EP0892761A1 - Process for producing a ceramic material based on calcium phosphate compounds and use of this material - Google Patents
Process for producing a ceramic material based on calcium phosphate compounds and use of this materialInfo
- Publication number
- EP0892761A1 EP0892761A1 EP97921595A EP97921595A EP0892761A1 EP 0892761 A1 EP0892761 A1 EP 0892761A1 EP 97921595 A EP97921595 A EP 97921595A EP 97921595 A EP97921595 A EP 97921595A EP 0892761 A1 EP0892761 A1 EP 0892761A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- reaction
- process according
- reaction solution
- diphosphate
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- 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
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, 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
- 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
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00179—Ceramics or ceramic-like structures
- A61F2310/00293—Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite
Definitions
- the invention relates to a method for producing a ceramic material based on calcium phosphate compounds for use in dentistry.
- plastic materials such as amalgams, plastics and inorganic cements are usually used to remove carious defects in the tooth enamel.
- Another method of restoring carious defects is to use cast metal fillings, e.g. B. Gold.
- cast metal fillings e.g. B. Gold.
- These conventional materials have disadvantages such as the allergies that may occur with amalgam, poor mechanical strength and high costs for cast fillings made of noble metal.
- EP-A-89 900 578 9 relates to a dental filling material made of calcium phosphate compounds which have a pore content of 20 to 70% by volume.
- the main idea of this document is to use the porous dental filling material to give the ions in the saliva the possibility of being in the saliva to diffuse with the porous hydroxyapatite body and to give rise to solid calcium phosphate there, whose chemical composition and crystalline structure largely resemble that of tooth enamel
- DE-A-3 935 060 describes a ceramic material for dental fillings and crowns based on calcium phosphate compounds in which the atomic ratio of calcium to phosphorus of the calcium phosphate compounds is less than 1.65 in total.
- These ceramic materials are made either by grinding a mixture of one Poorly soluble calcium phosphate compound with a more soluble calcium phosphate compound or by precipitation from an aqueous solution of calcium and phosphate compounds and subsequent sintering at 800 to 1,400 ° C.
- the object on which the invention is based was therefore to obtain a method for producing a ceramic material which can be used in dentistry and which has properties similar to those of natural tooth enamel, which leads to easily reproducible product quality and can therefore also be used on an industrial scale Process according to the invention solved
- This method according to the invention for producing a ceramic material based on calcium phosphate compounds for use in dentistry by adding a phosphate solution to a calcium salt solution, separating the precipitate formed in the reaction solution from the mother liquor, drying, crushing and sintering is characterized in that that at least one orthophosphate and at least one diphosphate are added to the calcium salt solution, the molar ratio of diphosphate to orthophosphate being in the range from 0.001 to 0.3 1, and the pH of the reaction solution in which the precipitate is formed Range from 7.5 to 1 2 stop
- the material can be de-and reminerahsible, i.e. demineralization in an acidic environment increases the surface porosity, while the action of saliva or administered remineralization media results in remineralization through growth or new formation of hydroxylapatite crystals, with the pores closing and in again a filling material is created with the cavity filled with ceramic material, which is comparable to natural hydroxyapatite.
- the tooth filling material as well as the surrounding enamel are firmly anchored to each other and have the same mechanical and physico-chemical properties
- the ceramic material produced according to the invention contains a sparingly soluble plastic phase from calcium phosphates, such as hydroxylapatite (Ca 5 [P0 4 ] 3 [OH]), fluoroapatite (Ca 5 [P0 4 ] 3 F) or mixtures thereof, in a more soluble matrix phase made from calcium ⁇ phosphate compounds such as T ⁇ calciumphosphat, Brushit (CaHP0 4.
- calcium phosphates such as hydroxylapatite (Ca 5 [P0 4 ] 3 [OH]
- fluoroapatite Ca 5 [P0 4 ] 3 F
- a more soluble matrix phase made from calcium ⁇ phosphate compounds such as T ⁇ calciumphosphat, Brushit (CaHP0 4.
- the preferred molar ratio of diphosphate to orthophosphate is in the range from 0 004 to 0.3 1, particularly from 0.01 to 0.02 1, so that 1 to 2 mol% of diphosphate are added per mole of orthophosphate - 4 -
- the pH of the reaction solution is adjusted by adding alkali before the start of the precipitation, preferably by adding ammonia solution, so that the pH remains at 7.5 or higher in the course of the reaction.
- the pH of the reaction solution is preferably kept in the range from 8 to 9 during the entire precipitation.
- Purely aqueous solutions are preferably used, although the idea of the invention is of course also realized with the addition of an organic solvent, such as ethanol or acetone. In this way, for example, the crystallinity of the precipitation product can be controlled.
- a calcium salt with an acid residue which is volatile when heated and phosphates with a cation which is volatile when heated are used as starting compounds, it being possible to use calcium salt mixtures, orthophosphate mixtures, diphosphate mixtures or monosubstances.
- the cations and acid residues which are volatile when heated have the purpose of not having to contaminate the product with undesired cations and anions or of having to wash them before drying, since such washing can also change the stoichiometry with regard to the ratio of calcium to phosphate and thus the product's own ⁇ can be changed undesirably.
- Such volatile ions when heated can be, for example, those which form C0 2 , nitrogen oxides and H 2 0 or NH 3 when heated. It is expedient and preferred to use calcium nitrate and ammonium phosphates.
- the reaction of the calcium salt with orthophosphate and diphosphate, with the latter in a defined amount in order to precisely adjust the tricalcium phosphate content of the sintered body is advantageously carried out in aqueous solution at a temperature in the range from 45 to 120 ° C., preferably in the range from 50 to 90 ° C. , especially in the range of 60 to 80 ° C.
- the calcium salt solution which has been heated to the desired reaction temperature, for example 75 ° C., is introduced and the aqueous solution of the adjusted mixture of orthophosphate and diphosphate is slowly added with vigorous mixing.
- the addition is expediently carried out by dropping while the reaction solution is being stirred in order to rapidly distribute the dropped phosphate solution in the calcium salt solution. Precipitation occurs almost instantaneously.
- the pH should still be at least 7.5.
- the precipitate in the reaction solution is then separated from the mother liquor, for example by filtration or centrifugation, dried, crushed and sintered.
- calcium salt and orthophosphate for example, can be reacted with one another in the stoichiometric molar ratio ⁇ 20% required for the formation of hydroxylapatite.
- the diphosphate added according to the invention serves to produce the desired amount of calcium phosphate in the sintered product
- the sintering is carried out in the customary manner at 800 to 1400 ° C., especially at 900 to 1200 ° C., preferably at 110 to 1200 ° C.
- the sintering time is expediently 1 5 min to 24 h.
- the precipitation product can expediently be ripened in tensioned water vapor, the tensioned water vapor advantageously having a temperature of 100 to 350 ° C. and the ripening of the crystals appropriately taking place over a period of 1 h to 10 days.
- the sintered body can then be comminuted again.
- a synthetic resin substance or a mixing or carrier liquid is added to the pulverized ceramic material.
- the precipitate ripens at room temperature and becomes after 1 2 h filtered off
- the pH value of the supernatant is 8.2 (at RT) 0.7 mmol / l Ca are contained in the supernatant, phosphate is not detectable after drying for 24 hours at 100 ° C, careful comminution in the rubbing machine, pressing and sintering 1 h at 1 1 50 ° C an opaque sintered body is obtained which comes very close to the behavior of enamel in terms of demmeralization and remineralization
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Transplantation (AREA)
- Dental Preparations (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19614016 | 1996-04-09 | ||
DE19614016 | 1996-04-09 | ||
PCT/DE1997/000653 WO1997037932A1 (en) | 1996-04-09 | 1997-03-29 | Process for producing a ceramic material based on calcium phosphate compounds and use of this material |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0892761A1 true EP0892761A1 (en) | 1999-01-27 |
Family
ID=7790805
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97921595A Withdrawn EP0892761A1 (en) | 1996-04-09 | 1997-03-29 | Process for producing a ceramic material based on calcium phosphate compounds and use of this material |
Country Status (5)
Country | Link |
---|---|
US (1) | US6110851A (en) |
EP (1) | EP0892761A1 (en) |
AU (1) | AU2762197A (en) |
DE (1) | DE19780312D2 (en) |
WO (1) | WO1997037932A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100353141B1 (en) * | 1998-09-17 | 2002-09-18 | 주식회사 오스코텍 | Method for preparation of the supersaturated solution of calcium phosphate and the thin film of calcium phosphate crystal by using the solution |
US6379453B1 (en) * | 1999-07-14 | 2002-04-30 | Jiin-Huey Chern | Process for producing fast-setting, bioresorbable calcium phosphate cements |
CN100390051C (en) * | 2005-11-15 | 2008-05-28 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3012852A (en) * | 1956-06-06 | 1961-12-12 | Monsanto Chemicals | Stabilized calcium phosphates and process therefor |
US3473889A (en) * | 1963-03-19 | 1969-10-21 | Monsanto Chemicals | Method for producing phosphates |
DE3433210C1 (en) * | 1984-09-10 | 1986-06-05 | Hans Dr.med. Dr.med.dent. 8000 München Scheicher | Means for filling bone and tooth defects, for bone building, for bone contact layers and for bone and tooth root replacement and use of carbonate apatite for this purpose |
DD253730A3 (en) * | 1985-11-14 | 1988-02-03 | Thale Eisen Huettenwerk | SELF-SLIPING FUEL WIRE FOR ARC FLASH WELDING OF WEAR-RESISTANT PLATFORMS |
ATE108319T1 (en) * | 1987-12-23 | 1994-07-15 | Herbst Bremer Goldschlaegerei | DENTAL FILLING MATERIAL. |
DE3935060C2 (en) * | 1989-10-20 | 1996-05-30 | Herbst Bremer Goldschlaegerei | Process for the production of a ceramic material for the dental field and its use |
GB9215356D0 (en) * | 1992-07-20 | 1992-09-02 | Univ Reading The | Bone materials |
DE4302072A1 (en) * | 1993-01-26 | 1994-07-28 | Herbst Bremer Goldschlaegerei | Ceramic material for dental fillings and / or dental prostheses and method for producing the same |
-
1997
- 1997-03-29 EP EP97921595A patent/EP0892761A1/en not_active Withdrawn
- 1997-03-29 DE DE19780312T patent/DE19780312D2/en not_active Expired - Fee Related
- 1997-03-29 US US09/155,953 patent/US6110851A/en not_active Expired - Fee Related
- 1997-03-29 AU AU27621/97A patent/AU2762197A/en not_active Abandoned
- 1997-03-29 WO PCT/DE1997/000653 patent/WO1997037932A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9737932A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19780312D2 (en) | 1999-05-12 |
AU2762197A (en) | 1997-10-29 |
US6110851A (en) | 2000-08-29 |
WO1997037932A1 (en) | 1997-10-16 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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Effective date: 19981006 |
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AK | Designated contracting states |
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17Q | First examination report despatched |
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GRAH | Despatch of communication of intention to grant a patent |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20010306 |