WO2021049371A1 - Resin composition for three-dimensional shaping - Google Patents

Abstract

Provided is a resin composition for three-dimensional shaping which enables a three-dimensionally shaped object containing inorganic filler particles to have sufficiently heightened mechanical strength.　The resin composition for three-dimensional shaping comprises inorganic filler particles and a curable resin, and is characterized in that the inorganic filler particles, in a particle size distribution examination by the laser diffraction/scattering method, have a ratio of the 50%-cumulative particle diameter (D₅₀) to the 10%-cumulative particle diameter (D₁₀), D₅₀/D₁₀, of 2.1 or greater.

Description

Resin composition for three-dimensional modeling

The present invention relates to a resin composition for three-dimensional modeling.

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

For example, the stereolithography method is excellent in fine modeling and accurate size expression, and is widely used. This method produces 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 ultraviolet laser to prepare a cured layer having a desired pattern. When one cured layer is formed in this way, 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 obtain the cured layer. Stack a new hardened layer on top. By repeating this operation, a predetermined three-dimensional model is obtained. Further, in the powder sintering method, a modeling stage is provided 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 obtain a desired pattern by softening and deforming. It prepares a hardened layer.

Japanese Unexamined Patent Publication No. 7-26060

It has been pointed out that resin-made three-dimensional objects produced by stereolithography, etc. are delicate and precise, but inferior in mechanical strength, etc. Therefore, as proposed in Patent Document 1, it has been proposed to add an inorganic filler to the photocurable resin. However, even if the inorganic filler particles are added, the mechanical strength of the three-dimensional model may not be sufficiently improved.

In view of the above, it is an object of the present invention to provide a resin composition for three-dimensional modeling capable of sufficiently increasing the mechanical strength of the three-dimensional modeling object containing the inorganic filler particles.

The resin composition for three-dimensional modeling of the present invention is a resin composition for three-dimensional modeling containing inorganic filler particles and a curable resin, and has a cumulative 10% particle diameter measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles. It is characterized in that the ratio D ₅₀ / D _{10 of} (D ₁₀ ) and the cumulative 50% particle size (D _{50) is 2.1 or more.} A _{large value of D 50} / D ₁₀ means that there are a considerable number of particles having a particle size considerably smaller than the median in the particle size distribution (hereinafter, also referred to as “small particle size particles”). For example, there is a case where the particle size distribution has a peak near the median and also has a peak near a value considerably smaller than the median (that is, has two or more peaks). In general, since the inorganic filler particles have a higher specific gravity than the curable resin, the inorganic filler particles are likely to settle and separate in the resin composition. As a result, the dispersibility of the inorganic filler particles in the resin composition may decrease, and the mechanical strength of the three-dimensional model may not be sufficiently increased. On the other hand, the resin composition of the present invention _{has a large D 50} / D ₁₀ of the inorganic filler particles as described above, and contains a considerable number of small particle size particles. Since the small particle size particles do not easily settle in the resin composition and play a role as a dispersant, the dispersibility of the inorganic filler particles in the resin composition is improved, and the mechanical strength of the three-dimensional structure is sufficiently increased. It becomes possible to increase.

_{The resin composition for three-dimensional modeling of the present invention preferably has a cumulative 50% particle diameter (D 50} ) of 3 to 25 μm as measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles.

The resin composition for three-dimensional modeling of the present invention _{preferably has a cumulative 10% particle diameter (D 10} ) of 0.5 to 10 μm or more as measured by laser diffraction / scattering particle size distribution measurement. By doing so, the proportion of the glass filler having a small particle size is reduced, so that the contact area between the glass filler and the curable resin is reduced, light scattering at the interface between the two is suppressed, and the transparency of the three-dimensional model is improved. Can be enhanced.

The resin composition for three-dimensional modeling of the present invention preferably has a plurality of peaks in the particle size distribution of the inorganic filler particles.

In the resin composition for three-dimensional modeling of the present invention, it is preferable that _{the inorganic filler particles are SiO 2} , MgO or Al ₂ O _3.

In the resin composition for three-dimensional modeling of the present invention, it is preferable that the inorganic filler particles are glass fillers.

Stereolithography resin composition of the present invention, the glass filler is a glass composition including, in _{mass%, SiO 2 20 ~ 70%} , B 2 O 3 0 ~ 50%, Nb 2 O 5 0 ~ 20%, WO 3 It preferably contains 0 to 20%.

The method for producing a resin composition for three-dimensional modeling of the present invention is characterized by mixing large particle size particles having different particle size distributions, inorganic filler particles containing small particle size particles, and a curable resin. In this way, since the small particle size particles serve as a dispersant, the dispersibility of the large particle size particles in the resin composition is improved. As a result, it is possible to sufficiently increase the mechanical strength of the three-dimensional model obtained from the resin composition.

In the method for producing the resin composition for three-dimensional modeling of the present invention, the cumulative 10% particle size (D ₁₀ ) and the cumulative 50% particle size (D _{50) by the laser diffraction scattering type particle size distribution measurement of the large particle size particles and the small particle size particles.} ), It is preferable that the following range is satisfied.
The large particle size D ₁₀ is 5-9 μm and the D ₅₀ is 8-15 μm.
_{D 10 of} small particle size particles is 0.5 to 3 μm, and D ₅₀ is 1 to 6 μm.

In the method for producing the resin composition for three-dimensional modeling of the present invention, the mixing ratio of the large particle size particles and the small particle size particles is preferably 95: 5 to 30:70 in terms of mass ratio.

The three-dimensional model of the present invention is formed by dispersing inorganic filler particles in a resin, and has a cumulative 10% particle diameter (D ₁₀ ) and a cumulative 50 by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles. % The ratio D ₅₀ / D ₁₀ to the particle size (D ₅₀ ) is 2.1 or more.

According to the present invention, it is possible to provide a resin composition for three-dimensional modeling capable of sufficiently increasing the mechanical strength of the three-dimensional modeling object containing inorganic filler particles.

It is a graph which shows the particle size distribution by the laser diffraction scattering type particle size distribution measurement of the inorganic filler particle in each sample of an Example.

The resin composition for three-dimensional modeling of the present invention contains inorganic filler particles and a curable resin. Each component will be described below.

(Inorganic filler particles)
2. The ratio D ₅₀ / D _{10 of the cumulative 10% particle diameter (D 10} ) to the cumulative 50% particle diameter (D ₅₀ ) measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles is 2.1 or more. It is preferably 5 or more, 3 or more, and particularly preferably 3.3 or more. In this way, for example, the particle size distribution has a peak near the median value and also has a peak near a value considerably smaller than the median value (that is, has two or more peaks). If D ₅₀ / D ₁₀ is too small, the amount of small particle size particles contained in the inorganic filler particles is small, and the dispersibility of the inorganic filler particles tends to decrease, so that the mechanical strength of the three-dimensional structure is sufficiently increased. It becomes difficult to raise. The upper limit of D ₅₀ / D ₁₀ is not particularly limited, but is actually 10 or less.

D ₁₀ is preferably 0.5 to 10 μm, 1 to 8 μm, and particularly preferably 1.5 to 5 μm. Further, D ₅₀ is preferably 3 to 25 μm, 3 to 20 μm, 3.5 to 15 μm, 4 to 12 μm, and particularly preferably 5 to 10 μm. If D10 or D50 is too small, light scattering between the inorganic filler particles and the curable resin increases, and it becomes difficult to obtain a highly transparent three-dimensional model. On the other hand, if D ₁₀ or D ₅₀ is too large, the dispersibility of the inorganic filler particles in the resin composition tends to decrease.

The _{inorganic filler particles in which D 50} / D ₁₀ satisfies a predetermined range can be produced, for example, by mixing two types of particles (large particle size particles and small particle size particles) having different particle size distributions. .. For example, the particle size D ₁₀ of the large particle size particles is preferably 5 to 9 μm, and the particle size D ₅₀ is preferably 8 to 15 μm. On the other hand, the particle size D ₁₀ of the small particle size particles is preferably 0.5 to 3 μm, and the particle size D ₅₀ is preferably 1 to 6 μm. In this way, it is possible to obtain a three-dimensional model having excellent dispersibility of the inorganic filler particles and, by extension, excellent mechanical strength.

The density of the inorganic filler particles is preferably 3.5 g / cm ³ or less, 3 g / cm ³ or less, 2.8 g / cm ³ or less, and particularly preferably 2.6 g / cm ³ or less. In this way, even when D ₅₀ / D ₁₀ is large, sedimentation separation is less likely to occur. The lower limit of the density is not particularly limited, but in reality, it is 2 g / cm ³ or more.

The density difference between the large particle size particles and the small particle size particles constituting the inorganic filler particles is 0.3 g / cm ³ or less, 0.2 g / cm ³ or less, 0.1 g / cm ³ or less, and particularly 0.05 g. It is preferably / cm ^{3 or less.} In this way, sedimentation separation due to the difference in particle size between the large particle size particles and the small particle size particles is less likely to occur. When the density of the large particle size particles and the density of the small particle size particles are different, it is advantageous that the density of the large particle size particles is smaller than the density of the small particle size particles from the viewpoint of suppressing sedimentation separation.

Here, when the small particle size particles are in a crushed state, the function as a dispersant is enhanced, and the effect of the present invention can be easily obtained. From this point of view, the specific surface area of the small particle size particles ^{is preferably 0.5 m 2} / g or more, particularly preferably 1 m ² / g or more. The upper limit of the specific surface area of the small particle size particles is not particularly limited, but is practically 5 m ² / g or less.

On the other hand, the large particle size particles are preferably substantially spherical (particularly true spherical) from the viewpoint of suppressing light scattering at the interface between the particles and the resin and obtaining a highly transparent three-dimensional model. From this point of view, the sphericity represented by the minor axis / major axis of the large particle size particles is preferably 0.8 or more, 0.9 or more, and particularly preferably 0.95 or more. The specific surface area of the large particle size particles is preferably 2 m ² / g or less, 1 m ² / g or less, and particularly preferably 0.5 m ² / g or less. The lower limit of the specific surface area of the large particle size particles is not particularly limited, but is practically 0.05 m ² / g or more.

The mixing ratio (mass ratio) of the large particle size particles and the small particle size particles is preferably 95: 5 to 30:70, more preferably 90:10 to 40:60, and 80:20 to 50. : 50 is more preferable. If there are too many large particle size particles (too few small particle size particles), the D ₅₀ / D ₁₀ of the inorganic filler particles becomes small, and the dispersibility of the inorganic filler particles tends to decrease. It becomes difficult to sufficiently increase the mechanical strength. On the other hand, if the number of large particle size particles is too small (the number of small particle size particles is too large), the viscosity of the resin composition tends to be high and three-dimensional modeling tends to be difficult.

The inorganic filler particles are preferably _{SiO 2} , MgO, and Al ₂ O ₃ from the viewpoint that they can be easily formed into a desired shape. In particular, SiO ₂ has a low density and is unlikely to undergo sedimentation separation after being mixed with a resin, and has a relatively dense structure, so that the specific surface area tends to be small, and when mixed with a resin, it has the effect of suppressing an increase in viscosity. high.

As the inorganic filler particles, a glass filler is also preferable because it can be easily formed into a desired shape. Glass filler, a glass composition, in _{mass%, SiO 2 20 ~ 70%} , B 2 O 3 0 ~ 50%, Nb 2 O 5 0 ~ 20%, include those containing WO 3 0 ~ 20% .. Hereinafter, the reason for limiting each component as described above will be described. In the description of the content range of each component, the% indication means mass%.

SiO ₂ is a component that forms a glass skeleton. It also has the effect of improving chemical durability and suppressing devitrification. The content of SiO ₂ is preferably 20 to 70%, 30 to 65%, and particularly preferably 40 to 60%. If _{the content of SiO 2} is too small, the chemical durability tends to decrease, and the glass tends to be devitrified, which may make manufacturing difficult. On the other hand, _{if the content of SiO 2} is too large, the meltability tends to decrease, and it becomes difficult to soften during molding, which may make manufacturing difficult.

B ₂ O ₃ is a component that forms a glass skeleton. It also has the effect of improving chemical durability and suppressing devitrification. The content of B ₂ O ₃ is preferably 0 to 50%, 2.5 to 40%, and particularly preferably 5 to 30%. If _{the content of B 2} O ₃ is too large, the meltability tends to decrease, and it becomes difficult to soften during molding, which may make manufacturing difficult.

Nb ₂ O ₅ is a component whose refractive index and Abbe number can be adjusted. The content of Nb ₂ O ₅ is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, and particularly preferably 1 to 5%. If _{the content of Nb 2} O ₅ is too large, the refractive index tends to increase and the Abbe number tends to decrease. Furthermore, the glass is easily devitrified.

WO ₃ is a component that can adjust the refractive index and Abbe number, and is a component that lowers the viscosity of glass. The content of WO ₃ is preferably 0 to 20%, 0.1 to 15%, 0.5 to 10%, and particularly preferably 1 to 5%. If the amount of WO ₃ is too large, the refractive index tends to be large and the Abbe number tends to be small. Furthermore, the glass tends to be easily colored.

In addition to the above components, for example, the following components can be contained.

Al ₂ O ₃ is a vitrification stabilizing component. It also has the effect of improving chemical durability and suppressing devitrification. The content of Al ₂ O ₃ is preferably 0 to 30%, 2.5 to 25%, and particularly preferably 5 to 20%. If _{the content of Al 2} O ₃ is too large, the meltability tends to decrease. In addition, it may be difficult to soften during molding, which may make manufacturing difficult.

Li ₂ O is a component that lowers the viscosity of glass and suppresses devitrification. The content of Li ₂ O is preferably 0 to 10%, 0.1 to 9%, 0.5 to 7%, and particularly preferably 1 to 5%. If _{the content of Li 2} O is too large, the chemical durability tends to decrease, and the glass tends to be devitrified, which may make manufacturing difficult.

Na ₂ O is a component that lowers the viscosity of glass and suppresses devitrification. The Na ₂ O content is preferably 0 to 10%, 0.1 to 7.5%, 0.5 to 5%, and particularly preferably 1 to 2.5%. If the Na ₂ O content is too high, the chemical durability tends to decrease, and the glass tends to be devitrified, which may make production difficult.

K 2 _O is with lowering the viscosity of the glass is a component to suppress devitrification. The content of K ₂ O is 0-10% from 0.1 to 8 percent, from 0.5 to 6%, particularly preferably 1-4%. If _{the content of K 2} O is too large, the chemical durability tends to decrease, and the glass tends to be devitrified, which may make manufacturing difficult.

The total amount of Li ₂ O, Na ₂ O and K ₂ O in the glass composition is preferably 10% or less, 6% or less, and particularly preferably 5% or less. If the total amount of these components is limited as described above, it becomes easy to suppress the evaporation of the alkaline components in the glass generated during resin curing. Further, since the decrease in chemical durability can be suppressed, the deterioration of the resin due to alkali elution can be suppressed, for example. Therefore, a colorless and transparent three-dimensional model can be easily obtained, and deterioration of the obtained model over time can be prevented. Furthermore, since the coefficient of thermal expansion of glass can be reduced, thermal shock and heat shrinkage during curing can be suppressed.

MgO, CaO, SrO, BaO and ZnO are components that act as intermediate substances in glass and enhance the stability of vitrification. The contents of these components are preferably 0 to 25%, 0.5 to 20%, and particularly preferably 1 to 15%, respectively. If the content of each component is too large, the chemical durability tends to decrease, and the glass tends to be devitrified, which may make manufacturing difficult.

TiO ₂ is a component that can adjust the refractive index and Abbe number, and is a component that lowers the viscosity of glass. The content of TiO ₂ is preferably 0 to 15%, 0.1 to 12%, 0.5 to 10%, and particularly preferably 1 to 5%. If _{the content of TiO 2} is too large, the refractive index tends to be large and the Abbe number tends to be small. In addition, the glass is easily colored.

The total amount of TiO ₂ , Nb ₂ O ₅ and WO _{3 in} the glass composition is preferably 0 to 30%, 0.1 to 25%, 1 to 20%, and particularly preferably 3 to 15. In this way, the refractive index and the Abbe number can be easily adjusted, and the devitrification of the glass can be easily suppressed. Furthermore, it becomes easier to obtain glass with high chemical durability.

The total amount of Nb ₂ O ₅ and WO _{3 in} the glass composition is preferably 0 to 30%, 0.1 to 25%, 1 to 20%, and particularly preferably 2 to 15%. In this way, the refractive index and the Abbe number can be easily adjusted, and coloring becomes difficult. In addition, it becomes easy to suppress devitrification of glass. Furthermore, it becomes easier to obtain glass with high chemical durability.

It is preferable that the surface of the inorganic filler particles is treated with a silane coupling agent. By treating with a silane coupling agent, the bonding force between the inorganic filler particles and the curable resin can be enhanced, and a three-dimensional model having higher mechanical strength can be obtained. Further, the inorganic filler particles and the curable resin become more familiar with each other, and bubbles and voids at the interface can be reduced. As a result, light scattering can be suppressed and the light transmittance can be increased. As the silane coupling agent, for example, aminosilane, epoxysilane, acrylicsilane and the like are preferable. The silane coupling agent may be appropriately selected depending on the curable resin used.

The content of the inorganic filler particles is preferably 1 to 300 parts by mass, 10 to 200 parts by mass, 20 to 150 parts by mass, and particularly preferably 30 to 100 parts by mass with respect to 100 parts by mass of the curable resin. If the amount of inorganic filler particles is too small, the mechanical strength of the three-dimensional model tends to decrease. On the other hand, if the amount of the inorganic filler particles is too large, the viscosity of the resin composition becomes too high, the fluidity of the resin decreases, and three-dimensional modeling tends to be difficult.

(Curable resin)
The curable resin may be either a photocurable resin or a thermosetting resin, and can be appropriately selected depending on the molding method to be adopted. For example, when the stereolithography method is used, a liquid photocurable resin may be selected.

Examples of the photocurable resin include polyamide resins, polyamideimide resins, polyacetal resins, (meth) acrylic resins, melamine resins, (meth) acrylic-styrene copolymers, polycarbonate resins, and styrene resins. , Polyvinyl chloride resin, benzoguanamine-melamine formaldehyde, silicone resin, fluorine resin, polyester resin, crosslinked (meth) acrylic resin, crosslinked polystyrene resin, crosslinked polyurethane resin, epoxy resin and the like.

Examples of the thermosetting resin include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins, phenol resins, and non-thermosetting resins. Examples thereof include saturated polyester-based resins, bismaleimide triazine resins, alkyd-based resins, furan-based resins, melamine-based resins, polyurethane-based resins, and aniline-based resins.

The content of the inorganic filler powder with respect to the total amount of the thermoplastic resin powder and the inorganic filler powder is 1 to 70% by volume, 1 to more than 60%, 5 to 50%, 10 to 40%, and particularly 15 to. It is preferably 30%. If the content of the inorganic filler powder is too small, the mechanical strength of the three-dimensional model tends to decrease. On the other hand, if the content of the inorganic filler powder is too large, the adhesion between the thermoplastic resin and the inorganic filler powder is inferior, and the mechanical strength of the three-dimensional model tends to decrease.

Next, an example of a method for manufacturing a three-dimensional model will be described. Specifically, a method for producing a three-dimensional model using a resin composition containing a photocurable resin will be described. The resin composition is as described above, and description thereof will be omitted here.

First, a single 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 upper surface of the stage is positioned so as to have a desired depth (for example, about 0.2 mm) from the liquid surface. By doing so, a liquid layer 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. As the active energy ray, laser light such as visible light or infrared light can be used in addition to ultraviolet light.

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

After that, the 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.

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

Table 1 shows the glass powders A and B used in Examples and Comparative Examples of the present invention. Table 2 shows Examples (No. 2 to 4) and Comparative Examples (No. 1) of the present invention.

 

 

(Preparation of inorganic filler particles)
Raw material powders were mixed to prepare raw material batches so as to have the glass compositions shown in Table 1. The obtained raw material batch was melted at 1580 to 1600 ° C. until it became homogeneous, and then poured between a pair of rollers to form a film.

The obtained film-shaped glass was crushed using a bead mill, the obtained glass powder was supplied into a furnace with a table feeder, and heated and melted at 1400 to 2000 ° C. with an air burner to form spheroids. Glass powder A was obtained by classifying the spheroidized glass powder with an air flow type classifier. On the other hand, the film-like glass obtained above was pulverized using a ball mill, and the obtained glass powder was classified by an air flow type classifier to obtain a crushed glass powder B. The glass powders A and B were surface-treated with aminosilane.

Inorganic filler particles were obtained by mixing the obtained glass powder A and glass powder B at the ratios shown in Table 2. FIG. 1 shows a graph showing the particle size distribution of the inorganic filler particles in each sample by laser diffraction scattering type particle size distribution measurement.

(Preparation of resin composition)
Weigh 100 parts by mass of curable resin (DL360 manufactured by Digital Wax Co., Ltd.) so that the amount of inorganic filler particles is 30 parts by mass, and mix the resin using a self-revolving mixer (ARE-310 manufactured by Shinky Co., Ltd.). The composition was obtained.

(Evaluation of dispersibility of inorganic filler particles)
10 g of the resin composition obtained above was placed in a glass container having a length of 5 mm, a width of 30 mm, and a height of 50 mm, and the depth (precipitation amount) of the inorganic filler particles settled on the bottom of the container was measured after 100 hours. The results are shown in Table 2.

As shown in Table 2, No. The resin compositions of Nos. 2 to 4 had a precipitation amount of 0.3 to 1.0 mm, whereas No. 2 to No. 4 was a comparative example. The resin composition of No. 1 had a sedimentation amount of 3.0 mm.

(Making a three-dimensional model)
The resin composition was poured into a Teflon (registered trademark) mold having an inner size of 50 mm □. Then, it was irradiated with light of 500 mW and a wavelength of 364 nm, cured, and cured at 80 ° C. The obtained three-dimensional model was processed into a rod shape of 3 mm × 4 mm × 50 mm, and the bending strength was measured. The results are shown in Table 2. Bending strength was measured by the method of JIS R1601.

As shown in Table 2, No. While the bending strength of the three-dimensional model 2 to 4 is 84 to 94 MPa, No. 2 is a comparative example. The bending strength of the three-dimensional model No. 1 was as low as 78 MPa.

Claims (11)

1. A resin composition for three-dimensional modeling containing inorganic filler particles and a curable resin, which has a cumulative 10% particle diameter (D ₁₀ ) and a cumulative 50% particle diameter (D 10) and a cumulative 50% particle diameter (D 10) measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles. A resin composition for three-dimensional modeling, characterized in that the ratio D ₅₀ / D _{10 to D 50) is 2.1 or more.}
2. The resin composition for three-dimensional modeling according to claim 1, wherein the _{cumulative 50% particle diameter (D 50} ) measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles is 3 to 25 μm.
3. The resin composition for three-dimensional modeling according to claim 1 or 2, wherein the _{cumulative 10% particle diameter (D 10} ) measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles is 0.5 to 10 μm.
4. The resin composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the inorganic filler particles have a plurality of peaks in the particle size distribution.
5. The resin composition for three-dimensional modeling according to any one of claims 1 to 4, wherein the inorganic filler particles are SiO ₂ , MgO or Al ₂ O _3.
6. The resin composition for three-dimensional modeling according to any one of claims 1 to 5, wherein the inorganic filler particles are glass fillers.
7. Glass filler is a glass composition including, in _mass%, and characterized in that it contains _{SiO 2 20 ~ 70%, B} 2 O 3 0 ~ 50%, Nb 2 O 5 0 ~ 20%, a WO 3 0 ~ 20% The resin composition for three-dimensional modeling according to claim 6.
8. A method for producing a resin composition for three-dimensional modeling, which comprises mixing large particle size particles having different particle size distributions, inorganic filler particles containing small particle size particles, and a curable resin.
9. A claim characterized in that the _{cumulative 10% particle size (D 10} ) and the cumulative 50% particle size (D ₅₀ ) by laser diffraction scattering type particle size distribution measurement of large particle size particles and small particle size particles satisfy the following ranges. Item 8. The method for producing a resin composition for three-dimensional modeling according to Item 8.
   The large particle size D ₁₀ is 5-9 μm and the D ₅₀ is 8-15 μm.
   _{D 10 of} small particle size particles is 0.5 to 3 μm, and D ₅₀ is 1 to 6 μm.
10. The method for producing a resin composition for three-dimensional modeling according to claim 8 or 9, wherein the mixing ratio of the large particle size particles and the small particle size particles is 95: 5 to 30:70 in terms of mass ratio.
11. It is a three-dimensional model in which inorganic filler particles are dispersed in a resin, and has a cumulative 10% particle diameter (D ₁₀ ) and a cumulative 50% particle diameter (D _{50) measured by laser diffraction / scattering particle size distribution measurement of the inorganic filler particles.} ) To D ₅₀ / D ₁₀ is 2.1 or more.

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