Acid-reactive dental fillers, compositions and methods

Acid-reactive fillers have been widely used in dental compositions. Acid-reactive fillers include, for example, metal oxides, metal salts, and glass. An example of acid-reactive glass is fluoroaluminosilicate (FAS) glass, a known fluoride-releasing material. FAS glass particles are typically prepared by the melting method, but the melting method effectively limits the particle size that can be used, typically with an average particle size of at least 0.5 micrometers.

In applications where the acid-reactive filler is dispersed in a curable resin to form a dental composition (eg, dental paste), the reactivity of the acid-reactive filler in the composition is generally such that the acid-reactive filler can be used. Limited by surface area. Therefore, high filling amounts (eg, greater than 50% by weight) of acid-reactive fillers are often used to obtain compositions with the desired level of reactivity. However, high filling amounts of acid-reactive fillers may limit the flexibility of mixing additional fillers (eg, non-acid-reactive fillers) into the composition.

Therefore, there is still a need for acid-reactive dental fillers with improved properties (including, for example, larger surface areas).

<patcit num="1"><text>U.S. Pat. No. 4,209,434</text></patcit><patcit num="2"><text>U.S. Pat. No. 4,872,936</text></patcit><patcit num="3"><text>EP323 120 B1 specification</text></patcit><patcit num="4"><text>U.S. Pat. No. 5,130,347</text></patcit><patcit num="5"><text>U.S. Patent Application No. 10 / 729,497</text></patcit><patcit num="6"><text>U.S. Pat. No. 4,259,075</text></patcit><patcit num="7"><text>U.S. Pat. No. 4,499,251</text></patcit><patcit num="8"><text>U.S. Pat. No. 4,537,940</text></patcit><patcit num="9"><text>U.S. Pat. No. 4,539,382</text></patcit><patcit num="10"><text>U.S. Pat. No. 5,530,038</text></patcit><patcit num="11"><text>U.S. Pat. No. 6,458,868</text></patcit><patcit num="12"><text>European Patent Application Publication EP712,622</text></patcit><patcit num="13"><text>EP1,051,961 specification</text></patcit><patcit num="14"><text>U.S. Pat. No. 4,652,274</text></patcit><patcit num="15"><text>U.S. Pat. No. 4,642,126</text></patcit><patcit num="16"><text>International Publication No. 00/38619 Pamphlet</text></patcit><patcit num="17"><text>International Publication No. 01/92271 Pamphlet</text></patcit><patcit num="18"><text>International Publication No. 01/07444 Pamphlet</text></patcit><patcit num="19"><text>International Publication No. 00/42092 Pamphlet</text></patcit><patcit num="20"><text>U.S. Pat. No. 5,076,844</text></patcit><patcit num="21"><text>U.S. Pat. No. 4,356,296</text></patcit><patcit num="22"><text>EP-0 373 No. 384</text></patcit><patcit num="23"><text>EP-0 201 03 No. 1</text></patcit><patcit num="24"><text>EP-0 201 778</text></patcit><patcit num="25"><text>U.S. Pat. No. 5,545,676</text></patcit><patcit num="26"><text>U.S. Patent Application Publication No. 2003/0166737</text></patcit><patcit num="27"><text>U.S. Pat. No. 4,298,738</text></patcit><patcit num="28"><text>U.S. Pat. No. 4,324,744</text></patcit><patcit num="29"><text>U.S. Pat. No. 4,385,109</text></patcit><patcit num="30"><text>U.S. Pat. No. 4,710,523</text></patcit><patcit num="31"><text>U.S. Pat. No. 4,737,593</text></patcit><patcit num="32"><text>U.S. Pat. No. 6,251,963</text></patcit><patcit num="33"><text>European Patent Application No. 0 173 567 A2</text></patcit><patcit num="34"><text>U.S. Pat. No. 4,772,530</text></patcit><patcit num="35"><text>U.S. Pat. No. 4,954,414</text></patcit><patcit num="36"><text>U.S. Pat. No. 4,874,450</text></patcit><patcit num="37"><text>U.S. Pat. No. 5,055,372</text></patcit><patcit num="38"><text>U.S. Pat. No. 5,057,393</text></patcit><patcit num="39"><text>U.S. Patent Application Publication 2003/0166740</text></patcit><patcit num="40"><text>U.S. Patent Application Publication 2003/0195273</text></patcit><patcit num="41"><text>U.S. Pat. No. 5,501,727</text></patcit><patcit num="42"><text>U.S. Pat. No. 5,154,762</text></patcit><patcit num="43"><text>U.S. Pat. No. 4,695,251</text></patcit><patcit num="44"><text>U.S. Pat. No. 4,503,169</text></patcit><patcit num="45"><text>U.S. Pat. No. 6,387,981</text></patcit><patcit num="46"><text>U.S. Pat. No. 6,572,693</text></patcit><patcit num="47"><text>International Publication No. 01/30305 Pamphlet</text></patcit><patcit num="48"><text>International Publication No. 01/30306 Pamphlet</text></patcit><patcit num="49"><text>International Publication No. 01/30307 Pamphlet</text></patcit><patcit num="50"><text>International Publication No. 03/063804 Pamphlet</text></patcit><patcit num="51"><text>U.S. Pat. No. 4,871,786</text></patcit><patcit num="52"><text>U.S. Pat. No. 5,925,715</text></patcit><patcit num="53"><text>U.S. Pat. No. 5,037,579</text></patcit><patcit num="54"><text>U.S. Pat. No. 5,980,697</text></patcit><patcit num="55"><text>U.S. Pat. No. 5,694,701</text></patcit>

<p> In one aspect, the present invention provides a composition that is a dental filler, as well as methods of making and using such dental fillers. In one embodiment, the dental filler is acid-reactive, non-molten, and comprises an oxyfluoride material containing trivalent metals, oxygen, fluorine, and alkaline earth metals. Preferably, the trivalent metal includes aluminum and / or lantern, and in a more preferred embodiment, the trivalent metal is aluminum. In some embodiments, the oxyfluoride material optionally comprises silicon and / or heavy metals. Preferably at least a portion of the oxyfluoride is nanostructured.</p><p> In another embodiment, the dental filler is acid reactive and comprises an oxyfluoride material containing trivalent metals, oxygen, fluorine, and alkaline earth metals, provided that the oxyfluoride material is silicon. Based on the total number of moles of trivalent metals, alkaline earth metals and any additional cations, the condition is that silicon is contained in an amount of 25 mol% or less, preferably 20 mol% or less.</p><p> In another aspect, the invention provides a dental composition, as well as a method of making and using the dental composition, wherein the dental composition is the dental filler and curable resin of the present invention. For example, polymerizable ethylenically unsaturated compounds and / or acids). The dental composition may be a single-part dental composition or a multi-part dental composition. Such dental compositions can include additional acid-reactive or non-acid-reactive fillers (including, for example, nanofillers) in addition to the dental fillers of the present invention. The dental composition of the present invention can be cured to produce a dental article comprising, for example, a crown, a filler, a mill blank, an orthodontic appliance, and a prosthesis.</p><p> Preferably, by mixing the acid-reactive filler of the present invention in the resin, for example, strength, smoothness, smoothness retention, fluoride release, abrasion resistance, aesthetics, and X-ray impermeableness can be obtained. Dental compositions (eg, dental restorations) can be prepared that exhibit an improvement in one or more properties, including.</p><p>Definition As used herein, "non-melted" material means that the material was not formed from the molten state. Non-molten materials can be formed, for example, by methods involving chemical synthesis, precipitation, and combinations thereof.</p><p> As used herein, a "dental filler" is a particulate material suitable for use in the oral environment. The average particle size of dental fillers is generally 100 micrometers or less.</p><p> As used herein, the term "paste" refers to a soft, viscous mass of solid dispersed in a liquid.</p><p> As used herein, the term "non-melted" refers to materials that have not been prepared by the melting method.</p><p> As used herein, an "acid-reactive" dental filler is a filler that chemically reacts in the presence of acidic constituents.</p><p> As used herein, "alkaline earth metal" is an element selected from the group consisting of Be, Mg, Ca, Sr, and Ba.</p><p> As used herein, oxyfluoride is a material in which an oxygen atom and a fluorine atom are bonded to the same atom (eg, aluminum in aluminum oxyfluoride). Generally, at least 50% of fluorine atoms are attached to atoms with oxygen atoms in the oxyfluoride material.</p><p> As used herein, "nanostructured" material refers to a material in the form of at least one dimension having an average of 200 nanometers or less (eg, nanosized particles). Thus, nanostructured materials are, for example, nanoparticles defined below; nanoparticles aggregates; materials coated on the particles with an average coating thickness of 200 nanometers or less; particle coagulation. Materials coated on aggregates with an average coating thickness of 200 nanometers or less; materials impregnated in porous structures with an average pore size of 200 nanometers or less; and combinations thereof. Refers to the material. Examples of the porous structure include porous particles, porous particle agglomerates, porous coatings, and combinations thereof.</p><p> As used herein, "nanoparticles" are used synonymously with "nanosized particles" to refer to particles with an average size of 200 nanometers or less. When used herein for spherical particles, "size" refers to the diameter of the particles. When used herein for non-spherical particles, "size" refers to the longest dimension of the particles.</p><p> As used herein, "agglomerated" usually refers to a weak bond of primary particles held together by charge or polarity. The aggregated particles can typically be crushed into smaller entities, for example, by the shear forces they receive as they disperse in the liquid.</p><p> In general, "aggregated" and "aggregates" represent strong bonds of primary particles that are often bound together by, for example, residual chemistry, covalent or ionic chemical bonds. Further disruption of the agglomerates into smaller entities is very difficult to achieve. Typically, the agglomerated particles are not crushed into smaller entities, for example by the shearing force that the agglomerated particles receive when they disperse in a liquid.</p><p> As used herein, "aggregated silica" refers to the bonding of primary silica particles that are often combined together, for example, by residual chemistry, covalent chemical bonding, or ionic chemical bonding. Complete crushing of agglomerated silica into smaller entities can be difficult to achieve, but limited or incomplete crushing can, for example, apply the shear forces that agglomerated silica receives as it disperses in a liquid. It may be observed under the conditions including. As used herein, "silica cluster" or "silica-zirconia cluster" refers to aggregated silica or silica-zirconia in which a significant amount of aggregated primary silica or zirconia particles are loosely bound. "Loose bond" refers to the nature of the bond between particles present in a silica cluster or a silica-zirconia cluster. Typically, the particles are bound by a relatively weak intermolecular force that agglomerates the particles. Preferably, when dispersed in a curable resin for dental materials, many of the clusters remain intact even if some clusters are destroyed into smaller structures during the dispersion process. Thus, silica clusters and silica zirconia clusters are typically referred to as "loosely bonded aggregated silica" or "loosely bonded aggregated silica-zirconia". The clusters disclosed in this application are preferably approximately spherical and preferably not fully compacted. As used herein, the term "fully densified" refers to the BET nitrogen method (N from a gas in contact with a sample).₂Particles close to theoretical density with virtually no open porosity detectable by standard analytical methods such as (based on molecular adsorption) will be described. By such measurements, the surface area per unit weight of the sample (eg, m)²Data on / g) are available, which can be compared to the surface area per unit weight of a complete mass of microspheres of the same size to detect open porosity. As used herein, the term "not fully densified" describes particles that are smaller than theoretical density and therefore have porosity. For porous particles with open porosity (eg, clusters of primary particles), the measured surface area is greater than the surface area calculated for solid particles of the same size. Such measurements may be made on a Quantasorb device manufactured by Quantachrome Corporation in Syosset, NY. Density measurements may be made using air, helium or water specific gravity bottles.</p><p> As used herein, "particle size" refers to the longest dimension (eg, diameter) of a particle.</p><p> The silica clusters disclosed in this application may be manufactured by a process involving drying and optionally heat treatment and / or calcining. The ratio of the surface area after heat treatment to the surface area before heat treatment is preferably greater than 50%, more preferably greater than 80%. Preferably, the change in surface area after heating is 10% or less, more preferably 5% or less.</p><p> As used herein, a "storage stable" composition refers to a composition having a shelf life of at least 1 year, preferably at least 2 years, at room temperature. The shelf life of the adhesive composition is typically determined by determining whether the aged composition provides acceptable binding strength when the aged composition is attached to the surface of the dental structure. Be measured.</p>

The present invention provides a dental filler containing an acid-reactive oxyfluoride material, and a method for producing and using the dental filler. As used herein, oxyfluoride is a material in which an oxygen atom and a fluorine atom are bonded to the same atom (eg, aluminum in aluminum oxyfluoride). In some embodiments, at least 50% of the fluorine atoms, in some cases at least 70%, and in other embodiments at least 80% have oxygen atoms in the oxyfluoride material, or oxygen in the oxyfluoride material. It is bonded or coordinated to an atom that is coordinated to an atom. The one-dosage dental composition and the multi-dosage form dental composition can contain a curable resin and / or a curable polyacid in addition to the dental filler of the present invention. Such dental compositions include, for example, dental adhesives, artificial crowns, anterior fillings, posterior fillings. It is useful as fillings), casting materials, cavity liners, cements, coating compositions, mill blanks, orthodontic appliances, orthodontic adhesives, restorations, prostheses, and sealants.

Dental filler containing acid-reactive oxyfluoride material The present invention provides a composition comprising an acid-reactive oxyfluoride material which is a dental filler. Oxyfluoride materials include trivalent metals, oxygen, fluorine, and alkaline earth metals. Preferably, the trivalent metal is aluminum, lantern or a combination thereof. More preferably, the trivalent metal is aluminum. Preferably, the alkaline earth metal is strontium, calcium, barium, or a combination thereof. In some embodiments of the invention, the oxyfluoride material may further contain silicon and / or heavy metals (eg, zirconium, lanthanum, niobium, yttrium, or tantalum), more specifically its oxidation. It may contain substances, fluorides and / or oxyfluorides. In some embodiments, the oxyfluoride material is 25 mol% or less of silicon relative to the total number of moles of silicon, trivalent metal, alkaline earth metal and any additional cations in the oxyfluoride material. , Preferably containing 20 mol% or less. In other embodiments, the oxyfluoride material is non-molten.

The molar ratio of trivalent metals to alkaline earth metals in oxyfluoride materials includes chemical and structural properties (eg, acid reactivity and efficiency in the curing reaction of acid-reactive fillers with polyacids). Can affect. For example, increasing the alkaline earth metal content can result in improved acid reactivity. However, in some embodiments, a trivalent metal content sufficient to promote the formation of a relatively homogeneous oxyfluoride structure is preferred. Increasing the content of trivalent metals can improve the efficiency of oxyfluoride materials in curing polyacids, thereby allowing those skilled in the art to use conventional FAS fillers in certain dental compositions. Can be eliminated or reduced. In some embodiments, the molar ratio of trivalent metal to alkaline earth metal in the oxyfluoride material is at least 50:50 and in other embodiments at least 70:30. In some embodiments, the molar ratio of trivalent metal to alkaline earth metal in the oxyfluoride material is 95: 5 or less, and in other embodiments 90: 10 or less.

The ratio of oxygen to fluorine in the oxyfluoride material can affect the physical properties and reactivity of the filler. Typically, increasing the fluoride content of the oxyfluoride material results in a decrease in the surface area of the precipitated filler, an increase in the primary particle size and a decrease in acid reactivity. However, a fluoride content sufficient to provide fluoride release from a given dental composition is desirable, and typically some fluoride is required for optimum reactivity. In some embodiments, the molar ratio of oxygen to fluorine in the oxyfluoride material is at least 50:50, in some cases at least 60:40, and in other embodiments at least 65:35. In some embodiments, the molar ratio of oxygen to fluorine in the oxyfluoride material is 95: 5 or less, in some cases 90:10 or less, and in other embodiments 85:15 or less.

In some embodiments of the invention, at least a portion of the oxyfluoride material is nanostructured. Such nanostructured materials include, for example, nanoparticles, coatings on particles, coatings on particle aggregates, impregnations in porous structures, and oxyfluoride materials in the form of combinations thereof. .. The oxyfluoride material is nanostructured, preferably at least 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight.

In some embodiments of the invention, at least a portion of the nanostructured oxyfluoride material can be in the form of aggregated or non-aggregated nanoparticles. In such embodiments, the oxyfluoride material is preferably in the form of nanoparticles, preferably at least 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight. Preferably, the average size of the nanoparticles is 100 nanometers or less, more preferably 50 nm or less, even more preferably 20 nm or less.

In embodiments where the oxyfluoride material is in the form of nanoparticles, the surface area of the oxyfluoride material is preferably at least 10 square meters (m) per gram.²/ g), more preferably at least 25m²/ g, most preferably at least 50m²/ g.

In some embodiments of the invention, the nanostructured oxyfluoride material can be in the form of a coating on particles (eg, nanoparticles). Suitable particles include, for example, metal oxide particles (eg, silica, zirconia, alumina, titania, yttrium oxide, lanthanum oxide, and composite metal oxides including, for example, zirconate or perovskite titanate), glass. Particles (eg, dental glass), non-oxide particles (eg, colloidal metal fluorides such as yttrium fluoride), and combinations thereof.

Coatings can be advantageously formed on conventional size filler particles, nanoparticles and aggregates. The average size of suitable conventional particles is typically at least 0.5 micrometers, often at least 1 micrometer. The average size of suitable conventional particles is typically 50 micrometers or less, often 10 micrometers or less.

The average coating thickness is typically at least 20 nanometers and is often at least 50 nanometers. The average coating thickness is typically 1000 nanometers or less, often 500 nanometers or less.

In some embodiments of the invention, the nanostructured oxyfluoride material can be in the form of a coating on agglomerates of particles (eg, agglomerates of nanoparticles). Suitable particles include, for example, metal oxide particles (eg, silica, zirconia, alumina, titania, yttrium oxide, lanthanum oxide, and composite metal oxides including, for example, zirconate or perovskite titanate), glass. Particles (eg, dental glass), non-oxide particles (eg, colloidal metal fluorides such as yttrium fluoride), and combinations thereof.

Suitable aggregates may be similar in size to conventional fillers (eg, at least 1 micrometer in some embodiments and 10 micrometers or less in other embodiments). The size of useful aggregates of particles smaller than conventional fillers (eg, nanofillers) is typically at least 50 nanometers in some embodiments and 1 micrometer or less in other embodiments. The average coating thickness is typically at least 20 nanometers in some embodiments and often less than half the aggregate size in other embodiments.

In some embodiments of the invention, the nanostructured oxyfluoride material is in the form of an impregnated material in a porous structure (eg, porous particles, porous particle agglomerates, porous coatings, or these. Combination). In embodiments where the porous structure comprises porous particles, the porous particles include, for example, metal oxide particles (eg, silica, zirconia, alumina, titania, yttrium oxide, lanthanum oxide, and, for example, zirconate. Alternatively, complex metal oxides containing perovskite titanate), glass particles (eg, dental glass), non-oxide particles (eg, colloidal metal fluorides such as yttrium fluoride), and combinations thereof. .. In embodiments where the porous structure comprises a porous particle agglomerate, the particles are preferably nanoparticles. Preferably, the average pore size is at least 20 nanometers, more preferably at least 50 nanometers. Preferably, the average pore size is 10 micrometers or less, more preferably 1000 nanometers or less.

The dental filler of the present invention can be provided by combining particles and a coating. For example, a porous coating can be formed on the conventional filler particles and impregnated with the oxyfluoride material of the present invention. Examples of such a structure include dental glass having a colloidal silica coating.

The dental filler of the present invention contains an acid-reactive oxyfluoride material. Preferably, the acid-reactive oxyfluoride material can react with acidic materials (eg, organic acids, inorganic acids, monomeric acids, oligomeric acids, and polymeric acids), preferably the polyacids described herein. .. Typically, the dental fillers of the present invention have a surface that is significantly corroded or exposed to various acids used in dental compositions such as poly (meth) acrylic acid or phosphonic acid. Dissolve. Corroded or dissolved fillers release fluoride ions into the ambient liquid or matrix. Multivalent cations that are useful for curing ionomers are also released. Typically, when an acid-reactive fluoride material comes into contact with an acid commonly used in dental compositions, significant surface corrosion or dissolution occurs at or near body temperature.

Preparation of dental filler The present invention provides a method for preparing a dental filler containing an acid-reactive oxyfluoride material containing trivalent metals, oxygen, fluorine, and alkaline earth metals.

In one embodiment, the method comprises combining a first liquid composition and a second liquid composition, separating (eg, filtering) the oxyfluoride material from the combined liquid. The first liquid composition comprises a source of trivalent metals and a source of alkaline earth metals. The second liquid composition comprises a source of fluorine and optionally a source of silicon.

Preferably, the trivalent metal is aluminum, lantern or a combination thereof. More preferably, the trivalent metal is aluminum. Preferably, at least one of the liquid compositions further comprises a source of hydroxide as a source of oxygen.

Optionally, at least one of the first liquid composition or the second liquid composition may contain water. Typically, at least one of the liquid compositions is an aqueous composition having a pH greater than 7, and in some cases greater than 9.

The first liquid composition comprises a source of trivalent metal. Sources of trivalent metals include, for example, trivalent metal salts and alkoxides. For example, suitable salts include lanthanum nitrate and its basic salt or oxy salt, lanthanum carboxylate and its basic salt or oxy salt, lanthanum halide and its basic salt or oxy salt, aluminum nitrate and its basic salt. Alternatively, examples thereof include oxy salts, aluminum carboxylates and their basic salts or oxy salts, aluminum halides and their basic salts or oxy salts, and combinations thereof. Suitable alkoxides include, for example, lanthanum isopropoxide, lanthanum sec-butoxide, aluminum isopropoxide, aluminum sec-butoxide, and combinations thereof.

The concentration of trivalent metal salts should be low enough to facilitate complete dissolution. Dilute solutions may be useful to promote fine precipitates. In many embodiments, the volume of the anion solution is a significant portion of the total reaction volume. Typically, the concentration of the trivalent metal source in the first liquid composition is at least 0.1 molar, or less than 2.5 molar in other embodiments.

The first liquid composition also includes a source of alkaline earth metals. Suitable sources of alkaline earth metals include, for example, strontium nitrate, strontium carboxylate, strontium nitrate, calcium nitrate, calcium carboxylate, calcium halide and combinations thereof. Typically, the concentration of the alkaline earth metal source in the first liquid composition is at least 0.1 molar, and in other embodiments 2.5 molar or less.

The molar ratio of trivalent to divalent cations in the reaction product is typically about the same as in the combined cation solution prior to precipitation. In many embodiments, the preferred ratio in solution is the same as the preferred ratio in filler.

The second liquid composition comprises a source of fluorine. Suitable sources of fluorine include, for example, ammonium fluoride, ammonium hydrogen difluoride, hexafluorosilicic acid and salts thereof, and combinations thereof. Dilute solutions tend to promote the precipitation of fine particles, while concentrated solutions can facilitate the separation and recovery of precipitated fillers. Typically, the fluorine concentration is at least 0.1 mol, and in some embodiments no more than 5 mol per liter.

Optionally, at least one of the first liquid composition or the second liquid composition can include a source of hydroxide as a source of oxygen. Suitable hydroxide sources include, for example, ammonium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof.

The amount of the second liquid composition (ie, the fluorine-containing liquid) is the amount that gives the desired fluoride content of the filler. When both fluoride and hydroxide are present in the second liquid, they are typically stoichiometrically 2-3 times higher (eg, fluoride and hydroxide per mole of trivalent aluminum). 9 mol of the combination is 3 times the stoichiometric amount) to ensure complete reaction with the cations in the first liquid composition and its precipitation. The fluorine content in the filler is determined by the F: OH ratio, not just the total amount of F in the second liquid. The F: O ratio in the filler is not necessarily equal to the F: OH ratio in the solution and depends on the reaction chemistry of the particular cation solution. One of ordinary skill in the art can readily determine the ratio in solution required to obtain the desired fluorine content, according to the guidelines of the examples described herein.

Optionally, the second liquid composition comprises a source of silicon. Suitable sources of silicon include, for example, sodium silicate, hexafluorosilicic acid and salts thereof, silicon alkoxides, and combinations thereof.

If present, the concentration of the silicon source in the second liquid composition is generally similar to the concentrations of fluoride and hydroxide described above. A useful concentration of silicon is typically sufficient to provide the desired number of silicon atoms relative to the number of divalent and trivalent atoms in the first liquid composition.

In some embodiments where silicon is present, preferably the silicon source is based on the total number of moles of silicon, trivalent metal, alkaline earth metal, and any additional cation in the oxyfluoride material. It is present in an amount sufficient to provide an oxyfluoride material containing 25 mol% or less of silicon, more preferably 20 mol% or less of silicon.

Preferably, the first and second liquid compositions are combined under conditions that include efficient agitation (eg, high speed agitation). For example, the first liquid composition can be added to a container containing the second liquid composition with high speed stirring. Typically, precipitation is rapid, but continued stirring (eg, 10 minutes or longer in some embodiments, 60 minutes or longer in other embodiments) to ensure a complete reaction. it can.

Typically, the reaction can be carried out at or near room temperature, but in certain embodiments, higher or lower temperatures can be used as needed.

The oxyfluoride material may be separated from the combined liquid by methods known in the art, including, for example, filtration, centrifugation, sedimentation, decantation, and combinations thereof. Preferably, the oxyfluoride material is filtered. Upon separation, the oxyfluoride can optionally be washed with a suitable liquid containing, for example, water, alcohol, and combinations thereof.

The method optionally comprises drying the separated oxyfluoride material at a temperature of 350 ° C. or lower, more preferably 250 ° C. or lower, and most preferably 150 ° C. or lower. Suitable drying methods are known in the art and include, for example, hot air drying (eg, oven drying).

Preferably, the method provides, for example, a precipitate, a coating on particles, a coating on particle aggregates, a material impregnated in a porous structure, or an oxyfluoride material in the form of a combination thereof. After separation or drying, the oxyfluoride material can optionally be redispersed in a liquid medium (eg, a medium containing water). By milling the dried or separated material, an oxyfluoride material that is particularly useful for dispersion in the dental composition can be formed. Mill milling can be done in water or other liquids, or in the presence of dental resin or other ingredients.

Methods known in the art for milling ceramic or inorganic particles, including ball mill milling, attritor or fluid energy mills, and jet mills, are suitable for milling the oxyfluoride material of the present invention. For dental compositions containing water, the preferred form of oxyfluoride material to disperse in the composition is a separated oxyfluoride material containing sufficient water to form a wet cake or plastic solid. is there. These forms of oxyfluoride material are typically more convenient to disperse when the separated oxyfluoride material is never completely dried. For example, a wet oxyfluoride material separated by filtration, centrifugation, or filter press after precipitation and washing can contain approximately 40-70% by weight of water, and the wet oxyfluoride material is dental in this form. Can be added to the composition for use.

Alternatively, if the washed precipitate is to be dried, the dried precipitate may be milled in water and then separated by filtration, filter press or centrifugation to form a dispersible wet oxyfluoride material. Dispersible wet cakes or plastic lumps can be formed.

After washing or milling in water, the oxyfluoride material can be coated on the particles, coated on the particle agglomerates, impregnated in the porous structure, or a combination thereof.

In another embodiment, the method provides a porous structure (eg, porous particles, porous particle agglomerates, and combinations thereof); a first liquid composition in the porous structure. And impregnating the porous structure with a second liquid composition to provide a porous structure impregnated with an acid-reactive oxyfluoride material. The first liquid composition comprises a source of trivalent metals and a source of alkaline earth metals. The trivalent metal is preferably aluminum, lantern, or a combination thereof. More preferably, the trivalent metal is aluminum. The second liquid composition comprises a source of fluorine and optionally ammonium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof. The second liquid composition may optionally further include a source of silicon. Preferably, at least one of the first or second liquid compositions further comprises water. The impregnation of the first liquid composition can be performed before, during, or after the impregnation of the second liquid composition.

Optionally, the present invention allows the porous structure impregnated with the acid-reactive oxyfluoride material to be dried at a temperature of 350 ° C. or lower, more preferably 250 ° C. or lower, and most preferably 150 ° C. or lower. Further included.

acid The acid used in the present invention can be an inorganic acid or an organic acid, and in the case of an organic acid, it can be a monomer, an oligomer, or a polymer (for example, a poly acid described later). The acid may be polymerizable or non-polymerizable. If desired, instead of the acid itself, an acid anhydride, an acid halide (including an inorganic acid halide such as Lewis acid (eg, ferric chloride) and an organic acid halide), or an acid such as an ester The precursor can be used to produce the desired acid in situ. Suitable acids include mineral acids, carboxylic acids, sulfonic acids, alkyl sulfonic acids, aryl sulfonic acids, and phosphonic acids. The acid can be a liquid or solid material.

Suitable inorganic acids include HBr, HCl, HNO₃, Sulfuric acid, phosphoric acid, and phosphonic acid. Suitable organic acids include acetic acid, 2-chloropropionic acid, 2-acrylamide-2-methylpropanesulfonic acid, (meth) acrylic acid, benzenesulfonic acid, benzoic acid, bromoacetic acid, 10-camperquinonesulfonic acid, 10. -Camfer sulfonic acid, chloroacetic acid, citraconic acid, citric acid, dibromoacetic acid, dichloroacetic acid, diHEMA ester of 1,2,4,5-benzenetetracarboxylic acid, 2,4-dinitrophenol, formic acid, fumaric acid, 2 -Hydroxy-4-methoxybenzophenone-5-sulfonic acid, maleic acid, 2-naphthalene sulfonic acid, oxalic acid, p-nitrophenol, phenol, dibutyl phosphate, di- (2-ethylhexyl) phosphate, di- (2-) Ethylhexyl) phosphite, hydroxyethyl methacrylate monophosphate, glyceryl dimethacrylate phosphate, glyceryl-2-phosphate, glyceryl phosphate, methacryloxyethyl phosphate, pentaerythritol triacrylate monophosphate, pentaerythritol trimethacrylate monophosphate, pivalic acid, propionic acid , Toluene sulfonic acid, tribromoacetic acid, trichloroacetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and trihydroxybenzoic acid. If desired, a mixture of such acids can be used.

Polyacid The dental composition of the present invention may contain at least one polyacid, which may be a non-curable or non-polymerizable polyacid or a curable or polymerizable polyacid (eg, resin-reinforced poly). It may be an acid). Polyoxometalates need not be completely water-soluble, but must be at least sufficiently miscible when combined with other aqueous constituents so that they do not settle too much. Suitable polyacids are listed in (Patent Document 1) (Wilson et al.), 2nd column, 62nd line to 3rd column, 6th line. The polyoxometalate must have a molecular weight sufficient to provide good storability, operability, and mixability. The preferred weight average molecular weight is 5,000 to 100,000 when calculated relative to polystyrene standards using gel permeation chromatography.

In one embodiment, the polyacid is a curable or polymerizable resin. That is, it contains at least one ethylenically unsaturated group. Suitable ethylenically unsaturated polyacids are (Patent Document 2) (Engelbrecht), eg, 3 and 4 stages, and (Patent Document 3) (Mitra), eg, page 3, 55. It is described in the 8th line on page 5 from the line. Preferably, the number of acidic and ethylenically unsaturated groups is adjusted to provide an appropriate balance of properties in the dental composition. A polyacid in which 10% to 30% of acidic groups are substituted with ethylenically unsaturated groups is preferable.

In other embodiments, the polyacid is curable in the presence of, for example, acid-reactive fillers and water, but does not contain ethylenically unsaturated groups. That is, it is an oligomer or polymer of unsaturated acids. Preferably, the unsaturated acid is a carbon, sulfur, phosphorus, or boron oxy acid (ie, an oxygen-containing acid). More preferably, it is a carbon oxyacid. Such polyacids include, for example, polyalkenoic acids such as unsaturated mono-, di- or tricarboxylic acid homopolymers and copolymers. Preferred polyalkenoic acids are unsaturated aliphatic carboxylic acids such as acrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-bromoacrylic acid, 3-bromoacrylic acid, methacrylic acid, itaconic acid, maleic acid, It can be prepared by homopolymerization and copolymerization of glutaconic acid, acrylic acid, citraconic acid, mesaconic acid, fumaric acid, and tigric acid. Suitable monomers copolymerizable with unsaturated aliphatic carboxylic acids include, for example, unsaturated aliphatic compounds such as acrylamide, acrylonitrile, vinyl chloride, allyl chloride, vinyl acetate, and 2-hydroxyethyl methacrylate. If necessary, a copolymer of three or more elements may be used. Acrylic acid homopolymers and copolymers are particularly preferred. The polyalkenoic acid must be substantially free of non-polymerized monomers.

Ethylene unsaturated compound with acid functionality The dental composition of the present invention may contain at least one ethylenically unsaturated compound having acid functionality.

As used herein, an ethylenically unsaturated compound having acid functionality is meant to include monomers, oligomers, and polymers having ethylenically unsaturated and acid and / or acid precursor functionality. Acid precursor functionality includes, for example, acid anhydrides, acid halides, and pyrophosphates. Preferably, the unsaturated acid is a carbon, sulfur, phosphorus, or boron oxy acid (ie, an oxygen-containing acid).

Examples of the ethylenically unsaturated compound having acid functionality include glycerol phosphate monomethacrylate, glycerol phosphate dimethacrylate, hydroxyethyl methacrylate phosphate, di- or trimethacrylate citrate, poly (meth) acrylicized oligomaleic acid, and poly (meth). ) Acrylic polymaleic acid, poly (meth) acrylicated poly (meth) acrylic acid, poly (meth) acrylicized polycarboxyl-polyphosphonic acid, poly (meth) acrylicized polychlorophosphate, poly (meth) acrylicized polysulfonate, and Examples thereof include α, β-unsaturated acid compounds such as poly (meth) acrylicized polyboric acid, which may be used as a constituent component in a curable resin system. Certain preferred compositions of the present invention include acid-functional ethylenically unsaturated compounds having at least one P-OH moiety.

Certain of these compounds are obtained, for example, as reaction products of isocyanatoalkyl (meth) acrylates with carboxylic acids. Further compounds of this type having both acid-functional and ethylenically unsaturated constituents are described in (Patent Document 2) (Engelbrecht) and (Patent Document 4) (Mitra). Has been done. Various such compounds containing both ethylenically unsaturated and acidic moieties can be used. If desired, a mixture of such compounds can be used.

Further ethylenically unsaturated compounds having acid functionality include, for example, polymerizable bisphosphonic acid, for example, those disclosed in (Patent Document 5) submitted on December 5, 2003; AA: ITA: Sufficient to convert some of the acid groups of the AA: ITA copolymer to the methacrylate groups of the pendant as described in Example 11 of IEM (eg, (Patent Document 4) (Mitra)). 2-Acrylic acid having pendant methacrylate: a copolymer of itaconic acid, produced by reacting with isocyanatoethyl methacrylate); and (Patent Document 6) (Yamauchi et al.), (Patent Document 7). (Omura et al.), (Patent Document 8) (Omura et al.), (Patent Document 9) (Omura et al.), (Patent Document 10) (Yamamoto et al.), (Patent Documents) 11) (Okada et al.), And (Patent Document 12) (Tokuyama Corp.) and (Patent Document 13) (Kuraray Co., Ltd.). Things can be mentioned.

Preferably, the composition of the present invention contains at least 1% by weight, more preferably at least 3% by weight, most preferably at least an acid-functional ethylenically unsaturated compound based on the total weight of the unfilled composition. Includes 5% by weight. Preferably, the composition of the present invention contains 80% by weight or less, more preferably 70% by weight or less, most preferably 60 of the ethylenically unsaturated compound having acid functionality based on the total weight of the unfilled composition. Includes less than% by weight.

Curable resin The dental composition of the present invention can contain a curable resin. In general, these resins are preferably thermosetting materials that can be cured to form polymer networks, such as acrylate-functional materials, methacrylate-functional materials, epoxy-functional materials, vinyl-functional materials, and these. Examples include mixtures. Preferably, the curable resin is made from one or more matrix-forming oligomers, monomers, polymers or blends thereof.

In a preferred embodiment where the dental composition disclosed in the present application is a dental composite, the suitable polymerizable materials for use are of sufficient strength to make them suitable for use in the oral environment. Examples include curable organic materials having hydrolysis stability and non-toxicity. Examples of such materials include acrylates, methacrylates, urethanes, carbamoyl isocyanurates, epoxies, and mixtures and derivatives thereof.

One class of preferred curable materials includes materials having free radical active functional groups. Examples of such materials include monomers with one or more ethylenically unsaturated groups, oligomers with one or more ethylenically unsaturated groups, polymers with one or more ethylenically unsaturated groups, and these. The combination of.

Free radical active material. A class of curable resins having free radical active functional groups, suitable materials for use in the present invention contain at least one ethylenically unsaturated bond and can undergo addition polymerization. Examples of such free radical polymerizable compounds include methyl (meth) acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and tri. Ethylene glycol dimethacrylate, 1,3-propanediol di (meth) acrylate, trimethyl propanetriacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetra (meth) acrylate , Sorbitol hexaacrylate, tetrahydrofurfuryl (meth) acrylate, bis [1- (2-acryloxy)]-p-ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2-hydroxy)]-p-propoxyphenyl Mono-, di-, or poly- (meth) acrylates such as dimethylmethane, ethoxylated bisphenol A di (meth) acrylate, and trishydroxyethyl-isocyanurate trimethacrylate (ie, acrylate and methacrylate); (meth) acrylamide, (Meta) acrylamides such as methylenebis (meth) acrylamide and diacetone (meth) acrylamide (ie, acrylamide and methacrylicamide); urethane (meth) acrylates; polyethylene glycol bis (meth) acrylates (preferably those with a molecular weight of 200-500). ); (Patent Document 14) A copolymerizable mixture of acrylated monomers such as those in (Boettcher et al.); (Patent Document 15) (Acrylate oligomers such as those described in Zador et al.); Also included are vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate. Other suitable free radically polymerizable compounds include, for example, (Patent Document 16) (Guggenberger et al.), (Patent Document 17) (Weinmann et al.), (Patent Document 18) (Gut Guggenberger et al.), The siloxane functional (meth) acrylate disclosed in (Patent Document 19) (Guggenberger et al.), And, for example, (Patent Document 20) (Fock et al.) ), (Patent Document 21) (Griffith et al.), (Patent Document 22) (Wagenknecht et al.), (Patent Document 23) (Reiners et al.), And (Patent Document 24) ( Included are fluoropolymer functional (meth) acrylates disclosed in Reiners et al.). If necessary, a mixture of two or more kinds of free radically polymerizable compounds can be used. Oropolymer functional (meth) acrylates can be mentioned. If necessary, a mixture of two or more kinds of free radically polymerizable compounds can be used. Oropolymer functional (meth) acrylates can be mentioned. If necessary, a mixture of two or more kinds of free radically polymerizable compounds can be used.

The polymerizable component may also contain a hydroxyl group and a free radical active functional group 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-, tetra-, or penta- (meth) acrylate; and 2, Examples thereof include 2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (bisGMA). Suitable ethylenically unsaturated compounds also include St. Louis, Mass., Sigma-Aldrich, St. Louis, MO and Malden, Massachusetts, Rohm Tech. Inc., Malden, MA. It is available from various commercial sources of. If desired, a mixture of ethylenically unsaturated compounds can be used.

Free radical initiation system. For free radical polymerization (eg, curing), the starting system can be selected from systems that initiate polymerization by radiation, heat, or a redox / auto-cure chemical reaction. Examples of the class of initiators capable of initiating the polymerization of free radical active functional groups include free radical generating photoinitiators, which are optionally combined with a photosensitizer or accelerator. Such initiators are typically capable of generating free radicals and undergoing addition polymerization when exposed to light energy having a wavelength of 200-800 nm.

Examples of the photoinitiator suitable for polymerizing the free radical photopolymerizable composition (that is, the photoinitiator system containing one or more compounds) include binary and ternary systems. Typical ternary photoinitiator systems include iodonium salts, photosensitizers, and electron donor compounds described in (Patent Document 25) (Palazzotto et al.). Preferred iodonium salts are diaryliodonium salts (eg, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate). Preferred photosensitizers are monoketones and diketones that absorb some light in the range of 400 nm to 520 nm (preferably 450 nm to 500 nm). More preferred compounds are α-diketones that have some light absorption in the range of 400 nm to 520 nm (even more preferably 450 nm to 500 nm). Preferred compounds are camphorquinone, benzyl, frills, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone, and other cyclic α-diketones. Most preferred is camphorquinone. Preferred electron donor compounds include substituted amines (eg, ethyldimethylaminobenzoate). Other suitable ternary photoinitiator systems useful for photopolymerizing cationically polymerizable resins are described, for example, in (Patent Document 26) (Dede et al.).

Other photoinitiators suitable for polymerizing free radical photopolymerizable compositions typically include the class of phosphine oxides having a functional wavelength range of 380 nm to 1200 nm. Preferred phosphine oxide-free radical initiators having a functional wavelength range of 380 nm to 450 nm are (Patent Document 27) (Lechtken et al.), (Patent Document 28) (Lechtken et al.), (Patent Document 29) (Patent Document 29). Lechtken et al.), (Patent Document 30) (Lechtken et al.), And (Patent Document 31) (Ellrich et al.), (Patent Document 32) (Kohler et al.), And (Patent Document 31). Reference 33) Acyl and bisacylphosphine oxides such as those described in Ying.

As a commercially available phosphine oxide photoinitiator capable of initiating free radicals when irradiated in the wavelength range higher than 380 nm to 450 nm, for example, Ciba Specialty Chemicals (Ciba), Tarrytown, NY under the trade name of IRGACURE 819. Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide available from Specialty Chemicals, Tarrytown, NY; Bis (2,,) available from Ciba Specialty Chemicals under the trade name CGI 403 6-Dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide; Ciba Specialty Chemicals under the trade name IRGACURE 1700 25:75 by weight of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide available from Chemicals) and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Mixtures; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2-hydroxy-2-methyl-1 available from Ciba Specialty Chemicals under the trade name DAROCUR 4265. -A 1: 1 mixture by weight with phenylpropan-1-one; and ethyl-2 available from BASF (BASF Corp., Charlotte, NC), Charlotte, North Carolina under the trade name LUCIRIN LR8893X. , 4,6-trimethylbenzylphenyl phosphinate.

Typically, the phosphine oxide initiator is present in the photopolymerizable composition in an amount effective as a catalyst (eg, 0.1% to 5% by weight based on the total weight of the composition).

A tertiary amine reducing agent may be used in combination with the acylphosphine oxide. Exemplary tertiary amines useful in the present invention include ethyl-4- (N, N-dimethylamino) benzoate and N, N-dimethylaminoethyl methacrylate. The amine reducing agent, if present, is present in the photopolymerizable composition in an amount of 0.1% to 5.0% by weight based on the total weight of the composition. Useful amounts of other initiators are well known to those of skill in the art.

Another free radical initiator system that can be used in place of the dental materials of the present invention includes the class of ionic dye-to-ion complex initiators, including borate anions and complementary cation dyes. Borate photoinitiators include, for example, (Patent Document 34) (Gottschalk et al.), (Patent Document 35) (Adair et al.), (Patent Document 36) (Gottschalk et al.), (Patent Document 37) (Shanklin et al.), And (Patent Document 38) (Shanklin et al.).

The curable resin of the present invention can include a redox curing system containing a polymerizable component (for example, an ethylenically unsaturated polymerizable component) and a redox agent containing an oxidizing agent and a reducing agent. Suitable polymerizable constituents and redox agents useful in the present invention are described in (Patent Document 39) (Mitra et al.) And (Patent Document 40) (Mitra et al.).

The reducing agent and the oxidizing agent must react with each other or otherwise cooperate to generate free radicals capable of initiating the polymerization of the resin system (eg, ethylenically unsaturated constituents). This type of curing is a dark reaction, i.e., independent of the presence of light and can proceed in the absence of light. Reducing agents and oxidizing agents preferably have sufficient storage stability to allow their storage and use under typical dental conditions and do not cause unwanted coloration. They must be sufficiently miscible with the resin system so that they can be easily dissolved in the other constituents of the polymerizable composition (and prevent separation of the polymerizable composition from the other constituents). (And preferably it must be water soluble).

Useful reducing agents include, for example, ascorbic acid, ascorbic acid derivatives, and ascorbic acid metal complex compounds described in (Patent Document 41) (Wang et al.); Amines, especially 4-t-butyldimethylaniline and the like. Tertiary amines; aromatic sulfinates such as p-toluenesulfinate and benzenesulfinate; 1-ethyl-2-thiourea, tetraethylthiourea, tetramethylthiourea, 1,1-dibutylthiourea, and Thioureas such as 1,3-dibutylthiourea; as well as mixtures thereof. Other secondary reducing agents include cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine (depending on the choice of oxidant), dithionous acid anion or salt of sulfite anion. , And combinations thereof. Preferably, the reducing agent is an amine.

Also, suitable oxidizing agents are well known to those skilled in the art and include, for example, persulfuric acid and salts thereof (such as sodium salt, potassium salt, ammonium salt, cesium salt, and alkylammonium salt). Further oxidizing agents include, for example, peroxides (such as benzoyl peroxide), hydroperoxides (such as cumyl hydroperoxide, t-butyl hydroperoxide, and amyl hydroperoxide), and salts of transition metals. (Cobalt (III) chloride and ferric chloride, cerium (IV) sulfate, etc.), perboric acid and its salts, permanganic acid and its salts, perphosphoric acid and its salts, and combinations thereof.

It may be desirable to use two or more oxidants or two or more reducing agents. Also, small amounts of transition metal compounds may be added to accelerate the rate of redox curing. In some embodiments, for example, as described in (Patent Document 40) (Mitra et al.), A secondary ionic salt is included to improve the stability of the curable composition. May be preferable.

The reducing and oxidizing agents are present in sufficient amounts to allow for a suitable free radical reaction rate. This can be evaluated by combining all the components of the polymerizable composition except the filler and observing whether a cured mass is obtained.

Preferably, the reducing agent is present in an amount of at least 0.01% by weight, more preferably at least 0.1% by weight, based on the total weight (including water) of the constituents of the curable composition. Preferably, the reducing agent is present in an amount of 10% by weight or less, more preferably 5% by weight or less, based on the total weight (including water) of the constituents of the polymerizable composition.

Preferably, the oxidizing agent is present in an amount of at least 0.01% by weight, more preferably at least 0.10% by weight, based on the total weight (including water) of the constituents of the polymerizable composition. Preferably, the oxidizing agent is present in an amount of 10% by weight or less, more preferably 5% by weight or less, based on the total weight (including water) of the constituents of the curable composition.

For example, reducing agents or oxidizing agents can be microencapsulated as described in (Patent Document 42) (Mitra et al.). This generally improves the storage stability of the polymerizable composition and allows the reducing and oxidizing agents to be packaged together, if desired. For example, with proper selection of encapsulants, oxidizing and reducing agents can be combined with acid-functional constituents and optional fillers to keep them in a stable storage state. Similarly, with proper selection of water-insoluble encapsulants, reducing and oxidizing agents can be combined with FAS glass and water to maintain stable storage.

Alternatively, heat may be used to initiate curing or polymerization of free radical active groups. Examples of heat sources suitable for the dental materials of the present invention include induction, convection, and radiation. The heat source must be able to generate temperatures of at least 40 ° C and 150 ° C or less under normal conditions or high pressure. This procedure is preferred to initiate polymerization of the material that occurs outside the oral environment.

Yet another alternative class of initiators capable of initiating the polymerization of free radical active functional groups in the curable resin is one that comprises a thermal initiator that generates free radicals. Examples include peroxides (eg, benzoyl peroxide and lauryl peroxide) and azo compounds (eg, 2,2-azobis-isobutyronitrile (AIBN)).

The photoinitiator compound is preferably provided in the dental composition disclosed in this application in an amount effective for initiating or speeding up the curing or curing of the resin system. Useful photopolymerizable compositions are prepared by simply mixing the above components under safe light conditions. When preparing this mixture, a suitable inert solvent may be used, if desired. A solvent that does not react well with the constituents of the composition of the present invention may be used. Examples of suitable solvents include, for example, acetone, dichloromethane, and acetonitrile.

Other fillers In addition to the dental filler containing the acid-reactive oxyfluoride material, the compositions of the present invention may optionally contain one or more other fillers. Such fillers are selected from one or more of a variety of materials suitable for inclusion in compositions used for dental applications, such as fillers currently used in dental restoration compositions. May be good.

Other fillers are preferably finely ground. The filler may have a monomodal or multimodal (eg, bimodal) particle size distribution. Preferably, the maximum particle size of the other filler (maximum particle size, typically diameter) is less than 5 micrometers, more preferably less than 0.5 micrometers, and most preferably less than 0.1 micrometers. Preferably, the average particle size of the filler is less than 0.1 micrometer, more preferably less than 0.075 micrometers.

Other fillers can be inorganic materials. It can also be a crosslinked organic material that is insoluble in the resin constituents of the composition and optionally filled with an inorganic filler. In all cases, the filler must be non-toxic and suitable for use in the mouth. The filler can be X-ray opaque or X-ray permeable. Typically, the filler is substantially insoluble in water.

Examples of suitable inorganic fillers are not limited to: quartz; nitrides (eg, silicon dioxide); eg, glass derived from Zr, Sr, Ce, Sb, Sn, Ba, Zn and Al; feldspar; silica. Acid glass; Kaolin; Tarku; Titania; (Patent Document 43) (Randklev) and other low-moth hardness fillers; and submicron silica particles (eg, Germany, Hanau, Degusa) (eg, Germany, Hanau, Degusa). Available from Degussa AG, Hanau, Germany) under the trade name of AEROSIL containing "OX50", "130", "150" and "200" silica, as well as Cabot Corp., Tascola, Illinois. , Tuscola, IL) CAB-O-SIL M5 It is a natural or synthetic material containing silica) such as silica. Examples of suitable organic filler particles include filled or unfilled finely divided polycarbonate, polyepoxides and the like.

Suitable non-acid-reactive filler particles are quartz, submicron silica, and non-glassy microparticles of the type described in (Patent Document 44) (Randklev). Mixtures of these non-acid-reactive fillers are conceivable as well as combination fillers made from organic and inorganic materials.

Further, in order to improve the bond between the filler and the resin, the surface of the filler particles can be treated with a coupling agent. Uses of suitable coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and the like.

Other suitable fillers are (Patent Document 45) (Zhang et al.) And (Patent Document 46) (Wu et al.), And (Patent Document 47) (Zhang et al.), (Patent Document 47). 48) (Windisch et al.), (Patent Document 49) (Zhang et al.) And (Patent Document 50) (Wu et al.). The filler constituents described in these references include nano-sized silica particles as well as yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, and lanthanide elements (ie, 57). Examples include metal oxides (elements having atomic numbers in the range ~ 71 (including 57 and 71)) and oxides of strontium, and combinations thereof.

In some embodiments of the invention that include other fillers (eg, dental restoration compositions), the composition preferably contains at least 1% by weight of the other filler relative to the total weight of the composition. It preferably contains at least 2% by weight, most preferably at least 5% by weight. In such an embodiment, the composition of the present invention contains 40% by weight or less, more preferably 20% by weight or less, and most preferably 15% by weight or less of other fillers based on the total weight of the composition.

In other embodiments of the invention, for example, the composition is a dental restore or orthodontic adhesive, and the other fillers are the majority of all fillers in the composition. Other fillers, preferably at least 40% by weight, more preferably at least 45% by weight, and most preferably at least 50% by weight, based on the total weight of the composition. In such an embodiment, the composition of the present invention contains 90% by weight or less of other fillers, more preferably 80% by weight or less, still more preferably 70% by weight or less, based on the total weight of the composition. Most preferably, it contains 50% by weight or less.

Other additives The dental compositions of the present invention optionally include, for example, colorants, flavors, antimicrobial agents, fragrances, stabilizers, viscosity modifiers, and inorganic and organic fluoride-releasing materials (eg, FAS glass and (Patented). It may contain additives suitable for use in the oral environment, including Document 51) (organic fluoride sources such as those described in Aasen et al.). For example, suitable additives include reagents that impart fluorescence and / or milky light.

Mixing of filler The filler disclosed in this application may be mixed into the curable resin and / or polyacid by any suitable means to form a dental composition. The acid-reactive dental filler may be added as a powder. Alternatively, the acid-reactive dental filler can be combined with another filler (eg, acid-reactive filler, non-acid-reactive filler, nano-sized filler) and / or optional additives to cure the curable resin or polyacid. May provide a material that can be added as a powder to. Alternatively, an acid-reactive dental filler may be combined with a liquid additive and added as a dispersion to the curable resin or polyacid. In addition, wet acid-reactive dental fillers can be combined with the resins described in the examples herein.

Dental composition In one embodiment, the dental filler of the present invention can be mixed in a curable resin to provide the above-mentioned useful dental composition. In some applications, the dental composition is preferably in the form of a paste. The dental composition of the present invention can be a chemically curable, thermosetting or photocurable composition. The photocurable material must have a suitable initiator system. The chemically curable material can be self-curing (eg, with a redox initiator). Alternatively, the composition can be cured by a combination of self-curing and photo-curing. The dental composition of the present invention may be a one-dose type dental composition or a multi-dose type dental composition. Preferably, the composition is a storage stable composition, i.e., having a room temperature shelf life stability of at least 1 year, preferably at least 2 years.

In another embodiment, the dental composition disclosed in this application comprises a dental filler containing an acid-reactive oxyfluoride material placed in a resin. The amount of filler used depends on the type of composition and the desired properties.

In other embodiments, the dental fillers of the invention are conventional glass ionomers, typically comprising polyacids, acid-reactive fillers, and water; and typically polyacids, acid-reactive. It is useful for ionomer-type compositions such as resin-reinforced glass ionomers, which contain fillers, curable resins (ie, polymerizable constituents) and water. The dental fillers of the present invention can be used as a partial or complete replacement for conventional FAS glass fillers, which are typically used as acid-reactive fillers.

Preferably, the dental fillers of the present invention have a large surface area and can be used in relatively small amounts, but nevertheless provide fluoride release and ionomer curing comparable to higher fills of conventional FAS glass. Since the dental fillers of the present invention are used in relatively small amounts, ionomers and / or ionomers containing more desired fillers such as X-ray opaque fillers, indexed matched fillers and / or nanofillers. Alternatively, a fluoride-releasing dental composition can be formulated. In some embodiments, such compositions are less than 15% by weight of the dental filler of the invention, or less than 10% by weight in other embodiments, or less than 5% by weight in yet other embodiments. Can have. In some embodiments, the dental filler in such a composition is at least 2 square meters per gram of the dental composition, and in other embodiments at least 5 square meters, despite the relatively low filling amount. In yet other embodiments, a filler surface area of at least 10 square meters can be provided.

The dental composition of the present invention may optionally contain a relatively large amount of additional filler in addition to the dental filler of the present invention. In some embodiments, the dental composition comprises 10% by weight or less of the dental filler of the present invention relative to the total weight of the dental composition, but further fillers are at least 40% by weight, and others. It comprises at least 50% by weight in embodiments and at least 60% by weight in other embodiments.

Primarily by using both relatively small amounts of the dental fillers of the invention (eg, nanostructured oxyfluoride materials, in particular primarily the nanosized fillers of the invention) and additional nanosized fillers. Alternatively, a dental composition having a filler system that is essentially completely nanofiller can be formulated. In some embodiments, the total filler content contains at least 75% nanofiller and in other embodiments at least 90% nanofiller.

In other embodiments, the dental composition comprises a higher filling amount of the dental filler of the present invention. Preferably, the dental composition contains 75% by weight or less, more preferably 70% by weight or less of the dental filler of the present invention based on the total weight of the dental composition.

In yet another embodiment, the dental composition preferably comprises at least 2% by weight, more preferably at least 5% by weight, of the dental filler of the present invention, based on the total weight of the dental composition.

The dental compositions disclosed in this application include, for example, dental adhesives, artificial crowns, anterior or posterior tooth fillers, cavity liners, cements, coatings, mill blanks, orthodontic appliances, orthodontic adhesives. It can be used as an agent, restoration material, prosthesis, and sealant. In a preferred embodiment, the dental composition is a dental restoration material. The dental restoration material of the present invention can be placed directly in the mouth and can be cured in situ, or it can be processed into a prosthesis outside the mouth and then glued in place in the mouth. May be good.

Preferably, the invention can be cured to provide a balance of desired properties (eg, high diameter tensile strength, high compressive strength, and high adhesive strength) detailed below, while at the same time providing excellent maneuverability. And provide a dental composition that retains rheological properties (eg, after storage at 25 ° C for 5 days, virtually no sedimentation). Preferably, the dental composition is non-adhesive when operated using procedures well known to those skilled in the art.

Multi-dose dental composition In one embodiment, the present invention provides a multi-dosage form (eg, two or more dosage forms) of a dental composition. Each agent may independently be, for example, a powder, liquid, or paste. Such a multi-agent dental system includes, for example, a composition containing an acid-reactive filler and a curable resin, and an acid-reactive filler, a polyacid, and an optional curable resin (that is, a polymerizable composition). Ingredients) include ionomer compositions. As described herein, the acid-reactive fillers of the present invention can replace all or part of the FAS glass filler typically contained in such compositions.

For example, the two-agent ionomer system can include agent A containing an acid-reactive filler and agent B containing a polyacid. A mixed ionomer composition can be formed by combining Agent A and Agent B. The viscosity of Agent A is typically 50,000 centipoise (cps) when measured at room temperature or near room temperature (usually 25 ° C) using a Brookfield viscometer and a TD spindle with a conversion factor of 32,000. ) Greater, preferably 150,000-300,000 cps. Typically, the dentist mixes the two agents just before use. When the two agents are mixed, the acid-base curing reaction begins. Preferably, the mixture has an operating time as defined in (Patent Document 52) (Mitra) of at least 30 seconds, more preferably at least 60 seconds. Optionally, if a polymerizable component is present, subsequent curing of the polymerizable component can be accelerated by a curing agent and / or light. Each component used to formulate Agent A and Agent B is described in detail herein. Certain components, such as polymerizable components and initiator components, may be present in either Agent A and Agent B, or both Agent A and Agent B, as further described below. The polyacid and the polymerizable constituents may be the same or different.

In one embodiment, the dental filler disclosed in the present invention may be used in agent A of the ionomer composition. Agent A may optionally contain a polymerizable component. When used in the A agent of an ionomer composition, the composition preferably contains at least 5% by weight, more preferably at least 10% by weight, of the dental filler of the present invention, based on the total weight of the A agent of the composition. , Most preferably at least 15% by weight. When used in the A agent of an ionomer composition, the composition preferably contains 85% by weight or less, more preferably 82% by weight or less, of the dental filler of the present invention, based on the total weight of the A agent of the composition. , Most preferably 80% by weight or less.

The amount of polyacid in the dental composition, whether part of the curable polymerizable resin or part of the non-polymerizable curable polyacid, is sufficient to provide the desired balance of properties. Must. The B agent preferably contains at least 5% by weight of a polyacid, more preferably at least 10% by weight of the polyacid, based on the total weight of the B agent. The B agent preferably contains 70% by weight or less of polyacid, and more preferably 60% by weight or less of polyacid based on the total weight of the B agent.

Agents A and / or B may optionally contain water, which may be present in the product at the time of sale or may be added by the dentist immediately prior to use. The water can be distilled water, deionized (DI) water, or tap water, with deionized water being preferred. Immediately prior to use, the entire dental composition preferably comprises at least 1% by weight of water, more preferably at least 3% by weight of water, and most preferably at least 5% by weight of water. Immediately prior to use, the entire dental composition preferably contains 35% by weight or less of water, more preferably 25% by weight or less of water. Generally, the amount of water used is not sufficient to provide the dental composition with sufficient maneuverability and mixing properties and to allow the transport of ions in the acid-reactive dental filler polyacid reaction. It doesn't become. When both water and the filler of the present invention are contained in Agent A, an aqueous paste of the filler or a hard clay-like form can be used in the formulation of Agent A.

Optionally, the multi-drug dental system of the present invention can include additional non-acid-reactive fillers or acid-reactive fillers, including, for example, nanofillers.

In some embodiments, the two-part composition of the invention can be provided in a dual barrel syringe having a first barrel and a second barrel, where Agent A is the first barrel. Being inside, Agent B is in the second barrel. In other embodiments, the two-dose dental composition of the invention can be provided in unit dose capsules. In some embodiments, a static mixer can be used to mix the multidrug dental agents together.

Hardened dental composition The dental composition disclosed in the present application contains the dental filler of the present invention to be blended with a curable resin (eg, a polymerizable component) and has particularly desirable operability (eg, rheological properties) in an uncured state. ), And has high strength in a cured state.

Strength can be characterized by mechanical measurements such as compressive strength (CS) and diameter tensile strength (DTS). High compressive strength of the dental material is advantageous due to the force that mastication exerts on dental reconstruction, replacement, and restoration. Diameter Tensile Strength indicates the ability of a dental material to withstand the compressive forces that cause tensile stress in the material. Each strength measurement test will be described later as an example.

The dental compositions disclosed in the present application, when cured, preferably have a compressive strength of at least 60 MPa, more preferably a compressive strength of at least 80 MPa, and most preferably a compressive strength of at least 90 MPa. The cured dental composition of the present invention preferably has a diameter tensile strength of at least 10 MPa, more preferably at least 15 MPa, most preferably at least 20 MPa.

Dental goods The dental compositions of the present invention may be cured to form, for example, dental articles (eg, crowns, fillers, mill blanks, and prostheses) and orthodontic appliances. In a preferred method of using a dental composition comprising a curable resin and the dental filler of the present invention, the composition is placed near or on the tooth surface and subsequently modified by the dentist or the topography of the composition. Manipulated by the tech room, the composition may subsequently be cured. These steps can be carried out sequentially or in a different order. For example, in a preferred embodiment where the dental composition is a mill blank or prosthesis, the curing step is generally completed before changing the topography of the composition. For example, topo of the composition in various ways, including engraving or manual operation using handheld equipment, or in the case of prostheses and mill blanks with mechanical or computer-aided equipment (eg, CAD / CAM milling machines). Topographical changes can be achieved. Optionally, a finishing step can be performed to polish, finish, or coat the dental article.

The following examples further illustrate the objectives and advantages of the invention, but the specific materials and amounts thereof, as well as other conditions and details listed in these examples, shall unreasonably limit the invention. Should not be considered. Unless otherwise specified, all parts and percentages are all weight-based, all water is deionized water, and all molecular weights are weight average molecular weights.

Test method Surface area determination Surface area is related to the "primary particle size" of the precipitated powder. Primary particle size refers to the small, individually nucleated particles that form during precipitation. The primary particles can be aggregated to form larger particles, which may or may not be individually dispersible. The surface area (S) of uniform, spherical, dense primary particles, and the aggregates or structures made from them, is about 3 m / ρr, where m is the mass, r is the radius of the primary particles, and ρ is the density. , S / m is the specific surface area. Therefore, r = 3m / ρS.

Micromeritics Gemini Surface Area Analyzer and Micromeritics Flow Prep outgassing The specific surface area (surface area per unit weight) of the filler powder was determined using unit) (Micromeritics, Norcross, GA, Georgia). After weighing the powder sample, it was placed in a glass sample tube. Both the powder sample and the glass sample tube and stopper were weighed and recorded. The powder sample was placed in a glass sample tube, weighed and recorded. After the nitrogen flow to the probe in the degassing device was discharged, it was gently flowed to the bottom of the glass sample tube. A stopper was loosely inserted into the upper part of the glass sample tube, and the tube was placed in the heating zone of the prep / degassing device. The sample was then degassed at 250 ° C. for 1 hour. The tube was then removed from the heating zone and placed on a cooling shelf and allowed to cool for 5 minutes. The stopper and probe were then removed from the glass tube. The stopper was then immediately refitted onto the top of the glass tube. The tube and plug were then weighed and the weight was subtracted from the initial weight of the glass tube and plug alone. Next, the glass tube containing the degassed powder was placed upright in the surface area analyzer. The dewar bottle was then filled with liquid nitrogen and placed in a surface area analyzer. The vacuum pump attached to the analyzer was then switched on. The Gemini control box was then used to enter the powder weight, saturation pressure, vacuum rate, date, and time. The analysis was then started by pressing the input button. Analysis was performed for several cycles and the surface area measurements were calculated programmatically.

Particle size determination Average particle size by particle size analyzer. Particle size (including cluster size) distribution (based on volume percent) using the Coulter LS 230 Particle Size Analyzer (Coulter Corporation, Hialeah, FL, Florida) To do) was decided. The analyzer was equipped with Polarized Scattering Intensity Difference (PIDS) software. 300 mg of filler sample, enough to wet all the filler Micro (MICRO) -90 Surfactant (Cole-Parmer, Vernon, Vernon Hills, NY) Hills, NY)) was added to a glass vial. Alicoat of Calgon solution (made by complete mixing of 0.20 g sodium fluoride, 4.00 g sodium pyrophosphate, 40.00 g sodium hexametaphosphate, 8.00 g micro (MICRO) -90 surfactant, and 3948 ml DI water) Add 30 ml and shake the resulting mixture for 15 minutes to probe sonicators (Model W-225 Sonicator, Heat Systems-Ultrasonics, Farmingdale, NY). )) For 6 minutes, sonicated with output control knob setting 9. Coulter LS 230 Particle characterization Software Version 3.01 (Coulter LS 230 Particle characterization Software Version) Particle analysis was performed using 3.01). The test conditions were an operating length of 90 seconds and a standby length of 0 seconds, and the test sample was added dropwise to the sample orifice until the PIDS reading reached 45% to 55%. Three sets of data per sample were averaged to obtain average particle size or average cluster size.

Average particle size by TEM (Transmission Electron Microscope): Carbon Stabilized Formbar Support (SPI Supplies, a division of Structure Probe, Inc., West, West Chester, PA) A sample having a thickness of about 80 nm was placed on a 200-mesh copper grid having Chester, PA)). Transmission electron at 200Kv using JEOL 200CX equipment (sold by JEOL, Ltd., of Akishima, Japan, JEOL USA, Inc., Akishima, Japan) A micrograph (TEM) was taken. The population size of about 50-100 particles was measured to determine the average particle size.

Fluoride release test method The amount of fluoride released from the filler powder sample was determined by the following procedure. Disc-shaped (1 mm thick x 20 mm diameter) paste samples exposed to VISILUX 2 curing lights (3M Company, St. Paul, MN, Minnesota) for 60 seconds. It was cured by letting it. The cured disc was then weighed and added to 25 ml of DI water in a plastic vial. The vial was then placed in an oven at 37 ° C for 24 hours. The vial is then removed from the oven and 10 ml of aqueous solution containing TISAB (DI water, sodium acetate, sodium chloride, acetic acid, and CDTA (1,2-cyclohexanediamine tetraacetic acid)) is a total ionic strength-adjusted buffer solution (Beverly, Massachusetts). , Thermo Orion (Beverly, MA) added to 10 ml. Magnetic stirrer was added and mixed on a stirrer. 1, 2, 5, 10, 50 and 100 ppm Orion. The Orion Fluoride Combination electrode model 96-09 was calibrated using the IonPlus standard solution (Orion, Boston, MA, Mass.). After calibration, the electrodes were placed in agitated water / TISAB solution and the values (in ppm units) were measured. Fluoride release was calculated taking into account the total amount of water initially used for the disc sample (25 ml) and the individual weight of the disc sample. This calculation was in units of μgF / g and represented the average of the three replicas.

Total fluoride content test method The total amount of fluoride present in the filler powder sample was determined by the following procedure. Fluoride release of the filler powder sample, as described in the fluoride release test method above, except that the sample was completely dissolved in an acetic acid solution to release all the fluoride present in the sample. analyzed. The results were reported as fluoride weight percent and represented the average of the three replicas.

Curing efficiency test method The curing efficiency of the filler powder sample was determined by the following procedure. Test resins were prepared by premixing and homogenizing a combination of VBCP (43 parts), HEMA (22.6 parts), and water (34.4 parts). Filler powder samples (various amounts) were added to the test resin (0.5 g), the resulting mixture was mixed on a mixing pad with a spatula until homogeneous, and then using a TEFLON mold about 2 cm in diameter. , Formed on a disk-shaped sample with a thickness of 1 mm. The resulting disc samples were inspected at regular intervals and the degree of curing was assessed using the following scale: 0--No change from the state at the time of mixing 1--Increased viscosity--Still liquid or fluid and pasty 2--Some solid, sticky 3--Solid, but flexible and weakly sticky 4--Completely solid, slight flexibility 5--Completely hardened, brittle Numbers (0-5) representing the quantitative degree of cure at various total cure times were recorded.

Test method for adhesion to enamel or dentin The adhesive strength of a given test sample to enamel or dentin was evaluated by the following procedure.

Tooth preparation. For each test sample, five cow teeth of similar age and appearance were partially implanted in a circular acrylic disc. To expose dentin or enamel, use a paper-supported grade 120 silicon carbide abrasive attached to the jewel polishing wheel to flatten the exposed areas of each tooth and parallel to the acrylic disc. Grinded to. During this time, and during the subsequent grinding and polishing steps, the teeth were continuously washed with water. The teeth were further ground and polished by attaching a paper-supported grade 600 silicon carbide abrasive to the gem polishing wheel. Polished teeth were stored in deionized water and used for testing within 2 hours after polishing. Polished teeth were removed from water, wiped and dried.

Tooth application: A plastic ring was lined into a prefabricated 2 mm thick TEFLON sheet mold with a 5 mm diameter hole to allow the test sample to be released from it (after curing). The mold was clipped to a wiped and dried tooth prepared by pre-grinding / polishing. Paste A and Paste B test samples were weighed and mixed together for 25 seconds to give a mixed paste test sample, which was then placed in a mold with a spatula. A slight pressure was applied to the mixed paste test sample to ensure it was at the mold / tooth intersection. After filling all the molds, the sample was exposed to radiation from the XL 3000 Dental Curing Light (3M Company) for 60 seconds. The sample was then placed in a humidity chamber set at 97% relative humidity and 37 ° C for 15 minutes. The sample was then removed from the humidity chamber and the clip removed from the assembly. The resulting teeth were then placed in 37 ° C deionized water in an oven set at 37 ° C for 24 hours, with the mold still attached.

Adhesive strength test. Assemble (as described above) into a jaw-tightened holder on an Instron testing machine (Instron 4505, Canton, Mass., Instron (Instron 4505, Instron Corp. Canton, MA)), polished tooth surface. The adhesive strength of the cured test sample was evaluated by attaching the canton so as to be parallel to the tensile direction. The sample mold was removed before the test. A loop of orthodontic wire (0.44 mm in diameter) was placed around the button sample adjacent to the polished tooth surface. The ends of the orthodontic wire were tightened with tensile jaws of the Instron device and pulled at a crosshead speed of 5 mm / min, thereby placing the bond under shear stress. Record the force when the bond breaks (in kilograms (kg)) and use this number as the force per unit area (kg / cm) using the known surface area of the button.²Or converted to the unit of MPa). The reported adhesions to enamel or dentin values each represent the average of 5 replicas.

Compressive strength (CS) test method First, the compressive strength was evaluated by injecting a test sample into a glass tube having an inner diameter of 4 mm and a length of 4 cm. A silicone stopper was inserted into the end of the glass tube. The filled tube was subjected to 0.275 megapascal (MPa) pressure for 5 minutes and irradiated with XL1500 curing light (3M Company) for 60 seconds. The tube sample was then placed in a 37 ° C water container for 24 hours. The tube was cut to a length of 7 mm and the sample was extruded from the glass tube. Using an INSTRON universal tester (Instron Corp. Canton, MA) operating at a crosshead speed of 1 mm / min according to ISO standard 7489. The compression strength was determined. The results were reported as the average of 5 replicas.

Diameter Tensile Strength (DTS) Test Method The diameter tensile strength was measured using the CS procedure described above, but the sample used was cut to a length of 2 mm. The results were reported as the average of 5 replicas.

Bending strength (FS) test method First, the bending strength was evaluated by injecting a test sample into a square glass tube having an inner diameter of 1 mm. The square tube was irradiated with XL1500 curing light (3M Company) for 30 seconds, then rotated 180 ° and irradiated for another 30 seconds. The sample was removed from the square tube and placed in water at 37 ° C for 1 day. Bending strength was measured using the CS procedure described above. The results were reported as the average of 5 replicas.

Visual opacity (Macbeth value) test method Disc-shaped (1 mm thick x 20 mm diameter) paste samples were cured by exposing them to illumination from VISILUX 2 Curing Light (3M Company) for 60 seconds. Through the thickness of the disc using the MacBeth transmission densitometer model TD-903 equipped with a visible light filter available from MacBeth (MacBeth, NY) (MacBeth (MacBeth, Newburgh, NY)). By measuring the light transmittance, the positive light transmission of the cured sample was measured. The lower the Macbeth value, the lower the visual impermeability of the material and the greater the translucency. The reported values are the average of the three measurements.

X-ray impermeable (Macbeth value) test method The same disc-shaped sample used in the visual impermeable measurement was used to perform the X-ray impermeable measurement. A sheet of X-ray film was placed on a sheet of lead with a thickness of 6.394 mm. Next, the sample and the aluminum staircase optical wedge were placed on the X-ray film. The sample, aluminum staircase optical wedge, and film were then irradiated with X-rays at 62 kV at a target film distance of 400 mm. The film was then developed using an Air Techniques Peri-Pro X-ray film developer (Air Techniques, Hicksville, NY). The developed film was then measured using the MacBeth transmission densitometer model TD-903. The measurements were then plotted against the aluminum staircase measurements and calculated against the thickness of each aluminum staircase.

Smoothness retention (toothbrush wear / gloss) test Slippery retention: The smoothness retention of the cured sample was determined by the following method. A square-shaped paste sample (length 20 mm x width 9 mm x thickness 3 mm) was cured with two VISILUX devices for 60 seconds. Attach the sample to the holder with double-sided adhesive tape (Scotch Brand Tape, Core series 2-1300, St. Paul, MN), as shown in the chart below. Polishing was carried out according to the following series of steps carried out sequentially. A Buehler ECOMET 4 Polisher with an AUTOMET 2 Polishing Head was used in a clockwise rotation.

<tables num="1"><img file="JP4842269B2_D0001.tif" /></tables>

Specular reflection from the sample surface after polishing and after brushing using a micro-tri-gloss instrument (BYK Gardner, Columbia, MD, Columbia, Maryland) Photoelectric measurements of light were collected. Following the procedures described in ASTM D 523-89 (1994, reapproved) Standard Test Method for Mirror Gloss for Measurements Made with 60 ° Geometry, with the following changes: Initial gloss after polishing (G_I) Was measured for the initial sample. Final luster after 2000 cycles of toothpaste (G_F) Was measured for the final sample. The value of ΔG was calculated using the following equation: ΔG = (G_F)-(G_I). In addition to the initial and final readings, gloss measurements at toothpaste 500 strokes, 1000 strokes, and 1500 strokes were read. CREST Regular Flavor (Ohaio) with the Oral B 40 medium Straight toothbrush (Oral B Laboratories, Belmont, CA.) Each sample was brushed using Proctor &amp; Gamble, Cincinnati, OH toothbrush. One operator brushed all the samples using the force of the toothpaste force. Each sample was brushed using the same toothbrush. One toothpaste cycle was one stroke forward and one stroke backward.

<tables num="2"><img file="JP4842269B2_D0002.tif" /></tables><img file="JP4842269B2_D0003.tif" />

Preparation of starting material DiHEMA-P (mixture of HEMA phosphate and tetra HEMA pyrophosphate) POCl in a 1 liter three-necked round-bottom flask fitted with a reflux condenser with a gas inlet, a stirrer, and a dropping funnel with a gas outlet.₃76.7 g and 500 ml of THF were added. A solution of 130.5 g of HEMA, 101.5 g of triethylamine (TMA), and 87 g of THF was placed in a dropping funnel. The flask was cooled to about -5 ° C in an ice-water-salt bath. The solution was added dropwise over 25 minutes with stirring, during which the temperature was maintained at 0 ° C to -5 ° C. The mixture was stirred for 3 hours and the temperature was raised to room temperature. An additional 200 ml of THF was added to the flask to facilitate stirring. A solution of 51 g of TEA and 6.8 g of water in 50 ml of THF was added to the dropping funnel. After cooling the flask to 0-5 ° C in an ice-water-salt bath, the solution was added dropwise for 16 minutes. The mixture was allowed to reach room temperature and stirred for 18 hours. The mixture was filtered to remove precipitated salts and THF was removed in vacuo. The product (168g) is a pale orange liquid,¹H,¹³C, and³¹P-NMR characterized a mixture of mono-, di-, and tri-HEMA phosphates and tetra-HEMA pyrophosphates.

Filler A (Silane-treated nano-sized silica particles) Silane-treated nano-sized non-aggregated silica particles in the form of dry powder were prepared according to the following procedure. Nalco 2329 silica sol (400.82 g) was placed in a 1 quart wide-mouthed bottle. Methoxy-2-propanol (250.28 g) and A174 (6.15 g) were mixed together and added to the silica sol with stirring for about 5 minutes. The wide-mouthed bottle was sealed and heated to 80 ° C for 16 hours. The resulting white dispersion was subjected to a dispersion coating thickness of approximately 35 mils (0.9) according to the procedures described in (Patent Document 54) (Kolb et al.) And (Patent Document 55) (Huelsman et al.). Dry using the gap drying method on mm) and residence time 1.6 minutes (heating platen temperature 143 ° C and condensing platen temperature 21 ° C), fine freedom called filler A A fluid white powder was obtained. The nominal particle size of Filler A was considered to be the same as in the starting Nalco silica sol, i.e. about 75 nanometers (nm).

Filler B (silane treated silica cluster) Silane-treated nano-sized silica particles, loosely aggregated as silica clusters, were prepared in the form of free-flowing dry powder according to the following procedure. Nalco 2329 silica sol (1.0 kg), 91 cm Niro Spray Drier (Niro MOBILE MINOR Spray Drier, Columbia, MD, Columbia, Maryland) ) Was spray-dried at an inlet temperature of 325 ° C and an outlet temperature of 120 ° C. 330 g of the obtained dry solid sample was added to a 5.5 liter ball mill and milled for 16 hours to give a white powder, which averaged according to the average particle size according to the particle size analyzer test method described herein. It was determined to consist of silica clusters of size 5 micrometer. The primary silica particles that make up the silica cluster were considered to be the same size as in the starting Nalco 2329 silica sol, i.e., with a nominal particle size of about 75 nanometers.

100 g of the white powder sample was completely mixed with deionized water (300 g) by stirring with a magnetic stir bar for 2 minutes. The resulting homogeneous mixture was adjusted to pH 8.5 with ammonium hydroxide. A174 (3.5 g) was added and the contents were thoroughly mixed for 120 minutes using a magnetic stir bar to adjust the resulting mixture to a final pH of 8.25. The mixture was then sprayed with Buchi / Brinkman Mini Spray Drier, Model 190, Brinkmann Instruments, Westbury, NY, Buchi / Brinkman Mini Spray Drier, Model 190, Brinkmann Instruments. , Inc., Westbury, NY)) was spray-dried at an inlet temperature of 200 ° C and an outlet temperature of 85 ° C. The obtained fine free-flowing silane-treated (S / T) white powder was referred to as filler B.

Filler C (Silane treated silica-zirconia cluster) Silane-treated nano-sized silica and zirconia particles, loosely aggregated as substantially amorphous clusters, were prepared in the form of dry powder according to the following procedure. A 5.0 kg portion of Nalco 1042 silica sol was adjusted to pH 2.5 using dilute nitric acid. The pH adjusted sol was slowly added to zirconyl acetate (2.95 kg) and the resulting mixture was stirred for 1 hour. The mixture was then injected using a 91 cm Niro Spray Drier (Niro MOBILE MINOR Spray Drier, Columbia, MD, Columbia, Maryland). It was spray-dried at a temperature of 325 ° C and an outlet temperature of 120 ° C. The obtained solid was heat-treated (temporarily baked) at 550 ° C for 4 hours. The calcined solid was ball milled for 160 hours to give a white powder, which was determined to consist of silica clusters of average size 2 micrometers according to the average particle size according to the particle size analyzer test method described herein. Was done.

A 20 g sample of white powder was thoroughly mixed with deionized (DI) water (40 g) by stirring with a magnetic stir bar for 2 minutes. The resulting homogeneous mixture was adjusted to pH 8.5 with ammonium hydroxide. A174 (1.7 g) was added and the contents were thoroughly mixed for 120 minutes using a magnetic stir bar to adjust the resulting mixture to a final pH of 8.25. The mixture was then sprayed with Buchi / Brinkman Mini Spray Drier, Model 190, Brinkmann Instruments, Westbury, NY, Buchi / Brinkman Mini Spray Drier, Model 190, Brinkmann Instruments. , Inc., Westbury, NY)) was spray-dried at an inlet temperature of 200 ° C and an outlet temperature of 85 ° C. The obtained fine free-flowing white powder was referred to as filler C.

Filler D (Silane-treated nano-sized zirconia particles) Zirconia sol (800.0 g; 184 g of zirconia) and MEEAA (72.08 g) were placed in a 1 liter round bottom flask. Water and acid were removed by a rotary evaporator to obtain a powder (291.36 g), which was further dried in a forced air oven (90 ° C) to obtain a dry powder (282.49 g). Deionized (DI) water (501.0 g) was added to redisperse the powder. The resulting dispersion was placed in a 2 liter beaker, followed by stirring 1-methoxy-2-propanol (783 g; Sigma-Aldrich), SILQUE ST A-174 (83.7). g) and SILQUE ST A-1230 (56.3 g) were added. The resulting mixture was stirred at room temperature for 30 minutes, then divided into two quart wide-mouthed bottles and sealed. The wide-mouthed bottle was heated to 90 ° C. for 4 hours and the contents were concentrated on a rotary evaporator to give a liquid concentrate (621 g).

DI water (2400g) and concentrated ammonia / water (80.0g; 29% NH)₃) Was placed in a 4 liter beaker, followed by the addition of a liquid concentrate for about 5 minutes to give a white precipitate. The precipitate was collected by vacuum filtration and washed with DI water. The obtained wet cake was dispersed in 1-methoxy-2-propanol (661 g) to obtain a dispersion containing 15.33% by weight of zirconia. The silane-treated nanozirconia filler was referred to as filler D.

Primary particle size and aggregate particle size of the filler D is the same as in the starting zirconia sol in, i.e., each about 5 nanometers and 50-60 Na was considered Bruno meters.

Examples 1-18 Dental filler containing acid-reactive oxyfluoride nanostructured material Example 1 Aluminum-strontium-oxyfluoride material A 2 molar aluminum nitrate DI aqueous solution (80 ml) was added to a 2 molar strontium nitrate DI aqueous solution (20 ml) to give a "cation" solution. A 2 molar aqueous ammonium hydroxide DI solution (720 ml) was added to a 2 molar ammonium fluoride DI aqueous solution (180 ml) to give an "anion" solution. The "cationic" solution was quickly added to the "anionic" solution with rapid stirring. The resulting white precipitate powder was collected on a coarse filter paper using vacuum Buchner filtration and washed with DI water. The resulting water-wet solid material (wet cake) was referred to as Example 1. All starting compounds were obtained from Sigma-Aldrich.

Examples 2 to 6 Heat treated aluminum-strontium-oxyfluoride material An oxyfluoride material was produced as described in Example 1, except that the amounts of the cation solution and the anion solution were changed. The amount of starting solution volume of Examples 2-6 is shown in Table 1A. The precipitate was dried overnight at 100 ° C., heated at 250 ° C. for 1 hour, crushed with a mortar and pestle and passed through a 150 mesh sieve to give a white powder called Examples 2-6. The calculated molar ratios of cations to anions, fluoride content, and surface area of the filler powder were determined according to the test methods described herein, and the results are shown in Table 1C. A particle size analysis was performed on the heat treated precipitate (Example 3) according to the average particle size according to the particle size analyzer test method described herein and was calculated to be 7.35 micrometers.

Examples 7-10 Heat treated aluminum-strontium-silicon-oxyfluoride material The following changes were made to the procedure to include silica to produce an oxyfluoride material as described in Example 1. An aqueous sodium silicate solution (SS solution) containing 14% by weight sodium hydroxide and 27% by weight silica (Sigma-Aldrich) was diluted with DI water to 2 mol of sodium hydroxide per liter and A sodium silicate solution containing 2 mol of silica was formed. For example, 100 g of a commercially available SS solution containing 27 g of silica and 14 g of sodium hydroxide has 0.45 mol of silica and 0.45 mol of sodium hydroxide. To prepare a 2 molar sodium silicate solution, the SS solution was diluted with DI water to a final solution volume of 225 ml.

Precipitation reactions as described for Examples 2-6, except that 2 molar sodium silicate was used in place of part of the ammonium hydroxide solution, as shown in Table 1B under the heading "Base Solution". Was carried out. Table 1B shows the amount of each solution used in Examples 7-10. As described above for Examples 2 to 6, the precipitate was dried, heated and pulverized. The calculated molar ratios of cations to anions and fluoride content of the filler powders (Examples 7-10) were determined according to the test methods described herein and the results are shown in Table 1C.

For comparison, Table 1C also lists the fluoride content values of conventional FAS (fluoroaluminosilicate) glass materials (Comparative Examples CE-1, CE-2, and CE-3) prepared by the melting method. Table 1C also lists the fluoride content calculated for the two hypothetical compositions as reference values. As shown, the fluoride content of the "80/20 mol% Al / Sr" Al-Sr-OF material, in which all oxygen is present as hydroxyl groups and F constitutes half of the anion, has an F content of 29.6%. .. Pure fluoride compounds with the same cationic composition have an F of 60.4% by weight. The filler samples in Table 1C have a fluoride content in the range of 11.5 to 50% by weight.

<tables num="3"><img file="JP4842269B2_D0004.tif" /></tables>

<tables num="4"><img file="JP4842269B2_D0005.tif" /></tables>

<tables num="5"><img file="JP4842269B2_D0006.tif" /></tables>

Example 11 Porous particle agglomerates containing acid-reactive oxyfluoride material ("Cluster" of silica nanoparticles) The acid-reactive oxyfluoride filler material was coated or impregnated into clusters of nano-sized silica particles according to the following procedure. A "cationic" solution and an "anion" solution were prepared as described for Example 1. Filler B (7 g; S / T silica cluster) was added to the "anion" solution and the resulting solution was stirred for 10 minutes. The "cationic" solution was then added to the "anionic" solution with high speed stirring. The obtained white precipitate powder was collected, dried, heated, pulverized and sieved as described in Examples 2 to 6 to obtain a white powder called a filler of Example 11. The weight ratio of the "cluster" to acid-reactive oxyfluoride material of the filler of Example 11 was about 1: 2.

Example 12 Porous particle agglomerates containing acid-reactive oxyfluoride material (Silica-zirconia nanoparticles "cluster") The acid-reactive oxyfluoride filler material was coated or impregnated into clusters of nano-sized silica-zirconia particles according to the following procedure. A "cationic" solution and an "anion" solution were prepared as described for Example 1. Filler C (7 g; S / T silica-zirconia clusters) was added to the "anion" solution and the resulting solution was stirred for 10 minutes. The "cationic" solution was then added to the "anionic" solution with high speed stirring. The obtained white precipitate powder was collected, dried, heated, pulverized and sieved as described in Examples 2 to 6 to obtain a white powder called a filler of Example 12. The weight ratio of the "cluster" to acid-reactive oxyfluoride material of the filler of Example 12 was about 1: 2.

Example 13 Ball mill crushed oxyfluoride material An acid-reactive oxyfluoride material was prepared as described in Example 1. After precipitation, filtration, and washing, the water-wet precipitate was heated at 250 ° C. for 1 hour. The heat treated precipitate was then added to DI water to form a 25% by weight suspension. The suspension was ball milled for 72 hours using a 1/4 inch alumina medium. The resulting milled suspension was collected and centrifuged at 10,000 rpm for 10 minutes. The wet cake is removed from the centrifuge tube and hand-pressed between sheets of coarse (hard) filter paper to further dehydrate to a water concentration of 50% by weight to obtain a hard clay-like mass called Example 13. It was. Some of the clay-like materials were easily dispersible in the resin constituents of the Paste A composition (see Table 4A). A particle size analysis was performed on the ball milled suspension according to the average particle size according to the particle size analyzer test method described herein and calculated to be 1.31 micrometers.

Example 14A Atreit Mill Milled Oxyfluoride Material After preparing the acid-reactive oxyfluoride material as described in Example 1, the Attritor Mill, Akron, Ohio, Union Process, Model 01, Akron, Mill crushed by using Ohio)). After precipitation, filtration, and washing, the water-wet precipitate was heated at 250 ° C. for 1 hour. In preparation for milling, the heat treated precipitate was added to DI water to form a 10 wt% suspension. This suspension, 2 mm ZrO₂The medium was used to grind attritor mills at 100% output for 1 hour. The resulting milled suspension was collected and centrifuged at 10,000 rpm for 10 minutes. The wet cake is removed from the centrifuge tube and further dehydrated by hand pressing between sheets of coarse (hard) filter paper to a concentration of 50% by weight of water to obtain a hard clay-like mass called Example 14A. It was. Some of the clay-like materials were easily dispersible in the resin constituents of the Paste A composition (see Table 4B). A particle size analysis was performed on the attritor milled suspension according to the average particle size according to the particle size analyzer test method described herein and was calculated to be 0.871 micrometers.

Example 14B Oxyfluoride material ground in an optimized attritor mill After preparing the acid-reactive oxyfluoride material as described in Example 1, by using an Attritor Mill (Union Process, Model 01). Mill crushed. After precipitation, filtration, and washing, the water-wet precipitate was heated at 250 ° C. for 1 hour. In preparation for milling, the heat treated precipitate was added to DI water to form a 10 wt% suspension. This suspension, 0.5 mm and 2 mm ZrO₂The medium was attritor milled at 100% power for 2 hours using a 25/75 ratio. The resulting milled suspension was collected and centrifuged at 9,600 rpm for 6 minutes. The wet cake is removed from the centrifuge tube and further dehydrated by hand pressing between sheets of coarse (hard) filter paper to a concentration of 50% by weight of water to obtain a hard clay-like mass called Example 14B. It was. Some of the clay-like material was easily dispersible in the resin component of the Paste A composition (see Table 4C). According to the average particle size according to the particle size analyzer test method described herein, particle size analysis was performed on suspensions ground in an optimized attritor mill and calculated to be 0.163 micrometers.

Example 15 Non-dry oxyfluoride material An acid-reactive oxyfluoride material was prepared as described in Example 1. The undried precipitate was then centrifuged at 9,600 rpm for 6 minutes. The wet cake is removed from the centrifuge tube and hand-pressed between sheets of coarse (hard) filter paper to further dehydrate to a water concentration of 50% by weight to obtain a hard clay-like mass called Example 15. It was. Some of the clay-like materials were easily dispersible in the resin constituents of the Paste A composition (see Table 4C).

Examples 16-18 Oxyfluoride material containing other metal ions The acid-reactive oxyfluoride material was prepared as described in Example 1, but the composition was substituted to contain ions such as La, Y and Ca. Further treatment was carried out according to the mill pulverization / centrifugation / dehydration process described in Example 14B to obtain a hard clay-like mass called Examples 16-18. The amount of solution is shown in Table 2 below. Some of the clay-like materials (Examples 16-18) were easily dispersible in the resin constituents of the Paste A composition (see Table 4C). According to the average particle size according to the particle size analyzer test method described herein, particle size analysis was performed on the optimized attritor mill ground suspension of Example 16 and calculated to be 0.2 micrometers. Was done.

<tables num="6"><img file="JP4842269B2_D0007.tif" /></tables>

Evaluation and Results-Oxyfluoride Material Evaluation of oxyfluoride material curing efficiency Oxyfluoride filler materials (Examples 3, 7, and 11) were prepared without milling and sieving steps, combined with test resins, and cured efficiency was evaluated according to the test methods described herein. The results are shown in Table 3A and compared with the curing results of conventional glass fillers (Comparative Examples CE-1 to CE-3). The set of four numbers represents the curing efficiency with respect to the degree of qualitative curing after 1 hour, 1 day, 2 days, and 3 days (see test method, scale 0-5).

<tables num="7"><img file="JP4842269B2_D0008.tif" /></tables>

Similarly, crushing and sieving (150 mesh) was performed to prepare the additional oxyfluoride filler material of Example 3 and the curing efficiency described in the paragraph above was evaluated. Table 3B shows the results of Example 3 prepared by crushing and sieving and the results of Examples 16 to 18 (samples crushed by an optimized attritor mill). In these samples, the set of four numbers shows the degree of qualitative cure after 1 hour, 3 hours, 5 hours, and 7 hours (based on a scale of 0-5, see test method). Represents efficiency.

<tables num="8"><img file="JP4842269B2_D0009.tif" /></tables>

Comparing the data in Tables 3A and 3B, it can be seen that Example 3 prepared by grinding and sieving drastically reduced the curing time compared to Example 3 without grinding and sieving. The former showed remarkable curing in 1 to 4 hours at a filling rate of only 20% (1: 4 ratio), while the latter took 3 days to completely cure. Examples 16-18 (mill-milled samples) were also completely cured in 3 hours. Complete curing of Example 3 prepared by grinding and sieving is observed in 1 hour at a filling rate of 33% (1: 2 ratio), whereas without grinding and sieving. Example 3 is one day.

Therefore, comparing the data in Tables 3A and 3B, the precipitated acid-reactive oxyfluoride filler material (after milling or milling) is a conventional melt-processed glass filler or oxyfluo that has not been milled or milled. It can be seen that it has a high curing efficiency as compared with the ride material. Therefore, it can be concluded that at least some dispersion is required to obtain the high curing efficiency imparted by the high surface area filler. The coarsely heat-treated granules of the oxyfluoride material exhibited a curing efficiency similar to that of conventional glass. Simply grinding and sieving the coarse granules (ie, aggregates) (150 mesh) significantly improved the curing efficiency of the acid-reactive oxyfluoride filler material. Mill-milled acid-reactive oxyfluoride filler materials with La or Y cations (instead of Al) or Ca cations (instead of Sr) also exhibit high curing efficiency.

Example 19 Two-dosage form composition First paste composition (pastes A1 to A20) An acid-reactive oxyfluoride filler material was prepared as described in Example 13. The obtained clay-like material containing 50% by weight of water was blended into the first paste compositions A1 to A5 described later.

In addition, an acid-reactive oxyfluoride filler material was prepared as described in Example 14A. The obtained clay-like material containing 50% by weight of water was blended into the first paste compositions A6 to A13 described later.

In addition, an acid-reactive oxyfluoride filler material was prepared as described in Example 14B. The obtained clay-like material containing 50% by weight of water was blended into the first paste compositions A14 to A15, A17 to A18, and A20 described later. Similarly, the filler material of Example 15 was prepared and blended into the first paste composition A16, and the filler material of Example 16 was prepared and blended into the first paste composition A19.

A first paste composition (pastes A1 to A20) was prepared by combining the components listed in Tables 4A, 4B, and 4C (shown as parts by weight). The composition was prepared by weighing the exact amounts of HEMA, DMAPE and ATU and then mixing at high speed for 30 seconds. Next, the following components CPQ and EDMAB were added, followed by high speed mixing for 30 seconds. Next, PEGDMA was added and mixed at high speed for 30 seconds. At this time, nano-sized acid-reactive fillers (Example 1) and DI water (treated together in a "clay" form, as described in Examples 13-16) were added. The resulting mixture was mixed manually and mixed at high speed until homogeneous. In the final step, optional non-acid-reactive filler components (eg, fillers A-D) were added and mixed for an additional minute or at high speed until the paste was homogeneous. The compositions of pastes A1 to A5 are listed in Table 4A, the compositions of pastes A6 to A13 are listed in Table 4B, and the compositions of pastes A14 to A20 are listed in Table 4C.

<tables num="9"><img file="JP4842269B2_D0010.tif" /></tables>

<tables num="10"><img file="JP4842269B2_D0011.tif" /></tables>

<tables num="11"><img file="JP4842269B2_D0012.tif" /></tables>

Second paste composition (pastes B1 to B21) A second paste composition (pastes B1 to B21) was prepared by combining the components listed in Tables 5A, 5B and 5C (indicated by parts by weight). After dissolving VBCP in HEMA, DPIPF6 was added and prepared by stirring at high speed for 30 seconds. For paste compositions B1-B4, Di-HEMA-P, GDMA / Bis-GMA (premixed together), and Ebecryl 1830 were added, followed by high speed stirring for 60 seconds. For paste compositions B5 to B21, Di-HEMA-P, BisGMA / UDMA / TEGDMA / BisEMA6 (premixed together), and Ebecryl 1830 were added, followed by high speed stirring for 60 seconds. KPS was then added, followed by high speed stirring for 60 seconds. The paste was then stirred at high speed for 30 seconds. In the final step, optional non-reactive filler components (eg, fillers A to C) are added and mixed at high speed for an additional minute or until the paste is homogeneous. The compositions of pastes B1 to B5 are listed in Table 5A, the compositions of pastes B6 to B14 are listed in Table 5B, and the compositions of pastes B15 to B21 are listed in Table 5C.

<tables num="12"><img file="JP4842269B2_D0013.tif" /></tables>

<tables num="13"><img file="JP4842269B2_D0014.tif" /></tables>

<tables num="14"><img file="JP4842269B2_D0015.tif" /></tables>

Evaluation and Results-Paste-Paste Composition Hardened Paste-Evaluation of Paste Composition By kneading a constant weight of the newly prepared first paste composition (paste A) with a constant weight of the newly prepared second paste composition (paste B) in a spatula for 25 seconds. A paste-paste combination composition was prepared. The resulting composition is referred to as a test sample and is subject to the following tests according to the test methods described herein: Compressive strength (CS), Diameter strength (DTS), Bending strength (FS), Adhesion to dentin (DA). , Adhesion to enamel (EA), visual impermeability (VO), X-ray impermeability (RO), lubricity retention, and one or more of fluoride release. The amount of paste used and subsequent test results are reported in Tables 6A (Experiments 1-8), Tables 6B (Experiments 9-19) and Tables 6C (Experiments 20-26), and in the text following the table.

<tables num="15"><img file="JP4842269B2_D0016.tif" /></tables>

<tables num="16"><img file="JP4842269B2_D0017.tif" /></tables>

<tables num="17"><img file="JP4842269B2_D0018.tif" /></tables>

From the data listed in Tables 6A to 6C, the cured paste-paste composition containing the acid-reactive oxyfluoride filler material of the present invention has high mechanical strength (CS, DTS and FS values). It can be seen that it shows good to excellent visual aesthetics (proven by a low value of visual impermeability) when it is (proven by high).

From the data listed in Tables 6B to 6C, nano-sized zirconia fillers with good X-ray opacity without loss of visual aesthetics when used in combination with acid-reactive oxyfluoride filler materials. It can be seen that a cured composition is obtained.

Fluoride release was measured for two of the cured compositions, which was 1,100 μg F / g after 29 days in Experiment 17, 1,992 μg F / g after 180 days, and 745 μg F / g after 29 days in Experiment 19. I found out.

Slippery retention was measured for one of the cured compositions (Experiment 23) and found to be greater than 80% after 2000 strokes of toothpaste.