Resin composition for 3D printer filament, 3D printer filament, and deposition model

Abstract

The present invention provides a resin composition for a 3D printer filament, the resin composition having heat resistance that is equal to or higher than a certain level and fluidity that is suitable for deposition modeling.　This resin composition for a 3D printer filament contains an acrylonitrile-styrene-butadiene resin, a first amide compound, and a second amide compound. The first amide compound is an amide compound which contains two or less amide bonds. The second amide compound is a polyamide compound which contains, as a starting material, a hydroxy-substituted aliphatic monocarboxylic acid having 12-30 carbon atoms. With respect to 100 parts by mass of the acrylonitrile-styrene-butadiene resin, the content of the first amide compound is 1-2 parts by mass and the content of the second amide compound is 0.2-1.2 parts by mass.

Description

Resin composition for 3D printer filament, 3D printer filament, and laminated object

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

[0002] 3D printers are a type of additive manufacturing machine that use 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 (Selective Laser Sintering) or SLM (Selective Laser Melting)) 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, and then laminated 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).

[0005] International Publication No. 2021 / 060278

[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 modeling, 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 object of the present disclosure is 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.

[0007] As a result of extensive research, the present inventors 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 thus completed the present invention. Specifically, 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, wherein the first amide compound is an amide compound containing two or less amide bonds, and 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, 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.

[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.

[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 is a resin composition for 3D printer filaments 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 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 of this embodiment is a resin composition that has a certain level of heat resistance or higher and has 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% by mass, more preferably 16 to 20% by 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 properties. 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 having an MFR (220°C, 10 kg load) of 15 to 50 g / 10 min and an ABS resin 2 having 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, from the viewpoint of easily ensuring the fluidity required for 3D printing using a 3D printer, the mass average molecular weight (Mw) of the ABS resin is preferably 90,000 to 140,000. 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 be within the aforementioned range (e.g., 100,000 to 140,000). Furthermore, when using a single ABS resin, from the viewpoint of the aforementioned fluidity, heat resistance, and impact resistance, it is particularly preferable to use an ABS resin with a Mw of 100,000 to 140,000. The Mw of the resin refers to a value measured using GPC using THF as the solvent, a measurement temperature of 40°C, and a polystyrene 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 the present embodiment, the first amide compound is an amide compound containing two or less amide bonds. Examples of amide compounds containing two or less amide bonds include monoamides and bisamides. Of these, bisamides are preferably used. Examples of the monoamide that can be used include lauric amide, palmitic amide, stearic amide, purified stearic amide, hydroxystearic amide, erucic amide, N-substituted stearic amide, and N-substituted erucic amide. Examples of bisamides that can be used include saturated fatty acid bisamides such as methylene bisstearamide, ethylene biscapric amide, ethylene bislauric amide, ethylene bisstearamide, ethylene bishydroxystearamide, ethylene bisbehenic amide, hexamethylene bisstearamide, hexamethylene bisbehenic amide, hexamethylene bishydroxystearamide, and N,N'-distearyl adipamide; and unsaturated fatty acid bisamides such as ethylene bisoleic amide, hexamethylene bisoleic amide, and N,N'-dioleyl adipamide. In this embodiment, the content of the first amide compound is 1 to 2 parts by mass per 100 parts by mass of the 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, and setting it to 2 parts by mass or less makes it possible to keep the compound content in the resin composition for 3D printer filaments below a certain level.

[0016] <Second Amide Compound> In this embodiment, 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. Among these, a polyamide compound containing 12-hydroxy-substituted stearic acid as a raw material is 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 per 100 parts by mass of the ABS resin is 0.2 to 1.2 parts by mass. 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, and setting it to 1.2 parts by mass or less makes it possible to keep the compound content in the resin composition for 3D printer filaments below a certain level.

[0017] <Plate-Like Particles> In one embodiment, the resin composition for 3D printer filaments contains plate-like particles. The content of the plate-like particles relative to 100 parts by mass of the ABS resin 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. By setting the content of the plate-like particles to 5 parts by mass or more, a resin composition can be obtained that can produce an additive manufacturing product with reduced warping, and by setting the content to 30 parts by mass or less, deterioration of the fluidity 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 greater. Therefore, plate-like particles can 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 the particles are thin and have an aspect ratio of 1.0 or greater. In one embodiment, the aspect ratio of the plate-like particles may be 10 to 90, 10 to 80, or 20 to 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, and 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 adjusting the proportion of crystalline silica in the resin composition to a certain value or less, the nozzle of the 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 crystalline silica is substantially not detected, as 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 silicic acid 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 silicic acid analysis. Then, a quantitative analysis of 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, a desktop rotating anode X-ray generator manufactured by Rigaku Corporation, product name "Ultrax18") Target: Cu Scan angle: 5° to 60° Step width: 0.02° Measurement time: 0.6 seconds Tube voltage: 40 kV Tube current: 30 mA Divergence slit: 1.00°, scattering slit: 1.00°, 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 and 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 no crystalline silica is 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. By having the proportion of crystalline silica in the resin composition less than 0.02% by mass, warping during modeling can be suppressed, and wear of the nozzle of the 3D printer can also be suppressed. From the viewpoint of more easily suppressing nozzle wear, 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. Furthermore, it is preferable that no crystalline silica is detected when measured under the above-mentioned measurement conditions for the crystalline silica content 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 measurement conditions. 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 size (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 and less than 1.5 μm, even more preferably 0.5 to 1.3 μm, even more preferably 0.5 μm or more and 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 and less than 2 μm, 0.1 μm to 1.8 μm, 0.1 μm or more and less than 1.5 μm, 0.1 μm or more and less than 1.3 μm, 0.1 μm or more and 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 the 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, making it easier to suppress warpage during modeling and also improving high-speed modeling capabilities. In the present disclosure, "high-speed modeling capabilities" refers to the ability to model 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 result in 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, it becomes easier to obtain layered manufactured products with excellent appearance even when manufactured at high speed.

[0026] The silane coupling agent (X) is not particularly limited, but in one embodiment, silane coupling agents containing a functional group such as a vinyl group, an amino group, a styryl group, an epoxy group, or a mercapto group 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) may contain 3-glycidoxypropyltrimethoxysilane. It is presumed 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 further reduces warpage. It is also presumed 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% by mass, 0.1 to 2% by mass, 0.5 to 1.5% by mass, or 0.5 to 1% by mass, relative to the total mass (100% by mass) of the plate-like particles. By setting the proportion of the surface treatment agent within the above range, the effect of suppressing warping during molding is more easily achieved. 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 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 is easier to obtain a resin composition that does not wear out the nozzle of a 3D printer, can suppress warping during molding, and is capable of high-speed molding.

[0034] The method for treating the surfaces of the raw material particles with a surface treatment agent is not particularly limited, and a general method can be used, such as dissolving the surface treatment agent in an organic solvent such as ethanol, spraying the agent 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 by 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 Components> 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 resins (e.g., PLA resins, PC resins, 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 bis(stearic 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% by mass or less relative to the total mass of the resin composition.

[0037] <Physical properties of resin composition for 3D printer filaments> In one embodiment, from the viewpoint of being more excellent in high-speed modeling and more likely to be 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, 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 viscosity of the resin reaches 10 Pa is preferably 100° C. or higher, more preferably 110° C. or higher, and even more preferably 120° C. or higher. ７From the viewpoint of reducing thermal shrinkage stress, the temperature at which the thermal contraction stress reaches 10 Pa is preferably 100°C or higher and 140°C or lower, and more preferably 100°C or higher and 130°C or lower. 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 10 Hz, a strain of 0.03%, a sample shape of 5 mm x 50 mm x 0.3 mm, and a chuck distance of 15 mm. ７ The heat resistance can be evaluated based on the temperature at which the pressure drops to 0.1 Pa or less.

[0039] [Method for Producing a Resin Composition for 3D Printer Filaments] 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. For example, an example is 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 molding the resin composition into a filament, the kneader preferably includes a strand spooler, gear pump, or the like for producing filaments. In one embodiment, when using a twin-screw kneader (e.g., "Process 11" (manufactured by Thermo Fisher Scientific Co., Ltd.)), mixing can be performed under the following conditions: a set temperature of 200 to 220°C, a discharge rate of 30 to 40 kg / hr, and a rotation speed of 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 a resin composition for a 3D printer filament.

[0041] [Layered Object] The layered 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 layered object according to this embodiment includes a resin composition for 3D printer filaments that contains plate-like particles. In a preferred embodiment, the layered object is composed solely of the resin composition according to this embodiment. Such layered object exhibits little warping. Therefore, the layered 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 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 (e.g., an evaluation sample plate measuring 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-modeled article 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-modeled article can be measured by measuring the surface of the layered-modeled article using a 3D measuring laser microscope (for example, "LEXT OLS5100" manufactured by Evident Co., Ltd.) in accordance with ISO 25178.

[0044] [Method for manufacturing an additively shaped object] A method for manufacturing an additively shaped object according to an embodiment of the present disclosure is a method for manufacturing an additively shaped object using, as a raw material, a resin composition containing an ABS resin, a first amide compound, a second amide compound, and plate-like particles. 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 additively shaped object. The manufacturing method according to this embodiment is preferably a method for manufacturing an additively shaped 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 formed into a filament shape.

[0045] FDM 3D printers generally include a heatable substrate (modeling table), an extrusion head (nozzle), a heat melter, a filament guide, a filament installation, and other raw 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 X-Y 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 X-Y 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. The filament 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 the CAD model, supplying and stacking the molten filament onto the substrate to form an additive manufacturing object. After this process is complete, the laminated object can be removed from the substrate, and the desired additive manufacturing object can be obtained by peeling off support materials or trimming 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, it is preferable to melt the filaments made of the resin composition by setting the nozzle temperature preferably to 220 to 260° C., more preferably to 230 to 260° C. The substrate temperature is preferably set to 110° C. or less, more preferably to 90° C. or more and 110° C. or less.

[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 printing atmosphere inside the 3D printer 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 additively shaped object manufactured using a 3D printer, or a method of using the resin composition. A method of 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 of manufacturing 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 additively shaped object.

[0054] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is 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, wherein 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. [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 resin composition for 3D printer filaments according to [1] or [2], wherein the storage modulus measured by viscoelasticity measurement is 10 ７

[0023]

[0024] The resin composition for 3D printer filaments according to any one of [1] to [3], wherein the temperature at which the viscosity reaches 100 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 according to [5], wherein the plate-like particles comprise talc with an average particle diameter of less than 2 μm. [7] A 3D printer filament comprising the resin composition for 3D printer filaments according to [5] or [6]. [8] An additively manufactured object made from the 3D printer filament according to [7]. The configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of configurations are possible as appropriate within the scope of the present disclosure.

[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 Resins) 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 Compounds) First Amide Compound 1: Bisamide "EB-P" (manufactured by 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.) (containing higher fatty acid polyamide and 12-hydroxy-substituted stearic acid as raw materials) (plate-like particles) Plate-like particles 1: talc (Mohs hardness: 1, product name "FG-15" by Nippon Talc Co., Ltd., average particle size (D50): 1.5 μm, aspect ratio: 20)

[0057] <Measurement of Crystalline Silica Content> The crystalline silica content in the plate-like particles was measured under the following conditions. The crystalline silica content 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 (tabletop rotating anode X-ray generator manufactured by Rigaku Corporation, product name "Ultrax18") Target: Cu Scan angle: 5° to 60° Step width: 0.02° Measurement time: 0.6 seconds Tube voltage: 40 kV Tube current: 30 mA Divergence slit: 1.00°, scattering slit: 1.00°, 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 particles 1 (undetected) using the above measurement method, the crystalline silica content in plate-like particles 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 K.K.) equipped with a strand spooler for producing monofilaments and a gear pump was used to mix 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). The mixture was mixed at 220°C and then extruded to produce a filament made of a resin composition having a diameter of 1.75 mm.

[0060] (Measurement of MFR) 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 Seisaku-sho, Ltd.) When the MFR was 24 g / 10 min or more, it was evaluated as having fluidity suitable for additive manufacturing.

[0061] (Evaluation of Heat Resistance) The dynamic viscoelasticity of the tensile deformation of the obtained filament was measured using 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 tensile deformation at a frequency of 10 Hz and a strain of 0.07%. ７ The temperature at which the storage modulus was 10 Pa or less was measured. ７ When the temperature at which the viscosity of the film reached 100 Pa or less was 100° C. or higher, the film was evaluated as having a certain level of heat resistance, and when the temperature was 120° C. or higher, the film was evaluated as having excellent heat resistance.

[0062] Furthermore, an additive manufacturing object was fabricated using the obtained filament under the following conditions, and warpage was evaluated. <Warpage Evaluation of Additive Manufacturing Objects> The warpage of the additive manufacturing object was measured under the following conditions, and a warpage of less than 1 mm was deemed acceptable. (Measurement Conditions) Using a 3D printer "Raise3D Pro2" (manufactured by Raise3D), an evaluation sample plate (additive manufacturing object) measuring 200 mm wide x 50 mm long x 4 mm thick was fabricated under the following conditions: substrate temperature: 100°C, nozzle temperature: 240°C, fabrication 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 compositions were formulated as shown in Table 1. The MFR and heat resistance of the resin compositions 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]

[0065] As shown in Table 1, the resin composition satisfying the configuration of this embodiment had excellent heat resistance and fluidity suitable for additive manufacturing. Furthermore, when additive manufacturing products were produced using a 3D printer, warping of the additive manufacturing products was suppressed. On the other hand, the resin compositions of Comparative Examples 1 to 9 had low MFR values, or had acceptable MFR values ​​but low heat resistance. Furthermore, when a resin composition with low heat resistance was used, warping of the additive manufacturing products was significant. 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, wherein the first amide compound is an amide compound containing two or less amide bonds, and 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, 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.

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

4. 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 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 claim 5.

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

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