JP2018119026A - Molding material and method for producing three-dimensional object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material, which can be easily removed by water after molding and mold a three-dimensional object that is hardly cracked even under an impact force.SOLUTION: A molding material comprises a low molecular saccharide and a water-soluble polymer. The water-soluble polymer is at least one selected from the group consisting of polyalkylene glycols and polyvinyl alcohols. The content of the water-soluble polymer is more than 1.0 mass% and less than 30 mass%, relative to 100 mass% of the entire molding material.SELECTED DRAWING: None

Description

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

  In recent years, as a method for manufacturing a three-dimensional object, a layered modeling method in which modeling materials are stacked based on cross-sectional data of a three-dimensional object (modeling object) to be produced has attracted attention.

  When a three-dimensional object having a complicated shape including an overhang part, a movable part, and the like is produced by an additive manufacturing method, the structure part is disposed on a region where the structure part constituting the three-dimensional object does not exist. In such a case, in order to support the structure part to be arranged, a support part may be provided below the structure part in the direction of gravity. That is, a support part is formed in the part which becomes the space | gap of a solid object as needed in the process of modeling by the additive manufacturing method. This support part is finally removed.

  Patent Document 1 describes that, in the additive manufacturing method, a water-soluble material such as saccharide, polyalkylene oxide, or polyvinyl alcohol is used as a support material for forming a support portion. By using a water-soluble material as the support material and using a water-insoluble material as the structural material to form the structure part, the three-dimensional object having the structure part and the support part is immersed in water to selectively dissolve and remove the support part. it can. Thus, it is preferable from a viewpoint of the ease of removal of a support part that a support part can be removed by making it contact with the liquid containing water.

JP2015-180537A

  Since a water-soluble material having a low molecular weight such as a saccharide has a high solubility in water, the use of a water-soluble material having a low molecular weight as a support material can improve the removability of the support part. However, a support portion formed using a water-soluble material having a low molecular weight such as saccharide is hard and fragile. The hard and fragile support portion is liable to generate cracks when an impact force is applied during or after layered modeling, and may reduce the modeling accuracy of a three-dimensional object.

  On the other hand, when a water-soluble material having a high molecular weight such as polyalkylene oxide or polyvinyl alcohol is used as the support material, the impact resistance of the formed support portion can be increased. However, these materials have significantly lower solubility in water than water-soluble materials having a low molecular weight such as saccharides. Therefore, when these materials are used as a support material, the removability of the support portion is significantly lowered.

  Therefore, the conventional modeling material which can be removed by water after modeling has a problem that it cannot achieve both the removability by water and the impact resistance.

  In view of the above-described problems, an object of the present invention is to provide a modeling material that can be easily removed by water after modeling and is less likely to crack even when an impact force is applied.

  The modeling material as one aspect of the present invention contains a low-molecular saccharide and a water-soluble polymer, and the water-soluble polymer is selected from the group consisting of polyalkylene glycols and polyvinyl alcohols. It is at least one, and the content of the water-soluble polymer is greater than 1.0% by mass and less than 30% by mass when the entire modeling material is 100% by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the modeling material which can be easily removed with water after modeling and can model the solid thing which does not produce a crack easily even if an impact force is added can be provided.

It is a figure which shows typically the 1st structural example of the modeling apparatus which concerns on this embodiment. It is a figure which shows typically the 2nd structural example of the modeling apparatus which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below. Further, in the present invention, the scope of the present invention also includes those in which the embodiments described below are appropriately modified and improved based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. include.

  In the present specification, the “modeling material” refers to a modeling material used when manufacturing a three-dimensional object. The modeling material is classified into a structural material (model material) constituting a target three-dimensional object and a support material that supports the lamination of the structural materials. The support portion made of the support material is a portion that supports the structural material disposed on the region where the structural material does not exist, and is a portion that is finally removed.

  Moreover, in this specification, "modeling material particle" refers to a particulate modeling material. The modeling material particles are classified into “structural material particles (model material particles)” that are particulate structural materials and “support material particles” that are particulate support materials. Further, in this specification, the powder containing modeling material particles is “support material”, the powder containing structural material particles is “structural material powder (model material powder)”, and the powder containing support material particles is “support material”. "Powder", respectively.

  In the present specification, the “water-soluble material” refers to a material having water solubility, and refers to a material having a solubility in water of 1 or more. That is, “water-soluble” refers to the property that the solubility in water is 1 or more. The “water-insoluble material” refers to a material that does not have water solubility, and refers to a material that has a solubility in water of less than 1. Here, the “solubility in water” is a numerical value representing the mass dissolved in 100 g of pure water having a water temperature of 20 ° C. at 1 atm in grams.

(First embodiment)
The modeling material which concerns on 1st Embodiment contains a low molecular sugar (A) and a water-soluble polymer (B). The low molecular sugar (A) has a high solubility in water due to its low molecular weight. Therefore, when the modeling material contains the low-molecular sugar (A), when the three-dimensional object formed using the modeling material is brought into contact with the liquid containing water, the portion formed by the modeling material (support part) And structural parts) can be efficiently removed. In the following description, the part formed with modeling material may be called "modeling part."

  However, when the modeling material is composed only of the low molecular sugar (A), the modeling part formed thereby tends to have low toughness. If the toughness of the support portion or the structure portion is low, cracks (cracks) are likely to occur when an impact force is applied to the support portion or the structure portion. If a crack occurs in the structure portion, the shape of the three-dimensional object itself changes, and the modeling accuracy of the three-dimensional object is lowered. In addition, if a crack occurs in the structure part or the support part, it affects the shape of the structure part laminated on the structure part or the support part, so that the shape of the three-dimensional object may change. Modeling accuracy may be reduced.

  Here, the “impact force” includes a physical impact force and a thermal impact force. Thermal impact force refers to a sudden change in the temperature of an object. For example, when a modeling material is applied to an additive manufacturing method and a three-dimensional object is modeled while heating and / or cooling the modeling material, the temperature is set to several hundred degrees C (for example, about 200 degrees C for several seconds (for example, 5 seconds)). ) May change. At this time, an internal stress accompanying the temperature change is generated in the support part and the structure part exposed to the temperature change, and this becomes a thermal impact force, which may lead to a crack in the support part or the structure part.

  Therefore, the modeling material according to the present embodiment contains a water-soluble polymer (B) in addition to the low molecular sugar (A). The water-soluble polymer (B) is a component having a larger molecular weight than the low molecular weight saccharide (A), has higher elasticity than the low molecular weight saccharide (A), and can be plastically deformed when an external force is applied. The modeling part formed by the modeling material containing such a water-soluble polymer (B) relieves stress even when an impact force is applied by the water-soluble polymer (B) functioning as an elastic component. be able to. Therefore, since the modeling material contains the water-soluble polymer (B) in addition to the low-molecular sugar (A), it is possible to suppress the generation of cracks in the formed modeling part, and improve the modeling accuracy of the three-dimensional object. be able to.

  However, since the water-soluble polymer (B) has a higher molecular weight than the low-molecular saccharide (A), it is a water-soluble material, but tends to be less water-soluble than the low-molecular saccharide (A). Moreover, the liquid in which the water-soluble polymer (B) is dissolved in water has a considerably higher viscosity than the liquid in which the same amount of the low-molecular sugar (A) is dissolved in water. As described above, since the water-soluble polymer (B) is low in water solubility and takes time to remove the dissolved liquid, a large amount of the water-soluble polymer (B) is added to the modeling material. And the removability by the water of a modeling part will fall remarkably.

  Therefore, in the modeling material according to this embodiment, the content of the water-soluble polymer (B) is larger than 1.0% by mass and less than 30% by mass when the total amount of the modeling material is 100% by mass. Contains water-soluble polymer (B). Thus, in the present embodiment, it is possible to provide a modeling material that can be easily removed with water after modeling and is less likely to crack even when an impact force is applied. In the present specification, “easy to remove” means that the time required for removal is short, or at least one of special work and environment is not required for removal.

  Hereinafter, each component contained in the modeling material will be described.

<Low molecular sugar (A)>
The low molecular weight saccharide (A) contained in the modeling material is a saccharide having a lower molecular weight than the water-soluble polymer (B). The low molecular weight saccharide (A) is a water-soluble material having a high solubility in water. The solubility of the low molecular weight saccharide (A) in water is preferably greater than 10 and more preferably greater than 50.

  The low molecular weight saccharide (A) is preferably a saccharide having a molecular weight of 100 or more and 1000 or less. The low molecular weight saccharide (A) is more preferably a saccharide or sugar alcohol having a molecular weight of 100 or more and 1000 or less. By setting the molecular weight of the low-molecular sugar (A) to 1000 or less, the removability of the portion constituted by the modeling material with water can be further improved.

  As the saccharide having a molecular weight of 100 or more and 1000 or less, it is preferable to use monosaccharide, disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, or oligosaccharide having a molecular weight of 1000 or less. The sugar alcohol having a molecular weight of 100 or more and 1000 or less includes a sugar alcohol derived from a monosaccharide, a sugar alcohol derived from a disaccharide, a sugar alcohol derived from a trisaccharide, a sugar alcohol derived from a tetrasaccharide, or an oligosaccharide having a molecular weight of 1000 or less. It is preferred to use a sugar alcohol derived from. The “sugar sugar derived from X sugar” herein refers to a sugar alcohol obtained by reducing X sugar.

  Low molecular sugar (A) is monosaccharide, disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, sugar alcohol derived from monosaccharide, sugar alcohol derived from disaccharide, sugar alcohol derived from trisaccharide, sugar alcohol derived from tetrasaccharide And at least one selected from the group consisting of sugar alcohols derived from pentasaccharides.

  The low molecular weight saccharide (A) may be composed of only one kind of saccharide, or may be composed of a plurality of kinds of saccharides. Here, it is assumed that the “type” of the low molecular sugar (A) is determined by the chemical structure, and that the type is different when the chemical structure is different.

  Specific examples of the low molecular weight saccharide (A) include monosaccharides such as glucose (molecular weight 180.2), xylose (molecular weight 150.1) and fructose (molecular weight 180.2); sucrose (molecular weight 342.3), Disaccharides such as lactose (molecular weight 342.3), maltose (molecular weight 342.3), trehalose (molecular weight 342.3), isomaltulose (palatinose (registered trademark); molecular weight 342.3); melezitose (molecular weight 504.4) ), Maltotriose (molecular weight 504.4), nigerotriose (molecular weight 504.4), raffinose (molecular weight 504.4), kestose (molecular weight 504.4), etc .; maltotetraose (molecular weight 666.6) ), Tetrasaccharides such as stachyose (molecular weight 666.6); pentasaccharides.

  Specific examples of the low molecular weight saccharide (A) include simple substances such as xylitol (molecular weight 152.2), sorbitol (molecular weight 182.2), mannitol (molecular weight 182.2), and erythritol (molecular weight 122.1). Sugar alcohol derived from sugar; sugar alcohol derived from disaccharides such as lactitol (molecular weight 344.3), maltitol (molecular weight 344.3); sugar alcohol derived from trisaccharide; sugar alcohol derived from tetrasaccharide; sugar derived from pentasaccharide Alcohol.

  Specific examples of the low molecular weight saccharide (A) include, for example, oligosaccharides such as isomaltoligosaccharide, fructooligosaccharide, xylooligosaccharide, soybean oligosaccharide, galactooligosaccharide, nigerooligosaccharide, and dairy oligosaccharide. And oligosaccharides having a molecular weight of 100 to 1,000.

  The blending ratio of the low molecular sugar (A) in the modeling material is preferably 50% by mass or more and 90% by mass or less when the entire modeling material is 100% by mass. Further, the blending ratio is more preferably 55% by mass or more and 80% by mass or less. The removability by the water of the modeling part formed with the said modeling material can be made high by making the mixture ratio of a low molecular sugar (A) into 50 mass% or more. Moreover, the impact resistance of the part formed with the said modeling material can be improved by the mixture ratio of a low molecular sugar (A) being 90 mass% or less.

<Water-soluble polymer (B)>
The water-soluble polymer (B) contained in the modeling material is a polymer having water solubility.

  The water-soluble polymer (B) preferably has a molecular weight of greater than 1000, more preferably a molecular weight of greater than 5000, still more preferably a molecular weight of greater than 10,000, and particularly preferably a molecular weight of greater than 20,000. Although the upper limit of the molecular weight of water-soluble polymer (B) is not specifically limited, From a viewpoint of the removability by the water after modeling, it is preferable that it is 100,000 or less, and it is more preferable that it is 50000 or less.

  The water-soluble polymer (B) according to this embodiment contains at least one selected from the group consisting of polyalkylene glycols and polyvinyl alcohols.

  Here, in the present specification, “polyalkylene glycols” include polyalkylene glycol and derivatives thereof, and “polyvinyl alcohols” include polyvinyl alcohol and derivatives thereof.

  The water-soluble polymer (B) may be composed of only one type of polymer or may be composed of a plurality of types of polymers. Here, the “type” of the water-soluble polymer (B) is determined by the chemical structure, and when the chemical structure is different, it is expressed that the type is different. When the water-soluble polymer (B) is composed of a plurality of types of polymers, it is preferable that the molecular weight of all types of polymers constituting the water-soluble polymer (B) is greater than 1000.

  Specific examples of the water-soluble polymer (B) include, for example, alkylene glycols such as polyethylene glycol (PEG), polyethylene oxide (PEO), polypropylene glycol (PPG), and polypropylene oxide (PPO); polyvinyl alcohol (PVA), And polyvinyl alcohols such as ethylene / vinyl alcohol copolymer (EVOH) and butenediol vinyl alcohol copolymer (BVOH).

  In this embodiment, the mixture ratio in the modeling material of water-soluble polymer (B) is larger than 1.0 mass% and less than 30 mass% when the whole modeling material is 100 mass%. The blending ratio is more preferably 5% by mass or more and less than 30% by mass, further preferably 5.0% by mass or more and 20% by mass or less, and more preferably 10% by mass or more and 20% by mass or less. Is particularly preferred. By making the blending ratio of the water-soluble polymer (B) less than 30% by mass, the removability of the modeling part formed by the modeling material with water can be increased. Moreover, the impact resistance of the part formed with the said modeling material can be improved by making the mixture ratio of water-soluble polymer (B) larger than 1.0 mass%.

<Other water-soluble components (C)>
The modeling material according to the present embodiment may contain other water-soluble components (C) in addition to the low-molecular sugar (A) and the water-soluble polymer (B).

  The mixing ratio of the water-soluble material containing the low-molecular saccharide (A), the water-soluble polymer (B), and the other water-soluble component (C) is 51 mass when the total amount of the modeling material is 100 mass%. % Is more preferable, and 60% by mass or more is more preferable. Moreover, it is especially preferable that the said mixture ratio is 70 mass% or more. By making the said mixture ratio larger than 51 mass% and making the main component of modeling material into a water-soluble material, the removability by the water of the modeling part formed with the said modeling material can be made high. The upper limit of the blending ratio is not particularly limited, but the blending ratio of the water-soluble material may be 95% by weight or less when the total amount of the modeling material is 100% by weight, It may be 90% by mass or less.

<Water-insoluble component (D)>
The modeling material according to the present embodiment may contain a water-insoluble component (D) in addition to the water-soluble material. Examples of the water-insoluble component (D) include, but are not limited to, fillers (fillers), pigments, dispersants, and the like.

(Filler)
It is preferable that the modeling material which concerns on this embodiment contains a filler (filler). The filler may be a water-insoluble inorganic material or a water-insoluble organic material. The filler may be particulate or fibrous. The filler is preferably a material that adjusts the characteristics of the modeling material, but is not limited thereto. When the modeling material is a particulate modeling material (modeling material particle), the filler is preferably smaller than the particle size of the modeling material particle.

  Specific examples of the particulate filler include, for example, calcium carbonate, alumina, talc, mica, wollastonite, zonolite, silicon carbide, silica, glass, carbon black, graphite, and metal powder. It is not limited. The particulate filler may be solid particles or hollow.

  Specific examples of the fibrous filler include, but are not limited to, aramid fibers, cellulose fibers, carbon fibers, glass fibers, aramid nanofibers, and cellulose nanofibers.

  Among these, it is preferable that the modeling material which concerns on this embodiment contains a fibrous filler. This is because by using the fibrous filler, a matrix made of the fibrous filler can be formed inside the modeling material, and the characteristics of the modeling material can be adjusted effectively. The characteristics of the modeling material that can be adjusted by the filler include, for example, viscoelasticity, mechanical properties such as strength, hardness, and toughness. For example, by forming a matrix made of a fibrous filler inside the modeling material, even if the viscosity of components other than the filler increases when the modeling material is heated, the above-described matrix of the fibrous filler The movement of the viscous flow of the components can be hindered. Thereby, the elasticity at the time of heating of modeling material can be raised, and viscoelasticity can be adjusted.

  As the fibrous filler, it is preferable to use a fiber material having a nano-sized diameter or length (hereinafter referred to as “nanofiber”). When the modeling material contains nanofibers, the nanofibers can be dispersed in the modeling material, and a three-dimensional network structure can be easily formed in the modeling material. Thereby, the characteristic of a modeling material can be adjusted more effectively.

  The nanofibers used in this embodiment preferably have an average fiber diameter of 1 nm to 500 nm, more preferably 1 nm to 100 nm, and particularly preferably 1 nm to 50 nm. Further, the length of the nanofiber is preferably 4 times or more of the average fiber diameter, more preferably 10 times or more, and further preferably 50 times or more. By making the length of the nanofiber sufficiently larger than the average fiber diameter, it is possible to improve the uniformity inside the modeling material having the network structure as described above.

  The filler is preferably a material that is dispersed in water. As described later, in the step of removing the support portion, the water-soluble material is dissolved in the removal liquid by bringing the intermediate shaped article into contact with a liquid (removal liquid) containing water. At this time, the filler remains because it does not dissolve in water, but since the region where the water-soluble material was present in the modeling portion becomes a void, the filler is pushed away by the removal liquid and removed. . At this time, if the filler is a material dispersed in water, the filler can be more easily removed, and the removability of the modeling material with water can be improved.

<Shell>
As will be described later, the shape of the modeling material according to the present embodiment is not particularly limited, but the modeling material may be a particulate modeling material (modeling material particle). When making the modeling material which concerns on this embodiment into modeling material particle | grains, it is preferable to further have the shell which covers at least one part of the surface of particle | grains. That is, the modeling material particle according to the present embodiment includes a core composed of a low-molecular sugar (A), a water-soluble polymer (B), another water-soluble component (C), and a water-insoluble component (D), It is preferable to have a shell covering at least a part of the surface.

  The material of the shell is not particularly limited and may be a water-soluble material or a water-insoluble material, but the solubility of the material most contained in the shell in water is the water content of the water-soluble material contained in the core. It is preferable that the solubility is smaller than that. In addition, the solubility in water of the material most contained in the shell is smaller than the solubility in water of the water-soluble material contained in the core is smaller than the solubility in water of any water-soluble material contained in the core. Say. Moreover, the shell may be comprised with multiple types of material. The material most contained in the shell is preferably a material having a solubility in water of less than 10, more preferably less than 5, and even more preferably less than 1.

The modeling material particle having such a structure is obtained by applying thermal energy or thermal energy and pressure under appropriate conditions according to the coverage of the shell to the core surface and the material of the core or shell. Can be exposed to the surface. For example, the shell material is destroyed by heating the modeling material particles above the softening temperature of the core or modeling material particles, or by heating and pressurizing at the same time as the softening temperature of the core or modeling material particles. Can be exposed to the surface. Here, in this specification, when the dynamic viscoelasticity is measured while increasing the temperature from room temperature, the temperature at which the loss elastic modulus becomes 10 ⁸ Pa or less is defined as “softening temperature”.

  Alternatively, a solution that selectively dissolves the shell material may be sprayed onto the shaped particles, and the shell material may be unevenly distributed on the particle surface using the surface tension of the droplets formed on the particle surface to expose the core material. Is possible.

  As described above, since the modeling material particles according to the present embodiment are formed with a material (shell) having low solubility in water on the surface thereof, aggregation is also caused by moisture absorption even in an atmosphere with a large amount of moisture in a powder state. It is suppressed and a decrease in fluidity is suppressed. Therefore, it is possible to maintain a powder state suitable for the additive manufacturing method without particularly managing the humidity.

  Examples of the material most often contained in the shell include organic substances typified by organic compounds and polymer compounds, inorganic substances typified by metals and ceramics, and organic / inorganic composite materials containing organic substances and inorganic substances. However, it is not limited to these materials.

  Examples of the organic substance include resin materials such as acrylic resins, vinyl resins, polyester resins, epoxy resins, and urethane resins, ester compounds such as glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, and ethyl cellulose. A part of the cellulose derivative can be suitably used.

  Moreover, if it is an inorganic substance, inorganic oxides, such as a silicon oxide, a titanium oxide, an alumina, can be used suitably. Further, those having a structure in which fluorine is directly bonded to these inorganic oxides are also preferably used.

<Viscoelasticity of modeling material>
The modeling material according to the present embodiment has a storage modulus of the modeling material in a temperature range of T ° C. or more and (T + 10) ° C. or less, where T (° C.) is a temperature at which the storage modulus of the modeling material is 1 MPa. It is preferred that it is always greater than the loss modulus of the modeling material. Since the modeling material according to the present embodiment has such viscoelastic characteristics, even if it is softened, it exhibits a behavior like rubber, does not flow, and tries to keep its shape. For this reason, it is easy to form a shaped part in a desired shape when heating and laminating, and the shape is less likely to change when the formed shaped part is heated. Therefore, the modeling accuracy of a three-dimensional object can be improved. In addition, the above-mentioned viscoelastic characteristic of the modeling material which concerns on this embodiment can be adjusted by selecting a filler appropriately according to the composition of water-soluble material.

  In addition, when the modeling material according to this embodiment is used as a support material and layered with other types of structural materials, the storage elastic modulus of the modeling material according to this embodiment is the temperature in the heating step of the layered modeling process. It is preferable that the elastic modulus is not less than the storage elastic modulus of the structural material.

  When the storage elastic modulus of the support material is smaller than the storage elastic modulus of the structural material to be laminated together, only the support material may be greatly deformed in the heating process or the lamination process. Since the support material is originally used to support the lamination of the structural material, if the deformation of the support material is increased, the shape of the structure portion formed by the structural material is changed. As a result, the modeling accuracy of the three-dimensional object decreases. Therefore, by making the storage elastic modulus of the support material larger than the storage elastic modulus of the structural material, the support material can always be in a harder state than the structural material. Thus, the structure portion can be supported.

  For example, the storage elastic modulus of the modeling material is preferably 0.1 MPa or more throughout the entire layered modeling process. Thereby, it can suppress that a support material remarkably softens and is washed away.

  Various characteristics such as viscoelasticity and softening temperature of the modeling material can be adjusted to desired values by mixing a plurality of materials. For example, as a low molecular sugar (A), maltotetraose and lactitol having a softening temperature lower than that of maltotetraose are mixed and used, and the ratio is adjusted so that the softening temperature of the low molecular sugar (A) is reduced. Can be adjusted. Moreover, viscoelastic characteristics can be adjusted by adding fillers, such as a cellulose nanofiber.

<Shape of modeling material>
The shape of the modeling material according to the present embodiment is not particularly limited. For example, when applying the modeling material according to the present embodiment to a layered modeling method in which modeling is performed using a powdered modeling material (modeling material powder), a particulate modeling material (modeling material particle) or It is good also as modeling material powder which is the aggregate. Examples of this type of additive manufacturing method include a powder sintering additive manufacturing method (SLS), a binder jetting (binder injection) method, and an electrophotographic method. Moreover, when applying the modeling material which concerns on this embodiment to the hot melt lamination method (FDM) type additive manufacturing method, it is good also as a pellet-shaped, rod-shaped, filament-shaped modeling material.

<Method for producing modeling material particles and modeling material powder>
The manufacturing method of the modeling material particle or modeling material powder which concerns on this embodiment is not specifically limited. The following method is mentioned as an example of the manufacturing method for obtaining modeling material particle or modeling material powder.

  The first method is a spray drying method. In this method, a water-insoluble component (D) such as a fiber material was dispersed in an aqueous solution containing a low-molecular sugar (A), a water-soluble polymer (B), and other water-soluble components (C). A thing is made into a raw material liquid. Then, the molding material particles (or modeling material powder) are obtained by spraying the raw material liquid into a gas and drying it rapidly. This method is preferable because the average particle diameter and circularity of the modeling material particles can be made relatively uniform.

  As the second method, there is a kneading pulverization method. In this method, a low-molecular sugar (A), a water-soluble polymer (B), other water-soluble components (C), and a water-insoluble component (D) were melt-kneaded to obtain a solid. Solid material is pulverized to obtain modeling material particles (or modeling material powder). According to this method, modeling material particles can be manufactured at low cost.

  As other methods, modeling material particles (or modeling material powder) may be manufactured using a mechanical pulverization method or a melt dispersion cooling method in which particles are obtained by being dispersed and cooled in a medium in a molten state. In these production methods, as described above, the other water-soluble component (C) and the water-insoluble component (D) are optional components and may not be added.

<Method for producing a three-dimensional object>
Next, an example of the additive manufacturing method using the modeling material of the present invention will be described. The manufacturing method of the three-dimensional object which concerns on this embodiment forms the material layer which consists of at least 1 type of modeling material containing the modeling material of this invention according to the slice data of a three-dimensional model, and laminates | stacks a material layer. This is a method of manufacturing a three-dimensional object that materializes a three-dimensional model (modeling object).

  The “slice data” referred to here may be a plurality of slice image data generated by slicing the modeling data of the three-dimensional model at predetermined intervals in the stacking direction. At this time, each slice image data is data including two-dimensional arrangement information of the modeling material for each layer. The slice image data can be suitably used for a layered modeling method of forming a material layer with a modeling material and laminating the formed material layer. Alternatively, the “slice data” may be tool path data including route information for arranging the modeling material. The tool path data can be suitably used for a hot melt lamination method (FDM) type additive manufacturing method.

  The method for manufacturing a three-dimensional object according to the present embodiment includes a material layer forming step of forming a material layer made of at least one type of modeling material including the modeling material of the present invention, and a material layer according to slice data of a three-dimensional model. It can also be said that it has a material layer laminating step of laminating. The material layer stacking step may be a step of forming the second material layer on the first material layer formed in the material layer forming step, or may be formed at a place other than on the first material layer. It may be a step of laminating the second material layer on the first material layer.

  Moreover, when applying the modeling material which concerns on this embodiment to a layered modeling method as a support material, the manufacturing method of the solid object which concerns on this embodiment has the process of following [1]-[2].

[1] A first process (modeled object forming process) of forming a modeled object including a structure part constituting a three-dimensional object and a support part supporting the structure part by a layered modeling method.
[2] A second step (removal step) of forming the three-dimensional object by removing the support part from the modeled object by bringing the modeled object into contact with a liquid containing water.
Hereinafter, each step will be described in detail.

[1] Modeled object formation process This process is a process of forming a modeled object including a structure part which constitutes a solid thing, and a support part which supports the structure part by a layered modeling method. According to the layered manufacturing method, according to the slice data of the three-dimensional model, the structure portion is formed using at least one type of structural material, and the support portion is formed using at least one type of support material. In the present embodiment, the modeling material of the present invention is used as a support material for forming the support portion.

  The molded object formation process may have the following processes [1a] to [1b].

[1a] Material Layer Formation Step This step is a step of forming a material layer by arranging a structural material and, if necessary, a support material according to slice data of a three-dimensional model.

  Here, combined data obtained by adding slice data of the support unit to slice data generated from the three-dimensional model of the modeling target is used. Note that before generating slice data from the three-dimensional model, slice processing may be performed in a state where the model data of the support unit is added to the three-dimensional model to generate slice data (composite data). Alternatively, the slice data of the support unit may be added to the slice data of the three-dimensional model after the slice data is generated from the three-dimensional model. The “slice data of the three-dimensional model” in this specification includes composite data to which the slice data of the support unit is added as necessary as described above.

  The method for arranging the structural material and the support material is not particularly limited, and various methods used in the additive manufacturing method can be used. Among them, it is preferable to use a hot melt lamination method (FDM) method or an electrophotographic method. According to these methods, each of a plurality of types of modeling materials can be easily arranged according to slice data.

[1b] Material Layer Lamination Step This step is a step in which the material layer formed in the material layer formation step is repeatedly laminated to form a shaped article. The material layer can be laminated by forming a separate material layer on the surface of the previously formed material layer, or by forming a new material layer directly on the surface of the previously formed material layer. May be laminated. In addition, when laminating the material layer formed separately on the surface of the previously formed material layer, the material layer is once formed on the substrate and then transferred to the surface of the previously formed material layer. good. The base material used at this time is called a transfer body. When transferring the material layer to the transfer body, a known transfer method such as electrostatic transfer using electrostatic energy or thermal transfer using thermal energy can be used.

  In the modeled object forming step, the above-described steps [1a] and [1b] are repeated a plurality of times, for example, the number of times corresponding to the slice data of the three-dimensional model to form a modeled object.

[2] Removal Step This step is a step of obtaining a three-dimensional object by removing the support part from the shaped object obtained by the process [1]. The support part is removed by bringing the shaped object into contact with a liquid containing water (hereinafter referred to as “removed liquid”).

  In the present embodiment, since the support portion is formed using the support material including the water-soluble material, the water-soluble material constituting the support portion is dissolved in the removal liquid. In the present embodiment, since the support material containing the low molecular weight saccharide (A) and the water-soluble polymer (B) is used as the support material, the low molecular weight saccharide (A) is quickly dissolved in the removing solution, and the support portion is removed. Easy to remove.

  The method for bringing the shaped article into contact with the removal liquid is not particularly limited, and the whole shaped article may be immersed in the removal liquid, or the removal liquid may be ejected in a shower shape and bathed on the shaped article. In the case of immersing the shaped article in the removing liquid, depending on the shape of the shaped article, it is preferable to add a water flow or ultrasonic vibration to the removing liquid because the removal of the support portion is promoted. It is preferable that the removing liquid is appropriately heated within a temperature range in which the structure portion is not thermally deformed.

<Modeling equipment>
A modeling apparatus for forming a modeled object including a structure part constituting a three-dimensional object and a support part supporting the structure part by a layered modeling method will be described with reference to FIGS. 1 and 2. The modeling apparatus which concerns on this embodiment uses the modeling material of this invention as a support material which forms a support part.

  FIG. 1 is a diagram schematically illustrating a first configuration example of a modeling apparatus according to the present embodiment. As illustrated in FIG. 1A, the modeling apparatus 100 of the first configuration example includes a particle layer forming unit 110, a stacking unit 120, and a particle layer formed by the particle layer forming unit 110 into the stacking unit 120. A conveyance body 130 for conveyance. The configuration and operation of the modeling apparatus 100 according to this embodiment will be described.

  The particle layer forming unit 110 includes a material supply unit 111, an image carrier 112, and an exposure device 113. The particle layer forming unit 110 forms a particle image of the structural material powder on the image carrier 112a and a particle image of the support material powder on the image carrier 112b. These particle images are transferred onto the carrier 130 to form a particle layer (material layer) composed of the structural material powder and the support material powder.

  Hereinafter, the material layer forming step will be described in detail. In the description common to the formation of each particle image, the subscripts a to d of the constituent members are omitted, and the material supply unit 111 and the image carrier 112 are omitted. And so on.

  First, the surface of the image carrier 112 is uniformly charged by a charging device (not shown). The charging method is not particularly limited.

  Using the exposure device 113, the charged image carrier 112 is exposed according to slice data (cross-section data) of a modeled object to be produced, and an electrostatic latent image is formed on the surface of the image carrier 112. Specifically, the electrostatic latent image of the structure portion region in the slice data of the modeled object to be produced is formed on the image carrier 112a, and the electrostatic latent image of the support portion region is formed on the image carrier 112b.

  Subsequently, modeling material powder (structural material powder or support material powder) is supplied from the material supply unit 111 to the image carrier 112. As a result, the electrostatic latent image on the surface of the image carrier 112 is arranged in either the region where the electrostatic latent image is formed or the region where the electrostatic latent image is not formed. As a result, the electrostatic latent image is visualized, and a particle image of the structural material powder is formed on the surface of the image carrier 112a, and a particle image of the support material powder is formed on the surface of the image carrier 112b. it can.

  Thereafter, the respective particle images respectively arranged on the image carriers 112a and 112b are transferred onto the carrier 130 at a predetermined timing. Thereby, the particle layer which consists of the particle image by structure material powder and the particle image by support material powder can be formed. That is, the particle layer is formed by transferring the second layer in which the other particle is arranged to the transfer body in which the first layer in which either the structural material powder or the support material powder is arranged is transferred. Form. The order in which the particle images are transferred to the carrier 130 is not particularly limited, and the particle image made of the support material powder may be transferred after transferring the particle image made of the structural material powder, or vice versa. You may transfer with.

  Here, the particle layer forming unit 110 has been described using an example in which the material supply unit 111, the image carrier 112, and the exposure apparatus 113 have two sets. However, the present invention is not limited to this. That is, in the case of modeling using a plurality of types of structural material powder and a plurality of types of support material powder, the particle layer forming unit 110 is the same as the number of types of modeling material powder (structural material powder and support material powder), What is necessary is just to have the said set.

  The particle layer formed on the carrier 130 is moved to the stacking position by the rotation of the carrier 130. When the particle layer is moved to the stacking position, the particles constituting the particle layer are fused with each other by being heated by the temperature control means 122. And it is transcribe | transferred and laminated | stacked on the modeling object in the middle of the production | generation currently formed on the upper surface of the stage 121 or the stage 121.

  Under the present circumstances, the area | region which consists of structural material powder among the particle | grain layers is laminated | stacked as a part (structure part 17a) which comprises a solid object, and the area | region which consists of support material powder is laminated | stacked as the support part 17b. That is, the laminating step in the method for manufacturing a three-dimensional object according to the present embodiment includes a heating and fusing step of fusing particles by heating the particle layer.

  The timing of heating the particle layer and fusing the particles constituting the particle layer to each other is not particularly limited, and may be performed before, simultaneously with, or after the lamination. It may be performed at a plurality of timings.

  In the heat fusion process, both the structural material particles and the support material particles in the particle layer are heated by a temperature control means (not shown), and these particles are temperature-controlled to substantially the same temperature. At this time, the temperature control means (not shown) preferably performs heating at a temperature at which both the structural material particles and the support material particles soften. Therefore, when the softening temperatures of the structural material particles and the support material particles are different, the temperature control means (not shown) is preferably heated at a temperature equal to or higher than the higher temperature.

  The modeling apparatus 100 according to the present embodiment repeats the material layer forming process and the material layer stacking process described above for the number of times corresponding to the slice data, thereby forming a modeled object 19 as shown in FIG. Then, the support part 17b is removed by making the modeling thing 19 contact a removal liquid, and the solid thing 20 as shown in FIG.1 (c) is obtained.

  FIG. 2 is a diagram illustrating a second configuration example of the modeling apparatus according to the present embodiment. The modeling apparatus 200 of the second configuration example is an apparatus that performs modeling by a hot melt lamination method (FDM) method. As illustrated in FIG. 2A, the modeling apparatus 200 according to the second configuration example includes a modeling controller 210, a stage 121, and a stage driving unit 230 that drives the stage 121. Further, the modeling apparatus 200 includes a nozzle 221a that discharges a structural material, a nozzle 221b that discharges a support material, and a nozzle driving unit 220 that drives the nozzle 221a and the nozzle 221b. The modeling apparatus 200 further includes a material supply unit 222a that supplies a structural material to the nozzle 221a and a material supply unit 222b that supplies a support material to the nozzle 221b.

  The modeling controller 210 generates a control signal for controlling the nozzle driving unit 220 and / or the stage driving unit 230 based on slice data (tool path data) of a modeled object to be manufactured. The nozzle driving unit 220 receives the control signal and controls the operation of the nozzles 221a and 221b and the material discharge amount, and the stage driving unit 230 receives the control signal and controls the operation of the stage 121. Thereby, the molded article 19 as shown in FIG. 2B is formed. Then, the support part 17b is removed by making the modeling thing 19 contact a removal liquid, and the solid thing 20 as shown in FIG.2 (c) is obtained.

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

(Preparation of molding material powder)
Modeling material powders 1-8 were prepared by the following method.

<Preparation Example 1>
As low molecular weight saccharide (A), 2.80 kg of maltotetraose (Eclipse Fujioligo # 450, manufactured by Nippon Food Chemicals Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 1.20 kg was used. Further, 0.25 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used as the water-soluble polymer (B). Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 1 composed of a plurality of modeling material particles 1 having an average particle diameter of 25 μm was obtained.

  Here, the particle size was measured using a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by HORIBA).

  First, the batch type cell containing the measurement solvent was set in a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by HORIBA), and the optical axis and background were adjusted. It is necessary to select a solvent that does not dissolve particles as the solvent used at this time. Here, isopropyl alcohol (special grade Kishida Chemical Co., Ltd.) was used. The powder to be measured was added to the batch cell until the transmittance of the tungsten lamp reached 95% to 90%, and the particle size distribution was measured. From the obtained measurement results, the volume-based average particle diameter was calculated. Hereinafter, the average particle size was measured in the same manner.

<Preparation Example 2>
As low molecular weight saccharide (A), 2.63 kg of maltotetraose (Eclipse Fujioligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 1.13 kg was used. As the water-soluble polymer (B), 0.50 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used. Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 2 composed of a plurality of modeling material particles 2 having an average particle diameter of 25 μm was obtained.

<Preparation Example 3>
As the low molecular weight saccharide (A), 2.28 kg of maltotetraose (Eclipse Fuji Oligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 0.98 kg was used. As the water-soluble polymer (B), 1.00 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used. Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 3 composed of a plurality of modeling material particles 3 having an average particle diameter of 25 μm was obtained.

<Preparation Example 4>
As low molecular weight saccharide (A), 2.63 kg of maltotetraose (Eclipse Fujioligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 1.13 kg was used. As the water-soluble polymer (B), 0.50 kg of butenediol vinyl alcohol copolymer (Nichigo G polymer OKS-1011, manufactured by Nippon Synthetic Chemical Co., Ltd., molecular weight 20000 to 40000) was used. Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 4 composed of a plurality of modeling material particles 4 having an average particle diameter of 25 μm was obtained.

<Preparation Example 5>
As low molecular weight saccharide (A), 2.94 kg of maltotetraose (Eclipse Fujioligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 1.26 kg was used. 0.05 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used as the water-soluble polymer (B). Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 5 composed of a plurality of modeling material particles 5 having an average particle diameter of 25 μm was obtained.

<Preparation Example 6>
As low molecular weight saccharide (A), 1.93 kg of maltotetraose (Nissan Fujioligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd., molecular weight 666), lactitol anhydrate LC-0 (manufactured by Food Science Co., Ltd., molecular weight 344) 0.83 kg was used. As the water-soluble polymer (B), 1.50 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used. Furthermore, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion is prepared by dissolving or dispersing the low-molecular sugar (A), the water-soluble polymer (B), and the water-insoluble component (D) in 17.0 kg of water, and powdered by a spray drying method using a spray drying apparatus. The body was made. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 6 composed of a plurality of modeling material particles 6 having an average particle diameter of 25 μm was obtained.

<Preparation Example 7>
As the low molecular weight saccharide (A), 2.98 kg of maltotetraose (Nissan Fujioligo # 450, manufactured by Nippon Shokuhin Kako Co., Ltd.) and 1.28 kg of lactitol anhydrous LC-0 (manufactured by Food Science Co., Ltd.) were used. . Moreover, 3.75 kg (cellulose nanofiber: water = 20: 80) of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem) was used as the water-insoluble component (D).

  A dispersion was prepared by dissolving or dispersing the low molecular weight saccharide (A) and the water-insoluble component (D) in 17.0 kg of water, and a powder was produced by a spray drying method using a spray drying apparatus. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 7 composed of a plurality of modeling material particles 7 having an average particle diameter of 25 μm was obtained.

<Preparation Example 8>
As the water-soluble polymer (B), 5.00 kg of polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd., average molecular weight 28000) was used.

  A solution in which the water-soluble polymer (B) was dissolved in 20.0 kg of water was prepared, and a powder was produced by a spray drying method using a spray drying apparatus. By classifying a plurality of particles constituting the obtained powder, a modeling material powder 8 composed of a plurality of modeling material particles 8 having an average particle diameter of 25 μm was obtained.

<Example 1>
(Evaluation of impact resistance (heat))
The impact resistance against thermal impact force was evaluated by the following procedure. About 0.05 g of the molding material powder 1 of Preparation Example 1 was charged into a pellet molding die having a diameter of 8 mm. Thereafter, a pressure of 0.1 MPa was applied with a pressure press apparatus (MASADA JACK MH-10 manufactured by Masada Seisakusho), and the temperature was kept at 120 ° C. with an electric heater while applying pressure to obtain pellets having a diameter of 8 mm and a thickness of 1 mm. The obtained pellet was placed on a slide glass, and this slide glass was placed on a hot plate (ND-1 ASONE) and heated to 220 ° C. to melt the pellet. After holding for 1 minute after heating, the slide glass was placed on an aluminum block (150 mm × 100 mm × 20 mm) at room temperature to rapidly cool the pellet. After rapid cooling, the surface on the slide glass side of the pellet was observed with an optical microscope through the slide glass, and it was confirmed whether or not the pellet had cracks (cracks).

  The evaluation criteria are as follows.

A No cracks observed B Less than 5 cracks C More than 5 cracks (Evaluation of removability by water)
Moreover, the removability by water was evaluated by putting the modeling material powder 1 into water and measuring the viscosity of the solution after the water-soluble component of the modeling material powder 1 was dissolved in water. 0.20 kg of modeling material powder 1 was added to 0.80 kg of water, and the mixture was stirred to dissolve the water-soluble component of the modeling material powder 1, and the viscosity of the solution was measured. The viscosity was measured using a rotational viscometer Bismetron VDA2 (manufactured by Shibaura Semtech Co., Ltd.). All viscosity measurements were performed at room temperature (25 ° C.).

  The evaluation criteria are as follows.

A The viscosity is 100 mPa · s or less B The viscosity is less than 1000 mPa · s C The viscosity is 1000 mPa · s or more <Example 2>
The molding material powder 2 of Preparation Example 2 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Example 3>
The molding material powder 3 of Preparation Example 3 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Example 4>
The molding material powder 4 of Preparation Example 4 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Comparative Example 1>
The molding material powder 5 of Preparation Example 5 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Comparative example 2>
The molding material powder 6 of Preparation Example 6 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Comparative Example 3>
The molding material powder 7 of Preparation Example 7 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

<Comparative example 4>
The molding material powder 8 of Preparation Example 8 was evaluated in the same manner as in Example 1 for impact resistance against thermal impact force and water removability. The results are shown in Table 1.

  In Table 1, PVA represents polyvinyl alcohol (PVA-505, manufactured by Kuraray Co., Ltd.), and BVOH represents butenediol vinyl alcohol copolymer (Nichigo G polymer OKS-1011, manufactured by Nippon Synthetic Chemical Co., Ltd.).

  In Example 1, in the evaluation of impact resistance, 1 to 2 cracks were observed, but the shape was maintained, and the result was generally good. In Examples 2 to 4, no cracks were observed in the impact resistance evaluation. Therefore, any of the modeling material powders 1 to 4 of Examples 1 to 4 could be evaluated as being able to model a three-dimensional object that does not easily crack even when an impact force is applied.

  The viscosity of the solution after being dissolved in water exceeded 100 mPa · s in Example 3 and less than 1000 mPa · s, but in Examples 1, 2, and 4, it was less than 100 mPa · s. Therefore, it could be evaluated that any of the modeling material powders 1 to 4 of Examples 1 to 4 can be easily removed with water after modeling.

  On the other hand, in Comparative Example 1, the viscosity of the solution after being dissolved in water was as low as 100 mPa · s or less, but 30 to 100 or more fine cracks were generated in the evaluation regarding impact resistance. In Comparative Example 2, no crack was observed in the impact resistance evaluation, but the viscosity of the solution after dissolving in water was as very high as 1600 mPa · s. When the viscosity of the solution increases in this way, it becomes difficult to exchange the solution around the three-dimensional object, and it cannot be easily removed with water.

  In Comparative Example 3, the viscosity of the solution after being dissolved in water was a low value of 100 mPa · s or less, but 30 to 100 or more fine cracks were generated in the evaluation regarding impact resistance. Furthermore, the modeling material fell off from the cracked part, and the fragments were scattered. Further, in Comparative Example 4, no crack was observed in the impact resistance evaluation, but the viscosity of the solution after being dissolved in water was as large as 5000 mPa · s or more.

17a Structure 17b Support part 19 Modeling object 20 Solid object

Claims (11)

Containing a low-molecular sugar and a water-soluble polymer,
The water-soluble polymer contains at least one selected from the group consisting of polyalkylene glycols and polyvinyl alcohols,
The modeling material, wherein the content of the water-soluble polymer is greater than 1.0% by mass and less than 30% by mass when the entire modeling material is 100% by mass.   The modeling material according to claim 1, wherein the low-molecular saccharide is a saccharide having a molecular weight of 100 or more and 1000 or less.   The low molecular weight saccharide is a monosaccharide, disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, sugar alcohol derived from monosaccharide, sugar alcohol derived from disaccharide, sugar alcohol derived from trisaccharide, sugar alcohol derived from tetrasaccharide, and The modeling material according to claim 1, wherein the modeling material is at least one selected from the group consisting of sugar alcohols derived from pentasaccharide.   The content of the low-molecular sugar is 50% by mass or more and 90% by mass or less when the entire modeling material is 100% by mass. The modeling material described.   The content of the water-soluble polymer is 5.0% by mass or more and 20% by mass or less when the entire modeling material is 100% by mass. The modeling material according to one item.   The modeling material according to any one of claims 1 to 5, further comprising a water-insoluble filler.   The modeling material according to claim 6, wherein the filler is cellulose nanofiber.   The modeling material according to any one of claims 1 to 7, wherein the modeling material is a modeling material used in an additive manufacturing method.   It is a modeling material as described in any one of Claims 1 thru | or 8, Comprising: The said modeling material is a support material, The modeling material characterized by the above-mentioned. A method of manufacturing a three-dimensional object that forms a three-dimensional object that materializes the three-dimensional model by forming a material layer made of at least one type of modeling material according to slice data of the three-dimensional model and laminating the material layer. There,
The said at least 1 type of modeling material contains the modeling material as described in any one of Claim 1 thru | or 9, The manufacturing method of the solid object characterized by the above-mentioned. A first step of forming a shaped article including a structure part constituting the three-dimensional object and a support part supporting the structure part by an additive manufacturing method;
A second step of forming the three-dimensional object by removing the support part from the three-dimensional object by bringing the model into contact with a liquid containing water,
The said 1st process WHEREIN: The manufacturing method of the solid object characterized by forming the said support part using the modeling material as described in any one of Claims 1 thru | or 9.

Images