Classifications

• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/55—Boron-containing compounds

Definitions

• Dental composition based on a crosslinkable and / or thermally polymerizable functionalized silicone.
• the field of the invention is that of dental compositions. More specifically, the dental compositions developed in the context of the present invention are based on crosslinkable and / or polymerizable functionalized silicone, and can be used for the production of dental prostheses, artificial teeth and dental restorative materials.
• the object of the present invention is to provide new dental compositions based on silicone which do not have the drawbacks of the prior art.
• These new dental compositions which can be polymerized and / or crosslinked in the oral environment, have markedly improved qualities, in particular with regard to the very marked reduction in the phenomenon of withdrawal of the materials and prostheses obtained from said compositions.
• These new dental compositions are particularly interesting in terms of reactivity; they are crosslinkable and / or polymerizable thermally, which makes it possible to use conventional crosslinking / polymerization methods and moreover at temperatures below 150 ° C.
• This reactivity is notably due to the presence of a new type of initiator based on boron derivative; indeed, it is active at low concentration and advantageously requires only small amounts of energy to effect crosslinking / polymerization.
• the claimed dental compositions therefore prove to be particularly advantageous in terms of effectiveness in use and in terms of profitability and cost for industrial processes.
• the thermally polymerizable and / or crosslinkable dental composition according to the invention comprises:
• R ⁇ represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, alkoxy radical, preferably a lower alkyl in C ⁇ -Cs,
• - Z is an organic substituent comprising at least one reactive epoxy function, and / or alkenylether and / or oxetane and / or dioxolane and / or carbonate, and preferably Z being an organic substituent comprising at least one reactive function epoxy, and / or dioxolane,
• R ' are identical or different and represent: a C 1 -C 12 , preferably C 8 -C 8 alkoxy radical, linear or branched, optionally substituted by at least one electron-withdrawing element, in particular a halogen atom (particularly fluorine), or an electron-withdrawing group such as for example the groups CF 3 , NO 2 , CN, - a phenyl radical substituted by at least (i) an electron-withdrawing element, in particular a halogen atom (especially fluorine), (ii) an electron-withdrawing group, in particular a group CF 3 , NO 2 , CN, or (iii) a C C- 2 hydrocarbon radical. preferably in linear, branched, mono- or polycyclic, saturated, unsaturated or aromatic and preferably substituted by at least one halogen atom element or a C r alkyl radical
• an aryl radical containing at least two aromatic rings such as biphenyl, naphthyl, optionally substituted with at least one electron-withdrawing element, in particular halogen atom (particularly fluorine), or an electron-withdrawing group in particular a group CF 3 , NO 2 , CN,
• R ′ can be linked to one another so as to constitute, with the boron atom to which they are linked, a ring with 5 or 10 atoms with said ring possibly being saturated, bridged unsaturated and / or aromatic and comprising one or more heteroatoms chosen from hydrogen, nitrogen and boron atoms with the boron atom present in said ring which can itself be substituted by a radical as defined for A or R 'in general formula I;
• - x represents 0 or the integer 1 or 2 and y the integer 1, 2 or 3 with the sum of x + y being equal to 3.
• the thermal activation is carried out at temperatures lower than 150 ° C, preferably lower than 100 ° C and even in particular at ambient temperature of mouthing.
• the boron-derived initiators used in dental compositions in accordance with the invention are generally very hygroscopic compounds. Consequently, these compounds can appear as a mixture between the compound as defined in general formula (I) and its different hydrated form (s).
• aprotic solvents such as ethers, esters and silicones
• protic solvents such as alcohols, carboxylic acids, silanols, amines, thiols, water or their mixtures.
• initiators can also be combined with a conventional initiator such as a cationic photoinitiator. This is particularly advantageous in terms of profitability, insofar as it is thus possible to significantly reduce the effective amount of conventional initiator of this type.
• a conventional initiator such as a cationic photoinitiator.
• the crosslinking and / or polymerization is also carried out completely.
• the symbols R ′ of the general formula (I) are chosen so as to give the boron atom to which they are linked a steric bulk sufficient to provide it with effective protection in particular to prevent its oxidation and / or hydration.
• the initiators of general formula (I) in which at least one of the symbols R 'and preferably at least two of them represent a phenyl or aryl radical are particularly advantageous.
• the initiators corresponding to the general formula (la) are especially preferred according to the invention: in which: n represents an integer between 1 and 3 and m an integer between 0 and 2 with the sum of n and m being equal to 3, - the symbols Y are identical or different and represent a) a hydroxyl group , b) a halogen atom, c) an alkoxy radical in linear or branched, preferably substituted by at least one electron-withdrawing element such as a halogen atom and in particular a fluorine atom, d) two Y groups can be linked together so as to constitute with the boron atom to which they are linked a C 5 -C 10 ring with said ring which can be saturated, unsaturated, bridged and / or aromatic and comprise one or more heteroatoms chosen from oxygen, nitrogen and boron atoms with the boron atom present in said cycle which itself can be substituted by a radical as defined for Y in general formula (la) and the symbols X ′
• halogen atom preferably a fluorine atom
• a C 12 -C 12 hydrocarbon radical preferably linear, branched, mono- or polycyclic, saturated, unsaturated or aromatic and preferably substituted by at least one electron-withdrawing element such as a halogen atom and in particular a fluorine atom or a C 1 -C 12 alkyl radical, preferably C, -C 8 , linear or branched, monopoly- or per-halogenated with in particular fluorine as a halogen atom, and - the indices p are identical or different and represent an integer between 0 and 5 , preferably with at least one of the symbols p greater than 3 and more preferably equal to 5.
• the initiators of general formula (la) in which Y meets the definitions a), b), and c) are particularly interesting. Mention may more particularly be made, as representative of the initiators claimed, of the following compounds:
• the initiators used in the compositions according to the invention can be used, as they are obtained at the end of their preparation process, for example in solid or liquid form, or in solution in at least one suitable solvent .
• suitable solvent currently includes products that dissolve solid initiators and products that dilute liquid or solid initiators.
• the initiators are generally used in solution in a solvent.
• the weight proportions between the initiator (s), on the one hand, and the solvent, on the other hand, are between 0.1 and 99 parts per 100 parts of solvent and, preferably from 10 to 50 parts.
• This initiator solution is therefore used to prepare a bath with the oligomer (s) and / or silicone polymers with crosslinkable functional groups, such that the concentration of the initiator or initiators present is between 0.01 and 5% by weight in said bath, and preferably between 0.05 and 0.5%.
• the solvents which can be used for the initiators are very numerous and varied and are chosen according to the initiator used and the other constituents of the composition of the invention.
• the solvents can be alcohols, esters, ethers, ketones, trace water and carbonates.
• the alcohols commonly used are para-tolyl-ethanol, isopropyl-benzyl alcohol, benzyl alcohol, methanol, ethanol, propanol, isopropanol and butanol.
• the ethers commonly used are methoxy-2-ethanol, ethoxy-2-ethanol, diethylene glycol.
• esters are dibutylmaleate, dimethyl-ethylmalonate, methyl salycilate, dioctyladipate, butyl tartrate, ethyl lactate, n-butyl lactate, isopropyl lactate.
• Other solvents which can be used for the initiator bath and which fall into the other categories of solvents mentioned above are acetonitrile, benzonitrile, acetone, cyclohexanone, and tetrahydrofuran.
• the initiator in the compositions according to the invention can develop into a solvated form.
• the type of initiator used in the compositions according to the invention also extends to the solvated forms of the claimed initiators.
• the reactive functions Z of the silicone polymer or oligomer (1) can be very varied.
• the silicone oligomer or polymer (1) comprises at least one unit (FS) in which Z represents an organic substituent Z1 comprising at least one reactive function epoxy, and / or dioxolane, and preferably at least one reactive epoxy function.
• the silicone oligomer or polymer (1) with at least one reactive Z1 epoxy and / or dioxolane function, and preferably at least one reactive epoxy function can:
• the dental composition can also comprise other oligomers and / or silicone polymers comprising other reactive functions Z2 such as the alkenylether, oxetane and / or carbonate functions and optionally reactive functions Z1 .
• reactive functions Z these can be chosen in particular from the following radicals:
• R represents a linear or branched C-1-C5 alkyl radical.
• the silicone polymer or oligomer consists of at least one silicone of the following average formula:
• the dental composition in addition to oligomers and / or polymers of silicone nature, can comprise monomers, oligomers and / or crosslinkable and / or polymerizable polymers of organic nature.
• monomers, oligomers and / or crosslinkable and / or polymerizable polymers of organic nature can in particular be chosen from the following organic species: ⁇ i i) cycloaliphatic epoxides and in particular:
• glycidic type epoxides such as: neopentylglycol, diglycidylether.le dibutanediol1-4 difglycidylétherje glycidyléther dodécyl e cyclohexanedimethanoldiglycidylether.le trimethylolpropanetriglycidylether,
• alpha-olefin epoxides NOVOLAC epoxies, epoxidized soybean oil, epoxidized linseed oil, and epoxidized polybutadiene; c-2) oxides of terpenes, and in particular: limonene dioxide; myrcene6-7 epoxide or myrcene dioxide, dihydromyrcene 6-7 epoxide; pinene oxide; epoxide 5-ethylidenenorbornene 5-8; and 5-vinyl 2,3 epoxynorbomene; 13) alkenyl ethers, linear or cyclic, and in particular:
• vinyl ethers in particular octylvinyl ether, dodecylvinyl ether (DDVE), cyclohexylvinylether (CVE), butanediol divinyl ether (BDVE), butanediol monovinyl ether (HBVE), cyclohexane dimethanol divinyl ether (CHDVEin) dimethyl ether (CHDVE)) (CHMVE), triethylene glycol divinyl ether (DVE-3) and the vinyl ethers of formula:
• fillers can be used to prepare the compositions according to the invention.
• the fillers are chosen according to the final use of the dental composition: these affect important properties such as appearance, as well as the mechanical and physical properties of the material obtained after crosslinking and / or polymerization of the dental composition. .
• charges of treated or untreated pyrogenic silica charges of amorphous silica, quartz, glasses or non-vitreous charges based on oxides of zirconium, boron, barium, calcium , fluorine, aluminum, titanium, strontium, zinc, borosilicates, aluminosilicates, talc, spherosil, yterbium trifluoride, fillers based on polymers in the form of ground powder such as polymethacrylates inert or functionalized methyl, polyepoxides or polycarbonates.
• the fillers and in particular the silica fillers are treated before use at 120 ° C. with an amount of less than 10% w / w of silicone comprising at least one unit of formula below:
• the material obtained after crosslinking exhibits significantly improved mechanical strength, modulus of elasticity, and compressive strength.
• pigments can be used to tint the dental composition according to the intended use and the ethnic groups.
• red pigments are used in the presence of microfibers for the dental compositions used for the preparation of dental prostheses in order to simulate the blood vessels.
• Pigments based on metal oxides are also used for the dental compositions used for the preparation of restorative material, in order to obtain a crosslinked material.
• metal oxides iron and / or titanium and / or aluminum and / or zirconium oxides, etc.
• co-reagents will advantageously be used Crosslinkable and / or polymerizable organic type
• co-reagents are liquid at room temperature or hot-melt at temperatures below 100 ° C, and each co-reagent comprises at least two reactive functions such as oxetane-alkoxy, oxetane-hydroxy, oxetane- alkoxysilyl, carboxy-oxetane, oxetane-oxetane, alkenylether-hydroxy, alkenylether-alkoxysilyl, epoxy-alkoxy, epoxy-alkoxysilyl, dioxolane-dioxolane-alcohol, etc.
• the dental compositions according to the invention can be used in the field of dental prosthesis, the field of dental restorative material, and the field of artificial tooth They can be formulated in one-component or two-component form
• the dental compositions for dental prosthesis comprise from 25 to 90% by weight of silicone and from 10 to 75% of filler (s) as well as an effective amount of the initiator of formula (I),
• the dental compositions for artificial teeth comprise from 5 to 50% by weight of silicone and from 50 to 95% of filler (s) as well as an effective amount of the initiator of formula (I), - the dental compositions for the dental restoration include from 15 a
• the stability before crosslinking and / or polymerization of the monocomponent or bicomponent dental compositions can be ensured by derivatives with amino functions, in particular sterically hindered amines such as the amines of the HALS type.
• sterically hindered amines such as the amines of the HALS type.
• the amines taught in the document can be used in particular.
• the products obtained from the dental composition according to the invention are non-porous.
• the surface of the dental prostheses obtained is smooth and shiny and therefore does not no varnish required
• the application in the field of dental prosthesis is essentially that of the denture, that I can be divided into two types - Total prosthesis (upper and lower jaw) in the case of completely edentulous patient, - and partial denture due to the absence of several teeth resulting in either a provisional prosthesis or a skeleton device
• This application also relates to the production of edges and the repair of prostheses (relining by casting or injection)
• the dental composition can be pretreated with a bonding primer or the dental composition can be prepared as a mixture with a bonding primer before its use.
• the dental composition being non-toxic and polymerizable in thick layers, it is not essential to polymerize the material in successive layers. In general, a single injection of the dental composition is sufficient.
• Examples 1 to 8 and 10 relate to pre-dental compositions [(without filler (s)] usable in particular for dental prosthesis.
• Examples 9 and 11 relate to dental compositions [with filler (s)].
• the products used in the compositions of the examples are as follows:
• the lifetime of the “pret-to-crosslink” compositions is regulated by the addition of a sterically hindered organic amine sold under the name Tinuvin 765 by the company Ciba.
• the shelf life corresponds to the time during which the composition can be handled. Examples 1 to 6.
• the oligomer of formula (I) is introduced into a mold for dental prostheses at the rate of 100 g over a thickness of 10 mm. Then added at room temperature 2.8 g of an isopropanolic solution of borane B (C 6 F 5 ) 3 to 3% by weight; this solution also contains a sterically hindered amine (Tinuvin 765® product).
• the amine concentration of the borane solution is different.
• the molar ratios R of the amine expressed as a nitrogen function relative to that of the borane expressed as a boron function are given in table 1 below.
• the gel time at 20 ° C. is measured and the Shore D hardness (according to DIN 43505 standard) obtained after initiation of the polymerization reaction is measured, allowing to return to ambient temperature of 22 ° C ⁇ 2 after 24 h and after demolding.
• the materials obtained do not have porosities.
• This example relates to a composition based on 100 g of oligomer (I) mixed with 2.8 g of borane initiator solution containing 1.66% by weight of Tinuvin 765 and 3% by weight of borane.
• the composition is crosslinked in an oven at 60 ° C for 10 minutes.
• the Shore D hardness measured after cooling is 85.
• the material obtained is completely transparent and colorless.
• the volume shrinkage of the material without fillers measured by pycnometry is between 3 and 4%.
• a borane solution is obtained by mixing 0.48 g of borane B (C 6 F 5 ) 3 hydrated at 18% in isopropanol, 2.3 grams of 3-ethyl (3-hydroxymethyl) oxetane and 39 mg of Tinuvin 765® product.
• a plastic pot containing 12.5 g of oligomer (I) is introduced; 0.5 g of initiator solution from Example 8; 25 g of quartz; and 12.5 g of combustion silica with a specific surface of 200 m 2 / g.
• the mixer is started successively 3 times 5 seconds after introduction of the quartz and 3 times 5 seconds during the introduction of the combustion silica so that the mixing temperature does not exceed 40 ° C.
• the mixture is then crosslinked at 80 ° C. for 10 minutes and a material of Shore D hardness greater than 90 is obtained.
• the volume shrinkage is less than 1%. (measurement by pyknometer).
• a borane solution is obtained by mixing 0.48 g of borane B (C 6 F 5 ) 3 hydrated at 18% in isopropanol, 2.3 g of resin (II) and 39 mg of Tinuvin 765® product. 2.8 g of this solution are added to 100 g of oligomer (I). The mixture is stable at
• a two-component mixture consisting of a composition A and a composition B is prepared.
• Composition A is prepared in a Hauschild Speedmixer DAC50® mixer of 12.5 g of oligomer (I) and 12.5 g of powdered polymethyl methacrylate filler (LUXASELF® product).
• Composition B consists of an initiator solution according to Example 10.
• composition A is then mixed using a small static mixer with 2 g of composition B.
• the mixture obtained is crosslinked at room temperature in 1 hour (or in 10 minutes at 60 ° C).

Landscapes

• 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)
• Dental Preparations (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicon Polymers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8858112

Family Applications (1)

Country Status (8)

Cited By (1)

Families Citing this family (6)

Citations (4)

Family Cites Families (2)

• 2000
  • 2000-12-22 FR FR0016922A patent/FR2818553B1/fr not_active Expired - Fee Related
• 2001
  • 2001-12-18 EP EP01989636A patent/EP1343453B1/fr not_active Expired - Lifetime
  • 2001-12-18 CA CA002431900A patent/CA2431900C/fr not_active Expired - Fee Related
  • 2001-12-18 AT AT01989636T patent/ATE395035T1/de not_active IP Right Cessation
  • 2001-12-18 US US10/450,492 patent/US7129282B2/en not_active Expired - Fee Related
  • 2001-12-18 JP JP2002552505A patent/JP4210114B2/ja not_active Expired - Fee Related
  • 2001-12-18 DE DE60134036T patent/DE60134036D1/de not_active Expired - Lifetime
  • 2001-12-18 WO PCT/FR2001/004044 patent/WO2002051357A1/fr not_active Ceased

Patent Citations (4)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events