JP2016172416A - Powder material for three-dimensional molding, three-dimensional molding material 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 powder material for three-dimensional molding, for manufacturing a three-dimensional molded object having a complicated shape and comprising various materials with high strength and high accuracy.SOLUTION: The powder material for three-dimensional molding comprises coated particles comprising base particles coated with a resin, in which the resin comprises polyvinyl alcohol containing a 1,2-glycol bond in a side chain. A modification degree of the 1,2-glycol bond included in the polyvinyl alcohol is preferably 4.0 mol% or less.SELECTED DRAWING: None

Description

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

  As an example of these methods, a method is proposed in which powder particles coated with a binder resin are stacked, and a modeling liquid containing a solvent or the like is ejected for modeling. For example, Patent Document 1 (Japanese Patent Publication No. 2006-521264) discloses a powder material in which particles such as metal and ceramics are coated with an active adhesive and a fine-grain material.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2005-297325) discloses a three-dimensional structure in which a powder material in which a base is coated with a resin is deposited, the coating resin is dissolved, and then a solidifying solvent is supplied to bind the powder material. A modeling method is disclosed. In this way, the method using the powder material in which the resin is coated on the surface of the base material has a high modeling speed, allows the resin to be arranged relatively evenly, and further prevents clogging of the ink jet nozzle. This is also an effective method for improving the strength and dimensional accuracy of the shaped object.

However, even if the clogging of the ink jet nozzle can be reduced by using the powder material coated with the resin in this manner, the strength and dimensional accuracy of the three-dimensional structure cannot be said to be practically sufficient.
Then, an object of this invention is to provide the powder material for three-dimensional modeling which manufactures a three-dimensional molded item with high intensity | strength and high precision.

As a result of intensive studies, the present inventors have found that delamination may occur between the laminated powder layers, and this delamination greatly reduces the adhesion between the layers, so only the three-dimensional model before sintering is obtained. In other words, the present inventors have found that the strength of the three-dimensional sintered product obtained by degreasing and further sintering the three-dimensional model is also a cause.
Furthermore, when delamination occurs, the space is included in the three-dimensional structure so that the dimensional accuracy is reduced accordingly. Therefore, in order to obtain a three-dimensional structure and a three-dimensional sintered body that can maintain a complicated shape and have high strength and high dimensional accuracy, it is necessary to reduce delamination of the three-dimensional structure.
This invention for solving the said subject concerns the powder material for three-dimensional modeling as described below.
3D modeling powder material comprising coated particles formed by coating substrate particles with resin, wherein the resin contains polyvinyl alcohol containing 1,2-glycol bond in the side chain Powder material.

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 of the three-dimensional molded item manufacturing apparatus of this invention.

  Hereinafter, an example of an embodiment in the present invention will be described.

<Powder material for three-dimensional modeling>
The powder material for three-dimensional modeling in the present invention is a powder material used when manufacturing a three-dimensional or three-dimensional model, and at least the base material particles described below and a resin that covers the base material particles including. The resin preferably covers part or all of the surface of the substrate. Thereby, the adhesive force of powder particles increases and it becomes possible to obtain the three-dimensional molded item which has high intensity | strength.

-Base material-
The substrate used in the present invention 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 of the base material include metal, ceramics, glass, carbon, polymer, wood, biocompatible material, and sand. From the viewpoint of obtaining an extremely high strength three-dimensional sintered product, finally, More preferred are metals and ceramics that can be sintered.

  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, copper, silver, titanium, zirconium, or alloys thereof are preferably used. Examples of stainless steel (SUS) include SUS304, SUS316, SUS317, SUS329, SUS410, SUS430, SUS440, and SUS630.

On the other hand, 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. However, these are merely examples, and the present invention is not limited to these. These materials may be used alone or in combination of two or more.

As these base materials, those commercially available can be used. As an example of a commercial product, stainless steel is PSS316L made by Sanyo Special Steel, silica is Excelica SE-15 made by Tokuyama, alumina is Tymicron TM-5D made by Daimei Chemicals, zirconia is made by Tosoh TZ-B53, etc. It can be illustrated.
The base material can be subjected to a surface treatment, and may be effective for improving adhesiveness with a resin and improving coating properties. A conventionally known surface treating agent can be used.

  There is no restriction | limiting in particular as an average particle diameter of the said base material, According to the objective, it can select suitably. For example, the thing of 0.5-500 micrometers is preferable, 5-150 micrometers is more preferable, and 10-100 micrometers is further more preferable. If the average particle size is smaller than this, the influence of aggregation increases, making it difficult to coat the resin on the base material, reducing the yield and manufacturing efficiency of the three-dimensional object, handling the base material, and handling. It may cause a decline in sex. On the other hand, if the average particle diameter is larger than this, the strength of the three-dimensionally shaped article and further the three-dimensionally sintered article may decrease due to the decrease in the contact between the particles and the increase in the voids.

  The particle size distribution of the substrate 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 average particle size of the substrate 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 shape and circularity of the base material are not particularly limited and can be appropriately selected according to the purpose. However, the shape is spherical and the circularity is higher (closer to 1.0). preferable. As a result, the base material is closely packed, and voids of the obtained three-dimensional modeled article and three-dimensional sintered product can be reduced, which may be effective in increasing the strength. 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).

  The said base material can be manufactured using a conventionally well-known method. Examples of the method for producing a powder or particulate base material include, for example, a pulverization method in which a solid is subjected to compression, impact, friction, and the like, a atomization method in which molten metal is sprayed to obtain a quenched powder, and a component dissolved in a liquid And a vapor phase reaction method of vaporizing and crystallizing. The base material used in the present invention is not limited to the production method, but a more preferable method is an atomizing method in which a spherical shape is obtained and particle size variation is small. 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.

-Resin-
The powder material for three-dimensional modeling of the present invention has a base material surface coated with a resin, and the resin contains polyvinyl alcohol containing 1,2-glycol bond in the side chain, and further contains other components as necessary. .
The 1,2-glycol bond represents a structural unit in which two adjacent carbon atoms are each substituted with one hydroxy group. In this invention, it is preferable to contain the 1, 2- glycol structural unit shown by following General formula (1).

In the above general formula (1), R ¹ , R ² and R ³ are each independently hydrogen or an alkyl group.

  Although it does not specifically limit as this alkyl group, For example, C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, are preferable. Such an alkyl group may have a substituent such as a halogen group, a hydroxy group, an ester group, a carboxylic acid group, or a sulfonic acid group, if necessary.

  A method for obtaining polyvinyl alcohol containing a 1,2-glycol bond in the side chain is not particularly limited. For example, a vinyl ester monomer (A) and a vinyl ethylene carbonate (B) represented by the following general formula (2) are used. ) Saponification and decarboxylation of the copolymer (A-B) with a vinyl ester monomer (A) and 2,2-dialkyl-4-vinyl-1,3 represented by the following general formula (3) -Saponification and deketalization of copolymer (AC) with dioxolane (C), copolymer of vinyl ester monomer (A) and glycerol monoallyl ether (D) (AD) A method of saponifying is preferably used.

However, R ¹ , R ² and R ³ are each independently hydrogen or an alkyl group.

However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ are each independently hydrogen or an alkyl group.

  Polyvinyl alcohol containing a 1,2-glycol bond in these side chains can be synthesized with reference to, for example, JP-A-2002-284818.

  The degree of modification of the 1,2-glycol bond of the polyvinyl alcohol used in the three-dimensional modeling powder material of the present invention is preferably low. In addition, the modification | denaturation degree of the 1, 2- glycol bond in this invention shows content of the structural unit of 1, 2- glycol contained in polyvinyl alcohol. As a specific example of the degree of modification of 1,2-glycol bond, it is preferably 4.0 mol% or less, more preferably 3.0% or less. If the degree of modification of the 1,2-glycol bond is higher than this, the strength of the three-dimensional structure may be somewhat lowered. In addition, the base materials are liable to cause slow aggregation, and the coating properties on the base materials may be slightly lowered.

  On the other hand, when the 1,2-glycol bond is not included, the influence of delamination of the three-dimensional model or the three-dimensional sintered product is remarkably increased, and the strength and the dimensional accuracy are significantly reduced. In addition, the solubility in ink is reduced, and it is necessary to increase the amount of ink in order to obtain strength, which may cause further reduction in dimensional accuracy.

  By using polyvinyl alcohol having a 1,2-glycol bond modification degree of 4.0 mol% or less, preferably 3.0 mol% or less, not only resin coating is facilitated but also delamination can be suppressed. It becomes possible and the intensity | strength of the three-dimensional molded item obtained and also three-dimensional sintered compact can be raised. Moreover, since the porosity of a three-dimensional molded item or a three-dimensional sintered product can be reduced, not only strength but also dimensional accuracy can be further improved. Furthermore, during storage time of the three-dimensional modeling powder material, problems such as aggregation can be prevented, and the effect of improving the storage stability can be obtained, which has a great advantage when used as a coating resin for the three-dimensional modeling powder material. Yes.

The degree of modification of 1,2-glycol bond can be determined from analysis of NMR spectrum. As an example, a sample prepared by dissolving the vinyl alcohol to be measured in DMSO-d6 and adding a few drops of trifluoroacetic acid is used as a measurement sample and measured at 50 ° C. using 500 MHz proton NMR. . The peak derived from methine of the vinyl alcohol unit is attributed to 3.2 to 4.0 ppm (integrated value A), and the peak derived from one methine of the 1,2-glycol bond is attributed to 3.25 ppm (integrated value B). From this, the degree of modification of 1,2-glycol bond can be calculated.
Degree of modification of 1,2-glycol bond (mol%) = (B / A) × 100

  Specific methods for measuring the degree of modification of 1,2-glycol bond can be calculated with reference to JP-A No. 2002-284818, JP-A No. 2004-75866, International Publication No. WO2008 / 093615A1, and the like. .

  These polyvinyl alcohols having a 1,2-glycol bond in the side chain are lined up as the Nichigo G polymer series (manufactured by Nippon Synthetic Chemical Industry), and can also be obtained as a manufacturer's product. As an example, AZF8035W, OKS-6026, OKS-1011, OKS-8049, OKS-1028, OKS-1027, OKS-1109, OKS-1081, OKS-1083, OKS-8041, OKS-8105, OKS-8089, Examples include OKS-8096, OKS-1080, and the like.

  In the present invention, it is also possible to mix and use polyvinyl alcohols having different degrees of modification of 1,2-glycol bonds. When polyvinyl alcohol having an optimum degree of modification cannot be obtained for the modeling liquid to be used, it can be optimized by mixing and using polyvinyl alcohol having a different degree of modification. When polyvinyl alcohol is mixed and used, if one polyvinyl alcohol has a 1,2-glycol structural unit, the other polyvinyl alcohol does not have a 1,2-glycol structural unit. However, it is possible to obtain the effect, and it is included in the category of the present invention.

  Generally, polyvinyl alcohol is manufactured by polymerizing a vinyl acetate monomer and saponifying the acetate group of the obtained polyvinyl acetate to a hydroxyl group. Therefore, the degree of polymerization and the degree of saponification are important characteristics that determine the properties of polyvinyl alcohol.

  The degree of polymerization of polyvinyl alcohol is the molecular chain length of vinyl acetate in the polymerization step. The degree of polymerization of the polyvinyl alcohol used in the present invention is not particularly limited and can be appropriately selected depending on the molding method, purpose of use and the like. The degree of polymerization is preferably 300 to 1700, more preferably 400 to 1200. When the degree of polymerization is 300 or more, the effect of improving the strength of the three-dimensional structure to be obtained can be sufficiently obtained, and when it is 1700 or less, coating failure due to thickening of the coating liquid, aggregation of powder material, It is possible to reduce a decrease in strength of the three-dimensional structure due to a decrease in solubility. In addition, the polymerization degree of polyvinyl alcohol can be measured using an aqueous solution viscosity measuring method (JIS K 6726). For example, the remaining unsaponified acetic acid groups are completely saponified using sodium hydroxide in advance, the relative viscosity with water is determined using a viscometer, and the average degree of polymerization is calculated from the relative viscosity.

  In the present invention, it is also possible to use a mixture of polyvinyl alcohols having different degrees of polymerization. For example, when polyvinyl alcohol having an optimum degree of polymerization is not available for the coating liquid for powder material used when the base material is coated with polyvinyl alcohol to produce the powder material for three-dimensional modeling, different polymerization is performed. Mixing and using polyvinyl alcohol having a degree is effective because it can be optimized.

  The degree of saponification of polyvinyl alcohol is represented by the change rate (mol%) of the hydroxyl group relative to the total amount of the ester part of the vinyl ester monomer, the acyloxy part, the carbonate part, the acetal part, etc. of the comonomer. The degree of saponification of the polyvinyl alcohol used in the present invention is not particularly limited and is appropriately selected according to the molding method, purpose of use, solubility, moisture resistance, etc., but it is more completely saponified than partially saponified. Is more preferable. Specifically, 80 mol% or more is preferable, 90 mol% or more is more preferable, and 95% or more is particularly preferable. When the degree of saponification is 80 mol% or more, the strength of the three-dimensional modeled product is reduced, the dimensional accuracy is reduced due to the aggregation of the three-dimensional modeled powder material, the preservability of the three-dimensional modeled powder material and the polyvinyl alcohol to the base It is possible to suppress a decrease in coating properties.

  The saponification degree of polyvinyl alcohol can be measured using a titration method (JIS K 6726). For example, the degree of saponification (mol%) can be determined by quantifying the residual acetic acid group (mol%) of polyvinyl alcohol with sodium hydroxide and subtracting it from 100.

  In the present invention, it is also possible to use a mixture of polyvinyl alcohols having different saponification degrees. For example, when the complete saponification mold is used and the solubility in the modeling liquid is lowered, it can be effectively improved by mixing polyvinyl alcohols having different saponification degrees.

  The average film thickness of the polyvinyl alcohol formed on the substrate is not particularly limited and can be appropriately selected depending on the molding method, the purpose of use, etc., but is preferably 1 nm to 1000 nm, more preferably 10 to 500 nm, still more preferably 50 to 400 nm, Especially preferably, it is 100-300 nm. When the average film thickness of the polyvinyl alcohol is 1 nm or more, an adhesion effect is obtained by supplying a modeling liquid to the powder material for three-dimensional modeling, and a high effect is obtained in maintaining the complicated shape of the three-dimensional modeling object. Can be obtained. On the other hand, when the average film thickness is 1000 nm or less, an increase in aggregates and an increase in shrinkage rate can be reduced, and a decrease in dimensional accuracy, a decrease in coating properties, and a powder storage stability can be prevented.

  The average film thickness can be measured, for example, by embedding the three-dimensional modeling powder material in an 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, interatomic Measurement can be performed by using a force microscope AFM, a scanning electron microscope SEM, or the like.

  The coverage (area ratio) of polyvinyl alcohol formed on the substrate 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 coating rate is low, the effect of the present invention can be obtained as long as polyvinyl alcohol is formed on the surface of the base material. However, the higher the coverage rate, the higher the strength of the three-dimensional structure and the strength. This is more effective because the anisotropy can be reduced.

  The coverage is obtained, for example, from an observation photograph using an optical microscope, a microscope, an SEM or the like of the powder material for three-dimensional modeling, and the area of the region covered with the polyvinyl alcohol with respect to the surface area of the powder material for three-dimensional modeling, It can calculate from the average value of those ratio (%). Moreover, it can measure also by performing the element mapping using the energy dispersive X-ray spectroscopy methods, such as SEM-EDS, about the part coat | covered with polyvinyl alcohol.

-Other ingredients-
Any other components can be added to the three-dimensional modeling powder material of the present invention, which may be effective. There is no restriction | limiting in particular as another component, Although it can select suitably according to the objective, For example, a filler, a leveling agent, a sintering aid, etc. are mentioned. The filler is an effective material mainly for adhering to the surface of the powder material for three-dimensional modeling or for filling gaps between the powder materials. As an effect, for example, the improvement in the fluidity of the powder material for three-dimensional modeling, the increase in the number of contacts between powder materials, and the reduction of voids can be effective in that the effect of increasing the strength and dimensional accuracy of the three-dimensional model can be obtained. It is.

  The leveling agent is an effective material mainly for controlling the wettability of the surface of the three-dimensional modeling powder material. As an effect, for example, the penetration of the modeling liquid into the powder material layer for three-dimensional modeling can be increased, the strength of the three-dimensional model can be increased and the speed thereof can be increased, and there are cases where it is effective in maintaining the shape stably. . The sintering aid is an effective material for increasing the sintering efficiency when the obtained three-dimensional structure is sintered. As effects, for example, the strength of the three-dimensional model can be improved, the sintering temperature can be lowered, and the sintering time can be shortened.

-Manufacturing method of powder material for three-dimensional modeling-
The three-dimensional modeling powder material of the present invention includes the polyvinyl alcohol as a base material and a resin, and specifically, the resin is coated on the surface of the base material. There is no restriction | limiting in particular as the coating method of the said polyvinyl alcohol to a base material, According to a well-known coating method, it can coat | cover. Examples thereof include a rolling flow method, a spray method, a dipping method, a stirring and mixing method, a spray drying method, and a kneader coating method. 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. However, when the heat fusion property and solubility of the polyvinyl alcohol used as the binder resin are remarkably high, the fluidized bed becomes unstable, causing excessive aggregation, and in the worst case, the coating cannot be continued. There is also.

  In the present invention, when the degree of modification of the 1,2-glycol bond increases, the effect may increase slightly, and in such a case, the coating conditions may be restricted, such as setting the temperature lower. When the degree of modification of the 1,2-glycol bond is 4 mol% or less, particularly 3 mol% or less, these effects are hardly observed, and it becomes possible to coat very stably.

-Powder material for solid modeling-
There is no restriction | limiting in particular as an average particle diameter of the powder material for three-dimensional modeling obtained as mentioned above, Although it can select suitably according to the objective, 0.5-500 micrometers is preferable, for example. 0-150 micrometers is more preferable and 10-100 micrometers is further more preferable.

When the average particle diameter is 0.5 μm or more, it is possible to reduce the influence of delamination of the three-dimensional structure, improve the yield and manufacturing efficiency of the three-dimensional structure, or handle and handle the powder material. It is also effective for improvement.
On the other hand, when the average particle diameter is 500 μm or less, it is possible to prevent an increase in the voids of the three-dimensional structure, and it is effective for improving the strength of the three-dimensional structure and further the three-dimensional structure.

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

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

  The fluidity of the three-dimensional modeling powder material is not particularly limited, and can be appropriately selected depending on the purpose. The fluidity of the three-dimensional modeling powder material can be measured using a conventionally known method, and examples thereof include a method of repose angle, degree of compression, outflow rate, and shear cell test. The angle of repose is represented by the angle between the slope of the mountain of the powder and the horizontal plane when the powder is dropped from a certain height and kept stable without spontaneous collapse, and is generally widely used. As an example, it can be measured using a powder characteristic measuring device (Powder Tester PT-N type, manufactured by Hosokawa Micron Corporation).

  The repose angle of the three-dimensional modeling powder material of the present invention is preferably 55 ° or less, more preferably 40 ° or less, and particularly preferably 35 ° or less. When the angle of repose exceeds this, when forming a layer of the powder material for three-dimensional modeling, the surface roughness of the layer becomes large, or it becomes easy to form a slow aggregate, and the dimensions of the three-dimensional modeled object to be obtained Accuracy may be reduced. It is known that the angle of repose is mainly influenced by particle diameter, particle shape, water content, humidity, and the like. The three-dimensional modeling powder material of the present invention is influenced by the degree of modification of the coated polyvinyl alcohol in addition to the particle diameter and shape, and the one with a lower degree of modification of 1,2-glycol bond is more preferable for the three-dimensional modeling powder material. In some cases, the fluidity is high and effective.

<3D modeling material set>
The three-dimensional modeling material set of the present invention includes the three-dimensional modeling powder material and a modeling liquid. The modeling liquid may contain any component as long as it is a liquid material capable of dissolving or swelling the polyvinyl alcohol contained in the three-dimensional modeling powder material.

  In the present invention, for example, a layer of the three-dimensional modeling powder material is formed, the modeling liquid is provided thereon, and a liquid component contained in the modeling liquid is formed on the surface of the three-dimensional modeling powder material. The polyvinyl alcohol is dissolved or swollen so that the adjacent powder materials for three-dimensional modeling are bonded to each other. By repeating these operations and drying, a three-dimensional model can be obtained. The three-dimensional modeling powder material and the modeling liquid used at this time are referred to as a three-dimensional modeling material set in the present invention. Also, the three-dimensional modeling material set of the present invention can be obtained by, for example, simply mixing the three-dimensional modeling powder material and the modeling liquid in a desired ratio and injecting the obtained slurry into a mold or forming it three-dimensionally. A three-dimensional model can be obtained, and these slurries are also included in the three-dimensional model material set. That is, the three-dimensional modeling material set of the present invention is not limited to the method of manufacturing a three-dimensional modeling object, and includes all combinations of the three-dimensional modeling powder material and the modeling liquid.

<Modeling liquid>
The modeling liquid contained in the three-dimensional modeling set of the present invention includes a liquid component that can dissolve or swell the polyvinyl alcohol contained in the three-dimensional modeling powder material as described above, and others as necessary. May be included.

-Liquid component-
The modeling liquid contains a liquid component because it is liquid at room temperature. As the liquid component, any liquid can be used as long as it can dissolve or swell the polyvinyl alcohol contained in the three-dimensional modeling powder material, but water or a water-soluble solvent is preferably used. In particular, water is used as the main component. Thereby, the solubility of the said polyvinyl alcohol increases and it becomes possible to manufacture a high-strength three-dimensional molded item. The proportion of water in the entire modeling liquid is preferably 40% by mass or more and 85% by mass or less, and more preferably 50% by mass or more and 80% by mass or less. When the ratio of water is less than this, the solubility of the polyvinyl alcohol of the three-dimensional modeling powder material may decrease, and the strength of the three-dimensional model may decrease. Further, if the ratio of water exceeds this, the inkjet nozzle may be dried during standby, and liquid clogging or nozzle missing may occur.

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

  Any water-soluble solvent can be used as long as it is a water-soluble liquid material. Examples thereof include alcohols such as ethanol, propanol and butanol, ethers and ketones. Specifically, 1,2,6-hexanetriol, 1,2-butanediol, 1,2-hexanediol, 1,2-pentanediol, 1,3-dimethyl-2-imidazolidinone, 1,3 -Butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,3-butane Diol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2-pyrrolidone, 2-methyl-1,3-propanediol, 2-methyl-2,4- Pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,3-hexanediol, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, β- Toxi-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, diglycerin Propylene glycol, dipropylene glycol n-propyl ether Ter, 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 Ethyl ether, can be used hexylene glycol, polyethylene glycol, polypropylene glycol. However, this is an example, and the present invention is not limited to these.

  The proportion of the water-soluble solvent in the entire modeling 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. If the amount of the water-soluble solvent is less than this, the water holding power of the modeling liquid is reduced, and the inkjet head may be dried during standby, resulting in ejection failure. Moreover, the amount of discharge at the time of a check performed in advance and the amount of discharge at the time of actual discharge are different, which may hinder the manufacture of a three-dimensional structure having a desired strength and shape. On the other hand, if the amount of the water-soluble solvent is larger than this, the viscosity of the modeling liquid becomes high, the discharge stability is lowered, or the solubility of polyvinyl alcohol contained in the powder material for three-dimensional modeling is reduced, and the resulting three-dimensional modeling is obtained. The strength of the object may decrease. Moreover, it takes time to dry the three-dimensional modeled object, which may cause a reduction in manufacturing efficiency and a deformation of the three-dimensional modeled object.

-Other ingredients-
The modeling liquid of the present invention includes, as other components, for example, a wetting agent, a drying inhibitor, a viscosity modifier, a surfactant, a penetrating agent, a crosslinking agent, an antifoaming agent, a pH adjusting agent, an antiseptic, an antifungal agent, Conventionally known materials such as a colorant, a preservative, and a stabilizer can be added without limitation.

  The surfactant is mainly used for the purpose of controlling wettability, permeability, and surface tension of the modeling 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. Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, oxalate sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like. Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide. Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

  Specific examples include those listed below, but are not limited thereto. Examples thereof include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, dimethyl lauryl betaine and the like. These surfactants are Nikko Chemicals Co., Ltd., Nippon Emulsion Co., Ltd., Nippon Shokubai Co., Ltd., Toho Chemical Co., Ltd., Kao Co., Ltd., Adeka Co., Ltd., Lion Co., Ltd., Aoki Yushi Co., Ltd. ), And a surfactant manufacturer such as Sanyo Kasei Co., Ltd.

  The acetylene glycol surfactants are 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5. An acetylene glycol type such as dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG from Air Products (USA)) can be used, and particularly Surfynol 465, 104 And TG are preferred.

  Fluorosurfactants include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compounds, Examples thereof include polyoxyalkylene ether polymers having a fluoroalkyl ether group in the side chain, sulfate salts thereof, and fluorine-based aliphatic polymer esters.

  Examples of commercially available fluorosurfactants include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, and S-145 (Asahi Glass Co., Ltd.), Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), FT-110, 250, 251 , 400S (manufactured by Neos), Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N, FSN-100, FS-300, FSK (manufactured by Dupont), poly There are Fox PF-136A, PF-156A, PF-151N (manufactured by OMNOVA), etc. Kill.

  The surfactant is not limited to these, and may be used alone or in combination. Even if it does not dissolve easily in the modeling liquid alone, it may be solubilized by mixing to obtain a stable liquid material.

  The content of the surfactant with respect to the modeling liquid is preferably 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and 0.5% by mass to 3% as the total amount of the surfactant. More preferred is mass%. If the total amount of the surfactant is less than this, the penetration of the modeling liquid into the three-dimensional modeling powder material may be reduced, and the strength of the three-dimensional model may be reduced. On the other hand, if the total amount of the surfactant is larger than this, the penetrability of the modeling liquid cannot be appropriately controlled, and the modeling liquid may permeate beyond the desired region, or the dimensional accuracy of the resulting three-dimensional model may be reduced. is there.

  The cross-linking agent is effective because it can further increase the strength of the resulting three-dimensional structure by crosslinking with the resin coated on the surface of the three-dimensional structure powder material. The crosslinking agent is not particularly limited as long as it crosslinks with the polyvinyl alcohol, and can be appropriately selected according to the purpose. Examples thereof include metal salts, metal complexes, polyvalent metal compounds such as organic zirconium compounds and organic titanium compounds, water-soluble organic crosslinking agents, chelating agents, blocked isocyanates, and melamine compounds.

  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.

  Moreover, there is no restriction | limiting in particular as a ligand of the said cationic metal, Although a conventionally well-known thing can be used, in this invention, it is excellent in the discharge stability of a pre-modeling liquid, and preservability with time. Therefore, lactate ions are preferably used. Since the cationic metal ligand is a carbonate ion crosslinking agent, for example, zirconium zirconium carbonate causes a self-polymerization reaction in an aqueous solution, the properties of the crosslinking agent are likely to change. Therefore, from the viewpoint of the ejection stability of the modeling liquid, it is preferable to use a lactic acid ion cross-linking agent as the cation ligand. Further, by adding a chelating agent such as gluconic acid or triethanolamine, the self-polymerization reaction in an aqueous solution of ammonium zirconium carbonate can be suppressed, and the discharge stability of the modeling liquid can be improved.

  Commercially available products can be used. Examples of the commercially available products include zirconium oxychloride octahydrate (manufactured by Daiichi Elemental Chemical Co., Ltd., zirconium oxychloride), aluminum hydroxide (Wako Pure Chemical Industries, Ltd.). Manufactured by Co., Ltd., Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), titanium lactate ammonium salt (manufactured by Matsumoto Fine Chemical Co., Ltd., Olgax TC-300, TC-310), zirconium lactate ammonium salt (manufactured by Matsumoto Fine Chemical Co., Ltd.) ORGATICS 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 salt (first Rare Element Chemical Co., Ltd., Zircosol A -7, AC-20), titanium triethanolamate (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS TC-400), zirconium oxychloride (manufactured by Daiichi Elemental Chemical Co., Ltd., zircosol ZC-20), zirconium oxynitrate (Zircozole ZN, manufactured by Daiichi Rare Element Chemical Co., Ltd.), glyoxylate (Safelink SPM-01, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), etc. A metal salt having a metal valence of 2 or more can improve the cross-linking strength, and is preferable for increasing the strength of the three-dimensional structure to be obtained.

  There is no restriction | limiting in particular as content of the said crosslinking agent in the said modeling liquid, According to the objective, it can select suitably. For example, the preferable addition amount of the crosslinking agent with respect to the polyvinyl alcohol contained in the powder material for three-dimensional modeling is 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably. Is 1% by mass to 10% by mass. If the content of the cross-linking agent is less than this, the strength of the three-dimensional structure may be insufficient. On the other hand, when there is more content of a crosslinking agent than this, a modeling liquid may thicken or gelatinize and liquid preservability and viscosity stability may fall.

  The antifoaming agent is used mainly for preventing foaming of the modeling liquid. As the antifoaming agent, a commonly used antifoaming agent can be used. For example, a silicone antifoaming agent, a polyether antifoaming agent, a fatty acid ester antifoaming agent and the like can be mentioned, and these may be used in combination with one or more types. Commercially available products may be used as the antifoaming agent, for example, silicone antifoaming agents (KS508, KS531, KM72, KM85, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Toray Dow Corning Co., Ltd. Silicone defoaming agents (Q2-3183A, SH5510, etc.), silicone defoaming agents (SAG30, etc.) manufactured by Nihon Unicar Co., Ltd., and antifoaming agents (Adecanate series, etc.) manufactured by Asahi Denka Kogyo Co., Ltd. It is done.

  A preferable content of the antifoaming agent with respect to the modeling liquid is 3% by mass or less, more preferably 0.5% by mass or less. When there is more addition amount of an antifoamer, solubility will fall and it may separate and precipitate.

  The pH adjuster is used mainly for adjusting the modeling liquid to a desired pH. Any material can be used as the pH adjuster as long as the pH of the modeling liquid can be controlled.

  In this invention, when using an inkjet system for the modeling liquid supply means of the three-dimensional model manufacturing apparatus, pH 5 (weakly acidic) to 12 (basic) is preferable from the viewpoint of preventing corrosion and clogging of the nozzle head portion, and pH 8 10 (weakly basic) is more preferable. The pH of the modeling liquid can be arbitrarily adjusted by adding the pH adjuster. Some of the crosslinking agents can also function as pH adjusting agents.

  Examples of pH adjusters include amines, alkali metal hydroxides, quaternary compound hydroxides, alkali metal carbonates when adjusting to basicity, and inorganic acids and organic acids when adjusting to acidity. . Specifically, amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary Examples thereof include alkali metal carbonates such as phosphonium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate. In addition, salts formed with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid and monovalent weak cations such as ammonium sulfate and ammonium phosphate, acetic acid, succinic acid, lactic acid, salicylic acid, benzoic acid, glucuronic acid, ascorbine Acid, arginic acid, cysteine, oxalic acid, fumaric acid, maleic acid, malonic acid, lysine, malic acid, citric acid, glycine, glutamic acid, succinic acid, tartaric acid, phthalic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid Organic acids such as furan carboxylic acid, pyridine carboxylic acid, coumarinic acid, thiophene carboxylic acid, nicotinic acid, carborane acid, or derivatives of these compounds. These pH adjusters are not limited to the above compounds.

These use the one with the optimal temporary dissociation constant pKa according to the characteristics according to the pH fluctuation of the modeling liquid, and may be used alone or in combination of two or more. You may use an agent together.
The antiseptic / antifungal agent is used mainly for preserving / preserving the modeling liquid. If the modeling liquid is stored, microorganisms may grow and pH may be lowered or components may be precipitated, and the antiseptic / antifungal agent can prevent it. Examples of antiseptic / antifungal agents include sodium benzoate, sodium dehydroacetate, potassium sorbitanate, sodium sorbate, thiabendazole, benzimidazole, 2-pyridinethiol 1-oxide sodium, pentachlorophenol sodium, and the like.

-Method for preparing modeling liquid-
There is no restriction | limiting in particular as a preparation method of the said modeling liquid, According to the objective, it can select suitably. For example, there may be mentioned a method in which the other components are added to the liquid components such as water and water-soluble solvent as necessary, and mixed and stirred.

<Method 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 powder material for three-dimensional modeling is formed by the step of forming the powder material layer for three-dimensional modeling, the modeling liquid is supplied to the layer by the step of supplying the modeling liquid, and these steps are repeated. It is a manufacturing method which manufactures a three-dimensional molded item by drying according to a drying process.

  The manufacturing method of the three-dimensional modeled object of the present invention can be manufactured using any method as long as a three-dimensional modeled object can be manufactured using the three-dimensional modeled material set of the present invention. It can be used effectively.

  In FIG. 1, an example of the process schematic for manufacturing a three-dimensional molded item is shown using the three-dimensional modeling material 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, The powder material for three-dimensional modeling of the present invention 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 a modeling liquid supply means 5 for discharging the modeling liquid 6 toward the powder material for three-dimensional modeling in the powder storage tank. 3D modeling powder material layer forming means 4 (hereinafter referred to as “3D modeling powder material layer forming means 4”) that can supply the 3D modeling powder material to the 3D modeling powder storage tank 1 and level the 3D modeling powder material (layer) surface of the modeling powder storage tank 1 , 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. 1C shows a step of dropping the modeling liquid 6 on the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the modeling liquid supply means 5. At this time, the position where the modeling liquid 6 is dropped onto the three-dimensional modeling powder material layer is determined by two-dimensional image data (slice data) obtained by slicing the three-dimensional modeled 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 of dripping the modeling liquid 6 again using the modeling liquid supply means 5 on the three-dimensional modeling powder material layer of the modeling powder storage tank 1.
By repeating these series of steps, drying as necessary, and removing the powder material for three-dimensional modeling to which the modeling 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. 2C shows a step of dropping the modeling liquid 6 on the three-dimensional modeling powder material layer of the modeling powder storage tank 1 using the modeling liquid supply means 5. At this time, the position where the modeling liquid 46 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 modeled 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 of dripping the modeling liquid 6 again using the modeling liquid supply means 5 on the three-dimensional modeling powder material layer of the modeling powder storage tank 1.

  By repeating these series of steps, drying as necessary, and removing the powder material for three-dimensional modeling to which the modeling 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.

<Manufacturing device for three-dimensional model>
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, it has a powder material layer forming means for forming a layer of the powder material for three-dimensional modeling, and a liquid material supply means for supplying the modeling liquid to the layer of the powder material for three-dimensional modeling, and if necessary, powder You may have a material storage part, a liquid material storage part, a drying means, etc.

-Powder material layer forming means for three-dimensional modeling-
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. .
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. A conventionally known method can also be used. For example, a method using a counter rotation mechanism (counter roller) described in Japanese Patent No. 3607300, or a three-dimensional modeling powder material such as a brush, a roller, or a blade is used. A method of forming a layer using a member, a method of forming a layer by pressing the surface of the powder material for three-dimensional modeling using a pressing member, and the like are preferably used.

  The layer of the powder material for three-dimensional modeling formed by the above method is preferably filled with a smooth surface and a high density. Thereby, delamination can be reduced and the intensity | strength and dimensional accuracy of the three-dimensional molded item obtained may be able to be improved. From such a viewpoint, a roller or a blade is preferably used among the powder material layer forming means.

  There is no restriction | limiting in particular as average thickness of the said powder material layer for three-dimensional model | molding, Although it can select suitably according to the objective, For example, 20-500 micrometers is preferable at the average thickness per layer, and 50-300 micrometers is more. preferable. If the thickness of the powder material layer for three-dimensional modeling is thinner than this, the modeling liquid may permeate beyond a desired region, or the dimensional accuracy may decrease. Moreover, much modeling time is needed and the manufacturing efficiency of a three-dimensional molded item falls.

  On the other hand, if the thickness of the powder material layer for three-dimensional modeling is thicker than this, delamination of the three-dimensional model to be obtained increases, and dimensional accuracy and strength may decrease. This increases the voids of the three-dimensional sintered product obtained by sintering the three-dimensional modeled product, and leads to a decrease in strength. 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.

-Modeling liquid supply means-
The modeling liquid supply means is a step of supplying the modeling liquid to the three-dimensional modeling powder material layer.
There is no restriction | limiting in particular as a supply means to the said powder material for three-dimensional model | molding of the said modeling liquid, According to the objective, it can select suitably, A conventionally well-known method can also be used effectively. For example, a dispenser system, a spray system, an inkjet system, etc. are mentioned.

  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 modeling liquid supply means in the present invention.

  In this invention, since binder resin is coat | covered with the powder material for three-dimensional modeling, it is not necessary to make it contain in modeling liquid. Therefore, the modeling liquid can keep the viscosity low, and it is possible to suppress the occurrence of nozzle clogging due to drying to form a film, so that the inkjet head can be used effectively. In addition, since the modeling liquid can efficiently penetrate when discharged into the three-dimensional modeling powder material layer, it is excellent in manufacturing a three-dimensional modeled object with excellent manufacturing efficiency of the three-dimensional modeled object and high strength and dimensional accuracy. It is.

-Other means-
As other means, for example, a powder material container, a liquid material container, a drying means, and the like may be included as necessary.
The powder material container is a member that can accommodate the powder material for three-dimensional modeling, and the size, shape, material, and the like of the powder material container are not particularly limited, and can be appropriately selected according to the purpose. For example, a storage tank, a bag, a cartridge, a tank, etc. are mentioned.

  The liquid material container is a member that can store the modeling liquid, and there is no particular limitation on the size, shape, material, and the like, and can be appropriately selected according to the purpose. For example, storage A tank, a bag, a cartridge, a tank, etc. are mentioned.

  The said drying means is a means to evaporate the modeling liquid contained in a three-dimensional molded item, and dry a three-dimensional molded item, and may be integrated with the manufacturing apparatus of a three-dimensional molded item, or may be separate. Further, all the three-dimensional modeling powder material layers may be laminated and dried, or may be dried each time in the process of laminating each layer. 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. Moreover, when making a modeling liquid contain a crosslinking agent, it may become possible to raise the intensity | strength of a three-dimensional molded item at an early stage by providing a drying means, and is effective. On the other hand, if drying is performed excessively, even the three-dimensional modeling powder material to which the modeling liquid is not attached may be heat-sealed, and the dimensional accuracy of the three-dimensional model may be reduced.

-Manufacturing equipment for 3D objects-
The three-dimensional structure manufacturing apparatus of the present invention includes a powder storage tank for supply (hereinafter also referred to as a supply tank), a powder storage tank for formation (hereinafter also referred to as a formation tank), a three-dimensional structure powder material layer comprising a roller and a powder removal plate. A forming liquid supply means including a forming means and a head and a head cleaning mechanism is provided. In addition, a powder material container is provided.

The powder storage tank has a tank shape or a box shape for supply and modeling, and the stage on the bottom surface thereof can be moved up and down in the vertical direction. Moreover, the supply tank and the modeling tank are provided adjacent to each other, and a three-dimensional modeled object is formed on the stage of the modeling tank.
The stage of the supply tank is raised, and the filled powder material is supplied onto the stage of the supply tank by using a solid material forming powder material layer forming means including a flattening roller. The three-dimensional modeling powder material layer forming means flattens the upper surface of the powder material loaded on the stage of the supply tank and the modeling tank to form a powder material layer.
Using the modeling liquid supply means using the head, the modeling liquid is discharged onto the three-dimensional modeling powder material layer formed on the stage. The head cleaning mechanism adheres to the head and sucks the modeling liquid, and wipes the discharge port.

Each configuration will be described below.
FIG. 3 shows a schematic diagram of the 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. Inside the three-dimensional model manufacturing apparatus, a plurality of tanks containing each of a cyan modeling liquid material, a magenta modeling liquid material, a yellow modeling liquid material, a black modeling liquid material, and a clear modeling liquid material are mounted. Each color head included in the head is connected to a tank containing a liquid material of the corresponding color by a flexible tube (not shown). The head discharges the liquid material of each color to the powder material layer under control. The number of heads and the type of liquid material to be ejected can be changed. For example, in the case where coloring is not necessary for the modeled object, only the clear head may be set and only the clear modeling liquid material may be discharged.

  The head can move in the Y-axis and Z-axis directions using the guide rail. When the 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 liquid material discharged by the head is mixed with the powder material, the resin contained in the powder material is dissolved, and adjacent powder materials are bonded to each other. As a result, a modeling layer having a thickness (Δt1−Δt2) is formed.

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

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

<Degreasing and sintering of 3D objects>
The obtained three-dimensional model is degreased and sintered as necessary.
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]
<Preparation of powder material 1 for three-dimensional modeling>
-Preparation of resin aqueous solution 1-
5 parts by weight of polyvinyl alcohol having a 1,2-glycol bond with stirring to 100 parts by weight of water (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1028, polymerization degree 600, saponification degree 98 to 99 mol%) The mixture was stirred while heating to 80 ° C. in a water bath to obtain [resin aqueous solution 1].

-Measurement of the degree of modification of polyvinyl alcohol-
The degree of modification of 1,2-glycol of the polyvinyl alcohol was measured by the following method with reference to Patent Document 6 (International Publication No. WO2008 / 093615A1).
50 mg of polyvinyl alcohol was dissolved in 0.6 ml of DMSO-d6 and measured by ¹ H-NMR (ECX-500, manufactured by JEOL Ltd.). Each sample was weighed three times, each was measured five times (15 times in total), and the average value was adopted. Moreover, measurement temperature was measured at 50 degreeC and 80 degreeC, respectively.

  In Patent Document 6, peaks indicating 1,2-glycol are A (4.2 to 4.3 ppm), B (3.4 to 3.6 ppm), and C (1.7 to 1.9 ppm). The peaks indicating hydroxyl groups directly bonded to the main chain are a1 (4.6 ppm), a2 (4.4 ppm), and a3 (4.2 ppm), and the peaks indicating methylene in the main chain are b1 (1 The degree of modification is determined from the formulas 1 to 3 described in paragraph [0050] of Patent Document 6 and α, β, and γ are obtained, and average values thereof are employed. However, as a result of measurement, B was good in quantification, but A was hidden in the peak of the hydroxyl group and difficult to quantify, and C changed greatly between the partially saponified type and the fully saponified type. It was suggested that the residual acetate of 9 to 2.0 ppm might be greatly influenced. From the above, β using the following formula (1) ([Formula 2] described in Patent Document 6) was adopted as the degree of modification of the 1,2-glycol bond in the present invention.

  As a result of measuring the degree of modification of 1,2-glycol of the polyvinyl alcohol by the above method, it was 2.5 mol% at 50 ° C, 2.4 mol% at 80 ° C, and the average value thereof was 2.5 mol%. there were.

-Production of powder material 1 for three-dimensional modeling-
Stainless steel (SUS316L) powder (PSS316L, volume average particle size 43 μm, manufactured by Sanyo Special Steel Co., Ltd.) is used as the base material, and [resin aqueous solution 1] is used as the coating liquid. ), Resin coating was performed on the substrate under the following conditions to produce [3D powder material 1]. The resin adhesion amount of [Three-dimensional modeling powder material 1] was 1.0% by mass. The resin adhesion amount was measured by using a thermogravimetric analyzer (TGA-50, manufactured by Shimadzu Corporation), raising the temperature to 400 ° C., and calculating the weight reduction rate. The volume average particle diameter of the obtained three-dimensional modeling powder material 1 was 45 μm as measured using a particle size distribution analyzer (Microtrac MT3000II, manufactured by Microtrac Bell).

(Coating conditions)
・ Substrate particle input: 1000 g
・ Spray conditions Nozzle type: 970
Nozzle diameter: 1.2mm
Coating liquid discharge pressure: 4.7 Pa · s
Coating liquid discharge speed: 3 g / min
Atomized air volume: 50 NL / min,
・ Rotor conditions Rotor model: M-1
Rotation speed: 60rpm
Rotational speed: 400%
・ Airflow conditions Supply air temperature: 75 ℃
Supply air volume: 0.8 m ³ / min
Bag filter pressure drop: 0.2 MPa
Bug filter dropout time: 0.3 seconds Bug filter interval: 5 seconds

<Preparation of modeling liquid 1>
60 parts by mass of water and 40 parts by mass of 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a wetting agent were mixed and stirred to prepare [Modeling solution 1].

<Preparation of three-dimensional model 1>
[3D modeling object 1] was produced in accordance with the following method using a 3D model manufacturing apparatus shown in FIG. 1 using a counter roller as the 3D modeling powder material layer forming means and using an inkjet head as the modeling liquid supply means. The [3D modeling powder material 1] is put in the powder material container of the three-dimensional model manufacturing apparatus, the [Modeling liquid 1] is put in the same liquid material container, and 3D data is input, as shown in FIG. The process was repeated to produce [3D object 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 100 μm, and a total of 30 layers were laminated.
Subsequently, after air-drying for about 2 hours, it put into the dryer and dried at 70 degreeC for 3 hours. After that, remove the three-dimensional modeling powder material with no modeling liquid attached with a brush, put it in the dryer again, dry at 100 ° C. for 12 hours, and let it cool to room temperature as it is to produce [three-dimensional model 1] did.

<Bending stress test of the three-dimensional structure 1>
The obtained [3D model 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-
◎: 9.0 MPa or more ○: 6.0 MPa or more and less than 9.0 MPa Δ: 3.0 MPa or more and less than 6.0 MPa ×: less than 3.0 MPa

<Dimensional accuracy evaluation of the three-dimensional structure 1>
The obtained [3D model 1] was evaluated for dimensional accuracy by visual observation. The results were classified according to the following criteria. The results are shown in Table 1.
-Evaluation criteria-
◎: The surface of the three-dimensional structure is smooth and has little unevenness, and no warpage occurs. ○: The surface of the three-dimensional structure has slight unevenness and a slight warp is observed.
Δ: Level at which clear irregularities and warpage are recognized on the surface of the three-dimensional structure ×: Level at which the surface of the three-dimensional structure is round and greatly different from the target shape

<Evaluation of delamination of 3D object 1>
The fracture surface of [three-dimensional model 1] that had been subjected to the bending stress test was observed using a scanning electron microscope and a laser microscope to evaluate delamination. The results were classified according to the following criteria. The results are shown in Table 1.
A: Level where there is almost no void between the powder layers and no delamination is observed. ○: A slight void is observed between the powder layers, but the layer is firmly adhered as a layer. Δ: A layered void is observed between the powder layers. Level where the parts are adhered X: Level at which it is clearly observed that the layers are peeled off visually, not by a microscope

<Degreasing and sintering of the three-dimensional structure 1>
The obtained [three-dimensional model 1] was put in a dryer and heated to 400 ° C. in a nitrogen atmosphere to perform a degreasing process. The obtained degreased product was transferred into a sintering furnace and subjected to sintering treatment at 1300 ° C. under vacuum conditions to produce [three-dimensional sintered product 1].

[Example 2]
[3D modeling powder material 2] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Stereoscopic modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 2], a [3D model 2] was produced in the same manner as in Example 1. Using the obtained [three-dimensional model 2], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1080, polymerization degree 600, saponification degree 98-99 mol%): 5 parts by mass 1,2-glycol of the polyvinyl alcohol The degree of modification of was measured in the same manner as in Example 1. As a result, it was 3.9 mol% at 50 ° C and 3.7 mol% at 80 ° C, and the average value thereof was 3.8 mol%.

[Example 3]
[3D modeling powder material 3] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Stereoscopic modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 3], in the same manner as in Example 1, [3D modeling product 3] was produced. Using the obtained [three-dimensional model 3], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-8049, polymerization degree 450, saponification degree 98-99 mol%): 7 parts by mass 1,2-glycol of the polyvinyl alcohol The degree of modification of was measured in the same manner as in Example 1. As a result, it was 3.7 mol% at 50 ° C and 3.6 mol% at 80 ° C, and the average value thereof was 3.7 mol%.

[Example 4]
[Position material for solid modeling 4] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Powder material for solid modeling] of Example 1. Using the obtained [3D modeling powder material 4], a [3D model 4] was produced in the same manner as in Example 1. Using the obtained [three-dimensional model 4], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1027, polymerization degree 1200, saponification degree 98 to 99 mol%): 2.5 parts by mass 1,2 of the polyvinyl alcohol The degree of modification of glycol was measured in the same manner as in Example 1. As a result, it was 2.1 mol% at 50 ° C and 2.0 mol% at 80 ° C, and the average value thereof was 2.1 mol%. .

[Example 5]
[Powder material 5 for three-dimensional modeling] was produced in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Powder material 1 for three-dimensional modeling] of Example 1. Using the obtained [3D modeling powder material 5], in the same manner as in Example 1, [3D modeling object 5] was produced. Using the obtained [three-dimensional model 5], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G-polymer OKS-1109, polymerization degree 1200, saponification degree 98-99 mol%): 2.5 parts by mass 1,2 of the polyvinyl alcohol -The degree of modification of glycol was measured in the same manner as in Example 1. As a result, it was 3.4 mol% at 50 ° C, 3.3 mol% at 80 ° C, and the average value thereof was 3.4 mol%. .

[Example 6]
[3D modeling powder material 6] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in the [3D modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 6], a [3D model 6] was produced in the same manner as in Example 1. Using the obtained [three-dimensional model 6], in the same manner as in Example 1, a bending stress test, dimensional accuracy evaluation, and delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-8039, polymerization degree 600, saponification degree 98-99 mol%): 5 parts by mass 1,2-glycol of the polyvinyl alcohol The degree of modification of was measured in the same manner as in Example 1. As a result, it was 4.7 mol% at 50 ° C and 4.6 mol% at 80 ° C, and the average value thereof was 4.7 mol%.

[Example 7]
[3D modeling powder material 7] was prepared in the same manner as in Example 1 except that the polyvinyl alcohol was changed to the following in the [3D modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 7], in the same manner as in Example 1, [3D modeling object 7] was produced. Using the obtained [three-dimensional model 7], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Polyvinyl alcohol having 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-8089, polymerization degree 600, saponification degree 88 mol%): 5 parts by mass Modification of 1,2-glycol of the polyvinyl alcohol The degree was measured in the same manner as in Example 1. As a result, it was 4.5 mol% at 50 ° C and 4.5 mol% at 80 ° C, and the average value thereof was 4.5 mol%.

[Example 8]
Except having changed polyvinyl alcohol into the mixture of the following polyvinyl alcohols A and B in [the powder material 1 for three-dimensional modeling] of Example 1, it is the same as that of Example 1 and [powder material for three-dimensional modeling 8]. Was made.
Using the obtained [3D modeling powder material 8], in the same manner as in Example 1, [3D modeling object 8] was produced. Using the obtained [three-dimensional model 8], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
A: Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1027, polymerization degree 1200, saponification degree 98-99 mol%): 1 part by mass B: 1,2-glycol Polyvinyl alcohol having a bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1028, polymerization degree 600, saponification degree 98 to 99 mol%): 3 parts by mass The average value of the degree of modification of the polyvinyl alcohols A and B is It was 2.4 when each average value was converted by the mixing ratio.

[Example 9]
[Powder material for three-dimensional modeling 9] in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following mixture of polyvinyl alcohols A and B in [Powder material for three-dimensional modeling] of Example 1. Was made. Using the obtained [three-dimensional modeling powder material 9], [three-dimensional model 9] was produced in the same manner as in Example 1. Using the obtained [three-dimensional model 9], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
A: Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1027, polymerization degree 1200, saponification degree 98-99 mol%): 1 part by mass B: 1,2-glycol Polyvinyl alcohol having a bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-8041, polymerization degree 300, saponification degree 89 mol%): 6 parts by mass The degree of modification of 1,2-glycol of polyvinyl alcohol B was As a result of measurement in the same manner as in Example 1, it was 3.4 mol% at 50 ° C and 3.2 mol% at 80 ° C, and the average value thereof was 3.3 mol%. Moreover, the average value of the modification degree of the polyvinyl alcohols A and B was 3.1 when each average value was converted by the mixing ratio.

[Example 10]
Except having changed polyvinyl alcohol into the following mixture of polyvinyl alcohols A and B in [Powder material for three-dimensional modeling 1] of Example 1, [Powder material for three-dimensional modeling 10] is the same as Example 1. Was made. Using the obtained [3D modeling powder material 10], in the same manner as in Example 1, [3D modeling object 10] was produced. Bending stress test, dimensional accuracy evaluation, and delamination evaluation were performed in the same manner as in Example 1 using the obtained [three-dimensional model 10]. The results are shown in Table 1.
A: Polyvinyl alcohol having a 1,2-glycol bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer OKS-1080, polymerization degree 600, saponification degree 98-99 mol%): 2 parts by mass B: 1,2-glycol Polyvinyl alcohol having a bond (manufactured by Nippon Synthetic Chemical Industry, Nichigo G polymer AZF-8035W, polymerization degree 300, saponification degree 98-99 mol%): 6 parts by mass The degree of 1,2-glycol modification of polyvinyl alcohol B is As a result of measurement in the same manner as in Example 1, it was 3.4 mol% at 50 ° C. and 3.2 mol% at 80 ° C., and the average value thereof was 3.3 mol%. The average value of the degree of modification of the polyvinyl alcohols A and B was 4.6 when each average value was converted by the mixing ratio.

[Comparative Example 1]
[3D modeling powder material 11] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Stereoscopic modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 11], in the same manner as in Example 1, [3D modeling object 11] was produced. Bending stress test, dimensional accuracy evaluation, and delamination evaluation were performed in the same manner as in Example 1 using the obtained [three-dimensional model 11]. The results are shown in Table 1.
Unmodified polyvinyl alcohol (manufactured by Kuraray, PVA-105, polymerization degree 500, saponification degree 98 to 99 mol%): 5 parts by mass

[Comparative Example 2]
[3D modeling powder material 12] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in [Stereoscopic modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 12], in the same manner as in Example 1, [3D modeling object 12] was produced. Bending stress test, dimensional accuracy evaluation, and delamination evaluation were performed in the same manner as in Example 1 using the obtained [three-dimensional model 12]. The results are shown in Table 1.
Special polyvinyl alcohol (manufactured by Nihon Acetate / Poval, JMR-30M, polymerization degree 100-400, saponification degree 65 mol%): 5 parts by mass

[Comparative Example 3]
[3D modeling powder material 13] was prepared in the same manner as in Example 1 except that polyvinyl alcohol was changed to the following in the [3D modeling powder material 1] of Example 1. Using the obtained [3D modeling powder material 13], in the same manner as in Example 1, [3D modeling product 13] was produced. Using the obtained [three-dimensional model 13], in the same manner as in Example 1, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Anion-modified polyvinyl alcohol (manufactured by Nippon Polyvinyl acetate / Poval, AP-10, polymerization degree 1000, saponification degree 89 mol%): 3 parts by mass

[Example 11]
In Example 2, except that the base material was changed to silica particles (Excelica SE-15K, manufactured by Tokuyama Co., Ltd., volume average particle size 24 μm), the same as in Example 2 [powder material 14 for three-dimensional modeling] Was made. Using the obtained [3D modeling powder material 14], in the same manner as in Example 2, a [3D model 14] was produced. Using the obtained [three-dimensional model 14], in the same manner as in Example 2, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.

[Example 12]
In Example 4, except that the base material was changed to spherical alumina particles (manufactured by Denki Kagaku Kogyo Co., Ltd., DAM-45, d50: 41.2 μm), the same as in Example 4 [Powder material 15 for three-dimensional modeling] Was made. Using the obtained [3D modeling powder material 15], in the same manner as in Example 4, [3D modeling product 15] was produced. Using the obtained [three-dimensional model 15], in the same manner as in Example 4, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.

[Example 13]
[Modeling solution 2] was produced in the same manner as Example 2 except that the following crosslinking agent was added to the [Modeling solution 1] of Example 2. Using the obtained [Modeling liquid 2], in the same manner as Example 2, [3D model 16] was produced. Using the obtained [three-dimensional model 16], in the same manner as in Example 2, a bending stress test, dimensional accuracy evaluation, and delamination evaluation were performed. The results are shown in Table 1.
Zirconium compound (Daiichi Rare Element Chemical Industries, Zircosol AC-20): 3 parts by mass

[Example 14]
[Modeling solution 3] was produced in the same manner as Example 3 except that the following crosslinking agent was added to [Modeling solution 1] of Example 3. Using the obtained [Modeling liquid 3], [3D model 17] was produced in the same manner as Example 3. Using the obtained [three-dimensional model 17], in the same manner as in Example 3, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Titanium compound (manufactured by Matsumoto Fine Chemical, ORGATICS TC-310): 7 parts by mass

[Example 15]
[Modeling solution 4] was prepared in the same manner as Example 7 except that the following crosslinking agent was added to [Modeling solution 1] of Example 7. Using the obtained [Modeling liquid 4], in the same manner as Example 7, [Three-dimensional modeled object 17] was produced. Using the obtained [three-dimensional model 17], in the same manner as in Example 7, a bending stress test, a dimensional accuracy evaluation, and a delamination evaluation were performed. The results are shown in Table 1.
Zirconium compound (manufactured by Daiichi Rare Element Chemical Industry, Zircosol AC-7): 5 parts by mass

  The three-dimensional modeling powder material of the present invention is coated with polyvinyl alcohol having 1,2-glycol bonds in the side chain, so that the three-dimensional model obtained using the modeling liquid has high strength and high dimensional accuracy. As a result, a three-dimensional object having a desired shape could be obtained without deformation even in a complicated shape. In addition, it was confirmed that the three-dimensional sintered product obtained by degreasing and sintering the three-dimensional modeled product maintained a complicated shape and was a hard and strong structure. However, it was confirmed that when the three-dimensional model of the comparative example was sintered, warpage and surface irregularities were conspicuous, the shape was partially deformed, and it was damaged when subjected to an impact, resulting in low strength.

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

JP-T 2006-521264 JP 2005-297325 A JP 2011-230422 A

Claims (14)

  3D modeling powder material comprising coated particles formed by coating substrate particles with resin, wherein the resin contains polyvinyl alcohol containing 1,2-glycol bond in the side chain Powder material.   The three-dimensional modeling powder material according to claim 1, wherein the degree of modification of 1,2-glycol bond contained in the polyvinyl alcohol is 4.0 mol% or less.   The three-dimensional modeling powder material according to claim 1 or 2, wherein the polyvinyl alcohol is a mixture of two or more kinds of polyvinyl alcohols having different degrees of modification of 1,2-glycol bonds.   The three-dimensional modeling powder material according to any one of claims 1 to 3, wherein the polyvinyl alcohol is a mixture of two or more kinds of polyvinyl alcohols having different degrees of polymerization.   The three-dimensional modeling powder material according to any one of claims 1 to 4, wherein a degree of polymerization of the polyvinyl alcohol is 400 to 1200.   The powder material for three-dimensional modeling according to any one of claims 1 to 5, wherein the degree of saponification of the polyvinyl alcohol is 97% or more.   The three-dimensional modeling powder material according to any one of claims 1 to 6, wherein the substrate is made of metal or ceramic.   A three-dimensional modeling material set comprising: the three-dimensional modeling powder material according to any one of claims 1 to 7; and a modeling liquid capable of dissolving the polyvinyl alcohol contained in the powder material.   The three-dimensional modeling material set according to claim 8, wherein the modeling liquid contains water and a water-soluble solvent.   The three-dimensional modeling material set according to claim 8 or 9, wherein the modeling liquid contains a crosslinking agent.   11. The solid modeling material set according to any one of claims 8 to 10, further comprising: a powder material layer forming means for forming a layer of the powder material for three-dimensional modeling; and supplying the modeling liquid to the layer of the powder material for three-dimensional modeling An apparatus for manufacturing a three-dimensional structure, characterized by comprising liquid material supply means for performing the processing.   The apparatus for producing a three-dimensional structure according to claim 11, wherein the liquid material supply means is an ink jet system.   A method for producing a three-dimensional structure, wherein the three-dimensional structure material set according to any one of claims 8 to 10 is used to supply the modeling liquid to the layer of the three-dimensional structure powder material.   The method for producing a three-dimensional structure according to claim 13, wherein a method of supplying the modeling liquid to the layer of the powder material for three-dimensional structure is an ink jet method.