Resin composition for three-dimensional printer filament

Abstract

To provide a resin composition for a three-dimensional printer filament that has a certain level of a heat resistance and fluidity suitable for additive manufacturing.SOLUTION: There is provided a resin composition for three-dimensional printer filament, comprising: an acrylonitrile-styrene-butadiene resin; a first amide compound; and a second amide compound, wherein the first amide compound is an amide compound containing two or less amide bonding, the second amide compound is a polyamide compound containing a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms as a raw material, a content of the first amide compound is 1 to 2 pts.mass and a content of the second amide compound is 0.2 to 1.2 pts.mass based on 100 pts.mass of the acrylonitrile-styrene-butadiene resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition for 3D printer filaments. [Background technology]

[0002] 3D printers are a type of additive manufacturing machine that uses 3D data created on a computer, such as CAD or CG, as blueprints to produce three-dimensional objects made of plastic or other materials.

[0003] Generally, 3D printers are classified by the deposition method, and known methods include binder jetting, fused deposition modeling, liquid vat photopolymerization, and powder sintering (SLS or SLM) methods.

[0004] 3D printers use resin materials to create additively manufactured objects. For example, in fused deposition modeling (FDM), filaments of thermoplastic resin are used as the material. These filaments are melted and extruded from the nozzle of the 3D printer, layering them to form the desired shape. Polylactic acid resin (PLA resin) and acrylonitrile-styrene-butadiene resin (ABS resin) are commonly used as FDM 3D printer filaments. ABS resin is easy to use to create additively manufactured objects with excellent heat resistance and has good post-processing properties, but warping often occurs during modeling. Therefore, a filament made of a thermoplastic resin, a thermoplastic elastomer, and talc has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2021 / 060278 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the resin composition of Patent Document 1 has poor fluidity, and a resin composition with fluidity more suitable for additive manufacturing is desired. Reducing the molecular weight of the ABS resin to improve fluidity makes the filament brittle, causing problems such as breakage during molding, making it unsuitable for practical use. Furthermore, when a compound that increases fluidity is added, the heat resistance decreases as the amount of the compound added increases. Therefore, an objective of the present disclosure is to provide a resin composition for 3D printer filaments that has a certain level of heat resistance and fluidity suitable for additive manufacturing. [Means for solving the problem]

[0007] As a result of extensive research, the inventors of the present application have discovered that the above-mentioned problems can be solved by blending specific amounts of an amide compound containing two or less amide bonds and a polyamide compound containing, as a raw material, a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms, and have thus completed the present invention. That is, the present disclosure includes the following aspects. [1] A resin composition for 3D printer filaments, comprising an acrylonitrile-styrene-butadiene resin, a first amide compound, and a second amide compound, the first amide compound is an amide compound containing two or less amide bonds; the second amide compound is a polyamide compound containing, as a raw material, a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms; A resin composition for 3D printer filaments, wherein the content of the first amide compound is 1 to 2 parts by mass and the content of the second amide compound is 0.2 to 1.2 parts by mass relative to 100 parts by mass of the acrylonitrile-styrene-butadiene resin. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a resin composition for 3D printer filaments that has a certain level of heat resistance or higher and fluidity suitable for additive manufacturing. DETAILED DESCRIPTION OF THE INVENTION

[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] [Resin composition for 3D printer filaments] The resin composition for 3D printer filaments in this embodiment includes an acrylonitrile-styrene-butadiene resin, a first amide compound, and a second amide compound, where the first amide compound is an amide compound containing two or less amide bonds, and the second amide compound is a polyamide compound containing a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms as a raw material, and the content of the first amide compound is 1 to 2 parts by mass and the content of the second amide compound is 0.2 to 1.2 parts by mass per 100 parts by mass of the acrylonitrile-styrene-butadiene resin. The resin composition for 3D printer filaments in this embodiment has a certain level of heat resistance and a flowability suitable for additive manufacturing.

[0011] <Acrylonitrile-styrene-butadiene resin (ABS resin)> The ABS resin preferably contains butadiene in an amount of 12 to 22 mass %, more preferably 16 to 20 mass %, relative to the total mass of the ABS resin. The ABS resin may also be a mixture of two or more types of ABS resin.

[0012] In one embodiment, the ABS resin preferably has an MFR (220°C, 10 kg load) of 20 to 40 g / 10 min, more preferably 20 to 35 g / 10 min, and even more preferably 20 to 30 g / 10 min. Using an ABS resin with such an MFR (220°C, 10 kg load) improves high-speed molding. When two or more types of ABS resins are used, the blending ratio of each ABS resin may be adjusted so that the MFR (220°C, 10 kg load) of the resulting ABS resin blend falls within the above-mentioned range. For example, an ABS resin 1 with an MFR (220°C, 10 kg load) of 15 to 50 g / 10 min and an ABS resin 2 with an MFR (220°C, 10 kg load) of 5 to 15 g / 10 min may be combined in a ratio of ABS resin 1:ABS resin 2 of 3 to 7:7 to 3.

[0013] In one embodiment, the mass-average molecular weight (Mw) of the ABS resin is preferably 90,000 to 140,000, from the viewpoint of easily ensuring the fluidity required for 3D printing. Furthermore, from the viewpoint of easily obtaining a 3D-modeled object with good impact resistance and heat resistance, the Mw may be 100,000 to 150,000. Two or more ABS resins with different Mws may be mixed to achieve the fluidity, heat resistance, impact resistance, and other properties. When two or more ABS resins are mixed, it is preferable to adjust the average Mw of the mixture to fall within the aforementioned range (e.g., 100,000 to 140,000). Furthermore, when using a single ABS resin, it is particularly preferable to use an ABS resin with a Mw of 100,000 to 140,000, from the viewpoint of the fluidity, heat resistance, and impact resistance. The Mw of the resin refers to a value measured using GPC, using THF as the solvent, at 40°C, and converted into polystyrene as the standard.

[0014] The proportion of ABS resin in the resin composition for 3D printer filaments is preferably 50% by mass or more, and more preferably 80% by mass or more, relative to the total mass of the resin composition for 3D printer filaments.

[0015] <First amide compound> In this embodiment, the first amide compound is an amide compound containing two or less amide bonds. Examples of the amide compound containing two or less amide bonds include monoamides and bisamides. Among them, bisamides are preferably used. Examples of the monoamide that can be used include lauric acid amide, palmitic acid amide, stearic acid amide, purified stearic acid amide, hydroxystearic acid amide, erucic acid amide, N-substituted stearic acid amide, and N-substituted erucic acid amide. Examples of bisamides that can be used include saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, and N,N'-distearyl adipic acid amide; and unsaturated fatty acid bisamides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, and N,N'-dioleyl adipic acid amide. In this embodiment, the content of the first amide compound is 1 to 2 parts by mass per 100 parts by mass of ABS resin. The content of the first amide compound is more preferably 1.1 to 1.9 parts by mass, and even more preferably 1.2 to 1.8 parts by mass. Setting the content of the first amide compound to 1 part by mass or more contributes to achieving an appropriate fluidity for the resin composition for 3D printer filaments, while setting it to 2 parts by mass or less allows the compound content in the resin composition for 3D printer filaments to be kept below a certain level.

[0016] <Second amide compound> In this embodiment, the second amide compound is a polyamide compound containing, as a raw material, a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms. Among them, a polyamide compound containing, as a raw material, 12-hydroxy-substituted stearic acid can be preferably used. In one embodiment, the second amide compound may be a polyamide compound containing, as raw materials, an aliphatic diamine having 2 to 10 carbon atoms and / or an aromatic diamine having 6 to 10 carbon atoms, a linear polybasic acid having 12 to 36 carbon atoms, and a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms. The content of the second amide compound is 0.2 to 1.2 parts by mass per 100 parts by mass of ABS resin. The content of the second amide compound is more preferably 0.2 to 0.9 parts by mass, and even more preferably 0.3 to 0.8 parts by mass. Setting the content of the second amide compound to 0.2 parts by mass or more contributes to achieving an appropriate fluidity for the resin composition for 3D printer filaments, while setting it to 1.2 parts by mass or less allows the compound content in the resin composition for 3D printer filaments to be kept below a certain level.

[0017] <Plate-shaped particles> In one embodiment, the resin composition for 3D printer filaments contains plate-like particles. The content of the plate-like particles is preferably 5 to 30 parts by mass, more preferably 8 to 25 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of ABS resin. By setting the content of the plate-like particles to 5 parts by mass or more, a resin composition that can produce an additive manufacturing product with reduced warpage can be obtained, and by setting the content to 30 parts by mass or less, deterioration of the flowability of the resin composition for 3D printer filaments can be suppressed.

[0018] Here, "plate-like particles" refers to particles that are thin and have an aspect ratio of 1.0 or more. Therefore, plate-like particles may include particles other than spherical particles, such as those described as scaly particles, rod-like particles, or needle-like (fibrous) particles. In a preferred embodiment, the plate-like particles include scaly particles such as talc, clay (kaolin, bentonite), and mica. Whether the particles in the resin composition are plate-like particles can be determined, for example, by observing the particles (100 or more) contained in the resin composition according to this embodiment with an electron microscope such as an SEM and determining whether more than 50% by number of particles have a thin thickness and an aspect ratio of 1.0 or more. In one embodiment, the aspect ratio of the plate-like particles may be 10-90, 10-80, or 20-70.

[0019] In one embodiment, the particles constituting the plate-like particles (hereinafter sometimes referred to as "raw material particles") preferably have a Mohs hardness of 3 or less. "Mohs hardness" is a hardness index expressed on a scale of 1 to 10. The "Mohs hardness" is a value obtained by rubbing a material to be measured against a corresponding standard material and evaluating the relative hardness of the material relative to the standard material based on whether scratches are produced. The standard materials, in order from softest (Mohs hardness 1) to hardest (Mohs hardness 10), are 1: talc, 2: gypsum, 3: calcite, 4: fluorite, 5: apatite, 6: feldspar, 7: quartz, 8: topaz, 9: corundum, and 10: diamond. The Mohs hardness is measured by preparing two smooth plates with known Mohs hardness, sandwiching the foreign material to be measured between the two plates, and rubbing the two plates together to check for scratches on the plate surface. The Mohs hardness of the raw material particles for the plate-like particles is more preferably 2 or less, and even more preferably 1 or less.

[0020] In one embodiment, the plate-like particles are preferably particles with a low content of crystalline silica or particles that are substantially free of crystalline silica. By combining such plate-like particles with the aforementioned ABS resin and setting the proportion of crystalline silica in the resin composition to a certain value or less, the nozzle of a 3D printer is prevented from wearing out and warping during modeling is easily suppressed. More specifically, "particles with a low content of crystalline silica or particles that are substantially free of crystalline silica" refers to particles in which the crystalline silica content is less than 0.2% by mass or in which substantially no crystalline silica is detected when measured by the X-ray diffraction method described below.

[0021] The content of crystalline silica in the plate-like particles can be measured by X-ray diffraction (base standard absorption correction method). Specifically, first, a qualitative analysis of free silica in the plate-like particles is performed using an X-ray diffraction analyzer. At this time, quartz, cristobalite, and tridymite (manufactured by the Japan Working Environment Measurement Association, a public interest incorporated association) are used as standard samples for free silica analysis. Then, a quantitative analysis of the crystalline silica in the plate-like particles is performed by X-ray diffraction (base standard absorption correction method). The measurement conditions for the X-ray diffraction method are as follows: Measurement device: X-ray generator (for example, Rigaku Corporation's tabletop rotating anode X-ray generator, product name "ultrax18") Target: Cu Scanning angle: 5°~60° Step width: 0.02 degrees Measurement time: 0.6 seconds Tube voltage: 40kV Tube current: 30mA Divergence slit: 1.00 degrees, scattering slit: 1.00 degrees, receiving slit: 0.3 mm

[0022] The detection limit for the crystalline silica content in the plate-like particles under the above measurement conditions is 0.1% by mass. The crystalline silica content of common talc and mica measured by the above method is about 1% by mass. In one embodiment, the plate-like particles have a lower crystalline silica content than common talc or mica. In a preferred embodiment, the crystalline silica content in the plate-like particles is less than 0.2% by mass, and in a more preferred embodiment, it is 0.1% by mass or less. In a further preferred embodiment, the plate-like particles are at least one particle selected from talc, mica, and clay, in which crystalline silica is not detected under the above measurement conditions.

[0023] The proportion of crystalline silica relative to the total mass of the resin composition is preferably less than 0.02% by mass, which can suppress warping during modeling and also helps to suppress wear on the nozzle of the 3D printer. The proportion of crystalline silica in the resin composition may be 0.015% by mass or less, or may be 0.01% by mass or less, from the viewpoint of more easily suppressing nozzle wear. Furthermore, it is preferable that no crystalline silica is detected when measured under the above-mentioned conditions for measuring the content of crystalline silica in the plate-like particles. The proportion of crystalline silica in the resin composition may be determined by heating the resin composition at 500°C in a nitrogen atmosphere to incinerate it, and then measuring the proportion of crystalline silica in the resulting residue under the above-mentioned conditions. Alternatively, the proportion of crystalline silica in the resin composition may be calculated from the content of crystalline silica in the plate-like particles.

[0024] (Average particle diameter (D50)) In one embodiment, the average particle size (D50) of the plate-like particles is less than 2 μm. In one embodiment, the average particle size (D50) of the plate-like particles is preferably 0.5 μm to 1.8 μm, more preferably 0.5 μm or more but less than 1.5 μm, even more preferably 0.5 to 1.3 μm, even more preferably 0.5 μm or more but less than 1 μm, and particularly preferably 0.5 μm to 0.8 μm. In one embodiment, the average particle size (D50) of the plate-like particles may be 0.1 μm or more but less than 2 μm, 0.1 μm to 1.8 μm, 0.1 μm or more but less than 1.5 μm, 0.1 μm or more but less than 1.3 μm, 0.1 μm or more but less than 1 μm, or 0.1 μm to 0.8 μm. If the average particle diameter (D50) is within the above range, the increase in storage modulus during mixing is small, so that filaments do not break during production, and productivity is likely to be good. Furthermore, it is possible to produce layered objects with reduced surface irregularities. The average particle diameter (D50) of plate-like particles refers to the volume-based cumulative diameter (D50) evaluated by laser diffraction scattering. Furthermore, "volume-based cumulative diameter (D50)" refers to the particle diameter corresponding to a cumulative value of 50% in the volume-based cumulative particle size distribution measured by laser diffraction scattering. The cumulative particle size distribution is represented by a distribution curve with particle diameter (μm) on the horizontal axis and cumulative value (%) on the vertical axis.

[0025] (Surface treatment agent) In one embodiment, the plate-like particles are treated with a surface treatment agent. The plate-like particles may be treated with one or more surface treatment agents selected from the group consisting of a silane coupling agent (X) and hexamethyldisilazane (HMDS). "Treated with a surface treatment agent" means that at least a portion of the surface of the plate-like particles is coated with the surface treatment agent. Treating the plate-like particles with a surface treatment agent to render the plate-like particles hydrophobic improves particle dispersibility, more effectively suppressing warpage during modeling, and also improves high-speed modeling capabilities. In the present disclosure, "high-speed modeling capabilities" refers to the ability to manufacture an additively manufactured object at a modeling speed of, for example, 80 to 150 mm / s. Resin materials with poor high-speed modeling capabilities may experience uneven discharge at the above-mentioned modeling speeds, or may develop holes or other defects in the appearance of the resulting additively manufactured object. By using particles whose surfaces have been treated with a surface treatment agent as the plate-like particles, additively manufactured objects with excellent appearances can be more easily manufactured at high speeds.

[0026] The silane coupling agent (X) is not particularly limited, but in one embodiment, silane coupling agents containing functional groups such as vinyl groups, amino groups, styryl groups, epoxy groups, and mercapto groups in the structure may be used alone or in combination of two or more.

[0027] Examples of silane coupling agents containing a vinyl group in the structure (vinyl-based silane coupling agents) include vinyltrimethoxysilane, vinyltriethoxysilane, etc. These may be used alone or in combination of two or more.

[0028] Examples of silane coupling agents containing an amino group in the structure (amino-based silane coupling agents) include N-2-(aminoethyl)-3-aminopropylmethyldimethoxylane, N-2-(aminoethyl)-3-aminopropylmethyltrimethoxylane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0029] Examples of silane coupling agents containing an epoxy group in their structure (epoxy-based silane coupling agents) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0030] Examples of silane coupling agents containing a styryl group in the structure (styryl-based silane coupling agents) include p-styryltrimethoxysilane.

[0031] Examples of silane coupling agents containing a mercapto group in the structure (mercapto-based silane coupling agents) include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0032] In one embodiment, the silane coupling agent (X) is preferably a silane coupling agent containing an amino group or an epoxy group in its structure, and more preferably a silane coupling agent containing an epoxy group (epoxy-based silane coupling agent). In a particularly preferred embodiment, the silane coupling agent (X) can contain 3-glycidoxypropyltrimethoxysilane. It is believed that the inclusion of plate-like particles having a Mohs hardness of 3 or less and having their surfaces treated with such a silane coupling agent (X) facilitates the development of adhesiveness derived from the functional groups, preferably epoxy groups, in the silane coupling agent (X), and thus further reduces warpage. It is also believed that the reaction between the carbonyl groups derived from the oxidation of the ABS resin and the functional groups (preferably amino groups or epoxy groups) in the silane coupling agent (X) further reduces thermal shrinkage.

[0033] In one embodiment, when the plate-like particles are surface-treated with a surface treatment agent, the amount of the surface treatment agent added to the plate-like particles may be 0.1 to 3 mass %, 0.1 to 2 mass %, 0.5 to 1.5 mass %, or 0.5 to 1 mass %, relative to the total mass (100 mass %) of the plate-like particles. By setting the proportion of the surface treatment agent within the above range, the effect of suppressing warpage during molding can be more easily obtained. As the plate-like particles whose surfaces are treated with a surface treatment agent, it is preferable to use at least one selected from the aforementioned talc, mica, and clay, each having a crystalline silica content of less than 0.2% by mass, and it is more preferable to use talc and / or mica. By using such plate-like particles, it becomes easier to obtain a resin composition that does not wear out the nozzle of a 3D printer, can suppress warping during modeling, and can be easily modeled at high speed.

[0034] The method for treating the surfaces of the raw material particles with the surface treatment agent is not particularly limited, and a general method can be adopted, such as dissolving the surface treatment agent in an organic solvent such as ethanol, spraying the solution onto the raw material particles, and heating the mixture while stirring. Whether the surfaces of the plate-like particles have been treated with a surface treatment agent may be determined by analyzing the surfaces of the plate-like particles in the resin composition with TEM-EDX and detecting Si elements.

[0035] Commercially available products such as "FG-15," "D-1000," and "D-800" manufactured by Nippon Talc Co., Ltd. may be used as the plate-like particles.

[0036] <Other ingredients> The resin composition according to this embodiment may contain components other than the above-described components (other components) within a range that does not impair the effects of the present disclosure. Examples of other components include thermoplastic resins other than ABS resin (e.g., PLA resin, PC resin, etc.); inorganic particles other than plate-like particles; polymer fillers; and additives such as ultraviolet absorbers, stabilizers, antioxidants, plasticizers, colorants, tinting agents, flame retardants, antistatic agents, fluorescent brighteners, matting agents, impact strength improvers, and lubricants (e.g., fatty acid esters, higher alcohols, ethylene bisstearic acid amide, etc.). These may be used alone or in combination of two or more. When the resin composition contains other components, they may be blended in an amount of 2 mass% or less relative to the total mass of the resin composition.

[0037] <Physical properties of resin composition for 3D printer filament> In one embodiment, from the viewpoint of being more excellent in high-speed modeling and easily producing a resin composition with good warpage suppression, the MFR (220 ° C., 10 kg load) of the resin composition for 3D printer filaments is preferably 24 g / 10 min or more and 40 g / 10 min or less, more preferably 25 g / 10 min or more and 35 g / 10 min or less, and even more preferably 26 g / 10 min or more and 33 g / 10 min or less. The MFR (220 ° C., 10 kg load) of the resin composition can be measured in accordance with JIS K7210 using an MFR / MVR measuring device such as "Melt Indexer G-02" manufactured by Toyo Seiki Seisakusho Co., Ltd.

[0038] In one embodiment, the resin composition for 3D printer filaments has a storage modulus of 10 or more as measured by viscoelasticity measurement, from the viewpoint of heat resistance. 7 The temperature at which the temperature reaches 100°C or higher is preferably 110°C or higher, and more preferably 120°C or higher. 7 The temperature at which the thermal shrinkage stress is reached is preferably 100°C or higher and 140°C or lower, and more preferably 100°C or higher and 130°C or lower, from the viewpoint of reducing the thermal shrinkage stress. The storage modulus by viscoelasticity measurement can be measured, for example, using a viscoelasticity evaluation device "RSA-GA" (manufactured by TA Instruments) in accordance with JIS K7244-1:1998, with the temperature rising from 50°C to 140°C at a rate of 3°C / min, a frequency of 10Hz, a strain of 0.03%, a sample shape of 5mm x 50mm x 0.3mm, and a chuck distance of 15mm. 7 The heat resistance can be evaluated based on the temperature at which the tensile strength becomes equal to or less than 100 kJ / cm 2 .

[0039] [Method of manufacturing resin composition for 3D printer filament] The method for producing the resin composition for 3D printer filaments according to this embodiment is not particularly limited as long as it achieves the effects of the present invention, and examples include a method in which an ABS resin, a first amide compound, a second amide compound, and, if necessary, other components are mixed in a twin-screw kneader or the like, and then extruded into a desired shape to obtain a resin composition. When the resin composition is molded into a filament, the kneader preferably includes a strand spooler, a gear pump, or the like for producing the filament. In one embodiment, when a twin-screw kneader (for example, "Process 11" (manufactured by Thermo Fisher Scientific)) is used, mixing can be performed under the following conditions: set temperature: 200 to 220°C, discharge rate: 30 to 40 kg / hr, and rotation speed: 250 to 350 rpm.

[0040] In one embodiment, the method for producing a resin composition for a 3D printer filament may include preparing plate-like particles, i.e., treating raw material particles with the surface treatment agent to obtain plate-like particles, and mixing an ABS resin, a first amide compound, a second amide compound, and the plate-like particles, followed by extruding the mixture into a desired shape to obtain the resin composition for a 3D printer filament.

[0041] [Layered objects] The additively manufactured object according to this embodiment is formed using as a raw material a resin composition for 3D printer filaments that contains plate-like particles. That is, the additively manufactured object according to this embodiment includes a resin composition for 3D printer filaments that contains plate-like particles. In a preferred embodiment, the additively manufactured object is composed solely of the resin composition according to this embodiment. Such additively manufactured objects exhibit little warping. Therefore, the additively manufactured object according to this embodiment can be suitably used for applications such as stationery; toys; covers for electronic devices such as smartphones; parts such as grips; educational materials, repair parts for home appliances and office automation equipment; various parts for automobiles, motorcycles, bicycles, etc.; building materials; and plastic shaping molds.

[0042] In one embodiment, the warpage of the layered object is preferably less than 1 mm, more preferably 0.7 mm or less, and even more preferably 0.5 mm or less. The warpage of the layered object is the maximum value of the gap (amount of lift) between the bottom surface of the layered object and a horizontal plate when the layered object (for example, an evaluation sample plate 200 mm wide x 50 mm long x 4 mm thick) is placed on the horizontal plate. The warpage can be determined by measuring the distance of the gap between the layered object and the horizontal plate with a curved ruler at a point where the bottom of the layered object is separated from the horizontal plate and lifts.

[0043] In one embodiment, the arithmetic mean height of the surface of the layered object is preferably less than 40 μm, more preferably less than 30 μm, and even more preferably less than 20 μm. The arithmetic mean height of the surface of the layered object can be measured using a 3D measuring laser microscope (for example, "LEXT OLS5100" manufactured by Evident Co., Ltd.) in accordance with ISO 25178.

[0044] [Layered manufacturing method] A method for producing an additive manufacturing method for an additive manufacturing method according to an embodiment of the present disclosure uses a resin composition containing an ABS resin, a first amide compound, a second amide compound, and plate-like particles as a raw material. In a preferred embodiment, the raw material resin is composed solely of the resin composition according to this embodiment. The manufacturing method according to this embodiment includes melting the resin composition and extruding the molten resin composition from a nozzle to form an additive manufacturing object. The manufacturing method according to this embodiment is preferably a method for manufacturing an additive manufacturing object using an FDM 3D printer. When the resin composition according to this embodiment is used as a raw material resin for an FDM 3D printer, it is used in the form of a filament.

[0045] FDM 3D printers generally have a heatable substrate (modeling table), an extrusion head (nozzle), a heat melter, a filament guide, a filament installation, and other material supply units. Some FDM 3D printers have an integrated nozzle and heat melter.

[0046] The nozzle is installed in a gantry structure, allowing it to move freely on the XY plane of the substrate. The substrate is a platform for constructing the desired three-dimensional object, support material, etc. The substrate configuration is not particularly limited, but a configuration that can be heated and kept warm is preferable from the perspective of easily improving the adhesion and dimensional stability of the laminate. Typically, at least one of the nozzle and the substrate is movable in the Z-axis direction, which is perpendicular to the XY plane.

[0047] In a preferred embodiment, a filament made of the resin composition of this embodiment is unwound from a raw material supply unit and fed into a nozzle by a pair of opposing rollers or gears. It is then heated and melted in the nozzle, and the molten filament is extruded from the tip of the nozzle. The nozzle moves in response to a signal transmitted based on a CAD model, supplying and stacking the molten filament onto a substrate to form an additive manufacturing object. After this process is complete, the laminate is removed from the substrate, and the desired additive manufacturing object can be obtained by peeling off support materials or cutting off excess portions as needed.

[0048] The filament may be supplied to the nozzle by unwinding it, for example. It is preferable that the filament be stored in a cartridge wound into a bobbin, from the viewpoints of stable unwinding, protection from environmental factors such as humidity, and prevention of twisting and kinking.

[0049] A preferred method for feeding the filament to the nozzle while unwinding it is to engage the filament with a driving roll such as a nip roll or a gear roll, and feed the filament to the nozzle while drawing it up. From the viewpoint of stabilizing the filament feeding by more firmly gripping the filament by the engagement between the filament and the driving roll, a fine concave-convex pattern may be transferred onto the surface of the filament.

[0050] In the manufacturing method according to the present embodiment, the nozzle temperature is preferably set to 220 to 260° C., more preferably 230 to 260° C., to melt the filaments made of the resin composition. The substrate temperature is preferably set to 110° C. or lower, more preferably 90° C. or higher and 110° C. or lower.

[0051] Furthermore, since the resin composition according to this embodiment has excellent high-speed modeling properties, the modeling speed can be set high. In one embodiment, the modeling speed may be 20 to 120 mm / s. In another embodiment, the modeling speed may be 80 to 150 mm / s.

[0052] In one embodiment, from the viewpoint of obtaining a layered object with less warping, the temperature of the atmosphere inside the 3D printer during modeling is preferably room temperature to 50°C, and more preferably 30 to 40°C.

[0053] Another embodiment of the present disclosure is a use of the aforementioned resin composition as a resin raw material (filament) for an additive manufacturing object produced using a 3D printer, or a method of using the same. A method for using the resin composition according to this embodiment as a resin raw material (filament) for a 3D printer includes, for example, obtaining a resin composition by the aforementioned method for producing a resin composition, supplying the resin composition to a 3D printer, and extruding the resin composition from a nozzle while melting it to form an additive manufacturing object.

[0054] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure are disclosed below. [1] A resin composition for 3D printer filaments, comprising an acrylonitrile-styrene-butadiene resin, a first amide compound, and a second amide compound, the first amide compound is an amide compound containing two or less amide bonds; the second amide compound is a polyamide compound containing, as a raw material, a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms; A resin composition for 3D printer filaments, wherein the content of the first amide compound is 1 to 2 parts by mass and the content of the second amide compound is 0.2 to 1.2 parts by mass relative to 100 parts by mass of the acrylonitrile-styrene-butadiene resin. [2] The resin composition for 3D printer filaments according to [1], wherein the hydroxy-substituted aliphatic monocarboxylic acid includes 12-hydroxy-substituted stearic acid. [3] The resin composition for 3D printer filaments according to [1] or [2], wherein the first amide compound includes a bisamide compound. [4] The storage modulus measured by viscoelasticity measurement is 10 7The resin composition for 3D printer filaments according to any one of [1] to [3], wherein the temperature at which the temperature reaches Pa is 120°C or higher. [5] The resin composition for 3D printer filaments according to any one of [1] to [4], further comprising plate-like particles. [6] The resin composition for 3D printer filaments described in [5], wherein the plate-like particles contain talc with an average particle diameter of less than 2 μm. [7] A 3D printer filament comprising the resin composition for a 3D printer filament according to [5] or [6]. [8] [7] An additively manufactured object made from the 3D printer filament described in [7]. The configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope that does not deviate from the gist of this disclosure. [Example]

[0055] The present disclosure will be explained in more detail below by showing examples, but interpretation of the present disclosure is not limited to these examples.

[0056] <Raw materials> (ABS resin) ABS resin 1: "GR0500" (manufactured by Denka Co., Ltd.), MFR (220°C, 10 kg load): 21 g / 10 min ABS resin 2: "GR3000" (manufactured by Denka Co., Ltd.), MFR (220°C, 10 kg load): 8 g / 10 min ABS resin 3: MFR (220°C, 10 kg load): 37 g / 10 min ABS resin 4: MFR (220°C, 10 kg load): 6 g / 10 min (First amide compound) First amide compound 1: Bisamide "EB-P" (Kao Corporation) (ethylene bisstearic acid amide) First amide compound 2: Bisamide "Lightamide WH-215" (manufactured by Kyoeisha Chemical Co., Ltd.) (polycondensate of ethylenediamine, stearic acid, and sebacic acid) First amide compound 3: Bisamide "Lightamide WH-255" (manufactured by Kyoeisha Chemical Co., Ltd.) (polycondensate of ethylenediamine, stearic acid, and sebacic acid) (Second Amide Compound) Second amide compound 1: Polyamide compound "WH-510K" (manufactured by Kyoeisha Chemical Co., Ltd.) (higher fatty acid polyamide, containing 12-hydroxy-substituted stearic acid as raw materials) (plate-like particles) Plate-like particle 1: Talc (Mohs hardness: 1, Nippon Talc Co., Ltd., product name "FG-15", average particle size (D50): 1.5 μm, aspect ratio: 20)

[0057] <Measurement of crystalline silica content> The content of crystalline silica in the plate-like particles was measured under the following conditions. The content of crystalline silica in the plate-like particles was measured by X-ray diffraction (base standard absorption correction method). Specifically, first, a qualitative analysis of free silicic acid in the plate-like particles was performed using an X-ray diffraction analyzer. Quartz, cristobalite, and tridymite (manufactured by the Japan Working Environment Measurement Association, a public interest incorporated association) were used as standard samples for free silicic acid analysis. Then, a quantitative analysis of crystalline silica in the plate-like particles was performed by X-ray diffraction (base standard absorption correction method). The measurement conditions for the X-ray diffraction method were as follows: Measurement device: X-ray generator (Rigaku Corporation tabletop rotating anode X-ray generator, product name "ultrax18") Target: Cu Scanning angle: 5°~60° Step width: 0.02 degrees Measurement time: 0.6 seconds Tube voltage: 40kV Tube current: 30mA Divergence slit: 1.00 degrees, scattering slit: 1.00 degrees, receiving slit: 0.3 mm

[0058] The detection limit for the crystalline silica content in the above measurement method is 0.1% by mass. Since no crystalline silica was detected in plate-like particle 1 (undetected) using the above measurement method, the crystalline silica content in plate-like particle 1 is presumed to be 0% by mass or more but less than 0.1% by mass.

[0059] [Example 1] A twin-screw kneader "Process 11" (manufactured by Thermo Fisher Scientific Inc.) was equipped with a strand spooler for producing monofilaments and a gear pump, and 64 parts by mass of (ABS resin 1), 34.5 parts by mass of (ABS resin 2), 1.2 parts by mass of (first amide compound 1), and 0.3 parts by mass of (second amide compound 1) were mixed and mixed at 220°C, followed by extrusion to produce a filament made of the resin composition with a diameter of 1.75 mm.

[0060] (MFR measurement) The MFR (220°C, 10 kg load) of the obtained filament was measured in accordance with JIS K7210 using an MFR / MVR measuring device "Melt Indexer G-02" (manufactured by Toyo Seiki Seisakusho, Ltd.). A material with an MFR of 24 g / 10 min or higher was evaluated as having fluidity suitable for additive manufacturing.

[0061] (Evaluation of heat resistance) The dynamic viscoelasticity of the obtained filament was measured by a dynamic viscoelasticity measuring device "DMS6100" (manufactured by SII Nano Technology Co., Ltd.) according to the method of JIS K7244-1:1998. The test was carried out by raising the temperature from -70°C to 300°C at a rate of 3°C / min, and when the filament was tensile deformed at a frequency of 10Hz and a strain of 0.07%, the storage modulus was 10 7 The temperature was measured when the pressure dropped below 1 Pa. Storage modulus is 10 7 When the temperature at which the resistance was 100°C or higher was 100 Pa or lower, the sample was evaluated as having a certain level of heat resistance, and when the temperature was 120°C or higher, the sample was evaluated as having excellent heat resistance.

[0062] Furthermore, a layered object was fabricated using the obtained filament under the following conditions, and warpage was evaluated. <Warpage evaluation of additive manufacturing products> The warpage of the layered manufactured object was measured under the following conditions, and if the warpage was less than 1 mm, it was considered to have passed. (Measurement conditions) Using the 3D printer "Raise3D Pro2" (manufactured by Raise3D), an evaluation sample plate (laminated object) measuring 200 mm wide x 50 mm long x 4 mm thick was produced under the following conditions: substrate temperature: 100°C, nozzle temperature: 240°C, build speed: 30 mm / s, and internal filling rate: 100%. The resulting sample plate was placed on a horizontal glass plate, and the maximum gap distance at the contact surface between the sample plate and the glass plate was measured with a curved ruler. Measurements of 1 mm or less were performed using a high-precision contact digital sensor GT2 (manufactured by Keyence Corporation). The results are shown in Table 1.

[0063] [Examples 2 to 12 and Comparative Examples 1 to 9] Filaments were produced under the same conditions as in Example 1, except that the resin composition had the composition shown in Table 1. The MFR and heat resistance of the resin composition and the warpage of the layered object were also evaluated under the same conditions as in Example 1. The results are shown in Table 1.

[0064] [Table 1]

[0065] As shown in Table 1, the resin composition satisfying the constitution of this embodiment had excellent heat resistance and fluidity suitable for additive manufacturing. Furthermore, when additive manufacturing was performed using a 3D printer, warping of the additive manufacturing was suppressed. On the other hand, the resin compositions of Comparative Examples 1 to 9 either had low MFR values ​​or had acceptable MFR values ​​but low heat resistance. When a resin composition with low heat resistance was used, the layered object exhibited significant warpage. From the above results, it was confirmed that the resin composition according to this embodiment has a certain level of heat resistance and fluidity suitable for additive manufacturing.

Claims

1. A resin composition for 3D printer filaments comprising an acrylonitrile-styrene-butadiene resin, a first amide compound, and a second amide compound, the first amide compound is an amide compound containing two or less amide bonds; the second amide compound is a polyamide compound containing, as a raw material, a hydroxy-substituted aliphatic monocarboxylic acid having 12 to 30 carbon atoms; The content of the first amide compound is 1 to 2 parts by mass and the content of the second amide compound is 0.2 to 1.2 parts by mass relative to 100 parts by mass of the acrylonitrile-styrene-butadiene resin. A resin composition for 3D printer filaments.

2. The resin composition for 3D printer filaments according to claim 1, wherein the hydroxy-substituted aliphatic monocarboxylic acid includes 12-hydroxy-substituted stearic acid.

3. The resin composition for 3D printer filaments according to claim 1 or 2, wherein the first amide compound includes a bisamide compound.

4. The storage modulus by viscoelasticity measurement is 10 ７ The resin composition for 3D printer filaments according to claim 1 or 2, wherein the temperature at which the viscosity reaches Pa is 120°C or higher.

5. The resin composition for 3D printer filaments according to claim 1 or 2, further comprising plate-like particles.

6. The resin composition for 3D printer filaments according to claim 5, wherein the plate-like particles contain talc having an average particle diameter of less than 2 μm.

7. A 3D printer filament comprising the resin composition for a 3D printer filament according to claim 5.

8. A layered object made from the 3D printer filament according to claim 7.

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