EP3829521A1 - Composition durcissable par rayonnement destinée à être utilisée dans un procédé de prototypage rapide ou de fabrication rapide - Google Patents

Composition durcissable par rayonnement destinée à être utilisée dans un procédé de prototypage rapide ou de fabrication rapide

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Publication number
EP3829521A1
EP3829521A1 EP19782920.3A EP19782920A EP3829521A1 EP 3829521 A1 EP3829521 A1 EP 3829521A1 EP 19782920 A EP19782920 A EP 19782920A EP 3829521 A1 EP3829521 A1 EP 3829521A1
Authority
EP
European Patent Office
Prior art keywords
acrylic acid
dental
acrylate
composition
composition according
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.)
Pending
Application number
EP19782920.3A
Other languages
German (de)
English (en)
Inventor
Alfred Hohmann
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
Kulzer GmbH
Kulzer and Co 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 Kulzer GmbH, Kulzer and Co GmbH filed Critical Kulzer GmbH
Publication of EP3829521A1 publication Critical patent/EP3829521A1/fr
Pending 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
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • 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
    • 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
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use

Definitions

  • the invention relates to a polymerizable, radiation-curable, in particular UV / Vis, UV or Vis-curable composition
  • a polymerizable, radiation-curable, in particular UV / Vis, UV or Vis-curable composition comprising (i) monomers and (ii) at least one further component, the (i) comprising monomers
  • composition according to the invention is suitable for the production of dental prosthetic parts, orthopedic apparatus or dental pre-forms, which are characterized by a) a flexural strength greater than or equal to 50 MPa and / or b) modulus of elasticity greater than or equal to 1500 MPa, and / or c) Bending fracture greater than or equal to 1, 1 MPa m 1/2 and / or d) Fracture work greater than or equal to 250 J / m 2 (DIN EN ISO 20795-2), this in a rapid prototyping or in a rapid manufacturing or rapid tooling processes can be produced.
  • Generative processes are e.g. already known in the form of laser sintering from CoCr, Ti or polymers for the production of crowns and bridges, implant components or models.
  • compositions of acrylates or derivatives of acrylates for the production of dentures with a corresponding property profile in relation to the mechanical have not been available (see Quintessenz Zahntech. 2017-43 (10): page 1325). Since only a few manufacturers have an MPG class IIa approval for their printable plastics and resins, and currently most resins can only be printed unfilled, the mechanical properties of currently available materials are always low. Therefore, these materials are not suitable for the production of permanent dentures. There is therefore a need for compositions for the production of definitive prosthetic parts, orthopedic devices or dental pre-forms.
  • the object of the invention was to provide a mixture of monomers, which may optionally comprise fillers which, after curing, in particular by means of radiation-curing processes, have good properties with respect to the bending fracture and the work at break.
  • the polymerized mixture should preferably have values for the bending fracture of greater than or equal to 1.1 MPa m 1/2 and / or for the breaking work of greater than 250 J / m 2 (DIN EN ISO 20795-2).
  • the composition should also be able to be used in radiation-curing rapid manufacturing (RM) or rapid prototyping (RP) processes.
  • Another object was to provide a composition which contains inorganic fillers and which, as a polymerizable composition or as a polymerized composition, has a high degree of transparency.
  • the invention is optionally additionally based on the object of specifying a filler which does not lead to a deterioration in the transparency of the polymerized compositions, as is known for silicon dioxide.
  • the filler should preferably also have a favorable influence on the physical and mechanical properties of the polymerized compositions.
  • dyes and / or fibers it should be possible to add dyes and / or fibers to the composition without impeding the suitability of the composition for use in these processes.
  • a further object was to provide a composition which, in addition to monomers, fillers, initiators, stabilizers, dyes, fibers and, if appropriate, additives, and from which dental products and dental prosthetic parts can be produced by means of light-curing RM processes or RP processes.
  • dental products are understood to mean, in particular, dental products which can be produced from polymerizable compositions, such as, for example, not finally, complete dentures, provisional crowns and bridges, inlays, onlays, full crowns, Bite splints, drilling templates for implantology, splints for orthodontic corrections (similar to Invisalign), mouthguards, artificial teeth.
  • polymerizable compositions such as, for example, not finally, complete dentures, provisional crowns and bridges, inlays, onlays, full crowns, Bite splints, drilling templates for implantology, splints for orthodontic corrections (similar to Invisalign), mouthguards, artificial teeth.
  • the invention relates to a composition
  • a composition comprising monomers and optionally prepolymers (oligomers) and / or polymers comprising at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or derivative of the aforementioned acrylic acid esters and optionally at least one inorganic filler.
  • the radiation-hardened composition has a high degree of transparency, preferably of at least 95%, in particular greater than 97%, preferably of 98% (measured on 1 mm thick color test specimens produced in metal molds using a color measuring device SF 600 (Datacolor)).
  • compositions that can be used in the dental field for the production of definitive dentures are highly transparent. This transparency is usually achieved by optimally adjusting the refractive indices of the fillers and the polymer matrix. However, due to various physical and chemical boundary conditions, there are very narrow limits when it comes to the choice of fillers and monomers.
  • Typical dental glass fillers have refractive indices in the range from 1.50 to 1.54. Likewise, many suitable monomers for dental materials also have a refractive index in this range. However, due to the significantly higher density of the dental glasses, the composition segregates, so that rheology modifiers such as e.g. pyrogenic silicas ("Aerosile") can be added. The fumed silicas, in turn, have a refractive index of 1.46, which is unfavorable for the desired transparency, and are thus far outside the optimal range of the desired refractive index (> 1, 50) for polymerizable compositions. With the addition of this rheology modifier, the transparency of the polymer material produced therefrom deteriorates.
  • rheology modifiers such as e.g. pyrogenic silicas ("Aerosile"
  • the fumed silicas have a refractive index of 1.46, which is unfavorable for the desired transparency, and are thus far outside the optimal range of the desired refractive index
  • a zirconium-doped silicon dioxide filler in particular with a mixed oxide of zirconium dioxide and silicon dioxide.
  • agglomerated mixed oxides comprising, with respect to the total composition of the mixed oxide, 75 to 99% by weight of silicon dioxide and from 1 to 25% by weight of zirconium dioxide, in particular the mixed oxide comprising from 85 to 90% by weight of silicon dioxide and 10 to 15 %
  • the primary particles of the agglomerated oxide particles comprise microcrystalline domains of 4 to 7 nm and advantageously the crystallinity index 0.6 to 0.7 - determined according to the method of Windisch et al.
  • agglomerated oxide particles are present in surface-modified form with at least one organofunctional silane which is reactive towards at least one monomer and / or polymer component.
  • organofunctional silane which is reactive towards at least one monomer and / or polymer component.
  • the monomers When selecting the monomers, it is also important to ensure that they combine well with the optional filler. As a rule, polyurethanes, acrylates, polyesters and other monomers do not bond well with the fillers used. For this reason, the fillers are usually silanized or hydrophobized for better binding with the monomers on the surfaces.
  • a composition which has a polymerizable monomer with a free carboxy group and / or an anhydride group, the composition additionally having a difunctional acrylate or methacrylate with alicyclic group and at least one photoinitiator.
  • inorganic fillers can be used in the polymerizable composition, for example due to the desired viscosity of the composition, there is the possibility in the composition for reflecting the radiation, in particular diffuse reflection or scattering of the irradiated radiation, dyes or Use pigments in the composition.
  • Dyes are compounds which are soluble in the polymerizable composition and preferably form a clear solution.
  • the radiation-curable compositions according to the invention can preferably be irradiated with a radiation source which emits light in the visible range, particularly preferred are radiation sources which emit radiation from 360 to 750 nm, in particular at approximately 385 nm, particularly preferably at approximately 405 nm the composition according to the invention with a polychromatic radiation source, such as a DLP projector, or preferably with a monochromatic radiation source, such as a laser projector, in the visible range from 380 to 660 nm.
  • the composition of the photoinitiator can be reduced.
  • An excessively high photoinitiator content can lead to a so-called “overcuring" of the irradiated composition, embrittlement, so that the dental parts produced accordingly cannot be used.
  • the use of the inorganic fillers, pigments or dyes according to the invention leads to a uniform scattering of the radiation sources, in particular the UV and Vis radiation sources in the monomer matrix of the composition, so that a more uniform curing of the composition is assumed. As a result, the polymerized compositions have increased levels of fracture work achieved.
  • the composition according to the invention After exposure to a radiation source in the visible range, in particular from 385 to 405 nm, the composition according to the invention, preferably after exposure in a stereolitography method and obtaining a polymerized composition, preferably in the form of a blank, dental prosthetic part, orthopedic apparatus or dental Pre-form, as well as optional post-treatment of the polymerized composition with a radiation source, the following properties for a) a flexural strength greater than or equal to 50 MPa, in particular greater than or equal to 75 MPa and / or b) an elastic modulus of greater than or equal to 1500 MPa, in particular greater than or equal to 2000 MPa, and / or c) bending fracture greater than or equal to 1.1 MPa m 1/2 , greater than or equal to 1.7 MPa m 1/2 and / or d) a fracture work of greater than 250 J / m 2 , in particular greater than or equal to 270 J / m 2 , each determined according to DIN EN ISO 20795-2.
  • the post-hardening or post-hardening can preferably e.g. with a laboratory light device (HiLite Power 3D) or in the light oven, preferably with a light spectrum of 390 - 540 nm.
  • the invention relates to a polymerizable, radiation-curable, in particular polymerizable by means of UV / VIS, UV or VIS radiation, comprising (i)
  • Monomers preferably a mixture of monomers, and (ii) at least one further component,
  • the (i) monomers comprise (a) at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or a derivative of the aforementioned acrylic acid esters, (b) at least one difunctional acrylate with a divalent alicyclic group and / or at least one difunctional methacrylate with a divalent alicyclic group, which is preferably selected from tricyclodecanedimethanol diacrylate (TCDDA), tricyclodecanedimethanoldimethacrylate (TCDA), tricyclodecanediethanol dodhanyl acrylate, tricyclodecanediethanol mixtures and this
  • R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4-alkyl
  • (d) comprises at least one photoinitiator for the UV and / or Vis range or a photoinitiator system.
  • the composition can additionally contain at least one polyether diacrylate, such as poly (ethylene glycol) diacrylate, poly (ethylene glycol) di (alkyl) acrylate, poly (propylene glycol) diacrylate, poly (propylene glycol) di (alkyl) acrylate, or a mixture of at least two containing said monomers.
  • Preferred polyether diacrylates can be selected from triethylene glycol dimethacrylate, diethylene glycol dimethacrylate and / or tetraethylene glycol dimethacrylate.
  • the composition may comprise diacrylates selected from decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, hexyldecanediol di (di) dii (meth) acrylate, butanediol di (meth) acrylate or mixtures containing at least one of the acrylates.
  • composition as (a) the at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or the at least one derivative of the aforementioned acrylic acid esters, in particular (alkyl contains acrylic acid esters with alkyl C1 to C4 alkyl groups, preferably with alkyl equal to methyl or ethyl, selected from an acrylic acid ester with an additional carboxy group of the formula II or III,
  • the invention also relates to a composition which, as (a), can comprise at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or derivative of the aforementioned acrylic acid esters, in particular 2-acryloyloxyethyl hydrogen phthalate, polyether - Functionalized acrylic acid esters with carboxy group, preferably the composition comprises polyether-functionalized acrylic acid esters with carboxy group on acrylic, polyether-functionalized acrylic acid esters with carboxy group on alkyl, the polyethers in particular being based on poly (propylene glycol) and poly (ethylene glycol) 1 to 6 glycol units, and / or 4- (2-methacryloxyethyltrimellitic anhydride (4-META, 2 - [(2-methyl-1-oxoallyl) oxy] ethyl-1, 3-dihydro-1, 3-dioxoisobenzofuran-5-carboxylate ).
  • a composition which, as (
  • the composition comprises 2-acryloyloxyethyl hydrogen phthalate optionally in a mixture with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or hydroxypropyl (meth) acrylate.
  • preferred monomers as at least one further monomer in the composition can be selected from:
  • hydroxyethyl acrylate is preferably used as the monofunctional monomer.
  • hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and / or hydroxyethyl acrylate can optionally be used as a mixture of at least two of the aforementioned monomers.
  • compositions which comprise inorganic fillers as a further component, which are selected from (f) inorganic fillers, inorganic oxides or inorganic mixed oxides, in particular oxides of zirconium and / or silicon and / or dental glasses, zirconium dioxide or mixed oxide is preferred of zirconium oxide or zirconium dioxide and silicon dioxide, silicon dioxide, particularly preferred fillers are mixed oxides of zirconium dioxide and silicon dioxide.
  • Mixed oxides of zirconium dioxide and silicon dioxide with primary particle sizes in the range of less than 100 nm, which are optionally present as agglomerates with 2 to 5 pm, are particularly preferred.
  • These oxides or mixed oxides are preferably essentially X-ray amorphous.
  • Aluminum glasses, fluoroaluminosilicate glasses and / or barium aluminum silicate can be used as dental glasses.
  • the oxides can be selected from the aforementioned and from amorphous spherical fillers based on oxide or mixed oxide.
  • the particle sizes of the inorganic fillers such as the at least one inorganic oxide, mixed oxide or dental glass, for example comprising barium aluminum oxide, have an average particle diameter of d 50 less than 10 pm for the present applications, particularly preferably the fillers have a particle diameter of approximately 3 up to 70 nm, in particular from 10 to 50 nm (nanometers), optionally the particles can be aggregated or agglomerated as particles with up to 10 pm.
  • the primary particle sizes of the inorganic fillers which can optionally be present as agglomerated and / or aggregated primary particles, have an average particle diameter of approximately 3 to 70 nm, in particular 10 to 50 nm.
  • the mixed oxides of zirconium dioxide with silicon dioxide preferably have a primary particle size of 3 up to 70 nm.
  • the advantage of the very small particle diameters, which may be aggregated and / or agglomerated, is that the light is essentially diffusely scattered on these particles during radiation curing and thus leads to improved curing in the stereolitography process or DLP process.
  • a specific composition according to the invention may include: (a) 1 to 60% by weight of at least one acrylic acid ester with an additional carboxy group, an acrylic acid ester with at least one additional anhydride of carboxy groups and / or derivatives of the aforementioned acrylic acid esters,
  • inorganic fillers comprising inorganic Oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of zirconium oxide and silicon dioxide, silicon dioxide
  • composition of the invention may include:
  • inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of zirconium oxide and silicon dioxide, silicon dioxide, the total composition being 100% by weight.
  • Another particularly preferred composition may include:
  • inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of zirconium oxide and silicon dioxide, silicon dioxide, the total composition being 100% by weight.
  • the composition is not thixotropic.
  • the composition has a viscosity of less than 5000 m-Pas, in particular from 500 to less than 4000 m-Pas, preferably from 500 to 3000 m-Pas, particularly preferably from 500 to 1500 m-Pas.
  • the viscosity is preferably measured according to DIN 1342-2; 2003-11 Newtonian liquids or DIN 1342-3; 2003-1 1 non-Newtonian liquids with a rheometer (Anton Par, physicist NCR 301, viscosity ranges 200-5000 m-Pas at 100 / s 23 ° C).
  • compositions according to the invention have no or preferably only a low thixotropy.
  • the compositions produced are pseudoplastic, it being preferred if the compositions are pseudoplastic both with and without fillers. According to a further embodiment, it is preferred that there are almost no changes in viscosity over a longer storage period. Furthermore, the compositions have very good reactivity when exposed to a laser or DLP projector.
  • workpieces or three-dimensional moldings can be printed with very good geometric precision / resolution. Good color stability can also be observed in the workpieces.
  • the invention relates to a polymerized composition, preferably as a dental prosthetic part, orthopedic apparatus or dental pre-form, obtainable by irradiating a polymerizable composition.
  • the polymerized, in particular radiation-hardened, composition preferably as a dental prosthetic part, orthopedic apparatus or dental pre-form, cumulatively has the following properties: a) a flexural strength of greater than or equal to 50 MPa, in particular greater than or equal to 70 MPa, and b) E modulus of greater than or equal to 1500 MPa, in particular greater than or equal to 2000 MPa, and c) bending fracture of greater than or equal to 1.1 MPa m 1/2 , in particular greater than or equal to 1.8 MPa m 1/2 , and d) a breaking work of greater than 250 J / m 2 , in particular greater than 270 J / m 2 , the properties being determined in accordance with DIN EN ISO 20795-2. Polymerized compositions without inorganic fillers can have a breaking work of greater than 390 J / m 2 .
  • polymerized compositions are obtainable, in particular radiation-hardened compositions, in particular UV / Vis-hardened compositions, which have preferably additionally been radiation-hardened on all sides and which, alternatively or cumulatively, have the following properties: or b) a modulus of elasticity greater than or equal to 2000 MPa, and / or c) bending fracture greater than or equal to 1.7 MPa m 1/2 and / or d) a fracture work of greater than 250 J / m 2 , each in accordance with DIN EN ISO 20795-2 can be determined. Additional all-round radiation curing is understood to mean, for example, post-treatment in a 3D light furnace.
  • the polymerized compositions preferably have a ratio of modulus of elasticity / flexural strength of less than or equal to 26, preferably less than 24, and in particular in combination with a breaking work of greater than 250 J / m 2 , preferably greater than or equal to 280 J / m 2 , in each case determined DIN EN ISO 20795-2.
  • the invention also relates to a blank in the form of a three-dimensional shaped body of a polymerized composition, which has preferably been additionally radiation-hardened on all sides and is suitable for producing dental prosthetic parts, orthopedic devices or dental pre-forms, the blank having a) a flexural strength of greater equal to 75 MPa, and / or b) a modulus of elasticity greater than or equal to 2000 MPa, and / or c) bending fracture greater than or equal to 1.7 MPa m 1/2 , and / or d) a fracture work greater than 250 J / m 2 , each determined according to DIN EN ISO 20795-2.
  • the blank can preferably be in the form of an artificial tooth, which only has to be polished for the final individual adaptation to the patient, or a slight reworking of the occlusal surface takes place.
  • the invention furthermore relates to the use of a composition for the production of dental prosthetic parts, orthopedic apparatus or dental pre-forms, in rapid prototyping or in rapid manufacturing, i.e. the manufacture of dental prosthetic parts or rapid tooling processes.
  • the following methods include rapid prototyping or rapid manufacturing, a method for producing workpieces, such as a dental prosthetic part, or rapid tooling, a method for producing tools, in each case stereolithography methods and DLP methods.
  • the polymerizable composition can optionally be re-coated with UV, Vis or UV / Vis light in the aforementioned processes.
  • the polymerized composition or the dental prosthetic parts, the orthopedic apparatus or dental pre-forms or blanks are preferably subsequently tempered simultaneously from at least three sides, preferably from five to six sides, as is possible in a light furnace.
  • the polymerized composition can additionally or alternatively be annealed.
  • the dental prosthetic parts comprise a prosthesis base or parts thereof, for example as a replica of a gingiva or a part thereof, artificial teeth, dental arches with at least two to 16 interdental material-integrally connected artificial teeth, crowns, provisional crowns, full dentures, full crowns, splints for orthodontic corrections (similar to Invisalign), dental bridges, abutments, superstructures, dental bars, inlays, onlays, orthopedic devices, such as bite splints, dental pre-forms of artificial teeth, surgical guides for implantology, mouthguards, and / or implants.
  • a prosthesis base or parts thereof for example as a replica of a gingiva or a part thereof, artificial teeth, dental arches with at least two to 16 interdental material-integrally connected artificial teeth, crowns, provisional crowns, full dentures, full crowns, splints for orthodontic corrections (similar to Invisalign), dental bridges, abutments, superstructures, dental bars, inlays, onlays, orthopedic devices
  • Color pigments can also be added to the composition to adjust the color.
  • Red fibers can also be added to the composition to mimic veining of the gingiva.
  • suitable color pigments are: PV Real Red - CAS 4948-15-6, Indian Blue 220943 - CAS 68186-87-8, Real Black 100 - 68186-91-4, Kronos 2220 - CAS 13463-67-7 and Light Yellow 3R - CAS 68186- 90-3.
  • Layer thicknesses in the range from 5 pm to 250 pm per curing layer can be achieved in the polymerized compositions.
  • a high degree of transparency can be achieved through the optimal selection of the recipe components with regard to their refractive indices.
  • the mono-functional monomer can contain at least one of the monomers mentioned: methyl methacrylate and optionally additionally ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol mono methacrylate,
  • Tetrahydrofuryl methacrylate polypropylene glycol mono methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, polypropylene glycol mono acrylate, acrylate, mono-acrylate, benzyl, furfuryl or phenyl (meth) acrylate a mixture containing at least one of these (meth) acrylates and / or copolymers comprising one or at least two of the aforementioned monomers.
  • a preferred composition is pseudoplastic, ie the composition changes its viscosity preferably under shear stress.
  • the composition can comprise monomers selected from tri-, tetra- or multi-functional monomer which is not urethane (meth) acrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate and / or pentaerythritol tetra (meth) acrylate
  • photoinitiators are benzoin alkyl ethers or esters, benzil monoketals, acylphosphine oxides or aliphatic and aromatic 1,2-diketo compounds, such as 2,2-diethoxyacetophenone; 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil or camphorquinone.
  • the photoinitiators are preferably used together with a reducing agent.
  • reducing agents are amines such as aliphatic or aromatic tertiary amines, for example N, N-dimethyl-p-toluidine or triethanolamine, cyanoethylmethylaniline, triethylamine, N, N-dimethylaniline, N-methyldiphenylamine, N, N-dimethyl-sym. -xylidine, N, N-3,5-tetramethylaniline and 4-dimethylaminobenzoic acid ethyl ester or organic phosphites.
  • Common photoinitiator systems are e.g.
  • 2,4,6-Trimethylbenzoyldiphenylphosphine oxide is particularly suitable as the initiator for the polymerization initiated by UV light.
  • UV photoinitiators can be used alone or in combination with an initiator for visible light.
  • Particularly preferred photoinitiators and / or initiator systems comprise a) at least one radical photoinitiator, in particular at least one peroxide and / or azo compound, in particular LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2, 2'-Azobis (isobutyronitrile), DTBP: di-tert-butyl peroxide, or an alpha-hydroxy ketone, camphorquinone, acylphosphine oxide.
  • LPO dilauroyl peroxide
  • BPO dibenzoyl peroxide
  • t-BPEH tert-butyl per-2-ethylhexanoate
  • AIBN 2, 2'-Azobis (isobutyronitrile)
  • DTBP di-tert-butyl peroxide
  • stabilizers can also be added and optionally b) at least one co-initiator such as an amine, usually a tert-amine, in particular at least one aromatic amine such as N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl p-toluidine and / or p-dibenzylaminobenzoic acid diethyl ester.
  • co-initiator such as an amine, usually a tert-amine, in particular at least one aromatic amine such as N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl p-toluidine and / or p-dibenzylaminobenzoic acid diethyl ester.
  • Typical stabilizers include 2,6-di-tert-butyl-4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ).
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEHQ hydroquinone monomethyl ether
  • Table 1a Compositions according to the invention
  • test specimens are printed on a 3D precision printer with a wavelength of 405 nm (Cara Print 4.0) for the subsequent tests.
  • the test specimens are rinsed with isopropanol and subjected to an after-tempering process. This is done by exposure on both sides for 5 min. or according to the manufacturer's instructions in a HiLite Power 3D laboratory light lamp, 200 W (Kulzer GmbH).
  • Table 1b Compositions according to the invention

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  • Plastic & Reconstructive Surgery (AREA)
  • Biophysics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dental Preparations (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
  • Dental Prosthetics (AREA)

Abstract

L'objet de la présente invention est une composition polymérisable, durcissable par rayonnement, en particulier durcissable par UV/Vis, par UV ou par Vis, comprenant (i) des monomères et (ii) au moins un autre composant, les (i) monomères comprenant (a) au moins un ester de l'acide acrylique comprenant un groupe carboxyle supplémentaire, des esters de l'acide acrylique comprenant au moins un groupe anhydride supplémentaire de groupes carboxyle et/ou un dérivé desdits esters de l'acide acrylique, (b) au moins un acrylate bifonctionnel comprenant un groupe alicyclique bivalent et/ou au moins un méthacrylate bifonctionnel comprenant un groupe alicyclique bivalent, (c) facultativement au moins un 4,4'-di(oxabenzol)dialkylméthane disubstitué de formule I, et (ii) le ou les autres composants comprenant (d) au moins un photoinitiateur pour plage UV et/ou Vis ou un système photoinitiateur. La composition selon l'invention est adaptée à la fabrication de pièces pour prothèses dentaires, d'appareils orthopédiques ou de préformes dentaires qui sont caractérisés par a) une rigidité en flexion supérieure ou égale à 50 MPa et/ou b) un module d'élasticité supérieur ou égal à 1500 MPa, et/ou c) une rupture en flexion supérieure ou égale à 1,1 MPa m1/2 et/ou d) un travail jusqu'à la rupture supérieur à 250 J/m2 DIN EN ISO 20795-2, ceux-ci pouvant être fabriqués selon un procédé de prototypage rapide ou de fabrication rapide ou d'outillage rapide.
EP19782920.3A 2018-09-21 2019-09-20 Composition durcissable par rayonnement destinée à être utilisée dans un procédé de prototypage rapide ou de fabrication rapide Pending EP3829521A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018123330.2A DE102018123330A1 (de) 2018-09-21 2018-09-21 Strahlenhärtbare Zusammensetzung zur Verwendung in Rapid-Prototyping oder Rapid-Manufacturing Verfahren
PCT/EP2019/075295 WO2020058464A1 (fr) 2018-09-21 2019-09-20 Composition durcissable par rayonnement destinée à être utilisée dans un procédé de prototypage rapide ou de fabrication rapide

Publications (1)

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EP3829521A1 true EP3829521A1 (fr) 2021-06-09

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Country Status (6)

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US (1) US20210353508A1 (fr)
EP (1) EP3829521A1 (fr)
JP (1) JP7490640B2 (fr)
CN (1) CN112689646B (fr)
DE (1) DE102018123330A1 (fr)
WO (1) WO2020058464A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111978479B (zh) * 2020-08-11 2021-11-12 珠海赛纳三维科技有限公司 三维成型用材料、三维物体及其切片层

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6730156B1 (en) 1999-10-28 2004-05-04 3M Innovative Properties Company Clustered particle dental fillers
DE102010003881A1 (de) * 2010-04-12 2011-10-13 Voco Gmbh Dentale Abdeckmasse
EP2436365B1 (fr) * 2010-09-30 2017-03-08 VOCO GmbH Matériau composite comprenant un monomère doté d'un élément structurel polyalicyclique
JP5901487B2 (ja) * 2012-09-28 2016-04-13 株式会社ジーシー 重合性組成物
US9408781B2 (en) * 2013-02-11 2016-08-09 Kerr Corporation Dental resin modified glass-ionomer composition
DE102015220373A1 (de) * 2014-10-23 2016-04-28 Voco Gmbh Härtbares Dentalmaterial
JP2017014453A (ja) * 2015-07-06 2017-01-19 日立化成株式会社 先供給型アンダーフィル材、その硬化物、それを用いた電子部品装置及びその製造方法
JP6852270B2 (ja) * 2016-03-31 2021-03-31 凸版印刷株式会社 金属加工板の製造方法

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JP7490640B2 (ja) 2024-05-27
DE102018123330A1 (de) 2020-03-26
CN112689646A (zh) 2021-04-20
WO2020058464A1 (fr) 2020-03-26
JP2022501385A (ja) 2022-01-06
CN112689646B (zh) 2023-05-09
US20210353508A1 (en) 2021-11-18

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