WO1992012698A1 - Compositions a usage dentaire - Google Patents

Compositions a usage dentaire Download PDF

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Publication number
WO1992012698A1
WO1992012698A1 PCT/GB1992/000103 GB9200103W WO9212698A1 WO 1992012698 A1 WO1992012698 A1 WO 1992012698A1 GB 9200103 W GB9200103 W GB 9200103W WO 9212698 A1 WO9212698 A1 WO 9212698A1
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WO
WIPO (PCT)
Prior art keywords
composition according
composition
filler
less
particles
Prior art date
Application number
PCT/GB1992/000103
Other languages
English (en)
Inventor
Brian Edward Causton
Original Assignee
Mccann, James, Michael
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 GB919101299A external-priority patent/GB9101299D0/en
Priority claimed from GB919121960A external-priority patent/GB9121960D0/en
Application filed by Mccann, James, Michael filed Critical Mccann, James, Michael
Publication of WO1992012698A1 publication Critical patent/WO1992012698A1/fr

Links

Classifications

    • 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

Definitions

  • COMPOSITIONS FOR USE IN DENTISTRY This invention relates to compositions for use in dentistry.
  • GB-A-2115799, GB-A-2075035, GB-A-1591741, GB-A- 2173206, US-A-4381918 and US-A-4540723 disclose dental materials comprising inorganic filler, monomer, polymerisation promoter and curing agent.
  • GB-A-2115799 additionally discloses the use of a solvent, for the purpose of dissolving silicon alkoxide and organic metal compound.
  • a composition comprises a filler in the form of particles capable of space filling to a void volume of less than 20% and an activatable binder resin precursor; the composition is mouldable under vibration at a frequency of 50 Hz to 50 JHz, and can be so used in dentistry.
  • the composition can be formed,- without heating, by mixing the components with the volatile diluent, e.g. with vibration, and removing the 8
  • the invention provides a method of placement and manufacture of composites having at least 85% filler loading, and as high as 95% volume fraction if combined with established computer particle size mixing techniques.
  • the chosen filler is first mixed to achieve a particle size distribution capable of space filling to a void volume of less than 20%.
  • the filler is preferably silane-coated, e.g. by proprietary methods, dried, then mixed with the premixed binder resin containing both active monomers and a demand curing system and a volatile diluent that is not a radical inhibitor.
  • the viscosity of the resulting mixture is controlled by the volume of inactive volatile diluent.
  • Any volatile organic liquid can be used, e.g. ethanol (absolute alcohol is preferred) , acetone, ether, chloroform, trichloroethane, CFC's, fluorocarbons and isopropyl alcohol.
  • the volatile diluent allows the setting up of hydrostatic capillary forces between the filler particles, which pull the particles together. Applying ultrasound to the mixture allows the solids to reach a high packing density and low energy state without having to apply too much energy. Application of the ultrasonic probe for a few minutes is sufficient to complete the process. Further application of ultrasound has no further effect on the material. Too vigorous application of the ultrasound may heat the material, boil off the volatile diluent, and cause cavitation.
  • the slurry, prior to drying, can be either spread out in a layer to dry or first ultrasonicated, then dried slowly as a plug in the container in which it is ultrasonicated.
  • the mixture is dried into a layer about 1-2 mm thick.
  • the volatile diluent is removed by surface evaporation, as boiling off will cause cavitation. This is performed in the dark, e.g. 8
  • each "grain” will be composed of many smaller micro particles packed around a larger macro grain, and will be about 200 ⁇ m across. The inter-grain boundaries will be filled by residual monomer. Formation of this structure is sensitive to the materials used. The grain structure is a good indication of the process having been carried out successfully.
  • the dried mixture is a friable cake material.
  • the material should be broken as little as possible, to reduce the ingress of air.
  • the dried mixture should be moved into a vacuum chamber and packed under low pressure.
  • ultrasonicated vibrated under pressure
  • a waxy dough is formed that, by further ultrasonication, can be packed, e.g. placed in a well.
  • more of the volatile diluent is squeezed out and the material becomes clearer.
  • the material When viewed under a microscope, the material has undergone a change similar to sintering, creating an amorphous secondary structure.
  • the waxy solid can be converted to a hard, cured composite by shining a light upon the wax for less than 40 seconds, the exact time for cure varying with the level of light-activatable activator and the composition of the filler particle mix.
  • the filler content of the final wax solid can be from 65-95% volume fraction.
  • the filler preferably comprises particles of inorganic glass, glass ceramic, metal/inorganic salt or oxide of particle sizes ranging from 0.01 to 100 ⁇ m in diameter.
  • the size is 0.05 to 20 ⁇ m, e.g. 0.1 to 15 ⁇ , and most preferably no more than 10 or, better, 5 ⁇ m. If necessary, suitable material of larger size may be subjected to ball- milling.
  • the filler may be radio-opaque or radio-translucent.
  • the filler may be coated with vinyl silanes to improve adhesion between the filler and the organic matrix. The particle size distribution of the fillers will be such that the interstitial volume between particles is reduced to a minimum by the filling of such spaces with ever finer particles, to achieve optimal filler loading.
  • the binder resin can be any form of radically- polymerising monomer.
  • the preferred monomers are acrylates having two acrylic groups per molecule. The molecular weight of such materials rises rapidly during the cure process, to levels at which structurally strong and stiff polymers result.
  • aromatic dimethacrylates such as BisGMA, based on a Bisphenol A core, are very successful. Lower molecular weight dimethacrylates can be used as viscosity modifiers; allyl methacrylates are also useful in this respect.
  • the curing systems are preferably of a demand-curing type.
  • Heat curing may involve the use of peroxides or azonitriles and other radical sources activated by heat. Radio frequency and magnetically-induced heat sources can be incorporated into the uncured paste.
  • the paste can be activated hy radiation, be it electro-magne i or ionising, with or without activators.
  • ⁇ -diketone amine systems can be used for blue light-curing, benzoin methyl ether for ultra-violet cures.
  • a stabiliser/catalyst may also be used.
  • a conventional material of this type is dibutyltin dilaurate, but alternative materials include dimethyl-p-toluidine.
  • the device is an ultrasonic probe. Conventional such devices vibrate at 30-42 kHz. Such a probe can thus be used to mix the components, to assist placement of the dried material into wells or other storage means, and also to fill a dental cavity.
  • the composite can be supplied as a powder in a compule, the vibrating device being used to extrude the powder from the mouth of the compule in the form of a waxy solid.
  • the compule may be designed to allow the extruded bolus of wax to be placed and compacted in the tooth cavity in one action, or a second vibrating device may be used for compaction.
  • the material may be placed in contact with a sheet of Perspex or other suitable material having a number of apertures, e.g. wells, and pushed into the wells by vibration with, for example, an ultrasonic probe.
  • the wax-like material may be packed, not in compules but as a sheet from which the bolus is picked up on the tip of a compacting vibrator.
  • This tip having the modification of a retractable cylindrical sheath that cuts a circular plug of wax, holds it to the vibrator tip, and then deposits the wax in the cavity as it is vibrated.
  • the wax sheet should be protected from light during transport and in the surgery during use.
  • a carousel arrangement that exposes only part of the s ee of wax to the vibrator sheath, yet protects the bulk of the wax, provides one solution to the packaging problem.
  • the carousel may contain the composite in the powder stage, the vibrator compacting and cutting a wax plug in one action.
  • the powder may be placed directly into the cavity, but this is less preferred.
  • the composite is normally cured in the mouth. However, the wax composite could be compacted into a die or mould outside the mouth. In this way, inlays and onlays can be produced for later cementation. If larger 98
  • structures are produced using vibrating extruders, they can be heat-cured into blanks for use in CAD/CAM cutting machines. In this way, devices can be precision-milled, then cemented into place in the tooth cavity.
  • the blanks can be cured by electron beams or induced heat sources, e.g. RF or magnetic.
  • a bolus is removed from its carrier/well, e.g. the block from the Perspex carrier, by applying the end of aplastic amalgam carrier (e.g. as available from Premier Dental) .
  • the amalgam condenser should be a push fit for the hole in the block.
  • the bolus is wedged into the cavity and is then carved into place by the vibrating tool. Application of vibration will shear the material along the grain boundaries. The material is then light-cured in situ.
  • the present invention allows the use of high filler levels: the higher the volume filler loading, the lower the setting shrinkage.
  • Setting shrinkage is clinically undesirable because it can cause pain, due to a flexing of the tooth, and increases the probability of marginal leakage.
  • Another advantage of the invention is that, the higher the filler content, the better the match between the
  • a further advantage is that the higher stiffness and lower shrinkage of the composition make the filling of large cavities more clinically feasible.
  • the high filler content allows the material to be carved to the required shape in the cavity, without slumping, using a vibrating tool; this is by contrast to existing materials that slump and make carving difficult and time-consuming. 8
  • a possible disadvantage of the high filler content can be that the material is abrasive. Particularly with a view to minimising wear on opposing teeth, it is preferred that the filler particles should not be too coarse. In order to avoid abrasion, all stainless steel surfaces should therefore be coated with a hardened layer. For example, a diamond-like carbon or a titanium nitride coating, ball-mill surfaces, and other exposed manufacturing surfaces, should be coated with a Teflon coating plus silica and replaced during use, e.g. at weekly intervals. These techniques are known in the industry.
  • Example 1 illustrates the invention.
  • a silanated lead glass (particle size distribution 15- 2 ⁇ m) is mixed at a ratio of 80:20 with a fumed silica of particle size ⁇ 0.75 ⁇ m.
  • the components are mixed by end- over-end rotation in a sealed vessel.
  • Silica OX50 (Degussa) are tumbled in a vee mixer for two hours. 1 part by weight of this powder is mixed with an equal weight of absolute alcohol. The resultant slurry is stirred with an ultrasonic probe for two minutes. 8
  • a liquid is prepared by mixing 1% dibutyltin dilaurate (Aldrich) , 1% camphorquinone (Aldrich) , 24% tetraethylene glycol di ethacrylate (Aldrich) and 74% Bis-GMA (Freeman Chemicals). Starting with 0.168 part of the liquid, it is added to the slurry which is stirred until homogeneous, then spread out into a layer about 3 mm thick and placed in a dark tunnel having a glass base. Air is blown through the tunnel until alcohol is undetected in the effluent. The process is initially conducted cool (15°C) , warming to ⁇ 60°C.
  • the resulting cake has a structure that should be broken as little as possible.
  • the cake is transferred to a packaging station of the type described above, in one piece, then pushed into the Perspex holders using an ultrasonic probe of sufficient diameter to be a push fit into the hole.
  • the ultrasonic probe can be obtained from Jencons (600W, 20 kHz) .
  • the probe should be wide enough to be modified for the packing of prototype blocks.
  • Example 2 The procedure of Example 2 is repeated, except that the Raysorb component is first ball-milled to ⁇ 5 ⁇ m. When this is done, the fumed silica content must be reduced to match the new particle size profile. This necessitates the reduction of the silica fraction by approximately 50%. Optimising the silica is preferably done using an optical microscope. When the silica content is right, the drying cake can form large hexagonally packed structures.
  • the cavity where the material is applied should be prepared in the usual way, as for other dental composites.
  • Young's modulus of the material are all better than existing composites.
  • the longitudinal shrinkage for the composite of Example 2 was 0.42%, whereas the value for one of the current market leaders (Heliomolar) was 4.0%.
  • Restrained shrinkage is probably the best approximation of what goes on in the mouth, as the material is usually restrained by the surface of the natural tooth.
  • the values for the novel composite and Heliomolar were respectively 0.38% and 1.3%.
  • the Heliomolar had internal cavities, causing points of weakness, formed during restrained shrinkage.

Landscapes

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

Abstract

Composition pouvant servir à la restauration dentaire et comprenant un matériau de remplissage ayant la forme de particules, capable de remplir un espace avec un volume de vide inférieure à 20 %, et un précurseur de résine de liaison pouvant être activé, ladite composition pouvant être moulée sous l'effet de vibrations à une fréquence comprise entre 50 Hz et 50 kHz.
PCT/GB1992/000103 1991-01-21 1992-01-17 Compositions a usage dentaire WO1992012698A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9101299.7 1991-01-21
GB919101299A GB9101299D0 (en) 1991-01-21 1991-01-21 Compositions for use in dentistry
GB919121960A GB9121960D0 (en) 1991-10-16 1991-10-16 Compositions for use in dentistry
GB9121960.0 1991-10-16

Publications (1)

Publication Number Publication Date
WO1992012698A1 true WO1992012698A1 (fr) 1992-08-06

Family

ID=26298302

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/000103 WO1992012698A1 (fr) 1991-01-21 1992-01-17 Compositions a usage dentaire

Country Status (2)

Country Link
AU (1) AU1173892A (fr)
WO (1) WO1992012698A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000048552A1 (fr) * 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
US6306927B1 (en) 1999-04-12 2001-10-23 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US6399037B1 (en) 1997-10-03 2002-06-04 Dentsply Detrey Gmbh Dental materials having a nanoscale filler
US6693143B2 (en) 1997-10-03 2004-02-17 Dentsply Detrey Gmbh Dental materials having a nanoscale filler
US7001932B2 (en) 1999-04-12 2006-02-21 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE765627R (fr) * 1971-04-13 1971-08-30 Varga Joseph Procede visant au raccourcissement de temps de durcissement desmatieresartificielles et a base de derives chimiques utilisees dans la
US4219619A (en) * 1978-09-08 1980-08-26 Zarow Merle C Vibrating dental instrument for setting crowns
EP0091990A2 (fr) * 1982-04-15 1983-10-26 Blendax-Werke R. Schneider GmbH & Co. Matériau pour la restauration des dents
GB2201093A (en) * 1987-01-26 1988-08-24 G C Dental Ind Corp A filling and forming system for dental viscous plastic materials
EP0395427A2 (fr) * 1989-04-27 1990-10-31 Btg International Limited Composition à réticulation sur commande
DE4032505A1 (de) * 1990-10-12 1991-08-14 Thera Ges Fuer Patente Verwendung von composite-fuellmaterialien zur befestigung von inlays, onlays, verblendschalen und dergleichen mittels hochfrequenter vibrationen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE765627R (fr) * 1971-04-13 1971-08-30 Varga Joseph Procede visant au raccourcissement de temps de durcissement desmatieresartificielles et a base de derives chimiques utilisees dans la
US4219619A (en) * 1978-09-08 1980-08-26 Zarow Merle C Vibrating dental instrument for setting crowns
EP0091990A2 (fr) * 1982-04-15 1983-10-26 Blendax-Werke R. Schneider GmbH & Co. Matériau pour la restauration des dents
GB2201093A (en) * 1987-01-26 1988-08-24 G C Dental Ind Corp A filling and forming system for dental viscous plastic materials
EP0395427A2 (fr) * 1989-04-27 1990-10-31 Btg International Limited Composition à réticulation sur commande
DE4032505A1 (de) * 1990-10-12 1991-08-14 Thera Ges Fuer Patente Verwendung von composite-fuellmaterialien zur befestigung von inlays, onlays, verblendschalen und dergleichen mittels hochfrequenter vibrationen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6399037B1 (en) 1997-10-03 2002-06-04 Dentsply Detrey Gmbh Dental materials having a nanoscale filler
US6693143B2 (en) 1997-10-03 2004-02-17 Dentsply Detrey Gmbh Dental materials having a nanoscale filler
WO2000048552A1 (fr) * 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
US6306927B1 (en) 1999-04-12 2001-10-23 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US7001932B2 (en) 1999-04-12 2006-02-21 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth

Also Published As

Publication number Publication date
AU1173892A (en) 1992-08-27

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