WO2016071301A1 - Technologie pour pré-coloration de granulat séché par pulvérisation, procédé de préparation et ses utilisations, et solution de coloration - Google Patents

Technologie pour pré-coloration de granulat séché par pulvérisation, procédé de préparation et ses utilisations, et solution de coloration Download PDF

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Publication number
WO2016071301A1
WO2016071301A1 PCT/EP2015/075509 EP2015075509W WO2016071301A1 WO 2016071301 A1 WO2016071301 A1 WO 2016071301A1 EP 2015075509 W EP2015075509 W EP 2015075509W WO 2016071301 A1 WO2016071301 A1 WO 2016071301A1
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Prior art keywords
colored
spray dried
dried granulate
ceramic
solution
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PCT/EP2015/075509
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English (en)
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Berthold Reusch
David Figge
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Pritidenta Gmbh
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Publication of WO2016071301A1 publication Critical patent/WO2016071301A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0006—Production methods
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0022—Blanks or green, unfinished dental restoration parts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/78—Pigments
    • 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
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/765—Tetragonal symmetry
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour

Definitions

  • the present invention relates to a novel coloring solution and to the use thereof for impregnating a spray dried granulate. Further, the invention relates to a process for the preparation of a colored spray dried granulate and to a colored spray dried granulate obtainable according to this process. The invention also relates to a process for the preparation of a colored shaped ceramic blank; to a colored shaped ceramic blank obtainable according to this process; and to the use of the colored shaped ceramic blank for the preparation of dental articles.
  • Preferred dental articles are crowns, bridges, inlays, onlays, veneers, facings, crown frameworks, bridged frameworks, implants, abutments, copings or orthodontic appliances.
  • zirconia ceramic is a popular artificial ceramic material for the preparation of dental restorations.
  • One drawback of the use of zirconia ceramic is the white color thereof, which does not resemble the color of a natural tooth. Therefore, several methods for coloring zirconia ceramic have been developed.
  • Zirconia ceramic may be colored by means of coloring solutions.
  • a pre-sintered body is milled and colored by dipping the zirconia ceramic into a coloring solution or by painting the zirconia ceramic with a coloring solution.
  • coloring solutions may in general result in significant changes of the microstructure of the zirconia ceramic and may cause unpredictable problems due to decreasing strength of the zirconia ceramic or chipping of the veneering ceramics.
  • DE 199 04 522 A1 discloses a process for coloring translucent dental ceramics, wherein a pre-sintered dental ceramic is provided, a metal ion coloring solution is applied to the pre-sintered ceramic to form an intermediate product, and the intermediate product is sintered to form a colored dental ceramic.
  • the solution can be applied to the ceramic by immersion of the ceramic into the solution, deposition of the solution to the ceramic by means of a brush or a swab, or by deposition of the solution to the ceramic by means of a spraying process.
  • a disadvantage of this process is that the color is applied only intergranular to the ceramic particles. Therefore, the process is not suitable for obtaining a colored ceramic with a homogeneous color gradient resembling the color and translucence of a natural tooth.
  • a multicolored zirconia ceramic may be obtained by combining a colored zirconia ceramic with coloring intermediate layers, for example opaque lines, which display no, or greatly reduced translucence.
  • coloring intermediate layers for example opaque lines, which display no, or greatly reduced translucence.
  • Such systems use as intermediate layers dye pastes or dye suspensions, which are applied to a framework ceramic by a dental technician in several procedures. This method is time-consuming and it is difficult to obtain a multicolored zirconia ceramic resembling the color gradient of a natural tooth.
  • a disadvantage of multicolor zirconia ceramic prepared by this method is that boundaries between the colored layers in the final dental restorations remain perceptible by the naked eye.
  • multicolor blanks provide a facility to prepare multicolored zirconia ceramic.
  • WO 2014/062375 A1 discloses a machinable multi- sectional block, where the individual sections are made for example of tetragonal zirconia crystallites having different translucencies.
  • a disadvantage of this technology is that the sections are arranged as layers and that a color difference between the layers is clearly visible.
  • colored spray dried granulates are not available in any desired VITA dental color, in particular not on a large scale. For certain qualities, colored spray dried granulates are not available at all. Consequently, based on the available colored spray dried granulates, it is not possible to prepare uniformly colored shaped blanks in any VITA dental color(s).
  • Fig. 1 is a photograph showing a multicolored shaped zirconia ceramic blank of the invention with a homogeneous color gradient.
  • Fig. 2 is a photograph showing a bicolored shaped zirconia ceramic blank of the state of the art without a color gradient and a clearly visible color difference between the layers.
  • the present invention relates to a solution comprising:
  • the invention relates to a process for the preparation of a colored spray dried granulate comprising the following steps:
  • the invention relates to a process for the preparation of a colored spray dried granulate comprising the following steps:
  • the invention relates to a process for the preparation of a colored spray dried granulate comprising the following steps:
  • the spray dried granulate contains a powder and a binder.
  • the spray dried granulate is a ceramic spray dried granulate, preferably a zirconia ceramic spray dried granulate.
  • the binder is non-redispersible in water.
  • the binder is an acrylate-based binder.
  • the impregnated spray dried granulate is dried at temperatures ranging from 100 °C to 130 °C.
  • the invention relates to a colored spray dried granulate obtainable according to the process as described above.
  • the invention relates to the use of a solution as defined above for impregnating a spray dried granulate, preferably for coloring a ceramic spray dried granulate.
  • the invention relates to a process for the preparation of a colored shaped ceramic blank comprising the following steps:
  • the invention relates to a colored shaped ceramic blank obtainable according to the process as defined herein, preferably to a multicolored shaped ceramic blank.
  • the colored shaped ceramic blank is a colored shaped zirconia ceramic blank.
  • the colored shaped ceramic blank is a preform, preferably of tooth- similar geometry, particularly preferred a dental milling block, a disc or a prefab.
  • the invention relates to a colored shaped ceramic blank as defined above for the preparation of a dental article.
  • the dental article is a crown, a bridge, an inlay, an onlay, a veneer, a facing, a crown framework, a bridged framework, an implant, an abutment, a coping or an orthodontic appliance.
  • the term "dental application” means any application or use in the dental or orthodontic field, especially a dental restoration, a preform, e.g. a dental milling block, a disc or a prefab for application in dental clinics (Chair side) or dental laboratories.
  • the term "dental article” means any article which can or is to be used in the dental or orthodontic field, especially for producing of or as dental restoration, a tooth model and parts thereof.
  • dental articles include but are not limited to crowns, bridges, inlays, onlays, veneers, facings, copings, crown frameworks, bridged frameworks, implants, abutments, orthodontic appliances (e.g. brackets, buccal tubes, cleats and buttons) and parts thereof.
  • a dental article should not contain components which are detrimental to the patient's health and thus be free of hazardous and toxic components being able to migrate out of the dental article.
  • the term “dental restoration” means any dental restorative material used to restore the function, integrity and morphology of missing tooth structure.
  • the term “preform” means any piece of a material, which has been preformed for further use, e.g. for use in a dental CAD/CAM machine, especially a dental milling block, a disc or a prefab.
  • the term “dental milling block” means a solid block (3-dim article) of a material from which a dental article or a dental restoration can or is to be machined.
  • disc means a disc (3-dim article) of a material from which a dental article or a dental restoration can or is to be machined.
  • prefab means any preformed body resembling the tooth geometry.
  • VITA dental color(s) means the gradual 16 VITA classical A1 - D4 shade guide serving to accurately determining tooth shade and the 32 3D-master shade guide VITA basic colors.
  • the arrangement of the shades in the VITA classical family of shades is as follows: A1 , A2, A3, A4 (reddish-brownish), B1 , B2, B3, B4 (reddish-yellowish), C1 , C2, C3, C4 (greyish shades), D2, D3, D4 (reddish-grey).
  • translucency is the light-transmitting capacity of a material, for example of a blank or a dental article, i.e. the ratio of transmitted to incident light intensity.
  • a solution comprising a source for a coloring oxide comprises any solution of any commercially available chemical composition, which is suitable as a source for a coloring oxide, including but not limited to nitrates, carbonates, oxalates and metal organic compositions, which are well known to the skilled person for forming coloring oxides after firing.
  • Examples for a solution comprising a source for a coloring oxide are iron nitrate solutions, erbium nitrates solutions, cobalt nitrate solutions, manganese nitrate solutions; iron carbonate solutions, erbium carbonate solutions, cobalt carbonate solutions, manganese carbonate solutions; iron oxalate solutions, erbium oxalate solutions, cobalt oxalate solutions and manganese oxalate solutions.
  • uniformly colored means constantly and thoroughly colored.
  • Coloring solution colored spray dried granulate, processes for the preparation and uses thereof
  • a problem of the invention is to provide an alternative solution for coloring granular materials, and colored granular materials, which are suitable for the preparation of uniformly colored shaped ceramic blanks, in particular colored spray dried granulates, which are available in any desired VITA dental color. It has now been found that this problem is surprisingly solved by a solution comprising: (a) from 0.01 wt.% to 5.0 wt.% iron nitrate,
  • the solution comprises
  • the solution further comprises
  • (b2) cobalt nitrate, preferably from 0.0001 wt.% to 1 .0 wt.% cobalt nitrate.
  • the solution further comprises
  • (b3) manganese nitrate preferably from 0.0001 wt.% to 1 .0 wt.% manganese nitrate.
  • the solution further comprises
  • (b2) cobalt nitrate, preferably from 0.0001 wt.% to 1 .0 wt.% cobalt nitrate, and
  • the solution as defined herein is suitable for impregnating a spray dried granulate, preferably for coloring a spray dried granulate. Furthermore, it has been found that with the solution as defined above, spray dried granulates covering the whole range of VITA dental colors and covering additional dental colors other than the VITA dental colors can be obtained. It is particular surprising that the solution of the invention allows the preparation of colored spray dried granulates in any desired VITA dental colors and in other dental colors on a large scale. In a preferred embodiment, the solution is a coloring solution. In one embodiment, the invention relates to a solution comprising:
  • the invention relates to a solution comprising:
  • (b2) cobalt nitrate, preferably from 0.0001 wt.% to 0.5 wt.% or
  • (b3) manganese nitrate preferably from 0.0001 wt.% to 0.5 wt.% and
  • the solution comprises (b3) manganese nitrate.
  • iron nitrates, erbium nitrates, cobalt nitrates and manganese nitrates are suitable as starting materials for the preparation of the solution of the invention, and for the preparation of an iron nitrate solution, an erbium nitrate solution, a cobalt nitrate solution or a manganese solution.
  • Iron nitrate or iron(lll)-nitrate is the chemical compound with the formula Fe(NOs)3 * 9 H 2 O.
  • Erbium nitrate or erbium(lll)- nitrate is the chemical compound with the formula Er(NOs)3 * 5 H 2 O .
  • Cobalt nitrate or cobalt(ll)-nitrate is the chemical compound with the formula Co(NOs) 2 * 6 H 2 O.
  • Manganese nitrate or manganese(ll)-nitrate is the chemical compound with the formula Mn(NO3) 2 * 6 H 2 O. All nitrates are commercially available.
  • the solution of the invention comprises also a solvent suitable for dissolving the metal nitrates.
  • solvents may be water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol or n-propyl alcohol; ketones such as acetone and mixtures of water with alcohols and/or ketones and/or ethylene glycol and/or glycerol.
  • the solvent is water, preferably distilled water, ethyl alcohol or a mixture of water with ethyl alcohol.
  • the amount of iron(l l l) nitrate in the solution ranges from 0.01 wt.% to 5.0 wt.% iron(l l l) nitrate based on the total weight of the solution, e.g.
  • the amount of iron(l l l) nitrate in the solution ranges from 0.1 wt.% to 1 .0 wt.% iron (III) nitrate.
  • the amount of erbium(ll l) nitrate in the solution ranges from 0.01 wt.% to 5.0 wt.% erbium(l l l) nitrate based on the total weight of the solution, e.g.
  • the amount of erbium(l l l) nitrate in the solution ranges from 0.1 wt.% to 2.5 wt.% erbium(l l l) nitrate.
  • the amount of cobalt(l l) nitrate in the solution ranges from 0.0001 wt.% to 1 .0 wt.% cobalt(l l) nitrate based on the total weight of the solution, e.g.
  • the amount of cobalt(l l) nitrate in the solution ranges from 0.0001 wt.% to 0.2 wt.% cobalt(l l) nitrate.
  • the amount of manganese(l l) nitrate in the solution ranges from 0.0001 wt.% to 1 .0 wt.% manganese(l l) nitrate based on the total weight of the solution, e.g.
  • the amount of manganese(l l) nitrate in the solution ranges from 0.0001 wt.% to 0.2 wt.% manganese(l l) nitrate.
  • the invention in another aspect, relates to a process for the preparation of a solution as defined above comprising dissolving iron nitrate (a), erbium nitrate (b1 ), if appropriate cobalt nitrate (b2) and/or manganese nitrate (b3) in a solvent, preferably in water.
  • An iron nitrate solution, an erbium nitrate solution, a cobalt nitrate solution or a manganese solution can be prepared by dissolving the respective nitrates in water.
  • the invention relates to the use of a solution as defined herein for impregnating a spray dried granulate.
  • the solution is used for coloring a ceramic spray dried granulate, preferably for coloring a zirconia ceramic spray dried granulate.
  • the invention relates to a process for the preparation of a colored spray dried granulate comprising the following steps:
  • the invention relates to a process for the preparation of a colored spray dried granulate comprising the following steps:
  • the process comprises a further process step (d) tumbling and sieving the impregnated spray dried granulate.
  • process step (d) the granulate flow ability of the impregnated material is optimized.
  • the spray dried granulate may be spreaded out and/or distributed, for example in a pot or in a tube.
  • Spray dried granulates used as starting material in process step (a) are commercially available.
  • the spray dried granulate is a glass, a ceramic or a glass- ceramic spray dried granulate, comprising stabilized ZrO2 and/or AI2O3, preferably a ceramic spray dried granulate based on partially (TZP/Tetragonal Zirconia Polycrystals, PSZ/Partially Stabilized Zirconium oxide) or fully stabilized zirconium oxide (FSZ/Full Stabilized Zirconiumoxide).
  • Glass, glass-ceramic and ceramic spray dried granulates are commercially available.
  • the spray dried granulate is a zirconia ceramic spray dried granulate.
  • the spray dried granulate is a colorless zirconia ceramic spray dried granulate.
  • a 3Y-TZP zirconia ceramic spray dried granulate comprising from 94.4 wt.% to 94.5 wt.% zirconium oxide, up to 2.0 wt.% hafnium oxide, 5.2 wt.% yttrium oxide and from 0.05 wt.% to 0.3 wt.% aluminia is used as starting material.
  • a 5Y-FSZ zirconia ceramic spray dried granulate comprising from 90.6 wt.% zirconium oxide, up to 2.0 wt.% hafnium oxide and 9.2 wt.% yttrium oxide is used as a starting material.
  • the spray dried granulate contains a powder and a binder.
  • the binder is non-redispersible in water.
  • Binders in terms of the present invention include, but are not limited to acrylic binders, and or non-reversible polyvinyl alcohols, polyethylene glycol, glycerine and cellulose or cellulose ethers.
  • the binder is an acrylate-based binder with or without additions of other binders.
  • an acrylate binder is used.
  • the spreaded spray dried granulate is impregnated with a solution as defined herein.
  • the solution as defined herein is a solution comprising a source for a coloring oxide, in particular the solution of the invention. Impregnating may be carried out by spraying the solution onto the spray dried granulate as well as mixing together. Impregnating may also take place under pressure.
  • the spray dried granulate is impregnated at room temperature with the solution for 10 seconds up to 60 minutes, e.g. from 2 to 30 minutes, from 2 to 20 minutes, from 2 to 10 minutes, from 2 to 5 minutes, from 2 to 4 minutes.
  • the spray dried granulate is impregnated for 2 to 3 minutes with the solution.
  • the impregnated spray dried granulate may be mixed, for example by a tumbling mixer or in a closed container on a ball milling machine before drying.
  • the impregnated spray dried granulate is dried at temperatures ranging from 100 °C to 130 °C, e.g. from 105 °C to 130 °C, from 1 10 °C to 125 °C or from 1 15 °C to 125 °C. If a low-boiling solvent is used, the drying is carried out in a rotary evaporator also under addition of vacuum (Buchi vacuum rotary evaporator).
  • the process of the invention allows the preparation of colored spray dried granulates containing up to 20 wt.% of the coloring solution of the invention as defined herein, e.g. up to 15 wt.% or up to 10 wt.% of the coloring solution.
  • the ratio between the spray dried granulate to be impregnated and the coloring solution of the invention ranges from 20:1 to 5:1 in order to obtain a uniformly colored spray dried granulate, for example from 15:1 to 5:1 , from 12:1 to 7:1 , from 10:1 to 5:1 .
  • 1 ,000 grams zirconia ceramic spray dried granulate are impregnated with from 100 to 150 g of the coloring solution of the invention.
  • an advantage of the process of the invention is that a uniformly colored spray dried granulate free of streaks or color differences can be obtained, wherein the color is intragranularly distributed. Furthermore, due to the diffusion of the metal salt ions of the coloring solution within the spray dried granulate multicolor transitions can be prepared purposively.
  • a further advantage of the process of the invention is that is allows coloring both small amounts and large batches of spray dried granulates.
  • the process of the invention allows the simple preparation of colored spray dried granulates in additional dental colors other than the VITA dental colors. Therefore, in another aspect, the invention relates to a colored spray dried granulate obtainable according to the process as described herein.
  • the spray dried granulate is uniformly colored in a VITA dental color.
  • An advantage of the colored spray dried granulate of the invention is that even after drying, the spray dried granulate does not stick together or sometimes bigger aggregates. Thus, the colored spray dried granulate is ready for further use after short loosing up, for example in a tumble mixer.
  • the colored spray dried granulate may be supplied in a kit, for example a kit containing colored spray dried granulates in 16 or 32 different VITA dental colors. Therefore, in another aspect, the invention relates to a kit comprising colored spray dried granulates of the invention in 16 to 32 different VITA dental colors. Colored shaped ceramic blank, process for the preparation and uses thereof
  • novel shaped colored ceramic blanks which are unicolored or multicolored, having a homogeneous color gradient closely resembling natural teeth.
  • novel shaped colored ceramic blanks which eliminate many of the disadvantages inherent in the colored shaped ceramic blanks known from the state of the art, such as clearly visible different colors within the shaped ceramic blank.
  • novel shaped colored ceramic blanks which allow the preparation of translucent dental restoration materials.
  • another problem of the invention is to provide a colored shaped ceramic blank having a homogeneous color gradient, preferably closely resembling natural teeth.
  • the invention relates to a process for the preparation of a colored shaped ceramic blank comprising the following steps:
  • the process of the invention yields a uniformly colored shaped ceramic blank.
  • EP 2 359 771 A2 discloses a process for the preparation of multicolored blanks.
  • US 2013/0224454 A1 discloses the preparation of a multi-layer zirconia dental blank that has a gradual change in chroma.
  • two or more differently colored ceramic materials that are granular in form are filled portionwise successively into a compression die. At least one of the materials is a colored ceramic spray dried granulate of the invention as defined herein.
  • the color of one of the ceramic materials is white and the other colored ceramic material is a colored spray dried granulate of the invention having a VITA dental color.
  • a white ceramic material is a colored ceramic material in an enamel similar color.
  • two differently colored ceramic spray dried granulates are filled into the compression die.
  • the colored ceramic spray dried granulates have two different VITA dental colors.
  • three differently colored ceramic spray dried granulates of the invention are filled into the compression die.
  • the colored ceramic spray dried granulates have three different VITA dental colors.
  • the colored ceramic spray dried granulates of the invention are filled into the compression die.
  • the colored ceramic spray dried granulates have four different VITA dental colors.
  • one white ceramic spray dried granulate and three differently colored ceramic spray dried granulates of the invention are filled into the compression die.
  • the colored ceramic spray dried granulates have three different VITA dental colors.
  • the two or more differently colored ceramic materials are mixed.
  • the two or more differently colored ceramic materials are compressed to obtain a shaped colored body. Compression may be carried out by any pressing techniques suitable for the preparation of dental ceramic bodies. Compression techniques include but are not limited to uniaxial pressing, biaxial uniaxial pressing, biaxial pressing with floating matrix, postisostatic pressing, uniaxial pressing and isostatic prepressing and pure isostatic pressing.
  • the two or more differently colored ceramic materials are uniaxially pressed and isostatically prepressed.
  • the shaped colored body is pre-sintered at temperatures ranging from 700 °C to 1 ,100 °C, e.g. at temperatures ranging from 850 °C to 1 ,150 °C, from 875 °C to 1 ,100 °C to yield a shaped colored ceramic blank.
  • the shaped colored body is pre-sintered at temperatures ranging from 900 °C to 1 ,050 °C.
  • the duration of the pre-sintering at the temperatures described above ranges from 1 hours to 10 hours, e.g. from 1 ,5 hours to 3,5 hours, from 2 hours to 3 hours depending from the pre-sintering temperature.
  • the shaped colored body is pre-sintered for 2 hours.
  • the colored shaped ceramic blank which is obtained according to the process of the invention, is surprisingly uniformly colored after the final sintering at a temperature between 1 ,450 and 1 ,550°C.
  • the use of the colored spray dried granulate of the invention has surprisingly the effect, that the coloring nitrate salts contained in the colored spray dried granulate of the invention diffuse already at short endsintering times. Furthermore, compressing of intermediate layers is not necessary since the colors are sufficiently mixed only by thermic diffusion.
  • the use of the spray dried granulates of the invention results in a high diffusion of the coloring substances resulting in a colored shaped ceramic blank having a homogeneous color gradient closely resembling natural teeth.
  • the colored shaped ceramic blanks of the invention are characterized by a high translucency. Therefore, in another aspect, the invention relates to a colored shaped ceramic blank obtainable according to the process as defined herein.
  • the colored shaped ceramic blank of the invention may be unicolored or multicolored, preferably uniformly unicolored or uniformly multicolored.
  • the colored shaped ceramic blank of the invention comprises
  • the colored shaped ceramic blanks of the invention are characterized by a high color homogeneity.
  • the colored shaped ceramic blank is a multicolored shaped ceramic blank.
  • the multicolored shaped ceramic blank of the invention is unlike the colored shaped ceramic blanks from the state of the art, characterized by a homogenous color gradient resembling natural teeth.
  • the colored shaped ceramic blank is a colored shaped zirconia ceramic blank.
  • the colored shaped ceramic blank is a preform, preferably of tooth- similar geometry, particularly preferred a dental milling block, a disc or a prefab.
  • Preforms for example dental milling blocks, discs or prefabs, can be generated in any requested geometries.
  • a holder for example a metal or polymer holder, can be fixed on the preform by common fixing techniques.
  • the fixing of the preform includes but is not limited to using glue, e.g. a two-part epoxy glue.
  • the invention relates to a colored shaped ceramic blank as defined herein for the preparation of a dental article.
  • the dental article is a crown, a bridge, an inlay, an onlay, a veneer, a facing, a crown framework, a bridged framework, an implant, an abutment, a coping or an orthodontic appliance.
  • any commercially available CAD/CAM milling machine may be used.
  • the so obtained "crude” dental article or dental restoration may be finished by polishing the surface thereof.
  • the "crude” dental article or dental restoration or a part thereof may also be treated with commercially available stain materials, glaze materials or veneering material. Any combinations of the embodiments of the invention described herein are considered to be within the scope of the invention.
  • Example 1 - Preparation of coloring solutions of the invention 1.1 General process for the preparation of a coloring solution of the invention
  • the coloring solution of the invention can be obtained according to the following general process:
  • the respective amounts of iron(l l l)-nitrate nonahydrate e.g. iron(l l l)-nitrate nonahydrate for analysis purchased from Merck, Darmstadt Germany; erbium(l l l)-nitrate hexahydrate, e.g. 99,9% erbium(ll l)-nitrate hexahydrate purchased from Auer Remy, Hamburg Germany; and cobalt(l l)-hexahydrate, e.g. 99% cobalt(l l)-hexahydrate purchased from ABCR, Düsseldorf Germany or manganese(l l)-hexahydrate, e.g. manganese(l l)-hexahydrate for analysis purchased from Merck, Darmstadt Germany, respectively are dissolved, if necessary under stirring, in 500 ml distilled water to yield a stock solution for the colorization of the spray dried powder.
  • the coloring solutions 1 .2.1 to 1 .2.6 having the VITA dental colors A1 , A2, A3, A3.5, B1 and B2 have been prepared according to the general process described in Section 1 .1 from the nitrate salts indicated in Table 1 below.
  • Example 2 Preparation of colored spray dried granulates of the invention 2.1
  • the coloring solution of the invention is filled into a spray attachment.
  • a commercially available spray dried granulate for example of a zirconia ceramic spray dried granulate purchased from Tosoh Corporation, Japan, type TZ-3YSB-E, Zpex or Zpex Smile ® , or from Daiichi Corporation, Japan type HSY-3FSD or HSY-3FSD-J, is spreaded out in a jar. Subsequently, the spreaded spray dried granulate is impregnated for 2 minutes with the respective amount of the coloring solution of the invention having a VITA dental color by spraying the coloring solution onto the spray dried granulate.
  • the spray dried granulate is mixed in a tumbling mixer or inside a ball mill without balls for 15 to 30 minutes.
  • the impregnated granulates are dried in a conventional drying chamber with circulating air at temperatures ranging from 1 15°C to 125°C to a constant weight or by controlling the residual moisture by means of moisture analyzer, for example by a Sartorius Moisture Analyzer MA100 or MA50.
  • the spray dried granulates 2.2.1 to 2.2.6 having the VITA dental colors A1 , A2, A3, A3.5, B1 and B2 have been prepared according to the general process described in Section 2.1 from a zirconia ceramic spray dried granulate and the coloring solutions of Examples 1 .2.1 to 1 .2.6 of the invention.
  • Example 3 Preparation of a unicolored shaped ceramic blank of the invention 3.1 General process for the preparation of a unicolored shaped ceramic blank of the invention
  • a unicolored blank e.g. with a dimension of 98.5 mm and a thickness of 14 mm
  • an amount of 345 g spray dried powder is necessary.
  • the powder is filled in a uniaxial pressing mold and pressed biaxially with a pressure of 100 MPa.
  • the pressed green body can additionally be put inside a vacuum polymer foil and afterpressed at pressures of between 1 .000 and 1 .500 bar postisostatically.
  • the shaped zirconia ceramic body is pre-sintered at 900 °C for about 120 minutes to generate the possibility to mill dental parts out of the pre-sintered porous blank. At this stage, the color has not yet generated.
  • the material is dense and the final VITA dental color is developed after densification.
  • the unicolored shaped zirconia ceramic blanks 3.2.1 to 3.2.6 having the VITA dental colors A1 , A2, A3, A3.5, B1 and B2 have been prepared according to the general process described in Section 3.1 from the colored zirconia ceramic spray dried granulates 2.2.1 to 2.2.6 of the invention.
  • the first layers consists of A1 , the second and the third of a mixture of A1 and A3 (67%/33%) and (33%/67%) and the fourth one consist of A3.
  • the powders are filled inside the mould with a filling system one layer by layer. After filling, the material is pressed biaxially with a pressure of 100 MPa. The pressed green body can additionally be put inside a vacuum polymer foil and afterpressed at pressures of between 1 .000 and 1 .500 bar postisostatically. Then, the shaped zirconia ceramic body is pre-sintered at 900 °C for about 120 minutes to generate the possibility to mille dental parts out of the prefired porous blank. In this stage the color is not yet generated. After a final firing at 1450°C up to 1 .550 °C the material is dense and the final multicolor is developed after sinter densification.
  • the multicolored shaped zirconia ceramic blank 4.2.1 has been prepared according to the general process described in Section 4.1 from the colored zirconia ceramic spray dried granulates 2.2.1 and 2.2.3 of the invention.
  • Fig. 1 is a photograph showing the multicolored shaped zirconia ceramic blank of Example 4.2.1 .
  • the photograph demonstrates that the multicolored shaped zirconia ceramic blank of the invention has a homogeneous color gradient closely resembling a natural teeth.
  • the first master batch to realize the yellow component is based on a yttria stabilized base powder, which is doped with 0.19% iron oxide (content after firing).
  • the addition of this iron is carried out by adding iron carbonate (FeCOs) to the powder preparation before spray drying. Daiichi adds directly iron oxide (Fe 2 Os) as a nanoscaled powder during the preparation resulting in a precolored optically red brown powder.
  • the pink color can be realized by doping the powder before the spray drying with erbium oxide (Er 2 O3) or by generating a coprecipitated erbium oxide stabilized zirconium oxide which has also a TZP crystal phase and high mechanical properties.
  • An erbium oxide stabilized zirconium oxide with the TZP crystal phase contains 9.3 wt.% erbium oxide inside.
  • the grey color can be realized with smallest amounts of cobalt oxide (C02O3), which is realized in the same way as the addition of the other possible oxides like iron oxide or erbium oxide.
  • these powders have to be mixed together with the respective amount to realize the requested tooth color.
  • the powder is mixed in a tubular mixer or put into a barrel without balls on a ball mill. After 60 to 120 minutes the powders are mixed together.
  • the comparative example has been prepared by mixing two base powders with an A1 and an A2 color.
  • a layer composition is obtained by two layers consisting of the following sub-mixed powders: layer 1 (100% A1 ) and layer 2 (100% A3).
  • the powders are filled layer by layer in a mold, and then pressed axially with a pressure of 100 MPa for densification.
  • a cross section of the blank is prepared to show the color gradient.
  • Fig. 2 is a photograph showing a bi-colored shaped zirconia ceramic blank of the state of the art obtainable according to this method.
  • Fig. 2 demonstrates that the blank of the state of the art does not have a color gradient, i.e. it does not show a fluent and smooth color intersection. In contrast, the layers are clearly separated and not interacting.
  • the blank of the state of the art lacks smooth interaction due to another chemical composition of the blank.
  • the blank of the state of the art comprises carbonates such as Fe2CO3 as coloring additive.
  • the qualitative comparison of the multicolored shaped zirconia ceramic blank of the invention with the multicolored shaped zirconia ceramic blank of the state of the art demonstrates that the multicolored shaped zirconia ceramic blank of the invention is characterized by a homogeneous color gradient.
  • the multicolored shaped zirconia ceramic blank of the state of the art is a bi-colored shaped zirconia ceramic blank with separated layers, which does not resemble a natural tooth.

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Abstract

La présente invention concerne une nouvelle solution de coloration et l'utilisation de la solution de coloration pour imprégner un granulat séché par pulvérisation. En outre, l'invention concerne un procédé pour la préparation d'un granulat coloré séché par pulvérisation, et un granulat coloré séché par pulvérisation pouvant être obtenu selon ce procédé. L'invention concerne également un procédé pour la préparation d'une ébauche céramique mise en forme colorée ; une ébauche céramique mise en forme colorée pouvant être obtenue selon ce procédé ; et l'utilisation de l'ébauche céramique mise en forme colorée pour la préparation d'articles dentaires. Des articles dentaires préférés sont des couronnes, des bridges, des incrustations, des appositions, des facettes, des structures de couronne, des structures de bridge, des implants, des butées, des chapes ou des appareils orthodontiques.
PCT/EP2015/075509 2014-11-03 2015-11-03 Technologie pour pré-coloration de granulat séché par pulvérisation, procédé de préparation et ses utilisations, et solution de coloration WO2016071301A1 (fr)

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WO2020191843A1 (fr) * 2019-03-22 2020-10-01 佛山市蓝之鲸科技有限公司 Procédé de préparation de poudre céramique au moyen d'un procédé humide à basse température
US20220184847A1 (en) * 2020-12-15 2022-06-16 Dentsply Sirona Inc. Method for producing a ceramic multilayer blank
WO2023025588A1 (fr) * 2021-08-25 2023-03-02 Ivoclar Vivadent Ag Procédé de production d'oxyde de zirconium granulaire

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WO2020191843A1 (fr) * 2019-03-22 2020-10-01 佛山市蓝之鲸科技有限公司 Procédé de préparation de poudre céramique au moyen d'un procédé humide à basse température
US20220184847A1 (en) * 2020-12-15 2022-06-16 Dentsply Sirona Inc. Method for producing a ceramic multilayer blank
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WO2022132647A1 (fr) * 2020-12-15 2022-06-23 Dentsply Sirona Inc. Procédé de fabrication d'une ébauche céramique multicouche
WO2023025588A1 (fr) * 2021-08-25 2023-03-02 Ivoclar Vivadent Ag Procédé de production d'oxyde de zirconium granulaire

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