Three-dimensional molding

Abstract

To provide a three-dimensional molding with suppressed warpage.SOLUTION: A three-dimensional molding includes a thermoplastic resin and has a ratio of a heat of fusion ▵H2 measured 72 hours after molding to a heat of fusion ▵H1 measured immediately after molding of 1.3 or over.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a three-dimensional object. [Background technology]

[0002] In recent years, 3D printers have rapidly spread, especially in industrial use. 3D printers can create objects based on information from 3D CAD, three-dimensional computer graphics, etc.

[0003] Patent Document 1 discloses a shaped object produced using a composition for three-dimensional printers, the shaped object comprising a propylene polymer (A) containing monomer units derived from propylene and having a content of the monomer units derived from propylene of 85 mol % or more, and a polymer (B), the crystallization half time of the polymer (B) being longer than the crystallization half time of the propylene polymer (A), and the crystallization half time of the composition for three-dimensional printers being 900 seconds or more. Patent Document 2 discloses a 3D printed article including a thermoplastic polymer, the thermoplastic polymer having a crossover temperature (G' / G") of less than 140°C as measured by parallel plate rheology, and an elongation at break in the XY direction of at least 50%. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2022-41914 A [Patent Document 2] Patent No. 7223126 Summary of the Invention [Problem to be solved by the invention]

[0005] Conventionally, objects created using 3D printers have sometimes warped and deviated from the desired shape.

[0006] An object of the present disclosure is to provide a three-dimensional object with reduced warping. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> Contains a thermoplastic resin, A three-dimensional object in which the ratio of the heat of fusion △H2 72 hours after printing to the heat of fusion △H1 immediately after printing is 1.3 or more. <2> The heat of fusion △H2 is 40J / g or more. <1> The three-dimensional object according to claim 1. <3> The tensile modulus is 300 MPa or more. <1> or <2> The three-dimensional object according to claim 1. <4> The crossover temperature is 140°C or higher. <1> ~ <3> 13. The three-dimensional object according to claim 12, <5> The thermoplastic resin includes a polymer containing structural units derived from 1-butene. <1> ~ <4> 13. The three-dimensional object according to claim 12, <6> The thermoplastic resin includes poly-1-butene. <1> ~ <5> 13. The three-dimensional object according to claim 12, <7> The thermoplastic resin has a melt flow rate (MFR) of 0.1 g / 10 min and 50.0 g / 10 min at 190°C and a load of 2.16 kg. <1> ~ <6> 13. The three-dimensional object according to claim 12, <8> The content of the thermoplastic resin is 80% by mass or more based on the total amount of the three-dimensional object. <1> ~ <7> 13. The three-dimensional object according to claim 12, <9> The ratio of the heat of fusion ΔH2 measured by raising the temperature at 10°C / min after 72 hours at a temperature of 23°C and a relative humidity of 50% to the heat of fusion ΔH1 measured by raising the temperature at 10°C / min using a differential scanning calorimeter is 1.3 or more. <1> ~ <8> 13. The three-dimensional object according to claim 12, Effect of the Invention

[0008] According to one embodiment of the present disclosure, a three-dimensional object with reduced warping is provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the three-dimensional structure of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the object of the present disclosure.

[0010] In the present disclosure, a numerical range expressed using "~" means a range including the numerical values ​​described before and after "~" as the lower and upper limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples. In this disclosure, when referring to the amount of each component in a composition, if multiple substances corresponding to each component are present in the composition, it means the total amount of multiple substances present in the composition, unless otherwise specified. In the present disclosure, the term "step" refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. Furthermore, in the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments.

[0011] [Three-dimensional object] The three-dimensional object of the present disclosure contains a thermoplastic resin, and the ratio of the heat of fusion ΔH2 72 hours after modeling to the heat of fusion ΔH1 immediately after modeling is 1.3 or more.

[0012] Three-dimensional objects are manufactured by, for example, fusion lamination. Thermoplastic resins with high crystallinity are excellent in terms of elastic modulus and heat resistance, but when a three-dimensional object is manufactured by using the fusion lamination method with a thermoplastic resin, warping is likely to occur. Therefore, a method of manufacturing a three-dimensional object using a material with a slow crystallization rate or a material with low crystallinity has been proposed. However, when a material with a slow crystallization rate or a material with low crystallinity is used, the modeling time becomes long and heat collapse is likely to occur during modeling. In contrast, the three-dimensional object of the present disclosure has a ratio of the heat of fusion ΔH2 72 hours after fabrication to the heat of fusion ΔH1 immediately after fabrication of 1.3 or more, and crystallization progresses immediately after fabrication, and warping is suppressed despite the high crystallinity. In the present disclosure, "warping" refers to a phenomenon in which a shaped object is distorted due to shrinkage or the like.

[0013] <Ratio of heat of fusion △H2 to heat of fusion △H1> The three-dimensional object of the present disclosure has a ratio of the heat of fusion ΔH2 72 hours after fabrication to the heat of fusion ΔH1 immediately after fabrication of 1.3 or more.

[0014] The heat of fusion ΔH1 immediately after molding and the heat of fusion ΔH2 72 hours after molding are measured by the following method in accordance with JIS K7121.

[0015] A sample of approximately 5 mg is prepared from the three-dimensional object. The sample is sealed in an aluminum pan for measurement of a differential scanning calorimeter (product name "Diamond DSC", manufactured by PerkinElmer) and heated from room temperature (25°C) to 220°C at a heating rate of 10°C / min. In order to completely melt the sample, it is held at 220°C for 5 minutes. It is then cooled from 220°C to -50°C at a heating rate of 10°C / min. After leaving it at -50°C for 5 minutes, it is heated a second time from -50°C to 200°C at a heating rate of 10°C / min. The heat of fusion in the second heating is designated as the heat of fusion ΔH1. After measuring ΔH1, the sample is cooled at a rate of 10°C / min and stored at 23°C and 50% RH for 72 hours. After 72 hours, the sample is heated from room temperature (25°C) to 220°C at a rate of 10°C / min. The heat of fusion is defined as ΔH2.

[0016] In other words, the three-dimensional object of the present disclosure preferably has a ratio of 1.3 or more of the heat of fusion ΔH2 measured by raising the temperature at 10° C. / min after 72 hours at a temperature of 23° C. and a relative humidity of 50% RH to the heat of fusion ΔH1 measured by raising the temperature at 10° C. / min using a differential scanning calorimeter.

[0017] In order to further suppress warping of the three-dimensional object, the ratio of the heat of fusion ΔH2 to the heat of fusion ΔH1 is preferably equal to or greater than 2.0, and more preferably equal to or greater than 2.2. The upper limit of the ratio is, for example, 3.5.

[0018] In order to increase the above ratio, the heat of fusion ΔH1 is preferably small, is preferably 0 J / g to 60 J / g, and is more preferably 10 J / g to 50 J / g.

[0019] To increase the above ratio, the heat of fusion ΔH2 is preferably large, is preferably 40 J / g or more, is more preferably 40 J / g to 100 J / g, and is further preferably 40 J / g to 90 J / g.

[0020] <Crossover temperature> The three-dimensional object of the present disclosure has a crossover temperature of preferably 140° C. or higher, and more preferably 150° C. or higher. The upper limit of the crossover temperature is not particularly limited, but is, for example, 180° C.

[0021] The crossover temperature is measured in the following manner.

[0022] Using a 100t electric automatic press (manufactured by Shoji Co., Ltd.), the three-dimensional model is press molded at 200°C for 5 minutes, and then cooled and pressed at room temperature (25°C) for 3 minutes to obtain a test piece with a thickness of 1.5 mm and a diameter of 25 mm. The obtained test piece is cooled from 200°C to 80°C using a rheometer (product name "ARES-G2", manufactured by TA Instruments) in a nitrogen atmosphere at a frequency of 1 Hz and a temperature drop rate of 5°C / min to obtain the storage modulus (G') and loss modulus (G"). The temperature at which G' and G" coincide is defined as the crossover temperature.

[0023] <Tensile modulus> The three-dimensional object of the present disclosure preferably has a tensile modulus of elasticity of 300 MPa or more, more preferably from 300 MPa to 2000 MPa, and even more preferably from 300 MPa to 1500 MPa.

[0024] The tensile modulus is measured by the following method.

[0025] A test piece (a 1BA type dumbbell as specified in JIS K 7161-2:2014) is sampled from the wall of the three-dimensional model. The longitudinal direction of the sample is perpendicular to the lamination direction (XY direction). Using the obtained sample, a tensile test is performed in accordance with JIS K 7161-2:2014 at a test temperature of 23°C and a tensile speed of 0.5 mm / min to measure the tensile modulus.

[0026] <Tensile strength, tensile elongation at break> The three-dimensional structure of the present disclosure preferably has a tensile strength of 10 MPa to 50 MPa, and more preferably 10 MPa to 40 MPa. The three-dimensional object of the present disclosure preferably has a tensile elongation at break of 50% to 1000%, and more preferably 100% to 800%.

[0027] The tensile strength and tensile elongation at break are measured by the following method.

[0028] A test piece (a 1BA type dumbbell as specified in JIS K 7161-2:2014) is sampled from the wall of the three-dimensional object. The longitudinal direction of the sample is perpendicular to the layering direction. Using the obtained sample, a tensile test is performed in accordance with JIS K 7161-2:2014 at a test temperature of 23°C and a tensile speed of 20 mm / min to measure the tensile breaking elongation and tensile strength.

[0029] (thermoplastic resin) The three-dimensional object of the present disclosure contains a thermoplastic resin.

[0030] Examples of thermoplastic resins include polyolefins such as polyethylene (PE), polypropylene (PP), glass-containing polypropylene (GF-containing PP), and poly-1-butene; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); polyethers such as polyether ketone ketone (PEKK), polyether ether ketone (PEEK), polyetherimide (PEI), and modified polyphenylene ether (m-PPE); polyamides such as nylon; polyimide, polycarbonate (PC), CF (carbon)-containing resin, polyacrylate, amorphous polyacrylate, polysulfone, fluororesin, liquid crystal polymer, polystyrene (PS), polyurethane, polyvinyl chloride, epoxy resin, and ethylene-vinyl acetate copolymer.

[0031] Among these, from the viewpoint of suppressing warpage of the three-dimensional object, the thermoplastic resin preferably contains a polymer containing a structural unit derived from 1-butene. The polymer containing a structural unit derived from 1-butene may be a polymer consisting only of structural units derived from 1-butene (poly-1-butene), or may be a copolymer containing structural units other than the structural units derived from 1-butene.

[0032] Examples of the other structural units include structural units derived from ethylene and structural units derived from propylene. When the polymer containing constitutional units derived from 1-butene is a copolymer, the copolymer may be a random copolymer or a block copolymer.

[0033] From the viewpoint of reducing the heat of fusion ΔH1 immediately after shaping, the proportion of the polymer containing a structural unit derived from 1-butene in the thermoplastic resin is preferably 80% by mass or more, more preferably 90% by mass or more. The above proportion may be 100% by mass.

[0034] From the viewpoint of reducing the heat of fusion ΔH1 immediately after shaping, the content of the structural units derived from 1-butene in the polymer containing the structural units derived from 1-butene is preferably 80% by mass or more, and more preferably 90% by mass or more. In particular, from the viewpoint of further reducing the heat of fusion ΔH1 immediately after shaping, the thermoplastic resin preferably contains poly-1-butene.

[0035] From the viewpoint of interlayer adhesion, the thermoplastic resin preferably has a melt flow rate (MFR) at 190° C. under a load of 2.16 kg of 0.1 g / 10 min to 50.0 g / 10 min, and more preferably 1.0 g / 10 min to 5.0 g / 10 min.

[0036] The melt flow rate (MFR) is a value measured under conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238-65T.

[0037] From the viewpoint of interlayer adhesion, the melting point of the thermoplastic resin is preferably 90°C or higher, more preferably 100°C to 200°C, and even more preferably 110°C to 180°C.

[0038] The thermoplastic resin may be a commercially available product, such as Tafmer BL, Viewlon (manufactured by Mitsui Chemicals), Akoalit, Akoafloor, Toppyl, or Koattro (manufactured by Lyonellbasell).

[0039] The content of the thermoplastic resin 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 amount of the three-dimensional object. The three-dimensional object of the present disclosure may be made only of the thermoplastic resin.

[0040] The three-dimensional object of the present disclosure may contain components other than the thermoplastic resin. Examples of other components include lubricants, compatibilizers, antioxidants, stabilizers such as heat stabilizers, hydrolysis resistance improvers, weather resistance stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, coloring inhibitors, antigelling agents, colorants, and mold release agents.

[0041] Furthermore, for the purpose of improving strength, the three-dimensional object of the present disclosure may contain a filler. The filler may be an inorganic filler or an organic filler.

[0042] Examples of the inorganic filler include inorganic powder, glittering inorganic powder, composite inorganic powder, and inorganic fiber.

[0043] Examples of inorganic powders include talc, titanium oxide, black titanium oxide, konjou, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, silica, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, aluminum magnesium silicate, mica, synthetic mica iron, sericite, moss-hige (magnesium sulfate whiskers), kaolin, silicon carbide, barium sulfate, bentonite, smectite, and boron nitride.

[0044] Examples of the shiny inorganic powder include bismuth oxychloride, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, iron oxide-titanium oxide sintered body, and aluminum powder.

[0045] Examples of the composite inorganic powder include fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silica, and zinc oxide-containing silica.

[0046] The inorganic fibers include glass fibers.

[0047] Among these, from the viewpoint of further suppressing warping of the three-dimensionally shaped object, the inorganic filler preferably contains an inorganic powder, and more preferably contains talc.

[0048] Examples of the organic filler include resin particles and pulp. Examples of the resin particles include carbon fiber, polyethylene, polypropylene, polystyrene, tetrafluoroethylene, silicone powder, and polyphenylene ether. Examples of pulp include cellulose and cellulose derivatives.

[0049] The shape of the filler may be any of spherical, plate-like, and needle-like. The filler may be porous or non-porous.

[0050] When the three-dimensional object contains a filler, the content of the filler is preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass, relative to the total mass of the three-dimensional object, from the viewpoint of further suppressing warping of the three-dimensional object.

[0051] The three-dimensional object of the present disclosure is manufactured, for example, by carrying out the steps of sending a three-dimensional modeling material to a modeling head, heating the sent three-dimensional modeling material in the modeling head, and ejecting the heated three-dimensional modeling material.

[0052] As the three-dimensional object manufacturing apparatus, a material extrusion type three-dimensional object manufacturing apparatus can be used. The material extrusion type three-dimensional object manufacturing apparatus is not particularly limited, and a known apparatus or a known apparatus configuration can be applied.

[0053] The three-dimensional object manufacturing device may be, for example, a device including a cylinder to which a three-dimensional modeling material is supplied, a nozzle provided on the cylinder downstream in the direction of discharging the three-dimensional modeling material and discharging the three-dimensional modeling material, and a heating means provided on the cylinder for heating and melting the three-dimensional modeling material. By using the three-dimensional object manufacturing device, the heated and melted three-dimensional modeling material can be extruded from the nozzle, and the three-dimensional modeling material extruded from the nozzle can be layered to form a three-dimensional object.

[0054] The cylinder may have a screw therein for kneading the materials. The three-dimensional object manufacturing apparatus may further include a table device disposed opposite the nozzle and configured to receive the molten material from the nozzle. The three-dimensional object manufacturing apparatus may further include a control means for controlling the spatial coordinates of the substrate and the nozzle, and the amount of the three-dimensional object material extruded from the nozzle. The control means is preferably a control means for controlling the ejection of the three-dimensional object material from the nozzle, and for controlling the movement of the nozzle and / or the table device in the X-axis, Y-axis, and Z-axis directions relative to a reference plane.

[0055] The method for forming a three-dimensional object according to the present disclosure may further include, as another step, for example, a processing step of processing the three-dimensional object formed in the forming step.

[0056] Examples of three-dimensional objects include, but are not limited to, automobile objects (e.g., console parts, switch parts, door trim parts, instrument panel parts, clips, covers, etc.), electrical appliance objects (electrical appliance parts, housings, etc.), furniture components, building components, construction materials, aircraft parts, toys, shoes, sporting goods, ornaments, cases, etc. In particular, the three-dimensional object according to the present disclosure is suitable for building components or automobile objects because warping during modeling is suppressed.

[0057] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. The heat of fusion ΔH1, the heat of fusion ΔH2, the crossover temperature, the storage modulus, the tensile modulus, the tensile strength, and the tensile elongation were measured by the methods described above.

[0058] The materials used in the examples and comparative examples are shown below.

[0059] <Synthesis of Poly-1-butene (PB-1)> -Preparation of solid titanium catalyst- 6.0 kg (63 mol) of anhydrous magnesium chloride, 26.6 L of decane, and 29.2 L (189 mol) of 2-ethylhexyl alcohol were reacted at 140°C for 3.5 hours to obtain a homogeneous solution. Then, 1.59 kg (7.88 mol) of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added to the solution, and the mixture was stirred and mixed at 110°C for another 1.5 hours. After the homogeneous solution obtained was cooled to room temperature (25°C), 37.0 kg of the above solution was dropped into 120 L (1080 mol) of titanium tetrachloride kept at -24°C for 7 hours. Then, the temperature of the obtained solution was raised over 6 hours, and after reaching 110°C, the solution was further stirred at 110°C for 2 hours to cause a reaction. Then, the solid portion was collected from the reaction mixture by hot filtration, and was put into 132 L of titanium tetrachloride to reslurry it. The slurry was heated at 110°C for 2 hours to cause a reaction. The solid portion was collected from the resulting reaction mixture by hot filtration and washed with 90°C decane and hexane. When titanium compounds were no longer detected in the washing solution, the washing was stopped to obtain solid titanium catalyst (c-1). A portion of the hexane slurry of solid titanium catalyst (c-1) was collected and dried, and the dried product was analyzed. The mass composition of solid titanium catalyst (c-1) was 3.9% titanium, 17% magnesium, and 15% 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.

[0060] -Polymerization of poly-1-butene- A continuous polymerization reactor with an internal volume of 200 L was fed with 114 L of hexane per hour, 21.4 kg of 1-butene per hour, 10.0 NL of hydrogen per hour, 0.97 mmol of solid titanium catalyst (c-1) per hour calculated as titanium atom, 48.5 mmol of triethylaluminum per hour, and 2.4 mmol of cyclohexylmethyldimethoxysilane per hour, while carrying out polymerization of 1-butene to obtain 4.2 kg of polymer (PB-1) per hour. The polymerization temperature was 60°C, the average residence time was 40 minutes, and the total pressure was 5×10 -1 The pressure was MPa·G.

[0061] <Synthesis of Poly-1-butene (PB-2) and (PB-3)> Poly-1-butenes (PB-2) and (PB-3) were obtained in the same manner as poly-1-butene (PB-1), except that the amount of hydrogen in the polymerization reaction was changed.

[0062] Poly-1-butene (PB-1) (MFR (190°C, 2.16 kg load) = 0.5 g / 10 min, melting point 115°C) Poly-1-butene (PB-2) (MFR (190°C, 2.16 kg load) = 3.0 g / 10 min, melting point 114°C) Poly-1-butene (PB-3) (MFR (190°C, 2.16 kg load) = 30.0 g / 10 min, melting point 114°C) 1-Butene-propylene random copolymer (MFR (190°C, 2.16 kg load) = 4.0 g / 10 min, melting point 103°C): product name "BL2491M", manufactured by Mitsui Chemicals Propylene-1-butene random copolymer (MFR (190°C, 2.16 kg load) = 3.0 g / 10 min, melting point 98°C): product name "XM-7090", manufactured by Mitsui Chemicals Polypropylene (MFR (230°C, 2.16 kg load) = 10.0 g / 10 min, melting point 160°C): Product name "J105G", manufactured by Prime Polymer Co., Ltd. Talc: Product name "HG-170", manufactured by Asada Flour Milling Co., Ltd., volume average particle size 5μm~10μm

[0063] (Examples 1 to 6 and Comparative Examples 1 to 4) In Examples 1 to 3, Comparative Examples 1, 2, and 4, pellets were obtained directly from the raw materials. In Examples 4 to 6 and Comparative Example 3, the components shown in Table 1 were mixed to the contents (by mass) shown in Table 1, and kneaded using an extruder (product number "KTX-30", manufactured by Kobe Steel, Ltd., cylinder temperatures: C1 = 50°C, C2 = 90°C, C3 = 100°C, C4 = 120°C, C5 = 180°C, C6 = 200°C, C7 to C14 = 200°C, die temperature: 200°C, screw rotation speed: 500 rpm, extrusion rate: 40 kg / h) to obtain pellets.

[0064] A square prism for measurement (170mm x 170mm x height 100mm) was created using a material extrusion type three-dimensional object manufacturing device (product name "GEM444D", manufactured by S.Lab Co., Ltd., nozzle diameter: 3mm) and application software ("Simplify3D" manufactured by Simplify3D).

[0065] First, pellets were put into a hopper and fed into a cylinder through the hopper. Next, the pellets were heated to a temperature of 180° C. to 240° C. by a heater provided in the cylinder and melted (melting step). A rectangular object (120mm x 350mm x 30mm height) was created using a material extrusion type three-dimensional object manufacturing device ("GEM444D" manufactured by S.Lab Co., Ltd., nozzle diameter: 3mm) and application software ("Simplify3D" manufactured by Simplify3D). Specifically, a three-dimensional object was created by layering molten pellets in sequence on a substrate based on three-dimensional coordinate data. <3D data> ·120mm x 350mm x 30mm height cuboid <Setting parameters for measurement object> 4mm nozzle - Build speed: 600mm / min Nozzle temperature: 300℃ Layer pitch: 2mm ·Width: 4.8mm

[0066] The obtained three-dimensional object was evaluated for warpage by the following method.

[0067] <Warping> The obtained three-dimensional object was placed on a flat surface with one surface (30 mm x 350 mm) facing downward. Warping was evaluated based on the amount of lift at the corners of the lower surface (30 mm x 350 mm). Specifically, the amount of lift was determined by the shortest distance between the flat surface and both ends of the 350 mm side of a 30 mm x 350 mm surface. The average value of the two ends was used. The evaluation criteria are as follows: A: The amount of lift is 3mm or less. B: The amount of floating is more than 3 mm and 5 mm or less. C: The amount of lift is more than 5 mm. D: Cannot be modeled.

[0068] [Table 1]

[0069] As shown in Table 1, in Examples 1 to 6, since a thermoplastic resin is contained and the ratio of the heat of fusion ΔH2 to the heat of fusion ΔH1 is 1.3 or more, it was found that warping was suppressed. On the other hand, in Comparative Examples 1 to 4, the ratio of the heat of fusion ΔH2 to the heat of fusion ΔH1 was less than 1.3, and it was found that warping occurred.

Claims

1. Contains a thermoplastic resin, A three-dimensional object in which the ratio of the heat of fusion ΔH2 72 hours after fabrication to the heat of fusion ΔH1 immediately after fabrication is 1.3 or more.

2. The three-dimensional structure according to claim 1 , wherein the heat of fusion ΔH2 is 40 J / g or more.

3. The three-dimensional structure according to claim 1 , having a tensile modulus of elasticity of 300 MPa or more.

4. The three-dimensional structure according to claim 1 , wherein the crossover temperature is 140° C. or higher.

5. The three-dimensional object according to any one of claims 1 to 4, wherein the thermoplastic resin includes a polymer containing a structural unit derived from 1-butene.

6. The three-dimensional object according to any one of claims 1 to 4, wherein the thermoplastic resin contains poly-1-butene.

7. The three-dimensional object according to any one of claims 1 to 4, wherein the thermoplastic resin has a melt flow rate (MFR) of 0.1 g / 10 min to 50.0 g / 10 min at 190°C under a load of 2.16 kg.

8. The three-dimensional object according to any one of claims 1 to 4, wherein a content of the thermoplastic resin is 80 mass % or more with respect to a total amount of the three-dimensional object.

9. 2. The three-dimensional structure according to claim 1, wherein a ratio of a heat of fusion ΔH2 measured by raising the temperature at 10° C. / min after 72 hours at a temperature of 23° C. and a relative humidity of 50% RH to a heat of fusion ΔH1 measured by raising the temperature at 10° C. / min using a differential scanning calorimeter is 1.3 or more.

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