JP2021146669A - Modeling liquid, three-dimensional modeling kit, and method for producing three-dimensional model - Google Patents

Abstract

To provide a method for producing three-dimensional model in which, when removing a powder adhered to a solidified product by using a powder removal liquid, the hardness of the solidified product can be maintained.SOLUTION: Provided is a method for producing three-dimensional model that comprises a solidified product formation step in which a modeling liquid containing an organometallic compound is applied to a powder containing a base material and an organic material to form a solidified product, and a powder removal step in which, by using a powder removal liquid, the powder adhering to the solidified product is removed from the solidified product.SELECTED DRAWING: Figure 1

Description

The present invention relates to a modeling liquid, a three-dimensional modeling kit, and a method for manufacturing a three-dimensional model.

Recently, the applicant of the present application has applied a cross-linking agent to a powder obtained by coating a base material such as metal, glass, or ceramics with a resin as a method for producing a three-dimensional model by a binder jetting method, and after dissolving the coated resin. , Proposes a method for producing a high-strength three-dimensional model in which solidified products are laminated by cross-linking a resin with a cross-linking agent (see, for example, Patent Document 1). In the proposed method for producing a three-dimensional model, excess powder adhering to the solidified material is removed by air blowing.

An object of the present invention is to provide a method for producing a three-dimensional molded product capable of maintaining the hardness of the solidified material when the powder adhering to the solidified material is removed using the powder removing liquid.

In the method for producing a three-dimensional molded product of the present invention as a means for solving the above problems, a molding liquid containing an organic metal compound is applied to a powder containing a base material and an organic material to form a solidified product. The solidification forming step of forming and the powder removing step of removing the powder adhering to the solidified material from the solidified material by using a powder removing liquid are included.

According to the present invention, it is possible to provide a method for producing a three-dimensional molded product capable of maintaining the hardness of the solidified material when the powder adhering to the solidified material is removed using the powder removing liquid.

FIG. 1 is a schematic view showing an example of an apparatus for manufacturing a three-dimensional model used in the method for manufacturing a three-dimensional model of the present invention. FIG. 2A is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus used in the method for manufacturing a three-dimensional model of the present invention. FIG. 2B is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus used in the method for manufacturing a three-dimensional model of the present invention. FIG. 2C is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus used in the method for manufacturing a three-dimensional model of the present invention. FIG. 2D is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus used in the method for manufacturing a three-dimensional model of the present invention. FIG. 2E is a schematic view showing an example of the operation of the three-dimensional model manufacturing apparatus used in the method for manufacturing a three-dimensional model of the present invention. FIG. 3 is a graph showing the results of immersing a three-dimensional model (green body) in which a solidified product is laminated on 1,4-dioxane in Examples and Comparative Examples for 1 hour, taking it out, and measuring the hardness of Type 00 durometer. .. FIG. 4 is a graph showing the results of immersing a three-dimensional model (green body) in which a solidified product is laminated on 1,4-dioxane in Examples and Comparative Examples for 24 hours, taking it out, and measuring the hardness of Type 00 durometer. .. FIG. 5 is an overall external view showing an example of a three-dimensional model (green body) in which solidified materials having a complicated inner tube structure are laminated. FIG. 6 is a transmission diagram showing a complicated inner tube structure inside the green body of FIG. FIG. 7 is a translucent view showing a complex inner tube structure inside the green body of FIG. FIG. 8 is a cross-sectional view of the green body of FIG. 5 in the X direction (No. 1). FIG. 9 is a cross-sectional view of the green body of FIG. 5 in the X direction (No. 2). FIG. 10 is a cross-sectional view of the green body of FIG. 5 in the X direction (No. 3). FIG. 11 is a cross-sectional view of the green body of FIG. 5 in the Z direction.

(Manufacturing method of three-dimensional model)
The method for producing a three-dimensional molded product of the present invention includes a solidification forming step of applying a molding liquid containing an organic metal compound to a powder containing a base material and an organic material to form a solidified material, and a powder. It includes a powder removing step of removing the powder adhering to the solidified material from the solidified material using a removing liquid, and further includes other steps as necessary.

In the present invention, "powder" may also be referred to as "powder material". The "modeling liquid" may also be referred to as a "modeling liquid", a "hardening liquid" or a "reaction liquid". In addition, the "solidified product" may also be referred to as a "cured product". In addition, a three-dimensional model in which solidified products are laminated may be referred to as a "green body", a "sintered body", a "molded body", or a "modeled body". A "green body" that has been heat-treated and degreased is sometimes referred to as a "defatted body". The "green body" and the "defatted body" may be collectively referred to as a "sintered precursor".

In the prior art, it is difficult to remove excess powder that was not used for modeling by air blowing for a solidified product (green body) having a complicated inner tube structure such as a hollow shape with a small inner diameter. , There is a problem that the green body is damaged when the pressure of the air blow is increased.
Further, in the air blow, it is difficult to remove the excess powder remaining in the complicated shape, and there is a problem that the powder cannot be completely removed and remains.

In the present invention, when the cross-linking reaction is carried out using a molding liquid containing an organic metal compound, not only the organic materials but also the organic materials and the metal powder or the metal powder are cross-linked. In particular, in the case of aluminum powder coated with an organic material, not only the organic materials are crosslinked with each other, but also the organic material is not coated (due to being dissolved by a modeling liquid, insufficient coating with the organic material, etc.). Cross-linking between bodies and cross-linking between aluminum powder and organic materials occur. Further, when the base material is a metal such as aluminum powder, since it has an OH group such as Al-OH (aluminol) or a carboxyl group on the surface, it can be effectively crosslinked. Even if it is immersed in a powder removing liquid that dissolves an organic material, excess powder adhering to the solidified material can be removed without deformation of the three-dimensional molded product (green body) in which the solidified material is laminated, which is complicated. A three-dimensional green body can be efficiently manufactured.

(Shaping liquid)
The molding liquid of the present invention forms a solidified product by applying a molding liquid containing an organic metal compound to a powder having a base material and an organic material, and adheres to the solidified material using a powder removing liquid. A molding liquid used for producing a three-dimensional molded product that removes the powder from the solidified product.
The organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.

Since the solidified product formed by using the modeling liquid of the present invention has sufficient strength, the solidified material can be immersed in the removing liquid for a long time, and the excess powder is difficult to remove. It is possible to manufacture even a three-dimensional model of.

<Organometallic compound>
Examples of the organometallic compound include organic titanium compounds and organic zirconia compounds.
Organic metal compounds such as organic titanium compounds and organic zirconia compounds are prone to alcoholism when water, ammonia, alcohol and the like are present as organic solvents. Alcoresis is a decomposition reaction or a compound decomposition reaction caused by an organic solvent molecule acting on a solute molecule of a reactant, and is also referred to as an organic solvent decomposition or an organic solvent decomposition. Except for some organometallic compounds with high water stability, hydrolysis easily proceeds in the presence of water. Therefore, it is usually difficult for the organometallic compound to stably exist in an organic solvent such as water, ammonia, or alcohol.

As a result of diligent studies by the present inventor, at least one of a powder having a resin (organic material) soluble in an organic solvent on the surface of the base material and an organic metal compound (preferably an organic titanium compound and an organic zirconium compound). It was found that the strength of the solidified substance is dramatically improved by using the molding liquid containing). That is, solidification by cross-linking between metals, between metal resins (between metal-organic materials), and between resins (between organic materials) by cross-linking reactions such as ester exchange reaction, acylation, and chelate exchange by adding a trace amount of organic metal compound. It was found that the solvent resistance of the solidified product to the removing liquid is improved by improving the strength of the product.

-Organic titanium compound-
As the organic titanium compound, a compound having an alkoxy group as a functional group and either an ethyl acetoacetate chelate or an acetylacetone chelate as a ligand is preferably used. The alkoxy group causes a cross-linking reaction accompanied by elimination of alcohol such as transesterification reaction and acylation shown in the following formula.

Examples of the organic titanium compound include titanium chelate, titanium acylate, and titanium alkoxide.

Since the titanium chelate reacts with a functional group such as an alkoxy group, a hydroxy group, or a carboxyl group, the presence of the hydroxy group or the carboxyl group on the surface coated with the metal particles or the resin promotes the reaction with the titanium chelate. Can be expected.
Examples of the titanium chelate include titanium diisopropoxybis (acetylacetonate), diisopropoxybis (ethylacetoacetate) titanium, tetrakis (2,4-pentandionato) titanium (IV), and titanium di-2-ethyl. Hexoxybis (2-ethyl-3-hydroxyhexoxide), di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminoto) titanium, titanium-i-propoxyoctylene glyco Examples include rate, titanium stearate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetylacetonate, titanium octylene glycolate, titanium ethylacetacetate, titanium lactate, titanium triethanolaminate and the like.

Examples of titanium acylate include titanium isostearate.

Examples of the titanium alkoxide include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethyl hexoxide and the like.

The organic titanium compounds are not limited to these, and these may be used alone or in combination of two or more.

-Organic zirconium compound-
Examples of the organic zirconia compound include zirconia alkoxide and zirconia chelate.

Examples of the zirconia alkoxide include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium dibutoxybis (ethylacetoacetate) and the like.

Examples of the zirconia chelate include tetrakis (2,4-pentanedionato) zirconium (IV), zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium stearate, and zirconium octylate compound.

The organic zirconia compounds are not limited to these, and these may be used alone or in combination of two or more.

The content of at least one of Ti derived from the organic titanium compound and Zr derived from the organic zirconia compound is preferably 0.1% by mass or more, preferably 0.1% by mass or more and 5% by mass or less, based on the total amount of the modeling liquid. More preferred. When the content is 0.1% by mass or more, the effect of improving the softening of the solidified material when the powder is removed using the powder removing liquid can be obtained.

<Surfactant>
The surfactant is preferably added for the purpose of adjusting the surface tension of the modeling liquid and the like.
Examples of the surfactant include anionic surfactants, nonionic surfactants, amphoteric surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, silicone-based surfactants and the like.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, amber acid ester sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide.
Examples of commercially available nonionic surfactants include the Latemul series (manufactured by Kao Corporation) such as Latemul PD420, 430, 450.
Examples of amphoteric surfactants include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Specific examples of the surfactant are not particularly limited and may be appropriately selected depending on the intended purpose. For example, lauryldimethylamine oxide, myristyldimethylamine oxide, stearyldimethylamine oxide, dihydroxyethyllaurylamine oxide, poly Oxyethylene palm oil alkyldimethylamine oxide, dimethylalkyl (palm) betaine, dimethyllauryl betaine and the like are preferably mentioned.

The acetylene glycol-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3, Acetylene glycol-based products such as 6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexin-3-ol (for example, Surfinol 104, 82, 465 manufactured by Air Products Co., Ltd. (USA)). , 485, TG, etc.) and the like. Of these, Surfinol 465, 104 and TG are preferred.

The fluorosurfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl. Examples thereof include ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compound, polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain or a sulfate ester salt thereof, and a fluorine-based aliphatic polymer ester.
Commercially available products can be used as the fluorine-based surfactant, and examples of the commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, and S-141. , S-145 (manufactured by Asahi Glass Co., Ltd.), Flurad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (Sumitomo 3M) FT-110, 250, 251 and 400S (manufactured by Neos), Zonir FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN-N, FSN-100 , FS-300, FSK (manufactured by DuPont), Polyfox PF-136A, PF-156A, PF-151N (manufactured by OMNOVA), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like.

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, BYK-345, BYK-346, BYK-347, BYK-348 (manufactured by Big Chemie Japan Co., Ltd.) and the like. Can be mentioned.

The surfactant is not limited to these, and these may be used alone or in combination of two or more.

The content of the surfactant is preferably 0.01% by mass or more and 5% by mass or less with respect to the total amount of the modeling liquid from the viewpoint of exerting the effect of penetrating the powder into the organic material. When the content of the surfactant is 0.01% by mass or more, the effect of imparting wettability is sufficient, and the effect of improving the sufficient permeability of the powder into the organic material can be obtained. Further, when the content of the surfactant is 5% by mass or less, the storage stability is good.

<Organic solvent>
The organic solvent is a liquid component for making the modeling liquid in a liquid state at room temperature.
The organic solvent is not particularly limited as long as it has a vapor pressure of 2,000 Pa or less at 25 ° C. and is insoluble or slightly soluble in water, and can be appropriately selected depending on the intended purpose.
When the organic solvent has a vapor pressure of 2,000 Pa or less at 25 ° C., the ejection stability can be improved by suppressing the nozzle from drying when the apparatus is not operating (standby). ..
Here, being insoluble or slightly soluble in water means that the solubility in water is 80 g / L or less.

Examples of the organic solvent include aliphatic hydrocarbons such as n-octane, m-xylene and solventnaphtha, aromatic hydrocarbons, diisobutyl ketones, ketones such as 3-heptanone and 2-octanone, butyl acetate and amyl acetate. N-hexyl acetate, n-octyl acetate, ethyl butyrate, ethyl valerate, ethyl caprylate, ethyl octylate, ethyl acetoacetate, ethyl 3-ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl succinate, adipic acid Esters such as diethyl, bis2-ethylhexyl maleate, triacetin, tributyrin, ethylene glycol monobutyl ether acetate, ethers such as dibutyl ether, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, dimethylsulfoxide, dihydroterpinyl acetate And so on. These may be used alone or in combination of two or more.
Even compounds not described here are not particularly limited as long as they have a vapor pressure of 2,000 Pa or less at 25 ° C. and are insoluble or slightly soluble in water, and may be appropriately selected according to the purpose. Can be done.

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

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, antidrying agents, viscosity regulators, penetrants, antifoaming agents, pH regulators, preservatives, fungicides, etc. Colorants, preservatives, stabilizers and the like can be mentioned.

-Physical characteristics of modeling liquid, etc.-
The viscosity of the modeling liquid is preferably 3 mPa · s or more and 20 mPa · s or less at 25 ° C., and more preferably 5 mPa · s or more and 10 mPa · s or less. When the viscosity is 3 mPa · s or more or 20 mPa · s or less, the ejection from the inkjet nozzle is stabilized, and the strength of the solidified material formed by applying the molding liquid to the powder (layer) can be sufficiently obtained. , The dimensional accuracy is good.
The viscosity of the molding liquid can be measured according to, for example, JIS K7117.

The surface tension of the modeling liquid is preferably 40 N / m or less, more preferably 10 N / m or more and 30 N / m or less at 25 ° C. When the surface tension is 40 N / m or less, the ejection from the inkjet nozzle is stabilized, the strength of the solidified material formed by applying the molding liquid to the powder (layer) is sufficiently obtained, and the dimensional accuracy is good. be.
The surface tension of the modeling liquid can be measured by, for example, DY-300 manufactured by Kyowa Interface Science Co., Ltd.

The modeling liquid of the present invention can be suitably used for simple and efficient production of various three-dimensional objects, and is used in the three-dimensional modeling kit of the present invention and the method for producing the three-dimensional object of the present invention described below. It can be used particularly preferably.

(Three-dimensional modeling kit)
The three-dimensional modeling kit of the present invention has a powder, a modeling liquid, and a powder removing liquid.

<Shaping liquid>
As the modeling liquid, the modeling liquid of the present invention containing an organometallic compound can be used by solidifying the powder to form a solidified product.
The organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.

<Powder remover>
The powder removing liquid contains an organic solvent and, if necessary, other components.
The organic solvent is not particularly limited as long as it is an organic solvent that does not dissolve the solidified product and dissolves the organic material in the powder, and can be appropriately selected depending on the intended purpose. Ketone, halogen, alcohol, ester, ether. , Hydrocarbons, glycols, glycol ethers, glycol esters, pyrrolidones, amides, amines and at least one selected from carbonate esters can be used.

Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, acetophenone, and diacetone alcohol.
Examples of the halogen include methylene chloride, trichlorethylene, perchloroethylene, HCFC141-b, HCFC-225, 1-bromopropane, chloroform, orthodichlorobenzene and the like.
Examples of alcohols include methanol, ethanol, butanol, isobutanol, isopropyl alcohol, normal propyl alcohol, tertiary butanol, secondary butanol, 1,3-butanediol, 1,4-butanediol, 2-ethylhexanol, and benzyl alcohol. And so on.
Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, sec butyl acetate, methoxybutyl acetate, 3-methoxybutyl acetate, 3-methoxy-3 methylbutyl acetate, ethyl-3-ethoxypropionate, and the like. Amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, ethyl 3-ethoxypropionate, dibasic acid ester (DBE), etc. Be done.
Examples of ethers include dimethyl ether, ethyl methyl ether, diethyl ether, ethylene oxide, tetrahydrofuran, furan, benzofuran, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1,4-dioxane, methyl tert-butyl ether (MTBE), and ethylene glycol. Examples thereof include dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol monomethyl ether.
Hydrocarbons include, for example, benzene, toluene, xylene, solventnaphtha, normal hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, cyclohexene, cycloheptane, cyclopentane, heptane, pentamethylbenzene, pentane, methylcyclopentane, normal. Examples thereof include heptane, isooctane, normal decane, normal pentane, isopentane, mineral spirit, dimethylsulfoxide, linear alkylbenzene and the like.
Examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dimethoxytetraethylene glycol and the like.
Examples of the glycol ester include ethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
Examples of the glycol ether include methyl carbitol, ethyl carbitol, butyl carbitol, methyl triglycol and the like.
Examples of pyrrolidone include 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and the like.
Examples of the amide include dimethylformamide, dimethylacetamide, formamide and the like.
Examples of amines include tetramethylethylenediamine, N, N-diisopropylethylamine, ethylenediamine, triethylamine, diethylamine, aniline, pyrrolidine, piperidine, morpholine, pyrrol, pyridine, pyridazine, oxazole, thiazole, 1,3-dimethyl-2-imidazole. Riginon and the like can be mentioned.
Examples of the carbonic acid ester include diethyl carbonate, dimethyl carbonate, propylene carbonate, ethyl methyl carbonate and the like.
Even compounds not described in these are not particularly limited as long as they have a vapor pressure of 2,000 Pa or less at 25 ° C. and are insoluble or slightly soluble in water, and are appropriately selected according to the purpose. Can be done. Only one of these may be used, or two or more thereof may be used in combination.

As other components, additives such as a surfactant, an antifoaming agent, an antiseptic and antifungal agent, a pH adjuster, a chelating agent, and a rust preventive can be added, if necessary.

<Powder>
The powder contains a base material and an organic material.

-Base material-
The base material is not particularly limited as long as it has the form of powder or particles, and can be appropriately selected depending on the intended purpose. The material thereof is, for example, metal, ceramics, carbon, polymer, wood, or biocompatible material. , Sand, magnetic materials, etc., but from the viewpoint of obtaining an extremely high-strength three-dimensional molded product, metals, ceramics, etc. that can be finally sintered (processed) are preferable.

The metal is not particularly limited as long as it contains a metal as a material, and for example, magnesium (Mg), aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), manganese ( Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), lead ( Examples thereof include Pd), silver (Ag), indium (In), tin (Sn), tantalum (Ta), tungsten (W), neodymium (Nd), or alloys thereof. Among these, stainless steel (SUS) steel, iron (Fe), copper (Cu), silver (Ag), titanium (Ti), aluminum (Al), alloys thereof and the like are preferably used. As the aluminum alloy, for _{example, AlSi 10 Mg, AlSi 12,} AlSi 7 Mg 0.6, AlSi 3 Mg, AlSi 9 Cu 3, Scalmalloy, ADC1 2 and the like. These may be used alone or in combination of two or more.

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

As the base material, a commercially available product can be used. Examples of commercially available products include pure Al (manufactured by Toyo Aluminum Co., Ltd., A1070-30BB), pure Ti (manufactured by Osaka Titanium Technologies), SUS316L (manufactured by Sanyo Special Steel Co., Ltd., trade name: PSS316L); AlSI10Mg (Toyo Aluminum). Si10MgBB manufactured by Co., Ltd.); SiO ₂ (manufactured by Tokuyama Corporation, product name: Excelica SE-15K), AlO ₂ (manufactured by Taimei Chemicals Co., Ltd., product name: Tymicron TM-5D), ZrO ₂ (Tosoh Corporation) Manufactured, trade name: TZ-B53) and the like.
The base material may be subjected to a known surface treatment (surface modification treatment) for the purpose of improving the adhesiveness with the organic material (resin) and the coating property.

The volume average particle diameter of the base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 2 μm or more and 100 μm or less, and more preferably 8 μm or more and 50 μm or less.
When the volume average particle size of the base material is 2 μm or more, it is possible to prevent the influence of agglutination from increasing, and it becomes easy to coat the base material with an organic material, resulting in a decrease in yield and a decrease in manufacturing efficiency of a modeled product. It is possible to prevent deterioration of the handleability and handleability of the material. Further, when the average particle size is 100 μm or less, it is possible to prevent a decrease in contact points between particles and an increase in voids, and it is possible to prevent a decrease in the strength of the three-dimensional model and its sintered body.
The particle size distribution of the base material is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferable that the particle size distribution is sharper.
The volume average particle size and particle size distribution of the base material can be measured using a known particle size measuring device, and examples thereof include a particle size distribution measuring device Microtrac MT3000II series (manufactured by Microtrac Bell).

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

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

-Organic material-
As an organic material, it has a reactive functional group, dissolves in a modeling solution, reacts with an organic metal compound (preferably at least one of an organic titanium compound and an organic zirconia compound) contained in the modeling solution, and crosslinks by a covalent bond. Anything that can form a structure will do.
Soluble (soluble) of an organic material means that, for example, when 1 g of an organic material is mixed with 100 g of a solvent constituting a modeling solution at 30 ° C. and stirred, 90% by mass or more of the organic material is dissolved. ..
As an organic material, it has low reactivity with highly active metal (highly active metal) powder as a base material, and the organic material before molding (before solidification) can be dissolved in the powder removing liquid, and after molding (before solidification). It is preferable that the organic material (after solidification and cross-linking) does not dissolve in the powder removing solution (it does not soften even when immersed in the powder removing solution). In particular, it is more preferable that it is soluble in a powder removing solution having low solubility in water.
By coating the surface of the base material with the organic material, it is possible to suppress a dust explosion that occurs when the size of the base material particles is small. Further, the organic material has low reactivity with a metal (active metal) powder having high activity as a base material, and the organic material before the addition of the molding liquid is soluble (soluble) in the powder removing liquid, and the molding is performed. If the organic material after liquid application (after cross-linking) does not dissolve in the powder removal liquid (does not soften even when immersed in the powder removal liquid), the base material is a highly active metal, that is, a water-prohibited material (for example, It can be applied even if it is (aluminum, titanium, etc.), and it is possible to prevent the produced solidified product (three-dimensional molded product) from collapsing even when immersed in a solvent-based solution.

The reactive functional group is not particularly limited as long as it can react with at least one of an organic titanium compound and an organic zirconia compound to form a covalent bond, and can be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, an amide group, a phosphoric acid group, a thiol group, an acetoacetyl group, and an ether bond.
Among these, it is preferable that the organic material has a hydroxyl group in terms of improving the adhesion to the base material and the reactivity with at least one of the organic titanium compound and the organic zirconia compound.

Furthermore, 95% by mass or more of the organic material is thermally decomposed when the organic material alone is heated at 450 ° C. so that the organic material does not remain in the solidified substance during sintering and cause sintering inhibition. It is preferable that it is one.

As the organic material, a resin having a hydroxyl group is preferable. Examples of the resin include polyvinyl acetal (glass transition temperature: 107 ° C.), polyvinyl butyral (glass transition temperature: 67 ° C.), polyacrylic polyol (glass transition temperature: 80 ° C.), polyester polyol (glass transition temperature: 133 ° C.), and the like. Examples thereof include polybutadiene polyol (glass transition temperature: −17 ° C.), ethyl cellulose (glass transition temperature: 145 ° C.), nitrocellulose (glass transition temperature: 50 ° C.), and the like. In addition, a partially saponified product of a vinyl acetate copolymer (vinyl chloride-vinyl acetate, ethylene-vinyl acetate, etc.), a polyether polyol, a phenol-based polyol, and the like can be mentioned. These may be used alone or in combination of two or more. Among these, polyvinyl acetal is preferable.

The glass transition temperature of an organic material refers to the glass transition temperature of a solidified product of a homopolymer of an organic material, where the glass transition temperature (Tg) is adopted if there is a catalog value of the resin manufacturer. However, if it does not exist, it is a value measured as follows by the differential scanning calorimetry (DSC) method.

-Glass transition temperature (Tg) measurement method-
The polymerization of the polymerizable monomer can be carried out by a general solution polymerization method.
A: Toluene solution of 10% by mass of polymerizable monomer B: 5% by mass of azobisisobutyronitrile as a polymerization initiator
A and B are purged with nitrogen, sealed in a test tube, and shaken in a warm bath at 60 ° C. for 6 hours to synthesize a polymer. The polymer is then reprecipitated in a solvent in which the polymerizable monomer is soluble and the polymer is insoluble (eg, methanol, petroleum ether, etc.) and filtered to remove the polymer. The obtained polymer is DSC-measured. As the DSC device, a DSC120U manufactured by Seiko Instruments Inc. is used, and the measurement temperature is 30 ° C. to 300 ° C., and the temperature rise rate is 2.5 ° C. per minute.

Among the organic materials, those having a large number of hydroxyl groups in the molecule rather than at the end of the molecule, and having a weight average molecular weight and a hydroxyl value of a certain value or more are preferable.
The weight average molecular weight is preferably 100,000 or less, more preferably 2,000 or more and 100,000 or less, and the weight average molecular weight is preferably 100,000 or less and is a solid at room temperature.
The hydroxyl value is preferably 50 mgKOH / g or more, and more preferably 100 mgKOH / g or more.

The resin as an organic material may be a commercially available product. Examples of commercially available products include polyacrylic polyols (DIC, Acrydic WFU-580, etc.) and polyester polyols (DIC, Polylite OD-X-668, etc., ADEKA, ADEKA New Ace YG-108, etc.). , Polybutadiene polyol (manufactured by Nippon Soda, GQ-1000, etc.), polyvinyl butyral (manufactured by Kuraray, Mobital B20H, etc.), polyvinyl acetal (manufactured by Sekisui Chemical Co., Ltd., Eslek BM-2, KS-1, etc.), ethyl cellulose (Japan) Evolution Co., Ltd., ETHOCEL, etc.), polyacryl (Kyoei Kagaku Co., Ltd., Oricox KC-3000, etc.) and the like can be mentioned.

The powder is preferably one in which the surface of the base material is coated with an organic material.
The average thickness of the base material coated with the organic material is preferably 5 nm or more and 1,000 nm or less, more preferably 5 nm or more and 500 nm or less, further preferably 50 nm or more and 300 nm or less, and particularly preferably 100 nm or more and 200 nm or less.
In the present invention, since the cross-linking reaction by at least one of the organic titanium compound and the organic zirconia compound is utilized, the coating thickness can be made smaller than that of the conventional one, and both strength and accuracy can be achieved even in a thin film. ..
When the average thickness as the coating thickness is 5 nm or more, the strength of the solidified material formed by applying the molding liquid to the powder is improved, and the mold is used during the subsequent processing or handling such as sintering. When it is 1,000 nm or less, which does not cause problems such as collapse, the dimensional accuracy of the solidified material formed by applying the molding liquid to the powder is improved.
The average thickness is, for example, after embedding powder in acrylic resin or the like and then performing etching or the like to expose the surface of the base material, and then scanning tunneling microscope STM, atomic force microscope AFM, scanning electron microscope SEM. It can be obtained by measuring the thickness of any 10 points and calculating the average value thereof.

The ratio of the organic material to the surface area of the base material (surface coverage) is not particularly limited as long as it covers the surface area of the base material to the extent that the effects of the present invention can be exhibited. For example, 15% or more is preferable, 50% or more is more preferable, and 80% or more is particularly preferable.
When the surface coverage is 15% or more, the strength of the solidified material formed by applying the molding liquid to the powder is sufficiently obtained, and the mold is obtained during the subsequent processing or handling such as sintering. Problems such as collapse do not occur, and the dimensional accuracy of the solidified material formed by applying the molding liquid to the powder is improved.
The surface coverage was determined, for example, by observing a photograph of the powder and coating the powder in the two-dimensional photograph with an organic material for any 10 particles with respect to the entire surface area of the particles of the powder. The ratio (%) of the area of the portion may be measured, the average value thereof may be calculated and used as the surface coverage ratio, or the portion coated with the organic material may be subjected to energy dispersion type X-ray spectroscopy such as SEM-EDS. It can be measured by performing element mapping by the method.

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

-Powder manufacturing method-
The method for producing the powder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of coating an organic material on a substrate according to a known coating method is preferable.
The method for coating the surface of the base material of the organic material is not particularly limited, and a known coating method can be appropriately adopted. Examples of such a coating method include a rolling flow coating method and a spray-drying method. , Stirring and mixing addition method, dipping method, kneader coating method, and the like are preferable. Further, these coating methods can be carried out by using various known commercially available coating devices, granulating devices and the like.

-Physical characteristics of powder, etc.-
The volume average particle size of the powder is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 250 μm or less, more preferably 3 μm or more and 200 μm or less, and further preferably 5 μm or more and 150 μm or less. It is particularly preferably 10 μm or more and 85 μm or less.
When the volume average particle size is 3 μm or more, the fluidity of the powder is improved, the powder (layer) is easily formed, and the smoothness of the laminated layer surface is improved. There is a tendency for dimensional accuracy to improve as well as for improved handling and handleability. Further, when the volume average particle diameter is 250 μm or less, the size of the space between the powder particles becomes small, so that the porosity of the three-dimensional object becomes small, which contributes to the improvement of the strength. Therefore, it is preferable that the volume average particle size is 3 μm or more and 250 μm or less in order to achieve both dimensional accuracy and strength.
The particle size distribution of the powder is not particularly limited and may be appropriately selected depending on the intended purpose.

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

The powder can be suitably used for simple and efficient production of various three-dimensional objects and structures, and the three-dimensional modeling kit of the present invention, the method for producing the three-dimensional object of the present invention, and the three-dimensional object. It can be particularly preferably used in a manufacturing apparatus.
By simply applying the modeling liquid of the present invention to the powder, a solidified product having a complicated three-dimensional shape can be produced easily, efficiently and with high dimensional accuracy. The solidified product thus obtained is a green body (sintered precursor) having sufficient hardness, and can be held by hand, put in and taken out of a mold, or air blown to remove excess powder. However, it does not lose its shape and is excellent in handleability and handleability. The solidified product may be used as it is, or may be further sintered as a green body to obtain a molded product (sintered body of a three-dimensional model).

(Manufacturing method of three-dimensional model)
The method for producing a three-dimensional model of the present invention includes a solidification forming step and a powder removing step, and further includes other steps as necessary.

<solidification process>
The solidification forming step is a step of applying a molding liquid to a powder having a base material and an organic material and binding the powder particles in a predetermined region of the powder to form a solidification.

The powder having the base material and the organic material is a powder that coats the surface of the base material with the organic material, and the molding liquid is an organic metal compound (preferably at least one of an organic titanium compound and an organic zirconia compound). ..
Since the organic material that coats the base material can be dissolved and crosslinked by the action of the modeling liquid, when the modeling liquid is applied to the organic material, the organic material dissolves and the organic metal compound contained in the modeling liquid Crosslink by action. Therefore, when a thin layer is formed using powder and a modeling liquid is allowed to act on the thin layer, the thin layer solidifies.

-Formation of powder layer-
The method of arranging the powder on the support (modeling stage) to form the powder layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a method of arranging the powder in a thin layer. , A method using a known counter rotation mechanism (flattening roller) or the like used in the selective laser sintering method described in Japanese Patent No. 3607300, and a thin layer of powder using a member such as a brush, a roller, or a blade. A method of spreading the powder in a thin layer by pressing the surface of the powder with a pressing member, a method of using a known powder laminating molding device, and the like are preferably mentioned.

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

When the molding liquid is allowed to act on the powder placed on the thin layer in this way, the layer is solidified (solidification step).
On the solidified material of the thin layer obtained here, the powder is placed on the thin layer in the same manner as described above, and the modeling liquid is allowed to act on the powder (layer) placed on the thin layer. , Solidification of powder occurs. The solidification at this time occurs not only in the powder (layer) placed on the thin layer, but also in the solidified material of the thin layer previously solidified and existing under the powder (layer). As a result, a solidified material having a thickness equivalent to about two layers of the powder (layer) placed on the thin layer can be obtained.

Further, in order to place the powder on the support in a thin layer, it can be automatically and easily performed by using a known three-dimensional model manufacturing apparatus. Generally, a device for manufacturing a three-dimensional object has a recorder (flattening roller) for laminating powder, a movable supply tank for supplying powder on a support, and a thin layer of powder. It is equipped with a movable modeling tank for laminating. In the powder laminating molding apparatus, the surface of the supply tank can always be slightly raised above the surface of the modeling tank by raising the supply tank, lowering the modeling tank, or both, and the supply tank side. The powder can be arranged in a thin layer using a recorder, and the thin layer powder can be laminated by repeatedly moving the recorder.

The thickness of the powder layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the average thickness per layer is preferably 30 μm or more and 500 μm or less, and more preferably 60 μm or more and 300 μm or less.
When the average thickness is 30 μm or more, the strength of the solidified material (sintering precursor) formed by applying the molding liquid to the powder to form the powder (layer) is sufficient, and the subsequent treatment such as sintering or the like is performed. When the size is 500 μm or less, which does not cause problems such as shape loss during handling, the dimensional accuracy of the solidified material formed by applying the molding liquid to the powder is improved.
The average thickness is not particularly limited and can be measured according to a known method.

The method for imparting a molding liquid containing a cross-linking agent capable of forming a covalent bond with a reactive functional group to the powder (layer) is not particularly limited and may be appropriately selected depending on the intended purpose, for example. Examples include a dispenser method, a spray method, and an inkjet method. In order to carry out these methods, a known device can be suitably used as a solidification forming means.
Among these, the dispenser method is excellent in the quantitativeness of droplets, but the coating area is narrow, and the spray method is able to easily form fine discharges, has a wide coating area, and is excellent in coating properties, but the droplets. The quantitativeness is poor, and powder is scattered due to the spray flow. Therefore, in the present invention, the inkjet method is particularly preferable. The inkjet method has the advantages of better quantification of droplets than the spray method, a wider coating area than the dispenser method, and is preferable in that a complicated three-dimensional shape can be formed accurately and efficiently.

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

<Powder removal process>
The powder removing step is a step of removing the powder adhering to the solidified material from the solidified material using a powder removing liquid. By using a powder removing solution that does not dissolve (do not soften) the solidified material and dissolves the organic material in the powder, excess powder adhering to the surface or inside of the solidified material can be removed.
That is, by immersing the solidified material in the powder removing liquid, the molding liquid is applied to the powder and the solidified molding portion is not dissolved (softened), and the molding liquid is applied to the powder. It is possible to dissolve the non-molded portion, which is a region that has not been formed.

The three-dimensional model (green body) in which the solidified material is laminated exists in a state of being buried in a non-modeled portion (unsolidified powder) to which a modeling liquid is not applied. When the green body is taken out from this buried state, excess (unsolidified) powder adheres to the surface and the inside of the structure of the green body around the green body, and it is difficult to easily remove the green body. It is even more difficult when the surface of the green body is complicated or the inside is like a flow path. In a general binder jetting method, the strength of the green body is not high, so if the air blow pressure is high (0.3 MPa or more), the green body may collapse.
The three-dimensional model (green body) in which the powder and the solidified product formed by the modeling liquid used in the present invention are laminated is coated with a compound contained in the modeling liquid capable of expressing a reactive group by heating. As the organic material dissolves and solidifies more, it has the strength to withstand the pressure of air blow.
At this time, the strength of the solidified product is preferably 3 MPa or more, more preferably 5 MPa or more in terms of the three-point bending stress.

In addition to improving the strength, the solidified organic material does not dissolve (does not soften) with respect to the powder removing liquid that can dissolve the organic material that coats the base material, and the unsolidified organic material becomes powder. Since it dissolves in the body removing liquid, excess powder adhering to the surface and inside of the green body can be easily removed by immersing it in the powder removing liquid.
In particular, in order to form a green body having a complicated inner tube structure as shown in FIGS. 5 to 11, it is necessary to be able to easily and surely remove excess powder inside the green body, and only air blow. Then, the air does not reach the inside and it is difficult to remove it.

The volume of the powder removing liquid with respect to the green body is not particularly limited and may be appropriately selected depending on the intended purpose.
Further, if the green body is softened by immersing it in the powder removing liquid, it is not possible to obtain a modeled object according to the modeling data due to crushing of the thin tube shape or the thin wall shape.
The type 00 durometer hardness after immersing the green body in the powder removing liquid (organic solvent) for 1 hour is preferably 80 or more, more preferably 90 or more, and further preferably 95 or more and 100 or less. If the type 00 durometer hardness is 90 or more, the shape does not collapse regardless of the shape.
A test piece having the same size as the JIS K 7139 type A2 test piece was molded, the organic solvent component in the molding liquid was dried, and the obtained green body test piece was immersed in the powder removing liquid on the entire surface. Leave it in a container tightly closed at 25 ° C. for 1 hour under atmospheric pressure, then remove it from the container, wipe off the powder removing liquid adhering to the surface, and statically stand directly on an A5052 plate with a plate thickness of 5 mm. Within 30 seconds after placing and taking out, an ASTM D 2240 compliant Type 00 durometer is manually pressed to bring the pressurized surface into close contact for measurement at 25 ° C. and atmospheric pressure.

The immersion time is preferably 1 hour to 3 hours.
The immersion temperature is preferably room temperature to 50 ° C.
Examples of the immersion method include standing, ultrasonic irradiation, stirring, and stirring after standing.

-Powder container-
The powder accommodating portion is a member accommodating powder, and its size, shape, material, etc. are not particularly limited and may be appropriately selected according to the purpose. For example, a storage tank, a bag, a cartridge, etc. , Tanks, etc.

-Modeling liquid storage unit-
The modeling liquid storage unit is a member that stores the modeling liquid, and its size, shape, material, and the like are not particularly limited and can be appropriately selected according to the purpose. For example, a storage tank, a bag, and a cartridge. , Tanks, etc.

<Other processes and other means>
Examples of other steps include a sintering step, a surface protection treatment step, a coating step, and the like.
Other means include, for example, sintering means, surface protection treatment means, coating means, and the like.

The drying step is a step of drying a three-dimensional model (green body) in which the solidified products obtained in the solidified product forming step are laminated. In the drying step, not only the water contained in the green body but also organic substances may be removed (defatted). Examples of the drying means include a known dryer, a constant temperature and humidity chamber, and the like.

The sintering step is a step of sintering a three-dimensional model (green body) in which the solidified products formed in the solidified product forming step are laminated. By performing the sintering step, the green body can be made into a densified and integrated metal or ceramic molded product (sintered body of a three-dimensional model). Examples of the sintering means include a known sintering furnace.

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

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

The mass of the organic material contained in the sintered body after the sintering step is 5% by mass or less of the mass of the organic material contained in the green body before the powder removing step.

Here, an embodiment of the method for manufacturing a three-dimensional model and the apparatus for manufacturing a three-dimensional model of the present invention will be described with reference to FIG. In addition, FIG. 1 shows one time point at the time of modeling.

The three-dimensional object manufacturing apparatus of FIG. 1 has a supply tank 21, a modeling tank 22, and a surplus powder receiving tank 29, and the supply tank 21 and the modeling tank 22 have a supply stage 23 and a modeling tank that can be moved up and down, respectively. It has a stage 24. The powder 20 for three-dimensional modeling is placed on the modeling stage 24 provided in the modeling tank 22, and the powder layer 31 made of the powder 20 is formed.

On the supply tank 21 and the modeling tank 22, the powder 20 is supplied from the supply tank 21 to the modeling tank 22, and the surface of the powder 20 in the modeling tank 22 is leveled to form a flattening powder layer 31. A roller 12 is provided. The flattening roller 12 is provided with a powder removing plate 13 which is a powder removing member for removing the powder 20 adhering to the flattening roller 12 in contact with the peripheral surface of the flattening roller 12. .. Of the powder 20 transferred and supplied by the flattening roller 12, the surplus powder 20 not used for forming the powder layer 31 falls into the surplus powder receiving tank 29.

An inkjet head 52 that discharges the modeling liquid 10 toward the powder 20 of the modeling tank 22 is provided on the modeling tank 22. Droplets are ejected from the inkjet head 52 to the powder layer 31 spread in layers in the modeling tank 22, and the modeling layer 30 is formed.
At this time, the position where the modeling liquid 10 is dropped is determined by the two-dimensional image data (slice data) obtained by slicing the three-dimensional shape to be finally modeled into a plurality of plane layers.
After the drawing for one layer is completed, the supply stage 23 of the supply tank 21 is raised, and the modeling stage 24 of the modeling tank 22 is lowered. The difference powder is moved to the modeling tank 22 by the flattening roller 12.

In this way, a new powder layer is further formed on the surface of the powder layer drawn earlier. The thickness of the powder layer layer at this time is about several tens of μm or more and 100 μm or less.
Drawing based on the slice data of the second layer is further performed on the newly formed powder layer, and this series of processes is repeated to obtain a solidified product (green body) having a three-dimensional shape.

Next, the flow of modeling in the method for manufacturing a three-dimensional model of the present invention will be described with reference to FIGS. 2A to 2E.
2A to 2E are schematic explanatory views for explaining the flow of modeling. Here, the state in which the first modeling layer 30 is formed on the modeling stage 24 of the modeling tank 22 will be described. When the next modeling layer is formed on the first modeling layer 30, the supply stage 23 of the supply tank 21 is raised and the modeling stage 24 of the modeling tank 22 is lowered, as shown in FIG. 2A.
At this time, the modeling stage 24 is lowered so that the distance (stacking pitch) between the upper surface of the surface (powder surface) of the powder layer 31 in the modeling tank 22 and the lower portion (lower tangential portion) of the flattening roller 12 is Δt1. Set the distance. The interval Δt1 is not particularly limited, but is preferably about several tens to 100 μm.

Next, as shown in FIG. 2B, the powder 20 located above the upper surface level of the supply tank 21 is moved to the modeling tank 22 side while rotating the flattening roller 12 in the opposite direction (arrow direction). , The powder 20 is transferred and supplied to the modeling tank 22 (powder supply).

Further, as shown in FIG. 2C, the flattening roller 12 is moved in parallel with the stage surface of the modeling stage 24 of the modeling tank 22, and the powder layer 31 having a predetermined thickness Δt1 on the modeling tank 22 of the modeling stage 24. Form (flattening). At this time, the surplus powder 20 not used for forming the powder layer 31 falls into the surplus powder receiving tank 29.
After forming the powder layer 31, the flattening roller 12 is moved to the supply tank 21 side and returned (returned) to the initial position (origin position) as shown in FIG. 2D.

After that, as shown in FIG. 2E, droplets 10 of the modeling liquid are ejected from the head 52 of the liquid discharge unit 50, and the modeling layer 30 having a desired shape is laminated on the next powder layer 31.

Next, the powder layer formation and the molding liquid discharge described above are repeated to form a new molding layer 30. At this time, the new modeling layer 30 and the underlying modeling layer 30 are integrated to form a part of the solidified product. After that, the formation of the powder layer and the discharge of the molding liquid are repeated to complete the molding of the solidified product (green body).

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

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

(Powder preparation example)
<Preparation of powder>
-Preparation of coating liquid 1-
As an organic material, 6 parts by mass of a polyacrylic polyol resin (manufactured by Toei Kasei Co., Ltd., 9515) having a hydroxyl value of 180 mgKOH / g is mixed with 114 parts by mass of acetone, and while heating at 50 ° C. in a water bath, a three-one motor (three-one motor) Using BL600) manufactured by Shinto Kagaku Co., Ltd., the mixture was stirred for 1 hour to dissolve the polyacrylic polyol resin in an organic solvent (acetone) to prepare 120 parts by mass of a 5% by mass polyacrylic polyol resin solution. The preparation liquid thus obtained was designated as a coating liquid 1.
The viscosity of a 5% by mass (w / w%) solution of the polyacrylic polyol resin at 25 ° C. was measured using a viscometer (Rotary viscometer manufactured by Brookfield, DV-E VISCOMETER HADVE115 type). It was 0 mPa · s to 4.0 mPa · s.

-Coating of coating liquid 1 on the surface of the substrate-
Next, using a commercially available coating device (Paurek Co., Ltd., MP-01), _{100 parts by mass of AlSi 10} Mg powder (manufactured by Toyo Aluminum Co., Ltd., Si ₁₀ Mg-30BB, volume average particle size 35 μm) was used as a base material. On the other hand, the coating liquid 1 was coated so that the coating thickness (average thickness) was 300 μm. In this coating, sampling was performed at any time during the process, and the coating time and interval were appropriately adjusted so that the coating thickness (average thickness) of the coating liquid 1 was 300 μm and the surface coverage (%) was 85%.
After the coating is completed, acrylic resin fine particles (MP1451 manufactured by Soken Chemical Co., Ltd.) are added to the surface of the coating film so that the surface coverage is 20%, and a mixing device (Symmal Enterprises Co., Ltd., DYNO) is added. -MILL) was used for mixing at 100 rpm for 5 minutes to obtain powder 1. The method for measuring the coating thickness of the coating film, the surface coverage of the coating film, and the coating conditions are shown below. Before mixing the resin fine particles, the coating thickness of the coating film and the surface coverage of the coating film were measured.

<Coating film thickness (average thickness>
For the coating thickness (average thickness), the surface of the powder 1 was polished with emery paper, and then the surface was lightly polished with a cloth containing toluene to dissolve the water-soluble resin portion, and an observation sample was prepared. Next, the boundary portion between the base material portion and the organic soluble resin portion exposed on the surface was observed with a field emission scanning electron microscope (FE-SEM), and the boundary portion was measured as the coating thickness. The average value of 10 measurement points was obtained and used as the coating thickness (average thickness).

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

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

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

(Example 1)
<Preparation of modeling liquid>
The materials shown in Table 1 were prepared and stirred with a magnetic stirrer for 30 minutes to prepare the modeling liquid 1 of Example 1. The content of each material in Table 1 indicates mass%.
Next, the viscosity of the obtained modeling liquid was measured as follows. The results are shown in Table 1.

<Viscosity of modeling liquid>
The viscosity of the modeling liquid was measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

<Three-dimensional modeling (manufacturing of green body)>
Using the obtained powder 1 and the molding liquid 1, a solidified product (green body) was produced as follows by a shape printing pattern of a size (length 70 mm × width 12 mm).

1) First, the powder 1 is transferred from the supply tank to the modeling tank using the three-dimensional model manufacturing apparatus as shown in FIG. 1, and a thin layer of the powder 1 having an average thickness of 100 μm is formed on the modeling stage. bottom.

2) Next, the modeling liquid 1 is applied (discharged) to the surface of the thin layer formed by the powder 1 from a nozzle of a known inkjet discharge head, and the polyacrylic polyol resin is dissolved in diethyl succinate contained in the modeling liquid. By the action of titanium diisopropoxybis (acetylacetate) as a cross-linking agent contained in the modeling liquid 1, 20% of all the hydroxyl groups of the polyacrylic polyol resin were cross-linked.

3) Next, the operations of 1) and 2) are repeated until the total average thickness of 5 mm is reached, and thin layers of the solidified powder 1 are sequentially laminated, and 4 at 50 ° C. using a dryer. After a period of time, a drying step of 100 ° C. for 2 hours was carried out to obtain a solidified product (green body).

4) After removing excess powder 1 from the dried solidified material (green body) by air blowing, it is immersed in a powder removing liquid (acetone) at 25 ° C. for 1 hour under atmospheric pressure. , It was left in a tightly closed state in the container. Then, it was taken out from a container and dried under vacuum at 100 ° C. for 2 hours.

Next, various properties of the obtained solidified product (green body) were evaluated as follows. The results are shown in Table 1.

<Bending strength of green body>
The solidified product (green body) taken out from the modeling tank after the three-dimensional modeling was heated to volatilize the modeling liquid and harden it. The bending strength of the solidified material (green body) was measured before and after immersion in the powder removing liquid. The solidified material (green body) immersed in the powder removing liquid was used for the measurement after the powder removing liquid was completely removed by heating or drying under reduced pressure. The solidified material before immersion in the powder removing liquid was used for measurement by removing excess powder with a spatula or the like. For the measurement, the bending strength of the obtained solidified product (green body) was measured using a universal testing machine (autograph, model AG-I) manufactured by Shimadzu Corporation. A 1 kN load cell and a 3-point bending jig were used. The distance between the fulcrums was 24 mm, the stress when the load point was displaced at a speed of 1 mm / min was plotted against the strain amount, and the stress at the break point was taken as the maximum stress. The value of the bending strength measured in this way is preferably 5 MPa or more.

<Hardness of solidified material (green body) when immersed>
The solidified product (green body) was immersed in 1,4-dioxane, and the hardness of the type 00 durometer immediately after removal was measured with a type 00 durometer at 1, 3, 6, 9, and 24 hours. The push needle of the durometer protruded downward from the pressure surface of the instrument, and the push needle was pressed against the test piece for measurement.
FIG. 3 shows the results of immersing the solidified product (green body) in 1,4-dioxane in Examples and Comparative Examples for 1 hour, taking it out, and measuring the hardness of Type 00 durometer. FIG. 4 shows the results of immersing the solidified product (green body) in 1,4-dioxane in Examples and Comparative Examples for 24 hours, taking it out, and measuring the hardness of Type 00 durometer.
Those having a Type 00 durometer hardness of less than 90 after being immersed in 1,4-dioxane for 1 hour cannot be used in practice. In Comparative Example 1, the hardness could not be measured because it collapsed after being immersed in 1,4-dioxane.

(Examples 2 to 6 and Comparative Examples 1 to 3)
<Preparation of modeling liquid>
In Example 1, the modeling liquids of Examples 2 to 6 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the materials shown in Tables 1 and 2 were changed. The content of each material in Tables 1 and 2 indicates mass%.
Next, the viscosity of the obtained modeling liquid was measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

<Three-dimensional modeling (manufacturing of green body)>
Three-dimensional modeling was performed in the same manner as in Example 1 to obtain a solidified product (green body).
Next, various properties of the obtained solidified product (green body) were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Details of each component in Tables 1 and 2 are as follows.
-Organic solvent-
* Diethyl succinate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
* Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
* Dihydroterpinyl acetate (manufactured by Nippon Terpene Chemical Co., Ltd.)

-Organic titanium compound or organic zirconia compound-
Details of the organic titanium compound or the organic zirconia compound are shown in Table 3 below. The manufacturer of the organic titanium compound or the organic zirconia compound is Matsumoto Fine Chemical Co., Ltd.

-Other cross-linking agents-
* MEH-7000 (Phenol resin cross-linking agent, manufactured by Meiwa Kasei Co., Ltd.)
* Celoxide 2021P (epoxy cross-linking agent, manufactured by Daicel Corporation)

-Surfactant-
* Surflon S-243 (manufactured by AGC Sane Chemical Co., Ltd.)

-Thermal cationic polymerization initiator-
* TA-100 (manufactured by Sun Appro Co., Ltd.)

-Thickener-
* Oricox KC1700P (manufactured by Kyoeisha Chemical Co., Ltd.)
* PVP K30 (manufactured by Tokyo Chemical Industry Co., Ltd.)

Aspects of the present invention are, for example, as follows.
<1> A solidification forming step of applying a molding liquid containing an organic metal compound to a powder containing a base material and an organic material to form a solidified material.
A method for producing a three-dimensional object, which comprises a powder removing step of removing the powder adhering to the solidified material from the solidified material using a powder removing liquid.
<2> The method for producing a three-dimensional model according to <1>, wherein the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.
<3> The method for producing a three-dimensional model according to <2>, wherein the organic titanium compound has an alkoxy group as a functional group and either an ethyl acetoacetate chelate or an acetylacetone chelate as a ligand. Is.
<4> The content of at least one of Ti derived from the organic titanium compound and Zr derived from the organic zirconia compound is 0.1% by mass or more and 5% by mass or less with respect to the total amount of the modeling liquid. The method for manufacturing a three-dimensional model according to any one of <3>.
<5> The powder removing solution that does not dissolve the solidified substance and dissolves the organic material in the powder is ketone, halogen, alcohol, ester, ether, hydrocarbon, glycol, glycol ether, glycol ester, pyrrolidone. , The method for producing a three-dimensional model according to any one of <1> to <4>, which contains at least one selected from amide, amine and carbonate ester.
<6> The method for producing a three-dimensional model according to any one of <1> to <5>, wherein the type 00 durometer hardness is 90 or more after the solidified material is immersed in the powder removing liquid for 1 hour. Is.
<7> The method for producing a three-dimensional model according to any one of <1> to <6>, wherein the base material is selected from metal and ceramics.
<8> The method for producing a three-dimensional model according to any one of <1> to <7>, which further comprises a sintering step of performing a sintering process on the solidified material after the powder removing step. ..
<9> A molding liquid containing an organic metal compound is applied to a powder having a base material and an organic material to form a solidified product, and the powder removing liquid is used to apply the powder to the solidified material. A modeling liquid used for producing a three-dimensional model to be removed from the solidified material.
The molding liquid is characterized in that the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.
<10> The modeling solution according to <9>, wherein the organic titanium compound has an alkoxy group as a functional group and either an ethyl acetoacetate chelate or an acetylacetone chelate as a ligand.
<11> The content of at least one of Ti derived from the organic titanium compound and Zr derived from the organic zirconia compound is 0.1% by mass or more and 5% by mass or less with respect to the total amount of the modeling liquid. The molding liquid according to any one of <10>.
<12> A powder containing a base material and an organic material,
A molding liquid containing an organometallic compound by solidifying the powder to form a solidified product,
It is a three-dimensional modeling kit having a powder removing liquid for removing the powder adhering to the solidified material from the solidified material.
<13> The three-dimensional modeling kit according to <12>, wherein the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.

The method for producing a three-dimensional model according to any one of <1> to <8>, the modeling liquid according to any one of <9> to <11>, and any of the above <12> to <13>. According to the three-dimensional modeling kit described in the above, various problems in the prior art can be solved and the object of the present invention can be achieved.

Japanese Patent No. 6471482

Claims (13)

A solidification forming step of applying a molding liquid containing an organic metal compound to a powder containing a base material and an organic material to form a solidified material.
A method for producing a three-dimensional object, which comprises a powder removing step of removing the powder adhering to the solidified material from the solidified material using a powder removing liquid. The method for producing a three-dimensional model according to claim 1, wherein the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound. The method for producing a three-dimensional model according to claim 2, wherein the organic titanium compound has an alkoxy group as a functional group and either an ethyl acetoacetate chelate or an acetylacetone chelate as a ligand. Any of claims 2 to 3, wherein the content of at least one of Ti derived from the organic titanium compound and Zr derived from the organic zirconia compound is 0.1% by mass or more and 5% by mass or less with respect to the total amount of the modeling liquid. A method for manufacturing a three-dimensional model described in Crab. The powder remover that does not dissolve the solidified substance and dissolves the organic material in the powder is a ketone, halogen, alcohol, ester, ether, hydrocarbon, glycol, glycol ether, glycol ester, pyrrolidone, amide, The method for producing a three-dimensional model according to any one of claims 1 to 4, which contains at least one selected from an amine and a carbonate ester. The method for producing a three-dimensional model according to any one of claims 1 to 5, wherein the type 00 durometer hardness is 90 or more after the solidified material is immersed in the powder removing liquid for 1 hour. The method for producing a three-dimensional model according to any one of claims 1 to 6, wherein the base material is selected from metal and ceramics. The method for producing a three-dimensional model according to any one of claims 1 to 7, further comprising a sintering step of performing a sintering process on the solidified material after the powder removing step. A molding liquid containing an organic metal compound is applied to a powder having a base material and an organic material to form a solidified product, and the powder that adheres to the solidified material is subjected to the solidified material using a powder removing liquid. It is a modeling liquid used for manufacturing a three-dimensional model to be removed from.
A molding liquid characterized in that the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound. The modeling solution according to claim 9, wherein the organic titanium compound has an alkoxy group as a functional group and either an ethyl acetoacetate chelate or an acetylacetone chelate as a ligand. Any of claims 9 to 10, wherein the content of at least one of Ti derived from the organic titanium compound and Zr derived from the organic zirconia compound is 0.1% by mass or more and 5% by mass or less with respect to the total amount of the modeling liquid. The molding liquid described in Crab. A powder containing a base material and an organic material,
A molding liquid containing an organometallic compound by solidifying the powder to form a solidified product,
A three-dimensional modeling kit comprising a powder removing liquid for removing the powder adhering to the solidified material from the solidified material. The three-dimensional modeling kit according to claim 12, wherein the organometallic compound contains at least one of an organic titanium compound and an organic zirconia compound.

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