WO2000055253A1 - Compositions de composite ionomere - Google Patents

Compositions de composite ionomere Download PDF

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Publication number
WO2000055253A1
WO2000055253A1 PCT/US2000/006974 US0006974W WO0055253A1 WO 2000055253 A1 WO2000055253 A1 WO 2000055253A1 US 0006974 W US0006974 W US 0006974W WO 0055253 A1 WO0055253 A1 WO 0055253A1
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acid
poly
composite composition
glass
bis
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PCT/US2000/006974
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English (en)
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Peter X. Ma
Anne E. Huber
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The Regents Of The University Of Michigan
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Priority to US09/936,692 priority Critical patent/US6979702B1/en
Priority to AU38904/00A priority patent/AU3890400A/en
Publication of WO2000055253A1 publication Critical patent/WO2000055253A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/28—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing organic polyacids, e.g. polycarboxylate cements, i.e. ionomeric systems
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • 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
    • A61K6/889—Polycarboxylate cements; Glass ionomer cements
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications

Definitions

  • the present invention relates generally to iono er composite compositions, and more specifically to such compositions useful for many dental applications, ranging from direct restorative materials to fabrication of preformed structure for dental and osseous tissue repair applications.
  • fluoride ions in the oral environment are beneficial to the reduction of recurrent caries, and formation of new caries. It is not currently known why fluoride ions contribute to a decrease in dental caries; theories include its effect on the bacteria, the formation of fluorapatite, and an increase in resistance to caries of both enamel and dentin.
  • the glass filler used in composites and glass ionomers contains sufficient fluoride to see a reduction in caries in filled and surrounding teeth.
  • the materials can be "recharged" through fluoride toothpaste and topical fluoride treatments .
  • dental silicate cements containing fluoride are therapeutic in preventing secondary caries and reducing plaque formation.
  • Acrylic denture base material, restorative materials and adhesives have been shown to be sites of bacterial and plague accumulation, which can be a precursor of irritation to soft tissues and caries attack on remaining natural dentition.
  • the release of fluoride ion from these dental restorative materials generally occurs either by surface release, or by dissolution of the fluorine-containing additives or the dental restorative material itself with consequent migration of fluoride ions into the underlying tooth structure .
  • fluorine-containing additives that have been tried in dental restorations consist of inorganic fluoride salts, organic bases such as amine hydrofluoride, fluorocarbons and fluoride-containing ion-exchange resins. These attempts to find suitable fluorine-containing additives which are both dispersed in dental restorative material and capable of reducing tooth caries through controlled long-term fluoride release have failed. Silicate cements have demonstrated cariostatic release of fluoride. However, the strictly rapid surface release of fluoride from the cement, the dissolution of the cement in oral fluids, and the low tensile strengths of the cements are major disadvantages.
  • a controlled, slow fluoride releasing additive comprising a Lewis base and a fluoride-containing Lewis acid which is therapeutic in preventing secondary caries and reducing plaque formation.
  • This additive is incorporated into polymeric dental restorative material and is capable of migrating from the interior to the surface of the material without dissolution thereof and with consequent release of fluoride.
  • this composition is merely an additive to existing dental restorative materials. Further, it does not increase desirable mechanical properties of the dental restorative material in which it is incorporated; nor does it improve adhesion between polymers.
  • Hybrid materials such as resin-modified glass ionomers and compomers lie somewhere between. Whereas both composite resins and glass ionomers have been known and used for a relatively long period of time, the hybrid materials such as the resin-modified glass ionomers and compomers are relatively new.
  • Ceramic filler reinforced polymeric composites are widely used in the area of dental restorative materials.
  • a typical dental composite is composed of a mixture of silicate glass or quartz particles with an acrylic monomer that is polymerized to form a hardened composite material.
  • the fillers are mostly glasses, occasionally glass-ceramics and quartz (a crystalline form of silica) , particulate polymers and glass-polymer composite particulates .
  • Strategies such as the development of smaller filler particles such as microfiller and nanofiller particles; the improvement of glass compositions; and the increase of filler volume fraction through the use of hybrid and heterogeneous filler systems have each been attempted in order to improve dental composites.
  • Composite restorations in low stress-bearing applications not involving cusps, have average lifetimes of less than 10 years.
  • dental amalgam restorations in high stress-bearing posterior applications with cusp replacement, have lifetimes of 15 years (Corbin and Kohn, 1994) .
  • Many changes have occurred in recent years concerning dental restorative materials. Among these changes is the use of fluoride-releasing glass ionomer materials. Glass ionomer materials are based on the acid-base reaction of an aqueous solution of a polycarboxylic acid with an ion leachable, fluoride- containing glass (Wilson and Kent, 1971, J. Appl . Chem. Biotechnol. 21: 313; Wilson and Kent, 1972, Br. Dent. J. 132: 133) . Glass ionomers are noted for their inherent adhesiveness to teeth and their ability to release fluoride to adjacent tooth structure in a sustained fashion to combat secondary caries .
  • glass ionomers possess inferior mechanical properties, including extreme brittleness and low strength (e.g., flexural strength of 10-20 MPa--McLean, 1990, J. Am.
  • Resin-modified glass ionomers (Mitra, EP Application 323,120, 1988; U.S. Pat. No. 5,154,762, 1992), where compatible resins (e.g., 2-hydroxyethyl methacrylate, or HEMA) are used with the polyacids, are only slightly stronger than glass ionomers (e.g., flexural strength of 60 MPa--Poolthong et al . , 1994, Dent. Mater. J. 13: 220; Hickel, 1996, Acad. Dent. Mater. Trans . 9: 105) . It has been generally accepted that the most intractable problem is likely to be lack of strength and toughness (Wilson, A.D. and J.W. McLean, Glass
  • Compomers are basically hybrid, glass ionomer- composites modified in their resin phase by a carboxylic acid monomer and in their filler phase by the inclusion of an acid-reactive, ion-leachable glass.
  • the name compomer is derived by combining the two words composite and ionomer, and is intended to suggest a combination of composite and glass-ionomer technology.
  • the liquid part of a compomer is a mixture of a dental resin monomer (such as UDMA, a uret ane dimethacrylate) and a carboxylic acid monomer (e.g., TCB, the reaction product of butane tetracarboxylic acid with HEMA) , with the resin being the major phase and TCB the minor phase.
  • a dental resin monomer such as UDMA, a uret ane dimethacrylate
  • TCB carboxylic acid monomer
  • the filler part of a compomer is a mixture of dental silicate glass and reactive fluorosilicate glass particles, with the reactive glass being the minor phase.
  • compomers In contrast to glass ionomers, compomers do not generally contain significant amounts of water.
  • the sole initial curing reaction is radical induced polymerization of the acrylic resin monomer matrix.
  • An acid-base reaction takes place between TCB and the ion leachable fluorosilicate glass only after water infuses the cured composite via exposure to oral fluids, which also causes the filling to release fluoride ions.
  • Flexural strength values of 90-125 MPa have been reported for compomers (Hickel, 1996, Acad. Dent. Mater. Trans. 9: 105). However, these strength values are still inferior to those of current dental amalgam (110-150 MPa) and composite resins (100-145 MPa) (Hickel, 1996) . Therefore, compomers are currently not recommended for use in large, stress-bearing posterior applications.
  • glasses and glass-ceramics are among the weakest and most brittle materials to use as reinforcement fillers.
  • Glass filler particles are sensitive to surface flaws produced during mixing, handling and wear. A crack in the resin matrix can easily cut through the reinforcing glass particles.
  • U.S. Patent No. 5,861,445 issued to Xu et al . further defined geometrical shapes of the filler particles as cause for failure.
  • the previously known glass fillers were either spherical or of irregular shapes, with length-to-diameter ratio only slightly larger than one. Xu et al . disclosed that this had at least two major short- comings .
  • rounded filler particles at occlusal surfaces are susceptible to facile dislodgement from the resin matrix during wear with foods bolus, resulting in high wear rates.
  • Xu et al proposed the use of ceramic filler particles and whiskers and/or chopped fibers to reinforce polymeric dental composites so that there are substantially improved mechanical properties and enhanced clinical longevity compared to conventional (or currently used) materials.
  • the elongated whiskers and chopped fibers were said to have high length-to-diameter ratio values to effectively bridge and resist micro-cracks.
  • whiskers were less likely to be dislodged out of the matrix during wear.
  • current plastic teeth offer low abrasion resistance, low crazing resistance, and low heat-distortion temperatures when compared to porcelain teeth. See, for example,
  • an ionomeric composite composition for dental application which advantageously improves the wear properties of the composition in the dental application. It is a further object of the present invention to provide such a composition having a highly crosslinked structure, thereby advantageously improving the strength and crazing resistance of the composition in the dental application. Still further, it is an object of the present invention to provide such a composition which utilizes the unique properties of glass ionomers by advantageously adapting them for use in preformed denture teeth and other preformed structure. It is yet another object of the present invention to provide an ionomeric composite advantageously utilizing a copolymer as one component thereof.
  • compositions which may advantageously be varied to suit a wide variety of dental applications, ranging from direct restorative materials, to intermediary dental materials such as liners, bases, and luting cement, to preformed structure for dental and osseous tissue repair applications. Yet further, it is an object of the present invention to provide such a composition which may advantageously be used for implants and/or tissue scaffolding (growing natural tissue within/on a porous synthetic material) . It is still further an object of the present invention to provide such a composition which advantageously provides continuous fluoride release.
  • the present invention addresses and solves the above-mentioned problems and meets the enumerated objects and advantages, as well as others not enumerated, by providing ionomer composite compositions useful for dental applications.
  • the composition consists essentially of a glass material containing at least one of divalent cations and multivending cations, and optionally containing fluoride; and at least one copolymer.
  • the copolymer comprises at least one hydrophilic monomer containing acid functional groups adapted to react with the divalent cations and/or multivending cations to form ionic crosslinks among polymer chains.
  • the hydrophilic monomer is present in an amount sufficient to impart a desired degree of aqueous solubility to the copolymer.
  • the copolymer further comprises at least one hydrophobic monomer present in an amount sufficient to impart a desired degree of structural stability to the composite composition when exposed to an aqueous environment .
  • the present ionomer composite composition is particularly advantageous in that, by varying the ratio of hydrophilic monomer to hydrophobic monomer, the copolymer may vary from water soluble to water insoluble .
  • the present ionomer composite composition may be used for a wide variety of dental applications, ranging from those requiring water soluble compositions, eg. direct restorative materials, to intermediary materials such as for example, liners, bases, and luting cement, to those requiring water insoluble compositions, eg. to fabricate preformed structure for dental and osseous tissue repair applications.
  • Fig. 1 is a graph showing compressive modulus data for an 80:20 PMMA-MAA copolymer having varying glass contents
  • Fig. 2 is a graph showing Vicker ⁇ hardness data for the glass filled 80:20 PMMA-MAA copolymers
  • Fig. 3 is a graph showing yield strength data for the glass filled 80:20 PMMA-MAA copolymers
  • Fig. 4 is a graph showing toughness data for the glass filled 80:20 PMMA-MAA copolymers
  • Fig. 5 is a graph showing modulus data for PMMA-MAA copolymers having varying MAA percentages, with 0 weight% and 50 weight% glass
  • Fig. 6 is a graph showing Vickers hardness data for PMMA-MAA copolymers having varying MAA percentages, with 0 weight% and 50 weight% glass
  • Fig. 7 is a graph showing yield strength data for PMMA-MAA copolymers having varying MAA percentages, with 0 weight% and 50 weight% glass,-
  • Fig. 8 is a graph showing toughness data for PMMA-MAA copolymers having varying MAA percentages, with 0 weight% and 50 weight% glass;
  • Fig. 9 is a graph showing fluoride release data for a 75:25 PMMA-MAA copolymer having 50 weight% glass
  • Fig. 10 is a graph showing fluoride release data for an 80:20 PMMA-MAA copolymer having from 0 weight% to 80 weight% glass.
  • the present invention provides novel ionomer composite compositions fortuitously useful for a heretofore unexpectedly wide range of dental applications .
  • Such applications may range from direct restorative materials, eg. cure-in-mouth cements, to intermediary materials such as for example, liners, bases and luting cement, to preformed structure for dental and osseous tissue repair applications.
  • the present inventive compositions may find uses outside of the dental field, such as in orthopedic applications. Further, the fluoride releasing agent may be eliminated, if desired, from the copolymer-glass ionomeric composition described further hereinbelow; and the ionomeric composition (s) may find use as structural materials .
  • the present novel and inventive composition does not lie on the established continuum (discussed hereinabove) between conventional glass ionomers, resin- modified glass ionomers, polyacid-modified composite resins (compomers), and composite resins. Rather, the novel composite compositions of the present invention possess unique properties.
  • the composition consists essentially of a glass material containing at least one of fluoride, divalent cations and multivending cations; and at least one copolymer.
  • the copolymer comprises at least one hydrophilic monomer containing acid functional groups adapted to react with the divalent cations and/or multivending cations to form ionic crosslinks among polymer chains .
  • the hydrophilic monomer is present in an amount sufficient to impart a desired degree of aqueous solubility to the copolymer.
  • the copolymer further comprises at least one hydrophobic monomer present in an amount sufficient to impart a desired degree of structural stability to the composite composition when exposed to an aqueous environment .
  • any suitable glass particles/materials may be chosen which contain divalent or/and multivending cations.
  • the glass material (s) optionally may contain fluoride (s) .
  • the glass material is selected from the group consisting of Si0 2 , Al 2 0 3 , A1F 3 , CaF 2 , NaF, Na 3 AlF 6 ,
  • A1P0 4 and mixtures thereof. If a combination of these glass materials is chosen, such materials may be advantageously combined at various ratios.
  • the glass to polymer weight ratio may be between about 1:99 and about 95:5. In a preferred embodiment, the glass to polymer weight ratio is between about 10:90 and about 90:10. Still more preferred, the glass to polymer weight ratio is between about 40:60 and about 85:15. It is to be understood that the composition of the present invention may comprise a copolymer or copolymers of two or more types of monomers, provided that at least one monomer is hydrophilic and at least one monomer is hydrophobic.
  • any hydrophilic monomer (s) may be chosen provided it contains the above-mentioned acid functional groups adapted to react with the glass material (s) ' divalent cations and/or multivending cations to form ionic crosslinks among polymer chains.
  • the acid functional groups also may react with calcium ions in teeth, leading to a desirable increase in the composition's adhesion properties with respect to the teeth.
  • Some exemplary suitable acid-containing hydrophilic monomers include the following: 1) Monomers containing carboxylic acid: acrylic acid, methacrylic acid, 4-vinylbenzoic acid, crotonic acid, oleic acid, elaidic acid, itaconic acid, maleic acid, fumaric acid, acetylenedicarboxylic acid, tricarbollylic acid, sorbic acid, linoleic acid, linolenic acid, eicosapentenoic acid, other unsaturated carboxylic acids, anhydrides, their derivatives, and mixtures thereof; 2) Other organic acids such as sulfonic acid, and/or phosphonic acid replacement of the carboxyl group of the above listed unsaturated carboxylic acids, their derivatives, and mixtures thereof.
  • hydrophilic monomers that do not have a reactive carboxyl group may be used as a co-monomer within the present inventive composition.
  • An example of such a non- acid-containing hydrophilic monomer is 2-hydroxyethyl methacrylate (HEMA) .
  • any hydrophobic monomer may be chosen, provided it imparts the desired degree of structural stability to the composite composition when exposed to an aqueous environment .
  • Some exemplary suitable hydrophobic unsaturated monomers include the following. Acrylates, methacrylates (eg. methyl methacrylate) , ethylene, propylene, tetra- fluoroethylene, styrene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, 2 , 2-bis [4- (2- hydroxy-3-methacryloyloxy-propyloxy) -phenyl] propane (Bis-GMA) , ethyleneglycol dimethacrylate (EGDMA) , tri- ethyleneglycol dimethacrylate (TEGDMA) , bis (2-methacryly- oxyethyl) ester of isophthalic acid (MEI) , bis(2-meth- acryly ⁇ xyethyl) ester of terephthalic acid (MET), bis (2- methacrylyoxyethyl) ester of phthalic acid (MEP) , 2,2- bis (4-methacryl
  • the ratio of the hydrophilic monomeric units to the hydrophobic monomeric units may vary between about 1:99 and about 99:1.
  • the hydrophilic monomer to hydrophobic monomer ratio is between about 5:95 and 95:5.
  • the copolymer could vary from water soluble (suitable for direct restorative dental applications) to water insoluble (suitable for fabrication of preformed dental structure and the like) .
  • the amount of hydrophilic monomer is increased, the copolymer (as well as the ionomer composite composition) becomes more water soluble.
  • any combination of the above hydrophilic and hydrophobic monomers may be suitable to form the copolymer component according to the present invention.
  • An exemplary list of some copolymers includes the following: poly (methyl methacrylate- methacrylic acid), poly (methyl acrylate-acrylic acid), poly (methyl methacrylate-acrylic acid) , poly (ethyl acrylate-acrylic acid), poly (ethyl methacrylate- methacrylic acid), poly (butyl acrylate-acrylic acid), poly (ethylene-acrylic acid), poly (ethylene-methacrylic acid), poly (acrylonitrile-maleic anhydride), poly (butadiene-acylonitrile-acrylic acid) , poly (butadiene-maleic acid), pol (butadiene-maleic anhydride), poly (acrylamide-acrylic acid), poly (2- hydroxyethyl methacrylate-methacrylic acid) , poly (propylene-acrylic acid), poly (propylene-acrylic
  • the copolymers in the ionomer composite systems of the present invention may be polymerized before, during or after the ionomer reactions (base-acid reactions) .
  • the polymers or copolymers are polymerized before the ionomer reaction in order to reduce the contents of unreacted monomers or oligomers to improve biocompatibility.
  • polymers in minor amounts may be added to the ionomer composite systems of the present invention.
  • examples of some such polymers which may be present as minor components include, but are not limited to poly (methyl methacrylate) (PMMA) , polycarbonates, polyethylenes, polyamides, poly (ether-ether ketone) (PEEK) polymers, epoxies, and mixtures thereof.
  • PMMA poly (methyl methacrylate)
  • PEEK poly (ether-ether ketone)
  • copolymers and/or polymers mentioned above may be obtained from a commercial source; or they may be synthesized from appropriate monomer (s) . If they are synthesized, the monomer (s) are suitably polymerized. The synthesized polymer/copolymer is then preferably subjected to a purification step in order to remove any unreacted monomer (s) . The copolymer and polymer (s) in minor amounts (if any) may then be mixed and reacted with glass particles as described further hereinbelow. It is further contemplated as being within the purview of the present invention to include other minor components in the ionomer composite composition (s) of the present invention. For example, pigments, surfactants, adhesion enhancers, fluoride releasing enhancers, and bioactive agents, such as for example, growth factors and hormones, and mixtures thereof may be incorporated thereinto if desired.
  • the glass particles and the copolymers are mixed and reacted to form ionomer composite materials/compositions.
  • the fluoride-containing glass particles can be dissolved or partially dissolved in a mixture of water and organic solvent (s), or in an aqueous solution.
  • the dissolved divalent and multivending cations form ionic bonds with the acid groups on the copolymer to impart the system with the characteristics of a glass ionomer.
  • the undissolved glass particles act as a reinforcing second phase.
  • a reinforcing polymerization may be carried out after the glass ionomer reaction, either thermally or photo-chemically, depending on the initiator type.
  • the mechanical properties such as strength, moduli such as shear modulus, compressive modulus and tensile modulus, and hardness may be adjustable by varying the polymer composition and glass content.
  • the ionomer composite materials of the present invention may advantageously be thermally molded or solution cast to fabricate preformed structure for dental and osseous tissue repair applications.
  • the present inventive materials may also be used for applications of traditional glass ionomers and resin composites.
  • the present inventive materials may be particularly adapted for use for inlays, onlays, artificial teeth, denture base, filling materials, cavity liner, adhesive, orthodontic resin, pit and fissure sealant, dental, orthopedic and bone implants.
  • a preferred embodiment useful for preformed dental structure comprises a novel glass ionomer: poly (methyl methacrylate-co-methacrylic acid) (PMMA-MAA) glass ionomer.
  • PMMA-MAA poly (methyl methacrylate-co-methacrylic acid)
  • This material differs from standard glass ionomers in that the copolymer, in certain hydrophilic monomer to hydrophobic monomer ratios, is not water soluble, thereby reducing undesirable reaction with the oral environment. It also differs from PMMA based ionomers (see, for example, Ma, X., J.A. Sauer, et al . , "Poly (methyl methacrylate) Based Ionomers. 1. Dynamic Mechanical Properties and Morphology, " Macromolecules 28(11): 3953-3962 (1995)) by utilizing glass as a reinforcing second phase and ions from the glass in the crosslinking.
  • the glass was chosen for its fluoride release capabilities. See, for example, Kent, B., B. Lewis, et al . , "Glass Ionomer Cement Formulations: I. The Preparation of Novel Fluoroaluminocilicate Glasses High in Fluorine," Journal of Dental Research 58(6): 1607-1619 (1979); Wilson, A.D., S. Crisp, et al . , "Aluminocilicate Glasses for Polyelectrolyte Cements, " Ind . Eng . Chem. Prod. Res. Dev. 19: 263-270 (1980); de Araujo, F.B., F. Garcia-Goody, et al .
  • the polymeric component of the composite composition comprises a copolymer, as opposed to a monomer(s), oligomers, or a completely water soluble polymer (s) .
  • a copolymer as opposed to a monomer(s), oligomers, or a completely water soluble polymer (s) .
  • This is preferable to in si tu polymerization of a monomer(s), in that unreacted monomers remaining in the patient's mouth may have a deleterious effect on the mechanical properties of the dental restorative material, as well as on the patient's health.
  • the addition of glass to the PMMA-MAA copolymer appears to increase the compressive modulus, yield strength, and hardness of the material. It is believed that the improvement is no longer significant above about 70 weight% glass due, at least in part, to a limit in the packing density.
  • EXAMPLE 1 Glass Incorporation Two sets of samples were prepared for testing. In the first group, an 80:20 PMMA- MAA random copolymer was used with the following glass contents: 0.00, 6.25, 14.29, 25.00, 33.33, 40.00, 45.45, 50.00, 60.53, 70.00, and 80.00 weight percent.
  • the second set includes the following PMMA-MAA random copolymers: 75:25, 80:20, 95:5, and 100:0, containing 0 wt% and 50 wt% glass.
  • the copolymers were obtained from Polysciences, Inc., Warrington, Pennsylvania, the PMMA from Sigma Chemical Co., St.
  • the glass particles are irregular in shape, range from 1-20 microns, and have no surface treatment .
  • the polymer was dissolved at a 1/12 g/ml ratio in a 20% methanol, 80% benzene solution. For the 75:25 copolymer it was necessary to use a 30:70 solvent mix. The polymer and solvent were placed in a vial and vibrated on a shaker overnight. After 24 hours, the glass and a stir bar were added, and the mixture was stirred for one hour to incorporate the glass and allow time for the glass ionomer reaction to occur. The sample was frozen in a -20°C freezer, then placed on a lyophilizer in ice/salt bath to remove the solvent . A liquid nitrogen solvent trap was maintained for two days, and the samples allowed to stay on the lyophilizer for a total of seven days .
  • EXAMPLE 2 Compression Molding Process The following protocol was used to make samples for hardness and compression testing.
  • a 4 mm diameter compression mold was filled with from 0.2 g to 0.3 g of sample (obtained by the procedure of Example 1) .
  • the sample amount was varied due to the density difference between the filled and unfilled polymer.
  • the mold was placed in an oven at 450 °F for two hours, then moved to a preheated 420°F press.
  • the plunger was pressed down with 2000 lbs. force which was applied for 45 minutes, being monitored every 15 minutes, and increased if it had fallen.
  • the pressure was then released and the plunger removed.
  • the sample was allowed to stay on the press at 420°F for another 45 minutes to remove any residual compressive stresses. At this time the heater was turned off, and the sample cooled to room temperature before being removed from the mold.
  • EXAMPLE 3 Compression Testing. The cylindrical samples prepared in the compression mold of Example 2 were ground so that the ends were parallel. All samples possessed a length to diameter (L/D) ratio of 2.5. The samples were compressed to failure using a compression jig on an Instron 8521 mechanical tester with a crosshead speed of 0.5 mm/min. Five specimens were tested for each data point .
  • EXAMPLE 4 Compression Testing. The cylindrical samples prepared in the compression mold of Example 2 were ground so that the ends were parallel. All samples possessed a length to diameter (L/D) ratio of 2.5. The samples were compressed to failure using a compression jig on an Instron 8521 mechanical tester with a crosshead speed of 0.5 mm/min. Five specimens were tested for each data point . EXAMPLE 4
  • Example 2 Hardness Testing. Samples prepared as in Example 2 were placed in liquid nitrogen and fractured with a hammer. A fragment no less than 2 mm thick was then mounted in Kould Mount . These samples were ground to 600 grit silicon carbide followed by polishing with a one micron diamond paste. A Tukon Microhardness Tester, model LR, was used to produce and measure Vickers indents using a 300g load. Three indents were made on each sample and averaged.
  • EXAMPLE 6 Fluoride Release Test Five glass ionomer samples 1 cm x 1 cm x 0.05 cm were made for all fourteen variations (see Example 7 below) of the material, including the different glass contents and the different copolymers containing 50 wt% glass. Each sample was placed in a vial containing 5 ml ddH 2 0. These samples were maintained on a shaker at 37°C for the duration of the experiment . Each day the water was removed for fluoride measurement, and fresh water was placed in the sample vial. The aliquots were measured on an Orion Model 720A pH meter, using an Orion F " detector, Model
  • EXAMPLE 7 Fluoride Release Test Two sets of samples were prepared for testing. In the first group, an 80:20 PMMA-MAA random copolymer was used with the following glass contents: 0.00, 6.25, 14.29, 25.00, 33.33, 40.00, 45.45, 50.00, 60.53, 70.00 and 80.00 weight% .
  • the second set includes the following PMMA-MAA random copolymers : 75:25, 80:20, 95:5 and 100:0, containing 0 weight% and 50 weight% glass . The copolymers were obtained from
  • Figure 1 shows the compressive modulus data for the glass filled 80:20 polymer.
  • the elastic modulus is comparable to that of the best commercial glass ionomer materials available (O'Brien 1997) .
  • a sigmoidal trend is observed, with the modulus remaining nearly the same until a critical glass percentage is reached, at which the modulus increases rapidly.
  • Another critical glass percentage is attained where additional glass no longer improves the modulus . It is believed that, upon optimization of the compositions of the present invention, even better modulus data may be obtained, thereby surpassing that of the best available commercial glass ionomer materials .
  • the carboxyl group on the methacrylic acid unit is able to bind with Ca +2 and Al +3 ions from the glass. Some of these ions are presumably leached out of the glass during the reaction creating crosslinking between polymer chains, and also forming links between the ionomer and the glass itself. This produces a polymeric matrix filled with glass particles surrounded by ionic aggregates. Without being bound to any theory, it is believed that, by developing these ionic interactions between the glass particles and the polymer matrix, the mechanical properties of the material are increased. When interpreting the strength data, it has been found in the present invention that it may be beneficial to consider several interactions.
  • the mechanical properties of the material may be attributed to a mechanical interaction between glass particles.
  • the glass and polymer packing density may also play an important role in the analysis of the data at high glass contents.
  • three chemical interactions may come into play: the polymer- glass ionic bonding, the polymer-polymer ionic bonding, and the polymer-polymer hydrogen bonding.
  • the glass-glass mechanical contact appears to dominate the modulus trend. As more glass particles are added to the material, it becomes less pliable and therefore more resistant to being compressed. Modulus is related to very small deformation, so at low glass contents, the particles are not forced to touch each other, showing little change in the modulus. Once a critical glass content is reached, the modulus increases rapidly. At about 50 wt% glass, the material assumes a continuous glass structure with the particles touching, and the resistance to being compressed levels off. At high glass content the effect of packing density comes into consideration. Since the glass possesses a range of sizes, the packing is improved over particles of all one size. See, for example, Cross, M., W.H.
  • Figure 3 exhibits the yield strength data for the 80:20 copolymer with glass filler. There is a linear increase in yield strength to approximately 60 wt% glass, where it then levels off. Unlike the modulus data, the yield strength at low glass content increases linearly starting at 0 wt% glass. It is believed that this is due to the fact that yield strength is a function of larger strain than the modulus, and the glass particles are forced to touch as the material yields . Other researchers have seen a linear increase in yield strength for a glass filled PMMA, for both silane treated and untreated glass. See, for example, Soderholm (1982); and Krause, W.R., S.-H. Park, et al . , “Mechanical properties of BIS-GMA resin short glass fiber composites, " Journal of Biomedical Materials Research 23: 1195-1211 (1989). It is believed that the packing density discussed above is most likely responsible for the bend in the yield strength curve at high glass content.
  • the toughness data is shown in Figure 4.
  • the addition of glass improved the toughness of 80:20 PMMA- MAA at glass concentrations below 70 wt% glass.
  • the toughness data are shown in Figure 8.
  • the properties of the novel and unique ionomer composite composition of the present invention may easily be adjusted by altering the ratio of hydrophilic monomer to hydrophobic monomer in the copolymer, and/or by altering the glass content. Bonding between acid-containing hydrophilic monomers and glass particles, along with monomer-monomer bonds are formed by acid leaching of cations from the glass particles, forming a strong interface between the filler and matrix. An added advantage of this ion leaching is that fluoride ions may also be released from the glass, if desired.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)

Abstract

L'invention concerne une composition de composite ionomère présentant des caractéristiques améliorées et exclusives, notamment un matériau de verre contenant au moins un cation divalent et/ou un cation polyvalent, et au moins un copolymère. Ce copolymère comprend au moins un monomère hydrophile contenant des groupes fonctionnels acides capables de réagir avec le(s) cation(s) divalent(s) et/ou polyvalent(s) afin de former des ponts ioniques entre les chaînes de polymère, ce monomère hydrophile étant présent en quantité suffisante pour conférer au copolymère le degré souhaité de solubilité dans l'eau, et au moins un monomère hydrophobe présent en quantité suffisante pour conférer un degré souhaité de stabilité structurale à la composition composite lorsqu'elle est exposée à un environnement aqueux.
PCT/US2000/006974 1999-03-17 2000-03-16 Compositions de composite ionomere WO2000055253A1 (fr)

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US09/936,692 US6979702B1 (en) 1999-03-17 2000-03-16 Ionomer composite compositions
AU38904/00A AU3890400A (en) 1999-03-17 2000-03-16 Ionomer composite compositions

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US60/124,819 1999-03-17

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002053107A1 (fr) * 2001-01-03 2002-07-11 3M Innovative Properties Company Materiaux dentaires
US6793592B2 (en) 2002-08-27 2004-09-21 Acushnet Company Golf balls comprising glass ionomers, or other hybrid organic/inorganic compositions
US6979702B1 (en) 1999-03-17 2005-12-27 The Regents Of The University Of Michigan Ionomer composite compositions
CN109369117A (zh) * 2018-12-26 2019-02-22 陕西天石实业有限责任公司 大体积混凝土
CN109517530A (zh) * 2018-11-27 2019-03-26 吉林省登泰克牙科材料有限公司 一种聚醚醚酮粘结剂组合物、其制备方法和应用

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Publication number Priority date Publication date Assignee Title
GB1507981A (en) * 1975-03-25 1978-04-19 Nat Res Dev Poly-(carboxylate)cements
US4089830A (en) * 1976-02-24 1978-05-16 G-C Dental Industrial Corp. Setting solution for dental glass ionomer cements
US4758612A (en) * 1985-10-25 1988-07-19 National Research Development Corporation Cement-forming compositions
US4872936A (en) * 1985-10-09 1989-10-10 Ernst Muhlbauer Kg Polymerizable cement mixtures
US5051453A (en) * 1988-02-08 1991-09-24 Tokuyama Soda Kabushiki Kaisha Cement composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1507981A (en) * 1975-03-25 1978-04-19 Nat Res Dev Poly-(carboxylate)cements
US4089830A (en) * 1976-02-24 1978-05-16 G-C Dental Industrial Corp. Setting solution for dental glass ionomer cements
US4872936A (en) * 1985-10-09 1989-10-10 Ernst Muhlbauer Kg Polymerizable cement mixtures
US4758612A (en) * 1985-10-25 1988-07-19 National Research Development Corporation Cement-forming compositions
US5051453A (en) * 1988-02-08 1991-09-24 Tokuyama Soda Kabushiki Kaisha Cement composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6979702B1 (en) 1999-03-17 2005-12-27 The Regents Of The University Of Michigan Ionomer composite compositions
WO2002053107A1 (fr) * 2001-01-03 2002-07-11 3M Innovative Properties Company Materiaux dentaires
US6613812B2 (en) 2001-01-03 2003-09-02 3M Innovative Properties Company Dental material including fatty acid, dimer thereof, or trimer thereof
JP2004517107A (ja) * 2001-01-03 2004-06-10 スリーエム イノベイティブ プロパティズ カンパニー 歯科材料
JP4907837B2 (ja) * 2001-01-03 2012-04-04 スリーエム イノベイティブ プロパティズ カンパニー 歯科材料
US6793592B2 (en) 2002-08-27 2004-09-21 Acushnet Company Golf balls comprising glass ionomers, or other hybrid organic/inorganic compositions
CN109517530A (zh) * 2018-11-27 2019-03-26 吉林省登泰克牙科材料有限公司 一种聚醚醚酮粘结剂组合物、其制备方法和应用
CN109517530B (zh) * 2018-11-27 2021-04-20 吉林省登泰克牙科材料有限公司 一种聚醚醚酮粘结剂组合物、其制备方法和应用
CN109369117A (zh) * 2018-12-26 2019-02-22 陕西天石实业有限责任公司 大体积混凝土

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