WO2023042598A1 - Ｘ線不透過性充填材、歯科用ｘ線不透過性充填材、ｘ線不透過性充填材の製造方法、及び、歯科用硬化性組成物 - Google Patents

Ｘ線不透過性充填材、歯科用ｘ線不透過性充填材、ｘ線不透過性充填材の製造方法、及び、歯科用硬化性組成物 Download PDF

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WO2023042598A1
WO2023042598A1 PCT/JP2022/031237 JP2022031237W WO2023042598A1 WO 2023042598 A1 WO2023042598 A1 WO 2023042598A1 JP 2022031237 W JP2022031237 W JP 2022031237W WO 2023042598 A1 WO2023042598 A1 WO 2023042598A1
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Prior art keywords
rare earth
ray opaque
fluoride particles
earth metal
ray
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PCT/JP2022/031237
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English (en)
French (fr)
Japanese (ja)
Inventor
龍太 吉良
秀明 三宅
宏伸 秋積
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Tokuyama Dental Corp
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Tokuyama Dental Corp
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Priority to JP2023548369A priority Critical patent/JPWO2023042598A1/ja
Priority to CA3227331A priority patent/CA3227331A1/en
Priority to AU2022345585A priority patent/AU2022345585A1/en
Priority to CN202280047439.2A priority patent/CN117642143A/zh
Priority to US18/580,274 priority patent/US20250082549A1/en
Priority to EP22869745.4A priority patent/EP4403161A4/en
Priority to KR1020247000381A priority patent/KR20240060585A/ko
Publication of WO2023042598A1 publication Critical patent/WO2023042598A1/ja
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/25—Compositions for detecting or measuring, e.g. of irregularities on natural or artificial teeth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/16—Refractive index
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size

Definitions

  • the present invention relates to a radiopaque filling material, a radiopaque dental filling material, a method for producing the radiopaque filling material, and a curable dental composition.
  • a dental filling material In dental treatment, after caries has been removed, the cavity is filled with a dental filling material, which is then hardened to close the cavity with a hardening material.
  • a dental filling material a curable composition containing a polymerizable monomer, a filler, and a polymerization initiator as main components is generally used.
  • Inorganic oxide fillers particularly silica-based fillers, are generally used as fillers to be blended in this curable composition.
  • silica-based fillers have low radiopacity. For this reason, during X-ray imaging and CT imaging during dental treatment, the hardened material in the cavity is not imaged, making it difficult to determine the treated area.
  • Patent Document 1 A radiopaque dental material based on a polymerizable organic binder, a radiopaque component, and an optional inorganic filler, and, as the radiopaque component, a fluoride of a rare earth metal of the periodic system of the elements (element numbers 57-71) or a mixture of these fluorides in an amount of 1-50% by weight, based on the total weight Radiopaque dental restoratives containing" are described.
  • the present invention provides an X-ray opaque filling material capable of imparting the necessary X-ray opacity to a dental curable composition, hardly reducing the permeability of the cured product, and enabling aesthetic restoration.
  • the present invention provides a dental radiopaque filling material comprising the radiopaque filling material, a method for producing the radiopaque filling material, and a method for producing the radiopaque filling material.
  • An object of the present invention is to provide a dental curable composition having a
  • the term "cured body” simply means a cured body of a curable composition or a dental curable composition, and a cured body obtained by curing a polymerizable monomer. is referred to as a "cured polymerizable monomer".
  • a first form of the present invention is a curable composition containing a polymerizable monomer and a cured product thereof by adding X-rays to the curable composition and its cured body.
  • An X-ray opaque filler that imparts opacity, comprising crystalline rare earth metal fluoride particles as a major component, and having an intensity maximum from said crystalline rare earth metal fluoride particles in an X-ray diffraction pattern.
  • a first powder having a peak full width at half maximum hereinafter also referred to as "maximum peak half width" of 0.3° or more, and a second powder obtained by surface-treating the first powder.
  • An X-ray opaque filler characterized by comprising any powder selected from the group.
  • the first powder is an average primary particle measured by an electron microscope At least one selected from the group consisting of crystalline rare earth metal fluoride particles having a diameter of 5 to 300 nm and agglomerated particles of crystalline rare earth metal fluoride particles having an average primary particle diameter of 1 to 500 nm.
  • a powder containing particles as a main component is preferred.
  • the crystalline rare earth metal fluoride particles are preferably crystalline ytterbium fluoride particles.
  • the crystalline rare earth metal fluoride particles preferably contain at least one particle selected from the group consisting of crystalline lanthanum fluoride particles, crystalline cerium fluoride particles, and crystalline gadolinium fluoride particles. .
  • the full width at half maximum is preferably 0.77° or less.
  • the full width at half maximum is preferably 0.47° to 0.68°.
  • the full width at half maximum is preferably 0.51° to 0.59°.
  • a second aspect of the present invention is a radiopaque dental filling material comprising the radiopaque filling material of the present invention (hereinafter referred to as "the radiopaque dental filling material of the present invention"). It is also called “material”.).
  • a third aspect of the present invention is a method for producing the X-ray opaque filler of the present invention, comprising crystalline rare earth metal fluoride particles as a main component, and said crystalline rare earth metal fluoride particles A raw material powder having a maximum peak half-value width of less than 0.3 ° derived from A method for manufacturing a filler.
  • the mechanochemical treatment is a wet bead mill treatment.
  • a fourth aspect of the present invention is a dental curable composition comprising a polymerizable monomer and the X-ray opaque filler of the present invention.
  • the crystalline rare earth metal fluoride particles are crystalline ytterbium fluoride particles
  • the cured product of the polymerizable monomer has a refractive index of 1.45 to 1.60 with respect to the sodium d-line at 25°C.
  • the radiopaque filling material of the present invention and the dental radiopaque filling material of the present invention contain a polymerizable monomer, unlike conventional radiopaque filling materials made of rare earth metal fluorides.
  • the transparency of the cured product is less likely to be lowered even if the blending amount is increased. Therefore, by using the dental curable composition of the present invention containing the X-ray opaque filler of the present invention, it is possible to perform treatment that is excellent in aesthetics and allows the treated area to be easily confirmed by an X-ray photograph or the like. .
  • the X-ray opaque filler of the present invention can be used not only in dental applications but also in polymerizable curable compositions for various applications such as adhesives and paints, and the transparency and X-ray opacity of the cured product can be improved. can be achieved. Furthermore, according to the manufacturing method of the present invention, the X-ray opaque filler of the present invention having the above-described excellent features can be efficiently manufactured using readily available materials.
  • This figure shows the relationship between the maximum peak half width of the crystalline rare earth metal fluoride particles contained in the X-ray opaque filler and the contrast ratio of the cured product for Examples 1 to 11 and Comparative Examples 1 to 4. graph.
  • This figure shows the mechanochemical treatment time and X-ray impermeability of the raw material powder (crystalline rare earth metal fluoride particles) used in the production of the X-ray opaque filler for Examples 1 to 11 and Comparative Examples 1 to 4.
  • 4 is a graph showing the relationship between the maximum peak half-value width of crystalline rare earth metal fluoride particles contained in a permeable filler.
  • This figure shows the mechanochemical treatment time of the raw material powder (crystalline rare earth metal fluoride particles) used in the production of the X-ray opaque filler and the cured product for Examples 1 to 11 and Comparative Examples 1 to 4. 4 is a graph showing the relationship with contrast ratio.
  • This figure shows the mechanochemical treatment time and X-ray impermeability of the raw material powder (crystalline rare earth metal fluoride particles) used in the production of the X-ray opaque filler for Examples 1 to 11 and Comparative Examples 1 to 4. 4 is a graph showing the relationship between the average primary particle size of crystalline rare earth metal fluoride particles contained in a permeable filler and the average primary particle size.
  • This figure shows the relationship between the refractive index of the polymerizable monomer or the cured product of the polymerizable monomer and the contrast ratio of the curable composition or the cured product for Examples 16 to 22 and Comparative Examples 7 to 13. It is a graph showing. This figure shows the relationship between the refractive index of the polymerizable monomer or the cured product of the polymerizable monomer and the contrast ratio of the curable composition or the cured product for Examples 23 to 29 and Comparative Examples 14 to 20. It is a graph showing. This figure shows the relationship between the refractive index of the polymerizable monomer or the cured product of the polymerizable monomer and the contrast ratio of the curable composition or the cured product for Examples 30 to 36 and Comparative Examples 21 to 27.
  • the present inventors have found the above-mentioned problem of conventional X-ray opaque fillers composed of rare earth metal fluorides, that is, when blended in a curable composition containing a polymerizable monomer, curing when the amount is increased Intensive studies were conducted to solve the problem that the transparency of the body is greatly reduced. As a result, the present inventors happened to find a powder obtained by subjecting crystalline ytterbium fluoride, known as an X-ray opaque filler, to mechanochemical treatment for a long period of time using a wet bead mill. is used, the transparency of the cured product is less likely to decrease even if the blending amount is increased.
  • the mechanochemical treatment reduces the crystallinity of the crystal grains.
  • the crystallinity of the crystal grains is grasped by the full width at half maximum (maximum peak half width) of the maximum intensity peak derived from crystalline ytterbium fluoride in the diffraction pattern obtained by X-ray diffraction measurement of the powder. Even in a state in which the powder is hardly finely divided, when the degree of crystallinity deterioration exceeds a certain level, an effect of preventing deterioration in transparency can be obtained.
  • the reason why the effect of the X-ray opaque filling material of the present invention is exhibited is presumed to be as follows.
  • the decrease in transparency in a system in which inorganic fine particles are dispersed in a resin matrix is greatly influenced by diffuse reflection of light at the interface between the two.
  • the vicinity of the surface of the crystalline rare earth metal fluoride particles is gradually made amorphous from the surface toward the inside by the mechanochemical treatment. Therefore, in the vicinity of the surface of the crystalline rare earth metal fluoride particles, a layer in which the refractive index gradually decreases with a constant gradient from the inside toward the surface (hereinafter also referred to as "gradient refractive index layer”) is formed.
  • gradient refractive index layer a layer in which the refractive index gradually decreases with a constant gradient from the inside toward the surface
  • the formed refractive index gradient layer includes a portion having a refractive index that matches the refractive index of the resin matrix.
  • the proportion of reflected light is reduced (the proportion of transmitted light is increased), and deterioration of transparency is suppressed.
  • the X-ray opaque filler of the present invention is added to the curable composition and its cured product by blending with the curable composition containing a polymerizable monomer. It is a radiopaque filler that provides radiopacity.
  • the polymerizable monomer contained in the curable composition which is the object to be imparted with X-ray opacity, is not particularly limited as long as it is a polymerizable compound, and those commonly used depending on the application are used. can.
  • the curable composition is a dental curable composition
  • radically polymerizable monomers and the like commonly used in the application can be used.
  • the polymerizable monomer used in the curable composition to be blended with the X-ray opaque filler of the present invention has a refractive index difference of “n X ⁇ n M ” is preferably within a specific range.
  • n X means the refractive index of the crystalline rare earth metal fluoride particles that are the main component of the X-ray opaque filler of the present invention
  • n M means the refractive index of the cured polymerizable monomer. means rate.
  • the mechanochemically treated crystalline rare earth metal fluoride particles are presumed to have a refractive index gradient layer near the surface as described above. However, since the ratio of the gradient refractive index layer to the entire mechanochemically treated crystalline rare earth metal fluoride particles is very small, the presence or absence of the gradient refractive index layer does not substantially affect the refractive index of the entire particle. Conceivable. The inventors also confirmed that there is substantially no significant difference in the refractive index of the crystalline rare earth metal fluoride particles before and after the mechanochemical treatment.
  • the X-ray opaque filler of the present invention comprises a first powder containing crystalline rare earth metal fluoride particles as a main component and having a maximum peak half width of 0.3° or more in an X-ray diffraction pattern; And, it must be composed of any powder selected from the group consisting of the second powder obtained by surface-treating the first powder. Even with a powder containing crystalline rare earth metal fluoride particles as a main component, if the maximum peak half width in the X-ray diffraction pattern is less than 0.3°, it is difficult to obtain the effect of preventing opacification.
  • the powder constituting the X-ray opaque filler of the present invention is simply referred to as "powder" when the first powder and the second powder are not distinguished from each other.
  • Components other than the crystalline rare earth metal fluoride particles include (i) a substance derived from a surface treatment agent such as a silane coupling agent, or (ii) used in the raw material powder in the production method of the present invention, which will be described later. Coating agents such as silica, surface treatment agents such as silane coupling agents, or substances derived from other trace additives used as necessary.
  • "contains crystalline rare earth metal fluoride particles as a main component” means that 85% by mass or more of the total mass of the powder is composed of crystalline rare earth metal fluoride particles. In this case, 90 mass % or more of the total mass of the powder is preferably composed of crystalline rare earth metal fluoride particles.
  • the crystalline rare earth metal fluoride particles that constitute the main component of the powder and the maximum peak half width will be described in detail below.
  • Crystalline Rare Earth Metal Fluoride Particles As rare earth metal fluorides in the crystalline rare earth metal fluoride particles, lanthanum fluoride (LaF 3 ), cerium fluoride (CeF 3 ), ytterbium fluoride (YbF) are selected from their color tone and safety. 3 ), or gadolinium fluoride (GdF 3 ) is preferably used, and ytterbium fluoride (YbF 3 ) is most preferably used from the viewpoint of X-ray opacity.
  • the crystal structure of the crystalline rare earth metal fluoride particles is not particularly limited, and usually, those having a stable crystal structure at normal temperature and normal pressure are used according to the type of rare earth metal fluoride.
  • the refractive index of these crystalline rare earth metal fluorides for sodium d-line at 25° C. is usually in the range of 1.50 to 1.65.
  • the first powder has an average primary particle size of 1 to 500 nm as measured by electron microscopic observation, from the viewpoint of the effect of maintaining transparency and the glossiness of the cured product when blended in the dental curable composition. It preferably contains crystalline rare earth metal fluoride particles and/or aggregated particles thereof as a main component. In this case, the average primary particle diameter of the crystalline rare earth metal fluoride particles is particularly preferably 5 to 300 nm.
  • the primary particle diameter measured by the electron microscope observation means that the primary particles in the observation image obtained by observing at a magnification of 100,000 times using a scanning electron microscope (SEM) means the average value of the particle diameters of individual particles.
  • the average particle size (of the entire powder including aggregated particles) measured by a laser diffraction/scattering method is preferably 0.1 to 0.6 ⁇ m, particularly 0.1 It is preferably ⁇ 0.3 ⁇ m.
  • the maximum half-value width of the peak in order to obtain the effect of preventing opacification, the maximum half-value width of the peak, that is, the crystalline rare earth metal fluoride particles in the X-ray diffraction pattern of the powder
  • the full width at half maximum of the maximum intensity peak derived from must be 0.3° or more.
  • the maximum peak half width is preferably 0.4° or more, and particularly preferably 0.5° or more.
  • the upper limit of the maximum peak half width is not particularly limited, it usually does not exceed 40°.
  • the maximum peak half width is preferably 0.77° or less, based on Table 1 described later.
  • the maximum peak half width is preferably 0.47° to 0.68°, and 0.51°. ⁇ 0.59° is more preferred.
  • the maximum peak half width in the present invention can be determined by performing X-ray diffraction measurement on the powder that becomes the X-ray opaque filler of the present invention. Specifically, by performing X-ray diffraction measurement of a measurement sample (powder) in the range of 20 to 120 ° with an X-ray diffractometer, the horizontal axis is 2 ⁇ (°) and the vertical axis is diffraction intensity. Obtain the X-ray diffraction pattern (chart) shown. Thereby, the peaks derived from the crystalline rare earth metal fluoride particles are identified, and the peak having the maximum intensity among them is specified.
  • the peak width at an intensity that is 50% of the maximum intensity (50% intensity) at the peak having the maximum intensity is obtained as the maximum peak half width.
  • the peak width is the absolute value of the difference in 2 ⁇ between two intersections of the peak line and a straight line parallel to the horizontal axis of the X-ray diffraction pattern (chart) and at the position of 50% intensity ( The unit is “deg [°]”).
  • the maximum peak half-value width increases with the length of the treatment time even in a system in which the primary particle diameter is originally small and the primary particle diameter does not change even if the treatment time is lengthened. It is considered that the crystallinity in the sample is non-uniform. However, it is difficult to analyze the state of the crystallites and the state of distortion of the crystal lattice for the individual crystalline rare earth metal fluoride particles that constitute the powder that becomes the X-ray opaque filler of the present invention. , is practically impossible.
  • the radiopaque filler of the present invention is specified using the maximum peak half width as an index of averaged crystallinity.
  • the X-ray-opaque filler of the present invention can also be said to be the X-ray-opaque filler obtained by the production method of the present invention.
  • the production method of the present invention is a method for producing the X-ray opaque filler of the present invention, which contains crystalline rare earth metal fluoride particles as a main component and has a maximum peak half width of is less than 0.3°, and mechanochemically treats the raw material powder so that the maximum peak half width is 0.3° or more.
  • the maximum peak half width of the (crystalline) rare earth metal fluoride powders available as rare earth metal fluoride-based X-ray opaque fillers and reagents generally used in the past is usually less than 0.3°. Therefore, such a powder can be used as the raw material powder without any particular limitation. If there is concern that the crystallinity of the raw material powder is low, perform X-ray diffraction measurement of the raw material powder and confirm that the maximum peak half width is less than 0.3° before use. is preferred.
  • the commercially available crystalline rare earth metal fluoride powders for X-ray opaque fillers include powders surface-coated with nanosilica and powders surface-treated with a silane coupling agent or the like.
  • these powders can be used as raw material powders as they are.
  • the particles are pulverized, the secondary particles (aggregated particles) and primary particles are crushed, and the particle size of the raw material powder is reduced.
  • mechanochemical treatment for several hours does not significantly change the particle size of the raw material powder.
  • the raw material powder has an average primary particle diameter of 1 as measured by electron microscope observation (similar to the powder constituting the X-ray opaque filler of the present invention).
  • It is preferably ⁇ 500 nm, particularly preferably 5 to 300 nm, and preferably has an average particle size of 0.1 to 0.6 ⁇ m, particularly 0.1, as measured by a laser diffraction/scattering method. It is preferably ⁇ 0.3 ⁇ m.
  • the raw material powder is subjected to mechanochemical treatment so that the maximum peak half width is 0.3° or more.
  • the mechanochemical treatment means a treatment that applies mechanical energy to the raw material powder, and means a treatment that performs at least one of mechanical grinding, pulverization, and dispersion. It is preferable to adopt a wet method as a mechanochemical treatment method because the crystallinity of the crystalline rare earth metal fluoride powder (or particles) can be reliably and efficiently controlled to the desired crystallinity. A processing method using a wet bead mill is particularly preferred.
  • a medium such as a solvent such as water or alcohol, or a polymerizable monomer can be used as the medium.
  • the medium is preferably liquid at room temperature (15 to 25°C).
  • the slurry which is a mixture of the raw material powder to be mechanochemically treated and the medium, is brought into contact with the media (beads) that have been moved by stirring or vibration. Thereby, the raw material powder is pulverized and crushed.
  • Materials for the beads used as media include glass, alumina, zircon, zirconia, steel, resin, and the like. Alumina and zirconia are preferred because of their excellent wear resistance and relatively low contamination. preferable.
  • the size of the beads to be used may be selected according to the particle size of the desired X-ray opaque filler, but there is no particular limitation, but it is usually preferable to use beads with a diameter of 0.01 mm to 0.5 mm. This makes it possible to obtain a radiopaque filler with a preferred particle size for addition to dental curable compositions.
  • a batch type in which slurry and beads are directly charged into the device for processing
  • a circulation type in which the slurry circulates between the tank and the device
  • a pass type in which the slurry passes through the device a predetermined number of times.
  • These operation methods may be selected according to the amount of raw material powder used in the mechanochemical treatment.
  • a circulating bead mill is preferably used because it has good productivity and can process a relatively large amount of raw material powder.
  • the bead separation method include a slit method, a screen method, a centrifugal method, and the like. These bead separation methods may be selected according to the particle size of the beads used, and any method can be used without particular limitation.
  • the concentration of the slurry used in the mechanochemical treatment is preferably 50 parts by mass or less of the raw material powder per 100 parts by mass of the medium. If the amount of the raw material powder in the slurry exceeds 50 parts by mass, the viscosity of the slurry increases, which may make the mechanochemical treatment difficult.
  • any known surfactant that is commonly used for dispersing treatment of fillers can be used without particular limitation.
  • examples include active agents, amphoteric surfactants, and polymeric surfactants thereof.
  • Specific examples include glycerol fatty acid esters and alkylene glycol adducts thereof, aliphatic monocarboxylates, alkylamine salts, and alkylbetaines.
  • a dental curable composition using a mechanochemically treated raw material powder (crystalline rare earth metal fluoride particles having a maximum peak half width of 0.3 ° or more), in the dental curable composition From the viewpoint of the dispersibility of the raw material powder after the mechanochemical treatment of (1), it is preferable to use a cationic surfactant as the dispersant.
  • the mechanochemical treatment conditions vary depending on the operation method of the wet bead mill equipment used, the bead diameter, the maximum peak half width of the raw material powder, and the concentration of the slurry. These conditions can be determined by performing a preliminary experiment using an apparatus that actually performs the mechanochemical treatment, and confirming the maximum peak half width of the raw material powder after the mechanochemical treatment with respect to the mechanochemical treatment time. In addition, during the production of the X-ray opaque filler, the treated slurry is sampled as necessary to appropriately confirm the maximum peak half-value width. As a result, it is possible to reliably produce an X-ray opaque filler containing crystalline rare earth metal fluoride particles as a main component having a desired maximum peak half-value width.
  • the raw material powder (mechanochemically treated crystalline rare earth metal fluoride particles) having a maximum peak half width of 0.3° or more by mechanochemical treatment is usually subjected to operations such as concentration, drying, and filtration.
  • a radiopaque filler according to the invention is obtained.
  • a polymerizable monomer is used as a medium in wet processing, it can be used as it is without performing these operations.
  • the obtained X-ray opaque filler can be subjected to a surface treatment to improve affinity with various polymerizable monomers and polymers thereof.
  • Compounds such as silane coupling agents and titanate coupling agents that are generally used can be used as the surface treatment agent.
  • the radiopaque filler of the present invention is a filler compounded in a dental curable composition (i.e., a dental radiopaque It is particularly useful as a flexible filler).
  • the curable dental composition contains a polymerizable monomer and a polymerization initiator in addition to the X-ray opaque filler of the present invention.
  • polymerizable monomer known ones used for the purpose can be used without limitation. Specific examples include methyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl mono (meth) acrylate.
  • a polymerizable monomer can be used individually or in combination of 2 or more types.
  • the polymerizable monomer has a refractive index difference “n X ⁇ n M ” within a specific range as described above. Specifically, it preferably satisfies formula (1), more preferably satisfies formula (2), and most preferably satisfies formula (3).
  • the refractive index of the cured product of the polymerizable monomer can be adjusted by combining a plurality of polymerizable monomers, and the known polymerizable monomers can be used by mixing at any ratio.
  • the amount of the X-ray opaque filler of the present invention to be blended in the curable dental composition of the present invention is not particularly limited as long as the curable dental composition becomes paste-like. It is preferably in the range of 1 to 80 parts by mass, more preferably in the range of 3 to 70 parts by mass, based on 100 parts by mass of the curable dental composition. Furthermore, from the viewpoint of imparting X-ray opacity to the cured body and various physical properties (e.g., mechanical strength and hardness), the amount of the X-ray opaque filler blended with respect to 100 parts by mass of the dental curable composition is It is more preferably 10 to 40 parts by mass. From the viewpoint of imparting X-ray opacity to the cured product, it is also preferable to blend 1 to 400 parts by mass of an X-ray opaque filler with respect to 100 parts by mass of the polymerizable monomer.
  • polymerization initiator chemical polymerization initiators, photopolymerization initiators, thermal polymerization initiators, etc., which are used as polymerization initiators capable of polymerizing polymerizable monomers, can be used without particular limitation. .
  • the amount of the polymerization initiator to be blended is not particularly limited as long as it is an amount capable of initiating polymerization, but it is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. From the viewpoint of the polymerization rate and various physical properties (eg, weather resistance and hardness) of the resulting cured product, it is preferable to blend 0.05 to 5 parts by mass based on the above criteria.
  • the type of polymerization initiator may be selected depending on the use of the dental curable composition.
  • the dental hardenable composition is a dental filling and restorative material that hardens in the oral cavity
  • a thermal polymerization initiator when a bulk body obtained by pre-curing a dental curable composition is cut in a dental clinic, a laboratory, or the like to be used as a mill blank, it is preferable to use a thermal polymerization initiator.
  • photopolymerization initiators examples include benzoin alkyl ethers, benzyl ketals, benzophenones, ⁇ -diketones, thioxanthone compounds, and bisacylphosphine oxides.
  • a reducing agent is often added to the photopolymerization initiator.
  • reducing agents include aromatic amines, aliphatic amines, aldehydes, and sulfur-containing compounds.
  • trihalomethyltriazine compounds, aryliodonium salts and the like can be added as necessary.
  • the dental curable composition of the present invention may contain other components known as components of dental curable compositions, particularly dental filling and restorative materials.
  • Such components include fillers other than the X-ray opaque filler of the present invention, polymerization inhibitors, ultraviolet absorbers, dyes, antistatic agents, pigments, fragrances, organic solvents, and thickeners. known additives.
  • organic fillers examples include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, Particles made of organic polymers such as acrylonitrile-styrene copolymers and acrylonitrile-butadiene-styrene copolymers can be mentioned.
  • inorganic fillers include inorganic particles such as quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass, and metal oxides.
  • the particle size and shape of these other fillers are not particularly limited, and spherical or amorphous particles having an average particle size of 0.001 ⁇ m to 100 ⁇ m, which are generally used as dental materials, are used depending on the purpose. It can be used appropriately.
  • the refractive index of these other fillers is not particularly limited, and those in the range of 1.4 to 2.6 that general dental curable composition fillers have can be used without limitation.
  • the amount of other fillers added to the curable composition for dental use is also not particularly limited as long as the curable composition for dental use becomes a paste. However, when the dental curable composition is used as a dental filling and restorative material, the total amount of the X-ray opaque filler and other fillers is It is preferably 25 to 400 parts by mass, more preferably 40 to 250 parts by mass.
  • the curable composition blended with the X-ray opaque filler of the present invention is not limited to the above-described dental uses, and can be used for adhesives, paints, optical materials, etc. In particular, it can be used as a dental filling and restorative material. It is preferred to use as
  • the method for producing the dental curable composition of the present invention is not particularly limited, and any known method for producing a curable composition may be employed as appropriate. Specifically, (i) in the dark in the case of a photopolymerizable dental curable composition, or (ii) in the case of a thermally polymerizable dental curable composition, at room temperature or at a low temperature. , Weighing a predetermined amount of the X-ray opaque filler, the polymerizable monomer, the polymerization initiator, and other optional ingredients that constitute the dental curable composition of the present invention, A paste-like curable dental composition may be prepared by mixing these. The curable dental composition of the present invention thus produced is stored in the dark, at room temperature, or at a low temperature until use.
  • the above photopolymerized or thermally polymerized dental curable composition is added in a state in which two or more components that generate active species when mixed are physically separated. It is manufactured and stored in the same manner as the composition.
  • known polymerization means may be employed as appropriate according to the polymerization initiation mechanism of the polymerization initiator used.
  • a curing means light irradiation from a light source such as carbon arc, xenon lamp, metal halide lamp, tungsten lamp, fluorescent lamp, sunlight, helium cadmium laser, argon laser, etc., or using a heat polymerization device, etc. Heating, a method combining these methods, or the like can be used without any limitation.
  • the irradiation time varies depending on the wavelength/intensity of the light source, the shape and material of the cured product, and may be determined in advance by preliminary experiments. Generally, however, it is preferable to adjust the mixing ratio of the various components contained in the dental curable composition so that the irradiation time is in the range of about 5 to 60 seconds.
  • the average primary particle size of the crystalline rare earth metal fluoride particles constituting the X-ray opaque filler was determined by the following procedure using a scanning electron microscope. First, after fixing an X-ray opaque filler on a sample table with carbon paste, a measurement sample was prepared by subjecting it to a conductive treatment (platinum vapor deposition). Next, this measurement sample was observed with an electron microscope (JSM-7800F PRIME, manufactured by JEOL Ltd.) at a magnification of 100,000 times, and the average particle of 100 primary particles in the observed image obtained The diameter was obtained as an average primary particle diameter. Also, the average primary particle size of the raw material powder was obtained by the same procedure.
  • the average secondary particle size of the crystalline rare earth metal fluoride particles constituting the X-ray opaque filler was determined by the following procedure by particle size distribution measurement. First, a suspension was prepared by suspending 0.1 g of powder (X-ray opaque filler) in 10 mL of deionized water. Next, while the suspension was irradiated with ultrasonic waves, the particle size distribution was measured using a particle size distribution meter (LS13-320, manufactured by BECKMAN COULTER) to obtain the volume particle size distribution. The average secondary particle size of the crystalline rare earth metal fluoride particles constituting the X-ray opaque filler was defined as the cumulative 50% particle size (D50v value) from the small size side of the volume particle size distribution. Also, the average secondary particle size of the raw material powder was obtained by the same procedure.
  • refractive index 2-3-1 Refractive index n 0 of the polymerizable monomer
  • refractive index n 0 of the polymerizable monomer used in the preparation of the curable composition was measured at 25 ° C. using an Abbe refractometer (DR-A1-Plus, manufactured by Atago Co., Ltd.). measured as a percentage.
  • Refractive index nM of polymer (cured polymerizable monomer) Polymerizable monomers used in the preparation of the curable composition (provided that trace amounts of polymerization initiators (0.2% by weight of camphorquinone and 0.35% by weight of N,N-dimethyl-p -ethyl benzoate) was filled into the through-hole (diameter 7 mm, through-hole length 0.5 mm) provided in the mold, and then the openings on both sides of the through-hole were sealed while being pressed with a polypropylene film. .
  • the polymerizable monomer filled in the through-holes is cured by light irradiation for 30 seconds using a halogen-type dental light irradiation device (Demetron LC, manufactured by Sypron Co., Ltd.) with a light intensity of 500 mW/cm 2 . let me Thereafter, the refractive index nM of the cured polymerizable monomer removed from the mold was measured in the same manner as in 2-3-1.
  • a halogen-type dental light irradiation device (Demetron LC, manufactured by Sypron Co., Ltd.) with a light intensity of 500 mW/cm 2 .
  • Refractive index n X of crystalline rare earth fluoride particles In a constant temperature room at 25° C., 1 g of crystalline rare earth fluoride particles was suspended in 50 mL of anhydrous toluene in a 100 mL sample bottle. While stirring this suspension with a stirrer, 1-bromotoluene was added dropwise little by little, and the refractive index of the suspension when it became most transparent was measured in the same manner as in 2-3-1. , the obtained value was defined as the refractive index nX of the crystalline rare earth fluoride particles. As described above, the refractive index nX of the crystalline rare earth fluoride particles after the mechanochemical treatment was substituted by the refractive index of the crystalline rare earth fluoride particles before the mechanochemical treatment.
  • the Y value was measured for each sample under a black background and a white background with a color difference meter (SE7700, manufactured by Nippon Denshoku Co., Ltd.), and the transparency was calculated according to the following formula (contrast ratio: Yb / Yw ) was calculated.
  • Yb/Yw Y value (Yb) under black background/Y value (Yw) under white background.
  • X-ray opaque filler As the X-ray opaque filler, crystalline rare earth metal fluoride particles (YbF 3 -40, YbF 3 -100, YbF 3 -100, YbF 3 -100, YbF 3 -200, YbF 3 -300, LaF 3 , CeF 3 and GdF 3 ), and powder obtained by subjecting these raw powders to mechanochemical treatment were used.
  • Table 1 shows the abbreviations of the X-ray opaque fillers of Examples and Comparative Examples, and the crystalline rare earth metal fluoride particles (raw material powder itself, or raw material powder Mechanochemically treated powder), raw material powder mechanochemical treatment time, average primary particle size (for mechanochemically treated raw material powder, value after mechanochemical treatment), maximum peak 2 ⁇ and maximum peak FWHM and refractive index nX are shown.
  • the mechanochemical treatment was performed using a wet bead mill SC50 ⁇ manufactured by Mitsui Mining Co., Ltd. ⁇ .
  • a slurry obtained by mixing 5.0 parts by mass of crystalline rare earth metal fluoride particles with 100 parts by mass of ion-exchanged water was dispersed using 100 g of ⁇ 0.3 mm zirconia beads as media at a rotation speed of 3000 rpm.
  • Table 1 shows the type of crystalline rare earth metal fluoride particles used in the dispersion treatment and the treatment time.
  • a measurement sample obtained by removing coarse particles with a sieve having an opening of 100 ⁇ m from the raw material powder or the powder after the mechanochemical treatment was used.
  • Example 1 Add 0.2 parts by weight of CQ and 0.35 parts by weight of DMBE as a polymerization initiator to 100 parts by weight of a polymerizable monomer consisting of 80 parts by weight of UDMA and 20 parts by weight of 3G, and stir for 6 hours.
  • a liquid composition was prepared.
  • F1 as an X-ray opaque filler was added to 100 parts by mass of the polymerizable monomer so as to be 150 parts by mass (60 wt%), and then mixed with an agate mortar.
  • a pasty curable composition was obtained by defoaming the resulting mixture under vacuum to remove air bubbles. The transparency (contrast ratio) of the obtained cured product of the curable composition was evaluated. Table 2 shows the results.
  • Examples 2-15, Comparative Examples 1-6 Examples 2 to 15 and Comparative Examples were prepared in the same manner as in Example 1, except that the materials shown in Table 2 were used as the polymerizable monomer, polymerization initiator, and X-ray opaque filler to be blended in Example 1. 1-6 curable compositions were prepared. Then, the transparency (contrast ratio) of the cured body of the obtained curable composition was evaluated. The results are also shown in Table 2.
  • Examples 16-22, Comparative Examples 7-13 In Example 2, curable compositions of Examples 16 to 22 were prepared in the same manner as in Example 2, except that the composition of the polymerizable monomers to be blended was changed as shown in Table 3. Curable compositions of Comparative Examples 7 to 13 were prepared in the same manner as in Comparative Example 1 except that the composition of the polymerizable monomers to be blended in Example 1 was changed as shown in Table 3. Then, the obtained paste-like curable composition and its cured product were evaluated for transparency. The results are also shown in Table 3.
  • the polymerizable monomer composition and the The refractive index of the cured body is different.
  • the examples and comparative examples having the same polymerizable monomer composition are compared, the X-ray opaque filler having a maximum peak half width of 0.3° or more: the example using F1-3h In 16 to 22, the contrast ratios of the curable composition and the cured body are lower than in Comparative Examples 7 to 13 using the radiopaque filler: RF1, which has a maximum peak half width of less than 0.3°. It was confirmed that the transparency is high.
  • the amount of the X-ray opaque filler of the present invention exhibiting X-ray opacity about the same as that of an aluminum material having the same thickness as the cured body is 100 parts by mass of the curable composition. It was about 3 to 10 parts by mass.
  • the curable composition of each example described above can be suitably used as a dental curable composition.
  • various graphs created based on the experimental data shown in Tables 1 to 6 are shown in FIGS. 1 to 8.
  • FIG. 1 to 8 various graphs created based on the experimental data shown in Tables 1 to 6 are shown in FIGS. 1 to 8.

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PCT/JP2022/031237 2021-09-14 2022-08-18 Ｘ線不透過性充填材、歯科用ｘ線不透過性充填材、ｘ線不透過性充填材の製造方法、及び、歯科用硬化性組成物 Ceased WO2023042598A1 (ja)

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CA3227331A CA3227331A1 (en) 2021-09-14 2022-08-18 X-ray opaque filler, dental x-ray opaque filler, method of producing the x-ray opaque filler, and dental curable composition
AU2022345585A AU2022345585A1 (en) 2021-09-14 2022-08-18 X-ray opaque filler material, x-ray opaque dental filler material, method for producing x-ray opaque filler material, and curable dental composition
CN202280047439.2A CN117642143A (zh) 2021-09-14 2022-08-18 X射线非穿透性填料、牙科用x射线非穿透性填料、x射线非穿透性填料的制造方法及牙科用硬化性组合物
US18/580,274 US20250082549A1 (en) 2021-09-14 2022-08-18 X-ray opaque filler material, x-ray opaque dental filler material, method for producing x-ray opaque filler material, and curable dental composition
EP22869745.4A EP4403161A4 (en) 2021-09-14 2022-08-18 RADIOPAQUE FILLING MATERIAL, RADIOPAQUE DENTAL FILLING MATERIAL, METHOD FOR PRODUCING RADIOPAQUE FILLING MATERIAL, AND POLYMERIZABLE DENTAL COMPOSITION
KR1020247000381A KR20240060585A (ko) 2021-09-14 2022-08-18 X선 불투과성 충전재, 치과용 x선 불투과성 충전재, x선 불투과성 충전재의 제조 방법, 및 치과용 경화성 조성물

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WO2024180894A1 (ja) * 2023-02-28 2024-09-06 株式会社トクヤマデンタル 歯科用硬化性組成物
WO2025022795A1 (ja) 2023-07-26 2025-01-30 株式会社トクヤマデンタル Ｘ線不透過性充填材の製造方法及び歯科用硬化性組成物の製造方法

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JP2023118513A (ja) * 2022-02-15 2023-08-25 株式会社トクヤマデンタル Ｘ線不透過性充填材、ｘ線不透過性充填材の製造方法、硬化性組成物および歯科用硬化性組成物
JP7795774B2 (ja) 2022-02-15 2026-01-08 株式会社トクヤマデンタル Ｘ線不透過性充填材、ｘ線不透過性充填材の製造方法、硬化性組成物および歯科用硬化性組成物
WO2024180894A1 (ja) * 2023-02-28 2024-09-06 株式会社トクヤマデンタル 歯科用硬化性組成物
WO2025022795A1 (ja) 2023-07-26 2025-01-30 株式会社トクヤマデンタル Ｘ線不透過性充填材の製造方法及び歯科用硬化性組成物の製造方法

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