WO2021132217A1 - Resin composition, resin composition for three-dimensional models, and dental resin composition - Google Patents

Resin composition, resin composition for three-dimensional models, and dental resin composition Download PDF

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Publication number
WO2021132217A1
WO2021132217A1 PCT/JP2020/047873 JP2020047873W WO2021132217A1 WO 2021132217 A1 WO2021132217 A1 WO 2021132217A1 JP 2020047873 W JP2020047873 W JP 2020047873W WO 2021132217 A1 WO2021132217 A1 WO 2021132217A1
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Prior art keywords
resin composition
inorganic particles
composition according
cured product
resin
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PCT/JP2020/047873
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French (fr)
Japanese (ja)
Inventor
俣野　高宏
俊輔 藤田
民雄 安東
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日本電気硝子株式会社
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Priority to JP2021567478A priority Critical patent/JPWO2021132217A1/ja
Publication of WO2021132217A1 publication Critical patent/WO2021132217A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • 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
    • C03C3/083—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
    • C03C3/087—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 containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a resin composition, a resin composition for a three-dimensional model, and a dental resin composition.
  • a method of laminating a curable resin or the like to obtain a three-dimensional model made of a cured product of the curable resin has been known.
  • methods such as a stereolithography method, a powder sintering method, and a fused deposition modeling (FDM) method have been proposed and put into practical use.
  • FDM fused deposition modeling
  • a three-dimensional model is manufactured as follows. First, a modeling stage is provided in a tank filled with an uncured curable resin, and the modeling surface of the modeling stage is irradiated with light rays (for example, ultraviolet rays) to cure the curable resin. As a result, a cured product layer having a desired pattern is formed on the molding surface. Next, the uncured curable resin is introduced again onto the cured product layer by moving the modeling stage by one layer. Next, the molding surface is irradiated with light rays again to form a new cured product layer on the cured product layer. By repeating this operation, a desired three-dimensional model is obtained.
  • light rays for example, ultraviolet rays
  • Patent Document 1 proposes to use a resin composition in which inorganic particles are added to a curable resin.
  • the resin composition of the present invention is a resin composition containing a curable resin and inorganic particles, and the difference in refractive index nd between the inorganic particles and the cured curable resin is within ⁇ 0.1, and the inorganic particles.
  • the light transmittance at a wavelength of 405 nm is 10% or more.
  • the resin composition of the present invention preferably has a light transmittance of 50% or more at a wavelength of 405 nm of the inorganic particles.
  • the resin composition of the present invention preferably has a light transmittance of 5% or more at a wavelength of 365 nm of the inorganic particles.
  • the inorganic particles are glass.
  • the resin composition of the present invention the glass, in mass%, SiO 2 30 ⁇ 75% , Al 2 O 3 1 ⁇ 20%, B 2 O 3 0 ⁇ 30%, Li 2 O + Na 2 O + K 2 O 0 ⁇ 20 %, MgO + CaO + SrO + BaO + ZnO 0.1 to 20% is preferable.
  • the glass contains 40% or more of SiO 2 + Al 2 O 3 + B 2 O 3 in mass%.
  • the resin composition of the present invention preferably has an average particle size of inorganic particles of 0.2 to 50 ⁇ m.
  • the resin composition of the present invention preferably contains 1 to 90% of inorganic particles in a volume%.
  • the resin composition of the present invention preferably has a Young's modulus of inorganic particles of 50 GPa or more.
  • the coefficient of thermal expansion of the inorganic particles is preferably 60 ⁇ 10 -7 / ° C. or less at 30 to 100 ° C.
  • the resin composition of the present invention preferably has a light reflectance of 10% or less at a wavelength of 250 to 440 nm of the inorganic particles.
  • the resin composition of the present invention preferably has a buffer layer on the surface of the inorganic particles.
  • the refractive index nd of the buffer layer is lower than the refractive index nd of the inorganic particles.
  • the resin composition for a three-dimensional model of the present invention is characterized by using the above resin composition.
  • the dental resin composition of the present invention is characterized by using the above resin composition.
  • a cured product layer made of an uncured resin composition is selectively irradiated with light rays to form a cured product layer having a predetermined pattern, and a new cured product layer is formed on the cured product layer.
  • a light beam is irradiated to form a new cured product layer having a predetermined pattern continuous with the cured product layer, and the lamination of the cured product layer is repeated until a predetermined three-dimensional model is obtained. It is a method for producing a three-dimensional model, and is characterized in that the above-mentioned resin composition is used as the resin composition.
  • the present invention it is possible to provide a resin composition having excellent transparency and excellent curability, a resin composition for a three-dimensional model, and a dental resin composition.
  • FIG. 1 shows Example No. It is a graph which shows the light transmittance of the cured product of 7-9.
  • the resin composition of the present invention contains a curable resin and inorganic particles, the difference between the refractive index nd of the inorganic particles and the cured resin after curing is within ⁇ 0.1, and the light transmittance of the inorganic particles at a wavelength of 405 nm. Is 10% or more.
  • the light transmittance in the present invention means the value of the total light transmittance measured at a thickness of 1 mm.
  • the ultraviolet ray in the present invention means light having a wavelength of 250 to 440 nm.
  • the curable resin for example, it is preferable to use an ultraviolet curable resin.
  • an ultraviolet curable resin it is preferable to use a resin that polymerizes with a radical species or a cationic species, and for example, an acrylic resin, an epoxy resin, or the like can be used.
  • the acrylic resin include ester acrylate resins and urethane acrylate resins.
  • the acrylic resin may contain the following compounds.
  • examples of the monofunctional compound include isobornyl acrylate, isobornyl methacrylate, dincropentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol acrylate, and vinylpyrrolidone.
  • examples thereof include acrylamide, vinyl acetate and styrene.
  • the polyfunctional compound include trimethyl propanetriacrylate, EO-modified trimethylpropantriacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-.
  • Examples thereof include hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, and diallyl phthalate. These monofunctional compounds and polyfunctional compounds can be used alone or in combination of two or more. It should be noted that these compounds are not limited to the above contents.
  • a photopolymerization initiator can be used as the polymerization initiator.
  • These polymerization initiators can be used alone or in combination of two or more. Further, these polymerization initiators are preferably contained in an amount of 0.1 to 10% by mass, respectively, with respect to the monofunctional compound and the polyfunctional compound. If necessary, a sensitizer such as an amine compound may be used in combination.
  • the epoxy resin may contain the following compounds.
  • -M-Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate and the like can be mentioned.
  • an energy-active cation initiator such as triphenylsulfonium hexafluoroantimonate can be used.
  • a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, an antistatic agent and the like may be added to the curable resin as needed.
  • the refractive index nd (nd re ) of the curable resin after curing is, for example, preferably 1.40 or more, 1.45 or more, and particularly preferably 1.5 or more. Further, the abbreviation number ⁇ d ( ⁇ d re ) of the curable resin after curing is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60.
  • the refractive index nd (nd rs ) of the curable resin before curing is preferably 1.35 or more, 1.4 or more, and particularly preferably 1.45 or more.
  • the Abbe number ⁇ d ( ⁇ d rs ) of the uncured curable resin is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60.
  • the curing shrinkage rate of the curable resin is preferably 10% or less, 9% or less, 8% or less, and particularly preferably 6% or less. By doing so, it becomes easy to reduce the dimensional variation of the cured resin composition (that is, the cured product).
  • the lower limit is not particularly limited, but is, for example, 0.5% or more.
  • the curing shrinkage rate can be calculated based on the following formula by measuring the specific gravity A1 of the uncured curable resin and the specific gravity A2 of the cured resin after curing.
  • Curing shrinkage rate (%) 100 x (A2-A1) / A2
  • the difference between the refractive index nd (nd g ) of the inorganic particles and the refractive index nd (nd re ) of the curable resin after curing is within ⁇ 0.1, within ⁇ 0.08, and within ⁇ 0.05. , Within ⁇ 0.03, particularly preferably within ⁇ 0.02. By doing so, it is possible to suppress light scattering due to the difference in refractive index between the curable resin and the inorganic particles, and it becomes easy to obtain a cured product having excellent transparency.
  • the difference between the refractive index nd (nd g ) of the inorganic particles and the refractive index nd (nd rs ) of the uncured curable resin is within ⁇ 0.1, within ⁇ 0.09, within ⁇ 0.08, ⁇ It is preferably within 0.07, particularly within ⁇ 0.05.
  • the difference between the Abbe number ⁇ d ( ⁇ d rs ) of the uncured curable resin and the Abbe number ⁇ d ( ⁇ d g ) of the inorganic particles is within ⁇ 10 (but not including 10), within ⁇ 9, especially within ⁇ 8. Is preferable.
  • the refractive index nd of the inorganic particles is preferably, for example, 1.40 to 1.90, 1.40 to 1.65, and particularly preferably 1.45 to 1.6.
  • the Abbe number ⁇ d is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60. In this way, it becomes easy to match the optical constants with many curable resins such as acrylic resins and epoxy resins. In addition, it suppresses light scattering caused by the difference in refractive index between the curable resin and the inorganic particles, making it easier to obtain a cured product having excellent transparency.
  • the light transmittance of the inorganic particles at a wavelength of 405 nm is 10% or more, preferably 20% or more, 30% or more, 50% or more, and particularly 70% or more. Further, the light transmittance of the inorganic particles at a wavelength of 365 nm is preferably 5% or more, 10% or more, 20% or more, 30% or more, and particularly preferably 50% or more. By doing so, it becomes easy to sufficiently irradiate the uncured resin composition with light rays in the depth direction, so that the curability of the resin composition can be improved. Further, this makes it easier to increase the thickness of the cured product layer that is cured by a single light irradiation, so that it becomes easier to improve the manufacturing efficiency of the three-dimensional modeled object.
  • the light transmittance of the inorganic particles at a wavelength of 600 nm is preferably 60% or more, 70% or more, and particularly preferably 80% or more. In this way, it becomes easy to obtain a cured product having excellent transparency.
  • the inorganic particles are preferably glass.
  • glass By using glass, it becomes easy to strictly control the difference in refractive index between the inorganic particles and the curable resin.
  • Specific glass compositions for example, in mass%, SiO 2 30 ⁇ 75% , Al 2 O 3 1 ⁇ 20%, B 2 O 3 0 ⁇ 30%, Li 2 O + Na 2 O + K 2 O 0 ⁇ 20%, It is preferable to contain MgO + CaO + SrO + BaO + ZnO 0.1 to 20%.
  • the glass containing this composition is excellent in weather resistance and light transmittance in the ultraviolet to visible region. Therefore, it is easy to improve the curability of the resin composition when irradiated with ultraviolet rays. Further, since the light transmittance in the visible region is also excellent, it becomes easy to obtain a cured product having excellent transparency.
  • SiO 2 is a component that forms a glass network and remarkably enhances the light transmittance in the ultraviolet to visible region. It is also a component that improves weather resistance.
  • the content of SiO 2 is preferably 30 to 75%, 35 to 73%, 40 to 70%, 50 to 70%, 51 to 65%, and particularly preferably 51 to 62%. If the content of SiO 2 is too small, it becomes difficult to obtain the above effect. On the other hand, if the content of SiO 2 is too large, the viscosity of the glass increases and the meltability tends to decrease.
  • Al 2 O 3 is a component that forms a glass network and enhances the light transmittance in the ultraviolet to visible region. Especially in glass having a high refractive index, it has an effect of easily increasing the light transmittance.
  • the content of Al 2 O 3 is preferably 1 to 20%, 2 to 20%, 3 to 20%, 5 to 20%, 10 to 20%, 11 to 18%, and particularly preferably more than 15% to 17%. .. If the content of Al 2 O 3 is too small, it becomes difficult to obtain the above effect. On the other hand, if the content of Al 2 O 3 is too large, the viscosity of the glass increases and the meltability tends to decrease.
  • B 2 O 3 is a component that forms a glass network and enhances the light transmittance in the ultraviolet to visible region.
  • the content of B 2 O 3 is preferably 0 to 30%, 1 to 27.5%, 2 to 25%, 3 to 25%, 5 to 25%, 10 to 25%, and particularly preferably 11 to 20%. .. If the content of B 2 O 3 is too large, the meltability tends to decrease.
  • the content of SiO 2 + Al 2 O 3 + B 2 O 3 is preferably 40% or more, 50% or more, 55% or more, and particularly preferably 60% or more. In this way, it becomes easy to improve the weather resistance while increasing the light transmittance in the ultraviolet region to the visible region.
  • the upper limit is not particularly limited, but if it is too large, the meltability tends to decrease. Therefore, for example, it may be 99% or less, particularly 98% or less.
  • Li 2 O, Na 2 O and K 2 O are components that lower the softening point.
  • the content of Li 2 O + Na 2 O + K 2 O is 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, especially 0.1 to 4%. Is preferable. If the content of Li 2 O + Na 2 O + K 2 O is too large, the weather resistance and the refractive index tend to decrease. Further, in the stage of producing the inorganic particles, the components are likely to evaporate from the surface of the particles, and the refractive index of the inorganic particles is likely to vary. Further, the resin composition is liable to deteriorate.
  • the contents of each component of Li 2 O, Na 2 O and K 2 O are preferably as follows.
  • the content of Li 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
  • the content of Na 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
  • the content of K 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
  • the ratio of Li 2 O + Na 2 O + K 2 O and SiO 2 + Al 2 O 3 + B 2 O 3 (Li 2 O + Na 2 O + K 2 O) / (SiO 2 + Al 2 O 3 + B 2 O 3 ) is 0.2 or less. , 0.1 or less, 0.08 or less, particularly preferably 0.05 or less. In this way, it becomes easier to suppress the decrease in weather resistance.
  • the lower limit is not particularly limited, but may be 0.001 or more, for example.
  • MgO, CaO, SrO, BaO and ZnO are components that act as flux. It also has the effect of suppressing devitrification and improving weather resistance and chemical durability.
  • the content of MgO + CaO + SrO + BaO + ZnO is preferably 0.1 to 20%, 0.2 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%. If the content of MgO + CaO + SrO + BaO + ZnO is too small, the devitrification resistance tends to decrease. On the other hand, if the content of MgO + CaO + SrO + BaO + ZnO is too large, it becomes difficult to obtain a highly dispersed glass. In addition, the light transmittance tends to decrease.
  • the contents of each component of MgO, CaO, SrO, BaO and ZnO are preferably as follows.
  • the content of MgO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
  • the CaO content is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
  • the content of SrO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
  • the content of BaO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
  • the ZnO content is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
  • the ratio of MgO + CaO + SrO + BaO + ZnO to SiO 2 + Al 2 O 3 + B 2 O 3 is 0.4 or less, 0.2 or less, 0.1 or less, in particular. It is preferably 0.05 or less. In this way, it becomes easier to suppress the decrease in weather resistance.
  • the lower limit is not particularly limited, but may be 0.001 or more, for example.
  • the content of Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO + ZnO is preferably 30% or less, 20% or less, 10% or less, and particularly preferably 8% or less. In this way, it becomes easy to suppress the decrease in the refractive index while reducing the Abbe number and to suppress the variation in the refractive index.
  • the lower limit is not particularly limited, but may be, for example, 0.1% or more and 1% or more.
  • the above glass can contain the following components.
  • TiO 2 is a component that tends to increase the refractive index and decrease the Abbe number.
  • the content of TiO 2 is preferably 0 to 15%, 0.1 to 10%, 0.2 to 5%, 0.5 to 3.5%, and particularly preferably 0.5 to 2%. If the content of TiO 2 is too high, the softening point tends to increase. In addition, the light transmittance tends to decrease.
  • Nb 2 O 5 is a component that easily improves weather resistance. It is also a component that easily increases the refractive index and decreases the Abbe number.
  • the content of Nb 2 O 5 is preferably 0 to 20%, 0.1 to 15%, 1 to 10%, 1 to 5%, and particularly preferably 1 to 4%. If the content of Nb 2 O 5 is too large, the softening point tends to increase. In addition, the light transmittance tends to decrease.
  • WO 3 is a component that tends to increase the refractive index and decrease the Abbe number.
  • the content of WO 3 is preferably 0 to 20%, 0.1 to 15%, and particularly preferably 1 to 5%. If the content of WO 3 is too high, the softening point tends to rise. In addition, the light transmittance tends to decrease.
  • the content of TiO 2 + Nb 2 O 5 + WO 3 is preferably 0 to 30%, 0.1 to 20%, and particularly preferably 1 to 15%. In this way, it becomes easy to obtain a glass having a high refractive index and a low Abbe number.
  • the content of TiO 2 + Nb 2 O 5 + WO 3 + SiO 2 + Al 2 O 3 + B 2 O 3 is preferably 50% or more, 60% or more, 70% or more, and particularly preferably 80% or more. In this way, it becomes easy to increase the light transmittance in the ultraviolet region to the visible region while reducing the Abbe number.
  • the upper limit is not particularly limited, but may be, for example, 99% or less and 98% or less.
  • P 2 O 5 is a component that forms a glass network and easily improves the light transmittance and devitrification resistance of glass. It is also a component that easily lowers the glass softening point.
  • the content of P 2 O 5 is preferably 0 to 5%, 0 to 4.5%, and particularly preferably 0 to 4%. If the content of P 2 O 5 is too large, the refractive index tends to decrease. In addition, pulse is likely to occur.
  • ZrO 2 is a component that improves weather resistance and easily increases the refractive index.
  • the content of ZrO 2 is preferably 0 to 10%, 0 to 7.5%, and particularly preferably 0 to 5%. If the content of ZrO 2 is too large, the softening point tends to increase. In addition, the devitrification resistance tends to decrease.
  • F 2 is a component that easily lowers the softening point. It is also a component that easily significantly increases the light transmittance in the ultraviolet region.
  • the content of F 2 is preferably 0 to 10%, 0 to 5%, 0 to 4%, and particularly preferably 0 to 3%. If the content of F 2 is too large, the weather resistance and devitrification resistance tend to deteriorate.
  • La 2 O 3 is a component that easily increases the refractive index and the Abbe number.
  • the content of La 2 O 3 is preferably 0 to 20%, 0 to 15%, 0 to 10%, and particularly preferably 0 to 5%. If the content of La 2 O 3 is too large, the softening point tends to increase. In addition, the devitrification resistance deteriorates, and the liquidus viscosity tends to decrease.
  • Fe 2 O 3 , NiO, Cr 2 O 3 and CuO are components that color glass and easily reduce the light transmittance in the ultraviolet to visible region. Therefore, these contents are preferably 1% or less, 0.75% or less, and particularly preferably 0.5% or less, respectively.
  • Sb 2 O 3 and Ce O 2 are components that easily suppress a decrease in light transmittance.
  • the contents of Sb 2 O 3 and CeO 2 are preferably 0 to 1%, 0 to 0.8%, 0 to 0.5%, 0 to 0.2%, and particularly preferably 0 to 0.1%, respectively. .. If these contents are too high, devitrification is likely to occur.
  • the lead component (PbO, etc.) and the arsenic component (As 2 O 3, etc.) are substantially not contained for environmental reasons.
  • substantially not contained means that it is intentionally not contained as a raw material, and specifically, it means that the content of each is less than 0.1%.
  • Inorganic particles can be used in the form of beads, powder, fibers, etc. These can be used alone or in combination. In particular, it is preferable to use bead-shaped inorganic particles.
  • the bead-shaped inorganic particles have excellent fluidity and can easily suppress an increase in the viscosity of the resin composition.
  • the bead-shaped inorganic particles are particularly suitable for, for example, a resin composition in which a large amount of inorganic particles is added.
  • the term "bead-shaped" in the present invention means particles formed into a spherical shape, but it does not necessarily have to be a true spherical shape.
  • the average particle size of the inorganic particles is 0.2 to 50 ⁇ m, 0.2 to 40 ⁇ m, 0.2 to 30 ⁇ m, 0.2 to 20 ⁇ m, 0.2 to 10 ⁇ m, 0.2 to 9 ⁇ m, 0.3 to 8 ⁇ m, In particular, it is preferably 0.5 to 6 ⁇ m. By doing so, it becomes easy to improve the surface smoothness of the cured product. If the average particle size of the inorganic particles is too small, the fluidity of the resin composition tends to decrease. On the other hand, if the average particle size of the inorganic particles is too large, light scattering due to the difference in refractive index increases, and it becomes difficult to obtain a cured product having excellent transparency.
  • Inorganic particles are contained in an amount of 1 to 90%, 5 to 85%, 10 to 80%, 15 to 80%, 15 to 70%, 15 to 65%, and particularly 15 to 55% by volume with respect to the curable resin. It is preferable to be done. By adding the inorganic particles, it becomes easy to improve the mechanical strength of the resin composition. In addition, the curable resin can be easily cured even by light irradiation for a short time. Further, it becomes easy to reduce the dimensional variation due to the shrinkage of the curable resin. In particular, when mechanical strength is required for the resin composition, such as when used as a dental resin composition, the inorganic particles are 25 to 90% by volume and 30 to 85% by volume of the curable resin.
  • the thickness of the cured product layer that is cured by a single light irradiation is reduced, so that the production efficiency of the three-dimensional model is likely to decrease. Further, the viscosity of the curable resin becomes too high, which makes it difficult to handle.
  • the Young's modulus of the inorganic particles is preferably 50 GPa or more, 55 GPa or more, and particularly preferably 60 GPa or more. If the Young's modulus of the inorganic particles is too low, the mechanical strength of the obtained cured product tends to be low.
  • the coefficient of thermal expansion of the inorganic particles is preferably 60 ⁇ 10 -7 / ° C. or less, 55 ⁇ 10 -7 / ° C. or less, and particularly preferably 50 ⁇ 10 -7 / ° C. or less at 30 to 100 ° C. In this way, it becomes easy to improve the dimensional stability of the obtained cured product.
  • the light reflectance of the inorganic particles at a wavelength of 250 to 440 nm is preferably 10% or less, 8% or less, and particularly preferably 5% or less. If the reflectance of the inorganic particles is too large, it becomes difficult to sufficiently irradiate the uncured resin composition with ultraviolet rays in the depth direction, so that the curability of the resin composition tends to decrease.
  • a buffer layer is provided on the surface of the inorganic particles. This further suppresses light scattering generated at the interface between the inorganic particles and the curable resin, and makes it easier to further increase the light transmittance of the cured product.
  • the buffer layer is preferably a heterogeneous glass layer in which some of the inorganic particles are altered and / or deformed.
  • the heterogeneous glass layer preferably has a lower refractive index nd than the inorganic particles.
  • the heterogeneous glass layer may have a porous shape or a moth-eye structure.
  • the buffer layer is preferably prepared by treating the inorganic particles with an acid.
  • an acid treatment method for example, it is preferable to adopt a method of immersing the inorganic particles in an acid solution. This facilitates the uniform formation of a buffer layer on the surface of the inorganic particles.
  • the acid solution may be sprayed on the inorganic particles.
  • the acid for example, hydrochloric acid, dilute hydrochloric acid, nitric acid, sulfuric acid and the like can be used.
  • the acid treatment time is preferably 10 minutes or more, 30 minutes or more, and particularly preferably 1 hour or more. Further, it is preferably 30 hours or less, 25 hours or less, and particularly preferably 20 hours or less. If the acid treatment time is too short, the formation of the buffer layer tends to be insufficient. If the acid treatment time is too long, the thickness of the buffer layer becomes too large, and the light transmittance tends to decrease.
  • the curing shrinkage rate of the resin composition is preferably 10% or less, 9% or less, 8% or less, 5% or less, 4% or less, and particularly preferably 3% or less. By doing so, it becomes easy to reduce the dimensional variation of the cured product.
  • the lower limit is not particularly limited, but is, for example, 0.5% or more.
  • the shrinkage as designed may not occur and the dimensional variation may occur.
  • the influence of shrinkage of the resin composition tends to be small. Therefore, the cured product obtained by curing the resin composition of the present invention tends to have small dimensional variation.
  • an uncured material layer made of an uncured resin composition More specifically, a modeling stage is provided in a tank filled with an uncured resin composition. At this time, the modeling surface of the modeling stage is positioned so as to have a desired depth from the surface of the uncured resin composition.
  • the uncured material layer is, for example, liquid or paste-like.
  • the uncured material layer is selectively irradiated with light rays to form a cured product layer having a predetermined pattern.
  • the cured product layer is formed on the molding surface.
  • a new uncured material layer is formed on the cured product layer. That is, the uncured resin composition is introduced again onto the cured product layer.
  • the uncured resin composition can be introduced onto the cured product layer by moving the modeling stage by one layer.
  • a new cured product layer having a predetermined pattern continuous with the cured product layer is formed by irradiating with light rays.
  • the resin composition of the present invention has a light transmittance of 10% or more at a wavelength of 405 nm of the contained inorganic particles, and is particularly excellent in light transmittance to ultraviolet rays. Therefore, the uncured resin composition is easily sufficiently irradiated with ultraviolet rays in the depth direction, and is excellent in curability when irradiated with ultraviolet rays. Further, in the obtained cured product, the difference in the refractive index nd between the inorganic particles and the cured resin after curing is within ⁇ 0.1, so that the inorganic particles dispersed in the curable resin are inconspicuous and become transparent. Are better.
  • the light transmittance T600 of the cured product at a wavelength of 600 nm can be 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, and particularly 75% or more.
  • the light transmittance T500 of the cured product at a wavelength of 500 nm can be 20% or more, 30% or more, particularly 40% or more.
  • the resin composition of the present invention can be suitably used, for example, as a resin composition for a three-dimensional model used when producing a three-dimensional model or a dental resin composition.
  • a resin composition for a three-dimensional model used when producing a three-dimensional model or a dental resin composition.
  • the dental resin composition for example, it can be used for dental composite resin, dental bonding material, abutment construction material, resin cement, glass ionomer cement, resin reinforced glass ionomer cement, resin block for CAD / CAM, and the like. .
  • the resin composition of the present invention can also be suitably used as, for example, a resin composition for an optical member.
  • Tables 1 and 3 show examples (No. 1 to 4, 7 to 9) and comparative examples (No. 5 and 6) of the present invention.
  • Table 2 shows the composition of glass used as inorganic particles.
  • the obtained uncured material layer was irradiated with an ultraviolet ray of 4500 mW / cm 2 for 5 seconds using a spot light source (LC8, manufactured by Hamamatsu Photonics) in a region of ⁇ 5 mm to obtain a plate-shaped cured product (that is, a plate).
  • a three-dimensional model was formed on the modeling surface. At this time, the cured thickness of the formed three-dimensional model was measured.
  • a plate-shaped three-dimensional object with a thickness of 1 mm is prepared, the surface is mirror-polished, and then the total light transmittance at a wavelength of 600 nm at a thickness of 1 mm is measured using a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation). did.
  • the refractive index (nd rs , nd re ) of the curable resin, the refractive index (nd g ) of the glass, and the number of abbreviations ( ⁇ d g , ⁇ rs ) are measured by a precision refractive index meter (KPR-2000, manufactured by Shimadzu Device). did.
  • a plate-shaped sample having the same composition as the inorganic particles and having a thickness of 1 mm ⁇ 0.01 mm was prepared, the surface was mirror-polished, and then a spectrophotometer (UV-Shimazu Seisakusho). It was measured using 3100).
  • the three-dimensional model of Examples (No. 1 to 4) had a total light transmittance T600 of 67% or more at a wavelength of 600 nm.
  • T600 was as low as 55% or less and the cured thickness was as low as 0.17 mm or less.
  • the glass was colored, the cured thickness was as small as 0.12 mm, and the value of T600 was also low.
  • Examples 7 to 9 were prepared as follows. First, the raw materials were mixed so as to have the composition shown in Table 2, and glass A was prepared. Glass beads A having an average particle diameter of 5 ⁇ m were prepared using glass A. The glass beads A were immersed in 10% dilute hydrochloric acid and subjected to acid treatment for the time shown in Table 3. The glass beads A'after the acid treatment were used as inorganic particles. Acrylic resin E was used as the curable resin. Next, the inorganic particles were added to the curable resin at the ratios shown in Table 3 and kneaded with three rollers to obtain an uncured resin composition in which the inorganic particles were uniformly dispersed.
  • the obtained uncured resin composition was irradiated with an ultraviolet ray of 4500 mW / cm 2 using a spot light source (LC8, manufactured by Hamamatsu Photonics) in a region of ⁇ 5 mm to obtain a cured product having a thickness of 2.5 mm. Obtained.
  • LC8 spot light source
  • the total light transmittance T500 at 500 nm was measured. The results are shown in Table 3 and FIG.
  • Example 9 a sample was prepared in the same manner as in Examples 7 and 8 except that the glass beads A were not treated with acid.
  • the cured product of Examples (No. 7 and 8) subjected to acid treatment has an acid total light transmittance T600 at a wavelength of 600 nm and a total light transmittance T500 at a wavelength of 500 nm. It was higher than that of the cured product of Example (No. 9) which was not treated.

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Abstract

The present invention provides a resin composition, a resin composition for three-dimensional models, and a dental resin composition, each of which has excellent transparency, while exhibiting excellent curability.　A resin composition which contains a curable resin and inorganic particles, while being characterized in that: the difference between the refractive indexes nd of the inorganic particles and the curable resin after curing is ±0.1 or less; and the light transmittance of the inorganic particles at the wavelength of 405 nm is 10% or more.

Description

樹脂組成物、立体造形物用樹脂組成物及び歯科用樹脂組成物Resin composition, resin composition for three-dimensional model and dental resin composition
　本発明は、樹脂組成物、立体造形物用樹脂組成物及び歯科用樹脂組成物に関する。 The present invention relates to a resin composition, a resin composition for a three-dimensional model, and a dental resin composition.
　従来、硬化性樹脂等を積層させて、硬化性樹脂の硬化物からなる立体造形物を得る方法が知られている。例えば、光造形法、粉末焼結法、熱溶解積層（Ｆｕｓｅｄ　ｄｅｐｏｓｉｔｉｏｎ　ｍｏｄｅｌｉｎｇ：ＦＤＭ）法等の方法が提案、実用化されている。 Conventionally, a method of laminating a curable resin or the like to obtain a three-dimensional model made of a cured product of the curable resin has been known. For example, methods such as a stereolithography method, a powder sintering method, and a fused deposition modeling (FDM) method have been proposed and put into practical use.
　例えば、光造形法では以下のように立体造形物を製造する。はじめに、未硬化の硬化性樹脂を満たした槽内に造形用ステージを設け、造形用ステージの造形面に光線（例えば、紫外光線）を照射して、硬化性樹脂を硬化させる。これにより、所望のパターンの硬化物層を造形面上に形成する。次に、造形ステージを１層分移動させることにより、硬化物層上に未硬化の硬化性樹脂を再び導入する。次に、造形面に再び光線を照射して、硬化物層上に新たな硬化物層を形成する。この操作を繰り返すことにより、所望の立体造形物を得る。 For example, in the stereolithography method, a three-dimensional model is manufactured as follows. First, a modeling stage is provided in a tank filled with an uncured curable resin, and the modeling surface of the modeling stage is irradiated with light rays (for example, ultraviolet rays) to cure the curable resin. As a result, a cured product layer having a desired pattern is formed on the molding surface. Next, the uncured curable resin is introduced again onto the cured product layer by moving the modeling stage by one layer. Next, the molding surface is irradiated with light rays again to form a new cured product layer on the cured product layer. By repeating this operation, a desired three-dimensional model is obtained.
特開平７－２６０６０号公報Japanese Unexamined Patent Publication No. 7-26060
　光造形法は精密な立体造形物を製造しやすい一方、硬化物の機械的強度が低くなりやすいという問題がある。この問題を改善するため、特許文献１では、硬化性樹脂に無機粒子を添加した樹脂組成物を用いることが提案されている。 While the stereolithography method makes it easy to manufacture a precise three-dimensional model, there is a problem that the mechanical strength of the cured product tends to decrease. In order to improve this problem, Patent Document 1 proposes to use a resin composition in which inorganic particles are added to a curable resin.
　ところが、このような樹脂組成物は、硬化性樹脂と無機粒子の界面で光が散乱し、硬化物の透明性が低下しやすくなる。また、樹脂組成物の硬化性が低下しやすくなる。例えば、立体造形物を製造する段階において、樹脂組成物の硬化性が低いと、立体造形物の製造効率が低下しやすくなる。 However, in such a resin composition, light is scattered at the interface between the curable resin and the inorganic particles, and the transparency of the cured product tends to decrease. In addition, the curability of the resin composition tends to decrease. For example, if the curability of the resin composition is low at the stage of manufacturing the three-dimensional model, the production efficiency of the three-dimensional model tends to decrease.
　また、例えば、樹脂組成物を歯科用樹脂組成物として用いる場合に、樹脂組成物の透明性や硬化性が低いと、歯科用途で使用しづらくなる。 Further, for example, when a resin composition is used as a dental resin composition, if the transparency and curability of the resin composition are low, it becomes difficult to use it in dental applications.
　以上に鑑み、本発明は透明性に優れ、硬化性に優れた樹脂組成物、立体造形物用樹脂組成物及び歯科用樹脂組成物を提供することを目的とする。 In view of the above, it is an object of the present invention to provide a resin composition having excellent transparency and excellent curability, a resin composition for a three-dimensional model, and a dental resin composition.
　本発明の樹脂組成物は、硬化性樹脂と無機粒子とを含む樹脂組成物であって、無機粒子と硬化後の硬化性樹脂の屈折率ｎｄの差が±０．１以内であり、無機粒子の波長４０５ｎｍにおける光透過率が１０％以上であることを特徴とする。 The resin composition of the present invention is a resin composition containing a curable resin and inorganic particles, and the difference in refractive index nd between the inorganic particles and the cured curable resin is within ± 0.1, and the inorganic particles. The light transmittance at a wavelength of 405 nm is 10% or more.
　本発明の樹脂組成物は、無機粒子の波長４０５ｎｍにおける光透過率が５０％以上であることが好ましい。 The resin composition of the present invention preferably has a light transmittance of 50% or more at a wavelength of 405 nm of the inorganic particles.
　本発明の樹脂組成物は、無機粒子の波長３６５ｎｍにおける光透過率が５％以上であることが好ましい。 The resin composition of the present invention preferably has a light transmittance of 5% or more at a wavelength of 365 nm of the inorganic particles.
　本発明の樹脂組成物は、無機粒子がガラスであることが好ましい。 In the resin composition of the present invention, it is preferable that the inorganic particles are glass.
　本発明の樹脂組成物は、ガラスが、質量％で、ＳｉＯ２　３０～７５％、Ａｌ２Ｏ３　１～２０％、Ｂ２Ｏ３　０～３０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　０～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ　０．１～２０％を含有することが好ましい。 The resin composition of the present invention, the glass, in mass%, SiO 2 30 ~ 75% , Al 2 O 3 1 ~ 20%, B 2 O 3 0 ~ 30%, Li 2 O + Na 2 O + K 2 O 0 ~ 20 %, MgO + CaO + SrO + BaO + ZnO 0.1 to 20% is preferable.
　本発明の樹脂組成物は、ガラスが、質量％で、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３を４０％以上含有することが好ましい。 In the resin composition of the present invention, it is preferable that the glass contains 40% or more of SiO 2 + Al 2 O 3 + B 2 O 3 in mass%.
　本発明の樹脂組成物は、無機粒子の平均粒子径が、０．２～５０μｍであることが好ましい。 The resin composition of the present invention preferably has an average particle size of inorganic particles of 0.2 to 50 μm.
　本発明の樹脂組成物は、体積％で、無機粒子を１～９０％含有することが好ましい。 The resin composition of the present invention preferably contains 1 to 90% of inorganic particles in a volume%.
　本発明の樹脂組成物は、無機粒子のヤング率が、５０ＧＰａ以上であることが好ましい。 The resin composition of the present invention preferably has a Young's modulus of inorganic particles of 50 GPa or more.
　本発明の樹脂組成物は、無機粒子の熱膨張係数が、３０～１００℃において６０×１０－７／℃以下であることが好ましい。 In the resin composition of the present invention, the coefficient of thermal expansion of the inorganic particles is preferably 60 × 10 -7 / ° C. or less at 30 to 100 ° C.
　本発明の樹脂組成物は、無機粒子の波長２５０～４４０ｎｍにおける光反射率が１０％以下であることが好ましい。 The resin composition of the present invention preferably has a light reflectance of 10% or less at a wavelength of 250 to 440 nm of the inorganic particles.
　本発明の樹脂組成物は、無機粒子の表面に緩衝層を有することが好ましい。 The resin composition of the present invention preferably has a buffer layer on the surface of the inorganic particles.
　本発明の樹脂組成物は、緩衝層の屈折率ｎｄが、無機粒子の屈折率ｎｄより低いことが好ましい。 In the resin composition of the present invention, it is preferable that the refractive index nd of the buffer layer is lower than the refractive index nd of the inorganic particles.
　本発明の立体造形物用樹脂組成物は、上記の樹脂組成物を用いることを特徴とする。 The resin composition for a three-dimensional model of the present invention is characterized by using the above resin composition.
　本発明の歯科用樹脂組成物は、上記の樹脂組成物を用いることを特徴とする。 The dental resin composition of the present invention is characterized by using the above resin composition.
　本発明の立体造形物の製造方法は、未硬化の樹脂組成物からなる未硬化物層に選択的に光線を照射して所定のパターンを有する硬化物層を形成し、硬化物層上に新たな未硬化物層を形成した後に光線を照射して前記硬化物層と連続した所定パターンを有する新たな硬化物層を形成し、所定の立体造形物が得られるまで硬化物層の積層を繰り返す立体造形物の製造方法であって、樹脂組成物として、上記の樹脂組成物を使用することを特徴とする。 In the method for producing a three-dimensional model of the present invention, a cured product layer made of an uncured resin composition is selectively irradiated with light rays to form a cured product layer having a predetermined pattern, and a new cured product layer is formed on the cured product layer. After forming the uncured material layer, a light beam is irradiated to form a new cured product layer having a predetermined pattern continuous with the cured product layer, and the lamination of the cured product layer is repeated until a predetermined three-dimensional model is obtained. It is a method for producing a three-dimensional model, and is characterized in that the above-mentioned resin composition is used as the resin composition.
　本発明によれば、透明性に優れ、硬化性に優れた樹脂組成物、立体造形物用樹脂組成物及び歯科用樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a resin composition having excellent transparency and excellent curability, a resin composition for a three-dimensional model, and a dental resin composition.
図１は、実施例Ｎｏ．７～９の硬化物の光透過率を示すグラフである。FIG. 1 shows Example No. It is a graph which shows the light transmittance of the cured product of 7-9.
　本発明の樹脂組成物は、硬化性樹脂と無機粒子を含み、無機粒子と硬化後の硬化性樹脂の屈折率ｎｄの差が±０．１以内であり、無機粒子の波長４０５ｎｍにおける光透過率が１０％以上であることを特徴とする。なお、本発明における光透過率は、別途記載がない限り、厚さ１ｍｍで測定した全光線透過率の値を意味する。また、本発明における紫外光線は、波長２５０～４４０ｎｍの波長の光を意味する。 The resin composition of the present invention contains a curable resin and inorganic particles, the difference between the refractive index nd of the inorganic particles and the cured resin after curing is within ± 0.1, and the light transmittance of the inorganic particles at a wavelength of 405 nm. Is 10% or more. Unless otherwise specified, the light transmittance in the present invention means the value of the total light transmittance measured at a thickness of 1 mm. Further, the ultraviolet ray in the present invention means light having a wavelength of 250 to 440 nm.
　（硬化性樹脂）
　硬化性樹脂としては、例えば、紫外線硬化樹脂を用いることが好ましい。紫外線硬化樹脂としては、ラジカル種又はカチオン種により重合する樹脂を用いることが好ましく、例えば、アクリル系樹脂、エポキシ系樹脂等を用いることができる。アクリル系樹脂としては、エステルアクリレート系樹脂、ウレタンアクリレート系樹脂等が挙げられる。 (Curable resin)
As the curable resin, for example, it is preferable to use 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, and for example, an acrylic resin, an epoxy resin, or the like can be used. Examples of the acrylic resin include ester acrylate resins and urethane acrylate resins.
　アクリル系樹脂は、下記の化合物を含んでいてもよい。例えば、単官能性化合物としては、イソボルニルアクリレート、イソボルニルメタクリレート、ジンクロペンテニルアクリレート、ボルニルアクリレート、ボルニルメタクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、プロピレングリコールアクリレート、ビニルピロリドン、アクリルアミド、酢酸ビニル、スチレン等が挙げられる。多官能性化合物としては、トリメチロールプロパントリアクリレート、ＥＯ変性トリメチロールプロパントリアクリレート、エチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、１，４－ブタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ジシクロペンテニルジアクリレート、ポリエステルジアクリレート、ジアリルフタレート等が挙げられる。これらの単官能性化合物及び多官能性化合物は、１種又は２種以上を組み合わせて使用することができる。なお、これらの化合物は上記内容に限定されるものではない。 The acrylic resin may contain the following compounds. For example, examples of the monofunctional compound include isobornyl acrylate, isobornyl methacrylate, dincropentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol acrylate, and vinylpyrrolidone. Examples thereof include acrylamide, vinyl acetate and styrene. Examples of the polyfunctional compound include trimethyl propanetriacrylate, EO-modified trimethylpropantriacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-. Examples thereof include hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, and diallyl phthalate. These monofunctional compounds and polyfunctional compounds can be used alone or in combination of two or more. It should be noted that these compounds are not limited to the above contents.
　アクリル系樹脂は、光重合開始剤を重合開始剤として用いることができる。例えば、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、アセトフェノン、ベンゾフェノン、キサントン、フルオレノン、ベズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、ミヒラーケトン等が挙げられる。これらの重合開始剤は、１種又は２種以上を組み合わせて使用することができる。また、これらの重合開始剤は、単官能性化合物及び多官能性化合物に対して、質量％で、それぞれ０．１～１０％含有されることが好ましい。なお、必要に応じてアミン系化合物等の増感剤を併用してもよい。 For the acrylic resin, a photopolymerization initiator can be used as the polymerization initiator. For example, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylacetophenone, acetophenone, benzophenone, xantone, fluorenone, bezaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler ketone and the like. Be done. These polymerization initiators can be used alone or in combination of two or more. Further, these polymerization initiators are preferably contained in an amount of 0.1 to 10% by mass, respectively, with respect to the monofunctional compound and the polyfunctional compound. If necessary, a sensitizer such as an amine compound may be used in combination.
　エポキシ系樹脂は、下記の化合物を含んでいてもよい。例えば、水素添加ビスフェノールＡジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート等が挙げられる。これらの化合物を用いる場合には、トリフェニルスルホニウムヘキサフルオロアンチモネート等のエネルギー活性カチオン開始剤を用いることができる。 The epoxy resin may contain the following compounds. For example, 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 can be mentioned. When these compounds are used, an energy-active cation initiator such as triphenylsulfonium hexafluoroantimonate can be used.
　さらに硬化性樹脂には、レベリング剤、界面活性剤、有機高分子化合物、有機可塑剤、帯電防止剤等を必要に応じて添加してもよい。 Further, a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, an antistatic agent and the like may be added to the curable resin as needed.
　硬化後の硬化性樹脂の屈折率ｎｄ（ｎｄｒｅ）は、例えば、１．４０以上、１．４５以上、特に１．５以上であることが好ましい。また、硬化後の硬化性樹脂のアッべ数νｄ（νｄｒｅ）は、例えば、２０～６５、３０～６５、特に４０～６０であることが好ましい。 The refractive index nd (nd re ) of the curable resin after curing is, for example, preferably 1.40 or more, 1.45 or more, and particularly preferably 1.5 or more. Further, the abbreviation number νd (νd re ) of the curable resin after curing is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60.
　硬化前の硬化性樹脂（すなわち、未硬化の硬化性樹脂）の屈折率ｎｄ（ｎｄｒｓ）は、例えば、１．３５以上、１．４以上、特に１．４５以上であることが好ましい。また、未硬化の硬化性樹脂のアッベ数νｄ（νｄｒｓ）は、例えば、２０～６５、３０～６５、特に４０～６０であることが好ましい。 The refractive index nd (nd rs ) of the curable resin before curing (that is, the uncured curable resin) is preferably 1.35 or more, 1.4 or more, and particularly preferably 1.45 or more. The Abbe number νd (νd rs ) of the uncured curable resin is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60.
　硬化性樹脂の硬化収縮率は、１０％以下、９％以下、８％以下、特に６％以下であることが好ましい。このようにすれば、硬化後の樹脂組成物（すなわち、硬化物）の寸法ばらつきを小さくしやすくなる。下限値は特に限定されないが、例えば０．５％以上である。なお、硬化収縮率は、未硬化の硬化性樹脂の比重Ａ１と、硬化後の硬化性樹脂の比重Ａ２を測定し、下記式に基づいて算出することができる。 The curing shrinkage rate of the curable resin is preferably 10% or less, 9% or less, 8% or less, and particularly preferably 6% or less. By doing so, it becomes easy to reduce the dimensional variation of the cured resin composition (that is, the cured product). The lower limit is not particularly limited, but is, for example, 0.5% or more. The curing shrinkage rate can be calculated based on the following formula by measuring the specific gravity A1 of the uncured curable resin and the specific gravity A2 of the cured resin after curing.
　硬化収縮率（％）＝１００×（Ａ２－Ａ１）／Ａ２ Curing shrinkage rate (%) = 100 x (A2-A1) / A2
　（無機粒子）
　無機粒子の屈折率ｎｄ（ｎｄｇ）と、硬化後の硬化性樹脂の屈折率ｎｄ（ｎｄｒｅ）との差は、±０．１以内であり、±０．０８以内、±０．０５以内、±０．０３以内、特に±０．０２以内であることが好ましい。このようにすれば、硬化性樹脂と無機粒子の屈折率差に起因する光の散乱を抑制することができ、透明性に優れた硬化物を得やすくなる。 (Inorganic particles)
The difference between the refractive index nd (nd g ) of the inorganic particles and the refractive index nd (nd re ) of the curable resin after curing is within ± 0.1, within ± 0.08, and within ± 0.05. , Within ± 0.03, particularly preferably within ± 0.02. By doing so, it is possible to suppress light scattering due to the difference in refractive index between the curable resin and the inorganic particles, and it becomes easy to obtain a cured product having excellent transparency.
　無機粒子の屈折率ｎｄ（ｎｄｇ）と、未硬化の硬化性樹脂の屈折率ｎｄ（ｎｄｒｓ）との差は、±０．１以内、±０．０９以内、±０．０８以内、±０．０７以内、特に±０．０５以内であることが好ましい。また、未硬化の硬化性樹脂のアッベ数νｄ（νｄｒｓ）と無機粒子のアッベ数νｄ（νｄｇ）の差は、±１０以内（ただし１０を含まない）、±９以内、特に±８以内であることが好ましい。このようにすれば、樹脂組成物を硬化させる段階において、硬化性樹脂と無機粒子の屈折率差に起因する光の散乱を抑制することができる。これにより、未硬化の樹脂組成物の深さ方向に光線を十分に照射しやすくなるため、樹脂組成物の硬化性を向上させることができる。 The difference between the refractive index nd (nd g ) of the inorganic particles and the refractive index nd (nd rs ) of the uncured curable resin is within ± 0.1, within ± 0.09, within ± 0.08, ± It is preferably within 0.07, particularly within ± 0.05. The difference between the Abbe number νd (νd rs ) of the uncured curable resin and the Abbe number νd (νd g ) of the inorganic particles is within ± 10 (but not including 10), within ± 9, especially within ± 8. Is preferable. In this way, at the stage of curing the resin composition, it is possible to suppress light scattering due to the difference in refractive index between the curable resin and the inorganic particles. This makes it easier to sufficiently irradiate the uncured resin composition with light rays in the depth direction, so that the curability of the resin composition can be improved.
　無機粒子の屈折率ｎｄは、例えば、１．４０～１．９０、１．４０～１．６５、特に１．４５～１．６であることが好ましい。また、アッべ数νｄは、例えば、２０～６５、３０～６５、特に４０～６０であることが好ましい。このようにすれば、アクリル系樹脂、エポキシ系樹脂等、多くの硬化性樹脂と光学定数を整合させやすくなる。また、硬化性樹脂と無機粒子の屈折率差に起因する光の散乱を抑制し、透明性に優れた硬化物を得やすくなる。 The refractive index nd of the inorganic particles is preferably, for example, 1.40 to 1.90, 1.40 to 1.65, and particularly preferably 1.45 to 1.6. Further, the Abbe number νd is preferably, for example, 20 to 65, 30 to 65, and particularly preferably 40 to 60. In this way, it becomes easy to match the optical constants with many curable resins such as acrylic resins and epoxy resins. In addition, it suppresses light scattering caused by the difference in refractive index between the curable resin and the inorganic particles, making it easier to obtain a cured product having excellent transparency.
　無機粒子の波長４０５ｎｍにおける光透過率は１０％以上であり、２０％以上、３０％以上、５０％以上、特に７０％以上であることが望ましい。また、無機粒子の波長３６５ｎｍにおける光透過率は５％以上、１０％以上、２０％以上、３０％以上、特に５０％以上であることが望ましい。このようにすれば、未硬化の樹脂組成物の深さ方向に光線を十分に照射しやすくなるため、樹脂組成物の硬化性を向上させることができる。また、これにより、一度の光線照射で硬化する硬化物層の厚みを大きくしやすくなるため、立体造形物の製造効率を向上させやすくなる。 The light transmittance of the inorganic particles at a wavelength of 405 nm is 10% or more, preferably 20% or more, 30% or more, 50% or more, and particularly 70% or more. Further, the light transmittance of the inorganic particles at a wavelength of 365 nm is preferably 5% or more, 10% or more, 20% or more, 30% or more, and particularly preferably 50% or more. By doing so, it becomes easy to sufficiently irradiate the uncured resin composition with light rays in the depth direction, so that the curability of the resin composition can be improved. Further, this makes it easier to increase the thickness of the cured product layer that is cured by a single light irradiation, so that it becomes easier to improve the manufacturing efficiency of the three-dimensional modeled object.
　無機粒子の波長６００ｎｍにおける光透過率は６０％以上、７０％以上、特に８０％以上であることが好ましい。このようにすれば、透明性に優れた硬化物を得やすくなる。 The light transmittance of the inorganic particles at a wavelength of 600 nm is preferably 60% or more, 70% or more, and particularly preferably 80% or more. In this way, it becomes easy to obtain a cured product having excellent transparency.
　無機粒子はガラスであることが好ましい。ガラスを用いることにより、無機粒子と硬化性樹脂の屈折率差を厳密に制御しやすくなる。例えば、ＳｉＯ２－Ｂ２Ｏ３－Ｒ’２Ｏ（Ｒ’はアルカリ金属元素）系ガラス、ＳｉＯ２－Ａｌ２Ｏ３－ＲＯ（Ｒはアルカリ土類金属元素）系ガラス、ＳｉＯ２－Ａｌ２Ｏ３－Ｒ’２Ｏ－ＲＯ系ガラス、ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３－Ｒ’２Ｏ系ガラス、ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３－Ｒ’２Ｏ－ＲＯ系ガラス、ＳｉＯ２－Ｒ’２Ｏ系ガラス、ＳｉＯ２－Ｒ’２Ｏ－ＲＯ系ガラスを使用することができる。 The inorganic particles are preferably glass. By using glass, it becomes easy to strictly control the difference in refractive index between the inorganic particles and the curable resin. For example, SiO 2 -B 2 O 3 -R '2 O (R' alkali metal element) based glass, SiO 2 -Al 2 O 3 -RO (R is an alkaline earth metal element) based glass, SiO 2 -Al 2 O 3 -R '2 O- RO -based glass, SiO 2 -Al 2 O 3 -B 2 O 3 -R' 2 O -based glass, SiO 2 -Al 2 O 3 -B 2 O 3 -R '2 O -RO based glass, SiO 2 -R a '2 O-based glass, SiO 2 -R' 2 O- RO -based glass can be used.
　具体的なガラス組成として、例えば、質量％で、ＳｉＯ２　３０～７５％、Ａｌ２Ｏ３　１～２０％、Ｂ２Ｏ３　０～３０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　０～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ　０．１～２０％を含有することが好ましい。当該組成を含有するガラスは、耐候性及び紫外域～可視域の光透過率に優れている。そのため、紫外光線を照射した際の樹脂組成物の硬化性を向上させやすい。また、可視域の光透過率にも優れているため、透明性に優れた硬化物を得やすくなる。 Specific glass compositions, for example, in mass%, SiO 2 30 ~ 75% , Al 2 O 3 1 ~ 20%, B 2 O 3 0 ~ 30%, Li 2 O + Na 2 O + K 2 O 0 ~ 20%, It is preferable to contain MgO + CaO + SrO + BaO + ZnO 0.1 to 20%. The glass containing this composition is excellent in weather resistance and light transmittance in the ultraviolet to visible region. Therefore, it is easy to improve the curability of the resin composition when irradiated with ultraviolet rays. Further, since the light transmittance in the visible region is also excellent, it becomes easy to obtain a cured product having excellent transparency.
　以下、上記のようにガラス組成範囲を限定した理由を説明する。なお、以下の各成分の含有量に関する説明において、特に断りがない限り、「％」は「質量％」を意味する。また、本明細書において、「○＋○＋・・・」は該当する各成分の含有量の合量を意味する。 The reason for limiting the glass composition range as described above will be described below. In the following description of the content of each component, "%" means "mass%" unless otherwise specified. Further, in the present specification, "○ + ○ + ..." Means the total amount of the contents of each corresponding component.
　ＳｉＯ２はガラスネットワークを形成し、紫外域～可視域の光透過率を顕著に高める成分である。また、耐候性を向上させる成分でもある。ＳｉＯ２の含有量は３０～７５％、３５～７３％、４０～７０％、５０～７０％、５１～６５％、特に５１～６２％であることが好ましい。ＳｉＯ２の含有量が少なすぎると、上記効果が得られにくくなる。一方、ＳｉＯ２の含有量が多すぎると、ガラスの粘度が上昇し、溶融性が低下しやすくなる。 SiO 2 is a component that forms a glass network and remarkably enhances the light transmittance in the ultraviolet to visible region. It is also a component that improves weather resistance. The content of SiO 2 is preferably 30 to 75%, 35 to 73%, 40 to 70%, 50 to 70%, 51 to 65%, and particularly preferably 51 to 62%. If the content of SiO 2 is too small, it becomes difficult to obtain the above effect. On the other hand, if the content of SiO 2 is too large, the viscosity of the glass increases and the meltability tends to decrease.
　Ａｌ２Ｏ３はガラスネットワークを形成し、紫外域～可視域の光透過率を高める成分である。特に高屈折率のガラスにおいて、光透過率を高めやすい効果を有する。Ａｌ２Ｏ３の含有量は１～２０％、２～２０％、３～２０％、５～２０％、１０～２０％、１１～１８％、特に１５％超～１７％であることが好ましい。Ａｌ２Ｏ３の含有量が少なすぎると、上記効果が得にくくなる。一方、Ａｌ２Ｏ３の含有量が多すぎると、ガラスの粘度が上昇し、溶融性が低下しやすくなる。 Al 2 O 3 is a component that forms a glass network and enhances the light transmittance in the ultraviolet to visible region. Especially in glass having a high refractive index, it has an effect of easily increasing the light transmittance. The content of Al 2 O 3 is preferably 1 to 20%, 2 to 20%, 3 to 20%, 5 to 20%, 10 to 20%, 11 to 18%, and particularly preferably more than 15% to 17%. .. If the content of Al 2 O 3 is too small, it becomes difficult to obtain the above effect. On the other hand, if the content of Al 2 O 3 is too large, the viscosity of the glass increases and the meltability tends to decrease.
　Ｂ２Ｏ３はガラスネットワークを形成し、紫外域～可視域の光透過率を高める成分である。Ｂ２Ｏ３の含有量は０～３０％、１～２７．５％、２～２５％、３～２５％、５～２５％、１０～２５％、特に１１～２０％であることが好ましい。Ｂ２Ｏ３の含有量が多すぎると溶融性が低下しやすくなる。 B 2 O 3 is a component that forms a glass network and enhances the light transmittance in the ultraviolet to visible region. The content of B 2 O 3 is preferably 0 to 30%, 1 to 27.5%, 2 to 25%, 3 to 25%, 5 to 25%, 10 to 25%, and particularly preferably 11 to 20%. .. If the content of B 2 O 3 is too large, the meltability tends to decrease.
　ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３の含有量は、４０％以上、５０％以上、５５％以上、特に６０％以上であることが好ましい。このようにすれば、紫外域～可視域の光透過率を高めつつ、耐候性を向上させやすくなる。上限は特に限定されないが、多すぎると溶融性が低下しやすくなるため、例えば、９９％以下、特に９８％以下としてもよい。 The content of SiO 2 + Al 2 O 3 + B 2 O 3 is preferably 40% or more, 50% or more, 55% or more, and particularly preferably 60% or more. In this way, it becomes easy to improve the weather resistance while increasing the light transmittance in the ultraviolet region to the visible region. The upper limit is not particularly limited, but if it is too large, the meltability tends to decrease. Therefore, for example, it may be 99% or less, particularly 98% or less.
　Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏは軟化点を低下させる成分である。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は０～２０％、０～１８％、０～１６％、０～１０％、０～６％、０～４％、特に０．１～４％であることが好ましい。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が多すぎると、耐候性や屈折率が低下しやすくなる。また、無機粒子を製造する段階において、粒子表面から成分が蒸発しやすくなり、無機粒子の屈折率にばらつきが生じやすくなる。さらに、樹脂組成物が劣化しやすくなる。なお、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの各成分の含有量については、以下の通りであることが好ましい。 Li 2 O, Na 2 O and K 2 O are components that lower the softening point. The content of Li 2 O + Na 2 O + K 2 O is 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, especially 0.1 to 4%. Is preferable. If the content of Li 2 O + Na 2 O + K 2 O is too large, the weather resistance and the refractive index tend to decrease. Further, in the stage of producing the inorganic particles, the components are likely to evaporate from the surface of the particles, and the refractive index of the inorganic particles is likely to vary. Further, the resin composition is liable to deteriorate. The contents of each component of Li 2 O, Na 2 O and K 2 O are preferably as follows.
　Ｌｉ２Ｏの含有量は０～２０％、０～１８％、０～１６％、０～１０％、０～６％、０～４％、特に０．１～４％であることが好ましい。 The content of Li 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
　Ｎａ２Ｏの含有量は０～２０％、０～１８％、０～１６％、０～１０％、０～６％、０～４％、特に０．１～４％であることが好ましい。 The content of Na 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
　Ｋ２Ｏの含有量は０～２０％、０～１８％、０～１６％、０～１０％、０～６％、０～４％、特に０．１～４％であることが好ましい。 The content of K 2 O is preferably 0 to 20%, 0 to 18%, 0 to 16%, 0 to 10%, 0 to 6%, 0 to 4%, and particularly preferably 0.1 to 4%.
　Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２ＯとＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３の比である（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）／（ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３）は、０．２以下、０．１以下、０．０８以下、特に０．０５以下であることが好ましい。このようにすれば、耐候性の低下を一層抑制しやすくなる。下限値は特に限定されないが、例えば０．００１以上としてもよい。 The ratio of Li 2 O + Na 2 O + K 2 O and SiO 2 + Al 2 O 3 + B 2 O 3 (Li 2 O + Na 2 O + K 2 O) / (SiO 2 + Al 2 O 3 + B 2 O 3 ) is 0.2 or less. , 0.1 or less, 0.08 or less, particularly preferably 0.05 or less. In this way, it becomes easier to suppress the decrease in weather resistance. The lower limit is not particularly limited, but may be 0.001 or more, for example.
　ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯは融剤として作用する成分である。また、失透を抑制し、耐候性や化学耐久性を向上させる効果もある。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量は、０．１～２０％、０．２～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量が少なすぎると、耐失透性が低下しやすくなる。一方、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量が多すぎると、高分散のガラスが得づらくなる。また、光透過率が低下しやすくなる。なお、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの各成分の含有量については、下記の通りであることが好ましい。 MgO, CaO, SrO, BaO and ZnO are components that act as flux. It also has the effect of suppressing devitrification and improving weather resistance and chemical durability. The content of MgO + CaO + SrO + BaO + ZnO is preferably 0.1 to 20%, 0.2 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%. If the content of MgO + CaO + SrO + BaO + ZnO is too small, the devitrification resistance tends to decrease. On the other hand, if the content of MgO + CaO + SrO + BaO + ZnO is too large, it becomes difficult to obtain a highly dispersed glass. In addition, the light transmittance tends to decrease. The contents of each component of MgO, CaO, SrO, BaO and ZnO are preferably as follows.
　ＭｇＯの含有量は０～２０％、０．１～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。 The content of MgO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
　ＣａＯの含有量は０～２０％、０．１～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。 The CaO content is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
　ＳｒＯの含有量は０～２０％、０．１～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。 The content of SrO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
　ＢａＯの含有量は０～２０％、０．１～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。 The content of BaO is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
　ＺｎＯの含有量は０～２０％、０．１～１５％、０．５～１０％、１～９％、１～５％、特に１～４％であることが好ましい。 The ZnO content is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, 1 to 9%, 1 to 5%, and particularly preferably 1 to 4%.
　ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯとＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３の比である（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ）／（ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３）は、０．４以下、０．２以下、０．１以下、特に０．０５以下であることが好ましい。このようにすれば、耐候性の低下を一層抑制しやすくなる。下限値は特に限定されないが、例えば０．００１以上としてもよい。 The ratio of MgO + CaO + SrO + BaO + ZnO to SiO 2 + Al 2 O 3 + B 2 O 3 (MgO + CaO + SrO + BaO + ZnO) / (SiO 2 + Al 2 O 3 + B 2 O 3 ) is 0.4 or less, 0.2 or less, 0.1 or less, in particular. It is preferably 0.05 or less. In this way, it becomes easier to suppress the decrease in weather resistance. The lower limit is not particularly limited, but may be 0.001 or more, for example.
　Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量は、３０％以下、２０％以下、１０％以下、特に８％以下であることが好ましい。このようにすれば、アッベ数を低下させつつ屈折率の低下を抑制し、かつ屈折率のばらつきを抑制しやすくなる。下限値は特に限定されないが、例えば０．１％以上、１％以上としてもよい。 The content of Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO + ZnO is preferably 30% or less, 20% or less, 10% or less, and particularly preferably 8% or less. In this way, it becomes easy to suppress the decrease in the refractive index while reducing the Abbe number and to suppress the variation in the refractive index. The lower limit is not particularly limited, but may be, for example, 0.1% or more and 1% or more.
　なお、上記ガラスには、上記成分以外にも、下記の成分を含有させることができる。 In addition to the above components, the above glass can contain the following components.
　ＴｉＯ２は屈折率を高め、アッベ数を低下させやすい成分である。ＴｉＯ２の含有量は、０～１５％、０．１～１０％、０．２～５％、０．５～３．５％、特に０．５～２％であることが好ましい。ＴｉＯ２の含有量が多すぎると、軟化点が上昇しやすくなる。また、光透過率が低下しやすくなる。 TiO 2 is a component that tends to increase the refractive index and decrease the Abbe number. The content of TiO 2 is preferably 0 to 15%, 0.1 to 10%, 0.2 to 5%, 0.5 to 3.5%, and particularly preferably 0.5 to 2%. If the content of TiO 2 is too high, the softening point tends to increase. In addition, the light transmittance tends to decrease.
　Ｎｂ２Ｏ５は耐候性を向上させやすい成分である。また、屈折率を高め、アッベ数を低下させやすい成分でもある。Ｎｂ２Ｏ５の含有量は０～２０％、０．１～１５％、１～１０％、１～５％、特に１～４％であることが好ましい。Ｎｂ２Ｏ５の含有量が多すぎると、軟化点が上昇しやすくなる。また、光透過率が低下しやすくなる。 Nb 2 O 5 is a component that easily improves weather resistance. It is also a component that easily increases the refractive index and decreases the Abbe number. The content of Nb 2 O 5 is preferably 0 to 20%, 0.1 to 15%, 1 to 10%, 1 to 5%, and particularly preferably 1 to 4%. If the content of Nb 2 O 5 is too large, the softening point tends to increase. In addition, the light transmittance tends to decrease.
　ＷＯ３は屈折率を高め、アッベ数を低下させやすい成分である。ＷＯ３の含有量は０～２０％、０．１～１５％、特に１～５％であることが好ましい。ＷＯ３の含有量が多すぎると、軟化点が上昇しやすくなる。また、光透過率が低下しやすくなる。 WO 3 is a component that tends to increase the refractive index and decrease the Abbe number. The content of WO 3 is preferably 0 to 20%, 0.1 to 15%, and particularly preferably 1 to 5%. If the content of WO 3 is too high, the softening point tends to rise. In addition, the light transmittance tends to decrease.
　ＴｉＯ２＋Ｎｂ２Ｏ５＋ＷＯ３の含有量は、０～３０％、０．１～２０％、特に１～１５％であることが好ましい。このようにすれば、屈折率が高く、かつアッベ数が低いガラスを得やすくなる。 The content of TiO 2 + Nb 2 O 5 + WO 3 is preferably 0 to 30%, 0.1 to 20%, and particularly preferably 1 to 15%. In this way, it becomes easy to obtain a glass having a high refractive index and a low Abbe number.
　ＴｉＯ２＋Ｎｂ２Ｏ５＋ＷＯ３＋ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３の含有量は、５０％以上、６０％以上、７０％以上、特に８０％以上であることが好ましい。このようにすれば、アッベ数を低下させつつ、紫外域～可視域の光透過率を高めやすくなる。上限値は特に限定されないが、例えば９９％以下、９８％以下としてもよい。 The content of TiO 2 + Nb 2 O 5 + WO 3 + SiO 2 + Al 2 O 3 + B 2 O 3 is preferably 50% or more, 60% or more, 70% or more, and particularly preferably 80% or more. In this way, it becomes easy to increase the light transmittance in the ultraviolet region to the visible region while reducing the Abbe number. The upper limit is not particularly limited, but may be, for example, 99% or less and 98% or less.
　Ｐ２Ｏ５はガラスネットワークを形成し、ガラスの光透過率や耐失透性を向上させやすい成分である。また、ガラス軟化点を下げやすい成分でもある。Ｐ２Ｏ５の含有量は０～５％、０～４．５％、特に０～４％であることが好ましい。Ｐ２Ｏ５の含有量が多すぎると、屈折率が低下しやすくなる。また、脈理が生じやすくなる。 P 2 O 5 is a component that forms a glass network and easily improves the light transmittance and devitrification resistance of glass. It is also a component that easily lowers the glass softening point. The content of P 2 O 5 is preferably 0 to 5%, 0 to 4.5%, and particularly preferably 0 to 4%. If the content of P 2 O 5 is too large, the refractive index tends to decrease. In addition, pulse is likely to occur.
　ＺｒＯ２は耐候性を向上させ、屈折率を高めやすい成分である。ＺｒＯ２の含有量は、０～１０％、０～７．５％、特に０～５％であることが好ましい。ＺｒＯ２の含有量が多すぎると、軟化点が上昇しやすくなる。また、耐失透性が低下しやすくなる。 ZrO 2 is a component that improves weather resistance and easily increases the refractive index. The content of ZrO 2 is preferably 0 to 10%, 0 to 7.5%, and particularly preferably 0 to 5%. If the content of ZrO 2 is too large, the softening point tends to increase. In addition, the devitrification resistance tends to decrease.
　Ｆ２は軟化点を低下させやすい成分である。また、紫外域の光透過率を顕著に高めやすい成分でもある。Ｆ２の含有量は０～１０％、０～５％、０～４％、特に０～３％であることが好ましい。Ｆ２の含有量が多すぎると、耐候性と耐失透性が悪化しやすくなる。 F 2 is a component that easily lowers the softening point. It is also a component that easily significantly increases the light transmittance in the ultraviolet region. The content of F 2 is preferably 0 to 10%, 0 to 5%, 0 to 4%, and particularly preferably 0 to 3%. If the content of F 2 is too large, the weather resistance and devitrification resistance tend to deteriorate.
　Ｌａ２Ｏ３は屈折率を高め、アッベ数を上昇させやすい成分である。Ｌａ２Ｏ３の含有量は０～２０％、０～１５％、０～１０％、特に０～５％であることが好ましい。Ｌａ２Ｏ３の含有量が多すぎると、軟化点が上昇しやすくなる。また、耐失透性が悪化し、液相粘度が低下しやすくなる。 La 2 O 3 is a component that easily increases the refractive index and the Abbe number. The content of La 2 O 3 is preferably 0 to 20%, 0 to 15%, 0 to 10%, and particularly preferably 0 to 5%. If the content of La 2 O 3 is too large, the softening point tends to increase. In addition, the devitrification resistance deteriorates, and the liquidus viscosity tends to decrease.
　Ｆｅ２Ｏ３、ＮｉＯ、Ｃｒ２Ｏ３及びＣｕＯは、ガラスを着色させ、紫外域～可視域の光透過率を低下させやすい成分である。そのため、これらの含有量はそれぞれ１％以下、０．７５％以下、特に０．５％以下であることが好ましい。 Fe 2 O 3 , NiO, Cr 2 O 3 and CuO are components that color glass and easily reduce the light transmittance in the ultraviolet to visible region. Therefore, these contents are preferably 1% or less, 0.75% or less, and particularly preferably 0.5% or less, respectively.
　Ｓｂ２Ｏ３及びＣｅＯ２は、光透過率の低下を抑制しやすい成分である。Ｓｂ２Ｏ３及びＣｅＯ２の含有量はそれぞれ０～１％、０～０．８％、０～０．５％、０～０．２％、特に０～０．１％であることが好ましい。これらの含有量が多すぎると、失透しやすくなる。 Sb 2 O 3 and Ce O 2 are components that easily suppress a decrease in light transmittance. The contents of Sb 2 O 3 and CeO 2 are preferably 0 to 1%, 0 to 0.8%, 0 to 0.5%, 0 to 0.2%, and particularly preferably 0 to 0.1%, respectively. .. If these contents are too high, devitrification is likely to occur.
　鉛成分（ＰｂＯ等）及びヒ素成分（Ａｓ２Ｏ３等）は、環境上の理由から実質的に含有しないことが好ましい。なお、上記において「実質的に含有しない」とは、意図的に原料として含有させないことを意味し、具体的には、各々の含有量が０．１％未満であることを意味する。 It is preferable that the lead component (PbO, etc.) and the arsenic component (As 2 O 3, etc.) are substantially not contained for environmental reasons. In addition, in the above, "substantially not contained" means that it is intentionally not contained as a raw material, and specifically, it means that the content of each is less than 0.1%.
　無機粒子は、ビーズ状、粉末状、ファイバー状等の形状で用いることができる。これらは単独又は混合して使用することができる。特にビーズ状の無機粒子を用いることが好ましい。ビーズ状の無機粒子は流動性に優れており、樹脂組成物の粘度上昇を抑制しやすい。ビーズ状の無機粒子は、例えば、無機粒子の添加量が多い樹脂組成物に特に好適である。なお、本発明における「ビーズ状」とは、球状に成形された粒子を意味するが、必ずしも真球状でなくともよい。 Inorganic particles can be used in the form of beads, powder, fibers, etc. These can be used alone or in combination. In particular, it is preferable to use bead-shaped inorganic particles. The bead-shaped inorganic particles have excellent fluidity and can easily suppress an increase in the viscosity of the resin composition. The bead-shaped inorganic particles are particularly suitable for, for example, a resin composition in which a large amount of inorganic particles is added. The term "bead-shaped" in the present invention means particles formed into a spherical shape, but it does not necessarily have to be a true spherical shape.
　無機粒子の平均粒子径は、０．２～５０μｍ、０．２～４０μｍ、０．２～３０μｍ、０．２～２０μｍ、０．２～１０μｍ、０．２～９μｍ、０．３～８μｍ、特に０．５～６μｍであることが好ましい。このようにすれば、硬化物の表面平滑性を向上させやすくなる。無機粒子の平均粒子径が小さすぎると、樹脂組成物の流動性が低下やすくなる。一方、無機粒子の平均粒子径が大きすぎると、屈折率差による光散乱が増大し、透明性に優れた硬化物を得づらくなる。また、未硬化の樹脂組成物の深さ方向に光線を十分に照射しづらくなるため、樹脂組成物の硬化性が低下しやすくなる。また、これにより、一度の光線照射で硬化する硬化物層の厚みが小さくなるため、立体造形物の製造効率が低下しやすくなる。さらに、硬化物の表面を鏡面加工しづらくなる。 The average particle size of the inorganic particles is 0.2 to 50 μm, 0.2 to 40 μm, 0.2 to 30 μm, 0.2 to 20 μm, 0.2 to 10 μm, 0.2 to 9 μm, 0.3 to 8 μm, In particular, it is preferably 0.5 to 6 μm. By doing so, it becomes easy to improve the surface smoothness of the cured product. If the average particle size of the inorganic particles is too small, the fluidity of the resin composition tends to decrease. On the other hand, if the average particle size of the inorganic particles is too large, light scattering due to the difference in refractive index increases, and it becomes difficult to obtain a cured product having excellent transparency. In addition, it becomes difficult to sufficiently irradiate the uncured resin composition with light rays in the depth direction, so that the curability of the resin composition tends to decrease. Further, as a result, the thickness of the cured product layer that is cured by a single light irradiation is reduced, so that the production efficiency of the three-dimensional model is likely to decrease. Further, it becomes difficult to mirror-process the surface of the cured product.
　硬化性樹脂に対して、無機粒子は、体積％で１～９０％、５～８５％、１０～８０％、１５～８０％、１５～７０％、１５～６５％、特に１５～５５％含有されることが好ましい。無機粒子を添加することにより、樹脂組成物の機械的強度を向上させやすくなる。また、短時間の光照射でも硬化性樹脂を硬化させやすくなる。さらに、硬化性樹脂の収縮による寸法ばらつきを小さくしやすくなる。特に、歯科用樹脂組成物として使用する場合等、樹脂組成物に機械的強度が求められる場合は、硬化性樹脂に対して、無機粒子は、体積％で２５～９０％、３０～８５％、４０～８５％、５０～８０％、特に５１～８０％含有されることが好ましい。無機粒子が少なすぎると、上記効果が得づらくなる。また、無機粒子の持つ強度や硬度を硬化物に反映しにくくなる。一方、無機粒子が多すぎると、光散乱が増大し、透明性に優れた硬化物を得づらくなる。また、未硬化の樹脂組成物の深さ方向に光線を十分に照射しづらくなるため、樹脂組成物の硬化性が低下しやすくなる。また、これにより、一度の光線照射で硬化する硬化物層の厚みが小さくなるため、立体造形物の製造効率が低下しやすくなる。さらに、硬化性樹脂の粘度が高くなり過ぎて、取り扱いが難しくなりやすくなる。 Inorganic particles are contained in an amount of 1 to 90%, 5 to 85%, 10 to 80%, 15 to 80%, 15 to 70%, 15 to 65%, and particularly 15 to 55% by volume with respect to the curable resin. It is preferable to be done. By adding the inorganic particles, it becomes easy to improve the mechanical strength of the resin composition. In addition, the curable resin can be easily cured even by light irradiation for a short time. Further, it becomes easy to reduce the dimensional variation due to the shrinkage of the curable resin. In particular, when mechanical strength is required for the resin composition, such as when used as a dental resin composition, the inorganic particles are 25 to 90% by volume and 30 to 85% by volume of the curable resin. It is preferably contained in an amount of 40 to 85%, 50 to 80%, and particularly 51 to 80%. If the amount of inorganic particles is too small, it becomes difficult to obtain the above effect. In addition, it becomes difficult to reflect the strength and hardness of the inorganic particles in the cured product. On the other hand, if there are too many inorganic particles, light scattering increases and it becomes difficult to obtain a cured product having excellent transparency. In addition, it becomes difficult to sufficiently irradiate the uncured resin composition with light rays in the depth direction, so that the curability of the resin composition tends to decrease. Further, as a result, the thickness of the cured product layer that is cured by a single light irradiation is reduced, so that the production efficiency of the three-dimensional model is likely to decrease. Further, the viscosity of the curable resin becomes too high, which makes it difficult to handle.
　無機粒子のヤング率は５０ＧＰａ以上、５５ＧＰａ以上、特に６０ＧＰａ以上であることが好ましい。無機粒子のヤング率が低すぎると、得られる硬化物の機械的強度が低くなりやすくなる。 The Young's modulus of the inorganic particles is preferably 50 GPa or more, 55 GPa or more, and particularly preferably 60 GPa or more. If the Young's modulus of the inorganic particles is too low, the mechanical strength of the obtained cured product tends to be low.
　無機粒子の熱膨張係数は、３０～１００℃において、６０×１０－７／℃以下、５５×１０－７／℃以下、特に５０×１０－７／℃以下であることが好ましい。このようにすれば、得られる硬化物の寸法安定性を向上させやすくなる。 The coefficient of thermal expansion of the inorganic particles is preferably 60 × 10 -7 / ° C. or less, 55 × 10 -7 / ° C. or less, and particularly preferably 50 × 10 -7 / ° C. or less at 30 to 100 ° C. In this way, it becomes easy to improve the dimensional stability of the obtained cured product.
　無機粒子の波長２５０～４４０ｎｍにおける光反射率は、１０％以下、８％以下、特に５％以下であることが好ましい。無機粒子の反射率が大きすぎると、未硬化の樹脂組成物の深さ方向に紫外光線を十分に照射しにくくなるため、樹脂組成物の硬化性が低下しやすくなる。 The light reflectance of the inorganic particles at a wavelength of 250 to 440 nm is preferably 10% or less, 8% or less, and particularly preferably 5% or less. If the reflectance of the inorganic particles is too large, it becomes difficult to sufficiently irradiate the uncured resin composition with ultraviolet rays in the depth direction, so that the curability of the resin composition tends to decrease.
　無機粒子の表面には、緩衝層が設けられていることが好ましい。これにより、無機粒子と硬化性樹脂の界面で生じる光散乱を一層抑制し、硬化物の光透過率を一層高めやすくなる。例えば、緩衝層は、無機粒子の一部が変質及び／又は変形した、異質ガラス層であることが好ましい。例えば、異質ガラス層は、無機粒子より屈折率ｎｄが低いことが好ましい。また、異質ガラス層は、多孔質状やモスアイ構造状であってもよい。 It is preferable that a buffer layer is provided on the surface of the inorganic particles. This further suppresses light scattering generated at the interface between the inorganic particles and the curable resin, and makes it easier to further increase the light transmittance of the cured product. For example, the buffer layer is preferably a heterogeneous glass layer in which some of the inorganic particles are altered and / or deformed. For example, the heterogeneous glass layer preferably has a lower refractive index nd than the inorganic particles. Further, the heterogeneous glass layer may have a porous shape or a moth-eye structure.
　緩衝層は、無機粒子を酸処理することにより作製されることが好ましい。酸処理の方法としては、例えば、酸溶液中に無機粒子を浸漬する方法を採用することが好ましい。これにより、無機粒子の表面に均一に緩衝層を形成しやすくなる。また、酸溶液を無機粒子に噴霧してもよい。酸としては、例えば、塩酸、希塩酸、硝酸、硫酸等を使用することができる。 The buffer layer is preferably prepared by treating the inorganic particles with an acid. As the acid treatment method, for example, it is preferable to adopt a method of immersing the inorganic particles in an acid solution. This facilitates the uniform formation of a buffer layer on the surface of the inorganic particles. Alternatively, the acid solution may be sprayed on the inorganic particles. As the acid, for example, hydrochloric acid, dilute hydrochloric acid, nitric acid, sulfuric acid and the like can be used.
　酸処理時間は、１０分以上、３０分以上、特に１時間以上であることが好ましい。また、３０時間以下、２５時間以下、特に２０時間以下であることが好ましい。酸処理時間が短すぎると、緩衝層の形成が不十分になりやすくなる。酸処理時間が長すぎると、緩衝層の厚みが大きくなりすぎて、かえって光透過率が低下しやすくなる。 The acid treatment time is preferably 10 minutes or more, 30 minutes or more, and particularly preferably 1 hour or more. Further, it is preferably 30 hours or less, 25 hours or less, and particularly preferably 20 hours or less. If the acid treatment time is too short, the formation of the buffer layer tends to be insufficient. If the acid treatment time is too long, the thickness of the buffer layer becomes too large, and the light transmittance tends to decrease.
　樹脂組成物の硬化収縮率は、１０％以下、９％以下、８％以下、５％以下、４％以下、特に３％以下であることが好ましい。このようにすれば、硬化物の寸法ばらつきを小さくしやすくなる。下限値は特に限定されないが、例えば０．５％以上である。 The curing shrinkage rate of the resin composition is preferably 10% or less, 9% or less, 8% or less, 5% or less, 4% or less, and particularly preferably 3% or less. By doing so, it becomes easy to reduce the dimensional variation of the cured product. The lower limit is not particularly limited, but is, for example, 0.5% or more.
　ところで、硬化物を得る場合に、樹脂組成物を構成する硬化性樹脂の収縮を加味した設計を行う必要があるが、設計通りの収縮が生じずに寸法ばらつきが生じることがある。本発明の樹脂組成物は、上述した無機粒子の添加により硬化性樹脂の量が相対的に減少しているため、樹脂組成物の収縮の影響が小さくなりやすい。そのため、本発明の樹脂組成物を硬化して得られる硬化物は、寸法ばらつきが小さくなりやすい。 By the way, when obtaining a cured product, it is necessary to design in consideration of the shrinkage of the curable resin constituting the resin composition, but the shrinkage as designed may not occur and the dimensional variation may occur. In the resin composition of the present invention, since the amount of the curable resin is relatively reduced by the addition of the above-mentioned inorganic particles, the influence of shrinkage of the resin composition tends to be small. Therefore, the cured product obtained by curing the resin composition of the present invention tends to have small dimensional variation.
　次に、本発明の立体造形物の製造方法の一例を説明する。なお、樹脂組成物は既述の通りであり、ここでは説明を省略する。 Next, an example of the method for manufacturing the three-dimensional model of the present invention will be described. The resin composition is as described above, and description thereof will be omitted here.
　はじめに、未硬化の樹脂組成物からなる未硬化物層を準備する。より詳細には、未硬化の樹脂組成物を満たした槽内に造形用ステージを設ける。このとき、造形用ステージの造形面が未硬化の樹脂組成物の表面から所望の深さとなるように位置させる。未硬化物層は、例えば、液状又はペースト状である。 First, prepare an uncured material layer made of an uncured resin composition. More specifically, a modeling stage is provided in a tank filled with an uncured resin composition. At this time, the modeling surface of the modeling stage is positioned so as to have a desired depth from the surface of the uncured resin composition. The uncured material layer is, for example, liquid or paste-like.
　次に、未硬化物層に選択的に光線を照射して所定のパターンを有する硬化物層を形成する。硬化物層は造形面上に形成される。 Next, the uncured material layer is selectively irradiated with light rays to form a cured product layer having a predetermined pattern. The cured product layer is formed on the molding surface.
　次に、硬化物層上に新たな未硬化物層を形成する。すなわち、硬化物層上に未硬化の樹脂組成物を再び導入する。例えば、造形用ステージを１層分移動させることにより、硬化物層上に未硬化の樹脂組成物を導入することができる。 Next, a new uncured material layer is formed on the cured product layer. That is, the uncured resin composition is introduced again onto the cured product layer. For example, the uncured resin composition can be introduced onto the cured product layer by moving the modeling stage by one layer.
　次に、光線を照射して、硬化物層と連続した所定パターンを有する新たな硬化物層を形成する。 Next, a new cured product layer having a predetermined pattern continuous with the cured product layer is formed by irradiating with light rays.
　以上の操作を所定の立体造形物が得られるまで繰り返す。これにより硬化物層が積層され、所望の立体造形物を得ることができる。 Repeat the above operation until a predetermined three-dimensional model is obtained. As a result, the cured product layers are laminated, and a desired three-dimensional model can be obtained.
　このように、本発明の樹脂組成物は、含有する無機粒子の波長４０５ｎｍにおける光透過率が１０％以上であり、特に紫外光線に対する光透過性に優れている。そのため、未硬化の樹脂組成物の深さ方向に紫外光線が十分に照射されやすく、紫外光線を照射した際の硬化性に優れる。また、得られる硬化物は、無機粒子と硬化後の硬化性樹脂の屈折率ｎｄの差が±０．１以内であることから、硬化性樹脂中に分散した無機粒子が目立ちにくく、透明性に優れている。例えば、硬化物の波長６００ｎｍにおける光透過率Ｔ６００を、３０％以上、４０％以上、５０％以上、６０％以上、７０％以上、特に７５％以上とすることができる。また、硬化物の波長５００ｎｍにおける光透過率Ｔ５００を、２０％以上、３０％以上、特に４０％以上とすることができる。 As described above, the resin composition of the present invention has a light transmittance of 10% or more at a wavelength of 405 nm of the contained inorganic particles, and is particularly excellent in light transmittance to ultraviolet rays. Therefore, the uncured resin composition is easily sufficiently irradiated with ultraviolet rays in the depth direction, and is excellent in curability when irradiated with ultraviolet rays. Further, in the obtained cured product, the difference in the refractive index nd between the inorganic particles and the cured resin after curing is within ± 0.1, so that the inorganic particles dispersed in the curable resin are inconspicuous and become transparent. Are better. For example, the light transmittance T600 of the cured product at a wavelength of 600 nm can be 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, and particularly 75% or more. Further, the light transmittance T500 of the cured product at a wavelength of 500 nm can be 20% or more, 30% or more, particularly 40% or more.
　本発明の樹脂組成物は、例えば、立体造形物を製造する際に用いられる立体造形物用樹脂組成物や、歯科用樹脂組成物として好適に用いることができる。歯科用樹脂組成物として、例えば、歯科用コンポジットレジン、歯科用ボンディング材、支台築造材、レジンセメント、グラスアイオノマーセメント、レジン強化型グラスアイオノマーセメント、ＣＡＤ／ＣＡＭ用レジンブロック等に用いることができる。また、本発明の樹脂組成物は、例えば、光学部材用樹脂組成物等としても好適に用いることができる。 The resin composition of the present invention can be suitably used, for example, as a resin composition for a three-dimensional model used when producing a three-dimensional model or a dental resin composition. As the dental resin composition, for example, it can be used for dental composite resin, dental bonding material, abutment construction material, resin cement, glass ionomer cement, resin reinforced glass ionomer cement, resin block for CAD / CAM, and the like. .. Further, the resin composition of the present invention can also be suitably used as, for example, a resin composition for an optical member.
　以下、実施例に基づいて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
　表１、３は本発明の実施例（Ｎｏ．１～４、７～９）、及び比較例（Ｎｏ．５、６）を示している。また、表２は無機粒子として用いるガラスの組成を示している。 Tables 1 and 3 show examples (No. 1 to 4, 7 to 9) and comparative examples (No. 5 and 6) of the present invention. Table 2 shows the composition of glass used as inorganic particles.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（第１の実施例）
　実施例（Ｎｏ．１～４）及び比較例（Ｎｏ．５、６）は以下のように作製した。はじめに、表２に示す組成となるよう原料を調合し、ガラスＡ、Ｂ、Ｃを作製した。ガラスＡ、Ｂ、Ｃを用いて平均粒子径５μｍのガラスビーズＡ、Ｂ、Ｃを作製し、これらを無機粒子とした。硬化性樹脂にはアクリル樹脂Ｄ、Ｅを用いた。次に、表１に示す割合で、硬化性樹脂に無機粒子を添加し、３本ローラーにより混練を行い、均質に無機粒子を分散させた未硬化の樹脂組成物を得た。この樹脂組成物をテフロン（登録商標）製３０ｍｍ型枠に流し入れ、未硬化の樹脂組成物からなる層を作製した。 (First Example)
Examples (No. 1 to 4) and Comparative Examples (No. 5 and 6) were prepared as follows. First, the raw materials were mixed so as to have the composition shown in Table 2, and glasses A, B, and C were prepared. Glass beads A, B, and C having an average particle diameter of 5 μm were prepared using glasses A, B, and C, and these were used as inorganic particles. Acrylic resins D and E were used as the curable resin. Next, the inorganic particles were added to the curable resin at the ratios shown in Table 1 and kneaded with three rollers to obtain an uncured resin composition in which the inorganic particles were uniformly dispersed. This resin composition was poured into a 30 mm mold made of Teflon (registered trademark) to prepare a layer made of an uncured resin composition.
　得られた未硬化物層に対して、スポット光源（ＬＣ８、浜松ホトニクス製）を用いて、４５００ｍＷ／ｃｍ２の紫外光線をφ５ｍｍの領域に５秒間照射し、板状の硬化物（すなわち、板状の立体造形物）を造形面上に形成した。このとき、形成された立体造形物の硬化厚みを測定した。また、厚み１ｍｍの板状の立体造形物を作製し、表面を鏡面研磨した後、分光光度計（島津製作所製ＵＶ－３１００）を用いて、厚み１ｍｍでの波長６００ｎｍにおける全光線透過率を測定した。 The obtained uncured material layer was irradiated with an ultraviolet ray of 4500 mW / cm 2 for 5 seconds using a spot light source (LC8, manufactured by Hamamatsu Photonics) in a region of φ5 mm to obtain a plate-shaped cured product (that is, a plate). A three-dimensional model) was formed on the modeling surface. At this time, the cured thickness of the formed three-dimensional model was measured. In addition, a plate-shaped three-dimensional object with a thickness of 1 mm is prepared, the surface is mirror-polished, and then the total light transmittance at a wavelength of 600 nm at a thickness of 1 mm is measured using a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation). did.
　硬化性樹脂の屈折率（ｎｄｒｓ、ｎｄｒｅ）及びガラスの屈折率（ｎｄｇ）、アッべ数（νｄｇ、νｒｓ）は、精密屈折率計（ＫＰＲ－２０００、島津デバイス製）により測定した。 The refractive index (nd rs , nd re ) of the curable resin, the refractive index (nd g ) of the glass, and the number of abbreviations (νd g , ν rs ) are measured by a precision refractive index meter (KPR-2000, manufactured by Shimadzu Device). did.
　無機粒子の波長４０５ｎｍ、３６５ｎｍにおける光透過率は、無機粒子と同じ組成を有する厚み１ｍｍ±０．０１ｍｍの板状試料を作製し、表面を鏡面研磨した後、分光光度計（島津製作所製ＵＶ－３１００）を用いて測定した。 For the light transmittance of the inorganic particles at wavelengths of 405 nm and 365 nm, a plate-shaped sample having the same composition as the inorganic particles and having a thickness of 1 mm ± 0.01 mm was prepared, the surface was mirror-polished, and then a spectrophotometer (UV-Shimazu Seisakusho). It was measured using 3100).
　表１から明らかなように、実施例（Ｎｏ．１～４）の立体造形物は、波長６００ｎｍにおける全光線透過率Ｔ６００が６７％以上となった。一方、比較例（Ｎｏ．５、６）の立体造形物は、Ｔ６００が５５％以下、硬化厚みが０．１７ｍｍ以下と低くなった。特にＮｏ．６の試料はガラスが着色しており、硬化厚みが０．１２ｍｍと小さく、かつＴ６００の値も低くなった。 As is clear from Table 1, the three-dimensional model of Examples (No. 1 to 4) had a total light transmittance T600 of 67% or more at a wavelength of 600 nm. On the other hand, in the three-dimensional model of Comparative Examples (No. 5 and 6), T600 was as low as 55% or less and the cured thickness was as low as 0.17 mm or less. Especially No. In the sample No. 6, the glass was colored, the cured thickness was as small as 0.12 mm, and the value of T600 was also low.
　（第２の実施例）
　実施例７～９は以下のように作製した。はじめに、表２に示す組成となるよう原料を調合し、ガラスＡを作製した。ガラスＡを用いて平均粒子径５μｍのガラスビーズＡを作製した。ガラスビーズＡを１０％希塩酸に浸漬させ、表３に示す時間、酸処理を行った。酸処理後のガラスビーズＡ´を無機粒子とした。硬化性樹脂にはアクリル樹脂Ｅを用いた。次に、表３に示す割合で、硬化性樹脂に無機粒子を添加し、３本ローラーにより混練を行い、均質に無機粒子を分散させた未硬化の樹脂組成物を得た。 (Second Example)
Examples 7 to 9 were prepared as follows. First, the raw materials were mixed so as to have the composition shown in Table 2, and glass A was prepared. Glass beads A having an average particle diameter of 5 μm were prepared using glass A. The glass beads A were immersed in 10% dilute hydrochloric acid and subjected to acid treatment for the time shown in Table 3. The glass beads A'after the acid treatment were used as inorganic particles. Acrylic resin E was used as the curable resin. Next, the inorganic particles were added to the curable resin at the ratios shown in Table 3 and kneaded with three rollers to obtain an uncured resin composition in which the inorganic particles were uniformly dispersed.
　得られた未硬化の樹脂組成物に対して、スポット光源（ＬＣ８、浜松ホトニクス製）を用いて、４５００ｍＷ／ｃｍ２の紫外光線をφ５ｍｍの領域に照射し、厚さ２．５ｍｍの硬化物を得た。得られた硬化物の表面を鏡面研磨した後、分光光度計（Ｖ－６７０、日本分光社製分光光度計）を用いて、厚み２．５ｍｍでの波長６００ｎｍにおける全光線透過率Ｔ６００、及び波長５００ｎｍにおける全光線透過率Ｔ５００を測定した。結果を表３及び図１に示す。 The obtained uncured resin composition was irradiated with an ultraviolet ray of 4500 mW / cm 2 using a spot light source (LC8, manufactured by Hamamatsu Photonics) in a region of φ5 mm to obtain a cured product having a thickness of 2.5 mm. Obtained. After mirror-polishing the surface of the obtained cured product, using a spectrophotometer (V-670, spectrophotometer manufactured by JASCO Corporation), the total light transmittance T600 at a wavelength of 600 nm at a thickness of 2.5 mm and the wavelength. The total light transmittance T500 at 500 nm was measured. The results are shown in Table 3 and FIG.
　実施例９は、ガラスビーズＡを酸処理しないことを除いて、実施例７、８と同様に試料を作製した。 In Example 9, a sample was prepared in the same manner as in Examples 7 and 8 except that the glass beads A were not treated with acid.
　表３及び図１に示すように、酸処理を行った実施例（Ｎｏ．７、８）の硬化物は、波長６００ｎｍにおける全光線透過率Ｔ６００、及び波長５００ｎｍにおける全光線透過率Ｔ５００が、酸処理を行わなかった実施例（Ｎｏ．９）の硬化物に比べて高くなった。 As shown in Table 3 and FIG. 1, the cured product of Examples (No. 7 and 8) subjected to acid treatment has an acid total light transmittance T600 at a wavelength of 600 nm and a total light transmittance T500 at a wavelength of 500 nm. It was higher than that of the cured product of Example (No. 9) which was not treated.

Claims (16)

  1. 　硬化性樹脂と無機粒子とを含む樹脂組成物であって、
    　前記無機粒子と硬化後の前記硬化性樹脂の屈折率ｎｄの差が±０．１以内であり、
    　前記無機粒子の波長４０５ｎｍにおける光透過率が１０％以上である、樹脂組成物。     A resin composition containing a curable resin and inorganic particles.
    The difference between the refractive index nd of the inorganic particles and the cured resin after curing is within ± 0.1.
    A resin composition having a light transmittance of 10% or more at a wavelength of 405 nm of the inorganic particles.
  2. 　前記無機粒子の波長４０５ｎｍにおける光透過率が５０％以上である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the light transmittance of the inorganic particles at a wavelength of 405 nm is 50% or more.
  3. 　前記無機粒子の波長３６５ｎｍにおける光透過率が５％以上である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the light transmittance of the inorganic particles at a wavelength of 365 nm is 5% or more.
  4. 　前記無機粒子がガラスである、請求項１～３のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the inorganic particles are glass.
  5. 　前記ガラスが、質量％で、ＳｉＯ２　３０～７５％、Ａｌ２Ｏ３　１～２０％、Ｂ２Ｏ３　０～３０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　０～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ　０．１～２０％を含有する、請求項４に記載の樹脂組成物。 The glass, in mass%, SiO 2 30 ~ 75% , Al 2 O 3 1 ~ 20%, B 2 O 3 0 ~ 30%, Li 2 O + Na 2 O + K 2 O 0 ~ 20%, MgO + CaO + SrO + BaO + ZnO 0.1 ~ The resin composition according to claim 4, which contains 20%.
  6. 　前記ガラスが、質量％で、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｂ２Ｏ３を４０％以上含有する、請求項４又は５に記載の樹脂組成物。 The resin composition according to claim 4 or 5, wherein the glass contains 40% or more of SiO 2 + Al 2 O 3 + B 2 O 3 in mass%.
  7. 　前記無機粒子の平均粒子径が、０．２～５０μｍである、請求項１～６のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 6, wherein the average particle size of the inorganic particles is 0.2 to 50 μm.
  8. 　体積％で、前記無機粒子を１～９０％含有する、請求項１～７のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, which contains 1 to 90% of the inorganic particles in a volume%.
  9. 　前記無機粒子のヤング率が、５０ＧＰａ以上である、請求項１～８のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 8, wherein the Young's modulus of the inorganic particles is 50 GPa or more.
  10. 　前記無機粒子の熱膨張係数が、３０～１００℃において６０×１０－７／℃以下である、請求項１～９のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 9, wherein the coefficient of thermal expansion of the inorganic particles is 60 × 10 -7 / ° C or less at 30 to 100 ° C.
  11. 　前記無機粒子の波長２５０～４４０ｎｍにおける光反射率が１０％以下である、請求項１～１０のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 10, wherein the light reflectance of the inorganic particles at a wavelength of 250 to 440 nm is 10% or less.
  12. 　前記無機粒子の表面に緩衝層を有する、請求項１～１１のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 11, which has a buffer layer on the surface of the inorganic particles.
  13. 　前記緩衝層の屈折率ｎｄが、前記無機粒子の屈折率ｎｄより低い、請求項１２に記載の樹脂組成物。 The resin composition according to claim 12, wherein the refractive index nd of the buffer layer is lower than the refractive index nd of the inorganic particles.
  14. 　請求項１～１３のいずれか一項に記載の樹脂組成物を用いた、立体造形物用樹脂組成物。 A resin composition for a three-dimensional model using the resin composition according to any one of claims 1 to 13.
  15. 　請求項１～１３のいずれか一項に記載の樹脂組成物を用いた、歯科用樹脂組成物。 A dental resin composition using the resin composition according to any one of claims 1 to 13.
  16. 　未硬化の樹脂組成物からなる未硬化物層に選択的に光線を照射して所定のパターンを有する硬化物層を形成し、前記硬化物層上に新たな未硬化物層を形成した後に前記光線を照射して前記硬化物層と連続した所定パターンを有する新たな硬化物層を形成し、所定の立体造形物が得られるまで前記硬化物層の積層を繰り返す立体造形物の製造方法であって、
    　樹脂組成物として、請求項１～１３のいずれか一項に記載の樹脂組成物を使用する、立体造形物の製造方法。
          The uncured material layer made of the uncured resin composition is selectively irradiated with light rays to form a cured product layer having a predetermined pattern, and after forming a new uncured material layer on the cured product layer, the above-mentioned It is a method for producing a three-dimensional model by irradiating light rays to form a new cured product layer having a predetermined pattern continuous with the cured product layer and repeating the lamination of the cured product layer until a predetermined three-dimensional model is obtained. hand,
    A method for producing a three-dimensional model using the resin composition according to any one of claims 1 to 13 as the resin composition.
PCT/JP2020/047873 2019-12-25 2020-12-22 Resin composition, resin composition for three-dimensional models, and dental resin composition WO2021132217A1 (en)

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JP2006111823A (en) * 2004-10-18 2006-04-27 Nitto Denko Corp Epoxy resin composition for sealing optical semiconductor element and optical semiconductor by using the same
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JP2017205303A (en) * 2016-05-18 2017-11-24 株式会社リコー Solid modeling material set, method of manufacturing solid model, apparatus for manufacturing solid model, and dental prosthesis
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* Cited by examiner, † Cited by third party
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JPH08259415A (en) * 1995-03-13 1996-10-08 Degussa Ag Polymerizable dental material
JP2000143430A (en) * 1998-10-27 2000-05-23 Carl Zeiss:Fa Barium-free x-ray-opaque dental glass and dental glass/ polymer composite material and use thereof
JP2006111823A (en) * 2004-10-18 2006-04-27 Nitto Denko Corp Epoxy resin composition for sealing optical semiconductor element and optical semiconductor by using the same
JP2010001496A (en) * 2009-10-05 2010-01-07 Nitto Denko Corp Epoxy resin composition for sealing optical semiconductor element, and optical semiconductor device
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JP2017205303A (en) * 2016-05-18 2017-11-24 株式会社リコー Solid modeling material set, method of manufacturing solid model, apparatus for manufacturing solid model, and dental prosthesis
JP2019202902A (en) * 2018-05-22 2019-11-28 日本電気硝子株式会社 Glass, glass filler, and resin mixture

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