Dental restorative composite

Abstract: The present invention provides a resin-based dental restorative that exhibits high condensability, low volumetric shrinkage and low shrinkage stress. To this end, a fluorocopolymer of a fluoroolefin, a cyclohexyl vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether is mixed with a methacrylate resin and a fine mineral filler in amounts effective to improve the condensability of the resulting composite to achieve amalgam-like condensation, to reduce the volumetric shrinkage to less than about 2% during polymerization, to improve wear resistance, and to provide a composite with generally improved physical properties.

Description: This invention relates to resin-based dental restoratives, and more specifically to restorative compositions that exhibit high condensability, low volumetric shrinkage and improved wear/abrasion resistance. Posterior and anterior tooth restoration is typically accomplished by excavating a tooth that has decayed or is otherwise in need of repair to form a cavity. This cavity is filled with a paste material, which is then compacted and shaped to conform to the original contour of the tooth. The paste is then hardened, typically by exposure to actinic light. The paste material is a tooth colored, packable, light curable, polymerizable restorative composition comprising a highly filled material. Posterior tooth restorations, especially the Class II type, require the use of a matrix band for proper application of a restorative. The restorative has to be condensable. That is, as it is packed into the cavity of a tooth surrounded by a matrix band, the restorative must deform the matrix band in such a way that the original tooth contour is achieved. In addition, proper deformation of the matrix band leads to appropriate contact with the adjacent teeth. Up to now, the only type of restorative having adequate rheological properties for use with a matrix band has been amalgam. Amalgams have been employed as restoratives for this purpose for a long time and they are known to have good wear characteristics, good marginal quality over time due to buildup of corrosion products at the border of the restoration and a small coefficient of thermal expansion. The metallic color, however, is a drawback for their use as is the uncertainty of the biological interactions of the metallic components of dental amalgams. Tooth colored dental restorative composites are usually composed of dispersions of glass filler particles below 50 µm in methacrylate-type monomer resin. Splintered pre-polymerized particles, which are ground suspensions of silica in pre-polymerized dental resins, may also be used. Additives such as pigments, initiators and stabilizers have also been used in these types of composites. Because the glass particle surface is generally hydrophilic, and because it is necessary to make it compatible with the resin for mixing, the glass filler is treated with a silane to render its surface hydrophobic. The silane-treated filler is then mixed with the resin at a proportion (load) to give a paste with a consistency considered usable, that is to allow the paste to be shaped without it flowing under its own weight during typical use. This paste is then placed on the tooth to be restored, shaped and cured to a hardened mass by chemical or photochemical initiation of polymerization. After curing, the mass has properties close to the structure of a tooth. Although it has been found that increasing the load of a resin-based composite leads to higher viscosity, amalgam-like condensability has not yet been achieved. There is thus a need in the dental profession to have a resin-based restorative that is condensable and compatible with the use of a matrix band. As stated previously, the resins typically used in dental restorative compositions are mostly comprised of dimethacrylate monomers. These monomers vitrify quickly upon initiation of polymerization by crosslinking. The added glass particles after polymerization give a higher modulus to the system and reduce crack propagation by dispersion reinforcement. A significant disadvantage in the use of methacrylate resin-based restorative composites is that they shrink significantly after cure. For example, a modem hybrid composite shrinks approximately 3% after cure. This shrinkage leads to further tooth decay because bacterial infiltration is possible. To address the problem of tooth decay, adhesives are used to coat the tooth surface to be restored before the application of the composite. The shrinkage stress during the initial phase of the vitrification process, however, is significant and on the order of 1 MPa or higher during the first 20 seconds of light exposure for a light cure composite. This initial stress development compromises the performance of the adhesive. So even with the use of an adhesive, significant marginal breakdown can occur, leading to bacterial infiltration. This process is defined as microleakage and is usually measured by dye penetration methods. Thus, there is also a need to make available to the dental profession a resin-based composite that has reduced volumetric shrinkage and shrinkage stress. The coefficient of thermal expansion of the glass fillers used in resin-based composites is much closer to tooth structure than that of the resins. So it is desirable to limit the amount of the resin in a dental composite and maximize the amount of filler material. The main factor limiting the volume fraction (load) of the inorganic filler in highly filled suspensions is particle-particle interactions. Dispersants, through their ability to reduce interactions between particles can improve the flow (reduce the viscosity) of the suspension, therefore allowing a higher load. Dispersants in non-aqueous systems reduce particle interactions by a steric stabilization mechanism. A layer of the dispersant is adsorbed on the surface of the particles keeping them apart from one another, reducing the viscosity. The dispersant structure must contain a chain that allows for steric stabilization in the resin and it also must be strongly adsorbed on the particle surface. There is thus a further need to provide a dispersant that will be effective with a non-aqueous, highly filled suspension containing polymerizable groups for use in a dental restoration. An additional critical area needing improvement in dental restorations is the wear and abrasion resistance of polymeric restorative compositions. For posterior restorations, the main wear mechanism is generally classified as the three body type, involving food bolus. For anterior restorations, wear is generally classified as the two body type, involving toothbrush abrasion, for example. Wear is caused by the heterogeneous nature of dental composites, occurring mostly through "plucking" of the filler particles from the surface followed by abrasion of the softer resin phase. Because wear in these systems is highly dependant on friction, friction reducing additives are expected to improve abrasion resistance. For example, in Temin U.S. Patent No. 4,197,234, polytetrafluoroethylene powder or another similar polyfluorocarbon resin or polyfluorochlorocarbon resin is added for improvement of abrasion resistance in a chemically cured dental composite. The polytetrafluoroethylene additive or other similar additives, however, also act as an opacifying agent, making the restoration nonaesthetic. In other words, the color of the restoration does not blend sufficiently with the surrounding dentition. In addition, when the opacity is high, light cure initiation cannot be used. Similarly, Fellman et al. U.S. Patent No. 4,433,958 describes the use of several fluoropolymers as solid particulate insoluble in the liquid monomer system in dental restorative formulations. Again, highly opaque materials are obtained. There is thus an additional need to provide a dental restorative composite with superior wear and abrasion resistance in both posterior and anterior applications, without causing undue opacity in the restorative. In summary, the dental profession is in need of a dental restorative that has improved shrinkage properties, higher load capabilities and superior wear and abrasion resistance, and that is condensable and compatible with the use of a matrix band. JP 61-161207 discloses a dental plate coating composition comprising a fluorine containing copolymer. The composition is obtained by copolymerizing 40-60 mol % fluoroolefin, 5-54 mol % alkyl vinyl ether, 3-15% hydroxyalkyl vinyl ether and up to 3 mol% other copolymerizable comonomer. The present invention provides a resin-based dental restorative that exhibits one or more of the following properties: high condensability, low volumetric shrinkage, low shrinkage stress, higher loading, lower coefficient of thermal expansion, and high wear and abrasion resistance. In its broadest form, the dental restorative composition of the present invention includes (1) a polymerizable (meth)acrylic monomer; (2) filler; and (3) a fluorocopolymer of a fluoroolefin, a cyclohexyl vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether that is preferably soluble in (meth)acrylate resin. One suitable fluorocopolymer for use in the present invention is soluble in (meth)acrylate resins and is comprised of about 40-60 mole percent fluoroolefin units, about 5-45 mole percent cyclohexyl vinyl ether units, about 5-45 mole percent alkyl vinyl ether units and about 3-15 mole percent hydroxyalkyl vinyl ether units. The inclusion of this type of fluorocopolymer reduces the wear of the composite material. The fluorocopolymer is preferably present in an amount of 10 weight percent or less of the total mixture. There is thus provided a dental restorative having improved thixotropic and physical properties and improved wear resistance. These and other objects and advantages of the present invention shall become more apparent from the description of the preferred embodiments and the examples. Detailed Description In connection with the present invention, it has been discovered that the addition of a suitable fluorocopolymer reduces the wear of the composite without negatively impacting physical and aesthetic properties. Dental Restorative Composite with Fluorocopolymer According to the present invention, an effective amount of a known fluorocopolymer material such as that disclosed in Yamabe et al. U.S. Patent No. 4,345,057, the entire disclosure of which is incorporated herein by reference, is added to the resin/filler mixture to provide a dental restorative composite of the present invention that possesses improved wear properties when used in the mouth. The material described in the Yamabe et al. patent and to be used as an additive for the dental restorative of the present invention is a fluorocopolymer of a fluoroolefin, a cyclohexyl vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether. For use in the present invention, the fluorocopolymer additive comprises the above four components at ratios of about 40-60 mole % fluoroolefin units, about 5-45 mole % cyclohexyl vinyl ether units, about 5-45 mole % alkyl vinyl ether units and about 3-15 mole % hydroxyalkyl vinyl ether units. Preferably, the fluorocopolymer additive comprises the above four components at ratios of about 45-55 mole % fluoroolefin units, about 10-30 mole % cyclohexyl vinyl ether units, about 10-35 mole % alkyl vinyl ether units and about 5-13 mole % hydroxyalkyl vinyl ether units. In a preferred embodiment of the present invention, the fluorocopolymer comprises about 10 weight percent or less of the composite paste, and more preferably, less than 1 weight percent. The fluorocopolymer used in the present invention is soluble in (meth)acrylate resins, in particular dimethacrylate resins, does not interfere in a deleterious manner with the curing of the paste and does not negatively influence the physical and aesthetic properties of the resultant composite after curing. The following examples will further illustrate this aspect of the present invention. EXAMPLE 1 Resin Composition BisGMA (Bisphenol A Diglycidyl ether dimethacrylate) 3.0 weight % Triethylene Glycol Dimethacrylate 24.7 weight % Ethoxylated Bisphenol A Dimethacrylate 71.1 weight % 2-Ethylhexyl-4-(dimethylamino)benzoate 0,49 weight % Camphorquinone 0.17 weight % 2-Hydroxy-4-methoxy Benzophenone 0.49 weight % (BHT) Butylated Hydroxytoluene 0.05 weight % Total 100 Filler Composition Barium Aluminum Borosilicate, silanated 91.4 weight % 20 nm Hydrophobic fumed silica (TS-530) 4.3 weight % 40 mn 1 Fumed Silica, silanated (OX-50) 4.3 weight % Total 100 It should be appreciated that alternative monomers to those listed in Table 1 above may be utilized in the resin composition. For example, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, diurethane dimethacrylate (Rohamere 6661-0, Huls America, Somerset NJ), trimethylolpropane trimethacrylate, glyceryl dimethacrylate, neopentylglycol dimethacrylate. Similarly, with respect to the filler components listed in Table 2 above, alternative filler components may be utilized for the filler composition. For example, inorganic glasses and crystalline compounds such as: quartz cristoballite, silica, alumina, glass ceramics such as aluminosilicate glass ceramic, zirconium silicate, strontium aluminumborosilicate; and organic materials such as splintered pre-polymerized particles used for the preparation of inhomogeneous microfill dental composites. Four samples (test samples 1-4) incorporating a fluorocopolymer into the composite resin of the present invention were prepared according to the following method. A methacrylate resin, as described in Table 1 above, was introduced in a planetary mixer and thermostated to 50°C. A fluorocopolymer LF-200 (supplied by Zeneca Resins Co., Wilmington, MA) was added to the resin. A suitable alternative fluorocopolymer is X-910LM (also available from Zeneca Resins). Initially, the fluorocopolymer is supplied as a 60% solution in xylene, but the xylene is evaporated in a vacuum at 80°C and 0.1 Torr. The resin mix used in test samples 1-4 contained the evaporated fluorocopolymer in an amount of 3.6 wt.% and the resin of Table 1 in an amount of 96.4 wt. %. The mixer was started for about five minutes to mix the resin phase and then the filler containing the physically admixed components listed in Table 2 above was slowly added over a period of 3-5 hours to a filler loading of 77 wt. %. Mixing was continued for another hour and the resultant paste was deaerated under attenuated oxygen pressure. Table 3 details the physical properties of the test sample pastes 1-4 prepared along with the properties of control sample 1. All measurements were carried out using standard ISO methods except where indicated, and the standard deviations are provided in parentheses. Physical Properties of Composites Control Sample 1 Test Sample 1 Test Sample 2 Test Sample 3 Test Sample 4 Wt. % Fluoro-copolymer 0 0.28 0.55 0.83 1.00 Wt. % Filler Load 77.0 77.0 77.0 77.0 77.0 Depth of Cure (mm) 2 at 600mw/cm (4mm diameter) 4.7 (0.1) 4.49 (0.02) 4.12 (0.01) 4.26 (0.20) 4.60 (0.0) Translucency (1mm) 25.2 25.6 23.6 23.4 22.1 Rockwell Hardness (15T) 79.7 (0.6) 82.4 (0.13) 82.0 (0.1) 82.6 (0.3) 81.2 (0.5) Compressive Strength (MPa) 379 (20) 383 (35) 392 (27) 384 (37) 311 (25) Flexural Strength (MPa) 137 (23) 132 (17) 139 (16) 126 (9) 121 (12) Flexural Modulus (MPa) 10,192 (599) 10,828 (954) 10,800 (950) 10,800 (900) 11,070 (541) Penetrometer (mm) , 0g (Needle, 1mm) 4.2 (0.1) 3.7 (0.2) 5.7 (0.2) 4.0 (0.3) 3.3 (0.2) Penetrometer (mm) , 0g (Flathead, 1mm) 2.8 (0.2) 3.3 (0.3) 1.6 (0.1) 1.5 (0.3) 1.2 (0.1) 3 Body Wear Rate (cc/cycle) 9.1x10 -9 1.2x10 -8 3.5x10 -9 3.95x10 -9 Number of Cycles Run 2.0x10 5 1.2x10 5 3.0x10 5 1.8.x10 5 The properties shown in Table 3 demonstrate that the addition of a soluble fluorocopolymer at a total concentration of less than 1 weight percent of the resin/filler mixture reduces the wear of the composite, in particular reduces the wear rate in a three body wear test to less than half the value for the composite without the addition. Furthermore, the physical and aesthetic properties of the composite are not significantly effected. Namely, the translucency, depth of cure and flexural strength and modulus of the resulting composite remained about the same as that of the composite not containing the fluorocopolymer additive (Control Sample 1). While the present invention has been illustrated by the description of an embodiment thereof, and while the embodiment has been described in considerable detail, additional advantages and modifications will readily appear to those skilled in the art. For example, the quantity of the rheological modifier, dispersant and/or fluorocopolymer to be added to the resin/filler mixture will vary based on the particular compositions used for the resin and the filler.

Claims: A dental restorative composition comprising a filler, a polymerizable acrylic monomer, and a fluorocopolymer of a fluoroolefin, a cyclohexyl vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether. A dental restorative composition as claimed in Claim 1, wherein the fluorocopolymer is soluble in a methacrylate resin. A dental restorative composition as claimed in Claim 1 or Claim 2, wherein the fluorocopolymer is comprised of 40-60 mole percent fluoroolefin units, 5-45 mole percent cyclohexyl vinyl ether units, 5-45 mole percent alkyl vinyl ether units and 3-15 mole percent hydroxyalkyl vinyl ether units. A dental restorative composition as claimed in any one of Claims 1 to 3, wherein the fluorocopolymer is comprised of 45-55 mole percent fluoroolefin units, 10-30 mole percent cyclohexyl vinyl ether units, 10-35 mole percent alkyl vinyl ether units and 5-13 mole percent hydroxyalkyl vinyl ether units. A dental restorative composition as claimed in any one of Claims 1 to 4, wherein the fluorocopolymer comprises 10 weight percent or less of the dental restorative composition. A dental restorative composition as claimed in any one of Claims 1 to 5, wherein the fluorocopolymer comprises 1 weight percent or less of the dental restorative composition.

Inventors: ANGELETAKIS CHRISTOS, ANGELETAKIS, CHRISTOS
Applicants: KERR CORP, KERR CORPORATION
Application year: 1999
Main classification: A61K6
IPC codes: A61K6