Source: https://patents.google.com/patent/EP3243499A1/en
Timestamp: 2018-09-25 08:01:23
Document Index: 518055406

Matched Legal Cases: ['Application No. 60', 'Application No. 0', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

EP3243499A1 - Dental compositions with fluorescent pigment - Google Patents
EP3243499A1
EP3243499A1 EP20170153582 EP17153582A EP3243499A1 EP 3243499 A1 EP3243499 A1 EP 3243499A1 EP 20170153582 EP20170153582 EP 20170153582 EP 17153582 A EP17153582 A EP 17153582A EP 3243499 A1 EP3243499 A1 EP 3243499A1
EP20170153582
The invention features a dental composition containing a fluorescent organic pigment, e.g. a hydroxyl substituted aryl guanamine and/or a fluorescent compound encapsulated in a thermo plastic or thermo set polymer, in an amount that provides the composition with fluorescence resembling that of natural teeth.
The dental industry's growing focus on aesthetic dentistry has led to the development of dental restorative compositions that more closely mimic the appearance of natural teeth. For example, tooth-colored, composite resin materials have been developed that can be used in place of, for example, metal amalgam fillings, to provide more natural looking dental restorations. In recent years, highly aesthetic composite materials, such as 3M ESPE™ FILTEK™ Supreme Plus Universal Restorative (3M Company, St. Paul, MN), have become available with shading systems and opacity options that make it possible for a dentist to create dental restorations so natural looking they are virtually undetectable to the casual observer.
Since human teeth fluoresce when irradiated with ultraviolet (UV) light, dental restorations that fail to exhibit fluorescence similar to that of natural teeth may become more noticeable when viewed under UV radiation or "black light" conditions. For example, dental restorative compositions that use resin systems that do not fluoresce as intensely as natural teeth and/or that contain components, such as color stabilizers, that diminish the fluorescence of the composition, may provide restorations that appear darker than surrounding teeth under UV light. Conversely, dental compositions that contain components with greater fluorescence than that of natural teeth may appear brighter than surrounding teeth under these conditions. Consequently, restorations made with such compositions, even if undetectable under normal visible light or full spectrum lighting conditions, may suffer from reduced aesthetic quality when exposed to UV light. As restorative dentistry has become increasingly focused on aesthetics of restorations, there is an increasing demand for aesthetic fluorescent composites that match natural tooth fluorescence.
As used herein, the phrase "natural tooth fluorescence" means that when viewed under ultraviolet light of 365nm the composition exhibits a fluorescence intensity and color resembling that of a natural tooth. Although the fluorescence of natural teeth varies from subject to subject and the desired closeness of the match of the composition's fluorescence to that of a natural tooth depends on the precise situation and/or aesthetic demands of the patient (e.g., molars and other teeth that are not easily visible may not need to match the natural tooth fluorescence as closely as front teeth). Typically, the compositions of the invention exhibit a fluorescence intensity in the range of about 20 counts per second to about 100 counts per second, more typically from about 30 counts per second to about 90 counts per second, and most typically from about 35 counts per second to about 85 counts per second.
By "non-natural tooth fluorescence" is meant fluorescence that is visibly less intense or more intense than the fluorescence exhibited by natural teeth, or exhibits a significantly different florescence color than that of natural teeth. When used in reference to an electron donor component (e.g. "an electron donor with non-natural tooth fluorescence," etc.), the term means that when the electron donor is compounded with the other components of the composition and the composition is subsequently cured, its fluorescence is visibly different in intensity or wavelength than that of natural teeth. By "non-fluorescent" is meant that when irradiated with UV radiation, the compound, composition, or material exhibits no visible fluorescence or is only weakly fluorescent, i.e. substantially below the fluorescence exhibited by a natural human tooth such that the difference is easily visible.
By "organic fluorescent pigment" is meant a material that (1) is an organic molecule (e.g. polymer) that either encapsulates or is attached to a fluorescent dye or compound or is itself an intrinsically fluorescent molecule and (2) is substantially insoluble in the dental resin system. A dye, by comparison, is substantially soluble in the dental resin.
As used herein, "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.
By "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. Oftentimes a dental composition can be used to bond a dental article to a tooth structure.
By "hardenable dental composition" is meant a dental composition, such as a paste, that can be hardened to form a dental article.
By "dental article" is meant an article that can be adhered (e.g., bonded) to an oral surface (e.g., a tooth structure). Typically, 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).
As used herein, 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.
By "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
By "filler" 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.
By "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. Typically the nanofiller comprises non-pyrogenic nanoparticles or nanoclusters. By "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). Thus, 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.
As used herein "nanoparticles" is synonymous with "nanosized particles," and refers to particles having an average size of at most 200 nanometers. As used herein for a spherical particle, "size" refers to the diameter of the particle. As used herein for a non-spherical particle, "size" refers to the longest dimension of the particle. In certain embodiments, the nanoparticles are comprises of discrete, non-aggregated and non-agglomerated particles.
By "nanocluster" is meant an association of nanoparticles drawn together by relatively weak intermolecular forces that cause them to clump together, i.e. to aggregate. Typically, nanoclusters have an average size of at most 10 micrometers.
As used herein, the term "ethylenically unsaturated compound " is meant to include monomers, oligomers, and polymers having at least one ethylenic unsaturation.
By "polymerization" is meant the forming of a higher weight material from monomer or oligomers. The polymerization reaction also can involve a cross-linking reaction.
The terms "comprises", "comprising" and variations thereof do not have a limiting meaning where these terms appear in the description and claims.
As used herein, "a" or "an" means "at least one" or "one or more" unless otherwise indicated. In addition, the singular forms "a", "an", and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds. As used in this specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.
FIG 1 is a graph showing fluorescence decay data for dental composites subjected to UV exposure.
The invention features polymerizable fluorescent dental compositions that contain an organic fluorescent pigment. It has been found, surprisingly, that the incorporation of fluorescent organic pigments into a dental composition can give greater durability of fluorescence than many fluorescent dyes, even though such pigments typically comprise encapsulated fluorescent dyes in a crosslinked polymer matrix. In addition, certain organic pigments can be added to a dental composite without causing a significant change in the optical characteristic of the material, such as CIELAB (i.e. CIE 1976 L*a*b* color space: a uniform-color space utilizing an Adams-Nickerson cube root formula, suggested in 1974 for adoption by the Commission Internationale de 1'Eclairage or the International Commission on Illumination (CIE) in 1976 for use in the measurement of small color differences" ( The Measurement of Appearance, pg322, R. S. Hunter)) parameters or contrast ratio, and particle size of the pigment does not appear to be a substantial factor in the aesthetics. Pigments with a median particle size of 10 microns do not seem to increase light scattering. As a result, the incorporation of fluorescent organic pigments at very low levels results in acceptably stable and aesthetic fluorescent composites with mechanical properties comparable to controls with no fluorescence. A concentration of fluorescent organic pigment as little as 50 to 20000 ppm range is effective to provide an A3 shaded dental restorative. This is far lower than the concentration needed for inorganic pigments.
The organic fluorescent pigment used in the dental compositions of the invention may be combined with one or more additional fluorescent agents, which may be selected from the group including, but not limited to, other organic fluorescent pigments, inorganic fluorescent pigments, and organic fluorescent dyes. Numerous examples of suitable classes of organic fluorescent dyes may be found in "Handbook of fluorescence spectra of aromatic molecules" by Isadore B. Berlman, 2nd ed., Academic Press, 1971 as well as in US 7,137,818 and US 7,114,951 . Numerous examples of suitable inorganic luminescent pigments may be found in "Inorganic Phosphors" by William Yen and Marvin Weber, CRC Press, 2004. The additional luminescent agent may, if desired, be selected so as not to negatively affect any aesthetic and functional property described herein.
The compositions, especially in photopolymerizable implementations, 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)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, ethoxylated bisphenolA di(meth)acrylate, and trishydroxyethyl-isocyanurate trimethacrylate; (meth)acrylamides (i.e., acrylamides and methacrylamides) such as (meth)acrylamide, methylene bis-(meth)acrylamide, and diacetone (meth)acrylamide; urethane (meth)acrylates; the bis-(meth)acrylates of polyethylene glycols (preferably of molecular weight 200-500), copolymerizable mixtures of acrylated monomers such as those in U.S. Pat. No. 4,652, 274 (Boettcher et al. ), acrylated oligomers such as those of U.S. Pat. No. 4,642,126 (Zador et al. ), and poly(ethylenically unsaturated) carbamoyl isocyanurates such as those disclosed in U.S. Pat. No. 4,648,843 (Mitra ); and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate. Other 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. 4,356,296 (Griffith et al. ), EP-0373 384 (Wagenknecht et al. ), EP-0201 031 (Reiners et al. ), and EP-0201 778 (Reiners et al. ). Mixtures of two or more free radically polymerizable compounds can be used if desired.
In certain embodiments, 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). Various combinations of these hardenable components can be used if desired.
In some embodiments, the polymerizable component may include one or more ethylenically unsaturated compounds with acid functionality. As used herein, 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, α,β-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, caprolactone methacrylate phosphate, citric acid di- or tri-methacrylates, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl-polyphosphonic acid, poly(meth)acrylated polychlorophosphoric acid, poly(meth)acrylated polysulfonate, poly(meth)acrylated polyboric acid, and the like, may be used as components in the hardenable component system. Also monomers, oligomers, and polymers of unsaturated carbonic acids such as (meth)acrylic acids, aromatic (meth)acrylated acids (e.g., methacrylated trimellitic acids), and anhydrides thereof can be used. Certain preferred 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. 4,259,075 (Yamauchi et al. ), 4,499,251 (Omura et al. ), 4,537,940 (Omura et al. ), 4,539,382 (Omura et al. ), 5,530,038 (Yamamoto et al. ), 6,458,868 (Okada et al. ), and European Pat. Application Publication Nos. EP 712,622 (Tokuyama Corp.) and EP 1,051,961 (Kuraray Co., Ltd.).
Compositions of the present invention can also include combinations of ethylenically unsaturated compounds with acid functionality as described, for example, in U.S. Provisional Application Serial No. 60/600,658 (Luchterhandt et al. ), filed on August 11, 2004. The compositions may also include a mixture of ethylenically unsaturated compounds both with and without acid functionality.
Suitable photoinitiators (i.e., photoinitiator systems that include one or more compounds) for polymerizing free radically photopolymerizable compositions 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 1-aryl-2-alkyl-1,2-ethanediones, and cyclic alpha diketones. Suitable electron donor compounds include substituted amines, e.g., ethyl dimethylaminobenzoate. Other 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. 4,298,738 (Lechtken et al. ), 4,324,744 (Lechtken et al. ), 4,385,109 (Lechtken et al. ), 4,710,523 (Lechtken et al. ), and 4,737,593 (Ellrich et al. ), 6,251,963 (Kohler et al. ); and EP Application No. 0 173 567 A2 (Ying ).
In certain embodiments, 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. 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. 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. ).
Typically, 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. Typically, 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 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. For example, through appropriate selection of an encapsulant, the oxidizing and reducing agents can be combined with an acid-functional component and optional filler and kept in a storage-stable state. Likewise, through appropriate selection of a water-insoluble encapsulant, 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 (Mitra et al. ).
Organic fluorescent pigments suitable for use in the invention may be divided into at least three major types. In all cases the fluorescent pigment is distinguished from a dye by being substantially insoluble in the resin system, which typically comprises a free radically polymerizable monomer. The first class of fluorescent pigments is fluorescent compounds that are used in the form of insoluble finely divided powders. Examples of classes of such compounds include, but are not limited to, coumarins, naphthalimides, xanthenes, thioxanthenes, naphtholactams, oxazines, thiazines, oxazoles, benzoxazoles, furans, benzofurans, pyrazolines, stilbenes, distyrylbenzenes, distyrylbiphenyls, benzimidazoles, 1,3,5-triazin-2yl derivatives, aryl benzoguanamines and polycyclic aromatic hydrocarbons. It is known to those skilled in the art that each of the above classes can be derivatized with functional groups such as amides, sulfonates or carboxy groups such that the compound is rendered substantially insoluble in typical free radically polymerizable monomers. The second class of fluorescent pigments includes derivatives of the above classes of fluorescent compounds covalently bonded to a polymer backbone. Additional classes of fluorescent compounds are disclosed in "Handbook of fluorescence spectra of aromatic molecules" by Isadore B. Berlman, 2nd ed., Academic Press, 1971 as well as in US 7,137,818 and US 7,114,951 . Polymer backbones to which the aforesaid classes of fluorescent compounds may be attached are known to those skilled in the art and may include but are not limited to polyacrylates, polyethers, polyurethanes, polyamides and polyesters. Additional examples of condensation and addition polymer backbones may be found in Principles of Polymerization, 4th. ed by George B. Odian, John Wiley & Sons (2004). The third class of fluorescent pigments includes, but is not limited to, the above classes of fluorescent compounds encapsulated in thermoset or thermoplastic polymer matrices. Examples of such polymer matrices include, toluenesulfonamide-melamine-formaldehyde resin matrix, polyamides, polyurethanes, polyesters although other polymer matrices can be anticipated by those skilled in the art. The method of preparing such encapsulated fluorescent pigments may involve polymerization of the matrix in the presence of the fluorescent compound followed by milling to a finely divided powder ( US 2,938,873 , US 3,412,036 , US 3,915,884 , US 3,922,232 , US 3,741,907 ) or by means of suspension polymerization to yield spherical encapsulated fluorescent pigments ( US 3,412,035 ). It is known to those skilled in the art that when polymeric backbones or encapsulants are present that these materials typically will not absorb incident ultraviolet light such that the fluorescence efficiency of the pigments will be significantly diminished.
Also the fluorescent pigments available from DayGlo Corp. (Cleveland, OH), J. Color Chemicals Corp (Hangzhou, China), Organic Dyestuffs Corp. (East Providence, RI), Beaver Luminescers (Newton, MA) are suitable provided that the selected pigment must be able to provide a hardened dental composition that exhibits natural tooth fluorescence. Useful fluorescent pigments also include those commercially known as "invisible fluorescent pigments".
The fluorescent organic pigments are typically present at about 10ppm to about 10,000ppm weight percent, more typically about 20ppm to about 5000ppm weight percent, and most typically about 50ppm to about 2000ppm weight percent, based on the overall composition. An advantage of some embodiments of the invention is that it allows one to add stable fluorescence to formulations regardless of the rest of the formulation, such as the UV stabilizer (e.g. tinuvin 796) concentration.
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-0 238 025 , and U.S. Patent No. 6,306,926 B1 .
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.
Examples of suitable inorganic fillers are naturally occurring or synthetic materials including, but not limited to: quartz (i.e. silica, SiO2); 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. 4,695,251 (Randklev ); and submicron 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). In some embodiments, the silica or nanosilica particles are non-pyrogenic, i.e. comprise non-fumed silica. Examples of suitable organic filler particles include filled or unfilled pulverized olycarbonates, polyepoxides, and the like.
The filler may be acid-reactive, non-acid-reactive, or a combination thereof. Suitable non-acid-reactive filler particles include quartz, submicron silica, nano silica, nano zirconia, and non-vitreous microparticles of the type described in U.S. Pat. No. 4,503,169 (Randklev ). Mixtures of these non-acid-reactive fillers are also contemplated, as well as combination fillers made from organic and inorganic materials. Silane-treated zirconia-silica (Zr-Si) filler is especially useful in certain embodiments. In some implementations of the invention, the filler system may contain a combination of at least one filler comprising heavy metal oxide nanoparticles (e.g., zirconia nanoparticles), and/or at least one filler comprising non-heavy metal oxide particles (e.g. silica nanoparticles), and/or at least filler comprising a heavy metal oxide and a non-heavy metal oxide (e.g. clusters of zirconia and silica nanoparticles).
In some implementations, 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.
Generally, 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, KETAC-MOLAR, and KETAC-FIL PLUS (3M ESPE Dental Products, St. Paul, MN), FUJI II LC and FUJI IX (G-C Dental Industrial Corp., Tokyo, Japan) and CHEMFIL Superior (Dentsply International, York, PA). Mixtures of fillers can be used if desired.
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 (Kolb et al. ).
In some implementations of the invention, the compositions are nonaqueous. In other implementation, 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. In such embodiments, 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. Generally, 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.
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. Typically, 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 iodonium complex salt, sensitizer, and electron donor in the polymerizable resin, with or without the use of mild heating to facilitate dissolution.
The invention encompasses a wide variety of dental compositions, which may be filled or unfilled. Exemplary dental materials include dental restoratives (e.g., composites, fillings, sealants, inlays, onlays, crowns, and bridges), orthodontic appliances, and orthodontic adhesives. Such 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.
2. The composition of item 1, wherein the composition upon hardening has natural tooth fluorescence.
3. The composition of item 1, wherein the fluorescent organic pigment comprises a fluorescent compound encapsulated within or attached to a polymer.
4. The composition of item 3, wherein the fluorescent organic pigment comprises an intrinsically fluorescent organic compound.
5. The composition of any of the preceding items, wherein the fluorescent organic pigment component is present in an amount less than 1 wt-% of the composition.
6. The composition of any of the preceding items, further comprising a polymerizable component.
7. The composition of item 6, wherein the polymerizable component comprises an ethylentically unsaturated compound.
8. The composition of item 7, wherein ethylenically unsaturated compound is a (meth)acrylate.
9. The composition of any of the preceding items, further comprising an initiator system.
10. The composition of item 9, wherein the composition is photo-curable and the initiator system comprises a photoinitiator.
11. The composition of any of the preceding items, further comprising a filler system.
12. The composition of item 11, wherein the filler system comprises silica nanoparticles, zirconia nanoparticles, nanoclusters of silica and zirconia nanoparticles, or a combination thereof.
13. The composition of item 12, wherein the nanoparticles or nanoclusters have been silane treated.
15. The method of item 14, further comprising the step of:
16. The method of item 14 or 15, wherein the resin system comprises an ethylentically unsaturated component.
17. The method of item 16, wherein ethylenically unsaturated component is a (meth)acrylate.
18. The method of any of items 14 to 17, wherein the composition further comprises an initiator system.
19. The method of item 18, wherein the composition is photo-curable and the initiator system comprises a photoinitiator.
20. The method of any of items 14 to 18, wherein the composition further comprises a filler system.
21. The method of item 20, wherein the filler system comprises silica nanoparticles, zirconia nanoparticles, nanoclusters comprising silica and zirconia nanoparticles, or a combination thereof.
22. The method of item 21, wherein the nanoparticles have been silane treated.
23. A dental product made by hardening the composition of any of items 1-13.
"CAMP" refers to 1-(2-methacryloyloxyethyl)-2-(7-methylene-1,5, dithiaoctan-3-yl) phalate, prepared as described in Example 1 of WO/ US2006/122081 ;
"TrisMAP" refers to 2-[4-(2-hydroxy-3-methacryloxypropoxy)phenyl-2-[4-(2-[2-methacryloxyethoxy]phthalyloxy-3-methacryloxypropoxy)phenyl]-propane. Prepared essentially as described in U.S. Provisional Application No. 60/984,785 filed November 2, 2007 (Kalgutkar et al. )
"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;
"TEGDMA" refers to triethyleneglycol dimethacrylate, obtained from Sartomer Co., Inc., Exton, PA;
"BisGMA" refers to 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane;
"BHT" refers to butylated hydroxytoluene;
"SiO2/ZrO2 Filler 1" refers to silane-treated zirconia-silica nanocluster filler prepared essentially as described in U.S. Patent No. 6,730,156 and surface treated as described below;
"SiO2/ZrO2 Filler 2" refers to silane-treated zirconia-silica nanocluster filler prepared essentially as described in U.S. Patent No. 6,730,156 and surface treated as described below;
"SiO2/ZrO2 Filler 3" refers to silane-treated zirconia-silica nanocluster filler prepared essentially as described in U.S. Patent No. 6,730,156
"ZrO2 Filler" refers to a silane-treated nano-sized zirconia prepared essentially as described in Preparatory Example 1A in U.S. Patent Publication No. 2005/0252413 , except that GF31 was used instead of a blend of A-174 and A-1230;
"SiO2 Filler" refers to a silane-treated nano-sized silica having a nominal particle size of approximately 20 nanometers, prepared essentially as described for FILLER F in U.S. Patent Publication No. 2005/0252413 ?
"ENMAP" refers to Ethyl-(N-methyl-N-phenyl)amino propionate prepared by Michael addition of N-methylaniline to ethyl acrylate (J. Chem. Soc., Supplement, p. 144-152 (1949)),63524US002;
"EDMAB" refers to ethyl 4-dimethylaminobenzoate;
"EDMOA" refers to 2-ethyl-9,10-dimethoxyanthracene;
"DPIPF6" refers to diphenyliodonium hexafluorophosphate, obtained from Alfa Aesar, Ward Hill, MA;
"Irgacure 819" refers to a Bis(2,4,6-Trimethylbenzoyl)phenylphosphine oxide obtained from Ciba, Inc., Tarrytown, NY;
"TINUVIN" refers to a polymerizable UV stabilizer obtained under the trade designation TINUVIN R 796 from Ciba Specialty Chemicals, Tarrytown, NY;
"L-88" refers to an organic fluorescent pigment obtained from Beaver Luminescers (Newton, MA);
"QBK58/UF-A2" refers to Y2Si05:Ce obtained from Phosphor Technology (Stevenage, Hertfordshire, England);
"A-594-5" or "A-594" refers to a fluorescent pigment obtained from DayGlo Corp, Cleveland, OH;
"Lumilux White" refers to Lumilux Natural White Z which was obtained from Honeywell Inc., Morristown, NJ;
"Uvitex OB" refers to 2,5-bis(5-tert-butyl-2-benzoxazolyl) thiophene (BBOT), obtained from Ciba Specialty Chemicals (Tarrytown, NY);
"GENIOSIL GF-31" or "GF-31" refers to a 3-methacryloxypropyltrimethoxysilane composition available from Wacker Chemie AG, Munich, Germany;
"Red pigment dispersion" refers to a dispersion containing a red iron III oxide pigment as described in U.S. Provisional Application No. 60/984,785, filed November 2, 2007 (Kalgutkar et al. )
"Yellow pigment dispersion" refers to a dispersion containing a yellow iron III oxide pigment as described in U.S. Provisional Application No. 60/984,785, filed November 2, 2007 (Kalgutkar et al. )
"White pigment dispersion" refers to a dispersion containing a rutile titanium dioxide pigment as described in U.S. Provisional Application No. 60/984,785 filed, November 2, 2007 (Kalgutkar et al. ).
Unless otherwise noted, reagents and solvents were obtained from Sigma-Aldrich Corp., St. Louis, MO. All mixing of the composites was done by mixing the components in a DAC-150FZ SpeedMixer (Flacktec Corp., Landrum SC). Mixing was carried out at progressively higher speeds from 2000 rpm to 2400 rpm for 20 seconds intervals with cooling between mix cycles until no further change in the composite was observed. Camphorquinone, EDMAB and Iodonium hexafluorophosphate were dissolved in the respective resins by rolling the formulation on a roller in a glass bottle until no solids were visible. All composites were filled into syringes and debubbled by applying a load to the plunger for 16 hours at 45°C. The composites were stored and handled under yellow lights.
Disks (3.0 cm x 0.11 cm) used for fluorescence testing and measurement of CIELAB parameters and contrast ratios were prepared by pressing composite pastes (prior to photo-curing) in a stainless steel mold at 10,000 psi for 90 seconds. A Carver lab press (Model 3912, Wabash, IN) fitted with a quartz-tungsten-halogen curing light was used for this purpose. Photocuring was accomplished either by irradiation in the press under 10,000 psi pressure for 120 seconds (Examples E-5 to E-9) or by removing the sample from the press and photocuring using two dental blue light for 20 seconds repeatedly until the entire area of the disk had been exposed at least once (Examples E-1 to E-4 and Comparative Examples CE-1 to CE-5). In all cases this was followed by irradiation using a high intensity pulsed Xenon light source (Kulzer UniXS, Hanau, Germany) for 90 seconds on each side of the disk.
Fluorescence stability was tested over a 4 hour period, using equipment and measuring technique for color stability described in ISO 4049:2000. A Hanau sun test apparatus was used with a medium intensity Xe arc lamp. The disks that were exposed to the fluorescence stability test were immersed in water maintained at 37°C using a circulating bath. Disks were removed from the apparatus and the fluorescence intensity was measured using a Tecan Infinite 200 fluorescence spectrometer (Durham, NC). All samples were irradiated at 365 nm and emission data was collected between 390 and 730 nm at 1 nm intervals. The gain was set manually at 70 and each data point was integrated for 20 microseconds with 10 averages. Care was taken to ensure that the same side of the disk that was exposed to the Xe arc lamp was used for the fluorescence measurement. The data was then analyzed as described in Section 3.3.8 in Gunter Wyszecki and W. S. Stiles, "Color Science. Concepts and Methods. Quantitative Data and Formulae.", 2nd edition, John Wiley (1982). Data for the 1931 CIE 2° standard observer color matching functions were obtained from the CIE publication CIE 15:2004 (ISBN 3901906339). The results of the analysis are reported in terms of CIE 2° Chromaticity Coordinates and correspond to the perceived color of fluorescence. CIELAB parameters and contrast ratio data was obtained on the same disks using a Hunterlab UltraScan VIS spectrophotometer (Reston, VA).
Preparation of Silane Treated (S/T) Y 2 SiO 5 :Ce
Y2SiO5:Ce is an inorganic luminescent pigment obtained from Phosphor Technology (Stevenage, Hertfordshire, England) was silane treated with 11.6 wt % of (3-methacryloxy)propyltrimethoxysilane (Genosil GF31) as follow. A slurry of 0.8010 gm of Y2SiO5:Ce was prepared in 10.0242 gm of 1:1 de-ionized water : 1-methoxy-2-propanol solvent with stirring. The pH was adjusted to 2.65 using a few drops of 10%wt trifluoroacetic acid. GF-31 (0.0932 gm) was added all at once and the reaction was run by magnetically stirring the round bottom reaction vessel with a condenser to prevent solvent loss for 5.25 hours at 70°C. The solvent was then stripped off using a rotvap (80°C, vacuum) over 52 minutes to yield S/T Y2SiO5:Ce as an off-white powder. The powder was ground up using a mortar and pestle and used without further processing.
Slurry of silica-zirconia nanoclusters (as described in US 6,572,693 ) was prepared in a 1:1 mixture of de-ionized water and 1-methoxy-2-propanol by magnetic mixing. The pH was adjusted to 3.00 using a few drops of 10%wt trifluoracetic acid. This slurry was silane treated with 17.98 gm of (3-methacryloxy)propyltrimethoxysilane (Genosil GF31) which was added all at once. The reaction was run overnight by rolling the sealed vial at room temperature. The next morning, the slurry was gap dried. The gap drier had a hot plate set point of 290°F, actual entrance of 263°F, exit of 255°F, hot to cold plate gap of approximately 2 inches, coating of 0.015 inches and a line speed of approximately 3 feet per minutes. The powder was passed through a 75 m sieve. No further processing was done prior to use.
The filler was made by preparing a mixture of 5.47g of Part A (described below) with 7.93g of Part B (described below).
Part A was prepared as follows. 31.3590 gm of (3-methacryloxy)propyltrimethoxysilane (Genosil GF31, 11-0021-2849-1) was added to a round bottom flask, next 330.3 gm ethyl acetate and 299.6 gm of silica-zirconia ( US 6,572,693 ) were added to the magnetically mixing flask. Next, 7.21 gm of ammonium hydroxide (28/30%) was added. The reaction was run overnight by magnetically stirring the sealed vial at room temperature. The next day the solvent was stripped off in a rotovap (35°C / vacuum) until most of the solvent was removed, then the bath was turned to 90°C until the powder was dry by visual inspection. This process took 35 minutes. Next the powder was placed in an 85°C oven for 2 hours. The powder was passed through a 75 m sieve. No further processing was done prior to use.
Part B was prepared as follows. 38.2841 gm of (3-methacryloxy)propyltrimethoxysilane (Genosil GF31, 11-0021-2849-1) was added to a round bottom flask, next 327.5 gm ethyl acetate and 298 gm of silica-zirconia ( US 6,572,693 ) were added to the magnetically mixing flask. Next, 7.21 gm of ammonium hydroxide (28/30%) was added. The reaction was run overnight by magnetically stirring the sealed vial at room temperature. The next day the solvent was stripped off in a rotovap (35°C / vacuum) until the solvent was removed. This process took 47 minutes. Next the powder was placed in an 85°C oven for 2 hours. The powder was passed through a 75 m sieve. No further processing was done prior to use.
The composites set forth in Table 1 were prepared by the general technique described above (all components listed by weight-percent) in order to compare CIELAB parameters and contrast ratios (measure of opacity) of compositions containing an organic fluorescent pigment, L-88, (examples E-1 and E-2) with those containing an inorganic luminescent pigment, QBK58/UF-A2 (examples CE-1, CE-2, and CE-3) or no fluorescent pigment (examples CE-4 and CE-5). L-88 is an organic fluorescent pigment that is a hydroxyl substituted aryl guanamine. QBK58/UF-A2 is an inorganic luminescent pigment material prepared from Y2SiO5 with Cerium doping. Table 1: Paste formulations for examples E-1 and E-2 and comparative examples CE-1 to CE-5 (amounts provided in wt-%).
The CIELAB parameters and contrast ratios for the above formulations were measured using the test protocol set forth above. The results are given in Table 2 (for pastes containing inorganic fluorescent pigment) and Table 3 (for pastes containing organic fluorescent pigment). Table 2: CIELAB parameters and contrast ratio for pastes containing Y2SiO5:C and control without pigment.
CE-4 (control) 0.00 86.58 -2.64 12.05 33.72
CE-1 0.15 86.46 -2.47 13.96 43.19
CE-2 0.20 86.96 -2.42 13.56 44.29
CE-3 0.25 86.81 -2.28 14.03 46.58
Table 3: CIELAB parameters and contrast ratio for pastes containing L-88 and control without pigment.
CE-5 (control) 0.00 85.70 -2.78 13.59 37.64
E-1 0.10 86.07 -3.17 12.94 36.03
E-2 0.15 86.36 -3.46 13.14 36.73
A timed exposure study for dental composites containing organic dyes and pigments was conducted. Pastes having the formulations set forth in Table 4 were prepared by the general technique described above. These formulations combine L-88, obtained from Beaver Luminescers (Newton, MA) with either another fluorescent pigment, A-594-5, obtained from DayGlo Corporation (Cleveland, OH), or with an organic fluorescent dye, 2,5-bis(5-tert-butyl-2-benzoxazolyl) thiophene (BBOT), obtained under the trade name Uvitex OB from Ciba Specialty Chemicals (Tarrytown, NY). Samples of each formulation were exposed to UV radiation and the change in fluorescence was measure over time. The Fluoresence decay data was then obtained are shown in Table 5. Table 4: Paste formulations for examples E-3 and E-4 (wt-%).
Table 5: Fluorescence decay data for dental composites containing organic fluorescent pigments or dyes exposed to UV radiation.
Time (Minutes) E-3 E-4
cps norm cps norm
Pastes having the formulations set forth in Table 6 were prepared by the general technique described above. These pastes contained combinations of organic fluorescent pigments L-88 and A-594-5 in varying ratios to modulate the perceived color of fluorescence. Table 6: Paste formulations for examples E-5 to E-9
BisGMA 5.27 % 5.27 % 5.27 % 5.28 % 5.28 %
TEGDMA 1.20 % 1.20 % 1.20 % 1.20 % 1.20 %
UDMA 7.38 % 7.38 % 7.39 % 7.39 % 7.39 %
BisEMA6 7.38 % 7.38 % 7.39 % 7.39 % 7.39 %
DPIPF6 0.11 % 0.11 % 0.11 % 0.11 % 0.11 %
CPQ 0.04 % 0.04 % 0.04 % 0.04 % 0.04 %
EDMAB 0.22 % 0.22 % 0.22 % 0.22 % 0.22 %
BHT 0.03 % 0.03 % 0.03 % 0.03 % 0.03 %
TINUVIN R-796 0.33 % 0.33 % 0.33 % 0.33 % 0.33 %
SiO2 FILLER 7.40 % 7.40 % 7.40 % 7.40 % 7.41 %
SiO2/ZrO2 FILLER 3 70.45 % 70.48 % 70.51 % 70.53 % 70.55 %
Table 7. Chromaticity Co-ordinates for dental composites containing A-594-5 and L-88.
Formulation A-594-5 (ppm) L-88 (ppm) x y Fluorescence Counts
A hardenable dental composition comprising a fluorescent organic pigment, wherein the fluorescent organic pigment comprises an aryl benzoguanamine.
The composition of claim 1, wherein the composition contains from 20 ppm to 5000 ppm by weight of the fluorescent organic pigment.
The composition of claim 1, wherein the fluorescent organic pigment comprises a fluorescent compound encapsulated within or attached to a polymer.
The composition of claim 1 or 3, wherein the fluorescent organic pigment is present in an amount of less than 1 wt-% of the composition.
The composition of any of the preceding claims, further comprising a polymerizable component.
The composition of claim 5, wherein the polymerizable component comprises an ethylenically unsaturated compound.
The composition of claim 6, wherein ethylenically unsaturated compound is a (meth)acrylate.
The composition of any of the preceding claims, further comprising an initiator system.
The composition of claim 8, wherein the composition is photo-curable and the initiator system comprises a photoinitiator.
The composition of any of the preceding claims, further comprising a filler system.
The composition of claim 10, wherein the filler system comprises silica nanoparticles, zirconia nanoparticles, nanoclusters of silica and zirconia nanoparticles, or a combination thereof.
The composition of claim 11, wherein the nanoparticles or nanoclusters have been silane treated.
A dental product obtainable by hardening the composition of any of claims 1 to 12.
The dental product of claim 13, wherein the dental product is a dental mill blank.
EP20170153582 2008-10-15 2009-10-09 Dental compositions with fluorescent pigment Pending EP3243499A1 (en)
EP20090744256 EP2344107B1 (en) 2008-10-15 2009-10-09 Dental compositions with fluorescent pigment
EP20090744256 Division EP2344107B1 (en) 2008-10-15 2009-10-09 Dental compositions with fluorescent pigment
EP3243499A1 true true EP3243499A1 (en) 2017-11-15
EP20170153582 Pending EP3243499A1 (en) 2008-10-15 2009-10-09 Dental compositions with fluorescent pigment
EP20090744256 Active EP2344107B1 (en) 2008-10-15 2009-10-09 Dental compositions with fluorescent pigment
CN102973416B (en) * 2012-12-07 2014-07-23 东华大学 Preparation method of dental restoring resin taking silicon dioxide and cluster of silicon dioxide as stuffing
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US20110200971A1 (en) 2011-08-18 application
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