JP2016172333A - Three-dimensional molding material set, method for manufacturing three-dimensional molded object, and three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensional molding material set from which a three-dimensional molding object using a material with a high melting point and high hardness and having a complicated three-dimensional shape can be easily, efficiently and fast manufactured with high strength.SOLUTION: The three-dimensional molding material set includes at least: a powder material for three-dimensional molding, which contains granular particles having a volume average particle diameter of 10 to 70 μm and comprising a resin and inorganic particles having a volume average particle diameter of 1 μm or less in the primary particles; and a liquid material for three-dimensional molding, which contains an amino group-containing compound. The three-dimensional molding material set is an aqueous solution, in which the above amino group-containing compound contains a metal; the metal is titanium or zirconium; and the amino group-containing compound is polyethylene imine having a weight average molecular weight of 10,000 or more and is included by 3 to 20 mass%.SELECTED DRAWING: None

Description

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

  Conventionally, dental prostheses (artificial teeth) have been made and used from metal materials such as cobalt chrome alloys, ceramic materials such as zirconia, and organic materials such as hybrid resins combined with fillers. These artificial teeth substitute for dysfunctional occlusal functions, but many of the artificial tooth materials not only cause changes over time, such as wear and corrosion, but are also more white than natural teeth. There is also a problem in terms of aesthetics. As a material expected to solve this problem, for example, zirconia is known. The zirconia has transparency, and if a color gradation is added, it is possible to create an artificial tooth that does not feel uncomfortable even if it is aligned with a natural tooth. However, since the zirconia is an extremely hard material and needs to be molded into a desired shape in order to handle it as a prosthesis, it not only takes a lot of time, but especially in the case of cutting such as CAD / CAM. When it is, delicate processing with an internal structure is impossible.

  On the other hand, in the powder additive manufacturing, it is expected that delicate processing having an internal structure is possible, and a method using a laser or an electron beam has been proposed (for example, see Patent Documents 1 and 2).

However, since the zirconia has a very high melting point, it cannot be sintered with a normal laser or the like and cannot be three-dimensionally shaped.
An object of the present invention is to provide a three-dimensional modeling material set that can easily and efficiently produce a three-dimensional object having a complicated three-dimensional shape using a high-melting-point and high-hardness material with high strength and speed.

The three-dimensional modeling material set of the present invention as a means for solving the above-mentioned problem has a volume average particle size of 10 μm or more and 70 μm or less consisting of at least a resin and inorganic particles whose primary particles have a volume average particle size of 1 μm or less. A powder material for three-dimensional modeling including granulated particles,
A three-dimensional modeling liquid material containing an amino group-containing compound.

  According to the present invention, it is possible to provide a three-dimensional modeling material set that can easily and efficiently produce a three-dimensional object having a complicated three-dimensional shape using a high melting point and high hardness material with high strength and speed.

FIG. 1 is a schematic view showing an example of a powder additive manufacturing apparatus used in the present invention. FIG. 2 is a schematic view showing another example of the powder additive manufacturing apparatus used in the present invention.

(3D modeling material set)
The three-dimensional modeling material set of the present invention (sometimes referred to as a “three-dimensional modeling material set”) includes a three-dimensional modeling powder material (sometimes referred to as a “three-dimensional modeling powder material”) and a three-dimensional modeling liquid material (“ It may also be referred to as a “layered manufacturing liquid material”), and may further include other materials as necessary.

<Powder material for three-dimensional modeling>
The powder material for three-dimensional modeling includes granulated particles, and further includes other components as necessary.

-Granulated particles-
The granulated particles are particles formed by granulating a resin and inorganic particles.

The volume average particle diameter of the granulated particles is 10 μm or more and 70 μm or less, and preferably 30 μm or more and 50 μm or less. When the volume average particle diameter is 10 μm or more, the fluidity of the powder material is good, and it is easy to supply the powder material from the supply tank during modeling. On the other hand, when the volume average particle diameter is 70 μm or less, the particle gap after modeling is appropriate, and the shrinkage during sintering is small, so the dimensional accuracy is good.
The volume average particle size of the granulated particles is measured according to a known method using a known particle size measuring device such as Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (manufactured by Sysmex Corporation). be able to.

The granulated particles preferably have a BET specific surface area of 6.0 m ² / g or more and 8.0 m ² / g or less, and more preferably 6.5 m ² / g or more and 7.5 m ² / g or less. When the BET specific surface area is 6.0 m ² / g or more, the amount of encapsulated resin is appropriate, and the elution amount of the resin at the time of modeling is appropriate. The mechanical strength is improved, and modeling with a desired shape is possible. On the other hand, when the BET specific surface area is 8.0 m ² / g or less, the state of irregularities on the outermost surface of the granulated particles is appropriate, and thus the fluidity is good, and the powder conveyance during modeling is good. You can go and model in the desired shape.

The average circularity represented by the following formula of the granulated particles is preferably 0.960 or more, and more preferably 0.980 or more.
Average circularity = (perimeter of a circle having the same area as the particle projection area / perimeter of the particle projection image) × 100
When the average circularity is 0.960 or more, when a thin layer is formed with the granulated particles, the filling rate of the granulated particles in the thin layer is sufficient and voids are not generated. It is possible to prevent voids and the like from being generated in the molded article.
The average circularity can be measured according to a known method using a known circularity measuring device such as FPIA-3000 (manufactured by Sysmex Corporation).

Loosed bulk density of the granulated particles is preferably 1.00 g / cm ³ or more 1.40 g / cm ³ or less, 1.10 g / cm ³ or more 1.30 g / cm ³ or less is more preferable. The loosed bulk density and is 1.00 g / cm ³ or more, or 1.40 g / cm ³ or less, wherein a flowability of the powder material is good, can the powder transfer during shaping without hindrance, in the desired shape Becomes easy to model.

Heavy SoTakashi density of the granulated particles is preferably 1.20 g / cm ³ or more 1.60 g / cm ³ or less, 1.30 g / cm ³ or more 1.50 g / cm ³ or less is more preferable. When the bulk density is not less than 1.20 g / cm ³ or not more than 1.60 g / cm ³ , the fluidity of the powder material is good, and the powder can be conveyed without difficulty during molding, and the desired shape can be obtained. It becomes easy to model with.
The lightly loaded bulk density and the heavily loaded bulk density can be measured using, for example, a powder tester (manufactured by Tsutsui Richemical Co., Ltd.).

The mass reduction rate before and after heating the granulated particles at 1,000 ° C. for 1 hour is preferably 5% by mass or less. When the mass reduction rate is 5% by mass or less, an adverse effect on crystallization due to the firing residue or crack generation can be suppressed.
The mass reduction rate can be measured by, for example, a differential thermothermal gravimetric simultaneous measurement apparatus (TG-DTA6200 EXSTAR6000, manufactured by SII Nano Technology Co., Ltd.).

--Inorganic particles--
There is no restriction | limiting in particular as a material of the said inorganic particle, According to the objective, it can select suitably, For example, a zirconia, an alumina, a silica etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, zirconia is preferable.
When zirconia is used as the inorganic particles, yttria as a sintering aid, alumina as an impurity, or the like may be contained.

  90 mass% or more is preferable and, as for content of the zirconia in the said inorganic particle, 94 mass% or more is more preferable. When the content of the zirconia is 90% by mass or more, the relative amount of the sintering aid or impurities is lowered, so that the mechanical strength is excellent and no discoloration occurs.

  The content of yttria in the inorganic particles is preferably 2% by mass or more and 6% by mass or less, and more preferably 3% by mass or more and 5% by mass or less. When the yttria content is in the range of 2% by mass or more and 6% by mass or less, the function as a sintering aid is sufficiently exhibited, and cracks are not generated during firing.

  The content of alumina in the inorganic particles is preferably 3% by mass or less, and more preferably 1% by mass or less. When the content of the alumina is 3% by mass or less, the function as a sintering aid is good and the color is not adversely affected.

  The contents of zirconia, yttria, and alumina in the inorganic particles can be measured by, for example, ICP emission spectrometry.

The volume average particle diameter of the primary particles of the inorganic particles is 1 μm or less. When the volume average particle diameter of the primary particles is 1 μm or less, zirconia is sufficiently dissolved during firing and can be easily sintered.
The volume average particle size of the inorganic particles is measured according to a known method using a known particle size measuring device such as Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (manufactured by Sysmex Corporation). Can do.

The monoclinic phase ratio of the inorganic particles is preferably 30% or less, and more preferably 20% or less. When the monoclinic phase rate is 30% or less, the tetragonal phase rate is appropriate and the mechanical strength is good.
The monoclinic phase ratio of the inorganic particles can be measured under predetermined conditions using, for example, an X-ray powder diffractometer.

  The method for producing the inorganic particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a thermal decomposition method, a coprecipitation method, a hydrolysis method, a method of synthesizing from an aqueous metal salt solution of zirconia or yttria. Etc. Among these, the method by a thermal decomposition method or a coprecipitation method is preferable.

In the thermal decomposition method, a predetermined amount of zirconium oxychloride and an aqueous solution of yttrium chloride are mixed, and sodium chloride (or potassium chloride) is added in an amount of 0.1% by mass to 1% by mass with respect to zirconium oxychloride and mixed. This mixture is subjected to instantaneous drying such as spray drying to obtain a dry powder.
The instantaneous drying is a technique that can be dried within 10 seconds, and the drying temperature is preferably performed in heated air of 200 ° C. or higher.
Next, the oxide powder is obtained by thermally decomposing the dry powder in air at a temperature of 800 ° C. to 1,200 ° C. The calcined oxide powder is pulverized by a wet pulverization method so that the pulverized diameter is 2 μm or less, and washed with water. There is no restriction | limiting in particular as the method of the said water washing, Although it can select suitably according to the objective, The continuous washing filtration method which uses a membrane filter is preferable.
By the water washing, the water is sufficiently washed so that the concentration of sodium (or potassium) in the inorganic particles is in the range of 10 ppm to 100 ppm as an amount converted to oxide. By drying the slurry after washing with water, inorganic particles (zirconia powder) are obtained.

  In the coprecipitation method, zirconium oxychloride and an yttrium chloride aqueous solution are mixed. Here, in order to form a metal complex so that the pH at which each hydrate from zirconium oxychloride and yttrium chloride precipitates is kept constant, the molar ratio of sodium sulfate (or potassium sulfate) to zirconia is preferably 0. 3. Add to 3 to 0.7, and react at a temperature of 50 to 100 ° C. for several hours or more. An alkaline aqueous solution such as sodium hydroxide or ammonia is added to this mixed solution with stirring, and the pH of the aqueous solution is adjusted to 8-10. The obtained coprecipitated hydrate fine particles are washed thoroughly with water, and it is confirmed that sodium (or potassium) in the range of 10 ppm to 100 ppm when converted to an oxide. Hydrated fine particles after water washing are dehydrated and dried, and calcined in air at a temperature of 800 ° C. to 1,200 ° C. to obtain a calcined oxide powder. The obtained oxide calcined powder is wet-pulverized to 2 μm or less and dried to obtain inorganic particles (zirconia powder).

--Resin--
A water-soluble resin is preferably used as the resin.
Water-soluble in the water-soluble resin means that 10% by mass or more dissolves in water at room temperature (25 ° C.).
The water-soluble resin is added to the inorganic particles, and a liquid material containing an amino group-containing compound that exhibits a crosslinking reaction with respect to the water-soluble resin is applied, so that the water-soluble resin dissolved in water is a liquid material. It reacts instantly with the amino group-containing compound in it, and a shaped article can be obtained quickly.
As said resin, what has an acidic functional group is preferable, For example, polyvinyl alcohol, polyacrylic acid, etc. are mentioned. Among these, polyacrylic acid having higher acidity is preferable.

The weight average molecular weight Mw of the polyacrylic acid is preferably from 500,000 to 1,000,000, more preferably from 600,000 to 900,000. When the weight average molecular weight Mw is 500,000 or more, it is easy to construct a cross-linked structure with the liquid material, and the curing time of the molded article is appropriate. On the other hand, when the weight average molecular weight Mw is 1,000,000 or less, the viscosity of the slurry is appropriate, and the sprayed dry granulation has good supply of the polyacrylic acid aqueous solution. There is no variation in grain size.
For the weight average molecular weight Mw, for example, the molecular weight distribution of the isolated polyacrylic acid can be obtained by gel permeation chromatography (GPC), and the weight average molecular weight can be calculated based on this.

The method for adding the resin to the inorganic particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the resin is added at the timing of granulation by spray drying, and the aggregate of inorganic particles ( And a method in which the resin is supported even inside the secondary particles.
0.1 mass% or more and 5 mass% or less are preferable, and, as for the addition amount with respect to the said inorganic particle of the said resin, 0.5 mass% or more and 3 mass% or less are more preferable. When the addition amount is 0.1% by mass or more, a crosslinking reaction occurs appropriately, and the strength of the shaped article is good. On the other hand, when the addition amount is 5% by mass or less, the mechanical strength of the shaped article after sintering is good.
The addition amount of the resin can be measured according to a known method using a known thermal analyzer, for example, DSC-200 (manufactured by Seiko Denshi).

  In the case of the existing three-dimensional modeling method, since the resin (binder) does not react or dissolve immediately, it is necessary to wait for a long time until the modeled object is taken out after modeling. For example, when water-based ink is landed on a metal or ceramic particle coated with a resin, if the resin dissolves and then solidifies, the resin existing between the particles acts as a binder to obtain a shaped object In this case, however, the time from dissolution to solidification becomes very long. Therefore, it is necessary to devise so that a molded article can be taken out immediately after modeling, for example, by improving the curing rate while adding another bonding accelerator or the like in addition to the resin.

  It is also possible to add a large amount of resin to obtain the strength of the molded object (green body), but in this case, a large amount of organic residue is present after sintering, and the mechanical strength of the sintered object is significantly reduced. There is a risk of letting you. Therefore, it is not a good idea to increase the amount of resin added in order to speed up the curing rate, but it is possible to improve the curing rate with as little amount as possible, and to improve the mechanical strength of the green body and the shaped article after sintering. It is desired.

<Other ingredients>
Other components that can be included in the three-dimensional modeling powder material are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a fluidizing agent, a filler, a leveling agent, and a sintering aid. .
When the powder material for three-dimensional modeling contains the fluidizing agent, it is preferable in that a layer of the powder material for three-dimensional modeling can be easily and efficiently formed, and a cured product (three-dimensional modeled product) obtained when the filler is included. In addition, it is preferable in that voids and the like are less likely to occur in the laminate modeled product and the cured product for sintering), and when the leveling agent is included, the wettability of the three-dimensional modeled powder material is improved and handling is facilitated. When the sintering aid is included, the sintered product can be sintered at a lower temperature when the obtained cured product (three-dimensional modeled product, layered modeled product, cured product for sintering) is subjected to a sintering process. Is preferable.

<Liquid material for 3D modeling>
The three-dimensional modeling liquid material includes an amino group-containing compound, preferably includes an aqueous medium and a surfactant, and further includes other components as necessary.

-Amino group-containing compound-
The amino group-containing compound is preferably liquid at 25 ° C. and water-soluble.
The water-soluble means that 10% by mass or more dissolves in water at room temperature (25 ° C.).
The amino group-containing compound is not particularly limited as long as it can form a crosslinked structure with respect to the resin, and can be appropriately selected depending on the purpose. If it is an imine or a low molecular weight material, a metal complex such as titanium lactate may be used. These may be used individually by 1 type and may use 2 or more types together.

The weight average molecular weight Mw of the polyethyleneimine is preferably 10,000 or more, and more preferably 10,000 or more and 80,000 or less. When the weight average molecular weight Mw is 10,000 or more, no precipitate is generated even after long-term storage, and the discharge stability is good. On the other hand, when the weight average molecular weight Mw is 80,000 or less, the viscosity does not increase, the liquid material can be stably discharged, the dimensional accuracy of the molded article is good, and the mechanical strength is also good.
For the weight average molecular weight Mw, for example, the molecular weight distribution of the isolated polyacrylic acid can be obtained by gel permeation chromatography (GPC), and the weight average molecular weight can be calculated based on this.

The content of the polyethyleneimine is preferably 3% by mass or more and 20% by mass or less with respect to the total amount of the liquid material.
For example, when polyethyleneimine having a weight average molecular weight Mw of 70,000 is used, 4 mass% or more and 7 mass% or less is more preferable.
When polyethyleneimine having a weight average molecular weight Mw of 10,000 is used, it is more preferably 15% by mass or more and 20% by mass or less.
When the content is 3% by mass or more, a crosslinked structure can be sufficiently constructed, and the mechanical strength of the molded article becomes good. On the other hand, when the content is 20% by mass or less, the viscosity does not increase, the liquid material can be stably discharged, the dimensional accuracy of the modeled object is improved, and the mechanical strength is also improved.

The low molecular material containing the amino group is preferably a compound containing a metal, and the metal species is preferably titanium or zirconium.
Examples of the metal-containing compound include titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybis (triethanolaminate), titanium aminoethylamino ethanolate, zirconium lactate, zirconium aminoethylamino ethanolate, and the like. .

-Aqueous medium-
Examples of the aqueous medium include water, alcohols such as ethanol, ethers, ketones, and the like, and water is preferable. In the aqueous medium, the water may contain some amount of components other than water such as the alcohol.
Examples of the water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, or ultrapure water.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, disulfonate, cholate, and deoxy. Anionic surfactants such as cholates (anionic surfactants); alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyls Cationic surfactants (cationic surfactants) such as quaternary ammonium salt types such as dimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride; fatty acid amide derivatives, polyhydric alcohol derivatives, poly ( Oxyethylene) = oct Nonionic surfactants such as phenyl ether; amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, CHAPS, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a surfactant that is liquid at room temperature is preferable from the viewpoint of suppressing clogging of the inkjet nozzle.
There is no restriction | limiting in particular in content of the said surfactant, Although it can select suitably according to the objective, 1 mass% or less is preferable with respect to the whole quantity of the said three-dimensional modeling liquid material. When the content is 1% by mass or less, a decomposed product does not remain in the shape when fired, and the mechanical strength is good.

<Other ingredients>
The other known components that can be included in the three-dimensional modeling liquid material are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include viscosity adjusters, pigments, preservatives, preservatives, and stabilization. Agents, pH adjusters and the like.

-Physical properties of liquid materials for 3D modeling-
The viscosity of the liquid material for three-dimensional modeling is 25 mC, preferably 4 mPa · s to 20 mPa · s, and more preferably 5 mPa · s to 8 mPa · s. When the viscosity is 4 mPa · s or more or 20 mPa · s or less, the ink can be stably ejected, the dimensional accuracy of the molded article is good, and the mechanical strength is also improved. In addition, the said viscosity can be measured at 25 degreeC based on JIS-K7117, for example.

  The surface tension of the three-dimensional modeling liquid material is preferably 50 mN / m or less, particularly preferably 30 mN / m or less. When the surface tension is 50 mN / m or less, the liquid material for three-dimensional modeling can be stably discharged, the dimensional accuracy of the modeled object is good, and the mechanical strength is also improved.

  The method for applying the three-dimensional modeling liquid material to the three-dimensional modeling powder material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispenser method, a spray method, and an inkjet method. . In order to carry out these methods, a known apparatus can be suitably used as the cured product forming 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 powder scattering occurs due to 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 cured product forming means has a nozzle capable of applying the ink to the powder material layer by the ink jet method. In addition, as this nozzle, the nozzle in a well-known inkjet printer can be used conveniently, and this inkjet printer can be used conveniently as said hardened | cured material formation means. In addition, as said inkjet printer, SG7100 by Ricoh Co., Ltd. etc. are mentioned suitably, for example. The ink jet printer is preferable in that it can increase the application speed because it has a large amount of ink that can be dropped from the head portion at a time and has a large application area. In the present invention, even when the ink jet printer capable of applying the ink with high accuracy and high efficiency is used, the liquid material contains solid matter such as particles and high viscosity material such as resin. Therefore, no clogging or the like occurs in the nozzle or its head, and no corrosion or the like occurs, so that it is excellent in manufacturing efficiency of a molded article and is not provided with a polymer component such as a resin. It is advantageous in that a cured product with good dimensional accuracy can be obtained easily and efficiently in a short time without causing an unscheduled increase in volume.

  The three-dimensional modeling material set of the present invention can be suitably used for simple and efficient production of various shaped objects and structures, and the three-dimensional modeling manufacturing method and three-dimensional modeled manufacturing apparatus of the present invention described later. It can be particularly preferably used.

(Manufacturing method of three-dimensional structure and manufacturing apparatus of three-dimensional structure)
The method for producing a three-dimensional structure of the present invention includes at least a layer forming step, preferably includes a layer curing step and a sintering step, and further includes other steps as necessary.
The apparatus for producing a three-dimensional object used in the present invention preferably includes at least a layer forming unit, preferably includes a layer curing unit and a sintering unit, and further includes other units as necessary.
The manufacturing method of the three-dimensional modeled object of the present invention can be preferably implemented using the manufacturing apparatus of the three-dimensional modeled object used in the present invention, and the layer forming step is preferably performed by the layer forming means. The layer curing step can be preferably performed by the layer curing unit, the sintering step can be preferably performed by the sintering unit, and the other steps can be performed by the other unit. It can implement suitably.

<Layer forming step and layer forming means>
The layer forming step is a step of forming a three-dimensional modeling powder material layer having a predetermined thickness on the support using the three-dimensional modeling powder material in the three-dimensional modeling material set of the present invention.
The layer forming means is a means for forming a three-dimensional modeling powder material layer having a predetermined thickness on the support using the three-dimensional modeling powder material in the three-dimensional modeling material set of the present invention.

-Support-
The support is not particularly limited as long as the powder material can be placed thereon, can be appropriately selected according to the purpose, and a table having a placement surface for the powder material, Japanese Patent Laid-Open No. 2000-328106 The base plate in the apparatus described in FIG. The surface of the support, that is, the placement surface on which the powder material is placed, for example, may be a smooth surface, a rough surface, or a flat surface, It may be a curved surface.

-Formation of powder material layer for three-dimensional modeling-
The method for arranging the powder material on the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the method for arranging the powder material in a thin layer is described in Japanese Patent No. 3607300. A method using a known counter rotation mechanism (counter roller) used in the selective laser sintering method, a method of spreading the powder material into a thin layer using a member such as a brush, roller, blade, etc., the powder material layer A method of pressing the surface of the film with a pressing member to expand it 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 in a thin layer on the support using the counter rotating mechanism (counter roller), the brush or blade, the pressing member, etc., for example, the following may be performed. it can. That is, for example, it is disposed in an 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 powder material is placed on the support using the counter rotating mechanism (counter roller), the brush, a roller or 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 powder material. The powder material is placed on the support while being positioned below by the thickness of the layer. As described above, the powder material can be placed on the support in a thin layer.

  In addition, hardening will arise when the liquid material by a laser, an electron beam, or the inkjet method is made to act on the said powder material mounted in the thin layer in this way. On the thin cured product obtained here, the powder material is placed in a thin layer in the same manner as described above, and the laser or the laser is applied to the powder material (layer) placed in the thin layer. Curing occurs when an electron beam or liquid material is applied. Curing at this time occurs not only in the powder material (layer) placed on the thin layer, but also between the cured material of the thin layer obtained by curing first, which exists under the powder material (layer). . As a result, a cured product (three-dimensional modeled product, layered modeled product, cured product for sintering) having a thickness of about two layers of the powder material (layer) placed on the thin layer is obtained.

  Moreover, in order to mount the said powder material on 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 has a recoater for laminating the powder material, a movable supply tank for supplying the powder material onto the support, and the powder material placed in a thin layer. And a movable molding tank for stacking. 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 powder material can be arranged in a thin layer using the recoater from the supply tank side, and the thin powder material can be laminated by repeatedly moving the recoater.

There is no restriction | limiting in particular as thickness of the said powder material layer, Although it can select suitably according to the objective, For example, 3 micrometers or more and 200 micrometers or less are preferable at the average thickness per layer, and 10 micrometers or more and 100 micrometers or less are more preferable. When the average thickness is 3 μm or more, the time until a shaped product is obtained is appropriate, and problems such as shape loss do not occur during processing such as sintering or handling. On the other hand, when the average thickness is 200 μm or less, the dimensional accuracy of the shaped article is sufficiently obtained.
The average thickness can be measured according to a known method.

<Layer curing step and layer curing means>
The layer hardening step applies the liquid material for three-dimensional modeling in the three-dimensional modeling material set of the present invention to the three-dimensional modeling powder material layer by an ink jet method, and cures a predetermined region of the three-dimensional modeling powder material layer. It is a process.
The layer curing means applies the liquid material for three-dimensional modeling in the three-dimensional modeling material set of the present invention to the three-dimensional modeling powder material layer by an inkjet method, and cures a predetermined region of the three-dimensional modeling powder material layer. Means.

  The method for applying the 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 layer curing 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 powder scattering occurs due to 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 layer curing means has a nozzle capable of applying the liquid material to the powder material layer by the ink jet method. In addition, as a nozzle, the nozzle in a well-known inkjet printer can be used conveniently, and the said inkjet printer can be used conveniently as said layer hardening means. In addition, as said inkjet printer, SG7100 by Ricoh Co., Ltd. etc. are mentioned suitably, for example. The ink jet printer is preferable in that the amount of liquid material 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 liquid material with high accuracy and high efficiency is used, the liquid material is a solid material such as particles or a high viscosity material such as a resin. Since it does not contain, clogging or the like does not occur in the nozzle or its head, and it does not cause corrosion or the like, so that it is excellent in manufacturing efficiency of a molded article and is not provided with a polymer component such as resin Therefore, it is advantageous in that a hardened material with good dimensional accuracy can be obtained easily and efficiently in a short time without causing an unscheduled increase in volume.

<Sintering process and sintering means>
The sintering step is a step of sintering a three-dimensional structure formed by sequentially repeating the layer forming step and the layer curing step, and is performed by a sintering means. By performing the sintering step, the cured product can be formed into an integrated molded body (sintered body). Examples of the sintering means include a known sintering furnace.

As the sintering step, there is a method of sintering at the stage of laminating powder materials in addition to the method of sintering after obtaining a cured product as described above.
The method of sintering in the step of laminating the powder material is a method of sintering the powder material layer by performing either laser irradiation or electron beam irradiation on the powder material layer.

-Laser irradiation-
As the laser in the laser irradiation is not particularly limited and may be appropriately selected depending on the intended purpose, for example, CO ₂ lasers, Nd-YAG lasers, fiber lasers, and semiconductor laser.
The conditions for the laser irradiation are not particularly limited and can be appropriately selected according to the purpose. For example, when a small laser is used, the powder material cannot be melted. It is preferable that the polyester adhesive is mixed and the adhesive is melted by laser irradiation for shaping. In that case, it is preferable to use a CO ₂ laser. As irradiation conditions, for example, a laser output of 15 W, a wavelength of 10.6 μm, and a beam diameter of about 0.4 mm are preferable.

-Electron beam irradiation-
There is no restriction | limiting other than irradiating the electron beam of the energy which the said powder material fuse | melts as said electron beam, According to the objective, it can select suitably. When irradiating an electron beam, the powder material needs to be handled in a vacuum environment.
The conditions for the electron beam irradiation are not particularly limited and can be appropriately selected according to the purpose. For example, the output is 1,500 W, the beam diameter is 0.1 mm, and the degree of vacuum is about 1.0 × 10 ⁻⁵ mbar. Is preferred.

<Other processes and other means>
Examples of the other steps include a drying step, a surface protection treatment step, and a painting step.
Examples of the other means include drying means, surface protection processing means, and painting means.

-Drying process and drying means-
The drying step is a step of drying the cured product obtained in the layer curing step, and is performed by a drying means. 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.

-Surface protection treatment process and surface protection treatment means-
The surface protection treatment step is a step of forming a protective layer on the shaped article formed in the layer curing step or the sintering step. By performing the surface protection treatment step, it is possible to give the surface of the modeled object durability or the like that allows the modeled object 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.

-Painting process and painting means-
The painting step is a step of painting the shaped object. By performing this coating process, the shaped article 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, FIG. 1 shows an example of a powder additive manufacturing apparatus used in the present invention. 1 has a modeling-side powder storage tank 1 and a supply-side powder storage tank 2, and each of these powder storage tanks has a stage 3 that can move up and down. A layer made of a powder material is formed.
On the modeling side powder storage tank 1, there is an inkjet head 5 that discharges the liquid material 4 toward the powder material in the powder storage tank, and further from the supply side powder storage tank 2 to the modeling side powder storage tank 1. And a leveling mechanism 6 (hereinafter also referred to as a recoater) for leveling the powder material layer surface of the modeling-side powder storage tank 1.

The liquid material 4 is dropped from the inkjet head 5 onto the powder material in the modeling-side powder storage tank 1. At this time, the position where the liquid material 4 is dropped is determined by two-dimensional image data (slice data) obtained by slicing a three-dimensional shape to be finally modeled into a plurality of plane layers.
After the drawing for one layer is completed, the stage 3 of the supply-side powder storage tank 2 is raised, and the stage 3 of the modeling-side powder storage tank 1 is lowered. The powder material of the difference is moved to the modeling side powder storage tank 1 by the leveling mechanism 6.

Thus, a new powder material layer is formed on the previously drawn powder material layer surface. At this time, the average thickness per layer of the powder material layer is about several tens μm to 100 μm.
On the newly formed powder material layer, drawing based on the slice data of the second layer is further performed, and this series of processes is repeated to obtain a modeled object, and the modeled object is heated and dried by a heating means (not shown). can get.

FIG. 2 shows another example of the powder additive manufacturing apparatus used in the present invention. The powder additive manufacturing apparatus of FIG. 2 is the same as that of FIG. 1 in principle, but the supply mechanism of the powder material is different. That is, the supply side powder storage tank 2 is arranged above the modeling side powder storage tank 1. When the drawing of the first layer is completed, the stage 3 of the modeling-side powder storage tank 1 is lowered by a predetermined amount, and while the supply-side powder storage tank 2 is moving, a predetermined amount of powder material is dropped into the modeling-side powder storage tank 1, A new powder material layer is formed. Thereafter, the powder material layer is compressed by the leveling mechanism 6 to increase the bulk density and uniformly level the height of the powder material layer.
According to the powder additive manufacturing apparatus having the configuration shown in FIG. 2, the apparatus can be made compact compared to the configuration of FIG. 1 in which two powder storage tanks are arranged in a plane.

<3D objects>
The three-dimensional structure of the present invention is manufactured by the method for manufacturing a three-dimensional structure of the present invention.
The three-dimensional model is preferably an artificial tooth because it can withstand the masticatory force in the oral cavity for a long period of time and has aesthetics.
The artificial tooth is an artificial tooth made to recover its function in place of a natural tooth lost due to caries, trauma, periodontal disease, etc., and includes dental prostheses such as bridges and crowns It is.

  According to the manufacturing method and the manufacturing apparatus of the three-dimensional structure of the present invention, the complicated three-dimensional structure is easily and efficiently deformed before the sintering or the like using the three-dimensional structure material set of the present invention. It does not occur and can be manufactured with high dimensional accuracy. The molded product (cured product) thus obtained has little transfer to non-absorbable hydroxyapatite even when transplanted in vivo, has no cytotoxicity, has sufficient strength, has excellent dimensional accuracy, and is fine. Since irregularities and curved surfaces can be reproduced, it has excellent aesthetic appearance, high quality, and is suitably used for various applications.

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

(Preparation Example 1 of Granulated Particles)
<Preparation of powder material 1 for three-dimensional modeling>
-Synthesis of inorganic particles-
An 18% by mass yttrium chloride aqueous solution was mixed with a 20% by mass zirconium oxychloride aqueous solution so that the converted molar ratio of yttria / zirconia was 2.8 / 97.2. To this, 0.5% by mass of sodium chloride with respect to zirconium oxychloride was added and dissolved.
Next, aluminum chloride was added to the obtained aqueous solution so as to be 0.4% by mass as alumina with respect to zirconia and dissolved. This aqueous solution was spray-dried in air at a temperature of 200 ° C. to obtain a dry powder. The obtained dry powder was fired in air at a temperature of 1,000 ° C. to synthesize a calcined powder. The monoclinic phase rate of the obtained calcined powder was 15%. This calcined powder was pulverized with a wet attritor to obtain a 30% by mass slurry.
Next, the obtained slurry was repeatedly diluted and concentrated by filtration with a membrane filter having an opening of 0.5 μm, and washed repeatedly until the electric conductivity of filtered water became 20 μS or less. In this way, inorganic particles 1 were synthesized.

-Granulation of powder material 1 for three-dimensional modeling-
Together with polyacrylic acid (PAA, manufactured by Nippon Shokubai Co., Ltd., AS-58) having a weight average molecular weight Mw of 800,000, the washed zirconia slurry is granulated and spray-dried with a spray dryer having an inlet air temperature of 230 ° C., A powder material 1 for three-dimensional modeling containing 3% by mass of polyacrylic acid was obtained.

  About the obtained inorganic particle 1 and the powder material 1 for three-dimensional modeling, various characteristics were evaluated as follows. The results are shown in Tables 1 and 2.

<Primary particle size of inorganic particles>
The particle size of the primary particles of the inorganic particles was measured using LA-920 (manufactured by Horiba, Ltd.). During the measurement of LA-920, analysis was performed using an application dedicated to LA-920 (Ver. 3.32) (manufactured by Horiba, Ltd.). Specifically, the LA-920 was measured by adjusting the optical axis with chloroform and then measuring the background. Thereafter, circulation was started and a zirconia dispersion was dropped. After confirming that the transmittance was stable, ultrasonic waves were irradiated under the following conditions. The dispersion particle diameter was measured under the condition that the transmittance value was in the range of 70% to 95% after irradiation. It is important for this measuring apparatus to measure under the condition that the transmittance value of LA-920 is in the range of 70% to 95% from the viewpoint of the measurement reproducibility of the particle diameter. In addition, if the transmittance deviates from the above value after ultrasonic irradiation, it is necessary to perform measurement again. In order to obtain the transmittance value, it is necessary to adjust the dripping amount of the dispersion. Measurement and analysis conditions were set as follows.
[Measurement and analysis conditions]
・ Data acquisition frequency: 15 times ・ Relative refractive index: 1.20
・ Circulation: 5
・ Ultrasonic intensity: 7

<Identification of crystal phase of inorganic particles>
Identification of the crystalline phase of zirconia as the synthesized inorganic particles 1 was performed under the following conditions using an X-ray powder diffractometer (RINT1100, manufactured by Rigaku Electric Co., Ltd.).
[Measurement condition]
・ Tube: Cu
・ Voltage: 40kV
・ Current: 40 mA
・ Starting angle: 3 °
・ End angle: 80 °
・ Scanning speed: 0.5 ° / min
Note that the monoclinic phase ratio (%) of zirconia is the reflection peak intensity of the monoclinic phase 111 plane and 11-1 plane, the tetragonal phase 111 plane, and the cubic phase 111 plane by powder X-ray diffraction measurement. It calculated by following formula (1) from Im (111), Im (11-1), It (111), and Ic (111).
[Formula (1)]
Monoclinic phase ratio (%) = [Im (111) + Im (11-1)] / [Im (111) + Im (11-1) + It (111) + Ic (111)]

<Volume average particle diameter Dv of powder material for three-dimensional modeling>
Using Coulter Multisizer III (manufactured by Coulter Counter) as a measuring device, an interface for outputting the number distribution and volume distribution (manufactured by Nikkaki Co., Ltd.) and a personal computer are connected. 1 mass% NaCl aqueous solution was prepared using it.
As a measuring method, 0.1 mL to 5 mL of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 mL to 150 mL of the aqueous solution as the electrolytic solution, and 2 mg to 20 mg of a three-dimensional modeling powder material is added, and ultrasonic dispersion is performed. Dispersion treatment was performed for 1 minute to 3 minutes using a vessel. Further, 100 mL to 200 mL of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and 50,000 particles are used by the Coulter Multisizer III using a 100 μm aperture as an aperture. The average of was measured. The measurement was performed by dropping the dispersion of the three-dimensional modeling powder material so that the concentration indicated by the apparatus was 8% ± 2%.

<Average circularity of powder material for three-dimensional modeling>
The average circularity was measured using a flow type particle image analyzer (“FPIA-3000”, manufactured by Sysmex Corporation), and measured using analysis software (FPIA-3000 Data Processing Program For FPIA Version 00-10). . More specifically, 0.1% to 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL beaker made of glass. 0.1 g to 0.5 g of a powder material for modeling was added and stirred with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). With respect to this dispersion, the shape and distribution of the powder material for three-dimensional modeling were measured using the FPIA-3000 until the concentration reached 5,000 / μL to 15,000 / μL.

<Light bulk density of powder material for three-dimensional modeling>
Using a powder tester (manufactured by Tsutsui Rikagaku Co., Ltd.), a 100 cm ³ container was filled with the powder material for three-dimensional modeling, and was ground and measured for weight. This was repeated 3 times, the average value of the weight was calculated | required, and the lightly loaded bulk density of the powder material for three-dimensional modeling was calculated | required by remove | dividing by the volume of a container.

<BET specific surface area of powder material for three-dimensional modeling>
It measured using the automatic specific surface area / pore distribution measuring apparatus (TriStar3000, Shimadzu Corp. make). 3 g of powder material for three-dimensional modeling was put into a dedicated cell, and degassing treatment was performed in the dedicated cell using a TriStar degassing dedicated unit, Bacuprep 061 (manufactured by Shimadzu Corporation). The deaeration treatment was performed at room temperature (25 ° C.), and was performed for 20 hours under a reduced pressure condition of 100 mtorr or less. About the exclusive cell which performed the deaeration process, the BET specific surface area was measured automatically using the said TriStar3000. Note that nitrogen gas was used as the adsorption gas in the degassing treatment.

<Mass reduction rate of powder material for three-dimensional modeling>
Using the differential thermothermal gravimetric simultaneous measurement device (TG-DTA6200 EXSTAR6000, manufactured by SII Nano Technology Co., Ltd.), the temperature increase condition: 30-600 ° C., the temperature increase rate: 10 ° C./min. The mass reduction rate (mass%) before and after heating to 1,000 ° C. and heating at 1,000 ° C. for 1 hour was measured.

<Flowability of powder material for three-dimensional modeling>
The surface of the powder surface after making a self-made apparatus having a supply powder storage tank and a modeling powder storage tank that can move up and down, and scanning the roller rotating in the counter direction with the three-dimensional modeling powder material spread over the apparatus. The fluidity was evaluated by determining the degree based on the following criteria. The roller is made of SUS316 and moves on the powder material at a scanning speed of 100 mm / s and a rotational speed of 300 rpm.
[Evaluation criteria]
○: The surface is a clean flat surface △: The surface is rough and pear skin ×: The surface is rough and grooves are formed

(Preparation Example 2 of Granulated Particles)
<Preparation of powder material 2 for three-dimensional modeling>
A powder material 2 for three-dimensional modeling is prepared in the same manner as in Preparation Example 1 except that in the preparation example 1 of granulated particles, the polyacrylic acid having a weight average molecular weight Mw of 500,000 (made by Nippon Shokubai Co., Ltd.) is changed. Various characteristics were evaluated. The results are shown in Tables 1 and 2.

(Preparation Example 3 of Granulated Particles)
<Preparation of powder material 3 for three-dimensional modeling>
In the preparation example 1 of granulated particles, the powder material 3 for three-dimensional modeling is the same as the preparation example 1 except that the weight average molecular weight Mw is changed to polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd.). And various properties were evaluated. The results are shown in Tables 1 and 2.

(Preparation Example 4 of Granulated Particles)
<Preparation of powder material 4 for three-dimensional modeling>
In the preparation example 1 of granulated particles, except that the content of polyacrylic acid was changed to 5% by mass, a powder material 4 for three-dimensional modeling was prepared and various properties were evaluated in the same manner as in Preparation example 1. did. The results are shown in Tables 1 and 2.

(Preparation Example 5 of Granulated Particles)
<Preparation of powder material 5 for three-dimensional modeling>
In Preparation Example 1 of granulated particles, except that the aperture of the membrane filter when diluting and filtering the calcined powder pulverized slurry at the time of inorganic particle synthesis was changed to 1.5 μm, the same as in Preparation Example 1, The three-dimensional modeling powder material 5 was produced and various characteristics were evaluated. The results are shown in Tables 1 and 2.

(Preparation Example 6 of Granulated Particles)
<Preparation of powder material 6 for three-dimensional modeling>
The powder material 1 for three-dimensional model | molding produced in the preparation example 1 of granulated particle was classified, the strength of air blow was adjusted weakly, and the powder material 6 for three-dimensional model | molding was obtained by cutting the coarse powder side. About the obtained powder material 6 for three-dimensional modeling, it carried out similarly to the preparation example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.

(Preparation Example 7 of Granulated Particles)
<Preparation of powder material 7 for three-dimensional modeling>
The powder material 1 for three-dimensional modeling produced in Preparation Example 1 of granulated particles was classified, and the powder material 7 for three-dimensional modeling was obtained by strongly adjusting the strength of air blow and cutting the fine powder side. About the obtained three-dimensional modeling powder material 7, it carried out similarly to the preparation example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.

(Preparation Example 8 of Granulated Particles)
<Preparation of powder material 8 for three-dimensional modeling>
In Preparation Example 1 of granulated particles, except that polyacrylic acid (PAA) as a resin when granulating the three-dimensional modeling powder material 1 is replaced with polyvinyl alcohol (PVA, weight average molecular weight Mw = 800,000) In the same manner as in Preparation Example 1, a powder material 8 for three-dimensional modeling was produced and various characteristics were evaluated. The results are shown in Tables 1 and 2.

(Preparation Example 9 of Granulated Particles)
<Preparation of three-dimensional modeling powder material 9>
In Preparation Example 1 of granulated particles, except that the aperture of the membrane filter when diluting and filtering the calcined powder pulverized slurry at the time of inorganic particle synthesis was changed to 1.5 μm, the same as in Preparation Example 1, Three-dimensional modeling powder material 9 was prepared and various characteristics were evaluated. The results are shown in Tables 1 and 2.

(Preparation Example 10 of Granulated Particles)
<Preparation of powder material 10 for three-dimensional modeling>
The powder material 1 for three-dimensional model | molding produced in the preparation example 1 of granulated particle was classified, the intensity | strength of air blow was adjusted weakly, and the powder material 10 for three-dimensional model | molding was obtained by significantly cutting the coarse powder side. About the obtained powder material 10 for three-dimensional modeling, it carried out similarly to the preparation example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.

(Preparation Example 11 of Granulated Particles)
<Preparation of powder material 11 for three-dimensional modeling>
The powder material 1 for three-dimensional modeling produced in the preparation example 1 of granulated particles was classified, and the powder material 11 for three-dimensional modeling was obtained by significantly cutting the fine powder side. About the obtained three-dimensional modeling powder material 11, it carried out similarly to the preparation example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.

(Liquid material preparation example 1)
<Preparation of liquid material 1 for three-dimensional modeling>
94.5 parts by mass of water, 5 parts by mass (5% by mass) of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., P-1000, liquid at 25 ° C., easily soluble in water) having a weight average molecular weight Mw of 70,000, A liquid material 1 for three-dimensional modeling was prepared by dispersing 0.5 part by mass of Tween 20 (manufactured by Tokyo Chemical Industry Co., Ltd.) as a surfactant using a homomixer for 30 minutes.
About the obtained three-dimensional modeling liquid material 1, the viscosity and the surface tension were measured as follows. The results are shown in Table 4.

<Viscosity>
The viscosity of the three-dimensional modeling liquid material 1 was measured at 25 ° C. using a TVB-10M B-type rotational viscometer manufactured by Toki Sangyo Co., Ltd.

<Surface tension>
The surface tension (mN / m) of the three-dimensional modeling liquid material 1 was measured by a Wilhelmy method (Pt plate) at 20 ° C. using DY-300 manufactured by Kyowa Interface Science Co., Ltd.

(Liquid material preparation example 2)
<Preparation of liquid material 2 for three-dimensional modeling>
Preparation of the liquid material in Preparation Example 1 of the liquid material, except that the weight average molecular weight Mw was changed to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., SP-200, liquid at 25 ° C., readily soluble in water). In the same manner as in Example 1, a three-dimensional modeling liquid material 2 was prepared, and various properties were evaluated. The results are shown in Table 4.

(Liquid material preparation example 3)
<Preparation of 3D modeling liquid material 3>
A liquid material 3 for three-dimensional modeling was prepared in the same manner as in Preparation Example 1 of the liquid material, except that the content of polyethyleneimine was changed to 3 parts by mass (3% by mass) in Preparation Example 1 of the liquid material. The characteristics were evaluated. The results are shown in Table 4.

(Liquid material preparation example 4)
<Preparation of liquid material 4 for three-dimensional modeling>
In Preparation Example 1 of the liquid material, the polyethyleneimine content was changed to 20 parts by mass (20% by mass), and the weight average molecular weight Mw was 10,000 (manufactured by Nippon Shokubai Co., Ltd., SP-200, liquid at 25 ° C. The liquid material 4 for three-dimensional modeling was prepared and various properties were evaluated in the same manner as in Preparation Example 1 of the liquid material, except that it was changed to water-soluble. The results are shown in Table 4.

(Liquid material preparation example 5)
<Preparation of liquid material 5 for three-dimensional modeling>
In Preparation Example 1 of the liquid material, polyethyleneimine as the amino group-containing compound was replaced with titanium aminoethylamino ethanolate (manufactured by Matsumoto Fine Chemical Co., Ltd., Olgatics TC-510, liquid at 25 ° C., easily soluble in water). Except for the above, a liquid material 5 for three-dimensional modeling was prepared in the same manner as in Preparation Example 1 of the liquid material, and various characteristics were evaluated. The results are shown in Table 4.

(Liquid material preparation example 6)
<Preparation of three-dimensional modeling liquid material 6>
In Preparation Example 1 of the liquid material, except that polyethyleneimine as the amino group-containing compound was replaced with zirconium aminoethylamino ethanolate (manufactured by Matsumoto Fine Chemical Co., Ltd., liquid at 25 ° C., easily soluble in water) In the same manner as in Preparation Example 1, a three-dimensional modeling liquid material 6 was prepared, and various characteristics were evaluated. The results are shown in Table 4.

(Liquid material preparation example 7)
<Preparation of three-dimensional modeling liquid material 7>
In the liquid material preparation example 1, the three-dimensional modeling liquid material 7 is the same as the liquid material preparation example 1 except that Tween 20 as the surfactant is replaced with Triton X-100 (manufactured by Tokyo Chemical Industry Co., Ltd.). Were prepared and various properties were evaluated. The results are shown in Table 4.

(Liquid material preparation example 8)
<Preparation of three-dimensional modeling liquid material 8>
In Preparation Example 2 of the liquid material, except that the viscosity was changed to 4.0 mPa · s by lowering the polyethyleneimine content from 5 parts by mass to 2 parts by mass (2% by mass), Similarly, the liquid material 8 for three-dimensional modeling was prepared and various characteristics were evaluated. The results are shown in Table 4.

(Preparation Example 9 of Liquid Material)
<Preparation of three-dimensional modeling liquid material 9>
In Preparation Example 1 of the liquid material, except that the viscosity was changed to 20.0 mPa · s by increasing the addition amount of polyethyleneimine from 5 parts by mass to 8 parts by mass (8% by mass) Similarly, the three-dimensional modeling liquid material 9 was prepared, and various characteristics were evaluated. The results are shown in Table 4.

(Liquid material preparation example 10)
<Preparation of three-dimensional modeling liquid material 10>
In liquid material preparation example 1, three-dimensional modeling liquid material 10 was prepared and various properties were evaluated in the same manner as in liquid material preparation example 1, except that polyethyleneimine as an amino group-containing compound was not added. . The results are shown in Table 4.

Example 1
<Production of 3D modeling material set>
The obtained three-dimensional modeling powder material 1 and the three-dimensional modeling liquid material 1 were combined to produce a three-dimensional modeling material set of Example 1. Using the three-dimensional modeling material set, a three-dimensional model 1 was manufactured as follows using a shape printing pattern of size (length 70 mm × width 12 mm).

(1) First, using the known powder layered modeling apparatus as shown in FIG. 1, the three-dimensional modeling powder material 1 is transferred from the supply-side powder storage tank to the modeling-side powder storage tank, and then on the support. A thin layer made of the three-dimensional modeling powder material 1 having an average thickness of 100 μm was formed.

(2) Next, the liquid material for three-dimensional modeling 1 is applied (discharged) from the nozzle to the surface of the thin layer made of the powder material for three-dimensional modeling formed using an inkjet printer (manufactured by Ricoh Co., Ltd., SG7100). Then, the three-dimensional modeling powder material 1 was cured.

(3) Next, the operations of (1) and (2) are repeated until a total average thickness of 3 mm is obtained, and the cured thin layer of the three-dimensional modeling powder material 1 is sequentially laminated, A three-dimensional model 1 was manufactured. When the excess three-dimensional modeling powder material was removed by air blowing, the resulting three-dimensional model 1 did not lose its shape. The three-dimensional structure 1 was excellent in strength and dimensional accuracy.

  Next, about the obtained three-dimensional molded item 1, the dimensional accuracy was evaluated according to the following criteria. The results are shown in Table 4.

<Dimensional accuracy>
×: The surface of the obtained three-dimensional structure is distorted and warped severely. Δ: The surface of the obtained three-dimensional structure is slightly distorted and slightly warped. ○: Obtained. The surface of the three-dimensional model is smooth and beautiful, with no warpage

(4) About the three-dimensional molded item 1 obtained by said (3), the sintering process was performed in vacuum conditions and 1,300 degreeC within the sintering furnace. The sintered body of the three-dimensional structure 1 was a completely integrated structure, and no damage or the like occurred even when it was hit against a hard floor.

  Next, about the sintered compact of the obtained three-dimensional molded item 1, the compression strength after sintering and the curing rate were evaluated as follows. The results are shown in Table 5.

<Compressive strength after sintering>
The compressive strength was evaluated by a compressive strength test under the following sample shape and measurement conditions. The test machine used was AUTOGRAPH-AGS-J manufactured by Shimadzu Corporation.
-Sample shape-
・ Diameter: 5mm
・ Height: 6mm-7mm
-Mass: 0.16 g to 0.18 g
-Compression strength test conditions (JIS R1608)-
・ Crosshead speed: 0.5mm ・ s ^-1
・ Set load: 5kN

<Curing speed>
The curing rate of the three-dimensional structure 1 was evaluated according to the following criteria.
×: The three-dimensional model is fragile and cannot be removed even after one hour has passed since the three-dimensional modeling. Δ: The three-dimensional model can be finally removed by hand after ten minutes after the three-dimensional modeling. ○: Only 10 seconds have elapsed after the three-dimensional modeling. Even if the 3D object can be removed by hand

(Examples 2 to 15 and Comparative Examples 1 to 4)
<Production of 3D modeling material set>
In Example 1, as shown in Table 1, Table 3, and Table 5, except that the three-dimensional modeling powder material and the three-dimensional modeling liquid material were combined to produce a three-dimensional modeling material set, the same as in Example 1 Each solid modeling thing was produced and evaluated. The results are shown in Table 5.

* Polyacrylic acid (PAA) having a weight average molecular weight Mw of 800,000 (manufactured by Nippon Shokubai Co., Ltd., AS-58)
* Polyacrylic acid (PAA) having a weight average molecular weight Mw of 500,000 (manufactured by Nippon Shokubai Co., Ltd.)
* Polyacrylic acid (PAA) having a weight average molecular weight Mw of 1,000,000 (manufactured by Nippon Shokubai Co., Ltd.)

* "-" In Comparative Example 4 in Table 5 means that measurement is impossible.

As an aspect of this invention, it is as follows, for example.
<1> A powder material for three-dimensional modeling including granulated particles having a volume average particle diameter of 10 μm or more and 70 μm or less, comprising at least a resin and inorganic particles having a volume average particle diameter of primary particles of 1 μm or less;
It is a three-dimensional modeling material set characterized by having a three-dimensional modeling liquid material containing an amino group-containing compound.
<2> The three-dimensional modeling material set according to <1>, wherein the amino group-containing compound is liquid at 25 ° C.
<3> The three-dimensional modeling material set according to any one of <1> to <2>, wherein the amino group-containing compound is water-soluble.
<4> The three-dimensional modeling material set according to any one of <1> to <3>, wherein the amino group-containing compound is polyethyleneimine.
<5> The three-dimensional modeling material set according to <4>, wherein the polyethyleneimine has a weight average molecular weight Mw of 10,000 or more.
<6> The solid modeling material set according to any one of <4> to <5>, wherein the polyethyleneimine content is 3% by mass or more and 20% by mass or less.
<7> The three-dimensional modeling material set according to any one of <1> to <2>, wherein the amino group-containing compound is a compound containing a metal.
<8> The three-dimensional modeling material set according to <7>, wherein the metal species of the compound containing the metal is titanium or zirconium.
<9> The three-dimensional modeling material set according to any one of <1> to <8>, wherein the three-dimensional modeling liquid material further includes a surfactant.
<10> The three-dimensional modeling material set according to any one of <1> to <9>, wherein the resin is a water-soluble resin.
<11> The three-dimensional modeling material set according to any one of <1> to <10>, wherein the resin has an acidic functional group.
<12> The three-dimensional modeling material set according to any one of <1> to <11>, wherein the resin is any one of polyacrylic acid and polyvinyl alcohol.
<13> The three-dimensional modeling material set according to <12>, wherein the polyacrylic acid has a weight average molecular weight Mw of 500,000 or more and 1,000,000 or less.
<14> The three-dimensional modeling material set according to any one of <1> to <13>, wherein a mass reduction rate before and after the granulated particles are heated at 1,000 ° C. for 1 hour is 5% by mass or less.
<15> Layer formation for forming a three-dimensional modeling powder material layer having a predetermined thickness on the support using the three-dimensional modeling powder material in the three-dimensional modeling material set according to any one of <1> to <14> It is a manufacturing method of the three-dimensional molded item characterized by including a process at least.
<16> The three-dimensional modeling powder material layer is provided with the three-dimensional modeling liquid material in the three-dimensional modeling material set according to any one of <1> to <14> to the three-dimensional modeling powder material layer by an inkjet method. It is a manufacturing method of the three-dimensional molded item as described in said <15> including the layer hardening process which hardens the predetermined area | region.
<17> The method for producing a three-dimensional structure according to <16>, further including a sintering step of sintering the three-dimensional structure formed by sequentially repeating the layer formation step and the layer curing step.
<18> The three-dimensional object according to <15>, including a sintering step in which the three-dimensional modeling powder material layer is subjected to either laser irradiation or electron beam irradiation to sinter the three-dimensional modeling powder material layer. It is a manufacturing method.
<19> A three-dimensional object manufactured by the method for manufacturing a three-dimensional object according to any one of <15> to <18>.
<20> The three-dimensional structure according to <19>, which is used for artificial teeth.

DESCRIPTION OF SYMBOLS 1 Modeling side powder storage tank 2 Supply side powder storage tank 3 Stage 4 Liquid material for three-dimensional modeling 5 Inkjet head 6 Leveling mechanism

Special table 2003-531034 gazette JP 2011-21218 A

Claims (20)

At least a powder material for three-dimensional modeling including granulated particles having a volume average particle size of 10 μm or more and 70 μm or less composed of a resin and inorganic particles having a volume average particle size of primary particles of 1 μm or less;
A three-dimensional modeling material set comprising: a three-dimensional modeling liquid material containing an amino group-containing compound.   The three-dimensional modeling material set according to claim 1, wherein the amino group-containing compound is liquid at 25 ° C.   The three-dimensional modeling material set according to claim 1, wherein the amino group-containing compound is water-soluble.   The three-dimensional modeling material set according to any one of claims 1 to 3, wherein the amino group-containing compound is polyethyleneimine.   The three-dimensional modeling material set according to claim 4 whose weight average molecular weight Mw of said polyethyleneimine is 10,000 or more.   The three-dimensional modeling material set according to any one of claims 4 to 5, wherein a content of the polyethyleneimine is 3 mass% or more and 20 mass% or less.   The three-dimensional modeling material set according to claim 1, wherein the amino group-containing compound is a compound containing a metal.   The solid modeling material set according to claim 7, wherein a metal species of the compound containing the metal is any one of titanium and zirconium.   The three-dimensional modeling material set according to any one of claims 1 to 8, wherein the three-dimensional modeling liquid material further includes a surfactant.   The three-dimensional modeling material set according to any one of claims 1 to 9, wherein the resin is a water-soluble resin.   The three-dimensional modeling material set according to any one of claims 1 to 10, wherein the resin has an acidic functional group.   The three-dimensional modeling material set according to any one of claims 1 to 11, wherein the resin is either polyacrylic acid or polyvinyl alcohol.   The three-dimensional modeling material set according to claim 12, wherein the polyacrylic acid has a weight average molecular weight Mw of 500,000 or more and 1,000,000 or less.   The three-dimensional modeling material set according to any one of claims 1 to 13, wherein a mass reduction rate before and after the granulated particles are heated at 1,000 ° C for 1 hour is 5 mass% or less.   It includes at least a layer forming step of forming a three-dimensional modeling powder material layer having a predetermined thickness on the support using the three-dimensional modeling powder material in the three-dimensional modeling material set according to any one of claims 1 to 14. The manufacturing method of the three-dimensional molded item to be characterized.   The liquid material for three-dimensional modeling in the three-dimensional modeling material set according to any one of claims 1 to 14 is applied to the three-dimensional modeling powder material layer by an inkjet method, and a predetermined region of the three-dimensional modeling powder material layer is cured. The manufacturing method of the three-dimensional molded item of Claim 15 including a layer hardening process.   The manufacturing method of the three-dimensional molded item of Claim 16 which further includes the sintering process which sinters the three-dimensional molded item formed by repeating the said layer formation process and the said layer hardening process sequentially.   The manufacturing method of the three-dimensional molded item of Claim 15 including the sintering process which performs any one of laser irradiation and electron beam irradiation to the said three-dimensional modeling powder material layer, and sinters the said three-dimensional modeling powder material layer.   A three-dimensional structure manufactured by the method for manufacturing a three-dimensional structure according to any one of claims 15 to 18.   The three-dimensional molded item according to claim 19, which is used for artificial teeth.