JP6686909B2 - Resin composition for three-dimensional modeling - Google Patents

Description

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

  BACKGROUND ART Conventionally, a method of obtaining a three-dimensional object by laminating resin materials and the like is known. For example, various methods such as a stereolithography method, a powder sintering method, and a hot melt deposition (Fused deposition modeling: FDM) method have been proposed and put into practical use.

  For example, the stereolithography is excellent in fine modeling and accurate size representation, and is widely used. This method is for producing 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. In this way, when one cured layer is formed, the molding stage is lowered by one layer, an uncured resin is introduced onto the cured layer, and the photocurable resin is similarly irradiated with an ultraviolet laser to irradiate the cured layer. Stack a new hardened layer on top. By repeating this operation, a predetermined three-dimensional object is obtained. In the powder sintering method, a modeling stage is provided in a tank filled with resin, metal, ceramics, and glass powders, and the powder on the modeling stage is irradiated with a laser such as a semiconductor to soften and deform a desired pattern. The hardened layer is produced.

JP, 7-26060, A

  It has been pointed out that a three-dimensional molded object made of a resin, which is 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 bead-shaped particles or the like to the photocurable resin.

  An object of the present invention is to provide a three-dimensional modeling resin composition capable of further increasing mechanical strength.

  The resin composition for three-dimensional modeling of the present invention is a resin composition for three-dimensional modeling containing a curable resin and inorganic filler particles, wherein the inorganic filler particles have a diameter of 1 to 20 μm and an aspect ratio (diameter / length). ) It is characterized by containing 0.01 to 1 columnar particles. Here, the “columnar particle” means a substantially columnar or substantially prismatic particle. The “diameter” means a value obtained by dividing the sum of the maximum diameter and the minimum diameter of the cross section (cross section orthogonal to the length direction) of the columnar body by 2. If the shape or size of the cross section varies, the average value is used. "Aspect ratio" means the ratio of the diameter to the length (height) of columnar particles.

  By adopting the above configuration, the mechanical strength of the three-dimensional molded item can be increased. In addition, it is possible to avoid a situation in which the viscosity of the resin composition increases too much and molding becomes difficult.

  Further, since the columnar particles having an appropriate aspect ratio are used as the filler, a large number of fillers do not stick out on the surface of the three-dimensional object. Further, in the hot melt laminating method, modeling can be performed without separating the filler from the wire-shaped resin during modeling.

  In the present invention, the columnar particles are preferably made of glass.

  By adopting the above configuration, it becomes easy to give a three-dimensional object a sense of transparency and texture, and aesthetics are improved. Further, when the stereolithography method is used, the irradiation of the active energy ray is not hindered by the inorganic filler particles. Therefore, it becomes possible to introduce a large amount of the inorganic filler particles into the curable resin, and it becomes easy to obtain a three-dimensional molded article having high mechanical strength.

  In the present invention, the columnar particles are preferably made of glass having a Knoop hardness of 200 or more. The columnar particles are preferably made of glass having a Young's modulus of 50 GPa or more. Here, the "Knoop hardness" is measured by the method of JIS B7734, and the "Young's modulus" is measured by the method of the resonance method.

  If the above configuration is adopted, it becomes easy to obtain a three-dimensional molded item having high mechanical strength.

In the present invention, it is preferable that the columnar particles are made of glass having a glass composition containing 50% by mass or more of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O _{5 in} mass%. Here, _{"SiO 2 + Al 2 O 3 +} B 2 O 3 + P 2 O 5 " _means the total content of _{SiO 2, Al 2 O 3,} B 2 O 3 and _P 2 _{O 5.}

  If the above configuration is adopted, the network component of the glass is increased, and the glass has high Young's modulus and Knoop hardness. As a result, it becomes easy to obtain a three-dimensional molded article having high mechanical strength.

  In the present invention, it is preferable to contain the curable resin in an amount of 10 to 99% and the inorganic filler particles in an amount of 1 to 90% by volume.

  In the present invention, the proportion of the columnar particles in the inorganic filler particles is preferably 0.1 to 100% by volume.

  If the above configuration is adopted, it becomes easy to obtain a three-dimensional molded item having high mechanical strength.

  The method for producing a three-dimensional molded article of the present invention is to form a cured layer having a predetermined pattern by selectively irradiating a liquid layer made of a resin composition with active energy rays, and forming a new liquid layer on the cured layer. A method for producing a three-dimensional object which is formed by irradiating an active energy ray to form a new hardened layer having a predetermined pattern continuous with the hardened layer and repeating stacking of the hardened layer until a predetermined three-dimensional object is obtained. The resin composition for three-dimensional modeling described above is used as the resin composition.

  According to the above configuration, a three-dimensional object having high mechanical strength can be easily manufactured.

  The three-dimensional modeling resin composition of the present invention contains a curable resin and inorganic filler particles. The mixing ratio of the curable resin and the inorganic filler particles is preferably 10 to 99% by volume of the curable resin and 1 to 90% of the inorganic filler particles by volume. More preferably, the curable resin is 20 to 95%, 30 to 90%, 40 to 85%, particularly 50 to 80%, and the inorganic filler particles are 5 to 80%, 10 to 70%, 15 to 60%. 20 to 50%, especially 25 to 45%. If the proportion of the inorganic filler particles is too high, the surface area for adhering to the resin is small and the mechanical strength is low. Further, when the stereolithography method is used, the viscosity of the curable resin becomes too high, which makes it difficult to form a new liquid layer on the modeling stage. If the proportion of the curable resin is too high, it becomes difficult to reflect the strength and hardness of the inorganic filler particles in the composite. Further, since the content of the inorganic filler particles is relatively reduced, the mechanical strength of the shaped article is reduced.

  The three-dimensional modeling resin composition of the present invention is preferably adjusted to have a viscosity of 0.5 to 150 Pa · s, 1.0 to 100 Pa · s, and particularly 1.5 to 50 Pa · s. If the viscosity of the resin composition is too low, the inorganic filler particles tend to settle and separate, which makes it difficult for the filler to enter the shaped article, and it becomes difficult to obtain a shaped article with high mechanical strength. On the other hand, if it is higher than 150 Pa · s, continuous lamination becomes difficult.

  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 adopted. For example, when the stereolithography method is used, a liquid photocurable resin may be selected.

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

  As the monofunctional compound of the polymerizable vinyl compound, isobornyl acrylate, isobornyl methacrylate, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol. Examples thereof include acrylate, vinylpyrrolidone, acrylamide, vinyl acetate and styrene. As the polyfunctional compound, 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.

  A photopolymerization initiator is used as the polymerization initiator of the vinyl compound. As the photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl 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 kinds. If necessary, a sensitizer such as an amine compound may be used in combination. The amount of each of these polymerization initiators used is preferably 0.1 to 10 mass% with respect to the vinyl compound.

  Epoxy compounds 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 cation initiator such as triphenylsulfonium hexafluoroantimonate can be used.

  Further, a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, etc. may be added to the photocurable resin, if necessary.

  When a powder sintering method, a hot melt laminating method or the like is adopted, polypropylene, polyethylene, ABS resin, polycarbonate, polyetheretherketone, polyamide, thermoplastic polyimide, polyamideimide, polyetherimide is used instead of the curable resin. Thermoplastic resins such as polyacetal, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyphenylene sulfide, polysulfone, and polyethersulfone may be used.

  In the powder sintering method, resin powder and columnar particles may be used as a mixed powder. In the hot melt laminating method, it may be used in the form of a wire in which resin is mixed with columnar particles. In the hot melt laminating method, it is important to mix the columnar particles with orientation in the axial direction of the wire.

  The inorganic filler particles used in the present invention include columnar particles. The columnar particles preferably have a diameter of 1 to 20 μm, 2.5 to 17.5 μm, 5 to 15 μm, 6 to 12.5 μm, particularly 7 to 10 μm, and an aspect ratio (diameter / length) of 0.01. It is 1 to 1, preferably 0.05 to 1, 0.1 to 1, 0.2 to 1, and more preferably 0.25 to 0.8. If the diameter of the columnar particles is too small, it is difficult to obtain the effect of improving the mechanical strength, and if it is too large, the viscosity of the curable resin increases and it becomes difficult to perform three-dimensional molding. Further, if the aspect ratio of the columnar particles is too small, the viscosity of the curable resin increases and it becomes difficult to perform three-dimensional molding. If the aspect ratio of the columnar particles is too large, the effect of improving the mechanical strength becomes small.

  The columnar particles are preferably made of glass from the viewpoints that they give a three-dimensional object a sense of transparency and texture, and do not prevent the curing of the photo-effect resin when a stereolithography method is used. The glass columnar particles can be produced by, for example, a jet mill pulverizing method or a method of pulverizing for a short time with a liqui machine. When produced by this method, edges are less likely to remain on the end faces of the particles, and it becomes easier to prevent columnar particles from being entangled with each other. As a result, it is possible to effectively avoid the situation where the tips of the columnar particles are projected on the surface of the shaped article.

The composition of the glass forming the columnar particles is not particularly limited, but it is preferable to use glass satisfying the ranges of Knoop hardness and Young's modulus described later. As a composition condition in which such characteristics are easily obtained, glass containing 50% by mass or more of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O _{5 in 5} % by mass, particularly 55% by mass or more, is preferable. It is preferable to select. If the content of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O ₅ is too small, the Young's modulus and Knoop hardness of the glass decrease, and the effect of improving the mechanical strength of the three-dimensional object decreases. Specific examples of the conditions are satisfied the glass, for example by _{mass%, SiO 2 30~80%, Al} 2 O 3 0~50%, B 2 O 3 0~50%, P 2 O 5 0~50%, SiO glass containing _{2 + Al 2 O 3 + B} 2 O 3 + P 2 O 5 50% or more can be mentioned. The reason for limiting the glass composition as described above will be described below. In the following description, “%” represents mass% unless otherwise specified.

SiO ₂ is a component that forms a glass skeleton. It is a component that can easily improve chemical durability and suppress devitrification. SiO ₂ is preferably 30 to 80%, 40 to 70%, and particularly preferably 45 to 65%. When the amount of SiO ₂ is large, the meltability is likely to be lowered, and it is difficult to soften the columnar particles during molding, which makes manufacturing difficult. Further, when the amount of SiO ₂ is small, the chemical durability is likely to be lowered and the glass is liable to be devitrified, which makes the production difficult.

Al ₂ O ₃ is a vitrification-stable component. It is a component that can easily improve chemical durability and suppress devitrification. Al ₂ O ₃ is preferably 0 to 50%, 2.5 to 40%, and particularly preferably 5 to 30%. When the amount of Al ₂ O ₃ is large, the meltability is likely to be lowered, and it is difficult to soften during the molding of the columnar particles, which makes the manufacturing difficult. Further, when the amount of Al ₂ O ₃ is small, the chemical durability is likely to be lowered, or the glass is likely to be devitrified, which may make the production difficult.

B ₂ O ₃ is a component that forms a glass skeleton. It is a component that can easily improve chemical durability and suppress devitrification. B ₂ O ₃ is preferably 0 to 50%, 2.5 to 40%, and particularly preferably 5 to 30%. When the amount of B ₂ O ₃ is large, the meltability is likely to be lowered, and it is difficult for the melt to be softened at the time of forming the columnar particles, which makes the production difficult. Further, when the amount of B ₂ O ₃ is small, the chemical durability is likely to be lowered, or the glass is likely to be devitrified, which may make the production difficult.

P ₂ O ₅ is a component that forms a glass skeleton. It is a component that can easily improve chemical durability and suppress devitrification. P ₂ O ₅ is 0 to 50% 2.5 to 40%, especially 5-30% is preferred. If the amount of P ₂ O ₅ is large, the meltability is likely to be lowered, and it is difficult to soften the columnar particles during molding, which makes the production difficult. Further, when the amount of P ₂ O ₅ is small, the glass tends to devitrify, which may make the production difficult.

  In addition to the above, it is preferable to add MgO, CaO, SrO, BaO and ZnO in the glass composition in a total amount of 0.1 to 50% by mass, 1.0 to 40%, and further 2 to 30%. These components are components that easily lower the viscosity of the glass without significantly lowering the durability of the glass.

In addition, in order to suppress coloring, the total content of Fe ₂ O ₃ , NiO, Cr ₂ O ₃ and CuO in the glass composition is 1% or less, 0.75% or less, 0.50% or less, 0. It is preferably 25% or less, 0.10% or less, 0.05% or less, and particularly preferably 0.01% or less. In addition, the content of TiO ₂ , WO ₃ , La ₂ O ₃ , Gd ₂ O _3, and Bi ₂ O _{3 in} the glass composition is 5% or less, 2.5% or less, and particularly 1.0% or less in total. Preferably. By limiting the range of these components as described above, it is possible to easily suppress the coloring of the columnar particles and to suppress the increase in the refractive index and the density, and thus it is possible to easily obtain a colorless, transparent and uniform three-dimensional object. it can. The total content of Na ₂ O, K ₂ O, and Li ₂ O in the glass composition may be 5% or less, 2.5% or less, 1.0% or less, and particularly 0.5% or less. preferable. By limiting the ranges of these components as described above, the durability of the glass can be improved and the deterioration of the resin can be suppressed. Further, for environmental reasons, the total content of lead, antimony, arsenic, chlorine and sulfur contained in the glass composition is preferably 1% or less, 0.5% or less, and particularly preferably 0.1% or less. .

  Furthermore, it is preferable that the amount of stainless steel or iron attached to the surface is 1000 μg / g or less, 500 μg / g or less, and particularly 100 μg / g or less. Stainless steel or iron attached to the surface causes coloring of the molded article to blacken, and remarkable coloring occurs when mixed with the resin. Stainless steel and iron adhering to the surface are often mixed in during the crushing process. Therefore, if columnar particles are produced using glass fibers, the crushing step is almost unnecessary, and the adhesion of stainless steel or iron can be greatly reduced.

  The columnar particles are preferably made of glass having a Knoop hardness of 200 or more, 300 or more, and particularly 350 or more. If glass having too low Knoop hardness is used, the effect of improving the mechanical strength of the three-dimensional molded item becomes small. In addition, the columnar particles may increase the viscosity of the resin more easily than the bead-shaped particles, and thus the content may be limited. In such a case, it is preferable to select glass having higher Knoop hardness.

  The columnar particles are preferably made of glass having a Young's modulus of 50 GPa or more, 55 GPa or more, and particularly 60 GPa or more. If glass having a too low Young's modulus is used, the effect of improving the mechanical strength of the three-dimensional model becomes small. In addition, the columnar particles may increase the viscosity of the resin more easily than the bead-shaped particles, and thus the content may be limited. In such a case, it is preferable to select a glass having a higher Young's modulus.

  The columnar particles are preferably made of glass having an average transmittance in the visible region (400 to 700 nm) of 30% or more, 50% or more, and particularly 70% or more, from the viewpoint of increasing the transparency of the obtained shaped article.

  The inorganic filler particles may be composed of only columnar particles, but crushed particles, bead-shaped particles, fiber-shaped particles and the like can be used together with the columnar particles. These particles may be made of glass, ceramics, or the like, but when glass particles are used, they give a three-dimensional object a sense of transparency and texture, and when a stereolithography method is used, the effect of photo-effect resin You can enjoy the merit that it does not prevent curing. Further, when it is made of glass, it is preferably composed of glass having the above-described composition and characteristics. If the bead-shaped particles and the crushed particles are made of the same material as the columnar particles, it is advantageous in terms of production cost. Further, bead-shaped particles may contain a large amount because it is difficult to increase the viscosity of the resin as compared with columnar particles, and in such a case bead-shaped particles have lower Knoop hardness and Young's modulus than columnar particles. It may be formed of glass.

  The proportion of columnar particles in the inorganic filler particles is preferably 1 to 100%, 2.5 to 90%, and particularly 5 to 80% by volume. If the proportion of the columnar particles is too low, the effect of improving the mechanical strength cannot be expected.

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

Further, the oxide nanoparticles may be added to the inorganic filler or the curable resin in a ratio of 1% or less with respect to the resin composition. As the oxide nanoparticles, ZrO ₂ , Al ₂ O ₃ , SiO ₂ or the like can be used. The oxide nanoparticles are particles that are smaller than the visible light wavelength, and are unlikely to cause light scattering.

  Next, a method for producing a three-dimensional object of the present invention using the above resin composition will be described using a stereolithography method. 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 is positioned such that the upper surface of the stage has a desired depth from the liquid surface (for example, about 0.2 mm). By doing so, 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 cure the photocurable resin to form a cured layer having a predetermined pattern. In addition to ultraviolet rays, visible light rays, laser rays such as infrared rays, and the like can be used as the active energy rays.

  Next, a new liquid layer made of the photocurable resin composition is prepared on the formed cured layer. For example, by lowering the above-described modeling stage by one layer, the photocurable resin can be introduced onto the cured layer to prepare a new liquid layer.

  Then, a new liquid layer prepared on the cured layer is irradiated with active energy rays to form a new cured layer continuous with the cured layer, and the cured layer is continuously laminated by repeating this operation. , Obtain a predetermined three-dimensional object.

  For the purpose of making the filling of the inorganic filler particles uniform and enhancing the orientation, vibration may be applied at the time of modeling. Further, if necessary, at least a part of the surface of the obtained three-dimensional shaped article may be subjected to mechanical processing such as polishing or grinding to obtain a final shaped article.

  Hereinafter, the resin composition for three-dimensional modeling of the present invention will be described based on Examples. Table 1 shows Examples (Sample Nos. 1 to 8) and Comparative Examples (Nos. 9 and 10) of the present invention. No. Reference numeral 9 is a reference example produced without including the inorganic filling powder.

(Preparation of photocurable resin)
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 put and stirred and mixed to cause a reaction. A 4-mol addition product of propylene oxide of pentaerythritol (one addition of 1 mol of propylene oxide 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 transparent acrylic photocurable resin. The acrylic photocurable resin had a viscosity of 1 Pa · s and a Knoop hardness of 11.

(Preparation of columnar particles)
First, a raw material prepared so as to be a glass containing, by mass% as a glass composition, SiO ₂ 69%, Al ₂ O ₃ 19%, MgO 2%, CaO 6%, SrO 3%, and BaO 1% at 1500 ° C. After melting for a period of time, it was supplied to a bushing furnace, and fibrous glass having an average diameter of 5 μm was pulled out from the bushing nozzle. By cutting this fibrous glass into the lengths shown in the table, glass-made substantially columnar particles were obtained. When the Knoop hardness and Young's modulus of the glass constituting the columnar particles were measured, the Knoop hardness was 540 and the Young's modulus was 79 GPa. Further, the contamination of stainless steel or iron adhered to the surface was measured and found to be 10 μg / g.

(Preparation of beaded particles)
The glass melted with the same glass composition as the columnar particles was crushed to prepare powder glass having an average particle diameter of 5 μm. This powder was applied to the frame of an oxygen burner and molded into a spherical shape (bead shape). Then, classification was performed to obtain glass bead-shaped particles having an average particle size of 5 μm.

(Preparation and curing of resin composition for stereolithography)
Inorganic filler particles (columnar particles and / or bead-shaped particles) were added to the photocurable resin in the proportions shown in Table 1, and kneading was performed with a three-roller to homogenously disperse the inorganic filler particles in a paste form. To obtain a photocurable resin. The viscosity of the photocurable resin (before curing) is shown in Table 1.

  The paste resin was poured into a mold made of Teflon (registered trademark) and having an inner size of 30 mm □. Then, it was irradiated with light of 500 mW and a wavelength of 364 nm to be cured, and cured at 80 ° C.

(Evaluation of mechanical strength)
When the Knoop hardness and the bending strength of the obtained sample were measured, the Knoop hardness was 18 or more and the bending strength was 90 MPa or more. On the other hand, sample No. containing no columnar particles. Sample No. 10 has the same content of the inorganic filler particles. Compared with No. 5, the Knoop hardness was equivalent, but the bending strength was low.

(Various measurements)
The viscosities of the photocurable resin and the photocurable resin composition were measured with a Brookfield viscometer (DV-3).

  The Knoop hardness of the photocurable resin after curing, the photocurable resin composition, and the glass forming the columnar particles and the bead-shaped particles is 20 mm □ with a mirror-polished surface, and a measurement sample having a plate thickness of 5 mm is prepared. A Knoop hardness tester (manufactured by Matsuzawa Seisakusho) was used and the load was measured at 50 g.

  The Young's modulus was measured by a resonance method (JE-RT manufactured by Nippon Techno Plus).

  The bending strength was measured by the method of JIS R1601.

  For the contamination of stainless steel or iron adhering to the surface, 30 ml of pure water and 20 ml of SSG hydrochloric acid were added to 5 g of the sample, and heat treatment was performed at 180 ° C. for 20 minutes to dissolve the surface adhering metal. The Fe, Ni, and Cr concentrations in this solution were measured.

  Since the resin composition for three-dimensional modeling of the present invention contains columnar particles as the inorganic filler particles, it is possible to prepare a three-dimensional molded article having high mechanical strength. In addition to the three-dimensional modeling application, it can also be used as a filling material for thermosetting resins such as epoxy, polyurethane, polyimide, unsaturated polyester, and silicone.

Claims (6)

A stereolithography resin composition containing a curable resin and inorganic filler particles, inorganic filler particles has a diameter of 1 to 20 [mu] m, an aspect ratio (diameter / length) of 0.01 to 1 Glass consisting saw including columnar particles, the ratio of the columnar grains accounting inorganic filler particles are, for stereolithography resin composition characterized in that 5 to 100% by volume%. The resin composition for three-dimensional modeling according to claim 1, wherein the columnar particles are made of glass having a Knoop hardness of 200 or more. The resin composition for three-dimensional modeling according to claim 1 or 2 , wherein the columnar particles are made of glass having a Young's modulus of 50 GPa or more. Columnar particles, as a glass composition, in any one of _{SiO 2 + Al 2 O 3 +} B 2 O 3 + P 2 O 5 according to claim 1 to 3, characterized in that it consists of glass containing more than 50 wt% in mass% The resin composition for three-dimensional modeling as described. By volume%, the curable resin 10% to 99%, stereolithography resin composition according to any one of claims 1 to 4, characterized in that it contains 1 to 90% inorganic filler particles. A liquid layer made of a resin composition is selectively irradiated with an active energy ray to form a cured layer having a predetermined pattern, and a new liquid layer is formed on the cured layer, and then an active energy ray is irradiated to form the cured layer. After forming a new hardened layer having a predetermined pattern continuous with the hardened layer and repeating the lamination of the hardened layer until a predetermined three-dimensional object is obtained, at least a part of the surface of the obtained three-dimensional object is machined. a method of manufacturing a three-dimensional object to be processed, the production of the as a resin composition, three-dimensional object, characterized by the use of stereolithography resin composition according to any one of claims 1 to 5 Method.