EP3145471A1 - Compositions dentaires pouvant être imprimées et frittées, servant à la fabrication de parties de prothèses dentaires, et procédés de fabrication correspondants - Google Patents

Compositions dentaires pouvant être imprimées et frittées, servant à la fabrication de parties de prothèses dentaires, et procédés de fabrication correspondants

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Publication number
EP3145471A1
EP3145471A1 EP15723719.9A EP15723719A EP3145471A1 EP 3145471 A1 EP3145471 A1 EP 3145471A1 EP 15723719 A EP15723719 A EP 15723719A EP 3145471 A1 EP3145471 A1 EP 3145471A1
Authority
EP
European Patent Office
Prior art keywords
dental
equal
μηη
ink
less
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Withdrawn
Application number
EP15723719.9A
Other languages
German (de)
English (en)
Inventor
Uwe Böhm
Mario Beyer
Yvonne Ziegler
Jürgen Steidl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kulzer GmbH
Original Assignee
Heraeus Kulzer GmbH
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 Heraeus Kulzer GmbH filed Critical Heraeus Kulzer GmbH
Publication of EP3145471A1 publication Critical patent/EP3145471A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • A61C13/0019—Production methods using three dimensional printing
    • 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
    • A61K6/836—Glass
    • 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
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/083—Porcelain or ceramic teeth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • 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
    • A61K6/833—Glass-ceramic composites
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/753—Medical equipment; Accessories therefor
    • B29L2031/7532—Artificial members, protheses
    • B29L2031/7536—Artificial teeth

Definitions

  • the invention relates to a dental composition of a free-flowing, ceramic powder of a powdery component comprising at least one dental glass, glass ceramic, metal oxide, mixed oxide selected from metal oxides and / or a mixture comprising at least two of said components and a printable, dental ink, a process for Production of dental prosthetic moldings.
  • Dental ceramic prostheses are currently produced by a subtractive process from blanks, so-called blanks.
  • the prosthetic restorations such as copings, crowns and bridges, are milled out of the blanks and sintered in processes with specific firing curves.
  • the known methods have the disadvantage of a high material usage.
  • very expensive 3 to 5-axis milling machines must be purchased for milling. Therefore, central milling centers have been created, which process the orders of the dental technicians and send the milled prosthesis parts back to the dental technician.
  • a decentralized production of the prosthetic restorations should be possible.
  • the object of the invention was to develop a method and compositions for the method, which allow a production of dental, prosthetic restorations without milling. Preferably, only a polishing finishing should be done.
  • the object of the invention was also the production of prostheses that can be fitted without further adaptation to the dimensions of the prostheses in the mouth of the patient. It was also an object of the invention to provide a method which at least partially allows the use of already existing instruments and equipment of the dental technician, such as sintering ovens. Furthermore, a method should be provided that enables decentralized the production of prostheses or parts of prostheses.
  • a free-flowing composition of dental ceramic powders according to claim 1 a printable, dental ink with a filler content of dental ceramic powdery components according to claim 8 and the method for printing dental moldings, which are suitable for the production of parts of dental prostheses or dental prostheses.
  • dental prostheses according to the invention are understood herein to mean all prosthetic restorations or also parts of the prosthetic restorations in the dental field.
  • dental prostheses or parts of dental prostheses according to the invention comprise both parts of removable dentures and parts of implant-supported dentures.
  • dental prosthetic moldings are detected under a dental prosthesis according to the invention.
  • a method for printing dental ceramics in which dental articles can be printed by contacting a dental ceramic powder present as a powder bed with a dental, printable ink having an increased filler content; in particular, the shaped articles can be printed in layers become.
  • the moldings are printed as a blank of a dental, prosthetic restoration, via an additive process.
  • the thus-printed three-dimensional shaped bodies are dried under defined conditions and a green body is obtained. Subsequently, the binder is removed and sintered. After sintering, a dental prosthetic restoration is obtained.
  • the invention relates to a dental composition of a free-flowing; especially flowable; dental, ceramic powder, in particular suitable for producing a printable powder bed, wherein the powder comprises a powdery component comprising at least one dental glass, glass ceramic, metal oxide, mixed oxide selected from metal oxides and / or a mixture comprising at least two of said components, wherein the Particle sizes, in particular the primary particles, the powdery component in the range of 2 nm to 200 ⁇ , preferably from 2 nm to 150 ⁇ , 1 nm to 100 ⁇ , 1 nm to 15 ⁇ . Particularly preferably, the particle size d 90 is less than or equal 500 nm.
  • the ceramic powder preferably has, as the total refractive index, a refractive index of 1.48 to 1.60 in the powdered components, in particular with a refractive index of 1.49 to 1.56, particularly preferably with a refractive index of 1.49 to 1, 55 further preferably from 1, 49 to 1, 51, preferably 1, 5 to 1, 51.
  • the powdery component has a very narrow particle size distribution, in order to avoid segregation during discharge from the vibrating bulk bucket and to enable the production of a homogeneous pressure bed or powder bed.
  • the particle size must not be too small, as this may favor the formation of cracks in the pressure bed.
  • the dental composition according to the invention of a free-flowing; especially flowable; dental ceramic powder preferably comprises at least one excipient which allows the introduction of the composition into a printing bed without the formation of pores, inclusions, voids and / or clumps.
  • the composition according to the invention therefore preferably has a particularly low angle of repose and preferably a particularly defined, preferably high bulk density.
  • the flowability of the composition and the homogeneity have a direct influence on the quality of the green compacts and thus on the quality of the sintered shaped bodies.
  • the glass products are formed in the molten state.
  • Compositions according to the invention are applied without application of external pressure via a 3D Printing process produced and then dried without further shaping processes, debindered and sintered to obtain the final shape of the molding.
  • Dental powders and dental solids are, in particular, dental glasses, dental ceramics and metal oxides which can be used in the dental field, which preferably fulfill the defined refractive index conditions and / or are used as X-ray opacifiers.
  • Other powdery components having a refractive index outside this range are preferably used only with a low content, in particular less than or equal to 5 wt .-% in the overall composition.
  • the refractive index of all the powdered components used is in the same narrow range, preferably from 1.49 to 1.51.
  • dental ceramic powders with a refractive index of 1.48 to 1.55.
  • the ceramic molding after sintering has a refractive index of 1.40 to 1.60, in particular from 1.49 to 1.56.
  • Particularly preferred pulverulent components for the production of the shaped bodies such as dental glasses or metal oxides, have a refractive index of 1.49 +/- 0.5.
  • Powdery components according to the invention can be selected from dental glass ceramics, dental glasses, oxide ceramics and metal oxides.
  • dental powdery components of the composition and the ink include precipitated silicas, dental glasses such as aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate, lithium disilicate, lithium aluminum silicate, phyllosilicates, calcium oxide, cerium oxide, potassium oxide, sodium oxide, boron silicates, borosilicate glasses, zeolites , Ytterbium-containing dental glasses, ytterbium fluoride-containing dental glasses, amorphous spherical filler on oxide or mixed oxide, in particular mixed oxides of Si0 2 and Zr0 2 , glass fibers.
  • dental glasses such as aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate, lithium disilicate, lithium aluminum silicate, phyllosilicates, calcium oxide, cerium
  • the aforementioned components may additionally comprise carbon fibers and mixtures comprising the pulverulent components.
  • dental pulverulent components comprising zirconium dioxide and ytterbium oxide or zirconium dioxide and ytterbium oxide and / or ytterbium fluoride.
  • dental powdery components include mixtures of
  • silica a) silica, mixed oxides of zirconium dioxide and silica or precipitated silicas, and optionally with
  • Dental glasses such as aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate, lithium disilicate, lithium aluminum silicate, boron silicates and / or borosilicate glasses, and optionally with
  • Components are used in the powder bed and / or in the ink.
  • composition according to the invention and the ink containing filler are used to produce three-dimensional blanks of parts of prostheses or whole prostheses in an additive printing process.
  • the shrinkage in the drying and sintering process is taken into account in the printing process and correspondingly larger-sized molded parts are printed.
  • a preferred powdery component may comprise lithium disilicate glass ceramics, in particular the following composition Si0 2 57.0 to 80.0 wt .-%, Al 2 0 3 0 to 5.0 wt .-%, La 2 0 3 0.1 to 6 , 0 wt .-%, MgO 0 to 5.0 wt .-%, ZnO 0 to 8.0 wt .-%, Li 2 0 1 1, 0 to 19.1 wt .-%, with La 2 0 3rd + La can comprise 0.1 to 9.0 wt .-% 2 0 2 0.1 to 7.0 wt .-% and MgO and ZnO.
  • the lithium disilicate may include Zr0 2 0 to 10.0 wt%, K 2 0 0 to 13.5 wt .-%, P 2 0 5 0 to 1 1, 0 wt .-%, color and fluorescent components 0 to 8.0 wt .-% and additional components from 0 to 6.0 wt .-%, ytterbium fluoride ,
  • a preferred dental powdery component may comprise in wt% Si0 2 57-80; Li 2 0 1 1 - 19; K 2 0 0.001 - 13; P 2 0 5 0.001 - 1 1; Zr0 2 0.001 - 8; Zno 0.001 - 8; other oxides and ceramic pigments 0 - 10.
  • Also preferred dental glasses comprising metal oxides such as Si0 2, Al 2 0 3 , B 2 0 3 , Na 2 0, K 2 0, Cs 2 0, Na 2 0 + K 2 0 + Cs 2 0, CaO, BaO, SrO, ZnO , Zr0 2 , La 2 0 3 , Sc 2 0 3 , Y 2 0 3 , Nb 2 0 5 , Gd 2 0 3 , Yb 2 0 3 , Y 2 0 3 Li 2 0 and P 2 0 5 , fluorine, YF 3 , Cer0 2 , Ti0 2 , Sn0 2 , MgO, Sb 2 0 3 .
  • metal oxides such as Si0 2, Al 2 0 3 , B 2 0 3 , Na 2 0, K 2 0, Cs 2 0, Na 2 0 + K 2 0 + Cs 2 0, CaO, BaO, SrO, ZnO , Zr0 2 , La 2 0 3 , Sc 2
  • the powdery components may comprise amorphous spherical fillers, in particular as a powdery component, in the dental ink, preferably on oxide or mixed oxide, in particular mixed oxides of Si0 2 and Zr0 2 , glass fibers.
  • amorphous spherical fillers in particular as a powdery component, in the dental ink, preferably on oxide or mixed oxide, in particular mixed oxides of Si0 2 and Zr0 2 , glass fibers.
  • powders with spherical particles are preferably used as pulverulent components.
  • Spherical particles with a subsequently defined aspect ratio are preferred.
  • the aspect ratio of the particles is less than or equal to 1.4.
  • powdered components having a particle size of d 90 less than or equal to 100 micrometers ( ⁇ ) used, preferably the particle sizes d 50 at less than or equal to 50 ⁇ , in particular from 0.001 to 50 ⁇ , especially at less is equal to 30 ⁇ , more preferably at less than or equal to 20 ⁇ , more preferably d 50 is less than or equal to 0.1 to 35 ⁇ .
  • the particle sizes are at d 90 is less than or equal to 2.5 ⁇ , more preferably at less than or equal to 1, 5 ⁇ .
  • d 50 is preferably less than or equal to 1, 0 ⁇ , preferably less than or equal to 0.8 ⁇ .
  • pulverulent components comprising zirconium dioxide, silicon dioxide, mixed oxides of zirconium dioxide and silicon dioxide, lithium disilicate having particle sizes with d 99 of less than 480 nm; particle sizes of d 50 equal to or less than 150 nm and d 99 equal to or less than 460 nm are particularly preferred preferably be used in the powder bed as at least one fraction and / or in the dental ink.
  • powdery components having particle sizes with d 99 smaller than 480 nm particularly preferred are particle sizes of d 50 is less than or equal to 150 nm and d 99 is less than 460 nm and optionally in a weight ratio of 0.01 to 50: 1 with dental, powdered components of Particle sizes are used with d 50 less than or equal to 5.0 ⁇ , in particular less than or equal to 1, 0 ⁇ , in particular less than or equal to 0.9 ⁇ , preferably less than or equal to 0.7 ⁇ , more preferably less than or equal to 0.6 ⁇ and greater than or equal to 500 nm , and optionally d 90 is less than or equal to 1 1, 0 ⁇ , in particular less than or equal to 2.0 ⁇ , in particular less than or equal to 1, 8 ⁇ , preferably less than or equal to 1, 4 ⁇ , particularly preferably less than or equal to 1, 0 ⁇ and each independently greater than or equal to 500 nm, and optionally d 99 is preferably less than or
  • the dental compositions have a bulk density of greater than or equal to 0.4 g / cm 3 , in particular greater than or equal to 0.75 g / cm 3 , particularly preferably greater than or equal to 0.80 g / cm 3 .
  • the dental compositions in particular in combination with the abovementioned bulk density, preferably have a repose angle of less than or equal to 60 °, in particular less than 55 °, preferably less than 50 °, more preferably less than or equal to 45 °.
  • pigments may be added to the dental composition in order to establish a basic coloration of the prosthesis parts or prostheses, which may be further colored as required by pigmenting the inks.
  • the pigments Preferably, have a similar particle size as the powdered components, so that the homogeneity of the powder bed is not impaired. In particular, there should be no segregation during application of the powder from a vibrating bulk bucket.
  • pigments generally have a particle size of d 90 less than or equal to 20 ⁇ to less than 15 ⁇ and also less than or equal to 10 ⁇ .
  • d 50 is 0.001 to 10 ⁇ . It may therefore be advantageous to formulate the pigments for producing the powder bed in order to adapt their particle size to that of the pulverulent components. This is possible by a formulation together with the powdery component and / or with binders, for example in a granulation.
  • compositions which are in the form of a powder bed, and the use of the compositions for producing powder beds for 3D printing processes.
  • the compositions are present as a planar powder bed, particularly preferably with a) a bulk density of greater than or equal to 0.45 g / cm 3 , in particular having a bulk density greater than or equal to 0.5 g / cm 3 , in particular greater than or equal to 0.80 g / cm 3 to 1, 2 g / cm 3 , more preferably greater than or equal to 0.85 g / cm 3 , more preferably greater than or equal to 0.90 g / cm 3 , 0.95 g / cm 3 and / or b) with a tamped density greater equal to 2.0 g / cm 3 , in particular greater than or equal to 3 g / cm 3 , more preferably greater than or equal to 4.0 g / cm 3 (DIN 51916), preferably greater than or equal to 5.0 g / cm 3 ,
  • the invention relates to dental compositions which are compacted as a printable powder bed.
  • the free-flowing composition comprises at least one adjuvant comprising dispersants, flow aids, peptizers, binders, solids surface tension adjuvant, lubricants, static charge additives (antistatic agents).
  • Pharmaceutical grade auxiliaries are particularly preferably used in the compositions, preferably those which are suitable for producing powders, since pharmaceutical powders generally have a particle size, ie a particle size of less than 100 micrometers.
  • antistatic agents can be selected from cationic surfactants such as quaternary ammonium compounds.
  • Suitable flow aids include precipitated silicas.
  • Suitable binders for the preparation of the free-flowing composition are, preferably at room temperature, solid and non-tacky binders which, if possible, do not impair the bulk properties of the composition but improve it.
  • a binder can also be formulated by means of spray drying onto the pulverulent components, if appropriate together with further auxiliaries, such as flow aids.
  • Possible solid binders include polyvinyl alcohol, sugars, polacrylic acids, celluloses, such as the cellulose ethers mentioned below, or also TEOS.
  • the invention furthermore relates to a composition which contains at least one adjuvant, the adjuvant comprising, in particular, flow aids (silicon dioxide, in particular having a primary particle size of less than or equal to 100 nm, such as sipernate, an aerosil, precipitated silica comprising primary particles less than or equal to 20 nm, binder, such as gum arabic, gum, cellulose ethers such as methylcellulose, ethylhydroxyethylcellulose (low surface tension), hydroxypropylcellulose, PEG, gelatin, alginate, starch, tragacanth, sugars, saccharides, dextrin, bentonites, especially one-free bentonites (platelet size: 5-10 nm thickness, 0 , 1 -2 ⁇ length), polyvinylpyrrolidone, polyvinyl alcohol, optionally resins, epoxy resins, polyacrylic acids or polyacrylates, urethane, wherein the auxiliaries preferably have a pharmaceutical grade with an impurity
  • the subject matter of the invention is a printable, liquid, dental ink, in particular a printable composition
  • At least one dental, powdery component (also called filler), comprising at least one dental glass, glass ceramic, metal oxide, mixed oxide selected from metal oxides and / or a mixture comprising at least two of said components, wherein preferably the refractive indices of the powdered components in the range of 1, 48 to 1, 60 and, in particular, the powdery component is at least partially silanized and / or functionalized with metal acid esters, and
  • the at least one adjuvant comprises dispersant, in particular a dispersant, polymeric dispersant, flow aids, peptizers, such as alkali and / or alkaline earth metal salt of carboxylic acids, such as citrates, tartrates, oxalates, or diphosphonates, silanolates; Binders, antistatic agents and / or adjuvant for the regulation of the surface tension.
  • dispersant in particular a dispersant, polymeric dispersant, flow aids, peptizers, such as alkali and / or alkaline earth metal salt of carboxylic acids, such as citrates, tartrates, oxalates, or diphosphonates, silanolates
  • peptizers such as alkali and / or alkaline earth metal salt of carboxylic acids, such as citrates, tartrates, oxalates, or diphosphonates, silanolates
  • Binders antistatic agents and / or adjuvant
  • the pulverulent components are silanized and preferably the ink is adjusted to a pH of less than 8, preferably less than 5, more preferably less than 4.
  • a particularly preferred ink comprises as powdery component zirconium dioxide and optionally other pulverulent components, wherein it is further preferred if the zirconium dioxide and optionally the further components are silanized or treated with a metal ester, more preferably the pH of the ink is reduced to less than pH is set equal to 8.
  • the pulverulent components preferably zirconium oxides, are provided with an organic coupling reagent. Suitable coupling reagents include metal acid esters such as zirconium aluminates of the following structure
  • Particularly suitable are zirconium aluminates based on the following carboxylic acids: HOOC- (CH 2) 4 -COOH; HOOC- (CH 2) 4 -NH 2, olefinic carboxylic acids, particularly preferred X is alkyl having 1 to 12 C-atoms.
  • a filler-loaded printable, liquid, dental ink comprising at least one inorganic pigment and preferably 1 to 30 wt .-% of dental, powdered component. At least one inorganic, colored pigment or a mixture of inorganic, colored pigments is preferably used.
  • inorganic pigments conventional inorganic pigments can be used. Suitable for the preparation of dental inks must have a temperature stability during the firing process. Thus, inorganic pigments are suitable which are substantially color-stable to above 850 ° C, preferably to 1200 ° C. Thus, the invention relates to a dental ink comprising at least one inorganic pigment having a color stability above 850 ° C, in particular from 850 to 1050 ° C, preferably from 900 to 930 ° C. The selected pigment is selected according to the chemical composition of the ceramic powders and components of the matrix.
  • Typical inorganic pigments include essentially oxides, oxide hydrates, sulfides, sulfates, carbonates and silicates of the transition metals, such as preferably pigments comprising zirconium and / or iron.
  • Known pigments include zirconium silicates, iron silicates, iron oxides, manganese oxides, chromium oxides, Y-Fe 2 O 3 , Fe 3 O 4 Fe 2 O 3 , Cr 2 O 3 , TiO 2 .
  • the inorganic pigments may include colored pigments, luster pigments, metallic effect pigments, in particular with luster pigments with flaky or flaky metal particles, such as iron oxide red, strontium yellow, aluminum or silver bronzes, pearlescent pigments or gold bronze, aluminum bronze.
  • Particularly preferred inorganic, colored pigments include iron oxides, zirconium praseodymium silicate (Zr, Pr) Si0 4 (CAS No .: 68187-15-5), zirconium iron silicate (Zr, Fe (Si0 4 )), (CAS No : 68412-79-3), zinc-iron-chromium-brown-spinel (Zn, Fe) (Fe, Cr) 2 0 4 , (CAS-No .: 68186-88-9), zinc-iron-chromium Brown spinel (Zn, Fe) (Fe, Cr) 2 0 4 , (CAS No .: 68186-88-9), chromium-tin-pink sphene CaO: Sn0 2 : Si0 2 : Cr 2 O 3 , ( CAS No .: 68187-12-2).
  • the liquid component may be selected from compounds that are liquid at room temperature (liquid). Preference is given to water, water-miscible solvents, such as alcohols, ethanol, isopropanol, polyols, esters, ketone, ethers, ethyl esters. Due to the subsequent sintering process and the lowest possible shrinkage sought, liquids are preferably used as the liquid component, which can be removed in the drying process almost residue-free and low volume shrinkage.
  • the inks according to the invention preferably comprise at least one adjuvant, the adjuvant comprising flow aids, such as silica, in particular finely divided silica having a primary particle size of less than or equal to 100 nm, such as sipernate, aerosil, precipitated silica comprising primary particles less than or equal to 20 nm, plasticizer, wetting agent, Binders, such as gum arabic, gum, cellulose ethers, such as methylcellulose, ethylhydroxyethylcellulose (low surface tension), hydroxypropylcellulose, polyethers, PEG, gelatin, alginate, starch, tragacanth, sugars, saccharides, dextrin, bentonites, in particular iron-free bentonites (platelet size: 5-10 nm thickness, 0.1-2 ⁇ m length) polyvinylpyrrolidone, polyvinyl alcohol, optionally resins, epoxy resins, urethane, polyacrylic acids, the auxiliaries preferably having an impur
  • the abovementioned peptizers may comprise alkali metal and / or alkaline earth metal salt of carboxylic acids, such as citrates, tartrates, oxalates, zinc (II) chloride, or else diphosphonates, silanolates.
  • the particle sizes of the auxiliaries are preferably both in the free-flowing composition and in the pulverulent component of the ink in the range of the pulverulent components, as disclosed above.
  • the particularly preferred inks according to the invention have in each case individually, in particular in combination, the following properties: a) has a viscosity of between 1 to 50 mPa ⁇ s, in particular 5 to 30 mPa ⁇ s, preferably 10 to 25 mPa ⁇ s, particularly preferably from 0.1 to 15 mPa ⁇ s, 5 to 15 mPa ⁇ s, and / or b) has a surface tension less than or equal to 50 mN / M, 35.1 mN / M, less than 40 mN / M, 35 mN / M, 30 mN / M, most preferably less than or equal to 20 mN / M, such as 0.01 to 50 mN / M, and / or c) the content of pulverulent components (solids content) is between 0.01 to 50 wt .-%, in particular between 1 to 30 wt .-%, 2 wt .-% to 30
  • % in particular 0.01 to 5% by weight, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15% by weight , preferably around 10% by weight.
  • powdery components whose refractive index, which corresponds to the powdered components of the composition for the preparation of the printing bed.
  • a high solids content or filler content in the ink is desired to minimize shrinkage on sintering.
  • the powdery component in the ink should not impart opacity to the sintered body.
  • highly translucent moldings and prostheses are desired.
  • the ink preferably has the properties a, b and c, particularly preferably 5 to 30 mPa s, less than or equal to 40 mN / M, in particular less than or equal to 30 mN / M, and 1 to 30% by weight content of pulverulent component , Particularly preferred is a content of pulverulent component in the dental ink of 1 to 35 wt .-%, particularly preferably from 5 to 35 wt .-%, 10 to 25 wt .-% alternatively preferably 12 to 35 wt .-%.
  • the ink has a surface tension of less than or equal to 50 mN / m, preferably the surface tension is less than or equal to 40 mN / m, less than or equal to 30 mN / m, preferably less than 20 mN / m.
  • the ink preferably each independently comprises at least one pigment to produce colored inks over which color gradients of the prosthetic parts defined in the printing process can be printed.
  • the subject of the invention is an ink which comprises
  • liquid component in turn comprises (a) 1 to 90 wt .-% water, in particular 15 to 60 wt .-%, preferably 15 to 55 wt .-% and
  • water-miscible diluents b) comprise b.1) mono-hydroxy-functional Alcohols, such as ethanol, isopropanol, and optionally as b.2) second component liquid di- and / or trifunctional to polyfunctional alcohols and / or polyethers, such as diols, triols, in particular ethylene glycol, glycerol, PEG,
  • the sum b) of components b.1) and b.2) comprises from 0 to 70% by weight b.1) 0 to 70% by weight mono-hydroxy alcohol, in particular 5 to 40% by weight, preferably 10 to 30% by weight,
  • At least one adjuvant such as a dispersing agent, preferably from 0.001 to 5% by weight, more preferably from 0.01 to 2% by weight, the total composition being present at 100% by weight, the Total composition of the ink is 100% by weight.
  • water-miscible diluents or organic solvents may include esters, ketone, ethers, ethyl esters, butyl esters. As well as other solvents known to those skilled in the art. Preference is given to using polar, organic solvents, such as aprotic or protic polar solvents.
  • the ink preferably has at least one pigment, preferably an inorganic pigment, wherein the at least one pigment is preferably added at 0 to 5 wt.%, In particular at 0.001 to 5 wt.%, Preferably at 0.01 to 2 wt. % in the ink, the total composition corresponding to 100% by weight in total.
  • the preferred particle sizes of the powdered component in the ink are preferably significantly smaller than that of the composition to allow good infiltration of the ink into the print bed. Therefore, the particle sizes of the pulverulent components in the ink are preferably less than or equal to 25 ⁇ m, in particular less than or equal to 20 ⁇ m, particularly preferably less than or equal to 5 ⁇ m, in particular less than or equal to 50 ⁇ m, particularly preferably less than or equal to 2 ⁇ m, in particular d 90 is less than or equal to 2 ⁇ , preferably d 50 is less than or equal to 1 ⁇ .
  • the particles preferably have a spherical habit.
  • the pH of the powdery component in the ink is preferably from 1 to 9.
  • the pH of the ink is adjusted to pH less than or equal to 5, more preferably to pH less than or equal to 4.
  • the adjustment can be done for example by adding quaternary ammonium compounds.
  • the invention furthermore relates to a dental ink comprising colored and / or white pigments or mixtures of pigments, in particular the pigments have a particle size of d 90 less than or equal to 20 ⁇ , preferably less than 15 ⁇ , more preferably less than or equal to 10 ⁇ , more preferably d 50 preferably by 0.001 to 10 ⁇ m, particularly preferably the ink comprises as pigments the listed inorganic pigments.
  • the pigments have a particle size profile according to the disclosure on page 3 for the powdery component.
  • a dental ink which can be distributed in drops having a diameter of 10 to 100 ⁇ m, in particular to a drop size of 40 to 80 ⁇ m, particularly preferably 40 to 70 ⁇ m, 40 to 60 ⁇ m, preferably 50 ⁇ m + / - 5 ⁇ .
  • the ink can be printed over a relatively long period of time, such as 30 minutes, preferably 1 to 24 hours, more preferably up to 1 week, with a substantially constant droplet size.
  • a dental ink from which drops having an aspect ratio of 0.2 to 5 are produced, in particular less than or equal to 2 to greater than 0.5, in particular from 1.4 to 0.7, of diameter 1 to diameter 2, wherein diameter 1 and diameter 2 are arranged approximately at 90 ° to each other.
  • approximately spherical drops can be produced from the ink.
  • Preferred droplet sizes are described above, particularly preferably droplets of less than or equal to 20 ⁇ m, preferably less than or equal to 10 ⁇ m, in particular less than or equal to 5 ⁇ m, can be produced, in which a suitable print head is selected.
  • Particularly preferred are dental inks whose drops remain approximately spherical after exiting the pressure nozzle.
  • the drops remain approximately spherical until they hit the powder bed.
  • the above-defined aspect ratio in particular with an aspect ratio of 1.4 to 0.7.
  • the production of the printable, dental ink is carried out by mixing the components together and preferably after-treatment with ultrasound, in particular to convert aggregates into individual particles of preferably 10 to 200 nm, and to homogenize the composition. An aggregation of powdery particles should be prevented.
  • the invention likewise relates to a dental ink comprising in the liquid component an organic diluent, such as monohydroxy-functional alcohols or ketones, such as acetone (b.1), and / or at least one anti-drying additive, such as in each case independently at least one polyether , Polyethylene glycol, polypropylene glycol, EO / PO polyether, wherein the polyether preferably have a molecular weight Mw 100 to 6000 g / mol, preferably 150 to 3000 g / mol.
  • Particularly preferred anti-drying agents include ethylene glycol and / or glycrine.
  • Particularly preferred are ethylene glycol and / or glycerol.
  • the anti-drying agent is classified as component b.2) and is preferably present at a level of from 0.001 to 50% by weight, in particular from 0.001 to 30% by weight, particularly preferably from 5 to 35% by weight.
  • the invention relates to a method for printing three-dimensional moldings, which are preferably suitable for the production of at least parts of dental prostheses, as well as three-dimensional moldings obtainable by the method, the method comprising the method section (A), with the steps :
  • a dental ink in particular a dispersion, comprising at least one liquid component and at least one pulverulent component, in particular at least one inorganic, particulate, dental solid,
  • a layer in particular a planar layer, of a composition
  • a dental ceramic powder of a powdery component comprising at least one dental glass, glass ceramic, metal oxide, mixed oxide selected from metal oxides and / or a mixture comprising at least two of the mentioned Components
  • the powdered components comprises at least one auxiliary, such as flow aids and / or binders,
  • the dental ceramic powder comprising the powdery component is solidified at least at the point of contact at least in this layer of the dental, ceramic powder or in the region of the contact point, in particular the pulverulent component
  • the steps (i) to (v) are carried out so often that at least the shaped part of a blank of a prosthetic shaped part, preferably a plurality of shaped parts of blanks, is formed in the powder bed.
  • webs may be provided on the molded parts in order to minimize the distortion of the moldings during sintering.
  • a blank of a prosthetic molding apply printed moldings that may contain binders. From these blanks can be prepared by debindering green compacts.
  • the powdery component in steps (i) and (iii) and (iv) are preferably in the form of a powder bed, printing bed or are formed into a powder bed.
  • the invention likewise relates to a method in which, after the method (A) has been carried out several times, at least one three-dimensional molded body is obtained, in particular a three-dimensional dental body at least partially a blank of a part of a dental prosthetic restoration equivalent.
  • a powder bed comprising shaped bodies of prosthetic parts obtainable by the method according to the invention, in particular of medical-technical, preferably of dental molded parts.
  • the shaped bodies are suitable for producing the green compacts.
  • the subject of the invention is a printed shaped body comprising a dental, ceramic powder in the form of a blank of a dental prosthesis, a part of a dental prosthesis, a part of a hoof, a medical prosthesis, a veneer, crown, bridge, inlay, onlay, veneer, Superstructure, substructure, implant post, abutment, spacer, bridge, a bone substitute, such as a part of a jawbone or other bones.
  • a printing of a ceramic framework around the shaped body so that the shaped body can remain connected via webs to a framework during sintering.
  • the invention further provides a process comprising a process section (B), with the steps (I) forming a green body from the shaped body, preferably from the blank, in particular by removing at least one volatile compound, preferably by drying at above 100 ° C, in particular at about greater than or equal to 1 10 ° C, preferably with a drying time of 1 to 36 hours, usually 24 hours, and
  • the exposure of the green body can be done by removing the non-solidified powder bed, in addition compressed air of variable thickness can be used. Alternatively or additionally, the powder bed may be vibrated to remove loose powder bed.
  • the method can be carried out in a one- to multi-color printing process, such as three-color printing, in order to produce particularly aesthetic dental prostheses, which particularly well imitate the color progression and the aesthetics of the natural teeth.
  • the invention likewise relates to a method which comprises a method section (C) with the steps (I) optionally removing the binder from the green body (II) sintering the green body (III) obtaining a three-dimensional dental shaped body of the at least one part of a dental prosthetic Supply corresponds.
  • the sintered molded body is only on the surface nachzubehandeln, for example, to polish, make a paint job, as corrected by painting and possibly in the bite.
  • the binder Before sintering, the binder is removed, referred to as debindering, at 500 ° C., in particular at a heating rate of up to 50 K / h, in particular at 50 K / h, the temperature being maintained for about 5 minutes to 4 hours, especially for 30 minutes.
  • the cooling is rapid, preferably up to 100 K / h to room temperature.
  • the (II) sintering takes place, in particular for glass ceramic, as for silicate compositions, preferably at a heating rate of up to 30 K / h at 700 to 1200 ° C, in particular 850 to 1050 ° C, preferably 850 to 950 ° C, Subsequently, it can be cooled to room temperature.
  • the sintering at a temperature above 700 ° C, preferably above 850 ° C, is preferably between 10 seconds to 2 hours, preferably sintered between about 40 seconds to 2 minutes.
  • Sintering at a temperature above 1000 ° C, preferably above 1350 ° C, is preferably between 10 seconds to 2 hours, preferably sintered between about 40 seconds to 2 minutes.
  • the (II) sintering takes place, in particular for aluminum oxide (Al 2 O 3 ) compositions, preferably at a heating rate of 30 K / h, or from 300 to 600 ° C / h to 700 to 1900 ° C, in particular up to 1450 or 1530 ° C, preferably at 1450 to 1530 ° C, below can be cooled to room temperature.
  • the sintering at a temperature above 1100 ° C., preferably above 1400 ° C. preferably takes place between 10 seconds and 2 hours, preferably sintering for about 40 seconds to 2 minutes.
  • a multiplicity of layers having the aforementioned layer thicknesses are applied, in particular applied in step (iv).
  • the invention relates to a method comprising the method sections (A), (B) and (C).
  • the invention likewise provides a process comprising a step with the subsequent firing curve, the firing curve optionally including a first temperature phase (debindering) in the range from 150 to 500 ° C., in particular from 1 to 48 h, preferably from 1 to 24 h, and a second temperature phase (sintering) in the range from 550 ° C to 1100 ° C, in particular from 830 ° C to 1100 ° C, preferably from 880 ° C to 1100 ° C, preferably around 900 ° C 1050 ° C, +/- 10 ° C, wherein the temperature is preferably increased at 5 ° C / minute, in particular 10 ° C / minute, preferably 20 ° C / minute, more preferably 30 ° C / minute until reaching the second Phase.
  • the temperature of the second phase is preferably kept for greater than or equal to 1 minute, up to 60 minutes, in particular between 0.25 and 5 minutes, preferably for 1 to 2 minutes.
  • a temperature of 860 ° C may be too low to produce a translucent sample, in which case the temperature may be increased stepwise up to 1250 ° C to find the dental material specific temperature for producing translucent samples.
  • a process comprising the step (iv) of applying a layer of free-flowing, ceramic powder, in particular the powdered component, by the ceramic powder from an oscillating Schüttbecher, with at least one opening, preferably provided on the bottom side elongated opening on the existing layer, or via an overflow edge.
  • a vibrating jar (hopper) is used to apply the dental composition of the flowable ceramic powder, preferably the jar vibrates at a defined frequency to apply a homogeneous layer of the powdered component.
  • the bulk bucket is associated with a rotary vibrator.
  • the bulk bucket is associated with soft rubber buffers.
  • a device in particular a doctor blade, a roller, antistatic roller is rolled over the ejected layer, which homogenizes and optionally densifies the layer.
  • the oscillating bulk hopper is preferably operated at a maximum frequency of 450 Hz, preferably less than or equal to 300 Hz, preferably between 100 to 300 Hz.
  • the speed at which the bulk hopper is moved over the layer is preferably between 10 mm / s to 500 mm / s, preferably between 50 to 400 mm / s, preferably by 200 mm / s +/- 20 mm / s.
  • the invention further provides a method, comprising the step of, after the application of the flowable, dental, ceramic powder, in particular the pulverulent component, from the bulk hopper or during the application of the dental ceramic powder from the bulk hopper, a device comprising the dental, ceramic powder densified and formed into a layer, in particular forms into a planar, printable layer, which is preferably infiltratable by drops of the dental ink.
  • the device may comprise a squeegee, a roller, preferably the roller has a diameter of 10 to 30 mm, preferably 10 to 25 mm, by 20 mm, or by 15 mm, 18 mm, 10 mm.
  • the invention likewise relates to a software for the production of dental prosthetic restorations with which a defined signal lead can be set in addition to the print motif per shift in the printing process.
  • a preferred signal advance can be to about -1.375 mm to place the drops exactly in the powder bed at the coordinates according to the CAD data. The aim is that there is no drop offset of superimposed Z data with the same x, y data in the printing bed.
  • the exact signal advance depends on the viscosity of the ink, the type of printer and the printhead, and is therefore adjustable.
  • the droplet size, the line spacing and / or the drop spacing can be set freely selectable with the software for creating prosthetic restorations.
  • the software can modify the datasets of CAD data from prosthetic moldings for print preparation.
  • the subject matter of the invention is a kit comprising starting materials for the three-dimensional printing of at least parts of ceramic prostheses, such as dental prostheses or for printing dental prostheses, wherein the kit as separated components (A) is a dental composition of a free-flowing, dental, ceramic powder as described above, in particular for producing a powder bed, and as component (B) comprises a printable, liquid dental ink as described.
  • A is a dental composition of a free-flowing, dental, ceramic powder as described above, in particular for producing a powder bed
  • component (B) comprises a printable, liquid dental ink as described.
  • a dental three-dimensional green body obtainable by the process according to the invention, in particular a pigmented green body is obtainable by the process according to the invention.
  • the invention also provides a part of a dental prosthesis or a dental prosthesis obtainable by the method according to the invention. More preferably, a pigmented prosthesis is obtainable by the method, more preferably a pigmented, translucent prosthesis, preferably a dental prosthesis, part of a dental prosthesis according to the method available.
  • the prostheses can be further adapted by conventional post-treatments, such as grinding, polishing, coloring. Preferably, only the sintered webs are removed on the prosthesis and can then be adapted to the patient.
  • the translucency of the at least one part of the dental prostheses or a dental prosthesis, such as veneer, anterior tooth, veneer, especially one Prosthesis for fully anatomical purposes obtainable by the method according to the invention greater than or equal to 5% [relative translucency], in particular greater than or equal to 8 to 20%, particularly preferably from 10 to 18% [relative translucency].
  • the translucency was measured by direct light transmission with a digital photoradiometer in a darkroom (light source: 150 W halogen lamp). Alternatively, the translucency can be measured with an SF-600 Datacolor.
  • the invention also provides the use of a three-dimensional printer for printing powdered, dental, ceramic compositions.
  • the invention likewise relates to the use of a three-dimensional printer for printing printable, dental inks for producing blanks, in particular by the combination of the printer, the powdered, dental compositions and the printable, dental ink for producing at least parts of dental prosthetic restorations, in particular of dental prostheses, bridges, crowns, veneers, artificial teeth, dental veneers, implants, implant posts, abutments, dental spacers, superstructures, substructures, telescopic crowns, onlays and / or inlays, or medical prostheses, such as parts of limbs, hoofs, hooves, Bony parts, vertebral bodies, facial bone parts.
  • an oscillating Schüttbechers with at least one bottom-side opening, preferably a bottom-side elongated opening for applying at least one layer of free-flowing ceramic powder, in particular the powdered component on the existing layer, or wherein the application is carried out via an overflow edge.
  • the invention likewise relates to the use of a roller in the printer, which serves to planarize the further layer of ceramic powder applied to the existing layer of ceramic powder from the oscillating pouring cup in one plane and, in particular, to homogenize the layer and optional to compact.
  • printers for printing veneers, dental caps, crowns, bridges, implant posts, abutments, spacers
  • printers ZPrinter® can be used, such as Z 150, Z 250, Z 350, Z 450, Z 650 and especially customized modifications to the printer or any other SD printer.
  • the openings preferably a Diameter of 50 to 200 ⁇ , preferably from 50 to 150 ⁇ , preferably by 100 ⁇ .
  • Particular preference is given to using printheads with a heatable nozzle.
  • the invention also relates to the use of a three-dimensional printer for printing ceramic, dental compositions.
  • Inks were prepared by blending components (i), (ii) and (iii) together to 100% by weight. For the preparation of homogeneous dispersions, the samples were post-treated in an ultrasonic bath. (i) filler in ink:
  • Ethylene glycol 5 to 40% by weight
  • the ink and the drops show sufficient stability during printing (FIGS. 1 a and b; drop setting: voltage / pulse length 58/28, frequency 500 Hz after approx. 5 min., Drop size approx. 48 ⁇ m).
  • Dental ceramic filler in the ink (powdered component): d 50 4.6
  • Table 2 Filler in% by weight in dental ink and powder bed - (composition material Si0 2 raw material: A3, A2, A1)
  • Powder bed (Table 3): Flowable dental ceramic powder zirconia stabilized with 3 mol% Y 2 O 3
  • Table 3 Powder Bed Samples 1 and 2 dental, ceramic powder zirconia
  • Lifting floor Process speed: max. 50 mm / s, internal axis resolution: 0.1 mm,
  • Vibration frequency max. 300 Hz
  • Example 1 Ceramic The line spacing, the drop spacing and the interference between the lines are defined.
  • Powder bed Sample A1, Ink Example 9, (A3) Cylindrical moldings are printed. Drying time Production of gudgeon: 1 10 ° C, 24 h. Debinding: t / T curve: heating 50K / h to 500 ° C, holding time 30 minutes,
  • Cooling 100 K / h to room temperature
  • Sintering a) heating: 30 K / h to 869 ° C, holding time 1 minute (from 300 ° C in vacuum),
  • FIG. 1 c shows the shaped body before sintering.
  • inorganic pigments such as zirconium praseodymium silicate (Zr, Pr) Si04.
  • Zr, Pr zirconium praseodymium silicate
  • SiO 4 zirconium iron silicate
  • CAS No: 68412-79-3 zirconium iron silicate (Zr, Fe (SiO 4), (CAS No: 68412-79-3) with d 50 ⁇ 5 m and using a printhead with four ink containers could be colored translucent molded bodies are produced.
  • Example 9 Using the ink of Example 9 and adding pigments, a molded article of a crown was printed (shrinkage calculated) and sintered. After sintering, a crown with translucent properties was obtained.
  • Example 2 Powder Bed: Sample A3 + PVA (Table 4), Ink Example 9. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 3 Powder Bed: Sample A1, Ink Example 10. The procedure is analogous to Example 1.
  • Example 4 Powder Bed: Sample A3 + PVA, Ink Example 10. The procedure is analogous to Example 1.
  • Example 5 An ink with added pigment and solid (Example 9 (A3), 0.5% by weight of Pigment 3240 yellow) was printed with powdered bed Sample A3 + PVA analogously to Example 1 and sintered.
  • Example 6 An ink with added pigment and solid (Example 9 (A3), 0.5% by weight of Pigment 3240 yellow) was printed with powdered bed Sample A2 analogously to Example 1 and sintered.
  • Example 7 An ink with pigment addition and solid (Example 9 (A3), 0.5 wt .-% pigment PS 3210 (pink)) was printed with powder bed sample A3 + PVA analogous to Example 1 and sintered.
  • Example 8 Powder Bed: Sample A3 + PVA, Ink Example 13. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 9 Powder Bed Sample A3 + PVA, Ink Example 14. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 10 Ceramics: Powder Bed: Table 3 Sample 1, Ink Example 8. The procedure is analogous to Example 1. Translucent and transparent shaped bodies were obtained. Air pockets were not observed.
  • Example 1 Ceramic: Powder Bed: Table 3 Sample 1, Ink Example 6b. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 12 Ceramics: Powder Bed: Table 3 Sample 1, Ink Example 12. The procedure is analogous to Example 1. Translucent and transparent moldings were obtained. Air pockets were not observed.
  • Example 13 Ceramic: Powder Bed: Table 3 Sample 2, Ink Example 8. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 14 Ceramic: Powder Bed: Table 4 Sample A3, Ink Example 9 (A3). The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.
  • Example 15 Ceramic: powder bed: Table 3 Sample 1 in the weight ratio 1: 1 with sample 1 * with d 99 less than or equal to 500 nm, ink Example 3. The procedure is analogous to Example 1. There were obtained translucent and transparent moldings. Air pockets were not observed.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Dentistry (AREA)
  • Dental Preparations (AREA)
  • Dental Prosthetics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne une composition dentaire d'une poudre céramique coulante d'un composant pulvérulent, comprenant au moins un verre dentaire, une vitrocéramique, un oxyde métallique, un oxyde mixte sélectionné parmi des oxydes métalliques et/ou un mélange comprenant au moins deux des composants susmentionnés. L'invention concerne aussi une encre dentaire pouvant être imprimée et un procédé de fabrication de corps moulés de prothèses dentaires.
EP15723719.9A 2014-05-23 2015-05-22 Compositions dentaires pouvant être imprimées et frittées, servant à la fabrication de parties de prothèses dentaires, et procédés de fabrication correspondants Withdrawn EP3145471A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014107330.4A DE102014107330A1 (de) 2014-05-23 2014-05-23 Druckbare und sinterbare dentale Zusammensetzungen zur Herstellung von Teilen dentaler Prothesen sowie Verfahren zu deren Herstellung
PCT/EP2015/061409 WO2015177348A1 (fr) 2014-05-23 2015-05-22 Compositions dentaires pouvant être imprimées et frittées, servant à la fabrication de parties de prothèses dentaires, et procédés de fabrication correspondants

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EP3145471A1 true EP3145471A1 (fr) 2017-03-29

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US (1) US20170196666A1 (fr)
EP (1) EP3145471A1 (fr)
JP (1) JP6615187B2 (fr)
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WO (1) WO2015177348A1 (fr)

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WO2017069778A1 (fr) * 2015-10-23 2017-04-27 Hewlett-Packard Development Company, L.P. Impression en trois dimensions (3d)
US10800108B2 (en) 2016-12-02 2020-10-13 Markforged, Inc. Sinterable separation material in additive manufacturing
US10000011B1 (en) 2016-12-02 2018-06-19 Markforged, Inc. Supports for sintering additively manufactured parts
EP3551365B1 (fr) 2016-12-06 2022-03-16 Markforged, Inc. Methode de fabrication additive avec alimentation en matériau assoupli à la chaleur
DE102017106101A1 (de) * 2017-03-21 2018-09-27 Decema Gmbh Verfahren zur generativen Herstellung eines Formkörpers, Formkörper und System zur generativen Herstellung eines Formkörpers
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WO2015177348A1 (fr) 2015-11-26
DE102014107330A1 (de) 2015-11-26
US20170196666A1 (en) 2017-07-13
KR20170009907A (ko) 2017-01-25
JP6615187B2 (ja) 2019-12-04
CN106456451A (zh) 2017-02-22

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