WO2010045105A1 - Fillers and composite materials with zirconia and silica nanoparticles - Google Patents
Fillers and composite materials with zirconia and silica nanoparticles Download PDFInfo
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- WO2010045105A1 WO2010045105A1 PCT/US2009/060104 US2009060104W WO2010045105A1 WO 2010045105 A1 WO2010045105 A1 WO 2010045105A1 US 2009060104 W US2009060104 W US 2009060104W WO 2010045105 A1 WO2010045105 A1 WO 2010045105A1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C01P2006/66—Hue (H*)
Definitions
- the present invention relates to nanoparticle fillers for use in composite materials, including dental composite materials. More specifically, the invention relates to filler materials with silica-zirconia nanoclusters that provide desirable optical properties, such as opalescence, for use in dental compositions.
- Natural tooth enamel has an opalescent quality to it in that it preferentially bends the shorter (blue) wavelengths of light, appearing bluish against a dark background, and more orange/yellow against a white background.
- opalescent dental composites have been developed, this property is often lacking from dental composites that use a silica-zirconia nanofiller system.
- silica-zirconia nanofillers lack of opalescence may be seen as a drawback.
- the present invention features fillers for use in composite materials.
- the fillers include clusters of zirconia and silica nanoparticles that provide opalescence and radiopacity, along with excellent optical clarity in both reflectance and transmission.
- the filler may be prepared by (a) providing a zirconia sol comprising preformed, crystalline zirconia nanoparticles with a diameter from about 3 nm to about 30 nm, (b) providing a silica sol comprising silica nanoparticles with a diameter from about 10 nm to about 100 nm, (c) combining the zirconia sol and the silica sol to form a mixture of zirconia and silica nanoparticles, and (d) heating the mixture to a temperature from about 450 0 C to about 950 0 C and subsequently milling the resultant material to form a filler comprising silica-zirconia nanoclusters with a diameter from about 0.25 micron to about 50 micron.
- the nanozirconia sol is acid reduced prior to mixing with the nanosilica sol.
- the silica nanoparticles and zirconia nanoparticles are uniformly distributed in the resulting nanoclusters.
- the method further includes a step of surface treating the silica-zirconia nanoclusters with, for example, a silane coupling agent or similar treatment to assist with incorporation into the resin component.
- the zirconia-silica fillers of the invention are useful in composite materials, including dental composite materials.
- Such composites typically include, a polymerizable component, such as a methacrylate or other ethylenically unsaturated compound, an initiator system, and a filler comprising the silica-zirconia nanoclusters.
- These composite materials typically have a C a b value of at least 15, more typically at least 18, and most typically at least 20.
- the dental composites of the invention have a refractive index from about 1.44 to about 1.65, more typically from about 1.50 to about 1.6, most typically from about 1.50 to about 1.56.
- the composites also typically exhibit excellent handling characteristics, radiopacity, low haze (typically less than 70, more typically less than 60, and most typically less than 55 haze units), and possess a directionally independent clarity or translucence, i.e. the clarity is less dependent on the angle of the transmitted light through the material, which make them useful in a variety of dental and orthodontic applications, including as dental restoratives (e.g. filling materials, flowable restoratives, preformed crowns and bridges, temporary restoratives), dental adhesives, dental cements, cavity liners, orthodontic adhesives, dental sealants, dental coatings, and the like.
- dental restoratives e.g. filling materials, flowable restoratives, preformed crowns and bridges, temporary restoratives
- dental adhesives e.g. filling materials, flowable restoratives, preformed crowns and bridges, temporary restoratives
- dental adhesives e.g. filling materials, flowable restoratives, preformed crowns and bridges,
- crystalline zirconia is meant a zirconia that exhibits significant crystalline (monoclinic, tetragonal, cubic or pseudo-cubic) peaks on X-ray diffraction.
- crytalline zirconia meets the crystallinity parameters of the zirconia sols described in U.S. Patent No. 6,376,590 (KoIb et al), filed on October 28, 1999, or in U.S. Patent No. 7,429,422 (Davidson et al), filed on June 7, 2007, both of which are incorporated by reference herein in their entirety.
- preformed crystalline zirconia nanoparticles is meant that the sol that is used to fabricate the filler has zirconia particles within it that are crystalline before drying and firing of the filler.
- sol is meant a colloid that has a continuous liquid phase in which a solid is suspended in a liquid.
- a sol is a stable colloidal suspension of solid particles of 1-500 nm in diameter in a liquid, and particles are usually not agglomerated or aggregated.
- hardenable is descriptive of a material or composition that can be cured (e.g., polymerized or crosslinked) or solidified, for example, by removing solvent (e.g., by evaporation and/or heating); heating to induce polymerization and/or crosslinking; irradiating to induce polymerization and/or crosslinking; and/or by mixing one or more components to induce polymerization and/or crosslinking.
- solvent e.g., by evaporation and/or heating
- heating to induce polymerization and/or crosslinking irradiating to induce polymerization and/or crosslinking
- and/or by mixing one or more components to induce polymerization and/or crosslinking.
- dental composition is meant an unfilled or filled (e.g. a composite) material (e.g., a dental or orthodontic material) that are capable of being applied or adhered to an oral surface.
- Dental compositions include, for example, adhesives (e.g., dental and/or orthodontic adhesives), cements (e.g., glass ionomer cements, resin-modified glass ionomer cements, and/or orthodontic cements), primers (e.g., orthodontic primers), restoratives (e.g., a restorative filling material), liners, sealants (e.g., orthodontic sealants), and coatings.
- adhesives e.g., dental and/or orthodontic adhesives
- cements e.g., glass ionomer cements, resin-modified glass ionomer cements, and/or orthodontic cements
- primers e.g., orthodontic primers
- restoratives e.g., a restorative filling material
- liners e.g., sealants
- coatings e.g., a dental sealants
- hardenable dental composition is meant a dental composition, such as a paste, that can be hardened to form a dental article.
- dental article is meant an article that can be adhered (e.g., bonded) to an oral surface (e.g., a tooth structure).
- the dental article is a restored dentition or a portion thereof. Examples include restoratives, replacements, inlays, onlays, veneers, full and partial crowns, bridges, implants, implant abutments, copings, anterior fillings, posterior fillings, cavity liners, sealants, dentures, posts, bridge frameworks and other bridge sturctures, abutments, orthodontic appliances and devices, and prostheses (e.g., partial or full dentures).
- the terms “dental composition” and “dental article” are not limited to compositions and articles used in dental applications, but also include orthodontic compositions (e.g., orthodontic adhesives) and orthodontic devices (e.g., orthodontic appliances such as retainers, night guards, brackets, buccal tubes, bands, cleats, buttons, lingual retainers, bite openers, positioners, and the like), respectively.
- orthodontic compositions e.g., orthodontic adhesives
- orthodontic devices e.g., orthodontic appliances such as retainers, night guards, brackets, buccal tubes, bands, cleats, buttons, lingual retainers, bite openers, positioners, and the like
- oral surface is meant a soft or hard surface in the oral environment.
- Hard surfaces typically include tooth structure including, for example, natural and artificial tooth surfaces, bone, tooth models, dentin, enamel, cementum, and the like [0019]
- fillers is meant a particulate material suitable for use in the oral environment. Dental fillers generally have an average particle size of at most 100 micrometers.
- nanofiller is meant a filler having an average primary particle size of at most 200 nanometers.
- the nanofiller component may be a single nanofiller or a combination of nanofillers.
- the nanofiller comprises non-pyrogenic nanoparticles or nanoclusters.
- nanostructured is meant a material in a form having at least one dimension that is, on average, at most 200 nanometers (e.g., nanosized particles).
- nanostructured materials refer to materials including, for example, nanoparticles as defined herein below; aggregates of nanoparticles; materials coated on particles, wherein the coatings have an average thickness of at most 200 nanometers; materials coated on aggregates of particles, wherein the coatings have an average thickness of at most 200 nanometers; materials infiltrated in porous structures having an average pore size of at most 200 nanometers; and combinations thereof.
- Porous structures include, for example, porous particles, porous aggregates of particles, porous coatings, and combinations thereof.
- nanoparticles is synonymous with “nanosized particles,” and refers to particles having an average size of at most 200 nanometers.
- size refers to the diameter of the particle.
- size refers to the longest dimension of the particle.
- the nanoparticles are comprises of discrete, non-aggregated and non- agglomerate particles.
- nanocluster is meant an association of nanoparticles drawn together by relatively weak intermolecular forces that cause them to clump together, i.e. to aggregate.
- nanoclusters typically have an average size of at most 10 micrometers.
- ethylenically unsaturated compound is meant to include monomers, oligomers, and polymers having at least one ethylenic unsaturation.
- polymerization is meant the forming of a higher weight material from monomer or oligomers.
- the polymerization reaction also can involve a cross-linking reaction.
- (meth)acrylate is a shorthand reference to acrylate, methacrylate, or combinations thereof
- (meth)acrylic is a shorthand reference to acrylic, methacrylic, or combinations thereof.
- (meth)acrylate-functional compounds are compounds that include, among other things, a (meth)acrylate moiety.
- FIGS. IA and B are diagrams showing the difference between angle- dependent translucent composites and angle-independent translucent composites.
- the composite material (2) is viewed straight on by the observer (1).
- Examples E1-E3 and Comparative Examples CEl and CE2 were clear.
- FIG IB the composite material (2) is viewed at an angle relative to the observer (1).
- Examples E1-E3 remained clear, but Comparative Examples CEl and CE2 were more opaque than when they were viewed straight on.
- the invention provides filler materials composed of nanoparticles of silica (SiO 2 ) and nanoparticles of zirconia (ZiO 2 ).
- the silica and zirconia nanoparticles are typically clumped together in the form silica-zirconia nanoclusters.
- the nanoparticles of silica and nanoparticles of zirconia are evenly distributed throughout the nanoclusters, which may optionally be surface treated with a silane or other suitable coupling agent to enhance their incorporation into a resin.
- the silica-zirconia nanocluster fillers of the invention are prepared by mixing a nanosilica sol together with a preformed nanozirconia particulate sol.
- the nanozirconia sol is typically composed of crystalline zirconia nanoparticles. It is believed that the source of zirconia affects the opalescence of the resulting filler material.
- the use of a preformed nanozirconia sol in certain circumstances, provides for silica-zirconia nanofillers with better opalescence properties than those derived from zirconyl acetate.
- composite materials containing the silica-zirconia nanocluster filler of the invention typically exhibit an opalescence value (C ab ) of at least 15, more typically at least 18, and most typically at least 20.
- Silica- zirconia nanocluster fillers derived from zirconyl acetate typically have a lower opalescence value, or lack opalescence altogether.
- the silica-zirconia nanocluster filler materials in some embodiments, also provide radiopacity, clarity and an optical transparency that is less dependent upon the angle at which the material is viewed when compared to fillers derived from zirconyl acetate.
- Such optical properties provide materials that are very lifelike in appearance when compared to natural dentition, and are desirable in a variety of product areas, including flowable dental restorative materials, preformed dental crowns and bridges, temporary dental materials, and other restorative dental materials.
- the silica-zirconia nanocluster fillers of the invention may be used in a variety of different composite materials, and are particularly suitable for use in hardenable dental compositions.
- Such materials typically include a polymerizable component, an initiatior system, one or more fillers, and one or more optional additives. Each of these components is discussed in more detail below.
- the dental compositions of the present invention are typically hardenable due the presence of a polymerizable component.
- the compositions can be hardened (e.g., polymerized by conventional photopolymerization and/or chemical polymerization techniques) prior to applying it to an oral surface.
- the compositions can be hardened (e.g., polymerized by conventional photopolymerization and/or chemical polymerization techniques) after it has been applied to an oral surface.
- the compositions are photopolymerizable, i.e., the compositions contain a photoinitiator system that upon irradiation with actinic radiation initiates the polymerization (or hardening) of the composition.
- the compositions are chemically hardenable, i.e., the compositions contain a chemical initiator (i.e., initiator system) that can polymerize, cure, or otherwise harden the composition without dependence on irradiation with actinic radiation.
- a chemical initiator i.e., initiator system
- Such chemically hardenable compositions are sometimes referred to as "self-cure" compositions.
- the polymerizable component typically includes one or more ethylenically unsaturated compounds with or without acid functionality.
- ethylenically unsaturated compounds include acrylic acid esters, methacrylic acid esters, hydroxy-functional acrylic acid esters, hydroxy-functional methacrylic acid esters, and combinations thereof.
- compositions may include compounds having free radically active functional groups that may include monomers, oligomers, and polymers having one or more ethylenically unsaturated group. Suitable compounds contain at least one ethylenically unsaturated bond and are capable of undergoing addition polymerization.
- Such free radically polymerizable compounds include mono-, di- or poly-(meth)acrylates (i.e., acrylates and methacrylates) such as, methyl (meth)acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1 ,4-cyclohexanediol diacrylate, pentaerythritol tetra(meth)acrylate, sorbitol hexacrylate, tetrahydrofurfuryl (meth)acrylate, bis[l-(2-acryloxy)]
- Suitable free radically polymerizable compounds include siloxane-functional (meth)acrylates as disclosed, for example, in WO-00/38619 (Guggenberger et al.), WO-01/92271 (Weinmann et al.), WO- 01/07444 (Guggenberger et al.), WO-00/42092 (Guggenberger et al.) and fluoropolymer- functional (meth)acrylates as disclosed, for example, in U.S. Pat. No. 5,076,844 (Fock et al.), U.S. Pat. No.
- the polymerizable component may also contain hydroxyl groups and ethylenically unsaturated groups in a single molecule.
- examples of such materials include hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2- hydroxypropyl (meth)acrylate; glycerol mono- or di-(meth)acrylate; trimethylolpropane mono- or di-(meth)acrylate; pentaerythritol mono-, di-, and tri-(meth)acrylate; sorbitol mono-, di-, tri-, terra-, or penta-(meth)acrylate; and 2,2-bis[4-(2-hydroxy-3- methacryloxypropoxy)phenyl]propane (bisGMA).
- Suitable ethylenically unsaturated compounds are also available from a wide variety of commercial sources, such as Sigma- Aldrich, St. Louis. Mixtures of ethylenically unsaturated compounds
- the polymerizable component includes PEGDMA (polyethyleneglycol dimethacrylate having a molecular weight of approximately 400), bisGMA, UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethyleneglycol dimethacrylate), bisEMA6 as described in U.S. Pat. No. 6,030,606 (Holmes), and/or NPGDMA (neopentylglycol dimethacrylate).
- PEGDMA polyethyleneglycol dimethacrylate having a molecular weight of approximately 400
- bisGMA bisGMA
- UDMA urethane dimethacrylate
- GDMA glycerol dimethacrylate
- TEGDMA triethyleneglycol dimethacrylate
- bisEMA6 as described in U.S. Pat. No. 6,030,606 (Holmes)
- NPGDMA neopentylglycol dimethacrylate
- compositions of the present invention typically include at most 95% by weight, more typically at most 90% by weight, and most typically at most 80% by weight ethylenically unsaturated compounds without acid functionality, based on the total weight of the unfilled composition.
- the polymerizable component may include one or more ethylenically unsaturated compounds with acid functionality.
- ethylenically unsaturated compounds "with acid functionality” is meant to include monomers, oligomers, and polymers having ethylenic unsaturation and acid and/or acid- precursor functionality.
- Acid-precursor functionalities include, for example, anhydrides, acid halides, and pyrophosphates.
- the acid functionality can include carboxylic acid functionality, phosphoric acid functionality, phosphonic acid functionality, sulfonic acid functionality, or combinations thereof.
- Ethylenically unsaturated compounds with acid functionality include, for example, ⁇ , ⁇ -unsaturated acidic compounds such as glycerol phosphate mono(meth)acrylates, glycerol phosphate di(meth)acrylates, hydroxyethyl (meth)acrylate (e.g., HEMA) phosphates, bis((meth)acryloxyethyl) phosphate, ((meth)acryloxypropyl) phosphate, bis((meth)acryloxypropyl) phosphate, bis((meth)acryloxy)propyloxy phosphate, (meth)acryloxyhexyl phosphate, bis((meth)acryloxyhexyl) phosphate, (meth)acryloxyoctyl phosphate, bis((meth)acryloxyoctyl) phosphate, (meth)acryloxydecyl phosphate, bis((meth)acryloxydecyl) phosphate, cap
- compositions of the present invention include an ethylenically unsaturated compound with acid functionality having at least one P-OH moiety.
- Additional ethylenically unsaturated compounds with acid functionality include, for example, polymerizable bisphosphonic acids as disclosed for example, in U.S. Provisional Application No. 60/437,106, filed December 30, 2002; AA:ITA:IEM (copolymer of acrylic acid:itaconic acid with pendent methacrylate made by reacting AA:ITA copolymer with sufficient 2-isocyanatoethyl methacrylate to convert a portion of the acid groups of the copolymer to pendent methacrylate groups as described, for example, in Example 11 of U.S. Pat. No. 5,130,347 (Mitra)); and those recited in U.S. Pat. Nos.
- compositions of the present invention can also include combinations of ethylenically unsaturated compounds with acid functionality as described, for example, in U.S. Patent Application Publication No.
- compositions may also include a mixture of ethylenically unsaturated compounds both with and without acid functionality.
- the composition contains an ethylenically unsaturated compound with acid functionality, it is generally present in an amount of at least 1% by weight, more typically at least 3% by weight, and most typically at least 5% by weight ethylenically unsaturated compounds with acid functionality, based on the total weight of the unfilled composition.
- compositions of the present invention typically include at most 80% by weight, more typically at most 70% by weight, and most typically at most 60% by weight ethylenically unsaturated compounds with acid functionality, based on the total weight of the unfilled composition.
- the compositions of the present invention are photopolymerizable, i.e., the compositions contain a photopolymerizable component and a photoinitiator system that upon irradiation with actinic radiation initiates the polymerization (or hardening) of the composition.
- Such photopolymerizable compositions can be free radically polymerizable or cationically polymerizable.
- Suitable photoinitiators i.e., photoinitiator systems that include one or more compounds
- Suitable photoinitiators include binary and tertiary systems.
- Typical tertiary photoinitiators include an iodonium salt, a photosensitizer, and an electron donor compound as described in U.S. Pat. No. 5,545,676 (Palazzotto et al).
- Suitable iodonium salts are the diaryl iodonium salts, e.g., diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, and tolylcumyliodonium tetrakis(pentafluorophenyl)borate.
- Suitable photosensitizers are monoketones and diketones that absorb some light within a range of 400 nm to 520 nm (preferably, 450 nm to 500 nm).
- Particularly suitable compounds include alpha diketones that have light absorption within a range of 400 nm to 520 nm (even more preferably, 450 to 500 nm).
- Suitable compounds are camphorquinone, benzil, furil, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone, 1 -phenyl- 1,2- propanedione and other l-aryl-2-alkyl-l,2-ethanediones, and cyclic alpha diketones.
- Suitable electron donor compounds include substituted amines, e.g., ethyl dimethylaminobenzoate.
- Suitable tertiary photoinitiator systems useful for photopolymerizing cationically polymerizable resins are described, for example, in U.S. Pat. No. 6,765,036 (Dede et al.).
- Other useful photoinitiators for polymerizing free radically photopolymerizable compositions include the class of phosphine oxides that typically have a functional wavelength range of 380 nm to 1200 nm.
- Preferred phosphine oxide free radical initiators with a functional wavelength range of 380 nm to 450 nm are acyl and bisacyl phosphine oxides such as those described in U.S. Pat. Nos.
- phosphine oxide photoinitiators capable of free- radical initiation when irradiated at wavelength ranges of greater than 380 nm to 450 nm include bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide (IRGACURE 819, Ciba Specialty Chemicals, Tarrytown, NY), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide (CGI 403, Ciba Specialty Chemicals), a 25:75 mixture, by weight, of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide and 2-hydroxy-2- methyl-1-phenylpropan-l-one (IRGACURE 1700, Ciba Specialty Chemicals), a 1 :1 mixture, by weight, of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide and 2-
- the phosphine oxide initiator is present in the photopolymerizable composition in catalytically effective amounts, such as from 0.1 weight percent to 5.0 weight percent, based on the total weight of the unfilled composition.
- Tertiary amine reducing agents may be used in combination with an acylphosphine oxide.
- Illustrative tertiary amines useful in the invention include ethyl 4- (N,N-dimethylamino)benzoate and N,N-dimethylaminoethyl methacrylate.
- the amine reducing agent is present in the photopolymerizable composition in an amount from 0.1 weight percent to 5.0 weight percent, based on the total weight of the unfilled composition.
- Useful amounts of other initiators are well known to those of skill in the art.
- the compositions of the present invention are chemically hardenable, i.e., the compositions contain a chemically hardenable component and a chemical initiator (i.e., initiator system) that can polymerize, cure, or otherwise harden the composition without dependence on irradiation with actinic radiation.
- a chemically hardenable component i.e., a chemical initiator (i.e., initiator system) that can polymerize, cure, or otherwise harden the composition without dependence on irradiation with actinic radiation.
- Such chemically hardenable compositions are sometimes referred to as "self-cure" compositions.
- the chemically hardenable compositions may include redox cure systems that include a polymerizable component (e.g., an ethylenically unsaturated polymerizable component) and redox agents that include an oxidizing agent and a reducing agent.
- a polymerizable component e.g., an ethylenically unsaturated polymerizable component
- redox agents that include an oxidizing agent and a reducing agent.
- Suitable polymerizable components, redox agents, optional acid-functional components, and optional fillers that are useful in the present invention are described in U.S. Pat. Publication Nos. 2003/0166740 (Mitra et al.) and 2003/0195273 (Mitra et al).
- the reducing and oxidizing agents should react with or otherwise cooperate with one another to produce free-radicals capable of initiating polymerization of the resin system (e.g., the ethylenically unsaturated component).
- This type of cure is a dark reaction, that is, it is not dependent on the presence of light and can proceed in the absence of light.
- the reducing and oxidizing agents are preferably sufficiently shelf-stable and free of undesirable colorization to permit their storage and use under typical dental conditions. They should be sufficiently miscible with the resin system (and preferably water-soluble) to permit ready dissolution in (and discourage separation from) the other components of the composition.
- Useful reducing agents include ascorbic acid, ascorbic acid derivatives, and metal complexed ascorbic acid compounds as described in U.S. Pat. No. 5,501,727 (Wang et al.); amines, especially tertiary amines, such as 4-tert-butyl dimethylaniline; aromatic sulfinic salts, such as p-toluenesulfinic salts and benzenesulfinic salts; thioureas, such as l-ethyl-2 -thiourea, tetraethyl thiourea, tetramethyl thiourea, 1,1-dibutyl thiourea, and 1,3- dibutyl thiourea; and mixtures thereof.
- secondary reducing agents may include cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine (depending on the choice of oxidizing agent), salts of a dithionite or sulfite anion, and mixtures thereof.
- the reducing agent is an amine.
- Suitable oxidizing agents will also be familiar to those skilled in the art, and include but are not limited to persulfuric acid and salts thereof, such as sodium, potassium, ammonium, cesium, and alkyl ammonium salts.
- Additional oxidizing agents include peroxides such as benzoyl peroxides, hydroperoxides such as cumyl hydroperoxide, t- butyl hydroperoxide, and amyl hydroperoxide, as well as salts of transition metals such as cobalt (III) chloride and ferric chloride, cerium (IV) sulfate, perboric acid and salts thereof, permanganic acid and salts thereof, perphosphoric acid and salts thereof, and mixtures thereof.
- oxidizing agent it may be desirable to use more than one oxidizing agent or more than one reducing agent. Small quantities of transition metal compounds may also be added to accelerate the rate of redox cure. In some embodiments it may be preferred to include a secondary ionic salt to enhance the stability of the polymerizable composition as described in U.S. Pat. Publication No. 2003/0195273 (Mitra et al).
- the reducing and oxidizing agents are present in amounts sufficient to permit an adequate free-radical reaction rate. This can be evaluated by combining all of the ingredients of the composition except for the optional filler, and observing whether or not a hardened mass is obtained.
- the reducing agent if used at all, is present in an amount of at least 0.01% by weight, and more typically at least 0.1% by weight, based on the total weight (including water) of the components of the composition.
- the reducing agent is present in an amount of no greater than 10% by weight, and more typically no greater than 5% by weight, based on the total weight (including water) of the components of the unfilled composition.
- the oxidizing agent if used at all, is present in an amount of at least 0.01% by weight, and more typically at least 0.10% by weight, based on the total weight (including water) of the components of the composition.
- the oxidizing agent is present in an amount of no greater than 10% by weight, and more typically no greater than 5% by weight, based on the total weight (including water) of the components of the unfilled composition.
- the reducing or oxidizing agents can be microencapsulated as described in U.S. Pat. No. 5,154,762 (Mitra et al.). This will generally enhance shelf stability of the composition, and if necessary permit packaging the reducing and oxidizing agents together.
- the oxidizing and reducing agents can be combined with an acid-functional component and optional filler and kept in a storage-stable state.
- the reducing and oxidizing agents can be combined with an FAS glass and water and maintained in a storage-stable state.
- a redox cure system can be combined with other cure systems, including photoinitiator systems or with a composition such as described U.S. Pat. No. 5,154,762
- the composition of the invention includes a silica-zirconia nanocluster filler that imparts the composition with opalescence. It is believed that the opalescent effect stems, at least in part, from the utilization of preformed nanozirconia particles when forming the silica-zirconia cluster. Use of these preformed particles provides a filler with superior opalescence over that obtained when starting from other precursors such as, for example, an acetate salt.
- the nanoclusters can be prepared by combining a sol of silica nanoparticles with a sol of preformed, crystalline zirconia nanoparticles.
- the silica sol typically comprises silica particles having a mean diameter from about 10 nm to about 100 nm, more typically from about 15 nm to about 60 nm, most typically from about 15 nm to about 35 nm, with a mean particle diameter of about 20 nm being particularly well-suited for fabrication of nanoclusters.
- the zirconia sol typically comprises zirconia particles that are small enough to not scatter the majority of visible light, but are large enough to bend shorter wavelength blue light to give the opalescent effect.
- a zirconia sol having a mean particle size from about 3 nm to about 30 nm is suitable for forming the nanoclusters.
- the zirconia particles in the sol have a mean particle diameter from about 5 nm to about 15 nm, more typically from about 6 nm to about 12 nm, and most typically from about 7 nm to about 10 nm.
- the preformed zirconia nanoparticles form a structure with the silica nanoparticles on gelling and drying that gives the desired opalescence character while maintaining a high level of optical transparency of the final composite material.
- NALCO 1042 silica sol (Nalco Chemical Company, Naperville, IL) or other commercially available colloidal silica sols may be used. If a base-stabilized sol is used, typically it will first be subjected to ion exchange in order to remove sodium, for example, with an Amberlite IR- 120 ion exchange resin, or pH adjusted with Nitric acid. It is usually desirable to pH adjust the silica to below 1.2, typically about 0.8 to about 1.0, and then add the zirconia to it slowly, to prevent localized gelation and agglomeration. The pH of the resultant mixture is typically about 1.1 to about 1.2.
- Suitable colloidal silica sols are available from a variety of vendors, including Nalco (Ondeo-Nalco, Grace chemical), H. C. Stark, Nissan Chemical (Snowtex), Nyacol, and Ludox (DuPont).
- the selected sol should have silica particles that are discrete and of the appropriate size specified herein.
- the silica sol may be treated to provide a highly acidic silica sol (e.g., nitrate stabilized) that can be mixed with the zirconia sol without gelation.
- the zirconia sol may be obtained using the process described in U.S. Patent No. 6,376,590 (KoIb, et al), filed on October 28, 1999, or U.S. Patent No. 7,429,422
- zirconia refers to various stoichiometries for zirconium oxides, most typically ZrO 2 , and may also be known as zirconium oxide or zirconium dioxide.
- the zirconia may contain up to 30 weight percent of other chemical moieties such as, for example, Y2O3 and organic material.
- the silica-zirconia nanoclusters can be prepared by mixing together the nanosilica sol with the nanozirconia sol, and heating the mixture to at least 450 0 C.
- the mixture is heated for 4 to 24 hours at a temperature between about 400 to about 1000 0 C, more typically from about 450 to about 950 0 C, to remove water, organic materials, and other volatile components, as well as to potentially weakly aggregate the particles (not required).
- the sol mixture may undergo a different processing step to remove water and volatiles.
- the resulting material may be milled or ground and classified to remove large aggregates.
- the filler may then be surface treated with, for example, a silane prior to mixing with a resin.
- the amount of filler used in the composite material will depend on the particular application, as described in more detail below. Typically, for dental restorative compositions, the filler content is between about 40 weight percent and 90 weight percent of the composition. It some implementations, it is also desirable for the refractive index (RI) of the filler to substantially match that of the resin (i.e., the RI of the filler only differs from the RI of the resin by an amount from about 0.02 to about 0.05 RI units).
- RI refractive index
- index of refraction refers to the absolute refractive index of a material (e.g., a monomer) that is understood to be the ratio of the speed of electromagnetic radiation in free space to the speed of the radiation in that material.
- the refractive index can be measured using known methods and, for example, using an Abbe refractometer in the visible light region (available commercially, for example, from Fisher Instruments of Pittsburgh, Pa.). It is generally appreciated that the measured index of refraction can vary to some extent depending on the instrument. Measurements are typically run in accordace with the instrument manufacturer's recommendations and good laboratory practices.
- the refractive index values of may also be measured by dispersing a test sample (typically at room temperature) into optical liquids with different known specific refractive indexes.
- a kit with calibrated optical liquids is available from Cargille Laboratories (Cedar Grove, N.J.) for this purpose. Observations of the dispersions are with a light microscope.
- the refractive index of the solid material may be determined using the Becke's line as a band of light that appears along the outer edge of the dispersed particles under microscopic investigation. The Becke's line indicates the relative difference or the equality between the refractive indices of the solid material and the optical liquid.
- compositions of the present invention may optionally contain one or more other fillers.
- these fillers may be selected from one or more of a wide variety of materials suitable for incorporation in compositions used for dental applications, such as fillers currently used in dental restorative compositions, and the like.
- the choice of filler affects important properties of the dental composite such as its appearance, radiopacity and physical and mechanical properties. Appearance is affected in part by adjustment of the amounts and relative refractive indices of the ingredients of the composite, thereby allowing alteration of the translucence, opacity or pearlescence of the composite. In this way, the appearance of the dental material can, if desired, be made to closely approximate the appearance of natural dentition.
- Radiopacity is a measurement of the ability of the dental composite to be detected by x-ray examination. Frequently a radiopaque dental composite will be desirable, for instance, to enable the dentist to determine whether or not a dental restoration remains sound. Under other circumstances a non-radiopaque composite may be desirable. Suitable fillers for radiopaque formulations are described in EP-A2-0 189 540, EP-B-O 238 025, and U.S. Patent No. 6,306,926 Bl.
- the amount of filler that is incorporated into the composite referred to herein as the "loading level” and expressed as a weight percent based on the total weight of the dental material, will vary depending on the type of filler, the curable resin and other components of the composition, and the end use of the composite.
- the compositions of the invention can be lightly filled (e.g., having a loading level of less than about 40 weight percent) or unfilled. In such implementations, the viscosity of the dental material is sufficiently low to allow its penetration into pits and fissures of occlusal tooth surfaces as well as into etched areas of enamel, thereby aiding in the retention of the dental material.
- the loading level can be as high as about 95 weight percent.
- a loading level is generally at least 40 weight percent, and more typically is between about 60 and 90 weight percent.
- the f ⁇ ller(s) used in the compositions of the invention is typically finely divided.
- the f ⁇ ller(s) can have a unimodial or polymodal (e.g., bimodal) particle size distribution.
- the maximum particle size (the largest dimension of a particle, generally, the diameter or by volumetric average) of the f ⁇ ller(s) is typically less than 50 micrometers, more typically less than 10 micrometers, and most typically less than 5 micrometers.
- number average particle size of the f ⁇ ller(s) is typically less than 0.5 micrometers, and more typically less than 0.2 micrometer, but in other embodiments the average particle size may be larger, and the material may include particles with a maximum particle size around 40 micrometers.
- the f ⁇ ller(s) may be an inorganic material. It may also be a crosslinked organic material that is insoluble in the resin system, and is optionally filled with inorganic filler.
- the f ⁇ ller(s) should in any event be nontoxic and suitable for use in the mouth.
- the f ⁇ ller(s) can be radiopaque or radiolucent.
- the filler typically is substantially insoluble in water.
- suitable inorganic fillers that may be included in the composition are naturally occurring or synthetic materials including, but not limited to: quartz (i.e.
- silica SiO 2
- nitrides e.g., silicon nitride
- glasses derived from, for example, Zr, Sr, Ce, Sb, Sn, Ba, Zn, and Al; feldspar; borosilicate glass; kaolin; talc; titania; low Mohs hardness fillers such as those described in U.S. Pat. No.
- silica particles e.g., pyrogenic silicas such as those available under the trade designations AEROSIL, including "OX 50," “130,” “150” and “200” silicas from Degussa Corp., Akron, OH and CAB-O-SIL M5 silica from Cabot Corp., Tuscola, IL.
- the silica or nanosilica particles are non-pyrogenic, i.e. comprise non-fumed silica.
- suitable organic filler particles include filled or unfilled pulverized olycarbonates, polyepoxides, and the like.
- the additional filler(s) may be acid-reactive, non-acid-reactive, or a combination thereof.
- Metallic fillers may also be incorporated, such as particulate metal filler made from a pure metal such as those of Groups IVA, VA, VIA, VIIA, VIII, IB, or HB, aluminum, indium, and thallium of Group IIIB, and tin and lead of Group IVB, or alloys thereof.
- Conventional dental amalgam alloy powders typically mixtures of silver, tin, copper, and zinc, may also optionally be incorporated.
- the particulate metallic filler preferably has an average particle size of about 1 micron to about 100 microns, more preferably 1 micron to about 50 microns. Mixtures of these fillers are also contemplated, as well as combination fillers made from organic and inorganic materials. Fluoroaluminosilicate glass fillers, either untreated or silanol treated, are particularly preferred. These glass fillers have the added benefit of releasing fluoride at the site of dental work when placed in the oral environment.
- the composition may include acid-reactive filler.
- Suitable acid-reactive fillers include metal oxides, glasses, and metal salts.
- Typical metal oxides include barium oxide, calcium oxide, magnesium oxide, and zinc oxide.
- Typical glasses include borate glasses, phosphate glasses, and fluoroaluminosilicate ("FAS") glasses.
- FAS glasses are particularly preferred.
- the FAS glass if present, typically contains sufficient elutable cations so that a hardened dental composition will form when the glass is mixed with the components of the hardenable composition.
- the glass also typically contains sufficient elutable fluoride ions so that the hardened composition will have cariostatic properties.
- Such glass can be made from a melt containing fluoride, alumina, and other glass-forming ingredients using techniques familiar to those skilled in the FAS glassmaking art.
- the FAS glass if present, is typically in the form of particles that are sufficiently finely divided so that they can conveniently be mixed with the other cement components and will perform well when the resulting mixture is used in the mouth.
- the average particle size (typically, diameter) for FAS glass used in such compositions is no greater than about 12 micrometers, typically no greater than 10 micrometers, and more typically no greater than 5 micrometers as measured using, for example, a sedimentation analyzer.
- Suitable FAS glasses will be familiar to those skilled in the art, and are available from a wide variety of commercial sources, and many are found in currently available glass ionomer cements such as those commercially available under the trade designations VITREMER, VITREBOND, RELY X LUTING CEMENT, RELY X LUTING PLUS CEMENT, PHOTAC-FIL QUICK, KET AC-MOLAR, and KETAC-FIL PLUS (3M ESPE Dental Products, St.
- the surface of the filler particles can also be treated with a coupling agent in order to enhance the bond between the filler and the resin.
- Suitable coupling agents include gamma-methacryloxypropyltrimethoxysilane, gamma- mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, and the like.
- Silane-treated zirconia-silica (ZrO 2 -SiO 2 ) fillers and nanofillers, silane -treated silica fillers and nanofillers, silane-treated zirconia fillers and nanofillers, and combinations thereof are especially suitable for certain restorative compositions.
- Other suitable fillers are disclosed in U.S. Pat. Nos. 6,387,981 (Zhang et al); 6,572,693 (Wu et al); 6,730,156 (Windisch); and 6,899,948 (Zhang); as well as in International Publication No. WO 03/063804 (Wu et al.). Filler components described in these references include nanosized silica particles, nanosized metal oxide particles, and combinations thereof.
- Nanofillers are also described in U.S. Patent Publication Nos. 2005/0252413 (Kangas et al.); 2005/0252414 (Craig et al.); and 2005/0256223 (KoIb et al.).
- compositions of the present invention typically include at least 1% by weight, more typically at least 2% by weight, and most typically at least 5% by weight filler, based on the total weight of the composition.
- compositions of the present invention typically include at most 40% by weight, more typically at most 20% by weight, and most typically at most 15% by weight filler, based on the total weight of the composition.
- compositions of the present invention typically include at least 40% by weight, more typically at least 45% by weight, and most typically at least 50% by weight filler, based on the total weight of the composition.
- compositions of the present invention typically include at most 90% by weight, more typically at most 80% by weight, even more typically at most 70% by weight filler, and most typically at most 50% by weight filler, based on the total weight of the composition.
- compositions of the present invention may contain solvents (e.g., alcohols (e.g., propanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone), esters (e.g., ethyl acetate), other nonaqueous solvents (e.g., dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1 -methyl -2 -pyrrolidinone)), or mixtures thereof.
- solvents e.g., alcohols (e.g., propanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone), esters (e.g., ethyl acetate), other nonaqueous solvents (e.g., dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1 -methyl -2 -pyrrolidinone)), or mixtures thereof.
- solvents e.g., alcohols (e
- the compositions are nonaqueous.
- the compositions may optionally contain water.
- the water can be distilled, deionized, or plain tap water. If present, the amount of water should be sufficient to provide adequate handling and mixing properties and/or to permit the transport of ions, particularly in a filler-acid reaction.
- water represents at least about 1 wt-%, and more preferably at least about 5 wt-%, of the total weight of ingredients used to form the hardenable composition.
- water represents no greater than about 75 wt-%, and more preferably no greater than about 50 wt-%, of the total weight of ingredients used to form the hardenable composition.
- compositions of the invention may contain additives such as indicators, dyes (including photobleachable dyes), pigments, inhibitors, accelerators, viscosity modifiers, wetting agents, antioxidants, tartaric acid, chelating agents, buffering agents, stabilizers, diluents, and other similar ingredients that will be apparent to those skilled in the art.
- additives such as indicators, dyes (including photobleachable dyes), pigments, inhibitors, accelerators, viscosity modifiers, wetting agents, antioxidants, tartaric acid, chelating agents, buffering agents, stabilizers, diluents, and other similar ingredients that will be apparent to those skilled in the art.
- Surfactants for example, nonionic surfactants, cationic surfactants, anionic surfactants, and combinations thereof, may optionally be used in the compositions.
- Useful surfactants include non-polymerizable and polymerizable surfactants.
- medicaments or other therapeutic substances can be optionally added to the dental compositions.
- Examples include, but are not limited to, fluoride sources, whitening agents, anticaries agents (e.g., xylitol), remineralizing agents (e.g., calcium phosphate compounds and other calcium sources and phosphate sources), enzymes, breath fresheners, anesthetics, clotting agents, acid neutralizers, chemotherapeutic agents, immune response modifiers, thixotropes, polyols, anti-inflammatory agents, antimicrobial agents, antifungal agents, agents for treating xerostomia, desensitizers, and the like, of the type often used in dental compositions. Combination of any of the above additives may also be employed. The selection and amount of any one such additive can be selected by one of skill in the art to accomplish the desired result without undue experimentation.
- the dental compositions of the present invention can be prepared by combining all the various components using conventional mixing techniques.
- the resulting composition may optionally contain fillers, solvents, water, and other additives as described herein.
- photopolymerizable compositions of the invention are prepared by simply admixing, under "safe light” conditions, the components of the inventive compositions. Suitable inert solvents may be employed if desired when affecting this mixture. Any solvent may be used which does not react appreciably with the components of the inventive compositions. Examples of suitable solvents include acetone, dichloromethane, acetonitrile and lactones. A liquid material to be polymerized may be used as a solvent for another liquid or solid material to be polymerized. Solventless compositions can be prepared by simply dissolving the (optional) iodonium complex salt, sensitizer, and electron donor in the polymerizable resin, with or without the use of mild heating to facilitate dissolution.
- each ingredient in the dental material should be adjusted to provide the desired physical and handling properties before and after polymerization.
- the polymerization rate, polymerization stability, fluidity, compressive strength, tensile strength and durability of the dental material typically are adjusted in part by altering the types and amounts of polymerization initiator(s) and the loading and particle size distribution of filler(s). Such adjustments typically are carried out empirically based on previous experience with dental materials.
- the tooth can optionally be pre-treated with a primer and/or an adhesive by methods known to those skilled in the art.
- compositions can be supplied in a variety of forms including one-part systems and multi-part systems, e.g., two-part powder/liquid, paste/liquid, paste/powder and paste/paste systems. Other forms employing multi-part combinations (i.e., combinations of two or more parts), each of which is in the form of a powder, liquid, gel, or paste are also possible.
- the various components of the composition may be divided up into separate parts in whatever manner is desired; however, in a redox multi-part system, one part typically contains the oxidizing agent and another part typically contains the reducing agent, though it is possible to combine the reducing agent and oxidizing agent in the same part of the system if the components are kept separated, for example, through use of microencapsulation.
- the dental composition is a resin-modified glass ionomer (RMGI)
- the polyacid, acid-reactive filler and water generally would not all be present in the same part, although any two of these may be grouped together in the same part along with any combination of other components.
- the components of the composition can be included in a kit, where the contents of the composition are packaged to allow for storage of the components until they are needed.
- the components of the composition can be mixed and clinically applied using conventional techniques. A curing light is generally required for the initiation of photopolymerizable compositions.
- the compositions may be in the form of composites or restoratives that adhere very well to dentin and/or enamel.
- a primer layer can be used on the tooth tissue on which the hardenable composition is used.
- the invention encompasses a wide variety of dental compositions.
- Exemplary dental materials include dental restoratives (e.g., composites, fillings, sealants, inlays, onlays, crowns, and bridges), orthodontic appliances, and orthodontic adhesives.
- dental materials include direct aesthetic restorative materials (e.g., anterior and posterior restoratives), prostheses, adhesives and primers for oral hard tissues, sealants, veneers, cavity liners, orthodontic bracket adhesives for use with any type of bracket (such as metal, plastic and ceramic), crown and bridge cements, artificial crowns, artificial teeth, dentures, and the like.
- These dental materials are used in the mouth and are disposed adjacent to natural teeth.
- the phrase "disposed adjacent to" as used herein refers to the placing of a dental material in temporary or permanent bonding (e.g., adhesive) or touching (e.g., occlusal or proximal) contact with a natural tooth.
- bisGMA refers to 2,2-bis[4-(2-hydroxy-3- methacryloyloxypropoxy)phenyl]propane
- TEGDMA refers to triethyleneglycol dimethacrylate, obtained from Sartomer Co., Inc., Exton, PA;
- UDMA refers to diurethane dimethacrylate, obtained under the trade designation "ROHAMERE 6661 -0” from Rohm America LLC, Piscataway, NJ;
- BisEMA6 refers to ethoxylated bisphenol A dimethacrylate, obtained from Sartomer Co., Inc., Exton, PA;
- BHT butylated hydroxytoluene
- BZT 2-(2-Hydroxy-5-Methacryloxyethylphenyl)-2H- Benzotriazole obtained from Ciba, Inc., Tarrytown, NY;
- ENMAP refers to ethyl-(N-methyl-N-phenyl)amino propionate, synthesized using known methods, such as those described by Adamson, et al.; JCSOA9; J. Chem. Soc; 1949; spl. 144,152, which is incorporated herein by reference;
- CPQ camphorquinone
- Irgacure 819 refers to a Bis(2,4,6-Trimethylbenzoyl)phenylphosphine oxide obtained from Ciba, Inc., Tarrytown, NY;
- PEG 600 DM refers to Polyethylene Glycol Dimethacrylate, avg MW -600, available from Sartomer Co., Inc., Exton, PA;
- GENIOSIL GF-31 or "GF-31” refers to a 3- methacryloxypropyltrimethoxysilane composition available from Wacker Chemie AG, Kunststoff, Germany. Preparation of Resin A
- a resin was made by mixing together the components in the relative amounts shown in table 1 below (all amounts are weight fractions):
- Filler A was prepared by weighing 105.24 g NALCO 1042 silica sol, adding 3.15 g 70 wt % HNO 3 solution, and adding this to 45.16 g of acid reduced zirconia sol (prepared essentially as described in U.S. Patent No. 7,429,422 (Davidson et al,), filed June 7, 2007). This resulted in an oxide mixture of approximately 73 wt % silica to 27 wt % zirconia on an oxide weight basis. To this mixture was added 100 g of granulated sugar. The resulting sol was poured into a ceramic vessel and fired at 625 C to remove volatile and organic materials.
- the resulting fired material was subsequently ground with a mortar and pestle and screened through a 75 micron nylon mesh to remove large agglomerates.
- the material was then silane treated by mixing together 25.000 g of the resultant ground oxide, 3.270 g GF-31 silane, 27.4 g ethyl acetate, and 0.447 g 30% NH4OH solution. This was allowed to mix for approximately 4 hours before flashing off the ethyl acetate in a pyrex tray, and then heating at 90 C for 30 minutes.
- Filler B was prepared by weighing 45.16 g acid reduced zirconia sol (prepared essentially as described in U.S. Patent No. 7,429,422, (Davidson, et al.), filed June 7, 2007), and to this was added a mixture of 105.65 g NALCO 1042 silica sol and 1.19 g 70 wt% nitric acid solution. This mixture was poured directly into a ceramic firing vessel, and fired at 625 C for 4 hours to remove water and organic volatiles. This resultant oxide was also approximately 73wt% silica to 27 wt % zirconia. The resulting filler was ground with a mortar and pestle, screened through a 75 micron nylon mesh to remove large agglomerates.
- Filler C was prepared with the same ratios of materials as described above for Filler B.
- the filler was heated to 825 C for 8 hours (instead of 625 C) and milled in a ball mill instead of a mortar and pestle and the filler was silane treated by dispersing in 1- methoxy-2-propanol, and heated to 80 C for 3 hours at a pH of 8.75 (NH40H adjusted) with an 11% GF-31 charge to the weight of the filler and the materials was then gap dried.
- a silane treated silica/zirconia filler derived from zirconyl acetate with a ratio of approximately 73 % silica to 27% zirconia was prepared essentially as described in Preparatory Examples A and B of U.S. Patent No. 6,730,156, except that the filler was calcined again after milling at 713 0 C for 11 hours before silanting to remove additional residuals.
- Pastes El, E2, E3, and CE2 showed significant opalescence to the naked eye, appearing orange/yellow on a white background, and blue/white on a black background.
- Pastes CEl did not show opalescent character to the naked eye, appearing yellow on both a black and white background, to the naked eye. All pastes appeared translucent to transparent.
- Samples were prepared by making in a metal ring an optical disc of the composites ( ⁇ 1.3 g each) of linch in diameter, and 1 mm thickness (+/- .02 mm) of the composite discs by pressing discs in a mold curing under mylar film with an XL 3000 dental curing light over the entire surface of the disc in 9 overlapping points for 20 seconds each to insure full cure.
- These discs were taken to the hunter unit, and after calibration for large sample usage (1 inch) and the larger aperature opening, measurements were taken in reflectance mode against a black background. The instrument was recalibrated for transmission measurements, and then readings were taken in transmission mode, and haze measurements were also taken in the transmission mode.
- C a b ((b* re f - b*tr ans ) 2 +(a* re f- a*trans) 2 ) 1/2
- Pastes made with this opalescent silica-zirconia filler (El, E2, and E3) also had the interesting optical effect of having less angular dependence on the transmission of light. This effect, illustrated in FIG. 1, has the potential to give a more vibrant, lifelike restoration when used in a dental restorative.
- the new materials also are able to transmit images more clearly through them when removed further from the object viewed behind them than conventional pastes.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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US13/123,749 US8722759B2 (en) | 2008-10-15 | 2009-10-09 | Fillers and composite materials with zirconia and silica nanoparticles |
RU2011114372/05A RU2472708C2 (en) | 2008-10-15 | 2009-10-09 | Filler and composite materials with zirconium and silica nanoparticles |
BRPI0914426-9A BRPI0914426B1 (en) | 2008-10-15 | 2009-10-09 | METHOD OF MANUFACTURING A LOAD FOR COMPOSITE MATERIAL, HARDENING DENTAL COMPOSITION AND DENTAL RESTORATION MATERIAL |
EP09737304.7A EP2370362B1 (en) | 2008-10-15 | 2009-10-09 | Fillers and composite materials with zirconia and silica nanoparticles |
CN2009801472219A CN102224106A (en) | 2008-10-15 | 2009-10-09 | Fillers and composite materials with zirconia and silica nanoparticles |
JP2011532156A JP5661040B2 (en) | 2008-10-15 | 2009-10-09 | Filler containing zirconia and silica nanoparticles, and composite material |
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US10548808P | 2008-10-15 | 2008-10-15 | |
US61/105,488 | 2008-10-15 |
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PCT/US2009/060104 WO2010045105A1 (en) | 2008-10-15 | 2009-10-09 | Fillers and composite materials with zirconia and silica nanoparticles |
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US (1) | US8722759B2 (en) |
EP (1) | EP2370362B1 (en) |
JP (1) | JP5661040B2 (en) |
CN (1) | CN102224106A (en) |
BR (1) | BRPI0914426B1 (en) |
RU (1) | RU2472708C2 (en) |
WO (1) | WO2010045105A1 (en) |
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WO2011149631A3 (en) * | 2010-05-25 | 2012-11-22 | 3M Innovative Properties Company | Method of surface treating inorganic oxide particles, hardenable dental compositions, surface treated particles, and surface treatment compounds |
WO2013055432A1 (en) * | 2011-10-10 | 2013-04-18 | 3M Innovative Properties Company | Aerogels, calcined and crystalline articles and methods of making the same |
US20130277873A1 (en) * | 2010-11-19 | 2013-10-24 | Michael Sadoun | Method for manufacturing a dental prosthesis |
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Also Published As
Publication number | Publication date |
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BRPI0914426B1 (en) | 2019-10-15 |
EP2370362A1 (en) | 2011-10-05 |
RU2472708C2 (en) | 2013-01-20 |
JP5661040B2 (en) | 2015-01-28 |
BRPI0914426A2 (en) | 2015-10-20 |
US8722759B2 (en) | 2014-05-13 |
US20110196062A1 (en) | 2011-08-11 |
JP2012505823A (en) | 2012-03-08 |
RU2011114372A (en) | 2012-10-20 |
CN102224106A (en) | 2011-10-19 |
EP2370362B1 (en) | 2013-11-27 |
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