Three dimensional modeling material

Abstract

To provide a material for three dimensional molding to be a material of a filament which is flexible and hardly broken.SOLUTION: A three dimensional modeling material comprising the following component A and the following component B: A water-soluble polyester resin having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having the hydrophilic group, and a diol monomer unit α component B: polyolefin resin SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a material for three-dimensional modeling. [Background technology]

[0002] 3D printers are a type of rapid prototyping technology that create three-dimensional objects based on 3D data such as 3D CAD and 3D CG. Known 3D printer methods include fused deposition modeling (FDM), inkjet UV curing, stereolithography, and laser sintering. Among these, FDM is a method of creating three-dimensional objects by heating and melting a modeling material, extruding it, and layering it. Polymer filaments and toner powders are the primary materials used, but unlike other methods, FDM does not rely on chemical reactions. Therefore, FDM 3D printers, especially those using polymer filaments as the modeling material, are compact, inexpensive, and require minimal post-processing, making them increasingly popular in recent years. To create three-dimensional objects with more complex shapes using the FDM method, the modeling material that makes up the three-dimensional object and the support material that supports the three-dimensional structure of the modeling material are stacked to obtain a three-dimensional object precursor, and then the support material is removed from the three-dimensional object precursor to obtain the desired three-dimensional object.

[0003] One method for removing a support material from a three-dimensional object precursor is to use a methacrylic acid copolymer as the support material and immerse the three-dimensional object precursor in a hot, strong alkaline aqueous solution to remove the support material (see, for example, Patent Document 1 below). This method utilizes the fact that the carboxylic acid in the methacrylic acid copolymer is neutralized by the alkali and dissolves in the strong alkaline aqueous solution.

[0004] However, when the methacrylic acid copolymer disclosed in Patent Document 1 is used as a support material, it is necessary to use a strong alkaline aqueous solution to remove the support material from the three-dimensional object precursor, but this strong alkaline aqueous solution is dangerous to people and places a heavy burden on the environment.

[0005] To address the above-mentioned issues, Patent Document 2 below discloses a soluble material for three-dimensional modeling that contains a specific water-soluble polyester resin. The soluble material for three-dimensional modeling disclosed in Patent Document 2 is suitable for manufacturing three-dimensional objects using the FDM method, has moisture absorption resistance, and dissolves rapidly in neutral water, making it possible to provide a support material that can be quickly removed from a three-dimensional object precursor without using a strong alkaline aqueous solution. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2012-509777 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-030346 Summary of the Invention [Problem to be solved by the invention]

[0007] In the FDM method, which uses polymer filaments as the modeling material, a filament-shaped modeling material and a soluble material for 3D modeling, which serves as a support material, are supplied to a 3D printer and layered together to form a 3D object. However, if the supplied filament breaks during modeling, the supply of material stops, resulting in a decrease in productivity and modeling accuracy. Therefore, a flexible, break-resistant filament is required.

[0008] The present invention provides a three-dimensional modeling material that can be used to make flexible and break-resistant filaments, a soluble material for three-dimensional modeling that includes the three-dimensional modeling material, and a method for manufacturing a three-dimensional object using the soluble material for three-dimensional modeling. [Means for solving the problem]

[0009] The present invention provides a material for three-dimensional modeling, which contains the following component A and component B: Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit Component B: Polyolefin resin

[0010] The present invention is a soluble material for three-dimensional modeling, which includes the material for three-dimensional modeling.

[0011] The present invention provides a method for manufacturing a three-dimensional object by a fused deposition modeling method, which includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removal step of removing the support material, The material of the support material is the soluble material for three-dimensional modeling. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a three-dimensional modeling material that can be used to make flexible and break-resistant filaments, a soluble material for three-dimensional modeling that includes the three-dimensional modeling material, and a method for manufacturing a three-dimensional object using the soluble material for three-dimensional modeling. DETAILED DESCRIPTION OF THE INVENTION

[0013] <Three-dimensional modeling materials> The three-dimensional modeling material of this embodiment is a three-dimensional modeling material containing the following component A and component B. Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit Component B: Polyolefin resin

[0014] According to the three-dimensional modeling material of this embodiment, it is possible to provide a three-dimensional modeling material that can be used as a material for filaments that are flexible and not easily broken.

[0015] [Component A] The component A is a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group (hereinafter also simply referred to as a hydrophilic group) other than the hydrophilic group constituting the polymerization for producing the water-soluble polyester resin α, a dicarboxylic acid monomer unit B having no hydrophilic group, and a diol monomer unit. In this specification, "water-soluble" means that 1 g of the component is dissolved in 100 g of neutral water at 60°C and does not precipitate even when the water temperature is subsequently maintained at 20°C. "Water-insoluble" means that 1 g of the component is not dissolved in 100 g of neutral water at 60°C, or that, even if dissolved, precipitates when the temperature is returned to 20°C.

[0016] The neutral water may be water or an aqueous solution having a pH of 6 to 8. Specific examples of the neutral water include deionized water, pure water, tap water, and industrial water. Deionized water or tap water is preferred due to its availability. The neutral water may also contain other components, such as a water-soluble organic solvent and a surfactant. Examples of the water-soluble organic solvent include lower alcohols such as methanol, ethanol, and 2-propanol; glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, and diethylene glycol monobutyl ether; and ketones such as acetone and methyl ethyl ketone. Examples of the surfactant include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, olefin sulfonates, and alkyl ether carboxylates; cationic surfactants such as alkyl trimethylammonium salts; and nonionic surfactants such as polyoxyethylene alkyl ethers and alkyl glycosides.

[0017] [Aromatic dicarboxylic acid monomer unit A] From the viewpoint of imparting removability with neutral water, the hydrophilic group may be one or more selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyalkylene group, a hydroxyl group, a carboxyl group, a carboxyl group, a phosphate group, a sulfonic acid group, and a sulfonate group. Among these, from the same viewpoint, one or more selected from the group consisting of a quaternary ammonium base, an oxyalkylene group, a carboxyl group, a phosphate group, and a sulfonate group are preferred, one or more selected from the group consisting of a quaternary ammonium base, an oxyalkylene group, and a sulfonate group are more preferred, and a sulfonate group is even more preferred.

[0018] The sulfonate group is -SO3M from the viewpoint of imparting removability with neutral water and facilitating the polymerization reaction during the production of the water-soluble polyester resin α. 3 (However, M 3 represents a counter ion of the sulfonic acid group constituting the sulfonate group, and from the viewpoint of imparting removability with neutral water, is preferably at least one or more selected from the group consisting of sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium ion, and zinc ion, more preferably at least one or more selected from the group consisting of sodium ion, potassium ion, lithium ion, magnesium ion, and ammonium ion, even more preferably at least one or more selected from the group consisting of sodium ion and potassium ion, and even more preferably sodium ion.

[0019] The content of the hydrophilic group in the water-soluble polyester resin α is preferably 0.2 mmol / g or more, more preferably 0.5 mmol / g or more, and even more preferably 0.7 mmol / g or more from the viewpoint of imparting removability with neutral water, and is preferably 3.0 mmol / g or less, more preferably 2.0 mmol / g or less, and even more preferably 1.5 mmol / g or less from the viewpoint of moisture resistance required for modeling using a 3D printer. In this specification, the content of the hydrophilic group can be determined by the method described in the examples.

[0020] The aromatic dicarboxylic acid for deriving the aromatic dicarboxylic acid monomer unit A is preferably one or more selected from the group consisting of sulfonate group-containing aromatic dicarboxylic acids and salts thereof, from the viewpoint of imparting removability with neutral water and the viewpoint of moisture resistance required for modeling using a 3D printer. Among these, from the same viewpoint, one or more selected from the group consisting of sulfophthalic acid, sulfonaphthalenedicarboxylic acid, and salts thereof are preferred, one or more selected from the group consisting of sulfophthalic acid and salts thereof are even more preferred, one or more selected from the group consisting of sulfoisophthalic acid, sulfoterephthalic acid, and salts thereof are even more preferred, and 5-sulfoisophthalic acid or a salt thereof is even more preferred.

[0021] The proportion of the aromatic dicarboxylic acid monomer unit A to the total amount of all monomer units in the water-soluble polyester resin α is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more from the viewpoint of imparting removability with neutral water, and is preferably 35 mol% or less, more preferably 25 mol% or less, and even more preferably 15 mol% or less from the viewpoint of moisture resistance required for 3D printer modeling. In this specification, the proportion of each monomer unit in the resin is calculated by the method described in the Examples.

[0022] The proportion of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units in the water-soluble polyester resin α is preferably 2 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, from the viewpoint of imparting removability with neutral water, and is preferably 75 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less, from the viewpoint of moisture resistance required for modeling using a 3D printer.

[0023] [Dicarboxylic acid monomer unit B] From the viewpoint of moisture resistance required for modeling using a 3D printer, the dicarboxylic acid from which the dicarboxylic acid monomer unit B is derived is preferably one or more selected from the group consisting of aromatic dicarboxylic acids having no hydrophilic groups and aliphatic dicarboxylic acids having no hydrophilic groups, and even more preferably one or more selected from the group consisting of aromatic dicarboxylic acids having no hydrophilic groups.

[0024] Examples of the aromatic dicarboxylic acid having no hydrophilic group include one or more selected from the group consisting of benzenedicarboxylic acid, furandicarboxylic acid, and naphthalenedicarboxylic acid. Among these, from the viewpoint of moisture resistance required for modeling using a 3D printer, one or more selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred.

[0025] Examples of the aliphatic dicarboxylic acid having no hydrophilic group include one or more selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid. Among these, adipic acid is preferred from the viewpoint of moisture resistance required for modeling using a 3D printer.

[0026] The ratio of the amount of substance of the dicarboxylic acid monomer unit B to the total amount of substance of all monomer units in the water-soluble polyester resin α is preferably 15 mol% or more, more preferably 25 mol% or more, and even more preferably 35 mol% or more, from the viewpoint of moisture resistance required for modeling using a 3D printer, and is preferably 49 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, from the viewpoint of imparting removability with neutral water.

[0027] The ratio of the amount of dicarboxylic acid monomer unit B to the sum of all dicarboxylic acid monomer units in the water-soluble polyester resin α is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, from the viewpoint of moisture resistance required for modeling using a 3D printer, and is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less, from the viewpoint of imparting removability with neutral water.

[0028] [Diol monomer unit] As the diol for deriving the diol monomer unit, an aliphatic diol, an aromatic diol, or the like can be used, but from the viewpoint of easy availability of raw materials for the water-soluble polyester resin, an aliphatic diol is preferred.

[0029] The number of carbon atoms in the diol is preferably 2 or more from the viewpoint of imparting removability with neutral water, and is preferably 31 or less, more preferably 25 or less, even more preferably 20 or less, and even more preferably 15 or less from the viewpoint of moisture resistance required for modeling using a 3D printer.

[0030] The aliphatic diol may be one or more selected from the group consisting of chain diols and cyclic diols, with chain diols being preferred from the viewpoint of easy availability of raw materials.

[0031] From the viewpoint of imparting removability with neutral water and the viewpoint of moisture resistance required for modeling using a 3D printer, the chain diol is preferably one or more selected from the group consisting of ethylene glycol, propanediol, butanediol, neopentyl glycol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol, and more preferably one or more selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,6-hexanediol.

[0032] The water-soluble polyester resin α may contain a monomer unit other than the aromatic dicarboxylic acid monomer unit A, the dicarboxylic acid monomer unit B, and the diol monomer unit, as long as the effect of this embodiment is not impaired.

[0033] The method for producing the water-soluble polyester resin α is not particularly limited, and any conventionally known method for producing a polyester resin can be applied.

[0034] The weight average molecular weight of the water-soluble polyester resin α is preferably 1000 or more, more preferably 3000 or more, and even more preferably 4000 or more from the viewpoint of moisture resistance required for modeling using a 3D printer, and is preferably 100000 or less, more preferably 80000 or less, and even more preferably 30000 or less from the viewpoint of imparting removability with neutral water. In this specification, the weight average molecular weight is measured by the method described in the examples.

[0035] The content of the water-soluble polyester resin α in the three-dimensional modeling material is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, from the viewpoint of imparting removability with neutral water, and is preferably 99% by mass or less, more preferably 95% by mass or less, from the viewpoint of the moisture resistance required for modeling using a 3D printer.

[0036] [Component B] There are no particular limitations on the polyolefin resin that can be used for Component B. Examples of the polyolefin resin include one or more selected from the group consisting of polyethylene resins such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE); polypropylene resins; and polybutylene resins. From the viewpoint of availability, it is preferable to include one or more selected from the group consisting of polyethylene resins and polypropylene resins, and it is more preferable to include polyethylene resins.

[0037] The content of the polyolefin resin in the three-dimensional modeling material is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of not impairing removability with neutral water, and is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of imparting high toughness to the three-dimensional modeling material.

[0038] The three-dimensional modeling material may contain other components as long as the effects of this embodiment are not impaired. Examples of such other components include polymers other than the water-soluble polyester resin α and the polyolefin resin, plasticizers such as benzoic acid polyalkylene glycol diesters, fillers such as calcium carbonate, magnesium carbonate, glass spheres, graphite, carbon black, carbon fiber, glass fiber, talc, wollastonite, mica, alumina, silica, kaolin, whiskers, and silicon carbide, viscosity reducers, compatibilizers, and elastomers.

[0039] [Viscosity reducer] The three-dimensional modeling material may contain a viscosity reducer from the viewpoint of controlling the molecular weight of the water-soluble polyester resin α during production and improving removability with neutral water. Examples of the viscosity reducer include organic salt compounds represented by the following general formula (1): (R-SO 3- ) n X n+ (1) (In the general formula (1), R represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, n represents the number 1 or 2, and X n+ indicates a cation, and when n is 1, X n+ represents a sodium ion, a potassium ion, a lithium ion, an ammonium ion, or a phosphonium ion; when n is 2, X n+ represents a magnesium ion, a calcium ion, a barium ion, or a zinc ion.

[0040] In the general formula (1), R represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, from the viewpoint of controlling the molecular weight during the production of the water-soluble polyester resin α and improving removability with neutral water. The hydrocarbon group may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 1 or more, more preferably 4 or more, and even more preferably 8 or more, from the viewpoint of controlling the molecular weight during the production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the three-dimensional modeling material. The number of carbon atoms is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. When the hydrocarbon group is an alicyclic hydrocarbon group, the number of carbon atoms in the hydrocarbon group is, from the viewpoints of molecular weight control during production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the three-dimensional modeling material, preferably 3 or more, more preferably 5 or more, even more preferably 6 or more, even more preferably 10 or more, and preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. When the hydrocarbon group is an aromatic hydrocarbon group, the number of carbon atoms in the hydrocarbon group is, from the viewpoints of molecular weight control during production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the three-dimensional modeling material, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 30 or less, and more preferably 25 or less.

[0041] Furthermore, from the viewpoint of improving removability with neutral water and imparting heat resistance and moisture resistance to the three-dimensional modeling material, the substituent preferably contains one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom. Among these, a hydrocarbon group or a halogenated alkyl group having 1 to 22 carbon atoms is preferred, a hydrocarbon group or a halogenated alkyl group having 1 to 16 carbon atoms is more preferred, a hydrocarbon group or a halogenated alkyl group having 1 to 12 carbon atoms is even more preferred, and a hydrocarbon group having 1 to 12 carbon atoms is even more preferred.

[0042] In the general formula (1), X n+ represents a sodium ion, potassium ion, lithium ion, ammonium ion, phosphonium ion, magnesium ion, calcium ion, barium ion, zinc ion, or phosphonium ion, from the viewpoints of molecular weight control during production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the three-dimensional modeling material, with sodium ion, potassium ion, lithium ion, magnesium ion, ammonium ion, or phosphonium ion being preferred, sodium ion, lithium ion, ammonium ion, or phosphonium ion being more preferred, lithium ion or phosphonium ion being even more preferred, and phosphonium ion being even more preferred. Among phosphonium ions, a tetraalkylphosphonium ion is preferred, and a tetrabutylphosphonium ion is more preferred, from the viewpoint of ensuring the heat resistance required during production of the water-soluble polyester resin α.

[0043] In the general formula (1), n ​​is preferably 1 from the viewpoints of molecular weight control during the production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the three-dimensional modeling material.

[0044] The content of the organic salt compound in the three-dimensional modeling material is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of improving removability with neutral water, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of imparting heat resistance and moisture resistance to the three-dimensional modeling material.

[0045] The method for producing the three-dimensional modeling material is not particularly limited, and the material can be produced by a known method. When producing a three-dimensional modeling material containing the water-soluble polyester resin α, the polyolefin resin, and the other components, the method for producing the three-dimensional modeling material may be a method for producing the three-dimensional modeling material by kneading the other components. The kneading can be performed using a kneader such as a batch kneader or a twin-screw extruder. The kneading is preferably melt kneading.

[0046] <Soluble materials for three-dimensional modeling> The three-dimensional modeling material may be used as a soluble material for three-dimensional modeling that is used as a material for a support material that supports a three-dimensional object when manufacturing the three-dimensional object using an FDM-type 3D printer. That is, the soluble material for three-dimensional modeling of the present embodiment may be a soluble material for three-dimensional modeling that includes the three-dimensional modeling material.

[0047] The shape of the soluble material for three-dimensional modeling is not particularly limited, and examples thereof include pellets, powder, and filaments. From the viewpoint of modeling properties using a 3D printer, the filaments are preferred.

[0048] The diameter of the filament is preferably 0.5 mm or more, more preferably 1.0 mm or more, from the viewpoint of the formability by a 3D printer and improving the precision of three-dimensional objects, and from the same viewpoint, is preferably 3.0 mm or less.

[0049] When producing filaments, drawing is preferably performed to enhance toughness. The draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, even more preferably 3 times or more, and even more preferably 5 times or more, from the viewpoint of both improving toughness and achieving water solubility. From the same viewpoint, it is preferably 200 times or less, more preferably 150 times or less, even more preferably 100 times or less, and even more preferably 50 times or less. Furthermore, the drawing temperature in the drawing process is preferably within a range from 20°C lower than the glass transition temperature of the soluble material for three-dimensional modeling to 110°C higher than the glass transition temperature. From the viewpoint of improving toughness and thermal stability, the lower limit of the drawing temperature is more preferably 10°C lower than the glass transition temperature, and even more preferably the same as the glass transition temperature. From the same viewpoint, the upper limit of the drawing temperature is more preferably 110°C higher than the glass transition temperature, more preferably 100°C higher than the glass transition temperature, and even more preferably 90°C higher than the glass transition temperature. The stretching may be performed while air-cooling the resin after it is discharged from the extruder, or by heating with hot air or a laser. The stretching may be performed in one step to a predetermined stretch ratio and filament diameter, or in multiple steps to a predetermined stretch ratio and filament diameter.

[0050] <Manufacturing method for three-dimensional objects> The method for manufacturing a three-dimensional object according to the present embodiment is a method for manufacturing a three-dimensional object by FDM, which includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material, and a step of removing the supporting material, wherein the supporting material is the soluble material for three-dimensional printing. This method for manufacturing a three-dimensional object allows for the manufacturing of a three-dimensional object with high modeling accuracy.

[0051] [Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material] The process for obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material can utilize the process for obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material in a known method for manufacturing a three-dimensional object using an FDM-type 3D printer, except that the material of the supporting material is the soluble material for three-dimensional modeling.

[0052] The molding material used to make the three-dimensional object can be any resin that is used as a molding material in conventional FDM manufacturing methods for three-dimensional objects, including thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide, with polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide being more preferred.

[0053] [Support material removal process for removing support material] In the support material removal step, the support material is removed by a physical method using a jig or the like, or by contacting the three-dimensional object precursor with neutral water. The method of contacting the three-dimensional object precursor with neutral water is preferred from the viewpoints of cost and ease of operation, and among these, the method of immersing the three-dimensional object precursor in neutral water is preferred. To improve the removability of the support material, ultrasonic waves can be irradiated during immersion to promote dissolution of the support material.

[0054] In the support material removal process, when the three-dimensional object precursor is brought into contact with neutral water to remove the support material, the amount of neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more, relative to the support material from the standpoint of the solubility of the support material, and from the standpoint of economy, it is preferably 10,000 times by mass or less, more preferably 5,000 times by mass or less, even more preferably 1,000 times by mass or less, and even more preferably 100 times by mass or less, relative to the support material.

[0055] In the support material removal step, when the three-dimensional object precursor is contacted with neutral water to remove the support material, the time for which the soluble material for three-dimensional modeling is contacted with neutral water is preferably 5 minutes or more from the viewpoint of removability of the support material, and is preferably 180 minutes or less, more preferably 120 minutes or less, and even more preferably 90 minutes or less from the viewpoint of reducing damage to the three-dimensional object caused by prolonged contact with neutral water and from the viewpoint of economy. The cleaning temperature, although depending on the type of model material, is preferably 15°C or more, more preferably 25°C or more, even more preferably 30°C or more, and even more preferably 40°C or more from the viewpoint of removability of the support material, reducing damage to the three-dimensional object, and from the viewpoint of economy, and is preferably 85°C or less, more preferably 70°C or less. [Example]

[0056] <Method for preparing water-soluble polyester resin composition> A 2L stainless steel separable flask (equipped with a K-shaped tube, stirrer, and nitrogen inlet) was charged with 97.7 g of dimethyl 2,6-naphthalenedicarboxylate (Tokyo Chemical Industry Co., Ltd., first grade), 40.6 g of sodium dimethyl 5-sulfoisophthalate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 76.7 g of ethylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 82 mg of titanium tetrabutoxide (Tokyo Chemical Industry Co., Ltd., first grade), and 506 mg of sodium acetate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade). The mixture was heated to 260°C over 1 hour under atmospheric pressure and nitrogen atmosphere with stirring. The temperature was then raised from 140°C to 260°C over 1 hour, and the mixture was stirred at that temperature for 6.5 hours to carry out the transesterification reaction. Then, 6.89 g of tetrabutylphosphonium dodecylbenzenesulfonate (Takemoto Oil & Fat Co., Ltd.: Elecut S-418) was added and stirred for 15 minutes. The heater surface temperature was then raised from 260 to 290°C over 30 minutes to allow the reaction to proceed. The reaction was then continued with stirring while gradually increasing the vacuum to 100 Pa, yielding a water-soluble polyester resin composition containing water-soluble polyester resin α. It was assumed that excess ethylene glycol was distilled off from the reaction system, and that the diol unit and dicarboxylic acid unit reacted in equal amounts. The contents of water-soluble polyester resin α and tetrabutyl phosphonium dodecylbenzenesulfonate contained in the water-soluble polyester resin composition, calculated from the amounts of raw materials added, are shown in Table 1. The ratios of aromatic dicarboxylic acid monomer unit A and dicarboxylic acid monomer unit B relative to the total of all dicarboxylic acid monomer units of water-soluble polyester resin α contained in the water-soluble polyester resin composition, as well as the weight-average molecular weight and hydrophilic group content, are shown in Table 2. The ratios of aromatic dicarboxylic acid monomer unit A and dicarboxylic acid monomer unit B were calculated from the amounts charged.

[0057] [Table 1]

[0058] [Table 2]

[0059] [Weight average molecular weight (Mw)] A calibration curve was prepared from standard polystyrene using gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight (Mw) was determined. Apparatus: HLC-8320 GPC (Tosoh Corporation, integrated detector) Column: α-M x 2 (Tosoh Corporation, 7.8 mm I.D. x 30 cm) Eluent: 60mmol / L phosphoric acid + 50mmol / L lithium bromide dimethylformamide Mido solution Flow rate: 1.0 mL / min Column temperature: 40°C Detector: RI detector Standard material: polystyrene

[0060] [Water Solubility Test] 100 g of deionized water at 60°C and a stirrer were placed in a beaker and stirred at 300 rpm. 1 g of the water-soluble polyester resin composition was placed in the stirred deionized water, and the time until complete dissolution was measured. It took 4 minutes for 1 g of the water-soluble polyester resin composition to completely dissolve in 100 g of deionized water at 60°C. The aqueous solution containing the water-soluble polyester resin composition was then cooled to 20°C, and it was confirmed that no precipitation occurred.

[0061] <Preparation of materials for 3D modeling (support materials)> Using a Labo Plastmill (Labo Plastmill 4C150 manufactured by Toyo Seiki Seisaku-sho, Ltd.), the raw materials were melt-kneaded under conditions of 230°C / 90 rpm / 10 min so as to obtain the compositions shown in Table 3, thereby obtaining three-dimensional modeling materials 1 to 3.

[0062] <Filament production> The three-dimensional modeling materials 1 and 2 were each melted at a barrel temperature of 200°C using a Capilograph (Capilograph 1D, manufactured by Toyo Seiki Seisakusho, Ltd.), extruded at an extrusion rate of 15 mm / min through a capillary having a diameter of 2.0 mm and a length of 10 mm, and wound up to a diameter of 1.7 mm. Similar attempts were made to produce filaments from the three-dimensional modeling material 3, but the filaments were not able to be produced because the material was very brittle.

[0063] <Evaluation method> [Evaluation of toughness] The breaking elongation was measured by a tensile test using a tension and compression tester (Shimadzu Corporation, trade name "Autograph AGS-X"). A 10 cm filament was set with a support distance of 50 mm, and the measurement was carried out at a crosshead speed of 10 mm / min to determine the breaking elongation (%). A high breaking elongation value indicates high toughness. Five points were tested per sample, and the average value was taken as the measured value. The evaluation results are shown in Table 3.

[0064] [Table 3]

Claims

1. A three-dimensional modeling material comprising the following component A and component B: Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit Component B: Polyolefin resin

2. The three-dimensional modeling material according to claim 1 , wherein the polyolefin resin comprises at least one resin selected from the group consisting of polyethylene resin and polypropylene resin.

3. The three-dimensional modeling material according to claim 1 , wherein the content of the polyolefin resin is 20% by mass or less.

4. A soluble material for three-dimensional modeling, comprising the material for three-dimensional modeling according to any one of claims 1 to 3.

5. The soluble material for three-dimensional fabrication according to claim 4 , which has a filamentous shape.

6. 6. The soluble material for three-dimensional fabrication according to claim 5, wherein the filament has a diameter of 0.5 to 3.0 mm.

7. A method for manufacturing a three-dimensional object, comprising: a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material; and a support material removal step of removing the support material, A method for manufacturing a three-dimensional object, wherein the material of the support material is the soluble material for three-dimensional modeling according to claim 4 .

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