Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • 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

Definitions

• the field of the invention is that of dental compositions. More specifically, the dental compositions developed in the context of the present invention can be used for the production of dental prostheses and for dental restoration.
• dental silicone compositions the qualities of which are improved, in particular as regards the very marked reduction in the phenomenon of withdrawal of the dental compositions used for the production of dental prostheses or dental restorative materials.
• application WO 00/19997 proposes dental compositions based on: - a crosslinkable or polymerizable silicone oligomer or polymer comprising:
• - a 0, 1 or 2
• - R ° identical or different, represents an al yl, cycloalkyl, aryl, vinyl, hydrogen, alkoxy radical, preferably a lower alkyl in CJ -CQ
• - Z identical or different, 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,
• At least one aromatic hydrocarbon photosensitizer with one or more substituted or unsubstituted aromatic rings having a residual absorption of light of between 200 and 500 nm.
• At least one dental filler present in a proportion of at least 10% by weight relative to the total weight of the composition.
• the main objective of the present invention is therefore to propose new dental compositions having after crosslinking / polymerization (i) a hardness of at least 30 HV (Vicker hardness) for a load of 500 grams, preferably at least 40 HV, and (ii) a degree of opacity which allows a homogeneous and simultaneous crosslinking and / or polymerization of said composition over a thickness of at least 3 mm in less than a minute under UV radiation of visible wavelength (200 to 500 nm, preferably greater than 400 nm).
• the polymerizable and / or crosslinkable dental composition according to the invention comprises:
• oligomer and / or silicone polymer comprising:
• - a 0, 1 or 2
• - R ⁇ identical or different, represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, hydroxy, alkoxy radical, preferably a lower alkyl
• Z is an organic substituent comprising at least one reactive epoxy, and / or alkenylether and / or oxetane and / or dioxolane and / or carbonate function,
• At least one photosensitizer (2) aromatic hydrocarbon with one or more aromatic rings substituted or not, having a residual absorption of light between 200 and 500 nm.
• - at least one photoinitiator (3) whose cationic entity of the initiator is selected from onium salts of formula (I):
• A represents an element from groups 15 to 17 [Chem. & Eng. News, vol. 63, No. 5, 26 of February 4, 1985] such as for example: I, S, Se, P or N
• R1 represents a carbocyclic or heterocyclic Cg-C20 aryl radical > said heterocyclic radical which may contain nitrogen or sulfur as heteroelements,
• R ⁇ represents R " ! OR a linear or branched C ⁇
• n is an integer ranging from 1 to v + 1, v being the valence of the element A,
• the polymerizable and / or crosslinkable dental composition according to the invention comprises:
• a concentrated silica solution consisting of 15 to 80% of colloidal particles of amorphous silica with an average diameter of between 10 ⁇ 6 and 10 ⁇ 9 in at least one continuous silicone phase consisting of crosslinkable silicone oligomer and / or polymer and / or polymerizable liquid at room temperature or hot melt at temperature below 100 ° C, the oligomer and / or silicone polymer comprising:
• R ⁇ represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, hydroxy, alkoxy radical, preferably a lower alkyl C- -CQ,
• Z is an organic substituent comprising at least one reactive epoxy, and / or alkenylether and / or oxetane and / or dioxolane and / or carbonate function,
• A represents an element of groups 15 to 17 such as for example: l, S, Se, P or N
• R " 1 represents a carbocyclic or heterocyclic aryl radical in C5-
• heterocyclic radical possibly containing as heteroelements nitrogen or sulfur
• R 2 represents R ⁇ OR a linear or branched C-1-C30 alkyl or alkenyl radical; said radicals R 1 and R 2 being optionally substituted by a C-1-C25 alkoxy, C-1-C25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto group,
• n is an integer ranging from 1 to v + 1, v being the valence of the element A,
• the dental composition is polymerizable and / or crosslinkable under activation (i) by photochemical route and / or (ii) by route photochemical and thermal.
• Photochemical activation is carried out under UN radiation. More particularly, UN radiation is used. wavelength in the range of 200 to
• visible wavelength greater than 400 nm for the production of restorative materials.
• a wavelength greater than 400 nm allows crosslinking and / or polymerization in an oral environment.
• the new dental composition based on amorphous silica dispersed in the silicone polymer or oligomer (1) has the advantage of being transparent to UV-visible light and therefore its use makes it possible to obtain very thick materials and whose photocrosslinking s 'performs in no time.
• the reactive functions Z of the silicone polymer or oligomer (1) can be very varied. However, particularly advantageous dental compositions are obtained when 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 epoxy and / or dioxolane function, 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-
• the silicone polymer or oligomer consists of at least one silicone of the following average formula:
• amorphous silica solution in the continuous silicone phase different procedures can be used; in the context of the invention, it will be preferred to use dispersion type silica solutions.
• the silica used can be from different sources: precipitation silica, combustion silica, silica aerogels, silica sol and / or natural silica.
• the amorphous silica contained mainly or completely in the silicone phase comes from silica sol and more particularly from silica organosols; a general description of silica soils is given in the document US 2,801,185 and "The colloid chemistry of silica and silicates" (Ralph K.ller, Cornell University Press - 1955, see in particular pages 120-121).
• the process for preparing the dispersion of silica in the continuous silicone phase is generally (i) mixing the silica organosol with the silicone (1), the organosol being selected such that its solvent is compatible with said silicone , 0 then (ii) to delete [for example under reduced pressure and / or heating] the solvent and (iii) thus obtaining a dispersion of amorphous silica in the continuous silicone phase.
• silica organosols examples include those from the companies Clariant, Fuso Chemicals, Nalco, Degussa-Huls and Dupont Chemicals.
• Clariant the following products may be mentioned: Highiink® OG 1-32; Highiink® OG4-
• Highiink® OG8-32 Highiink® OG 401-31; Highiink® OG401-51; Highlink®OG502-30; Highiink® OG502-31 and Highiink® OG600-51.
• the anionic entity of the cationic initiator is a borate of formula [BX a R ⁇ ] " in which:
• a phenyl radical substituted by at least one electron-withdrawing group such as for example OCF3, CF3, NO2, CN, and / or by at least 2 halogen atoms (especially fluorine), and this when the cationic entity is an onium an element from groups 15 to 17,
• a phenyl radical substituted by at least one element or an electron-withdrawing group in particular a halogen atom (especially fluorine), CF3, OCF3, NO2, CN, and this when the cationic entity is an organometallic complex of an element of the groups 4 to 10> an aryl radical containing at least two aromatic rings such as for example biphenyl, naphthyl, optionally substituted by at least one element or an electron-withdrawing group, in particular a halogen atom (fluorine in particular), OCF3, CF3, NO2 , CN, whatever the cationic entity.
• 03/051317 a phenyl radical substituted by at least one element or an electron-withdrawing group, in particular a halogen atom (especially fluorine), CF3, OCF3, NO2, CN, and this when the cationic entity is an organometallic complex of an element of the groups 4 to 10> an aryl radical containing at least two aromatic rings such as for example bipheny
• the species of the anionic borate entity those which are particularly suitable are the following: l: [B (C 6 F 5 ) 4 ] - 5 ': [B (C 6 H 3 (CF 3 ) 2 ) 4 ] -
• the odionium salts which can be used are those described in particular in patents US-A-4,026,705, US-A-4,032,673, US-A-4,069,056, US-A -4 136 102, US-A-4 173 476.
• the following cations will be particularly favored:
• the photosensitizer contained in the dental composition according to the invention can be of very varied nature. In the context of the invention, this can be chosen from the photosensitizers described in application WO 00/19967, and in particular those of "formulas (IV) to (XXII)” and more particularly those corresponding to formulas (IV), (VII) and (VIII) ". Their selection is made according to the same criteria as those indicated in this request.
• the percentage of filler (s) by weight relative to the total weight of the dental composition of at least 10%, preferably at least 15% and at most 90%.
• the filler of the dental composition can consist solely of amorphous silica resulting from the concentrated dispersion of silica in the silicone phase. However, additional charges may be used. These fillers are chosen as a function of the final use of the dental composition: these affect important properties such as the appearance, the penetration of UN radiation, 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 [in addition to those contained in the dispersion (1)], quartz, glasses or non-vitreous charges based on oxides of zirconium, barium, calcium, fluorine, aluminum, titanium, zinc, borosilicates, aluminosilicates, talc, spherosil, yterbium trifluoride, polymer-based fillers in the form ground powder such as inert or functionalized polymethyl methacrylates, 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 mechanical strength, a modulus of elasticity, and a markedly improved resistance to compression.
• 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 material cross-linked in ivory color.
• additives can be incorporated into the dental compositions according to the invention.
• biocides stabilizers, flavoring agents, plasticizers and adhesion promoters.
• crosslinkable and / or polymerizable co-reagents of the organic type will advantageously be used.
• 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 for numerous dental applications, and in particular in the field of dental prostheses, in the field of dental restoration and in the field of temporary teeth.
• the dental composition according to the invention is preferably in the form of a single product containing the various components ("single-component") which facilitates its implementation, in particular in the field of dental prostheses.
• the stability of this product can be ensured by organic derivatives with amino functions according to the teaching of document WO 98/07798.
• Single component can be deposited using a syringe directly on the plaster model or in a core. Then it is polymerized (polymerization by possible successive layers) using a UV lamp (visible light spectrum 200 - 500 nm).
• the products obtained from the dental composition according to the invention are non-porous.
• the surface of dental prostheses obtained is smooth and shiny and therefore does not require the use of varnish.
• Applications in the field of dental prostheses are essentially those of the denture, that can be divided into two types:
• the dental composition according to the invention can be used as filling material for anterior and posterior teeth in different colors (e.g., shades ⁇ ITA "), fast and easy to implement.
• 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.
• the tooth can be pretreated with a bonding primer or the dental composition can be prepared as a mixture with a bonding primer before its use.
• a bonding primer it is not essential to use the dental composition according to the invention.
• compositions of the examples are the following - the silicone oligomer with epoxy functionality of formula (A): the onium borate initiator (P1):
• Tinuvin® 765 the stabilizer marketed Tinuvin® 765 from the company CIBA
• Example- 1 Preparation of the dispersion of amorphous silica in the silicone phase.
• a dispersion of silica in the siloxane A monomer is obtained at 47% by weight of silica and with a particle size less than 40 nm.
• the average size of the silica particles is 15 nm.
• the solution is clear, colorless and with a viscosity of 5000 mPas.s
• Example -2 Preparation of a control dental composition.
• a control composition is obtained by mixing: 52.18% by weight of monomer A, 47% by weight of ground quartz (Sifraco C60), 0.8% by weight of initiator P1, 70 ppm of isopropylthioxanthone and 90 ppm of Tinuvin 765.
• the photoinitiator P1 and the photosensitizer are in solid form and are mixed beforehand with the monomer A containing the product Tinuvin765 with stirring. Quartz is introduced last when the ITX and the photoinitiator are perfectly dissolved. A dark brown paste is obtained.
• the composition crosslinks only to a thickness less than 1 mm through a polyester sheet of thickness 100 microns.
• Example 3 Preparation of a dental composition according to the invention.
• a composition according to the invention is obtained by mixing: 99.18% of silica dispersion according to Example 1, 0.8% of initiator P1, 70 ppm of PS1 and 90 ppm of Tinuvin765.
• a clear and colorless solution is obtained by pouring the photosensitizer, photoinitiator mixture into the dispersion obtained in Example 1 with stirring for one minute.
• the composition After exposure under a UV lamp of wavelength greater than 400 nm and of power 600mW / cm 2 , the composition is crosslinked to a thickness of at least 3 mm through a polyester sheet of thickness 100 microns in 40 seconds .
• the hardness is 40 HV (Hardness Vickers) under a load of 500 grams.
• Example 4 Preparation of a dental composition according to the invention.
• a composition according to the invention is obtained by mixing 50% of dispersion of Example 1, 44.2% of ground quartz SiO2 (particle diameter such that the average distribution is 3.5 micron + 1), 5% of YbF 3 , and 0.8% of initiator P1, 100 ppm of sensitizer PS1, and 90 ppm of Tinuvin765, the latter three being contained in solution in monomer A. (30% of P1 in monomer A).
• a translucent composition is obtained by mixing with stirring for 15 minutes.
• This composition crosslinks to a thickness of at least 3 mm under a UV lamp (wavelength greater than 400 nm and power 600 mW / cm 2 ) through a polyester sheet of thickness 100 microns in 40 seconds.
• the hardness is 60 HV (Hardness Vickers) under a load of 500 grams.
• Example 5 Preparation of a dental composition according to the invention.
• a composition according to the invention is obtained by mixing 50% of dispersion of Example 1, 24.2%) of ground quartz SiO2 (particle diameter such that the average distribution is 3.5 micron + 1), 20% of combustion silica, 5% of YbF 3 , and 0.8% of initiator P1, 100 ppm of sensitizer PS1, and 90 ppm of Tinuvin765, the latter three being contained in solution in monomer A. (30% of P1 in the monomer A).
• This composition crosslinks to a thickness of at least 3 mm under a UV lamp (wavelength greater than 400 nm and power 600 mW / cm 2 ) through a polyester sheet of thickness 100 microns in 40 seconds.
• the hardness is 70 HV (Hardness Vickers) under a load of 500 grams.

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• Health & Medical Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Life Sciences & Earth Sciences (AREA)
• Epidemiology (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Biophysics (AREA)
• Dental Preparations (AREA)

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