JP6670478B2 - Three-dimensional modeling resin composition - Google Patents

Description

  The present invention relates to a three-dimensionally formed resin composition and a method for producing a three-dimensionally formed product using the same.

  Conventionally, a method of obtaining a three-dimensional structure by laminating resin materials and the like has been known. For example, various methods such as a stereolithography method, a powder sintering method, and a fused deposition modeling (FDM) method have been proposed and put to practical use.

  For example, the optical molding method is excellent in fine modeling and accurate size expression, and is widely used. This method is to create a three-dimensional object as follows. First, a modeling stage is provided in a tank filled with a liquid photocurable resin, and the photocurable resin on the modeling stage is irradiated with an ultraviolet laser to form a cured layer having a desired pattern. When one hardened layer is formed in this way, the molding stage is lowered by one layer, an unhardened resin is introduced onto the hardened layer, and similarly, the hardened layer is irradiated with an ultraviolet laser to the hardened resin. Stack a new hardened layer on top. By repeating this operation, a predetermined three-dimensional object is obtained. In the powder sintering method, a molding stage is provided in a tank filled with resin, metal, ceramic, and glass powders, and a laser of a semiconductor or the like is irradiated on the powder on the molding stage, and a desired pattern is formed by softening deformation. Create a cured layer.

JP-A-7-26060

  It has been pointed out that a three-dimensional molded article made of resin produced by an optical molding method or the like is fine and precise, but is inferior in mechanical strength and the like. Therefore, as proposed in Patent Document 1, it has been proposed to add an inorganic filler to a photocurable resin.

  However, when the inorganic filler particles are added, the presence of the inorganic filler particles makes it difficult for the photocurable resin to be sufficiently irradiated with ultraviolet rays, so that the curing speed of the photocurable resin is reduced, and the production efficiency of the three-dimensional structure is reduced. Is reduced.

  An object of the present invention is to provide a resin composition for three-dimensional modeling which has a high curing rate of a photocurable resin and is excellent in the production efficiency of a three-dimensional molded article.

  The three-dimensional structure resin composition of the present invention is a three-dimensional structure resin composition including a photocurable resin and inorganic filler particles, the refractive index nd of the inorganic filler particles is 1.57 or more, at a wavelength of 400 nm. The light transmittance is 1% or more.

  Since the inorganic filler particles in the resin composition for three-dimensional modeling of the present invention have a relatively high refractive index as described above, the refractive index difference from the photocurable resin can be increased. As a result, the degree of light reflection at the interface between the inorganic filler particles and the photocurable resin increases. In addition, since the light transmittance at a wavelength of 400 nm of the inorganic filler particles is 1% or more, the active energy rays are less likely to be excessively shielded by the inorganic filler particles. As described above, the entirety of the photocurable resin is appropriately irradiated with the active energy ray, the curing speed of the photocurable resin is increased, and the production efficiency of the three-dimensional structure is improved. Therefore, a large amount of the inorganic filler particles can be introduced into the curable resin, and a three-dimensional structure having high mechanical strength can be obtained. The “refractive index nd” is a value measured with respect to the d-line (587.6 nm) of a helium lamp.

  In the three-dimensional structure forming resin composition of the present invention, the inorganic filler particles preferably have a light reflectance at a wavelength of 400 nm of 5% or more.

  In the resin composition for three-dimensional modeling of the present invention, the inorganic filler particles are preferably glass beads.

  By appropriately selecting the composition of the glass beads, a high refractive index and a high light transmittance can be easily achieved. Further, the fluidity of the photocurable resin is hardly impaired. Therefore, by using glass beads as the inorganic filler particles, the effect of the present invention can be easily enjoyed. In the present invention, “glass beads” means glass particles formed into a sphere, but does not necessarily have to be a true sphere.

In stereolithography resin composition of the present invention, glass beads, by mass _percent, preferably contains TiO 2 0.1 to 50%.

Since TiO ₂ has a large effect of improving the refractive index, according to the above configuration, the refractive index of the glass beads can be increased.

In the three-dimensional structure forming resin composition of the present invention, the glass beads contain 1 to 80% by mass% of La ₂ O ₃ + Gd ₂ O ₃ + Ta ₂ O ₅ + Nb ₂ O ₅ + WO ₃ + Bi ₂ O ₃ + TeO _2. Is preferred. “La ₂ O ₃ + Gd ₂ O ₃ + Ta ₂ O ₅ + Nb ₂ O ₅ + WO ₃ + Bi ₂ O ₃ + TeO ₂ ” means the total amount of these components.

  With this configuration, the refractive index of the glass beads can be increased.

In the three-dimensional structure forming resin composition of the present invention, the content of glass beads is preferably not more than 50% by mass of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O ₅ . Note that “SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O ₅ ” means the total amount of these components.

Since SiO ₂ , Al ₂ O ₃ , B ₂ O _3, and P ₂ O ₅ are components that lower the refractive index, by controlling the content of these components as described above, glass having excellent light transmittance is obtained. Beads are easily obtained.

In stereolithography resin composition of the present invention, glass beads, by mass _percent, preferably contains _{Sb 2 O 3 + CeO 2 0.01~1} %. “Sb ₂ O ₃ + CeO ₂ ” means the total amount of these components.

By including Sb ₂ O ₃ and CeO ₂ in the above range, it is possible to suppress a decrease in light transmittance due to the Fe component.

  In the resin composition for three-dimensional modeling of the present invention, the average particle diameter D50 of the inorganic filler particles is preferably 0.1 to 300 µm.

  The resin composition for three-dimensional modeling of the present invention preferably contains 30 to 99% of a photocurable resin and 1 to 70% of inorganic filler particles by volume%.

  In the method for producing a three-dimensional structure according to the present invention, a liquid layer made of a resin composition is selectively irradiated with active energy rays to form a cured layer having a predetermined pattern, and a new liquid layer is formed on the cured layer. Forming a new cured layer having a predetermined pattern continuous with the cured layer by irradiating with an active energy ray, and repeating the lamination of the cured layer until a predetermined three-dimensional molded object is obtained. The present invention is characterized in that the above-mentioned resin composition for three-dimensional modeling is used as the resin composition.

  The resin composition for three-dimensional modeling of the present invention includes a photocurable resin and inorganic filler particles. It is preferable that the mixing ratio of the photocurable resin and the inorganic filler particles is 30% to 99% by volume, and that the inorganic filler particles be 1% to 70% by volume. More preferably, the photocurable resin is 35 to 95%, 40 to 90%, especially 45 to 85%, and the inorganic filler particles are 5 to 65%, 10 to 60%, especially 15 to 55%. If the proportion of the inorganic filler particles is too high, the surface area to be bonded to the resin is small and the mechanical strength is low. In addition, the viscosity of the photocurable resin becomes too high, which causes problems such as difficulty in forming a new liquid layer on the molding stage. If the proportion of the photocurable resin is too high, it becomes difficult to reflect the strength and hardness of the inorganic filler particles in the composite. In addition, since the content of the inorganic filler particles relatively decreases, the mechanical strength of the molded article decreases.

As the photocurable resin, various resins such as a polymerizable vinyl compound and an epoxy compound can be selected. Further, a monomer or oligomer of a monofunctional compound or a polyfunctional compound is used. These monofunctional compounds and polyfunctional compounds are not particularly limited.
For example, representative photocurable resins are listed below.

  Monofunctional compounds of polymerizable vinyl compounds include isobornyl acrylate, isobornyl methacrylate, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol Acrylate, vinylpyrrolidone, acrylamide, vinyl acetate, styrene and the like can be mentioned. Examples of the polyfunctional compound include trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6. -Hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, diallyl phthalate and the like. One or more of these monofunctional compounds and polyfunctional compounds can be used alone or in the form of a mixture.

  As the polymerization initiator of the vinyl compound, a photopolymerization initiator is used. Examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, acetophenone, benzophenone, xanthone, fluorenone, bezaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, and 3-methylacetophenone. , Michler's ketone and the like can be mentioned as typical examples, and these initiators can be used alone or in combination of two or more. If necessary, a sensitizer such as an amine compound can be used in combination. The amount of these polymerization initiators used is preferably 0.1 to 10% by mass based on the vinyl compound.

  Examples of the epoxy compound include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4. -Epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate and the like. When these epoxy compounds are used, an energy-active cation initiator such as triphenylsulfonium hexafluoroantimonate can be used.

  Further, a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, and the like may be added to the photocurable resin as needed.

  As the inorganic filler particles used in the present invention, for example, glass beads, glass powder, glass fiber, ceramic powder, ceramic fiber, and the like can be used alone or in combination.

  The inorganic filler particles have a refractive index nd of 1.57 or more, preferably 1.6 or more, 1.7 or more, 1.8 or more, particularly preferably 1.9 or more. If the refractive index nd is too low, the degree of light reflection at the interface between the inorganic filler particles and the photocurable resin becomes small, and it becomes difficult to irradiate the entire photocurable resin with active energy rays. The upper limit of the refractive index nd is not particularly limited, but is actually 2.5 or less. In addition, when inorganic filler particles made of a glass material such as glass beads are used, if the refractive index nd is too high, the glass tends to be unstable, so that it is 2.3 or less, especially 2.2 or less. Is preferred.

  The light transmittance of the inorganic filler particles at a wavelength of 400 nm is 1% or more, preferably 10% or more, 30% or more, 50% or more, 70% or more, particularly preferably 80% or more. If the light transmittance at a wavelength of 400 nm is too low, the active energy rays are likely to be shielded by the inorganic filler particles, and it becomes difficult to irradiate the active energy rays over the entire photocurable resin.

  The light reflectance of the inorganic filler particles at a wavelength of 400 nm is preferably 5% or more, 7% or more, particularly preferably 8% or more. If the light reflectance at a wavelength of 400 nm is too low, it is difficult to appropriately apply the active energy ray to the entire photocurable resin, and the curing speed of the photocurable resin tends to decrease.

The density of the inorganic filler particles, 3 g / cm ³ or more, 3.5 g / cm ³ or more, particularly 4g / cm ³ or more. If the density of the inorganic filler particles is too low, the refractive index nd tends to decrease. On the other hand, the upper limit is not particularly limited, but if the density of the inorganic filler particles is too large, the light transmittance at a wavelength of 400 nm tends to decrease, so that the upper limit is 8 g / cm ³ or less, particularly 7.5 g / cm ³ or less. Is preferred.

  As the inorganic filler particles, glass beads, rods having a columnar shape, a prismatic shape, or the like can be used alone or in combination. Compared to powdered glass produced by pulverization or the like, glass beads are excellent in fluidity because they are spherical. Therefore, there is a feature that an increase in the viscosity of the photocurable resin can be suppressed. In addition, if it is manufactured by a method such as fire polishing, a surface finish with a small surface roughness can be achieved, and the fluidity can be further improved.

  Regarding the particle size of the inorganic filler particles, the average particle size D50 is preferably 0.1 to 300 μm, particularly preferably 1 to 200 μm, and more preferably 3 to 100 μm. The maximum particle diameter of the inorganic filler particles is preferably 500 μm or less, particularly 300 μm or less, and the minimum particle diameter is preferably 0.1 μm or more, particularly preferably 0.5 μm or more. The smaller the particle size of the inorganic filler particles, the higher the filling ratio. However, the fluidity of the photocurable resin is reduced, and interfacial bubbles are difficult to be removed. On the other hand, as the particle size of the inorganic filler particles increases, the filling rate tends to decrease.

The specific surface area of the inorganic filler particles is preferably 0.1 to ² m ² / g, 0.25 to 1.5 m ² / g, and particularly preferably 0.5 to 1 m ² / g. If the specific surface area of the inorganic filler particles is too small, the fluidity of the resin composition will be reduced, and it will be difficult for interfacial bubbles to escape. On the other hand, if the specific surface area of the inorganic filler particles is too large, the packing ratio is reduced, and the adhesion strength to the photocurable resin is likely to be reduced.

The ratio (specific surface area / theoretical specific surface area) of the specific surface area of the inorganic filler particles to the theoretical specific surface area calculated by the following formula (1) is preferably 3 or less, 2.5 or less, and particularly preferably 2 or less. If the value of the specific surface area / theoretical specific surface area is too large, the unevenness of the surface of the inorganic filler particles becomes large, the light reflectance on the surface of the inorganic filler particles decreases, and the active energy rays are moderately spread over the entire photocurable resin. Irradiation becomes difficult.
Theoretical specific surface area (m ² / g) = 6 / (density (g / cm ³ ) × average particle diameter D50 (μm))

  The sedimentation speed of the inorganic filler particles in the photocurable resin is calculated by the following Stokes' formula.

ν _s = (D _p ² (ρ _p −ρ _f ) g) / 18η
ν _s : sedimentation velocity of inorganic filler particles D _p : particle diameter of inorganic filler particles ρ _p : density of inorganic filler particles ρ _f : density of photocurable resin g: gravitational acceleration η: viscosity of photocurable resin

  When the inorganic filler particles are likely to settle and separate in the photocurable resin, it becomes difficult to produce a uniform three-dimensional structure. As shown in the above formula, the sedimentation speed of the inorganic filler particles in the photocurable resin is proportional to the particle size and density of the inorganic filler particles. It is preferable to appropriately adjust the sedimentation speed. The sedimentation velocity of the inorganic filler particles calculated by the above equation is 1 m / h or less, 0.5 mm / h or less, 0.2 mm / h or less, from the viewpoint of suppressing sedimentation and separation in the photocurable resin. It is preferably 0.1 mm / h or less, particularly preferably 0.075 mm / h or less. On the other hand, if the sedimentation speed of the inorganic filler particles is too low, the dispersibility of the inorganic filler particles in the photocurable resin is deteriorated. h or more.

Hereinafter, the glass beads will be described in more detail. The composition of the glass beads is not limited as long as the above-mentioned optical constants are satisfied. For example _{SiO 2 -B 2 O 3 -R '} 2 O (R' is an 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 glass, SiO ₂ —R ′ ₂ O glass, SiO ₂ —R ′ ₂ O—RO glass, and the like can be used.

TiO ₂ is a component having a large effect of improving the refractive index. The content of TiO ₂ is preferably at least 0.1%, at least 1%, at least 5%, at least 10%, particularly at least 30% by mass. However, if the content of TiO ₂ is too large, the light transmittance tends to decrease, so the upper limit is preferably 50% or less, particularly preferably 45% or less. In particular, TiO ₂ tends to significantly reduce light transmittance by forming a complex with Fe ₂ O ₃ . Therefore, it is preferable that Fe ₂ O ₃ is 0.1% or less by mass%, and particularly substantially not contained. In addition, “substantially not contained” means not actively contained as a raw material, and does not exclude inclusion of unavoidable impurities.

La ₂ O ₃ , Gd ₂ O ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , Bi ₂ O ₃ and TeO ₂ are components for improving the refractive index. However, if the content is too large, the raw material cost tends to increase. Therefore, the content of La ₂ O ₃ + Gd ₂ O ₃ + Ta ₂ O ₅ + Nb ₂ O ₅ + WO ₃ + Bi ₂ O ₃ + TeO ₂ is preferably 1 to 80%, 10 to 70%, particularly preferably 20 to 60%.

  RO (R is an alkaline earth metal) is a component that works as a flux. The content of RO is preferably 0 to 70%, 1 to 60%, particularly preferably 5 to 55%. If the content of RO is too large, devitrification tends to occur, and vitrification tends to be difficult. The content of each alkaline earth metal oxide (MaO, CaO, SrO, BaO) is preferably 0 to 70%, 1 to 60%, and particularly preferably 5 to 55%. Since BaO has an effect of improving the refractive index, it is preferable to contain BaO in an amount of 10% or more, 20% or more, particularly 30% or more from the viewpoint of increasing the refractive index.

Since SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and P ₂ O ₅ are components that lower the refractive index, the content of these components is 50% or less, 40% or less, particularly 30% or less in total. Is preferred. In order to obtain glass beads having excellent devitrification resistance, the total content of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and P ₂ O ₅ is 1% or more, 5% or more, especially 10% or more is preferable.

Sb ₂ O ₃ and CeO ₂ have an effect of suppressing a decrease in light transmittance due to the Fe component. The content of Sb ₂ O ₃ + CeO ₂ is preferably 0.01 to 1%, particularly preferably 0.1 to 0.8%. If the content of Sb ₂ O ₃ + CeO ₂ is too small, it is difficult to obtain the above effects. On the other hand, if the content of Sb ₂ O ₃ + CeO ₂ is too large, on the other hand, the light transmittance tends to decrease or the glass beads are easily devitrified during molding. Incidentally, it is preferable that the content of each of the _Sb 2 _{O 3} and CeO ₂ are also within the above range.

Further, since Fe ₂ O ₃ , NiO, Cr ₂ O ₃ and CuO also cause a decrease in light transmittance, their content is 1% or less, 0.75% or less, especially 0.5% in mass%. % Is preferable.

The content of Na ₂ O, K ₂ O, and Li ₂ O is preferably 5% or less, 2.5% or less, and particularly preferably 1.0% or less in the total amount of mass%. If the ranges of these components are limited as described above, the evaporation of alkali components in the glass that occurs when the resin is cured can be suppressed. In addition, deterioration of chemical durability can be suppressed.

  For environmental reasons, the total content of fluorine, lead, antimony, arsenic, chlorine and sulfur is preferably 1% by mass or less, 0.5% by mass or less, particularly preferably 0.1% by mass or less.

  The surface of the inorganic filler particles such as glass beads is preferably treated with a silane coupling agent. By treating with a silane coupling agent, the bonding force between the inorganic filler particles and the photocurable resin can be increased, and it is possible to obtain a molded article having more excellent mechanical strength. Further, the affinity between the inorganic filler particles and the photocurable resin is improved, and the bubbles at the interface can be reduced. As the silane coupling agent, for example, amino silane, epoxy silane, acrylic silane and the like are preferable. The silane coupling agent may be appropriately selected depending on the photocurable resin to be used. For example, when a vinyl-based unsaturated compound is used as the photocurable resin, an acrylic silane-based silane coupling agent is most preferable, and an epoxy-based compound is used. When using, it is desirable to use an epoxysilane-based silane coupling agent.

Further, for the purpose of improving mechanical strength, oxide nanoparticles may be added to the inorganic filler or the photocurable resin at a ratio of 1% by volume or less based on the resin composition. As the oxide nanoparticles, ZrO ₂ , Al ₂ O _3, SiO ₂ or the like can be used.

  Next, a method for producing a three-dimensional structure according to the present invention using the above-described resin composition will be described. The resin composition is as described above, and the description is omitted here.

  First, one liquid layer made of the photocurable resin composition is prepared. For example, a molding stage is provided in a tank filled with a liquid photocurable resin composition, and the stage upper surface is positioned so as to have a desired depth from the liquid surface (for example, about 0.2 mm). In this way, a liquid layer having a thickness of about 0.1 to 0.2 mm can be prepared on the stage.

  Next, the liquid layer is irradiated with an active energy ray, for example, an ultraviolet laser, to make the photocurable resin effective, thereby forming a cured layer having a predetermined pattern. As the active energy ray, laser light such as visible light and infrared light can be used in addition to ultraviolet light.

  Subsequently, a new liquid layer made of a photocurable resin composition is prepared on the formed cured layer. For example, by lowering the modeling stage by one layer, a photocurable resin is introduced onto the cured layer, and a new liquid layer can be prepared.

  Thereafter, a new liquid layer prepared on the hardened layer is irradiated with active energy rays to form a new hardened layer continuous with the hardened layer.

  By repeating the above operation, the cured layers are continuously laminated to obtain a predetermined three-dimensional structure.

  Hereinafter, the resin composition for three-dimensional modeling according to the present invention will be described based on examples. Table 1 shows Examples (Samples Nos. 1 to 7) and Comparative Examples (Samples Nos. 8 to 10) of the present invention.

  First, isophorone diisocyanate, morpholine acrylamide and dibutyltin dilaurate were heated in an oil bath. A liquid in which methylhydroquinone was uniformly mixed and dissolved in glycerin monomethacrylate monoacrylate was added, stirred and mixed, and reacted. A 4-mol propylene oxide adduct of pentaerythritol (1 mol of propylene oxide added to each of the four hydroxyl groups of pentaerythritol) was added and reacted to produce a reaction product containing a urethane acrylate oligomer and morpholine acrylamide.

Morpholine acrylamide and dicyclopentanyl diacrylate were added to the obtained urethane acrylate oligomer and morpholine acrylamide. Further, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was added to obtain a colorless and transparent acrylic photocurable resin. This acrylic photocurable resin had a viscosity of 1 Pa · s, a density of 1.05 g / cm ^{3 and} a refractive index nd after curing of 1.5103.

Glass beads were produced as follows. Raw materials prepared so as to have the respective glass compositions shown in Table 1 were melted and then pulverized to produce powdered glass having an average particle diameter of 5 μm and a specific surface area of 0.9 m ² / g. This powder was applied to a frame of an oxygen burner and formed into a spherical shape. Thereafter, classification was performed to obtain glass beads having an average particle diameter of 5 μm. The density and refractive index of the obtained glass beads were measured. In addition, No. For 10, a zirconia powder having the same size as the glass powder was used.

  Subsequently, 70% by volume of an acrylic photocurable resin and 30% by volume of glass beads were mixed and kneaded with three rollers to obtain a paste resin in which the glass beads were uniformly dispersed. This paste-like resin was poured into a 30 mm square inner mold made of Teflon (registered trademark). Thereafter, light of 500 mW and a wavelength of 405 nm was irradiated for 10 seconds, and cured at 80 ° C. to form a cured resin layer. The curing speed (thickness of cured resin layer / 10 (μm / sec)) was calculated from the thickness of the cured resin layer. Table 1 shows the results.

  The refractive index nd of the photocurable resin and the glass beads is a value measured by a precision refractometer (KPR-2000 manufactured by Shimadzu Device).

  The density of the glass beads was measured by the Archimedes method.

  The light transmittance of the glass beads was measured as follows. After melting the raw materials prepared so as to have the respective glass compositions, the raw materials were molded into a plate shape, and both surfaces were mirror-polished so as to have a thickness of 1 mm, thereby preparing a measurement sample. The light transmittance of the obtained sample at a wavelength of 400 nm was measured using a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation).

The light reflectance of the glass beads is {(1−refractive index nd) ² / (1 + refractive index nd) ² } × 10
It was calculated by the equation of 0 (%).

  The sedimentation speed of the glass beads in the photocurable resin was calculated from the above Stokes' equation.

  As is evident from Table 1, No. 1 of the example was used. In Nos. 1 to 7, the curing speed was 18 μm / sec or more, whereas in Comparative Examples No. In Nos. 8 to 10, the cured thickness was 16 µm / sec or less, and the curing speed was inferior.

Claims (8)

A three-dimensional molding resin composition comprising a photocurable resin and inorganic filler particles, wherein the inorganic filler particles are glass beads, the refractive index nd is 1.57 or more, and the light transmittance at a wavelength of 400 nm is 1 der least% is, furthermore, stereolithography resin composition having an average particle diameter D50 is characterized 0.1~300μm der Rukoto.   The resin composition according to claim 1, wherein the inorganic filler particles have a light reflectance of 5% or more at a wavelength of 400 nm. It said glass beads, by _mass%, stereolithography resin composition according to claim 1 or 2, characterized in that it contains TiO 2 0.1 to 50%. Said glass beads, by _{mass%, La 2 O 3 + Gd} 2 O 3 + Ta 2 O 5 + Nb 2 O 5 + WO 3 + Bi 2 O 3 + TeO 2 claims 1 to 3, characterized in that it contains 1 to 80% The resin composition for three-dimensional modeling according to any one of the above. Said glass beads, in _{mass%, SiO 2 + Al 2 O} 3 + B 2 O 3 + P 2 O 5 50% stereolithographic resin according to any one of claims 1 to 4, wherein the less is Composition. It said glass beads, by _mass%, Sb ₂ O ₃ + stereolithographic resin composition according to any one of claims 1 to 5, characterized in that it contains CeO 2 0.01 to 1%. The three-dimensionally shaped resin composition according to any one of claims 1 to 6 , wherein the resin composition contains 30 to 99% of the photocurable resin and 1 to 70% of the inorganic filler particles by volume%. . A liquid layer composed of a resin composition is selectively irradiated with active energy rays to form a cured layer having a predetermined pattern, and the liquid layer is irradiated with active energy rays after forming a new liquid layer on the cured layer. Forming a new cured layer having a predetermined pattern continuous with the cured layer, a method of manufacturing a three-dimensional structure that repeats the lamination of the cured layer until a predetermined three-dimensional structure is obtained, as the resin composition, Item 10. A method for producing a three-dimensional structure, comprising using the resin composition for three-dimensional structure according to any one of Items 1 to 7 .