Basic core material encapsulated in an inorganic shell, suitable for use as a biocarrier material.

Abstract

To provide a hardenable dental composition comprising an encapsulated material.SOLUTION: Provided is a composition comprising (e.g. a first part comprising) an encapsulated material comprising a basic core material and an inorganic shell material comprising a metal oxide surrounding the core; and (e.g. a second part comprising) water or an acidic component. Also provided is an encapsulated material suitable for use in a biological carrier material. The material comprises a basic core material and an inorganic shell material comprising a metal oxide surrounding the core.SELECTED DRAWING: None

Description

[Background technology]

[0001] Various cements suitable for medical and dental use have been described. See, for example, U.S. Patent No. 5,154,762, International Publication No. 2016 / 005822, and U.S. Patent Application No. 2008 / 0058442 by Mitra et al. [Overview of the project]

[0002] In one embodiment, a curable dental composition is described, the curable dental composition comprising a first part including an encapsulated material, wherein the encapsulated material comprises a basic core material and an inorganic shell material containing a metal oxide surrounding the core, A second part comprising water or an acidic component.

[0003] In a typical embodiment, when the first and second parts are combined, the composition initially has an acidic or neutral pH. The shell is decomposable by water or the acidic component of the second part. The basic core material releases -OH during the decomposition of the shell, thereby increasing the pH.

[0004] In some embodiments, the basic core material is curable, as in the case of calcium silicate. In some embodiments, the composition further comprises at least one second filler, such as fluoroaluminosilicate (FAS) glass and / or nanoscale particulate fillers. In some embodiments, the first and / or second parts comprise a polymerizable material.

[0005] In another embodiment, a composition is described which comprises an enclosed material including a basic core material and an inorganic shell material containing a metal oxide surrounding the core, and water or an acidic component.

[0006] In another embodiment, an encapsulated material suitable for use in a biocarrier material comprises a basic core material and an inorganic shell material containing a metal oxide surrounding the core. Curable (e.g., dental) compositions containing the encapsulated material are also described. In some embodiments, the curable composition further comprises a second filler and / or polymerizable material as described herein. In some embodiments, the curable or curable composition comes into contact with water or acidic components (e.g., biological fluids) during use.

[0007] Curable or hardened (e.g., cured) compositions as described herein Various methods of use are also described, including preparing and applying the composition to a tooth or bone structure. In some embodiments, the composition comprises a polymerizable material, and the method further comprises curing the composition by exposing it to a radiation source. Curable or hardened (e.g., cured) compositions have delayed release of basic core material, delayed increase of basicity, Various technical effects can be achieved, such as promoting remineralization of tooth or bone structures and increasing the average ALP activity of dental pulp cells. In some embodiments, the composition is a dental adhesive or cement used to bond dental articles to tooth structures. In other embodiments, the composition is a dental restorative agent. [Modes for carrying out the invention]

[0008] This specification describes encapsulated materials. Encapsulated materials are suitable for use in biocarrier materials such as curable dental compositions. Encapsulated materials comprise a chemically basic core material and an inorganic shell material surrounding the core. The shell material and the thickness of the shell can be selected to allow control and / or delayed release or reaction of the basic core material. In some embodiments, the release of the basic core material is utilized to increase basicity after a long period of time.

[0009] The encapsulated filler contains a basic core material. The basic core material, as well as the material (e.g., compound) in which the core is formed, are generally solid at 25 °C.

[0010] The basic core can be a single particle or a plurality of smaller associated particles. As used herein, the term "associated" refers to a group of two or more primary particles that are aggregated and / or agglomerated. Similarly, the term "non-associated" refers to a group of two or more primary particles that do not include aggregation and / or agglomeration formation.

[0011] In some embodiments, the basic core may include a plurality of aggregated particles. "Aggregation" or "aggregation" refers to a strong association between primary particles. For example, the primary particles can be chemically bonded to each other. Decomposing the aggregate into smaller particles (e.g., primary particles) is typically not achieved during the production and encapsulation of the core material such that the aggregated core particles remain as aggregates. Similarly, the term "non-aggregated" refers to primary particles that do not include a strong association with other primary particles.

[0012] In other embodiments, the basic core may include a plurality of agglomerated particles. As used herein, the term "agglomeration formation" or "agglomeration" refers to a weak association of primary particles. For example, the primary particles may be held together by charge or polarity. Decomposing the aggregate into smaller particles (e.g., primary particles) can occur during the production and encapsulation of the core material. Similarly, the term "non-agglomerated" refers to primary particles that do not include a strong association with other primary particles.

[0013] The average (e.g., primary, associated, or agglomerated) particle size of the core, when measured using, for example, a sedimentation analyzer, is typically at least 0.2, 0.5, 1, 2, 3, 4, or 5 micrometers, typically less than 1 mm, less than 750 micrometers, or less than 500 micrometers. In some embodiments, such as in the case of curable dental compositions, the basic core material typically has an average (e.g., primary, associated, or agglomerated) particle size of 250, 200, 150, 100, or less than 50 micrometers. Since the shell is typically thin, the encapsulated material also falls within the range of average particle sizes described above.

[0014] The core material is basic. Chemically basic materials are those that donate electrons, accept protons, and typically provide hydroxyl ions to aqueous solutions.

[0015] The core of the enclosed material is considered basic if it has or exhibits one or more of the following properties, including containing a sufficient amount of high pKa components, resulting in a basic pH when added to deionized water (according to the test methods further described in the Examples), or resulting in a basic pH when added to an acidic buffer (according to the test methods further described in the Examples).

[0016] Basic materials function to react with acids and acidic buffers to produce an increase in pH. The change in pH and the rate of pH change depend on the strength of the basic component, the chemical and physical form of the basic component within it, and the amount of basic component in the core material.

[0017] In some embodiments, the core of the encapsulated material is strongly basic. The strongly basic material typically comprises and is prepared from a sufficient amount of strongly basic material (e.g., compounds) having a pKa in the range of about 11–14. Examples of strongly basic compounds include oxides and hydroxides of alkali and alkaline earth metals, and strongly basic salts such as alkali phosphates. Specific examples of strongly basic core compounds include oxides and hydroxides of Na, K, Ca, Sr, and Ba, silicates of Na, K, Ca, Sr, and Ba, and aluminates of Na, K, Ca, Sr, and Ba. Strongly basic silicates and glasses typically contain at least 1, 2, or 3 moles of strongly basic core compound (e.g., CaO) per mole of silica, on a cation molar basis. Similarly, strongly basic aluminates typically contain at least 1, 2, or 3 moles of strongly basic core compound (e.g., CaO) per mole of alumina, on a cation molar basis.

[0018] In some embodiments, the strongly basic material may be a heterogeneous physical mixture of at least one strongly basic compound and a weakly basic or neutral material. For example, the strongly basic material may be a physical mixture of silica and sodium hydroxide. Sodium hydroxide is a strongly basic material having a pKa of 13.8. A 0.1N aqueous solution of sodium hydroxide has a pH of 13. On a weight percentage basis, 1 gram of a mixture of 96 wt% silica and 4 wt% sodium hydroxide in 1 liter of water will provide a 0.1N aqueous solution of sodium hydroxide. If the enclosed material is a physical mixture, substantially all strongly basic compounds are reachable upon shell decomposition. Therefore, in this embodiment, the basic core material may contain a small amount (e.g., at least 1, 2, or 3 wt% of the strongly basic material) to provide a delayed pH of at least 8.5 or 9 in deionized water (according to the test method described in the examples). However, a higher concentration of chemically basic core material may be required to provide a delayed pH of at least 8.5 or 9 in an acidic buffer solution. For example, depending on the pKa of the strongly basic material, the amount of the strongly basic material may be at least 5, 6, 7, 8, 9, or 10% by weight of the total encapsulated material.

[0019] In other embodiments, the core of the encapsulated material is a multicomponent crystalline compound comprising at least one strongly basic material (e.g., a compound) and other components (e.g., alkaline earth silicates) prepared therefrom. In yet another embodiment, the core of the encapsulated material can be characterized as a multicomponent amorphous glass prepared from at least one strongly basic material (e.g., a compound). The strongly basic material (e.g., a compound) can be distributed homogeneously or heterogeneously within the glass structure. When the core of the encapsulated material is a molten multicomponent material such as glass, the concentration of the strongly basic compound (which can be determined by X-ray fluorescence (XRF) or inductively coupled plasma (ICP)) is typically in the range of at least 25, 30, 35, 40, 45, or 50% by weight to a maximum of 75% by weight or more, based on the entire basic core material.

[0020] In some preferred embodiments, the core comprises and is prepared from CaO having a pKa of 11.6. The CaO can be utilized to provide both a calcium ion source and a delay in the rise of pH. The amount of CaO is typically at least 5, 10, 15, 20, or 25% by weight, and can extend up to 75% by weight or more. The amount of Ca is approximately 71% of such a value.

[0021] Specific examples of strongly basic multi-component core materials containing CaO include Portland cement (reported to contain 60-70% by weight of CaO), tricalcium silicate (containing approximately 75% by weight of CaO), and bioactive glass (containing approximately 25% by weight of CaO and approximately 25% by weight of Na2O), such as that available from 3M Advanced Material Division.

[0022] In other embodiments, the core of the encapsulated material is weakly basic. The weakly basic material comprises at least one material (e.g., a compound) having a pKa of at least 8 but less than 11. Examples of weakly basic core compounds include oxides of Cu, Zn, and Fe, as well as weakly basic salts such as NaF, Ca acetate, and hydrogen phosphate.

[0023] Alternatively, the weakly basic core material may contain or be prepared from a smaller amount of a strongly basic compound. A weakly basic core material alone typically cannot provide a sufficient amount of hydroxyl ions to adequately raise the pH of an acidic solution. However, a weakly basic core material alone can provide a sufficient amount of hydroxyl ions to adequately raise the pH of water. Furthermore, encapsulated weakly basic core materials can be used in combination with encapsulated strongly basic core materials.

[0024] The embedded basic material is typically not a reducing agent in a redox curing system. In some preferred curable materials (e.g., dental or medical), a preferred technical effect is to control the pH so that the composition is acidic for a sufficient time to promote adhesion, and then becomes basic to promote remineralization. This pH change is sufficiently delayed so that it occurs after curing. The embedding of a reducing agent will delay the redox curing reaction. Furthermore, since reducing agents are typically weak bases used at relatively low concentrations, the embedded reducing agent alone will not produce the desired increase in pH.

[0025] In preferred embodiments, the core material further comprises and is prepared from one or more neutral compounds, as defined herein, having a pKa of at least 6, 6.5, or 7 and less than 8. In some embodiments, such neutral compounds exhibit low solubility in deionized water and / or weak acid solutions and / or weak base solutions. Weak acid solutions typically have a pH greater than 4 but less than 7. Weak base solutions typically have a pH greater than 10 but greater than 7. Low solubility means that less than 100 grams (i.e., 10% by weight) dissolves per liter. In some embodiments, less than 50, 25, 5, or 1 gram dissolves per liter. Examples of neutral compounds include silica, zirconia, titania, alumina, and combinations thereof. A pKa greater than 7 is slightly basic, but such basicity is less than that of weakly basic core materials and significantly less than that of strongly basic core materials, as described above.

[0026] If the core material is prepared from only basic materials (e.g., compounds) or from a combination of basic materials and neutral materials, the basicity of the core material can be estimated based on the weight of the components. Therefore, the core material contains the aforementioned amount of basic materials (e.g., compounds).

[0027] However, if the core material further contains acidic materials (e.g., compounds), it can be more difficult to estimate its basicity. In particular, for embodiments where it is difficult to estimate the basicity of the core material based on its composition or compositional analysis, the basicity of the core material or encapsulated core material can be defined by the change in pH of a specific amount of the material in deionized water or an acidic (e.g., buffer) solution. These tests can also be used to confirm that the core material or encapsulated core material is indeed basic.

[0028] For example, fluoroaluminosilicate (FAS) glass is a homogeneous glass structure prepared from approximately 19% by weight of a strongly basic compound (SrO), with the remainder being neutral (SiO2) and other compounds. Referring to Table 11, when tested in deionized water according to the test method described in the examples, FAS glass reduces the pH to 6.5 within 15 minutes and is therefore considered a weakly acidic core material.

[0029] In some embodiments, the basicity of the core material or encapsulated core material can be determined by the pH change of a specific amount (0.25 g) of the material in 25 g of deionized water. Unencapsulated core material typically changes the pH of the deionized water from neutral to at least 8.5 or 9. This typically occurs within 1, 2, 3, 4, or 5 minutes, but may take up to 1 or 24 hours. For example, referring to Table 10, an unencapsulated (e.g., bioactive glass) core material can bring the water to a pH of 10 within 20 seconds. The same encapsulated core material takes longer to bring about such a pH time because the core material cannot release hydroxyl ions until the inorganic shell material has sufficiently decomposed by dissolution or other means. However, if there is only a small amount of unencapsulated material or less encapsulated material than the bulk of the sample, even in the case of encapsulated material, a rapid but smaller pH change may occur in DI water.

[0030] In preferred embodiments, the basicity of the core material or encapsulated material can be determined by the change in pH of a specific amount (0.25 g) of the material in a buffer solution, or by the change in pH of 15 g of deionized water and 10 g of aqueous potassium bituminate buffer (e.g., buffer BDH5018 having a pH of 4) adjusted to pH 4.00 at 25°C (with hydrochloric acid). This test is referred to herein as the “buffer test”. When a strongly basic core material or encapsulated material is subjected to the buffer test, it may reach a pH of at least 8.5 or 9. It is understood that a larger amount of hydroxyl ions is required to change an acidic solution to a basic pH compared to deionized water. Therefore, this pH change may take a longer time compared to the same material in deionized water. In some embodiments, such a pH change occurs within 5, 10, or 15 minutes, but may take up to 1 hour or 24 hours. Since the core material cannot release hydroxyl ions that react with the acid until the inorganic shell material has sufficiently decomposed by dissolution and / or decomposition, it takes a much longer time for the same encapsulated core material to produce such a pH change. In one embodiment, referring to Table 8, an unencapsulated (e.g., bioactive glass) core material achieves a pH of 8.5 according to a buffering test within 15 minutes and a pH of 9 within 40 minutes. The same encapsulated (e.g., bioactive glass) core material achieves a pH of 8.5 according to a buffering test within 35 minutes, and the pH continues to rise after 1 hour.

[0031] Weakly basic core materials may result in a small increase in pH when tested according to a buffering test. For example, the pH may rise from 4 to 5. However, weakly basic core materials do not provide a sufficient amount of hydroxyl ions to bring the pH to at least 8.5 or 9 when tested according to a buffering test.

[0032] Therefore, the enclosed basic core material does not change pH initially (i.e., immediately after immersion of the material in water or buffer solution) as described herein, but the pH increases at various rates depending on the shell and basic core material.

[0033] In some embodiments, the basic core material is curable or self-curing when mixed with water, as in the case of various natural and synthetic cements. Conventional natural (e.g., Portland) and synthetic cements typically contain a large amount of calcium silicate (e.g., 3CaO-SiO2, 2CaO-SiO2) alone or in combination with one or more calcium aluminates (e.g., 3CaO-Al2O3, 4CaO-Al2O3-Fe2O3). If the basic core material is curable or self-curing, such a basic core material may be the only curable material in a curable composition. Therefore, the first part of the composition may contain 100% encapsulated basic core material.

[0034] Water-based medical and dental cements, such as those described in U.S. Patent No. 5,154,762 by Mitra et al., typically do not contain large amounts of calcium silicate. Rather, such compositions generally contain particulate materials that can be characterized as acid-reactive metal oxides or acid-reactive glass fillers (e.g., FAS glass). These types of fillers do not self-cur when mixed with water. However, such acid-reactive fillers can be combined with polyfunctional acid components to provide curable materials.

[0035] In some embodiments, the encapsulated material is an encapsulated (e.g., dental) filler. The encapsulated (e.g., dental) filler may contain a substantial amount of a neutral metal oxide having low solubility in water or an acidic solution having a pH of 3-4, as described above. Examples of neutral metal oxides include silica, zirconia, titania, and alumina. The amount of neutral metal oxide may range from at least 10, 15, 20, 25, 30% by weight to a maximum of 50, 60, 70, 80, or 90% by weight of the total weight of the basic core material. The encapsulated calcium silicate may also be characterized as a filler due to its silica content.

[0036] The curable dental composition or other suitable (e.g., biological) carrier material comprises materials that promote remineralization, such as materials that release calcium ions, phosphorus-containing ions (e.g., phosphates), fluoride ions, or combinations thereof. These materials may be present within the core of an encapsulated filler, provided as a second filler such as FAS glass, or provided as separate components in the curable dental composition.

[0037] In some embodiments, the core of the encapsulated (e.g., filler) material preferably includes a material that promotes remineralization, such as a material that releases calcium ions, phosphorus ions, fluoride ions, or a combination thereof. CaO can function as both a highly basic material (e.g., a compound) and a calcium ion source, as described above. If the basic core material includes a strongly basic material that does not release calcium ions, the core may further include another calcium material, such as a calcium salt (e.g., calcium glycerophosphate).

[0038] In some embodiments, the core of the encapsulated (e.g., dental) filling further comprises and is prepared from a material that promotes remineralization by the release of fluoride ions. In other embodiments, the (e.g., dental) composition further comprises a second filling containing a material that promotes remineralization by the release of fluoride ions. The core or second filling material comprises and is prepared from a fluoride compound such as AlF3, Na2AlF3, and mixtures thereof in an amount ranging from about 5 to 40% by weight. In some embodiments, the amount of AlF3 is in the range of 10 to 30% by weight of the core or second filling material. In some embodiments, the amount of Na2AlF3 is in the range of 2 to 10% by weight of the core or second filling material.

[0039] In some embodiments, the core of the encapsulated (e.g., dental) filling further comprises a material that promotes remineralization by the release of phosphorus ions. In other embodiments, the (e.g., dental) composition further comprises a second filling that comprises a material that promotes remineralization by the release of fluoride ions. In some embodiments, the core or second filling material comprises and is prepared from phosphorus compounds such as P2O5, AlPO4, and mixtures thereof in an amount ranging from 2 to 25% by weight. In some embodiments, the amount of P2O5 is in the range of 2 to 15% by weight of the core or second filling material. In some embodiments, the amount of AlPO4 is in the range of 2 to 10% by weight of the core or second filling material.

[0040] The basic core can be encapsulated in an inorganic shell containing a metal oxide by any suitable method, such as vapor deposition, atomic layer deposition (ALD), sputtering, or evaporation, which are well known in the art.

[0041] In some embodiments, the method for producing the encapsulation material includes, as described above, preparing basic core particles and encapsulating the basic core particles with an inorganic coating (e.g., a continuous non-particulate coating) using at least one of the vapor deposition techniques. Examples of vapor deposition techniques include chemical vapor deposition (CVD) methods such as atmospheric pressure chemical vapor deposition (APCVD), hydrolysis CVD, and plasma CVD.

[0042] An advantage of vapor deposition techniques for producing coatings is that the coating is constructed from molecular-sized species without interference from solvents or liquid media. Some coating methods (e.g., ALD and CVD) tend to produce coatings consisting of conformal layers on irregular materials (e.g., powders or porous microparticles).

[0043] ALD and CVD are coating processes involving chemical reactions, and the chemical reactants used are called chemical precursors. That is, they are precursors to the coating material to be formed (e.g., a metal oxide coating) (i.e., coating precursors). In some embodiments, a single coating precursor is used, while in other embodiments, at least two coating precursors are used. At least one coating precursor contains at least one metal cation required for the coating (e.g., a metal oxide coating).

[0044] A single coating precursor can be used if simple decomposition of the precursor (e.g., thermal decomposition or plasma-enhanced decomposition) is sufficient to form a coating. At least two coating precursors (e.g., metal oxide precursors) are used when at least one coating precursor contains at least one metal cation and chemically reacts with at least one additional precursor (i.e., a co-reactant) to form a coating (e.g., a metal oxide coating). The additional coating precursor is a co-reactant to the coating precursor containing at least one metal cation. The co-reactant chemically reacts with the coating precursor containing at least one metal cation to form a coating.

[0045] ALD coatings generally deposit one monolayer at a time via alternative pulses of a chemical precursor (e.g., a coating precursor containing at least one metal cation), absorption of a monolayer of the precursor, removal of excess precursor, and pulsed co-reactants (e.g., co-reactants to a coating precursor containing at least one metal cation). Therefore, these coatings tend to be conformal and uniform. Alternatively, for example, ALD systems can also deposit thicker, non-self-limiting coatings, where significantly larger amounts of each chemical reactant adsorb to the substrate during each pulse or cycle than are adsorbed in a monolayer, resulting in the deposition of a much larger volume of coating.

[0046] CVD coatings can involve similar chemical reactions, but both precursors are typically supplied simultaneously and sequentially. Homogeneity can be improved by continuously mixing the powder being coated.

[0047] An effective coating method for producing the encapsulated materials described herein is atmospheric pressure CVD (APCVD). APCVD can be carried out in simple equipment such as glassware. In some embodiments, a hydrolysis reaction is used to form a (e.g., continuous) metal oxide coating at temperatures ranging from room temperature (about 22°C) to about 180°C.

[0048] Examples of precursors for ALD and CVD processes include coating precursors (e.g., metal oxide precursors) containing at least one metal cation, such as metal alkyls (e.g., trimethyl or triethylaluminum, diethylzinc), volatile metal chlorides (titanium tetrachloride, silicon tetrachloride, aluminum trichloride), silanes, metal alkoxides (titanium isopropoxide, aluminum isopropoxide, silicon ethoxide), mixed alkyls, halides, hydrides, alkoxys, and compounds having other groups, as well as other volatile metal-organic compounds. Examples of co-reactants for coating precursors containing at least one metal cation (e.g., metal oxide precursors containing at least one metal cation) include water, oxygen, ozone, ammonia, and alkylamines. In addition to metal oxides, other inorganic and non-metallic coating materials are deposited using chemical reactions between the coating precursor and co-reactants for the coating precursor (e.g., metal nitride coatings are deposited using a metal nitride precursor containing at least one metal cation and a co-reactant for the metal nitride precursor).

[0049] Exemplary (e.g., continuous) coatings include nonmetallic inorganic materials such as metal oxides (e.g., Al, Si, Ti, Zr, Mg, and Zn). In some embodiments, the shell material includes at least 50, 60, 70, 80, 90, or 100% by weight of a single metal oxide or a combination thereof. Exemplary metal oxides include forms such as hydroxides and hydrated oxides, as well as forms containing mixed anions (e.g., halides, hydroxyls, small amounts of alkyl or carboxylates in addition to oxides). The shell material is mainly inorganic with a carbon content of 20, 10, 5, or 1% by weight or less. Furthermore, the encapsulated basic material may also have a carbon content of 20, 10, 5, or 1% by weight or less. The shell material may further include metal nitrides, metal sulfides, metal oxysulfides, and metal oxynitrides. The coating may be amorphous, crystalline, or a mixed single-phase or multiphase, and may contain one or more cations and one or more anions. In some embodiments, the coating is amorphous alumina containing or not containing some hydroxyl or bound water.

[0050] The shell material may be a weakly basic material. However, the basicity of the shell material is not sufficient to produce the desired pH change, particularly according to the buffering test or disk buffering test described above (as described below).

[0051] In some embodiments, encapsulation of basic particles in a continuous coating is carried out via an APCVD coating process, where an alumina-based coating is obtained using trimethylaluminum (TMA) and water. Precursors can be introduced into the reaction chamber by flowing carrier gases through bubblers for each liquid precursor. Generally, as is typical of CVD processes, carrier gases containing each component are delivered simultaneously and continuously into the reaction chamber. The desired flow rates and ratios can be adjusted to produce the desired amount and properties of the coating. In some embodiments, the flow rates of trimethylaluminum (TMA) and water are independently set to at least 50 or 100 cm³. 3 / min to 1000, 1500, or 2000cm 3 The flow rate is in the range of / min. The water flow rate is typically higher than the TMA flow rate by a coefficient in the range of 2 to 10 times or more. In some embodiments, one of the precursor flows can be started or maintained independently for periods when other precursor flows are not present. In some embodiments, the precursor flows can be changed or adjusted one or more times throughout the entire process.

[0052] In some embodiments, the ratio of a co-reactant (e.g., water) to a coating precursor containing at least one metal cation (e.g., TMA) is higher initially than after the process. In other embodiments, the ratio of a co-reactant (e.g., water) to a coating precursor containing at least one metal cation is lower initially than after the process. In some embodiments, the composite particles are exposed to the co-reactant (e.g., water) alone for an initial period before being exposed to a coating precursor containing at least one metal cation. In some embodiments, the composite particles are exposed to the coating precursor alone before being exposed to a second reactant (e.g., a co-reactant to the coating precursor). In some embodiments, different flow rate conditions are maintained for a range of at least 5 minutes (or at least 10, 15, 20, 30, 45, 60, or 90 minutes in other embodiments) up to a maximum of 150 minutes.

[0053] In some embodiments, a coating of a first composition is deposited, followed by a coating of a second composition. For example, an alumina-based coating can be deposited from TMA and water, followed by a titania-based coating deposited from TiCl4 and water.

[0054] In some embodiments, the shell, or in other words, the encapsulating material, has an average thickness of at least 5, 10, 15, 20, or 25 nm. The shell thickness may range up to 250, 500, 750, or 1000 nm (1 micrometer). In some embodiments, for example, in the case of encapsulated dental fillings, the shell thickness is typically in the range up to 100, 150, or 200 nm.

[0055] On a weight percentage basis, the shell material is typically at least 0.1, 0.2, 0.3, 0.4, or 0.5% by weight of the total encapsulated material. The amount of shell material on a weight percentage basis can range up to 15 or 20% by weight of the total encapsulated material, but is more typically 10, 9, 8, 7, 6, or 5% by weight or less.

[0056] In a preferred embodiment, the shell material and shell thickness can be selected to allow control and / or delayed release or reaction of the basic core material.

[0057] In a preferred embodiment, the shell is initially impermeable (i.e., materials from the composition and core material cannot interact by simple diffusion through the shell). Interaction occurs after the shell has been altered by interaction with other materials (e.g., decomposition, corrosion, or dissolution). The composition (e.g., a two-component composition) may be designed to contain a component such as water or an acid that decomposes the shell. In other embodiments, decomposition of the shell may occur by contact with water or an acidic component during use. In this embodiment, the source or water or acidic component may be a biological fluid (e.g., saliva or water retained within the soft tissue surrounding a tooth or bone).

[0058] Referring to Tables 4-7 of the following examples, in one embodiment, an unencapsulated basic material (e.g., Portland cement or tricalcium silicate) yields a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 1 minute when subjected to the buffering test described above. However, an encapsulated basic material (e.g., Portland cement or tricalcium silicate) does not yield a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes according to the buffering test described above. In some embodiments, an encapsulated basic material (e.g., Portland cement) does not yield a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 15, 20, 25, 30, 35, 40, or 45 minutes. In some embodiments, the encapsulated basic material (e.g., Portland cement) does not result in a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) for 100, 200, or 300 minutes.

[0059] Referring to Table 8 of the following examples, in another embodiment, an unencapsulated (e.g., bioactive glass) basic material yields a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 5 minutes when subjected to the buffering test described above. However, an encapsulated (e.g., bioactive glass) basic material does not yield a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 30-40 minutes according to the buffering test described above.

[0060] Referring to Table 9 of the following examples, in another embodiment, an unencapsulated (e.g., Portland cement) basic material yields a basic pH of 11.5 within 20 seconds when tested in deionized water. However, an encapsulated (e.g., Portland cement) basic material yields a basic pH of at least 8.5 within 20 seconds when tested in deionized water. Referring to Table 10 of the following examples, in another embodiment, an unencapsulated (e.g., bioactive glass) basic material yields a basic pH of 10.5 within 20 seconds when tested in deionized water. However, an encapsulated (e.g., bioactive glass) basic material yields a basic pH of at least 9.8 within 20 seconds. Therefore, the pH change of an acidic (e.g., buffer solution) can occur at a significantly slower rate than in deionized water.

[0061] In preferred embodiments, the delayed release or reaction of a basic core material is utilized to increase the basicity of a (e.g., biological) carrier material, such as a curable dental material, at a later point in time, typically after application to a tooth or bone structure, such as after curing. Unencapsulated basic materials can produce a desirable large (and even more undesirable rapid) increase in pH. The same encapsulated basic material can produce a desired increase in pH, but it may occur after a longer period of time.

[0062] The basicity of a (e.g., biological) carrier material, such as a curable (e.g., dental) composition containing encapsulated basic material, is determined by immersing a hardened (i.e., cured) material disk (3.1 mm high × 1.3 mm wide) in 1.5 ml of 10 mM Na2HPO4 (commonly known as PBS) buffer contained in a 2 ml plastic centrifuge tube. The pH change (mm) can be evaluated by measuring it. PBS buffer can be prepared by dissolving 8 g of NaCl, 0.2 g of KCl, 1.44 g of Na2HPO4, and 0.24 g of KH2PO4 in 800 ml of distilled H2O, adjusting the pH to 7.4 with HCl, adjusting the volume to 1 L with additional distilled water, and sterilizing by autoclaving. This test will subsequently be referred to herein as the “disk buffer test”.

[0063] A typical two-component curable (e.g., dental) composition that can be used for the purpose of evaluating encapsulated (e.g., dental) basic materials comprises a first part described below and a second part containing the encapsulated basic material. The first and second parts are combined (in a 1:1 weight ratio) and radiation-cured as described in further detail in the examples. In one embodiment, the second part comprises 65 wt% of the encapsulated basic material described herein, 33.7 parts of hydroxyethyl methacrylate (HEMA), and 1 wt% of fumed silica. In another embodiment, the second part comprises 33.7 parts of hydroxyethyl methacrylate (HEMA), 16.25 to 65 wt% (e.g., 32.5 wt%) of the encapsulated basic material described herein, 0 to 32.5 wt% of FAS glass, and 1 wt% of fumed silica.

[0064] [Table 1]

[0065] In some embodiments, the concentration of the encapsulated basic material is typically in the range of at least 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight to a maximum of 100% of the second portion of the curable (e.g., dental) composition. The entire curable (e.g., dental) composition contains half of such a concentration of the encapsulated basic material. Thus, the concentration of the encapsulated basic material is typically in the range of at least 1, 1.5, 2, 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5, 30, or 32.5% by weight to a maximum of 50% by weight of the entire curable (e.g., dental) composition. The formulation containing 16.25% by weight of bioactive glass in the second portion (total 8% by weight) showed limiting performance, but it is hypothesized that increasing the concentration of the highly basic material (CaO, Na2O) in the bioactive glass can result in a lower concentration that can delay the rise to at least 8.5 or 9 pH.

[0066] Referring to Tables 12-22 of the following examples, in one embodiment, the unencapsulated basic material, for compositions containing more than 16.25% by weight of encapsulated basic material, results in a basic pH (e.g., at least 8.5, 9, 9.5, 10, or 10.5) within 46, 72, 100, 147, 260, 360, or 500 hours.

[0067] Curable (e.g., dental) compositions are typically acidic (pH 1, 2, 3, 4, 5, or 6) before curing by containing acidic components for a sufficient time to provide good adhesion to bone or tooth structure. This period may vary to some extent, but is initially acidic (immediately after immersion of the curable or cured composition in water or buffer) and typically acidic for at least 30 seconds, 1, 2, 3, 4, or 5 minutes. In other embodiments, the curable or cured (e.g., dental) composition is initially neutral (pH 7–7.5) and increases in basicity (e.g., at least 8, 8.5, 9, 9.5, 10, 10.5, or 11) after various periods ranging from 1 hour to 1 day, and in some embodiments, after various periods ranging up to 2, 3, 4, 5, 6, or 7 days or longer.

[0068] In some embodiments, a curable (e.g., dental) composition can be characterized as a cement having multiple curing modes. In some embodiments, the cement cures through a first mechanism via an ionic reaction between an acid and an acid-reactive filler (e.g., FAS glass). The reaction of the encapsulated basic (e.g., filler) material is delayed as described above and therefore typically does not impair the curing reaction. The cement also cures through a second mechanism via photoinitiated free radical crosslinking of the ethylenically unsaturated component. The cement optionally cures through a third mechanism via redox-initiated free radical crosslinking of the ethylenically unsaturated component.

[0069] Such cements are typically formulated in two parts: the first part is a powder or liquid portion typically containing an encapsulated basic filler and an acid-reactive (e.g., FAS-glass) filler for curing; the second part is typically an aqueous liquid portion containing an acidic polymer and water. In some cases, the encapsulated filler can be designed to provide controlled curing, after which the pH continues to rise.

[0070] The cement may optionally contain a water-soluble reducing agent and a water-soluble oxidizing agent in separate portions. If the reducing agent is present in the liquid portion, then the oxidizing agent is typically present in the powder portion, and vice versa. Suitable reducing agents include ascorbic acid, sulfinic acid, barbituric acid and its derivatives, cobalt(II) chloride, iron chloride, iron sulfate, hydrazine, hydroxylamine (depending on the choice of oxidizing agent), oxalic acid, thiourea, and dithionates or salts of sulfite anions. Suitable oxidizing agents are the same as those described above.

[0071] The amounts of reducing agents and oxidizing agents are sufficient to provide the desired degree of polymerization of the ethylenically unsaturated components. The amount of reducing agent is typically in the range of at least 0.01 or 0.02 to a maximum of 5, 6, 7, 8, 9, or 10% by weight, based on the total weight (including water) of the unhardened cement composition. The amount of oxidizing agent is typically in the range of at least 0.01 or 0.02 to a maximum of 5, 6, 7, 8, 9, or 10% by weight, based on the total weight (including water) of the unhardened cement composition.

[0072] The reducing or oxidizing agent can be encapsulated in a polymer, such as those described in U.S. Patent No. 5,154,762 by Mitra et al. When a curable (e.g., dental) composition cures through redox-initiated free radical crosslinking of an ethylenically unsaturated component, the composition contains a sufficient amount of oxidizing agent for the crosslinking reaction that is not encapsulated within an inorganic shell containing a metal oxide. The curable (e.g., dental) composition may also contain an oxidizing agent encapsulated within an inorganic shell containing a metal oxide for the purpose of increasing the pH over a period of time.

[0073] The cement is not limited to a two-component powder-liquid composition. For example, a one-component anhydrous formulation can be prepared. These are sold in dry form and can be prepared for use by adding water. Alternatively, a two-component paste-paste formulation can be prepared by adding a suitable polymerizable liquid (e.g., 2-hydroxyethyl methacrylate, or "HEMA") that does not react with an enclosed basic and / or additional acid-reactive (e.g., FAS glass) filler to obtain a first paste. The aforementioned acidic polymer is then combined with a suitable filler (e.g., quartz) that does not react with the acidic polymer to obtain a second paste. The two pastes are then mixed together to prepare them for use.

[0074] Cement contains water at the time of use. Water may be present in the composition sold or may be added immediately before use. The water may be distilled water, deionized water, or plain water. It may be tap water. The amount of water is generally sufficient to provide appropriate handling and mixing properties, and to allow ion transport in the filler-acid reaction. The amount of water is typically at least 1, 2, 3, 4, or 5% of the total weight of the cement, typically 20 or 25% or less (i.e., any combination of the first and second parts and any water added).

[0075] Cement is typically ionic, meaning it can harden through ionic reactions. These ionic reactions primarily occur between acidic groups on the polymer and acid-reactive fillers (e.g., FAS glass).

[0076] In some embodiments, acid-reactive (FAS) glass is used in combination with an embedded basic (e.g., filler) material. In some embodiments, the amount of FAS glass ranges from at least 5, 10, 15, 20, 25, 30, 35, or 40% by weight to a maximum of about 50, 55, or 60% by weight of the first part of the two-component composition. Since the first part typically corresponds to half of the total curable (e.g., dental) composition, the total concentration of acid-reactive (FAS) glass is just half of the concentrations described. In addition to its involvement in ionic reactions, FAS glass releases phosphate and fluoride ions, which are known to promote remineralization.

[0077] In some embodiments, the concentration of acid-reactive (FAS) glass is higher than the concentration of the encapsulated basic (e.g., filler) material. In other embodiments, the concentration of the encapsulated basic (e.g., filler) material is higher than the concentration of acid-reactive (FAS) glass. In some embodiments, the weight ratio of the encapsulated basic filler to the unencapsulated acid-reactive (FAS) glass is typically at least 1:1 or greater than 1:1 in the second part of the two-component composition, for example, ranging from 1.5:1, 2:1, 2.5:1, or 3:1 to a maximum of 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0078] The cement may further contain at least one ethylenically unsaturated moiety. The ethylenically unsaturated moiety may exist as a separate component (for example, as an acrylate-functional monomer or a methacrylate-functional monomer) or as a base on another component, such as an acidic polymer.

[0079] Ethylene-unsaturated groups are typically (e.g., terminal) free radical polymerizable groups, such as (meth)acrylics, e.g., (meth)acrylamides (H2C=CHCON- and H2C=CH(CH3)CON-) and (meth)acrylates (CH2CHCOO- and CH2C(CH3)COO-). Other ethylenically unsaturated polymerizable groups include vinyls (H2C=C-), such as vinyl ethers (H2C=CHO-). Ethylene-unsaturated terminal polymerizable groups are preferably (meth)acrylate groups, especially in compositions cured by exposure to chemical rays (e.g., UV or blue light). Furthermore, methacrylate functional groups are typically preferred over acrylate functional groups in dental curable compositions.

[0080] In some embodiments, the ethylenically unsaturated component is a water-miscible or water-soluble (meth)acrylate such as 2-hydroxyethyl methacrylate, hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, glycerol mono- or di-methacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol (e.g., 400 and other molecular weights) dimethacrylate, urethane methacrylate, acrylamide, methacrylamide, methylenebis-acrylamide, or methacrylamide, with diacetone acrylamide and methacrylamide being preferred. Mixtures of the ethylenically unsaturated moieties may be used as needed. Preferably, the ethylenically unsaturated moieties exist as groups on the acidic polymer, as described in more detail below.

[0081] The second part comprises an organic or inorganic acid component. In some embodiments, the acid component is a polycarboxylic acid such as poly(maleic acid) or poly(itaconic acid). In other embodiments, the acid component is polyacrylic acid or a phosphorus-containing acid.

[0082] In some embodiments, the acid component is an acidic polymer. Suitable acidic polymers are those listed in column 2, line 62 to column 3, line 6 of U.S. Patent No. 4,209,434. Preferred acidic polymers include homopolymers and copolymers of alkenic acids such as acrylic acid, itaconic acid, and maleic acid.

[0083] In some embodiments, the acidic polymer can be characterized as a photocurable ionomer, i.e., a polymer having pendant free radical polymerizable groups that can be cured, i.e., the resulting mixture can be polymerized, i.e., cured, when exposed to radiant energy.

[0084] For example, as described in U.S. Patent No. 5,130,347, a photocurable ionomer has the general formula: B(X) m (Y) n It has, During the ceremony, B represents an organic skeleton chain, Each X is an independently ionic group, Each Y is independently a photocurable group, m is a number with an average value of 2 or greater. n is a number with an average value of 1 or greater.

[0085] Preferably, the skeletal chain B is a carbon-carbon bonded oligomer or polymer skeletal chain, and optionally contains non-interfering substituents such as oxygen, nitrogen, or sulfur heteroatoms. As used herein, the term “non-interfering” refers to a substituent or linking group that does not excessively interfere with any of the photocuring reactions of the photocurable ionomer.

[0086] The preferred X group is an acidic group, and a carboxyl group is particularly preferred.

[0087] Suitable Y groups include, but are not limited to, polymerizable ethylenically unsaturated groups and polymerizable epoxy groups. Ethylene-unsaturated groups, in particular those that can be polymerized by a free radical mechanism, are preferred, and examples include substituted and unsubstituted acrylates, methacrylates, alkenes, and acrylamides.

[0088] The X and Y groups can be attached to the skeletal chain B directly, or using any non-interfering organic linking group such as substituted or unsubstituted alkyl, alkoxyalkyl, aryl, aryloxyalkyl, alkoxyaryl, aralkyl, or alkalil groups.

[0089] A preferred photocurable ionomer is one in which each X is a carboxyl group and each Y is an ethylenically unsaturated group such as a (meth)acrylate group that can be polymerized by a free radical mechanism. Such an ionomer is a polyalkenoic acid (e.g., formula B(X) m+n It is easily prepared by reacting a polymer (wherein each X is a carboxyl group) with a coupling compound containing both an ethylenically unsaturated group and a group that can react with a carboxylic acid group, such as an NCO group. The resulting photocurable ionomer preferably has at least one free radical polymerizable group (e.g., a (meth)acrylate group) bonded to the ionomer by an amide bond. The molecular weight of the resulting photocurable ionomer is typically about 1,000 to about 100,000 g / mol.

[0090] Acidic polymers (e.g., photocurable ionomers) typically have a (weight-average) molecular weight ranging from at least 5,000 g / mol to a maximum of about 100,000 g / mol when measured using gel permeation chromatography and polystyrene standards. In some embodiments, acidic polymers (e.g., photocurable ionomers) have a molecular weight of less than 50,000 or 25,000 g / mol.

[0091] The concentration of the acidic component, such as the photocurable ionomer, is typically at least 5, 6, 7, 8, 9, or 10% by weight of the first part of the two-component composition, and typically 30, 25, 20, or 15% by weight or less. Since the first part typically corresponds to only half of the total curable (e.g., dental) composition, the total concentration of the acidic component, such as the photocurable ionomer, is just about half of the stated concentration.

[0092] In some embodiments, the acid component is a curable component in the form of an ethylenically unsaturated compound having an acid and / or acid precursor functional group. Examples of acid precursor functional groups include anhydrides, acid halides, and pyrophosphates. Examples of acid functional groups include phosphoric acid functional groups, phosphonic acid functional groups, sulfonic acid functional groups, or combinations thereof. Typically, the adhesive compositions described herein, when the composition includes a radiopaque filler containing a basic surface such as zirconia, contain little to no ethylenically unsaturated compounds having a carboxylic acid functional group (e.g., less than 10% by weight, less than 5% by weight, or less than 1% by weight), or do not contain any ethylenically unsaturated compounds having a carboxylic acid functional group.

[0093] Examples of ethylenically unsaturated compounds having acidic functional groups include α,β-unsaturated acidic compounds such as glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl (meth)acrylate phosphate (e.g., HEMA-P), bis((meth)acrylooxyethyl) phosphate, ((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxy)propyl phosphate, (meth)acrylooxyhexyl phosphate, bis((meth)acrylooxyhexyl) phosphate (e.g., MHP), (meth)acrylooxyoctyl phosphate, bis((meth)acrylooxyoctyl) phosphate, (meth)acrylooxydecyl phosphate, bis((meth)acrylooxydecyl) phosphate, and caprolactone methacrylate phosphate.

[0094] In some embodiments, the composition (e.g., for dental use) further comprises other (i.e., second) fillers in addition to the encapsulated fillers described herein. The second filler typically does not contain (e.g., strongly) basic core materials as described herein. The second filler typically contains a neutral metal oxide having low solubility, as described above. The second filler may also be weakly basic or weakly acidic.

[0095] In some embodiments, the second filler is an acid-reactive (FAS glass) filler, as described above.

[0096] In some embodiments, other fillers include (e.g., inorganic metal oxide) nanoparticles. Such nanoparticles, or in other words, "nanoscopic fillers," can be used as viscosity and thixotropy modifiers. Such nanoparticles may also contribute in part to the mechanical properties of dental curable compositions. Such nanoparticles also contribute to the refractive index of polymerizable resins, depending on their size.

[0097] In some embodiments, inorganic oxide nanoparticles have a primary particle size of 100 nm or less. Primary particle size typically refers to the size of the discrete particles in a non-aggregated state. In other, less general embodiments, nanoparticles may be aggregates of two or more (e.g., fused or covalently) bonded particles, which have a particle size of 100 nm or less. The average particle size can be determined by cutting a thin sample of the cured dental composition, measuring the particle diameter of about 50 to 100 particles using a transmission electron microscope image at a magnification of 300,000, and calculating the average. Nanoparticles may have a unimodal or multimodal (e.g., bimodal) particle size distribution. In some embodiments, (e.g., zirconia) nanoparticles have an average particle size of at least about 2, 3, 4, or 5 nanometers (nm). In some embodiments, (e.g., zirconia) nanoparticles have an average particle size of about 50, 40, 30, 25, 15, or 10 nanometers (nm) or less.

[0098] The dental composition optionally further comprises nanoparticles having a relatively low refractive index (e.g., inorganic metal oxides), such as silica. The inclusion of low refractive index nanoparticles can reduce the refractive index of the polymerizable resin. Suitable silica nanoparticles are commercially available from Ecolab (St. Paul, MN) under the trade name NALCO COLLOIDAL SILICAS. For example, preferred silica particles can be obtained using NALCO products 1034A, 1040, 1042, 1050, 1060, 2327, and 2329.

[0099] Silica nanoparticles are preferably prepared from an aqueous colloidal dispersion of silica (i.e., a sol or aquasol). Colloidal silica is typically present in the silica sol at a concentration of about 1 to 50 weight percent. Colloidal silica sols with different colloidal sizes are commercially available; see Surface & Colloid Science, Vol. 6, ed. Matijevic, E., Wiley Interscience, 1973. Preferred silica sols for use in the manufacture of fillers are dispersions of amorphous silica in an aqueous medium (e.g., Nalco colloidal silica from Ecolab) and those with a low sodium concentration that can be acidified by miscible with a suitable acid (e.g., Ludox colloidal silica from EIDupont de Nemours & Co., or Nalco 2326 from Ecolab).

[0100] In some embodiments, the dental composition contains at least 0.5, 1, 1.5, or 2 wt% of low refractive index (e.g., silica) nanoparticles. The amount of low refractive index (e.g., silica) nanoparticles is typically 30, 25, 20, 15, or 5 wt% or less of the dental composition. In other embodiments, the dental composition contains less than 1, 0.5, 0.25, 0.1, or 0.005 wt% of low refractive index (e.g., silica) nanoparticles, or is substantially free of low refractive index (e.g., silica) nanoparticles.

[0101] When low refractive index (e.g., silica) nanoparticles are included in a dental composition, the concentration of low refractive index (e.g., silica) nanoparticles is generally less than the concentration of high refractive index (e.g., zirconia) nanoparticles. Therefore, the weight or volume concentration of high refractive index (e.g., zirconia) nanoparticles is typically greater than that of low refractive index (e.g., silica) nanoparticles. In some embodiments, the weight or volume ratio of high refractive index (e.g., zirconia) nanoparticles to low refractive index (e.g., silica) nanoparticles is at least 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1. In some embodiments, the weight or volume ratio of high refractive index (e.g., zirconia) nanoparticles to low refractive index (e.g., silica) nanoparticles is at least 2.1:1, 2.2:1, 2.3:1, or 2.4:1. In some embodiments, the weight or volume ratio of high refractive index (e.g., zirconia) nanoparticles to low refractive index (e.g., silica) nanoparticles is 100:1, 75:1, 50:1, 25:1, 10:1, or 5:1 or less.

[0102] Several suitable low refractive index (e.g., silica) and high refractive index (e.g., zirconia) nanoparticles are disclosed in U.S. Patent No. 6,387,981 (Zhang et al.) and No. 6,572,693 (Wu et al.), as well as PCT International Publication No. WO 01 / 30304 (Zhang et al.), No. WO 01 / 30305 (Zhang et al.), No. WO 01 / 30307 (Zhang et al.), No. WO 03 / 063804 (Wu et al.), U.S. Patent No. 7,090,721 (Craig et al.), No. 7,090,722 (Budd et al.), No. 7,156,911 (Kangas et al.), U.S. Patent No. 7,241,437 (Davidson et al.), and U.S. Patent No. 7,649,029 (Kolb et al.).

[0103] The dental compositions described herein preferably contain a recognizable amount of an inorganic metal oxide filler. The properties of fillers used in dental applications are typically ceramic.

[0104] The filler can be selected from one or more of a broad range of materials suitable for incorporation into compositions used for dental applications, such as fillers currently used in dental composites and dental articles (e.g., crowns). The fillers are generally non-toxic and suitable for use in the oral cavity. The fillers may be radiopaque, radiolucent, or opaque. In some embodiments, the fillers typically have a refractive index of at least 1.500, 1.510, 1.520, 1.530, or 1.540.

[0105] To increase radiopaqueness, it is common to include components such as YbF3 in up to approximately 5% by weight. In some embodiments, the radiopaqueness of the cured dental composition is due to aluminum with a thickness of at least 3 mm.

[0106] The properties of fillers can be either particulate or fibrous. Particulate fillers can generally be defined as having a length-to-width ratio or aspect ratio of 20:1 or less, and more generally 10:1 or less. Fibrous fillers can be defined as having an aspect ratio greater than 20:1, or more generally greater than 100:1. The shape of the particles can vary widely, from spherical to elliptical, or more planar, such as flakes or discs. Macroscopic properties can be highly dependent on the shape of the filler particles, particularly the uniformity of their shape.

[0107] The dental compositions described herein include inorganic metal oxide filler materials that are larger in size than nanoparticles. As previously described, nanoparticles are typically non-aggregated discrete particles having a particle size of 100 nm or less. In contrast, inorganic metal oxide fillers are particulate or fibrous materials having at least one dimension greater than 100 nm, for example, at least 150 nm or at least 200 nm. In the case of particulate fillers, the average particle size of the non-aggregated discrete or aggregated particles is at least 200 nm. Inorganic metal oxide fillers are very effective for improving wear properties after curing.

[0108] In some embodiments, the filler may include a crosslinked organic material insoluble in polymerizable resin, and may optionally be filled with an inorganic filler. Examples of suitable organic filler particles include filled or unfilled ground polycarbonates, polyepoxides, poly(meth)acrylates, and the like.

[0109] In some embodiments, the dental compositions described herein include non-acid-reactive fillers such as quartz, fumed silica, non-glassy microparticles of the type described in U.S. Patent No. 4,503,169 (Randklev), and nanocluster fillers, such as those described in U.S. Patent No. 6,730,156 (Windisch et al.), U.S. Patent No. 6,572,693 (Wu et al.), and U.S. Patent No. 8,722,759 (Craig).

[0110] In some embodiments, the filler includes nanoparticles, which are nanoclusters, i.e., groups of two or more particles bound together by relatively weak but sufficient intermolecular forces to aggregate even when dispersed in a curable resin. Preferred nanoclusters may include lightly aggregated, substantially amorphous clusters of non-heavy metal oxide (e.g., silica) particles and heavy metal oxides (i.e., having an atomic number greater than 28), such as zirconia. The zirconia may be crystalline or amorphous. In some embodiments, the zirconia may exist as particles. The particles forming the nanoclusters preferably have an average diameter of less than about 100 nm. However, the average particle size of lightly aggregated nanoclusters is typically considerably larger.

[0111] In some embodiments, the composition (e.g., dental) further comprises a second filler containing a neutral metal oxide, such as a zirconia / silica nanocluster filler. In the case of a two-component dental composition, the filler containing the neutral metal oxide is present in a substantial amount in the first or second liquid-containing portion. In some embodiments, the neutral or non-reactive filler is present in either or both the acidic portion and the non-acidic portion, while the acid-reactive filler (e.g., FAS glass) and / or the encapsulated basic core is present in the non-acidic portion and reacts with the acidic portion after mixing.

[0112] In some embodiments, the first portion of the curable (e.g., dental) composition contains a second filler containing a neutral metal oxide, such as a zirconia / silica nanocluster filler, in an amount ranging from at least 5, 10, 15, or 20% by weight to a maximum of 30, 35, or 40% by weight. The total curable (e.g., dental) composition contains about half such a concentration of the second filler containing a neutral metal oxide, such as a zirconia / silica nanocluster filler.

[0113] In some embodiments, the second filler may also be encapsulated in a shell material containing a metal oxide, such as that described in U.S. Patent No. 7,396,862.

[0114] A mixture of fillers can also be used.

[0115] In a typical embodiment, the second filler may include a surface treatment to enhance the bond between the nanoparticles, the inorganic oxide filler, and the resin. Various surface treatments have been described in the art and include, for example, organometallic coupling agents and carboxylic acids, such as those described in U.S. Patent No. 8,647,510 (Davidson et al.). The encapsulated basic material may also optionally include a surface treatment.

[0116] Suitable copolymerizable organometallic compounds are those with the general formula: CH2=C(CH3) m Si(OR) n Or CH2=C(CH3) m C=OOASi(OR)n [where m is 0 or 1, R is an alkyl group having 1 to 4 carbon atoms, A is a divalent organic linking group, and n is 1 to 3] may be included. The organometallic coupling agent may be functionalized with reactive curable groups such as acrylates, methacrylates, vinyl groups, and the like. Preferred coupling agents include gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, and the like.

[0117] In some embodiments, combinations of surface modifiers may be useful, and at least one of these agents has a functional group that is copolymerizable with the curable resin. Other surface modifiers that do not generally react with the curable resin may be included to enhance dispersibility or rheological properties. Examples of this type of silane include, for example, aryl polyethers, alkyl, hydroxyalkyl, hydroxyaryl, or aminoalkyl functional silanes.

[0118] Surface modification can be performed either following mixing with the monomer or at any time after mixing. Typically, it is preferred to combine the organosilane surface treatment compound with the nanoparticles before incorporation into the resin. The amount of surface modifier required depends on several factors such as particle size, type of particle, molecular weight of the modifier, and type of modifier. Generally, it is preferred to deposit a substantially monolayer of the modifier on the surface of the particles.

[0119] Various ethylenically unsaturated monomers can be utilized in dental compositions. The ethylenically unsaturated monomers of the dental composition are typically liquids that are stable at about 25 °C, which means that the monomers do not substantially polymerize, crystallize, or otherwise cure when stored at room temperature (about 25 °C) for a typical shelf life of at least 30, 60, or 90 days. The viscosity of the monomer typically does not change (e.g., increase) by more than 10% of its initial viscosity.

[0120] In particular, in the case of dental restorative compositions, ethylenically unsaturated monomers generally have a refractive index of at least 1.50. In some embodiments, the refractive index is at least 1.51, 1.52, 1.53, or higher. The inclusion of sulfur atoms and / or the presence of one or more aromatic moieties can increase the refractive index (compared to monomers of the same molecular weight that do not contain such substituents).

[0121] The curable components of a curable (e.g., dental) composition may include a wide range of "other" ethylenically unsaturated compounds (with or without acidic function), epoxy-functionalized (meth)acrylate resins, vinyl ethers, and the like.

[0122] (For example, photopolymerizable) dental compositions may include free-radical polymerizable monomers, oligomers, and polymers having one or more ethylenically unsaturated groups. Preferred compounds contain at least one ethylenically unsaturated bond and are capable of addition polymerization. Examples of useful ethylenically unsaturated compounds include acrylic acid esters, methacrylic acid esters, hydroxy-functional acrylic acid esters, hydroxy-functional methacrylic acid esters, and combinations thereof.

[0123] Such free radical polymerizable compounds include mono, di, or poly-(meth)acrylates (i.e., acrylates and methacrylates), for example, methyl(meth)acrylate, ethyl(meth)acrylate, isopropyl(meth)acrylate, n-hexyl(meth)acrylate, stearyl(meth)acrylate, allyl(meth)acrylate, glycerol tri(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, sorbitol hexa(meth)acrylate Examples include acrylates, tetrahydrofurfuryl (meth)acrylate, bis[1-(2-acrylooxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acrylooxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, ethoxylated bisphenol A di(meth)acrylate, and trishydroxyethyl-isocyanurate tri(meth)acrylate; (meth)acrylamides (i.e., acrylamide and methacrylamide), such as (meth)acrylamide, methylenebis-(meth)acrylamide, and diacetone(meth)acrylamide; urethane (meth)acrylates; bis-(meth)acrylates of polyethylene glycol (preferably with a molecular weight of 200-500); and vinyl compounds, such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate. Other suitable free radical polymerizable compounds include siloxane-functionalized (meth)acrylates. If desired, a mixture of two or more free radical polymerizable compounds may be used.

[0124] Curable (e.g., dental) compositions may contain monomers having both a hydroxyl group and an ethylenically unsaturated group within a single molecule. Examples of such materials include hydroxyalkyl (meth)acrylates, e.g., 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 2,2-bis[4-(2-hydroxy-3-methacrylateoxypropoxy)phenyl]propane (bisGMA). Suitable ethylenically unsaturated compounds are available from a wide range of commercial suppliers, e.g., Sigma-Aldrich, St. Louis.

[0125] In some embodiments, the first part of a two-component curable (e.g., dental) composition comprises a monomer having a hydroxyl group and an ethylenically unsaturated group in a single molecule, such as HEMA. In some embodiments, the amount of the ethylenically unsaturated compound having an acidic functional group (e.g., HEMA) ranges from at least 5, 10, 15, 20, 25, 30% by weight to a maximum of about 35, 40, 45, or 50% by weight of the first part of the two-component composition. Since the first part constitutes only half of the total curable (e.g., dental) composition, the total concentration of the ethylenically unsaturated compound having an acidic functional group (e.g., HEMA) is just about half of the concentrations described.

[0126] The compositions described herein (for example, for dental use) may contain one or more curable components in the form of ethylenically unsaturated compounds having acidic functional groups. Such components contain both an acidic group and an ethylenically unsaturated group within a single molecule. If present, this polymerizable component optionally contains an ethylenically unsaturated compound having an acidic functional group. Preferably, the acidic functional group includes oxyacids of carbon, sulfur, phosphorus, or boron (i.e., oxygen-containing acids). However, in some embodiments, the dental compositions are substantially free of ethylenically unsaturated compounds having acidic functional groups (less than 1, 0.5, 0.25, 0.1, or 0.005% by weight).

[0127] As used herein, ethylenically unsaturated compounds having acidic functional groups are intended to include monomers, oligomers, and polymers having ethylenically unsaturated and acidic and / or acid precursor functional groups. Examples of acid precursor functional groups include anhydrides, acid halides, and pyrophosphates. Examples of acidic functional groups include carboxylic acid functional groups, phosphoric acid functional groups, phosphonic acid functional groups, sulfonic acid functional groups, or combinations thereof.

[0128] Examples of ethylenically unsaturated compounds having acidic functional groups include α,β-unsaturated acidic compounds, such as glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate (GDMA-P), hydroxyethyl (meth)acrylate (e.g., HEMA) phosphate, bis((meth)acrylooxyethyl) phosphate, ((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxy)propyl phosphate, (meth)acrylooxyhexyl phosphate, bis((meth)acrylooxyhexyl) phosphate, and (meth)acrylooxyoctyl phosphate. Examples of materials that can be used as components include bis((meth)acryloxyoctyl) phosphate, (meth)acryloxydecyl phosphate, bis((meth)acryloxydecyl) phosphate, caprolactone methacrylate phosphate, di or tri-methacrylate citrate, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl-polyphosphonic acid, poly(meth)acrylated polychlorophosphonic acid, poly(meth)acrylated polysulfonate, poly(meth)acrylated polyboric acid, and similar materials. In addition, monomers, oligomers, and polymers such as unsaturated carbonic acid, for example (meth)acrylic acid, aromatic (meth)acrylated acids (for example, methacrylated trimellitic acid), and their anhydrides can also be used.

[0129] The dental composition may contain an ethylenically unsaturated compound having an acidic functional group having at least one P-OH moiety. Such a composition is self-adhesive and non-aqueous. For example, such a composition may contain at least one (meth)acrylooxy group and at least one -OP(O)(OH) x A first compound containing the group, wherein x=1 or 2, and at least one -OP(O)(OH) xA first compound in which a group and at least one (meth)acrylooxy group are linked together by a C1-C4 hydrocarbon group; at least one (meth)acrylooxy group and at least one -OP(O)(OH) x A second compound containing the group, wherein x=1 or 2, and at least one -OP(O)(OH) x The compound may include a second compound in which the group and at least one (meth)acrylooxy group are linked together by a C5-C12 hydrocarbon group; an ethylenically unsaturated compound without an acid functional group; an initiator system; and a filler.

[0130] Initiators are typically added to a mixture of polymerizable components. The initiator is well miscible with the resin system so that it can readily dissolve in the polymerizable composition (and prevent separation therefrom). Typically, the initiator is present in the composition in an effective amount, such as about 0.1% to about 5.0% by weight, based on the total weight of the composition.

[0131] In some embodiments, the monomer mixture is photopolymerizable, and the composition contains a photoinitiator (i.e., a photoinitiator system) that initiates polymerization (or curing) of the composition when irradiated with a chemical beam. Such a photopolymerizable composition may also be free radical polymerizable. The photoinitiator typically has an effective wavelength range of about 250 nm to about 800 nm. Suitable photoinitiators (i.e., photoinitiator systems comprising one or more compounds) for polymerizing free radical photopolymerizable compositions include two-component and three-component systems. A typical three-component photoinitiator comprises an iodonium salt, a photosensitizer, and an electron donor compound, as described in U.S. Patent No. 5,545,676 (Palazzotto et al.). Examples of iodonium salts include diaryliodonium salts, such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate. Some preferred photosensitizers include monoketones and diketones (e.g., alpha-diketones) that absorb some light in the range of about 300 nm to about 800 nm (preferably about 400 nm to about 500 nm), such as camphorquinone, benzyl, furyl, 3,3,6,6-tetramethylcyclohexanedione, phenanthaquinone, and other cyclic alpha-diketones. Among these, camphorquinone is typically preferred. Preferred electron donor compounds include substituted amines, such as ethyl 4-(N,N-dimethylamino)benzoate.

[0132] Other photoinitiators suitable for polymerizing free radical photopolymerizable compositions include a class of phosphine oxides, typically having an effective wavelength range of about 380 nm to about 1200 nm. Preferred phosphine oxide free radical initiators having an effective wavelength range of about 380 nm to about 450 nm are acyl and bisacylphosphine oxides.

[0133] Commercially available phosphine oxide photoinitiators that can initiate free radical reactions when irradiated in the wavelength range of approximately 380 to 450 nm include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819 (Ciba Specialty Chemicals (Tarrytown, NY))), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (CGI 403 (Ciba Specialty Chemicals)), and a mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one in a 25:75 weight ratio (IRGACURE 1700 (Ciba Specialty Chemicals)). Examples include a 1:1 mixture by weight of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 4265 (Ciba Specialty Chemicals)), and ethyl-2,4,6-trimethylbenzylphenylphosphine (LUCIRIN LR8893X (BASF Corp. (Charlotte, NC))).

[0134] Tertiary amines may be used in combination with acylphosphine oxides. Examples of tertiary amines include ethyl 4-(N,N-dimethylamino)benzoate and N,N-dimethylaminoethyl methacrylate. If present, the amine reducing agent is present in the photopolymerizable composition in an amount of about 0.1% to about 5.0% by weight, based on the total weight of the composition. In some embodiments, the dental curable composition may be irradiated with ultraviolet (UV) light or blue light. In this embodiment, suitable photoinitiators include those available from Ciba Speciality Chemical Corp., Tarrytown, NY under the trade names IRGACURE and DAROCUR, such as 1-hydroxycyclohexylphenyl ketone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (IRGACURE 369), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE Examples include 907) and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173).

[0135] Photopolymerizable compositions are typically prepared by mixing various components of the composition. In embodiments where the photopolymerizable composition does not cure in the presence of air, the photoinitiator is combined under "safe light" conditions (i.e., conditions that do not cause premature curing of the composition). When preparing the mixture, a suitable inert solvent may be used if desired. Examples of suitable solvents include acetone and dichloromethane.

[0136] Curing occurs by exposing the composition to a radiation source, preferably a visible light source. Light sources emitting chemical rays in the 250 nm to 800 nm range (particularly blue light with wavelengths of 380 nm to 520 nm) are convenient, such as quartz halogen lamps, tungsten halogen lamps, mercury arcs, carbon arcs, low, medium, and high-pressure mercury lamps, plasma arcs, light-emitting diodes, and lasers. Generally, useful light sources have a power output of 0.200 to 6000 mW / cm². 2 It has an intensity in the range of 1000 mW / cm² for 20 seconds. 2 Depending on the intensity, the desired curing can generally be achieved. Various conventional lights can be used to cure such compositions.

[0137] Optionally, the composition may contain a solvent (e.g., alcohol (e.g., propanol, ethanol), ketone (e.g., acetone, methyl ethyl ketone), ester (e.g., ethyl acetate), other non-aqueous solvents (e.g., dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone)), and water. In some embodiments, the dental composition (e.g., one component) typically contains water in an amount of 5% by weight or less of the total dental composition.

[0138] If desired, the composition may contain additives, such as indicators, dyes such as photobleaching dyes, pigments, inhibitors, accelerators, viscosity modifiers, wetting agents, buffers, radical and cationic stabilizers (e.g., BHT), and other similar components that would be obvious to those skilled in the art.

[0139] In addition, pharmaceuticals or other therapeutic substances may be optionally added to dental compositions. Examples, but not limited to, of substances commonly used in dental compositions include fluoride sources, whitening agents, anticariogenic agents (e.g., xylitol), calcium sources, phosphorus sources, remineralizing agents (e.g., calcium phosphate compounds), enzymes, breath fresheners, anesthetics, coagulants, acid neutralizers, chemotherapeutic agents, immune response modifiers, thixotropic agents, polyols, anti-inflammatory agents, antibacterial agents (in addition to antibacterial lipid components), antifungal agents, xerostomia treatments, desensitizers, and similar substances. Any combination of the above additives may be used. A person skilled in the art can select any of these additives and their quantities to achieve the desired results without excessive experimentation.

[0140] Curable dental compositions can be used to treat oral surfaces such as teeth, as is known in the art. In some embodiments, the compositions can be hardened by curing after application. For example, when a curable dental composition is used as a restorative material such as a tooth filling, this method generally involves applying the curable composition to an oral surface (e.g., a caries) and curing the composition. In some embodiments, a dental adhesive may be applied before applying the curable dental restorative material described herein. The dental adhesive is typically hardened by curing simultaneously with the curing of the highly filled dental restorative composition. A method for treating an oral surface may include preparing a dental article and adhering the dental article to an oral surface (e.g., a tooth).

[0141] In one embodiment, the cured dental composition can be used for pulp capping. In this embodiment, cell proliferation of pulp stem cells in contact with the cured dental composition (e.g., the same molded disc used in buffer disc testing) was evaluated in the manner described in further detail in the Examples. Mean cell proliferation was at least 75% of the control (no disc of cured dental composition was present). In some embodiments, mean cell proliferation was at least 80, 85, or 90% of the control. Mean alkaline phosphatase (ALP) activity also increased compared to the control. In some embodiments, mean ALP activity ranged from at least 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0 mU / mL to a maximum of 1.1 or 1.2 mU / mL or higher.

[0142] In another embodiment, the cured dental composition can be used as an adhesive. The cured dental composition can exhibit an adhesive strength of at least 1, 2, 3, 4, 5, 6, 8, 9, or 10 MPa when measured according to the test methods described in the examples. In some embodiments, the adhesive strength may be in the range of 20 MPa or more.

[0143] As used herein, “dental composition” refers to a material containing a filler that can be adhered to or bonded to an oral surface. Dental curable compositions may be used to bond dental articles to tooth structures, to form coatings (e.g., sealants or varnishes) on tooth surfaces, to be placed directly in the oral cavity and cured in situ as restorative materials, or alternatively, to fabricate prostheses outside the oral cavity that will later be bonded in the oral cavity.

[0144] Examples of hardening dental compositions include adhesives (e.g., dental and / or orthodontic adhesives), cements (e.g., two-component cements), primers (e.g., orthodontic primers), liners (applied to the base of caries to reduce tooth sensitivity), root restorations and pulp capping, coatings such as sealants (e.g., pits and fissures), and varnishes; as well as resin restorative materials such as tooth fillings (also called direct composites), and articles for crowns, bridges, and dental implants. Highly dense dental compositions are also used in mill blanks, from which crowns can be milled. Composites are highly dense pastes designed to be suitable for filling substantial defects in tooth structure. Dental cements are somewhat less dense and less viscous than composites and typically act as bonding agents for additional materials such as inlays, onlays, and similars, or act as filling materials themselves when applied and hardened as layers. Furthermore, dental cement is used to permanently bond dental restorative items such as crowns, bridges, or orthodontic appliances to tooth surfaces or implant abutments.

[0145] As used herein, “dental articles” refers to articles that can be bonded to (e.g., attached to) tooth structures or dental implants. Examples of dental articles include crowns, bridges, veneers, inlays, onlays, fillings, orthodontic appliances and devices.

[0146] "Orthodontic appliances" refer to, but are not limited to, any devices intended to be bonded to a tooth structure, including, but are not limited to, orthodontic brackets, buccal tubes, tongue restraints, orthodontic bands, mouth retractors, buttons, and cleats. The appliance has a base for receiving adhesive, which may be a flange made of metal, plastic, ceramic, or a combination thereof. Alternatively, the base may be a custom base formed from a cured adhesive layer (i.e., a single-layer or multi-layer adhesive).

[0147] "Oral surface" refers to soft or hard surfaces in the oral environment. Typical examples of hard surfaces include, for example, natural and artificial tooth surfaces, bone, and tooth structures such as the same.

[0148] "Hardenable" and "curable" refer to the ability to polymerize and / or harden upon heating. This section describes materials or compositions that can be cured (e.g., polymerized or crosslinked) by inducing crosslinking; by inducing polymerization and / or crosslinking by irradiation with a chemical beam; and / or by inducing polymerization and / or crosslinking by mixing one or more components. "Mixing" can be carried out, for example, by combining and mixing two or more components to form a homogeneous composition. Alternatively, two or more components may be prepared as separate layers, and these layers may be mixed at the interface (e.g., spontaneously or by applying shear stress) to initiate polymerization.

[0149] "Hardened" means cured (for example, polymerized or crosslinked) ) Refers to materials or compositions.

[0150] A "curing agent" refers to a substance that initiates the curing of a resin. Examples of curing agents include polymerization initiators, photoinitiators, thermal initiators, and / or oxidation-reduction initiators.

[0151] "(meth)acrylate" is an abbreviation for acrylate, methacrylate, or a combination thereof; "(meth)acrylic acid" is an abbreviation for acrylic acid, methacrylic acid, or a combination thereof; and "(meth)acrylic" is an abbreviation for acrylic, methacrylic, or a combination thereof.

[0152] As used herein, “a,” “an,” “the,” “at least one type,” and “one or more types” are interchangeable.

[0153] Furthermore, in this specification, the description of a numerical range with endpoints includes all numbers contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). [Examples]

[0154] material Hydroxyethyl methacrylate (HEMA) was obtained from Evonik Industries, Sarasota, FL. Ethyl 4-dimethylaminobenzoate (EDMAB) was obtained from Sigma-Aldrich Corporation, St. Louis, MO. Camphorquinone (CPQ) was obtained from Sigma-Aldrich. 2,6-di-tert-butyl-4-methylphenol (BHT) was obtained from PMC Specialties Incorporated, Cincinnati, OH. The fumed silica R812S was obtained from Degussa-Huls Corporation, Parsippany, NJ. Calcium glycerophosphate was obtained from Spectrum Laboratory Products, Gardena, CA. Ytterbium fluoride (YbF3) was obtained from Treibacher Industrie Incorporated, Toronto, Canada. The buffer BDH5018 (aqueous potassium bitophosphate buffer adjusted to pH 4.00 with hydrochloric acid at 25°C) was obtained from VWR International, Radnor, PA. The VBP polymer was prepared by reacting the PAA:ITA copolymer with a sufficient amount of IEM (2-isocyanatoethyl methacrylate) and converting 16 mole percent of the copolymer's acidic groups to pendant methacrylate groups, according to the dry polymer preparation of Example 11 of U.S. Patent No. 5,130,347 (Mitra). The PAA:ITA copolymer was prepared from an acrylic acid:itaconic acid in a 4:1 molar ratio according to Example 3 of U.S. Patent No. 5,130,347. The Zr / Si nanocluster filler is a silane-treated zirconia / silica nanocluster filler prepared essentially as described in U.S. Patent No. 6,730,156 [Preparation Example A (lines 51-64) and Example B (column 25, lines 65-26, line 40)]. Portland cement: White Portland cement (Federal White Type 1, ASTM designation C150) was purchased from Federal White Cement, Woodstock, Ontario, Canada. The main components of the composition reported by the manufacturer are tricalcium silicate (3CaO-SiO2), dicalcium silicate (2CaO-SiO2), tricalcium aluminate (3CaO-Al2O3), tetracalcium aluminolite (4CaO-Al2O3-Fe2O3), magnesium oxide, calcium oxide, potassium sulfate, and sodium sulfate. Portland cement is a strongly basic material containing multiple components. Each major component (excluding the trace components of magnesium oxide, potassium sulfate, and sodium sulfate) contains a considerable amount of strong base (CaO). Portland cement typically contains approximately 61%–69% CaO, 18%–24% SiO2, 2%–6% Al2O3, 1%–6% Fe2O3, and 0.5%–5% MgO. Bioactive glass [45S5] was prepared using the following composition: SiO2 (45 wt%), Na2O (24.5 wt%), CaO (24.5 wt%), P2O5 (6 wt%). Bioactive glass is a strongly basic material. It is homogeneous, containing two strongly basic components (Na2O and CaO) totaling 49 wt% of the composition. Tricalcium silicate (3CaOSiO2) powder was prepared by the sol-gel method. 0.5 mol of Si(OC2H5)4 (tetraethyl orthosilicate, TEOS), 200 mL of water and nitric acid solution as catalysts were combined under continuous stirring. Then, 1.5 mol of Ca(NO3)2-4H2O was added to the solution. The solution was heated to 60°C and maintained until gelation occurred. The gel was then dried at 200°C and calcined at 1500°C for 6 hours. Tricalcium silicate is a strongly basic homogeneous compound containing approximately 74% by weight of a strong basic component (CaO). Fluoroaluminosilicate (FAS) glass was prepared essentially as described in Example 1 of U.S. Patent No. 5,154,762. Powder components of SiO2 (34.6 wt%), AlF3 (21.5 wt%), SrO (18.7 wt%), Al2O3 (9.4 wt%), AlPO4 (6.5 wt%), Na2AlF6 (5.6 wt%), and P2O5 (3.7 wt%) were mixed and melted in an arc furnace at 1350-1450°C, then roller-quenched in amorphous single-phase FAS glass. The glass was then ball-milled to 2.6 m³. 2 A pulverized product with a surface area of ​​ / g was obtained (measured according to the Brunauer-Emmett-Teller (BET) method).

[0155] calculation The shell thickness, weight % of core material, and weight % of shell material for the encapsulated material prepared by the processes described in Examples 1 to 5 were calculated using the following equations 1 to 6. In the calculation, the total surface area of ​​the core material was calculated by treating the particles of the core material powder as spheres (surface area = 4π(d / 2)). 2 Volume = (4 / 3)(π)(d / 2) 3 It was determined by expressing it. Formula 1:

number

number

number

number

number

[0156] For encapsulated materials with tricalcium silicate cores, the core particles possessed additional porosity that affected the apparent surface area measurement. For tricalcium silicate encapsulated materials, the effective surface area of ​​the core and the thickness of the shell coating were estimated using an indirect method. Tricalcium silicate encapsulated materials and Portland cement encapsulated materials (with the same shell material) that had approximately the same time required to change the pH of buffers 4-9 (following the procedures of Examples 6-9) were estimated to have the same shell thickness. Therefore, the shell thickness of the tricalcium silicate encapsulated materials was based on the value calculated for the corresponding Portland cement encapsulated materials.

[0157] Example 1. Encapsulated material having a bioactive glass core Bioactive glass (BG) powder was sealed with aluminum oxide (AO)-based material using atmospheric pressure chemical vapor deposition (APCVD). The bioactive glass was coated with trimethylaluminum (obtained from Strem Chemicals, Newburyport, MA, and dispensed from a stainless steel bubbler) by reacting it with water vapor in a fluidized bed reactor. The reactor was a glass frit funnel tube (2 cm in diameter, 18 cm in height). The reactor had an inlet tube extending from below the frit routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled at 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the trimethylaluminum (TMA) bubbler was 100–330 cm³. 3 The flow rate through the water bubbler was in the range of (250-1250 cm³). 3 The flow rate was in the range of ( / minute). The total coating time was in the range of 20 to 100 minutes. Encapsulated materials A to J were prepared by varying the following parameters: the amount of bioactive glass added, the particle size of the bioactive glass powder, the TMA flow rate, the water flow rate, and the coating time. Table 1 lists the encapsulation parameters for encapsulated materials A to J. For encapsulated materials G to J, a larger reactor was used (4 cm in diameter, 30 cm in height). For encapsulated materials A to C and G to J, the particle size of the bioactive glass powder was selected by passing the powder through a 45 micron sieve and collecting it on a 38 micron sieve before adding it to the reactor. For encapsulated materials D to F, the bioactive glass powder was pulverized using a ball mill with a 5 mm medium before adding it to the reactor to obtain a particle size of 10 microns. The average particle size of each powder after pulverization was measured using a Model LA950 Laser Particle Size Analyzer (Horiba Scientific, Edison, NJ) with water.

[0158] Table 1a reports the calculated shell thickness (nanometers), core weight percentage, and shell weight percentage for the enclosed materials A to J.

[0159] [Table 2]

[0160] [Table 3]

[0161] Example 2. Encapsulated material having a tricalcium silicate core. Tricalcium silicate (TCS) was sealed with aluminum oxide-based material using atmospheric pressure chemical vapor deposition (APCVD). Tricalcium silicate powder (30 g) was coated with trimethylaluminum (obtained from Strem Chemicals and dispensed from a stainless steel bubbler) by reacting it with water vapor in a fluidized bed reactor. The reactor was a glass frit funnel tube (4 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled at 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the trimethylaluminum (TMA) bubbler was 500 cm³. 3 The flow rate through the water bubbler was 1750 cm³ / minute. 3 The rate was / minute. The total coating time was 40 minutes. Table 2 lists the average particle size of the tricalcium silicate powder added to the reactor and other encapsulation parameters. Following the coating procedure, the resulting encapsulated material was individually sieved to collect encapsulated material with a particle size of less than 38 microns. These sieved encapsulated materials were denoted as encapsulated material K and L.

[0162] Table 2a reports the calculated shell thickness (nanometers), core weight percentage, and shell weight percentage for the enclosed materials K to L.

[0163] [Table 4]

[0164] [Table 5]

[0165] Example 3. Encapsulated material with a Portland cement core Portland cement (PC) was sealed with aluminum oxide-based material using atmospheric pressure chemical vapor deposition (APCVD). The Portland cement powder was coated with trimethylaluminum (obtained from Strem Chemicals and dispensed from a stainless steel bubbler) by reacting it with steam in a fluidized bed reactor. The reactor was a glass frit funnel tube (4 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled at 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the trimethylaluminum (TMA) bubbler was 240–1000 cm³. 3 The flow rate through the water bubbler was in the range of (610-2500 cm³). 3 The range was ( / minute). The total coating time was in the range of 10 to 105 minutes. The encapsulated materials M to U were prepared by varying the following parameters: the amount of Portland cement added, the particle size of the Portland cement powder, the TMA flow rate, the water flow rate, and the coating time. Table 3 lists the encapsulation parameters for the encapsulated materials M to U.

[0166] Regarding the enclosed material M, the Portland cement powder added to the reactor was used in its as-received state and measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company, Brea, CA). It had an average particle size of 17.1 microns (D10 to D90 range of 6.0 to 33.5 microns).

[0167] Before adding the enclosed materials N to S to the reactor, fine particles were removed from the Portland cement sample by air classification using an AVEKA CCE centrifugal air classifier Model 100 (AVEKA CCE LLC, Cottage Grove, MN). By selecting parameters, crude material with a yield of 56% was obtained, and when measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company), the sample had an average particle size of 24.4 microns (D10 to D90 range of 13.8 to 38.4 microns).

[0168] Before adding the enclosed materials T to U to the reactor, fine and coarse particles were removed from the Portland cement samples using an AVEKA CCE centrifugal air classifier model 100. In the first step, approximately 24% of the coarse portion was removed from the initial sample total, and then in the second step, approximately 25% of the fine portion was removed from the remaining sample. The resulting Portland cement powder had an average particle size of 19.6 microns (D10 to D90 range of 9.4 to 31.5 microns) when measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company).

[0169] Table 3a reports the calculated shell thickness (nanometers), core weight percentage, and shell weight percentage for the enclosed materials M to U.

[0170] [Table 6]

[0171] [Table 7]

[0172] Example 4. Encapsulated material having a Portland cement core and a titanium dioxide shell. Portland cement was encapsulated with titanium dioxide-based material using atmospheric pressure chemical vapor deposition (APCVD). Portland cement powder (50 g) was coated with titanium tetrachloride (obtained from Strem Chemicals and dispensed from a stainless steel bubbler) by reacting it with steam in a fluidized bed reactor. Before filling the reactor, fine particles were removed from the Portland cement sample using the air classification procedure described for the encapsulated materials N-S in Example 3. The average particle size of the resulting powder was 24.4 microns (D10-D90 range of 13.8-38.4 microns) when measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company). The reactor was a glass frit funnel tube (4 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled at 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the titanium tetrachloride bubbler was 1000 cm³. 3 The flow rate through the water bubbler was 1000 cm³ / minute. 3 The time was per minute. The total coating time was 57 minutes.

[0173] Example 5. Encapsulated material having a Portland cement core and a silicon dioxide shell. Portland cement was sealed with silicon dioxide-based material using atmospheric pressure chemical vapor deposition (APCVD). Portland cement powder (50 g) was coated with silicon tetrachloride (obtained from Strem Chemicals and dispensed from a stainless steel bubbler) by reacting it with water vapor in a fluidized bed reactor. Before filling the reactor, fine particles were removed from the Portland cement sample using the air classification procedure described for the sealed materials N-S in Example 3. The average particle size of the resulting powder was 24.4 microns (D10-D90 range of 13.8-38.4 microns) when measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company). The reactor was a glass frit funnel tube (4 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled at 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the silicon tetrachloride bubbler was 60 cm³. 3 The flow rate through the water bubbler was 1300 cm³ / minute. 3 The time was per minute. The total coating time was 58 minutes.

[0174] Table 3b reports the calculated shell thickness (nanometers), core weight %, and shell weight % for the encapsulated materials in Examples 4 and 5.

[0175] [Table 8]

[0176] Example 6. Each of the four glass vials was filled with 15 g of deionized water and 10 g of pH 4 buffer (Buffer BDH5018, VWR International), and the solutions in the vials were stirred. Unsealed Portland cement (0.25 g, particle size 24.4 microns) was added to the first vial. Unsealed FAS glass (0.25 g) was added to the second vial. Sealed material O (0.25 g) was added to the third vial. Sealed material Q (0.25 g) was added to the fourth vial. Stirring in the vials was continued, and the pH of each solution was measured over 8-10 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation, Columbus, OH). The thickness of the shell of the sealed material was corrected by changing the coating time to a longer time to produce a thicker shell. The shell of the encapsulated material O was approximately 4.25 times thicker than the shell of the encapsulated material Q. The results are presented in Table 4, showing that the encapsulated material caused a delayed reaction with the basic core material or a delayed release of the basic core material.

[0177] [Table 9]

[0178] Example 7. Each of the two glass vials was filled with 15 g of deionized water and 10 g of pH 4 buffer (Buffer BDH5018, VWR International), and the solutions in the vials were stirred. 0.25 g of the titanium dioxide-encapsulated material from Example 4 was added to the first vial. 0.25 g of the silicon dioxide-encapsulated material from Example 5 was added to the second vial. Stirring was continued in the vials, and the pH of each solution was measured over 45 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The results are shown in Table 5, indicating that the encapsulated material resulted in a delayed reaction with the basic core material or a delayed release of the basic core material.

[0179] [Table 10]

[0180] Example 8. Each of the three glass vials was filled with 15 g of deionized water and 10 g of pH 4 buffer (Buffer BDH5018, VWR International), and the solutions in the vials were stirred. Unsealed tricalcium silicate (0.25 g) was added to the first vial. Sealed material K (0.25 g) was added to the second vial. Sealed material L (0.25 g) was added to the third vial. Stirring in the vials was continued, and the pH of each solution was measured over 12 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The results are shown in Table 6, indicating that the sealed material caused a delayed reaction with the basic core material or a delayed release of the basic core material.

[0181] [Table 11]

[0182] Example 9. Each of the four glass vials was filled with 15 g of deionized water and 10 g of pH 4 buffer (Buffer BDH5018, VWR International), and the solutions in the vials were stirred. Encapsulated material O (0.25 g) was added to the first vial. Encapsulated material P (0.25 g) was added to the second vial. Encapsulated material Q (0.25 g) was added to the third vial. Encapsulated material R (0.25 g) was added to the fourth vial. Stirring was continued in the vials, and the pH of each solution was measured using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The time it took for each solution to reach pH 9 was recorded. The results are shown in Table 7, demonstrating that the delayed release of the basic core material depends on the shell thickness. The shell thickness of the encapsulated material was modified by changing the coating time to a longer time to produce a thicker shell. The thickness of the aluminum oxide shells of the enclosed materials O to R decreased progressively as follows: shell thickness: enclosed material O > enclosed material P > enclosed material Q > enclosed material R. The relative shell thicknesses of the enclosed materials O to R were approximately 8.5:4.5:2:1 (Table 7).

[0183] [Table 12]

[0184] Example 10. Each of the two glass vials was filled with 15 g of deionized water and 10 g of pH 4 buffer (Buffer BDH5018, VWR International), and the solutions in the vials were stirred. Unsealed bioactive glass (0.25 g, particle size 38-45 microns) was added to the first vial. Sealed material J (0.25 g) was added to the second vial. Stirring was continued in the vials, and the pH of each solution was measured over 60 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The results are shown in Table 8, indicating that the sealed material caused a delayed reaction with the basic core material or a delayed release of the basic core material.

[0185] [Table 13]

[0186] Example 11. Each of the two glass vials was filled with 25 g of deionized water. Unencapsulated Portland cement (0.25 g, 24.4 micron particle size) was added to the first vial. Encapsulated material P (0.25 g) was added to the second vial. The contents were stirred, and the pH of each solution was measured over 5 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The results are shown in Table 9, indicating that the encapsulated material resulted in a delayed reaction or release with the basic core material.

[0187] [Table 14]

[0188] Example 12. Each of the two glass vials was filled with 25 g of deionized water. Unsealed bioactive glass (0.25 g, particle size 38.45 microns) was added to the first vial. Sealed material J (0.25 g) was added to the second vial. The contents were stirred and measured using a Mettler Toledo M300 pH Meter (Mettler The pH of each solution was measured over 3 minutes using a Toledo Corporation (Toledo Corporation) analyzer. The results are shown in Table 10, indicating that the enclosed material resulted in a delayed reaction with the basic core material or a delayed release of the basic core material.

[0189] [Table 15]

[0190] Example 13 (Comparative Example). A glass vial was filled with 25 g of deionized water, and 0.25 g of unsealed FAS glass (0.25 g) was added to the vial. The contents were stirred, and the pH of the solution was measured over 3 minutes using a Mettler Toledo M300 pH Meter (Mettler Toledo Corporation). The results are shown in Table 11.

[0191] [Table 16]

[0192] Example 14. Dental composition containing bioactive glass-encapsulated material Dental compositions 1 to 6 (DC-1 to DC-6) were prepared using pastes selected from pastes B1 to B6 as the first part of the composition and paste A as the second part of the composition.

[0193] The composition of Paste A is reported in Table 12 (each component is reported in weight %). Paste A was prepared in bulk. BHT and CPQ were added to a mixing cup containing HEMA. The filled cup was placed in a FlackTek SPEEDMIXER (FlackTek Incorporated, Landrum, SC) and the contents were mixed at 2500 rpm until a homogeneous mixture was obtained. Next, the VBP mixture in water was added to the cup and mixing was continued. CGP, Zr / Si nanocluster filler, and ytterbium fluoride component were combined to form a homogeneous mixture, and this mixture was then added to the cup. Mixing was continued until the mixture was homogeneous. The resulting paste was stored at 4°C when not in use.

[0194] The compositions of pastes B1-B4 and paste BA are reported in Table 13 (each component is reported in weight %). Pastes B1-B4 and paste BA were prepared by adding EDMAB to a flask containing HEMA and mixing. In a separate beaker, a homogeneous mixture was formed by mixing FAS glass, sealed material H (from Table 1), and fumed silica. Next, the EDMAB / HEMA mixture was added to the mixture in the beaker and stirred until the contents were homogeneous. The beaker was covered and the paste was used within 24 hours of preparation.

[0195] The compositions of pastes B5 and B6 are reported in Table 14. Pastes B1 to B4 were prepared according to the general method described above.

[0196] For dental composition 1, paste B1 was the first part of the composition. Paste A and paste B1 (1:1 by weight) of DC-1 were combined on a mixing pad and stirred until homogeneous (mixing for approximately 10-30 seconds). The pH of the resulting paste was immediately measured using an ORION PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher Scientific Company, Waltham, PA). The pH measurement was recorded 30 seconds after the probe was inserted into the paste. The recorded pH was 4.3. A Teflon disc mold (3.1 mm in diameter and 1.3 mm in height) was immediately filled with the paste, and then the paste was cured on each side of the mold for 20 seconds using an ELIPAR S10 curing light (3M Oral Care, Maplewood, MN). The resulting molded disc was immediately removed from the mold and placed in a 2 mL plastic centrifuge tube containing 1.5 mL of GIBCO phosphate-buffered saline (PBS) solution (1×, pH 7.4) (Thermo Fisher Scientific). The discs were completely immersed in PBS solution. The tubes were stoppered and stored at room temperature.

[0197] For dental composition 2 (DC-2), paste B2 replaced paste B1 as the first part of the composition. A molded disc was prepared using DC-2 according to the procedure described for DC-1. The pH of the paste, measured immediately before filling the mold, was 3.8.

[0198] For dental composition 3 (DC-3), paste B3 replaced paste B1 as the first part of the composition. A molded disc was prepared using DC-3 according to the procedure described for dental composition 1. The pH of the paste, measured immediately before filling the mold, was 3.7.

[0199] For dental composition 4 (DC-4), paste B4 replaced paste B1 as the first part of the composition. A molded disc was prepared using DC-4 according to the procedure described for DC-1. The pH of the paste, measured immediately before filling the mold, was 3.6.

[0200] For dental composition 5 (DC-5), paste B5 replaced paste B1 as the first part of the composition. A molded disc was prepared using DC-5 according to the procedure described for DC-1. The pH of the paste, measured immediately before filling the mold, was 4.9.

[0201] For dental composition 6 (DC-6), paste B6 replaced paste B1 as the first part of the composition. A molded disc was prepared using DC-6 according to the procedure described for DC-1. The pH of the paste, measured immediately before filling the mold, was 3.8.

[0202] For comparative dental composition A (comparative DC-A), paste BA replaced paste B1 as the first component of the composition. Paste BA did not contain any encapsulated material. Molding discs were prepared using comparative DC-A according to the procedure described for DC-1. The pH of the paste, measured immediately before filling the mold, was 3.6.

[0203] For each immersed disk, the pH of the PBS solution was periodically measured over 364 hours using an ORION PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher). The sample was gently shaken before each measurement. The pH profiles of the PBS solution are reported in Tables 15 and 16. The pH measurement recorded at "0 hours" was performed immediately after immersion of the disk in the PBS solution.

[0204] Table 15 shows that the concentration (wt%) of encapsulated material H incorporated into the dental compositions decreased from DC-1 to DC-4 compared to comparative DC-A, which did not contain encapsulated material H (i.e., the concentration of incorporated encapsulated material was DC-1 > DC-2 > ​​DC-3 > DC-4 > comparative DC-A). Table 16 shows that the shell thickness of the encapsulated material in dental compositions DC-1, DC-5, and DC-6 was varied such that DC-6 contained the encapsulated material with the thickest shell, and DC-5 contained the encapsulated material with the thinnest shell.

[0205] [Table 17]

[0206] [Table 18]

[0207] [Table 19]

[0208] [Table 20]

[0209] [Table 21]

[0210] Example 15. Dental composition containing Portland cement-encapsulated material Dental compositions (DC-7 to DC-11) were prepared using pastes selected from pastes B7 to B11 as the first part of the composition and paste A as the second part of the composition.

[0211] Paste A was prepared as reported in Example 14.

[0212] The compositions of pastes B7-B9 are reported in Table 17 (each component is reported in weight %). Pastes B7-B9 were prepared by adding EDMAB to a flask containing HEMA and mixing. In a separate beaker, a homogeneous mixture was formed by mixing FAS glass, sealed material P (from Table 3), and fumed silica. Next, the EDMAB / HEMA mixture was added to the mixture in the beaker and stirred until the contents were homogeneous. The beaker was covered and the paste was used within 24 hours of preparation.

[0213] The composition of paste B10 is reported in Table 18. Paste B10 was prepared according to the general method described above for pastes B7 to B9, except that the encapsulated material P was replaced with the encapsulated material of Example 4 (titanium dioxide-encapsulated Portland cement).

[0214] The composition of paste B11 is reported in Table 19. Paste B11 was prepared according to the general method described above for pastes B7 to B9, except that the encapsulated material P was replaced with the encapsulated material of Example 5 (silicon dioxide-encapsulated Portland cement).

[0215] For dental composition 7 (DC-7), paste B7 was the first part of the composition. Paste A and paste B7 (1:1 by weight) of DC-7 were combined on a mixing pad and stirred until homogeneous (mixing for about 10-30 seconds). The pH of the resulting paste was adjusted using ORION The pH was measured immediately using a PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher Scientific Company). The pH measurement was recorded 30 seconds after inserting the probe into the paste. The recorded pH was 3.5. A Teflon disc mold (3.1 mm in diameter and 1.3 mm in height) was immediately filled with the paste, and then the paste was cured for 20 seconds on each side of the mold using an ELIPAR S10 curing light (3M Oral Care, Maplewood, MN). The resulting molded disc was immediately removed from the mold and placed in a 2 mL plastic centrifuge tube containing 1.5 mL of GIBCO phosphate-buffered saline (PBS) solution (1×, pH 7.4) (Thermo Fisher Scientific). The disc was completely immersed in the PBS solution. The tube was stoppered and stored at room temperature.

[0216] For dental composition 8 (DC-8), paste B8 replaced paste B7 as the first part of the composition. A molded disc was prepared using DC-8 according to the procedure described for DC-7. The pH of the paste, measured immediately before filling the mold, was 3.5.

[0217] For dental composition 9 (DC-9), paste B9 replaced paste B7 as the first part of the composition. A molded disc was prepared using DC-9 according to the procedure described for DC-7. The pH of the paste, measured immediately before filling the mold, was 3.6.

[0218] For dental composition 10 (DC-10), paste B10 replaced paste B7 as the first part of the composition. A molded disc was prepared using DC-10 according to the procedure described for DC-7. The pH of the paste, measured immediately before filling the mold, was 3.3.

[0219] For the dental composition 11 (DC-11), paste B11 replaced paste B7 as the first part of the composition. A molded disk was prepared using DC-11 following the procedure described for DC-7. The pH of the paste measured immediately before filling the mold was 3.3.

[0220] For each immersion disk, the pH of the PBS solution was periodically measured over 333 or 646 hours using an ORION PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher). The sample was gently shaken before each measurement. The pH profiles of the PBS solution are reported in Tables 20 and 21. The pH measurement recorded at "0 hours" was performed immediately after immersion of the disk in the PBS solution.

[0221] In Table 20, dental compositions with various concentrations of incorporated encapsulated material P were evaluated. DC-7 contained approximately twice the amount of encapsulated material P (by weight %) as DC-9. Comparative DC-A did not contain encapsulated material P.

[0222] [Table 22]

[0223] [Table 23]

[0224] [Table 24]

[0225] [Table 25]

[0226] [Table 26]

[0227] Example 16. Dental composition containing tricalcium silicate-encapsulated material A molded disc was prepared using dental composition DC-12 according to the procedure reported in Example 14. DC-12 was prepared using paste B12 (composition in Table 22) as the first part of the composition and paste A as the second part of the composition. The pH of the stirred paste, measured immediately before filling the mold, was 3.7. The pH of the PBS solution surrounding the disc was measured periodically over 790 hours according to the procedure described in Example 14, and the results are reported in Table 23. The pH measurement recorded at "0 hours" was performed immediately after immersion of the disc in the PBS solution.

[0228] [Table 27]

[0229] [Table 28]

[0230] Example 17. Cell proliferation of dental pulp stem cells in contact with a dental composition containing encapsulated bioactive glass. Molded discs (3.1 mm in diameter and 1.3 mm in height) of dental compositions 1-4 and comparative dental composition A were prepared using the general mixing and curing procedure for preparing molded discs described in Example 14. Individual discs were also prepared from commercially available dental base / liner products (Comparative Example X) and commercially available pulp cap / liner products (Comparative Example Y). The discs were individually sterilized by placing them continuously in a 70% ethanol bath for 20 minutes and rinsing them with PBS (3 times), and then incubated overnight in pulp stem cell (DPSC) basal medium (Lonza Group LTD., Basel, Switzerland) (37°C, 5% CO2, 98% relative humidity). Human pulp stem cells (DPSC, Lonza Group LTD.) were seeded at a rate of 20,000 cells / mL per well in COSTAR 48-well cell culture plates (Corning Incorporated, Corning, NY) containing DPSC basal medium. Each well was loaded with a disc, and the cells were cultured for 7 days (37°C, 5% CO2, 98% relative humidity). As a control, human dental pulp stem cells were seeded in additional wells, but no molded discs were added to any of these wells.

[0231] On day 7, DPSC samples were evaluated for cell proliferation using absorbance measurements taken at 540 nm with a microplate reader (Tecan Group LTD., Mannedorf, Switzerland) along with an MTT colorimetric assay kit (Invitrogen Corporation, Carlsbad, CA). Table 24 records the average OD540 (n=6) for DPSC samples in contact with dental compositions 1-4 (containing various concentrations of encapsulated bioactive glass material), comparative dental composition A (without encapsulated material), comparative examples X and Y, and the control.

[0232] [Table 29]

[0233] Cell proliferation of dental pulp stem cells contacted with a dental composition containing encapsulated Portland cement or encapsulated tricalcium silicate Molded disks (3.1 mm in diameter and 1.3 mm in height) of dental compositions 8, 10, 11, 12, comparative dental composition A, comparative example X, and comparative example Y were prepared and tested for cell proliferation according to the procedure described in Example 17. As described in Example 17, a control (well seeded with DPSCs but without the addition of a molded disk) was also prepared. In Table 25, the average OD540 (n = 4) for DPSC samples contacted with dental compositions 8, 10, 11, 12 (containing encapsulated materials with different shell coatings and having a Portland cement or tricalcium silicate core), comparative dental composition A (not containing an encapsulated material), comparative examples X and Y, and the control are recorded.

[0234]

Table 30

[0235] Example 19. ALP activity of dental pulp stem cells contacted with a dental composition Molded discs (3.1 mm in diameter and 1.3 mm in height) of dental compositions 1-4, comparative dental composition A, comparative example X, and comparative example Y were prepared using the general mixing and curing procedure for preparing molded discs described in Example 14. The discs were individually sterilized by placing them continuously in a 70% ethanol bath for 20 minutes and rinsing them with PBS (3 times), and then incubated overnight in dental pulp stem cell (DPSC) basal medium (Lonza Group LTD.) (at 37°C, 5% CO2, and 98% relative humidity). Human dental pulp cells (DPSC, Lonza Group LTD.) were seeded at 20,000 cells / mL per well in COSTAR 48-well cell culture plates (Corning Incorporated, Corning, NY) containing DPSC basal medium. Discs were loaded into each well, and the cells were cultured for 7 days (at 37°C, 5% CO2, and 98% relative humidity). As a control, human dental pulp stem cells were seeded in additional wells, but no molded discs were added to any of these wells.

[0236] On day 7, DPSC cells were collected, and the cell lysates of each sample were analyzed for alkaline phosphatase (ALP) activity using a human ALP ELISA kit (BioVision Incorporated, San Francisco, CA) according to the manufacturer's instructions. Table 26 records the average ALP concentration (n=2) in mU / mL for dental compositions 1-4 (containing various concentrations of encapsulated bioactive glass material), comparative dental composition A (without encapsulated material), comparative examples X and Y, and DPSC samples that were in contact with the control.

[0237] [Table 31]

[0238] Example 20. ALP activity of dental pulp stem cells in contact with dental composition. Molded discs (3.1 mm in diameter and 1.3 mm in height) were prepared for dental compositions 8, 10, 11, and 12, comparative dental composition A, comparative example X, and comparative example Y, and tested for ALP activity according to the procedure described in Example 19. A control example (a well in which DPSC was seeded but no molded disc was added) was also prepared as described in Example 19. In Table 27, the average ALP concentration (n=1~3) in mU / mL is recorded for DPSC samples in contact with dental compositions 8, 10, 11, and 12 (containing encapsulated material with Portland cement or tricalcium silicate core with different shell coatings), comparative dental composition A (without encapsulated material), comparative examples X and Y, and the control example.

[0239] [Table 32]

[0240] Example 21. Encapsulated material having a calcium hydroxide core or a mixed-phase calcium silicate core. Calcium hydroxide (CH) powder was obtained from Jost Chemical (St. Louis, MO, product number: 2242). The material was passed through a 25-micron sieve.

[0241] Mixed-phase calcium silicate (MPCS) was prepared by mixing 14.1% by weight of SiO2, 50.3% by weight of CaCO3, 34.7% by weight of H2O, and 0.8% by weight of BYK-W9012. The wetting and dispersing additives for BYK-W9012 were obtained from BYK-Chemie GmbH, Wesel, Germany. After mixing, the resulting slurry was dried at 100°C for 12 hours and then sintered at 1500°C for 2 hours. The resulting particles were ground using a mortar and pestle to obtain a powder with an average particle size of 11.35 microns, as measured by laser diffraction.

[0242] Calcium hydroxide (CH) and mixed-phase calcium silicate (MPCS) were sealed with aluminum oxide using the APCVD process and apparatus described in Example 2 (except for heating the reactor with a heating tape), and the amount of powder and flow rate are reported in Table 28.

[0243] [Table 33]

[0244] Example 22. pH buffering test of enclosed material The tests described in Example 6 were performed on both unencapsulated CH and MPCS, as well as on encapsulated CH and MPCS sampled from the batches listed in Table 28. The pH of the buffer solution immediately before powder addition was 4.1 for all four samples. The results are shown in Table 29, indicating that the encapsulated material resulted in a delayed reaction with the basic core material or a delayed release of the basic core material.

[0245] [Table 34]

[0246] Example 23. Portland cement core sealed using atomic layer deposition (ALD). Portland cement powder (5g) was microencapsulated using the atomic layer deposition (ALD) process. An aluminum oxide coating was deposited on a targeted particle material via a self-limiting surface reaction using a flow-through atomic layer deposition (FTALD) reactor incorporating a sequential four-step process (precursor A, purge, precursor B, purge).

[0247] The sequential four-step process consisted of the following sequence: (1) Precursor A (i.e., trimethylaluminum (TMA)) pulse, (2) N2 purge, (3) Precursor B (i.e., ozone @ 20% pulse), and (4) N2 purge. The TMA precursor pulse time and pressure were set to 1.125 seconds at a pressure of 1–3 Torr inside the reactor. The ozone precursor pulse time and pressure were set to 1.000 seconds at a pressure of 1–4 Torr inside the reactor. The purge time was in the range of 100–120 seconds per half-cycle. The four-step sequence is referred to herein as 1 ALD cycle. A 5g sample of Portland cement was processed using a total of 200 ALD cycles at a process temperature of 150°C.

[0248] The internal sample chamber consisted of a 34 mm frit tube with one end closed and the other open end fitted with a fitting (VCR8 fitting). The fitting was then attached to a precursor delivery system that allowed various gases to be added to the inside of the frit tube and evacuated through the walls of the frit tube.

[0249] The precursor delivery system was designed using a rotating union so that the frit tube (sample chamber) rotated independently of the rest of the reactor system. The frit tube attached to the precursor delivery system was then placed inside a temperature control sleeve or tube used to control the temperature of the particles and precursors during the deposition process.

[0250] During the deposition process, the tube containing the particles was rotated, thereby lifting the particles along the tube walls and allowing them to free-fall to the bottom of the tube. While free-falling, the particles were sequentially exposed to various precursor and purging processes as the gas flowing into the open end of the frit tube was expelled through the walls. A vibrating motor was also attached to the reactor assembly to provide additional agitation to maintain free flow of particles during the deposition process. All gases were heated to 80°C to prevent the gas flow from cooling the sample.

[0251] To ensure that a sufficient amount of precursor was supplied to the reactor, the precursor packing was monitored using a residual gas analyzer (obtained from Stanford Research Systems, Inc., Sunnyvale, CA under the trade name "SRS RESIDUAL GAS ANALYZER").

[0252] The resulting enclosed powder was measured for pH change using the procedure described in Example 6. The results are reported in Table 30.

[0253] [Table 35]

[0254] Example 24. Measurement of adhesive strength of dental composition 8 (DC-8) and comparative dental composition A (DC-A) applied to the dentin surface. Bovine incisors (10) were individually embedded in resin packs measuring 25 mm in diameter and 10-20 mm in height (one tooth per pack). Each resulting pack was crushed with 120-grit sandpaper to expose the dentin layer of the tooth, and then polished with 320-grit sandpaper. All experiments were conducted indoors at a constant temperature of 75°C, 50% humidity, and using a light filtered to 450 nm. The surface of each tooth was blotted to remove excess water, and a 5 mm diameter circle of exposed dentin was framed using 3M 201+ masking tape (3M Company, Maplewood, MN) as a mask. DC-8 (prepared as described in Example 15) was applied to cover the exposed dentin area, wiped to the same height as the mask using a spatula, and then cured for 20 seconds using an ELIPAR S10 LED curing light (3M Company). Next, using a disposable applicator, SCOTCHBOND universal adhesive (3M Company) was applied to the cured surface for 20 seconds. This area was dried with a gentle airflow for 5 seconds, and then photocured for 10 seconds with an ELIPAR S10 LED curing light. A Teflon mask with a 5mm diameter hole lined with gelatin, 2-5mm deep, was aligned with the tape mask and secured with metal clips. The hole was then filled with FILTEK Z250 dental composite resin (3M Company) and photocured for 20 seconds with an ELIPAR S10 LED curing light to create a peg. The dental specimen was then placed in a chamber (37°C and 95% humidity) for 0.5 hours. The metal clips were removed from the dental specimen, and each specimen was immersed in deionized water at 37°C for 24 hours. After 24 hours, the gelatin was dissolved and the Teflon mask was removed. The resin pack was placed in an Instron The assembly was fixed to a circular grip fixture on the upper arm of a 5944 (Instron Corporation, Norwood, MA) unit. The lower fixture had a wire loop approximately 90 mm long. The wire was looped onto a FILTEK Z250 peg and fixed coplanar with the tooth / resin surface. Then, tension was applied until breakage occurred (i.e., the assembly broke away from the tooth surface or the tooth broke) to determine the adhesion strength of the cured dental composition DC-8 to the tooth.

[0255] This procedure was repeated using comparative dental composition A (DC-A prepared as in Example 14) instead of DC-8. The average (n=10) adhesive strength values ​​(MPa) determined for dental compositions DC-A and DC-8 are reported in Table 31.

[0256] [Table 36]

[0257] Example 25. Dental composition (DC-13) Dental composition B (DC-B) was prepared by adding 120 mg of IRGACURE 819 (a photoinitiator obtained from BASF Corporation, Wyandotte, MI) to 40 g of SR 603 (polyethylene glycol (400) dimethacrylate obtained from Sartomer Americas, Exton, PA). The mixture was mixed three times for 1 minute at 3000 rpm in a FlackTek DAC 150 FVZ speed mixer. A Teflon disc mold (3.1 mm in diameter and 1.3 mm in height) was immediately filled with DC-B and then cured for 20 seconds on each side of the mold using an Elipar® DeepCure-S LED curing light (3M Company). The resulting molded disc was immediately removed from the mold and placed in a 2 mL plastic centrifuge tube containing 1.5 mL of GIBCO phosphate-buffered saline (PBS) solution (1×, pH 7.4) (Thermo Fisher Scientific). The disc was completely immersed in the PBS solution. The tubes were capped and stored at room temperature. Discs from dental composition B served as a control (without encapsulated material).

[0258] Dental composition 13 (DC-13) was prepared by combining 3 g of enclosed material P with 1 g of DC-B. This mixture was mixed three times for 1 minute at 3000 rpm. A molded disc was prepared using DC-13 according to the procedure described for DC-B.

[0259] Dental composition C (DC-C) was prepared by combining 3 g of unencapsulated Portland cement with 1 g of DC-B. This mixture was mixed three times for 1 minute at 3000 rpm. Molded discs were prepared with DC-C according to the procedure described for DC-B. Discs from dental composition C served as a control (containing unencapsulated Portland cement).

[0260] For each immersed disc, the pH of the PBS solution was periodically measured over 90.4 hours using an ORION PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher). Each sample was gently shaken before each measurement. The pH profile of the PBS solution is reported in Table 32. The pH measurement recorded at "0 hours" was performed immediately after immersion of the disc in the PBS solution.

[0261] [Table 37] Examples of embodiments of the present invention are listed in the following sections [Aspect 1] to [Aspect 55]. [Aspect 1] A hardening dental composition, A first part comprising an enclosed material, wherein the enclosed material comprises a basic core material and an inorganic shell material containing a metal oxide surrounding the core, A curable dental composition comprising a second part containing water or an acidic component. [Aspect 2] When the first and second parts are combined, the composition has an acidic or neutral pH initially, as described in Embodiment 1. [Aspect 3] The dental composition according to embodiment 1 or 2, wherein the shell is detachable by the second part. [Aspect 4] The dental composition according to any one of embodiments 1 to 3, wherein the basic core material releases -OH when the shell decomposes. [Aspect 5] The dental composition according to any one of embodiments 1 to 4, wherein the basic core material comprises a component having a pKa in the range of 8 to 14. [Aspect 6] The dental composition according to any one of embodiments 1 to 5, wherein the basic core material comprises a component having a pKa in the range of 11 to 14. [Aspect 7] The dental composition according to any one embodiment of embodiments 1 to 6, wherein the basic core material includes a material that releases calcium ions. [Aspect 8] The dental composition according to any one embodiment of embodiments 1 to 7, wherein the basic core material comprises at least 25, 30, 35, 40, or 45% by weight of a component having a pKa in the range of 11 to 14. [Aspect 9] The dental composition according to any one embodiment of embodiments 1 to 8, wherein the shell is a continuous film having a thickness of less than 500 nm. [Aspect 10] The dental composition according to any one of embodiments 1 to 9, wherein the inorganic shell material is less basic than the basic core material. [Aspect 11] The dental composition according to any one embodiment of embodiments 1 to 10, wherein the inorganic shell material comprises a metal oxide having a pKa of 6 to 8. [Aspect 12] A dental composition according to any one embodiment of embodiments 1 to 11, wherein when 0.25 grams of the enclosed material is combined with 25 g of deionized water, a pH of at least 8.5 or 9 is obtained within 24 hours. [Aspect 13] A dental composition according to any one embodiment of embodiments 1 to 12, wherein when 0.25 grams of the enclosed material is combined with a solution of 15 g of deionized water and 10 g of aqueous potassium bituminate buffer adjusted to a pH of 4.00 with hydrochloric acid at 25°C, a pH of at least 8.5 or 9 is obtained within 24 hours. [Aspect 14] The dental composition according to any one embodiment of embodiments 1 to 13, wherein the basic core material is curable. [Aspect 15] The dental composition according to embodiment 14, wherein the basic core material contains calcium silicate. [Aspect 16] The dental composition according to any one embodiment of embodiments 1 to 15, wherein the basic core material is a dental filler containing a neutral metal oxide having low solubility in the second portion. [Aspect 17] The dental composition according to any one embodiment of embodiments 1 to 16, wherein the hardening dental composition comprises a material that promotes remineralization by releasing calcium ions, phosphorus ions, fluoride ions, or a combination thereof. [Aspect 18] A dental composition according to any one embodiment of embodiments 1 to 16, further comprising at least one second filler. [Aspect 19] The dental composition according to embodiment 18, wherein the second filler comprises a nanoscale particulate filler. [Aspect 20] The dental composition according to embodiment 19, wherein the second filler comprises zirconia, silica, or a mixture thereof. [Aspect 21] The dental composition according to any one embodiment of embodiments 19 to 20, wherein the second filler comprises a nanocluster filler. [Aspect 22] A dental composition according to any one embodiment of embodiments 1 to 21, wherein the first and / or second portion comprises a polymerizable material. [Aspect 23] The dental composition according to embodiment 22, wherein the polymerizable material comprises a hydroxy-functional (meth)acrylate monomer, an acidic polymer, or a combination thereof. [Aspect 24] A dental composition according to any one embodiment of embodiments 1 to 23, wherein the cured dental composition provides a pH of at least 8.5 or 9 within 500 hours according to a disc buffering test. [Aspect 25] The dental composition according to any one embodiment of embodiments 1 to 24, wherein the average cell proliferation of dental pulp cells is at least 75% of that of a control sample when in contact with the hardened dental composition. [Aspect 26] A dental composition according to any one embodiment of embodiments 1 to 25, wherein the average ALP activity of dental pulp cells increases when in contact with the hardened dental composition. [Aspect 27] A composition, A first part comprising an enclosed material, wherein the enclosed material comprises a basic core material and an inorganic shell material containing a metal oxide surrounding the core, A composition comprising a second part containing water or an acidic component. [Aspect 28] A composition, A encapsulated material comprising a basic core material and an inorganic shell material containing a metal oxide surrounding the core, A composition comprising water or an acidic component. [Aspect 29] The composition according to embodiment 27 or 28, further characterized by any one embodiment or combination thereof of embodiments 2 to 26. [Aspect 30] An encapsulated material suitable for use as a biocarrier, comprising a basic core material and an inorganic shell material containing a metal oxide surrounding the core. [Aspect 31] The enclosed material according to embodiment 30, further characterized by any one embodiment from embodiments 4 to 16 or a combination thereof. [Aspect 32] The encapsulated core material according to embodiment 30 or 31, wherein the composition is curable or self-curing when mixed with water. [Aspect 33] A curable composition comprising an enclosed material as described in any one of embodiments 30 to 32. [Aspect 34] A curable dental composition according to embodiment 33, which is a dental or medical composition. [Aspect 35] A curable composition according to any one of the embodiments 30 to 34, further comprising a second filler and / or polymerizable material according to any one of the embodiments 18 to 23 or a combination thereof. [Aspect 36] A curable composition according to any one embodiment of embodiments 32 to 35, which comes into contact with water or an acidic component during use. [Aspect 37] The curable composition according to embodiment 36, wherein the water or acidic component is a biological fluid. [Aspect 38] A method for delaying the release of basic core material, Prepare the composition described in any one of embodiments 1 to 37, and A method comprising applying the composition to a tooth or bone structure. [Aspect 39] A method that results in a delayed increase in basicity, Prepare the composition described in any one of embodiments 1 to 37, and A method comprising applying the composition to a tooth or bone structure. [Aspect 40] A method for promoting remineralization, The preparation of a composition according to any one embodiment of embodiments 1 to 37, wherein the basic core further comprises a material that promotes remineralization, and A method comprising applying the composition to a tooth or bone structure. [Aspect 41] The method according to embodiment 40, wherein the material that promotes remineralization releases calcium ions, phosphorus-containing ions, fluoride ions, or a combination thereof. [Aspect 42] A method for increasing the average ALP activity of dental pulp cells, The preparation of a composition according to any one embodiment of embodiments 1 to 35, wherein the basic core further comprises a material that promotes remineralization, and A method comprising applying the composition to a tooth or bone structure. [Aspect 43] A composition according to any one embodiment of embodiments 1 to 37 for use in application to a tooth or bone structure, wherein the composition is This results in delayed release of the basic core material, This results in a delayed increase in basicity. Promote remineralization, It increases the average ALP activity of dental pulp cells, Or compositions that combine these. [Aspect 44] A method of using the composition, Prepare the composition described in any one of embodiments 1 to 37, and A method comprising applying the composition to a tooth or bone structure. [Aspect 45] The method according to embodiment 44, wherein the composition comprises a polymerizable material, and the method further comprises curing the composition by exposing it to a radiation source. [Aspect 46] The method according to embodiment 44 or 45, wherein the composition results in delayed release of the basic core material. [Aspect 47] The method according to any one embodiment of embodiments 44 to 46, wherein the composition results in a delayed increase in basicity. [Aspect 48] The method according to any one embodiment of embodiments 44 to 47, wherein the composition promotes remineralization of tooth or bone structures. [Aspect 49] The method according to any one embodiment of embodiments 44 to 48, wherein the composition increases the average ALP activity of dental pulp cells. [Aspect 50] The method according to any one embodiment of embodiments 44 to 49, wherein the composition is a dental adhesive or cement used to bond dental articles to tooth structures. [Aspect 51] The method according to any one embodiment of embodiments 44 to 49, wherein the composition is a dental restorative agent. [Aspect 52] A method for manufacturing encapsulated materials, comprising preparing a basic core material, and A method for manufacturing the basic core material, comprising encapsulating it with an inorganic shell material containing a metal oxide by at least one vapor deposition technique. [Aspect 53] The manufacturing method according to embodiment 52, comprising atomic layer deposition or atmospheric pressure chemical vapor deposition. [Aspect 54] The manufacturing method according to embodiment 52 or 53, wherein the shell material and the thickness of the shell are selected to allow for the delayed release of the basic core material. [Aspect 55] The manufacturing method according to embodiment 52 or 53, wherein the enclosed material causes an increase in pH after a longer duration than the same material that is not enclosed.

Claims

1. A dental composition, The enclosed material, It is the core, Dicalcium silicate and Tricalcium silicate and It contains tricalcium aluminate, The core consists of 61% to 69% CaO and 18% to 24% SiO ２ , 2% to 6% Al ２ O ３ , 1% to 6% Fe ２ O ３ It contains 0.5% to 5% MgO, A core characterized by having an average particle size of 17.1 to 24.4 micrometers, A shell comprising aluminum oxide, silicon oxide, titanium oxide, or a combination thereof, characterized in having a thickness of 13 to 204 nm, Includes enclosed materials containing A dental composition in which the shell surrounds the core.

2. A dental composition which is one part of a two-component curable composition, wherein the one part is The enclosed material, It is the core, Dicalcium silicate and Tricalcium silicate and It contains tricalcium aluminate, The aforementioned core contains 61% to 69% CaO, 18% to 24% SiO₂, 2% to 6% Al₂O₃, 1% to 6% Fe₂O₃, and 0.5% to 5% MgO. A core characterized by having an average particle size of 17.1 to 24.4 micrometers, A shell comprising aluminum oxide, silicon oxide, titanium oxide, or a combination thereof, characterized in having a thickness of 13 to 204 nm, Includes enclosed materials containing The shell surrounds the core, A dental composition in which the enclosed material is present in an amount of 35 to 40% by weight relative to the weight of the dental composition.

3. The dental composition according to claim 1 or 2, further comprising an acid-reactive filler.

4. The dental composition according to claim 1 or 2, further comprising fluoroaluminosilicate glass.

5. The dental composition according to claim 1 or 2, further comprising a polymerizable liquid, wherein the dental composition is a paste.

6. The dental composition according to claim 1, further comprising a polymerizable liquid, wherein the dental composition is a paste, and the enclosed material is present in an amount of 17.5 to 20% by weight relative to the weight of the dental composition.

7. The dental composition according to claim 5, further comprising an acid-reactive filler.

8. The dental composition according to claim 5, further comprising fluoroaluminosilicate glass.

9. The dental composition according to claim 1, which is in powder form.

10. A sealed material, It is the core, Dicalcium silicate and Tricalcium silicate and It contains tricalcium aluminate, The aforementioned core contains 61% to 69% CaO, 18% to 24% SiO₂, 2% to 6% Al₂O₃, 1% to 6% Fe₂O₃, and 0.5% to 5% MgO. A core characterized by having an average particle size of 17.1 to 24.4 micrometers, A shell comprising aluminum oxide, silicon oxide, titanium oxide, or a combination thereof, characterized in having a thickness of 13 to 204 nm, Includes, The aforementioned shell is an enclosed material surrounding the aforementioned core.

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