Three-dimensional shaped article and method for manufacturing same

Abstract

Provided are: a three-dimensional shaped article having a controlled molecular orientation; and a method for manufacturing same.　The three-dimensional shaped article contains a thermoplastic resin, wherein the thermoplastic resin contains 55-100 mass% of a liquid crystalline resin in the entirety of the thermoplastic resin. The three-dimensional shaped article is used in an environment where an electric field and / or heat is applied. The thermoplastic resin is molecularly oriented in at least a portion of the three-dimensional shaped article. At least one of the directions of the molecular orientation is a direction of an electric field applied to the three-dimensional shaped article and / or a direction in which heat applied to the three-dimensional shaped article is dissipated.

Description

Three-dimensional object and method for manufacturing the same

[0001] The present disclosure relates to a three-dimensional object with controlled molecular orientation and a method for manufacturing the same.

[0002] Liquid crystal polymers (LCPs) have high rigidity and elasticity, as well as excellent heat resistance, insulating properties, impact resistance, and chemical resistance, and are therefore widely used in a variety of fields. Due to their molecular structure, LCPs have the property of being prone to molecular orientation, and therefore exhibit strong anisotropy in the properties they exhibit in molded products. Therefore, if the molecular orientation of LCPs can be more precisely controlled, the properties of the LCP can be controlled at a desired location and in a desired direction. However, in the case of injection molding, the melt flow is required during the process, making it difficult to control the molecular orientation. Therefore, for example, to obtain properties such as a low dielectric tangent or high thermal conductivity, it was necessary to modify the material itself, such as by forming a composite using a low dielectric filler or a high thermal conductivity filler. In recent years, 3D printing technologies such as Fused Filament Fabrication (FFF) have made it possible to manufacture objects with more complex shapes without using molds or large-scale melting equipment, and the application of LCP to 3D printing technologies has been considered. However, LCP has properties that make it unsuitable for application to 3D printing technologies, such as a fast solidification rate and transparency to light such as lasers.

[0003] Patent Document 1 describes a resin composition for three-dimensional modeling using an FFF (FDM) method, which is characterized in that the thermoplastic resin contains a liquid crystalline resin and the content of the liquid crystalline resin in the thermoplastic resin is 0.5 to 40 mass %. Patent Document 2 describes the use of filamentous units formed from a polymer composition containing a thermotropic liquid crystalline polymer and having a predetermined minimum thickness in an additive manufacturing method.

[0004] Japanese Patent Application Laid-Open No. 2018-123263 Japanese Patent Application Laid-Open No. 2021-529685

[0005] The resin composition for 3D modeling described in Patent Document 1 is a thermoplastic resin whose main component is a crystalline resin or amorphous resin whose properties differ from those of LCP, and Patent Document 1 does not describe 3D modeling of a thermoplastic resin containing LCP as the main component. Furthermore, Patent Document 2 describes improving the mechanical properties of the resulting object by adjusting the minimum thickness of the filamentous units, but does not describe improving the properties of the resulting object by adjusting the physical properties of the LCP or the manufacturing conditions of the additive manufacturing method. The present disclosure aims to provide a 3D model with controlled molecular orientation and a method for manufacturing the same.

[0006] The present disclosure encompasses the following aspects: A three-dimensionally shaped object comprising a thermoplastic resin, wherein the thermoplastic resin comprises 55 to 100% by mass of a liquid crystalline resin in the entire thermoplastic resin, the three-dimensionally shaped object being used in an environment where an electric field and / or heat is applied, the thermoplastic resin is molecularly oriented in at least a portion of the three-dimensionally shaped object, and at least one of the directions of the molecular orientation is the direction of an electric field applied to the three-dimensionally shaped object and / or a direction in which heat applied to the three-dimensionally shaped object is dissipated.

[0007] According to the present disclosure, it is possible to provide a three-dimensional object with controlled molecular orientation and a method for manufacturing the same.

[0008] 1 is a schematic diagram showing a printing direction when a test piece of Example 1 is produced. FIG. 2 is a schematic diagram showing a printing direction when a test piece of Comparative Example 1 is produced.

[0009] An embodiment of the present disclosure will be described in detail below. However, the scope of the present disclosure is not limited to the embodiment described herein, and various modifications can be made without departing from the spirit of the present disclosure. Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, when multiple upper and lower limit values ​​are described for a specific parameter, any of these upper and lower limit values ​​can be combined to form a suitable numerical range. Furthermore, the lower and / or upper limit values ​​of a numerical range described in this disclosure are numerical values ​​within that numerical range and may be replaced with numerical values ​​shown in the examples. The expression "X to Y" indicating a numerical range means "X or more and Y or less." If a specific description described for one embodiment also applies to other embodiments, that description may be omitted in other embodiments.

[0010] [Three-dimensionally shaped object] A first embodiment of the present disclosure relates to a three-dimensionally shaped object. The three-dimensionally shaped object according to this embodiment is a three-dimensionally shaped object containing a thermoplastic resin, wherein the thermoplastic resin contains 55 to 100 mass % of a liquid crystalline resin in the entire thermoplastic resin, the three-dimensionally shaped object is used in an environment where an electric field and / or heat is applied, the thermoplastic resin is molecularly oriented in at least a portion of the three-dimensionally shaped object, and at least one of the directions of the molecular orientation is the direction of an electric field applied to the three-dimensionally shaped object and / or a direction in which heat applied to the three-dimensionally shaped object is dissipated.

[0011] Liquid crystal resins have a fast solidification rate due to the properties of liquid crystal polymers (hereinafter also referred to as LCPs). Therefore, when laminating molten filaments in the filament melting process, the layer that was laminated first tends to solidify. If molten filaments are laminated on a solidified layer, the bonding between the print lines may be insufficient, resulting in an insufficient shape. Therefore, it can be said that liquid crystal resins have properties that make them unsuitable for the filament melting process. Liquid crystal resins are resins that are difficult to relax their orientation, so their molecular orientation is unlikely to deviate from the direction of the print lines. Therefore, they are highly anisotropic, making it difficult to produce isotropic films.

[0012] The inventors have conducted extensive research and have succeeded in achieving molecular orientation of a thermoplastic resin containing a liquid crystalline resin in a desired location and direction within a single object by enabling more flexible filament melting processes using a thermoplastic resin containing a liquid crystalline resin than previously possible. The resulting object allows for control of the properties of the desired location and direction. Because the three-dimensional object of the present disclosure has more controlled molecular orientation, it possesses the characteristics of a thermoplastic resin containing a liquid crystalline resin, such as better control of its dielectric properties and thermal conductivity. For example, as shown in the examples described below, controlling the molecular orientation of the thermoplastic resin in the three-dimensional object allows for a three-dimensional object with a low dielectric loss tangent (a dielectric loss tangent equivalent to or lower than that of an injection-molded product). Furthermore, because the direction of molecular orientation of the thermoplastic resin is controlled to be the same as the direction of an electric field or the direction of heat dissipation in the environment in which the three-dimensional object is used, it is possible to achieve a dielectric loss tangent lower than that of an injection-molded product and increase the thermal conductivity by 60% or more. The three-dimensional object of the present disclosure has controlled properties in desired locations and directions in at least a portion of a single object, even though the fillers and additives that have conventionally been required to obtain desired properties are reduced or eliminated.

[0013] <Thermoplastic Resin> In this embodiment, the three-dimensionally shaped object contains a thermoplastic resin. The thermoplastic resin contains 55 to 100 mass % of a liquid crystalline resin relative to the total thermoplastic resin (100 mass %). By containing the liquid crystalline resin in the above-mentioned range, a three-dimensionally shaped object having excellent properties derived from LCP can be obtained.

[0014] In one embodiment, the thermoplastic resin preferably contains 60 to 100 mass % of the liquid crystalline resin, more preferably 70 to 100 mass % of the liquid crystalline resin, even more preferably 80 to 100 mass % of the liquid crystalline resin, and particularly preferably 90 to 100 mass % of the liquid crystalline resin, based on the total thermoplastic resin (100 mass %). In one embodiment, the total thermoplastic resin (100 mass %) may be a thermoplastic liquid crystalline resin, i.e., the three-dimensionally shaped object may be made of a thermoplastic liquid crystalline resin.

[0015] (Liquid Crystalline Resin) "Liquid crystallinity" refers to the ability to form an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope to observe a molten sample placed on a Leitz hot stage at 40x magnification under a nitrogen atmosphere. When a resin with liquid crystallinity is examined between crossed polarizers, polarized light usually passes through, even in a molten, stationary state, and the resin exhibits optical anisotropy.

[0016] In one embodiment, the liquid crystalline resin preferably contains at least one selected from liquid crystalline polyesters and liquid crystalline polyesteramides. The liquid crystalline polyesters and liquid crystalline polyesteramides are not particularly limited, but are preferably aromatic polyesters or aromatic polyesteramides, more preferably at least one resin selected from wholly aromatic polyesters and wholly aromatic polyesteramides, and even more preferably aromatic polyesters or aromatic polyesteramides having, as a constituent component, a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives. Examples of aromatic hydroxycarboxylic acid derivatives include alkyl esters (e.g., having 1 to 4 carbon atoms), halides, and acylates. Polyesters partially containing aromatic polyesters or aromatic polyesteramides in the same molecular chain can also be used. By including the liquid crystalline resin in the thermoplastic resin, the molecular orientation of the liquid crystalline resin can be further improved, enabling the production of three-dimensional objects in a filament melt manufacturing process.

[0017] As the aromatic polyester or aromatic polyester amide, an aromatic polyester or aromatic polyester amide having an aromatic hydroxycarboxylic acid as a constituent is particularly preferred.

[0018] More specifically, the aromatic polyesters or aromatic polyesteramides include: (1) polyesters mainly composed of one or more aromatic hydroxycarboxylic acids and their derivatives; (2) polyesters mainly composed of (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives; (3) polyesters mainly composed of (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, and (c) one or more aromatic diols, alicyclic diols, aliphatic diols, and their derivatives; (4) polyesteramides mainly composed of (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic hydroxyamines, aromatic diamines, and their derivatives, and (c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives; (5) Examples include polyesteramides primarily composed of (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic hydroxyamines, aromatic diamines, and their derivatives, (c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, and (d) one or more aromatic diols, alicyclic diols, aliphatic diols, and their derivatives. Furthermore, a molecular weight modifier may be used in combination with the above components, if necessary. Examples of the "derivatives" in (1) to (5) above include alkyl esters (e.g., having 1 to 4 carbon atoms), halides, acylation products, etc.

[0019] Preferred specific examples of compounds (monomers) constituting the liquid crystalline polyester and the liquid crystalline polyesteramide include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, aromatic diols such as 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I) and compounds represented by the following general formula (II), aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III), and aromatic amines such as 4-aminophenol, 1,4-phenylenediamine and N-acetyl-p-aminophenol. (X: alkylene (C １ ~C ４ ), alkylidene, —O—, —SO—, —SO ２ is a group selected from —, —S—, and —CO—. (Y:-(CH ２ ) ｎ -(n=1 to 4) and -O(CH ２ ) ｎ O- (n = 1 to 4).

[0020] The method for producing liquid crystalline polyesters and liquid crystalline polyesteramides is not particularly limited, and they can be produced by known methods such as direct polymerization or transesterification using the above-mentioned monomer compounds (or monomer mixtures). Usually, melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used. When the compound has the ability to form an ester, it may be used in polymerization as is, or it may be modified from a precursor to a derivative having the ability to form an ester using an acylating agent or the like in the pre-polymerization stage. Examples of the acylating agent include carboxylic anhydrides such as acetic anhydride.

[0021] Various catalysts can be used in the polymerization. Typical usable catalysts include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is generally about 0.001 to 1 mass % relative to the total weight of the monomers, and preferably about 0.01 to 0.2 mass %.

[0022] Various fibrous, granular, or plate-like inorganic and organic fillers can be blended into the liquid crystalline resin during the manufacturing process. Specific examples of fillers include the same fillers that can be contained in the three-dimensionally shaped objects described below. The content of the filler can be, for example, 0 to 100 parts by mass, for example, 0 to 80 parts by mass, 5 to 75 parts by mass, or 10 to 50 parts by mass, per 100 parts by mass of the liquid crystalline resin. Furthermore, the liquid crystalline resin may contain additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, pigments, and crystal nucleating agents as other components.

[0023] In one embodiment, the content of the liquid crystalline resin in the three-dimensionally shaped object may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount (100% by mass) of the three-dimensionally shaped object. In one embodiment, the content of the liquid crystalline resin in the three-dimensionally shaped object may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount (100% by mass) of the three-dimensionally shaped object.

[0024] (Other Thermoplastic Resins) The thermoplastic resin may contain a thermoplastic resin other than the liquid crystalline resin. The type of thermoplastic resin that can be contained other than the liquid crystalline resin is not particularly limited, and may be any thermoplastic resin used in the filament melt manufacturing method, such as polylactic acid (PLA), acrylonitrile butadiene styrene copolymer (ABS), nylon, polypropylene, polycarbonate, polyarylate, polyetherimide, polyaryletherketone, etc. By containing a thermoplastic resin other than the liquid crystalline resin, the solidification rate is slowed and adhesion at the lamination interface is likely to be improved. The content of the thermoplastic resin other than the liquid crystalline resin is preferably 40% by mass or less, more preferably 0 to 30% by mass, even more preferably 5 to 25% by mass, and particularly preferably 5 to 20% by mass, based on the total thermoplastic resin (100% by mass).

[0025] In one embodiment, the total content of the thermoplastic resin in the three-dimensionally shaped object may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount (100% by mass) of the three-dimensionally shaped object. In one embodiment, the content of the liquid crystalline resin in the three-dimensionally shaped object may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount (100% by mass) of the three-dimensionally shaped object.

[0026] (Resin composition) In order to reduce the shrinkage rate and linear expansion coefficient of the molded object, various fibrous, powdery, and plate-shaped inorganic and organic fillers can be blended into the thermoplastic resin. Examples of fibrous fillers include inorganic fibrous materials such as glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, silicate fibers such as wollastonite, magnesium sulfate fiber, aluminum borate fiber, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A particularly representative fibrous filler is glass fiber. High-melting point organic fibrous materials such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used. Examples of powdery fillers include carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, and other ferrites, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of plate-like fillers include mica, glass flakes, talc, and various metal foils. These inorganic and organic fillers can be used alone or in combination.

[0027] The content of the filler can be, for example, 0 to 100 parts by mass, for example, 0 to 80 parts by mass, 5 to 75 parts by mass, or 10 to 50 parts by mass, relative to 100 parts by mass of the thermoplastic resin. Furthermore, the resin composition may contain additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, pigments, and crystal nucleating agents as other components.

[0028] <Molecular Orientation> In this embodiment, the thermoplastic resin is molecularly oriented in at least a portion of the three-dimensionally shaped object. By achieving molecular orientation in at least a portion of the three-dimensionally shaped object, the three-dimensionally shaped object can have excellent properties in a desired direction. "Molecularly oriented" means that, in at least a portion of the three-dimensionally shaped object, almost all molecules are molecularly oriented in a certain direction. This does not necessarily mean that all molecules are molecularly oriented in a certain direction; some molecules may be molecularly oriented in other directions. Molecular orientation can be confirmed by calculating the scattering intensity value of (direction A of the electric field applied to the three-dimensionally shaped object and / or direction B of the heat dissipation applied to the three-dimensionally shaped object) / (plane direction perpendicular to A and B) (Equation I) in two-dimensional wide-angle X-ray diffraction. For example, if the three-dimensionally shaped object has a plate shape, the degree of molecular orientation in the thickness direction can be confirmed by calculating the value of (scattering intensity in the thickness direction / scattering intensity in the plane direction) (Equation II) in two-dimensional wide-angle X-ray diffraction. In this case, a larger value for the scattering intensity in the thickness direction / the scattering intensity in the plane direction indicates a greater degree of molecular orientation in the thickness direction. In two-dimensional wide-angle X-ray diffraction, the values ​​of the above formulas I and II are preferably greater than 1.0, more preferably greater than 2.0, even more preferably greater than 3.0, and particularly preferably greater than 4.0. The degree of molecular orientation (degree of molecular orientation) can be adjusted by adjusting the modeling speed, which is the relative movement speed between the nozzle portion and the stage of the three-dimensional modeling device, the distance from the nozzle to the stage (layer height), the difference between the filament melting point Tm2 and the crystallization temperature Tc (Tm2-Tc) measured with a differential scanning calorimeter, the filament diameter, and the nozzle diameter. For example, by setting Tm2-Tc within the numerical range described below and increasing the modeling speed, the degree of molecular orientation tends to be higher. Furthermore, the smaller the filament diameter and nozzle diameter, and the faster the nozzle movement speed, the higher the degree of molecular orientation tends to be.

[0029] In this embodiment, the three-dimensionally shaped object is used in an environment where an electric field and / or heat is applied, and the thermoplastic resin has molecular orientation in the direction of the electric field applied to the three-dimensionally shaped object and / or in the direction of heat conduction (direction of heat dissipation) of the heat applied to the three-dimensionally shaped object. This molecular orientation in this direction tends to enable the three-dimensionally shaped object to have superior dielectric properties and thermal conductivity in this direction. In this specification, the "direction in which an electric field is applied to the three-dimensionally shaped object" refers to the direction of the electric field acting on the three-dimensionally shaped object in the environment in which the three-dimensionally shaped object is used. LCPs are known to have low dielectric properties in the high frequency band and excellent insulating properties. The dielectric loss tangent is a numerical representation of the proportion of energy converted to heat when an AC electric field is applied to a dielectric. The molecular orientation of the thermoplastic resin, including the LCP, is tightly controlled relative to the direction of the electric field applied to the three-dimensionally shaped object, resulting in a low dielectric loss tangent in the direction of the electric field applied to the three-dimensionally shaped object. This three-dimensionally shaped object can be suitably used in flexible circuit boards, millimeter-wave radar substrates, and the like, which require low dielectric properties. In this specification, the "direction in which heat applied to the three-dimensionally shaped object is dissipated" refers to the direction in which heat applied to the three-dimensionally shaped object is dissipated (the direction of heat conduction) in the environment in which the three-dimensionally shaped object is used. It is known that the thermal conductivity of LCP changes depending on its molecular orientation. By further controlling the molecular orientation of the thermoplastic resin, including the LCP, with respect to the direction in which heat is dissipated in the three-dimensionally shaped object, the three-dimensionally shaped object has high thermal conductivity in the direction in which heat is dissipated. This three-dimensionally shaped object can be suitably used in various electronic substrates and electronic components, which require high heat dissipation properties.

[0030] In one embodiment, when the three-dimensionally shaped object has a plate shape, the thermoplastic resin may have molecular orientation in the thickness direction of the plate-shaped three-dimensional object. The molecular orientation may be controlled by changing the orientation of the object so that better properties are exhibited in the desired direction. By having molecular orientation in the thickness direction of the plate-shaped three-dimensional object, the three-dimensional object can be easily placed so that better properties are exhibited in the desired direction. "Having a plate shape" means that at least a portion or the entire three-dimensional object is plate-shaped, and the detailed shape is selected depending on the application. The shape of the main surface of the plate shape is not particularly limited, and examples thereof include polygonal shapes (e.g., rectangular), circular shapes, elliptical shapes, etc. The surface shape in the thickness direction of the plate shape (the shape of the surface perpendicular to the main surface) is also not particularly limited, and examples thereof include polygonal shapes (e.g., rectangular), circular shapes, elliptical shapes, etc. When a plate-shaped three-dimensional object is formed, it is generally formed so that the main surface is parallel to the modeling stage of the 3D printer, but in this case, the thermoplastic resin has molecular orientation in the direction of extension of the main surface. Therefore, in this embodiment, it is preferable to form the object so that the thickness direction is parallel to the modeling stage of the 3D printer.

[0031] The three-dimensionally shaped object of this embodiment has excellent dielectric properties in the molecular orientation direction of the thermoplastic resin. In one embodiment, the three-dimensionally shaped object has a dielectric loss tangent at 1 MHz measured at 23°C in accordance with IEC 60250 using a cavity resonator perturbation method complex dielectric constant evaluation device, of preferably 0.025 or less, more preferably 0.021 or less, even more preferably 0.020 or less, and particularly preferably 0.015 or less, in the molecular orientation direction of the thermoplastic resin.

[0032] In the three-dimensionally shaped object of this embodiment, the thermoplastic resin has molecular orientation, and therefore has excellent thermal conductivity in that direction. In one embodiment, the thermal conductivity of the three-dimensionally shaped object, measured by a hot disk method in accordance with ISO 22007-2, in the molecular orientation direction of the thermoplastic resin, is preferably 0.35 W / (m / K) or more, more preferably 0.38 W / (m / K) or more, even more preferably 0.50 W / (m / K) or more, and particularly preferably 0.65 W / (m / K) or more.

[0033] Because the three-dimensionally shaped object of this embodiment has controlled molecular orientation, it can be preferably used in various fields as a component that is desired to have excellent properties in a desired location or direction, and can be used as a component for a connector or a printed circuit board. Examples of connectors include DDR connectors, SATA connectors, board-to-board connectors (BtoB connectors), connectors for flexible printed circuit boards (FPC connectors), and CPU sockets. Examples of printed circuit boards include rigid boards, flexible boards (FPC), and rigid-flexible boards.

[0034] The three-dimensional structure of this embodiment can be manufactured by the method for manufacturing a three-dimensional structure of the second embodiment described below.

[0035] [Method for manufacturing a three-dimensional object] A second embodiment of the present disclosure relates to a method for manufacturing a three-dimensional object. The method for manufacturing a three-dimensional object according to this embodiment includes: forming a three-dimensional object by a filament melting process using a filament containing the above-described thermoplastic resin; and the forming includes controlling the printing direction of the filament to the direction of molecular orientation. The "fuel melting process" is a type of additive manufacturing method, in which a thermoplastic filament is melted by heat and layered to produce a model. The term "filament" refers to a thermoplastic resin softened by heating and extruded into a string or thread shape (strand), which is then solidified.

[0036] <Filament> In this embodiment, the filament contains a thermoplastic resin. The thermoplastic resin contains 55 to 100% by mass of a liquid crystalline resin relative to the total thermoplastic resin (100% by mass). By including the liquid crystalline resin in the filament in the above-mentioned range, a three-dimensional object can be obtained in which the properties derived from LCP are more strongly exhibited. In one embodiment, the thermoplastic resin preferably contains 60 to 100% by mass of a liquid crystalline resin relative to the total thermoplastic resin (100% by mass), more preferably 70 to 100% by mass of a liquid crystalline resin, even more preferably 80 to 100% by mass of a liquid crystalline resin, and particularly preferably 90 to 100% by mass of a liquid crystalline resin. In one embodiment, the total thermoplastic resin (100% by mass) may be a thermoplastic liquid crystalline resin; that is, the filament may be made of a thermoplastic liquid crystalline resin. The filament may contain a thermoplastic resin other than the liquid crystalline resin, which may be included in the above-mentioned thermoplastic resin, or other components that may be included in the three-dimensional object. The liquid crystalline resin, the thermoplastic resin other than the liquid crystalline resin, and other components, as well as their contents, have been described above, and therefore will not be described here. In one embodiment, the content of the thermoplastic resin in the filament may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount of the filament (100% by mass). In one embodiment, the content of the liquid crystalline resin in the filament may be 50 to 100% by mass, 55 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass, relative to the total amount of the filament (100% by mass).

[0037] (Difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament) In this embodiment, the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament measured with a differential scanning calorimeter is 25 to 60°C. When Tm2 - Tc is in the above-mentioned range, the solidification speed during modeling falls within a suitable range, making it possible to perform three-dimensional modeling at high modeling speeds using a filament containing a liquid crystalline resin by a filament melting method, and to produce three-dimensional objects with improved molecular orientation. In this embodiment, the melting point Tm2 and the crystallization temperature Tc of the filament measured with a differential scanning calorimeter are determined as follows. According to a method based on JIS K-7121 (1999), a differential scanning calorimeter is used to measure the peak top temperature (melting point Tm1) of the endothermic peak observed when heated from room temperature at a heating rate of 20°C / min (1st RUN), and then the sample is held at a temperature of (melting point Tm1 + 40)°C for 2 minutes, and then cooled to room temperature at a heating rate of 20°C / min. The peak top temperature of the exothermic peak observed when the sample is then heated again from room temperature at a heating rate of 20°C / min is taken as the melting point Tm2.

[0038] In one embodiment, the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament measured by a differential scanning calorimeter is preferably 30 to 60°C, more preferably 30 to 55°C, even more preferably 30 to 50°C, and particularly preferably 30 to 45°C. In one embodiment, the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament measured by a differential scanning calorimeter may be 40 to 60°C. The method for adjusting the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament to 25 to 60°C is not limited, and can be performed by, for example, the following method. (1) By increasing the content of structural units derived from aromatic hydroxycarboxylic acids and derivatives thereof in the liquid crystalline resin (for example, 50% by mass or more relative to 100% by mass of all monomers), the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc can be adjusted to a large value. By reducing the content of structural units derived from aromatic hydroxycarboxylic acids and their derivatives (for example, 0.1 to 3.0% by mass relative to 100% by mass of all monomers), the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc) can be adjusted to a small value. (2) By blending a thermoplastic resin other than the liquid crystalline resin, the melting point Tm2 and the crystallization temperature Tc can be adjusted, and the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc) can be adjusted to 25 to 60°C. (3) By adding a certain amount of a monomer having a kink structure to the filament, the crystallization temperature Tc can be lowered, thereby adjusting the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc). A kink structure refers to a monomer that changes the molecular chain direction (the direction in which monomers are connected) in a liquid crystalline polymer. Examples of monomers having a kink structure include 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid, and isophthalic acid.In this case, the content of the monomer having a kink structure is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, relative to the total monomer (100% by mass), from the viewpoint of easily adjusting the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc) to a range of 25 to 60 ° C. (4) When the filament contains a polymer that can be transesterified, such as polycarbonate, the crystallization temperature Tc can be lowered by transesterification. Therefore, when the crystallization temperature Tc is high, the crystallization temperature Tc can be adjusted lower by mixing a certain amount of a polymer that can be transesterified, and the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc) can be adjusted. In this case, the content of the polymer that can be transesterified is preferably less than 30% by mass, more preferably 0 to 25% by mass, relative to the total thermoplastic resin (100% by mass), from the viewpoint of easily adjusting the difference between the melting point Tm2 and the crystallization temperature Tc (Tm2 - Tc) to a range of 25 to 60 ° C.

[0039] In one embodiment, the melting point Tm2 of the filament measured with a differential scanning calorimeter is preferably 250 to 400°C, more preferably 260 to 380°C, and even more preferably 280 to 360°C. By setting the melting point Tm2 to 250 to 400°C, the heat resistance of the three-dimensionally shaped object can be further improved. In one embodiment, the crystallization temperature Tc of the filament measured with a differential scanning calorimeter is preferably 200 to 400°C, more preferably 210 to 350°C, and even more preferably 220 to 330°C. By setting the crystallization temperature Tc to 200 to 400°C, the heat resistance of the three-dimensionally shaped object can be further improved.

[0040] (Filament Diameter) In one embodiment, the filament diameter is preferably 0.5 to 3.0 mm, more preferably 0.5 to 2.5 mm, even more preferably 1.0 to 2.5 mm, and particularly preferably 1.0 to 2.0 mm. By setting the filament diameter within the above range, it can be used as a modeling material in a commercially available three-dimensional modeling device to easily produce a three-dimensional model with improved molecular orientation of the liquid crystalline resin. The "filament diameter" refers to the average diameter of the solidified filament cross section. Specifically, it refers to the arithmetic mean value obtained by taking a 5-m filament, randomly selecting 20 locations, measuring the diameters (or the longest linear distances in the cross section) of the filament to three decimal places using a micrometer, and rounding the resulting value to the nearest whole number. The filament diameter can be adjusted, for example, by cooling and solidifying the extruded strand with water, and then adjusting the winding speed when winding it on a filament winder to obtain the desired diameter. In one embodiment, the filament can be wound around a core material to form a wound body. By making it into a winding body, it becomes easier to attach to commercially available 3D printers that use the filament fusion method, making it easier to create shapes using a 3D printer that uses the filament fusion method.

[0041] (Melt viscosity) In one embodiment, the melt viscosity is measured at a cylinder temperature 15° C. higher than the melting point Tm2 and a shear rate of 1000 sec －１ The melt viscosity of the filaments measured under these conditions is preferably 15 to 50 Pa·s, more preferably 17.5 to 50 Pa·s, even more preferably 20 to 50 Pa·s, and particularly preferably 20 to 48 Pa·s. By setting the melt viscosity of the filaments within the above range, the properties of the print lines during modeling can be set within a suitable range, and a three-dimensional model with improved molecular orientation of the liquid crystalline resin can be easily produced. The melt viscosity can be adjusted, for example, by adjusting the final polymerization temperature during melt polymerization of the liquid crystalline resin.

[0042] <Modeling Speed> The method for manufacturing a three-dimensional object according to the present embodiment preferably includes controlling the modeling speed, which is the relative movement speed between the nozzle unit and the stage of the three-dimensional modeling apparatus, to a speed faster than 35 mm / sec and slower than 1000 mm / sec (i.e., a speed greater than 35 mm / sec and less than 1000 mm / sec). The modeling speed can be controlled, for example, by inputting a value within the above-mentioned predetermined range as the relative movement speed between the nozzle unit and the stage into software provided with the three-dimensional modeling apparatus, or by inputting the movement speed of the nozzle unit and the movement speed of the stage so that the relative movement speed between the nozzle unit and the stage falls within the above-mentioned predetermined range. In this specification, the term "nozzle unit" refers to a part of a three-dimensional modeling apparatus using a filament melting process, which has a nozzle through which a filament is ejected and is controlled to move freely in three-dimensional space. The term "stage" refers to a base on which a three-dimensional object is formed by stacking filaments in a three-dimensional modeling apparatus using a filament melting process. "Relative movement speed between the nozzle unit and the stage" refers to the relative speed between any one point on the "nozzle unit" and the "stage" during modeling. Among 3D modeling devices using the filament melting method, there are those in which the stage on which the modeled object is formed is stationary and only the nozzle unit that discharges the filament moves during modeling, and those in which not only the nozzle unit that discharges the filament but also the stage on which the modeled object is formed moves during modeling. In either case, the relative movement speed between the nozzle unit and the stage is defined as the modeling speed. More specifically, the relative movement speed V between the nozzle unit and the stage in a 3D modeling device using the filament melting method is defined as follows: V = [(dX ２ +dY ２ +dZ ２ ) １／２] / dt (where dX, dY, and dZ are the movement distances of the stage in the X-axis, Y-axis, and Z-axis directions at any point on the nozzle unit during time dt, respectively.) As described above, due to the characteristics of liquid crystal polymers, liquid crystal resins have a fast solidification rate. Therefore, when molten filaments are stacked in a filament melting process, the layer stacked first tends to solidify. When molten filaments are stacked on a solidified layer, distortion easily occurs, making it difficult to align the molecular orientation of the resin due to stress relaxation. By controlling the above-mentioned modeling speed at a high speed, such as faster than 35 mm / sec and slower than 1000 mm / sec, high shear orientation is easily achieved, and a three-dimensional model can be produced with improved molecular orientation of the liquid crystal resin. This allows for the production of a three-dimensional model with superior properties (e.g., dielectric properties, thermal conductivity, etc.) in desired locations and directions. Furthermore, the high modeling speed shortens modeling time and improves productivity.

[0043] In one embodiment, a method for manufacturing a three-dimensional object by a filament melting process using a filament containing a thermoplastic resin preferably includes controlling a modeling speed, which is the relative movement speed between a nozzle unit and a stage of a three-dimensional modeling device, to a speed faster than 35 mm / sec and slower than 800 mm / sec, more preferably includes controlling it to a speed of 40 mm / sec or more and 700 mm / sec or less, even more preferably includes controlling it to a speed of 45 mm / sec or more and 600 mm / sec or less, and particularly preferably includes controlling it to a speed of 50 mm / sec or more and 500 mm / sec or less. From the viewpoint of obtaining a three-dimensional object having a smooth surface and a more excellent appearance, in addition to having various more excellent properties in desired locations and directions, the method for manufacturing a three-dimensional object preferably includes controlling the modeling speed to a speed faster than 35 mm / sec and slower than 500 mm / sec, more preferably includes controlling the modeling speed to a speed of 40 mm / sec or more and 450 mm / sec or less, even more preferably includes controlling the modeling speed to a speed of 45 mm / sec or more and 300 mm / sec or less, and particularly preferably includes controlling the modeling speed to a speed of 50 mm / sec or more and 200 mm / sec or less.

[0044] <Other Conditions> In one embodiment, the nozzle temperature may be set to, for example, a temperature 5 to 25° C. higher than the melting point Tm2 of the filament. In one embodiment, the discharge speed of the molten filament from the nozzle is not limited, and may be, for example, 0.5 to 10 mm ３ The method for manufacturing a three-dimensional object according to this embodiment may include a step of cooling and drying the three-dimensional object after fabrication, or a step of heat-treating the three-dimensional object at a high temperature at which the three-dimensional object does not substantially deform (for example, a temperature of up to the melting point −10° C.).

[0045] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below: [1] A three-dimensionally shaped object comprising a thermoplastic resin, wherein the thermoplastic resin comprises 55 to 100 mass % (preferably 60 to 100 mass %, more preferably 70 to 100 mass %, even more preferably 80 to 100 mass %, and particularly preferably 90 to 100 mass %) of a liquid crystalline resin relative to the total mass of the thermoplastic resin (100 mass %), the three-dimensionally shaped object is used in an environment where an electric field and / or heat is applied, the thermoplastic resin is molecularly oriented in at least a portion of the three-dimensionally shaped object, and at least one of the directions of the molecular orientation is the direction of an electric field applied to the three-dimensionally shaped object and / or a direction in which heat applied to the three-dimensionally shaped object is dissipated. [2] The three-dimensionally shaped object according to [1], wherein the three-dimensionally shaped object has a plate shape, at least one of the directions of molecular orientation is a thickness direction of the plate shape, and the value of (scattering intensity in the thickness direction / scattering intensity in the plane direction) in two-dimensional wide-angle X-ray diffraction is greater than 1.0 (preferably greater than 2.0, more preferably greater than 3.0, and even more preferably greater than 4.0). [3] The three-dimensionally shaped object according to [1] or [2], wherein the liquid crystalline resin is an aromatic polyester or aromatic polyester amide having, as a constituent component, a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof. [4] A method for producing a three-dimensionally shaped object according to any one of [1] to [3], comprising: modeling the three-dimensionally shaped object by a filament melt-forming method using filaments containing the thermoplastic resin; and the modeling step comprises controlling the printing direction of the filaments to coincide with the direction of molecular orientation.[5] The method for manufacturing a three-dimensional object according to [4], wherein the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament measured with a differential scanning calorimeter is 25 to 60°C (preferably 30 to 60°C, more preferably 30 to 55°C, even more preferably 30 to 50°C, and particularly preferably 30 to 45°C), and the modeling includes controlling a modeling speed, which is the relative movement speed between a nozzle unit and a stage of a three-dimensional modeling device, to a speed faster than 35 mm / sec and slower than 1000 mm / sec. [6] The method for manufacturing a three-dimensional object according to [5], wherein the manufacturing step of the three-dimensional object includes controlling the manufacturing speed to a speed faster than 35 mm / sec and slower than 500 mm / sec (preferably to a speed of 40 mm / sec or more and 700 mm / sec or less, more preferably to a speed of 45 mm / sec or more and 600 mm / sec or less, and even more preferably to a speed of 50 mm / sec or more and 500 mm / sec or less). [7] The method for manufacturing a three-dimensional object according to any of [4] to [6], wherein the diameter of the filament is 0.5 to 3.0 mm (preferably 0.5 to 2.5 mm, more preferably 1.0 to 2.5 mm, and even more preferably 1.0 to 2.0 mm). [8] The method for producing a three-dimensionally shaped object according to any one of [4] to [7], wherein the three-dimensionally shaped object is used in an environment where an electric field and / or heat is applied, and the modeling comprises controlling at least one of the printing directions of the filaments to a direction of an electric field applied to the three-dimensionally shaped object and / or a direction in which heat applied to the three-dimensionally shaped object is dissipated. [9] The method for producing a three-dimensionally shaped object according to any one of [4] to [8], wherein the three-dimensionally shaped object has a plate shape, and the modeling comprises controlling at least one of the printing directions of the filaments to a thickness direction of the plate shape.

[10] The method for producing a three-dimensionally shaped object according to any one of [4] to [9], wherein the liquid crystalline resin is an aromatic polyester or aromatic polyesteramide having, as a constituent component, a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.

[0046] The present invention will be explained in more detail below by showing examples, but interpretation of the present disclosure is not limited to these examples.

[0047] (Preparation of Liquid Crystalline Resin) The following raw material monomers, fatty acid metal salt catalyst, and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen inlet, and vacuum / outlet line, and nitrogen substitution was initiated. Raw material monomers: (I) 4-hydroxybenzoic acid: 1,660 g (73 mol%) (HBA) (II) 6-hydroxy-2-naphthoic acid: 837 g (27 mol%) (HNA) Fatty acid metal salt catalyst: potassium acetate catalyst: 165 mg Acylating agent: acetic anhydride: 1,714 g After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further raised to 325°C over 3.5 hours, and the pressure was reduced to 5 Torr (i.e., 667 Pa) over 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from reduced pressure to normal pressure and then to pressurized pressure, and the polymer was discharged from the bottom of the polymerization vessel and the strands were pelletized.

[0048] [Fabrication of Filaments] [Fabrication Example 1] Using the liquid crystalline resin pellets obtained above, filaments having a diameter of 1.75 mm were fabricated by the following method. The liquid crystalline resin pellets were fed into a single-screw extruder (manufactured by Collin, product name: Teach-Line (registered trademark) E20 T), and extrusion was carried out under the following conditions. The extruded strand was cooled and solidified in a water bath, and then wound on a filament winder at a winding speed such that the filament diameter became 1.75 mm±0.1 mm, thereby obtaining a filament. Barrel temperature: Example 1: 290°C Screw speed: 60 rpm

[0049] The melting point Tm2 and crystallization temperature Tc of the obtained filament were measured by the following method. The results are shown in Table 1. (Melting Point Tm2, ​​Crystallization Temperature Tc) Using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, product name: DSC7000X), the peak top temperature (melting point Tm1) of the endothermic peak observed when heated from room temperature at a heating rate of 20 ° C. / min (1st RUN) was measured, and then the temperature was held at a temperature of (melting point Tm1 + 40) ° C. for 2 minutes, and then cooled to room temperature at a heating rate of 20 ° C. / min. The peak top temperature of the exothermic peak observed when heated again from room temperature at a heating rate of 20 ° C. / min was measured as the melting point Tm2.

[0050] [Example 1] A three-dimensional object was produced using the obtained filament by the following method. The prepared filament was set in a filament melting 3D printer (manufactured by NematX, product name: NEX01), and modeling was performed under the modeling conditions shown in Table 1. Two types of three-dimensional objects were produced for Examples 1 and 2: a 40 mm x 40 mm x 3 mm test piece (hereinafter, Test Piece I) and a 35 mm x 35 mm x 3 mm test piece (hereinafter, Test Piece II). Hereinafter, the "thickness direction of the test piece" refers to the measurement direction of the dielectric loss tangent and thermal conductivity, and is the same direction as the Z direction in Figures 1 and 2. For Example 1, the test piece was modeled so that the thickness direction plane (Y-Z plane) of the test piece was horizontal to the plane of the stage of the 3D printer, the longitudinal direction (X direction) of the test piece was the modeling direction (stacking direction), and the thickness direction (Z direction) of the test piece was the printing direction. For Comparative Example 1, the test piece was modeled so that the longitudinal surface (X-Y surface) of the test piece was horizontal to the plane of the 3D printer stage, the thickness direction (Z direction) of the test piece was the modeling direction, and the longitudinal direction (X direction) of the test piece was the printing direction. In the modeling method shown in Figures 1 and 2, symbol B indicates the printing direction, which is the direction in which the nozzle unit moves, and symbol A indicates the end of the filament. In Figure 1, the thickness direction surface (Y-Z surface) of the test piece I is formed on the plane of the 3D printer stage as the first layer. After the first layer is formed, the thickness direction surface (Y-Z surface) of the test piece I is further formed on top of it as the second layer. This is repeated until a predetermined height (test piece width) is reached in the X direction, thereby modeling the test piece I. In Figure 2, the main surface (X-Y surface) of the test piece I is formed on the plane of the 3D printer stage as the first layer. After the first layer is formed, the main surface (X-Y surface) of the test piece I is further formed on top of it as the second layer. This process is repeated in the Z direction until a predetermined height (thickness of the test piece) is reached, thereby forming the test piece I.

[0051] [Comparative Example 1] The above liquid crystalline resin pellets were molded using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to prepare test pieces I and II having the same shapes as those of Example 1 and Comparative Example 1. [Molding conditions] Cylinder temperature: 300°C Mold temperature: 80°C Injection speed: 33 mm / sec

[0052] (Thickness direction scattering intensity / plane direction scattering intensity) For each test piece I of Example 1 and Comparative Examples 1 and 2, an X-ray diffractometer (D8 Discover, manufactured by Bruker) was used to calculate the ratio of the thickness direction scattering intensity to the plane direction (direction perpendicular to the thickness direction) scattering intensity from the two-dimensional intensity profile obtained by wide-angle X-ray diffraction. The value of the thickness direction scattering intensity / plane direction scattering intensity indicates the degree of molecular orientation, with a larger value indicating a higher degree of molecular orientation in the thickness direction. The results are shown in Table 1.

[0053] (Evaluation of Dielectric Loss Tangent) For each test piece I, measurement was performed in accordance with IEC 62631-2-1 using a Concept 42 measurement system manufactured by Novocontrol Technologies (Montabaur, Germany). Each sample, with Dotite (Fujikura Chemical Industries, Ltd., "D-500") applied to the surface of the test piece, was placed between two optically polished brass disks (diameter 36 mm), and the dielectric loss tangent at 23°C and 1 MHz was measured in the thickness direction of the test piece (Z direction in Figures 1 and 2). The results are shown in Table 1.

[0054] (Thermal Conductivity) For each test piece II, the thermal conductivity was measured at 23°C in the thickness direction of the test piece (Z direction in Figs. 1 and 2) using a hot disc method thermal property measuring device (manufactured by Kyoto Electronics Manufacturing Co., Ltd., "TPA-501") by the hot disc method in accordance with ISO 22007-2. The results are shown in Table 1.

[0055]

[0056] As shown in Table 1, the values ​​of (thickness direction scattering intensity / plane direction scattering intensity) indicate that the three-dimensionally shaped object of Example 1 exhibited molecular orientation in the thickness direction (Z direction in FIGS. 1 and 2 ), while the three-dimensionally shaped object of Comparative Example 1 exhibited molecular orientation in the length direction of the main surface (X direction in FIGS. 1 and 2 ). In other words, it can be seen that the three-dimensionally shaped objects of Examples satisfying the configuration of this embodiment exhibited more controlled molecular orientation. Because the molecular orientation was controlled, it was possible to produce a three-dimensionally shaped object that exhibited excellent properties in desired locations and directions, such as a low dielectric loss tangent and high thermal conductivity, as shown in Table 1. Comparing the dielectric loss tangent and thermal conductivity measured in the thickness direction (Z direction in FIGS. 1 and 2 ) of the test specimens, the three-dimensionally shaped object of Example 1, which exhibited molecular orientation in the thickness direction, exhibited a lower dielectric loss tangent and a higher thermal conductivity than the three-dimensionally shaped object of Comparative Example 1, which exhibited molecular orientation in the length direction of the main surface (low molecular orientation in the thickness direction). In other words, a lower dielectric loss tangent was achieved by aligning the direction of molecular orientation with the direction of the electric field applied to the three-dimensionally shaped object. Furthermore, by aligning the molecular orientation in the desired direction of heat dissipation, higher thermal conductivity was achieved. For example, the three-dimensionally shaped object of Example 1 had a thermal conductivity 1.6 times (60% higher) than that of the three-dimensionally shaped object of Comparative Example 1. This is due to the molecular orientation of the thermoplastic resin in the thickness direction (Z direction in Figures 1 and 2 ) of the three-dimensionally shaped object of the Example, and is consistent with the value (thickness direction scattering intensity / plane direction scattering intensity), which is an indicator of molecular orientation in the thickness direction. It can be seen that the three-dimensionally shaped object of the Example satisfying the configuration of this embodiment has more controlled molecular orientation, thereby exhibiting low dielectric tangent and high thermal conductivity characteristics more strongly in specific locations and directions. In other words, the method of the Example satisfying the configuration of this embodiment can produce a three-dimensionally shaped object with more controlled molecular orientation. In other words, by using the method of the example that satisfies the configuration of this embodiment, it is possible to control the molecular orientation within the same object, and therefore the direction of the electric field applied to the three-dimensional object and the direction in which heat is desired to be dissipated coincide with the length direction of the test piece, rather than the thickness direction of the test piece, and it is easy to understand that the three-dimensional object of the example can exhibit better dielectric properties and thermal conductivity.

[0057] The three-dimensionally shaped object of the present embodiment is a three-dimensionally shaped object in which the molecular orientation is more controlled, and therefore the characteristics of a thermoplastic resin including a liquid crystalline resin, such as the dielectric properties and thermal conductivity, are more controlled, and therefore the three-dimensionally shaped object can be suitably used as various components, etc., and has industrial applicability. The method for producing a three-dimensionally shaped object of the present embodiment can obtain a three-dimensionally shaped object in which the molecular orientation is controlled, and therefore the method can be suitably used for producing three-dimensionally shaped objects, and has industrial applicability.

[0058] 1 Test piece A Filament end B Double arrow indicating printing direction

Claims

1. A three-dimensionally shaped object comprising a thermoplastic resin, wherein the thermoplastic resin contains 55 to 100% by mass of a liquid crystalline resin in the entire thermoplastic resin, the three-dimensionally shaped object being used in an environment where an electric field and / or heat is applied, the thermoplastic resin is molecularly oriented in at least a portion of the three-dimensionally shaped object, and at least one of the directions of the molecular orientation is the direction of an electric field applied to the three-dimensionally shaped object and / or a direction in which heat applied to the three-dimensionally shaped object is dissipated.

2. The three-dimensional structure according to claim 1, wherein the three-dimensional structure has a plate shape, at least one of the directions of molecular orientation is a thickness direction of the plate shape, and in two-dimensional wide-angle X-ray diffraction, the value of (scattering intensity in the thickness direction / scattering intensity in the surface direction) is greater than 1.

0.

3. The three-dimensional object according to claim 1 or 2, wherein the liquid crystalline resin is an aromatic polyester or aromatic polyester amide having, as a constituent component, a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.

4. A method for manufacturing a three-dimensional object according to claim 1, comprising: forming the three-dimensional object by a filament melting process using a filament containing the thermoplastic resin; and the forming comprises controlling the printing direction of the filament in the direction of molecular orientation.

5. The method for manufacturing a three-dimensional object according to claim 4, wherein the difference (Tm2 - Tc) between the melting point Tm2 and the crystallization temperature Tc of the filament measured with a differential scanning calorimeter is 25 to 60°C, and the modeling includes controlling the modeling speed, which is the relative movement speed between the nozzle part and the stage of the three-dimensional modeling device, to a speed faster than 35 mm / sec and slower than 1000 mm / sec.

6. The method for manufacturing a three-dimensional object according to claim 5, wherein the forming step includes controlling the forming speed to a speed faster than 35 mm / sec and slower than 500 mm / sec.

7. The method for producing a three-dimensional object according to claim 4 or 5, wherein the filament has a diameter of 0.5 to 3.0 mm.

8. The method for manufacturing a three-dimensional object according to claim 4 or 5, wherein the three-dimensional object is used in an environment where an electric field and / or heat is applied, and the modeling includes controlling at least one of the printing directions of the filament to the direction of the electric field applied to the three-dimensional object and / or the direction in which the heat applied to the three-dimensional object is dissipated.

9. The method for manufacturing a three-dimensional object according to claim 4 or 5, wherein the three-dimensional object has a plate shape, and the forming includes controlling at least one of the printing directions of the filament to a thickness direction of the plate shape.

10. A method for producing a three-dimensional object according to claim 4 or 5, wherein the liquid crystalline resin is an aromatic polyester or aromatic polyester amide having, as a constituent component, a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.

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