Three-dimensional modeling material, three-dimensional modeling object, and method for producing three-dimensional modeling object

Abstract

The three-dimensional modeling material comprises a thermoplastic resin, a thermoplastic elastomer, and a filler. The filler comprises talc. The content of the filler is 5 mass % or more and 70 mass % or less relative to the total mass of the three-dimensional modeling material.

Description

Technical Field

[0001] The present disclosure relates to a three-dimensional modeling material, a three-dimensional modeling object, and a method for manufacturing a three-dimensional modeling object. Background Art

[0002] In recent years, as one of the efficient modeling technologies, a method of modeling a three-dimensional object using a manufacturing device for three-dimensional modeling has attracted attention. In order to model a three-dimensional object, it is considered that three-dimensional coordinate data of the three-dimensional object (hereinafter referred to as "3D data") is required. Slicer software cuts the 3D data into slices to generate a plurality of two-dimensional data. The manufacturing device for three-dimensional modeling stacks two-dimensional layers in sequence based on the plurality of two-dimensional data. Thus, a three-dimensional object is modeled (for example, see Patent Document 1).

[0003] As the molding method of three-dimensional objects, there are material extrusion (MEX), optical molding, inkjet, powder fixation, powder sintering, etc. Among these methods, the material extrusion method has attracted particular attention because of its wide selection of materials.

[0004] The material extrusion method is a method of molding a three-dimensional object by extruding a thermoplastic resin melted by heat from a nozzle and stacking the resin. Patent Document 2 discloses a method of molding a three-dimensional object using the material extrusion method.

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-189885

[0006] Patent Document 2: International Publication No. 2015 / 129733 Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, the conventional method for molding three-dimensional objects by material extrusion uses thermoplastic resin alone as the molding material. Therefore, when the molten thermoplastic resin extruded from the nozzle is solidified as a three-dimensional object, there is a concern that deformation may occur in the three-dimensional object due to the influence of heat shrinkage, etc. The deformation of the three-dimensional object includes the warping of the three-dimensional object. As a result, a three-dimensional object with high precision may not be obtained in some cases.

[0009] The present disclosure has been completed in view of the above circumstances.

[0010] An object of one embodiment of the present disclosure is to provide a three-dimensional modeling material in which deformation (particularly warping) of a three-dimensional modeled object is suppressed.

[0011] Another problem to be solved by another embodiment of the present disclosure is to provide a three-dimensional object with suppressed deformation (particularly warping) and a method for manufacturing the same.

[0012] Means for solving problems

[0013] Specific means for solving the problem include the following methods.

[0014] <1> A three-dimensional modeling material comprising a thermoplastic resin, a thermoplastic elastomer, and a filler,

[0015] The aforementioned filler material comprises talc,

[0016] The content of the filler is 5 mass % or more and 70 mass % or less relative to the total mass of the three-dimensional modeling material.

[0017] <2> The three-dimensional modeling material according to <1>, wherein the content of the thermoplastic resin is 0.1% by mass or more and less than 100% by mass based on the total mass of the three-dimensional modeling material.

[0018] <3> The three-dimensional modeling material according to <1> or <2>, wherein the content of the thermoplastic elastomer is 10% by mass or more and less than 100% by mass based on the total mass of the three-dimensional modeling material.

[0019] <4> The three-dimensional modeling material according to any one of <1> to <3>, wherein the thermoplastic resin contains a propylene-based polymer.

[0020] <5> The three-dimensional modeling material according to any one of <1> to <4>, wherein the tensile elastic modulus X (MPa) of the hot-pressed product for measurement according to JIS K7161-2:2014 satisfies the following formula (I),

[0021] The average warpage amount Y (mm) of the honeycomb shaped article for measurement when stacked and shaped into the honeycomb shaped article for measurement satisfies the following formula (IIa):

[0022] The hot-pressed product for measurement is a 1BA-shaped test piece specified in JIS K7161-2:2014 obtained by hot-pressing the three-dimensional modeling material.

[0023] The aforementioned honeycomb shaped object for measurement comprises:

[0024] A rectangular parallelepiped frame portion of 250 mm × 100 mm × 15 mm in height, wherein the rectangular parallelepiped frame portion is obtained by laminating the three-dimensional modeling material by a material extrusion method in such a manner that a filling rate representing the ratio of the volume of the three-dimensional modeling material to the volume of a unit space becomes 100%, and

[0025] A honeycomb structure part, wherein the honeycomb structure part is obtained by laminating and shaping the three-dimensional shaping material in the rectangular parallelepiped frame part in such a manner that the filling rate becomes 30% by using the material extrusion method;

[0026] The average warpage amount Y represents the arithmetic mean of the floating amounts of the four corners of the rectangular parallelepiped frame portion from the flat plate when the honeycomb shaped product for measurement is placed on the flat plate.

[0027] Formula (I) 50≤X≤4000

[0028] Formula (IIa) 0≤Y≤6.0

[0029] <6> The three-dimensional modeling material according to any one of <1> to <5>, wherein the content of the thermoplastic elastomer is 10% by mass or more and less than 70% by mass relative to the total mass of the three-dimensional modeling material,

[0030] The content of the filler is 10 mass % or more and less than 50 mass % relative to the total mass of the three-dimensional modeling material.

[0031] The total content of the thermoplastic elastomer and the filler is 20% by mass or more and less than 90% by mass based on the total mass of the three-dimensional modeling material.

[0032] <7> The three-dimensional modeling material according to any one of <1> to <6>, wherein when the three-dimensional modeling material is laminated and molded into a measurement modeling object, the breaking stress α [MPa] of the measurement modeling object in a tensile test according to JIS K7161-2:2014 satisfies the following formula (III),

[0033] The average warpage amount Y [mm] of the honeycomb shaped article for measurement when stacked and shaped into the honeycomb shaped article for measurement satisfies the following formula (IIb):

[0034] The aforementioned object for measurement is a 1BA-shaped test piece specified in JIS K7161-2:2014 obtained by laminating and machining the aforementioned three-dimensional modeling material by a material extrusion method in such a manner that the filling rate representing the ratio of the volume of the aforementioned three-dimensional modeling material to the volume of a unit space is 100% and the overlapping direction of the aforementioned three-dimensional modeling material is parallel to the tensile direction of the aforementioned object for measurement in the aforementioned tensile test.

[0035] The aforementioned honeycomb shaped object for measurement comprises:

[0036] A rectangular parallelepiped frame portion of 250 mm × 100 mm × 15 mm in height, wherein the rectangular parallelepiped frame portion is obtained by laminating the three-dimensional modeling material in such a manner that the filling rate becomes 100% by using the material extrusion method, and

[0037] A honeycomb structure part, wherein the honeycomb structure part is obtained by laminating and shaping the three-dimensional shaping material in the rectangular parallelepiped frame part in such a manner that the filling rate becomes 30% by using the material extrusion method;

[0038] The average warpage amount Y represents the arithmetic mean of the floating amounts of the four corners of the rectangular parallelepiped frame portion from the flat plate when the honeycomb shaped product for measurement is placed on the flat plate.

[0039] Formula (III) 6.5≤α<200

[0040] Formula (IIb) 0≤Y≤4.0

[0041] <8> A method for producing a three-dimensional object, comprising the following steps:

[0042] A melting step of melting the three-dimensional modeling material described in any one of <1> to <7>; and

[0043] In the shaping step, the melted three-dimensional shaping material is extruded from a nozzle of a three-dimensional shaping object manufacturing device to shape the three-dimensional shaping object.

[0044] <9> A three-dimensional modeled object, which is a modeled object of the three-dimensional modeling material according to any one of <1> to <7>.

[0045] Effects of the Invention

[0046] According to one embodiment of the present disclosure, there is provided a three-dimensional modeling material in which deformation (particularly warping) of a three-dimensional modeled object is suppressed.

[0047] According to other embodiments of the present disclosure, a three-dimensional object with suppressed deformation (particularly warping) and a method for manufacturing the same are provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] [ Figure 1 ] is a three-dimensional photograph showing the honeycomb structure used for measurement.

[0049] [ Figure 2 ] is a side view of a honeycomb structure used for measuring to illustrate the average warping amount Y. DETAILED DESCRIPTION

[0050] Hereinafter, embodiments of the present disclosure will be described. These descriptions and examples are provided to illustrate the embodiments and do not limit the scope of the embodiments.

[0051] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0052] In the numerical range recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment.

[0053] In the present disclosure, each component may include a plurality of corresponding substances. In the present disclosure, when referring to the amount of each component in a composition, when there are a plurality of substances belonging to each component in the composition, unless otherwise specified, it refers to the total amount of the plurality of substances present in the composition.

[0054] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0055] 《Materials for 3D Modeling》

[0056] The three-dimensional modeling material of the present disclosure is a raw material supplied to the modeling process of a three-dimensional object.

[0057] The three-dimensional modeling material of the present disclosure comprises a thermoplastic resin, a thermoplastic elastomer, and a filler. The filler comprises talc. The content of the filler is 5 mass % or more and 70 mass % or less relative to the total mass of the three-dimensional modeling material.

[0058] Therefore, deformation such as warping of a three-dimensional object obtained by molding the three-dimensional modeling material of the present disclosure is suppressed.

[0059] (Filling material)

[0060] The three-dimensional modeling material of the present disclosure includes a filling material.

[0061] 〔talc〕

[0062] The filling material includes talc. The talc does not undergo volume change at the molding temperature, and the thermal expansion coefficient of the talc is lower than the thermal expansion coefficients of the thermoplastic resin and the thermoplastic elastomer, so that the deformation (especially warping) of the three-dimensional molded object is suppressed. When the three-dimensional molded object is molded by the material extrusion method, the so-called molding temperature refers to the nozzle temperature of the three-dimensional molded object manufacturing device. The so-called talc does not undergo volume change at the molding temperature means that the talc does not melt, the talc does not dissolve, and the talc does not undergo phase transformation at the molding temperature.

[0063] Talc is called talcum. Talc is hydrous magnesium silicate. Hydrous magnesium silicate is a type of layered clay mineral, composed of magnesium (Mg) and silicon (Si) connected with oxygen and hydroxyl groups.

[0064] The chemical structure of talc is usually [Mg3Si4O 10 (OH)2] or [3MgO·4SiO2·H2O].

[0065] The shape of talc is not particularly limited, and for example, a scale shape, an elliptical shape, or the like is preferred.

[0066] The upper limit of the volume average particle size of talc is preferably 30 μm or less, and more preferably 10 μm or less. The lower limit of the volume average particle size of talc is preferably 1 μm or more, and more preferably 5 μm or more.

[0067] The volume average particle size of talc refers to the particle size value at which the cumulative volume becomes 50% of the total volume when the volumes of each particle based on the particle size of each particle (which is measured using a particle size distribution measuring apparatus such as a laser diffraction / scattering particle size distribution measuring apparatus in a state where talc is dispersed in water) are accumulated from the smaller particle size side.

[0068] The content of talc is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the total amount in the filler.

[0069] The filler may include, in addition to talc, an inorganic filler, an organic filler, a glittering powder, a pigment powder, and a composite filler thereof, etc. The filler may be used alone or in combination of two or more.

[0070] The filler material may include an inorganic filler material.

[0071] For example, examples of the inorganic filler include inorganic powders other than talc (hereinafter, simply referred to as “inorganic powders”), flashing inorganic powders, composite inorganic powders, inorganic fibers, and the like.

[0072] Examples of the inorganic powder include titanium oxide, black titanium oxide, iron blue pigment, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, silicon dioxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic mica iron, sericite, moth Heidi (magnesium sulfate whisker), kaolin, silicon carbide, barium sulfate, bentonite, montmorillonite, and boron nitride.

[0073] Examples of the flashing inorganic powder include bismuth oxychloride, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, iron oxide-titanium oxide sintered bodies, and aluminum powder.

[0074] Examples of the composite inorganic powder include mica titanium coated with titanium oxide fine particles, mica titanium coated with zinc oxide fine particles, mica titanium coated with barium sulfate, silicon dioxide encapsulated in titanium oxide, and silicon dioxide encapsulated in zinc oxide.

[0075] Examples of the inorganic fibers include glass fibers and the like.

[0076] Among the above, from the viewpoint of further suppressing deformation (particularly warping) of a three-dimensional object, the inorganic filler preferably contains at least one of an inorganic powder and an inorganic fiber.

[0077] From the viewpoint of increasing the tensile modulus of elasticity of the three-dimensional object and making the appearance of the three-dimensional object smooth, the inorganic filler may include both talc and glass fiber. In this case, the content ratio (Talc: Fiber) of talc (Talc) and glass fiber (Fiber) is preferably 90:10 to 40:60 by mass ratio, and more preferably 85:15 to 45:55. In particular, if the aforementioned content ratio (Talc: Fiber) is 85:15 or more, there is a tendency that the fuzzing on the surface of the three-dimensional object is further suppressed. The generation of fuzzing on the surface of the three-dimensional object is not limited to glass fiber, but is a problem unique to three-dimensional modeling materials containing fiber-based materials such as carbon fiber.

[0078] The filler material may include an organic filler material.

[0079] For example, examples of the organic filler include resin particles and pulp.

[0080] Examples of the resin particles include carbon fibers, polyethylene, polypropylene, polystyrene, tetrafluoroethylene, silicone powder, and polyphenylene ether.

[0081] Examples of pulp include cellulose and cellulose derivatives.

[0082] The shape of the filler may be any of spherical, plate-like, and needle-like.

[0083] The filling material can be porous or non-porous.

[0084] From the viewpoint of further suppressing the deformation (especially warping) of the three-dimensional modeling object, the content of the filling material is 5 mass % to 70 mass % relative to the total mass of the three-dimensional modeling material, preferably higher than 5 mass % and lower than 55 mass %, and more preferably higher than 5 mass % and lower than 45 mass %.

[0085] When the content of the filler is 5 mass % or more and 70 mass % or less, deformation (particularly warping) of the three-dimensional object is suppressed.

[0086] (Thermoplastic resin)

[0087] The three-dimensional modeling material of the present disclosure contains a thermoplastic resin.

[0088] In the present disclosure, the tensile modulus of the thermoplastic resin at 25°C is 6.0×10 8 Pa or above.

[0089] The thermoplastic resin is not particularly limited, and known thermoplastic resins can be used. The thermoplastic resin may be used alone or in combination of two or more.

[0090] For example, examples of thermoplastic resins include general-purpose plastics, engineering plastics, and super engineering plastics.

[0091] Examples of general-purpose plastics include high-density polyethylene (HDPE), low-density polyethylene (LDPE), propylene polymers (propylene homopolymer (PP), etc.), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), styrene acrylonitrile copolymer (AS resin), and acrylic resin (PMMA, etc.).

[0092] Examples of engineering plastics include polyamide (PA), polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), syndiotactic polystyrene (SPS), and cyclic polyolefin (COP).

[0093] Examples of super engineering plastics include polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), polyetheretherketone (PEEK), thermoplastic polyimide (PI), and polyamideimide (PAI).

[0094] Among them, the thermoplastic resin preferably includes one or more selected from the group consisting of high-density polyethylene (HDPE), propylene polymers, polyamide (PA), polybutylene terephthalate (PBT), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS) and polyacetal (POM), and more preferably includes a propylene polymer.

[0095] The thermoplastic resin may be a crystalline thermoplastic resin or an amorphous thermoplastic resin. For example, from the viewpoint of affinity with a thermoplastic elastomer and the viewpoint of appropriately dispersing the filler in the thermoplastic resin, the thermoplastic resin preferably includes a crystalline thermoplastic resin, more preferably includes at least one selected from the group consisting of high-density polyethylene (HDPE), propylene polymers, polyamides (PA), polybutylene terephthalate (PBT), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS) and polyacetal (POM), and further preferably includes a crystalline propylene polymer. It should be noted that the so-called "crystallinity" of a thermoplastic resin refers to having an endothermic peak in differential scanning calorimetry. On the other hand, the so-called "amorphousness" of a thermoplastic resin refers to the fact that no clear endothermic peak is observed in differential scanning calorimetry.

[0096] The propylene-based polymer is a polymer having at least propylene as a structural unit.

[0097] The propylene polymer may be a homopolymer of propylene or a copolymer of propylene and other monomers. When the propylene polymer is a copolymer, examples of the propylene polymer include copolymers of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). Examples of the copolymers of propylene and an α-olefin having 2 to 20 carbon atoms include propylene·ethylene copolymers, propylene·1-butene copolymers, propylene·ethylene·1-butene copolymers, propylene·4-methyl-1-pentene copolymers, and mixtures thereof.

[0098] When the propylene-based polymer is a copolymer, the propylene-based polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.

[0099] When the propylene polymer is a copolymer, the ratio of the structural unit derived from propylene in the propylene polymer can be appropriately designed according to the properties of the desired three-dimensional modeling object. For example, relative to 100 mol% of all structural units in the propylene polymer, the ratio of the structural unit derived from propylene in the propylene polymer is preferably 50 mol% or more, more preferably 70 mol% to 99.5 mol%, and further preferably 80 mol% to 98 mol%.

[0100] The stereoregularity of the propylene-based polymer may be isotactic, syndiotactic, or a mixture thereof.

[0101] The content of the propylene-based polymer is preferably 95.0% by mass or more, more preferably 98.0% by mass or more, and even more preferably 99.9% by mass or more, based on 100% by mass of the total amount of the thermoplastic resin.

[0102] The crystallization temperature (Tc) of the thermoplastic resin is preferably 90°C to 140°C, more preferably 110°C to 130°C.

[0103] The crystallization temperature of the thermoplastic resin is measured using a differential scanning calorimeter (DSC) at a temperature drop rate of 10° C. / min.

[0104] The crystallinity of the thermoplastic resin is preferably 2% to 80%, more preferably 5% to 75%.

[0105] The crystallinity of the thermoplastic resin is calculated from the heat of fusion derived from the melting of the main component in the heat flow curve obtained using a differential scanning calorimeter (DSC). The heat flow curve is obtained by keeping the thermoplastic resin at -40°C for 5 minutes under a nitrogen atmosphere and then heating it at 10°C / minute. Specifically, a differential scanning calorimeter (DSC-7, manufactured by PerkinElmer) is used to keep 5 mg of the sample at -40°C for 5 minutes under a nitrogen atmosphere and then heating it at 10°C / minute to obtain a heat flow curve. The heat of fusion derived from the melting of the main component in the obtained heat flow curve is calculated using the following formula.

[0106] Crystallinity = (ΔH / ΔH0) × 100 (%)

[0107] Wherein, ΔH is the melting heat (J / g) obtained from the melting heat curve of the main component of the thermoplastic resin, and ΔH0 is the melting heat (J / g) of the complete crystallization of the main component. For example, when the main component is ethylene, ΔH0 is 293 J / g, and when the main component is propylene, ΔH0 is 210 J / g.

[0108] The melting point of the thermoplastic resin is preferably 90°C or higher, more preferably 110°C or higher and 200°C or lower, and even more preferably 110°C or higher and 180°C or lower.

[0109] The melting point can be measured in the same manner as the method for measuring the melting point of a thermoplastic elastomer described below.

[0110] From the viewpoint of further suppressing deformation (especially warping) of three-dimensional modeling objects, the content of the thermoplastic resin can be in the range of more than 0.1 mass % and less than 100 mass % relative to the total mass of the three-dimensional modeling material, more preferably in the range of 10 mass % to 70 mass %, and further preferably in the range of 20 mass % to 60 mass %.

[0111] (Thermoplastic Elastomer)

[0112] The three-dimensional modeling material of the present disclosure includes a thermoplastic elastomer.

[0113] By including a thermoplastic elastomer in the three-dimensional modeling material, deformation of the three-dimensional modeled object can be effectively suppressed.

[0114] Thermoplastic elastomers have rubber-like elasticity. The so-called rubber-like elasticity refers to the property that the shape of the resin is deformed when a load is applied to the resin, and the shape of the resin returns to its original shape when the load applied to the resin is removed. Specifically, the so-called thermoplastic elastomer refers to a thermoplastic elastomer with a tensile elastic modulus of less than 6.0×10 8 Thermoplastic resin of Pa. In this point, thermoplastic elastomer is distinguished from thermoplastic resin.

[0115] The thermoplastic elastomer is preferably a copolymer containing a structural unit derived from an α-olefin and a structural unit derived from an olefin different from the α-olefin.

[0116] The α-olefin may generally contain one kind of α-olefin having 2 to 20 carbon atoms alone or two or more kinds thereof in combination. Among them, the α-olefin is preferably an α-olefin having 3 or more carbon atoms, and particularly preferably an α-olefin having 3 to 8 carbon atoms.

[0117] Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, etc. The α-olefin may be used alone or in combination of two or more.

[0118] Among them, from the viewpoint of easy availability, the α-olefin is preferably 1-butene, 1-pentene, 1-hexene, or 4-methyl-1-pentene.

[0119] As the other olefin different from the α-olefin, an olefin having 2 to 4 carbon atoms is preferred, and examples thereof include ethylene, propylene, butene, etc. Among them, the other olefin different from the α-olefin is more preferably an olefin having 2 to 3 carbon atoms.

[0120] Examples of the thermoplastic elastomer copolymer include ethylene·α-olefin copolymer, propylene·α-olefin copolymer, and butene·α-olefin copolymer.

[0121] Examples of the thermoplastic elastomer include ethylene-propylene copolymer (EPR), ethylene-1-butene copolymer (EBR), ethylene-1-pentene copolymer, ethylene-1-octene copolymer (EOR), propylene-1-butene copolymer (PBR), propylene-1-pentene copolymer, propylene-1-octene copolymer (POR), and the like.

[0122] Among them, as a thermoplastic elastomer, a copolymer containing a structural unit derived from an α-olefin having 2 to 8 carbon atoms and a structural unit derived from an olefin having 2 to 3 carbon atoms is preferred. From the perspective of excellent compatibility with thermoplastic resins (especially propylene polymers) and further suppression of deformation of three-dimensional shaped objects, a propylene elastomer is preferred.

[0123] Furthermore, the α-olefin may form a random copolymer or a block copolymer.

[0124] The melting point of the thermoplastic elastomer is preferably 30°C to 120°C.

[0125] If the melting point is 30°C to 120°C, the thermoplastic elastomer acts as an adhesive between the modeling layers of the three-dimensional modeling object obtained by the material extrusion method. As a result, the bonding strength between the modeling layers of the three-dimensional modeling object obtained by the material extrusion method is improved. In the material extrusion method, the modeling layer is composed of the three-dimensional modeling material extruded from the nozzle.

[0126] The melting point is a value determined as the temperature Tm of the melting peak position appearing in the endothermic curve by differential scanning calorimetry (DSC).

[0127] The melting point was obtained from the following endothermic curve: the sample was placed in an aluminum dish, heated to 230°C at 100°C / min, maintained at 230°C for 5 minutes, cooled to -70°C at -10°C / min, and then heated at 10°C / min.

[0128] The lower limit of the melt flow rate (MFR; 230°C, 2.16 kg load) of the thermoplastic elastomer is preferably 0.5 g / 10 min or more, more preferably 1 g / 10 min or more, further preferably 2 g / 10 min or more, particularly preferably 5 g / 10 min.

[0129] The upper limit of the melt flow rate (MFR; 230°C, 2.16 kg load) of the thermoplastic elastomer is preferably 70 g / 10 min or less, more preferably 35 g / 10 min or less, and further preferably 30 g / 10 min.

[0130] When the upper limit and the lower limit of the MFR of the thermoplastic elastomer are within the above range, deformation of the three-dimensional object can be more effectively suppressed.

[0131] The melt flow rate (MFR) is a value measured in accordance with ASTM D1238-65T under the conditions of 230° C. and a load of 2.16 kg.

[0132] The thermoplastic elastomer is preferably a thermoplastic elastomer having a Shore A hardness of 50 to 99, or a thermoplastic elastomer having a Shore D hardness of 30 to 60.

[0133] If the hardness of the thermoplastic elastomer is 50 or more in Shore A hardness or 30 or more in Shore D hardness, the thermoplastic elastomer is not easily deformed. In other words, the shape of the thermoplastic elastomer is easily maintained. Therefore, when the three-dimensional modeling object is molded using the three-dimensional modeling object manufacturing device described later, the thermoplastic elastomer is easy to enter the screw of the barrel. As a result, the ejection efficiency of the three-dimensional modeling material in the molten state becomes better. As a result, it is easy to obtain a three-dimensional modeling object with a smooth surface and excellent appearance.

[0134] For the same reasons as above, the lower limit of the hardness is preferably 55 or more in Shore A hardness or 40 or more in Shore D hardness, more preferably 60 or more in Shore A hardness or 50 or more in Shore D hardness. In addition, the upper limit of the hardness is not particularly limited, but is preferably 96 or less in Shore A hardness or 60 or less in Shore D hardness. Regarding the lower limit of the hardness, among the above, for the same reasons as above, it is more preferably 40 or more in Shore D hardness, and more preferably 50 or more in Shore D hardness.

[0135] The Shore A hardness and the Shore D hardness are values ​​measured according to the method described in ASTM D2240.

[0136] Specific examples of the thermoplastic elastomer include TAFMER (registered trademark) series manufactured by Mitsui Chemicals, Inc. (for example, TAFMER DF605, TAFMER DF610, TAFMER DF640, TAFMER DF710, TAFMER DF740, TAFMER DF7350, TAFMER DF810, TAFMER DF840, TAFMER DF8200, TAFMER DF940, TAFMER DF9200, TAFMER DF110, TAFMER H-0530S, TAFMER H-1030S, TAFMER H-5030S, TAFMER XM-7070, TAFMER XM-7080, TAFMER XM-7090, TAFMER BL2491M, TAFMER BL2481M, TAFMER BL3110M, TAFMER BL3450M, TAFMER MA8510, TAFMER MH7010, TAFMER MH7020, TAFMER MH5020, TAFMER PN-2070, TAFMER PN-3560), etc.

[0137] Among the above, TAFMER XM series of propylene-based elastomers are preferred because they are excellent in compatibility with thermoplastic resins (particularly propylene-based polymers) and deformation of three-dimensional objects is further suppressed.

[0138] TAFMER XM series has excellent compatibility with thermoplastic resins (especially propylene polymers) and can maintain the fracture stress α required for three-dimensional objects. As a result, the bonding strength between the modeling layers of three-dimensional objects formed by material extrusion is improved.

[0139] The thermoplastic elastomer is preferably a propylene-based elastomer. The propylene-based elastomer is a thermoplastic elastomer having at least propylene as a structural unit.

[0140] The thermoplastic elastomer is a propylene elastomer, preferably having a melting point of 80°C to 120°C, a Shore D hardness of 40 to 60, and an MFR of 2 g / 10 min to 20 g / 10 min. Thus, the stress strain of the three-dimensional object is smaller and less prone to warping.

[0141] Examples of the propylene-based elastomer having a melting point of 80° C. to 120° C., a Shore D hardness of 40 to 60, and an MFR of 2 g / 10 min to 20 g / 10 min include TAFMER XM-7090.

[0142] Relative to the total mass of the material for three-dimensional modeling, the content of the thermoplastic elastomer is preferably in the range of higher than 0.1 mass % and lower than 100 mass %, more preferably in the range of higher than 10 mass % and lower than 100 mass %, further preferably in the range of 10 mass % to 70 mass %, and particularly preferably in the range of 20 mass % to 50 mass %.

[0143] The three-dimensional modeling material preferably satisfies the following (a1), (b1), and (c1).

[0144] (a1) The content of the thermoplastic elastomer is 10% by mass or more and less than 70% by mass relative to the total mass of the three-dimensional modeling material.

[0145] (b1) The content of the filler is 10% by mass or more and less than 50% by mass relative to the total mass of the three-dimensional modeling material.

[0146] (c1) The total content of the thermoplastic elastomer and the filler is 20% by mass or more and less than 90% by mass relative to the total mass of the three-dimensional modeling material.

[0147] The three-dimensional modeling material more preferably satisfies any one of the following (a2), (b2) and (c2).

[0148] A three-dimensional object formed using a three-dimensional modeling material that satisfies any one of the following (a2), (b2), and (c2) has smaller stress strain, is less likely to break, and is less likely to warp.

[0149] (a2) The content of the thermoplastic elastomer is 15% by mass or more and 25% by mass or less, and the content of the filler is 35% by mass or more and 45% by mass or less, relative to the total mass of the three-dimensional modeling material.

[0150] (b2) The content of the thermoplastic elastomer is 25% by mass or more and 35% by mass or less, and the content of the filler is 15% by mass or more and 45% by mass or less, relative to the total mass of the three-dimensional modeling material.

[0151] (c2) The content of the thermoplastic elastomer is 35% by mass or more and 45% by mass or less, and the content of the filler is 15% by mass or more and 35% by mass or less, relative to the total mass of the three-dimensional modeling material.

[0152] The three-dimensional modeling material further preferably satisfies any one of the above-mentioned (a2), (b2) and (c2) and the following (a3) ​​and (b3).

[0153] The stress strain of a three-dimensional object formed using a three-dimensional modeling material that satisfies any one of the following (a3) ​​and (b3) is further reduced, and 3D data can be materialized more realistically.

[0154] (a3) The content of the thermoplastic elastomer is 25% by mass or more and 35% by mass or less, and the content of the filler is 25% by mass or more and 35% by mass or less, relative to the total mass of the three-dimensional modeling material.

[0155] (b3) The content of the thermoplastic elastomer is 35% by mass or more and 45% by mass or less, and the content of the filler is 15% by mass or more and 35% by mass or less, relative to the total mass of the three-dimensional modeling material.

[0156] (Properties of materials for 3D modeling)

[0157] From the viewpoint of further suppressing deformation (particularly warping) of a three-dimensional object, the melting point of the three-dimensional modeling material is preferably 90°C or higher, more preferably 110°C or higher and 200°C or lower, and even more preferably 110°C or higher and 180°C or lower.

[0158] The method for adjusting the melting point of the three-dimensional modeling material to the above range is not particularly limited, and examples thereof include a method in which the type of filler, thermoplastic resin or thermoplastic elastomer is changed to the type described below.

[0159] For the three-dimensional modeling material of the present disclosure, for example, it is preferred that the tensile elastic modulus X (MPa) satisfies the following formula (I), and when a three-dimensional modeled object is made into a rectangular shape of 250mm×100mm×15mm in height and a filling rate of 30% in the entire honeycomb, the average warping amount Y (mm) satisfies the formula (IIa), and it is more preferred that it satisfies the following formula (I), and the average warping amount Y (mm) satisfies the formula (IIb).

[0160] Formula (I) 50≤X≤4000

[0161] Formula (IIa) 0≤Y≤6.0

[0162] Formula (IIb) 0≤Y≤4.0

[0163] In formula (I), X is preferably 300≤X≤4000. In one embodiment of the present disclosure, X can be 1000≤X≤2500.

[0164] [Measurement of tensile elastic modulus X of hot pressed product]

[0165] The lower limit of the tensile modulus X of the hot-pressed product for measurement when the three-dimensional modeling material is molded into a hot-pressed product for measurement (hereinafter referred to as "tensile modulus X of the hot-pressed product for measurement") is preferably 50 MPa or more, more preferably 300 MPa or more, and further preferably 1000 MPa or more.

[0166] The upper limit of the tensile elastic modulus X of the hot-pressed product for measurement is preferably 4000 MPa or less, and more preferably 2500 MPa or less.

[0167] In the present disclosure, the tensile modulus X of the hot-pressed product for measurement is measured in accordance with JIS K7161-2: 2014. The test speed is 0.5 mm / min.

[0168] The hot-pressed product for measurement is a 1BA-shaped test piece specified in JIS K7161-2: 2014 obtained by hot-pressing a material for three-dimensional modeling. The total length of the hot-pressed product for measurement is 75 mm. The thickness of the hot-pressed product for measurement is 2 mm.

[0169] The heating temperature of the hot press molding was 200° C. The pressing pressure of the hot press molding was 50 MPa and the pressing time of the hot press molding was 3 minutes.

[0170] The hot-pressed product for measurement may be a machined product obtained by subjecting a three-dimensional modeling material to hot-press molding and subjecting it to mechanical processing.

[0171] [Thermal expansion coefficient of hot pressed products for measurement]

[0172] From the viewpoint of further suppressing deformation (particularly warpage) of the honeycomb molded article 10 for measurement, the thermal expansion coefficient of the hot-pressed article for measurement when the three-dimensional molding material is molded into the hot-pressed article for measurement (hereinafter referred to as the "thermal expansion coefficient of the hot-pressed article for measurement") is preferably 1×10 -6 ( / ℃)~1×10 -3 ( / °C), more preferably 1×10 -6 ( / ℃)~5×10 -4 ( / ℃).

[0173] The thermal expansion coefficient of the hot-pressed product for measurement was measured in accordance with JIS K7197:2012.

[0174] [Measurement of crystallization temperature of hot pressed products]

[0175] The crystallization temperature (Tc) of the hot-pressed product for measurement when the three-dimensional modeling material is molded into a hot-pressed product for measurement (hereinafter referred to as "the crystallization temperature (Tc) of the hot-pressed product for measurement") is preferably 80°C to 140°C, and more preferably 100°C to 130°C.

[0176] The method for measuring the crystallization temperature (Tc) of the hot-pressed product for measurement is the same as the method for measuring the crystallization temperature of a thermoplastic resin.

[0177] [Determination of melting point of hot pressed product]

[0178] From the viewpoint of further suppressing deformation (especially warping) when a three-dimensional modeled object is made, the melting point of the hot-pressed product for measurement when the three-dimensional modeling material is molded into a hot-pressed product for measurement (hereinafter referred to as "the melting point of the hot-pressed product for measurement") is preferably above 90°C, more preferably above 110°C and below 200°C, and even more preferably above 110°C and below 180°C.

[0179] The method for measuring the melting point of the hot pressed product for measurement is the same as the method for measuring the melting point of the thermoplastic elastomer.

[0180] [Average warpage amount Y of honeycomb molded article for measurement]

[0181] The average warping amount Y of the measuring honeycomb shaped object 10 when the three-dimensional modeling material is stacked and molded into the measuring honeycomb shaped object 10 (hereinafter referred to as "the average warping amount Y of the measuring honeycomb shaped object 10"). is preferably 6.0 mm or less, more preferably 4.0 mm or less, the lower the better, and particularly preferably 0 mm.

[0182] The above-mentioned "when a three-dimensional shaped object with a rectangular shape of 250mm×100mm×15mm in height and a filling rate of 30% in the entire honeycomb is made, the average warping amount Y (mm) satisfies the formula (IIa)" means: the average warping amount Y (mm) of the honeycomb shaped object 10 used for measurement satisfies the formula (IIa).

[0183] Next, refer to Figure 1 , the honeycomb shaped object 10 for measurement will be described. Figure 1 It is a three-dimensional photograph of the honeycomb shaped object 10 for measurement.

[0184] like Figure 1 As shown, the honeycomb shaped object 10 for measurement includes a honeycomb structure portion 11 and a rectangular parallelepiped frame portion 12. The honeycomb structure portion 11 is located in the rectangular parallelepiped frame portion 12. The honeycomb structure portion 11 and the rectangular parallelepiped frame portion 12 are integrated. The honeycomb shaped object 10 for measurement is a substantially rectangular parallelepiped object.

[0185] The rectangular parallelepiped frame portion 12 is in the vertical direction (see Figure 1 ) surrounds the periphery of the honeycomb structure 11 in a direction orthogonal to the direction of the honeycomb structure 11. The rectangular parallelepiped frame 12 is obtained by laminating the three-dimensional modeling material in a manner that the filling rate becomes 100% by using the material extrusion method. The rectangular parallelepiped frame 12 is 250mm×100mm×15mm in height. In detail, Figure 1 In the embodiment, the length of the rectangular parallelepiped frame portion 12 in the front-to-back direction is 250 mm. The length of the rectangular parallelepiped frame portion 12 in the left-to-right direction is 100 mm. The length in the up-down direction is 15 mm. The rectangular parallelepiped frame portion 12 is composed of 4 plate portions. The thickness of each of the 4 plate portions is 5 mm.

[0186] The structure of the honeycomb structure part 11 is a honeycomb structure. The honeycomb structure part 11 is obtained by laminating a three-dimensional modeling material in a rectangular parallelepiped frame part 12 by a material extrusion method so that the filling rate becomes 30%.

[0187] The filling rate refers to the ratio of the volume of the three-dimensional modeling material to the volume of a unit space.

[0188] Next, refer to Figure 2 Next, the average warping amount Y of the measuring honeycomb shaped object 10 will be described. Figure 2 It is a side view of the honeycomb shaped object 10 for explaining the average warpage amount Y for measurement.

[0189] The average warpage amount Y of the honeycomb shaped object 10 for measurement represents the floating amount Y of the rectangular parallelepiped frame portion 12 from the four corners of the flat plate 20 when the honeycomb shaped object 10 for measurement is placed on the flat plate 20. A The arithmetic mean of .

[0190] The floating amount Y of the corner E12 of the rectangular parallelepiped frame portion 12 A The determination is as follows. Figure 2 As shown in the figure, the honeycomb shaped object 10 for measurement is placed on the surface of the flat plate 20 in such a manner that the first surface TS10 of the honeycomb shaped object 10 for measurement faces upward. Next, the highest height of the lower surface BS10 of the corner E12 of the honeycomb shaped object 10 for measurement from the surface of the flat plate 20 is measured. The highest height can be measured using an altimeter. The measured value obtained represents the floating amount Y of the corner E12 of the rectangular parallelepiped frame portion 12. A .

[0191] The average warpage amount Y of the honeycomb shaped object 10 for measurement is calculated by calculating the floating amounts Y of the four corners of the honeycomb shaped object 10 for measurement measured in this way. A Add and divide the sum by 4 to obtain.

[0192] When a three-dimensional object is formed by a material extrusion method, from the viewpoint of improving the bonding strength between the modeling layers of the three-dimensional object, it is preferred that a modeling layer formed by a molten three-dimensional modeling material extruded from a nozzle (hereinafter referred to as the "first modeling layer") and a modeling layer on which the first modeling layer is deposited (hereinafter referred to as the "second modeling layer") are melt-bonded. It is further preferred that the second modeling layer is melted by the heat of the first modeling layer, or that the second modeling layer is not crystallized until the first modeling layer is completely deposited on the second modeling layer. Therefore, the crystallization temperature (Tc) of the three-dimensional modeling material is preferably 80°C to 140°C, and more preferably 100°C to 130°C.

[0193] The crystallization temperature of the three-dimensional modeling material can be measured in the same manner as the measurement method for the thermoplastic resin described above.

[0194] [Breaking stress of the modeled object for measurement]

[0195] The lower limit of the fracture stress α of the measuring object when the three-dimensional modeling material is stacked and molded into a measuring object (hereinafter referred to as "fracture stress α of the measuring object") is preferably 4.0 MPa or more, more preferably 5 MPa or more, more preferably 6.5 MPa or more, and further preferably 8.0 MPa or more.

[0196] The upper limit of the fracture stress α of the shaped object for measurement is preferably 200.0 MPa.

[0197] Regarding the fracture stress α of a three-dimensional object, a test piece (JIS K7161-2 1BA: 2014) is punched out from the wall of a quadrangular prism object with a thickness of 2 mm in such a way that the tensile direction becomes the stacking direction, and the test piece is measured in accordance with JIS K7161-2: 2014 (test speed: 50 mm / min). Thus, the fracture stress α of the three-dimensional object in the stacking direction of the three-dimensional object is confirmed. The fracture stress α of the three-dimensional object in the stacking direction of the three-dimensional object is usually the smallest among the fracture stresses of the three-dimensional object. It should be noted that in the case where the three-dimensional object yields before the fracture of the three-dimensional object, the smaller of the fracture stress and the yield stress is used as the fracture stress α.

[0198] In other words, the fracture stress α of the shaped object for measurement is a value measured by a tensile test in accordance with JIS K7161-2:2014.

[0199] The object for measurement was a 1BA-shaped test piece specified in JIS K7161-2: 2014 obtained by laminating and machining a three-dimensional modeling material using a material extrusion method. The total length of the object for measurement was 75 mm. The thickness of the object for measurement was 2 mm.

[0200] The object for measurement before mechanical processing (hereinafter referred to as "the object for measurement before mechanical processing") is, for example, a quadrangular prism-shaped object with a thickness of 2 mm. The object for measurement before mechanical processing is obtained by laminating the three-dimensional modeling material by a material extrusion method in such a manner that the filling rate is 100% and the overlapping direction of the three-dimensional modeling material is parallel to the tensile direction of the object for measurement in the tensile test.

[0201] [Tensile elastic modulus Z of the object to be measured]

[0202] The lower limit of the tensile modulus Z of the measuring object when the three-dimensional modeling material is stacked and molded into the above-mentioned measuring object (hereinafter referred to as "tensile modulus Z of the measuring object") is preferably 200 MPa or more, more preferably 800 MPa or more, and further preferably 1000 MPa or more.

[0203] The upper limit of the tensile elastic modulus X of the three-dimensional modeling material is preferably 4000 MPa or less, more preferably 2500 MPa or less, and further preferably 2000 MPa or less.

[0204] In the present disclosure, the tensile modulus Z of the shaped object for measurement is measured in accordance with JIS K7161-2: 2014. The test speed is 0.5 mm / min.

[0205] In the measurement object, the stacking direction of the three-dimensional modeling material and the tensile direction of the measurement object in the tensile test in accordance with JIS K7161-2:2014 are parallel to each other.

[0206] In the three-dimensional modeling material, it is preferred that the fracture stress α (MPa) of the measurement modeled object satisfies the following formula (III), and the average warpage amount Y (mm) of the measurement honeycomb modeled object 10 satisfies the following formula (IIb).

[0207] Formula (III) 6.5≤α<200

[0208] Formula (IIb) 0≤Y≤4.0

[0209] (Other ingredients)

[0210] The three-dimensional modeling material in the present disclosure may contain other components in addition to the above-mentioned thermoplastic elastomer and thermoplastic resin.

[0211] Examples of other components include ultraviolet absorbers, stabilizers, antioxidants, plasticizers, colorants, toners, flame retardants, antistatic agents, fluorescent brighteners, matting agents, and impact strength improvers.

[0212] (Form of materials for three-dimensional modeling)

[0213] The material for three-dimensional modeling may be a molded product.

[0214] The molding method of the molded article is not particularly limited, and the molded article may be obtained by molding using a known molding method such as extrusion molding.

[0215] The molded product can be in the form of pellets or filaments.

[0216] Pellets are small amounts of solid matter that have been given a shape in advance.

[0217] Filament refers to a long, thin ribbon-like object with a uniform cross section. Filament is usually used in the form of being wound on a reel.

[0218] The three-dimensional modeling material may be in the form of pellets or filaments, or may be a mixture of both. From the perspective of molding a relatively large three-dimensional object, the three-dimensional modeling material is preferably in the form of pellets.

[0219] When the three-dimensional modeling material is formed into pellets, the forming method is not limited. As a forming method of pellets, for example, a method of mixing and extruding the three-dimensional modeling material using a melt extruder (e.g., a twin-screw extruder) and cutting the extruded rod-shaped wire bundle using a granulator can be cited. In addition, the three-dimensional modeling material fed into the melt extruder can also be a dry blend. The dry blend is prepared by mixing part or all of the three-dimensional modeling material in advance using a Henschel mixer or the like.

[0220] <Method for producing three-dimensional objects>

[0221] The method for manufacturing a three-dimensional object of the present disclosure comprises the following steps: a melting step, in which the three-dimensional modeling material of the present disclosure as described above is melted; and a molding step, in which the melted three-dimensional modeling material is extruded from a nozzle of a three-dimensional modeling object manufacturing device to mold the three-dimensional modeling object. The melting step and the molding step are performed sequentially.

[0222] (Melting process)

[0223] The melting step in the present disclosure melts the three-dimensional modeling material of the present disclosure described above.

[0224] The heating mechanism for melting the three-dimensional modeling material is not particularly limited, and a known heating mechanism can be applied.

[0225] In the melting step, it is preferable to use a three-dimensional object manufacturing apparatus equipped with a heating mechanism such as an electric heater.

[0226] The temperature at which the three-dimensional modeling material is melted is not particularly limited and can be appropriately set according to the properties of the thermoplastic resin. The temperature at which the three-dimensional modeling material is melted can be set to a temperature of +10°C to 150°C based on, for example, the higher temperature of the melting point or glass transition temperature (Tg) of the thermoplastic resin.

[0227] In the melting process, for example, the three-dimensional modeling material can be melted and kneaded. In particular, when the three-dimensional modeling material includes glass fiber, it is preferred to melt and knead the three-dimensional modeling material in the melting process. By melting and kneading the three-dimensional modeling material, there is a tendency for the three-dimensional modeling material to be mixed more uniformly. Therefore, it is easy to suppress the occurrence of uneven materials of the obtained three-dimensional modeling object. As a result, there is a tendency for the deformation of the three-dimensional modeling object to be further suppressed.

[0228] (Modeling process)

[0229] In the shaping step in the present disclosure, the three-dimensional shaping material melted in the melting step is extruded from a nozzle to shape a three-dimensional shape.

[0230] In the modeling process, for example, a molten three-dimensional modeling material can be extruded from a nozzle of a three-dimensional modeling object manufacturing device, and two-dimensional layers can be sequentially stacked on a substrate based on a plurality of two-dimensional data, thereby modeling a three-dimensional modeling object. The plurality of two-dimensional data are generated by slicing the three-dimensional coordinate data of the three-dimensional modeling object to be modeled into discs using slicing software.

[0231] The three-dimensional object manufacturing apparatus can use a material extrusion method of three-dimensional object manufacturing apparatus. The material extrusion method of three-dimensional object manufacturing apparatus is not particularly limited, and a known apparatus or a known apparatus configuration can be applied.

[0232] The three-dimensional object manufacturing device may include, for example, a barrel, a nozzle, and a heating mechanism. The three-dimensional modeling material is supplied to the barrel. The nozzle is disposed at a position on the downstream side of the barrel in the ejection direction of the three-dimensional modeling material. The nozzle ejects the three-dimensional modeling material. The heating mechanism is disposed in the barrel. The heating mechanism heats and melts the three-dimensional modeling material.

[0233] The three-dimensional object manufacturing device extrude the heated and molten three-dimensional modeling material from a nozzle, and performs layered modeling on the three-dimensional modeling material extruded from the nozzle, thereby modeling a three-dimensional modeling object.

[0234] The barrel may have a screw inside thereof, and the screw mixes the three-dimensional modeling material.

[0235] The three-dimensional object manufacturing apparatus may further include a table device. The table device is arranged opposite to the nozzle. The molten three-dimensional modeling material extruded from the nozzle is stacked on the table device.

[0236] The three-dimensional object manufacturing device may further include a control mechanism. The control mechanism controls the spatial coordinates of the substrate and the nozzle, and the amount of the three-dimensional modeling material extruded from the nozzle. Preferably, the control mechanism controls the ejection of the molten three-dimensional modeling material extruded from the nozzle, and controls the movement of the nozzle and / or the workbench device in the X-axis, Y-axis, and Z-axis directions relative to the reference plane.

[0237] (Other processes)

[0238] The method for producing a three-dimensional object of the present disclosure may further include, for example, a processing step. In the processing step, the three-dimensional object formed in the forming step is processed.

[0239] <Three-dimensional objects>

[0240] The three-dimensional modeled object of the present disclosure is a modeled object of the three-dimensional modeling material of the present disclosure as described above.

[0241] The three-dimensional modeling material of the present disclosure is used as a raw material of the three-dimensional modeling object of the present disclosure. Therefore, deformation of the three-dimensional modeling object due to heat shrinkage or the like is suppressed.

[0242] The three-dimensional object of the present disclosure is not particularly limited as long as it is the object of the three-dimensional object material of the present disclosure as described above, and can be an object obtained by any method. Among them, the three-dimensional object of the present disclosure is preferably an object obtained by the manufacturing method of the three-dimensional object of the present disclosure as described above.

[0243] Example

[0244] Hereinafter, the present disclosure will be described in more detail using examples, but the present disclosure is not limited to the following examples as long as it does not exceed its purport. It should be noted that, unless otherwise specified, "parts" are based on mass. The melting point, Shore hardness, MFR, crystallization temperature, crystallinity, tensile modulus X, thermal expansion coefficient, breaking stress, average warpage Y, and tensile modulus Y shown below are each measured using the aforementioned method.

[0245] -Material preparation-

[0246] The details of the materials used in this example (that is, the components contained in the three-dimensional modeling material) are as follows.

[0247] (Thermoplastic Elastomer)

[0248] DF8200: TAFMER (registered trademark; the same applies to the following) DF8200 (Mitsui Chemicals, Inc.)

[0249] ·XM7090: TAFMER XM-7090 (Mitsui Chemicals Co., Ltd.)

[0250] ·DF610: TAFMER DF610 (Mitsui Chemicals Co., Ltd.)

[0251] ·DF710: TAFMER DF710 (Mitsui Chemicals Co., Ltd.)

[0252] ·PN2070: TAFMER PN-2070 (Mitsui Chemicals Co., Ltd.)

[0253] ·PN3560: TAFMER PN-3560 (Mitsui Chemicals Co., Ltd.)

[0254] ·EP1001: ABSORTOMER EP1001 (Mitsui Chemicals Co., Ltd.)

[0255] ·TS6000N: MILASTOMER TS6000N (Mitsui Chemicals Co., Ltd.)

[0256] ·6030NS: MILASTOMER 6030NS (Mitsui Chemicals Co., Ltd.)

[0257] (Thermoplastic resin)

[0258] J966HP: PRIMEPOLYPRO (registered trademark; the same applies to the following) J-966HP (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0259] J105G: PRIMEPOLYPRO J-105G (propylene homopolymer, Prime Polymer Co., Ltd.)

[0260] J108M: PRIMEPOLYPRO J108M (propylene homopolymer, Prime Polymer Co., Ltd.)

[0261] J721GR: PRIMEPOLYPRO J721GR (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0262] J229E: PRIMEPOLYPRO J229E (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0263] J707G: PRIMEPOLYPRO J707G (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0264] J705UG: PRIMEPOLYPRO J705UG (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0265] J708UG: PRIMEPOLYPRO J708UG (propylene-ethylene copolymer, Prime Polymer Co., Ltd.)

[0266] (Filling material)

[0267] Talc: Volume average particle size 5μm to 10μm

[0268] Glass fiber (GF): weight average fiber length is 0.5 to 2 mm

[0269] Tables 1 to 6 show the melting point, Shore hardness, and MFR of the thermoplastic elastomer, and the crystallization temperature and crystallinity of the thermoplastic resin, as well as the manufacturer's catalog values.

[0270] In the table, "A" before the value in the "Shore Hardness" column indicates Shore A hardness. In the table, "D" before the value in the "Shore Hardness" column indicates Shore D hardness. For example, "A86" of Example 1 indicates that the Shore A hardness is 86. Similarly, "D58" of Example 9 indicates that the Shore D hardness is 58.

[0271] In the table, the items "Melting point: Tm [°C]", "Shore hardness", and "MFR [g / min]" immediately below the item "(thermoplastic elastomer)" indicate catalog values ​​of the melting point, Shore hardness, and MFR of the thermoplastic elastomer.

[0272] In the table, the items "Crystallization temperature: Tc [°C]" and "Crystallinity [%]" located immediately below the item "(Thermoplastic resin)" represent the product catalog values ​​of the crystallization temperature and crystallinity of the thermoplastic resin (propylene polymer) which is a constituent component of the three-dimensional modeling material.

[0273] [Example 1 to Example 38 and Comparative Example 1 to Comparative Example 19]

[0274] -Determination of tensile elastic modulus X of hot pressed product for measurement-

[0275] The three-dimensional modeling material was hot-pressed under the conditions of a heating temperature of 200°C, a press pressure of 50 MPa, and a press time of 3 minutes to obtain the above-mentioned hot-pressed product for measurement. The obtained hot-pressed product for measurement is a 1BA-shaped test piece specified in JIS K7161-2:2014. The total length of the hot-pressed product for measurement is 75 mm. The thickness of the hot-pressed product for measurement is 2 mm.

[0276] The tensile elastic modulus X of the obtained hot-pressed product for measurement was measured. The measurement results are shown in Tables 1 to 6.

[0277] In the table, the item "tensile elastic modulus X [MPa]" immediately below the item "(hot pressed product)" indicates the measurement result of the tensile elastic modulus X of the hot pressed product for measurement.

[0278] In the table, the content (%) recorded together with the thermoplastic resin refers to the mass content of the thermoplastic resin relative to the total mass of the three-dimensional modeling material. The content (%) recorded together with the thermoplastic elastomer refers to the mass content of the thermoplastic elastomer relative to the total mass of the three-dimensional modeling material. The content (%) recorded together with the filler refers to the content of the filler relative to the total mass of the three-dimensional modeling material.

[0279] -Determination of melting point, crystallization temperature and thermal expansion coefficient of hot pressed products-

[0280] A hot pressed product for measurement was obtained in the same manner as in "Measurement of tensile elastic modulus X of hot pressed product for measurement". The melting point, crystallization temperature, and thermal expansion coefficient of the hot pressed product for measurement were measured. The measurement results are shown in Tables 1 to 6.

[0281] In the table, the "Melting point: Tm [°C]", "Crystallization temperature: Tc [°C]", and "Thermal expansion coefficient [10 -5 / °C]" indicates the measurement results of the melting point, crystallization temperature, and thermal expansion coefficient of the hot pressed product for measurement.

[0282] In the table, "-" in the "Components and Contents" column indicates that the component is not contained, and "-" is also indicated in the corresponding physical property column.

[0283] In the table, “-” in the column “Physical properties and evaluation” means that the corresponding measurement or evaluation was not performed.

[0284] -Measurement of deformation (average warpage amount Y) of honeycomb shaped article 10 for measurement-

[0285] In molding the above-mentioned measurement honeycomb molded object 10, a three-dimensional molded object manufacturing device of a material extrusion method ("DeltaWASP 3MT Industrial" manufactured by WASP Co., Ltd., nozzle diameter: 3 mm) and application software ("Simplify3D" manufactured by Simplify3D Co., Ltd.) were used.

[0286] First, the three-dimensional modeling materials listed in Tables 1 to 6 are added to the feed hopper, and the three-dimensional modeling materials are supplied to the barrel through the feed hopper. As components constituting the three-dimensional modeling materials, thermoplastic elastomers, thermoplastic resins, and fillers shown in the respective tables are used. Next, the temperature of the three-dimensional modeling materials is heated to 180°C to 240°C by a heater provided in the barrel to melt the materials (melting process).

[0287] Next, the following 3D data is sliced ​​into discs using the application software to generate multiple 2D data. Based on the multiple 2D data, the application software setting parameters are set as follows, and the material extrusion method (MEX) is used to shape the Figure 1 Specifically, based on the three-dimensional coordinate data, the molten three-dimensional molding material is sequentially stacked on the substrate to form a three-dimensional molded object of a rectangular parallelepiped shape of 250 mm×100 mm×15 mm in height and with a filling rate of 30% in the entire honeycomb (molding step).

[0288] <3D data>

[0289] ·250mm×100mm×15mm high rectangular block

[0290] <Setting parameters of the honeycomb structure portion 11 of the honeycomb shaped object 10 for measurement>

[0291] Molding speed: 3000mm / min

[0292] Nozzle temperature: 240℃

[0293] · Stacking distance: 1.5mm

[0294] Filling rate: 30%

[0295] Fill pattern: Honeycomb

[0296] <Setting Parameters of the Rectangular Parallel Frame 12 of the Honeycomb Molded Article 10 for Measurement>

[0297] Molding speed: 3000mm / min

[0298] Nozzle temperature: 240℃

[0299] · Stacking distance: 1.5mm

[0300] Filling rate: 100%

[0301] Fill pattern: Solid

[0302] The average warpage amount Y (mm) of the obtained measurement honeycomb shaped article 10 was measured. The measurement results are shown in Tables 1 to 6.

[0303] It should be noted that in this evaluation, the examples marked with "-" in the table mean that the honeycomb molded product 10 for measurement required for measurement could not be obtained due to deformation in molding.

[0304] In the table, “average warping amount Y” under the item “(three-dimensional shaped object)” indicates the average warping amount Y of the honeycomb shaped object 10 for measurement.

[0305] - Evaluation of the appearance and surface of the honeycomb shaped article 10 for measurement -

[0306] The honeycomb shaped article 10 for measurement was visually evaluated for its appearance and surface condition according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 6.

[0307] In the table, “Appearance and Surface Evaluation” under the item “(Three-dimensional Modeled Object)” shows the evaluation results of the appearance and surface of the honeycomb modeled object 10 for measurement.

[0308] <Evaluation Criteria>

[0309] G1: The surface of the honeycomb shaped object 10 for measurement is smooth and has a good appearance, and further, 3D data (three-dimensional coordinate data) can be reproduced more faithfully.

[0310] G2: The surface of the measurement honeycomb shaped object 10 is smooth and has a good appearance.

[0311] G3: There are some irregularities on the surface of the honeycomb shaped object 10 for measurement, but the appearance is tolerable.

[0312] G4: Unacceptably significant irregularities are observed on the surface of the honeycomb shaped object 10 for measurement, or 3D data (three-dimensional coordinate data) cannot be reproduced.

[0313] -Measurement of the fracture stress α and tensile elastic modulus Z of the molded object for measurement-

[0314] In the formation of the above-mentioned measurement object, a three-dimensional object manufacturing device using a material extrusion method ("DeltaWASP 3MT Industrial" manufactured by WASP Co., Ltd., nozzle diameter: 2 mm) and application software ("Simplify3D" manufactured by Simplify3D Co., Ltd.) were used.

[0315] First, the three-dimensional modeling materials listed in Tables 1 to 6 are added to the feed hopper, and the three-dimensional modeling materials are supplied to the barrel through the feed hopper. As components constituting the three-dimensional modeling materials, thermoplastic elastomers, thermoplastic resins, and fillers shown in the respective tables are used. Next, the temperature of the three-dimensional modeling materials is heated to 180°C to 240°C by a heater provided in the barrel to melt the materials (melting process).

[0316] Next, the 3D data described below is sliced ​​into discs using application software to generate a plurality of two-dimensional data. Based on the plurality of two-dimensional data, the application software setting parameters are set as described below, and the material extrusion method (MEX; MaterialExtrusion) is used to shape the measurement model before machining (molding process).

[0317] <3D data>

[0318] ·130mm×130mm×2mm thick rectangular block

[0319] <Setting parameters>

[0320] Molding speed: 3000mm / min

[0321] Nozzle temperature: 240℃

[0322] · Stacking distance: 1.0mm

[0323] Filling rate: 100%

[0324] Fill pattern: Solid

[0325] Next, the obtained measurement molded object before machining was machined to obtain a measurement molded object. The obtained measurement molded object was a 1BA-shaped test piece specified in JIS K7161-2:2014. The total length of the measurement hot-pressed product was 75 mm. The thickness of the measurement molded object was 2 mm.

[0326] The fracture stress α and tensile modulus Z of the test object were measured. When measuring the fracture stress α and tensile modulus Z of the test object, the overlapping direction of the three-dimensional modeling material and the tensile direction of the test object in the tensile test were parallel. The measurement results are shown in Tables 1 to 6.

[0327] In the table, "fracture stress α [MPa]" and "tensile elastic modulus Z [MPa]" under the item "(three-dimensional shaped object)" indicate the measurement results of the fracture stress and tensile elastic modulus Z of the measured shaped object.

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334] As shown in Tables 1 to 6, the three-dimensional modeling materials of Examples 1 to 38 include thermoplastic resins, thermoplastic elastomers, and fillers. The fillers include talc. The content of the fillers is 5% by mass or more and 70% by mass or less relative to the total mass of the three-dimensional modeling material. Therefore, the average warpage amount Y of the honeycomb modeling object 10 for measurement is 6.0 mm or less. That is, it can be seen that the deformation (especially warpage) of the three-dimensional modeling object using the three-dimensional modeling materials of Examples 1 to 38 is suppressed.

[0335] In addition, the three-dimensional modeling materials of Examples 7 to 9 are fillers combining talc and glass fiber. Therefore, it is known that the three-dimensional modeling objects using the three-dimensional modeling materials of Examples 7 to 9 have small stress strain and smooth appearance.

[0336] On the other hand, the three-dimensional modeling materials of Comparative Examples 1 to 8 are formed of thermoplastic resins, and do not contain thermoplastic elastomers and fillers. The three-dimensional modeling materials of Comparative Examples 9 to 19 are formed of thermoplastic resins and thermoplastic elastomers, and do not contain fillers. Therefore, the average warpage amount Y of the honeycomb modeled object 10 for measurement is higher than 6.0 mm. That is, it can be seen that the deformation (especially warpage) of the three-dimensional modeled object using the three-dimensional modeling materials of Comparative Examples 1 to 19 is not suppressed.

[0337] The disclosed contents of Japanese Patent Application No. 2019-174751 filed on September 25, 2019, and the disclosed contents of Japanese Patent Application No. 2020-071719 filed on April 13, 2020 are all incorporated into this specification by reference.

[0338] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A three-dimensional modeling material comprising a thermoplastic resin, a thermoplastic elastomer, and a filling material, The filler material comprises talc, The content of the filler material is 25 mass % or more and 50 mass % or less relative to the total mass of the three-dimensional modeling material. The content of the thermoplastic elastomer is 20% by mass or more relative to the total mass of the three-dimensional modeling material. The thermoplastic elastomer is a propylene-based elastomer with a melting point of 80° C. to 120° C., a Shore D hardness of 40 to 60, and an MFR of 2 g / 10 min to 20 g / 10 min.

2. The three-dimensional modeling material according to claim 1, in, The content of the thermoplastic resin is 0.1% by mass or more and less than 100% by mass based on the total mass of the three-dimensional modeling material.

3. The three-dimensional modeling material according to claim 1 or claim 2, in, The thermoplastic resin includes a propylene-based polymer.

4. The three-dimensional modeling material according to claim 1 or claim 2, wherein the tensile elastic modulus X (MPa) of the hot-pressed product for measurement according to JIS K7161-2:2014 satisfies the following formula (I): When the honeycomb shaped article for measurement is stacked and molded, the average warpage amount Y (mm) of the honeycomb shaped article for measurement satisfies the following formula (IIa): The hot-pressed product for measurement is a 1BA-shaped test piece specified in JIS K7161-2:2014 obtained by hot-pressing the three-dimensional modeling material. The honeycomb structure for measurement comprises: A rectangular parallelepiped frame portion of 250 mm × 100 mm × 15 mm in height, wherein the rectangular parallelepiped frame portion is obtained by laminating the three-dimensional modeling material by a material extrusion method in such a manner that a filling rate representing a ratio of the volume of the three-dimensional modeling material to the volume of a unit space becomes 100%, and A honeycomb structure portion, wherein the honeycomb structure portion is obtained by laminating and shaping the three-dimensional shaping material in the rectangular parallelepiped frame portion in such a manner that the filling rate becomes 30% by using the material extrusion method; The average warpage amount Y represents the arithmetic mean of the floating amounts of the four corners of the rectangular parallelepiped frame portion from the flat plate when the honeycomb shaped article for measurement is placed on the flat plate. Formula (I) 50≤ X ≤4000 Formula (IIa) 0≤Y≤6.

0.

5. The three-dimensional modeling material according to claim 1 or claim 2, in, The content of the thermoplastic elastomer is 20 mass % or more and less than 70 mass % relative to the total mass of the three-dimensional modeling material. The content of the filler material is 25 mass % or more and less than 50 mass % relative to the total mass of the three-dimensional modeling material. The total content of the thermoplastic elastomer and the filler is 45% by mass or more and less than 90% by mass based on the total mass of the three-dimensional modeling material.

6. The three-dimensional modeling material according to claim 1 or claim 2, wherein when the three-dimensional modeling material is laminated and molded into a measurement modeling object, the fracture stress α [MPa] of the measurement modeling object in accordance with the tensile test of JIS K7161-2:2014 satisfies the following formula (III), When the honeycomb shaped article for measurement is stacked and molded, the average warpage amount Y [mm] of the honeycomb shaped article for measurement satisfies the following formula (IIb): The object for measurement is a 1BA-shaped test piece specified in JIS K7161-2:2014 obtained by laminating and machining the three-dimensional modeling material by a material extrusion method in such a manner that the filling rate representing the ratio of the volume of the three-dimensional modeling material to the unit space volume is 100% and the overlapping direction of the three-dimensional modeling material is parallel to the tensile direction of the object for measurement in the tensile test, The honeycomb structure for measurement comprises: A rectangular parallelepiped frame portion of 250 mm × 100 mm × 15 mm in height, wherein the rectangular parallelepiped frame portion is obtained by laminating the three-dimensional modeling material in such a manner that the filling rate becomes 100% by using the material extrusion method, and A honeycomb structure portion, wherein the honeycomb structure portion is obtained by laminating and shaping the three-dimensional shaping material in the rectangular parallelepiped frame portion in such a manner that the filling rate becomes 30% by using the material extrusion method; The average warpage amount Y represents the arithmetic mean of the floating amounts of the four corners of the rectangular parallelepiped frame portion from the flat plate when the honeycomb shaped article for measurement is placed on the flat plate. Formula (III) 6.5≤ α <200 Formula (IIb) 0≤Y≤4.

0.

7. A method for manufacturing a three-dimensional object, comprising the following steps: A melting step of melting the three-dimensional modeling material according to any one of claims 1 to 6; and The shaping step is to extrude the melted three-dimensional shaping material from a nozzle of a three-dimensional shaping object manufacturing device to shape the three-dimensional shaping object.

8. A three-dimensional modeled object, which is a modeled object of the three-dimensional modeling material according to any one of claims 1 to 6.

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