Search

JP-2026075554-A - Dental curable composition

JP2026075554AJP 2026075554 AJP2026075554 AJP 2026075554AJP-2026075554-A

Abstract

[Problem] To provide a dental curable composition that exhibits appropriate fluidity in a paste state, has fluorescence similar to natural teeth and high radiopacity, and conforms to the color stability test of ISO 4049:2019. [Solution] A dental curable composition comprising a specific amount each of a silica-based composite oxide powder composed of a polymerizable monomer (A), an amine compound, a fluorescent agent containing a phthalate ester, silica-based composite oxide primary particles (d) having a specific average primary particle size, and an X-ray contrast material consisting of crystalline rare earth metal fluoride primary particles (e) having a specific average primary particle size and specific crystallinity, wherein the total amount of (e) blended is 5 to 50 parts by mass per 100 parts by mass of (A), of which 2 to 25 parts by mass are included in the form of primary particles, and the remainder is included as aggregated particles with an average aggregated particle size of 3 to 30 μm. [Selection Diagram] None

Inventors

  • 藤盛 雄士
  • 橋本 明香里

Assignees

  • 株式会社トクヤマデンタル

Dates

Publication Date
20260508
Application Date
20241213
Priority Date
20241022

Claims (6)

  1. Polymerizable monomer (A): 100 parts by mass, Amine compound (B): 0.01 to 3.0 parts by mass, Phthalate ester (C): 0.0005 to 0.05 parts by mass, It contains 170 to 270 parts by mass of silica-based composite oxide powder (D), which is composed of silica-based composite oxide primary particles (d) with an average particle size of 50 nm to 1 μm, and 5 to 50 parts by mass of X-ray contrast material (E), which is composed of fluorine atom-containing inorganic particles. The above (E) consists of a plurality of crystalline rare-earth metal fluoride primary particles (e) in which the full width at half maximum of the maximum intensity peak originating from the crystalline rare-earth metal fluoride in the X-ray diffraction pattern obtained by X-ray diffraction measurement is 0.3° or more, and the average primary particle size measured by electron microscopy is 10 to 300 nm. (e1), which is a portion of the plurality of crystalline rare earth metal fluoride primary particles (e), is dispersed in the composition as a plurality of primary particles, and the remainder (e2) is dispersed in the composition as a plurality of aggregated particles consisting only of (e2), which has an average aggregated particle diameter of 3 to 30 μm, defined as the median diameter in the volume-based particle size distribution measured by laser diffraction-scattering, and the amount of (e1) is 2 to 25 parts by mass per 100 parts by mass of polymerizable monomer (A). A dental hardening composition characterized by the following features.
  2. The dental curable composition according to claim 1, wherein (e) comprises ytterbium fluoride primary particles.
  3. The amine compound (B) is given by the following general formula (1) (In the formula, R1 and R2 are independent of each other. A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group or a halogen atom as a substituent; or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms excluding the substituent, which may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thiomethyl group or a halogen atom as a substituent; R 3 is, The above-mentioned substituted or unsubstituted alkyl groups; the above-mentioned substituted or unsubstituted aryl groups; C2-C12 alkenyl groups; C1-C10 alkoxy groups; C1-C10 alkyloxycarbonyl groups; benzoyl groups having 7-12 carbon atoms excluding the substituent, which may have an alkyl-substituted amino group having C1-C6 as a substituent; acetyl groups; carboxyl groups; nitro groups; or cyano groups; n is an integer between 0 and 5. When n is between 2 and 5, the multiple R3 elements may be distinct from each other, and they may also be bonded together to form a ring . The compound comprises at least one tertiary aromatic amine compound represented by The dental curable composition according to claim 1 or 2.
  4. A method for producing the dental curable composition described in claim 1, The process includes a mixing step of mixing: 100 parts by mass of polymerizable monomer (A), 0.01 to 3.0 parts by mass of amine compound (B), 0.0005 to 0.05 parts by mass of phthalate ester (C), 170 to 270 parts by mass in terms of total mass of (d) for a first raw material powder containing only the silica-based composite oxide primary particles (d) as inorganic primary particles, and 5 to 50 parts by mass in terms of total mass of (e) for a second raw material powder containing only the crystalline rare earth metal fluoride primary particles (e) as inorganic primary particles; As the second raw material powder, a non-aggregated powder (E1) consisting of substantially non-aggregated particles of (e) and an aggregated powder (E2) composed of aggregated particles of (e) having an average aggregated particle diameter of 3 to 30 μm is used, or a powder consisting only of (E2) is used. The aforementioned mixing step is (A): The process includes a first e-mixing step in which 2 to 25 parts by mass of a second raw material powder or granules is blended in a total mass equivalent to (e) per 100 parts by mass, and then the mixture is mixed so that (e) in the blended second raw material powder or granules is dispersed in a primary particle state, and a second e-mixing step in which the agglomerated powder or granules (E2) containing the remaining amount of (e) is blended after the first e-mixing step, and then the mixture is mixed in a manner that does not cause the agglomerated particles constituting (E2) to break down. The first raw material powder is mixed at any time between the start and end of the mixing process. The manufacturing method characterized by the above.
  5. A method for producing the dental curable composition described in claim 1, The process includes a mixing step of mixing a first raw material powder containing only the silica-based composite oxide primary particles (d) as inorganic primary particles, a second raw material powder containing only the crystalline rare earth metal fluoride primary particles (e) as inorganic primary particles, and a composite aggregate powder (F) composed of composite aggregate particles (f) formed by the aggregation of (d) and (e), wherein the content of (e) is 2.0 to 92.6% by mass and the average aggregate particle diameter is 1 to 50 μm. In the aforementioned mixing step, As the second raw material powder, a non-aggregated powder (E1) consisting of substantially non-aggregated particles of (e) and an aggregated powder (E2) composed of aggregated particles of (e) having an average aggregated particle diameter of 3 to 30 μm is used, or a powder consisting only of (E2) is used. The amount of the composite aggregated powder (F) is such that, when the amounts of (d) and (e) contained in (F) relative to 100 parts by mass of (A) are Q(Fd) and Q(Fe), respectively, Q(Fd) is 2 to 100 parts by mass and Q(Fe) is 2 to 25 parts by mass. The amount of the first raw material powder is such that the sum of the amount of (d) in terms of total mass relative to 100 parts by mass of (A) and Q(Fd) is between 170 and 270 parts by mass. The amount of the second raw material powder is such that the sum of the amount of (e) in terms of total mass relative to 100 parts by mass of (A) and Q(Fe) is between 5 and 50 parts by mass. The aforementioned mixing step is The process includes an ed mixing step in which (F) or (F) and the second raw material powder are blended in an amount equivalent to 2 to 25 parts by mass of the total mass of (e) contained therein relative to 100 parts by mass of (A), and then mixed so that (e) is dispersed in the blended second raw material powder in the form of primary particles, and a second e mixing step in which the agglomerated powder (E2) containing the remaining amount of (e) is blended after the ed mixing step, and then mixed so as not to break down the agglomerated particles constituting (E2). The first raw material powder is mixed at any time between the start and end of the mixing process. The manufacturing method characterized by the above.
  6. A flowable composite resin comprising the dental curing composition described in claim 1.

Description

This invention relates to a dental curable composition. Dental curing compositions primarily consist of polymerizable monomers, inorganic fillers (aggregates of inorganic particles), and polymerization initiators. Among these, composite resin (sometimes abbreviated as "CR") is one of the most widely used materials in dental treatment for repairing tooth defects and cavities after caries removal. Composite resins are required to have excellent handling properties in the paste state before polymerization and curing, as well as superior aesthetics (or transparency), mechanical strength, and radiopaque properties of the cured product after polymerization and curing. In recent years, flowable composite resins have been developed that utilize a syringe containing composite resin paste, equipped with a needle tip (a needle with a small hole), allowing the paste to be directly filled into the cavity through the needle tip. This design makes tooth restoration simpler and has led to increased use in clinical practice. In the above-mentioned flowable composite resin, fluidity (handling properties) is required in paste form, depending on the case and preference. Flowable composite resins achieve dispensing from syringes by increasing fluidity through a relatively low inorganic powder content. However, high fluidity can sometimes make it difficult to achieve good shape retention (the property of being resistant to deformation due to natural flow during standing and maintaining its shape). Therefore, appropriate fluidity is necessary. To address these challenges, Patent Document 1 discloses a technique for improving the various properties of composite resins by using two types of inorganic powders and granules in a specific ratio, each exhibiting opposite zeta potentials (in water) and possessing specific average particle sizes and specific surface areas. Specifically, a dental curable composition is disclosed that has good dispensability (having a consistency suitable for dispensing from a syringe) and exhibits moderate fluidity that suppresses paste dripping, comprising: an inorganic filler (B) consisting of particles such as silica-based composite oxides with an average particle diameter of 50 nm to 1 μm and a negative zeta potential; and an inorganic filler (C) consisting of particles such as rare earth metal fluorides with a specific surface area of 25 to 100 m² /g (approximately 10 to 300 nm in particle size) measured by nitrogen adsorption, and a positive zeta potential; each comprising 170 to 270 parts by mass and 5 to 50 parts by mass per 100 parts by mass of polymerizable monomer. On the other hand, for the diagnosis of tooth damage, it is common practice to incorporate rare-earth metal fluoride powders into dental hardening compositions. These powders are radiopaque and, even when incorporated, easily achieve transparency similar to natural teeth. Furthermore, composite resins can sometimes exhibit aesthetic problems, such as the restoration appearing black under ultraviolet or short-wavelength visible light. To avoid this, fluorescent agents are sometimes added. Among these, phthalate ester-based fluorescent agents are widely used because they are readily available, and the restorations they produce emit fluorescence similar to natural teeth, resulting in superior aesthetics. However, when the above-mentioned phthalate ester-based fluorescent agent, an amine compound which is a component of the photopolymerization initiator, and rare-earth metal fluoride powder granules which are an X-ray contrast-enabled acidic filler, strong discoloration may be observed in the cured product after curing. Patent Document 2 discloses a technique to prevent discoloration by specifying the respective blending ratios, including the polymerizable monomer, as a solution. Specifically, Patent Document 2 describes a "curable composition comprising (A) a polymerizable monomer, (B) an amine compound, (C) a fluorescent agent containing a phthalate ester, and (D) an X-ray contrast-enabled acidic filler consisting of inorganic particles containing fluorine atoms, wherein the composition contains 0.01 to 3.0 parts by mass of (B) the amine compound, 0.0005 to 0.05 parts by mass of (C) the fluorescent agent containing a phthalate ester, and 1 to 100 parts by mass of (D) the X-ray contrast-enabled acidic filler consisting of inorganic particles containing fluorine atoms, per 100 parts by mass of (A) the polymerizable monomer." Furthermore, it is known that as the amount of rare-earth metal fluoride powders is increased to enhance X-ray contrast, the transparency of the hardened material decreases, making aesthetic restoration difficult. As a technology to solve this problem, Patent Document 3 discloses an X-ray opaque filler that can suppress the decrease in transparency of the hardened material after curing. This filler is characterized by comprising "a first powder mainly composed of crystalline rare-earth metal fluoride particles, wherei