EP1203033A1 - Composition durcissable a la lumiere visible et son utilisation - Google Patents

Composition durcissable a la lumiere visible et son utilisation

Info

Publication number
EP1203033A1
EP1203033A1 EP00949417A EP00949417A EP1203033A1 EP 1203033 A1 EP1203033 A1 EP 1203033A1 EP 00949417 A EP00949417 A EP 00949417A EP 00949417 A EP00949417 A EP 00949417A EP 1203033 A1 EP1203033 A1 EP 1203033A1
Authority
EP
European Patent Office
Prior art keywords
ether
methacrylate
composition according
composition
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00949417A
Other languages
German (de)
English (en)
Inventor
Michael Zimmermann
Rüdiger Lange
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.)
Deltamed Medizinprodukte GmbH
Original Assignee
Deltamed Medizinprodukte 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
Priority claimed from DE19938463A external-priority patent/DE19938463A1/de
Priority claimed from DE19950284A external-priority patent/DE19950284A1/de
Application filed by Deltamed Medizinprodukte GmbH filed Critical Deltamed Medizinprodukte GmbH
Publication of EP1203033A1 publication Critical patent/EP1203033A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/896—Polyorganosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and 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 one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0006—Production methods
    • A61C13/0013—Production methods using stereolithographic techniques

Definitions

  • the invention relates to a composition curable with visible light and its use in a shaping process.
  • EP 0 897 710 A2 known for use in dental products.
  • the object of the invention is to provide an improved plastic which cures in visible light and which is particularly suitable for shaping processes such as microphotopinning, for other rapid prototyping processes such as stereolithography or for the production of dental products.
  • composition according to claim 1 a use of the composition according to one of claims 17 to 20, a method according to one of claims 21 to 24 or an object according to claim 25.
  • Developments of the invention are specified in the subclaims.
  • FIG. 1 shows a device for the method of producing a three-dimensional object by means of microphotographic bonding from a plastic according to the invention which cures under the action of visible light.
  • composition according to the invention is explained below using an exemplary embodiment of its use, namely the production of a three-dimensional object by means of microphotopinning.
  • the device has a container 1 with an upper edge 2 that is open on its upper side.
  • a carrier 3 for carrying an object 4 to be formed is arranged in the container with an essentially flat and horizontally oriented construction platform 5 which can be moved and positioned in the container 1 by means of a height adjustment device.
  • the entire container 1 is filled to the level below the upper edge 2 with the composition according to the invention in the form of a liquid plastic 6 which cures in visible light.
  • a flat transparent plate 7 made of a material transparent to visible light is provided in such a way that, while the container 1 is filled with the liquid plastic 6, it has a predetermined amount in the liquid Immerse plastic 6.
  • an exposure device 8 with a light source 9, such as a halogen, deuterium, plasma, Mercury vapor lamp or a laser, for generating visible light in a wavelength range from 350 to 700 nm, for example.
  • the exposure device 8 also has a Pro optics and a mask generating device and a mask 10 for the selective exposure of a respective layer of the three-dimensional object 4 to be formed in a corresponding cross section.
  • an aperture 11 which can be pivoted into the beam path.
  • a controller 12 is provided, which is designed in such a way that it controls the diaphragm 11, the mask generating device 10 and the height adjustment device of the carrier 3 or the construction platform as a function of predetermined object data.
  • the container 1 is filled with the liquid plastic 6 which cures with visible light, and the building platform 5 is displaced by the associated height adjustment device in such a way that there is between the top of the building platform 5 and the bottom of the transparent Plate 7 forms a layer of the liquid plastic 6 which cures with visible light in a predetermined layer thickness.
  • the plastic layer is then exposed in a cross section corresponding to the three-dimensional object 4 to be formed.
  • the construction platform 5 is shifted vertically downward in order to form the next layer of the liquid light-curable plastic 6 between the upper surface of the object 4 and the transparent plate 7.
  • the mask generating device 10 is controlled via the controller 12 in such a way that the exposure takes place with a light intensity which is sufficient to penetrate the layer of the liquid plastic 6 between the upper surface of the object 4 and the transparent plate 7 and with the layer which has already solidified underneath to connect the object 4.
  • the plastic 6 consists of a composition that cures with or in visible light
  • (a) 2-99% by weight of at least one compound, the acrylate and / or methacrylate groups, and / or vinyl and / or epoxy and / or oxetane groups and / or acrylic-epoxy-oligomer groups and / or methacrylic-epoxy-oligomer groups contains, and / or at least one resin composition based on polymerizable polysiloxanes, in particular Ormocere,
  • modifiers such as fillers, dyes, pigments, flow improvers, thixotropy agents, polymeric thickeners, oxidizing additives, stabilizers and retarders.
  • the compound or compounds of component (a) of the composition which contain acrylate and / or methacrylate groups, harden in the visible light by radical polymerization.
  • the following crosslinkable and non-crosslinkable monomers are particularly suitable: aliphatic diurethane methacrylate, tetra-ethoxylated bisphenol A diethyl acrylate, aliphatic urethane methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-butyl methacrylate, iso-propyl methacrylate
  • 2-ethylhexyl methacrylate methacrylic acid ester with an ester group of 1 to 13 carbon atoms, isobornyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, ethyl triglycol methacrylate, tetrahydrofurfuryl methacrylate, hydroxyalkyl methacrylate with an alkyl group from 1 to 4 methacrylate, such as 2-C-A, such as 2-C-A , Alkoxyethyl methacrylate with an alkoxy group of 1 to 4 carbon atoms, allyl methacrylate, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-
  • the epoxy and / or an oxetane group-containing compound or compounds of component (a) cure under the action of visible light by cationic polymerization.
  • examples include aliphatic or aromatic epoxides, cycloaliphatic epoxides or oxetanes, such as 1,3, 5, 7-tetrakis (2, 1-ethanediyl-3, 4-epoxycyclohexyl) -l, 3, 5, 7-tetramethylcyclo- tetrasiloxane, 1, 10-decanediylbis (oxymethylene) bis (3-ethyloxetane), 1,3,5,7, 9-pentakis (2, l-ethanediyl-3, 4-epoxycyclohexyl) - 1,3,5,7, 9-pentamethylcyclopentasiloxane, vinylcyclohexene oxide, vinylcyclohexene dioxide, 3,4-epoxy-6-methylcyclohex
  • the compound containing vinyl groups or compounds of component (a) of the composition such as, for example, monovinyl ether, divinyl ether, hydroxyvinyl ether, aminovinyl ether, trivinyl ether, cure by free radicals and cationically (mostly cationically) by light.
  • Examples are triethylene glycol divinyl ether, 4-hydroxybutyl vinyl ether, propenyl ether of propylene carbonate, dodecyl vinyl ether, triethylene glycol divinyl ether, alkyl vinyl ether with an alkyl group of 2 to 18 carbon atoms, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, butanediol , Butanediol divinyl ether, hexanediol divinyl ether, ethylene glycol butyl vinyl ether, cyclohexane dimethanol mono- and divinyl ether, 2-ethyl hexyl vinyl ether, poly-THF divinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, Tert.
  • -a yl vinyl ether ethylene glycol divinyl ether, diethylene glycol monovinyl ether, hexanediol monovinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether.
  • the compound or compounds of component (a) which contain or contain acrylic-epoxy-oligomer groups and / or methacrylic-epoxy-oligomer groups polymerize under the action of visible light both cationically and radically in the form of a so-called dual curing.
  • the combination of one or more of the above-mentioned cationically polymerizing compounds with one or more of the above-mentioned free-radically polymerizing compounds also leads to dual curing.
  • the resin composition or resin compositions based on polymerizable polysiloxanes contains or contain, for example, compounds as described in the patents DE 4133494 C2 or DE 3903407 A1.
  • it is a photochemically or thermally curable or self-curing resin composition based on polymerizable polysiloxanes in the presence of initiators, obtainable by hydrolytic condensation of one or more hydrolytically condensable compounds of silicon and optionally other elements from the group B, Ba, Ti, Zr, Al, Sn, the transition metals, the lanthanides and the actinides, and / or precondensates derived from the abovementioned compounds, optionally in the presence of a catalyst and / or a solvent, by the action of water or moisture, 1 to 100 mol%, based on monomeric compounds, from silanes of the general formula (I),
  • R alkyl, alkenyl, aryl, alkylaryl or arylalkyl
  • X hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or NR ' 2 with
  • R ' hydrogen, alkyl or aryl
  • radicals A, R, R 2 and X are identical or different and have the following meaning:
  • R alkyl, alkenyl, aryl, alkylaryl or arylalkyl
  • R alkylene, arylene or alkylene arylene
  • X hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR ' 2 , with
  • fillers are selected, optionally containing fillers and / or copolymerizable monomers.
  • one of the structural element E 2 and at least one of the structural elements is in the resin composition; E 1 and / or E 3 and / or E 4 compound of the general formula
  • R x is a methyl, ethyl, n-propyl, isopropyl or an optionally CH 3 -C 3 H 7 -substituted phenyl radical
  • n 0,1,2 or 3 and M means titanium or zirconium.
  • the molar ratio of the structural element E 2 to the structural elements E 1 and / or E 3 and / or E 4 is in each case between 50: 1 and 10: 1 or the molar ratio of the structural elements E2: E1: E3: E4 is approximately 25 : 1: 1: 1.
  • the polymerisation of the polysiloxanes takes place radically and / or cationically.
  • one or more of the following compounds which initiate the polymerization are provided as component (b) of the composition: phosphine oxides, acylphosphine oxides, diphenyl-2, 4, 6-trimethylbenzoylphosphine oxide; Benzoin ethers, such as benzoin or the benzoin alkyl ether; Benzil ketals such as benzil dialkyl ketal; ⁇ -hydroxyketones; aminoketones; Acetophenones, such as .alpha.-hydroxyacetophenones, dialkoxyacetophenones, .alpha.-aminoacetophenones, benzophenones; Thioxanthones such as i-propylthioxanthone; ⁇ -dicarbonyl compounds such as camphorquinone; bisimidazoles; Metallocenes such as titanocenes and ferrocenes; Aryl tert. -butyl-peresters
  • constituent (b) of the composition contains one or more of the following compounds as initiator: aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts and / or phenylphosphonium benzophenone salts.
  • component (b) is a combination of one or more of the above-mentioned, the radical see polymerization initiating compounds provided with one or more of the above, the cationic polymerization initiating compounds.
  • the dual-curing composition and / or desired properties can thus be set.
  • Component (c) may contain one or more of the following compounds as co-initiators for radical curing: tertiary amines, preferably N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-dialkyl dialkylaniline and other structurally related amines, preferably in combination with initiators such as benzophenones and ⁇ -dicarbonyl compounds such as camphorquinone; Diaryliodonium compounds, preferably in combination with the fluorone initiators; Borates such as butyrylcholine triphenylbutyl borate and other structurally related borates; organic phosphites; Thioxanthones as a sensitizer for the ⁇ -aminoacetophenone initiators.
  • tertiary amines preferably N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, N,
  • One or more of the following compounds can be provided as the co-initiators of component (c) for the cationic curing: xanthenes; fluorenes; fluorones; ⁇ -dicarbonyl compounds, such as. B. camphorquinone as a sensitizer for the diaryliodonium initiators.
  • a combination of one or more of the above-mentioned co-initiators for free-radical polymerization with one or more of the above-mentioned co-initiators for cationic polymerization such as e.g. a combination of fluorones, diaryliodonium salts, tert. Amines and / or borates can be provided.
  • the component (d) can contain at least one modifier, for example at least one pigment and / or a dye such as anthraquinone, preferably in an amount of 0-3% by weight.
  • the dye / pigment is precisely matched to the light source used or its emission spectrum. The that is, if you use a different light source, the dye / pigment may also have to be changed.
  • At least one of the following substances can be provided as a suitable filler of the component (d) of the composition: silicon dioxide, such as pyrogenic silicon dioxide and / or amorphous silica, aluminum oxide, ceramic, quartz, ground glasses, splinter polymers, silica gels and minerals.
  • the filler can be pretreated with a silane, such as 3-methacryloyloxypropyltrimethoxysilane.
  • the grain sizes of the inorganic fillers are usually 0.01-100 ⁇ m, preferably 0.01-20 ⁇ m.
  • Fibers and fabrics such as glass fiber, carbon fiber, textile fiber, metal fiber, can also be embedded as fillers. This includes fibers and fabrics individually or in ribbon, mat, tube or cord form or a bundle of continuous fibers. It does not matter whether the filler is contained in the plastic from the outset or whether the polymerization process is interrupted, for example to insert a glass fiber mat. If the plastic preparation contains the filler, a liquid, semi-solid to solid paste is obtained depending on the filler content. Deviating from Fig. 1, semi-solid or solid pastes are brought to the defined layer thickness (e.g. 10 - 150 ⁇ m) with a roller system. The introduction of fillers enables a variety of other areas of application, such as dental, otoplastic, facial and bone surgery applications.
  • component (d) of the composition can contain stabilizers such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and / or 2,6-di-tert. -butyl-4-methylphenol, preferably contained in an amount of 0-5% by weight.
  • stabilizers such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and / or 2,6-di-tert. -butyl-4-methylphenol, preferably contained in an amount of 0-5% by weight.
  • the composition is produced by the following essential steps: First, prescribed amounts of the initiators, co-initiators, dyes, pigments and stabilizers are dissolved in a low-viscosity part of component (a) of the composition, for example in the monomer ethyl methacrylate or butanediol dimethacrylate, the resulting mixture depending on the solubility of the ingredients used, stirred between 1-36 h at 20-80'C. The resulting solution is then mixed with the rest of component (a) of the composition in 10-60 minutes. One or more fillers are then optionally added to the resulting solution in small portions and mixed intensively after each addition.
  • the choice of the type and the amount of fillers, pigments, dyes and stabilizers of the composition can influence physical properties, such as the hardness or depth hardness of a layer, the modulus of elasticity, the color, the layer thickness and the durability of the object to be formed and set as needed.
  • the initiators and / or co-initiators can be used in various combinations in order to vary them in accordance with the type of shaping process, the light source used and the desired physical properties of the object to be formed therewith.
  • the accuracy of fit of the object to be formed can be improved, since, for example, the polymerization shrinkage and the disruptive influence of an oxygen inhibition layer are reduced in comparison with a purely radical-curing composition.
  • the thickness of a layer to be hardened in the shaping process can be adjusted to the desired thickness.
  • the layer thickness and the depth hardness can be influenced via the polymerization depth and the polymerization time ,
  • the plastic of the abovementioned composition can be used in the above-described method for forming a three-dimensional object, that is to say in microphotopinning, as in other rapid prototyping methods, for example in laser sintering or in stereolithography.
  • composition according to the invention is not based on microphotopinning or on rapid prototyping. Procedure limited.
  • the composition of the invention is rather also in other shaping processes, such as. B. in film casting of plastics, in the production of plastic sintered parts or in microstructuring, such as. B. in photolithography in semiconductor technology.
  • the composition according to the invention can be used in the dental, facial and bone surgery and otoplastic fields for the production of inlays, onlays, tooth fillings, attachments, crowns, bridges, artificial teeth, pin teeth, dental prostheses, dental implants, facial implants, bone implants and hearing aids (otoplastic). Accordingly, both models and individually manufactured individual products or mass-produced sales products can be produced with the composition according to the invention.
  • a specific use of the composition according to the invention is given in dental technology in a method for producing plastic inlays.
  • a camera is first used to record a cavity of a tooth to be filled and a computer model of the inlay to be inserted into the cavity is produced.
  • the computer model is then broken down into flat layers by means of software, the layer data generated in this way being fed to the control of a microphotographic consolidation system described above, where the inlay is built up layer by layer in accordance with the layer data. Due to the good resolution in the process of microphotopinning, inlays can be produced in a precise manner.
  • a plastic is used as described above, which is tooth-colored by the addition of appropriate dyes / pigments.
  • the inlay can also be produced by using a plastic which is pasty through a filler of component (d), each layer being produced by rolling out the pasty material.
  • a special rigidity of the inlay produced can be achieved if glass fiber components are added to the plastic mass to be cured.
  • one or glass fiber mat can be placed in between several plastic layers.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Veterinary Medicine (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition durcissable à la lumière visible contenant (a) 2-99 % en poids au moins d'un composé qui renferme des groupes acrylate et/ou méthacrylate, et/ou des groupes vinyle et/ou époside et/ou oxétane et/ou des groupes acryl-époxy-oligomère et/ou des groupes méthacryl-époxy-oligomère, et/ou au moins un mélange de résine à base de polysiloxanes polymérisables, (b) 0,01-7 % en poids au moins d'un initiateur, (c) 0-5 % au moins d'un co-initiateur, (d) 0-85 % en poids au moins d'un modificateur, tel qu'une matière de charge, un colorant, un pigment, un fluidifiant, un agent de thixotropie, un épaississant polymère, un adjuvant d'action oxydante, un stabilisateur et un retardateur.
EP00949417A 1999-08-13 2000-07-28 Composition durcissable a la lumiere visible et son utilisation Withdrawn EP1203033A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19938463 1999-08-13
DE19938463A DE19938463A1 (de) 1999-08-13 1999-08-13 Mit sichtbarem Licht aushärtende Zusammensetzung und deren Verwendung
DE19950284 1999-10-19
DE19950284A DE19950284A1 (de) 1999-10-19 1999-10-19 Mit sichtbarem Licht aushärtende Zusammensetzung und deren Verwendung
PCT/EP2000/007317 WO2001012679A1 (fr) 1999-08-13 2000-07-28 Composition durcissable a la lumiere visible et son utilisation

Publications (1)

Publication Number Publication Date
EP1203033A1 true EP1203033A1 (fr) 2002-05-08

Family

ID=26054598

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00949417A Withdrawn EP1203033A1 (fr) 1999-08-13 2000-07-28 Composition durcissable a la lumiere visible et son utilisation

Country Status (3)

Country Link
EP (1) EP1203033A1 (fr)
JP (1) JP2003507499A (fr)
WO (1) WO2001012679A1 (fr)

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US20050040551A1 (en) 2003-08-19 2005-02-24 Biegler Robert M. Hardenable dental article and method of manufacturing the same
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EP2052693B2 (fr) 2007-10-26 2021-02-17 Envisiontec GmbH Procédé et système de fabrication de forme libre pour produire un objet tridimensionnel
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