WO2016114031A1 - Resin composition for 3d modeling - Google Patents

Abstract

Provided is a resin composition for optical modeling in which it is possible to raise the mechanical strength. A resin composition for 3D modeling containing a curable resin and inorganic filler particles, wherein the resin composition is characterized in that the inorganic filler particles are columnar particles having a diameter of 1-20 μm and an aspect ratio (length/diameter) of 0.01-1.

Description

Three-dimensional modeling resin composition

The present invention relates to a resin composition for three-dimensional modeling and a method for manufacturing 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 sintering method, and a hot-melt lamination (FDM) method have been proposed and put into practical use.

For example, stereolithography is excellent in detailed modeling and accurate size expression, and is widely used. This method creates a three-dimensionally shaped object as follows. First, a modeling stage is provided in a tank filled with a liquid photocurable resin, and an ultraviolet laser is irradiated to the photocurable resin on the modeling stage to create 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 resin is introduced onto the cured layer, and similarly, the cured layer is irradiated with an ultraviolet laser. Stack a new hardened layer on top. By repeating this operation, a predetermined three-dimensional model is obtained. In addition, the powder sintering method has a modeling stage in a tank filled with resin, metal, ceramics, and glass powder, and the powder on the modeling stage is irradiated with a laser such as a semiconductor to form a desired pattern by softening deformation. A cured layer is produced.

Japanese Unexamined Patent Publication No. 7-26060

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

An object of the present invention is to provide a resin composition for three-dimensional modeling that can further increase mechanical strength.

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

採用 By adopting the above configuration, the mechanical strength of the three-dimensional model can be increased. Further, it is possible to avoid a situation in which molding becomes difficult due to excessive increase in the viscosity of the resin composition.

Furthermore, since columnar particles having an appropriate aspect ratio are used as the filler, a large number of fillers do not protrude from the surface of the three-dimensional structure. Moreover, in the hot melt lamination 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.

If the above configuration is adopted, it becomes easy to impart a sense of transparency and texture to the three-dimensional modeled object, and the aesthetics are improved. Moreover, when using an optical modeling method, irradiation of an active energy ray is not prevented by the inorganic filler particle. Therefore, it becomes possible to introduce a large amount of inorganic filler particles into the curable resin, and it becomes easy to obtain a three-dimensionally shaped article with 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, “Knoop hardness” is measured by the method of JIS B7734, and “Young's modulus” is measured by the method of resonance method.

If the above configuration is adopted, it becomes easy to obtain a three-dimensional shaped object with high mechanical strength.

In the present invention, the columnar particles, as a glass composition, it is preferably made of glass containing _{SiO 2 + Al 2 O 3 +} B 2 O 3 + P 2 O 5 50 wt% or more in mass%. Here, “SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O ₅ ” means the total content of the contents of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and P ₂ O ₅ .

If the above configuration is adopted, the glass has many network components, resulting in a glass having a high Young's modulus and Knoop hardness. As a result, it becomes easy to obtain a three-dimensional shaped object with high mechanical strength.

In the present invention, it is preferable that 10% to 99% of the curable resin and 1% to 90% of the inorganic filler particles are contained by volume.

In the present invention, the ratio of 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 shaped object with high mechanical strength.

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 above-described resin composition for three-dimensional modeling is used as the resin composition.

According to the above configuration, a three-dimensional shaped object with high mechanical strength can be easily produced.

The resin composition for three-dimensional modeling of the present invention includes a curable resin and inorganic filler particles. The mixing ratio of the curable resin and the inorganic filler particles is preferably 10 to 99% for the curable resin and 1 to 90% for 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%. When the ratio of the inorganic filler particles is too high, the surface area to be bonded to the resin is small and the mechanical strength is lowered. Moreover, when using an optical modeling method, the malfunction of the viscosity of curable resin becoming high too much and it becomes difficult to form a new liquid layer on a modeling stage arises. If the ratio of the curable resin is too high, it becomes difficult to reflect the strength and hardness of the inorganic filler particles in the composite. Moreover, since the content of the inorganic filler particles is relatively lowered, the mechanical strength of the shaped article is lowered.

The resin composition for three-dimensional modeling of the present invention is preferably adjusted so that the viscosity is 0.5 to 150 Pa · s, 1.0 to 100 Pa · s, particularly 1.5 to 50 Pa · s. If the viscosity of the resin composition is too small, the inorganic filler particles are likely to settle and separate, making it difficult for the filler to enter the shaped article and obtaining 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 employed. For example, when using an optical modeling method, 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. 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.

Monofunctional compounds of the polymerizable vinyl compound include isobornyl acrylate, isobornyl methacrylate, ginklopentenyl 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 the polymerization initiator for the vinyl compound, a photopolymerization initiator is used. Photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, bezaldehyde, 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. The amount of these polymerization initiators used is preferably 0.1 to 10% by mass relative 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 cationic initiator such as triphenylsulfonium hexafluoroantimonate can be used.

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

In addition, when adopting powder sintering method, heat melting lamination method, etc., instead of curable resin, polypropylene, polyethylene, ABS resin, polycarbonate, polyetheretherketone, polyamide, thermoplastic polyimide, polyamideimide, polyetherimide A thermoplastic resin such as polyacetal, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyphenylene sulfide, polysulfone, or polyethersulfone may be used.

In the powder sintering method, a mixed powder obtained by mixing resin powder and columnar particles may be used. In the hot melt lamination method, a wire shape in which columnar particles are blended in a resin may be used. In the hot melt lamination method, it is important to blend 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. To 1, preferably 0.05 to 1, 0.1 to 1, 0.2 to 1, particularly 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 is increased and three-dimensional molding becomes difficult. On the other hand, if the aspect ratio of the columnar particles is too small, the viscosity of the curable resin is increased and three-dimensional molding becomes difficult. If the aspect ratio of the columnar particles is too large, the effect of improving the mechanical strength is decreased.

The columnar particles are preferably made of glass from the viewpoint of giving a three-dimensional structure a sense of transparency and texture, and not hindering the curing of the light-effective resin when using an optical modeling method. The glass columnar particles can be produced by, for example, a jet mill pulverization method or a method of pulverizing for a short time using a likai machine. If it produces by this method, it will become difficult to leave an edge on a particle | grain end surface, and it will become easy to prevent that columnar particle | grains get entangled. As a result, it is possible to effectively avoid the situation where the tip of the columnar particle protrudes from the surface of the shaped article.

The composition of the glass constituting the columnar particles is not particularly limited, but it is preferable to employ a glass that satisfies the Knoop hardness and Young's modulus ranges described below. As composition conditions for easily obtaining such characteristics, glass containing SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O _{5 in an} amount of 50% by mass or more, 52.5% by mass or more, and particularly 55% by mass or more is contained. It is preferable to select. When 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 is lowered and the effect of improving the mechanical strength against the three-dimensional object is reduced. Specific examples of the glass satisfying the above conditions include, 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 2 Examples include glass containing 50% or more of ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O ₅ . 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%, particularly 45 to 65%. When SiO ₂ is large, it tends to decrease the melting property, hardly softened when the columnar particles forming, manufacturing becomes difficult. Further, when SiO ₂ is small, or made chemically durability tends to decrease, it becomes easy glass devitrified, production becomes 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%, particularly preferably 5 to 30%. When al ₂ O ₃ is large, it tends to decrease the melting property, hardly softened when the columnar particles forming, manufacturing becomes difficult. Further, when the Al ₂ O ₃ is small, or made chemically durability tends to decrease, it becomes easy glass devitrified, there is a possibility that the production becomes 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%, particularly preferably 5 to 30%. When B ₂ O ₃ is large, it tends to decrease the melting property, hardly softened when the columnar particles forming, manufacturing becomes difficult. Also, when the B ₂ O ₃ is small, or made chemically durability tends to decrease, it becomes easy glass devitrified, there is a possibility that the production becomes 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 preferably 0 to 50%, 2.5 to 40%, particularly preferably 5 to 30%. When P ₂ O ₅ is large, it tends to decrease the melting property, hardly softened when the columnar particles forming, manufacturing becomes difficult. Further, when the P ₂ O ₅ is less, the glass is easily devitrified, there is a possibility that the production becomes difficult.

In addition to the above, MgO, CaO, SrO, BaO and ZnO in the glass composition are preferably added in a total amount of 0.1 to 50% by mass, 1.0 to 40%, and more preferably 2 to 30%. These components are components that tend to lower the viscosity of the glass without significantly reducing the durability of the glass.

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. Further, the total 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, particularly 1.0% or less. It is preferable to do. If the range of these components is limited as described above, it is easy to suppress the coloring of the columnar particles and the increase in the refractive index and density can be suppressed, so that it is possible to easily obtain a colorless, transparent, and uniform three-dimensional structure. it can. The total content of Na ₂ O, K ₂ O, and Li ₂ O in the glass composition is 5% or less, 2.5% or less, 1.0% or less, and particularly 0.5% or less. preferable. If the range of these components is limited as described above, the durability of the glass can be improved and the deterioration of the resin can be suppressed. Furthermore, 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, particularly preferably 0.1% or less. .

Furthermore, it is preferable that stainless steel or iron adhering to the surface is 1000 μg / g or less, 500 μg / g or less, particularly 100 μg / g or less. Stainless steel and iron adhering to the surface cause a coloring to blacken the modeled object, and remarkable coloring occurs when mixed with the resin. Stainless steel and iron adhering to the surface are often mixed from the grinding process. Therefore, if columnar particles are produced using glass fiber, the pulverization step is almost unnecessary, so that the adhesion of stainless steel and iron can be greatly reduced.

The columnar particles are preferably made of glass having a Knoop hardness of 200 or more, 300 or more, particularly 350 or more. If glass with Knoop hardness is too low, the effect of improving the mechanical strength of the three-dimensional structure is reduced. Moreover, since the columnar particles tend to increase the viscosity of the resin compared to the bead-shaped particles, the content may be limited. In such a case, it is preferable to select a glass having a 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, particularly 60 GPa or more. If glass with a Young's modulus that is too low is used, the effect of improving the mechanical strength of the three-dimensional structure is reduced. Moreover, since the columnar particles tend to increase the viscosity of the resin compared to the bead-shaped particles, 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 of 30% or more, 50% or more, particularly 70% or more in the visible region (400 to 700 nm) from the viewpoint of enhancing the transparency of the resulting molded article.

The inorganic filler particles may be composed only of 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 any material such as glass or ceramic. However, when glass particles are used, a three-dimensional object is given transparency and texture, or a photo-effective resin is used when using an optical modeling method. Benefit from not hindering curing. Moreover, when making it from glass, it is preferable to comprise by the glass which has the composition and characteristic as stated above. It is advantageous from the viewpoint of production cost if the bead-like particles and the crushed particles are made of the same material as the columnar particles. In addition, since the bead-like particles are difficult to increase the viscosity of the resin as compared with the columnar particles, it may be contained in a large amount. In such a case, the bead-like particles have lower Knoop hardness or Young's modulus than the columnar particles. It may be formed of glass.

The ratio of the columnar particles in the inorganic filler particles is preferably 1 to 100%, 2.5 to 90%, particularly 5 to 80% by volume. If the ratio 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, it is possible to increase the bonding strength between the inorganic filler particles and the curable resin, and it is possible to obtain a shaped article with more excellent mechanical strength. Furthermore, the familiarity between the inorganic filler particles and the curable resin is improved, the bubbles at the interface can be reduced, and light scattering can be suppressed. 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 depending on 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 is most preferable, and an epoxy compound is used. When used, it is desirable to use an epoxy silane-based silane coupling agent.

Furthermore, you may add an oxide nanoparticle to an inorganic filler and curable resin in the 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. Note that the oxide nanoparticles are particles smaller than the visible light wavelength, and hardly cause light scattering.

Next, the manufacturing method of the three-dimensional model | molding of this invention using the above-mentioned resin composition is demonstrated using the optical modeling 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 the stage upper surface is positioned so as to have a desired depth (for example, about 0.2 mm) from the liquid surface. 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 cure the photocurable resin, thereby forming a cured layer having a predetermined pattern. As the active energy beam, in addition to ultraviolet rays, laser beams such as visible rays and infrared rays can be used.

Next, a new liquid layer made of the 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, and a new liquid layer can be prepared.

Subsequently, 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, and the cured layer is continuously laminated by repeating this operation. A predetermined three-dimensional model is obtained.

In addition, you may give a vibration at the time of shaping | molding in order to make the filling of an inorganic filler particle uniform or to improve orientation. If necessary, the obtained three-dimensional object can be subjected to mechanical processing such as polishing or grinding on at least a part of its surface to obtain a final object.

Hereinafter, the resin composition for three-dimensional modeling of the present invention will be described based on examples. Table 1 shows examples of the present invention (sample Nos. 1 to 8) and comparative examples (Nos. 9 and 10). No. Reference numeral 9 is a reference example prepared without containing inorganic filler 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 added and mixed by stirring to react. A propylene oxide 4 mol adduct of pentaerythritol (1 mol of propylene oxide added to 4 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 and a Knoop hardness of 11.

(Preparation of columnar particles)
First, raw materials prepared so as to contain a glass composition containing 4% by mass of SiO ₂ 69%, Al ₂ O ₃ 19%, MgO 2%, CaO 6%, SrO 3%, BaO 1% at 1500 ° C. After melting for a time, it was supplied to a bushing furnace, and fiber glass with an average diameter of 5 μm was drawn out from the bushing nozzle. The fiber-like glass was cut to a length shown in the table to obtain a substantially cylindrical columnar particle made of glass. 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. Moreover, when the contamination of stainless steel and iron adhering to the surface was measured, it was 10 μg / g.

(Preparation of bead-like particles)
Glass melted with the same glass composition as the columnar particles was pulverized to produce powdered glass having an average particle size of 5 μm. This powder was applied to an oxygen burner frame and formed into a spherical shape (bead shape). Thereafter, classification was performed to obtain glass bead-like particles having an average particle diameter of 5 μm.

(Preparation and curing of resin composition for stereolithography)
Paste form in which inorganic filler particles (columnar particles and / or bead-like particles) are added to the photocurable resin at the ratio shown in Table 1 and kneaded with three rollers to uniformly disperse the inorganic filler particles. The photocurable resin was obtained. The viscosity of the photocurable resin (before curing) is shown in Table 1.

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

(Evaluation of mechanical strength)
When the Knoop hardness and 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. No. 10 is a sample No. 10 having the same content of inorganic filler particles. Compared to 5, Knoop hardness was equivalent, but bending strength was low.

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

As for the Knoop hardness of the glass constituting the photocurable resin after curing, the photocurable resin composition, and the columnar particles and bead-shaped particles, a measurement sample having a surface polished to 20 mm □ and a plate thickness of 5 mm is prepared. Using a Knoop hardness tester (manufactured by Matsuzawa Seisakusho), the measurement was performed with a load of 50 g.

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

Bending strength was measured by the method of JIS R1601.

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

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

Claims (8)

1. A resin composition for three-dimensional modeling comprising a curable resin and inorganic filler particles, wherein the inorganic filler particles are columnar particles having a diameter of 1 to 20 μm and an aspect ratio (diameter / length) of 0.01 to 1 A resin composition for three-dimensional modeling characterized by containing.
2. 2. The resin composition for three-dimensional modeling according to claim 1, wherein the columnar particles are made of glass.
3. 3. The resin composition for three-dimensional modeling according to claim 1 or 2, wherein the columnar particles are made of glass having a Knoop hardness of 200 or more.
4. 4. The resin composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the columnar particles are made of glass having a Young's modulus of 50 GPa or more.
5. The columnar particles are made of glass containing, as a glass composition, 50% by mass or more of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ + P ₂ O _{5 by} mass%, according to any one of claims 1 to 4. The resin composition for three-dimensional modeling described.
6. The resin composition for three-dimensional modeling according to any one of claims 1 to 5, wherein the resin composition contains 10% to 99% curable resin and 1% to 90% inorganic filler particles in a volume%.
7. The resin composition for three-dimensional modeling according to any one of claims 1 to 6, wherein the proportion of the columnar particles in the inorganic filler particles is 0.1 to 100% by volume.
8. 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. After forming a new hardened layer having a predetermined pattern continuous with the hardened layer and repeating the lamination of the hardened layers 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 for producing a three-dimensional structure to be processed, wherein the three-dimensional structure resin composition according to any one of claims 1 to 7 is used as the resin composition. Method.