EP4126545A1 - Composition photodurcissable pour la production de composants dentaires à surfaces mates - Google Patents

Composition photodurcissable pour la production de composants dentaires à surfaces mates

Info

Publication number
EP4126545A1
EP4126545A1 EP21715234.7A EP21715234A EP4126545A1 EP 4126545 A1 EP4126545 A1 EP 4126545A1 EP 21715234 A EP21715234 A EP 21715234A EP 4126545 A1 EP4126545 A1 EP 4126545A1
Authority
EP
European Patent Office
Prior art keywords
light
solid polymer
polymer particles
curing
curing composition
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
EP21715234.7A
Other languages
German (de)
English (en)
Inventor
Klaus Ruppert
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 EP4126545A1 publication Critical patent/EP4126545A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • 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
    • 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
    • A61K6/889—Polycarboxylate cements; Glass ionomer cements
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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

Definitions

  • the invention relates to a light-curing composition for the production of dental components in the DLP process or SLA process, a process for the production of light-curing compositions, the use of corresponding light-curing compositions for the production of dental components with matt surfaces in a DLP process or SLA process and a Kit for the preparation of a corresponding light-curing composition.
  • the use of solid polymer agglomerates in the production of light-curing compositions, the use of solid polymer particles in light-curing compositions to reduce the gloss property of dental components obtained by light-curing, an uncoated dental component with matt surfaces and a system for producing a dental component in one are also disclosed DLP process or SLA process.
  • the subject matter of the invention is defined in the claims.
  • CAD computer-aided design
  • CAM computer-aided manufacturing
  • 3D printers can process solid raw materials, for example in the form of granules or filaments. What many of these processes have in common is that the component to be produced is built up in layers from layers arranged one on top of the other in order to produce a three-dimensional component.
  • SLA stereolithography
  • DLP digital light processing
  • a light-curable composition is presented and cured layer by layer at the desired locations by means of spatially resolved, targeted irradiation.
  • the resulting component is, for example, gradually lowered into the composition or lifted out of it step by step, so that after each increment there is only a thin film of the photohardenable composition over the last layer that is roughly the same as the thickness of the next layer to be polymerized.
  • SLA and DLP processes are similar in terms of their basic principle, but are quite different in terms of the design of the equipment, with the SLA process using, for example, a laser that runs through the structure to be produced one after the other, whereas with the DLP process using a suitable projection technique simultaneous exposure of an entire area takes place.
  • the most important aspect in practice is the digital scannability of the component, which can be significantly limited with glossy surfaces.
  • dental components produced by additive manufacturing processes are, for example, processed manually in the further course and then have to be digitized again using suitable scanners.
  • This renewed digitization is made significantly more difficult if the surface of the dental component, unlike the plaster model, shines, so that the CAD data obtained is partially qualitatively inadequate or errors occur that make it necessary to carry out the scanning process several times, which increases the amount of work and increase the cost.
  • the problem of the often inadequate scannability of glossy structures is known in the art.
  • the inventors have made the experience that the undesirable tendency towards shiny surfaces is particularly pronounced when certain monomers are used in the light-curing composition. Unfortunately, the corresponding, mostly high-boiling,
  • Monomers in the light-curing composition are mostly of essential importance in order to impart the desired product properties such as mechanical stability or temperature resistance to the dental components obtained from them, so that these cannot simply be substituted by monomers with a lower tendency to gloss.
  • DE 100038564 A1 teaches, for example, the use of a metal powder or a powder with a metallic effect in a molding compound, for example plaster of paris, in order to improve its scannability.
  • Matting effect is often also undesirable, since the increased adhesion to roughened surfaces can make working with the dental component more difficult because, for example, impression or modeling compounds adhere too strongly.
  • these matting liquids also contain pigments such as titanium dioxide.
  • pigments such as titanium dioxide.
  • Matting liquid represents an additional work step, which noticeably extends the production time and thus increases the costs. Furthermore, the precision of the digitization of the surface geometry of the dental component can be negatively influenced in any subsequent 3D scanning step by inhomogeneous layer thicknesses of the matting liquid. Since the dental components to be coated are also usually medical products, the corresponding use of a matting liquid disadvantageously also requires that this also be approved as a further medical product, which significantly increases the regulatory effort for marketing.
  • compositions which can optionally be designed as light-curing compositions and in which so-called “silicone-acrylic-based rubber impact modifiers” are used, which are designed as core-shell particles. These core-shell particles preferably have a diameter in the range from 0.01 to 100 ⁇ m and serve to improve the mechanical properties of the cured compositions.
  • WO 2018/167213 discloses shaped dental bodies which have an opacity of 70 to 78% and contain organic filler and / or a powdery composite material. According to the disclosed exemplary embodiments, the composition for the production of these molded bodies comprises approximately 66% by weight of polymer particles with mean particle sizes in the range from 15 to 60 ⁇ m.
  • the primary object of the invention was therefore to provide a light-curing composition for the production of dental components in the DLP process or SLA process, which makes it possible to produce dental components that are advantageous in particular without further treatment on their surface
  • the light-curing composition should preferably have a comparatively low, preferably easily adjustable, viscosity in order to enable problem-free handling in SLA or DLP processes.
  • the light-curing composition should be curable using typical photoinitiators. It was desirable here that no inorganic additives or fillers are required to achieve the effect, in particular no metals or metal oxides, since these potentially affect the weight and / or the surface hardness and / or the mechanical
  • the dental components produced from the light-curing composition did not have any increased roughness on the surface that could artificially modify the surface structure desired according to the CAD data and / or lead to an undesirably strong adhesion of applied molding compounds. It was an aim of the present invention that the light-curing composition can be produced to a large extent from substances that are already regularly used in dental technology.
  • the light-curing composition should also be able to include those monomers which have a particularly high tendency towards shiny surfaces.
  • a secondary object of the invention was to provide a method for producing light-curing compositions by means of which light-curing compositions can be produced in a cost-effective and reproducible manner, from which dental components can be produced by means of SLA or DLP processes, the surface of which has at most a satin gloss shows.
  • the stipulation here was that the method can be carried out using conventional devices and that, in particular, only those starting products are used that can be easily handled and stored, it being particularly desirable that the operating staff do not carry small nanoparticles into the process when carrying out the method dry or dusty form comes into contact in order to ensure the highest possible operational safety and also to avoid contamination of the environment.
  • Another object of the invention was to provide uses for corresponding light-curing compositions and for solid polymer agglomerates and for solid polymer particles.
  • a supplementary object of the invention to provide a kit for producing corresponding light-curing compositions, a system for producing a dental component and an uncoated dental component with a matt surface.
  • the inventors have now recognized that the objects described above can be achieved if a light-curing composition with a high proportion of liquid monomers also contains solid polymer particles with a particle diameter in the range from 0.4 to 4 ⁇ m and a combined mass fraction in the range from 0, 1 to 30% can be added when these solid polymer particles are dispersed in the liquid monomer composition.
  • the solid polymer particles in the cured material are present as small separate domains distributed in the material, in which the resulting component has a different chemical composition and, as a result, a different optical refraction or scattering behavior than in the polymerized monomer composition.
  • the inventors assume that it is probably the distribution of these small areas over the surface of the dental component that contributes to the significant matting effect that is observed experimentally.
  • the inventors have developed an efficient process with which corresponding light-curing compositions can be obtained.
  • An essential aspect of this process is based on the fact that the solid polymer particles are not added to the liquid monomer composition in isolation, but in the form of larger polymer agglomerates, which are sometimes also referred to as agglomerated polymer beads.
  • These Polymer agglomerates are added to the liquid monomer composition to create a master batch.
  • the solid polymer particles are only produced by mechanical treatment of the basic mixture for breaking down the solid polymer agglomerates and for dispersing the polymer particles of the liquid monomer composition, in particular with a three-roll process. This gives a light-curing composition which can produce the advantageous gloss properties described above during further processing.
  • the invention relates to a light-curing composition for the production of dental components in the DLP process or SLA process, comprising, based on the total mass of the light-curing composition: a liquid monomer composition with a mass fraction of 60% or more, comprising one or more radically polymerizable monomers, preferably consisting of one or more radically polymerizable monomers, one or more photoinitiators with a combined mass fraction in the range from 0.001 to 10%, and solid polymer particles with a particle diameter in the range from 0.4 to 4 ⁇ m and a combined mass fraction in the range from 0.1 to 30%, the solid polymer particles being dispersed in the liquid monomer composition.
  • a liquid monomer composition with a mass fraction of 60% or more comprising one or more radically polymerizable monomers, preferably consisting of one or more radically polymerizable monomers, one or more photoinitiators with a combined mass fraction in the range from 0.001 to 10%
  • solid polymer particles with a particle diameter in the range from
  • the term light-curing which is used above to characterize the composition, corresponds to the technical term used in the industry.
  • the expression is to be understood as the property of the composition to cure through the application of electromagnetic radiation, in particular light, in that the radiation induces the polymerization of radically polymerizable monomers in the composition by means of a photoinitiator.
  • the wavelength of the radiation used for this does not necessarily have to be in the visible light range, but also includes the adjacent wavelength ranges in the infrared or UV range, with wavelengths between 200 and 500 nm, ie in the blue and ultraviolet range, being used particularly frequently.
  • dental components denotes all components and three-dimensional structures that are manufactured as an intermediate stage or end product in the field of dental technology, that is, regardless of the underlying dental indication, for example dental models, gingival masks, bite splints, CAD-to- cast molds, impression trays or drilling templates.
  • DLP method and SLA method denote the above-described methods of digital light processing and the
  • Stereolithography which are known as methods to those skilled in the art.
  • the specification of the suitability of the light-curing composition for the production of dental components in this process places in particular a functional requirement on the viscosity of the material, insofar as it should be sufficiently low.
  • many light-curing compositions that are used elsewhere in the dental field, in particular those with high filler contents, for example ceramic slips, are excluded.
  • the person skilled in the art easily recognizes whether a Monomer composition is qualitatively liquid. In the context of the present invention, it is assumed that any monomer composition which, at 23 ° C., has a dynamic viscosity of 10 Pa s or less, preferably 5 Pa s or less, can be referred to as a liquid.
  • the mass fractions defined above for the liquid monomer composition, the photoinitiators and the solid polymer particles each relate to the total mass of the light-curing composition.
  • the person skilled in the art understands that the mass fractions are defined with the proviso that the total mass fractions of the light-curing composition add up to 100%. This means that if, for example, an additive with a mass fraction of 10% is added to the composition, the photoinitiators and the solid polymer particles together can only have a mass fraction of 30% or less.
  • the free-radically polymerizable monomers are characterized by their property of crosslinking with one another in a chain reaction on contact with a free-radical initiator, the free-radical initiator being regularly provided in light-curing compositions by the photoinitiator (s).
  • the present invention is not restricted to certain radically polymerizable monomers, but can be used for all radically polymerizable monomers, these mostly having a terminal unsaturated double bond via which the radical polymerization can proceed.
  • (meth) acrylates are of outstanding importance as monomers, the expression (meth) acrylates denoting both acrylates and methacrylates in the understanding of the person skilled in the art.
  • the solid polymer particles to be used according to the invention in the light-curing composition have a particle diameter in the range from 0.4 to 4 ⁇ m. It has been shown experimentally that even small amounts of this additive lead to a considerable improvement in the gloss properties of the dental component to be produced from the light-curing composition.
  • the polymer particles are solid, i.e. already substantially fully polymerized, i.e. at least 80%, preferably at least 90%, particularly preferably at least 98%, fully polymerized.
  • the solid polymer particles are dispersed in the liquid monomer composition. This means that there is essentially no concentration gradient of solid polymer particles in the light-curing composition in the light-curing composition between two macroscopic volume sections. This preferably means that the concentration differences between two separate, macroscopic volumes of the composition of one milliliter each in the light-curing composition show less than 10%, preferably less than 5%, particularly preferably less than 2%, deviation in the concentration of the solid polymer particles.
  • the solid polymer particles are in particular not dispersed in the liquid monomer composition when they float on the surface of the liquid monomer composition, as was observed, for example, for agglomerated particles in polymer agglomerates, for which the advantageous effect of the invention has not been shown . Accordingly, light-curing compositions are preferred in which the solid polymer particles are essentially not agglomerated. This means that the polymer particles are preferably less than 50%, particularly preferably less than 20%, very particularly preferably less than 10%, in the agglomerated state.
  • a light-curing composition according to the invention is preferred, the light-curing composition not containing any metallic particles or metal oxides.
  • the light-curing composition according to the invention enables dental components to be produced in the SLA or DLP process, which show advantageous gloss properties, i.e. a low gloss, on their surface without further treatment. Due to the high proportion of liquid monomer composition, the light-curing composition according to the invention has a comparatively low viscosity that is at the same time easily adjustable due to the polymer particles.
  • the light-curing composition according to the invention can be cured using typical photoinitiators and can be produced to a large extent from substances that are already regularly used in dental chemistry, even from monomers with a high tendency to gloss.
  • no inorganic additives or small nanoparticles with a diameter of 300 nm or less are required to achieve the effect, and the dental components produced from the light-curing composition do not have a significantly increased surface roughness.
  • a light-curing composition according to the invention is preferred, the solid polymer particles consisting of polymers of monomers selected from the group consisting of monofunctional (meth) acrylates and polyfunctional (meth) acrylates, preferably consisting of polymethyl methacrylate, the solid polymer particles preferably consisting of polymers of monomers that are not part of the liquid monomer composition.
  • the above-mentioned light-curing composition is preferred because the above-mentioned polymer particles, when used in light-curing compositions, have proven to be particularly advantageous for reducing the surface gloss of the dental components produced therefrom. It has proven to be particularly advantageous if the polymer particles consist of polymers of monomers which themselves are not part of the liquid monomer composition or which have a mass fraction of less than 10% in the liquid monomer composition and consequently the physico-chemical properties of the Completely polymerized monomer composition affect comparatively little.
  • the gradient of the chemical composition between the solid polymer particles and the material of the dental component obtained by polymerization from the liquid monomer composition is particularly pronounced, the optical properties in the The small domains introduced by the solid polymer particles are particularly different from those that arise when the liquid monomer composition cures.
  • the solid polymer particles being at least partially transparent polymer particles, the refractive index of which differs from the refractive index that results when the liquid monomer composition is polymerized.
  • a light-curing composition according to the invention is preferred, the solid polymer particles having an essentially spherical particle shape and having preferably been produced by spray drying.
  • Corresponding light-curing compositions are considered to be preferred because the investigation of the polymer particles used in the experiments has regularly shown a corresponding spherical, ie spherical, particle shape.
  • the relatively uniform spatial expansion in the spherical polymer particles contributes to the changed scattering properties of the surfaces, for example in comparison to flat, disk-shaped polymer particles.
  • a light-curing composition according to the invention is preferred, the radically polymerizable monomers being selected from the group consisting of monofunctional (meth) acrylates and polyfunctional (meth) acrylates, preferably selected from the group consisting of diurethane dimethacrylate, tris (2-acryloyloxyethyl) isocyanurate, alkoxylated bisphenol A dimethacrylate, tricyclo [5.2.1.0 2 ' 6 ] decanedimethanol diacrylate and dicyclopentanylmethyl acrylate, and / or wherein the free-radically polymerizable monomers contain no silicon atoms.
  • the radically polymerizable monomers being selected from the group consisting of monofunctional (meth) acrylates and polyfunctional (meth) acrylates, preferably selected from the group consisting of diurethane dimethacrylate, tris (2-acryloyloxyethyl) isocyanurate, alkoxylated bisphenol A dimethacrylate, tricycl
  • the corresponding light-curing compositions are preferred because particularly good results have been achieved in practice with the corresponding free-radically polymerizable monomers.
  • These free-radically polymerizable monomers are also established components in the field of dental chemistry, for which comprehensive approvals are available and whose hazard potential has been well researched. In addition, these
  • (Meth) acrylates photopolymerize very efficiently and, thanks to the wide range of possible components, allow a particularly flexible setting of the physicochemical properties.
  • a light-curing composition which contains diurethane dimethacrylate, tris (2- acryloyloxyethyl) isocyanurate, alkoxylated bisphenol A dimethacrylate,
  • Tricyclo [5.2.1.0 2 ' 6 ] decanedimethanol diacrylate and dicyclopentanylmethyl acrylate contains, as this has been identified in our own tests as a suitable starting material for the production of dental components that have particularly favorable mechanical properties.
  • a light-curing composition according to the invention is preferred, the liquid monomer composition comprising radically polymerizable monomers whose boiling point at 101.3 kPa pressure is above 100.degree. C., preferably above 120.degree. C., particularly preferably above 140.degree.
  • Corresponding light-curing compositions are particularly preferred because the inventors have recognized that the problem of the gloss of the surface in dental components occurs above all when using radically polymerizable monomers that have a low vapor pressure, i.e. their boiling point at ambient pressure is above a certain temperature. At the same time, however, correspondingly high-boiling monomers are regularly essential for setting the physico-chemical properties of dental components. Admittedly, undesirable ones appear
  • the liquid monomer composition preferably comprises a mass fraction of at least 20%, preferably at least 40%, very particularly preferably at least 60%, of the free-radically polymerizable monomers with the boiling point defined above.
  • the inventors assume that the increased gloss tendency of high-boiling monomers is related to the process temperature, which occurs locally for example in the SLA process at the moment of light-induced polymerization.
  • a light-curing composition according to the invention is preferred, wherein the mass fraction of the liquid monomer composition is 70% or more, preferably 80% or more, particularly preferably 85% or more, and / or wherein the combined mass fraction of the photoinitiators is in the range from 0.01 to 5 %, preferably 0.1 to 2%, particularly preferably 0.2 to 1%, and / or where the combined mass fraction of the solid polymer particles is in the range from 0.2 to 20%, preferably 0.5 to 15%, particularly preferably 1 to 10%.
  • Corresponding light-curing compositions are preferred because light-curing compositions with a high mass fraction of the liquid monomer composition with a comparatively low proportion of solid polymer particles at the same time show particularly good processability and are also particularly easy and cost-effective to produce. In addition, it is particularly cost-effective to use the smallest possible amounts of photoinitiators, which is also very beneficial for the storage stability of the material obtained.
  • satisfactory results are advantageously achieved even with small amounts of photoinitiators, the inventors having observed that even small amounts of solid polymer particles which are added to the light-curing composition, even with compositions rich in monomers, have a particularly pronounced effect on the Have gloss properties.
  • a light-curing composition according to the invention is preferred, the solid polymer particles having a particle diameter in the range from 0.5 to 2.5 ⁇ m, preferably in the range from 0.7 to 2 ⁇ m, and / or the solid polymer particles having ad50 value in the range from 0.7 to 2 pm, preferably in the range from 0.8 to 1.6 pm, particularly preferably in the range from 0.9 to 1.2 pm.
  • the rheological properties of the light-curing composition in the liquid state in particular the dynamic viscosity at 23 ° C., can advantageously be adjusted in a targeted manner.
  • smaller particle diameters also regularly correlate with a significantly more homogeneous distribution in the material.
  • the inventors have established that a particularly pronounced reduction in the gloss value can be achieved precisely with particularly small particles, which is attributed to this particularly homogeneous distribution in the light-curing composition.
  • a light-curing composition according to the invention is preferred, the light-curing composition having a dynamic viscosity in the range from 0.1 to 10 Pa s, preferably in the range from 0.5 to 5 Pa s, particularly preferably in the range from 0.7 to 2.5 Pa s.
  • the above-specified light-curing composition is preferred because it can be processed particularly efficiently and at the same time enables adequate stabilization of the solid polymer particles in the light-curing composition.
  • the viscosity defined above contributes to increased storage stability, which is particularly advantageous in the case of the light-curing compositions according to the invention.
  • the dynamic viscosity is determined at 23 ° C. using an Anton Paar rheometer, physicist NCR 301, in accordance with DIN 1342-2; 2003-11 Newtonian liquids and DIN 1342-3; 2003-11 non-Newtonian liquids.
  • the photoinitiators causing the polymerization reaction on irradiation with electromagnetic radiation in the wavelength range of 200 and 500 nm can initiate preferably in the wavelength range from 350 to 450 nm, particularly preferably in the wavelength range from 380 and 420 nm.
  • Corresponding photoinitiators regularly have a particularly high level of compatibility with the (meth) acrylates usually used.
  • the use of radiation in the wavelength range between ultraviolet and blue is also particularly preferred because this radiation is more energetic than, for example, red radiation and thus regularly enables cleaner and faster initiation of photo-induced curing.
  • a light-curing composition according to the invention is preferred, additionally comprising one or more additives with a combined mass fraction in the range from 0.01 to 10%, preferably in the range from 0.1 to 5%, particularly preferably 0.2 to 2%, the additives are selected from the group consisting of fillers, dyes, pigments, flow improvers, thixotropic agents, thickeners and stabilizers.
  • a particular advantage of the light-curing composition according to the invention is that further additives can be added without adversely affecting the positive effects on the gloss properties of the dental component to be produced.
  • the invention also relates to a method for producing a light-curing composition for the production of dental components in the DLP process or SLA process, preferably a light-curing composition according to the invention, comprising the steps:
  • the liquid monomer composition in step A) and the solid polymer agglomerates in step B) can be produced in the course of the process or provided separately, for example by purchasing from a supplier. It is essential for the process according to the invention that the solid polymer particles are not used in isolated form, i.e. incorporated into the liquid monomer composition, but in the form of solid polymer agglomerates, which are sometimes also referred to as agglomerated polymer beads. These solid polymer agglomerates comprise a multiplicity of solid polymer particles as primary particles and are mixed with the monomer composition in step C) in order to obtain a basic mixture therewith.
  • the solid polymer agglomerates tend not to be homogeneously dispersed in the basic mixture, but rather to float in the liquid monomer composition.
  • the basic mixture is not suitable for use in the SLA process or DLP process, and the resulting dental component shows no improvements in terms of gloss properties.
  • Only through the mechanical treatment of the basic mixture in step D) is a light-curing composition obtained which shows the positive effect according to the invention.
  • the mechanical treatment of the basic mixture takes place to break down the solid polymer agglomerates and to disperse the polymer particles in the liquid monomer composition.
  • the polymer agglomerates disintegrate into the primary particles, ie into the solid polymer particles, and an essentially homogeneous dispersion of the solid polymer particles in light-curing compositions is achieved.
  • the photoinitiators necessary for the light-curing must also be added to the basic mixture for the production of the light-curing composition.
  • the point in time at which the photoinitiators are added is not relevant. This can take place, for example, after the mechanical treatment or even before the two components are combined, for example by adding them to the liquid monomer mixture, but ensuring thorough mixing is expedient in all cases.
  • the method according to the invention enables the production of light-curing compositions according to the invention in a cost-effective and reproducible manner.
  • the process can be carried out using relatively common devices, the required starting products being able to be handled and stored comparatively easily, since the operating personnel do not come into contact with small nanoparticles in dry or dusty form when carrying out the process, which ensures a high level of operational reliability .
  • the polymer agglomerates having a particle diameter in the range from 5 to 200 ⁇ m, preferably in the range from 10 to 150 ⁇ m, particularly preferably in the range from 15 to 75 ⁇ m.
  • polymer agglomerates can be distributed better and more evenly in the basic mixture even before the mechanical treatment and are easier to break down by mechanical treatment. This advantageously gives more homogeneous light-curing compositions. It should be noted, however, that larger Polymer agglomerates can definitely have advantages, in particular with regard to handling and with a view to health aspects, in particular if dust is formed during processing.
  • a method according to the invention is preferred in which the polymer agglomerates have an essentially spherical shape.
  • a method according to the invention is preferred, the mechanical treatment being carried out by a grinding process and / or stirring process and / or rolling process, in particular with a ball mill and / or a dissolver and / or a three-roll mill, preferably in a rolling process, in particular in a three-roll mill.
  • the mechanical treatment of the basic mixture can in principle be carried out by any suitable method that is suitable for breaking down the solid polymer agglomerates.
  • grinding processes, stirring processes and rolling processes have proven to be particularly useful for this purpose, with the use of a three-roll process, i.e. using a three-roll mill, being particularly preferred, as this is particularly efficient and targeted by setting a gap between the rolls that is as narrow as possible Destruction of the agglomerates after incorporation into the basic mixture allows.
  • the use of a three-roll mill allows in particular the adequate destruction of the polymer agglomerates, which in some cases is more difficult to achieve over the entire volume of the basic mixture, especially in the case of stirring processes.
  • the person skilled in the art adjusts the intensity of the mechanical treatment on the basis of routine experiments in order to identify the optimal degree of stress depending on the materials used. If the mechanical load is not chosen to be sufficiently high, significant proportions of polymer agglomerates can remain, which reduces the technical effect of the light-curing composition according to the invention. In addition, it has been observed that too great a mechanical load on the basic mixture leads to a deterioration in the overall properties of the produced light-curing composition and a decrease in quality in the resulting dental component.
  • a light-curing composition which has been produced by the above process.
  • the invention also relates to the use of a light-curing composition according to the invention for the production of dental components with matt surfaces in a DLP process or SLA process, the surface of the dental component having a gloss value of 10 GU or less, preferably 5 GU or less, particularly preferably 2 GU or less.
  • a light-curing composition according to the invention in the DLP process or SLA process, dental components can be obtained which have particularly favorable gloss properties and a matt surface.
  • gloss properties in GU i.e. H. Gloss unit, indicated with which the person skilled in the art is familiar.
  • gloss values are determined using a gloss measurement method in which a device from BYK of the micro-TRI gloss type is used using an angle of 60 °.
  • solid polymer agglomerates comprising agglomerated solid polymer particles with a particle diameter in the range from 0.4 to 4 ⁇ m in the production of light-curing compositions for the production of dental components in the DLP process or SLA process, preferably for the production of light-curing compositions according to the invention, is also disclosed Compositions. It has surprisingly been found that the use of solid polymer agglomerates in the production of light-curing compositions makes it possible to obtain light-curing compositions according to the invention particularly efficiently without undesirable dust formation occurring when the solid polymer particles are handled.
  • solid polymer particles with a particle diameter in the range from 0.4 to 4 ⁇ m in a light-curing composition for the production of dental components in the DLP process or SLA process to reduce the gloss property of the dental components obtained by light curing is also disclosed.
  • an uncoated dental component is disclosed, produced in a DLP process or SLA process from a composition according to the invention, the surface of the dental component having a gloss value of 10 GU or less, preferably 5 GU or less, particularly preferably 2 GU or less , and wherein the surface has an average surface roughness Ra of 2.5 ⁇ m or less, preferably 2.0 ⁇ m or less.
  • Ra is determined in accordance with the specifications of DIN EN ISO 4287: 2010.
  • uncoated dental components which were produced from the light-curing composition according to the invention in the DLP process or SLA process, have particularly advantageous gloss properties on their surface and do not show any increased surface roughness, which is reflected in an average surface roughness Ra of 2.5 pm or less. In this way, particularly smooth surfaces are advantageously obtained, on which, for example, molding compound can be applied and later removed again without leaving any residue.
  • Corresponding uncoated dental components advantageously also have a large contact angle with water, which means that they can be cleaned particularly efficiently.
  • a system for producing a dental component in a DLP process or SLA process comprising a DLP printer or an SLA printer with a liquid reservoir for receiving a light-curing composition, the liquid reservoir comprising the light-curing composition according to the invention.
  • kits for producing a light-curing composition according to the invention comprising as separate components in separate containers: U solid polymer agglomerates comprising agglomerated solid polymer particles with a particle diameter in the range from 0.4 to 4 ⁇ m, and
  • V a liquid monomer composition comprising one or more radically polymerizable monomers.
  • the solid polymer agglomerates are advantageously large enough to enable comparatively safe handling in the laboratory.
  • the dentist or dental technician only has to mix the two components together and ensure by mechanical treatment that the solid polymer agglomerates are broken down into the solid polymer particles, which are then dispersed in the light-curing composition.
  • the kit can also comprise one or more photoinitiators as a further component W, whereby these can alternatively also already be added to the liquid monomer composition.
  • one or more photoinitiators as a further component W, whereby these can alternatively also already be added to the liquid monomer composition.
  • 1 shows a micrograph of spray-dried polymer agglomerates made of polymethyl methacrylate in a 200x magnification
  • FIG. 2 shows a microscope image of the primary particles of a spray-dried polymer agglomerate made of polymethyl methacrylate in an 8000x magnification
  • 3 shows a microscope image of the primary particles of a spray-dried polymer agglomerate made of polymethyl methacrylate, magnified 10,000 times; 4 a plot of the experimentally determined gloss number (Y) of test specimens which were produced from light-curing compositions, as well as the dynamic viscosity (Z) of the corresponding light-curing compositions against the mass fraction of solid polymer particles (X) in the light-curing compositions.
  • the reference system here comprises in particular five free-radically polymerizable monomers with very different chemical structures, which represent a broad spectrum of (meth) acrylates that are particularly frequently used in practice.
  • PMMA particles were selected in the reference system because these were available as sufficiently small particles and experience has shown that solid PMMA is a relatively representative representative of polymerized (meth) acrylates. Neither in the experiments shown here nor in the accompanying experiments carried out by the inventors Made observations that would have questioned the assumption that the results could be transferred to other systems.
  • a liquid monomer composition consisting of a mixture of a first and a second monomer mixture in a mass-related mixing ratio of 1 to 1.67, the first monomer mixture in equal proportions by mass of tris (2-acryloyloxyethyl) isocyanurate, dicyclopentanyl methyl acrylate and tricyclo [5.2.1.0 2 ' 6 ] decanedimethanol diacrylate and wherein the second monomer mixture consists of bisphenol A and ethoxylate dimethacrylate
  • Diurethane dimethacrylate exists in a mass ratio of 2 to 1.
  • Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide as a photoinitiator
  • additive 1 2-hydroxy-4-methoxybenzophenone
  • additive 2 Titanium (IV) oxide
  • additive 3 flame black
  • PV real blue A2R in diurethane dimethacrylate additive 4
  • Polymer particles made of polymethyl methacrylate i.e. the polymer of methacrylic acid methyl ester.
  • compositions as listed in Table 1 were prepared from these substances, the values being given as a percentage by mass. Of these compositions, Ex.1 to Ex.5 are light-curing compositions according to the invention, whereas composition Comp.1 is a comparative composition which does not contain any solid polymer particles. Table 1: Composition of the investigated light-curing agents
  • compositions with various contents of solid polymer particles Compositions with various contents of solid polymer particles.
  • the liquid monomer composition comprises five radical polymerizable monomers, and is prepared by mixing the components.
  • the photoinitiator is suitable for bringing about polymerization of the liquid monomer composition by irradiating the composition with light.
  • the polymer particles are solid, spherical polymer particles with a diameter in the range from 0.7 to 2.0 ⁇ m.
  • the compositions described above were produced using the method according to the invention, the polymer particles being introduced into the compositions by adding spherical polymer agglomerates with a diameter of approx. 15 to 75 ⁇ m. The addition of the
  • Additives and the photoinitiator to the liquid monomer composition were made prior to mixing with the polymer agglomerates.
  • the mechanical treatment of the basic mixture for breaking down the solid polymer agglomerates took place with a 3-roll process using a three-roll mill, the mixture being homogenized twice through a roll gap of 5 ⁇ m.
  • the polymer particles are present in the compositions according to the invention in the form of non-agglomerated particles dispersed, with the light-curing particles over the volume No concentration gradients of solid polymer particles were observed across compositions.
  • Figures 1 to 3 show microscopic photographs of the polymer agglomerates used at different magnifications (200x, 8000x and 10000x), the solid polymer particles as the primary particles of the
  • Table 2 Dynamic viscosities (Z) of the investigated light-curing compositions with different contents of solid polymer particles.
  • the measured values clearly show that the viscosity of the light-curing compositions according to the invention is still sufficiently low, even with a mass fraction of solid polymer particles of 10%, to enable use in the SLA or DLP process.
  • mass fractions of up to 30% can be achieved without the fundamental suitability of the composition according to the invention for use in SLA or DLP processes being omitted.
  • the viscosity of the light-curing compositions can be set particularly easily by adding the solid polymer particles in the light-curing compositions according to the invention and can be adapted to the respective requirements without the need, for example, of inorganic additives.
  • test specimens measuring 60 mm ⁇ 10 mm ⁇ 3.3 mm were produced using a DLP process, using a DLP printer from Kulzer of the cara Print 4.0 type became.
  • the test specimen was manufactured horizontally or vertically, i.e. the material layers produced in the DLP process are built up parallel or perpendicular to the surface measured in the course of the gloss measurement.
  • the gloss numbers were determined using a gloss measuring method which was operated with a device from BYK of the micro-TRI gloss type using a 60 ° angle. The values obtained are summarized in Table 3.
  • Table 3 Gloss number (Y) of the test specimens tested, which were produced from light-curing compositions with different contents of solid polymer particles, including standard deviation.
  • Table 4 Average surface roughness (Ra) of the tested specimens, which were produced from light-curing compositions with different contents of solid polymer particles. It is found that the mean surface roughness of the test specimens produced with the light-curing compositions according to the invention is advantageously not significantly increased compared with the comparison sample. Accordingly, it is advantageously possible to manufacture dental components that have smooth surfaces. Such dental components can be cleaned particularly easily and make it possible to remove applied molding compounds without leaving any residue.

Abstract

L'invention concerne une composition photodurcissable pour la production de composants dentaires dans un procédé DLP ou un procédé SLA, comprenant, par rapport à la masse totale de la composition photodurcissable : une composition de monomère liquide ayant une fraction massique égale ou supérieure à 60 %, comprenant un ou plusieurs monomères polymérisables par voie radicalaire, un ou plusieurs photoinitiateurs ayant une fraction massique combinée dans la plage de 0,001 à 10 %, et des particules de polymère solide ayant un diamètre de particule dans la plage de 0,4 à 4 µm et une fraction massique combinée dans la plage de 0,1 à 30 %, les particules de polymère solide étant dispersées dans la composition de monomère liquide.
EP21715234.7A 2020-04-02 2021-03-26 Composition photodurcissable pour la production de composants dentaires à surfaces mates Pending EP4126545A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020109280.6A DE102020109280A1 (de) 2020-04-02 2020-04-02 Lichthärtende Zusammensetzung für die Herstellung dentaler Bauteile mit matten Oberflächen
PCT/EP2021/057941 WO2021198071A1 (fr) 2020-04-02 2021-03-26 Composition photodurcissable pour la production de composants dentaires à surfaces mates

Publications (1)

Publication Number Publication Date
EP4126545A1 true EP4126545A1 (fr) 2023-02-08

Family

ID=75278038

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21715234.7A Pending EP4126545A1 (fr) 2020-04-02 2021-03-26 Composition photodurcissable pour la production de composants dentaires à surfaces mates

Country Status (5)

Country Link
US (1) US20230142551A1 (fr)
EP (1) EP4126545A1 (fr)
JP (1) JP2023521628A (fr)
DE (1) DE102020109280A1 (fr)
WO (1) WO2021198071A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116945600B (zh) * 2023-08-04 2024-02-23 北京易加三维科技有限公司 粉末床熔融热塑性弹性体的表面处理方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4575330A (en) 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
JPH0627047B2 (ja) 1988-12-16 1994-04-13 而至歯科工業株式会社 歯科用グラスアイオノマーセメント組成物
US5418112A (en) 1993-11-10 1995-05-23 W. R. Grace & Co.-Conn. Photosensitive compositions useful in three-dimensional part-building and having improved photospeed
DE19536892A1 (de) * 1995-10-04 1997-04-10 Basf Ag Formteile aus thermoplastischen Formmassen
DE10038564A1 (de) 2000-08-03 2002-02-14 S & C Polymer Silicon & Compos Durch optische Systeme abtastbare Formkörper
DE102006056451A1 (de) 2006-11-28 2008-06-05 Kettenbach Gmbh & Co. Kg Verfahren zur Herstellung eines Dentalprodukts und scannbares Material
DE102012201371A1 (de) 2012-01-31 2013-08-01 Leica Microsystems (Schweiz) Ag Multiphotonenfluoroskopievorsatzmodul für ein Operationsmikroskop
DE102012011371B9 (de) 2012-06-11 2018-10-18 Kulzer Gmbh Herstellung individueller dentaler Prothesen via CAD/CAM und Rapid Manufacturing/Rapid Prototyping aus digital erhobenen Daten der Mundsituation
CN104853693B (zh) 2012-11-14 2018-06-26 邓特斯普里国际公司 用于生产牙科产品的三维制作材料体系
DE102013110549A1 (de) 2013-09-24 2015-03-26 Andreas Huber Mattierungsflüssigkeit
DE102014116402A1 (de) 2014-11-11 2016-05-12 Voco Gmbh Verwendung radikalisch härtbarer Zusammensetzungen in generativen Fertigungsverfahren
DE102016107935A1 (de) 2016-04-28 2017-11-02 Kulzer Gmbh Verfahren zum Herstellen einer realen Verblendung sowie Verblendung und Brücke erhältlich nach dem Verfahren
EP3472218B1 (fr) 2016-06-20 2023-08-09 Dentsply Sirona Inc. Systèmes de matériaux de fabrication en trois dimensions et procédés de production de produits dentaires constitués de couches
CN109562026A (zh) * 2016-08-02 2019-04-02 三井化学株式会社 光固化性组合物、义齿基托及带托义齿
EP3335687B1 (fr) * 2016-12-15 2020-02-12 Ivoclar Vivadent AG Matière à modeler dentaire calcinable
EP3375429A1 (fr) 2017-03-17 2018-09-19 Ivoclar Vivadent AG Corps dentaire moulé monochromatique et ébauche destinée à la fabrication de restaurations dentaires

Also Published As

Publication number Publication date
US20230142551A1 (en) 2023-05-11
JP2023521628A (ja) 2023-05-25
WO2021198071A1 (fr) 2021-10-07
DE102020109280A1 (de) 2021-10-07

Similar Documents

Publication Publication Date Title
DE60115194T2 (de) Photohärtbares material für zahnreparaturen
DE19524362C2 (de) Anorganische Zusammensetzung, insbesondere für dentale Zwecke
DE69927638T2 (de) Restaurativer Dentalverbundstoff
DE60027076T2 (de) Dental-Verbundwerkstoff
DE3525720A1 (de) Dentalmaterial
EP0040232A1 (fr) Utilisation de granules d'acide silicique comme charges pour masses dentaires.
EP3760181B1 (fr) Bloc composite dentaire destiné à la fabrication de restaurations indirectes permanentes dans le procédé cad/cam
EP1945178B1 (fr) Procede pour realiser des composites destines au domaine dentaire
EP0802221B1 (fr) Charge à base de silice, procédé pour sa production et son utilisation
WO2014033280A2 (fr) Matériau dentaire polymérisable par polymérisation radicalaire, produit durci et utilisation
DE102005016762A1 (de) Photopolymerisierbares Einkomponenten-Kronen- und Brückenmaterial
EP0648484A1 (fr) Matière de change ayant des rétentions, son procédé de préparation et son utilisation
EP1262162B1 (fr) Composition colorante pour la coloration de résines synthétiques pour prothèses
WO2021198071A1 (fr) Composition photodurcissable pour la production de composants dentaires à surfaces mates
EP1128798B1 (fr) Materiau d'empreinte
DE102012013514A1 (de) Polymerisierbare Mischungszusammensetzung, Verwendung der Mischungszusammensetzung sowie eine Dentalprothese
DE4412831A1 (de) Künstlicher Zahn
EP4306099A1 (fr) Procédé de fabrication de ébauches dentaires
EP0753017B1 (fr) Matiere pouvant etre coulee et cuite, utilisee pour produire des pieces moulees en plastique
DE2462271A1 (de) Dentale formkoerper
EP3335687B1 (fr) Matière à modeler dentaire calcinable
DE2408640A1 (de) Acrylpolymermischungen
DE102012006152A1 (de) Polymerisierbare Dentalkomposite mit verbesserten Gebrauchseigenschaften, Verfahren zur Einstellung der Gebrauchseigenschaften polymerisierbarer Dentalkompositen, und nach diesen Verfahren optimierte Dentalkomposite
EP3373991B1 (fr) Matériau de prothèse transparent à haute résistance aux chocs et faible teneur résiduelle en mma
DE102018123330A1 (de) Strahlenhärtbare Zusammensetzung zur Verwendung in Rapid-Prototyping oder Rapid-Manufacturing Verfahren

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221028

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)