de phosphate de calcium

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TW (1) TW550245B (fr)
WO (1) WO2002068357A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8906817B2 (en) 2009-01-12 2014-12-09 National Taiwan University Sintered calcium sulfate ceramic material and sinterable calcium sulfate ceramic material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6437445A (en) * 1987-07-31 1989-02-08 Nat Inst Res Inorganic Mat Calcium phosphate hydraulic cement composition
JPH0248479A (ja) * 1988-08-10 1990-02-19 Tokuyama Soda Co Ltd 硬化性組成物の硬化方法
JPH04314449A (ja) * 1991-04-15 1992-11-05 Mitsubishi Materials Corp 生体用リン酸カルシウムセメント
JPH06172007A (ja) * 1992-12-08 1994-06-21 Mitsubishi Materials Corp 高強度リン酸カルシウムセメント
JPH06321515A (ja) * 1993-05-18 1994-11-22 Osaka Cement Co Ltd 高強度硬化性材料
JPH078548A (ja) * 1993-06-24 1995-01-13 Mitsui Toatsu Chem Inc 硬化性生体用粉材
JPH0733489A (ja) * 1993-07-19 1995-02-03 Mitsubishi Materials Corp 超速硬性リン酸カルシウムセメントの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6437445A (en) * 1987-07-31 1989-02-08 Nat Inst Res Inorganic Mat Calcium phosphate hydraulic cement composition
JPH0248479A (ja) * 1988-08-10 1990-02-19 Tokuyama Soda Co Ltd 硬化性組成物の硬化方法
JPH04314449A (ja) * 1991-04-15 1992-11-05 Mitsubishi Materials Corp 生体用リン酸カルシウムセメント
JPH06172007A (ja) * 1992-12-08 1994-06-21 Mitsubishi Materials Corp 高強度リン酸カルシウムセメント
JPH06321515A (ja) * 1993-05-18 1994-11-22 Osaka Cement Co Ltd 高強度硬化性材料
JPH078548A (ja) * 1993-06-24 1995-01-13 Mitsui Toatsu Chem Inc 硬化性生体用粉材
JPH0733489A (ja) * 1993-07-19 1995-02-03 Mitsubishi Materials Corp 超速硬性リン酸カルシウムセメントの製造方法

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