JP2018080359A - Powder material for stereoscopic molding, material set for stereoscopic molding, and apparatus and method for manufacturing a stereoscopic molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder material for stereoscopic molding that does not produce aggregates in a surplus powder, can stably obtain a resin powder mixture ratio upon recycling, is excellent in recyclability, and can stably obtain a strength of a stereoscopic molded object.SOLUTION: A powder material for stereoscopic molding containing a resin particle and a base material particle satisfies the following formula (1-1) provided that an electro static charge amount (μc/g) of the resin particle and base material particle is Q1, which Q1 is an electro static charge amount as measured by a blow-off method after mixing 99 pts.mass of the base material particle and 1 pt.mass of the resin particle respectively for 10 minutes with a Turbula mixer. 1.0≤|Q1|≤60 ... formula (1-1)SELECTED DRAWING: None

Description

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

  In recent years, there is an increasing need to manufacture a three-dimensional model having a complicated shape. The method of manufacturing a three-dimensional model using a conventional mold has many problems such as the limitation of manufacturing complex and fine models, the mold is expensive and cannot be applied to low-lot production. Yes.

On the other hand, 3D modeling (sometimes referred to as “laminated modeling” or “additional modeling”) that directly manufactures a 3D model while laminating various materials using shape data is effective in solving these problems. It is attracting attention as a method.
There are many methods such as powder sintering lamination method, stereolithography method, heat melting lamination method, material jet method, binder jet method, etc. It is preferable that surplus powder (unused powder) that has not been used is recovered and used repeatedly, so-called recyclable.

For example, a production method has been proposed in which a particle powder coated with a resin having low water solubility is used as a material for three-dimensional modeling, and a binding liquid composed of an organic solvent having a water content of 45% or less has been proposed. Alcohol (PVA) is disclosed (for example, refer to Patent Document 1).
Moreover, the said three-dimensional modeling is carried out by dripping the modeling liquid which uses water as a solvent to the said layer formed in the layer formation process which forms a layer with the three-dimensional modeling powder containing water-soluble polymer, and the said layer formation process. A production method of a three-dimensional structure including a generation step of generating a layer having a product generated by dissolving powder in the modeling liquid has been proposed, and the water-soluble polymer is in a powder shape, Partially saponified polyvinyl alcohol (PVA) is disclosed (for example, see Patent Document 2).

  The present invention is a three-dimensional modeling powder material in which aggregates are not generated in the surplus powder, the resin powder mixing ratio during recycling is stably obtained, the recycling property is excellent, and the strength of the three-dimensional modeling object can be stably obtained. The purpose is to provide.

The three-dimensional modeling powder material of the present invention as a means for solving the above problems is a three-dimensional modeling powder material including resin particles and base material particles,
When the charge amount (μc / g) between the resin particles and the base particles is Q1, the Q1 mixes 99 parts by weight of the base particles and 1 part by weight of the resin particles with a tumbler mixer for 10 minutes. The charge amount measured by the blow-off method after satisfying the following formula (1).
1.0 ≦ | Q1 | ≦ 60 Formula (1)

  According to the present invention, there is no agglomeration in the surplus powder, the resin powder mixing ratio at the time of recycling can be stably obtained, the recyclability is excellent, and the strength of the three-dimensional structure can be obtained stably. Material can be provided.

FIG. 1A is a schematic diagram illustrating an example of a process of supplying a three-dimensional modeling powder material from a supply powder storage tank to a modeling powder storage tank in the manufacturing process of the three-dimensional modeling object of the present invention. FIG. 1B is a schematic diagram illustrating an example of a process of forming a three-dimensional modeling powder material layer having a smooth surface by a three-dimensional modeling powder material layer forming unit in the manufacturing process of the three-dimensional modeling object of the present invention. FIG. 1C is a step of dripping a three-dimensional modeling liquid material using a three-dimensional modeling liquid material supply unit on a three-dimensional modeling powder material layer of a modeling powder storage tank in the manufacturing process of the three-dimensional modeling object of the present invention. It is the schematic which shows an example. FIG. 1D shows that the stage of the powder storage tank for supply is raised and the stage of the powder storage tank for molding is lowered in the manufacturing process of the three-dimensional structure of the present invention, and the gap is controlled so as to have a desired layer thickness. It is the schematic which shows an example of a process. FIG. 1E shows the manufacturing process of the three-dimensional structure according to the present invention, after controlling the gap, and again moving the three-dimensional modeling powder material layer forming means from the supply powder storage tank to the modeling powder storage tank. It is the schematic which shows an example of the process of forming the powder material layer for three-dimensional modeling newly in the powder storage tank. FIG. 1F is a step of dropping the liquid material for three-dimensional modeling using the three-dimensional liquid material supplying means to the three-dimensional modeling powder material layer of the modeling powder storage tank again in the manufacturing process of the three-dimensional modeled object of the present invention. It is the schematic which shows an example. FIG. 2A is a schematic diagram illustrating an example of a process of supplying a three-dimensional modeling powder material from a supply powder storage tank to a modeling powder storage tank in the manufacturing process of the three-dimensional modeling object of the present invention. FIG. 2B illustrates a three-dimensional modeling powder manufacturing process according to the present invention, in which a three-dimensional modeling powder material is supplied to a modeling powder storage tank, and then the gap is adjusted so as to obtain a desired layer thickness. It is the schematic which shows an example of the process of forming the powder material layer for three-dimensional modeling in the powder storage tank for modeling by moving a material layer formation means. FIG. 2C is a step of dripping the liquid material for three-dimensional modeling using the three-dimensional liquid material supply means on the three-dimensional modeling powder material layer of the modeling powder storage tank in the manufacturing process of the three-dimensional modeled object of the present invention. It is the schematic which shows an example. FIG. 2D shows a step of lowering the stage of the modeling powder storage tank and supplying the modeling powder storage tank from the supply powder storage tank to the modeling powder storage tank again in the manufacturing process of the three-dimensional modeled object of the present invention. It is the schematic which shows an example. FIG. 2E illustrates the manufacturing process of the three-dimensional object according to the present invention, after the three-dimensional powder material is supplied to the three-dimensional powder storage tank, the gap is controlled so as to obtain a desired layer thickness, and the three-dimensional object is formed again. It is the schematic which shows an example of the process of forming the powder material layer for three-dimensional modeling newly in the powder storage tank for modeling by moving the powder material layer forming means for modeling. FIG. 2F shows that the three-dimensional modeling liquid material is dropped again on the three-dimensional modeling powder material layer of the modeling powder storage tank in the manufacturing process of the three-dimensional modeling object of the present invention. It is the schematic which shows an example of the process to do. FIG. 3 is a schematic view showing an example of a powder storage tank of the three-dimensional structure manufacturing apparatus of the present invention. FIG. 4 is a comparison with the conventional method when mixing base material particles and resin particles, during three-dimensional modeling using a three-dimensional modeling powder material including base material particles and resin particles, and when recycling three-dimensional modeling powder material. It is the schematic which shows a method and the method of this invention in contrast. FIG. 5 is a schematic view showing a method for measuring the liberation rate by mass change before and after the compressed air is blown by the blow-off method.

(Powder material for 3D modeling)
The three-dimensional modeling powder material of the present invention is a three-dimensional modeling powder material including resin particles and base material particles,
When the charge amount (μc / g) between the resin particles and the base particles is Q1, the Q1 mixes 99 parts by weight of the base particles and 1 part by weight of the resin particles with a tumbler mixer for 10 minutes. The charge amount measured by the blow-off method is satisfied, satisfies the following formula (1-1), and further contains other components as necessary.
1.0 ≦ | Q1 | ≦ 60 Formula (1-1)

The powder-sintering lamination method, in which the powder material layer is laminated while being sintered by irradiating it with laser light, has the merit that the final model can be directly modeled, but because it is exposed to a high-temperature laser in the modeling tank, Since the agglomeration occurs in the non-powder powder or foreign matters due to sparks are mixed, the composition and particle size of the unused powder change, so that the stability of the molding quality during recycling becomes a problem. In addition, when preheating the periphery of the modeled object for the purpose of suppressing warpage during modeling, unused powder agglomerates and the like becomes more difficult to recycle.
On the other hand, even in the binder jet method using an inkjet head, unused powder around the modeled product is agglomerated by the splash of the binder component ejected from the inkjet head or contaminated by contamination of the binder component, and the molding quality at the time of recycling is high. Stability is an issue. For this reason, conventionally, addition of resin particles to the three-dimensional modeling powder material side has been studied.

  In the three-dimensional modeling powder material of the present invention, in the conventional method of adding resin particles to the three-dimensional modeling powder material, since the mixed state of the resin particles and the base particles is not constant, the three-dimensional modeling object (green body) The strength cannot be obtained uniformly, and the defect of the three-dimensional structure becomes a problem. In addition, when handling the three-dimensional modeling powder material in recycling, the resin powder mixing ratio fluctuates, the recyclability is lowered, and the strength of the green body cannot be obtained stably. is there.

Therefore, in the present invention, when the charge amount (μc / g) between the resin particles and the base material particles is Q1, the Q1 uses 99 parts by weight of the base material particles and 1 part by weight of the resin particles, respectively. It is a charge amount measured by a blow-off method after mixing for 10 minutes with a blur mixer (manufactured by Shinmaru Enterprises Co., Ltd.), preferably satisfies the following formula (1-1) and preferably satisfies the following formula (1-2). More preferably, the following formula (1-3) is satisfied.
Thereby, the said base material particle can be charged and the said resin particle can be coat | covered uniformly and electrostatically stably on the surface of the said base material particle. That is, by satisfying the following formula (1-1), no agglomerates are generated in the surplus powder, the resin powder mixing ratio at the time of recycling is stably obtained, the recyclability is improved, and the strength of the three-dimensional structure is stabilized. Can be obtained.
1.0 ≦ | Q1 | ≦ 60 Formula (1-1)
5 ≦ | Q1 | ≦ 40 Formula (1-2)
10 ≦ | Q1 | ≦ 30 (1-3)

  Here, Q1, which is the charge amount (μc / g) between the resin particles and the base material particles, is 99 parts by weight of the base material particles and 1 part by weight of the resin particles. It can be determined by measuring the supply after mixing for 10 minutes with Enterprises) using a blow-off method (TB-200, manufactured by Toshiba Chemical Corporation).

The free rate ε measured from the mass change before and after the compressed air is blown (before and after blow-off) by the blow-off method (see FIG. 5) of the three-dimensional modeling powder material satisfies the following formula (2-1). Preferably, the following formula (2-2) is satisfied. By satisfy | filling following formula (2-1), an aggregate does not arise in an excess powder, the resin powder mixing ratio at the time of a recycling can be obtained stably, and the intensity | strength of a three-dimensional molded item can be obtained stably.
0% ≦ ε ≦ 75% Formula (2-1)
5% ≦ ε ≦ 60% Formula (2-2)
Here, in FIG. 5, 107 represents a blow-off device, 105 represents resin particles, and 103 represents substrate particles.
However, in the formulas (2-1) and (2-2), the liberation rate ε is, for example, a supply after mixing base material particles and resin particles under the following conditions by using a blow-off device (manufactured by Toshiba Chemical Corporation). , TB-200) and can be determined from the mass change before and after the compressed air is blown (before and after blow-off).
-Condition-
・ Resin particle mass W1: 1 g
・ Substrate particle mass W2: 2 g

The mass W1 of the resin and the mass W2 of the base material preferably satisfy the following formula (3) from the viewpoint of adhesion between the base material particles and the resin particles.
1 ≦ [W1 / (W1 + W2)] × 100 ≦ 10 (3)

<Base material particles>
The material of the substrate particles is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include metals, ceramics, glass, carbon, resin materials, wood, biocompatible materials, sand, and magnetic materials. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, metals, ceramics, and resin materials that can be finally sintered are preferable from the viewpoint of obtaining a three-dimensional sintered product with extremely high strength.

The metal is not particularly limited as long as it contains a metal as a material, and can be appropriately selected according to the purpose. For example, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Ta, W, Nd, or alloys thereof may be used. Among these, stainless steel (SUS) steel, iron, copper, silver, titanium, zirconium, or alloys thereof are preferable.
Examples of the stainless steel (SUS) include SUS304, SUS316, SUS317, SUS329, SUS410, SUS430, SUS440, and SUS630.

Examples of the ceramic include oxides, carbides, nitrides, and hydroxides. Among these, an oxide is preferable.
As the oxide is not particularly limited and may be appropriately selected depending on the purpose, for example, silica _(SiO 2), alumina _{(Al 2 O} 3), zirconia _(ZrO 2), titania (TiO ₂₎ etc. Is mentioned.

  As the resin material, a thermoplastic resin is mainly used. For example, polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), styrene-acrylonitrile copolymer ( AS), styrene-butadiene-acrylonitrile copolymer (ABS), polyvinyl chloride (PVC), polycarbonate (PC), polyamide (PA), acrylic resin (PMMA), fluororesin (PVDF, PTFE) and the like.

  A commercial item can be used as said base particle. Examples of the commercially available products include PSS316L manufactured by Sanyo Special Steel Co., Ltd. for stainless steel, Excelica SE-15, SE-40, SE-8 manufactured by Tokuyama Co., Ltd., and Thailand manufactured by Daimei Chemical Co., Ltd. Micron TM-5D, zirconia includes TZ-B53 manufactured by Tosoh Corporation, and titanium includes Osaka Titanium Technologies, Inc.

  The substrate particles can be subjected to a surface treatment using a surface treatment agent, and may be effective for improving adhesion with resin particles and improving coating properties. There is no restriction | limiting in particular as said surface treating agent, A conventionally well-known thing can be used.

The volume average particle diameter D1 of the substrate particles is preferably 2 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less.
When the volume average particle diameter D1 is 2 μm or more, the influence of aggregation is reduced, the resin coating on the substrate particles is improved, the yield and the production efficiency of the three-dimensional model are improved, and the handling properties of the substrate particles are improved. And handling properties are improved. In addition, when the volume average particle diameter D1 is 100 μm or less, the contact points and voids between the base material particles and the resin particles are appropriate, and the strength of the three-dimensional modeled product and further the three-dimensional sintered product becomes good.
There is no restriction | limiting in particular as a particle size distribution of the said base particle, Although it can select suitably according to the objective, It is preferable that the said particle size distribution is sharper.
The average particle size of the substrate particles is not particularly limited and can be measured using a known particle size measuring device. For example, a particle size distribution measuring device (Microtrack MT3000II series, Microtrack Bell) Manufactured).

The method for producing the substrate particles is not particularly limited, and can be produced by using a conventionally known method. For example, a pulverization method in which a solid is subjected to compression, impact, friction, or the like, and a molten metal is used. Examples thereof include an atomizing method for obtaining a rapidly cooled powder by spraying, a precipitation method for precipitating components dissolved in a liquid, and a gas phase reaction method for vaporizing and crystallizing. Among these, the atomizing method is preferable because a spherical shape is obtained and there is little variation in particle diameter.
Examples of the atomizing method include a water atomizing method, a gas atomizing method, a centrifugal atomizing method, and a plasma atomizing method.

<Resin particles>
The resin particles may be any resin particles that are soluble in the three-dimensional modeling liquid material and have a property capable of being cross-linked by the action of the cross-linking agent contained in the three-dimensional modeling liquid material.

The solubility of the resin particles means that, for example, when 1 g of the resin particles are mixed and stirred in 100 g of a solvent constituting the liquid material for three-dimensional modeling at 30 ° C., 90% by mass or more thereof is dissolved.
The resin particles preferably have a viscosity at 20 ° C. of a 4 mass% (w / w%) solution of 40 mPa · s or less, more preferably 1 mPa · s or more and 35 mPa · s or less, and more preferably 5 mPa · s or more and 30 mPa · s. The following are particularly preferred:
When the viscosity is 40 mPa · s or less, the strength of a cured product (three-dimensional modeled object) formed by the three-dimensional model powder material (layer) formed by applying the three-dimensional model liquid material to the three-dimensional model powder material is high. It becomes difficult to cause problems such as loss of shape during subsequent processing or handling such as sintering. Moreover, it exists in the tendency for the dimensional accuracy of the hardened | cured material (three-dimensional molded item) by the three-dimensional modeling powder material (layer) formed by providing the said three-dimensional modeling liquid material to the said three-dimensional modeling powder material.
The viscosity can be measured according to, for example, JIS K7117.

The resin in the resin particles is not particularly limited and may be appropriately selected depending on the purpose. However, from the viewpoints of handleability and environmental load, it is preferably water-soluble, for example, water-soluble resin, water-soluble resin For example, a functional prepolymer.
For the three-dimensional modeling powder material employing the water-soluble resin, an aqueous medium can be used as the medium of the three-dimensional modeling liquid material, and when the powder material is discarded and recycled, a water treatment is performed. Therefore, it is easy to separate the resin particles and the base particles.

Examples of the water-soluble resin include polyvinyl alcohol resin, polyacrylic acid resin, cellulose resin, starch, gelatin, vinyl resin, amide resin, imide resin, acrylic resin, and polyethylene glycol. These may be homopolymers (homopolymers) or heteropolymers (copolymers) as long as they exhibit the above-mentioned water solubility, may be modified, are publicly known A functional group may be introduced or may be in the form of a salt. Among these, polyvinyl alcohol resin, polyacrylic acid resin, and cellulose resin are preferable.
Therefore, for example, the polyvinyl alcohol resin may be polyvinyl alcohol, or modified polyvinyl alcohol (acetoacetyl group-modified polyvinyl alcohol, acetyl group-modified polyvinyl alcohol, silicone-modified with acetoacetyl group, acetyl group, silicone, etc.) Polyvinyl alcohol, etc.), butanediol vinyl alcohol copolymer, and the like. Moreover, if it is the said polyacrylic acid resin, polyacrylic acid may be sufficient and salts, such as sodium polyacrylate, may be sufficient.
If it is the said cellulose resin, a cellulose, carboxymethylcellulose (CMC), etc. may be sufficient, for example. Moreover, if it is the said acrylic resin, polyacrylic acid, an acrylic acid / maleic anhydride copolymer, etc. may be sufficient, for example.
As said water-soluble prepolymer, the adhesive water-soluble isocyanate prepolymer etc. which are contained in a water stop agent etc. are mentioned, for example.

  Examples of resins other than water-soluble resins include acrylic, maleic acid, silicone, butyral, polyester, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, ethylene / vinyl acetate copolymer, ethylene / (Meth) acrylic acid copolymer, α-olefin / maleic anhydride copolymer, esterified product of α-olefin / maleic anhydride copolymer, polystyrene, poly (meth) acrylic ester, α-olefin / Maleic anhydride / vinyl group-containing monomer copolymer, styrene / maleic anhydride copolymer, styrene / (meth) acrylic ester copolymer, polyamide, epoxy resin, xylene resin, ketone resin, petroleum resin, rosin or its Derivatives, coumarone indene resin, terpene resin, poly Tan resins, styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, synthetic rubbers such as ethylene / propylene rubber, nitrocellulose, and the like.

In the present invention, among the resin particles, those having a crosslinkable functional group are preferable. The crosslinkable functional group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group, a carboxyl group, an amide group, a phosphate group, a thiol group, an acetoacetyl group, and an ether bond. It is done.
It is preferable that the resin has the crosslinkable functional group in that the resin can be easily cross-linked to form a cured product (three-dimensional model).
Among these, a polyvinyl alcohol resin having an average degree of polymerization of 400 or more and 1,100 or less is preferable.
As said resin particle, 1 type may be used individually, 2 or more types may be used together, and what was synthesize | combined suitably may be sufficient and a commercial item may be sufficient.
Examples of the commercially available products include polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205C, PVA-220C), polyacrylic acid (manufactured by Toagosei Co., Ltd., Jurimer AC-10), and sodium polyacrylate (Toagosei Co., Ltd.). Manufactured by Jurimer AC-103P), acetoacetyl group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosennex Z-300, Gohsenx Z-100, Gohsenx Z-200, Gohsenx Z-205, Gohsenx Z-210, Gohsenx Z) -220), carboxy group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosennex T-330, Gosennex T-350, Gosennex T-330T), butanediol vinyl alcohol copolymer (Nippon Synthesis) Gaku Kogyo Co., Ltd., Nichigo G-polymer OKS-8041), sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., Serogen 5A, Serogen 6A), starch (Sanwa Starch Kogyo Co., Ltd., Hystad PSS-5), Examples thereof include gelatin (manufactured by Nitta Gelatin Co., Ltd., B-matrix gelatin).

The volume average particle diameter D2 of the resin particles is preferably 0.1 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less.
When the volume average particle diameter D2 is 0.1 μm or more, the uniform mixing property of the base material and the resin particles, the solubility by the three-dimensional modeling liquid material, and the binding property are improved. Further, when the volume average particle diameter D2 is 20 μm or less, uniform mixing and dissolution are possible, and a good green body can be formed.
The volume average particle size of the resin particles is not particularly limited, and can be measured using a known particle size measuring device. For example, a particle size distribution measuring device (Microtrack MT3000II series, Microtrack Bell) Manufactured).

The volume average particle diameter of the substrate particles is larger than the volume average particle diameter of the resin particles, and the substrate particles are charged to electrostatically coat the resin particles on the surface of the substrate particles. It is preferable from the point.
Here, as shown in the lower diagram of FIG. 4, when the base particles and the resin particles are uniformly mixed, since the resin particles are smaller than the base particles, the resin particles uniformly adhere to the surface of the base particles. The coated state of the resin particles on the surface of the substrate particles is stabilized.
Next, when three-dimensional modeling is performed using the powder material for three-dimensional modeling in which the resin particles are uniformly coated on the surface of the base material particles, a three-dimensional model with a stable strength is obtained.
Moreover, since the adhesion amount of the resin particles to the surface of the substrate particles is stable, the resin powder mixing ratio at the time of recycling is stably obtained, and the recyclability is improved.
On the other hand, as shown in the intermediate diagram of FIG. 4, the volume average particle diameter of the resin particles is large, and the three-dimensional modeling powder material in which the resin particles are not uniformly attached to the surface of the base particles And the resin particles are not uniformly mixed, and the coating state of the resin particles on the surface of the base material particles in the three-dimensional modeling powder material becomes unstable.
Next, when three-dimensional modeling is performed using such a three-dimensional modeling powder material, the strength of the three-dimensional model cannot be obtained uniformly, and a three-dimensional model having a weak strength defect is obtained.
In addition, the amount of resin particles adhering to the surface of the substrate particles becomes unstable, the resin powder mixing ratio at the time of recycling varies, and the recyclability decreases.
In addition, as for the powder material for solid modeling containing the base material particle | grains coat | covered with the conventional resin shown in the upper figure of FIG. 4, the intensity | strength of a solid modeling thing is obtained uniformly, and the adhesion amount of the resin particle to the surface of a base material particle Is stable and has excellent recyclability.

  There are several methods for atomizing the resin particles. For example, a collision type crushing method (jet mill, counter jet mill) using high-pressure air, bead crushing using ceramic beads, or a blade rotating at high speed. There are methods of granulating by crushing using pins or pins, or spray drying, which can be selected as appropriate.

  There is no restriction | limiting in particular as a charge control agent of the said resin particle, According to the objective, it can select suitably, For example, a silane coupling agent etc. are mentioned.

  The silane coupling agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyl. Methyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyl Trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3 -(G Methoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, allyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, dimethyl Examples include diethoxysilane, 1,3-divinyltetramethyldisilazane, and methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride. These may be used alone or in combination of two or more.

  As the silane coupling agent, an appropriately prepared product or a commercially available product may be used. Examples of the commercially available product include AY43-059, SR6020, SZ6023, SH6020, SH6026, SZ6032, SZ6050, AY43-310M, SZ6030, SH6040, AY43-026, AY43-031, sh6062, Z-6911, sz6300, sz6075, sz6079, sz6083, sz6070, sz6072, Z-6721, AY43-004, Z-6187, AY43-021 AY43-043, AY43-040, AY43-047, Z-6265, AY43-204M, AY43-048, Z-6403, AY43-206M, AY43-206E, Z6341, AY43-210MC AY43-083, AY43-101, AY43-013, AY43-158E, Z-6920, Z-6940 (all manufactured by Toray Silicone Co., Ltd.).

There is no restriction | limiting in particular as content of the said silane coupling agent, Although it can select suitably according to the objective, 0.1 mass% or more and 10 mass% or less are preferable with respect to the said resin particle.
When the content is 0.1% by mass or more and 10% by mass or less, the adhesion between the substrate particles and the resin particles is improved.

-Other ingredients-
Other components can be added to the three-dimensional modeling powder material of the present invention as necessary.
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a filler, a leveling agent, a sintering adjuvant, etc. are mentioned.

--Filler--
The filler is an effective material mainly for adhering to the surface of the powder material for three-dimensional modeling or for filling the space between the powder materials for three-dimensional modeling. As an effect, for example, the improvement in the fluidity of the powder material for three-dimensional modeling, the increase in the number of contacts between powder materials, and the reduction of voids can be effective in that the effect of increasing the strength and dimensional accuracy of the three-dimensional model can be obtained. It is.

--Leveling agent--
The leveling agent is an effective material mainly for controlling the wettability of the surface of the three-dimensional modeling powder material. As the effect, for example, the permeability of the liquid material for three-dimensional modeling increases to the powder material layer for three-dimensional modeling, the strength of the three-dimensional model can be increased and the speed thereof can be increased, and it is effective in maintaining the shape stably. There is a case.

--- Sintering aid--
The sintering aid is an effective material for increasing the sintering efficiency when the obtained three-dimensional structure is sintered. As effects, for example, the strength of the three-dimensional structure can be improved, the sintering temperature can be lowered, and the sintering time can be shortened.

There is no restriction | limiting in particular as a volume average particle diameter of the said powder material for three-dimensional modeling, Although it can select suitably according to the objective, For example, the thing of 100 nm or more and 100 micrometers or less is preferable, and the thing of 100 nm or more and 50 micrometers or less is more. preferable.
When the volume average particle size is 100 nm or more and 100 μm or less, the control of particles becomes easy during recoating, smoothness of the recoating layer is obtained, the density of the sintered body is improved, and sufficient strength is obtained.

About the sharpness of the particle size distribution of the said powder material for three-dimensional modeling, it can confirm by the ratio of the 10% value of a cumulative value, and a 90% value in a volume average particle diameter.
When the particle size distribution is sharp, (Dv: 90% value of volume average particle size: 10% value) is closer to 1.
On the other hand, when the numerical value of the ratio increases, it can be confirmed that there is a shift from sharp to broad distribution. When the particle size distribution is broad, when recoating, separation of the large particle size side particle and the small particle size side particle occurs, the smoothness of the surface of the recoat layer is impaired due to the particle size difference, and the discharged ink is uniform. Since it does not penetrate, there is a possibility that the interparticle strength and the interlaminar strength may vary. Therefore, the broad particle size is not preferable.

  There is no restriction | limiting in particular as a particle size distribution of the said powder material for three-dimensional model | molding, Although it can select suitably according to the objective, It is more preferable that a particle size distribution is sharper. The volume average particle size of the three-dimensional modeling powder material can be measured using a known particle size measuring device. For example, the above-described particle size distribution measuring device Microtrack MT3000II series (manufactured by Microtrack Bell) It can measure using.

  The aspect ratio of the three-dimensional modeling powder material and the base material particles is preferably 0.9 or more. In general, the higher the aspect ratio is (close to 1.0), the closer to a spherical shape, the closer the base particles are packed, and the voids in the resulting three-dimensional shaped product and three-dimensional sintered product can be reduced. However, it is not always effective in the present invention. Even in the present invention, as the aspect ratio is higher, the closest packing can be obtained at the time of FIG. 1B. However, the liquid material in which the water-soluble resin coating the base particles of FIG. In the step of producing a green body by dissolving the base material, the base particles are rearranged by the liquid crosslinking force, which causes coarseness, voids, and delamination.

Since the formation of fine particles of the base material is necessary from the viewpoint of the sintered density of the three-dimensional structure, it is a problem in using small particle diameter particles in this method. In the present invention, when the aspect ratio is 0.9 or more, the movement of the base particles by the distortion of the base particles is used to suppress the particle movement due to the liquid crosslinking force.
Further, in the distorted substrate particles having an aspect ratio of less than 0.9, the substrate particles can be sufficiently caught, but it is difficult to uniformly and smoothly fill the substrate particles in the step of FIG. 1B. Therefore, it is not preferable.
When the aspect ratio becomes small, the uneven state on the surface of the recoat layer becomes large, and the liquid material for three-dimensional modeling to be discharged does not penetrate uniformly, resulting in variations in resin solubility between base particles and between layers, The strength of the three-dimensional model itself (green body) may be deteriorated.

Here, the aspect ratio can be measured using a known particle shape measuring apparatus, and an example thereof is Morphologi G3-SE manufactured by Spectris.
The measurement conditions of the aspect ratio are: dispersion pressure 4 bar, pressure application time 10 ms, milking time 60 sec, measurement number of particles 50,000, filtering by envelope degree, and analysis is performed only with particles assumed to be primary particles.
The aspect ratio (Mean value) is a value obtained by calculating the minor axis / major axis ratio of each of the particles used in the analysis and weighting the degree to which the particles having the aspect ratio are present in the entire analysis. Specifically, it is calculated by the following formula.
The number of measured particles after filtering is preferably 20,000 or more from the viewpoint of measurement stability.
Aspect ratio (Mean value) = X1 * Y1 / 100 + x2 * Y2 / 100 +... + Xn * Yn / 100
Y1 + Y2 + ... + Yn = 100 (%)
Xn: aspect ratio (minor axis / major axis)
Yn: abundance ratio of particles having an aspect ratio of Xn (%)

  The shape and circularity of the powder material for three-dimensional modeling are not particularly limited and can be appropriately selected according to the purpose. However, the shape is spherical and the circularity is high (close to 1.0). Is more preferable. As a result, the three-dimensional modeling powder material is closely packed, and voids of the three-dimensional modeled product and the three-dimensional sintered product obtained can be reduced, which may be effective in increasing the strength. The circularity can be measured using a known circularity measuring device, and examples thereof include a flow type particle image analyzer FPIA-3000 (manufactured by Malvern Instruments).

There is no restriction | limiting in particular about the fluidity | liquidity of the said powder material for three-dimensional model | molding, According to the objective, it can select suitably. The fluidity of the three-dimensional modeling powder material can be measured using a conventionally known method, and examples thereof include a method of repose angle, degree of compression, outflow rate, and shear cell test.
The angle of repose is expressed by the angle between the slope of the mountain of the powder and the horizontal plane when the powder is dropped from a certain height and kept stable without spontaneous collapse, and is widely used in general. . As an example, it can be measured using a powder characteristic measuring device (Powder Tester PT-N type, manufactured by Hosokawa Micron Corporation). The repose angle of the three-dimensional modeling powder material of the present invention is preferably 55 ° or less, more preferably 40 ° or less, and particularly preferably 35 ° or less.
When the angle of repose exceeds this, when forming the layer of the powder material for three-dimensional modeling, unevenness of the surface of the layer becomes large or it becomes easy to form a slow aggregate, Dimensional accuracy may be reduced. It is known that the angle of repose is mainly influenced by particle diameter, particle shape, water content, humidity, and the like. The three-dimensional modeling powder material of the present invention is influenced by the degree of modification of the coated polyvinyl alcohol in addition to the particle diameter and shape, and the one with a lower degree of modification of 1,2-glycol bond is more preferable for the three-dimensional modeling powder material. In some cases, the fluidity is high and effective.

(3D modeling material set)
The three-dimensional modeling material set of the present invention includes the three-dimensional modeling powder material of the present invention and the three-dimensional modeling liquid material, and further includes other components as necessary.

  In the present invention, for example, a layer of the three-dimensional modeling powder material is formed, and the three-dimensional modeling liquid material is provided thereon, and the liquid component contained in the three-dimensional modeling liquid material is used for the three-dimensional modeling. The coating resin formed on the surface of the powder material is dissolved or swollen, whereby the adjacent three-dimensional modeling powder materials are bonded to each other. By repeating these operations and drying, a three-dimensional model can be obtained. The three-dimensional modeling powder material and the three-dimensional modeling liquid material used at this time are referred to as a three-dimensional modeling material set in the present invention.

  Further, the three-dimensional modeling material set of the present invention is, for example, simply mixing the three-dimensional modeling powder material and the three-dimensional modeling liquid material in a desired ratio, and pouring the obtained slurry into a mold or forming three-dimensionally. The three-dimensional modeled object can also be obtained, and these slurries are also included in the three-dimensional model material set. That is, the three-dimensional modeling material set of the present invention is not limited to the method of manufacturing a three-dimensional modeling object, and includes all combinations of the three-dimensional modeling powder material and the three-dimensional modeling liquid material.

<Liquid material for 3D modeling>
The three-dimensional modeling liquid material includes a liquid component capable of dissolving the resin contained in the three-dimensional modeling powder material, preferably includes a crosslinking agent, and includes other components as necessary. Also good.

  The three-dimensional modeling liquid material is used to cure the three-dimensional modeling powder material. The “curing” means a state in which the base particles are fixed or agglomerated through the resin particles, and the three-dimensional modeling powder material can maintain a certain three-dimensional shape by the curing.

  When the three-dimensional modeling liquid material is applied to the resin particles included in the three-dimensional modeling powder material, the resin is dissolved by the liquid component included in the three-dimensional modeling liquid material, and preferably for the three-dimensional modeling. Crosslinking is performed by the action of the crosslinking agent contained in the liquid material.

-Liquid component-
The three-dimensional modeling liquid material contains a liquid component because it is liquid at room temperature.
As the liquid component, any liquid can be used as long as it is possible to dissolve the resin particles contained in the powder material for three-dimensional modeling, and water and a water-soluble solvent are preferably used. Water is used as the main component. Thereby, the solubility of the said resin particle increases and it becomes possible to manufacture a high-strength three-dimensional molded item. The proportion of water in the entire three-dimensional modeling liquid material is preferably 40% by mass to 85% by mass, and more preferably 50% by mass to 80% by mass.
When the ratio of the water is 40% by mass or more and 85% by mass or less, the solubility of the resin of the powder material for three-dimensional modeling is good, the strength of the three-dimensional model can be maintained, and the inkjet nozzle is dried during standby. Therefore, it is possible to prevent liquid clogging and nozzle missing.

  The water-soluble solvent is particularly effective in increasing moisture retention and ejection stability when the liquid material for three-dimensional modeling is ejected using an inkjet nozzle. When these are lowered, the nozzle is dried, the ejection becomes unstable, or liquid clogging occurs, which may cause a decrease in strength and dimensional accuracy of the three-dimensional structure. Many of these water-soluble solvents have a higher viscosity and boiling point than water, and they are particularly effective because they can function as a wetting agent, an anti-drying agent, and a viscosity adjusting agent for a three-dimensional modeling liquid material.

  The water-soluble solvent is particularly effective in increasing moisture retention and ejection stability when the liquid material for three-dimensional modeling is ejected using an inkjet nozzle. When these are lowered, the nozzle is dried, the ejection becomes unstable, or liquid clogging occurs, which may cause a decrease in strength and dimensional accuracy of the three-dimensional structure. Many of these water-soluble solvents have a higher viscosity and boiling point than water, and they are particularly effective because they can function as a wetting agent, an anti-drying agent, and a viscosity adjusting agent for a three-dimensional modeling liquid material.

-Water-soluble solvent-
The water-soluble solvent is not particularly limited as long as it is a liquid material exhibiting water solubility, and can be appropriately selected according to the purpose. For example, ethanol, 1,2,6-hexanetriol, 1,2-butane Diol, 1,2-hexanediol, 1,2-pentanediol, 1,3-dimethyl-2-imidazolidinone, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl -1,3-hexanediol, 2-pyrrolidone, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3 Butanediol, 3-methyl-1,3-hexanediol, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, β-butoxy-N, N-dimethylpropionamide, β-methoxy-N, N-dimethylpropionamide , Γ-butyrolactone, ε-caprolactam, ethylene glycol, ethylene glycol-n-butyl ether, ethylene glycol-n-propyl ether, ethylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoethyl ether, glycerin, diethylene glycol Diethylene glycol-n-hexyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, die Tylene glycol monomethyl ether, diglycerin, dipropylene glycol, dipropylene glycol n-propyl ether, dipropylene glycol monomethyl ether, dimethyl sulfoxide, sulfolane, thiodiglycol, tetraethylene glycol, triethylene glycol, triethylene glycol ethyl ether, triethylene glycol Ethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol methyl ether, tripropylene glycol, tripropylene glycol-n-propyl ether, tripropylene glycol methyl ether, trimethylol ethane, trimethylol propane, propyl propylene diglycol, propylene glycol , Propylene glycol-n-butyl Ether, propylene glycol-t-butyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, hexylene glycol, polyethylene glycol, polypropylene glycol, aliphatic hydrocarbons, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, Examples include ether solvents such as glycol ethers. These may be used individually by 1 type and may use 2 or more types together.

  The content of the water-soluble solvent is preferably 5% by mass or more and 60% by mass or less with respect to the entire liquid material for three-dimensional modeling from the viewpoints of discharge stability, resin solubility, and drying properties of the three-dimensional modeling. 10 mass% or more and 50 mass% or less are more preferable, and 15 mass% or more and 40 mass% or less are still more preferable.

-Crosslinking agent-
The crosslinking agent is effective because it can further increase the strength of the resulting three-dimensional structure by crosslinking with the resin coated on the surface of the base material of the three-dimensional modeling powder material.
The cross-linking agent is not particularly limited as long as it has a property capable of cross-linking the resin, and can be appropriately selected according to the purpose. Examples thereof include metal salts, metal complexes, organic zirconium compounds, and organic titanium compounds. And a chelating agent, and a metal compound containing a metal element is preferable.
Examples of the organic zirconium compound include zirconium oxychloride, ammonium zirconium carbonate, zirconium ammonium lactate and the like.
Examples of the organic titanium compound include titanium acylate and titanium alkoxide.
These may be used individually by 1 type and may use 2 or more types together.

Suitable examples of the metal compound include those that ionize divalent or higher cation metals in water. Specific examples of the metal compound include zirconium oxychloride octahydrate (tetravalent), aluminum hydroxide (trivalent), magnesium hydroxide (divalent), titanium lactate ammonium salt (tetravalent), basic aluminum acetate (Trivalent), zirconium carbonate ammonium salt (tetravalent), titanium triethanolamate (tetravalent), glyoxylate, zirconium lactate ammonium salt and the like are preferable. Among these, a zirconium compound is preferable, and ammonium zirconium carbonate is particularly preferable because the strength of the three-dimensional structure to be obtained is excellent.
Moreover, these can use a commercial item, As this commercial item, for example, a zirconium oxychloride octahydrate (Daiichi Rare Element Chemical Co., Ltd. product, zirconium oxychloride), aluminum hydroxide (Wako Pure) Yaku Kogyo Co., Ltd.), Magnesium Hydroxide (Wako Pure Chemical Industries, Ltd.), Titanium Lactate Ammonium Salt (Matsumoto Fine Chemical Co., Ltd., Orugatix TC-300), Zirconium Lactate Ammonium Salt (Matsumoto Fine Chemical Co., Ltd., Olga) Chicks ZC-300), basic aluminum acetate (manufactured by Wako Pure Chemical Industries, Ltd.), bisvinylsulfone compound (manufactured by Fuji Fine Chemical Co., Ltd., VS-B (K-FJC)), zirconium carbonate ammonium salt (first rare element) Chemical Industry Co., Ltd., Zircosol AC-20) Titanium triethanolaminate (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS TC-400), glyoxylate (Safelink SPM-01, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), etc. It is done.

  The “crosslinking agent” in the present invention is a compound having a site capable of undergoing a crosslinking reaction with a functional group of a crosslinking target (resin). It is a component. Therefore, for example, like radicals (organic peroxides) and reducing substances, they generate free radicals when they themselves decompose by heat and light, add them to unsaturated monomers, and open double bonds. At the same time, a new radical reaction is generated and the process is repeated to promote polymerization, or hydrogen bonded to the carbon of the saturated compound is extracted to generate a new radical. Is different from so-called "initiators" for initiating or promoting radical reactions that themselves do not constitute components of cross-linking sites, such as the formation of a bridge between saturated compounds by recombination. It is a concept and is clearly distinguished from the “crosslinking agent” in the present invention.

There is no restriction | limiting in particular as content of the said crosslinking agent in the said liquid material for three-dimensional model | molding, According to the objective, it can select suitably, For example, 0.1 with respect to the said resin in the said powder material for three-dimensional model | molding The mass% is preferably 50% by mass or less, and more preferably 0.5% by mass or more and 30% by mass or less.
When the content is 0.1% by mass or more and 50% by mass or less, the liquid material is not thickened or gelled, and the strength of the three-dimensional structure to be obtained is improved.

-Other ingredients-
The liquid material for three-dimensional modeling includes, for example, a surfactant, a wetting agent, an anti-drying agent, a viscosity adjusting agent, a penetrating agent, an antifoaming agent, a pH adjusting agent, an antiseptic, an antifungal agent, and a coloring agent. Conventionally known materials such as preservatives and stabilizers can be added without limitation. Among these, surfactants are preferable.

The surfactant is mainly used for the purpose of controlling wettability, permeability and surface tension of the three-dimensional modeling liquid material to the three-dimensional modeling powder material.
The content of the surfactant with respect to the three-dimensional modeling liquid material is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less as the total amount of the surfactant. 5 mass% or more and 3 mass% or less are still more preferable.
If the total amount of the surfactant is smaller than this, the permeability of the liquid material for three-dimensional modeling to the powder material for three-dimensional modeling may decrease, and the strength of the three-dimensional model may decrease. On the other hand, if the total amount of the surfactant is larger than this, the permeability of the three-dimensional modeling liquid material cannot be appropriately controlled, and the three-dimensional modeling liquid material permeates beyond the desired region, and the resulting three-dimensional modeling object Dimensional accuracy may be reduced.

  There is no restriction | limiting in particular as a preparation method of the said liquid material for three-dimensional model | molding, According to the objective, it can select suitably, For example, said other components are needed for liquid components, such as the said water and a water-soluble solvent, for example. The method of adding and mixing and stirring is mentioned.

(Manufacturing method and three-dimensional object manufacturing apparatus for three-dimensional object)
The manufacturing method of the three-dimensional molded item of this invention contains a powder material layer formation process and a liquid material supply process, and also includes another process as needed.
The three-dimensional structure manufacturing apparatus of the present invention preferably includes a powder storage tank, a powder material layer forming unit, and a liquid material supply unit, and preferably includes a liquid material container, and further includes other units as necessary. Have.

-Powder material layer forming step and powder material layer forming means-
The said powder material layer formation process is a process of forming the layer of the said powder material with the powder material for three-dimensional model | molding in the powder material set for three-dimensional model | molding of this invention.
The powder material layer forming means is means for forming a layer of powder material for three-dimensional modeling.
The three-dimensional modeling powder material layer is preferably formed on a support.

--- Support--
The support is not particularly limited as long as the three-dimensional modeling powder material can be placed thereon, can be appropriately selected according to the purpose, and has a table having a mounting surface for the three-dimensional modeling powder material. Examples thereof include a base plate in the apparatus shown in FIG. 1 of Japanese Utility Model Publication No. 2000-328106.
The surface of the support, that is, the mounting surface on which the three-dimensional modeling powder material is mounted, for example, may be a smooth surface, a rough surface, or a flat surface. Although it may be a curved surface, it is preferable that the affinity with the organic material is low when the organic material in the powder material for three-dimensional modeling is dissolved and crosslinked by the action of the crosslinking agent.
When the affinity between the placement surface and the dissolved and crosslinked organic material is lower than the affinity between the base material and the dissolved and crosslinked organic material, the obtained three-dimensional structure is placed. It is preferable in that it can be easily removed from the surface.

--Formation of powder material layer--
There is no restriction | limiting in particular as a method of arrange | positioning the said three-dimensional modeling powder material on the said support body, According to the objective, it can select suitably, For example, as a method of arrange | positioning in a thin layer, patent 3607300 gazette A method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in 1., and a method of spreading the three-dimensional modeling powder material into a thin layer using a member such as a brush, a roller, or a blade A method of pressing the surface of the powder material for three-dimensional modeling using a pressing member to expand the surface into a thin layer, a method of using a known powder additive manufacturing apparatus, and the like are preferable.

In order to place the powder material for three-dimensional modeling in a thin layer on the support using the counter rotating mechanism (counter roller), the brush or blade, the pressing member, etc., for example, as follows: It can be carried out.
That is, the support disposed in the outer frame (sometimes referred to as “mold”, “hollow cylinder”, “tubular structure”, etc.) so as to be movable up and down while sliding on the inner wall of the outer frame. The three-dimensional modeling powder material is placed on the body using the counter rotation mechanism (counter roller), the brush, a roller or a blade, the pressing member, and the like. At this time, when using the support that can move up and down in the outer frame, 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 three-dimensional modeling powder material is placed on the support by being positioned below the thickness of the powder material layer for use. By the above, the said three-dimensional modeling powder material can be mounted in a thin layer on the said support body.

In addition, if the said three-dimensional modeling liquid material is made to act on the said three-dimensional modeling powder material placed in the thin layer in this way, the said layer will harden | cure (the said liquid material supply process).
On the thin layer cured product obtained here, in the same manner as described above, the three-dimensional modeling powder material was placed in a thin layer, and the three-dimensional modeling powder material (layer) placed on the thin layer On the other hand, when the three-dimensional modeling liquid material is allowed to act, curing occurs. The hardening at this time is not only in the powder material (layer) for three-dimensional modeling placed on the thin layer, but also with the hardened product of the thin layer obtained by hardening first, which exists under the material. It also occurs between. As a result, a cured product (three-dimensional model) having a thickness of about two layers of the three-dimensional model powder material (layer) placed on the thin layer is obtained.

  Moreover, in order to mount the said powder material for three-dimensional modeling in a thin layer on the said support body, it can also carry out automatically and simply using the said well-known powder lamination modeling apparatus. The powder additive manufacturing apparatus generally includes a recoater for stacking 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. A movable molding tank for placing and laminating materials in a thin layer. In the powder additive manufacturing apparatus, the surface of the supply tank can always be slightly raised from the surface of the molding tank by raising the supply tank, lowering the molding tank, or both. The three-dimensional modeling powder material can be arranged in a thin layer from the supply tank side using the recoater, and the thin-layer three-dimensional modeling powder material can be laminated by repeatedly moving the recoater. .

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 model powder material (layer) formed by applying the three-dimensional model liquid material to the three-dimensional model powder material is sufficient. 3D modeling formed by applying the liquid material for 3D modeling to the powder material for 3D modeling as it is 500 μm or less without causing problems such as loss of shape during subsequent processing such as sintering or handling. The dimensional accuracy of the cured product (three-dimensional model) by the powder material (layer) for use is improved.
The average thickness is not particularly limited and can be measured according to a known method.

-Liquid material supply process and liquid material supply means-
The liquid material supplying step is a step of supplying the three-dimensional modeling liquid material in the three-dimensional modeling material set of the present invention to the powder material layer formed in the powder material layer forming step.
A predetermined region of the powder material layer supplied with the three-dimensional modeling liquid material is cured.
The liquid material supply means is means for supplying a three-dimensional modeling liquid material capable of dissolving the resin particles contained in the three-dimensional modeling powder material to the powder material layer.

The method of supplying the three-dimensional modeling liquid material 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 ink jet method. In order to carry out these methods, a known apparatus can be suitably used as the liquid material supply means.
Among these, the dispenser method is excellent in droplet quantification, but the application area is narrow, and the spray method can easily form a fine discharge, the application area is wide, and the application property is excellent. The quantitative property of the droplets is poor, and the powder material for three-dimensional modeling is scattered by the spray flow. For this reason, in the present invention, the ink jet method is particularly preferable. The ink jet method is advantageous in that the quantitative property of droplets is better than the spray method, and there is an advantage that the application area can be widened compared with the dispenser method, and a complicated three-dimensional shape can be formed accurately and efficiently. .

In the case of the ink jet method, the liquid material supply means includes a nozzle that can apply the three-dimensional modeling liquid material to the powder material layer by the ink jet method. In addition, as the nozzle, a nozzle (discharge head) in a known ink jet printer can be suitably used, and the ink jet printer can be suitably used as the three-dimensional modeling liquid material applying unit. In addition, as said inkjet printer, SG7100 by Ricoh Co., Ltd. etc. are mentioned suitably, for example. The inkjet printer is preferable in that the amount of liquid material for three-dimensional modeling that can be dropped from the head portion at a time is large and the application area is large, so that the application speed can be increased.
In the present invention, even when the ink jet printer capable of applying the three-dimensional modeling liquid material with high accuracy and high efficiency is used, the three-dimensional modeling liquid material is a solid material such as particles or a resin or the like. Since no high-viscosity molecular material is contained, clogging or the like does not occur in the nozzle or its head, corrosion does not occur, and when applied (discharged) to the three-dimensional modeling powder material layer Since the resin particles in the three-dimensional modeling powder material can efficiently penetrate, the manufacturing efficiency of the three-dimensional model is excellent, and no polymer component such as a resin is added. This is advantageous in that a cured product with good dimensional accuracy can be obtained easily and efficiently in a short time.

  In the three-dimensional modeling liquid material, the cross-linking agent can also function as a pH adjuster. As the pH of the three-dimensional modeling liquid material, when the three-dimensional modeling liquid material is applied to the three-dimensional modeling powder material layer by the ink jet method, the viewpoint of preventing corrosion and clogging of the nozzle head portion of the nozzle to be used. Is preferably 5 (weakly acidic) to 12 (basic), more preferably 8 to 10 (weakly basic). A known pH adjusting agent may be used for adjusting the pH.

-Powder storage tank-
The powder storage tank is a member in which the powder material for three-dimensional modeling of the present invention is stored, and the size, shape, material, etc. are not particularly limited and can be appropriately selected according to the purpose. A storage tank, a bag, a cartridge, a tank, etc. are mentioned.

-Liquid material container for 3D modeling-
The three-dimensional modeling liquid material container is a member in which the three-dimensional modeling liquid material is stored, and the size, shape, material, and the like thereof are not particularly limited and can be appropriately selected according to the purpose. For example, a storage tank, a bag, a cartridge, a tank, etc. are mentioned.

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

The said drying process is a process of drying the hardened | cured material (three-dimensional molded item) obtained in the said liquid material supply process. In the drying step, not only moisture contained in the cured product but also organic matter may be removed (degreasing). Examples of the drying means include known dryers.
The sintering step is a step of sintering the cured product (three-dimensional model) formed in the liquid material supply step. By performing the sintering step, the cured product can be formed into an integrated metal or ceramic molding (sintered three-dimensional model). Examples of the sintering means include a known sintering furnace.
The said surface protection treatment process is a process of forming a protective layer etc. on the hardened | cured material (three-dimensional molded item) formed in the said liquid material supply process. By performing this surface protection treatment step, it is possible to provide the surface of the cured product (three-dimensional model) with durability that allows the cured product (three-dimensional model) to 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, and a glossy layer. Examples of the surface protection treatment means include known surface protection treatment devices such as a spray device and a coating device. The coating process is a process of coating the cured product (three-dimensional model) formed in the liquid material supply process. By performing the coating step, the cured product (three-dimensional model) can be colored in a desired color. Examples of the coating means include known coating apparatuses, such as a coating apparatus using a spray, a roller, a brush, and the like.

Here, in FIG. 1A-FIG. 1F, an example of the schematic of the process for manufacturing a three-dimensional molded item is shown using the three-dimensional modeling material set of this invention.
1A to 1F includes a modeling powder storage tank 1 and a supply powder storage tank 2, and each of these powder storage tanks has a stage 3 that can move up and down. And the powder material for three-dimensional modeling of this invention is mounted on this stage 3, and the layer which consists of the said powder material for three-dimensional modeling is formed. On the powder storage tank 1 for modeling, it has the liquid material supply means 5 for three-dimensional modeling which discharges the liquid material 6 for three-dimensional modeling toward the powder material for three-dimensional modeling in the said powder storage tank, and also for supply 3D modeling powder material capable of leveling the surface of the 3D modeling powder material (layer) in the modeling powder storage tank 1 while supplying the 3D modeling powder material from the powder storage tank 2 to the modeling powder storage tank 1 It has a layer forming means 4 (hereinafter also referred to as “recoater”).

1A and 1B show a process of supplying a three-dimensional modeling powder material from the supply powder storage tank 2 to the modeling powder storage tank 1 and forming a three-dimensional modeling powder material layer having a smooth surface. Each stage 3 of the powder storage tank 1 for modeling and the powder storage tank 2 for supply is controlled, the gap is adjusted so as to have a desired layer thickness, and the powder material layer forming means 4 for three-dimensional modeling is used as the powder storage tank for supply By moving from 2 to the modeling powder storage tank 1, the three-dimensional modeling powder material layer is formed in the modeling powder storage tank 1.
FIG. 1C shows a step of dropping the three-dimensional modeling liquid material 6 onto the three-dimensional modeling powder material layer of the modeling powder storage tank 1 by using the three-dimensional modeling liquid material supply means 5. At this time, the position where the three-dimensional modeling liquid material 6 is dropped on the three-dimensional modeling powder material layer is determined by two-dimensional image data (slice data) obtained by slicing the three-dimensional modeling object into several planes.
1D and 1E show that the stage 3 of the supply powder storage tank 2 is raised, the stage 3 of the modeling powder storage tank 1 is lowered, the gap is controlled so as to obtain a desired layer thickness, and the three-dimensional modeling is performed again. By moving the powder material layer forming means 4 for supply from the powder storage tank 2 for supply to the powder storage tank 1 for modeling, a powder material layer for three-dimensional modeling is newly formed in the powder storage tank 1 for modeling.
FIG. 1F is a step of dropping the three-dimensional modeling liquid material 6 onto the three-dimensional modeling powder material layer of the modeling powder storage tank 1 again using the three-dimensional modeling liquid material supply means 5.
By repeating these series of steps, drying as necessary, and removing the three-dimensional modeling powder material to which the three-dimensional modeling liquid material is not attached, a three-dimensional modeled object can be obtained.

Drawing 2A-Drawing 2F show other examples of a process schematic diagram for manufacturing a solid fabrication thing using a solid fabrication material set of the present invention. 2A to 2F are in principle the same as those of FIGS. 1A to 1F, but the supply mechanism of the powder material for three-dimensional modeling is different.
2A and 2B show a process of supplying a three-dimensional modeling powder material from the supply powder storage tank 2 to the modeling powder storage tank 1 and forming a three-dimensional modeling powder material layer having a smooth surface. After the powder material for three-dimensional modeling is supplied to the powder storage tank 1 for modeling, the powder is stored for modeling by adjusting the gap so as to have a desired layer thickness and moving the powder material layer forming means 4 for three-dimensional modeling. A three-dimensional modeling powder material layer is formed in the tank 1.
FIG. 2C shows a step of dropping the three-dimensional modeling liquid material 6 onto the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the three-dimensional modeling liquid material supply means 5. At this time, the position where the three-dimensional modeling liquid material 6 is dropped on the three-dimensional modeling powder material layer is determined by two-dimensional image data (slice data) obtained by slicing the three-dimensional modeling object into several planes.
2D and 2E, the stage 3 of the modeling powder storage tank 1 is lowered, and the three-dimensional modeling powder material is again supplied from the supply powder storage tank 2 to the modeling powder storage tank 1 to obtain a desired layer thickness. By controlling the gap and moving the three-dimensional modeling powder material layer forming means 4 again, a three-dimensional modeling powder material layer is newly formed in the modeling powder storage tank 1.
FIG. 2F is a step of dropping the three-dimensional modeling liquid material 6 onto the three-dimensional modeling powder material layer of the modeling powder storage tank 1 again using the three-dimensional modeling liquid material supply means 5.
By repeating these series of steps, drying as necessary, and removing the three-dimensional modeling powder material to which the three-dimensional modeling liquid material is not attached, a three-dimensional modeled object can be obtained.
The three-dimensional structure manufacturing apparatus having the configuration shown in FIGS. 2A to 2F has an advantage that it can be made more compact. In addition, these are examples which show the process which manufactures a three-dimensional molded item, Comprising: This invention is not limited to these.

  Here, the three-dimensional structure manufacturing apparatus of the present invention specifically includes a powder storage tank for supply (hereinafter also referred to as “supply tank”) and a powder storage tank for modeling (hereinafter “modeling tank”). 3D modeling powder material layer forming means comprising a roller and a powder removing plate, and three-dimensional modeling liquid material supply means comprising a head and a head cleaning mechanism, and if necessary, Other members such as a powder material container are provided.

The powder storage tank has a tank shape or a box shape provided for supply and modeling, and the stage on the bottom surface of the powder storage tank can be moved up and down in the vertical direction. Moreover, the said supply tank and the said modeling tank are provided adjacently, and a three-dimensional molded item is formed on the stage of the said modeling tank. The stage of the supply tank is raised, and the filled powder material is supplied onto the stage of the supply tank using a three-dimensional modeling powder material layer forming means including a flattening roller. The three-dimensional modeling powder material layer forming means flattens the upper surface of the powder material loaded on the supply tank and the stage of the modeling tank, thereby forming a powder material layer.
The liquid material for three-dimensional modeling is discharged to the powder material layer for three-dimensional modeling formed on the stage using the three-dimensional modeling liquid material supply means using the head. The head cleaning mechanism is in close contact with the head, sucks the liquid material for three-dimensional modeling, and wipes the discharge port.

Here, the schematic of the powder storage tank 100 of a three-dimensional molded item manufacturing apparatus is shown in FIG. The powder storage tank 100 has a box shape and includes a tank in which two upper surfaces of a supply tank 102 and a modeling tank 101 are opened.
Inside each of the supply tank 102 and the modeling tank 101, a stage is held so as to be movable up and down. The side surfaces of the stage are arranged so as to contact the frame of each tank, and the upper surface of the stage is kept horizontal. Around these powder storage tanks 100, a powder drop port 103 having a concave shape with an open upper surface is provided. When the powder material layer is formed, surplus powder material collected by the flattening roller falls on the powder dropping port 103. The surplus powder that has fallen to the powder dropping port 103 is returned to the powder supply unit located above the modeling tank 101 by an operator or a suction mechanism as necessary.

The powder material container (not shown) has a tank shape and is disposed above the supply tank 102. During the initial operation of modeling or when the amount of powder material in the supply tank 102 decreases, the powder in the tank is supplied to the supply tank 102. Examples of the powder conveying method for supplying powder include a screw conveyor method using a screw and an air transportation method using air.
The flattening roller (not shown) has a function of transporting the powder material from the supply tank 102 to the modeling tank 101 and forming a powder material layer having a predetermined thickness (for example, thickness (Δt1−Δt2)). doing. As shown in FIG. 3, the flattening roller is a bar longer than the inner dimensions of the modeling tank 101 and the supply tank 102 (that is, the width of the “part where the powder material is provided or charged”). It is a material, and both ends are supported by the reciprocating device. The flattening roller moves horizontally from the outside of the supply tank 102 while rotating so as to pass over the supply tank 102 and the modeling tank 101, thereby supplying the powder material onto the modeling tank 101. it can. Specifically, the stage of the supply tank 102 is raised and the stage of the modeling tank 101 is lowered.

At this time, it is preferable to set the lowering distance of the stage so that the distance between the uppermost powder material layer of the modeling tank 101 and the lower portion (downward tangent portion) of the flattening roller is Δt1. In the present embodiment, the Δt1 is preferably 50 μm or more and 300 μm or less, for example, about 150 μm.
Next, the powder positioned above the upper surface level of the supply tank 102 is supplied to the modeling tank by rotating and moving the flattening roller, and a powder layer having a predetermined thickness Δt1 is formed on the stage of the modeling tank 101. Form. Here, the flattening roller can move while maintaining a constant distance from the upper surface level of the modeling tank 101 and the supply tank 102. As a result of being kept constant, the powder material layer having a uniform thickness can be formed on the modeling tank 101 or on the already formed modeling tank 101 while conveying the powder onto the modeling tank 101 with a flattening roller. .

  The flattening roller preferably rotates in the counter direction (reverse rotation) with respect to the horizontal movement direction for conveying the powder material, but in the opposite direction to the counter direction in order to improve the density of the powder material. It is also possible to rotate (forward rotation). Further, after the roller is horizontally moved while rotating in the reverse direction, the stage of the modeling tank 101 is raised by Δt2, and the roller is moved horizontally while being rotated in the forward direction, thereby obtaining the effect of conveying powder and improving the density. In the present embodiment, Δt2 is preferably 50 μm or more and 100 μm or less, for example, about 50 μm. This (Δt1-Δt2) corresponds to the thickness of the modeling layer 101, that is, the stacking pitch.

  The planarizing roller is preferably provided with a powder removing plate for removing the adhering powder material. In order to prevent the powder adhering to the roller from scattering in the flattened region, the powder removing plate is preferably a non-planarized region of the powder and in contact with the roller at a position below the roller rotation center. The flattening member can be not only a roller but also a square blade. Depending on the characteristics of the powder material (for example, the degree of particle condensation and fluidity) and the storage state of the powder material (for example, storage in a high humidity environment), the selection of the planarizing member and the driving conditions can be changed. Further, the driving conditions can be changed in the same way for the densification conditions.

  The head includes a cyan head, a magenta head, a yellow head, a black head, and a clear head. Inside the three-dimensional model manufacturing apparatus, a plurality of tanks containing each of a cyan modeling liquid material, a magenta modeling liquid material, a yellow modeling liquid material, a black modeling liquid material, and a clear modeling liquid material are mounted. Each color head included in the head is connected to a tank containing a liquid material of the corresponding color by a flexible tube (not shown). The head discharges the liquid material of each color to the powder material layer under control. The number of heads and the type of liquid material to be ejected can be changed.

For example, when coloring is not required for the three-dimensional model, only the clear head may be set and only the clear modeling liquid material may be discharged. The head can move in the Y-axis and Z-axis directions using the guide rail. When the surfaces of the supply tank and the modeling tank are flattened and densified by the flattening roller, the head can be retracted to a position where it does not interfere.
When the liquid material discharged by the head is mixed with the powder material, the resin contained in the powder material is dissolved, and adjacent powder materials are bonded to each other. As a result, a modeling layer having a thickness (Δt1−Δt2) is formed.

  Next, a new modeling layer is formed by repeating the above-described powder supply process, planarization process, densification process, and liquid material discharge process using the head. At this time, the new modeling layer and the lower modeling layer are integrated to form a part of the three-dimensional modeled object. Thereafter, the three-dimensional object is completed by repeating the powder material supply / flattening step, the densification step, and the liquid material discharging step by the head as many times as necessary.

The head cleaning mechanism is mainly composed of a cap and a wiper blade. The cap is brought into close contact with the nozzle surface below the head, and the liquid material is sucked from the nozzle. This is because the powder material clogged in the nozzle is discharged or the liquid material having a high viscosity is discharged. Thereafter, the nozzle surface is wiped (wiped) to form a meniscus for the nozzle (the inside of the nozzle is in a negative pressure state). The head cleaning mechanism covers the nozzle surface of the head when the liquid material is not discharged, and prevents the powder material from being mixed into the nozzle and the liquid material from drying.
Note that the thickness of the powder material layer, the driving condition of the flattening means, and the high density driving condition may be appropriately changed according to the material and particle size of the powder material to be used and the required accuracy.

<Degreasing and sintering of 3D objects>
The obtained three-dimensional model is degreased and sintered as necessary.
The degreasing means a treatment for removing a resin component. If the resin component is not sufficiently removed in the degreasing treatment, deformation and cracks may occur in the three-dimensional sintered product in the subsequent sintering treatment. Examples of the degreasing method include a sublimation method, a solvent extraction method, a natural drying method, and a heating method. Among these, the heating method is preferable.
The heating method is a method of heat-treating the obtained three-dimensional structure at a temperature at which degreasing is possible. In addition to performing in an air atmosphere, a method of heat treatment in a vacuum or reduced pressure atmosphere, a non-oxidizing atmosphere, a pressurized atmosphere, or a gas atmosphere such as nitrogen gas, argon gas, hydrogen gas, or ammonia decomposition gas is also used as necessary. Although the temperature and time of the degreasing treatment can be appropriately set depending on the base material and the resin, the three-dimensional modeling powder material of the present invention uses the polyvinyl alcohol as a resin, and therefore has a relatively degreasing temperature. Is low, it is possible to shorten the time, and is effective in that the production efficiency of the three-dimensional sintered product is increased.
Moreover, degreasing by such heat treatment can be performed in a plurality of steps and is effective. For example, it is possible to change the heat treatment temperature in the first half and the second half, or to repeatedly perform low and high temperatures.

The resin may not be completely removed by the degreasing treatment, and a part of the resin may remain at the time when the degreasing treatment is completed. On the other hand, sintering refers to a method in which powder is consolidated at a high temperature. A three-dimensional sintered product can be obtained by sintering the degreased product obtained by the aforementioned degreasing treatment in a sintering furnace. By sintering, the base material of the powder material for three-dimensional modeling is diffused and grain-grown, and a high-strength three-dimensional sintered product with a dense and few voids as a whole can be obtained.
Conditions such as temperature, time, atmosphere, and heating rate during sintering are appropriately set depending on the composition of the base material, the degreased state of the three-dimensional structure, size, shape, and the like. However, if the sintering temperature is too low, the sintering does not proceed sufficiently, and the strength and density of the three-dimensional sintered product may decrease. On the other hand, if the sintering temperature is too high, the dimensional accuracy of the three-dimensional sintered product may decrease. The sintering atmosphere is not particularly limited, but may be performed in an atmosphere other than an air atmosphere, such as a vacuum or reduced pressure atmosphere, a non-oxidizing atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas.
Sintering may be performed in two stages or more. For example, it is possible to perform primary sintering and secondary sintering with different sintering conditions, or to change the sintering temperature, time, and sintering atmosphere of primary sintering and secondary sintering.

By the above-described manufacturing method and manufacturing apparatus for a three-dimensional object according to the present invention, a three-dimensional object having a complicated three-dimensional shape (three-dimensional (3D)) is used as a three-dimensional object powder material or a three-dimensional object material set according to the present invention. It can be used easily and efficiently, and can be manufactured with good dimensional accuracy without causing deformation before sintering or the like.
The three-dimensional model and the sintered body thus obtained have sufficient strength, excellent dimensional accuracy, and can reproduce fine irregularities, curved surfaces, etc., so they have excellent aesthetic appearance, high quality, and various uses. Can be suitably used.

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

<Preparation of base particle 1>
The following substrate particles 1 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
PSS316L (-20μm)
Volume average particle diameter: 13 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 2>
The following substrate particles 2 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
PSS316L (-53μm / + 20μm)
Volume average particle diameter: 45 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 3>
The following substrate particles 3 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
PSS316L (-105μm / + 53μm)
Volume average particle diameter: 80 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 4>
The following substrate particles 4 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
Product name: PSS316L (-210 μm / + 63 μm)
Volume average particle diameter: 150 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 5>
The following substrate particles 5 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
Product name: PSS316L (-10 μm)
Volume average particle diameter: 8 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 6>
The following substrate particles 6 were prepared.
Stainless steel (SUS316L) made by Daido Steel Co., Ltd.
Product Name: DAP316L
Volume average particle diameter: 13 μm
Specific gravity: 8
Aspect ratio: 0.91

<Preparation of base particle 7>
The following substrate particles 7 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
Product name: PSS316L (-20μm)
Volume average particle diameter: 13 μm
Specific gravity: 8
A Zr bead with a diameter of 1 mm was charged in a range of beads: base particles = 10: 1 to 3: 1 (mass ratio) in a container, and the aspect ratio was adjusted to 0.85 by adding a share for 1 hour with a vibrator. .

<Preparation of base particle 8>
The following substrate particles 8 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
Product name: PSS316L (-20μm)
Volume average particle diameter: 13 μm
Specific gravity: 8
In the same manner as the base particle 7, the shear ratio was added to Zr beads having a diameter of 1 mm for 2 hours to adjust the aspect ratio to 0.79.

<Preparation of base particle 9>
The following substrate particles 9 were prepared.
Sanyo Special Steel Co., Ltd. Stainless Steel (SUS316L)
Product name: PSS316L (-20μm)
Volume average particle diameter: 13 μm
Specific gravity: 8
In the same manner as the base particle 7, the aspect ratio was adjusted to 0.67 by adding a share for 3 hours with Zr beads having a diameter of 1 mm.

<Preparation of base particle 10>
The following substrate particles 10 were prepared.
Osaka Titanium Technologies Co., Ltd. Product name: TILOP45
Volume average particle diameter: 45 μm

<Preparation of base particle 11>
The following substrate particles 11 were prepared.
Silica particles made by Tokuyama Corporation Product name: Excelica SE-8
Volume average particle diameter: 8 μm
Specific gravity: 4.5
Aspect ratio: 0.9

(Example of production of polyvinyl alcohol (PVA) resin particles)
-PVA manufacturing conditions (PVA1-5)-
As shown in Table 1-2, 99.0 parts by mass of ion-exchanged water was mixed with 1.0 part by mass of acetoacetyl group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Z-100, average polymerization degree: 500). Then, while heating to 80 ° C. in a water bath, the mixture was stirred for 2 hours using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., BL600), and cooled in that state for 3 hours, so that 1% by mass of acetoacetyl group A modified polyvinyl alcohol solution was prepared.
Next, the obtained acetoacetyl group-modified polyvinyl alcohol solution was obtained by spray drying using a twin jetter manufactured by Okawahara Chemical Co., Ltd. to obtain PVA resin particles having a volume average particle diameter shown in Table 1-2.
If necessary, to the acetoacetyl group-modified polyvinyl alcohol solution, amino silane for positive charge and chlorosilane for negative charge are added as charge adjusting agents so as to have the charge amount shown in Table 1-3, and this is used. Similarly, spray drying was performed to obtain PVA resin particles having a volume average particle diameter shown in Table 1-2.

<Polyacrylic acid particles>
Three-one motor (Shinto) was prepared by mixing 99.0 parts by mass of ion-exchanged water with 1.0 part by mass of polyacrylic acid resin (manufactured by Toagosei Co., Ltd., Jurimer AC-10) and heating to 80 ° C. in a water bath. A 1 mass% polyacrylic acid resin solution was prepared by stirring for 2 hours using BL600) manufactured by Kagaku Co., Ltd. and cooling for 3 hours in that state. Using this, the spray-drying method was performed similarly to polyvinyl alcohol, and the polyacrylic acid particle was obtained.

<Polyester resin particles>
<Method for producing polyester resin>
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 781 parts by mass of bisphenol A propylene oxide 3 mol adduct, 218 parts by mass of terephthalic acid, 48 parts by mass of adipic acid, and 2 parts by mass of dibutyltin oxide were added. And after reacting at 230 ° C. for 8 hours under normal pressure and further 5 hours at a reduced pressure of 10 to 15 mmHg, 65 parts by weight of trimellitic anhydride is put in a reaction vessel, and reacted at 180 ° C. and normal pressure for 4 hours. A polyester resin was obtained. The polyester resin had a weight average molecular weight of 5,500 and a number average molecular weight of 3,200.
Next, 1 part by mass of a polyester resin was mixed with 99 parts by mass of ethyl acetate while stirring to prepare a 1% by mass polyester resin solution. Using this, the spray-drying method was performed like polyvinyl alcohol, and the polyester resin particle was obtained.

<Dry resin particle coating method>
-Coating production method 1-
The resin particles and substrate particles having the prescribed amounts shown in Table 1-3 were put into a stirring pot, and mixed for 30 minutes with a tumbler mixer (manufactured by Shinmaru Enterprises Co., Ltd.).

-Coating production method 2-
The resin particles and substrate particles having the prescribed amounts shown in Table 1-3 are mixed for 2 minutes at 10,000 rpm using an aster (Osaka Chemical Co., Ltd., Oster Blender ST-1), and stopped for 3 minutes. The cycle was repeated 5 times to mix.

-Coating production method 3-
The resin particles and the base particles having the formulation amounts shown in Table 1-3 were mixed at 3,500 rpm for 5 minutes using a Henschel mixer FM-10 type (manufactured by Mitsui Mining Co., Ltd.).

-Coating production method 4-
The resin particles and substrate particles having the prescribed amounts shown in Table 1-3 were mixed at 13,000 rpm for 3 minutes using a hybridization system NHS-0 manufactured by Nara Machinery Co., Ltd.

-Coating production method 5-
The resin particles and the base particles of the prescribed amounts shown in Table 1-3 were shaken and mixed (put into a sealed container and held in hand and mixed up and down 300 times).

(Preparation example 1 of liquid material for three-dimensional modeling)
-Preparation of liquid material 1 for three-dimensional modeling-
60 parts by mass of water and 40 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred to prepare a liquid material 1 for three-dimensional modeling.

(Preparation example 2 of liquid material for three-dimensional modeling)
-Preparation of liquid material 2 for three-dimensional modeling-
50 parts by mass of ethyl acetate and 50 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred to prepare a liquid material 2 for three-dimensional modeling.

Example 1
<Preparation of powder material 1 for three-dimensional modeling>
As shown in Table 1-1 to Table 1-3, using the base particle 1 and the PVA resin particles having a volume average particle diameter of 8 μm produced under the PVA production conditions (PVA1), the coating production method 1 Thus, a powder material 1 for three-dimensional modeling was produced. In addition, the adhesion amount of the resin particle with respect to the base material particle | grains of the said three-dimensional modeling powder material 1 was 1.0 mass% aiming.

<Preparation of three-dimensional model>
A three-dimensional object 1 was prepared according to the following method using a three-dimensional object manufacturing apparatus shown in FIG. 3 using a counter roller as the three-dimensional powder material layer forming means and using an ink jet head as the three-dimensional liquid material supply means.
The 3D modeling powder material 1 is placed in the powder storage tank of the 3D model manufacturing apparatus, the 3D modeling liquid material 1 is placed in the same liquid material container, and 3D data is input. FIG. 1A to FIG. 1F The process to show was repeated and the three-dimensional molded item which has a strip shape was produced. In addition, the average thickness of one layer of the powder material layer for three-dimensional modeling was adjusted to be about 100 μm, and a total of 30 layers were laminated. Subsequently, after air-drying for about 2 hours, it put into the dryer and dried at 70 degreeC for 3 hours. Thereafter, the powder material for three-dimensional modeling that did not adhere was removed with a brush or the like, placed in a drier again, dried at 100 ° C. for 12 hours, and allowed to cool to room temperature to produce a three-dimensional modeled object.

<Degreasing and sintering of 3D objects>
The obtained three-dimensional model was put into a dryer and heated to 500 ° C. over 4 hours in a nitrogen atmosphere. Subsequently, after maintaining at 400 degreeC for 4 hours, it heated up to 30 degreeC over 4 hours, and performed the degreasing process. The obtained degreased product was sintered at 1,200 ° C. under vacuum in a sintering furnace to produce a three-dimensional sintered product.

(Examples 2-32 and Comparative Examples 1-3)
In Example 1, the kind of base particle of Table 1-1 to Table 1-3, prescription amount, the manufacturing method of resin particle, the kind of resin particle, prescription amount, the coating method of resin particle, and three-dimensional modeling Except for changing the liquid material, etc., each three-dimensional modeled product and each three-dimensional modeled product were produced in the same manner as in Example 1.

  Next, various characteristics were evaluated as follows about each obtained powder material for solid modeling, each solid modeling thing, and each solid sintering thing. The results are shown in Tables 2-1 to 2-3.

<Measurement of charge amount of powder material for three-dimensional modeling>
The charge amount of the powder material for three-dimensional modeling was measured by a blow-off method (Toshiba Chemical Co., Ltd., TB-200) after mixing 99 parts by mass of base material particles and 1 part by mass of resin particles with a tumbler mixer for 10 minutes. did.

<Measurement of volume average particle size of powder material for three-dimensional modeling>
The volume average particle diameter of the three-dimensional modeling powder material was measured using a laser diffraction / scattering particle size distribution measuring device (Microtrac MT3000II, manufactured by Microtrac Bell) to obtain a cumulative volume distribution curve. The volume average particle diameter (D ₅₀ ) was determined from the obtained cumulative volume distribution curve.

<Measurement of aspect ratio of powder material for three-dimensional modeling>
The aspect ratio of the obtained powder material for three-dimensional modeling was measured using Morphology G3-SE manufactured by Spectris.

<Free amount measurement test>
Mass before and after blowing the compressed air by the blow-off method (Toshiba Chemical Co., Ltd., TB-200, see FIG. 5) after mixing the base material particles and the resin particles under the following conditions From the change, the liberation rate ε (%) was determined.
-Condition-
・ Resin particle weight W1: 1g
・ Substrate particle weight W2: 2 g

<Evaluation of dimensional accuracy of 3D objects>
About the obtained three-dimensional molded item, the dimensional accuracy was evaluated according to the following reference | standard by visual observation.
[Evaluation criteria]
◎: The surface of the three-dimensional structure is smooth, has little unevenness, and has no warpage. ○: The surface of the three-dimensional structure has slight unevenness, and a slight warp is observed. △: The surface of the three-dimensional structure. Level where obvious irregularities and warping are recognized ×: Level of the three-dimensional object is rounded and is significantly different from the target shape

<Evaluation of dimensional accuracy of sintered product>
About the obtained three-dimensional sintered product, the degree of deviation from the target shape from the modeling data was measured and evaluated according to the following criteria.
[Evaluation criteria]
◎: Deviation is less than ± 1% ○: Deviation is ± 1% or more and less than ± 3% △: Deviation is ± 3% or more and less than ± 5% ×: Deviation is ± 5% or more

<Repetitive modeling stability>
For confirmation of recycling, using a three-dimensional model that has been modeled again by reusing powder that has been modeled once, a bending stress test was performed using a precision universal testing machine (Autograph AGS-J, manufactured by Shimadzu Corporation). went. For the measurement, a three-point bending test jig and a load cell for 1 kN were used, the distance between fulcrums was set to 24 mm, and the stress at the time of fracture was defined as the maximum stress.
Next, a standard deviation (variation) σ when a similar bending stress test was repeated five times was determined and evaluated according to the following criteria.
[Evaluation criteria]
A: Variation σ is less than 0.2 ○: Variation σ is 0.2 or more and less than 0.5 Δ: Variation σ is 0.5 or more and less than 1 ×: Variation σ is 1 or more

Aspects of the present invention are as follows, for example.
<1> A powder material for three-dimensional modeling including resin particles and substrate particles,
When the charge amount (μc / g) between the resin particles and the base particles is Q1, the Q1 mixes 99 parts by weight of the base particles and 1 part by weight of the resin particles with a tumbler mixer for 10 minutes. It is the amount of charge measured by the blow-off method, and satisfies the following formula (1-1).
1.0 ≦ | Q1 | ≦ 60 Formula (1-1)
<2> The three-dimensional modeling powder material according to <1>, wherein a charge amount Q1 between the resin particles and the base material particles satisfies the following formula (1-2).
5 ≦ | Q1 | ≦ 40 Formula (1-2)
<3> The volume average particle diameter of the substrate particles is larger than the volume average particle diameter of the resin particles,
<1> to <2> in which the free rate ε measured from the mass change before and after the compressed air is blown on the three-dimensional modeling powder material by the blow-off method satisfies the following formula (2-1) It is the powder material for three-dimensional modeling described.
0% ≦ ε ≦ 75% Formula (2-1)
<4> The three-dimensional modeling powder material according to <3>, wherein the liberation ratio ε satisfies the following formula (2-2).
5% ≦ ε ≦ 60% Formula (2-2)
<5> The three-dimensional modeling powder material according to any one of <1> to <4>, wherein a mass W1 of the resin particles and a mass W2 of the base particles satisfy the following formula (3).
1 ≦ [W1 / (W1 + W2)] × 100 ≦ 10 (3)
<6> The three-dimensional modeling powder material according to any one of <1> to <5>, wherein the resin particles include a water-soluble resin.
<7> The three-dimensional modeling powder material according to <6>, wherein the water-soluble resin is at least one selected from a polyvinyl alcohol resin, a polyacrylic acid resin, and a cellulose resin.
<8> The three-dimensional modeling powder material according to any one of <6> to <7>, wherein the water-soluble resin is a modified polyvinyl alcohol.
<9> The three-dimensional modeling powder material according to any one of <1> to <8>, wherein a volume average particle diameter D1 of the base material particles is 2 μm ≦ D1 ≦ 100 μm.
<10> The three-dimensional modeling powder material according to <9>, wherein the base particles have a volume average particle diameter D1 of 10 μm ≦ D1 ≦ 50 μm.
<11> The three-dimensional modeling powder material according to any one of <1> to <10>, wherein the resin particles have a volume average particle diameter D2 of 0.1 μm ≦ D2 ≦ 20 μm.
<12> The three-dimensional modeling powder material according to <11>, wherein the resin particles have a volume average particle diameter D2 of 1 μm ≦ D2 ≦ 10 μm.
<13> The three-dimensional modeling powder material according to any one of <1> to <12>, wherein the base particle is at least one selected from metal particles, ceramic particles, and a resin material.
<14> The powder material for three-dimensional modeling according to any one of <1> to <13>, wherein an aspect ratio (minor axis / major axis) of the base particle is 0.9 or more.
<15> The three-dimensional modeling powder material according to any one of <1> to <14>, wherein an aspect ratio (minor axis / major axis) of the three-dimensional modeling powder material is 0.9 or more.
<16> The three-dimensional modeling powder material according to any one of <1> to <15>, and the three-dimensional modeling liquid material capable of dissolving the resin particles contained in the three-dimensional modeling powder material. This is a featured three-dimensional modeling material set.
<17> The three-dimensional modeling material set according to <16>, wherein the three-dimensional modeling liquid material contains water and a water-soluble solvent.
<18> The three-dimensional modeling material set according to any one of <16> to <17>, wherein the three-dimensional modeling liquid material contains a crosslinking agent.
<19> The three-dimensional modeling material set according to <18>, wherein the crosslinking agent is at least one selected from a water-soluble organic crosslinking agent and a metal salt.
<20> a powder storage tank in which the three-dimensional modeling powder material according to any one of <1> to <15> is stored;
A powder material layer forming means for forming a layer of the powder material for three-dimensional modeling;
Liquid material supply means for supplying the powder material layer with a liquid material for three-dimensional modeling that can dissolve the resin particles contained in the powder material for three-dimensional modeling;
It is a three-dimensional molded item manufacturing apparatus characterized by having.
<21> The three-dimensional structure manufacturing apparatus according to <20>, wherein the liquid material supply unit is an inkjet discharge unit.
<22> A powder material layer forming step of forming a layer of the three-dimensional modeling powder material with the three-dimensional modeling powder material in the three-dimensional modeling material set according to any one of <16> to <19>,
A liquid material supplying step of supplying the three-dimensional modeling liquid material in the three-dimensional modeling material set according to any one of <16> to <19> to the layer of the three-dimensional modeling powder material;
It is a manufacturing method of the three-dimensional molded item characterized by including.
<23> The method for producing a three-dimensional structure according to <22>, wherein the liquid material supply step is an inkjet discharge method.

  The powder material for three-dimensional modeling according to any one of <1> to <15>, the three-dimensional modeling material set according to any one of <16> to <19>, and any one of <20> to <21> According to the three-dimensional structure manufacturing apparatus described in 1) and the method of manufacturing a three-dimensional structure described in any one of <22> to <23>, the conventional problems are solved and the object of the present invention is achieved. be able to.

JP-T 2006-521264 JP 2011-230422 A

1 Modeling powder storage tank (modeling tank)
2 Powder storage tank for supply (supply tank)
3 Stage 4 3D modeling powder material layer forming means 5 3D modeling liquid material supply means (inkjet head)
6 Liquid material for 3D modeling

Claims (12)

A powder material for three-dimensional modeling including resin particles and substrate particles,
When the charge amount (μc / g) between the resin particles and the base particles is Q1, the Q1 mixes 99 parts by weight of the base particles and 1 part by weight of the resin particles with a tumbler mixer for 10 minutes. 3D modeling powder material, characterized in that it is a charge amount measured by a blow-off method and satisfies the following formula (1-1).
1.0 ≦ | Q1 | ≦ 60 Formula (1-1) The volume average particle diameter of the substrate particles is larger than the volume average particle diameter of the resin particles,
The three-dimensional modeling powder material according to claim 1, wherein a free rate ε measured from a mass change before and after the compressed air is blown on the three-dimensional modeling powder material by a blow-off method satisfies the following formula (2-1).
0% ≦ ε ≦ 75% Formula (2-1) The powder material for three-dimensional modeling according to any one of claims 1 to 2, wherein a mass W1 of the resin particles and a mass W2 of the base particles satisfy the following formula (3).
1 ≦ [W1 / (W1 + W2)] × 100 ≦ 10 (3)   The powder material for three-dimensional modeling according to any one of claims 1 to 3, wherein the resin particles include a water-soluble resin.   The powder material for three-dimensional modeling according to claim 4, wherein the water-soluble resin is at least one selected from a polyvinyl alcohol resin, a polyacrylic acid resin, and a cellulose resin.   The three-dimensional modeling powder material according to any one of claims 1 to 5, wherein a volume average particle diameter D1 of the base particles is 2 µm ≤ D1 ≤ 100 µm.   The volume average particle diameter D2 of the resin particles is 0.1 μm ≦ D2 ≦ 20 μm. The powder material for three-dimensional modeling according to any one of claims 1 to 6.   The three-dimensional modeling powder material according to any one of claims 1 to 7, wherein the base particle is at least one selected from metal particles, ceramic particles, and a resin material.   A three-dimensional modeling material comprising: the three-dimensional modeling powder material according to any one of claims 1 to 8; and a three-dimensional modeling liquid material capable of dissolving the resin particles contained in the three-dimensional modeling powder material. set.   The three-dimensional modeling material set according to claim 9, wherein the three-dimensional modeling liquid material contains a crosslinking agent. A powder storage tank in which the powder material for three-dimensional modeling according to any one of claims 1 to 8 is stored;
A powder material layer forming means for forming a layer of the powder material for three-dimensional modeling;
Liquid material supply means for supplying the powder material layer with a liquid material for three-dimensional modeling that can dissolve the resin particles contained in the powder material for three-dimensional modeling;
The three-dimensional molded item manufacturing apparatus characterized by having. A powder material layer forming step of forming a layer of the three-dimensional modeling powder material with the three-dimensional modeling powder material in the three-dimensional modeling material set according to any one of claims 9 to 10,
A liquid material supplying step of supplying a three-dimensional modeling liquid material in the three-dimensional modeling material set according to any one of claims 9 to 10 to the layer of the three-dimensional modeling powder material,
The manufacturing method of the three-dimensional molded item characterized by including.