Method for producing three-dimensional model, and three-dimensional model

Abstract

The present invention provides a method for producing a three-dimensional model by means of a fused deposition modeling method using a thermoplastic resin.　The present invention specifically provides a method for producing a three-dimensional model, the method including the formation of a model part by depositing, on a base part that contains a first modeling material which has a difference (Tm2(i) – Tc(i)) between the melting point Tm2(i) and the crystallization temperature Tc(i) measured by a differential scanning calorimeter of 15°C to 105°C inclusive, and a melt flow rate of 0.8 g / 10 min to 1,000 g / 10 min inclusive as measured at a temperature higher than the melting point by 10°C under a load of 2.16 kg, a second modeling material which is different from the first modeling material in the composition and / or the physical properties by means of a fused deposition modeling method. The first modeling material and the second modeling material contain a thermoplastic resin.

Description

Method for manufacturing three-dimensional object and three-dimensional object

[0001] The present disclosure relates to a method for manufacturing a three-dimensional object and a three-dimensional object.

[0002] 3D printers have become increasingly popular in recent years because they can produce three-dimensional objects without using molds or large-scale melting equipment. Known 3D printer modeling methods include the material extrusion method (MEX (MATERIAL EXTRUSION) method), the stereolithography method (STL (Stereolithography) method), and the selective laser sintering method (SLS (Selective Laser Sintering) method). The material extrusion method is also known as the fused filament fabrication method (FFF (Fused Filament Fabrication) method). The fused deposition modeling method is a method of forming three-dimensional objects by heating, melting, and laminating thermoplastic resins (see, for example, Patent Document 1). Due to the low cost of the equipment, the method is becoming increasingly popular not only for industrial use but also for personal use.

[0003] International Publication No. 2024 / 063137A1

[0004] A first object of the present disclosure is to provide a method for manufacturing a three-dimensional object by a fused deposition modeling method using a thermoplastic resin.A second object of the present disclosure is to provide a three-dimensional object containing a thermoplastic resin.

[0005] The present disclosure includes the following aspects. In one embodiment, a method for producing a three-dimensionally shaped object, comprising: （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）a first modeling material having a melting point Tm2 of 15°C or more and a melt flow rate Tm3 of 0.8 g / 10 min or more and 1,000 g / 10 min or less, measured at a melting point Tm2+10°C and a load of 2.16 kg, on a base portion including the first modeling material, and a second modeling material having a composition and / or physical properties different from those of the first modeling material, by a fused deposition modeling method, to form a modeling portion, wherein the first modeling material and the second modeling material contain a thermoplastic resin. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a first modeling material having a melt flow rate (Tm2) of 0.8 g / 10 min or more and 8.0 g / 10 min or less, measured at a temperature of 190°C under a load of 2.16 kg, on a base portion including a first modeling material having a melt flow rate (Tm2) of 0.8 g / 10 min or more and 8.0 g / 10 min or less, measured at a temperature of 190°C under a load of 2.16 kg, and a second modeling material having a composition and / or physical properties different from that of the first modeling material, by a fused deposition modeling method to form a modeling portion. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） and a modeling portion formed by layering, by a fused deposition modeling system, a second modeling material having a composition and / or physical properties different from those of the first modeling material, wherein the first modeling material and the second modeling material contain a thermoplastic resin. In one embodiment, the three-dimensional modeling object comprises a polyacetal resin (A), and the first modeling material has a melting point Tm2 measured by a differential scanning calorimeter. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）a base portion containing a first modeling material having a viscosity of 22°C or higher and 40°C or lower and a melt flow rate of 0.8 g / 10 min or higher and 8.0 g / 10 min or lower, measured at a temperature of 190°C and a load of 2.16 kg; and a modeling portion located on the base portion, containing a polyacetal resin (B) and a second modeling material having a composition and / or physical properties different from those of the first modeling material, wherein a drawing line is formed on the surface of the modeling portion.

[0006] According to the present disclosure, it is possible to provide a method for manufacturing a three-dimensional object by fused deposition modeling using a thermoplastic resin. According to the present disclosure, it is possible to provide a three-dimensional object containing a thermoplastic resin.

[0007] An embodiment of the present disclosure will be described in detail below. However, the scope of the present disclosure is not limited to the embodiment described herein, and various modifications can be made without departing from the spirit of the present disclosure. Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, when multiple upper and lower limit values ​​are described for a specific parameter, any of these upper and lower limit values ​​can be combined to form a suitable numerical range. Furthermore, the lower and / or upper limit values ​​of a numerical range described in this disclosure are numerical values ​​within that numerical range and may be replaced with numerical values ​​shown in the examples. The expression "X to Y" indicating a numerical range means "X or more and Y or less." If a specific description described for one embodiment also applies to other embodiments, that description may be omitted in other embodiments.

[0008] [Method of Manufacturing a Three-Dimensional Object] A method of manufacturing a three-dimensional object according to an embodiment is a method of manufacturing a three-dimensional object by measuring a melting point Tm2 （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）The method includes forming a modeling portion by layering a second modeling material having a composition and / or physical properties different from that of the first modeling material on a base portion including a first modeling material having a melting point (Tc) of 15°C or higher and 105°C or lower, and a melt flow rate (MFR) of 0.8 g / 10 min or higher and 1,000 g / 10 min or lower, measured at a melting point +10°C and a load of 2.16 kg, using a fused deposition modeling method, where the first modeling material and the second modeling material include a thermoplastic resin. The first modeling material and the second modeling material may contain the same type of resin or different resins. If the first modeling material and the second modeling material contain the same type of resin, the compositions and / or physical properties of the first modeling material and the second modeling material may be different by, for example, different monomer compositions of the resins, different amounts of resin in each modeling material, or different types and / or amounts of other components in each modeling material.

[0009] Thermoplastic resins are not limited. Among them, polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, polyamide resin, etc., have excellent mechanical properties and are therefore useful as modeling materials for 3D printers. However, crystalline resins have high crystallinity and a fast crystallization rate, which can lead to problems such as warping due to solidification shrinkage during modeling using the fused deposition modeling method, causing the three-dimensional object to peel off from the modeling stage, or peeling at the layer interface within the model, resulting in poor modeling. For this reason, it has been difficult to model three-dimensional objects using crystalline resins using the fused deposition modeling method. According to the manufacturing method disclosed herein, three-dimensional objects can be manufactured using the fused deposition modeling method regardless of the type of thermoplastic resin.

[0010] Examples of polyacetal resins include the same polyacetal resin (A) and / or polyacetal resin (B) described below. For example, when both the first modeling material and the second modeling material contain polyacetal resins, the first modeling material may contain the polyacetal resin (A) described below, and the second modeling material may contain the polyacetal resin (B) described below. Examples of polypropylene resins include propylene homopolymers and propylene-α-olefin copolymers. Examples of polyethylene terephthalate resins and polybutylene terephthalate resins include polyesters obtained by condensing 1,4-butanediol or ethylene glycol with terephthalic acid or its lower alcohol ester. Examples of polyphenylene sulfide resins include crystalline plastics that use p-phenylene groups as the arylene group and have p-phenylene sulfide groups as repeating units. Examples of polyamide resins include polyamide 46 resin, polyamide 6 resin, polyamide 11 resin, polyamide 12 resin, polyamide 66 resin, polyamide 610 resin, polyamide 612 resin, polyamide 1010 resin, etc. The first modeling material and the second modeling material are thermoplastic resins, and the thermoplastic resin contains one or more resins selected from polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin. By providing a base layer made of the first modeling material having predetermined physical properties, a three-dimensional model can be modeled without peeling off the three-dimensional model from the modeling stage or peeling at the layer interface during modeling.

[0011] According to one embodiment, a method for manufacturing a three-dimensional object includes the step of: （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）) is 22°C or more and 40°C or less, and the melt flow rate measured at a temperature of 190°C and a load of 2.16 kg is 0.8 g / 10 min or more and 8.0 g / 10 min or less, and a second modeling material containing polyacetal resin (B) and having a composition and / or physical properties different from those of the first modeling material is laminated on the base portion by a fused deposition modeling method to form a modeling portion.

[0012] According to the manufacturing method of the three-dimensional object according to the embodiment, even when a modeling material containing a polyacetal resin is used, the three-dimensional object is less likely to peel off from the modeling stage during modeling, and peeling at the layer interface is less likely to occur. As a result, it is possible to manufacture a three-dimensional object using a polyacetal resin by fused deposition modeling.

[0013] Patent Literature 1 discloses a method for producing a three-dimensional object by fused deposition modeling using a filament containing a polyacetal resin and having predetermined physical properties. It has been thought that using only filaments with such predetermined physical properties makes it easier to produce a three-dimensional object by fused deposition modeling. Furthermore, using only one type of filament generally eliminates the need to replace the filament, and is less likely to reduce work efficiency.

[0014] However, the inventors' research has revealed that by providing a base layer made of a first modeling material containing polyacetal resin and having predetermined physical properties, a 3D object can be produced without peeling from the modeling stage or peeling at the layer interface during modeling, even when the modeling portion laminated on top of the base layer is modeled using a second modeling material containing polyacetal resin and having a different composition and / or physical properties from the first modeling material. In this case, for example, using a modeling machine (3D printer) with two or more nozzles and spools can prevent a decrease in work efficiency. Similar effects can be obtained with resins with lower crystallinity than polyacetal resin, such as polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin.

[0015] Since it is possible to model using a second modeling material that has a different composition and / or physical properties from the first modeling material, it is now possible to produce a three-dimensional model by the fused deposition modeling method using a resin composition containing a crystalline resin such as a general polyacetal resin, which has previously been difficult to model by the fused deposition modeling method.In addition, the range of materials to achieve the physical properties required for a three-dimensional model is broadened.

[0016] The materials and properties used in each step of the method for producing a three-dimensional object according to the present disclosure will be described first, and the details of each step will be described later.

[0017] (First Modeling Material) The first modeling material used to form the base portion in the first step has a melting point Tm2 measured by a differential scanning calorimeter. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The thermoplastic resin has a melting point Tm2 of 15°C or higher and a melt flow rate of 0.8 g / 10 min or higher and 1,000 g / 10 min or lower, measured at a melting point Tm2+10°C and a load of 2.16 kg. The thermoplastic resin includes one or more resins selected from polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin. The polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin are as described above. In one embodiment, the first modeling material used to form the base portion in the first step includes polyacetal resin (A) and has a melting point Tm2 of 15°C or higher and a melt flow rate of 0.8 g / 10 min or higher and 1,000 g / 10 min or lower, measured at a melting point Tm2+10°C and a load of 2.16 kg. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The first modeling material has a melt flow rate of 0.8 g / 10 min to 8.0 g / 10 min measured at a temperature of 190°C and a load of 2.16 kg. The shape of the first modeling material is not limited and may be a filament, pellet, or the like, but is preferably a filament in view of ease of handling.

[0018] (Polyacetal Resin (A)) The polyacetal resin (A) contained in the first modeling material may be a polyacetal homopolymer or a polyacetal copolymer. In one embodiment, from the viewpoint of the balance between mechanical and thermal properties, the polyacetal resin (A) preferably contains a polyacetal copolymer. The polyacetal resin (A) may have not only linear molecules but also branched or crosslinked structures, and may be a known modified polyoxymethylene into which other organic groups have been introduced.

[0019] Polyacetal homopolymer consists of oxymethylene units (-CH ２ Polyacetal copolymers are polymers that have only oxymethylene units (-CH ２ The term "main structural unit" refers to a monomer unit that accounts for 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more of all structural units (100% by mass) that constitute the polyacetal copolymer.

[0020] The comonomer unit contained in the polyacetal copolymer may be one type or two or more types. In one embodiment, the comonomer unit is preferably an oxyalkylene unit having 2 or more carbon atoms, preferably 2 to 6 carbon atoms. When the comonomer unit is an oxyalkylene unit having 2 or more carbon atoms, the thermal stability tends to be good. The comonomer unit is more preferably at least one oxyalkylene unit selected from an oxyethylene group, an oxypropylene group, and an oxytetramethylene group, and particularly preferably contains an oxyethylene group.

[0021] The proportion of the comonomer units in the polyacetal copolymer is preferably 1.0% by mass or more and 6.0% by mass or less, more preferably 1.5% by mass or more and 5.5% by mass or less, even more preferably 2.0% by mass or more and 5.0% by mass or less, even more preferably 2.2% by mass or more and 5.0% by mass or less, and particularly preferably 2.5% by mass or more and 4.5% by mass or less, relative to the total constituent units (100% by mass) of the polyacetal copolymer. By having the proportion of the comonomer units be 1.0% by mass or more and 6.0% by mass or less, relative to the total constituent units (100% by mass) of the polyacetal copolymer, the base portion is more easily fixed to the modeling stage, making it less likely that the three-dimensional object will peel off from the modeling stage during modeling. Furthermore, since adhesion to the modeling portion is improved, peeling at the lamination interface between the base portion and the modeling portion is less likely to occur. As a result, three-dimensional modeling by fused deposition modeling is easier. Furthermore, three-dimensional objects with excellent appearance can be produced. When oxyethylene units are contained as comonomer units, the proportion of the oxyethylene units in the total comonomer units (100% by mass) is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less. １ For example, a sample is prepared by dissolving the filament (A) in deuterated hexafluoroisopropanol to a concentration of 5% by mass. １ It can be calculated by a method of analyzing by H-NMR to determine the ratio of the integral fraction of the peaks of comonomer units (for example, oxyalkylene units having 2 or more carbon atoms, as described later) to the integral fraction of the peaks of all monomers in the polyacetal copolymer.

[0022] The polyacetal copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer, with a random copolymer being preferred from the viewpoint of thermal stability.

[0023] The degree of polymerization, branching, and crosslinking of the polyacetal resin (A) can be adjusted appropriately so that the MFR of the first modeling material is in the range of 0.8 to 8.0 g / 10 min.

[0024] The weight-average molecular weight (Mw) of the polyacetal resin (A) is not particularly limited as long as the effects of the present disclosure are achieved, and can be appropriately adjusted within a range such that the MFR of the first modeling material is 0.8 to 8.0 g / 10 min. In one embodiment, the Mw of the polyacetal resin (A) may be 10,000 or more and 400,000 or less from the viewpoint of suppressing warpage due to shrinkage stress during the modeling process. The weight-average molecular weight (Mw) is a value measured (in terms of polystyrene) by size exclusion chromatography (SEC).

[0025] The first modeling material may contain only one type of polyacetal resin (A), or may contain a combination of two or more types selected from polyacetal homopolymers and polyacetal copolymers. When the first modeling material contains a polyacetal copolymer, the first modeling material may contain two or more types of polyacetal copolymers that differ in the type and / or content of comonomers and / or form (random copolymer, block copolymer, graft copolymer, etc.). When the first modeling material contains two or more types of polyacetal resins (A), the melting point Tm2 of the first modeling material may be 1000 kJ / s. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The blending ratio is adjusted so as to satisfy the values ​​of the saturation temperature, saturation rate, and MFR.

[0026] The content of polyacetal resin (A) in the first molding material is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or even 100% by mass, of the total mass (100% by mass) of the first molding material.

[0027] The content of polyacetal resin (A) in the resin components constituting the first molding material is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, of the total resin components (100% by mass), and may be 100% by mass.

[0028] (Method for Producing Polyacetal Resin (A)) Polyacetal resin (A) can be produced by bulk polymerization of a monomer (or a monomer mixture) containing a cyclic trimer or tetramer of formaldehyde (preferably trioxane, which is a cyclic trimer of formaldehyde) and, if necessary, a comonomer, with the addition of an appropriate amount of a molecular weight modifier, using a cationic polymerization catalyst. Trioxane is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is purified by distillation or other methods before use. The trioxane used in the polymerization preferably contains as little impurities as possible, such as water, methanol, and formic acid.

[0029] The polymerization apparatus is not particularly limited, and known apparatuses can be used. Also, any method, such as a batch method or a continuous method, can be employed. The polymerization temperature is preferably maintained at 65 to 135°C. The polymerization catalyst after polymerization can be deactivated by adding a basic compound or an aqueous solution thereof to the reaction product recovered from the polymerization apparatus or to the reaction product in the polymerization apparatus.

[0030] Examples of the cationic polymerization catalyst include lead tetrachloride; tin tetrachloride; titanium tetrachloride; aluminum trichloride; zinc chloride; vanadium trichloride; antimony trichloride; phosphorus pentafluoride; antimony pentafluoride; boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetic anhydrate, boron trifluoride coordination compounds such as boron trifluoride triethylamine complex compounds; perchloric acid, acetyl perchlorate, t-butyl Examples of suitable catalysts include inorganic and organic acids such as perchlorate, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, and p-toluenesulfonic acid; complex salt compounds such as triethyloxonium tetrafluoroborate, triphenylmethylhexafluoroantimonate, allyldiazonium hexafluorophosphate, and allyldiazonium tetrafluoroborate; alkyl metal salts such as diethylzinc, triethylaluminum, and diethylaluminum chloride; heteropolyacids; and isopolyacids. Among these, boron trifluoride coordination compounds such as boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetic anhydrate, and boron trifluoride triethylamine complex compounds are particularly preferred. These catalysts can also be used by diluting them in advance with an organic solvent or the like.

[0031] The molecular weight regulator may be a linear formal compound. Examples of the linear formal compound include methylal, ethylal, dibutoxymethane, bis(methoxymethyl) ether, bis(ethoxymethyl) ether, and bis(butoxymethyl) ether. Among these, at least one selected from the group consisting of methylal, ethylal, and dibutoxymethane is preferred.

[0032] Examples of basic compounds that can be used to neutralize and deactivate the polymerization catalyst include ammonia; amines such as triethylamine, tributylamine, triethanolamine, and tributanolamine; hydroxide salts of alkali metals and alkaline earth metals; and other known catalyst deactivators. After the polymerization reaction is complete, it is preferable to quickly add an aqueous solution of these to the reaction product to deactivate it. After the polymerization and deactivation methods, if necessary, washing, separation and recovery of unreacted monomers, drying, and the like can be carried out by conventional methods to obtain a polyacetal resin.

[0033] If necessary, various stabilizers can be added to the polyacetal resin to perform stabilization treatment such as decomposition and removal or blocking of unstable terminals. Conventional known antioxidants, thermal stabilizers, etc. can be used as stabilizers. For example, hindered phenol compounds, nitrogen-containing compounds, hydroxides, inorganic salts, and carboxylates of alkali or alkaline earth metals can be used alone or in combination of two or more.

[0034] (Other Components) The first modeling material may contain other components as needed. Examples of other components include fibrous, powdery, or plate-like inorganic or organic fillers, thermoplastic resins other than polyacetal resins (other thermoplastic resins), etc. The first modeling material may contain one or more general additives for thermoplastic resins as needed, such as weather (light) stabilizers, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, surfactants, etc.

[0035] (Inorganic or Organic Filler) In one embodiment, the first modeling material may contain an inorganic or organic filler. Examples of inorganic or organic fillers include powdery or platy fillers having an average particle size of 2 nm to 400 μm, preferably 20 nm to 100 μm, and fibrous fillers having an average fiber length of 0.1 to 600 μm, preferably 1 to 300 μm, and an average fiber diameter of 0.001 to 20 μm, preferably 0.01 to 15 μm. By including an inorganic or organic filler, the strength of the resulting three-dimensional model is likely to be improved. The average particle size of the inorganic or organic filler refers to the particle size D50 at which the cumulative frequency is 50% in the arithmetic average particle size on a volume basis determined by a laser diffraction / scattering particle size distribution measurement method. The average particle size can be measured, for example, using a laser diffraction / scattering particle size distribution measurement device (manufactured by Horiba, Ltd., product name: LA-960). The average fiber length is the arithmetic mean value of values ​​obtained by measuring 500 fibrous fillers with an image measuring device (manufactured by Nicole Co., Ltd., product name: LUZEXFS). The average fiber diameter is the arithmetic mean value of values ​​obtained by measuring the longest linear distance in a cross section perpendicular to the longitudinal direction of 500 fibrous fillers with an image measuring device (manufactured by Nicole Co., Ltd., product name: LUZEXFS).

[0036] Examples of powdery and granular fillers include carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, as well as ferrite, silicon carbide, silicon nitride, boron nitride, and various metal powders. These powdery and granular fillers may be used alone or in combination of two or more.

[0037] Examples of fibrous fillers include inorganic fibrous materials such as glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, silicate fibers such as wollastonite, magnesium sulfate fiber, aluminum borate fiber, and metal fibers such as stainless steel, aluminum, titanium, copper, and brass. A particularly representative fibrous filler is glass fiber. High-melting-point organic fibrous materials such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used. These fibrous fillers may be used alone or in combination.

[0038] Examples of the plate-like filler include mica, glass flakes, talc, various metal foils, etc. These plate-like fillers may be used alone or in combination of two or more.

[0039] When the first modeling material contains an inorganic or organic filler, the content of the inorganic or organic filler is （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The content of the inorganic or organic filler can be, for example, 0 to 50% by mass of the total mass (100% by mass) of the first modeling material.

[0040] (Other Thermoplastic Resins) When the first modeling material contains a polyacetal resin (A), the first modeling material may contain another thermoplastic resin other than the polyacetal resin (A). That is, in one embodiment, the first modeling material may contain another thermoplastic resin other than the polyacetal resin (A). Examples of the other thermoplastic resins include polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and polyamide resin. These may be used alone or in combination of two or more. When the first modeling material contains another thermoplastic resin, the blending amount of the other thermoplastic resin is determined based on the melting point Tm2 of the first modeling material. （ｉ） and crystallization temperature Tc（ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The content of the other thermoplastic resin may be, for example, 0 to 15 parts by mass, or may also be 1 to 10 parts by mass, per 100 parts by mass of the polyacetal resin (A).

[0041] (Melting point Tm2 （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） The first molding material has a melting point Tm2 measured by a differential scanning calorimeter. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） ) is 22°C or more and 40°C or less. （ｉ） -Tc （ｉ） When the temperature (Tm2) of the first modeling material is 22°C or higher and 40°C or lower, the base portion is easily fixed to the modeling stage, and the three-dimensional model is less likely to peel off from the modeling stage during modeling. In addition, peeling at the lamination interface between the base portion and the modeling portion is less likely to occur. （ｉ） -Tc （ｉ） ) of the first modeling material is more preferably 22° C. or higher and 35° C. or lower, and even more preferably 22° C. or higher and 30° C. or lower. （ｉ） -Tc （ｉ） ) may be 22° C. or more and 25° C. or less. In one embodiment, the (Tm2 （ｉ） -Tc （ｉ） ) may be 23.4°C, or may be the upper or lower limit of the above numerical range.

[0042] Melting point Tm2 （ｉ） The temperature refers to the peak top temperature of the endothermic peak observed in the second run, in which a first modeling material is heated from 40°C to 200°C at a heating rate of 200°C / min (first run), held at 200°C for 5 minutes, cooled to 40°C at a heating rate of 10°C / min, held at 40°C for 5 minutes, and then heated again from 40°C to 200°C at a heating rate of 10°C / min (second run), according to a method based on JIS K-7121 (2012).

[0043] Crystallization temperature Tc （ｉ） This refers to the peak top temperature of the exothermic peak observed when the first modeling material is heated from 40°C to 200°C at a heating rate of 200°C / min (1st RUN) using a method based on JIS K-7121 (2012), held at 200°C for 5 minutes, and then cooled to 40°C at a cooling rate of 10°C / min.

[0044] In one embodiment, the melting temperature Tm2 of the first building material （ｉ） The crystallization temperature Tc of the first modeling material may be 160° C. or more and less than 170° C., or 162° C. or more and 165° C. or less. （ｉ） The temperature may be 130°C or higher and 145°C or lower, or 135°C or higher and 143°C or lower.

[0045] When the polyacetal resin (A) is a copolymer, the melting point Tm2 （ｉ） The melting point Tm2 can be adjusted by adjusting the proportion of the comonomer unit in the polyacetal resin. For example, the larger the proportion of the comonomer unit, the lower the melting point Tm2 （ｉ） The crystallization temperature Tc tends to be lower. （ｉ） The crystallization temperature Tc can be adjusted by adjusting the proportion of the comonomer unit. For example, the larger the proportion of the comonomer unit, the lower the crystallization temperature Tc （ｉ） tends to be lower.

[0046] (Melt flow rate (MFR)) The first modeling material has an MFR measured at a temperature of 190°C and a load of 2.16 kg of 0.8 g / 10 min or more and 8.0 g / 10 min or less, preferably 1.0 g / 10 min or more and 7.0 g / 10 min or less, and more preferably 1.2 g / 10 min or more and 6.0 g / 10 min or less. （ｉ） -Tc （ｉ）When the MFR of the first modeling material is within the above-mentioned range, the MFR of the first modeling material is 0.8 g / 10 min or more and 8.0 g / 10 min or less, so that the base portion is easily fixed to the modeling stage and the three-dimensional model is less likely to peel off from the modeling stage during modeling. Furthermore, the adhesion between the base portion and the modeling portion is improved, so that peeling at the lamination interface between the base portion and the modeling portion is less likely to occur. The MFR of the first modeling material is measured at a temperature of 190°C and a load of 2.16 kg in accordance with ISO 1133-1:2011 (Condition D).

[0047] The MFR can be adjusted mainly by the weight-average molecular weight (Mw) of the polyacetal resin (A). For example, the larger the weight-average molecular weight (Mw) of the polyacetal resin (A), the lower the MFR of the first modeling material tends to be. When the first modeling material contains another thermoplastic resin, the MFR of the first modeling material can be adjusted by adjusting the amount of the other thermoplastic resin.

[0048] (Method for Manufacturing First Modeling Material) When the first modeling material is in the form of pellets, for example, the polyacetal resin (A) obtained by the above-mentioned manufacturing method can be extruded using an extruder together with other components that may be contained as needed, and pelletized to produce a pellet-shaped first modeling material. When the first modeling material is in the form of filaments, for example, the polyacetal resin (A) obtained by the above-mentioned manufacturing method can be extruded using an extruder together with other components that may be contained as needed, and the extruded strand can be cooled and solidified, and then wound up using a winder at a winding speed that results in the filament having a desired diameter, to produce a filament-shaped first modeling material.

[0049] In the method for producing a first modeling material, when the first modeling material contains a polyacetal resin (A), the polyacetal resin (A) may be used alone or in combination of two or more types selected from polyacetal homopolymers and polyacetal copolymers. When a polyacetal copolymer is used, two or more polyacetal copolymers with different comonomer types and / or comonomer contents and / or comonomer forms (random copolymer, block copolymer, graft copolymer, etc.) may be used in combination. When two or more polyacetal resins (A) are used in combination, the melting point Tm2 of the first modeling material may be higher than the melting point Tm2 of the first modeling material. （ｉ） and the crystallization temperature Tc (Tm2 （ｉ） -Tc （ｉ） The blending ratio can be adjusted so as to satisfy the values ​​of .gtoreq..times ...

[0050] (Second Modeling Material) The second modeling material used to form the modeling portion in the second step has a composition and / or physical properties different from those of the first modeling material and includes a thermoplastic resin. The thermoplastic resin includes one or more resins selected from polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin. The polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin are as described above. In one embodiment, the second modeling material used to form the modeling portion in the second step includes polyacetal resin (B) and has a composition and / or physical properties different from those of the first modeling material. By including the first modeling material in the base layer, the modeling portion can be made of a modeling material having a composition and / or physical properties different from those of the first modeling material. As a result, for example, a general polyacetal resin composition (e.g., a polyacetal resin composition used in injection molding), which has previously been difficult to model using the fused deposition modeling method, can also be used as the second modeling material. The shape of the second modeling material is not limited and may be the same as or different from that of the first modeling material, for example, filaments, pellets, etc., but filaments are preferred for ease of handling.

[0051] In one embodiment, the second modeling material may have a different composition from the first modeling material. For example, when the first modeling material and the second modeling material are both polyacetal resins, the "different compositions" may refer to different monomer compositions of the polyacetal resins contained in each modeling material; different amounts of polyacetal resin in each modeling material; or different types and / or amounts of other components in each modeling material. Preferably, one or more of these may be selected. When the second modeling material has a "different composition" from the first modeling material, the physical properties of the second modeling material may be the same as or different from those of the first modeling material. Furthermore, the different compositions may be due to, for example, different resin types being used in the first modeling material and the second modeling material.

[0052] Examples of polyacetal resins having different monomer compositions include polyacetal resin (A) being a copolymer and polyacetal resin (B) being a homopolymer; polyacetal resin (A) being a homopolymer and polyacetal resin (B) being a copolymer; polyacetal resin (A) and polyacetal resin (B) being copolymers, and the type and / or proportion of the comonomer component in polyacetal resin (B) being different from the type and / or proportion of the comonomer component in polyacetal resin (A); and the like.

[0053] Differences in the type and / or content of other components in each modeling material may include: the first modeling material does not contain a colorant, and the second modeling material does contain a colorant; the second modeling material does not contain a colorant, and the first modeling material contains a colorant; the type of colorant contained in the second modeling material is different from the type of colorant contained in the first modeling material; etc.

[0054] In one embodiment, the second modeling material may have different physical properties from the first modeling material. "Different physical properties" refers to, for example, different hues; different thermal properties such as melting points, crystallization temperatures, and melt flow rates; different physical properties such as specific gravity, refractive index, and transparency; different mechanical properties such as strength and elastic modulus; different molding temperatures; different machinability; different chemical properties such as chemical resistance; and different electrical properties such as dielectric constant. Preferably, the second modeling material has at least one difference selected from these. When the second modeling material has "different physical properties" from the first modeling material, the second modeling material may generally have the same or different composition as the first modeling material.

[0055] In one embodiment, the second modeling material may be configured to have a hue different from that of the first modeling material. When the hue of the second modeling material is different from that of the first modeling material, the base portion and the modeling portion can be easily distinguished visually, which makes it easier to mechanically separate (peel off) the base portion and the modeling portion after manufacturing the three-dimensional object.

[0056] In one embodiment, the second build material can be configured to have different thermal properties than the first build material.

[0057] In one embodiment, the melting temperature Tm2 of the second build material （ｉｉ） The temperature is preferably 160°C or higher and lower than 180°C, and more preferably 165°C or higher and 175°C or lower.

[0058] In one embodiment, the crystallization temperature Tc of the second build material （ｉｉ） The temperature is preferably 140°C or higher and 155°C or lower, and more preferably 143°C or higher and 150°C or lower.

[0059] In one embodiment, the MFR of the second modeling material measured at a temperature of 190°C and a load of 2.16 kg is preferably 0.8 g / 10 min or more and 50 g / 10 min or less, and more preferably 2.0 g / 10 min or more and 30 g / 10 min or less.

[0060] Melting point Tm2 （ｉｉ） , crystallization temperature Tc （ｉｉ）The method for measuring and adjusting the MFR is based on the melting point Tm2 of the first modeling material described above. （ｉ） , and crystallization temperature Tc （ｉ） The same method as for MFR is exemplified.

[0061] In one embodiment, the second modeling material has a melting point Tm2 measured by a differential scanning calorimeter, similar to the first modeling material, in order to further reduce the occurrence of warping in the modeling portion and further suppress peeling at the layer interface. （ｉｉ） and crystallization temperature Tc （ｉｉ） Difference from (Tm2 （ｉｉ） -Tc （ｉｉ） ) is 22°C or more and 40°C or less, and the melt flow rate measured at a temperature of 190°C and a load of 2.16 kg is 0.8 g / 10 min or more and 8.0 g / 10 min or less. In this embodiment, the second modeling material has a melting point Tm2 （ｉｉ） and crystallization temperature Tc （ｉｉ） Difference from (Tm2 （ｉｉ） -Tc （ｉｉ） ), and melt flow rate may be within the above ranges and different from the first modeling material.

[0062] In another embodiment, the second molding material is a polyacetal resin having a melting point Tm2 measured by a differential scanning calorimeter, which is lower than the melting point Tm2 （ｉｉ） and crystallization temperature Tc （ｉｉ） Difference from (Tm2 （ｉｉ） -Tc （ｉｉ） ) is 20° C. or more and 25° C. or less, and the melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg is 0.8 g / 10 min or more and 50 g / 10 min or less.

[0063] (Polyacetal Resin (B)) The polyacetal resin (B) contained in the second modeling material may be a polyacetal homopolymer or a polyacetal copolymer. In one embodiment, from the viewpoint of the balance between the mechanical and thermal properties of the resulting three-dimensional model, it is preferable that the polyacetal resin (B) contains a polyacetal copolymer. The polyacetal resin (B) may have not only linear molecules but also branched or crosslinked structures, and may be a known modified polyoxymethylene into which other organic groups have been introduced. The polyacetal resin (B) contained in the second modeling material may be a polyacetal resin having the same monomer composition, degree of polymerization, degree of branching, degree of crosslinking, etc. as the polyacetal resin (A) contained in the first modeling material, or may be a polyacetal resin having a different monomer composition, degree of polymerization, degree of branching, degree of crosslinking, etc. When polyacetal resin (B) has the same monomer composition, degree of polymerization, degree of branching, degree of crosslinking, etc. as polyacetal resin (A), a second modeling material having a different composition and / or physical properties from the first modeling material can be obtained, for example, by making the content of polyacetal resin in each material or the type and / or content of additives different.

[0064] Polyacetal homopolymer consists of oxymethylene units (-CH ２ Polyacetal copolymers are polymers that have only oxymethylene units (-CH ２ The "main structural unit" is as described above in the section on polyacetal resin (A).

[0065] Examples of the comonomer units contained in the polyacetal copolymer include those exemplified in the section on polyacetal resin (A) above.

[0066] The proportion of comonomer units in the polyacetal copolymer is preferably 0.5% by mass or more and 6.0% by mass or less, more preferably 5.5% by mass or less, even more preferably 5.0% by mass or less, even more preferably 4.5% by mass or less, and particularly preferably 4.0% by mass or less, relative to the total structural units (100% by mass) of the polyacetal resin (B). Having a comonomer unit proportion of 6.0% by mass or less relative to the total structural units (100% by mass) of the polyacetal copolymer reduces the likelihood of peeling at the lamination interface in the modeling portion and the lamination interface with the base portion, making it easier to produce three-dimensional objects by fused deposition modeling. Furthermore, three-dimensional objects with excellent appearance can be produced. When oxyethylene units are included as comonomer units, the proportion of oxyethylene units relative to the total comonomer units (100% by mass) is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less. The method for calculating the proportion of the comonomer unit in the polyacetal copolymer is as described above in the section on polyacetal resin (A).

[0067] The polyacetal copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer, with a random copolymer being preferred from the viewpoint of thermal stability.

[0068] The degree of polymerization, branching, and crosslinking of the polyacetal resin (B) are not particularly limited as long as they achieve the effects of the present disclosure, and can be adjusted appropriately within ranges that achieve the physical properties required for the three-dimensionally shaped object.

[0069] The weight-average molecular weight (Mw) of the polyacetal resin (B) is not particularly limited as long as it has the effects of the present disclosure and can be appropriately adjusted within a range that achieves the physical properties required for the three-dimensionally shaped object. In one embodiment, the Mw of the polyacetal resin (B) may be 10,000 or more and 400,000 or less, since this tends to improve the strength of the resulting shaped object. The method for measuring the weight-average molecular weight (Mw) is as described above in the section on polyacetal resin (A).

[0070] The second modeling material may contain only one type of polyacetal resin (B), or may contain a combination of two or more types selected from polyacetal homopolymers and polyacetal copolymers. When the second modeling material contains a polyacetal copolymer, the polyacetal copolymer may contain two or more types of polyacetal copolymers that differ in the type and / or content of comonomers and / or form (random copolymer, block copolymer, graft copolymer, etc.).

[0071] The content of polyacetal resin (B) in the second molding material is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or even 100% by mass, of the total mass (100% by mass) of the second molding material.

[0072] The content of the polyacetal resin (B) in the resin components constituting the second modeling material is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total resin components (100% by mass), and may be 100% by mass. The polyacetal resin (B) can be produced by the same method as that for the polyacetal resin (A) described above.

[0073] (Other Components) In an embodiment, the second modeling material may contain other components, as necessary, similar to the first modeling material. The types and amounts of the other components are exemplified as in the first modeling material, and may be the same as or different from the types and / or amounts of the other components contained in the first modeling material.

[0074] (Other Thermoplastic Resins) In one embodiment, the second modeling material may contain other thermoplastic resins other than the polyacetal resin (B). The types and contents of the other thermoplastic resins are exemplified as described above for the first modeling material, and the types and / or contents of the other thermoplastic resins may be the same as or different from those of the other thermoplastic resins contained in the first modeling material. Examples of the manufacturing method for the second modeling material include the same methods as described above for the first modeling material.

[0075] <Method for manufacturing a three-dimensional object by fused deposition modeling> <First step: base portion preparation step> The method for manufacturing a three-dimensional object according to the present disclosure includes a step of preparing a base portion containing a first modeling material prior to the step of forming a modeling portion. The base portion may be prepared in advance by injection molding or the like and attached to a modeling stage using a fixture, or may be modeled by fused deposition modeling using a 3D printer used to form the modeling portion. From the perspective of improving work efficiency, it is preferable to use a 3D printer used to form the modeling portion to model by fused deposition modeling. The first modeling material is as described above.

[0076] (Method for forming the base portion) In one embodiment, the base portion is preferably formed by using a fused deposition modeling 3D printer to eject a molten first modeling material onto a modeling stage and stacking one or more (preferably, 2 to 4) layers containing the first modeling material.

[0077] In one embodiment, the base preparation step preferably includes setting the temperature Ts of the modeling stage and the ambient temperature Ta of the modeling area in the fused deposition modeling 3D printer to temperatures that satisfy the following formula 2: Tm2 （ｉ） >Ts≧Tc （ｉ） ... (Equation 2) [In Equation 2, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ） represents the crystallization temperature (°C) of the first modeling material, and Tm2 （ｉ） indicates the melting point Tm2 (°C) of the first modeling material measured by a differential scanning calorimeter.

[0078] The temperature Ts of the modeling stage is set to Tc of the first modeling material. （ｉ） The melting point Tm2 （i） By controlling the temperature to the following range, the first layer of the sheet formed on the modeling stage becomes amorphous and functions as a base layer, which makes it easier to prevent the base layer from peeling off from the modeling stage.

[0079] The "modeling area" refers to a space on the modeling stage where a three-dimensional object can be formed. In one embodiment, the modeling area is preferably a chamber that forms an enclosed space to facilitate temperature control.

[0080] The ambient temperature (Ta) of the build area and the build stage temperature (Ts) can be adjusted by increasing or decreasing the settings on the fused deposition modeling 3D printer. However, the ambient temperature (Ta) of the build area and the build stage temperature (Ts) do not refer to the temperature as a set value for the operation of the 3D printer, but rather to the actual measured values ​​of the build stage temperature and the ambient temperature of the build area under certain set conditions. （ｉ） and crystallization temperature Tc （ｉ） The measurement method is as described above.

[0081] It is preferable that the temperature Ts of the modeling stage and the ambient temperature Ta of the modeling area are kept constant during the formation of the base portion. （i） The temperature is preferably +30 to +60°C, for example, 190 to 220°C.

[0082] In one embodiment, for example, the melting point Tm2 of the first build material （ｉ） is 165 to 175°C, and the crystallization temperature Tc （ｉ） is 140 to 145°C, the temperature of the modeling stage is preferably set to 140 to 175°C, and the ambient temperature of the modeling area is preferably set to 40 to 140°C.

[0083] The inner diameter of the nozzle (first nozzle) of the 3D printer that ejects the melted first modeling material is not limited, but is preferably 0.4 to 1.0 mm, more preferably 0.4 to 0.6 mm, from the viewpoint of improving production efficiency or preventing nozzle clogging even when the first modeling material contains a filler. The layer pitch (thickness per layer) of the base portion is preferably 0.05 to 0.3 mm, more preferably 0.1 to 0.2 mm. The drawing speed is preferably 10 mm / s to 80 mm / s, more preferably 20 mm / s to 40 mm / s.

[0084] (Configuration of base portion) The base portion may be one layer or two or more layers. Two or more layers are preferred from the viewpoint of preventing peeling from the modeling stage. The upper limit of the number of layers is not limited, and from the viewpoint of shortening the modeling time, it is preferably 10 or less, more preferably 4 or less. Furthermore, from the viewpoint of suppressing anisotropy of shrinkage and making it more difficult for the base portion to peel from the modeling stage, it is preferred that the drawing directions of the first and second layers intersect. Even when there are more than two layers, it is preferred that the drawing directions of each layer to be stacked intersect. The thickness of the base portion is preferably 0.2 to 2.0 mm, more preferably 0.3 to 1.0 mm, and even more preferably 0.4 to 0.8 mm.

[0085] The shape of the base part is not limited and may be any shape such as a sheet, plate, rod, or column, and may be a shape in which at least a partial region of these shapes is raised to form the core of the shaped part described below. The base part may act as a base for the shaped part, and in this case, the base part may be formed with an area larger than the bottom surface (the surface in contact with the base layer) of the shaped part and / or so as to prevent voids or gaps from forming.

[0086] <Second Step: Forming a Modeling Portion> The method for manufacturing a three-dimensional object according to the present disclosure includes a forming step of a modeling portion, in which a second modeling material containing polyacetal resin (B) and having a composition and / or physical properties different from those of the first modeling material is layered on a base portion containing the first modeling material prepared as described above by a fused deposition modeling method to form a modeling portion. The second modeling material is as described above. "On the base portion" means covering at least a portion of the base portion.

[0087] (Method for forming the modeling unit) The modeling unit is preferably formed by using a fused deposition modeling 3D printer to eject a melt of the second modeling material onto a base unit, and stacking one or more layers (preferably sheet-like layers) containing the second modeling material. In one embodiment, the step of forming the modeling unit preferably includes setting the temperature Ts of the modeling stage in the fused deposition modeling 3D printer and the ambient temperature Ta of the modeling area to temperatures that satisfy the following formula 1: Tc （ｉｉ） >Ta>Tc （ｉｉ） -100...(Formula 1) [In Formula 1, Tc （ｉｉ） represents the crystallization temperature (°C) of the second modeling material, and Ta represents the ambient temperature (°C) of the modeling area.

[0088] The ambient temperature Ta in the printing area is (Tc （ｉｉ） By controlling the crystallization temperature (Tc) of the second modeling material to be greater than -100, it is possible to further suppress the occurrence of warping and make it more difficult for peeling to occur at the layer interface. The "modeling area" is as described above. The method for adjusting the ambient temperature (Ta) of the modeling area is the same as that described for Equation 2 above. （ｉｉ） The measurement method is as described above.

[0089] The ambient temperature Ta of the modeling area is preferably kept constant during the formation of the base portion. The temperature of the second nozzle that discharges the melted second modeling material is set to a value equal to or higher than the melting point Tm2 （ii） The temperature is preferably +30 to +60°C, for example, 190 to 220°C.

[0090] In one embodiment, for example, the melting point Tm2 of the second build material （ｉｉ） is 165 to 175°C, and the crystallization temperature Tc （ｉｉ） is 140 to 145°C, the temperature of the modeling stage is preferably set to 140 to 175°C, and the ambient temperature of the modeling area is preferably set to 40 to 140°C.

[0091] The inner diameter of the nozzle (second nozzle) of the 3D printer that ejects the melted second modeling material is preferably 0.1 to 1.0 mm, more preferably 0.4 to 0.6 mm, from the viewpoint of easily improving the appearance of the resulting three-dimensional model. Furthermore, the layer pitch (thickness per layer) is preferably 0.05 to 0.3 mm, more preferably 0.1 to 0.2 mm. The drawing speed is preferably 10 mm / s to 80 mm / s, more preferably 20 mm / s to 40 mm / s. The first modeling material used as the modeling material for the base portion described above may also be used as the second modeling material for forming the modeling portion. In this case, the first modeling material for the base portion may have a different hue from the second modeling material for the modeling portion. The difference in color between the first modeling material and the second modeling material allows the base portion and the modeling portion to be visually recognized. For example, the base portion may be made of a black colored material, and the shaped portion may be made of a white material.

[0092] (Configuration of the shaping part) The shaping part may be one layer or two or more layers. Furthermore, it is preferable that the drawing directions of the first and second layers intersect, from the viewpoint of reducing anisotropy of shrinkage and further suppressing peeling at the lamination interface. Even when there are more than two layers, it is preferable that the drawing directions of the stacked layers intersect.

[0093] In one embodiment, the above-described base portion preparation step and shaping portion formation step are preferably performed using a shaping machine (3D printer) having two or more nozzles (preferably having two or more nozzles and two or more spools) because the shaping portion formation step can be easily performed subsequently after the base portion formation. For example, the base portion can be easily formed by ejecting a molten first shaping material from one of the two or more nozzles, and the shaping portion can be easily formed by ejecting a molten second shaping material from another nozzle. In this specification, the nozzle ejecting the molten first shaping material is also referred to as the "first nozzle," and the nozzle ejecting the molten second shaping material is also referred to as the "second nozzle."

[0094] When using a fused deposition modeling 3D printer having two or more nozzles and spools (for example, a FUNMAT PRO 310 manufactured by INTAMSYS, etc.), a filament (filament (A)) of a first modeling material prepared in advance is set on a first spool (filament box), and the molten first modeling material is ejected from the first nozzle, and a filament (filament (B)) of a second modeling material prepared in advance is set on a second spool (filament box), and the molten second modeling material is ejected from the second nozzle. This eliminates the need to replace the filament or nozzle when forming the modeling section described below, and further improves production efficiency.

[0095] In another embodiment, it is preferable to use a 3D printer with one nozzle, as this allows the use of a general 3D printer. In this embodiment, the same nozzle is used when forming the base portion and when forming the modeling portion described below. Furthermore, if there is only one spool (filament box), after forming the base portion, the filament (filament (A)) of the first modeling material is replaced with a filament (filament (B)) of the second modeling material for forming the modeling portion described below. When using a fused deposition modeling machine (3D printer) with one nozzle and one spool, the inner diameter of the nozzle used to form the base portion and the modeling portion can be, for example, 0.1 to 0.4 mm.

[0096] <Third Step: Peeling-Off Step of Modeled Object> The method for producing a three-dimensionally shaped object according to the present disclosure may include a step of peeling off the base portion from the modeling stage after forming the modeled portion. The step of peeling off the base portion from the modeling stage may include a step of peeling off the base portion from the modeling stage after forming the three-dimensionally shaped object according to the following formula 3: Tc （ｉ） >Ts (Equation 3) [In Equation 3, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ） is the crystallization temperature (°C) of the first modeling material]. （ｉ）By setting the temperature of the modeling stage at a temperature lower than 145°C, the base portion can be easily peeled off from the modeling stage, and a three-dimensional model can be easily obtained. In one embodiment, the temperature of the modeling stage can be set to 145°C to 155°C.

[0097] The method for manufacturing a three-dimensional object according to the present disclosure can, if necessary, produce a three-dimensional object, then separate the base portion and the shaped portion by cutting, polishing, or the like, remove the base portion, and further polish the shaped portion with a polishing machine if necessary, thereby obtaining a three-dimensional object consisting of the shaped portion.

[0098] [Three-dimensional Structure] The three-dimensional structure according to this embodiment is a three-dimensional structure formed using the first and second modeling materials described above, and includes a base portion containing the first modeling material and a modeling portion containing the second modeling material. In one embodiment, the three-dimensional structure may be a three-dimensional structure formed by a fused deposition modeling method using a filament (A) of the first modeling material and a filament (B) of the second modeling material described above. The fact that the three-dimensional structure is formed using the filament (A) and the filament (B) can be determined by observing the surface of the three-dimensional structure visually or with a stereomicroscope, and by identifying modeling lines (drawing lines) and layering marks.

[0099] In one embodiment, the polyacetal resin (A) has a melting point Tm2 measured by a differential scanning calorimeter. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a base portion containing a first modeling material having a viscosity of 22°C or higher and 40°C or lower and a melt flow rate of 0.8 g / 10 min or higher and 8.0 g / 10 min or lower, measured at a temperature of 190°C and a load of 2.16 kg; and a modeling portion located on the base portion, containing a second modeling material containing polyacetal resin (B) and having a composition and / or physical properties different from those of the first modeling material, wherein a drawing line is formed on the surface of the modeling portion.

[0100] In one embodiment of the present invention, the three-dimensional object may be a three-dimensional object in which the base portion and the filling portion inside the modeling portion are formed from a first modeling material, and the outer surface surrounding the filling portion of the modeling portion is formed from a second modeling material.

[0101] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below. [1] A method for producing a three-dimensional object, comprising: （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） [2] A method for manufacturing a three-dimensional object according to [1], comprising: forming a modeling part by layering, on a base part including a first modeling material having a melting point Tm2 of 15°C or more and 105°C or less, and a melt flow rate of 0.8 g / 10 min or more and 1,000 g / 10 min or less, measured at a melting point Tm2+10°C and under a load of 2.16 kg, a second modeling material having a composition and / or physical properties different from that of the first modeling material, by a fused deposition modeling method; wherein the first modeling material and the second modeling material comprise thermoplastic resins. [2] The thermoplastic resin is one or more resins selected from polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin. [3] A method for manufacturing a three-dimensional object according to [1], comprising: a polyacetal resin (A) having a melting point Tm2 of 15°C or more and 105°C or less, and a melt flow rate of 0.8 g / 10 min or more and 1,000 g / 10 min or less, measured at a melting point Tm2+10°C and a load of 2.16 kg, （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）a first modeling material having a melt flow rate (MFR) of 0.8 g / 10 min to 8.0 g / 10 min measured at a temperature of 190°C under a load of 2.16 kg, and a second modeling material having a polyacetal resin (B) and a composition and / or physical properties different from those of the first modeling material, on a base portion comprising the first modeling material, the second modeling material being formed by a fused deposition modeling method. [4] A method for manufacturing a three-dimensional object according to [3], wherein the polyacetal resin (A) contained in the first modeling material contains a comonomer unit in an amount of 1.0 mass% to 6.0 mass% of all constituent units (100 mass%). [5] The method for manufacturing a three-dimensional object according to [3] or [4], wherein the comonomer unit is at least one oxyalkylene unit selected from an oxyethylene group, an oxypropylene group, and an oxytetramethylene group. [6] The method for manufacturing a three-dimensional object according to any one of [3] to [5], wherein the polyacetal resin (B) contained in the second modeling material includes a polyacetal homopolymer and / or a polyacetal copolymer. [7] The method for manufacturing a three-dimensional object according to any one of [3] to [6], wherein the polyacetal resin (B) contained in the second modeling material includes a polyacetal copolymer including 6.0% by mass or less of comonomer units among all structural units (100% by mass). [8] The method for manufacturing a three-dimensional object according to any one of [1] to [7], wherein the second modeling material has a hue different from that of the first modeling material. [9] The method for manufacturing a three-dimensional object according to any one of [1] to [8], wherein the first modeling material and / or the second modeling material is a filament.

[10] The method for manufacturing a three-dimensional object according to any one of [1] to [8], wherein forming the modeling portion is carried out by satisfying the following formula 1: Tc （ｉｉ） >Ta>Tc （ｉｉ） -100...(Formula 1) [In Formula 1, Tc （ｉｉ）

[11] The method for manufacturing a three-dimensional object according to any one of [1] to [9], wherein the method is performed under temperature conditions shown in [1] to [9].

[11] The method for manufacturing a three-dimensional object according to any one of [1] to

[10] , which includes forming the base portion by a fused deposition modeling method using the first modeling material prior to forming the modeling portion.

[12] The method for manufacturing a three-dimensional object according to any one of [1] to

[10] , wherein the formation of the base portion satisfies the following formula 2: Tm2 （ｉ） >Ts≧Tc （ｉ） ... (Equation 2) [In Equation 2, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ） represents the crystallization temperature (°C) of the first modeling material, and Tm2 （ｉ）

[13] The method for manufacturing a three-dimensional object according to any one of [1] to

[12] , wherein forming the base portion comprises laminating two or more layers containing the first modeling material.

[14] After forming the modeling portion, a temperature range of Tc expressed by the following formula 3: Tc （ｉ） >Ts (Equation 3) [In Equation 3, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ）

[15] The method for manufacturing a three-dimensional object according to any one of [1] to

[14] , wherein forming the base portion is performed using a nozzle having an inner diameter of 0.4 to 1 mm, and forming the modeled portion is performed using a nozzle having an inner diameter of 0.1 to 0.4 mm.

[16] The method for manufacturing a three-dimensional object according to any one of [1] to

[15] , wherein forming the base portion and forming the modeled portion are performed using a modeling machine having one nozzle.

[17] The method for manufacturing a three-dimensional object according to any one of [1] to

[16] , wherein forming the base portion and forming the modeled portion are performed using a modeling machine having two or more nozzles.

[18] The method for manufacturing a three-dimensional object according to any one of [1] to

[16] , wherein forming the base portion and forming the modeled portion are performed using a modeling machine having two or more nozzles.

[19] The method for manufacturing a three-dimensional object according to any one of [1] to

[18] , wherein forming the base portion is performed using a nozzle having an inner diameter of 0.4 to 1 mm, and forming the modeled portion is performed using a nozzle having an inner diameter of 0.1 to 0.4 mm. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）

[19] A three-dimensional modeling object according to

[18] , comprising: a base portion including a first modeling material having a melting point Tm2 of 15°C or more and a melt flow rate of 0.8 g / 10 min or more and 1,000 g / 10 min or less, measured at a melting point Tm2+10°C and a load of 2.16 kg; and a modeling portion formed by layering a second modeling material having a composition and / or physical properties different from those of the first modeling material by a fused deposition modeling system, wherein the first modeling material and the second modeling material comprise a thermoplastic resin.

[19] The three-dimensional modeling object according to

[18] , wherein the thermoplastic resin is one or more resins selected from polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin.

[20] The three-dimensional modeling object according to

[18] , comprising a polyacetal resin (A), having a melting point Tm2 of 15°C or more and a melt flow rate of 0.8 g / 10 min or more and 1,000 g / 10 min or less, measured at a melting point Tm2+10°C and a load of 2.16 kg. （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ）A three-dimensional modeled object comprising: a base portion including a first modeling material having a melt flow rate (MFR) of 0.8 g / 10 min or more and 8.0 g / 10 min or less, measured at a temperature of 190°C under a load of 2.16 kg, and a modeling portion located on the base portion, the first modeling material including a polyacetal resin (B) and a second modeling material having a composition and / or physical properties different from those of the first modeling material, wherein a drawing line is formed on a surface of the modeling portion. Each configuration and combination thereof in each embodiment is merely an example, and configurations and combinations thereof may be added, omitted, substituted, and otherwise modified as appropriate within a scope that does not deviate from the gist of the present disclosure.

[0102] The present disclosure will be explained in more detail below by showing examples, but interpretation of the present disclosure is not limited to these examples.

[0103] Synthesis Example 1 (Production of Polyacetal Resin (A) (POM-A Resin)) Polymerization was carried out using a continuous mixer / reactor equipped with an external jacket for passing a heat transfer medium (or coolant) and a rotating shaft equipped with paddles having a cross section in the shape of two partially overlapping circles. Specifically, trioxane and a comonomer (1,3-dioxolane) were added to the reactor in the proportions shown in Table 1 while the two rotating shafts with paddles were rotated at 150 rpm. Methylal was also added as a molecular weight modifier in the proportion shown in Table 1. Next, a catalyst mixture prepared by mixing boron trifluoride gas as a catalyst with trioxane at a concentration of 0.005% by mass, calculated as boron trifluoride, was continuously added to carry out bulk polymerization. After completion of the polymerization, the reaction product discharged from the reactor was quickly passed through a crusher and added to an aqueous solution containing 0.1% by mass of triethylamine at 80°C to deactivate the catalyst. After separation, washing, and drying, a crude polyacetal resin was obtained. Next, 4 parts by mass of a 5% by mass aqueous solution of triethylamine and 0.03 parts by mass of pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant) were added to 100 parts by mass of this crude polyacetal resin, and the mixture was melt-kneaded at 210°C in a twin-screw extruder to remove unstable portions of the crude polyacetal resin. 0.3 parts by mass of pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] as a stabilizer and 0.15 parts by mass of melamine were further added to 100 parts by mass of the polyacetal resin obtained by the above method, and the mixture was melt-kneaded at 210°C in a twin-screw extruder to obtain pelletized polyacetal resin (A) (POM-A resin). The amount of comonomer in the resulting POM-A resin relative to the total monomer content (100% by mass) was 5.9% by mass. The proportion of comonomer units (calculated as oxyethylene units) relative to all structural units (100% by mass) of the POM-A resin was 3.5% by mass, as calculated by 1H-NMR. The detailed method for calculating the comonomer units will be described later.

[0104] Synthesis Examples 2 to 5 (Production of Polyacetal Resins (B1 to B4) (POM-B1 to B4 Resins)) Pellet-shaped polyacetal resins (B1 to B4) (POM-B1 resin, POM-B2 resin, POM-B3 resin, POM-B4 resin) were produced in the same manner as for the polyacetal resin (A) (POM-A resin) described above, except for the formulation shown in Table 1. The proportions of comonomer units (oxyethylene unit equivalent) relative to all structural units (100% by mass) of the POM-B1 resin, POM-B2 resin, POM-B3 resin, and POM-B4 resin calculated by 1H-NMR were 2.1% by mass (POM-B1 resin), 2.1% by mass (POM-B2 resin), 0.8% by mass (POM-B3 resin), and 0.8% by mass (POM-B4 resin), respectively. The detailed calculation method for the comonomer units is as follows.

[0105] [Method for Measuring Comonomer Unit Proportion] The obtained pellet-like POM-A resin and POM-B1 to POM-B4 resins were each cut into small pieces with nippers to facilitate solubility in solvents, and then dissolved in deuterated hexafluoroisopropanol to a concentration of 5% by mass to prepare samples. These samples were analyzed by 1H-NMR (manufactured by Bruker, product name: AvanceIII 400, magnetic field strength: 400 MHz, reference material: tetramethylsilane, temperature: 27°C, number of accumulations: 128) to determine the ratio of the integral fraction of the comonomer unit (oxyethylene group) to the integral fraction of the peak of all monomers in each of the POM-A resin and POM-B1 to POM-B4 resins.

[0106] [Fabrication of Filament] (Filament (A)) Using the pelletized POM-A resin obtained by the method described above, a filament (A) having an average diameter of 1.75 mm was produced by the following method. The POM-A resin pellets were fed into a benchtop extruder (AS-1, Apex Japan Co., Ltd.) and extruded at a barrel temperature of 200°C and a screw speed of 40 rpm. The extruded strand was cooled and solidified with water, and then wound up using a filament winder (Spooler, Philabot Co., Ltd.) at a winding speed such that the filament diameter became 1.75 mm±0.1 mm, thereby obtaining a filament (A) made of POM-A resin as a first modeling material.

[0107] (Filaments (B1) to (B4)) Filament (B1) (POM-B1 resin), filament (B2) (POM-B2 resin), filament (B3) (POM-B3 resin), and filament (B4) (POM-B4 resin) were obtained as the second modeling material using the same method as filament (A), except that POM-B1 resin, POM-B2 resin, POM-B3 resin, or POM-B4 resin was used.

[0108] [Measurement of physical properties of filaments] The MFR, melting point Tm2, ​​and crystallization temperature Tc of the obtained filaments (A) and filaments (B1) to (B4) were measured by the following methods. The MFR, melting point Tm2, ​​crystallization temperature Tc, difference between the melting point and crystallization temperature (Tm2 - Tc), and average diameter of the filaments of each of the filaments (A) and (B1) to (B4) are shown in Table 1.

[0109] (Melt Flow Rate (MFR)) The MFR was measured in accordance with ISO 1133 (Condition D) at a temperature of 190° C. under a load of 2.16 kg.

[0110] (Melting point Tm2, ​​crystallization temperature Tc) Using a differential scanning calorimeter (manufactured by Parkin Elmer, product name: DSC8500), according to JIS K-7121 (2012), after heating from 40 ° C. to 200 ° C. at a heating rate of 200 ° C. / min (1st RUN), the temperature at 200 ° C. was held for 5 minutes, and then cooled to 40 ° C. at a heating rate of 10 ° C. / min. The peak top temperature of the exothermic peak observed when cooled to 40 ° C. was measured as the crystallization temperature Tc. Then, the temperature was held at 40 ° C. for 5 minutes, and again heated from 40 ° C. to 200 ° C. at a heating rate of 10 ° C. / min. The peak top temperature of the endothermic peak observed when heated to 200 ° C. in the 2nd RUN was measured as the melting point Tm2. The melting point Tm2 of the filament (A), which is the first shaping material, is the melting point Tm2 in the above-mentioned formula 2. （i） The melting point Tm2 of the filaments B1 to B4, which are the second modeling material, corresponds to Tm2 in the above formula 1. （ii） This applies to:

[0111] (Difference between Melting Point and Crystallization Temperature (Tm2 - Tc)) The difference between the melting point and crystallization temperature (Tm2 - Tc) of each of the filaments (A) and (B1) to (B4) was calculated by subtracting the value of the crystallization temperature Tc from the value of the melting point Tm2 measured above.

[0112] (Measurement of average diameter of filament) A 5 m sample was taken from the obtained filament, and 20 points were randomly selected to measure the diameters of the samples to three decimal places using a micrometer (manufactured by Mitutoyo Corporation, product name: ABSOLUTE). Next, the average value was rounded off to two decimal places to obtain the average diameter of the filament.

[0113] [Example 1] The filament (A) prepared above was set on the first spool (filament box) of a fused deposition model 3D printer (manufactured by INTAMSYS, product name: FUNMAT PRO 310) having two nozzles and two spools, and the filament (B1) prepared above was set on the second spool (filament box).

[0114] (First Step: Method for Forming Base Portion (Base Layer)) Using the filament (A) prepared on the first spool, the base portion (base layer) of a three-dimensionally shaped object was formed by the following method. First, the temperature Ts of the shaping stage and the ambient temperature Ta of the shaping area of ​​a fused deposition modeling 3D printer (manufactured by INTAMSYS, product name: FUNMAT PRO 310) were set to the temperature conditions for the first step described below. The temperature of the first nozzle that ejected the filament (A) was also set to the temperature conditions for the first step described below. Melted filament (A) was ejected from the first nozzle to form a base portion (90 mm × 20 mm × 14 mm) of a three-dimensionally shaped object. Specifically, first, a sheet-like first layer having a size that allowed a 1 cm margin with respect to the bottom shape of the shaping portion to be set was formed under the temperature conditions described below, and then a sheet-like second layer of the same size was laminated on top of the first layer. The inner diameter of the nozzle (first nozzle) that ejects the filament (A) in the 3D printer was 0.4 mm, the layer pitch (thickness per layer) was 0.2 mm, and the drawing speed was 30 mm / s. <Temperature conditions for the first step> Temperature of the ejection nozzle 1: 215°C Modeling stage temperature (Ts): 150°C Modeling area ambient temperature (Ta): 100°C The stage temperature Ts in the first step and the ambient temperature Ta in the modeling area are constant.

[0115] (Second Step: Method for Forming a Modeled Part) After the base portion was formed, a modeled part (modeled layer) of a three-dimensional object was formed using the filament (B1) prepared on the second spool by the following method. First, the temperature Ts of the modeling stage and the ambient temperature Ta of the modeling area of ​​a fused deposition modeling 3D printer (manufactured by INTAMSYS, product name: FUNMAT PRO 310) were set to the temperature conditions for the second step described below. The temperature of the second nozzle ejecting the filament (B1) was also set to the temperature conditions for the second step described below. The molten filament (B1) was ejected from the second nozzle and layered on the base portion to form a modeled part (80 mm x 10 mm x 4 mm). Specifically, a sheet-like first layer was formed on the base portion formed above, 1 cm inward from the base portion, and sheet-like second and subsequent layers were then layered on top of that. The inner diameter of the second nozzle (discharge nozzle 2) in the 3D printer that discharges the filament (B) was 0.4 mm, the layer pitch (thickness per layer) was 0.2 mm, and the drawing speed was 30 mm / s.

[0116] <Temperature Conditions for the Second Step> Temperature of the discharge nozzle 2: 215°C Modeling stage temperature (Ts): 150°C Modeling area ambient temperature (Ta): 100°C The stage temperature Ts in the second step and the ambient temperature Ta in the modeling area are constant.

[0117] (Step 3: Method for Peeling the Modeling Portion) After Step 2 was completed, the temperature of the modeling stage was lowered to 120°C, and the three-dimensional object was peeled off from the surface of the modeling stage. The resulting three-dimensional object did not peel off from the modeling stage during modeling, and no peeling occurred at the layering interface, and the modeling layers were stacked without any problems until the end. This enabled the production of a three-dimensional object by fused deposition modeling using polyacetal resin. Furthermore, the base portion was separated from the modeling portion using a grinder, resulting in a three-dimensional object with dimensions of 80 mm x 10 mm x 4 mm. <Temperature Conditions for Step 3> Modeling stage temperature (Ts): 120°C

[0118] [Examples 2 to 4] A base portion was formed under the same temperature conditions and manufacturing method as in Example 1. Next, a modeling portion was layered on the base portion under the same temperature conditions and manufacturing method as in Example 1, except that filament (B2), (B3), or (B4) was used instead of filament (B1). The three-dimensional object was then peeled from the surface of the modeling stage using the same method as in Example 1. Furthermore, the base portion was separated from the modeling portion using the same method as in Example 1, yielding three-dimensional objects of Examples 2 to 4 with dimensions of 80 mm x 10 mm x 4 mm. In Examples 2 to 4, the three-dimensional object did not peel from the modeling stage during modeling, and no peeling occurred at the layering interface. The modeling layers were layered without any problems until the end. This enabled the production of three-dimensional objects using polyacetal resin by fused deposition modeling.

[0119] [Example 5] A base portion was formed under the same temperature conditions and manufacturing method as in Example 1. Next, a modeling portion was layered on the base portion under the same temperature conditions and manufacturing method as in Example 1, except that filament (A) was used instead of filament (B1). The three-dimensional object was then peeled from the surface of the modeling stage using the same method as in Example 1. The base portion was then separated from the modeling portion using the same method as in Example 1, yielding a three-dimensional object of Example 5 having dimensions of 80 mm x 10 mm x 4 mm. In Example 5, the three-dimensional object did not peel from the modeling stage during modeling, and no peeling occurred at the layering interface. The modeling layers were layered without any problems until the end. This enabled the production of a three-dimensional object using polyacetal resin by fused deposition modeling.

[0120] [Comparative Example 1] A base part was formed under the same temperature conditions and by the same manufacturing method as in Example 1, except that a filament (B1) was used for the base part. Next, a modeling part was laminated on the base part using the filament (B1) under the same temperature conditions and by the same manufacturing method as in Example 1. In Comparative Example 1, the base part peeled off from the stage during modeling, and a three-dimensional model could not be obtained.

[0121] [Evaluation of Three-Dimensional Model] Whether or not a three-dimensional model that peeled off from the modeling stage was obtained is shown in Table 1. The symbols in Table 1 are as follows: A: A three-dimensional model was obtained. B: The base layer peeled off from the stage during modeling, and a three-dimensional model was not obtained.

[0122]

[0123] The method for manufacturing a three-dimensional object according to this embodiment can provide a method for manufacturing a three-dimensional object by fused deposition modeling using polyacetal resin, which does not limit the type of material used for modeling, and can manufacture three-dimensional objects of various sizes and made from materials that are in high demand in the market.

Claims

1. A method for manufacturing a three-dimensional object, the melting point Tm2 measured by a differential scanning calorimeter （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a first modeling material having a melting point of 10°C or higher and a melt flow rate of 0.8 g / 10 min or higher and 1,000 g / 10 min or lower, measured under a load of 2.16 kg, and a base part including the first modeling material, the second modeling material having a composition and / or physical properties different from those of the first modeling material, and the first modeling material and the second modeling material each including a thermoplastic resin.

2. The method for manufacturing a three-dimensional object according to claim 1, wherein the thermoplastic resin is one or more resins selected from the group consisting of polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin.

3. A method for producing a three-dimensional object, comprising: a polyacetal resin (A) having a melting point Tm2 measured by a differential scanning calorimeter; （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a second modeling material that contains polyacetal resin (B) and has a composition and / or physical properties different from those of the first modeling material, and that has a base part containing a first modeling material having a melt flow rate of 0.8 g / 10 min or more and 8.0 g / 10 min or less, measured at a temperature of 190°C and a load of 2.16 kg, and that has a temperature of 22°C or more and a melt flow rate of 0.8 g / 10 min ... 8.0 g / 10 min or less, measured at a temperature of 190°C and a load of 2.16 kg, by a fused deposition modeling method to form a modeling part.

4. A method for manufacturing a three-dimensional object as described in claim 3, wherein the polyacetal resin (A) contained in the first modeling material contains 1.0 mass% or more and 6.0 mass% or less of comonomer units among all constituent units (100 mass%).

5. The method for producing a three-dimensionally shaped object according to claim 4, wherein the comonomer unit is at least one oxyalkylene unit selected from an oxyethylene group, an oxypropylene group, and an oxytetramethylene group.

6. A method for manufacturing a three-dimensional object according to claim 3 or 4, wherein the polyacetal resin (B) contained in the second modeling material includes a polyacetal homopolymer and / or a polyacetal copolymer.

7. A method for manufacturing a three-dimensional object described in claim 3 or 4, wherein the polyacetal resin (B) contained in the second modeling material includes a polyacetal copolymer containing 6.0 mass% or less of comonomer units among all constituent units (100 mass%).

8. The method for manufacturing a three-dimensional object according to claim 1 or 3, wherein the second modeling material has a different hue from the first modeling material.

9. The method for manufacturing a three-dimensional object according to claim 1 or 3, wherein the first modeling material and / or the second modeling material is a filament.

10. The formation of the shaped portion is carried out by the method according to the following formula 1: Tc （ｉｉ） >Ta>Tc （ｉｉ） -100...(Formula 1) [In Formula 1, Tc （ｉｉ） represents a crystallization temperature (°C) of the second material for modeling, and Ta represents an ambient temperature (°C) in the modeling area.

11. A method for manufacturing a three-dimensional object according to claim 1 or 3, which includes forming the base portion using the first modeling material by fused deposition modeling prior to forming the modeling portion.

12. Forming the base portion is a process for forming a film having a thickness of 100 μm or less, the thickness of which is determined by the following formula 2: Tm2 （ｉ） >Ts≧Tc （ｉ） ... (Equation 2) [In Equation 2, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ） represents the crystallization temperature (°C) of the first modeling material, and Tm2 （ｉ） The method for manufacturing a three-dimensional object according to claim 11 , wherein the method is performed under temperature conditions shown in the following formula: Tm2 (° C.) is the melting point Tm2 (° C.) of the first material for modeling measured with a differential scanning calorimeter.

13. The method for manufacturing a three-dimensional object according to claim 11, wherein forming the base portion includes stacking two or more layers containing the first modeling material.

14. After forming the feature, the following formula 3: Tc （ｉ） >Ts (Equation 3) [In Equation 3, Ts represents the temperature of the modeling stage (°C), and Tc （ｉ） and (c) peeling the base portion from the modeling stage under temperature conditions shown in [wherein C represents a crystallization temperature (°C) of the first modeling material].

15. The method for manufacturing a three-dimensional object according to claim 11, wherein forming the base portion is performed using a nozzle having an inner diameter of 0.4 to 1 mm, and forming the modeled portion is performed using a nozzle having an inner diameter of 0.1 to 0.4 mm.

16. The method for manufacturing a three-dimensional object according to claim 11, wherein forming the base portion and forming the shaped portion is performed using a shaping machine having one nozzle.

17. The method for manufacturing a three-dimensional object according to claim 11, wherein forming the base portion and forming the shaped portion is carried out using a shaping machine having two or more nozzles.

18. Melting point Tm2 measured by differential scanning calorimetry （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a base portion including a first modeling material having a melting point of 15°C or higher and a melt flow rate of 0.8g / 10min or higher and 1000g / 10min or lower, measured at a melting point of 10°C or higher and a load of 2.16kg; and a modeling portion formed by layering, by a fused deposition modeling system, a second modeling material having a composition and / or physical properties different from that of the first modeling material, wherein the first modeling material and the second modeling material include a thermoplastic resin.

19. The three-dimensional object according to claim 18, wherein the thermoplastic resin is one or more resins selected from the group consisting of polyacetal resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin.

20. Polyacetal resin (A) containing a melting point Tm2 measured by a differential scanning calorimeter （ｉ） and crystallization temperature Tc （ｉ） Difference from (Tm2 （ｉ） -Tc （ｉ） a base portion containing a first modeling material having a viscosity of 22°C or higher and 40°C or lower and a melt flow rate of 0.8 g / 10 min or higher and 8.0 g / 10 min or lower, measured at a temperature of 190°C and a load of 2.16 kg; and a modeling portion located on the base portion, the first modeling material containing a polyacetal resin (B) and having a composition and / or physical properties different from those of the first modeling material, wherein a drawing line is formed on a surface of the modeling portion.

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