JP2021011107A - Powder material for producing three-dimensional object, kit for producing three-dimensional object, and method and apparatus for producing three-dimensional object - Google Patents

Abstract

To provide a powder material for producing a three-dimensional object capable of producing a three-dimensional object excellent in strength before sintering, high sintered density, and dimensional accuracy.SOLUTION: There is provided a powder material for producing a three-dimensional object including: a base material; a resin; and resin particles, in which an amount W (mass %) of carbon remaining in the powder material after heating in a vacuum of 10-2 Pa or lower at 450°C for 2 hours satisfies the following formula: W (mass%)<0.9/M, in which M represents a specific gravity of the base material.SELECTED DRAWING: None

Description

The present invention relates to a powder material for three-dimensional modeling, a kit for three-dimensional modeling, and a method and an apparatus for manufacturing a three-dimensional model.

Recently, there is an increasing need for low-lot production of complex and fine three-dimensional objects. As a technique for meeting this need, a powder sintering method, a powder bonding method, and the like have been proposed (see, for example, Patent Documents 1 to 3).
In the powder sintering method, a thin layer of powder is formed, the thin layer is irradiated with laser light to form a thin sintered body, and by repeating this operation, the thin sintered body is placed on the thin layer. This is a method in which thin sintered bodies are sequentially laminated to obtain a desired three-dimensional model. Further, in the powder bonding method, instead of performing laser sintering in the powder sintering method, a powder thin layer is cured by using an adhesive material, and the powder thin layers are laminated to obtain a desired three-dimensional model. How to get it.
As this powder bonding method, for example, a method of supplying an adhesive material to a thin powder layer by an inkjet method, or a method of laminating a powder material in which powder particles and adhesive particles are mixed and applying a binder is applied. Adhesive material A method for producing a three-dimensional model by dissolving and solidifying particles, a powder material in which a substrate such as glass or ceramic is coated with a hydrophobic resin, and a resin coated with a hydrophobic solvent such as limonene. A method of producing a three-dimensional model by solidifying it by dissolving it has been proposed (see, for example, Patent Document 4).
Further, in order to prevent clogging and increase the variation of adhesive materials that can be used, a method for manufacturing a three-dimensional model in which the material of the curing liquid to be used is selected has been proposed (see, for example, Patent Document 5).

An object of the present invention is to provide a powder material for three-dimensional modeling capable of obtaining a three-dimensional model having excellent strength before sintering, high sintering density, and dimensional accuracy.

The means for solving the above-mentioned problems are as follows. That is, the powder material for three-dimensional modeling of the present invention has a base material, a resin, and resin fine particles.
It is a powder material for three-dimensional modeling, characterized in that the residual carbon amount W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)

According to the present invention, it is possible to provide a powder material for three-dimensional modeling capable of obtaining a three-dimensional model having excellent strength before sintering, high sintering density, and dimensional accuracy.

FIG. 1A is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus of the present invention. FIG. 1B is a schematic view showing another example of the operation of the three-dimensional model manufacturing apparatus of the present invention. FIG. 1C is a schematic view showing another example of the operation of the three-dimensional model manufacturing apparatus of the present invention. FIG. 1D is a schematic view showing another example of the operation of the three-dimensional model manufacturing apparatus of the present invention. FIG. 1E is a schematic view showing another example of the operation of the three-dimensional model manufacturing apparatus of the present invention.

(Powder material for 3D modeling)
The powder material for three-dimensional modeling of the present invention has a base material, a resin, and resin fine particles, and further has other components as required.
It is preferable that the powder material for three-dimensional modeling of the present invention has a coating film of the resin in which the resin contains a non-aqueous first resin and covers the surface of the base material.
Further, in the powder material for three-dimensional modeling of the present invention, it is preferable that the resin fine particles contain a second resin and the resin fine particles are contained on the coating film.
Further, the powder material for three-dimensional modeling of the present invention is suitably used for the method for producing a three-dimensional model of the present invention, which will be described later, and the apparatus for producing a three-dimensional model of the present invention.

In the powder material for three-dimensional modeling of the present invention, the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)
When AlSi10Mg, which will be described later, is used as the base material, the value of M (g / cm ³ ) is 2.65 g / cm ³ , and the W (mass%) is less than 0.34, which is 0. Less than .17 is preferred. When the W (mass%) is less than 0.34, a three-dimensional model having a high sintering density can be obtained.
When titanium, which will be described later, is used as the base material, the value of M (g / cm ³ ) is 4.51 g / cm ³ , and the W (mass%) is less than 0.20, which is 0. It is preferably less than 10. When the W (mass%) is less than 0.20, a three-dimensional model having a high sintering density can be obtained.

The residual carbon amount W (mass%) can be measured by, for example, the following measuring method.
First, the powder material for three-dimensional modeling of the present invention is heated using a known vacuum degreasing furnace under the following conditions to obtain a powder material for three-dimensional modeling after heating.
・ Heating temperature: 450 ℃
・ Heating time: 2 hours ・ Heating environment: ^10-2 Pa or less under vacuum ・ Heating rate: 200 ° C / h
The residual carbon amount W of the obtained powder material for three-dimensional modeling after heating is measured under the following conditions using a solid carbon analyzer (EMIA-STEP) manufactured by Horiba Seisakusho Co., Ltd.
Purge time: 0 seconds, integration waiting time: 5 seconds, integration time: 60 seconds Comparator level: 1.0% Comparator waiting time: 15 seconds Set temperature: 1350 ° C. Time: 1500 seconds Sample weight: 0.1 g
Flame retardant: tin 0.5g
When Ti is used as the base material, 0.5 g of pure iron, 1.5 g of tungsten, and 0.3 g of tin are used as the combustion improver.

The resin content of the three-dimensional model produced by using the powder material for three-dimensional modeling satisfying the above formula is constant with respect to a constant volume. Since the resin content is constant, the residual carbon amount W (mass%) per mass of the three-dimensional model varies depending on the specific gravity of the base material (metal).
When the powder material for three-dimensional modeling in which the residual carbon amount W (mass%) measured by the above measuring method is 0.34 mass% or more is sintered, the sintering does not proceed and the high sintering density is obtained. It was found that the three-dimensional model of was not obtained. The formula is a formula for deriving a powder material for a three-dimensional model in which the residual carbon amount measured by the measuring method is less than 0.34 mass%.
Further, the present inventors are particularly difficult to sinter aluminum among difficult-sintered bodies such as aluminum (Al), titanium (Ti), and copper (Cu) as the base material, and the cause is the residual carbon amount W. It was found to be (mass%). It is considered that this is because the residual carbon hinders the contact between the aluminum particles in the sintering process, causing a sintering failure. The above formula is based on the case where aluminum, which is difficult to sinter, is used as a base material.

-Base material-
The base material is not particularly limited as long as it has the form of powder or particles, and can be appropriately selected depending on the intended purpose. As the material thereof, for example, metals, ceramics and the like are preferable.

The metal is not particularly limited as long as it contains a metal as a material, and for example, a difficult-to-sinter body such as aluminum (Al), titanium (Ti), copper (Cu), magnesium (Mg), and the like. Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), Molybdenum (Mo), lead (Pd), silver (Ag), indium (In), tin (Sn), tantalum (Ta), tungsten (W), neodium (Nd) and alloys thereof. Among these, stainless (SUS) steel, iron (Fe), copper (Cu), silver (Ag), titanium (Ti), aluminum (Al), alloys thereof and the like are preferable, and aluminum (Al) and titanium (Al) Hard-sintered bodies such as Ti) and copper, and alloys thereof are more preferable. Examples of the aluminum alloy include AlSi10Mg, AlSi12, AlSi7Mg0.6, AlSi3Mg, AlSi9Cu3, Scalmalloy, and ADC12.
These may be used alone or in combination of two or more.

Examples of the ceramics include oxides, carbides, nitrides, hydroxides and the like.
Examples of the oxide include metal oxides and the like. Examples of the metal oxide include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), and titania (TIO ₂ ). However, these are examples, and the present invention is not limited to these. These may be used alone or in combination of two or more.

A commercially available product can be used as the base material. Examples of the commercially available product include pure Al (manufactured by Toyo Aluminum Co., Ltd., A1070-30BB), pure Ti (manufactured by Osaka Titanium Technologies Co., Ltd.), SUS316L (manufactured by Sanyo Special Steel Co., Ltd., trade name: PSS316L); AlSi10Mg (Toyo). Aluminum Co., Ltd., Si10Mg30BB); SiO ₂ (Tokuyama Co., Ltd., trade name: Excelica SE-15K), AlO ₂ (Daimei Chemicals Co., Ltd., trade name: Taimicron TM-5D), ZrO ₂ (Tosoh Co., Ltd.) Made by a company, product name: TZ-B53) and the like.
The base material may be subjected to a known surface treatment (surface modification treatment) for the purpose of improving the adhesiveness with the resin and the coating property.

The volume average particle diameter of the base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2 μm or more and 80 μm or less is preferable, and 8 μm or more and 50 μm or less is more preferable.
When the volume average particle diameter of the base material is 2 μm or more, it is possible to prevent the influence of agglutination from increasing, and it becomes easy to perform resin coating on the base material, resulting in a decrease in yield and a decrease in production efficiency of a model. It is possible to prevent deterioration of the handleability and handleability of the material. Further, when the volume average particle diameter is 80 μm or less, when a thin layer is formed by using the three-dimensional modeling powder material, the filling rate of the three-dimensional modeling powder material in the thin layer is improved and obtained. It is difficult for voids to occur in the three-dimensional model.
The particle size distribution of the base material is not particularly limited and may be appropriately selected depending on the intended purpose, but the particle size distribution is preferably sharper.

The content of the base material having a volume average particle diameter of 10 μm or less with respect to the total amount of the base material is preferably 1.5% or more. When the content of the base material having a volume average particle diameter of 10 μm or less with respect to the total amount of the base material is 1.5% or more, the filling rate of the powder material for three-dimensional modeling in the powder material layer is improved. , It becomes difficult for voids and the like to occur in the obtained three-dimensional model. Among the base materials, the highly active metal (for example, aluminum, titanium, etc.) is difficult to use for three-dimensional modeling because the dust explosiveness becomes extremely high when the fine particles are 10 μm or less, but the resin in the present invention. As a result, the dust explosiveness is extremely reduced, so that the highly active metal powder material can be used. Being able to handle powders with a smaller particle size leads to reduction of surface roughness and improvement of sintered body density.
The volume average particle size and particle size distribution of the base material can be measured using a known particle size measuring device, and examples thereof include a particle size distribution measuring device Microtrack MT3000II series (manufactured by Microtrack Bell).

The outer shape, surface area, circularity, fluidity, wettability, etc. of the base material can be appropriately selected depending on the intended purpose.

The base material can be produced by using a conventionally known method. Examples of the method for producing a powder or particulate base material include a pulverization method in which a solid is subdivided by applying compression, impact, friction, etc., an atomization method in which a molten metal is sprayed to obtain a rapidly cooled powder, and a method in which the solid is dissolved in a liquid. Examples thereof include a precipitation method in which a component is precipitated, a gas phase reaction method in which the component is vaporized and crystallized.
The base material is not limited to the production method thereof, but a more preferable method is, for example, an atomizing method because a spherical shape can be obtained and the particle size does not vary much. Examples of the atomizing method include a water atomizing method, a gas atomizing method, a centrifugal atomizing method, a plasma atomizing method, and the like, all of which are preferably used.

-Resin-
The resin preferably contains a non-aqueous first resin, and further contains other components as needed. Further, the powder material for three-dimensional modeling of the present invention preferably has a coating film of the resin that covers the surface of the base material.
The composition of the resin may be the same as or different from the composition of the resin fine particles described later.
The resin may have a property of being soluble in a curing liquid and curable by the action of a curing agent contained in the curing liquid. When the three-dimensional modeling powder material has the resin, it is possible to prevent the occurrence of dust explosion and the like, and to obtain a three-dimensional modeling powder material having excellent safety.
In the present invention, the resin is soluble (soluble), for example, when 1 g of the non-aqueous first resin is mixed with 100 g of a solvent constituting a curing solution at 50 ° C. and stirred. It means a solvent in which mass% or more is dissolved.
Further, the non-aqueous first resin in which the residual carbon amount (mass%) of the three-dimensional modeling powder material satisfies the above formula can be selected by the following selection method. Eg, _{N 2} gas flow of the TG-DTA (200mL / min) , then heated under conditions of heating rate 10 ° C. / min, is not less than 97% weight loss at 400 ° C., no carbon residue 550 ° C. The resin can be selected as the preferred non-aqueous first resin.

The non-aqueous first resin has low reactivity with a metal (highly active metal) having high activity as the base material and water with respect to powder, and the resin before applying the curing solution is an organic solvent (described later). The resin is soluble (soluble) in the first and second organic solvents), and the resin after the curing liquid is applied (after curing) is insoluble (insoluble) in the organic solvent. In particular, it is preferable that it has low solubility in water and is soluble in an organic solvent.
By forming a coating film in which the resin covers the surface of the base material, it is possible to suppress a dust explosion that occurs when the size of the particles of the base material is small. Further, having the coating film makes it possible to work in an air atmosphere.
Further, the coating film has low reactivity with a metal (highly active metal) powder having high activity as the base material, and the coating film before applying the curing solution can be dissolved (soluble) in the organic solvent. Therefore, if the coating film after applying the curing solution (after curing) is insoluble (insoluble) in the organic solvent, it can be applied even if the base material is a water-prohibited material such as a highly active metal. It is possible to prevent the three-dimensional model produced from collapsing even when immersed in a solvent-based solution. That is, by having the coating film on the surface of the base material, it is possible to suppress unintended deterioration of the base material surface and generation of gas.

As the non-aqueous first resin, if the solubility in water is 0.5 (g / 100 g-H2O) or less (dissolves in the range of 0.5 g or less with respect to 100 g of water at 25 ° C.). There are no particular restrictions, and examples thereof include acrylic, acrylic polyol, polyester, epoxy, polyol, urethane, polyether, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride, vinyl acetate, paraffin-olefin type, and ethyl cellulose. Further, as long as it exhibits solubility in the cured liquid, there is no particular limitation, and it may be a homopolymer (homopolymer) or a heteropolymer (copolymer), and it may be modified. Alternatively, a known functional group may be introduced. These may be used alone or in combination of two or more. If the resin in the first half is soluble in an organic solvent, dust explosion can be suppressed and molding quality can be guaranteed.
The weight average molecular weight of the non-aqueous first resin is preferably 150,000 or less, more preferably 20,000 or more and 100,000 or less, and preferably a weight average molecular weight of 100,000 or less and being a solid at room temperature. ..

The non-aqueous first resin may be a commercially available product. Examples of the commercially available product include polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., BM-5), a copolymer of vinyl acetate and vinyl chloride (manufactured by Nissin Chemical Co., Ltd., Solveine A), and a polyacrylic polyol (manufactured by DIC: ADEKA CORPORATION). Dick WFU-580, etc.), Polyester polyol (DIC: Polylite OD-X-668, etc., ADEKA: Adeka New Ace YG-108, etc.), Polybutadiene polyol (Nippon Soda, GQ-1000, etc.), Polyvinyl Butyral and polyvinyl ADEKA (manufactured by Sekisui Chemical Co., Ltd .: Eslek BM-2, KS-1, etc., manufactured by Kuraray: Mobital B20H, etc.), acrylic polyol (manufactured by Toei Kasei Co., Ltd .: TZ9515), ethyl cellulose (manufactured by Nikkei Seisei Co., Ltd .: ETHOCEL) and the like.

The average thickness of the coating film is preferably 10 nm or more and 800 nm or less, and more preferably 100 nm or more and 600 nm or less. When the average thickness of the coating film is 10 nm or more, the dust explosiveness of the powder material for three-dimensional modeling can be suppressed. Further, since the coating film is dissolved by the curing liquid described later and causes adhesion between the powder materials, it functions as a binder component, so that it is not necessary to add a binder component to the curing liquid and clogging of the nozzle head is suppressed. be able to. As a result, it is possible to manufacture a high-quality three-dimensional model without any modeling defect.
Further, by adjusting the coating film thickness, it is possible to control how the coating spreads when it comes into contact with the organic solvent-based ink, and it is possible to perform modeling with high resolution. When the average thickness as the coating thickness is 10 nm or more, it becomes effective against a dust explosion. Further, when the average thickness is 800 nm or less, the dimensional accuracy of the cured product (three-dimensional model) by the three-dimensional model powder material (layer) formed by applying the organic solvent-based ink to the three-dimensional model powder material is high. improves. If the average thickness exceeds 800 nm, the ratio of the base material to the modeled object decreases, and even powder lamination cannot be filled at high density, and as a result, only a low-density sintered body can be obtained.
The average thickness is determined, for example, by embedding the powder material for three-dimensional modeling in acrylic resin or the like and then performing etching or the like to expose the surface of the base material, and then scanning tunneling microscope STM, atomic force microscope AFM. , It can be measured by using a scanning electron microscope SEM or the like.

The effect of the present invention is given as the ratio of the non-aqueous first resin covering the surface of the base material with respect to the surface area of the base material, that is, the surface coverage ratio of the coating film covering the base material. It may be coated to such an extent that it can be played, and there is no particular limitation, but for example, 15% or more is more preferable, 50% or more is further preferable, and 80% or more is particularly preferable. The state in which the resin covers the surface of the base material may be a continuous film or a discontinuous film when the surface coverage is not 100%.
When the coverage is 15% or more, the effect of suppressing dust explosiveness is large even in highly active metals. The coverage is determined, for example, by observing a photograph of the powder material for three-dimensional modeling, and covering the powder material for three-dimensional modeling shown in the two-dimensional photograph with the organic material with respect to the entire surface area of the powder material particles. The average value of the ratio (%) of the area of the portion may be calculated and used as the coverage, or the portion covered with the organic material may be subjected to energy dispersive X-ray spectroscopy such as SEM-EDS. It can be measured by performing element mapping.

-Resin fine particles-
The resin fine particles preferably contain a second resin, and further contain other components as needed. Further, the powder material for three-dimensional modeling of the present invention preferably has the resin fine particles on the coating film.
As the resin fine particles, it is preferable that the cured liquid dissolves 1/4 or more of the diameter of the resin fine particles.

The volume average particle diameter of the resin fine particles is preferably 600 nm or less, more preferably 200 nm or less.
When the volume average particle diameter of the resin fine particles is 600 nm or less, the adhesive force between the particles (powder) can be significantly reduced by the Spencer effect, and the fluidity can be significantly improved. Therefore, since a uniform and high-density powder bed can be formed, the uniformity, density, accuracy, and hardness of the three-dimensional model (green body) to be produced can be significantly improved. Therefore, even if the manufactured three-dimensional model is held by hand or the excess powder material is removed by air blow treatment, the subsequent treatment can be performed without collapsing. Further, the uniform and high-density powder bed has uniform ink permeability, and can form a three-dimensional model having uniform and good hardness and accuracy. In the obtained three-dimensional model, the base material exists at a high density and the amount of the resin around the base material is small, so that the molded product (sintered body) obtained by sintering the three-dimensional model is unnecessary. There are few voids, and the appearance can be beautiful.
Further, when the volume average particle size of the resin fine particles is 200 nm or less, the Spencer effect becomes more effective with respect to the powder material for three-dimensional modeling having a small particle size of 10 μm or less, and the effect of improving the fluidity is large. .. Therefore, a smaller particle size base material can be used, and the sinterability and the surface roughness of the modeled object can be improved.
When the volume average particle diameter of the resin fine particles is more than 600 nm, the size of the resin fine particles is close to that of the base material for a powder material for three-dimensional modeling of 10 μm or less, the Spencer effect is weakened, and the fluidity is deteriorated. In addition, the distance between particles becomes large during sintering, and the liquid phase does not join between adjacent particles, causing pores to occur inside the three-dimensional model, or the density of the three-dimensional model decreases, resulting in poor sintering. May occur.

Further, it is preferable that the coating ratio of the resin fine particles on the surface of the base material having the coating film is 3% or more. If the coverage of the resin fine particles is less than 3%, the spencer effect cannot be sufficiently exerted and the fluidity deteriorates. As a result, the modeling quality may deteriorate significantly.
The volume average particle diameter and the coverage of the resin fine particles are determined, for example, by observing a photograph of the powder material for three-dimensional modeling, and for the powder material for three-dimensional modeling shown in the two-dimensional photograph, the resin fine particles existing in the powder material particles. It can be calculated by measuring the average size of 100 grains. Further, with respect to the coverage of the resin fine particles, the ratio (%) of the area of the resin fine particles to the total area of the surface of the powder material particles can be calculated and measured as the coverage.

The second resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it preferably contains acrylic, styrene, amino and the like. Of these, acrylic is preferred. These may be used alone or in combination of two or more.
Examples of the amino include benzoguanamine and the like.

The second resin in which the residual carbon content (mass%) of the three-dimensional modeling powder material satisfies the above formula can be selected by using the same method as the method for selecting the first resin.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a fluidizing agent, a filler, a leveling agent, and a sintering aid.
The fluidizing agent is preferable in that a layer or the like made of the powder material for three-dimensional modeling can be easily and efficiently formed.
The filler is a material that is mainly effective for adhering to the surface of the three-dimensional modeling powder and filling the voids between the powder materials. As an effect, for example, the fluidity of the three-dimensional modeling powder can be improved, the number of contacts between the three-dimensional modeling powder materials can be increased, and the voids can be reduced, so that the strength of the three-dimensional modeling object and its dimensional accuracy can be improved. ..
The leveling agent is mainly an effective material for controlling the wettability of the surface of the modeling powder. As an effect, for example, the permeability of the modeling liquid to the powder layer is increased, the strength of the modeled object can be increased and the speed thereof can be increased, and the shape can be stably maintained.
The sintering aid is an effective material for increasing the sintering efficiency when sintering the obtained modeled object. As an effect, for example, the strength of the modeled object can be improved, the sintering temperature can be lowered, and the sintering time can be shortened.

-Manufacturing method of powder material for 3D modeling-
The method for producing the powder material for three-dimensional modeling is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of coating the resin on the base material according to a known coating method is preferable. Can be mentioned.
The coating method of the resin on the surface of the base material is not particularly limited and may be appropriately adopted from known coating methods. Such coating methods include, for example, a rolling flow coating method and a spray. Preferable examples thereof include a dry method, a stirring and mixing addition method, a dipping method, and a kneader coating method. Further, these coating methods can be carried out by using various known commercially available coating devices, granulating devices and the like.

-Physical characteristics of powder materials for 3D modeling-
The volume average particle diameter of the three-dimensional modeling powder material is not particularly limited and may be appropriately selected depending on the intended purpose. However, the volume average particle diameter is preferably 2 μm or more and 80 μm or less, and the volume average particle diameter is 2 μm or more. Since the fluidity of the powder material is improved, the powder material layer is easily formed, and the smoothness of the laminated layer surface is improved, the manufacturing efficiency of the three-dimensional model is improved, the handling and handling are improved, and the dimensional accuracy is improved. There is a tendency. Further, when the average particle diameter is 80 μm or less, the size of the space between the powder material particles becomes small, so that the porosity of the three-dimensional model becomes small, which contributes to the improvement of the strength. It is preferable that the volume average particle diameter is 2 μm or more and 80 μm or less in order to achieve both dimensional accuracy and strength.
The particle size distribution of the three-dimensional modeling powder material is not particularly limited and may be appropriately selected depending on the intended purpose.

As the characteristics of the powder material for three-dimensional modeling, when the angle of repose is measured, it is preferably 60 degrees or less, more preferably 50 degrees or less, and even more preferably 40 degrees or less.
When the angle of repose is 60 degrees or less, the three-dimensional modeling powder material can be efficiently and stably arranged at a desired place on the support.
The angle of repose can be measured using, for example, a powder property measuring device (Powder tester PT-N type, manufactured by Hosokawa Micron Co., Ltd.) or the like.

The powder material for three-dimensional modeling of the present invention can be suitably used for simple and efficient production of various molded products and structures, and the three-dimensional modeling kit of the present invention, the curing liquid, and the three-dimensional object of the present invention described later. It can be particularly preferably used in the method for producing a modeled object and the apparatus for producing a three-dimensional modeled object of the present invention.
By simply applying the curing liquid to the powder material for three-dimensional modeling of the present invention, a structure having a complicated three-dimensional shape can be manufactured easily, efficiently and with high dimensional accuracy. The structure thus obtained is a cured product (three-dimensional model) having sufficient hardness, and the excess powder material for three-dimensional modeling is removed by holding it by hand, putting it in and out of a mold, or performing an air blow treatment. Even if it does, it does not lose its shape and is excellent in handleability and handleability. The cured product may be used as it is, or may be further subjected to a sintering treatment as a cured product for sintering to obtain a molded product (sintered product of a three-dimensional molded product). Then, when the sintering treatment is performed, unnecessary voids and the like are not generated in the molded product after sintering, and a molded product having a beautiful appearance can be easily obtained.

(Manufacturing method of three-dimensional model and equipment for manufacturing three-dimensional model)
The method for producing a three-dimensional model of the present invention includes a powder material layer forming step of forming a powder material layer using the powder material for three-dimensional modeling of the present invention, and applying a curing liquid to the powder material layer to obtain a cured product. It includes a cured product forming step to be formed, and further includes other steps such as a surplus powder removing step and a sintering step, if necessary.
It is characterized in that a three-dimensional model is produced by repeating the powder material layer forming step and the cured product forming step.
The apparatus for producing a three-dimensional object of the present invention includes a powder material layer forming means, a cured product forming means, and if necessary, other means such as a surplus powder removing means and a sintering means.

The present inventor examined the following problems in the prior art and obtained the following findings.
When the adhesive material is supplied by the inkjet method, there are problems such as clogging of the nozzle head to be used, restrictions on the selection of the adhesive material that can be used, cost and inefficiency.
Further, in the prior art, even if the bonding material is applied and the adhesive particles are dissolved, the dissolved adhesive liquid is difficult to spread uniformly between the powder particles, so that the three-dimensional model is given sufficient strength and accuracy. The problem is that things can be difficult.
Further, in the conventional technique, limonene has low volatility and tends to remain in a three-dimensional model, which may cause a decrease in strength. Further, low volatile solvents such as toluene have a safety problem. Further, the coating resin alone has problems that the fluidity is deteriorated, the accuracy of the three-dimensional model is not sufficiently obtained, and the density of the base material with respect to the three-dimensional model is low.
Further, in the conventional technique, water is contained in the resin or the curing liquid that coats the base material, and it cannot be applied when the base material used is a material having high reactivity with water. There's a problem. Further, since the cross-linking agent is an organometallic salt and the cross-linking structure formed is a chelate complex and the cross-linking reaction is reversible, the water resistance effect is low, and a removal liquid immersion method for collectively treating excess powder of a plurality of shaped products. There is a problem that it cannot be used. Further, in the case of a metal chelate complex, there is a problem that not a little metal component remains in the sintered body and the influence of the metal species causes sintering inhibition.
Furthermore, when modeling by irradiating laser light, in the case of aluminum or titanium, which are highly active metals, it is necessary to model in an inert atmosphere because of its high reactivity. Furthermore, aluminum and titanium powders can easily cause a dust explosion even with static electricity, and it is necessary to prepare a dedicated inert gas replaceable device when handling metal powder in order to suppress the dust explosion. .. Therefore, since the binder jet method is usually carried out in an atmospheric atmosphere, there is a problem that it cannot be handled by modeling using highly active metal powder because of the risk of dust explosion.
Further, conventionally, Al sintering is difficult due to the influence of the oxide film, and if there is a small amount of foreign matter, the way the liquid phase exudes changes, and it is difficult to increase the density while maintaining the shape. In particular, the residual carbon of the binder component hinders the interfacial bond between the powders, causing a problem that the sintering density does not increase.

In the method for producing a three-dimensional model of the present invention, the base material, the resin, and the resin fine particles are provided, and the residual carbon amount W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours. ), However, it has been found that a three-dimensional model having high sintering density and excellent dimensional accuracy can be obtained by using a powder material for three-dimensional modeling that satisfies the following formula.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)

-Powder material layer forming process and powder material layer forming means-
The powder material layer forming step includes a base material, a resin, and resin fine particles, and the residual carbon amount W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. This is a step of forming a powder material layer using a powder material for three-dimensional modeling.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)
The powder material layer forming means contains a base material, a resin, and resin fine particles, and the residual carbon amount W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. It is a means for forming a powder material layer using a powder material for three-dimensional modeling.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)

--Support ---
The support is not particularly limited as long as the powder material for three-dimensional modeling can be placed on it, and can be appropriately selected depending on the purpose. A table having a surface on which the powder material for three-dimensional modeling is placed, Examples thereof include a base plate in the apparatus shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2000-328106.
The surface of the support, that is, the mounting surface on which the powder material for three-dimensional modeling is placed may be, for example, a smooth surface, a rough surface, or a flat surface. It may be curved or curved, but when the resin in the powder material for three-dimensional modeling is dissolved and cured by the action of the curing agent, it is preferable that the affinity with the resin is low.
When the affinity between the above-mentioned mounting surface and the melted and cured resin is lower than the affinity between the base material and the melted and cured resin, the obtained three-dimensional model is obtained from the mounting surface. It is preferable because it is easy to remove.

--Formation of powder material layer ---
The method of arranging the powder material for three-dimensional modeling on the support to form the powder material layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a method of arranging the powder material in a thin layer. Is a method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in Japanese Patent No. 3607300, and the powder material for three-dimensional modeling is used as a member such as a brush, a roller, or a blade. Preferable examples thereof include a method of spreading the powder material for three-dimensional modeling by using a pressing member to spread the surface of the powder material for three-dimensional modeling into a thin layer, and a method of using a known powder layered manufacturing apparatus.

To place the powder material for three-dimensional modeling on the support in a thin layer by using the counter rotation mechanism (counter roller), the brush or blade, the pressing member, or the like as the powder material layer forming means. For example, it can be performed as follows.
That is, the support arranged so as to be able to move up and down while sliding on the inner wall of the outer frame in the outer frame (sometimes referred to as "mold", "hollow cylinder", "cylindrical structure", etc.). The powder material for three-dimensional modeling is placed on the body by using the counter rotation mechanism (counter roller), the brush, the roller or blade, the pressing member, and the like. At this time, when a support that can move up and down in the outer frame is used, the support is arranged at a position slightly lower than the upper end opening of the outer frame, that is, the three-dimensional modeling. The powder material for three-dimensional modeling is placed on the support so as to be positioned below by the thickness of the powder material layer for three-dimensional modeling. As described above, the powder material for three-dimensional modeling can be placed on the support in a thin layer.

When the curing liquid described later is allowed to act on the powder material for three-dimensional modeling placed on the thin layer in this way, the layer is cured (the cured product forming step).
On the cured product of the thin layer obtained here, the powder material for three-dimensional modeling is placed on the thin layer in the same manner as described above, and the powder material for three-dimensional modeling (layer) placed on the thin layer. On the other hand, when the curing liquid is allowed to act, curing occurs. The curing at this time is not only in the powder material (layer) for three-dimensional modeling placed on the thin layer, but also with the cured product of the thin layer previously cured and existing under the powder material (layer) for three-dimensional modeling. It also occurs between. As a result, a cured product (three-dimensional model) having a thickness equivalent to about two layers of the powder material (layer) for three-dimensional modeling placed on the thin layer can be obtained.

Further, in order to place the powder material for three-dimensional modeling on the support in a thin layer, it can be automatically and easily performed by using the known powder lamination modeling apparatus. The powder laminating modeling apparatus generally includes a recorder for laminating the three-dimensional modeling powder material, a movable supply tank for supplying the three-dimensional modeling powder material onto the support, and the three-dimensional modeling powder. It is provided with a movable molding tank for placing the material on a thin layer and laminating it. In the powder laminating molding apparatus, the surface of the supply tank can always be slightly raised above the surface of the molding tank by raising the supply tank, lowering the molding tank, or both. The powder material for three-dimensional modeling can be arranged in a thin layer from the supply tank side using the recorder, and the powder material for three-dimensional modeling can be laminated by repeatedly moving the recorder. ..

The thickness of the powder material layer for three-dimensional modeling is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the average thickness per layer is preferably 30 μm or more and 500 μm or less, and 60 μm or more and 300 μm or less. More preferred.
When the thickness is 30 μm or more, the strength of the cured product (three-dimensional model) by the three-dimensional modeling powder material (layer) formed by applying the curing liquid to the three-dimensional modeling powder material is sufficient, and then A powder material for three-dimensional modeling (layer) formed by applying the curing liquid to the powder material for three-dimensional modeling when the thickness is 500 μm or less, which does not cause problems such as shape loss during processing or handling such as sintering. The dimensional accuracy of the cured product (three-dimensional model) is improved.
The average thickness is not particularly limited and can be measured according to a known method.

-Cured product forming process and cured product forming means-
The cured product forming step is a step of applying a curing liquid to the powder material layer to form a cured product.
The cured product forming means is a means for applying a curing liquid to the powder material layer to form a cured product.

--Curing liquid ---
The curing liquid contains a curing agent, a first organic solvent, and if necessary, other components.

--Hardener ---
The curing agent is capable of forming a covalent bond with the reactive functional group. The curing agent can form a crosslinked structure by forming a covalent bond with the reactive functional group of the resin, further increase the strength of the obtained three-dimensional model, and improve the solvent resistance. In the present invention, "hardener" is synonymous with "crosslinking agent".

As the curing agent, those having at least two or more of isocyanate, acid anhydride, and epoxy in the molecule or at the end of the molecule are preferable.
Examples of the isocyanate include diisocyanate and polyisocyanate.
Examples of the diisocyanate include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polypeptide MDI (MDI), trizine diisocyanate (TODI), naphthaline diisocyanate (NDI), xylene diisocyanate (XDI), paraphenylenedi isocyanate, and the like. Aromatic or aromatic-derived polyisocyanates; aliphatic isocyanates such as isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI); other lysine diisocyanates (LDI), tetramethylxylene diisocyanate (TMXDI) and the like.
Examples of the polyisocyanate include an adduct form, an isocyanurate form, and an allophanate form of the diisocyanate.
Examples of the acid anhydride include acid dianhydride and the like.
Examples of the acid dianhydride include pyromellitic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4-carbonyldiphthalic anhydride, and bicyclo [2]. .2.2] Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, diphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenyl-2,3 , 3', 4'-tetracarboxylic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1, , 2,3,4-Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic hydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic acid anhydride, 4- (2,5-dioxo tetrahydrofuran-3-yl) -tetraline-1,2-dicarboxylic acid anhydride, 5,5'-(ethin-1,2) -Diyl) bis (isobenzofuran-1,3-dione), 5,5'-(9H-fluoren-9,9-diyl) bis (2-benzofuran-1,3-dione), naphthalene-1,4, 5,8-Tetracarboxylic dianhydride, 4,4'-(4,4'-isopropyridenediphenoxy) bis (phthalic anhydride), 1,2,3,4-tetramethyl-1,2, 3,4-Cyclobutanetetracarboxylic dianhydride, octahydrobiphenylene-4a, 8b: 4b, 8a-tetracarboxylic hydride, bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic) Acid) 1,4-phenylene, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-ethylenebis (2,6-morpholindione), N, N-bis [2- (2) , 6-Dioxomorpholino) ethyl] glycine and the like.
Examples of the epoxy include epoxy resins and the like.
These may be used alone or in combination of two or more.

The content of the curing agent with respect to the total amount of the curing liquid is not particularly limited and may be appropriately selected depending on the intended purpose. The content of the curing agent is preferably 1.0% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. When the content of the curing agent with respect to the total amount of the curing liquid is 1.0% by mass or more and 50% by mass or less, it is possible to prevent the strength of the obtained three-dimensional model from being insufficient, and the viscosity of the curing liquid is increased or It is possible to prevent gelation and prevent deterioration of liquid storage stability and viscosity stability. In particular, the content of the curing agent with respect to 3 parts by mass of the resin in the powder material for three-dimensional modeling is preferably 1.0% by mass or more and 50% by mass or less with respect to the total amount of the curing liquid.

--First organic solvent ---
The first organic solvent is not particularly limited as long as it can dissolve the non-aqueous first resin, and can be appropriately selected depending on the intended purpose. Examples of the first organic solvent include aliphatic compounds, aromatic compounds, ketones, esters, and sulfoxides.
Examples of the aliphatic compound include alcohols and ethylene glycols.
Examples of the aromatic compound include toluene, xylene and the like.
Examples of the ketone include acetone, methyl ethyl ketone and the like.
Examples of the ester include butyl acetate, ethyl acetate, propylene acetate, methyl acetate, diethyl succinate and the like.
Examples of the sulfoxide include dimethyl sulfoxide and the like.

The content of the first organic solvent with respect to the total amount of the curing liquid is preferably 30% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less. When the content of the first organic solvent with respect to the total amount of the curing liquid is 30% by mass or more and 90% by mass or less, the solubility of the resin can be improved and the strength of the three-dimensional model can be improved. In addition, it is possible to prevent the nozzle from drying when the device is not operating (during standby), and to prevent liquid clogging and nozzle omission.

--Other ingredients ---
The other components can be appropriately selected in consideration of various conditions such as the type of means for applying the curing liquid, frequency of use and amount, and for example, when the curing liquid is applied by an inkjet method. , It can be selected in consideration of the influence of clogging on the nozzle head in an inkjet printer or the like. Examples of the other components include preservatives, preservatives, stabilizers, pH regulators and the like.

The method for preparing the curing liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method in which the other components are added to the organic solvent as necessary and mixed and dissolved is used. Can be mentioned. Further, the coating coating resin component may be dissolved in order to have a binder component as well. Examples of the early binder component include acrylic, acrylic polyol, polyester, epoxy, polyol, urethane, polyether, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride, vinyl acetate, paraffin olefin, ethyl cellulose and the like.

The method for applying the cured liquid to the powder material layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispenser method, a spray method, and an inkjet method. In order to carry out these methods, a known device can be suitably used as the cured product forming means.
Among these, the dispenser method is excellent in quantification of droplets, but the coating area is narrow, and the spray method can easily form fine ejected substances, has a wide coating area, and is excellent in coating property. The quantification of droplets is poor, and the powder material is scattered by the spray flow. Therefore, in the present invention, the above-mentioned inkjet method is particularly preferable. The inkjet method is preferable in that the quantification of droplets is better than that of the spray method, the coating area can be widened as compared with the dispenser method, and a complicated three-dimensional shape can be formed accurately and efficiently. ..

In the case of the inkjet method, the cured product forming means has a nozzle capable of applying the cured liquid to the powder material layer by the inkjet method. As the nozzle, a nozzle (discharge head) in a known inkjet printer can be preferably used, and the inkjet printer can be suitably used as the cured product forming means. As the inkjet printer, for example, SG7100 manufactured by Ricoh Co., Ltd. and the like are preferably mentioned. The inkjet printer is preferable in that the amount of curing liquid that can be dropped from the head portion at one time is large and the coating area is large, so that the coating speed can be increased.
In the present invention, even when the inkjet printer capable of applying the curing liquid with high accuracy and high efficiency is used, the curing liquid is a solid substance such as particles or a polymer high-viscosity material such as resin. Since it is not contained, clogging or the like does not occur in the nozzle or its head, corrosion or the like does not occur, and when it is applied (discharged) to the three-dimensional modeling powder material layer, the three-dimensional modeling powder Since it can efficiently permeate the organic material in the material, it is excellent in the production efficiency of the three-dimensional model, and since a polymer component such as a resin is not added, an unexpected volume increase or the like does not occur. It is advantageous in that a cured product having good dimensional accuracy can be easily and efficiently obtained in a short time.

In the curing liquid, the curing agent can also function as a pH adjuster. The pH of the curing liquid is 5 (weak) from the viewpoint of preventing corrosion and clogging of the nozzle head portion of the nozzle used when the curing liquid is applied to the powder material layer for three-dimensional modeling by the inkjet method. It is preferably acidic) to 12 (basic), and more preferably 8 to 10 (weakly basic). A known pH adjuster may be used to adjust the pH.

-Powder material container-
The powder material accommodating portion is a member accommodating the powder material for three-dimensional modeling, and the size, shape, material, and the like thereof are not particularly limited and can be appropriately selected according to the purpose, for example, storage. Examples include tanks, bags, cartridges, tanks, etc.

-Curing liquid container-
The curing liquid accommodating portion is a member accommodating the curing liquid, and the size, shape, material, and the like thereof are not particularly limited and may be appropriately selected depending on the purpose. For example, a storage tank, a bag, etc. , Cartridges, tanks, etc.

-Other processes and other means-
Examples of the other steps include a surplus powder removing step, a drying step, a sintering step, a surface protection treatment step, a painting step, and the like.
Examples of the other means include a surplus powder removing step, a drying means, a sintering means, a surface protection treatment means, a coating means, and the like.

The excess powder removing step is a step of removing the uncured three-dimensional modeling powder material using a second organic solvent after the cured product forming step.
The three-dimensional model is in a state of being embedded in a non-modeled portion (uncured powder material for three-dimensional modeling) to which the curing liquid is not applied. When the three-dimensional model is taken out from this buried state, excess (uncured) powder material for three-dimensional modeling adheres to the surface and the inside of the structure of the three-dimensional model, which is convenient. Difficult to remove. It is even more difficult when the surface of the three-dimensional model has complicated irregularities or when the inside is like a flow path. In the general binder jetting method, the strength of the sintered precursor (same as the three-dimensional model) is not high, so if the air blow pressure is high (0.4 MPa or more), the sintered precursor may collapse. is there.
The three-dimensional modeled product formed by the three-dimensional modeling powder and the curing liquid used in the present invention can impart high fluidity to the powder by the effect of the resin fine particles, so that the powder is clogged with high density and high reliability. As a result, the resin is uniformly dissolved when the curing liquid is dropped, and the resin has strength to withstand the pressure of air blow. Further, the resin coated on the base material is more dissolved and solidified by the curing agent contained in the curing liquid, and has strength to withstand the pressure of air blow.
At this time, the strength of the sintered precursor is preferably 3 MPa or more, more preferably 5 MPa or more in terms of the three-point bending stress.

Further, not only the strength is improved, but also the cured coating resin is not dissolved in the first and second organic solvents capable of dissolving the resin coated on the base material, and is coated with excess powder. Since the resin before curing is dissolved in the second organic solvent, excess powder adhering to the surface or the inside can be easily removed by immersing the resin in the removing liquid.
Examples of the second organic solvent include ethanol, methanol, cyclohexane, methyl ethyl ketone, ethyl acetate, ethyl lactate, tetrahydrofuran, diethyl ether, toluene and the like.

The drying step is a step of drying the cured product (three-dimensional model) obtained in the cured product forming step. In the drying step, not only water contained in the cured product but also organic substances may be removed (defatted). Examples of the drying means include known dryers.

The sintering step is a step of sintering a cured product (three-dimensional model) formed in the cured product forming step. By performing the sintering step, the cured product can be made into a densified and integrated metal or ceramic molded product (sintered product of a three-dimensional molded product). Examples of the sintering means include known sintering furnaces.

The surface protection treatment step is a step of forming a protective layer on the cured product (three-dimensional model) formed in the cured product forming step. By performing this surface protection treatment step, it is possible to impart durability to the surface of the cured product (three-dimensional model) so that the cured product (three-dimensional model) can be used as it is, for example. Specific examples of the protective layer include a water resistant layer, a weather resistant layer, a light resistant layer, a heat insulating layer, a glossy layer, and the like. Examples of the surface protection treatment means include known surface protection treatment devices such as a spray device and a coating device.

The coating step is a step of coating the cured product (three-dimensional model) formed in the cured product forming step. By performing the painting step, the cured product (three-dimensional model) can be colored in a desired color. Examples of the coating means include known coating devices, such as a coating device using a spray, a roller, a brush, or the like.

The mass of the resin contained in the three-dimensional model after the sintering step is 5% by mass or less of the mass of the resin contained in the three-dimensional model before the excess powder removing step.

Here, an example of an apparatus for manufacturing a three-dimensional model used in the method for manufacturing a three-dimensional model of the present invention will be described with reference to the drawings.

The flow of modeling in the method for manufacturing a three-dimensional model of the present embodiment will be described with reference to FIG. 1A to 1E are schematic explanatory views for explaining the flow of modeling. Here, the state in which the first modeling layer 30 is formed on the modeling stage of the modeling tank will be described. When the next modeling layer is formed on the first modeling layer 30, the supply stage 23 of the supply tank is raised and the modeling stage 24 of the modeling tank is lowered, as shown in FIG. 1A.
At this time, the modeling stage 24 is lowered so that the distance (stacking pitch) between the upper surface of the surface (powder surface) of the powder layer 31 in the modeling tank 22 and the lower portion (lower tangential portion) of the flattening roller 12 is Δt1. Set the distance. The interval Δt1 is not particularly limited, but is preferably about several tens to 100 μm.
In the present embodiment, the flattening roller 12 is arranged so as to form a gap with respect to the upper end surfaces of the supply tank 21 and the modeling tank 22. Therefore, when the powder 20 is transferred and supplied to the modeling tank 22 to be flattened, the surface (powder surface) of the powder layer 31 is located higher than the upper end surfaces of the supply tank 21 and the modeling tank 22.
As a result, the flattening roller 12 can be reliably prevented from coming into contact with the upper end surfaces of the supply tank 21 and the modeling tank 22, and damage to the flattening roller 12 is reduced. When the surface of the flattening roller 12 is damaged, streaks are generated on the surface of the powder layer 31 and the flatness tends to decrease.
Next, as shown in FIG. 1B, the powder 20 located above the upper surface level of the supply tank 21 is moved to the modeling tank 22 side while rotating the flattening roller 12 in the opposite direction (arrow direction). , The powder 20 is transferred and supplied to the modeling tank 22 (powder supply).
Further, as shown in FIG. 1C, the flattening roller 12 is moved in parallel with the stage surface of the modeling stage 24 of the modeling tank 22, and the powder layer 31 having a predetermined thickness Δt1 on the modeling layer 22 of the modeling stage 24. Form (flattening). At this time, the surplus powder 20 not used for forming the powder layer 31 falls into the surplus powder receiving tank 29.
After forming the powder layer 31, the flattening roller 12 is moved to the supply tank 21 side and returned (returned) to the initial position (origin position) as shown in FIG. 1D.
Here, the flattening roller 12 can move while keeping a constant distance from the upper surface level of the modeling tank 22 and the supply tank 21. Since the powder 20 can be moved while being kept constant, the powder 20 is conveyed onto the modeling tank 22 by the flattening roller 12, and has a uniform thickness h (stacking pitch) on the modeling tank 22 or on the already formed modeling layer 30. The powder layer 31 (corresponding to Δt1) can be formed.
Hereinafter, the thickness h of the powder layer 31 and the stacking pitch Δt1 may be described without distinction, but unless otherwise specified, they have the same thickness and have the same meaning. Further, the thickness h of the powder layer 31 may be actually measured and obtained, and in this case, it is preferable to use an average value of a plurality of locations.
After that, as shown in FIG. 1E, droplets 10 of the modeling liquid (modeling liquid) are discharged from the head 52 of the liquid discharge unit 50, and the modeling layer 30 having a desired shape is laminated on the next powder layer 31. To do (modeling).
In the modeling layer 30, for example, when the droplets 10 of the modeling liquid discharged from the head 52 are mixed with the powder 20, the adhesive contained in the powder 20 is dissolved, and the dissolved adhesives are mixed with each other. Is bonded and the powder is bonded to form the powder.
Next, the powder layer forming step and the discharging step described above are repeated to form a new molding layer 30. At this time, the new modeling layer 30 and the underlying modeling layer 30 are integrated to form a part of the modeled object (also referred to as a three-dimensional shaped object, a three-dimensional modeled object, or the like). After that, the powder layer forming step and the discharging step are repeated to complete the molding of the modeled object.

By the above-mentioned method and apparatus for manufacturing a three-dimensional object of the present invention, a three-dimensional object having a complicated three-dimensional (three-dimensional (3D)) shape can be produced by the powder material for three-dimensional modeling of the present invention or the kit for three-dimensional modeling of the present invention. It is possible to manufacture the product easily and efficiently with high dimensional accuracy without losing its shape before sintering or the like.
The three-dimensional model obtained in this way and its sintered body have sufficient strength, excellent dimensional accuracy, and can reproduce fine irregularities, curved surfaces, etc., so that they have excellent aesthetic appearance, are of high quality, and are used for various purposes. Can be suitably used for.

(Three-dimensional modeling kit)
The three-dimensional modeling kit of the present invention includes a three-dimensional modeling powder material having a base material, a resin, and resin fine particles, a curing liquid containing a curing agent, and further contains other components as necessary.
The three-dimensional modeling kit of the present invention contains the three-dimensional modeling powder material used in the method and apparatus for producing the three-dimensional model of the present invention, the curing liquid, and other components as necessary. ..
In the three-dimensional modeling kit of the present invention, the curing agent may be contained in a solid form instead of in the curing liquid, and is a kit prepared by mixing with a solvent at the time of use to prepare the curing liquid. It doesn't matter if you do.
The powder material for three-dimensional modeling and the curing liquid in the three-dimensional modeling kit of the present invention are the same as those described in the method for producing a three-dimensional model and the apparatus for producing a three-dimensional model of the present invention.

The three-dimensional modeling kit of the present invention can be suitably used for producing various molded products and structures, and the method for producing a three-dimensional object of the present invention described later, the apparatus for producing a three-dimensional object of the present invention, and the present invention. It can be particularly preferably used for the three-dimensional model obtained by the invention.
When a structure is manufactured using the three-dimensional modeling kit of the present invention, the cured liquid is allowed to act on the three-dimensional modeling powder material, and if necessary, it is simply dried to easily produce a structure having a complicated three-dimensional shape. It can be manufactured efficiently and with high dimensional accuracy. The structure thus obtained is a cured product (three-dimensional model) having sufficient hardness, and the excess powder material for three-dimensional modeling is removed by holding it by hand, putting it in and out of a mold, or performing an air blow treatment. Even if it does, it does not lose its shape and is excellent in handleability and handleability. The cured product may be used as it is, or may be further subjected to a sintering treatment as a cured product for sintering to obtain a molded product (sintered product of a three-dimensional molded product). Then, when the sintering treatment is performed, unnecessary voids and the like are not generated in the molded product after sintering, and a molded product having a beautiful appearance can be easily obtained.

<Three-dimensional model>
The three-dimensional molded product obtained by the present invention uses the cured product obtained by applying the curing liquid of the present invention to the powder material for three-dimensional molding of the present invention, and the three-dimensional molding kit of the present invention. Any of the cured products obtained by applying the curing liquid to the powder material for three-dimensional molding in the three-dimensional molding kit, which is a pre-sintered model such as a sintered precursor or a green body, or a sintered body. , A molded product after sintering such as a molded product.

The three-dimensional model is obtained only by applying the curing liquid to the powder material for three-dimensional modeling, but has sufficient strength. In the three-dimensional model, the base material is densely present (at a high filling rate), and the organic material is present in a very small amount around the base materials. When a sintered body) is obtained, unlike conventional cured powders or particles using an adhesive or the like, the amount of volatilization (solvent degreasing) of organic components can be reduced, so unnecessary voids (solvent degreasing marks) are present. A molded product (sintered body) with a beautiful appearance can be obtained without this.
The strength of the three-dimensional model is such that it does not lose its shape even if the surface is rubbed, and an air blow process is performed from a distance of 5 cm using an air gun having a nozzle diameter of 2 mm and an air pressure of 0.4 MPa. Even if it does, cracks and the like do not occur.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

-Preparation of powder material 1 for three-dimensional modeling-
--Preparation of coating liquid 1 ---
As shown in Table 1, as the non-aqueous first resin (“No. 1” in Table 1), 6 parts by mass of polyvinyl butyral (manufactured by Sekisui Chemical Industry Co., Ltd., BM-5) and 114 mass of toluene. The parts were mixed and stirred for 1 hour using a three-one motor (BL600, manufactured by Shinto Kagaku Co., Ltd.) while heating to 50 ° C. in a water bath to dissolve the polyvinyl butyral in the organic solvent (toluene). 120 parts by mass of a 5 mass% polyvinyl butyral solution was prepared. The prepared solution thus obtained was designated as a coating solution 1.
The viscosity of the 4% by mass (w / w%) solution of polyvinyl butyral at 20 ° C. was measured using a viscometer (Rotary viscometer manufactured by Brookfield, DV-E VISCOMETER HADVE115 type) and found to be 5.0 mPa. -S to 6.0 mPa · s.

--Coating of the coating liquid 1 on the surface of the substrate --- Next, using a commercially available coating device (MP-01 manufactured by Paulec), AlSi10Mg (“No. 1” in Table 1) was used as the substrate (“No. 1” in Table 1). The coating liquid 1 was coated on 100 parts by mass of Si10Mg30BB manufactured by Toyo Aluminum K.K., Ltd., volume average particle size 35 μm) so as to have the average thickness (nm) of the coating film shown in Table 1. In this coating, sampling is performed at any time during the process, and the coating time and interval are set so that the average thickness (nm) and surface coverage (%) of the coating film of the coating liquid 1 become the values shown in Table 1. Adjusted appropriately. After the coating is completed, acrylic resin fine particles (MP1451 manufactured by Soken Chemical Co., Ltd.) are added to the surface of the coating film so that the surface coverage is 20%, and a mixing device (Symmal Enterprises Co., Ltd., DYNO) is added. -MILL) was mixed at 100 rpm for 5 minutes to obtain a powder material 1 for three-dimensional modeling. The methods for measuring the average thickness (nm) and surface coverage (%) of the coating film and the coating conditions are shown below. The average thickness (nm) and surface coverage (%) of the coating film were measured before mixing the resin fine particles.

<Average thickness of coating film>
The average thickness of the coating film was determined by polishing the surface of the three-dimensional modeling powder material 1 with emery paper and then lightly polishing the surface with a cloth containing toluene to dissolve the coating resin to prepare an observation sample. .. Next, the boundary portion between the base material portion and the coating resin exposed on the surface was observed with a field emission scanning electron microscope (FE-SEM), and the boundary portion was measured as the coating thickness. The average value of 10 measurement points was obtained, and this was used as the average thickness of the coating film.

<Surface coverage>
Using a field emission scanning electron microscope (FE-SEM), take a reflected electron image (ESB) under the following conditions with a visual field setting in which about 10 powder materials 1 for three-dimensional modeling fit within the screen, and use ImageJ software. Binarization was performed by image processing. The black part was the coating part and the white part was the base material part, and the area of the black part / (area of the black part + area of the white part) × 100 in one particle was determined. 10 particles were measured, and the average value was taken as the surface coverage (%).
-SEM observation conditions-
-Signal: ESB (reflected electron image)
・ EHT: 0.80kV
・ ESB Grid: 700V
・ WD: 3.0 mm
・ Aperture Size: 30.00 μm
・ Contrast: 80%
・ Magnification: Set for each sample so that about 10 pieces fit in the horizontal direction of the screen

<Coating conditions>
・ Spray setting Nozzle model 970
Nozzle diameter 1.2 mm
Coating liquid discharge pressure 4.7 Pa · s
Coat liquid discharge speed 3 g / min
Atomize air volume 50NL / min
・ Rotor setting Rotor model M-1
Rotation speed 60 rpm
Rotation speed 400%
・ Airflow setting Air supply temperature 80 ℃
Air supply air volume 0.8m ³ / min
Bag filter removal pressure 0.2 MPa
Bag filter removal time 0.3 seconds Bag filter interval 5 seconds, coating time 40 minutes

The volume average particle size of the obtained three-dimensional modeling powder material 1 was measured using a commercially available particle size measuring device (Microtrac HRA manufactured by Nikkiso Co., Ltd.) and found to be 35 μm.

<Measurement of residual carbon amount W>
The powder material 1 for three-dimensional modeling was heated using a known vacuum degreasing furnace under the following conditions to obtain the powder material 1 for three-dimensional modeling after heating.
・ Heating temperature: 450 ℃
・ Heating time: 2 hours ・ Heating environment: ^10-2 Pa or less under vacuum ・ Heating rate: 200 ° C / h
The residual carbon amount W of the obtained powder material 1 for three-dimensional modeling after heating was measured under the following conditions using a solid carbon analyzer (EMIA-STEP) manufactured by Horiba Seisakusho Co., Ltd.
Purge time: 0 seconds, integration waiting time: 5 seconds, integration time: 60 seconds Comparator level: 1.0% Comparator waiting time: 15 seconds Set temperature: 1350 ° C. Time: 1500 seconds Sample weight: 0.1 g
Flame retardant: tin 0.5g
When Ti was used as the base material, 0.5 g of pure iron, 1.5 g of tungsten, and 0.3 g of tin were used as the combustion improver.
<Minimum ignition energy>
The minimum ignition energy of the three-dimensional modeling powder material 1 was measured by the following method using a blow-up type dust explosion test device (DES-10) and an ignition energy device (MIES-1).
(1) Place an amount of sample corresponding to the concentration evenly on the sample dish of the blow-up type dust explosion tester.
(2) 50 kPa of compressor air is stored in a 1.3 liter pressure tank and opened in a glass cylinder by a solenoid valve to form a dust cloud.
(3) The ignition energy is changed by selecting a capacitor and adjusting the applied voltage.
(4) Energy is applied to the discharge electrode 0.1 seconds after the solenoid valve is opened.
(5) Ignition is determined when the flame crosses the ignition mark line marked 100 mm above the discharge electrode.
(6) The measured concentration is 3 or more, and the minimum ignition energy is obtained. If ignition is not observed after measuring 10 times at 1 concentration and 1 energy, it is judged that there is no ignition at that concentration and energy.

[Evaluation criteria]
○ ・ ・ ・ Ignition energy is 100mJ or more (the risk of ignition due to static electricity is low)
△ ・ ・ ・ 30mJ or more and 100mJ or less (Containers and installation measures are required, and it is necessary to use an inert gas to further improve safety)
× ・ ・ ・ 30 mJ or less (strict control such as explosion suppression by inert gas and antistatic measures is required)

-Preparation of curing solution 1-
97 parts by mass of dimethyl sulfoxide and 3 parts by mass of acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd., trade name: KC1700P) were dispersed for 10 minutes using a homomixer, and the curing solution 1 (“No. 1” in Table 1). Was prepared.

(Example 1)
Using the obtained powder material 1 for three-dimensional modeling and the curing liquid 1, the three-dimensional model 1 was manufactured as follows by a shape printing pattern of a size (length 70 mm × width 12 mm).

1) First, the powder material 1 for three-dimensional modeling is transferred from the supply-side powder storage tank to the modeling-side powder storage tank using a known powder laminating modeling device as shown in FIG. 1, and averaged onto the support. A thin layer made of the three-dimensional modeling powder material 1 having a thickness of 100 μm was formed.

2) Next, the curing liquid 1 was applied (discharged) from a nozzle of a known inkjet ejection head to the surface of the formed thin layer made of the three-dimensional modeling powder material 1 to cure the powder material layer.

3) Next, the operations 1) and 2) are repeated until a predetermined total average thickness of 3 mm is obtained, and the cured thin layers of the three-dimensional modeling powder material 1 are sequentially laminated, and a dryer is used. Then, it was maintained at 50 ° C. for 4 hours and then at 100 ° C. for 10 hours, and a drying step was carried out to obtain a three-dimensional model 1.
The excess powder material 1 for three-dimensional modeling was removed from the three-dimensional model 1 after drying by air blowing.

Next, "strength (hardness) of the three-dimensional model (before sintering)", "dimensional accuracy", and "sintered body density" were evaluated according to the following evaluation criteria. The results are shown in Table 2.

<Strength (hardness) of three-dimensional model (before sintering)>
◎ ・ ・ ・ The three-dimensional object is sufficiently hardened and does not break easily. ○ ・ ・ ・ The three-dimensional object is unnecessary even if a strong air blow (0.6 MPa, 50 mm, 1 minute) is performed. Only the powder material for modeling is removed, and the three-dimensional model itself maintains its shape. Δ ... The three-dimensional model can be taken out from the laminated powder material layer, and the air blow pressure can be adjusted. Alternatively, by using a brush, it is possible to take out an unnecessary powder material for three-dimensional modeling, and the three-dimensional modeled object is in a state where the shape can be maintained. × ・ ・ ・ The powder material for three-dimensional modeling is sufficiently cured. Therefore, the three-dimensional model cannot be taken out from the laminated powder material layer, and when it is taken out, the predetermined shape cannot be maintained.

4) The three-dimensional model 1 obtained in 3) above was heated to 450 ° C. over 2 hours in a nitrogen atmosphere using a dryer, and then maintained at 450 ° C. for 2 hours to perform a degreasing step. Further, the sintering process was performed in a sintering furnace under vacuum conditions at 600 ° C. As a result, a three-dimensional model 1 (sintered body) having a beautiful surface was obtained. This three-dimensional model 1 is a completely integrated aluminum structure (metal block), and even if it is struck against a hard floor (concrete), it is not damaged at all.

<Dimensional accuracy>
◎ ・ ・ ・ The surface of the three-dimensional model is smooth and beautiful, and there is no warpage ○ ・ ・ ・ The surface condition of the three-dimensional model is good, but there is slight warpage △ ・ ・ ・A state in which the surface of the three-dimensional model is slightly distorted and uneven. × ・ ・ ・ The surface of the three-dimensional object is distorted, and when the surface is observed, uneven distribution of the base material and the organic material is observed. State

<Sintered body density>
After the sintered body was impregnated with oil under vacuum, the density was measured by the Archimedes method and evaluated based on the following evaluation criteria.

[Evaluation criteria]
◎ ・ ・ ・ Density 90% or more ○ ・ ・ ・ Density 80% or more and less than 90% △ ・ ・ ・ Density 70% or more and less than 80% × ・ ・ ・ Density 70% or less

(Example 2)
In Example 1, a three-dimensional model 2 was produced in the same manner as in Example 1 except that the powder material 2 for three-dimensional modeling was prepared in which the type of the base material was changed to titanium, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 2.

(Example 3)
In Example 1, a three-dimensional model 3 was produced in the same manner as in Example 1 except that the curing solution 2 was prepared by changing the solvent type of the curing solution to butyl acetate (manufactured by Sankyo Chemical Co., Ltd.). The same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 4)
In Example 1, a three-dimensional model 4 was produced in the same manner as in Example 1 except that the curing liquid 3 was prepared by changing the solvent type of the curing liquid to acetone (manufactured by Hayashi Junyaku Kogyo Co., Ltd.). The same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 5)
In Example 1, a three-dimensional model was prepared in the same manner as in Example 1 except that the powder material 3 for three-dimensional modeling was prepared by changing the non-aqueous first resin to KC-500 (acrylic, manufactured by Kyoeisha Chemical Co., Ltd.). 5 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 6)
In Example 1, the three-dimensional modeled product was prepared in the same manner as in Example 1 except that the powder material 4 for three-dimensional modeling was prepared by changing the non-aqueous first resin to TZ9515 (acrylic polyol, manufactured by Toei Kasei Co., Ltd.). 6 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 7)
In Example 1, a three-dimensional model was prepared in the same manner as in Example 1 except that the powder material 5 for three-dimensional modeling was prepared in which the non-aqueous first resin was changed to UE-3380 (ester, manufactured by Unitica). 7 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 8)
In Example 1, the same as in Example 1 except that the powder material 6 for three-dimensional modeling was prepared by changing the non-aqueous first resin to KS-1 (polyvinyl acetal, manufactured by Sekisui Chemical Co., Ltd.). The three-dimensional model 8 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 9)
In Example 1, except that the powder material 7 for three-dimensional modeling was prepared in which the type of the resin fine particles was changed to FS-107 ( ₂ NHs added to the functional group of acrylic, manufactured by Nippon Paint Industrial Coatings Co., Ltd.). A three-dimensional model 9 was manufactured in the same manner as in 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 10)
In Example 1, a three-dimensional shape was prepared in the same manner as in Example 1, except that the powder material 8 for three-dimensional modeling was prepared in which the type of resin fine particles was changed to FS-102 (styrene acrylic, manufactured by Nippon Paint Industrial Coatings). The model 10 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 11)
In Example 1, the three-dimensional model 11 was manufactured in the same manner as in Example 1 except that the powder material 9 for three-dimensional modeling was prepared by adding resin fine particles so that the surface coverage was 3%. The same evaluation as was performed. The results are shown in Table 2.

(Example 12)
In Example 1, the three-dimensional model 12 was manufactured in the same manner as in Example 1 except that the powder material 10 for three-dimensional modeling was prepared by adding resin fine particles so that the surface coverage was 5%. The same evaluation as was performed. The results are shown in Table 2.

(Example 13)
In Example 1, the three-dimensional model 13 was manufactured in the same manner as in Example 1 except that the powder material 11 for three-dimensional modeling was prepared by adding resin fine particles so that the surface coverage was 2%. The same evaluation as was performed. The results are shown in Table 2.

(Example 14)
In Example 1, a three-dimensional model 14 was manufactured in the same manner as in Example 1 except that resin fine particles were added so that the surface coverage was 50% to prepare a powder material 12 for three-dimensional modeling. The same evaluation as was performed. The results are shown in Table 2.

(Example 15)
In Example 1, except that the three-dimensional modeling powder material 13 having the average thickness (nm) of the coating film shown in Table 1 was prepared by adjusting the formation time of the coating film by changing it to 2 minutes. The three-dimensional model 15 was manufactured in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 16)
In Example 1, the coating time was changed to 4 minutes and adjusted, except that the powder material 14 for three-dimensional modeling having the average thickness (nm) of the coating film shown in Table 1 was prepared, as in Example 1. In the same manner, the three-dimensional model 16 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 17)
In Example 1, the coating time was changed to 200 minutes and adjusted, except that the powder material 15 for three-dimensional modeling having the average thickness (nm) of the coating film shown in Table 1 was prepared, as in Example 1. In the same manner, the three-dimensional model 17 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 18)
In Example 1, the coating time was changed to 240 minutes and adjusted, except that the powder material 16 for three-dimensional modeling having the average thickness (nm) of the coating film shown in Table 1 was prepared, as in Example 1. In the same manner, the three-dimensional model 18 was manufactured, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 19)
In Example 1, the coating time was changed to 320 minutes and adjusted, except that the powder material 17 for three-dimensional modeling having the average thickness (nm) of the coating film shown in Table 1 was prepared, as in Example 1. In the same manner, the three-dimensional model 19 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 20)
In Example 1, the coating time was changed to 360 minutes and adjusted, except that the powder material 18 for three-dimensional modeling having the average thickness (nm) of the coating film shown in Table 1 was prepared, as in Example 1. In the same manner, the three-dimensional model 15 was manufactured, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 21)
In Example 1, the coating liquid flow rate was changed to 15 g / min to increase the coating unevenness of the coating film, and by adjusting the coating liquid flow rate, the three-dimensional modeling powder having the surface coverage of the resin shown in Table 1 was obtained. A three-dimensional model 21 was produced in the same manner as in Example 1 except that the material 19 was prepared, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 22)
In Example 1, the coating liquid flow rate was changed to 13 g / min to increase the coating unevenness of the coating film, and by adjusting the coating liquid flow rate, the three-dimensional modeling powder having the surface coverage of the resin shown in Table 1 was obtained. A three-dimensional model 22 was produced in the same manner as in Example 1 except that the material 20 was prepared, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 23)
In Example 1, AlSi10Mg to be used is classified by a sieve having a # 795 mesh, and a powder material 21 for three-dimensional modeling having a volume average particle diameter of the base material shown in Table 1 and a particle ratio of 10 μm or less in volume particle size is prepared. A three-dimensional model 23 was manufactured in the same manner as in Example 1 except for the above, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 24)
In Example 1, AlSi10Mg to be used is classified by a # 795 mesh sieve to prepare a powder material 22 for three-dimensional modeling having a volume average particle size of the base material shown in Table 1 and a particle ratio of 10 μm or less. A three-dimensional model 24 was manufactured in the same manner as in Example 1 except for the above, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 25)
In Example 1, the three-dimensional model 25 was manufactured in the same manner as in Example 1 except that the volume average particle diameter of AlSi10Mg used was 8 μm and the powder material 23 for three-dimensional modeling was prepared. Evaluation was performed. The results are shown in Table 2.

(Example 26)
In Example 1, the three-dimensional model 26 was manufactured in the same manner as in Example 1 except that the volume average particle diameter of AlSi10Mg used was 50 μm and the powder material 24 for three-dimensional modeling was prepared. Evaluation was performed. The results are shown in Table 2.

(Example 27)
In Example 1, a three-dimensional model 27 was produced in the same manner as in Example 1 except that the volume average particle diameter of AlSi10Mg used was 60 μm and the powder material 25 for three-dimensional modeling was prepared. Evaluation was performed. The results are shown in Table 2.

(Example 28)
In Example 1, a three-dimensional model 28 was produced in the same manner as in Example 1 except that the volume average particle diameter of AlSi10Mg used was 80 μm and the powder material 26 for three-dimensional modeling was prepared. Evaluation was performed. The results are shown in Table 2.

(Example 29)
In Example 1, a three-dimensional model 29 was produced in the same manner as in Example 1 except that the volume average particle diameter of AlSi10Mg used was 90 μm and the powder material 27 for three-dimensional modeling was prepared. Evaluation was performed. The results are shown in Table 2.

(Example 30)
For three-dimensional modeling in the same manner as in Example 1 except that MX-80H3wT (acrylic, manufactured by Soken Kagaku Co., Ltd., volume average particle size: 500 nm (prepared by air flow classification)) was used as the resin fine particles in Example 1. A powder material 28 was produced, a three-dimensional model 30 was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 31)
For three-dimensional modeling in the same manner as in Example 1 except that MX-80H3wT (acrylic, manufactured by Soken Kagaku Co., Ltd., volume average particle size: 600 nm (prepared by air flow classification)) was used as the resin fine particles in Example 1. A powder material 29 was produced, a three-dimensional model 31 was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 32)
For three-dimensional modeling in the same manner as in Example 1 except that MX-80H3wT (acrylic, manufactured by Soken Kagaku Co., Ltd., volume average particle size: 800 nm (prepared by air flow classification)) was used as the resin fine particles in Example 1. The powder material 30 was produced, the three-dimensional model 31 was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, a powder material 31 for three-dimensional modeling was produced in the same manner as in Example 1 except that the base material was not coated with the non-aqueous first resin, and three-dimensionally formed in the same manner as in Example 1. The model 33 was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
In Example 1, a powder material 32 for three-dimensional modeling was produced in the same manner as in Example 1 except that the resin fine particles were not coated, and a three-dimensional model 34 was produced in the same manner as in Example 1. The same evaluation as in 1 was performed. The results are shown in Table 2.

(Comparative Example 3)
In Example 1, the weight loss after heating the non-aqueous first resin to TH-500 (polyvinyl chloride, manufactured by Taiyo PVC Co., Ltd., TG-DTA at 400 ° C.): 50%, after heating to 550 ° C. A three-dimensional model 35 was produced in the same manner as in Example 1 except that the powder material 33 for three-dimensional modeling was changed to (carbon residue: present), and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative Example 4)
In Example 1, the type of resin fine particles was changed to Epostal SS (melamine, manufactured by Nippon Catalyst Co., Ltd., weight loss after heating to 400 ° C. by TG-DTA: 70%, carbon residue after heating to 550 ° C.: Yes). A three-dimensional model 36 was produced in the same manner as in Example 1 except that the powder material 34 for three-dimensional modeling was prepared, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative Example 5)
In Example 1, the weight loss after heating the first non-aqueous resin to 400 ° C. by DF-05 (acrylic, manufactured by Japan Vam & Poval Co., Ltd., TG-DTA: 90%) and after heating to 550 ° C. The three-dimensional model 37 was produced in the same manner as in Example 1 except that the powder material 35 for three-dimensional modeling was prepared using (with carbon residue: Yes), the solvent type was changed to purified water, and the curing solution 4 was prepared. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

The details of the materials used in Examples and Comparative Examples are as follows.
-Base material-
-AlSi10Mg: manufactured by Toyo Aluminum K.K., trade name: Si10Mg30BB
-Pure Ti: Made by Osaka Titanium Technologies Co., Ltd., Product name: TILO P64-45
-Non-aqueous first resin-
-Polyvinyl butyral: manufactured by Sekisui Chemical Co., Ltd., product name: BM-2
-Acrylic resin: manufactured by DIC Corporation, product name: AU-7007
-Ester resin: manufactured by DIC Corporation, product name: Talisbon AH-420
-Acrylic polyol resin: manufactured by Toei Kasei Kogyo Co., Ltd., product name: TZ9515
-Polyvinyl acetal resin: manufactured by Sekisui Chemical Co., Ltd., product name: KS-1
-Second resin-
-Acrylic resin: manufactured by Soken Chemical Co., Ltd., product name: MP-1451
・ Melamine resin: manufactured by Nippon Shokubai Co., Ltd., product name: Epostal SS
-Styrene acrylic resin: manufactured by Nippon Paint Industrial Coatings, trade name: FS-102
-Acrylic resin (NH ₂ functional group): manufactured by Nippon Paint Industrial Coatings, trade name: FS-107

From Tables 1 and 2, in Examples 1 and 3 to 32 in which the alloy (AlSi10Mg) was used as the base material, the residual carbon amount W (mass%) was less than 0.34, and titanium was used as the base material. In Example 2, it was less than 0.2. As a result, in Examples 1 to 32, the evaluation results of "strength", "dimensional accuracy", "sintering density" and "minimum ignition E" were good.

Aspects of the present invention are, for example, as follows.
<1> Has a base material, resin, and resin fine particles,
It is a powder material for three-dimensional modeling, characterized in that the residual carbon amount W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)
<2> The resin contains a non-aqueous first resin.
The powder material for three-dimensional modeling according to <1>, which has a coating film of the resin that covers the surface of the base material.
<3> The resin fine particles contain a second resin,
The powder material for three-dimensional modeling according to <2>, which has the resin fine particles on the coating film.
<4> The powder material for three-dimensional modeling according to <3>, wherein the coating ratio of the resin fine particles on the surface of the base material having the coating film is 3% or more.
<5> The powder material for three-dimensional modeling according to any one of <1> to <4>, wherein the volume average particle diameter of the resin fine particles is 600 nm or less.
<6> The powder material for three-dimensional modeling according to any one of <1> to <5>, wherein the base material contains at least one of Al, Ti, and copper.
<7> The powder material for three-dimensional modeling according to any one of <1> to <6>, wherein the resin fine particles contain at least one of acrylic, styrene, and amino.
<8> The first non-aqueous resin is at least acrylic, acrylic polyol, polyester, epoxy, polyol, urethane, polyether, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride, vinyl acetate, paraffin olefin, and ethyl cellulose. Contains either
The three-dimensional modeling powder according to any one of <2> to <7>, wherein the non-aqueous first resin has a solubility in water of 0.5 (g / 100 g-H ₂ O) or less. It is a material.
<9> The powder material for three-dimensional modeling according to any one of <2> to <8>, wherein the average thickness of the coating film is 10 nm or more and 800 nm or less.
<10> The powder material for three-dimensional modeling according to any one of <2> to <9>, wherein the coating film covers the base material with a surface coverage of 15% or more.
<11> The solid according to any one of <1> to <10>, wherein the content of the base material having a volume average particle diameter of 10 μm or less with respect to the total amount of the base material is 1.5% or more. It is a powder material for modeling.
<12> The powder material for three-dimensional modeling according to any one of <1> to <11>, wherein the volume average particle diameter of the powder material for three-dimensional modeling is 2 μm or more and 80 μm or less.
<13> Has a base material, resin, and resin fine particles,
Forming a powder material layer using a powder material for three-dimensional modeling in which the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. Process and
A method for producing a three-dimensional model, which comprises a cured product forming step of applying a curing liquid to the powder material layer to form a cured product.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)
<14> The resin contains a non-aqueous first resin.
The method for producing a three-dimensional model according to <13>, wherein the three-dimensional modeling powder material has a coating film of the resin that covers the surface of the base material.
<15> The resin fine particles contain a second resin, and the resin fine particles contain a second resin.
The method for producing a three-dimensional model according to <14>, wherein the powder material for three-dimensional modeling has the resin fine particles on the coating film.
<16> The curing liquid is an organic solvent, and the organic solvent contains at least one of an aliphatic compound, an aromatic compound, a ketone, an ester, and a sulfoxide in the molecular skeleton, from <13> to <15. > Is the method for manufacturing a three-dimensional model according to any one of.
<17> The method for producing a three-dimensional model according to any one of <13> to <16>, wherein the resin fine particles are dissolved in the curing liquid by 1/4 or more in the diameter of the resin fine particles.
<18> The method for producing a three-dimensional model according to any one of <13> to <17>, further comprising a sintering step of performing a sintering process on the cured product after the cured product forming step. is there.
<19> The method for producing a three-dimensional model according to any one of <13> to <18>, wherein the cured product forming step applies the cured liquid by an inkjet method.
<20> Has a base material, resin, and resin fine particles,
Forming a powder material layer using a powder material for three-dimensional modeling in which the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. Means and
An apparatus for producing a three-dimensional model, comprising: a cured product forming means for applying a curing liquid to the powder material layer to form a cured product.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material)
<21> A three-dimensional modeling kit comprising the powder material for three-dimensional modeling according to any one of <1> to <12> and a curing liquid containing a curing agent.

The powder material for three-dimensional modeling according to any one of <1> to <12>, the method for producing a three-dimensional model according to any one of <13> to <19>, and the three-dimensional modeling according to <20>. According to the product manufacturing apparatus and the three-dimensional modeling kit described in <21>, the conventional object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2000-328106 Japanese Unexamined Patent Publication No. 2006-200030 Japanese Unexamined Patent Publication No. 2003-48253 Japanese Unexamined Patent Publication No. 2005-297325 Japanese Patent No. 5920498

Claims (21)

It has a base material, resin and resin fine particles,
A powder material for three-dimensional modeling, characterized in that the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material) The resin contains a non-aqueous first resin,
The powder material for three-dimensional modeling according to claim 1, which has a coating film of the resin that covers the surface of the base material. The resin fine particles contain a second resin,
The powder material for three-dimensional modeling according to claim 2, which has the resin fine particles on the coating film. The powder material for three-dimensional modeling according to claim 3, wherein the coating ratio of the resin fine particles on the surface of the base material having the coating film is 3% or more. The powder material for three-dimensional modeling according to any one of claims 1 to 4, wherein the volume average particle diameter of the resin fine particles is 600 nm or less. The powder material for three-dimensional modeling according to any one of claims 1 to 5, wherein the base material contains at least one of Al, Ti, and copper. The powder material for three-dimensional modeling according to any one of claims 1 to 6, wherein the resin fine particles contain at least one of acrylic, styrene, and amino. The non-aqueous first resin contains at least one of acrylic, acrylic polyol, polyester, epoxy, polyol, urethane, polyether, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride, vinyl acetate, paraffin olefin, and ethyl cellulose. Contains,
The powder material for three-dimensional modeling according to any one of claims 2 to 7, wherein the non-aqueous first resin has a solubility in water of 0.5 (g / 100 g-H ₂ O) or less. The powder material for three-dimensional modeling according to any one of claims 2 to 8, wherein the average thickness of the coating film is 10 nm or more and 800 nm or less. The powder material for three-dimensional modeling according to any one of claims 2 to 9, wherein the coating film covers the base material with a surface coverage of 15% or more. The powder material for three-dimensional modeling according to any one of claims 1 to 10, wherein the content of the base material having a volume average particle diameter of 10 μm or less with respect to the total amount of the base material is 1.5% or more. The powder material for three-dimensional modeling according to any one of claims 1 to 11, wherein the volume average particle diameter of the powder material for three-dimensional modeling is 2 μm or more and 80 μm or less. It has a base material, resin and resin fine particles,
Forming a powder material layer using a powder material for three-dimensional modeling in which the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. Process and
A method for producing a three-dimensional model, which comprises a cured product forming step of applying a curing liquid to the powder material layer to form a cured product.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material) The resin contains a non-aqueous first resin,
The method for producing a three-dimensional model according to claim 13, wherein the powder material for three-dimensional modeling has a coating film of the resin that covers the surface of the base material. The resin fine particles contain a second resin,
The method for producing a three-dimensional model according to claim 14, wherein the powder material for three-dimensional modeling has the resin fine particles on the coating film. The invention according to any one of claims 13 to 15, wherein the curing liquid is an organic solvent, and the organic solvent contains at least one of an aliphatic compound, an aromatic compound, a ketone, an ester, and a sulfoxide in the molecular skeleton. Method of manufacturing three-dimensional shaped products. The method for producing a three-dimensional model according to any one of claims 13 to 16, wherein the resin fine particles are dissolved in the curing liquid by 1/4 or more in the diameter of the resin fine particles. The method for producing a three-dimensional model according to any one of claims 13 to 17, further comprising a sintering step of performing a sintering process on the cured product after the cured product forming step. The method for producing a three-dimensional model according to any one of claims 13 to 18, wherein the cured product forming step applies the cured liquid by an inkjet method. It has a base material, resin and resin fine particles,
Forming a powder material layer using a powder material for three-dimensional modeling in which the residual carbon content W (mass%) after vacuuming at ^10-2 Pa or less and heating at 450 ° C. for 2 hours satisfies the following formula. Means and
An apparatus for producing a three-dimensional model, comprising: a cured product forming means for applying a curing liquid to the powder material layer to form a cured product.
W (mass%) <0.9 / M
(However, the M represents the specific gravity of the base material) A three-dimensional modeling kit comprising the powder material for three-dimensional modeling according to any one of claims 1 to 12 and a curing liquid containing a curing agent.