JP2016169355A - Resin composition for three-dimensional molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for three-dimensional molding that makes it possible to prepare a three-dimensional molding with higher mechanical strength compared to the conventional art.SOLUTION: A resin composition for three-dimensional molding comprises curable resin and inorganic filler particles, where a specific surface of each inorganic filler particle is at least twice a theoretical specific surface represented by the following formula: theoretical specific surface (m/g)=6/(density (g/cm)×average particle diameter D(μm)).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for three-dimensional modeling and a method for producing a three-dimensional model using the same.

  Conventionally, a method of obtaining a three-dimensional model by laminating resin materials or the like is known. For example, various methods such as an optical modeling method, a powder bed fusion sintering method, and a hot melt deposition (FDM) method have been proposed and put into practical use (see, for example, Patent Document 1).

  Among them, stereolithography is excellent in detailed modeling and accurate size expression, and is widely used. The stereolithography method is to produce a three-dimensional model 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 active energy ray such as an ultraviolet laser to form a cured layer having a desired pattern. When one cured layer is formed in this way, the modeling stage is lowered by one layer, an uncured photocurable resin is introduced onto the cured layer, and the active energy rays are irradiated onto the photocurable resin in the same manner. A new hardened layer is stacked on the hardened layer. By repeating this operation, a predetermined three-dimensional model is obtained. In the powder sintering method, a modeling stage is provided in a tank filled with resin, metal, ceramics, or glass powder, and the powder on the modeling stage is irradiated with active energy rays to harden a desired pattern by softening deformation. The layer is formed.

  The three-dimensional structure obtained by the above method is required to have high mechanical strength depending on the application. Patent Document 1 describes that the mechanical strength (mechanical rigidity) of the three-dimensional structure to be obtained is improved by including inorganic solid fine particles in the resin composition.

Japanese Patent Laid-Open No. 7-26060

  In recent years, the possibility of further expansion of applications of a three-dimensional model has been studied, and accordingly, further improvement in mechanical strength is required for the three-dimensional model.

  In view of the above, an object of the present invention is to provide a resin composition for three-dimensional modeling that can produce a three-dimensional molded product having higher mechanical strength than conventional ones.

  The three-dimensional modeling resin composition of the present invention is a three-dimensional modeling resin composition containing a curable resin and inorganic filler particles, and the specific surface area of the inorganic filler particles is represented by the following formula. It is characterized by being 2 times or more.

Theoretical specific surface area (m ² / g) = 6 / (Density (g / cm ³ ) × Average particle diameter D ₅₀ (μm))

Theoretical specific surface area is the specific surface area in the case where the inorganic filler particles is assumed to be spherical with a diameter of average particle diameter D _50. The resin composition for three-dimensional modeling of the present invention is characterized in that the specific surface area of the inorganic filler particles is as large as twice or more than the theoretical specific surface area, and the surface irregularities are large. For this reason, the anchor effect at the interface between the resin and the inorganic filler particles is increased and the two are firmly bonded, and the mechanical strength of the resulting three-dimensional structure is increased.

In the three-dimensional modeling resin composition of the present invention, the specific surface area of the inorganic filler particles is preferably 0.1 to ⁵ m ² / g or less.

In the three-dimensional modeling resin composition of the present invention, the average particle diameter D50 of the inorganic filler particles is preferably 1 to ₅₀₀ μm.

  In the three-dimensional modeling resin composition of the present invention, the inorganic filler particles are preferably made of glass or crystallized glass. Glass or crystallized glass is preferable because it has excellent processability and can easily form surface irregularities.

  In the three-dimensional modeling resin composition of the present invention, the surface of the inorganic filler particles is preferably subjected to a surface roughening treatment after being subjected to flame polishing. In this way, it is possible to easily obtain inorganic filler particles having a specific surface area and a theoretical specific surface area that satisfy the above-mentioned relationship and that has a relatively small specific surface area.

In the resin composition for three-dimensional modeling of the present invention, the liquid phase viscosity log η of the inorganic filler particles is preferably 1.0 or less. If it does in this way, it becomes possible to precipitate a crystal | crystallization simultaneously with shaping | molding by selecting a shaping | molding method suitably.

In the resin composition for three-dimensional modeling of the present invention, the density of the inorganic filler particles is preferably 2.4 to 7 g / cm ³ .

  In the three-dimensional modeling resin composition of the present invention, the curable resin is preferably a photocurable resin or a thermosetting resin.

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

  In the method for producing a three-dimensional structure according to the present invention, 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 a new liquid layer is formed on the cured layer. A manufacturing method of a three-dimensional structure that repeats lamination of the hardened layer until a predetermined three-dimensional structure is obtained by forming a new hardened layer having a predetermined pattern continuous with the hardened layer by irradiation with active energy rays Then, the resin composition for three-dimensional modeling is used as the resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for three-dimensional modeling which can produce the three-dimensional molded item whose mechanical strength is higher than before can be provided.

  The three-dimensional modeling resin composition of the present invention contains a curable resin and inorganic filler particles. Each content ratio is volume%, and is preferably 30 to 99% of the curable resin and 1 to 70% of the inorganic filler particles. More preferably, the curable resin is 35 to 95%, 40 to 90%, particularly 45 to 85%, and the inorganic filler particles are 5 to 65%, 10 to 60%, particularly 15 to 55%. If the content of the inorganic filler particles is too small, it is difficult to obtain the effect of improving the mechanical strength of the three-dimensional structure to be obtained. On the other hand, when the content of the inorganic filler particles is too large, the contact area with the curable resin in each inorganic filler particle tends to be small, and the mechanical strength of the resulting three-dimensional structure tends to be low. Further, in the case of the optical modeling method, the viscosity of the resin composition becomes too high, and problems such as difficulty in forming a new liquid layer on the modeling stage are likely to occur.

  The curable resin used in the present invention may be either a photocurable resin or a thermosetting resin, and can be appropriately selected depending on the modeling method employed. For example, when using an optical modeling method, a liquid photocurable resin may be selected, and when a powder sintering method is used, a powdery thermosetting resin may be selected.

  As the photocurable resin, various resins such as a polymerizable vinyl compound and an epoxy compound can be selected. Monofunctional or polyfunctional compound monomers or oligomers are also used. These monofunctional compounds and polyfunctional compounds are not particularly limited. For example, typical examples of the photocurable resin are listed below.

  Examples of the monofunctional compound of the polymerizable vinyl compound include isobornyl acrylate, isobornyl methacrylate, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol Examples include acrylate, vinyl pyrrolidone, acrylamide, vinyl acetate, and styrene. 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, 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 a polymerization initiator for the vinyl compound, a photopolymerization initiator is used. As the photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler's ketone and the like can be mentioned as typical ones, 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. It is preferable that the usage-amount of these polymerization initiators is 0.1-10 mass% with respect to a vinyl type compound, respectively.

  Examples of the epoxy compound include 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. When using these epoxy compounds, an energy active cationic initiator such as triphenylsulfonium hexafluoroantimonate can be used.

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

  The specific surface area of the inorganic filler particles is at least twice the theoretical specific surface area represented by the following formula, preferably at least 2.5 times, particularly preferably at least 3 times. In this way, since the irregularities on the surface of the inorganic filler particles are increased, the anchor effect at the interface between the resin and the inorganic filler particles is increased and the two are firmly bonded, and the mechanical strength of the resulting three-dimensional structure is obtained. Can be increased.

Theoretical specific surface area (m ² / g) = 6 / (Density (g / cm ³ ) × Average particle diameter D ₅₀ (μm))

  The inorganic filler particles satisfying the above-mentioned relationship between the specific surface area and the theoretical specific surface area are: (1) a method in which the inorganic filler particles collide with each other by vibration mixing to form irregularities on the surface; (2) inorganic A method of forming irregularities on the surface by etching the surface of the filler particles with an acidic solution or the like, (3) crystallizing the inorganic filler particles made of glass, and projecting the crystals from the surface of the inorganic filler particles, And a method of forming irregularities.

  In addition, if the specific surface area of the inorganic filler particles is too large (for example, a crushed shape), there is a tendency that problems as described later occur. Therefore, after reducing the surface roughness of the inorganic filler particles by a method such as flame polishing (fire polishing) so as to reduce the specific surface area of the inorganic filler particles, or after forming the inorganic filler particles into a substantially spherical shape, It is preferable to perform the steps (1) to (3). Alternatively, it is preferable to form the molten glass directly into a substantially spherical shape and precipitate the crystals at the same time.

The specific surface area of the inorganic filler particles is preferably 0.1 to ⁵ m ² / g, 0.5 to ⁴ m ² / g, and particularly preferably 0.75 to ³ m ² / g. If the specific surface area of the inorganic filler particles is too small, the particle diameter tends to increase, and the fluidity of the resin composition tends to decrease. On the other hand, if the specific surface area of the inorganic filler particles is too large, the fluidity of the curable resin tends to be lowered, or the interfacial foam tends to be difficult to escape. Moreover, the mechanical strength of the obtained three-dimensional molded item tends to be lowered.

The average particle diameter D ₅₀ of the inorganic filler particles is preferably 1 to ₅₀₀ μm, 1.5 to 100 μm, 2 to ₅₀ μm, and particularly preferably 2.5 to 20 μm. The mean particle diameter D ₅₀ of the inorganic filler particles can be enhanced more filling factor decreases, the fluidity is lowered curable resin, surfactant foam is less likely to escape. On the other hand, when the average particle diameter D ₅₀ of the inorganic filler particles are too large, the filling rate tends to decrease.

In the present invention, the average particle diameter D ₅₀ represents the 50% volume cumulative diameter of the median diameter of the primary particles refers to a value measured by a laser diffraction type particle size distribution measuring apparatus.

  The material of the inorganic filler particles is not particularly limited, and glass, crystallized glass, metal, ceramics and the like can be used. Among these, glass or crystallized glass is preferable because it is excellent in processability and can easily form surface irregularities.

The density of the inorganic filler particles is preferably 2.4 to 7 g / cm ³ , 2.5 to 6 g / cm ³ , and particularly preferably 2.6 to 5 g / cm ³ . If the density of the inorganic filler particles is too low, the softening point tends to increase, and it becomes difficult to reduce the surface roughness by flaming polishing or the like, or to process such as spheroidization. On the other hand, if the density of the inorganic filler particles is too large, the inorganic filler particles are likely to settle and separate in the resin composition when the optical modeling method is applied.

As the glass or crystallized glass constituting the inorganic filler particles, for example, SiO ₂ —B ₂ O ₃ —R ′ ₂ O (R ′ is an alkali metal element) glass, SiO ₂ —Al ₂ O ₃ —RO (R Is an alkaline earth metal element) glass, SiO ₂ —Al ₂ O ₃ —R ′ ₂ O—RO glass, SiO ₂ —Al ₂ O ₃ —B ₂ O ₃ —R ′ ₂ O 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.

  In addition, a solid feeling can be given to a three-dimensional molded item obtained by using a high-density thing as an inorganic filler particle. From the viewpoint of increasing the density of the inorganic filler particles, the glass composition preferably contains an element having a relatively large atomic weight such as Ba, La, Gd, Ta, Nb, W, Bi, and Te. For example, it is preferable to regulate the content of these oxides as follows.

  The content of BaO is 1% or more, 10% or more, 20% or more, particularly 30% or more in mass%. When there is too much content of BaO, it will become easy to devitrify and it will become difficult to vitrify, Therefore 60% or less, Especially 50% or less are preferable.

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 mass%, preferably 1% or more, 10% or more, and particularly preferably 20% or more. However, if the total amount of these components is too large, the raw material cost tends to increase, so 80% or less, 70% or less, particularly 60% or less is preferable.

In addition, from the viewpoint of the design properties of the three-dimensional structure, when it is desired to increase the refractive index of the inorganic filler particles, it is preferable to contain TiO ₂ having a high effect of improving the refractive index. The content of TiO ₂ is preferably 0.1% or more, 1% or more, 5% or more, 10% or more, and particularly preferably 30% or more in mass%. However, if the content of TiO ₂ is too large, the light transmittance may be lowered and the designability may be impaired. Therefore, the upper limit is preferably 50% or less, particularly 45% or less. In particular, TiO ₂ tends to significantly reduce the 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, particularly not substantially contained by mass%. In addition, “substantially not containing” means not actively containing as a raw material, and does not exclude the inclusion of inevitable impurities.

Since SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and P ₂ O ₅ are components that lower the density, when obtaining a high-density three-dimensional object, the content of these components is 50% in total. Hereinafter, 40% or less, particularly 30% or less is preferable. From the viewpoint of obtaining inorganic filler particles having excellent devitrification resistance, the total amount of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and P ₂ O ₅ is 1% or more, 5% or more, particularly 10 % Or more may be contained.

Sb ₂ O ₃ and CeO ₂ have an effect of suppressing a decrease in light transmittance caused by 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%. When Sb ₂ O ₃ + CeO ₂ content is too small, the effect is difficult to obtain. On the other hand, if the content of Sb ₂ O ₃ + CeO ₂ is too large, the light transmittance tends to decrease, or the glass tends to devitrify 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 NiO, Cr ₂ O ₃ and CuO also cause a decrease in light transmittance, the total content thereof is 1% or less, 0.75% or less, particularly 0.5% or less in terms of the total mass. Is preferred.

The content of Na ₂ O, K ₂ O and Li ₂ O is 5% or less, 2.5% or less, and particularly preferably 1% or less in terms of the total mass. If the range of these components is regulated as described above, evaporation of the alkaline component during resin curing can be suppressed. Moreover, 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, and particularly preferably 0.1% by mass or less.

  The liquid phase viscosity log η of the inorganic filler particles is preferably 1.0 or less, 0.9 or less, and particularly preferably 0.8 or less. When the liquid phase viscosity log η of the inorganic filler particles satisfies this range, it becomes easy to form a substantially spherical shape. Moreover, it becomes easy to precipitate a crystal | crystallization simultaneously with shaping | molding.

  The surface of the inorganic filler particles is preferably treated with a silane coupling agent. By treating with a silane coupling agent, it is possible to increase the bonding strength between the inorganic filler particles and the curable resin, and to obtain a three-dimensionally shaped article with better mechanical strength. Furthermore, the familiarity between the inorganic filler particles and the curable resin is improved, and the interface foam can be reduced. As the silane coupling agent, for example, aminosilane, epoxy silane, acrylic silane and the like are preferable. The silane coupling agent may be appropriately selected according to the curable resin to be used. For example, when a vinyl unsaturated compound is used as the photocurable resin, an acrylic silane silane coupling agent or an epoxy compound is used. It is preferable to use an epoxy silane-based silane coupling agent.

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

  Next, an example of the manufacturing method of the three-dimensional molded item of this invention is demonstrated. Specifically, the manufacturing method of the three-dimensional molded item using the resin composition containing photocurable resin is demonstrated. The resin composition is as described above, and the description is omitted here.

  First, one liquid layer made of a photocurable resin composition is prepared. For example, a modeling 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 (for example, about 0.2 mm) from the liquid surface. By doing in this way, a liquid layer can be prepared on a stage.

  Next, the liquid layer is irradiated with an active energy ray, for example, an ultraviolet laser to cure the photocurable resin, 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.

  Then, the new liquid layer which consists 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 can be introduced onto the cured layer to prepare a new liquid layer.

  Thereafter, an active energy ray is irradiated to a new liquid layer prepared on the cured layer to form a new cured layer continuous with the cured layer.

  By repeating the above operation, the hardened layer is continuously laminated to obtain a predetermined three-dimensional object.

  Hereinafter, the resin composition for three-dimensional modeling of the present invention will be described based on examples. Table 1 shows Examples 1 and 2 of the present invention and comparative examples.

(Production of photocurable resin)
First, isophorone diisocyanate, morpholine acrylamide and dibutyltin dilaurate were heated in an oil bath. Next, a liquid in which methylhydroquinone was uniformly mixed and dissolved in glycerin monomethacrylate monoacrylate was added and stirred and mixed to react. Further, a reaction product containing a urethane acrylate oligomer and morpholine acrylamide is obtained by adding and reacting a propylene oxide 4 mol adduct of pentaerythritol (1 mol of propylene oxide added to 4 hydroxyl groups of pentaerythritol). Produced.

  Morpholine acrylamide and dicyclopentanyl diacrylate were added to the obtained reaction product. 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 and a refractive index nd after curing of 1.5103.

(Preparation of inorganic filler particles)
As a glass composition, TiO ₂ 37%, BaO 46%, Al ₂ O ₃ 3%, SiO ₂ 9%, and CaO 5% were melted uniformly to obtain a glass composition. After forming into a film with a forming roller, it was pulverized to produce a glass powder. The obtained glass powder was applied to an oxygen burner frame and formed into a spherical shape. Thereafter, the average particle size D ₅₀ by classification to obtain glass beads 5 [mu] m.

  Inorganic filler particles A were obtained by subjecting the glass beads to a heat treatment at 1000 ° C. for 60 minutes to precipitate crystals. An uneven shape was formed on the surface of the inorganic filler particles A due to protruding precipitated crystals.

  Moreover, the inorganic filler particle B was obtained by carrying out the vibration mixing of said glass bead for 1 hour within a vibration mixing apparatus. As the particles collided with each other in the mixing step, irregularities were formed on the surface of the inorganic filler particles B.

  As the inorganic filler particles C, the above glass beads were used as they were.

  Each characteristic of the inorganic filler particles was measured as follows.

  The specific surface area was measured by the BET method.

  The density was measured by the Archimedes method.

  The liquid phase viscosity log η was measured by the platinum ball pulling method for the viscosity at the liquid phase temperature of the glass having the above composition.

(Production of 3D objects)
The mixture was mixed at a ratio of 70% by volume of acrylic photocurable resin and 30% by volume of inorganic filler particles, and kneaded with three rollers to obtain a paste-like resin in which glass beads were uniformly dispersed. This pasty resin was poured into a mold made of Teflon and having an inner size of 30 mm □. Then, the light of 500 mW and wavelength 405nm was irradiated for 10 seconds, and it cured at 80 degreeC, and obtained the three-dimensional molded item. About the obtained three-dimensional molded item, bending strength and rigidity were measured. The results are shown in Table 1.

  The bending strength of the three-dimensional structure was measured according to the three-point bending strength test of JIS R 1601. In addition, the sample of width 4mm * length 40mm * thickness 3mm was used for the measurement, and the span was 30 mm.

  The rigidity of the three-dimensional structure was measured by a resonance method. For the measurement, a sample having a width of 20 mm, a length of 40 mm, and a thickness of 2 mm was used.

  As is clear from Table 1, the three-dimensionally shaped objects of Examples 1 and 2 were excellent in mechanical strength with a bending strength of 30 MPa or more and a rigidity of 14 GPa or more. On the other hand, the three-dimensional model of the comparative example had a bending strength of 28 MPa and a rigidity of 12 GPa or more, and was inferior in mechanical strength as compared with Examples 1 and 2.

Claims (10)

A resin composition for three-dimensional modeling containing a curable resin and inorganic filler particles, wherein the specific surface area of the inorganic filler particles is at least twice the theoretical specific surface area represented by the following formula: Three-dimensional modeling resin composition.
Theoretical specific surface area (m ² / g) = 6 / (Density (g / cm ³ ) × Average particle diameter D ₅₀ (μm)) The resin composition for three-dimensional modeling according to claim 1, wherein the specific surface area of the inorganic filler particles is 0.1 to ⁵ m ² / g. 3. The resin composition for three-dimensional modeling according to claim 1, wherein the inorganic filler particles have an average particle diameter D ₅₀ of 1 to ₅₀₀ μm.   The resin composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the inorganic filler particles are made of glass or crystallized glass.   The resin composition for three-dimensional modeling according to claim 4, wherein the surface of the inorganic filler particles is subjected to a surface roughening treatment after being subjected to flame polishing.   6. The resin composition for three-dimensional modeling according to claim 4, wherein the liquid phase viscosity log η of the inorganic filler particles is 1.0 or less. The density of inorganic filler particles is 2.4 to 7 g / cm ³ , and the resin composition for three-dimensional modeling according to any one of claims 1 to 6.   The resin composition for three-dimensional modeling according to any one of claims 1 to 7, wherein the curable resin is a photocurable resin or a thermosetting resin.   The resin composition for three-dimensional model | molding as described in any one of Claims 1-8 characterized by containing 30-99% of curable resin and 1-70% of inorganic filler particles by volume%.   The liquid layer made of the resin composition is selectively irradiated with active energy rays to form a cured layer having a predetermined pattern, and after forming a new liquid layer on the cured layer, the active energy ray is irradiated to form the cured layer. A method for producing a three-dimensional structure that forms a new hardened layer having a predetermined pattern continuous with the hardened layer and repeats the lamination of the hardened layers until a predetermined three-dimensional structure is obtained, wherein the resin composition is a claim. The manufacturing method of the three-dimensional molded item characterized by using the resin composition for three-dimensional modeling in any one of 1-9.