JP2016179638A - Composition liquid for three-dimensional molding, three-dimensional molding set, apparatus for manufacturing three-dimensional molded object, and method for manufacturing three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition liquid for three-dimensional molding, from which a three-dimensional molded object having a complicated three-dimensional shape with high strength and high dimensional accuracy can be efficiently and inexpensively manufactured by using a powder material.SOLUTION: The composition liquid for three-dimensional molding is to be used for molding a three-dimensional object made of a powder material for three-dimensional molding by supplying the liquid to a powder material layer formed of the powder material for three-dimensional molding. The liquid comprises water and urethane resin particles. The composition liquid for three-dimensional molding may contain a crosslinking agent.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a three-dimensional modeling composition solution, a three-dimensional modeling set, a three-dimensional modeling manufacturing apparatus using them, and a three-dimensional modeling manufacturing method.

  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. It was. On the other hand, layered modeling (also referred to as additive modeling) that directly manufactures a three-dimensional modeled object while laminating various materials using shape data has attracted attention as an effective method that can solve these problems.

  Among these, the binder jet method using an inkjet head has been attracting attention because of its high modeling speed and wide applicability of materials. For example, in Patent Document 1 (Japanese Patent No. 2729110), a binder material is applied to a selected region of a powder layer spread in a flat shape, and this is repeatedly laminated to remove unbonded powder material. Thus, a method for obtaining a three-dimensional molded product is disclosed. In Patent Document 2 (Japanese Patent Laid-Open No. 08-192468), two kinds of large and small metal particles having a predetermined diameter and mixing ratio are dispersed, a binder is injected from a nozzle, and after molding, the melting temperature of the small particle metal As mentioned above, the manufacturing method of the three-dimensional model heated below the melting temperature of a large particle metal is disclosed.

  Furthermore, in Patent Document 3 (Japanese Patent Laid-Open No. 2014-24252), in a three-dimensional modeling apparatus that discharges a modeling liquid from an inkjet head to a powder containing hemihydrate gypsum, the most surface side of the three-dimensional modeled object is configured. A method is disclosed in which the average concentration of the emulsion additive of the modeling liquid to be discharged to the surface portion is higher than the average concentration of the emulsion additive to be discharged to the portion constituting the inner side of the outermost surface portion. Yes.

  It is an object of the present invention to provide a three-dimensional composition liquid that is capable of producing a three-dimensional structure having a complicated three-dimensional shape while achieving both high strength and dimensional accuracy.

Means for solving the problems are as follows.
That is, the present invention is a three-dimensional modeling composition liquid used for modeling a three-dimensional object made of a three-dimensional modeling powder material, which is characterized by containing water and urethane resin particles. .

  ADVANTAGE OF THE INVENTION According to this invention, the strength and dimensional accuracy of the three-dimensional molded item which has a complicated shape can be improved, and the composition liquid for three-dimensional modeling which can manufacture these with high efficiency and low cost can be provided.

It is the schematic which shows an example of the three-dimensional molded item manufacturing process of this invention. It is the schematic which shows another example of the three-dimensional molded item manufacturing process of this invention. It is the schematic which shows an example of the powder storage tank which accommodates the powder material for three-dimensional modeling in the three-dimensional molded item manufacturing apparatus of this invention.

The composition liquid for three-dimensional modeling of the present invention contains water and urethane resin particles.
For example, when the composition liquid for three-dimensional modeling of the present invention is provided to a desired region of a layer of powder material for three-dimensional modeling formed in advance, water and urethane resin particles contained in the three-dimensional modeling composition liquid are the powder. It penetrates into the gaps between the materials, and countless urethane resin particles adhere to the surface of the powder material. When the powder material layer forming step and the three-dimensional modeling composition liquid donating step are repeated, and then the liquid component mainly composed of water contained in the three-dimensional modeling composition liquid is evaporated, the powder material surface is covered. The urethane resin particles become a film. Adjacent powder materials adhere to each other in the process of forming these films. Furthermore, when it becomes more than minimum film forming temperature, the film | membrane which consists of urethane resin particles will fuse | melt firmly, and a three-dimensional molded item will be formed. On the other hand, the region where the composition liquid has not been supplied is removed without being taken in as a three-dimensional structure because the powder materials are not bonded to each other.

  The three-dimensional modeling composition liquid of the present invention contains water and urethane resin particles, and the urethane resin particles are not dissolved in water but dispersed or emulsified. Therefore, it becomes possible to keep a viscosity low compared with the case where binder resin is dissolved. As a result, particularly when an ink jet method is used, it is possible to improve ejection stability and to suppress nozzle clogging, and to increase the strength and dimensional accuracy of a three-dimensional structure.

  In addition, when the binder resin is dissolved, if the molecular weight or the addition amount of the binder resin is increased in order to improve the strength, the viscosity is remarkably increased and the restriction is large. However, since the urethane resin particles in the present invention are dispersed or emulsified in water, increasing the molecular weight or the added amount has little effect on the viscosity, and the strength of the three-dimensional structure is higher than when the binder resin is dissolved. It is very effective in increasing

  Furthermore, the three-dimensional modeling composition liquid containing water and urethane resin particles of the present invention can be applied to various three-dimensional modeling powder materials, and has high strength and dimensional accuracy without adding a binder resin. Since it is realizable, a three-dimensional molded item can be manufactured simply, highly efficiently, and at low cost. In addition, it is also possible to separately include a binder resin in the three-dimensional modeling composition liquid or the three-dimensional modeling powder material, thereby maintaining high dimensional accuracy and further increasing the strength of the three-dimensional modeling object. Is possible, effective and useful.

Hereinafter, an example of an embodiment in the present invention will be described. However, the present invention is not limited to these.
The composition for three-dimensional modeling of the present invention can produce a three-dimensional model by combining with the three-dimensional modeling powder material. For example, a three-dimensional model can be manufactured by forming a layer of the three-dimensional model powder material, supplying the three-dimensional model composition liquid thereon, repeating these operations, and drying. Furthermore, a three-dimensional sintered product can be manufactured by performing a degreasing process and a sintering process as necessary.

<Composition liquid for three-dimensional modeling>
The composition liquid for three-dimensional modeling of the present invention contains water and urethane resin particles, and further contains other components as necessary.

-Urethane resin particles-
The three-dimensional modeling composition liquid of the present invention contains urethane resin particles. The urethane resin particles in the present invention refer to those in which a resin having one or more urethane bonds and / or urea bonds is contained in the composition liquid. For example, a urethane resin can be obtained by, for example, a polyaddition reaction between an isocyanate group and a polyol, an amine, or the like, as in the known urethane resin, and can be obtained by dispersing or emulsifying this in water.

  When the composition liquid for three-dimensional modeling containing the urethane resin particles and water is supplied to the powder material layer for three-dimensional modeling, the urethane resin particles soak into the surface of the powder material together with water downward from the interface of the powder material. Adhere to. The process of forming the powder material layer and the process of supplying the composition liquid are repeated, and when the liquid component mainly composed of water contained in the composition liquid is evaporated in the process, the urethane resin particles are concentrated and densely packed. Then, a film made of an aggregate of urethane resin particles that are thin and closely adhered to the surface of the powder material is formed. At this time, it adheres to the adjacent powder material on which a film of urethane resin particles is similarly formed. When the drying further proceeds and the temperature reaches a minimum film-forming temperature (MFT) or more, the urethane resin particles are fused with each other while adhering to the adjacent powder material, and further, the polymer chains mutually diffuse. Thereby, it becomes possible to obtain a three-dimensional molded article having high strength. On the other hand, the region where the composition liquid has not been supplied is removed without being taken in as a three-dimensional structure because the powder materials are not bonded to each other.

  Since the composition liquid of the present invention contains at least water and urethane resin particles, the urethane resin particles are contained in a state dispersed in water if they are solid, and contained in a state emulsified in water if they are liquid. Is done. In the present invention, it can be used in either state, but since it is less affected by nozzle clogging and is easy to form a film on the surface of the powder material, it is effective in increasing the strength of a three-dimensional molded object. More preferably, the particles are contained in an emulsified state in the composition liquid.

  Those obtained by pre-emulsifying the urethane resin particles in water are also called urethane resin emulsions or colloids, and can be used particularly effectively in the present invention. In this case, since the urethane resin is contained in water in the form of particles, it is an oil-in-water (O / W) type emulsion. As a method of emulsifying urethane resin particles in water, a method of emulsifying a urethane resin having a hydrophilic group or a hydrophilic segment introduced into water (self-emulsifying type), or emulsifying a hydrophobic urethane resin in water with a surfactant. It is roughly divided into the method (forced emulsification type). The self-emulsification type is a conventionally known method such as an acetone method in which a high molecular weight is obtained in a solvent and the solvent is removed after dispersion in water, or a prepolymer mixing method in which a prepolymer is dispersed in water and then polymerized with diamine or the like. Can be produced. In the forced emulsification type, for example, a solution-polymerized polyurethane is emulsified and dispersed in the presence of a surfactant, and then a solvent-removed forced emulsification method in which the solvent is removed or a terminal isocyanate prepolymer is emulsified and dispersed, and then chain-extended with diamine. It can be prepared by a conventionally known method such as a prepolymer forced emulsification method.

  In the present invention, it is preferable to use urethane resin particles having a hydrophilic group introduced (self-emulsifying type). The reason is that the hydrophilic group is introduced on the surface of the urethane resin particles, so that the wettability is improved with respect to the powder material for three-dimensional modeling having a hydrophilic surface, and the urethane resin particles are evenly distributed on the surface of the powder material. This is because, as a result, not only the strength of the three-dimensional model can be improved, but also the strength uniformity can be improved. Moreover, adhesiveness improves with respect to the powder material for three-dimensional model | molding whose surface has hydrophilicity, and collapse of the three-dimensional model | molding object by peeling of a film | membrane can be suppressed. The three-dimensional modeling powder material has many hydrophilic surfaces such as metals and ceramics, and these can be used effectively. In addition, even if the surface is a hydrophobic powder material, the above-described effects can be obtained by performing a hydrophilic treatment.

  On the other hand, when a forced emulsification type emulsion was used, even if the wettability to the powder material could be improved by the surfactant, the surfactant was formed by bleeding out on the surface during or after drying. The adhesiveness of the film by the urethane resin may be reduced, and the strength of the three-dimensional model may be reduced. Moreover, only a thing with a low molecular weight may be obtained, or a dispersion | distribution particle size may become large, and the strength improvement effect of a three-dimensional molded item may fall a little. From the above, in the present invention, it is more preferable to use a self-emulsifying urethane resin emulsion. In addition, the urethane resin emulsion includes a self-emulsifying type and a forced emulsifying type, but if the urethane resin emulsion includes a self-emulsifying type in which a hydrophilic group is introduced into the urethane resin, it can be used more preferably.

  The hydrophilic group introduced into the self-emulsifying type urethane resin is classified into three groups, anionic, cationic and nonionic, depending on its ionicity. Representative examples of anionic hydrophilic groups include carboxyl groups and sulfo groups, representative examples of cationic hydrophilic groups include amino groups and ammonium groups, and representative examples of nonionic hydrophilic groups include ethylene oxide and A polyol etc. are mentioned. In the present invention, although not particularly limited, an anionic hydrophilic group is more preferable among these hydrophilic groups. By using self-emulsifying urethane resin particles having an anionic hydrophilic group, the effect of increasing the strength of the resulting three-dimensional structure is high.

  The urethane resin particles used in the present invention can introduce a reactive group in addition to a hydrophilic group, and are extremely effective because the strength of the three-dimensional structure can be further increased by a crosslinking effect. is there. The urethane resin particles having a reactive group also include a self-emulsifying type and a forced emulsifying type. In the present invention, the self-emulsifying type is more preferable as described above. The urethane resin particles into which the reactive group is introduced are effective for further improving the strength of the three-dimensional structure by crosslinking with the reactive group to form a three-dimensional network structure.

  Any reactive group may be used as long as it causes a crosslinking reaction, and those having an isocyanate group are particularly preferable. Isocyanate groups are highly reactive and are particularly effective in improving the strength of three-dimensional structures. In this case, a blocked isocyanate in which an isocyanate group is protected with a blocking agent is particularly preferably used. When the blocked isocyanate is subjected to a heat treatment later, the blocking agent is dissociated and the isocyanate group is regenerated. Therefore, a remarkable effect of increasing the strength can be obtained by performing a heat treatment after modeling. Moreover, even if it is in the state of being included in the composition liquid for three-dimensional modeling, the reactive group is protected with a blocking agent unless heat is applied, so that the viscosity can be prevented from increasing or solidifying. Is very effective.

The molecular weight of the urethane resin particles is from 10 ^{3 to} 10 ⁷ , more preferably from 10 ^{4 to} 10 ^{6 in} terms of weight average molecular weight. When the molecular weight is 10 ³ or more, the effect of increasing the strength of the three-dimensional structure is sufficiently exhibited, and when the molecular weight is 10 ⁷ or less, the increase in the viscosity of the three-dimensional composition liquid and the decrease in the life of the liquid are prevented. Can do. In addition, the weight average molecular weight of a urethane resin can be measured using gel permeation chromatography (GPC), for example.

  As described above, when the binder resin is dissolved in the three-dimensional modeling composition liquid, when the molecular weight of the resin increases, the liquid viscosity increases, the viscosity increases with time, or insoluble matter is mixed, and the inkjet method is used. When used, the discharge stability of the composition liquid is lowered, and nozzle clogging is likely to occur. This causes a decrease in strength and uniformity of the three-dimensional modeled object, and a decrease in dimensional accuracy. However, when urethane resin particles are used as in the present invention, since it is not necessary to dissolve the resin in water, the molecular weight of the urethane resin can be increased without greatly affecting the liquid viscosity. Strength and dimensional accuracy can be further increased.

  Furthermore, the urethane resin contained in the urethane resin emulsion can be crosslinked in a network form to form a high molecular weight internal crosslinked structure. For example, an internal cross-linked structure can be formed by synthesizing a prepolymer having an isocyanate group at the end and emulsifying it according to a conventionally known method, and then chain-extending the internal isocyanate group. As described above, the internal cross-linked structure and the high molecular weight body as described above can be used for the urethane resin particles, and the addition amount can be relatively increased, so it is very effective in increasing the strength of the three-dimensional structure. And useful.

  The average particle diameter of the urethane resin particles used in the present invention is preferably from 0.001 μm to 1.0 μm, more preferably from 0.005 μm to 0.6 μm, and still more preferably from 0.01 μm to 0.3 μm. In general, these dispersed particle sizes are often classified as emulsions of 0.1 μm or more, colloids of less than 0.1 μm, and aqueous solutions of less than 1 nm. The urethane resin particles of the present invention are regions containing colloids and emulsions. It is. When the average particle diameter of the urethane resin particles is 0.001 μm or more, the adhesive force between the powder materials for three-dimensional modeling is improved, and the strength of the three-dimensional model can be increased. On the other hand, when the average particle size of the urethane resin particles is 1.0 μm or less, nozzle clogging can be prevented, permeability and film forming ability are improved, strength variation of the three-dimensional structure is reduced, and dimensional accuracy is increased. Is possible.

  The glass transition temperature of the urethane resin particles used in the present invention is preferably 20 ° C. or higher, and more preferably 40 ° C. or higher. When the glass transition temperature is 20 ° C. or higher, the hardness of the urethane resin tends to increase, which is effective in increasing the strength of the three-dimensional structure. The glass transition temperature can be measured with a dynamic viscoelasticity measuring device, a differential scanning calorimeter (DSC) or the like.

  The urethane resin particles preferably have a higher film-forming ability since the effects of the present invention can be obtained by forming a film on the surface of the powder material as described above. The basic structure of urethane resin consists of a soft segment composed mainly of non-crystalline part of polyol with weak cohesion and a hard segment composed mainly of crystalline part of urethane bond or urea bond with strong cohesion. . The soft segment has a weak intermolecular force and gives flexibility, flexibility, flexibility, and the like, and the hard segment has a strong intermolecular force and gives toughness, heat resistance, wear resistance and the like. It is the characteristic of urethane resin that it has these conflicting properties in a well-balanced manner, and it has excellent film-forming ability, and the film obtained is tough, so that it is possible to produce a three-dimensional structure with high strength. It is considered a thing. In addition, the hard segment also has an effect of secondary bonding based on hydrogen bonding, which is considered to contribute to an increase in strength of the three-dimensional structure.

  The urethane resin particles used in the present invention may be resin fine particles having a urethane bond and / or a urea bond, and have any other functional group, substituent, or segment for forming a copolymer. May be. For example, a polyether type urethane resin containing an ether bond, a polyester type urethane resin containing an ester bond, a polycarbonate type urethane resin containing a carbonate bond, and the like can be used.

  In addition, the urethane resin particles used in the present invention may be a composite emulsion of a urethane resin and other resins. For example, a urethane acrylic composite emulsion can be used effectively. This is a product that contains acrylic and urethane in the particles. For example, urethane can be modified into an acrylic polymer, or reactive acrylic and urethane can be included in the emulsion and crosslinked by evaporation of water. Those having a core-shell structure in which the component is a core and the urethane component is a shell are known and can be used effectively in the present invention. Such compounding is effective in improving durability, weather resistance, adhesion to the powder material, and the like, and is effective in further increasing the strength and durability of the three-dimensional structure.

The urethane resin particles can be synthesized, but some are commercially available as aqueous urethane resin emulsions, and can be used effectively in the present invention.
Examples of the urethane resin emulsion include Superflex series, Superflex E series, Superflex R series, Elastron series, Elastron BN series (Daiichi Kogyo Seiyaku brand name), Takelac W series, Takelac WS series (Mitsui Chemicals). Product name), Adeka Bon titer HUX series (Adeka product name), Permarin series, U-Coat series, Euprene series (Sanyo Chemical Industries product name), and the like. Specific examples include Superflex 110, 126, 130, 150, 170, 210, 620, 800, 820, 830HS, 860, 870, Elastron BN-11, BN-69, BN-77, etc. (manufactured by Daiichi Kogyo Seiyaku) Product name), Takerak W-615, W-6010, W-6020, W-6061, W-511, W-405, W-7004, W-605, W-512A6, W-635, W-635C, WS -7000, WS-5000, WS-5070X, WS-4000, XW-75-X35, etc. (trade name, manufactured by Mitsui Chemicals), Adekabon titer HUX-290H, HUX-395D, HUX-394, HUX-232, HUX- 240, HUX-320, HUX-350, HUX-380, HUX-381, HUX-388, HUX-38 A, HUX-386, HUX-401, HUX-750, HUX-670, HUX-680, HUX-575, HUX-580, HUX-822, HUX-830, etc. (trade names made by Adeka), Permarin UA-310, Examples include UA-368, U-coat US-230, Uprene UXA-307 (trade name, manufactured by Sanyo Chemical Industries). However, these are only examples and are not limited. These urethane resin emulsions may be used alone or in combination of two or more. Further, the urethane resin emulsion can be used by mixing with other resin emulsion.

  Although content of the said urethane resin particle can be suitably determined as needed without being restrict | limited especially, 1-50 mass% is preferable with respect to the total mass of the three-dimensional modeling composition liquid, and 5-30 mass%. Is more preferable. When the content of the urethane resin particles is 1% by mass or more, an effect of increasing the strength of the three-dimensional model can be obtained, and when the content is 50% by mass or less, the viscosity of the three-dimensional model composition liquid increases over time. As a result, the discharge stability can be improved and the dimensional accuracy can be improved.

-Water-
The composition liquid for three-dimensional modeling of the present invention contains water. The urethane resin particles of the present invention are an oil-in-water (O / W) type, and the urethane resin particles are stably dispersed or emulsified by containing water.
The water is not particularly limited, and pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water can be used. The water content is not particularly limited and may be appropriately determined as necessary, but is preferably 20 to 95% by mass and more preferably 40 to 90% by mass with respect to the total mass of the three-dimensional composition liquid. Preferably, 50 to 85% by mass is more preferable.

-Water-soluble solvent-
The composition solution for three-dimensional modeling of the present invention can contain a water-soluble solvent and is effective. The water-soluble solvent is effective in increasing the moisture retention and ejection stability, particularly when the 3D modeling composition liquid is ejected from the inkjet nozzle. When these are lowered, the head is dried, the ejection becomes unstable, or nozzle clogging occurs, and as a result, a fragile portion is formed in the three-dimensional structure, or the dimensional accuracy is lowered.

  Any water-soluble solvent can be used as long as it is a water-soluble liquid material. For example, alcohol, polyhydric alcohol, ether, ketone and the like can be mentioned. Specifically, ethanol, propanol, butanol, 1,2,6-hexanetriol, 1,2-butanediol, 1,2-hexanediol, 1,2-pentanediol, 1,3-dimethyl-2-imidazo Lidinone, 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-pi Lidon, 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 , Diethylene 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 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 may be employed. However, this is an example, and the present invention is not limited to these.

  The proportion of the water-soluble solvent in the total three-dimensional modeling composition liquid of the present invention is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and further preferably 15% by mass to 40% by mass. . When the water-soluble solvent is 5% by mass or more, the moisture retention of the three-dimensional modeling composition liquid can be maintained, and drying during storage of the inkjet head is prevented, resulting in suppression of ejection failure and nozzle clogging. It becomes possible to do. Moreover, the amount of discharge at the time of the check performed in advance and the amount of discharge at the time of actual discharge can be matched, and the three-dimensional molded item having desired strength and shape can be manufactured. On the other hand, when the water-soluble solvent is 60% by mass or less, the increase in viscosity of the three-dimensional modeling composition liquid can be reduced, the discharge stability can be improved, and the drying property of the three-dimensional model can be improved. It becomes possible to suppress a deformation | transformation of a three-dimensional molded item.

-Crosslinking agent-
The composition liquid for three-dimensional modeling of the present invention can contain a crosslinking agent and is effective. The cross-linking agent can cross-link the film made of the urethane resin particles formed on the surface of the three-dimensional modeling powder material, and is effective in increasing the strength of the three-dimensional model. As will be described later, when the resin is previously coated on the surface of the powder material for three-dimensional modeling, it is possible to crosslink with the coated resin, which is effective in further increasing the strength of the three-dimensional modeled object.

  The cross-linking agent is not particularly limited as long as the urethane resin particles or the powder material for three-dimensional modeling are coated with a resin, and can be appropriately selected depending on the purpose. Examples of the crosslinking agent for the urethane resin particles include an isocyanate crosslinking agent, a blocked isocyanate crosslinking agent, a water-soluble melamine resin, a water-soluble epoxy resin, an oxazoline compound, a carbodiimide compound, and an aziridine compound. Among these, from the viewpoint of the strength of the three-dimensional model and the liquid life of the three-dimensional model composition, a blocked isocyanate crosslinking agent is preferably used. Blocked isocyanate has a structure in which an isocyanate group is protected with a blocking agent and does not react at room temperature. Therefore, it is possible to suppress thickening and solidification of the composition liquid, which is very effective. Examples of the blocking agent include phenolic, alcoholic, active methylene, lactam, oxime, mercaptan and the like.

  Besides, for example, metal salts, metal complexes, polyvalent metal compounds such as organic zirconium compounds and organic titanium compounds, water-soluble organic crosslinking agents, and crosslinking agents such as chelating agents can also be used effectively. These can be used also as a crosslinking agent for the resin when the powder material for three-dimensional modeling is coated with a resin.

As the metal salt, one that ionizes a divalent or higher cation metal in water is preferably used. Specific examples include zirconium oxychloride octahydrate (tetravalent), aluminum hydroxide (trivalent), water Magnesium oxide (divalent), titanium lactate ammonium salt (tetravalent), basic aluminum acetate (trivalent), zirconium carbonate ammonium salt (tetravalent), titanium triethanolamate (tetravalent), etc. are preferably used. It is done.
As the organozirconium-based compound and organotitanium-based compound, mainly alkoxide, chelate, acylate and the like are preferably used. Examples of the former include zirconium oxychloride, ammonium zirconium carbonate, zirconium oxychloride, zirconium oxynitrate, zirconium lactate. Examples of the organic titanium-based compounds such as ammonium, zirconium stearate, zirconium lactate ammonium salt, and the like include titanium acylate, titanium alkoxide, titanium lactate, titanium lactate ammonium salt, and titanium triethanolamate. Examples of the water-soluble organic crosslinking agent include carbodiimide group-containing compounds and bisvinyl sulfonic acid compounds, and examples of the melamine compound include methylolated melamine. In addition, these may be used individually by 1 type and may use 2 or more types together.

  Commercially available products can be used. Examples of the commercially available products include Elastrone BN series (Daiichi Kogyo Seiyaku Co., Ltd.), zirconium oxychloride octahydrate (Daiichi Rare Element Chemical Co., Ltd., acidification). Zirconium), aluminum hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), titanium lactate ammonium salt (manufactured by Matsumoto Fine Chemical Co., Ltd., Organics TC-300, TC-310), Zirconium lactate ammonium salt (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATIZ 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 oxide ammonium carbonate ( One rare element chemical industry, Zircosol AC-7, AC-20), Titanium triethanolamate (Matsumoto Fine Chemical Co., Ltd., Organics TC-400), Zirconium oxychloride (First rare element chemical industry) Zircosol ZC-20), zirconium oxynitrate (Daiichi Rare Element Chemical Co., Ltd., Zircosol ZN), glyoxylate (Safelink SPM-01, Nippon Synthetic Chemical Industry Co., Ltd.), adipic acid dihydrazide (Otsuka Chemical) Etc.).

There is no restriction | limiting in particular as content of the said crosslinking agent in the said three-dimensional modeling composition liquid, According to the objective, it can select suitably. For example, it is 0.1 mass%-50 mass% with respect to the said urethane resin particle, More preferably, it is 0.5 mass%-30 mass%, More preferably, it is 1 mass%-10 mass%. Moreover, when resin is coat | covered to the powder material for three-dimensional modeling, said range is preferable also with respect to the said resin. When the content of the crosslinking agent is 0.1% by mass or more, an effect of increasing the strength of the three-dimensional structure can be obtained. On the other hand, when the content of the crosslinking agent is 50% by mass or less, thickening and gelation of the three-dimensional composition liquid can be prevented, and the effect of improving liquid storage stability and viscosity stability can be obtained.
-Other ingredients-
As other components contained in the three-dimensional modeling composition liquid, for example, a conventionally known material such as a surfactant, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, a preservative, and a stabilizer may be added. Is possible.

--Surfactant--
The surfactant is mainly used for the purpose of controlling wettability, permeability, and surface tension of the three-dimensional modeling composition liquid into the three-dimensional modeling powder material. As the surfactant used in the present invention, conventionally known materials can be used, and the following are particularly preferably used.
As the surfactant, an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant is used.

--PH adjuster--
The pH adjuster is used mainly for the purpose of adjusting the composition liquid for three-dimensional modeling to a desired pH. Any material can be used as the pH adjuster as long as it can control the pH of the three-dimensional composition liquid.
In this invention, when using an inkjet system for the composition liquid supply means for three-dimensional structure manufacturing apparatus, the 5 (weakly acidic) to 12 (basic) are used from the viewpoint of preventing corrosion and clogging of the nozzle head portion. 8-10 (weakly basic) is more preferable. By adding the pH adjusting agent, the pH of the three-dimensional modeling composition liquid can be arbitrarily adjusted. Some of the crosslinking agents can also function as pH adjusting agents.

-Preparation method of three-dimensional modeling composition liquid-
The method for preparing the three-dimensional modeling composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. First, an emulsion in which the urethane resin particles are dispersed or emulsified in a liquid mainly composed of water. It is preferable to prepare and add additives such as water, a water-soluble solvent, and a surfactant as necessary. Moreover, when it contains a crosslinking agent, it is preferable to make it melt | dissolve in water previously.

<3D modeling set>
The three-dimensional modeling set of the present invention includes the three-dimensional modeling composition liquid and the three-dimensional modeling powder material. The three-dimensional modeling composition liquid is provided to the layer of the three-dimensional modeling powder material, and the urethane resin particles contained in the three-dimensional modeling composition liquid adhere to the surface of the three-dimensional modeling powder material, and then the three-dimensional modeling powder. Liquids such as water and water-soluble solvents contained in the composition liquid for modeling evaporate, so that the urethane resin particles are finely packed and a film is formed. Adhere to each other. Furthermore, when it becomes more than minimum film forming temperature, a urethane resin particle will fuse | melt and the three-dimensional molded item which has high intensity | strength can be obtained.

-Powder material for solid modeling-
The powder material for three-dimensional modeling included in the three-dimensional modeling set of the present invention is in a powder form, and the three-dimensional modeling powder material is bonded to each other by supplying the three-dimensional modeling composition liquid of the present invention and then drying. Any material that can form a three-dimensional model can be used. In addition, the three-dimensional modeling powder material of the present invention may be used as a three-dimensional modeling powder material as it is as a powdered base material of various materials, or the surface of the base material may be coated with a resin, The surface treatment may be performed, or the substrate may have a core-shell structure.

  The substrate is not particularly limited as long as it has a powder or particle form, and can be appropriately selected according to the purpose. Examples of the material include metal, ceramics, carbon, polymer, wood, biocompatible material, and sand. From the viewpoint of obtaining a high-strength three-dimensional modeled object, a metal that can be finally sintered, Ceramics and the like are more preferable.

  The metal is not particularly limited as long as it contains a metal as a material. For example, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Ta, W, and alloys thereof may be mentioned. Among these, stainless steel (SUS) steel, iron, silver, copper, titanium, zirconium, or alloys thereof are preferably used. Examples of the stainless steel (SUS) include SUS304, SUS316L, SUS317, SUS329, SUS410, SUS430, SUS440, and SUS630.

Examples of the ceramic include oxides, carbides, nitrides, and hydroxides. Examples of the oxide include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), and the like. Examples of the carbon include graphite, graphene, carbon nanotube, carbon nanohorn, and fullerene.

  Examples of the polymer include known resin fine particles that are insoluble in water. Examples of the wood include wood chips and cellulose. Examples of the biocompatible material include polylactic acid and calcium phosphate. These materials may be used alone or in combination of two or more.

  As these base materials, commercially available materials can also be used. For example, PSS316L made by Sanyo Special Steel for stainless steel, Excelica SE-15 made by Tokuyama for silica, Tymicron TM-5D made by Daimei Chemical Industry, TZ-B53 made by Tosoh, etc. for zirconia. Can do.

The three-dimensional modeling composition liquid of the present invention contains water and urethane resin particles. In this case, since the urethane resin is aqueous, it can form a state dispersed or emulsified in water, and thus is particularly preferable in the present invention. As the aqueous urethane resin particles, for example, the aforementioned self-emulsifying type or forced emulsifying type urethane resin emulsion can be preferably used.
When using these water-based urethane resin particles, the surface of the powder material for three-dimensional modeling is preferably hydrophilic. Since the surface of the powder material for three-dimensional modeling is hydrophilic, the wettability and permeability of the urethane resin particles to the powder material for three-dimensional modeling, or the adhesion to the base material is improved, and the resulting three-dimensional model is obtained. This is effective for increasing strength and making the strength uniform. From this point, metals and ceramics are particularly preferably used as the base material. Among the substrates, those having a hydrophobic surface can be hydrophilized by coating the surface with a hydrophilic film or by surface treatment. Since the wettability and penetrability of the liquid are increased, it is possible to obtain an effect of improving the strength of the three-dimensional structure.

  As described above, the three-dimensional modeling powder material included in the three-dimensional modeling set of the present invention can use the base material itself as the three-dimensional modeling powder material. It can also be used as a powder material. By coating the resin, it becomes possible to increase the wettability and permeability of the composition liquid for three-dimensional modeling, and the resin can increase the adhesion between the powder materials and further improve the strength of the three-dimensional modeled object to be obtained. Therefore, it is effective.

  When the resin is coated on the surface of the base material, a conventionally known resin can be used. Although it does not specifically limit as said base material coating resin, From viewpoints, such as handleability and an environmental load, it is preferable that it is water-soluble, for example, water-soluble resin, a water-soluble prepolymer, etc. are mentioned. 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.

  For example, the polyvinyl alcohol resin may be unmodified, modified polyvinyl alcohol (acetoacetyl group-modified polyvinyl alcohol, acetylated modified polyvinyl alcohol, silicone modified) by acetoacetyl group, acetyl group, silicone or the like. Polyvinyl alcohol). Further, it may be a copolymer such as a butanediol vinyl alcohol copolymer.

  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. Examples of the water-soluble prepolymer include an adhesive water-soluble isocyanate prepolymer contained in a water-stopping agent and the like. These substrate coating resins may be used singly or in combination of two or more, or may be appropriately synthesized.

  In the present invention, among the resins, those having a crosslinkable functional group are more 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. The above-mentioned modified polyvinyl alcohol can also be used effectively. When the surface of the three-dimensional modeling powder material is coated with a resin having a crosslinkable functional group and a cross-linking agent is contained in the three-dimensional modeling composition liquid, when the composition liquid is provided to the powder material layer, the powder material The resin coated on the surface of the solid solution is dissolved by the composition liquid and adheres to the adjacent powder material, and at the same time, the cross-linking agent contained in the composition liquid crosslinks the powder material to obtain the strength of the three-dimensional structure to be obtained. Is very effective. As the crosslinking agent, the aforementioned crosslinking agents can be preferably used.

  When polyvinyl alcohol is used for the substrate coating resin, the average degree of polymerization is preferably 300 or more and 1700 or less, and more preferably 400 or more and 1200 or less. When the average degree of polymerization is 300 or more, it is effective in increasing the strength of the three-dimensional structure, and when the average degree of polymerization is 1700 or less, the coating property is improved when the substrate is coated with the resin. Thus, a resin-coated powder material can be produced with high efficiency. As these resins, resins having different degrees of polymerization and saponification may be used singly or in combination of two or more.

  Commercially available products can also be used as the substrate coating resin. Examples of the commercially available products include polyvinyl alcohol (manufactured by Kuraray, PVA series), polyacrylic acid (manufactured by Toagosei, Julimer series), sodium polyacrylate (manufactured by Toagosei, Julimer series), and acetoacetyl group-modified polyvinyl. Alcohol (manufactured by Nippon Synthetic Chemical Industry, Goosefimer), carboxy group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry, Gohsenx series), butanediol vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Industry, Nichigo G-polymer series) ), Carboxymethylcellulose (Daiichi Kogyo, Cellogen 5A), starch (Sanwa Starch Kogyo, Hystad PSS-5), gelatin (Nitta Gelatin, Bee Matrix Gelatin) and the like.

  When the resin is coated on the substrate, the average film thickness of the resin is preferably 5 nm to 1,000 nm, more preferably 10 nm to 500 nm, still more preferably 30 nm to 300 nm, and particularly preferably 50 nm to 200 nm. When the average film thickness of the resin is 5 nm or more, the effect of increasing the strength of the three-dimensional structure can be obtained, and the shape loss before sintering can be prevented, while the average film thickness is 1,000 nm or less. And the fall of the dimensional accuracy of the three-dimensional molded item obtained can be prevented. The average film thickness of the resin is, for example, after embedding the powder material for three-dimensional modeling in an acrylic resin or the like, and performing etching or the like to expose the surface of the base material, and then scanning tunnel microscope STM, It can be measured by using an atomic force microscope AFM, a scanning electron microscope SEM or the like.

  The coverage (area ratio) of the resin formed on the substrate surface is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 15% or more, more preferably 50% or more, 80% or more is particularly preferable. Even if the coverage is low, the effect of the present invention can be obtained as long as the resin is formed on the substrate surface. However, the higher the coverage, the strength of the three-dimensional structure can be improved, and the strength Since anisotropy can be reduced, it is more effective. The coverage is obtained by, for example, determining the area of the region covered with the resin with respect to the surface area of the powder material for three-dimensional modeling from an observation photograph of the powder material for three-dimensional modeling using an optical microscope, a microscope, or an SEM. It can calculate from the average value of the ratio (%). Moreover, it can measure also by performing the element mapping using the energy dispersive X-ray spectroscopy, such as SEM-EDS, about the part coat | covered with resin.

  The average particle diameter of the powder material for three-dimensional modeling is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 μm or more and 500 μm or less, more preferably 5 μm or more and 150 μm or less, and more preferably 10 μm or more and 100 μm. The following is more preferable. By the said average particle diameter being 0.5 micrometer or more, the fall of the manufacture efficiency of a three-dimensional molded item, the increase in the time which a three-dimensional modeling requires, the handleability of a base material, and the handleability, etc. can be suppressed. On the other hand, when the average particle diameter is 500 μm or less, the strength of the three-dimensional object or the three-dimensional sintered object obtained by sintering the three-dimensional object due to an increase in the voids of the three-dimensional object or a decrease in the contacts between the base materials is prevented. Can do. The average particle size of the powder material for three-dimensional modeling can be measured using, for example, the above-described particle size distribution measuring device Microtrac MT3000II series (manufactured by Microtrac Bell).

  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. Thereby, the said powder material for three-dimensional model | molding is closely packed, the space | gap of the three-dimensional model | molded article and three-dimensional sintered article obtained can be reduced, and it may be effective for strength improvement. The circularity can be measured by using a known circularity measuring device, and examples thereof include a flow type particle image analyzer FPIA-3000 (manufactured by Malvern Instruments).

-Other ingredients-
There is no restriction | limiting in particular as another component, Although it can select suitably according to the objective, For example, a fluidizing agent, a filler, a leveling agent, a sintering aid, etc. are mentioned. It is preferable that the three-dimensional modeling powder material contains the fluidizing agent in that a layer of the three-dimensional modeling powder material can be efficiently formed with high smoothness. The inclusion of the filler is preferable in that voids or the like are less likely to occur in the three-dimensional structure to be obtained. The inclusion of the leveling agent is preferable in that the wettability of the three-dimensional modeling powder material is improved and handling becomes easy. When the sintering aid is included, it is preferable in that sintering can be performed at a lower temperature when the obtained three-dimensional structure is subjected to a sintering process.

-Manufacturing method of powder material for three-dimensional modeling-
The three-dimensional modeling powder material used in the present invention can use the base material as it is. These base materials can be manufactured using a conventionally known method. For example, a pulverization method that compresses solids by applying compression, impact, friction, etc., an atomization method that sprays molten metal to obtain a quenched powder, a precipitation method that precipitates components dissolved in a liquid, and a gas that vaporizes and crystallizes. Examples include a phase reaction method. Although it does not restrict | limit especially in the manufacturing method as said powder material for three-dimensional modeling used for this invention, As a more preferable method, the spherical shape is obtained and the atomizing method with few dispersion | variation in a particle size is mentioned. Examples of the atomizing method include a water atomizing method, a gas atomizing method, a centrifugal atomizing method, a plasma atomizing method, and the like, and any of them is preferably used.

  On the other hand, also when using what coated the resin to the said base material as a powder material for three-dimensional modeling, there is no restriction | limiting in particular in the method, According to the objective, it can select suitably. For example, a tumbling flow method, a spray drying method, a stirring and mixing addition method, a dipping method, a kneader coating method, and the like are preferable. Moreover, these coating methods can be implemented using various well-known commercially available coating apparatuses, granulating apparatuses, and the like.

  Among these, the rolling flow method is preferably used because of the high resin coverage and excellent film thickness uniformity. The rolling flow method is a method of coating particles by feeding hot air from below, winding powder into the air to form a fluidized bed, and spraying a liquid containing a binder resin on it. The coating can be performed using a commercially available rolling fluid coating apparatus.

  In addition to a resin, a method of coating a metal, a metal oxide, or the like by using a chemical method or a physical method on a substrate surface is also known, and these can also be used effectively. Also known are a method for hydrophilizing the substrate surface and a method for washing the substrate surface, which can also be used effectively.

<Method and apparatus for manufacturing a three-dimensional model>
Although the conventionally well-known method can be used for the manufacturing method of the three-dimensional molded item of this invention, it is preferable to use the following methods, for example.
That is, the layer of the three-dimensional modeling powder material is formed by the three-dimensional modeling powder material layer forming step, and the three-dimensional modeling composition liquid is supplied to the layer by the three-dimensional modeling composition liquid supplying step. It is a manufacturing method which repeats a process and manufactures a three-dimensional molded item. Furthermore, other processes, such as a drying process, are included as needed.

  Moreover, although the conventionally well-known apparatus can be used for the manufacturing apparatus of the three-dimensional molded item of this invention, it is preferable to use the following apparatuses, for example. That is, a layer of the three-dimensional modeling powder material is formed by the three-dimensional modeling powder material layer forming unit, and the three-dimensional modeling composition liquid supply unit is supplied to the layer by the three-dimensional modeling composition liquid supply unit. It is a manufacturing apparatus which repeats a process and manufactures a three-dimensional molded item. Furthermore, other means such as a powder material container, a composition liquid container, and a drying unit are included as necessary.

  The obtained three-dimensional model may have any shape as long as it has a three-dimensional shape. The three-dimensional structure obtained in this manner can be obtained by performing a degreasing process and a sintering process as necessary, thereby obtaining a sintered body of the three-dimensional structure, that is, a three-dimensional sintered object.

  The manufacturing method of the three-dimensional model | molding of this invention supplies the said three-dimensional model | molding composition liquid on the layer of the three-dimensional model | molding powder material layer formation process which forms the layer of the three-dimensional model | molding powder material, and the said three-dimensional model | molding powder material layer A three-dimensional modeling composition liquid supply step, wherein the three-dimensional modeling composition liquid contains water and urethane resin particles.

  In FIG. 1, an example of the process schematic for manufacturing a three-dimensional molded item is shown using the three-dimensional modeling set of this invention. The three-dimensional structure manufacturing apparatus shown in FIG. 1 has a modeling powder storage tank 1 and a supply powder storage tank 2, each of which has a stage 3 movable up and down, A powder material for three-dimensional modeling is placed on the stage 3, and a layer made of the powder material for three-dimensional modeling is formed. On the powder storage tank 1 for modeling, it has the composition liquid supply means 5 for three-dimensional modeling which discharges the composition liquid 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 a 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. Indicates. 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. 1 (c) shows a step of dripping the three-dimensional modeling composition liquid 6 onto the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the three-dimensional modeling composition liquid supply means 5. At this time, the position at which the three-dimensional modeling composition liquid 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.

1 (d) and (e), the stage 3 of the supply powder storage tank 2 is raised, the stage 3 of the modeling powder storage tank 1 is lowered, and the gap is controlled so as to have a desired layer thickness. By moving the three-dimensional modeling powder material layer forming means 4 from the supply powder storage tank 2 to the modeling powder storage tank 1 again, a new three-dimensional modeling powder material layer is formed in the modeling powder storage tank 1. .
FIG. 1 (f) is a step in which the three-dimensional modeling composition liquid 6 is dropped on the three-dimensional modeling powder material layer of the modeling powder storage tank 1 again using the three-dimensional modeling composition liquid 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 composition liquid is not attached, a three-dimensional modeled object can be obtained.

FIG. 2 shows another example of the three-dimensional structure manufacturing apparatus of the present invention. 2 is the same as that of FIG. 1 in principle, but the supply mechanism of the powder material for three-dimensional modeling is different.
FIGS. 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. Indicates. 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. 2 (c) shows a step of dropping the three-dimensional modeling composition liquid 6 on the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the three-dimensional modeling composition liquid supply means 5. At this time, the position at which the three-dimensional modeling composition liquid 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 supplied from the supply powder storage tank 2 to the modeling powder storage tank 1 again. By controlling the gap so as to have a layer thickness 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. 2 (f) is a step in which the three-dimensional modeling composition liquid 6 is dropped again on the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the three-dimensional modeling composition liquid 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 composition liquid is not attached, a three-dimensional modeled object can be obtained. The three-dimensional structure manufacturing apparatus having the configuration shown in FIG. 2 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.

-Powder material layer forming step for three-dimensional modeling and powder material layer forming means-
The three-dimensional modeling powder material layer forming step is a step of forming a three-dimensional modeling powder material layer having a predetermined thickness on the support or the three-dimensional modeling powder material using the three-dimensional modeling powder material. is there.
The three-dimensional modeling powder material layer forming means is a means for forming a three-dimensional modeling powder material layer having a predetermined thickness on the support or the three-dimensional modeling powder material using the three-dimensional modeling powder material. is there.

  The support is a base plate on which the three-dimensional modeling powder material is placed, and a conventionally known one can be used. The surface of the support may be smooth, rough, flat, or curved, but preferably has excellent surface releasability. .

  There is no restriction | limiting in particular as a method of mounting the said powder material for three-dimensional model | molding on the said support body, According to the objective, it can select suitably. Conventionally known methods can also be used, for example, a method using a counter rotation mechanism (counter roller), a method of forming a layer of the three-dimensional modeling powder material using a member such as a brush, a roller, or a blade, A method of forming a layer by pressing the surface of the powder material for three-dimensional modeling using a pressing member is preferably used. In this case, the layer thickness of the three-dimensional modeling powder material can be adjusted by controlling the gap between the modeling powder storage tank and the supply powder storage tank that can be moved up and down.

  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 20 μm or more and 500 μm or less, and 50 μm or more and 300 μm or less. More preferred. When the thickness is 20 μm or more, it is possible to prevent the three-dimensional modeling composition liquid from permeating beyond a desired region and the dimensional accuracy from being lowered. Moreover, modeling time can increase notably and the significant fall of the manufacturing efficiency of a three-dimensional molded item can be suppressed. On the other hand, when the thickness of the three-dimensional modeling powder material layer is 500 μm or less, delamination of the three-dimensional model to be obtained can be reduced, and dimensional accuracy and strength can be improved. In addition, the average thickness of the said powder material layer for three-dimensional model | molding can be measured in accordance with a well-known method, For example, the method of observing the cross section of a three-dimensional model | molded object using a scanning electron microscope, a laser microscope, etc. is mentioned.

  FIG. 3 shows an example of a schematic diagram of a powder storage tank. The powder storage tank 10 has a box shape and includes a tank in which two upper surfaces of the supply tank 2 and the modeling tank 1 are opened. Inside each of the supply tank 2 and the modeling tank 1, a stage is held so that it can be raised and lowered. 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, a powder drop opening 7 having a concave shape with an open upper surface is provided. When the powder layer is formed, surplus powder collected by the flattening roller falls on the powder dropping port 7. The surplus powder that has fallen to the powder dropping port 7 is returned to the powder supply unit located above the modeling tank 1 by an operator or a suction mechanism as necessary.

  The powder material container has a tank shape and is disposed above the supply tank 2. In the initial operation of modeling or when the amount of powder in the supply tank decreases, the powder in the tank is supplied to the supply tank. 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 has a function of conveying powder from the supply tank 2 to the modeling tank 1 and forming a powder layer having a predetermined thickness (for example, thickness (Δt1−Δt2)). As shown in the figure, the flattening roller is a bar longer than the inner dimension of the modeling tank 1 and the supply tank 2 (that is, the width of the “part where the powder is supplied or charged”), and both ends are It is supported by a reciprocating device. The flattening roller moves horizontally so as to pass above the supply tank 2 and the modeling tank 1 from the outside of the supply tank 2 while rotating, whereby powder can be supplied onto the modeling tank 1. Specifically, the stage of the supply tank 2 is raised and the stage of the modeling tank 1 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 1 and the lower portion (downward tangent portion) of the flattening roller is Δt1.

  In the present embodiment, Δt1 is preferably about 50 to 300 μm, for example, about 150 μm. Next, the powder positioned above the upper surface level of the supply tank 2 is supplied to the modeling tank 1 by rotating and moving the flattening roller, and a powder layer having a predetermined thickness Δt1 is placed on the stage of the modeling tank 1. Form. Here, the flattening roller can move while maintaining a constant distance from the upper surface level of the modeling tank 1 and the supply tank 2. As a result of being kept constant, the powder layer having a uniform thickness can be formed on the modeling tank 1 or on the already formed modeling layer while conveying the powder onto the modeling tank 1 with a flattening roller.

  The flattening roller is preferably rotated in the counter direction (reverse rotation) with respect to the horizontal movement direction for conveying the powder material. However, in order to improve the density of the powder material, the flattening roller is opposite to the counter direction ( It is also possible to rotate forward. In addition, after the roller is moved horizontally while rotating in the reverse direction, the stage of the modeling tank 1 is raised by Δt2 and moved horizontally while rotating the roller in the forward direction, thereby obtaining the effect of conveying powder and improving the density. In the present embodiment, Δt2 is preferably about 50 to 100 μm, for example, about 50 μm. This (Δt1-Δt2) corresponds to the thickness of the modeling layer, that is, the stacking pitch.

  The flattening roller is preferably provided with a powder removing plate for removing the adhered powder. The powder removing plate is desirably provided so as to be in contact with the roller in the powder non-planarized region and at a position below the roller rotation center in order to prevent the powder adhering to the roller from scattering in the flattened region. 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. A plurality of tanks that contain a cyan modeling composition liquid, a magenta modeling composition liquid, a yellow modeling composition liquid, a black modeling composition liquid, and a clear modeling composition liquid are mounted inside the three-dimensional modeled object manufacturing apparatus. Each of the heads of each color included in the head is connected to a tank containing a composition liquid of the corresponding color by a flexible tube (not shown). The head discharges the composition liquid of each color to the powder material layer under control. The number of heads and the type of composition liquid to be discharged can be changed. For example, in the case where coloring is not necessary for the modeled object, only the clear head may be set and only the clear modeling composition liquid may be discharged.

  The head can move in the Y-axis and Z-axis directions using the guide rail. When the surface of the supply tank / modeling tank is flattened and densified by the flattening roller, the head can be retreated to a position where it does not interfere. When the composition liquid 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 / flattening step, high-density step, and composition liquid discharge step by 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 composition liquid 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 modeling liquid is sucked from the nozzle. This is for discharging the powder material clogged in the nozzle and discharging the composition liquid with increased viscosity. 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). Further, the head cleaning mechanism covers the nozzle surface of the head when the composition liquid is not discharged, and prevents the powder material from being mixed into the nozzle and the composition liquid 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.

-Composition liquid donating step and composition liquid donating means for three-dimensional modeling-
The three-dimensional modeling composition liquid donating step is a step of donating the three-dimensional modeling composition liquid to the powder material layer formed in the powder material layer forming step.
The three-dimensional modeling composition liquid donating means is a means for donating the three-dimensional modeling composition liquid to the three-dimensional modeling powder material layer formed by the powder material layer forming means.
The means for providing the three-dimensional modeling composition liquid to the three-dimensional modeling powder material layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispenser method, a spray method, and an inkjet method. It is done.

  The dispenser system is a general term for apparatuses that can accurately and accurately supply a liquid. Although it is excellent in the quantitative property of a droplet, an application area is narrow and the size of a three-dimensional molded item may be restricted. The spray method refers to a device that atomizes a liquid into fine droplets using compressed air, high-pressure gas, or the like. Although the coating area is wide and the coating property is excellent, the quantification accuracy of the droplets is low, and the scattering of the powder due to the spray flow occurs. The inkjet system is an apparatus that can eject very fine droplets using a piezoelectric element or a heater. A small amount of liquid droplets can be ejected, and its quantitativeness is high, and a three-dimensional structure having a complicated three-dimensional shape can be manufactured with high accuracy and high efficiency. From the above, the ink jet system is particularly preferably used as the three-dimensional modeling composition liquid supply means in the present invention.

  A nozzle (discharge head) by a known ink jet printer can be suitably used as the three-dimensional modeling composition liquid supply means by the ink jet method. The nozzle by the ink jet printer is preferable in that the amount of ink that can be dropped from the head portion at a time is large and the application area is large, so that the application can be speeded up. Moreover, since the said nozzle can discharge the said composition liquid for three-dimensional modeling with a sufficient precision, it is possible to manufacture the three-dimensional molded item which has a high dimensional accuracy. In the present invention, when producing a three-dimensional structure using the nozzle, water and urethane resin particles are contained in the three-dimensional composition liquid, and the resin is not dissolved, so the viscosity of the composition liquid increases. Since it is possible to suppress clogging of nozzles and decrease in discharge stability and to obtain a three-dimensional shaped object with high dimensional accuracy, it is very effective.

-Other processes and other means-
The three-dimensional structure manufacturing apparatus of the present invention may have any other means. For example, the powder material container for accommodating the three-dimensional modeling powder material is a member in which the three-dimensional modeling powder material is stored, and there is no particular limitation on the size, shape, material, and the like, depending on the purpose. It can select suitably, For example, a storage tank, a bag, a cartridge, a tank, etc. are mentioned.

  Further, the three-dimensional modeling composition liquid storage portion that stores the three-dimensional modeling composition liquid is a member in which the three-dimensional modeling composition liquid is stored, and there is no particular limitation on the size, shape, material, and the like. The storage tank, bag, cartridge, tank, etc. can be mentioned as appropriate.

  Moreover, a drying process is a process of evaporating the three-dimensional modeling composition liquid contained in a three-dimensional molded item, and drying a three-dimensional molded item, and is effective. The drying step may be performed after all the three-dimensional modeling powder material layers are laminated, or may be dried each time in the process of laminating each layer. As the drying means, any conventionally known means can be used as long as it can accelerate the evaporation of the three-dimensional composition liquid contained in the three-dimensional structure by heating, for example, using a heat dryer or the like. can do. Moreover, a drying means may be integrated with the manufacturing apparatus of a three-dimensional molded item, and is good also as another body.

  By providing the drying means, the strength of the three-dimensional structure can be increased at an early stage, and therefore, the risk that the three-dimensional structure is deformed or deformed can be reduced. At this time, it is preferable to dry at a temperature equal to or higher than the minimum film-forming temperature of the urethane resin particles contained in the three-dimensional modeling composition liquid. Thereby, the intensity | strength of a three-dimensional molded item can be raised significantly. In addition, when a cross-linking agent is included in the three-dimensional modeling composition liquid, it is effective in some cases that it is possible to increase the strength of the three-dimensional modeled product at an early stage by providing a drying means. On the other hand, if the drying is performed excessively, even the three-dimensional modeling powder material to which the three-dimensional modeling composition liquid is not attached may be heat-sealed, and the dimensional accuracy of the three-dimensional model may be reduced.

Examples of other processes include a surface protection treatment process and a painting process. Examples of other means include surface protection treatment means and painting means.
The surface protection treatment step is a step of forming a protective layer on the three-dimensional structure. By performing this surface protection treatment step, a three-dimensional model having high durability can be obtained. 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 painting step is a step of painting the three-dimensional structure. By performing the coating process, the 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.

<Degreasing and sintering of 3D objects>
The obtained three-dimensional model is degreased and sintered as necessary.
Degreasing refers to a treatment for removing the resin component. If the resin content 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, and among them, 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 the air atmosphere, a heat treatment method 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, ammonia decomposition gas, or the like may be 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 inert gas atmosphere such as a vacuum or reduced pressure atmosphere, a non-oxidizing atmosphere, nitrogen gas, argon gas, etc. in addition to an air atmosphere. 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. .

  The density of the three-dimensional sintered product obtained as described above varies depending on the application and the like, but is preferably 90% or more, and preferably 94% or more from the viewpoint of the strength of the three-dimensional sintered product. Since the powder material for three-dimensional modeling of the present invention contains a resin in the base material, the amount of the resin is small, and deformation and shrinkage of the modeled object are not likely to occur before and after degreasing and sintering. A sintered product can be obtained.

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

[Example 1]
<Powder material 1 for three-dimensional modeling>
As the three-dimensional modeling powder material 1, stainless steel (SUS316L) powder (PSS316L, volume average particle size 43 μm, manufactured by Sanyo Special Steel Co., Ltd.) was used.
<Composition liquid 1 for three-dimensional modeling>
Aqueous urethane resin emulsion (Superflex 210, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 6-8, anionic, average particle size 0.05 μm, minimum film-forming temperature about 23 ° C., glass transition to 70 parts by mass of water 10 parts by mass of a point 41 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a composition solution 1 for three-dimensional modeling.

<Three-dimensional model 1>
A three-dimensional object 1 was prepared according to the following method using the three-dimensional object manufacturing apparatus shown in FIG. 1 using a counter roller as the three-dimensional object powder material layer forming means and using an ink jet head as the three-dimensional object composition supplying means. . The process shown in FIG. 1 is performed by putting the 3D modeling powder material 1 in the powder material container of the three-dimensional model manufacturing apparatus and the 3D modeling composition liquid 1 in the same composition liquid container and inputting 3D data. Was repeated to produce a three-dimensional model 1 having a strip shape. In addition, the average thickness of one layer of the powder material layer for three-dimensional modeling was adjusted to be about 90 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 three-dimensional modeling powder material to which the three-dimensional modeling composition liquid is not attached is removed with a brush or the like, placed in a dryer again, dried at 120 ° C. for 8 hours, and allowed to cool to room temperature. Produced.

<Bending stress test of the three-dimensional structure 1>
The obtained three-dimensional structure 1 was subjected to a bending stress test using a precision universal testing machine (Autograph AGS-J, manufactured by Shimadzu Corporation). 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. The obtained measurement results were classified according to the following criteria. The results are shown in Table 1.
-Evaluation criteria-
A: 12.0 MPa or more B: 9.0 MPa or more and less than 12.0 MPa C: 6.0 MPa or more and less than 9.0 MPa D: 3.0 MPa or more and less than 6.0 MPa E: Less than 3.0 MPa

<Dimensional accuracy evaluation of the three-dimensional structure 1>
The obtained three-dimensional structure 1 evaluated the dimensional accuracy by visual observation. The results were classified according to the following criteria. The results are shown in Table 1.
-Evaluation criteria-
A: Level in which the surface of the three-dimensional structure is smooth, less unevenness, and no warpage occurs B: Level in which unevenness or warpage is slightly observed on the surface of the three-dimensional structure C: Concavities and convexities in part of the three-dimensional structure Permitted level D: Level where unevenness and warpage are recognized in more than half of the three-dimensional structure E: Level where unevenness and warpage are recognized throughout the three-dimensional structure, clearly different from the target shape

<Degreasing and sintering of the three-dimensional structure 1>
About the three-dimensional molded object 1 obtained above, using a dryer, the temperature is raised to 400 ° C. in a nitrogen atmosphere to perform a degreasing step, and further sintering is performed at 1,300 ° C. under vacuum in a sintering furnace. Processed.

[Example 2]
A three-dimensional object 2 was produced in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 2. Using the obtained three-dimensional model 2, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 2 for solid modeling>
Aqueous urethane resin emulsion (Superflex 210, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 6-8, anionic, average particle size 0.05 μm, minimum film-forming temperature about 23 ° C., glass transition to 50 parts by mass of water 30 parts by mass of a point 41 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed with stirring to prepare a composition liquid 2 for three-dimensional modeling.

[Example 3]
A three-dimensional object 3 was prepared in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 3. Using the obtained three-dimensional structure 3, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling liquid 3>
Aqueous urethane resin emulsion (Superflex 210, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 6-8, anionic, average particle size 0.05 μm, minimum film-forming temperature about 23 ° C., glass transition to 50 parts by mass of water 50 parts by mass of a point 41 ° C. (Daiichi Kogyo Seiyaku Co., Ltd.) was added and mixed by stirring to prepare a composition liquid 3 for three-dimensional modeling.

[Example 4]
A three-dimensional object 4 was prepared in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 4. Using the obtained three-dimensional structure 4, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 4 for three-dimensional modeling>
In 70 parts by mass of water, an aqueous urethane resin emulsion (Superflex 130, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 7.5 to 9.5, anionic, average particle size 0.02 μm, minimum film-forming temperature about 55 5 parts by mass of glass transition point 101 ° C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 25 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) are added and mixed by stirring. Was made.

[Example 5]
A three-dimensional object 5 was prepared in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 5. Using the obtained three-dimensional model 5, the bending stress test and the dimensional accuracy were evaluated in the same manner as in Example 1.
<3D modeling composition 5>
In 60 parts by mass of water, an aqueous urethane resin emulsion (Superflex 130, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 7.5 to 9.5, anionic, average particle size 0.02 μm, minimum film-forming temperature about 55 20 parts by mass of glass transition point 101 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), and mixed by stirring. Was made.

[Example 6]
A three-dimensional object 6 was produced in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 6. Using the obtained three-dimensional model 6, a bending stress test and evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 6>
In 50 parts by mass of water, an aqueous urethane resin emulsion (Superflex 126, self-emulsifying type, non-volatile content 30 ± 1 wt%, pH 7-9, anionic, average particle size 0.01 μm, minimum film forming temperature of about 5 ° C. or less, glass 30 parts by mass of transition point 72 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and further 20 parts by mass of 1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a composition liquid 6 for three-dimensional modeling. .

[Example 7]
A three-dimensional object 7 was produced in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 7. Using the obtained three-dimensional model 7, the bending stress test and the dimensional accuracy were evaluated in the same manner as in Example 1.
<3D modeling composition 7>
In 50 parts by mass of water, an aqueous urethane resin emulsion (Superflex 170, self-emulsifying type, nonvolatile content 33 ± 1 wt%, pH 7-9, anionic, average particle size 0.02 μm, minimum film-forming temperature of about 5 ° C. or less, glass 30 parts by mass of transition point 75 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 20 parts by mass of 1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare 3D modeling composition liquid 7. .

[Example 8]
A three-dimensional object 8 was produced in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 8. Using the obtained three-dimensional structure 8, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 8>
In 60 parts by mass of water, an aqueous urethane resin emulsion (Superflex 820, self-emulsifying type, non-volatile content 30 ± 1 wt%, pH 7-9, anionic, average particle size 0.03 μm, minimum film forming temperature about 40 ° C., glass transition A point 46 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (20 parts by mass) was added, and further 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) (20 parts by mass) was added and mixed by stirring to prepare a three-dimensional modeling composition liquid 8.

[Example 9]
A three-dimensional object 9 was prepared in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 9. Using the obtained three-dimensional model 9, the bending stress test and dimensional accuracy were evaluated in the same manner as in Example 1.
<3D modeling composition 9>
60 parts by mass of water, aqueous urethane resin emulsion (Superflex 110, self-emulsifying type, nonvolatile content 30 ± 1 wt%, pH 7-9, anionic, average particle size 0.09 μm, minimum film-forming temperature 5 ° C. or less, glass transition 20 parts by mass of a point 48 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a composition solution 9 for three-dimensional modeling.

[Example 10]
The three-dimensional structure 10 was prepared in the same manner as in Example 2 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional structure composition liquid 10 and the drying temperature was changed to 120 ° C. Using the obtained three-dimensional structure 10, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 10>
In 56.8 parts by weight of water, an aqueous urethane resin emulsion (Superflex 210, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 6-8, anionic, average particle size 0.05 μm, minimum film-forming temperature of about 23 ° C., Glass transition point 41 ° C., Daiichi Kogyo Seiyaku Co., Ltd. 20 parts by mass, blocked isocyanate crosslinking agent (Elastolon BN-77, self-emulsifying type, nonvolatile content 30.0-32.0%, pH 6.5-8.5) , Anionic, dissociation temperature of 120 ° C. or higher, Daiichi Kogyo Seiyaku Co., Ltd.) 3.2 parts by mass, and 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 20 parts by mass are added, stirred and mixed, and the composition for three-dimensional modeling 1 was produced.

[Example 11]
The three-dimensional object 11 is changed in the same manner as in Example 5 except that the three-dimensional modeling powder material 1 is changed to the following three-dimensional modeling powder material 2 and the three-dimensional modeling composition liquid 5 is changed to the three-dimensional modeling composition liquid 11. Produced. Using the obtained three-dimensional model 11, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Powder material 2 for 3D modeling>
Silica particles (Excellica SE-15K, volume average particle size 24 μm, manufactured by Tokuyama Corporation) were used as the substrate.
As a base material coating resin solution, 5 parts by mass of 95 parts by mass of water with stirring and acetoacetyl group-modified polyvinyl alcohol (Gocenex Z-100, average polymerization degree 500, saponification degree 98.5 mol%, manufactured by Nippon Synthetic Chemical Industry) Then, the mixture was heated and stirred to prepare a substrate coating resin solution 1.
The substrate is put into a rolling fluidized coating apparatus (MP-01, manufactured by POWREC), and the substrate-coated resin solution is spray-sprayed to perform resin coating on the substrate and resin-coated for three-dimensional modeling Powder material 2 was produced.

<3D modeling composition 11>
In 60 parts by mass of water, an aqueous urethane resin emulsion (Superflex 130, self-emulsifying type, non-volatile content 35 ± 1 wt%, pH 7.5 to 9.5, anionic, average particle size 0.02 μm, minimum film-forming temperature about 55 ° C, glass transition point 101 ° C, Daiichi Kogyo Seiyaku Co., Ltd. 20 parts by mass, zirconium-based crosslinking agent (Zircozol AC-20, Daiichi Rare Chemicals) 5 parts by mass, and 1,2-butanediol (Tokyo Kasei) 20 parts by mass of (industrial product) was added and mixed by stirring to prepare a three-dimensional modeling composition liquid 11.

[Example 12]
A three-dimensional model 12 was produced in the same manner as in Example 1 except that the three-dimensional modeling powder material 1 was changed to the following three-dimensional modeling powder material 3. Using the obtained three-dimensional model 12, the bending stress test and the dimensional accuracy were evaluated in the same manner as in Example 1.
<Powder material 3 for 3D modeling>
Stainless steel (SUS316L) powder (PSS316L, volume average particle size 12 μm, manufactured by Sanyo Special Steel Co., Ltd.) was used as the substrate.
As a base material coating resin solution, 5 parts by mass of 95 parts by mass of water with stirring and acetoacetyl group-modified polyvinyl alcohol (Gocenex Z-100, average polymerization degree 500, saponification degree 98.5 mol%, manufactured by Nippon Synthetic Chemical Industry) Then, the mixture was heated and stirred to prepare a substrate coating resin solution 1.
The substrate is put into a rolling fluidized coating apparatus (MP-01, manufactured by POWREC), and the substrate-coated resin solution is spray-sprayed to perform resin coating on the substrate and resin-coated for three-dimensional modeling Powder material 3 was produced.

[Example 13]
A three-dimensional object 13 was produced in the same manner as in Example 12 except that the three-dimensional composition liquid 1 was changed to the three-dimensional composition liquid 4. Using the obtained three-dimensional structure 13, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.

[Example 14]
A three-dimensional object 14 was produced in the same manner as in Example 12 except that the three-dimensional composition liquid 1 was changed to the three-dimensional composition liquid 8. Using the obtained three-dimensional structure 14, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.

[Example 15]
A three-dimensional model 15 was produced in the same manner as in Example 11 except that the three-dimensional model powder material 2 was changed to the following three-dimensional model powder material 4. Using the obtained three-dimensional model 15, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Powder material 4 for 3D modeling>
As the substrate, spherical alumina particles (DAM-45, d50: 41.2 μm, manufactured by Denki Kagaku Kogyo) were used.
As a base material coating resin solution, 5 parts by mass of 95 parts by mass of water with stirring and acetoacetyl group-modified polyvinyl alcohol (Gocenex Z-100, average polymerization degree 500, saponification degree 98.5 mol%, manufactured by Nippon Synthetic Chemical Industry) Then, the mixture was heated and stirred to prepare a substrate coating resin solution 1.
The substrate is put into a rolling fluidized coating apparatus (MP-01, manufactured by POWREC), and the substrate-coated resin solution is spray-sprayed to perform resin coating on the substrate and resin-coated for three-dimensional modeling Powder material 3 was produced.

[Example 16]
A three-dimensional model 16 was produced in the same manner as in Example 12 except that the three-dimensional modeling powder material 3 was changed to the following three-dimensional modeling powder material 5. Using the obtained three-dimensional structure 16, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Powder material 5 for three-dimensional modeling>
Stainless steel (SUS316L) powder (PSS316L, volume average particle size 12 μm, manufactured by Sanyo Special Steel Co., Ltd.) was used as the substrate.
As a base coating resin solution, 5 parts by mass of diacetone-modified polyvinyl alcohol (D polymer DF-05, average polymerization degree 500, saponification degree 99.0 mol%, manufactured by Nippon Vinegar Bipovar) is added to 95 parts by mass of water with stirring. The substrate coating resin solution 2 was prepared by heating and stirring.
The base material is put into a tumbling fluidized coating apparatus (MP-01, manufactured by POWREC), and the base material coating resin solution 2 is sprayed and sprayed onto the base material to form a resin-coated three-dimensional model. A powder material 5 was prepared.

[Example 17]
A three-dimensional object 17 was produced in the same manner as in Example 16 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 12. Using the obtained three-dimensional model 17, the bending stress test and dimensional accuracy were evaluated in the same manner as in Example 1.
<3D modeling composition 12>
In 60 parts by mass of water, an aqueous urethane resin emulsion (Superflex 620, self-emulsifying type, non-volatile content 30 ± 1 wt%, pH 7-9, cationic, average particle size 0.03 μm, minimum film-forming temperature 30 ° C., glass transition point 20 parts by mass of 43 ° C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and further 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a composition liquid 12 for three-dimensional modeling.

[Example 18]
A three-dimensional object 18 was produced in the same manner as in Example 16 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 13. Using the obtained three-dimensional structure 18, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 13>
In 57.7 parts by mass of water, an aqueous urethane resin emulsion (Superflex 620, self-emulsifying type, nonvolatile content 30 ± 1 wt%, pH 7-9, cationic, average particle size 0.03 μm, minimum film-forming temperature 30 ° C., glass Transition point 43 ° C., Daiichi Kogyo Seiyaku Co., Ltd. 20 parts by mass, blocked isocyanate crosslinking agent (Elastolon BN-04, self-emulsifying type, non-volatile content 32.5-34.5%, pH 6.0-8.0, Anionicity, dissociation temperature of 120 ° C. or higher, Daiichi Kogyo Seiyaku Co., Ltd. (2.3 parts by mass) and 1,2-butanediol (Tokyo Chemical Industry Co., Ltd.) (20 parts by mass) are added and mixed by stirring. Was made.

[Example 19]
A three-dimensional model 19 was produced in the same manner as in Example 16 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 14. Using the obtained three-dimensional model 19, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 14>
In 58 parts by mass of water, an aqueous urethane resin emulsion (Superflex 620, self-emulsifying type, non-volatile content 30 ± 1 wt%, pH 7-9, cationic, average particle size 0.03 μm, minimum film-forming temperature 30 ° C., glass transition point Add 43 parts by mass of 43 ° C., Daiichi Kogyo Seiyaku Co., Ltd. 20 parts by mass, 2 parts by mass of a cross-linking agent (Adipic acid dihydrazide ADH, Nippon Hydrazine Kogyo), and 20 parts by mass of 1,2-butanediol (Tokyo Chemical Industry). The three-dimensional modeling composition liquid 14 was prepared by mixing.

[Example 20]
A three-dimensional object 20 was produced in the same manner as in Example 16 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 15. Using the obtained three-dimensional model 20, the bending stress test and the dimensional accuracy were evaluated in the same manner as in Example 1.
<3D modeling composition 15>
In 57 parts by mass of water, an aqueous urethane resin emulsion (Superflex R-5002, reaction type, forced emulsification type, nonvolatile content 39.5 ± 1 wt%, pH 5-7, nonionic properties, average particle size 0.50 μm, minimum film formation Temperature 25 ° C, glass transition point -43 ° C, Daiichi Kogyo Seiyaku Co., Ltd. 20 parts by mass, cross-linking agent (adipic acid dihydrazide ADH, Nippon Hydrazine Kogyo) 3 parts by mass, and 1,2-butanediol (Tokyo Chemical Industry) ) 20 parts by mass was added and mixed by stirring to prepare a composition solution 15 for three-dimensional modeling.

[Example 21]
A three-dimensional object 21 was produced in the same manner as in Example 16 except that the three-dimensional composition liquid 1 was changed to the following three-dimensional composition liquid 16. Using the obtained three-dimensional structure 21, a bending stress test and evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 16 for three-dimensional modeling>
In 60 parts by mass of water, an aqueous urethane resin emulsion (Permarin UA-350, forced emulsification type, non-volatile content 32 wt%, pH 8.0, anionic, average particle size 0.07 μm, minimum film forming temperature 5 ° C. or less, glass transition point 25 parts by mass of −65 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 15 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a three-dimensional modeling composition liquid 16.

[Comparative Example 1]
In Example 1, the three-dimensional molded item 22 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 17. Using the obtained three-dimensional structure 22, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 17 for three-dimensional modeling>
To 80 parts by mass of water, 5 parts by mass of acetoacetyl group-modified polyvinyl alcohol (Gocenex Z-100, average polymerization degree 500, saponification degree 98.5 mol%, manufactured by Nippon Synthetic Chemical Industry) was added with stirring, and the mixture was stirred with heating. Thus, a resin solution was prepared. Further, 15 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed by stirring to prepare a composition liquid 17 for three-dimensional modeling.

[Comparative Example 2]
In Example 1, the three-dimensional molded item 23 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 18. Using the obtained three-dimensional structure 23, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 18>
While stirring, 5 parts by mass of acetoacetyl group-modified polyvinyl alcohol (Gosenx Z-100, average polymerization degree 500, saponification degree 98.5 mol%, manufactured by Nippon Synthetic Chemical Industry) was added to 73 parts by mass of water, followed by stirring with heating. Thus, a resin solution was prepared. Next, 2 parts by mass of a zirconium-based cross-linking agent (Zircozol AC-20, manufactured by Daiichi Rare Element Chemical Industry) was added and stirred, and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added, followed by stirring and mixing. The composition liquid 18 for three-dimensional modeling was produced.

[Comparative Example 3]
In Example 1, the three-dimensional molded item 24 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 19. Using the obtained three-dimensional structure 24, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 19>
To 75 parts by mass of water, 5 parts by mass of diacetone-modified polyvinyl alcohol (D polymer DF-05, average polymerization degree 500, saponification degree 99.0 mol%, manufactured by Nihon Vinegar Bipoval) was added with stirring. A resin solution was prepared. Furthermore, 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed by stirring to prepare a composition liquid 19 for three-dimensional modeling.

[Comparative Example 4]
In Example 1, the three-dimensional molded object 25 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 20. Using the obtained three-dimensional structure 25, the bending stress test and the evaluation of the dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 20 for three-dimensional modeling>
While stirring, 5 parts by mass of diacetone-modified polyvinyl alcohol (D polymer DF-05, average polymerization degree 500, saponification degree 99.0 mol%, manufactured by Nihon Vinegar Bipovar) was added to 73 parts by mass of water, and the mixture was heated and stirred. A resin solution was prepared. Next, 2 parts by mass of a crosslinking agent (adipic acid dihydrazide ADH, manufactured by Nippon Hydrazine Kogyo) was added and stirred, and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added, stirred and mixed, and the composition for three-dimensional modeling 20 was produced.

[Comparative Example 5]
In Example 1, the three-dimensional molded object 26 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 21. Using the obtained three-dimensional structure 26, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.
<Composition liquid 21 for three-dimensional modeling>
To 60 parts by mass of water, 20 parts by mass of an acrylic resin emulsion (Rheovis AS1130, nonvolatile content 30 wt%, manufactured by BASF) is added, and further 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) is added and mixed by stirring. The composition liquid 21 for three-dimensional modeling was produced.

[Comparative Example 6]
In Example 1, the three-dimensional model 27 was produced in the same manner as in Example 1 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 22. Using the obtained three-dimensional model 27, the bending stress test and the evaluation of the dimensional accuracy were performed in the same manner as in Example 1.
<3D modeling composition 22>
57 parts by weight of water, 20 parts by weight of acrylic resin emulsion (Rheovis AS1130, non-volatile content 30 wt%, manufactured by BASF), blocked isocyanate-based crosslinking agent (Elastolon BN-77, self-emulsifying type, non-volatile content 30.0-32.0 %, PH 6.5-8.5, anionic, dissociation temperature 120 ° C. or higher, Daiichi Kogyo Seiyaku Co., Ltd.) 3 parts by mass, and 1,2-butanediol (Tokyo Kasei Kogyo Co., Ltd.) 20 parts by mass are added and stirred. And the three-dimensional modeling composition liquid 22 was produced.

[Comparative Example 7]
In Example 11, a three-dimensional object 28 was prepared in the same manner as in Example 11 except that the three-dimensional composition liquid 11 was changed to the three-dimensional composition liquid 21 described above. Using the obtained three-dimensional structure 28, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.

[Comparative Example 8]
In Example 16, a three-dimensional object 29 was produced in the same manner as in Example 16 except that the three-dimensional composition liquid 1 was changed to the three-dimensional composition liquid 21 described above. Using the obtained three-dimensional structure 29, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 1.

[Comparative Example 9]
In Example 12, the three-dimensional molded object 30 was produced in the same manner as in Example 12 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 23. Using the obtained three-dimensional structure 30, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 12.
<3D modeling liquid 23>
50 parts by mass of water, styrene acrylic resin emulsion (mobile 747, non-volatile content 43%, pH 6.0 to 8.0, nonionic properties, minimum film forming temperature 15 ° C., glass transition temperature 42 ° C., manufactured by Nippon Synthetic Chemical Industry) 30 Mass parts were added, and further 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to prepare a three-dimensional modeling composition liquid 23.

[Comparative Example 10]
In Example 12, the three-dimensional model 31 was produced in the same manner as in Example 12 except that the three-dimensional modeling composition liquid 1 was changed to the following three-dimensional modeling composition liquid 24. Using the obtained three-dimensional model 31, the bending stress test and the evaluation of dimensional accuracy were performed in the same manner as in Example 12.
<Solid modeling composition 24>
In 50 parts by mass of water, an acrylic resin emulsion (containing vinyl 8020, colloidal silica, non-volatile content 43%, pH 8.5 to 10.0, anionic, minimum film-forming temperature 0 ° C., glass transition temperature −22 ° C., Nippon Synthetic Chemical 30 parts by mass of Kogyo Co., Ltd. was added, and 20 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed by stirring to prepare a three-dimensional modeling composition liquid 24.

  Table 1 shows the composition of the three-dimensional modeling composition liquid, and Table 2 shows the evaluation results.

The composition liquid for three-dimensional modeling of the present invention produces a three-dimensional modeled article having high strength and high dimensional accuracy even if the base material itself is used as a three-dimensional modeling powder material by containing urethane resin particles. I was able to. Furthermore, further strength improvement of a three-dimensional model | molding object was realizable by making the composition liquid for three-dimensional model | molding contain a crosslinking agent, or coat | covering resin on the surface of the powder material for three-dimensional model | molding. In addition, the urethane resin particles contained in the three-dimensional modeling composition liquid are less affected by thickening and are less likely to cause nozzle clogging of the inkjet head, so the ejection stability of the three-dimensional modeling composition liquid is improved and high dimensional accuracy is achieved. Was able to be maintained stably. Using these methods, a three-dimensional object having a complicated three-dimensional shape is produced, and the three-dimensional sintered object obtained by sintering after the degreasing process maintains a complicated shape and is a hard and durable three-dimensional object. It was confirmed that it was a structure.
On the other hand, the three-dimensional modeled object of the comparative example has a lower discharge stability of the three-dimensional modeling composition liquid and the discharge amount is changed, or a bias is seen in the amount of the three-dimensional modeling composition liquid discharged into the powder layer, As a result, the strength of the three-dimensional model is low overall, the strength varies depending on the location, there are some parts that are very fragile, and there are places where the shrinkage is large when the three-dimensional model is dried, and the target shape Could not be reproduced, and a number of problems were recognized. In addition, using these methods, a three-dimensional molded article having a complicated three-dimensional shape is prepared, and the three-dimensional sintered article obtained by sintering after the degreasing treatment has many voids inside and the thin portion is brittle. As a result, it was confirmed that the appearance was also warped and swollen, the target shape was not maintained, and the strength and dimensional accuracy were inferior.

DESCRIPTION OF SYMBOLS 1 Modeling side powder storage tank 2 Supply side powder storage tank 3 Stage 4 Three-dimensional modeling composition liquid 5 Inkjet head 6 Leveling mechanism 7 Powder drop port 10 Powder storage tank

Japanese Patent No. 2729110 Japanese Patent Laid-Open No. 08-192468 JP 2014-24252 A

Claims (15)

  A three-dimensional modeling composition liquid used for modeling a three-dimensional object made of a three-dimensional modeling powder material, comprising water and urethane resin particles.   The three-dimensional modeling composition liquid according to claim 1, wherein the urethane resin constituting the urethane resin particles has a hydrophilic group.   The composition liquid for three-dimensional modeling according to claim 2, wherein the hydrophilic group is anionic.   The composition liquid for three-dimensional modeling according to any one of claims 1 to 3, wherein the urethane resin particles have an average particle size of 0.2 µm or less.   The composition liquid for three-dimensional modeling according to any one of claims 1 to 4, wherein a glass transition point of the urethane resin particles is 20 ° C or higher.   The said three-dimensional modeling composition liquid contains a crosslinking agent further, The three-dimensional modeling composition liquid in any one of Claim 1 thru | or 5 characterized by the above-mentioned.   The three-dimensional modeling composition liquid according to any one of claims 1 to 6, wherein the three-dimensional modeling composition liquid further contains a water-soluble solvent.   A three-dimensional modeling set comprising the three-dimensional modeling powder material and the three-dimensional modeling composition liquid according to any one of claims 1 to 7.   The three-dimensional modeling set according to claim 8, wherein the three-dimensional modeling powder material is at least one of a metal and a ceramic.   The three-dimensional modeling set according to claim 8 or 9, wherein a surface of the powder material for three-dimensional modeling is coated with a water-soluble resin.   The three-dimensional modeling set according to claim 10, wherein the water-soluble resin is polyvinyl alcohol.   A three-dimensional modeling set according to any one of claims 8 to 11, further comprising a powder material layer forming means for forming a layer of the three-dimensional modeling powder material, and the three-dimensional modeling powder material layer. An apparatus for producing a three-dimensional structure, comprising a three-dimensional composition liquid supply means for supplying a composition liquid.   The three-dimensional structure manufacturing apparatus according to claim 12, wherein the three-dimensional composition liquid supply means is an ink jet system.   A method for producing a three-dimensional structure, comprising using the three-dimensional structure set according to any one of claims 8 to 11, wherein the three-dimensional structure composition liquid is supplied to the layer of the three-dimensional structure powder material.   The method for producing a three-dimensional structure according to claim 14, wherein a method of supplying the three-dimensional structure composition liquid to the layer of the three-dimensional structure powder material is an ink jet method.