Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
• • 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

Definitions

• the present invention relates to photopolymerizable compositions based on resins. These compositions are specially intended for the dental field, in particular for producing preforms and / or dental prosthesis models, and even more particularly removable dental prosthesis models.
• An assistant dental prosthesis is a device intended to replace one or more teeth and their supporting tissues (bone and gum) which would have resorbed, or more simply to reconstitute a badly dilapidated tooth. Depending on whether or not the dental prosthesis can be put in place and removed by the patient, it is qualified as removable or irremovable.
• These prostheses can be made of metals, synthetic resins or ceramics.
• the production of a dental prosthesis in the case of a removable metallic dental prosthesis comprises the following steps: - a step of taking an impression, carried out by applying to the buccal part to provide a prosthesis, quick setting material (such as alginates, an elastomer, a hydrocolloid) so as to obtain a relief reproduction (said negative reproduction) of said buccal part; a step of producing a model of a material, for example plaster or a polyurethane resin (said model being commonly designated by the terminology "master model”), consisting in casting said material in the impression previously prepared; - a new step of impression taking in gelatin or silicone by counter-molding of the previous model; - a step of producing a coating model, by casting the coating in the gelatin or silicone imprint; - a step of making a wax model on the coated model; - A step of positioning the assembly consisting of the model and the model in a cylinder followed by coating said assembly, so as to obtain a model of a material, for example plaster or
• compositions described in the prior art thus all have one or more of the following drawbacks: - after photopolymerization, they exhibit a shrinkage greater than 1%, which makes them unreliable for the production of models with appropriate dimensions; - They lead to low calcination rates, in particular due to the presence of mineral fillers; - they do not lend themselves easily to modeling; - they have no shape memory, which would make it possible to obtain a faithful model, after disinsertion of this model from its model; - They do not offer sufficient elasticity to produce a model, which can be removed from its model without altering its shape.
• the aim of the present invention is to propose new compositions which do not have the abovementioned drawbacks, and which more particularly have a shrinkage of less than 1% after photopolymerization, advantageous mechanical properties such as tensile stress. ranging from 10 to 100 Mpa and an elongation at break which may be approximately 5%, a rate of calcination of 100%.
• a photopolymerizable composition comprising: - at least one epoxyvinyl ester resin; - at least one urethane acrylate resin; - at least one non-silicone organic particulate filler having an average particle size of less than 10 ⁇ m and a specific surface of more than 10 m / g; and - at least one photoiniator.
• a composition appears in the form of a paste having the following characteristics: - a reduction in shrinkage on polymerization, compared with compositions of the prior art, this thanks in particular to the combination in the composition of the invention of at least one epoxyvinyl ester resin and at least one urethane acrylate resin; - high rigidity, making it possible to obtain tensile stresses of 10 to 100 Mpa; - sufficient elasticity to give the composition the desired final properties, know an elongation at break which can be about 5%; - an easy formatting faculty due in particular to the presence of an organic filler having the above-mentioned particular characteristics.
• the composition of the invention comprises at least one epoxyvinyl ester resin.
• epoxyvinylester is understood to mean, in the foregoing and what follows, a resin resulting from the addition of an acrylic or methacrylic acid to an epoxy resin.
• advantageous epoxyvinyl ester resins can correspond to the following general formula:
• - R ⁇ represents a hydrogen atom or a methyl group
• - R 2 represents a hydrogen atom or an al yl group comprising from 1 to 3 carbon atoms
• - X represents a bisphenolic motif A
• - n is an integer ranging from 1 to 10.
• epoxyvinyl ester resins in the context of this invention are: - bis-GMA or [2, 2-bis (4- ⁇ 2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane] corresponding to the following formula:
• the resins of this invention may be commercially available from suppliers Cray-Valley, UCB, Sigma-Aldrich.
• the epoxyvinyl ester resins of the present invention can also be readily prepared as mentioned above by reaction of a epoxy resin with an acrylic or methacrylic acid, optionally followed by an alkylation reaction of the —OH functions present.
• the epoxyvinyl ester resins are present in the composition at a content ranging from 18 to 50% by weight relative to the total weight of the composition.
• the presence of at least one epoxyvinyl ester resin in the composition contributes to giving the latter a reduction in shrinkage upon polymerization, a decrease in water absorption.
• the composition of the invention also comprises at least one urethane acrylate resin.
• the urethane acrylate resins are resins resulting from the reaction of an isocyanate compound (for example, a diisocyanate or triisocyanate compound) with an -OH group of an acrylate or methacrylate monomer.
• an isocyanate compound for example, a diisocyanate or triisocyanate compound
• Advantageous acrylate urethane resins of the invention can be represented by the following general formula:
• - R 3 represents a group of formula -CH 2 - (CH 2 ) n -0-CO- with n being an integer equal to 1 or 2; - Y represents H or -CH 3 ; - R 4 represents an alkylene group comprising from 1 to 10 carbon atoms.
• Particularly advantageous acrylate urethane resins in the context of the invention can be commercially available resins, such as those available from Cray-Valley, under the names CN945A60 and CN934.
• resins can also be prepared, as mentioned by reacting an isocyanate compound with an -OH group of an acrylate or methacrylate monomer.
• a suitable isocyanate compound may be the compound corresponding to the formula below: NCO OCN-CH 2 - (CH 2 ⁇ CH- (CH 2 ) CH 2 - CO
• Suitable acrylate or methacrylate monomers can be chosen, for example, from those of formula: O
• the urethane acrylate resins are present in the composition at a content ranging from 1 to 50% by weight relative to the total weight of the composition.
• the presence of at least one urethane acrylate resin in the composition contributes to giving it a high rigidity as well as a high viscosity, as well as a low water absorption.
• the composition of the invention also comprises a non-silicone particulate organic filler. It is specified that, in the foregoing and what follows, the term “non-silicone particulate organic charge” means a charge comprising exclusively organic compounds, namely compounds based on carbon and hydrogen, and optionally nitrogen, oxygen and fluorine, but devoid of silicon, said charge being in the form of solid particles.
• This filler must have specific characteristics which give the composition great malleability, a certain elasticity and rigidity for its own weight, an improvement in the stability of the composition as well as a reduction in the tackiness of the abovementioned resins.
• the particulate non-silicone organic filler of the invention has an average particle size (that is to say an average diameter) of less than 10 ⁇ m, preferably from 2 to 7 ⁇ m and a specific surface greater than 10 m ? / g, preferably from 15 to 25 m 2 / g.
• This filler is preferably non-reactive, that is to say that it does not contain groups capable of polymerizing during the photopolymerization of the composition.
• this filler can be chosen from particulate polymers from the group consisting of polyamides, polyacrylates such as polymethyl methacrylate (PMMA), optionally fluorinated polyolefins such as polyethylene tetrafluoride (PTFE), polysaccharides, such as starch.
• PMMA polymethyl methacrylate
• PTFE polyethylene tetrafluoride
• starch polysaccharides
• This polyamide in particular has excellent mechanical properties, such as a breaking stress of 48 MPa and an elongation at break of 5%.
• a PMMA which can be very advantageously used in the context of this invention can be that supplied by Atoglas, UCB, which has an average particle size ranging from 5 to 10 ⁇ m and a specific surface of 12 m 2 / g. This PMMA has in particular a breaking stress of 62 Mpa and an elongation at break of 2.5%.
• a PTFE which can be very advantageously used in the context of this invention is that supplied by Goodfellow, which has an average particle size ranging from 2 to 4 ⁇ m and a specific surface of 35 m 2 / g.
• This PTFE has in particular a breaking stress of 35 Mpa and an elongation at break of more than 100%.
• Polysaccharides which can be advantageously used are the soluble starch supplied by VWR.
• the non-silicone particulate filler of the composition is present in the composition at a content ranging from 10 to 25% by weight relative to the total weight of the composition.
• composition according to the invention also comprises one or more photoinitiators, said photoinitiators being species, the photolysis of which releases reactive species.
• these photoinitiators are able, after photolysis, to release free radicals.
• Photoinitiators in accordance with the present invention can be aromatic ketones, such as benzophenone, thioxanthone of formulas represented below:
• Particularly effective photoinitiators in the context of this invention may also be initiators of the bis-acyl phosphine oxide type (known as the BAPO type), such as the photoinitiator Irgacure 819 sold by the company CIBA represented by the following formula: 14
• This photoinitiator has the advantage of breaking down, under the action of UV light, into four free radicals, each of which can initiate the crosslinking of the composition of the invention and makes it possible to greatly accelerate the rate of polymerization compared to conventional photoinitiators, degrading in only 1 or 2 free radicals under the action of UV light.
• the photoinitiator is present in the composition at a content ranging from 0.1 to 2% by weight relative to the total weight of the composition.
• the composition according to the invention can also comprise an elastomeric compound or an elastomeric composition, such as that sold by Ugine Dentaire under the name Plastiform®.
• an elastomeric compound or elastomeric composition means a compound or a polymeric composition having a glass transition temperature of between 20 and 70 ° C.
• copolymers capable of advantageously entering into the composition of the invention, mention may be made of copolymers
• the elastomeric compound and / or the elastomeric composition is (are) present in the composition at a content ranging from
• the composition of the invention may also comprise at least one polyester resin, preferably crosslinked.
• polyester resin means a resin resulting from the reaction of an anhydride compound with a diol.
• a suitable polyester resin can be a resin comprising, after polymerization, the motif of the following formula:
• - M is a unit derived from a styrenic or acrylate monomer
• - Y 1 represents a group of formula: -CO-0-CH 2 -CH (CH 3 ) -O-CO-
• Suitable polyester resins are available in particular from Gazechim under the name Norsodyne, from Dow Plastics, from BASF.
• At least one oil preferably a non-silicone oil.
• This oil can be a vegetable oil or a synthetic oil, such as oils of the Voltalef® brand corresponding to the general formula: Cl- (CF 2 -CFCl) n -Cl with n being an integer ranging from 3 to 4.
• the oil is present in the composition at a content ranging from 0.5 to 3% by weight relative to the total weight of the composition.
• the composition may also comprise one or more reactive solvents, that is to say solvents capable of dissolving the resins while being capable of reacting during the photopolymerization.
• the reactive solvent can be chosen from solvents corresponding to one of the following formulas:
• TPGDA Tripropylene glycol diacrylate
• the reactive solvent content can be any organic compound having 2-neopentylglycol propoxylated diacrylate (PONPGDA) and mixtures thereof.
• the reactive solvent content can be any organic compound having 2-neopentylglycol propoxylated diacrylate (PONPGDA) and mixtures thereof.
• the reactive solvent content can be any organic compound having 2-neopentylglycol propoxylated diacrylate (PONPGDA) and mixtures thereof.
• compositions of the invention can be used in many fields. Thus, they can be used for the production of molded parts and burn-out models for numerous applications. In particular, the compositions of the invention can be used in the dental field. Thus, the invention also relates to the use of a composition as described above, for the manufacture of a preform and / or a model of dental prosthesis, more particularly of a removable assistant dental prosthesis. It is specified that, in the foregoing and what follows, the term “preform” is understood to mean a project carried out with the composition of the invention, said project being intended to define the structure of future fixed or removable prostheses.
• a preform can be a typical element of a removable dental prosthesis, such as the plate, the hooks, the bars.
• This preform serves as a basis for the dental technician, to produce a model of the future dental prosthesis, the model corresponding to all of the above-mentioned assembled preforms.
• the dental technician can add suitable complementary elements, for example, in wax, such as replacement teeth.
• the model is light-cured in order to keep its modeled shape.
• the invention also relates to a preform and / or a model based on a photopolymerizable composition as described above.
• Such a model can be produced by a process comprising the following steps: - an impression-taking step, performed by applying to an oral portion to be provided with a prosthesis, an adequate material, so as to obtain an imprint of said portion buccal; - a step of producing a plaster model, consisting of pouring plaster into the previously prepared impression; - A modeling step on the plaster model of the desired model with the photopolymerizable composition as described above; - a step of photopolymerization of said model; - a step of separating said model thus light-cured from the plaster model.
• this model is the basis for the production of a dental prosthesis.
• the invention also relates to a process for developing a dental prosthesis successively comprising: - the implementation of the process for developing the model described above; - A step of coating said cylinder in a cylinder, at the end of which a mold is obtained for coating the dental prosthesis; - a step of calcining said model; a step of filling the mold with a coating of a molten metal or metallic alloy, followed by cooling, so as to solidify the metal or metallic alloy; - a step of destroying the coated mold, so as to release the dental prosthesis.
• the impression-taking step, a preliminary step to producing the model consists in reproducing in negative the buccal part to be provided with a prosthesis, so as to obtain an imprint of this part.
• this step consists in interposing in the oral cavity, for example, an impression tray, that is to say a device of suitable shape comprising the impression material.
• This impression material is a fast setting material, that is to say which has the capacity, after molding, to harden at room temperature.
• Such materials can be chosen, for example, from alginates, hydrocolloids.
• This imprint serves as the basis for the production of a plaster model, which corresponds to the master model, said master model being produced by casting plaster in the aforementioned impression. Thanks to the properties inherent in the compositions of the invention (namely malleability, elasticity), these can be directly applied to the master model in order to constitute the model of the dental prosthesis.
• This modeling step consists, more precisely, in training on the master model the precursor elements (or preforms) of the future prosthesis, namely for example the base plate, the hooks, the possible bars, which will constitute for example the future chassis of the prosthesis, all of these preforms constituting a model of the future dental prosthesis.
• the composition mock-up is light-cured, during a photopolymerization step, said step being able to take place as the construction of the constituent elements of the mock-up or at the end of the development of the model. More specifically, this photopolymerization step can be carried out by subjecting the elements constituted from the compositions of the invention to UV light, supplied for example by a UV lamp emitting light of wavelength ranging from 400 to 500 nm .
• the model thus light-cured is separated from the plaster model.
• This model has the particularity of retaining, after said separation, its initial shape (namely the shape established on the plaster model), because of the elastic properties of the photopolymerizable compositions of the invention.
• This model is the basis for the realization of the dental prosthesis. It is specified that this model can possibly be finalized by shaping suitable elements thereon into materials, such as wax, said elements possibly being, for example, replacement teeth.
• the method of producing the dental prosthesis according to the invention comprises, as mentioned previously, the implementation of the method of developing a model as set out above.
• the model then undergoes a coating step in a cylinder, said step consisting in covering the material of the model with coating.
• a mold is obtained for coating the dental prosthesis, this mold conforming to the shape of the model. It is specified that, by coating, is meant in what precedes and what follows, a refractory molding material.
• the method comprises, after the coating step, a step of calcining the model. More specifically, this step consists in heating to an adequate temperature the assembly consisting of the coated mold and the model based on the photopolymerizable composition of the invention.
• This temperature is chosen so as to calcine the model, this temperature possibly being a temperature of 1000 ° C. in air.
• the photopolymerizable composition of the invention because of its burnable nature, disappeared without leaving any residue and there remains only the mold coated with the dental prosthesis.
• This coated mold is then filled with a metal, preferably a noble metal (such as Ag, Pd, Pt) or molten metal alloy such as an alloy based on chromium, cobalt, titanium. After cooling, accompanied by solidification of said metal or alloy, the coated mold is destroyed, for example, by fracture, so as to release the metallic dental prosthesis.
• a noble metal such as Ag, Pd, Pt
• molten metal alloy such as an alloy based on chromium, cobalt, titanium.
• the process for the preparation of a dental prosthesis of the invention proves to be faster and less expensive than the conventional processes, such as that described in the state part of the Prior art of the present description.
• the use of the compositions according to the invention for producing a dental prosthesis model makes it possible to dispense with two conventional stages of the processes for producing dental prostheses, namely the gelatin impression step or in silicone by counter-molding the plaster model and the step of producing a model in coating, by casting the coating in the gelatin or silicone impression. Consequently, we are witnessing, thanks to the invention, a considerable saving of time and also a reduction in the consumption of coating.
• the fact of placing only the model based on a composition of the invention in the cylinder for coating makes it possible to obtain a significant saving of space in this cylinder compared to the coatings conventionally produced from a model generally made of wax modeled on a model coated. Thanks to the space saving obtained, it is thus possible, according to the invention, to carry out the simultaneous coating of several models in the same cylinder.
• compositions presented below and in accordance with the invention are compositions having the following criteria: - low shrinkage ( ⁇ 1%) after photopolymerization; - a breaking stress of between 10 and 100 Mpa while having an elongation at break of around 5%; - a high viscosity to facilitate the implementation, in the form of a paste, for modeling the desired preforms; - a certain memory of shape or intrinsic rigidity; - low tack before light-curing; - a calcination rate of 100% at 1000 ° C in air; - an elastic character.
• EXAMPLE 1 A photopolymerizable composition in accordance with the invention and having the above characteristics comprises the following elements:
• a photopolymerizable composition in accordance with the invention and having the abovementioned characteristics comprises the following elements: - Epoxyvinylester resin CN104: 35.9% - Urethane acrylate resin CN934: 24.0% - Voltalef® oil: 2.0% - Polyamide 12 Orgasol: 10.5% - Norsodyne G703 polyester resin: 10.0% - Irgacure 819 photoinitiator: 0.1%
• a photopolymerizable composition in accordance with the invention comprises the following constituents:
• a photopolymerizable composition in accordance with the invention comprises the following elements:
• a photopolymerizable composition in accordance with the invention comprises the following elements: - CN104 epoxyvinylester resin: 39.0% - CN934 urethane acrylate resin: 6.5% - PLASTIFORM: 27.4% - ORGASOL 2001 UD NAT2: 26.5% - Irgacure photoinitiator: 0.6%

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Epidemiology (AREA)
• Plastic & Reconstructive Surgery (AREA)
• General Chemical & Material Sciences (AREA)
• Dental Preparations (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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• 2003
  • 2003-07-16 FR FR0350334A patent/FR2857668B1/fr not_active Expired - Fee Related
• 2004
  • 2004-07-15 EP EP04767894A patent/EP1644441A2/de not_active Withdrawn
  • 2004-07-15 US US10/537,007 patent/US20060052470A1/en not_active Abandoned
  • 2004-07-15 CN CNA2004800019430A patent/CN1723244A/zh active Pending
  • 2004-07-15 WO PCT/FR2004/050333 patent/WO2005007743A2/fr not_active Ceased
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