Polycarbonate resin composition for 3D printers

Abstract

The present invention provides a polycarbonate resin composition for 3D printers that has good filament diameter accuracy and roundness, and has high strength when used primarily with general-purpose FFF 3D printers. [Solution] A polycarbonate-based resin composition for 3D printers contains (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer. The polycarbonate-based resin (A) is a polycarbonate resin or a mixture of a polycarbonate-based resin and a PBT resin, or a mixture of a polycarbonate resin and an ASA resin, with the mixture ratio being 100 to 55% by weight of polycarbonate resin and 0 to 45% by weight of PBT resin or ASA resin. The polycarbonate resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin. The resin-modified polymer (B) is a core-shell polymer. The heat-fusion polymer (C) is polycaprolactone or a crystalline copolymer polyester resin.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate-based resin composition for 3D printers using the Material Extrusion Fabrication (MEX) method. The MEX method includes the Fused Filament Fabrication (FFF) method and the Fused Granular Fabrication (FGF) method. The present invention relates to a polycarbonate-based resin composition for 3D printers that is suitable for use in three-dimensional printers (hereinafter referred to as "3D printers") that use these methods to output three-dimensionally shaped objects.

[0002] Among the MEX extrusion lamination methods, there are two types of FFF 3D printers on the market, as shown in Table 1: relatively inexpensive general-purpose 3D printers and expensive high-temperature 3D printers.

[0003] [Table 1]

[0004] In the present invention, the main application field is a polycarbonate-based resin composition for molding high-strength 3D objects using a general-purpose 3D printer, but this is not limited to this, and this polycarbonate-based resin composition can also be used with high-temperature 3D printers and even with the fused granular fabrication (FGF) method. [Background technology]

[0005] Conventionally, for example, many types of thermoplastic resins have been used for automotive interior materials, and injection molding has been used as a molding method for them. In injection molding, a molten thermoplastic resin is injected and pressed into a heated mold, thereby producing a molded article having high strength.

[0006] On the other hand, 3D printing using the MEX extrusion lamination method involves heating and melting thermoplastic resin through the nozzle of the 3D printer and laminating it onto a heated molding plate using only the weight of the resin, so no pressure is applied between the laminated resin layers. In other words, there is no pressure between the laminated resin layers.

[0007] Therefore, in 3D printing using the MEX extrusion lamination method, the only pressure applied between the laminated resin layers is the weight of the resin itself, which is very different from the state in which molten thermoplastic resin is firmly fused together by being injected and pressed into the closed space of a mold, as in injection molding, and the strength of objects printed using the MEX extrusion lamination method is significantly inferior to that of injection molding.In particular, a major problem with 3D printing using the MEX extrusion lamination method is that the strength of 3D printed objects in the vertical axis direction is inferior to that in the horizontal axis direction.

[0008] Patent Document 1 discloses a thermoplastic resin filament consisting of two layers, an inner layer and an outer layer, and describes that the main component resin of both the inner layer and the outer layer is a polycarbonate resin with a viscosity average molecular weight of 18,000 to 28,000, and describes that the difference in melt flow rate (ASTM D1238, load of 1.2 kg at the melting point of the resin) between the resin compositions constituting the inner layer and the outer layer is 30 (g / 10 min) or less. It discloses that by making the difference in melt flow rate between the resin compositions of the inner layer and the outer layer 30 (g / 10 min) or less, the two layers can be integrated without peeling, but does not describe anything regarding 3D printed objects.

[0009] Patent Document 2 discloses a polycarbonate resin composition for 3D printers that provides excellent tensile strength and appearance in 3D printed molded products produced by melt deposition modeling. This polycarbonate resin is a polycarbonate resin composition for 3D printers that contains 100 parts by weight of aromatic polycarbonate resin (component A) and 5 to 50 parts by weight of inorganic filler (component B).

[0010] In the examples of the polycarbonate resin composition for 3D printers described in Patent Document 2, it is stated that the 3D printer was used to model at a cylinder temperature of 300°C, but there is no mention of the build plate or chamber temperature. Furthermore, Patent Document 2 describes the tensile fracture stress in the X-axis and Z-axis directions of 3D-printed objects in Examples 1 to 16, but the Z-axis / X-axis ratios for the tensile fracture stress are all only 0.44 to 0.25. Therefore, the technology described in Patent Document 2 does not contribute to the primary objective of the present application, which is to provide a polycarbonate resin composition for molding high-strength 3D-printed objects using a general-purpose 3D printer.

[0011] Patent Document 3 discloses that a composition containing a thermoplastic polyester resin (polycaprolactone resin, polyester-based resin) that is compatible with polycarbonate resin and has a glass transition temperature of 100°C or less and an aromatic polycarbonate resin has good heat resistance and impact resistance, suppresses warping of three-dimensionally shaped objects, and can provide a filament for three-dimensional shaping that has excellent interlayer adhesion.

[0012] Furthermore, although Patent Document 3 states that it is preferable to increase the accuracy and roundness of the filament diameter, the examples do not mention the accuracy of the filament diameter. Furthermore, Patent Document 3 does not mention the pulling speed in the tensile test described in the examples. It is common knowledge for those skilled in the plastics industry that the pulling speed has a significant effect on tensile strength. From this perspective, the technology described in Patent Document 3 does not achieve the primary objective of the present invention, which is to provide a polycarbonate-based resin composition for molding a 3D-modeled object having high strength using a general-purpose 3D printer.

[0013] Patent Document 4 discloses a filament for three-dimensional printing composed of a polycarbonate resin (A) and a polyester resin (B), and describes that the polyester resin (B) is a polybutylene terephthalate resin. Patent Document 4 describes that a resin composition for three-dimensional printing composed of a polycarbonate resin (A) and a polybutylene terephthalate resin (B) can provide a filament for three-dimensional printing that suppresses warping of the molded object and has excellent adhesion to the table of a 3D printer without impairing the inherent properties of polycarbonate resin, such as heat resistance and impact resistance.

[0014] In the examples of Patent Document 4, it is stated that a filament with a diameter of 1.75 mm was produced using a twin-screw kneader, but there is no mention of the diameter precision or roundness of the filament. Therefore, it must be said that the technology described in Patent Document 4 cannot provide a thermoplastic resin composition for molding a 3D-modeled object having high strength using a general-purpose 3D printer, which is the main objective of the present application.

[0015] Patent Document 5 was previously filed by the applicant of the present application and aims to provide a resin composition for additive manufacturing that has sufficient adhesive strength in the height direction. It relates to a resin composition for additive manufacturing that contains a polycarbonate resin, an impact resistance improver that is a styrene-based thermoplastic elastomer or a core-shell polymer, and a heat-softening material that has at least one of a crystalline copolymer polyester resin, polycaprolactone, and a polyester-based thermoplastic elastomer.

[0016] As a result of further research and consideration, the inventors of the present application have found that there are technical issues that need to be improved regarding the technology described in Patent Document 5. That is, the technology described in Patent Document 5 contains three components: a polycarbonate resin, an impact resistance improver, and a heat softening agent. However, it has been found that many of the specific materials specified in Patent Document 5 do not provide the physical properties required for a 3D printed object.

[0017] Furthermore, of the three components, polycarbonate resins have a melt volume rate (MVR) range that is too wide, and it was found that, among the materials specified as heat-softening materials, only certain crystalline copolymer polyester resins and polycaprolactone were able to obtain the physical properties required for 3D printing objects. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] Patent Publication No. 2017-065111 [Patent Document 2] Patent Publication No. 2019-167498 [Patent Document 3] Patent No. 7400809 [Patent Document 4] WO2022 / 138954 A1 [Patent Document 5] Patent No. 7162942 Summary of the Invention [Problem to be solved by the invention]

[0019] The present inventors further investigated polycarbonate resin compositions suitable for 3D printers and found that it is important to solve the following problems.

[0020] In other words, the accuracy of the filament diameter is extremely important. Regarding wire diameter precision, the best commercially available filament is the PC filament, with a diameter precision of 1.75mmφ at 1.75±0.05mmφ, but generally it is around 1.75±0.10mmφ.

[0021] For example, if the filament diameter exceeds 1.85 mm, the filament will clog the nozzle of the 3D printer, making it difficult to perform 3D printing. Even if the average diameter is 1.75 ± 0.10 mm, if the filament is elliptical and the major axis (thicker axis) exceeds 1.85 mm, clogging will occur.

[0022] On the other hand, if the wire diameter is thinner than 1.65 mm, for example, the clogging described above does not occur. However, when the nozzle of the 3D printer moves at high speed in the XY direction (horizontal direction) to create a 3D print using the heated and melted filament, the molten filament breaks between the nozzle and the object on the build plate, causing the 3D print to stop. As such, the accuracy of the filament diameter is extremely important when performing 3D printing.

[0023] In view of the above-described conventional problems, an object of the present invention is to provide a polycarbonate-based resin composition that has the physical properties required for a 3D printed object, such as good filament diameter accuracy and roundness, and that has high strength when used primarily with general-purpose FFF-type 3D printers. [Means for solving the problem]

[0024] The present inventors have conducted extensive research to solve the above problems, and as a result have found a polycarbonate resin composition that can solve the above problems, leading to the completion of the present invention described below.

[0025] [1] A polycarbonate-based resin composition for 3D printers, comprising (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer, the polycarbonate resin (A) is a polycarbonate resin, or a mixture of a polycarbonate resin and a polybutylene terephthalate resin (hereinafter referred to as "PBT resin"), or a mixture of a polycarbonate resin and an acrylonitrile-styrene-acrylic terpolymer (hereinafter referred to as "ASA resin"), and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 100 to 55% by weight of the polycarbonate resin and 0 to 45% by weight of the PBT resin or the ASA resin, and the polycarbonate resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin; The resin-modified polymer (B) is a core-shell polymer, the heat-fusion polymer (C) is polycaprolactone or a crystalline copolyester resin, When the total weight of the polycarbonate-based resin (A), the resin-modified polymer (B), and the heat-fusion polymer (C) is 100% by weight, the ratio of the polycarbonate-based resin (A) to the total weight is in the range of 65% by weight to 92% by weight, the ratio of the resin-modified polymer (B) to the total weight is in the range of 5% by weight to 20% by weight, and the ratio of the heat-fusion polymer (C) to the total weight is in the range of 3% by weight to 15% by weight. A polycarbonate-based resin composition for 3D printers.

[0026] [2] The polycarbonate-based resin composition for 3D printers according to [1] above, wherein the polycarbonate-based resin (A) is a mixture of polycarbonate resin and PBT resin or a mixture of polycarbonate resin and ASA resin, and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 95 to 55% by weight of the polycarbonate resin and 5 to 45% by weight of the PBT resin or the ASA resin.

[0027] [3] The polycarbonate-based resin composition for 3D printers according to [1] or [2] above, wherein the polycarbonate-based resin (A) has an MVR of 8 to 19 g / min measured at 300°C under a load of 1.2 kg, the core material of the core-shell polymer that is the resin-modified polymer (B) is an acrylic rubber or a silicone-acrylic composite rubber and has an average particle size of 100 to 700 nmφ, the number-average molecular weight of the polycaprolactone that is the heat-fusion polymer (C) is 10,000 to 25,000, and the glass transition temperature of the crystalline copolymer polyester resin is 5°C or lower.

[0028] [4] The polycarbonate-based resin composition for 3D printers according to any one of [1] to [3], wherein the tensile breaking strength in the longitudinal axis (ZX) direction of a molded object produced using a general-purpose FFF type 3D printer from the polycarbonate-based resin composition is 35 MPa or more.

[0029] [5] The polycarbonate-based resin composition for 3D printers according to any one of [1] to [4], wherein the ratio of the tensile strength at break of a molded object formed using a general-purpose FFF 3D printer from the polycarbonate-based resin composition along the vertical axis (ZX) to the horizontal axis (XY) is 0.6 or more.

[0030] [6] The polycarbonate-based resin composition for 3D printers according to any one of [1] to [4] above, wherein the ratio of the tensile breaking strength of a molded article formed by injection molding to the tensile breaking strength of a horizontal axis (XY) of a molded object formed by a general-purpose FFF 3D printer of the polycarbonate-based resin composition is 0.6 or more. [Effects of the Invention]

[0031] The polycarbonate resin composition for 3D printers of the present invention makes it possible to form 3D shaped objects with high strength and excellent filament diameter accuracy and roundness in the case of the FFF method. [Brief explanation of the drawings]

[0032] [Figure 1A] FIG. 1 is a plan view showing an example of a multipurpose test piece (full-size dumbbell-shaped test piece). [Figure 1B] FIG. 1B is a side view of the multipurpose test strip shown in FIG. 1A. [Figure 2A] FIG. 1 is a plan view showing an example of a deflection temperature under load test piece. [Figure 2B] FIG. 2B is a side view of the deflection temperature under load test piece shown in FIG. 2A. [Figure 3] FIG. 1 is an explanatory diagram showing the maximum and minimum diameters of a cross section of a filament. [Figure 4A] FIG. 1 is a plan view showing an example of a multipurpose test piece (short-size dumbbell-shaped test piece). [Figure 4B] FIG. 4B is a side view of the multipurpose test strip shown in FIG. 4A. DETAILED DESCRIPTION OF THE INVENTION

[0033] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. In other words, appropriate changes and modifications may be made to the following embodiments based on the ordinary knowledge of a person skilled in the art, without departing from the spirit of the present invention.

[0034] 1. Polycarbonate resin composition for 3D printers A polycarbonate-based resin composition for 3D printers (hereinafter sometimes referred to as the "resin composition") according to one embodiment of the present invention is primarily composed of (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer, and can be used primarily as a filament for FFF-type 3D printers.

[0035] In this polycarbonate resin composition for 3D printers, the polycarbonate resin (A) is a polycarbonate resin (hereinafter referred to as "PC resin"), or a mixture of PC resin and PBT resin, or a mixture of PC resin and ASA resin, and the mixing ratio of the PC resin to the PBT resin or ASA resin is 100 to 55% by weight of the PC resin and 0 to 45% by weight of the PBT resin or ASA resin. The PC resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin, the resin-modified polymer (B) is a core-shell polymer, and the heat-fusion polymer (C) is polycaprolactone or a crystalline copolymer polyester resin.

[0036] Here, in one embodiment, a PC resin, which constitutes one component of a resin composition that can be used as a filament, is a type of engineering plastic that has excellent characteristics such as heat resistance and impact resistance, and is widely used as an industrial material for various applications. In the present invention, an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin is preferably used as the PC resin.

[0037] Aromatic polycarbonate resins are obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonate diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and known methods can be used. Examples include a method in which an aromatic dihydric phenol compound is directly reacted with phosgene or the like (interfacial polymerization method), and a method in which an aromatic dihydric phenol compound is subjected to a transesterification reaction with a carbonate diester such as diphenyl carbonate in a molten state (melt method).

[0038] Regarding the melt volume rate (MVR), which is a value that indicates the fluidity of a thermoplastic resin when melted, for such PC resins, the MVR measured at 300°C and a load of 1.2 kg is 8 to 19 cm. 3 It is preferable that the MVR value of PC resin is in the range of 8cm / 10min. 3By setting the MVR to 19cm / min or more, good fusion between the resin layers of the 3D printed object can be achieved. 3 By setting the speed to 10 min or less, good diameter precision and roundness of the filament can be obtained.

[0039] Examples of commercially available aromatic polycarbonate resins include Panlite L-1225L, L-1225Y, and L-1250Y (manufactured by Teijin Limited), Europin S-2000 and S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation), and Toughlon 1900, 2200, and 2500 (manufactured by Idemitsu Kosan Co., Ltd.).

[0040] Siloxane copolymer polycarbonate resin is a high-performance polycarbonate resin obtained by chemically bonding (copolymerizing) polydimethylsiloxane to polycarbonate resin. Commercially available siloxane copolymer polycarbonate resins include Toughlon Neo AG1950, AG2030, VG1950, and RC2031 (manufactured by Idemitsu Kosan Co., Ltd.), and Panlite SS1230 (manufactured by Teijin Limited).

[0041] PBT resin is a thermoplastic crystalline resin produced by polycondensation of terephthalic acid and 1,4-butanediol as basic raw materials. It has a melting point of 224°C, a crystallization temperature of 170-175°C, and a glass transition temperature of 37-53°C. It has excellent chemical resistance and UV resistance, low water absorption, excellent dimensional stability, and good melt-mixability with polycarbonate resin. Commercially available PBT resins include NOVADURAN 5510R1 and 5010TRXA (manufactured by Mitsubishi Chemical Corporation) and DURANEX 2002EF2001 (manufactured by Polyplastics Co., Ltd.).

[0042] ASA resin is an acrylonitrile-styrene-acrylic terpolymer, a thermoplastic resin that is particularly excellent in UV resistance and has good melt-mixability with polycarbonate resin. Examples of commercially available products include DIALACS210B, DIALACS310, DIALACS510, and DIALACS411A (manufactured by Techno UMG Co., Ltd.).

[0043] Furthermore, the resin-modified polymer, which constitutes one component of the resin composition, is used to improve the mechanical strength of the resin. While rubber-containing graft polymers are generally used, "core-shell graft polymers" can be preferably used. As the core-shell graft polymer, particularly preferred are "core-shell graft polymers" in which the core component is an acrylic rubber or a silicone-acrylic composite rubber and the shell component is an acrylic polymer. Furthermore, since this "core-shell graft polymer" exhibits a fine particle structure, its average particle size is preferably 100 to 700 μm.

[0044] Core-shell graft polymers are impact resistance improvers obtained by polymerizing vinyl monomers in the presence of rubber, with the rubber component forming the core and the polymerized vinyl monomer forming the shell.

[0045] Examples of rubber components include silicone rubber made from organosiloxane or the like, acrylic rubber made from alkyl acrylate or alkyl methacrylate or the like, and composite rubbers of these. These rubbers may be used alone or in combination of two or more types.

[0046] Examples of vinyl monomers that form the shell include methacrylates such as methyl methacrylate and ethyl methacrylate. Examples of these core-shell type graft polymers include silicone-acrylic composite rubbers (Metablen S-2100, etc., manufactured by Mitsubishi Chemical Corporation) and acrylic rubber impact resistance improvers (Metablen W-600A, etc., manufactured by Mitsubishi Chemical Corporation).

[0047] Next, the heat-fusible polymer, which is one component of the resin composition, contains at least one of a crystalline copolymer polyester resin and polycaprolactone.

[0048] The crystalline copolymer polyester resin usable as the heat-sealing polymer is a crystalline copolymer polyester, and preferably a crystalline copolymer polyester having a glass transition temperature of 5°C or less. The crystalline copolymer polyester is a crystalline copolymer polyester composed of a polycarboxylic acid component and a polyglycol component. The polycarboxylic acid component may be terephthalic acid, isophthalic acid, hexahydroterephthalic acid, or the like, and the polyglycol component may be ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like, and has properties such as heat resistance and weather resistance.

[0049] The glass transition temperature of these crystalline copolyesters is preferably 5° C. or lower, and more preferably in the range of 5 to −70° C. Examples of commercially available products of such crystalline copolyesters include Byron GM913, Byron GM920, and Byron GM6400 (manufactured by Toyobo Co., Ltd.).

[0050] Polycaprolactone is a type of biodegradable plastic. Polycaprolactone can be produced by ring-opening polymerization of caprolactone in the presence of a catalyst such as an acid, a base, or an organometallic compound. The terminals of the polycaprolactone may be subjected to terminal treatment such as esterification. The melting point of polycaprolactone is 60°C, and the glass transition temperature is approximately -60°C. The number average molecular weight (hereinafter sometimes referred to as "molecular weight") of these polycaprolactones is preferably in the range of 9,000 to 30,000, and more preferably in the range of 10,000 to 25,000.

[0051] Commercially available polycaprolactones that can be suitably used include Plaxel H1P (number average molecular weight 10,000: manufactured by Daicel Corporation), Capa 2803 (number average molecular weight 10,000: manufactured by Ingevity), and Capa 6250 (number average molecular weight 25,000: manufactured by Ingevity).

[0052] The resin composition of this embodiment is composed of the above three components (polycarbonate resin, resin-modified polymer, and heat-bonded polymer), and these three components are mixed in a predetermined ratio (weight ratio), heated, and then molded into a filament using well-known resin molding techniques so that it can be used as a filament for a 3D printer.

[0053] Here, when the total weight of the polycarbonate-based resin, resin-modified polymer, and heat-sealed polymer is 100% by weight, the weight percentage (weight ratio) of the polycarbonate-based resin to the total weight can be set to be in the range of 65% by weight to 92% by weight, more preferably in the range of 75% by weight to 90% by weight, the weight ratio of the resin-modified polymer shown in the total weight can be set to be in the range of 5% by weight to 20% by weight, more preferably in the range of 5% by weight to 15% by weight, and the weight ratio of the heat-sealed polymer to the total weight can be set to be in the range of 3% by weight to 15% by weight, more preferably in the range of 3% by weight to 10% by weight.

[0054] The mixing ratio of PC resin and PBT resin or PC resin and ASA resin is 100 to 55% by weight, preferably 100 to 60% by weight, of PC resin, and 0 to 45% by weight, preferably 0 to 40% by weight of PBT resin or ASA resin.

[0055] Furthermore, compared to PC resin alone, a mixture of PC resin and PBT resin or a mixture of PC resin and ASA resin is preferable. The blend ratio is preferably 95 to 55 wt% PC resin and 5 to 45 wt% PBT resin or ASA resin, and even more preferably 90 to 56 wt% PC resin and 10 to 44 wt% PBT resin or ASA resin. Thus, when a mixture of PC resin and PBT resin or a mixture of PC resin and ASA resin is used, the tensile break strength in the longitudinal (ZX) direction is higher than when PC resin is used alone. Furthermore, the ratio of the tensile break strength in the longitudinal (ZX) direction to the transverse (XY) direction and the ratio of the tensile break strength in the transverse (XY) direction to the tensile break strength of a molded product molded by injection molding are higher, resulting in a 3D-printed object with an excellent balance of tensile break strength in the longitudinal and transverse directions.

[0056] By adjusting the three components (A) polycarbonate resin, (B) resin-modified polymer, and (C) heat-sealing polymer within the above weight ratio ranges, it is possible to obtain a 3D printer filament with excellent formability (diameter accuracy and roundness) and excellent strength in the vertical axis direction (ZX) of the 3D printed object.

[0057] In addition, in the resin composition of the present invention, other components may be added in addition to the above three components, as long as the physical properties and basic functions are not impaired, or for the purpose of adding other functions.

[0058] For example, carbon fiber (CF) or cellulose nanofiber (CNF) can be added to the resin composition to form a composite. In this case, the appropriate amount of addition is about 5 to 30% by weight. An antistatic agent can also be mixed into the resin composition. As the antistatic agent, for example, an ionic liquid is preferred because of its excellent transparency, heat resistance, and antistatic properties.

[0059] 2. Resin composition characteristics The resin composition of this embodiment contains the three components in the weight ratios described above, and has excellent filament formability (diameter accuracy and roundness) and excellent strength in the longitudinal axis direction (ZX) of the 3D printed object (details will be described later).

[0060] Furthermore, preferably, the tensile break strength in the vertical axis (ZX) direction of the 3D printed object obtained from the polycarbonate resin composition of this embodiment is 35 MPa or more, the ratio of the tensile break strength in the vertical axis (ZX) direction to the horizontal axis (XY) direction is 0.6 or more, the ratio of the tensile break strength in the horizontal axis (XY) direction of the 3D printed object to the tensile break strength of the injection molded product is 0.6 or more, and the deflection temperature under load at a load of 0.45 MPa is 100°C or more.

[0061] The tensile breaking strength was measured in accordance with "ISO527", and the deflection temperature under load was measured in accordance with "ISO75 Measurement method for deflection temperature under load". [Example]

[0062] The resin composition of the present invention will be described in more detail below based on the following examples, but the present invention is not limited to these examples. In addition to the following examples, various modifications and improvements can be made to the present invention based on the knowledge of those skilled in the art, as long as they do not deviate from the spirit of the present invention.

[0063] First, the materials and properties of each component of the PC resin, resin-modified polymer, and heat-fusion polymer used in the examples and comparative examples are shown below.

[0064] 1.PC resin [PC-1] Idemitsu Toughlon 1900: Aromatic polycarbonate resin, MVR = 19 cm 3 / 10min (300℃, 1.2kg load) [PC-2] Idemitsu Toughlon 2200: Aromatic polycarbonate resin, MVR = 12 cm 3 / 10min (300℃, 1.2kg load) [PC-3] Idemitsu Toughlon 2500: Aromatic polycarbonate resin, MVR = 8 cm 3 / 10min (300℃, 1.2kg load) [PC-4] Idemitsu Toughlon Neo AG1950: Siloxane copolymer polycarbonate resin, MVR = 13 cm 3 / 10min (300℃, 1.2kg load) [PC-5] Idemitsu Toughlon Neo AG2030: Siloxane copolymer polycarbonate resin, MVR = 9 cm 3 / 10min (300℃, 1.2kg load)

[0065] [PC-6] Idemitsu Toughlon 1700: Aromatic polycarbonate resin, MVR = 27 cm 3 / 10min (300℃, 1.2kg load) [PC-7] Teijin Panlite K-1300Y: Aromatic polycarbonate resin, MVR = 2.8 cm 3 / 10min (300℃, 1.2kg load) [PC-8] Teijin Panlite SS1230: Siloxane copolymer polycarbonate resin, MVR = 20.4 cm 3 / 10min (300℃, 1.2kg load) [PC-9] Idemitsu Toughlon Neo VC2260: Siloxane copolymer polycarbonate resin, MVR = 4 cm 3 / 10min (300℃, 1.2kg load)

[0066] 2. PBT resin [PBT-1] Mitsubishi Chemical NOVADURN5510R1: Polybutylene terephthalate resin, MVR=90cm 3 / 10min (250℃, 1.2kg load) [PBT-2] Mitsubishi Chemical NOVADURN5010TRXA: Polybutylene terephthalate resin, MVR=19cm 3 / 10min (250℃, 1.2kg load)

[0067] 3.ASA resin [ASA-1] Techno UMG DIALAC S5110: ASA resin, MVR=14cm 3 / 10min (220℃, load 98N) [ASA-2] Techno UMG DIALAC S210B: ASA resin, MVR=25cm 3 / 10min (220℃, load 98N)

[0068] 4. Resin-modified polymer [Core-Shell-1] Mitsubishi Chemical's Metablen W600A: Core material = acrylic rubber, Shell material = (meth)acrylic polymer, Average particle size = 100-200 μm [Core-Shell-2] Mitsubishi Chemical's Metablen S2100: Core material = silicone-acrylic composite rubber, Shell material = (meth)acrylic polymer, Average particle size = 600-700 μm

[0069] 5. Heat-sealing polymer [PCL-1] Daicel Plaxel H1P: Polycaprolactone, molecular weight = 10,000, granular [PCL-2] Ingevity Capa 6250: Polycaprolactone, molecular weight = 25,000, granular [PCL-3] Ingevity Capa 6500: Polycaprolactone, molecular weight = 50,000, granular [PCL-4] Daicel Plaxel 240: Polycaprolactone diol, molecular weight = 4000, waxy

[0070] [GM-1] Toyobo GM913: Crystalline copolymer polyester resin, molecular weight = 35,000, glass transition temperature = -70°C [GM-2] Toyobo GM350: Crystalline copolymer polyester resin, molecular weight = 35,000, glass transition temperature = 3°C [GM-3] Toyobo GM400: Crystalline copolymer polyester resin, molecular weight = 25,000, glass transition temperature = 19°C [RV-1] Toyobo RV103: amorphous copolymer polyester resin, molecular weight = 23,000, glass transition temperature = 47°C [RV-2] Toyobo RV200: amorphous copolymer polyester resin, molecular weight = 17,000, glass transition temperature = 7°C

[0071] (Production of polycarbonate resin composition) The various raw materials for the polycarbonate resin composition were weighed out based on the blending ratios (wt%) shown in Tables 2 to 9, charged into a mixer (Supermixer SMV-10, manufactured by Kawata Corporation), and stirred for 5 minutes. After that, the mixture was melt-extruded and pelletized using a twin-screw extruder equipped with a vacuum vent and strand die (TEX30α, manufactured by The Japan Steel Works, Ltd.) at an extrusion temperature of 260°C.

[0072] (Preparation of test specimens by injection molding) Polycarbonate resin compositions (pellets) produced using a twin-screw extruder were placed in a vacuum dryer and dried at 110°C for at least 2 hours. An injection molding machine (Shibaura Machine Co., Ltd.) with a clamping force of 980 kN was then used to mold a multipurpose test specimen (full-size dumbbell-shaped test specimen) conforming to ISO standards, as shown in Figures 1A and 1B. The multipurpose test specimen (1) had a length (L) of 170 mm, a thickness (T) of 4±0.2 mm, a width (W) of 10±0.2 mm, an edge width (EW) of 20 mm, a first length (L1) of 114 mm, and a second length (L2) of 80 mm.

[0073] (Measurement of physical properties of test pieces by injection molding) (1) Measurement of tensile strength: Using a multipurpose test piece conforming to ISO standards, the test piece was conditioned for one day and one night in a laboratory at 23±2°C, and then the tensile strength was measured at a tension speed of 50 mm / min in accordance with ISO-527.

[0074] (2) Measurement of deflection temperature under load: Test specimens with a length L = 80 ± 2.0 mm, a width W = 10 ± 0.2 mm, and a thickness T = 4 ± 0.2 mm, as shown in Figures 2A and 2B, were cut out from the ISO standard multipurpose test specimen, and the deflection temperature under load (DTUL) was measured using an HDT testing machine 3M-2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with ISO 75, at a load of 0.45 MPa and a heating rate of 10°C / min.

[0075] (Filament forming and measurement of diameter accuracy and roundness) The polycarbonate resin composition (pellets) produced using a twin-screw extruder was placed in a vacuum dryer and dried at 110°C for at least 2 hours. After that, a monofilament was melt-extruded at an extrusion temperature of 250°C using a 30 mmφ single-screw extruder equipped with a vacuum vent and a monofilament die (manufactured by Plagiken Co., Ltd.). After cooling, the monofilament was produced into a 1.75 mmφ monofilament using a take-up and winding machine.

[0076] As shown in Figure 3, the maximum diameter (2a) and minimum diameter (2b) of each filament were measured at five locations at 1 m intervals, and the average diameter, maximum diameter, minimum diameter, and flatness (f) were calculated. The flatness (f) = (ab) / a = 1-(b / a) It can be calculated as follows. Therefore, when the maximum diameter (2a) and the minimum diameter (2b) are the same (a = b), the flattening ratio (f) is f = 0, indicating that the cross section is a perfect circle.

[0077] (Modeled using a 3D printer) Using a general-purpose 3D printer (Rasise3D Pro3HS, sold by Japan 3D Printer Co., Ltd.), a "short-size dumbbell-shaped test piece" shown in Figures 4A and 4B was printed in the vertical axis (ZX) direction and horizontal axis (XY) direction of the object under the following printing conditions. The test piece 10 shown in Figure 4 has a length L of 130 mm, a thickness T of 4 ± 0.2 mm, a width W of 10 ± 0.2 mm, an edge width EW of 20 mm, a first length L1 of 74 mm, and a second length L2 of 40 mm. Nozzle temperature = 280°C, build plate temperature = 120°C, chamber temperature = 50-60°C

[0078] (Measurement of tensile strength of 3D printed objects) The tensile strength at break was measured at a tension speed of 50 mm / min in accordance with ISO-527.

[0079] (Examples 1 to 8) In Examples 1 to 8 shown in Table 2, the (A) polycarbonate resin was an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin, and the MVR was 8 to 19 cm 3 A core-shell polymer was used as the (B) resin-modified polymer, and polycaprolactone (molecular weight 10,000) was used as the (C) heat-fusion polymer. These three components were blended in the weight ratios shown in Table 2 to produce a resin composition (pellets).

[0080] The obtained resin composition (pellets) was used to mold multipurpose test pieces by injection molding as described above, and their physical properties were measured. Furthermore, filaments were produced using the resin composition (pellets) as described above, and their physical properties (diameter accuracy and roundness (flatness)) were measured. Furthermore, a shaped object (short-sized dumbbell-shaped test piece) was produced using a general-purpose 3D printer (Rasise3DPro3HS), and its physical properties were measured. These physical properties are shown in Table 2.

[0081] Examples 9 to 18 In Examples 9 to 18, as shown in Table 3, aromatic polycarbonate resin (MVR 12 cm 3 (B) A core-shell polymer was used as the resin-modifying polymer, and (C) polycaprolactone (molecular weight 10,000, 25,000) or a crystalline copolymer polyester resin (glass transition temperature -70°C, 3°C) was used as the heat-fusion polymer. These three components were blended in the weight ratios shown in Table 2 to produce a resin composition (pellets).

[0082] Using the obtained resin composition (pellets), multipurpose test pieces and filaments were injection molded and objects were manufactured using a general-purpose 3D printer in the same manner as in Examples 1 to 8, and their physical properties were measured. Table 3 shows these physical properties.

[0083] (Examples 19 to 22) In Examples 19 to 22, as shown in Table 4, an aromatic polycarbonate resin (MVR 12 cm 3 (B) A core-shell polymer was used as the resin-modifying polymer, and (C) polycaprolactone (molecular weight 10,000) was used as the heat-fusion polymer. These three components were blended in the weight ratios shown in Table 4 to produce a resin composition (pellet).

[0084] Using the obtained resin composition (pellets), multipurpose test pieces and filaments were injection molded and objects were manufactured using a general-purpose 3D printer in the same manner as in Examples 1 to 8, and their physical properties were measured. Table 4 shows these physical properties.

[0085] (Comparative Examples 1 to 10) In Comparative Examples 1 to 10 shown in Table 5, the (A) polycarbonate resin was an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin, and the MVR was 12 cm 3 / 10min, MVR27cm 3 / 10 min, 2.8 cm 3 / 10min, 20.4cm 3 / 10min, 4cm 3 / 10 min, and a mixture of aromatic polycarbonate resin and PBT resin was used, (B) a core-shell polymer was used as the resin-modified polymer, and (C) polycaprolactone (molecular weight 10,000, 50,000, 4,000), crystalline copolymer polyester resin (glass transition temperature 19 ° C), or amorphous copolymer polyester resin (glass transition temperature 47 ° C, 7 ° C) was used as the heat-fusion polymer. These three components were blended in the weight ratios shown in Table 5 to produce resin compositions (pellets).

[0086] Using the obtained resin composition (pellets), multipurpose test pieces and filaments were injection molded and objects were manufactured using a general-purpose 3D printer in the same manner as in Examples 1 to 8, and their physical properties were measured. Table 5 shows these physical properties.

[0087] (Comparative Examples 11 to 15) In Comparative Examples 11 to 15 shown in Table 6, (A) the polycarbonate resin was an aromatic polycarbonate resin, and the MVR was 12 cm 3 A mixture of aromatic polycarbonate resin and ASA resin was used, a core-shell polymer was used as the resin-modifying polymer (B), and polycaprolactone (molecular weight 10,000) was used as the heat-fusion polymer (C). These three components were blended in the weight ratios shown in Table 6 to produce resin compositions (pellets).

[0088] Using the obtained resin composition (pellets), multipurpose test pieces and filaments were injection molded and objects were manufactured using a general-purpose 3D printer in the same manner as in Examples 1 to 8, and their physical properties were measured. Table 6 shows these physical properties.

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] [Table 6]

[0094] (Discussion: Evaluation of Resin Compositions of Examples and Comparative Examples) (Evaluation of Resin Compositions of Examples 1 to 8) As described above, in the resin compositions of Examples 1 to 8, the (A) polycarbonate resin was an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin, and the MVR was 8 to 19 cm 3 (B) a core-shell polymer was used as the resin-modified polymer, and (C) polycaprolactone (molecular weight 10,000) was used as the heat-fusion polymer, and these three components were blended in the weight ratios shown in Table 2. The multipurpose test pieces, filaments, and 3D printed objects obtained using these resin compositions (pellets) have good heat resistance, good filament diameter accuracy, and roundness, and have a high tensile breaking strength in the vertical axis (ZX) direction of 43 MPa or more. Furthermore, the ratio of the tensile breaking strength in the vertical axis (ZX) direction to the horizontal axis (XY) direction is also high at 0.83 or more, and the balance of tensile breaking strength in the vertical axis and horizontal axis directions is excellent.

[0095] (Evaluation of Resin Compositions of Examples 9 to 10 and 15 to 18) Furthermore, Examples 9 and 10 shown in Table 3 are obtained by changing the blending ratio of polycaprolactone (molecular weight 10,000) as the (C) heat-fusion polymer among the three components of Example 2. Example 15 shown in Table 3 is obtained by changing the type of core-shell polymer as the (B) resin-modified polymer among the three components of Example 2. Furthermore, Examples 16 to 18 shown in Table 3 are obtained by using, among the three components of Example 2, polycaprolactone as the (C) heat-fusion polymer with a molecular weight of 25,000 (Example 16), a crystalline copolyester resin (glass transition temperature -70°C) as the (C) heat-fusion polymer (Example 17), and a crystalline copolyester resin (glass transition temperature 3°C) as the (C) heat-fusion polymer (Example 18).

[0096] The multipurpose test pieces, filaments, and 3D printed objects obtained using these resin compositions (pellets) have good heat resistance, good filament diameter accuracy, and roundness, and have a high tensile breaking strength in the vertical axis (ZX) direction of 36 MPa or more.In addition, the ratio of the tensile breaking strength in the vertical axis (ZX) direction to the tensile breaking strength in the horizontal axis (XY) direction is also high at 0.83 or more, demonstrating an excellent balance of tensile breaking strength in the vertical axis and horizontal axis directions.

[0097] (Evaluation of Resin Compositions of Examples 11 to 14) Examples 11 to 14 shown in Table 3 are examples in which a mixture of aromatic polycarbonate resin and PBT resin was used as the (A) polycarbonate resin out of the three components of Example 2. Examples 11 to 13 use a mixture of MVR 90 cm3 as the PBT resin. 3 In Example 14, the PBT resin was MVR 19 cm3. 3 / 10 min (250 °C, load 1.2 kg) was used. The multipurpose test pieces, filaments, and 3D printed objects obtained using these resin compositions (pellets) have physical properties equivalent to or better than those of Example 2. In particular, the tensile breaking strength in the vertical axis (ZX) direction is high at 44 to 47 MPa, and the ratio of the tensile breaking strength in the vertical axis (ZX) direction to the tensile breaking strength in the horizontal axis (XY) direction is 0.92 or more, and the ratio of the tensile breaking strength in the horizontal axis (XY) direction to the tensile breaking strength of the molded product molded by injection molding is also high at 0.88 to 0.98, indicating an excellent balance of tensile breaking strength in the vertical axis and horizontal axis directions.

[0098] (Evaluation of Resin Compositions of Examples 19 to 22) Examples 19 to 22 shown in Table 4 are examples in which a mixture of aromatic polycarbonate resin and ASA resin was used as the (A) polycarbonate-based resin among the three components of Example 2. Examples 19 to 21 use a mixture of MVR 14 cm as the ASA resin. 3 In Example 22, the ASA resin was MVR25cm3 / 10 min (220°C, load 98N) and the mixing ratio was changed. 3 / 10 min (220 °C, load 98 N) was used. The multipurpose test pieces, filaments, and 3D printed objects obtained using these resin compositions (pellets) have physical properties equivalent to or better than those of Example 2, and in particular, the tensile breaking strength in the vertical axis (ZX) direction is high at 43 to 46 MPa, the ratio of the tensile breaking strength in the vertical axis (ZX) direction to the tensile breaking strength in the horizontal axis (XY) direction is high at 0.92 or more, and the ratio of the tensile breaking strength in the horizontal axis (XY) direction to the tensile breaking strength of the molded product molded by injection molding is high at 0.85 to 0.96, and the balance of the tensile breaking strength in the vertical axis and horizontal axis directions is excellent.

[0099] (Evaluation of Resin Compositions of Comparative Examples 1 to 4) On the other hand, in Comparative Examples 1 to 4 shown in Table 5, among the three components of Examples 1 to 5, (A) the polycarbonate resin is an aromatic polycarbonate resin, and the MVR is 27 cm 3 / 10min (Comparative Example 1), MVR is 2.8cm 3 / 10 min (Comparative Example 2), (A) a siloxane copolymer polycarbonate resin as the polycarbonate resin, with an MVR of 20.4 cm 3 / 10min (Comparative Example 3), MVR is 4cm 3 / 10 min (Comparative Example 4).

[0100] Regarding the multipurpose test pieces, filaments, and 3D-printed objects obtained using these resin compositions (pellets), Comparative Example 1 showed good results in terms of heat resistance and the tensile breaking strength in the longitudinal axis (ZX) direction of the 3D-printed object, and the ratio of the tensile breaking strength in the longitudinal axis (ZX) direction to the horizontal axis (XY) direction, but the filament diameter accuracy and roundness were poor. Comparative Example 2 showed excellent heat resistance and filament properties, but the tensile breaking strength in the longitudinal axis (ZX) direction of the 3D-printed object was low.

[0101] For Comparative Example 3, similar to Comparative Example 1, good results were obtained for heat resistance, the tensile breaking strength in the longitudinal axis (ZX) direction of the 3D printed object, and the ratio of the tensile breaking strength in the longitudinal axis (ZX) direction to the horizontal axis (XY) direction, but the filament diameter accuracy and roundness were poor. For Comparative Example 4, similar to Comparative Example 2, the heat resistance and filament physical properties were excellent, but the tensile breaking strength in the longitudinal axis (ZX) direction of the 3D printed object was low.

[0102] (Evaluation of the resin composition of Comparative Example 5) In Comparative Example 5, a mixture of aromatic polycarbonate resin and PBT resin was used as the (A) polycarbonate-based resin, with the mixing ratio of aromatic polycarbonate resin / PBT resin being 50 / 50, as compared to Example 13. The multipurpose test pieces, filaments, and 3D-printed objects obtained using this resin composition (pellets) had a deflection temperature under load of less than 100°C, exhibiting poor heat resistance, and the filament had poor diameter accuracy and roundness.

[0103] (Evaluation of Resin Compositions of Comparative Examples 6 to 10) Comparative Examples 6 to 10 shown in Table 5 are those in which, of the three components of Example 2, the heat-sealing polymer (C) was changed to polycaprolactone (molecular weight 50,000) (Comparative Example 6), polycaprolactone diol (molecular weight 4,000) (Comparative Example 7), a crystalline copolymer polyester resin (glass transition temperature 19°C) (Comparative Example 8), an amorphous copolymer polyester resin (glass transition temperature 47°C) (Comparative Example 9), or an amorphous copolymer polyester resin (glass transition temperature 7°C) (Comparative Example 10).

[0104] Regarding the multipurpose test pieces, filaments, and 3D-printed objects obtained using these resin compositions (pellets), the tensile breaking strength in the longitudinal axis (ZX) direction of the 3D-printed objects was low in all of Comparative Examples 6 to 10. Comparative Example 7 also had poor filament properties (diameter accuracy and roundness).

[0105] (Evaluation of Resin Compositions of Comparative Examples 11 and 13) Comparative Examples 11 and 13 shown in Table 6 are those that do not contain (C) the thermally fused polymer (Comparative Example 11) and those that do not contain (B) the resin-modified polymer (Comparative Example 13) among the three components of Example 2. Regarding the multipurpose test pieces, filaments, and 3D-printed objects obtained using these resin compositions (pellets), Comparative Example 11 had extremely low tensile breaking strength in the longitudinal axis (ZX) direction of the 3D-printed object, and Comparative Example 13 had poor filament properties (diameter accuracy and roundness) and also low tensile breaking strength in the longitudinal axis (ZX) direction of the 3D-printed object.

[0106] (Evaluation of Resin Compositions of Comparative Examples 12 and 14) For Comparative Example 12 shown in Table 6, the blending ratio (ratio) of (C) polycaprolactone (molecular weight 10,000), a thermally fused polymer, among the three components of Example 2, was 20 wt%. The multipurpose test piece, filament, and 3D printer-modeled object obtained using this resin composition (pellets) had a deflection temperature under load of less than 100°C, exhibiting poor heat resistance, and the filament properties (diameter accuracy and roundness) were poor. For Comparative Example 14, the blending ratio (ratio) of (B) core-shell polymer, a resin-modified polymer, among the three components of Example 2 was 25 wt%. The multipurpose test piece, filament, and 3D printer-modeled object obtained using this resin composition (pellets) exhibited poor filament properties (diameter accuracy and roundness).

[0107] (Evaluation of the resin composition of Comparative Example 15) In Comparative Example 15 shown in Table 6, the blend ratio of the aromatic polycarbonate resin and ASA resin mixture was changed to aromatic polycarbonate resin / ASA resin = 50 / 50 compared to Example 21. The multipurpose test pieces, filaments, and 3D printed objects obtained using this resin composition (pellets) had poor heat resistance with deflection temperatures under load of less than 100°C, and the filament properties (diameter accuracy and roundness) were also poor.

[0108] As described in detail above, according to the resin composition of this embodiment, by blending three components, namely, polycarbonate resin, resin-modified polymer, and heat-fusion polymer, within a predetermined weight ratio range, it is possible to obtain a filament for 3D printers that has excellent moldability (diameter accuracy and roundness) and excellent strength in the longitudinal axis direction (ZX) of a 3D printed object.

[0109] Although the polycarbonate resin composition used in a filament melting 3D printer has been described above based on an embodiment of the present invention, the present invention is not limited to these embodiments. That is, the present embodiment is not only preferably applicable to a filament melting 3D printer that uses a filament, but also to a molten granular 3D printer that does not require a filament. [Industrial Applicability]

[0110] The resin composition of the present invention can provide a polycarbonate-based resin composition that can be suitably used not only in 3D printers using a filament melting method, but also in 3D printers using a molten granular method. [Explanation of symbols]

[0111] 1: Multipurpose test piece, L: Length, L1: First length, L2: Second length, T: Thickness, W: Width, EW: edge width, a: radius at maximum diameter of filament cross section, b: radius at minimum diameter of filament cross section, 10: test piece

Claims

1. A polycarbonate-based resin composition for 3D printers containing (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer, the polycarbonate-based resin (A) is a polycarbonate resin, or a mixture of a polycarbonate resin and a PBT resin, or a mixture of a polycarbonate resin and an ASA resin, and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 100 to 55% by weight and 0 to 45% by weight, respectively, and the polycarbonate resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin; The resin-modified polymer (B) is a core-shell polymer, the heat-fusion polymer (C) is polycaprolactone or a crystalline copolymer polyester resin, When the total weight of the polycarbonate-based resin (A), the resin-modified polymer (B), and the heat-fusion polymer (C) is 100% by weight, the ratio of the polycarbonate-based resin (A) to the total weight is in the range of 65% by weight to 92% by weight, the ratio of the resin-modified polymer (B) to the total weight is in the range of 5% by weight to 20% by weight, and the ratio of the heat-fusion polymer (C) to the total weight is in the range of 3% by weight to 15% by weight, a tensile strength ratio of the vertical axis (ZX) to the horizontal axis (XY) of an object produced from the polycarbonate-based resin composition using a general-purpose FFF 3D printer is 0.6 or more (wherein the object has a length L of 130 mm, a thickness T of 4±0.2 mm, a width W of 10±0.2 mm, an edge width EW of 20 mm, a first length L1 of 74 mm, and a second length L2 of 40 mm, a nozzle temperature of 280°C, a build plate temperature of 120°C, and a chamber temperature of 50 to 60°C); Polycarbonate resin composition for 3D printers.

2. 2. The polycarbonate-based resin composition for 3D printers according to claim 1, wherein the polycarbonate-based resin (A) is a mixture of a polycarbonate resin and a PBT resin or a mixture of a polycarbonate resin and an ASA resin, and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 95 to 55% by weight, and 5 to 45% by weight of the PBT resin or the ASA resin.

3. The polycarbonate-based resin (A) has an MVR of 8 to 19 g / min measured at 300 ° C. under a load of 1.2 kg, the core material of the core-shell polymer that is the resin-modified polymer (B) is acrylic rubber or silicone-acrylic composite rubber, and has an average particle diameter of 100 to 700 nmφ, the number average molecular weight of the polycaprolactone that is the heat-fusion polymer (C) is 10,000 to 25,000, and the glass transition temperature of the crystalline copolymer polyester resin is 5 ° C. or less. The polycarbonate-based resin composition for 3D printers according to claim 1 or 2.

4. A polycarbonate-based resin composition for a 3D printer, comprising (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer, the polycarbonate-based resin (A) is a polycarbonate resin, or a mixture of a polycarbonate resin and a PBT resin, or a mixture of a polycarbonate resin and an ASA resin, and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 100 to 55% by weight and 0 to 45% by weight, respectively, and the polycarbonate resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin; The resin-modified polymer (B) is a core-shell polymer, the heat-fusion polymer (C) is polycaprolactone or a crystalline copolymer polyester resin, When the total weight of the polycarbonate-based resin (A), the resin-modified polymer (B), and the heat-fusion polymer (C) is 100% by weight, the ratio of the polycarbonate-based resin (A) to the total weight is in the range of 65% by weight to 92% by weight, the ratio of the resin-modified polymer (B) to the total weight is in the range of 5% by weight to 20% by weight, and the ratio of the heat-fusion polymer (C) to the total weight is in the range of 3% by weight to 15% by weight, A polycarbonate-based resin composition for 3D printers, wherein a shaped body formed using a general-purpose FFF 3D printer from the polycarbonate-based resin composition has a tensile break strength in the vertical axis (ZX) direction of 35 MPa or more.

5. A polycarbonate-based resin composition for a 3D printer, comprising (A) a polycarbonate-based resin, (B) a resin-modified polymer, and (C) a heat-fusion polymer, the polycarbonate-based resin (A) is a polycarbonate resin, or a mixture of a polycarbonate resin and a PBT resin, or a mixture of a polycarbonate resin and an ASA resin, and the mixing ratio of the polycarbonate resin to the PBT resin or the ASA resin is 100 to 55% by weight and 0 to 45% by weight, respectively, and the polycarbonate resin is an aromatic polycarbonate resin or a siloxane copolymer polycarbonate resin; The resin-modified polymer (B) is a core-shell polymer, the heat-fusion polymer (C) is polycaprolactone or a crystalline copolymer polyester resin, When the total weight of the polycarbonate-based resin (A), the resin-modified polymer (B), and the heat-fusion polymer (C) is 100% by weight, the ratio of the polycarbonate-based resin (A) to the total weight is in the range of 65% by weight to 92% by weight, the ratio of the resin-modified polymer (B) to the total weight is in the range of 5% by weight to 20% by weight, and the ratio of the heat-fusion polymer (C) to the total weight is in the range of 3% by weight to 15% by weight, A polycarbonate-based resin composition for 3D printers, in which the ratio of the tensile breaking strength along the horizontal axis (XY) of a molded object produced from the polycarbonate-based resin composition using a general-purpose FFF 3D printer to the tensile breaking strength of a molded article produced by injection molding is 0.6 or more.

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