Classifications

• • 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
  • A61K6/77—Glass
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C12/00—Powdered glass; Bead compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
  • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
  • C03C4/087—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for X-rays absorbing glass

Definitions

• the present invention relates to X-ray opaque glass, glass filler and resin composition suitable as dental materials.
• dental resin compositions which are mixtures of resins and inorganic fillers, have been used for applications such as dental restorative materials, dental bases, crowns, and temporary teeth.
• UV curable resins are usually used for dental resin compositions.
• treatment is carried out by applying a dental resin composition to the treatment site of the tooth and then curing it by irradiating it with UV light.
• a glass filler with high light transmittance as an inorganic filler (see, for example, Patent Document 1).
• the above glass filler is required to be X-ray opaque so that the treated area of the tooth can be confirmed when an X-ray is taken.
• the glass filler In order to increase the X-ray opacity of the glass filler, it is effective to include an element with a large atomic weight such as Ba or La in the glass composition. However, the inclusion of these elements in the glass composition tends to increase the refractive index of the glass filler. As a result, the difference in refractive index from the resin matrix increases, the light transmittance of the resin composition decreases, and there is a risk that the aesthetics of the tooth after treatment will be impaired.
• an object of the present invention is to provide a glass capable of achieving desired light transmittance and X-ray opacity when mixed with a resin.
• the X-ray opaque glass of the present invention contains, in mass %, SiO 2 25 to 75%, B 2 O 3 0 to 15%, Al 2 O 3 5 to 23%, K 2 O 0 to 15%, It contains 0 to 30% Cs 2 O and substantially does not contain a Pb component, and the aluminum equivalent thickness, which is an index of X-ray opacity, and the refractive index nd are such that the aluminum equivalent thickness/refractive index nd ⁇ 1 It is characterized by satisfying the relationship of .6.
• the X-ray opaque glass of the present invention contains, in weight percent, SiO 2 25-75%, B 2 O 3 0-15%, Al 2 O 3 5-23%, K 2 O 0-15%, Cs 2 It contains 0 to 30% O, 10 to 40% Cs 2 O+BaO+SnO 2 +La 2 O 3 , and substantially does not contain a Pb component.
• the X-ray opaque glass of the present invention preferably has a refractive index nd of 1.48 to 1.58.
• the X-ray opaque glass of the present invention preferably has an X-ray opacity of 2.5 mm or more in aluminum equivalent thickness.
• the X-ray opaque glass of the present invention preferably contains substantially no F component.
• the X-ray opaque glass of the present invention preferably contains 10% or more of Cs 2 O+BaO+SnO 2 +La 2 O 3 in mass %.
• x+y+ means the total amount of each component.
• the X-ray opaque glasses of the invention are preferably substantially free of TiO2 .
• the X-ray opaque glass of the present invention preferably contains 0 to 6% by weight of WO 3 .
• the glass filler of the present invention is characterized by being made of the X-ray opaque glass described above.
• the glass filler of the present invention is preferably approximately spherical.
• the glass filler of the present invention preferably has an average particle size of 0.01 to 50 ⁇ m.
• the surface of the glass filler of the present invention is preferably silanized.
• the resin composition of the present invention is characterized by containing the above glass filler and curable resin.
• the resin composition of the present invention preferably contains 1 to 90% by weight of the glass filler.
• the resin composition of the present invention is preferably for dental use.
• the present invention it is possible to provide a glass capable of achieving desired light transmittance and X-ray opacity when mixed with a resin.
• SiO2 is a component that forms the glass skeleton. It is also a component that has the effect of improving chemical durability and suppressing devitrification.
• the content of SiO 2 is preferably 25-75%, 30-70%, 40-65%, especially 45-63%. If the amount of SiO 2 is too small, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult. On the other hand, if the amount of SiO2 is too large, the meltability tends to decrease.
• B 2 O 3 is a component that forms a glass skeleton. In addition, it is a component that has the effect of improving chemical durability and suppressing devitrification without substantially increasing the refractive index.
• the content of B 2 O 3 is preferably 0-15%, 0.5-10%, especially 1-8%. Too much B 2 O 3 tends to lower the meltability.
• B 2 O 3 is a component that is relatively easily volatilized in the flame polishing process for spheroidizing the glass filler, which will be described later. Therefore, if the amount of B 2 O 3 is too large, volatilization increases during the spheroidizing step, making it difficult to obtain a glass filler having a desired composition.
• Al 2 O 3 is a vitrification stabilizing component. In addition, it is a component that has the effect of improving chemical durability and suppressing devitrification without substantially increasing the refractive index.
• the content of Al 2 O 3 is 5-23%, 6-20%, 6.4-18%, 6.8-17%, 7-16%, 7.2-15%, 7.4-15% , 7.5-15%, more than 7.5-15%, 7.6-15%, 7.8-15%, especially 8-15%. If the amount of Al 2 O 3 is too small, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult. On the other hand, if Al 2 O 3 is too much, the meltability tends to be lowered.
• Al 2 O 3 /B 2 O 3 is preferably 0.6 or more, 0.8 or more, 1 or more, 1.2 or more, 1.5 or more, 1.8 or more, particularly 2 or more. In this way, when the glass filler is spheroidized by flame polishing, composition fluctuation due to volatilization of the glass component is less likely to occur. As a result, it becomes easier to obtain a substantially spherical glass filler having a desired composition.
• the upper limit of Al 2 O 3 /B 2 O 3 is not particularly limited, it is preferably 100 or less, 50 or less, 30 or less, particularly 10 or less from the viewpoint of easiness of vitrification.
• "x/y" means the value which divided
• K 2 O is a component that reduces the viscosity of glass and suppresses devitrification.
• the content of K 2 O is preferably 0-15%, 0.1-14%, 0.5-13%, especially 1-12%. If the K 2 O content is too high, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• Cs 2 O is a component highly effective in improving X-ray opacity. In addition, like other alkali metal oxides, it has the effect of reducing viscosity and suppressing devitrification.
• Cs 2 O is a component that does not easily increase the refractive index.
• the content of Cs 2 O is preferably 0-30%, 5-27%, especially 10-25%. If the content of Cs 2 O is too small, it becomes difficult to obtain the above effects. On the other hand, if the Cs 2 O content is too large, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• the X-ray opaque glass of the present invention can contain the following components in addition to the above components.
• BaO like Cs 2 O, is a component highly effective in improving X-ray opacity. It also has the effect of stabilizing vitrification as an intermediate substance.
• the content of BaO is preferably 0-20%, 0.1-10%, 0.3-6%, 0.5-4%, 1-3%, especially 1-2%. If the BaO content is too high, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult. Also, the refractive index tends to be unduly high.
• SnO 2 is also a component highly effective in improving X-ray opacity.
• SnO 2 is a component that hardly increases the refractive index.
• the SnO 2 content is preferably 0-20%, 0.1-10%, especially 0.5-6%. Too much SnO 2 tends to shift the absorption edge wavelength of the glass, resulting in undesirable yellowish coloration and reduced chemical durability. Moreover, the glass tends to devitrify, which may make the production difficult.
• La 2 O 3 is also a component highly effective in improving X-ray opacity.
• the content of La 2 O 3 is preferably 0-20%, 0.1-10%, especially 0.5-6%. If the amount of La 2 O 3 is too large, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult. Also, the refractive index tends to be unduly high.
• the content of Cs 2 O+BaO+SnO 2 +La 2 O 3 is preferably 10% or more, 15% or more, particularly 20% or more.
• the upper limit of Cs 2 O+BaO+SnO 2 +La 2 O 3 is preferably 40% or less, 30% or less, particularly 25% or less.
• the total amount of two or more components selected from Cs 2 O, BaO, SnO 2 and La 2 O 3 is also preferably within the above range.
• Cs 2 O/(Cs 2 O+BaO+SnO 2 +La 2 O 3 ) is preferably 0.2 or more, 0.3 or more, 0.4 or more, particularly 0.5 or more.
• WO 3 also has the effect of improving radiopacity.
• WO3 is a component that can adjust the refractive index , and also has the effect of lowering the viscosity of the glass.
• the content of WO 3 is preferably 0-6%, 0.1-5%, especially 1-4.5%. If the WO3 content is too high , the glass tends to devitrify.
• Nb 2 O 5 is a component that increases the refractive index.
• the content of Nb 2 O 5 is preferably 0-20%, 0.1-15%, 0.5-10%, especially 1-5%. Too much Nb 2 O 5 tends to devitrify the glass.
• ZrO 2 is a component that can improve weather resistance and adjust the refractive index.
• the content of ZrO 2 is preferably 0-10%, 0-7.5%, especially 0-5%. If the content of ZrO2 is too high , the softening point tends to rise. In addition, devitrification resistance tends to decrease.
• P 2 O 5 is a component that forms a glass network and improves the light transmittance and devitrification resistance of the glass. It is also a component that tends to lower the softening point of glass.
• the content of P 2 O 5 is preferably 0-20%, 0-15%, 0-10%, especially 0.1-5%. If the content of P 2 O 5 is too large, the chemical durability tends to be lowered, and the refractive index tends to be lowered. In addition, striae are likely to occur.
• Li 2 O is a component that reduces the viscosity of glass and suppresses devitrification.
• the content of Li 2 O is preferably 0-10%, 0.1-9%, 0.5-7%, especially 1-5%. If the amount of Li 2 O is too large, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• Na 2 O is a component that reduces the viscosity of glass and suppresses devitrification.
• the content of Na 2 O is preferably 0-20%, 0.1-18%, 0.5-15%, especially 1-10%. If there is too much Na 2 O, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• the content of R 2 O should be 5 to 50%, 10 to 45%, 15 to 40%, particularly 20 to 35%. is preferred. If the content of R 2 O is too small, it becomes difficult to obtain the above effects. On the other hand, if the content of R 2 O is too large, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• MgO, CaO and SrO are components that stabilize vitrification as intermediate substances. In addition, it is a component that easily lowers the viscosity of the glass without significantly lowering the chemical durability of the glass.
• the contents of MgO, CaO and SrO are preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, particularly 1 to 4%, respectively. . If the content of these components is too high, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• R'O is at least one selected from MgO, CaO, SrO and BaO
• the content of R'O is 0 to 20%, 0.1 to 10%, particularly 0.5 to 6%. is preferred. If the content of R'O is too high, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• ZnO like the R'O component, is a component that stabilizes vitrification as an intermediate substance. In addition, it is a component that easily lowers the viscosity of the glass without significantly lowering the chemical durability of the glass.
• the content of ZnO is preferably 0-20%, 0.1-15%, 0.5-10%, 1-9%, 1-5%, especially 1-4%. If the ZnO content is too high, the chemical durability tends to decrease, and the glass tends to devitrify, which may make production difficult.
• NiO, Cr 2 O 3 and CuO are components that color the glass and tend to lower the transmittance of light, particularly in the ultraviolet to visible regions. Therefore, the contents of these are preferably 1% or less, 0.75% or less, and 0.5% or less, respectively, and particularly preferably not substantially contained.
• substantially not contained means that the material is not actively contained as a raw material, and does not exclude the contamination of unavoidable impurities. Objectively, it means that the content is less than 0.1%.
• Sb 2 O 3 and CeO 2 are components that easily suppress a decrease in light transmittance. Moreover, when the content of these components is too large, devitrification tends to occur. Therefore, the contents of Sb 2 O 3 and CeO 2 are preferably 1% or less, 0.8% or less, 0.5% or less, and 0.2% or less, respectively, and particularly preferably not substantially contained. .
• TiO 2 is a component that excessively increases the refractive index or colors the glass to reduce the transmittance.
• TiO2 has a low X - ray opacity comparable to that of ZnO and ZrO2, adding it only increases the refractive index, making it difficult to achieve both a low refractive index and a high X-ray opacity.
• the glasses of the invention are preferably substantially free of TiO 2 .
• F is a component that can lower the melting temperature and adjust the refractive index.
• F is highly volatile, there is a risk that the volatilized components will adhere to the surface of the glass filler and deteriorate the surface properties when the substantially spherical glass filler is produced by, for example, flame polishing.
• F is contained, the chemical durability of the glass tends to decrease. Therefore, it is preferred that the glass of the present invention does not substantially contain F.
• the glass of the present invention does not substantially contain a Pb component (such as PbO) for environmental reasons. Also, it is preferred that arsenic components (As 2 O 3 etc.) are not substantially contained for environmental reasons as well.
• the X-ray opaque glass of the present invention is used, for example, as particulate glass filler (glass beads). If the glass filler is approximately spherical, it is preferable because, when mixed in the resin, the increase in viscosity of the resin composition can be easily suppressed. Therefore, a large amount of X-ray opaque glass filler can be contained in the resin composition, and as a result, X-ray contrastability can be effectively improved.
• the shape of the X-ray opaque glass of the present invention may be fiber-like or bulk-like, in addition to being particulate.
• the average particle size of the glass filler is 0.01 to 50 ⁇ m, 0.05 to 40 ⁇ m, 0.1 to 40 ⁇ m, 0.2 to 30 ⁇ m, 0.3 to 20 ⁇ m, 0.5 to 10 ⁇ m, particularly 0.8 to 6 ⁇ m. Preferably. By doing so, it becomes easier to improve the surface smoothness of the molded article made of the cured product of the resin composition. If the average particle size of the glass particles is too small, the fluidity of the resin composition is lowered, and air bubbles entrapped inside become difficult to escape to the outside. On the other hand, if the average particle size of the glass particles is too large, the curability of the resin composition tends to be lowered.
• the "average particle size” refers to the value measured by a laser diffraction device, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the cumulative amount is accumulated from the smaller particle. Represents the particle size that is 50%.
• the aluminum equivalent thickness which is an index of X-ray opacity
• the refractive index nd satisfy the relationship of aluminum equivalent thickness/refractive index nd ⁇ 1.6. This makes it possible to achieve the desired light transmittance and X-ray opacity when blended in a resin.
• the aluminum equivalent thickness/refractive index nd is preferably 1.8 or more, 2 or more, 2.2 or more, particularly 2.5 or more. Although the upper limit is not particularly limited, it is practically 7 or less, 6 or less, and further 5 or less.
• the refractive index (nd) of the X-ray opaque glass of the present invention is, for example, 1.48 to 1.58, preferably 1.49 to 1.54, particularly 1.50 to 1.52. is preferably In this way, it becomes easy to match the refractive index with many curable resins such as acrylic resins and epoxy resins, and a resin composition having excellent transparency and a molded product made of a cured product of the resin composition. easier to obtain.
• the refractive index of the X-ray opaque glass of the present invention can be measured using a precision refractometer using the V-block method in the case of bulk glass. In the case of particulate (or fibrous) glass, it can be measured by the following method.
• the refractive index of glass particles can be measured as follows.
• the light transmittance of the dispersion alone and the light transmittance of the dispersion in which the glass particles are dispersed are measured when the refractive index of the dispersion is changed. There is a correlation between the difference in light transmittance between the two and the refractive index of the dispersion. Specifically, plotting the refractive index of the dispersion on the x-axis and the light transmittance difference on the y-axis yields a quadratic function with a minimum value.
• the refractive index of the dispersion when the light transmittance difference is the minimum value can be regarded as the refractive index of the glass particles.
• the dispersion liquid is prepared, for example, by mixing two types of known liquids having refractive indices around the estimated refractive index of the glass particles. Since the refractive index of a liquid is additive, a dispersion having a specific refractive index can be produced by appropriately changing the mixing ratio of two types of liquids.
• the dispersion When measuring the light transmittance of a dispersion in which glass particles are dispersed, it is preferable to select a specific gravity of the dispersion that is as close as possible to the specific gravity of the glass particles in order to suppress sedimentation of the glass particles. Alternatively, it is preferable to increase the amount of glass particles added so that the dispersion has a paste-like viscosity.
• the glass of the present invention preferably has an aluminum equivalent thickness of 2.5 mm or more, 3 mm or more, 3.5 mm or more, particularly 4 mm or more, which is an index of X-ray opacity.
• the upper limit of the aluminum equivalent thickness is not particularly limited, it is practically 10 mm or less.
• the surface of the glass filler is preferably silanized with a silane coupling agent or the like.
• the silanization treatment can increase the bonding strength between the glass filler and the curable resin, making it possible to obtain a molded article with more excellent mechanical strength. Furthermore, the compatibility between the glass filler and the curable resin is improved, the generation of interfacial bubbles can be suppressed, and as a result, excessive light scattering can be suppressed.
• silane coupling agents include aminosilane, epoxysilane, and acrylsilane.
• the X-ray opaque glass of the present invention can be produced by melting and molding raw materials and then subjecting them to processes such as pulverization and classification as necessary.
• the melting temperature is not particularly limited, and any temperature can be used as long as the raw material can be melted homogeneously. For example, it is preferably 1400 to 1700°C, more preferably 1500 to 1650°C.
• the molten glass is flowed between a pair of cooling rollers to form a film, and then the obtained film-shaped molded product is subjected to a predetermined Pulverize to size and classify if necessary. Further, by flame-polishing the obtained glass particles with an air burner or the like, the glass particles can be softened and flowed to be formed into a substantially spherical shape.
• the resin composition of the present invention contains a curable resin and the above glass filler. Specific examples of the curable resin are described below.
• an ultraviolet curable resin As the ultraviolet curable resin, it is preferable to use a resin that polymerizes with a radical species or a cationic species.
• a resin that polymerizes with a radical species or a cationic species For example, an acrylic resin, an epoxy resin, or the like can be used. Examples of acrylic resins include ester acrylate resins and urethane acrylate resins.
• the acrylic resin may contain the following compounds.
• monofunctional compounds include isobornyl acrylate, isobornyl methacrylate, zinclopentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol acrylate, vinylpyrrolidone, acrylamide, vinyl acetate, styrene, and the like.
• polyfunctional compounds include trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6- hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, diallyl phthalate and the like. These monofunctional compounds and polyfunctional compounds can be used singly or in combination of two or more. In addition, these compounds are not limited to the above content.
• a photopolymerization initiator can be used as a polymerization initiator for acrylic resins.
• examples include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, bezaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler's ketone, and the like. be done.
• These polymerization initiators can be used singly or in combination of two or more. Further, these polymerization initiators are preferably contained in an amount of 0.1 to 10% by mass with respect to the monofunctional compound and the polyfunctional compound, respectively.
• a sensitizer such as an amine compound may be used in combination as necessary.
• the epoxy resin may contain the following compounds.
• hydrogenated bisphenol A diglycidyl ether 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane -m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate and the like.
• an energy active cationic initiator such as triphenylsulfonium hexafluoroantimonate can be used.
• leveling agents may be added to the curable resin as necessary.
• the content of the glass filler in the resin composition is preferably 1 to 90%, 5 to 80%, 10 to 70%, particularly 15 to 65% by weight. If the content of the glass filler is too low, the mechanical strength of the molded article made of the cured resin composition tends to be lowered. On the other hand, if the content of the glass filler is too high, light scattering increases, making it difficult to obtain a molded article with excellent transparency. In addition, the curability of the resin composition tends to decrease. Furthermore, the viscosity of the curable resin tends to be too high, making handling difficult.
• the difference in refractive index nd between the glass filler and the curable resin before curing is within ⁇ 0.1, within ⁇ 0.09, within ⁇ 0.08, within ⁇ 0.07, and particularly within ⁇ 0.05. is preferred. By doing so, it is possible to suppress scattering of light due to the difference in refractive index between the curable resin and the glass filler in the step of curing the resin composition.
• the difference in refractive index nd between the glass filler and the curable resin after curing is within ⁇ 0.1, within ⁇ 0.08, within ⁇ 0.05, within ⁇ 0.03, and particularly within ⁇ 0.02. Preferably. By doing so, it is possible to suppress the scattering of light due to the difference in refractive index between the cured resin and the glass filler, making it easier to obtain a molded article with excellent transparency.
• a molded article can be obtained by curing the resin composition of the present invention by irradiating it with light.
• ultraviolet light may be applied as the light beam.
• the resin composition is used as a dental restorative material (so-called dental composite resin)
• the resin composition is applied to the treatment site of the tooth, and then irradiated with light to cure the treatment. It can be carried out.
• Tables 1 to 6 show examples (No. 1 to 22) and comparative examples (No. 23 to 31) of the present invention.
• the raw material powders were prepared and uniformly mixed so that the composition shown in the table was obtained.
• the obtained raw material batch was melted at 1450 to 1650° C. until it became homogeneous, and then molded to obtain a glass.
• the obtained glass was evaluated for refractive index nd, density, aluminum equivalent thickness (X-ray contrastability), and chemical durability as follows.
• the refractive index was measured using a precision refractometer (Kalnew PR-2000).
• the density was measured by the Archimedes method.
• the aluminum equivalent thickness was measured using a digital X-ray device according to a method based on JIS T6514:2015 for a sample processed to a thickness of 1.0 mm. Specifically, the grayscale values obtained by the digital X-ray device were processed by image analysis software to determine the X-ray absorption aluminum equivalent thickness.
• the chemical durability was evaluated by the HAST test. Specifically, using a HAST tester PC-242HSR2 manufactured by Hirayama Seisakusho, after holding for 24 hours under the conditions of 21 ° C., 95% humidity, and 2 atm, the sample surface was visually observed, and a change in appearance was observed. A case where no change was observed was evaluated as " ⁇ ”, and a case where a change in appearance was observed was evaluated as "X”.
• Glasses of 1-22 had the desired properties of aluminum equivalent thickness/refractive index nd of 1.64-3.68.
• the refractive index nd has a desired refractive index of 1.501 to 1.531, and the aluminum equivalent thickness is 2.5 to 5.6 mm, which is excellent in X-ray opacity. rice field. Moreover, it was excellent also in chemical durability.
• radiopaque glass, glass filler, and resin composition of the present invention are suitable for dental composite resins, cores, bonds, dental crown fillers, glass ionomer cements, and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Epidemiology (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Inorganic Chemistry (AREA)
• Glass Compositions (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85086797

Family Applications (1)

Country Status (3)

Citations (4)

Family Cites Families (1)

• 2022
  • 2022-07-06 JP JP2023538381A patent/JPWO2023008122A1/ja active Pending
  • 2022-07-06 WO PCT/JP2022/026820 patent/WO2023008122A1/ja not_active Ceased
  • 2022-07-06 EP EP22849187.4A patent/EP4378904A4/en active Pending

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events