WO2011065873A1 - Matériau céramique chimiquement lié à base d'oxyde de trioxyde de calcium d'aluminium (c3a), poudre et pâte pour former celui-ci et son utilisation - Google Patents

Matériau céramique chimiquement lié à base d'oxyde de trioxyde de calcium d'aluminium (c3a), poudre et pâte pour former celui-ci et son utilisation Download PDF

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Publication number
WO2011065873A1
WO2011065873A1 PCT/SE2009/051331 SE2009051331W WO2011065873A1 WO 2011065873 A1 WO2011065873 A1 WO 2011065873A1 SE 2009051331 W SE2009051331 W SE 2009051331W WO 2011065873 A1 WO2011065873 A1 WO 2011065873A1
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WO
WIPO (PCT)
Prior art keywords
paste
liquid
chemically bonded
powder
composition
Prior art date
Application number
PCT/SE2009/051331
Other languages
English (en)
Inventor
Leif Hermansson
Helena Bergman
Original Assignee
Doxa Ab
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
Application filed by Doxa Ab filed Critical Doxa Ab
Priority to PCT/SE2009/051331 priority Critical patent/WO2011065873A1/fr
Publication of WO2011065873A1 publication Critical patent/WO2011065873A1/fr

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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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/0047—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L24/0052—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with an inorganic matrix
    • A61L24/0068—Inorganic materials not covered by groups A61L24/0057 or A61L24/0063
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • 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
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/54—Filling; Sealing
    • 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
    • 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
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the present invention relates to a chemically bonded ceramic material based on 3CaOAl203 (also denoted as C3A) and its use in applications wherein the ambient temperature is above 25°C.
  • the main binder system forms a chemically bonded ce- ramie upon hydration thereof and is based on powdered calcium aluminate, and may optionally contain minor amounts of other phases of calcium aluminate and /or calcium silicate.
  • An optimal second binder system is a crosslinking organic binder system which provides for initial crosslinking of the freshly mixed paste forming the biomaterial.
  • the material also comprises inert filler particles.
  • the in- vention relates to a powdered composition for preparing the inventive chemically bonded ceramic material, and a paste from which the material is formed, as well as a kit comprising the powdered composition and liquid, as well as methods of using the material as a biomaterial in small volume applications, and the use of the general material as a construction material.
  • CBCs chemically bonded ceramics
  • bioma- terials bioma- terials
  • the materials should be as biocompatible as possible.
  • biomaterials that are required especially for dental applications include good handling ability of the material with simple applicability in a cavity, moulding that permits good shaping ability, a hardening/solidification of the material that is sufficiently rapid for filling work without detrimental heat generation and that provides serviceability directly following therapy, a high hardness and strength, corrosion resistance of the resulting hardened material, good bonding between the hardened biomaterial and biological tissue, radio-opacity, good long time properties and good aesthetics of the re- suiting hardened material.
  • the biomaterials may also comprise one or more additives, such as expansion compensating additives adapted to give the ceramic mate- rial dimensionally stable long-term attributes.
  • the system comprises additives and / or is based on raw materials that contribute to translucency of the hydrated material.
  • Calcium aluminate based chemically bonded ceramics are known in the art and have been described in numerous patent applications, such as for example WO2005/039508 and WO2004/028577.
  • WO2004/028577 discloses an injectable biocompatible cement composition formed from a hydraulic powder raw material, predominantly comprising calcium aluminate phases, of which phases more than 50 vol.% is CA and C12A7, and less than 10 vol.% is C3A, and an aqueous hydration liquid.
  • the injectable cement composition can be used for e.g. treatment of cancer by means of the heat generated in vivo upon curing of the cement composition disclosed therein.
  • the present invention is based on the use of the specific calcium aluminate phase C3A.
  • This phase has some unique properties related to hydration, reaction rate, temperature and volume aspects which can be utilized for specific applications as biomaterials, as well as a general construction material for specific environments with improved properties.
  • the present invention relates to a material based on the phase C3A for specific applications within dentistry and as a general biomaterial, as well as in the construction field.
  • the use of the C3A phase is according to the invention based on the properties of this phase with regard to how this phase is applied taking the following aspects into account, namely the reaction rate, temperature developed, the phase structure developed, as well as the volume of the reacting material.
  • the present invention relates to a powdered composition for preparing a chemically bonded ceramic biomaterial, which powdered composition comprises a powdered inorganic cement, which cement comprises the phase 3CaO»Al203 (i.e. C3A) and, optionally, minor amounts of other calcium aluminate phases and/ or cal- cium silicate.
  • a poly acrylic acid, and a stable, inert phase based on oxides or glass with a mean particle size of less than 2 ⁇ , and/or based on mi- crosilica of a particle size below 100 nm may be added.
  • the invention relates to a paste forming a chemically bonded ce- ramie biomaterial obtained by mixing the C3A powder composition with a physiologically acceptable liquid which is soluble and / or miscible with water.
  • the invention relates to a kit comprising the C3A powder and an aqueous hydration liquid based on water.
  • the kit comprises a capsule mixing system containing the C3A powder and an aqueous hydration liquid based on water.
  • the invention in another aspect relates to a capsule mixing system containing the CsA-powder and a physiologically acceptable non-aqueous hydration liquid.
  • the formed paste is transformed into a hydrating paste after some time in contact with body liquid in vivo and/or added water-containing liquid in vivo.
  • the volume of the paste has greater freedom than when the reaction takes place with the full amount of water already from start of the hydration.
  • the invention relates to a method of restabilising a damaged implant as bone void filler due to peri-implantitus. In yet a further aspect the invention relates to a method of sealing an implant to another implant and/or to tooth or bone tissue using the paste of the invention.
  • the invention in another aspect relates to a method of cementing a veneer to a tooth using the paste of the invention.
  • the invention in another aspect relates to a method of fissure sealing of teeth.
  • the invention in another aspect relates to a method of tooth filling for small cavities with volumes up to 20 mm 3 .
  • filling in a step-wise manner using about 10 mm 3 of the paste in each step is conceivable.
  • the invention in another aspect relates to a method of cementing loose nails to the natural nail.
  • the invention relates to the use of the material as a construction material for environments (natural or artificially controlled) with temperatures above 25°C during hydration of the material. This guaranties the direct develop- ment of the C3AH6 phase, without any transitions between different hydrates.
  • construction material is intended to embrace applications of the material as a construction material for buildings, tools and the like.
  • the present invention addresses the issues for materials based on chemically bonded ceramics for applications where sealing of the contact zone between the biomaterial and biological tissue is crucial, and wherein optimized early age properties as well as final properties are maintained.
  • some unique properties of the C3A phase during hydration can be utilized.
  • the present invention is based on the surprising finding that the calcium aluminate phase C3A favorably can be used in biomaterial applications in spite of its generally too exothermic properties.
  • the inventive material should be used in applications wherein the ambient temperature during hydration of the material is above 25°C. Thereby, the formation of a single phase from the C3A will be secured.
  • the calcium aluminate phase C3A is generally considered to be too reactive to be used in biomaterial applications.
  • the present inventors have found that the exothermic reaction during hydration can be controlled by using small volumes of the inventive material.
  • the surrounding large contact surface will then act as a cooling surface, effectively dissipating the heat without any detrimental impact on the surrounding biological tissues.
  • the temperature can thus be controlled so as to be no more than 41 °C.
  • the inventors have also found that when using the C3A in the high amounts according to the invention, the reaction rate will be essentially determined by the particle size, while the content of C3A within the claimed range will not affect the reaction rate. Accordingly, within the claimed range the temperature will not be affected by the content of C3A.
  • the phase C3A is hydrated to just one phase with the same C:A ratio as the original phase, without any transition between different possible hydrates.
  • the hydration occurs according to the following reaction: 3CaOAl 2 0 3 + 6H 2 0 -» 3CaOAl 2 0 3 ⁇ 6H 2 0 (katoite) (also denoted as C 3 AH 6 ).
  • the hydration of C3A yields only one phase, viz. katoite, while other Ca- aluminate compositions yield also the phase gibbsite, i.e. Al(OH)3.
  • the formation of one single phase upon hydration will result in improved microstructure properties, having a positive impact on strength and translucency of the material obtained.
  • the C3A phase no transition between different hydrated phases is possible.
  • the hydrates Ca02Al 2 03 ⁇ 8H 2 0 and/or CaOAl 2 03 ⁇ 13H 2 0 may be formed.
  • Up to 20 % by volume of other calcium alumi- nate and/ or calcium silicate phases in the cement phase may be tolerated, without risking the desired properties of the C3A phase. It is preferred that such content is kept as low as possible.
  • the material when using the C3A phase as a construction cement material, such as for tool constructions, the material is especially advantageous for use in environments where the ambient temperature during hydration is above 25°C.
  • the material of the invention accordingly represents a more uniform hydrating phase in terms of composition over time, and also at the same time also a simpler composition of the cement phase thereof.
  • the exothermic C3A phase according to the present invention is especially well suited for use in a paste when the paste to be injected is formed from a nonaqueous liquid.
  • a high reactivity of the cement phase is desirable, since the reaction (hydration) will rely upon diffusion of water from the surrounding body liquid into the inventive material.
  • the liquid must be able to be replaced by water in situ in the body in order for the material to be properly hydrated.
  • the non-aqueous liquid can thus be any liquid which is physiologically acceptable and which is water soluble or miscible with water. Examples of suitable liquids are alcohols, such as e.g. glycerol.
  • the invention is aimed at producing biomaterials with special reference to properties related to small application volumes. Additional aspects of the invention will be described below.
  • the chemically bonded ceramic system of the invention is based on calcium alu- minate.
  • the total amount of calcium aluminate, together with any calcium silicate present, is comprised of at least 80% by C3A. Any contents of other calcium aluminate and/ or calcium silicate phases should be kept to a minimum in order not to interfere with the desired properties of the inventive material and must therefore not exceed 20 % by volume of the total cement powder phase.
  • the pre- ferred calcium aluminate phase is pure C3A.
  • the mean average particle size should be below 5 pm, preferably below 4 ⁇ , but not below 2 ⁇ .
  • the particle size of the hydrates formed is below 60 nm.
  • the inventive material may comprise a second binder system, such as described in e.g. WO2005/039508, in order to provide desired rheological features and early-age working properties of the material.
  • the powdered material and/or the hydration liquid may comprise a polycarboxylic acid (or a co-polymer thereof, or a polycarboxylate, i.e. a salt or ester of a polycarboxylic acid), such as e.g. a poly- acrylic acid and/ or a salt thereof.
  • the polycarboxylic acid can be applied as a solution and / or as a solid acid component.
  • the polycarboxylic acid may e.g. be selected from poly(maleic acid), poly(itaconic acid) or tricarballylic acid) or carboxylates thereof, such as phosphate esters.
  • the polycarboxylic has a molecular weight of preferably 5,000- 100,000 and is present in an amount of up to 20 %, preferably 5- 15 %, and most preferably 7- 12 % by weight, calculated on the powdered material including any dry additives, such as e.g. used for dental applications.
  • the initial low pH of the system due to the presence of a polycarboxylic acid, a co- polymer thereof, or a polycarboxylate (i.e. a salt or ester of a polycarboxylic acid), such as polyacrylic acid and/ or a salt thereof, will induce a rapid dissolution of the basic cement system.
  • the bulk of the liquid with which the powdered composition is mixed is water.
  • the pH is increased to over 8, at which pH the final hydration of the C3A occurs.
  • the control of the pH is essential for transforming the initial acid system into a bioactive system, i.e. for reaching conditions for apatite formation.
  • the rapid change into high pH-values according to the present invention reduces the risk of free metal ion release, which is enhanced by acid conditions.
  • the amount of water, when used, according to the invention is selected so as to be sufficient to fully hydrate all the chemically bonding inorganic cement, so as to thereby enable the forming the chemically bonded ceramic. Thus, no or low contents of the original cement particles will remain in the end product.
  • inert filler particles used according of the invention stable glasses and/or oxides and/or pre-hydrated C3AH6 can be mentioned.
  • Other possibilities according to the invention is to use micro-silica and/or nano-scale single crystal of hydrates.
  • inert, stable glass additives may be included to achieve improved physical properties for both initial paste and the cured material.
  • the improved properties of the cured material are specifically related to strength, wear resistance and fracture toughness, and optical properties.
  • the system comprises inert nanosize glass, as an inert filler in the powdered material at high content, preferably a content corresponding to 20-50 % by volume of the overall powder.
  • the particle size is critical in establishing high homogeneity and related strength development. It is preferred that the particle size is 0.1 -0.4 ⁇ .
  • the parti- cle size is selected specifically with regard to the desired translucency of the resulting cured material, where the particle size in the preferred size range is below the lower region of the visual light, i.e. 400 nm.
  • the inert glass particle composition should be comprised of glasses containing the element Sr and/ or Ba and/ or Zr, or other heavy element with a density >5 g/cm 3 .
  • Zirconium oxide is a preferred oxide for enhanced radiopacity.
  • the paste of the invention may be used as a dental luting cement, tooth fillings, fissure sealings, and as endo products (including orthograde and retrograde fillings) where a small volume of the paste is used.
  • the present invention is preferably used for sealing and related applications, such as dental luting cements, small dental fillings including endodontic fillings, and cements for veneers, as well as bone void filling material for restabilisation of implants.
  • b Deionised water. (The water should be treated so that the main part of its ionic content has been removed). The water could also preferably be further treated in order to remove microorganisms and other impurities).
  • the calcium aluminate used for this material was synthesised using high purity AI2O3 and either of CaO and CaC03.
  • the appropriate amounts of the raw materials are weighed in to a suitable container (3: 1 molar ratio of Al:Ca).
  • the powders are intimately mixed by tumbling in excess isopropanol or tumbled dry using a dry powder mixer. If mixing in isopropanol is performed the next step will be removing the isopropanol, such as by evaporation of the solvent using an evaporator combining vacuum and heat and finally heating in oven.
  • the next step is filling high purity AI2O3 crucibles with the powder mix and heat treating it above 1390°C for the ap-litiste period of time in order to get nearly mono-phase calcium aluminate according to the description above.
  • the material is crushed using a high energy crusher, in this case a roller crusher with alumina rollers.
  • the calcium aluminate is milled using an air jet mill (Hosokawa Alpine) to the specified particle size distribution with a d(99)v of ⁇ 9 ⁇ and an average parti- cle size of 3.5 ⁇ .
  • the final powder formulation is obtained in the following way: All powder components are weighed in with high accuracy according to the composition in Table 1.
  • the cement binder phase of the powder prepared in this example comprised 100 % by volume of C3A.
  • Table 1 Composition of the final powder formulation.
  • the LiCl is first dried at 150°C for at least 2 hours in order to remove physically bound water.
  • the LiCl is weighed into a PE bottle so that the final composition after addition of the water will be 25 mM of LiCl. After the water has been added the bottle is shaken until all the salt has dissolved. The liquid is now ready for use.
  • the powder and liquid described above were tested together in the below tests using a powder to liquid (P:L) ratio of 3.5: 1.0.
  • the material is mixed using a capsule sys- tern.
  • the capsule is then transferred to a capsule mixing machine and mixed for a sufficient period of time. Using a 3M/ESPE Rotomix the time should be > 6 s with a 3 s centrifuge stage in the end.
  • the ready material is dispensed using a conventional applicator into any desired sample mould or container._The tests performed on the material are the tests shown in Table 2.
  • the maximum temperature achieved as a function of the paste volume used determined by measuring the temperature in pastes injected into cavities drilled in ex- trated teeth.
  • the start tooth temperature was controlled to 35°C.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Surgery (AREA)
  • Dental Preparations (AREA)

Abstract

La présente invention porte sur un matériau céramique chimiquement lié à base de 3CaO•Al2O3 (également désigné par C3A) et sur son utilisation dans des applications dans lesquelles la température ambiante pendant l'hydratation est supérieure à 25°C. Le système de liant principal, qui forme une céramique chimiquement liée lors de son hydratation, est à base d'un aluminate de calcium pulvérulent, et peut facultativement contenir des quantités mineures d'autres phases d'aluminate de calcium et/ou de silicate de calcium. Un second système de liant optimal est un système de liant organique réticulant qui fournit une réticulation initiale de la pâte fraîchement mélangée formant le biomatériau. Le matériau comporte également des particules de charge inertes. L'invention porte également sur une composition pulvérulente pour préparer le matériau céramique chimiquement lié de l'invention, et sur une pâte à partir de laquelle le matériau est formé, ainsi que sur un nécessaire qui comporte la composition pulvérulente et un liquide, ainsi que des procédés d'utilisation du matériau comme biomatériau dans des applications de petit volume, et sur l'utilisation du matériau général comme matériau de construction.
PCT/SE2009/051331 2009-11-24 2009-11-24 Matériau céramique chimiquement lié à base d'oxyde de trioxyde de calcium d'aluminium (c3a), poudre et pâte pour former celui-ci et son utilisation WO2011065873A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/SE2009/051331 WO2011065873A1 (fr) 2009-11-24 2009-11-24 Matériau céramique chimiquement lié à base d'oxyde de trioxyde de calcium d'aluminium (c3a), poudre et pâte pour former celui-ci et son utilisation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SE2009/051331 WO2011065873A1 (fr) 2009-11-24 2009-11-24 Matériau céramique chimiquement lié à base d'oxyde de trioxyde de calcium d'aluminium (c3a), poudre et pâte pour former celui-ci et son utilisation

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WO2011065873A1 true WO2011065873A1 (fr) 2011-06-03

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003041662A1 (fr) * 2001-09-26 2003-05-22 Doxa Aktiebolag Materiau en poudre et materiau ceramique fabrique a partir de ce materiau en poudre
US6620232B1 (en) * 1998-10-12 2003-09-16 Doxa Aktiebolag Dimension stable binding agent systems for dental application
US20040206272A1 (en) * 2001-09-26 2004-10-21 Leif Hermansson Method for the manufacturing of a powdered material, the powdered material and a ceramic material manufactured there from

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6620232B1 (en) * 1998-10-12 2003-09-16 Doxa Aktiebolag Dimension stable binding agent systems for dental application
WO2003041662A1 (fr) * 2001-09-26 2003-05-22 Doxa Aktiebolag Materiau en poudre et materiau ceramique fabrique a partir de ce materiau en poudre
US20040206272A1 (en) * 2001-09-26 2004-10-21 Leif Hermansson Method for the manufacturing of a powdered material, the powdered material and a ceramic material manufactured there from

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