Resin composition for three-dimensional molding apparatus, filament for three-dimensional molding apparatus, molded article, pellet for three-dimensional molding apparatus, and resin composition for injection molding

Abstract

To provide a resin composition for a three-dimensional molding apparatus which can reduce warpage of a molded article having an edge without using a predetermined sheet and adhesive during molding, a filament for a three-dimensional molding apparatus, a molded article, a pellet for a three-dimensional molding apparatus, and a resin composition for injection molding.SOLUTION: A resin composition for a three-dimensional molding apparatus contains (A) a thermoplastic resin, and (B) a modified thermoplastic resin containing butene-based polyolefin in a skeleton, wherein (B) the modified thermoplastic resin containing the butene-based polyolefin in the skeleton is (C) a modified resin composed of a polymer which has a reactive group and has a molecular chain composed of a non-polar polymer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resin composition for a three-dimensional modeling device, a filament for a three-dimensional modeling device, a shaped object, a pellet for a three-dimensional modeling device, and a resin composition for injection molding. In particular, the present invention relates to a resin composition for a three-dimensional modeling device, a filament for a three-dimensional modeling device, a shaped object, a pellet for a three-dimensional modeling device, and a resin composition for injection molding, which contain a butene-based polyolefin. [Background technology]

[0002] Conventionally, a resin molding material for a three-dimensional modeling device is known, which contains 30 to 80 mass% of a thermoplastic resin (A), 1 to 45 mass% of a thermoplastic elastomer (B), 0.5 to 15 mass% of a modifier (C), and 5 to 35 mass% of a tackifier resin (D) (however, when the thermoplastic elastomer (B) is a functionalized thermoplastic elastomer to which a functional group is added, the modifier (C) may not be included) (see, for example, Patent Document 1). According to the resin molding material for a three-dimensional modeling device according to Patent Document 1, a general-purpose resin such as polypropylene resin can be used, and a resin molding material for a three-dimensional modeling device having low density, heat resistance, durability, impact resistance, moldability, and low shrinkage can be provided. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-157609 A Summary of the Invention [Problem to be solved by the invention]

[0004] Here, in the conventional technology including the resin molding material for a three-dimensional modeling device described in Patent Document 1, warping of the modeled object is reduced by adding elastomer or rubber to the resin molding material for a three-dimensional modeling device. However, for example, in the resin molding material for a three-dimensional modeling device described in Patent Document 1, even though the three-dimensional object to be modeled is merely a flat plate with a thickness of 2 mm, it is an essential requirement to attach a polyimide film onto the stage of the three-dimensional modeling device and further apply a 3D stage sealant (a water-soluble adhesive) onto the polyimide film in order to reduce warping (see paragraph 0075 of Patent Document 1).

[0005] This is because the warping of the bottom surface of a model produced using a 3D modeling apparatus increases as the number of layers increases, and therefore the prior art including Patent Document 1 is unable to ensure adhesion of the resin molding material for the 3D modeling apparatus to the stage (stage of the modeling apparatus). Therefore, the prior art cannot omit the adhesive application process to the stage or film. For example, when producing a model using a crystalline resin such as polypropylene, even if a model with a small number of layers such as a flat plate can be produced with relatively little warping, a model with a large number of layers such as a box will warp and the model cannot be produced, making the adhesive application process an essential process.

[0006] Therefore, an object of the present invention is to provide a resin composition for a three-dimensional modeling device, a filament for a three-dimensional modeling device, a model, a pellet for a three-dimensional modeling device, and a resin composition for injection molding that can reduce warping of objects with edges without using a specific sheet or adhesive during modeling. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, the present invention provides a resin composition for a three-dimensional modeling device, which contains (A) a thermoplastic resin and (B) a modified thermoplastic resin that has been modified with a polymer that has reactive groups and whose molecular chain is a nonpolar polymer, and contains a butene-based polyolefin in its skeleton.

[0008] In addition, in order to achieve the above-mentioned object, the present invention provides a filament for a three-dimensional modeling device comprising the above-mentioned resin composition for a three-dimensional modeling device, a molded object comprising the above-mentioned resin composition for a three-dimensional modeling device, a pellet for a three-dimensional modeling device comprising the above-mentioned resin composition for a three-dimensional modeling device, and a resin composition for injection molding containing (A) a thermoplastic resin and (B) a modified thermoplastic resin that has been modified with a polymer that has reactive groups and whose molecular chain is a nonpolar polymer and contains a butene-based polyolefin in its skeleton. Effect of the Invention

[0009] The resin composition for a three-dimensional modeling device, the filament for a three-dimensional modeling device, the shaped object, the pellets for a three-dimensional modeling device, and the resin composition for injection molding according to the present invention can provide a resin composition for a three-dimensional modeling device, the filament for a three-dimensional modeling device, the shaped object, the pellets for a three-dimensional modeling device, and the resin composition for injection molding that can reduce warping of objects with edges without using a specified sheet or adhesive during modeling. [Brief description of the drawings]

[0010] [Figure 1] FIG. 11 is a diagram showing the relationship between the crystallization temperature and warpage of resin compositions for a three-dimensional object modeling apparatus according to each of Experimental Examples and Comparative Examples. [Diagram 2] FIG. 13 is a diagram showing the relationship between the amount of maleic acid introduced into the resin composition for a three-dimensional object modeling apparatus and warpage according to each experimental example. [Diagram 3] FIG. 13 is a diagram showing the relationship between the amount of component (B) added to the resin composition for a three-dimensional object modeling apparatus and warpage according to each experimental example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Embodiment Mode] In general, in a model manufactured using a three-dimensional modeling device (3D printer), the warping of the bottom surface (warping in the height direction of the model) increases with an increase in the number of layers. This is because when a molten resin is newly layered on top of the bottom surface of the resin composition that was initially injected and solidified, the newly layered molten resin shrinks as it solidifies, generating a pulling force toward the inside of the model on the upper side of the model. When this pulling force occurs, the bottom surface of the model is pulled in the height direction, causing warping (that is, when a model is layered on the stage of the modeling device, each layer shrinks, generating a force that pulls the bottom surface of the model upward in the height direction of the model, causing warping). This warping occurs significantly in three-dimensional objects having edges, such as a rectangular box. This is thought to be because stress due to the pulling force is concentrated on the edge parts (i.e., corner parts) of a three-dimensional object having edges, making it easy for large warping to occur.

[0012] Here, it is desired to adopt a general-purpose resin such as polypropylene (PP), which has extremely low water absorption, good post-processing properties, excellent impact resistance, chemical resistance, and heat resistance, and can be applied to various uses, as the resin composition for a three-dimensional modeling apparatus used in the three-dimensional modeling apparatus. However, for example, PP is a crystalline resin, and since its shrinkage rate is large at 1% to 2.5%, it is easy for a large warp due to shrinkage to occur during modeling (low moldability). Therefore, conventionally, adhesive is applied to the stage of the three-dimensional modeling apparatus or a dedicated PP sheet or the like is placed on the stage to maintain adhesion between the stage and a model made of the resin composition for a three-dimensional modeling apparatus, thereby physically suppressing the occurrence of warp. However, since PP has extremely weak adhesion to the sheet placed thereon (protective sheet, platform tape, etc.), it peels off from the stage even if modeled on the stage, and even if PP is used as it is as a resin composition for a three-dimensional modeling apparatus, it cannot withstand practical use. Furthermore, when creating large objects or objects with edges, if a conventional resin composition for a 3D modeling device, which is mainly made of PP, is used, warping may not be suppressed even if a specified sheet or adhesive is used.

[0013] As described above, since the adhesiveness of PP is extremely weak, when manufacturing a model on the stage of a three-dimensional modeling apparatus or on a sheet protecting the stage, it is necessary to fix the model to the stage and the sheet by applying a specific adhesive to the stage or the sheet. If modeling is performed without applying an adhesive, the model will peel off from the stage or the sheet due to insufficient adhesive strength or warping of the PP, making it impossible to model. When applying an adhesive to the stage or the sheet, not only is a process of drying the adhesive required after application, but it also requires the effort of cleaning the bottom surface of the model and the stage and the surface of the sheet after modeling. Furthermore, since a process of cleaning the stage and the surface of the sheet and applying adhesive is required every time modeling is performed, it is not suitable for continuous production of models.

[0014] There is also a method of using a dedicated PP sheet (PP sheet) as the sheet to adhere the model to the sheet. However, when a PP sheet is used, the bottom surface of the model and the PP sheet are fused, and the components of the PP sheet remain on the bottom surface of the model. In addition, if the PP sheet is fused to the bottom surface of the model, it is necessary to replace the PP sheet. Therefore, since commercially available PP sheets are expensive, the cost required for modeling increases. Furthermore, when replacing the PP sheet on the stage, it is difficult to clean the components (adhesive components) of the PP sheet remaining on the stage. Note that, although the protective sheet used in modeling using polylactic acid (PLA) and the like does not have an adhesive effect on the stage, it is difficult to break and can be used multiple times, and the adhesive components do not remain on the stage, the model and the protective sheet do not fuse, and the adhesive components of the protective sheet do not remain on the model. However, since the protective sheet does not have an adhesive effect, when modeling is performed with a three-dimensional modeling device using a resin filament made of PP, the model by the first layer modeling peels off from the protective sheet, and modeling cannot be performed in the first place.

[0015] In other words, since adhesives and sheets generally cannot be reused, it is necessary to reattach the sheet and reapply the adhesive every time modeling is performed, which not only requires the labor of manufacturing and replacing the sheet, but also requires the disposal of the adhesive and sheet resources. Therefore, when using a general-purpose resin such as PP as a resin composition for a three-dimensional modeling device, it is required to at least improve the moldability (improvements in warping and shrinkage rate correspond to improvements in moldability) and the adhesiveness.

[0016] Here, the present inventor attempted to further improve the resin composition for a three-dimensional modeling device developed so far in order to obtain a resin composition for a three-dimensional modeling device that can form a three-dimensional object having edges such as a rectangular parallelepiped using a three-dimensional modeling device without using a PP sheet or a dedicated adhesive and can reduce warping of the modeled object. The present inventor then investigated various blends of resin compositions and discovered a resin composition for a three-dimensional modeling device that can significantly reduce warping of the modeled object and can form a three-dimensional object having an edge. That is, the present inventor discovered that by using a resin composition for a three-dimensional modeling device in which a specific modified resin is contained in a thermoplastic resin, it is possible to ensure appropriate adhesion to the stage (and / or ensure appropriate adhesion to the extent that the sheet placed on the stage is not damaged) and to significantly reduce warping of the modeled object even if it is a model with edges such as a box. The specific modified resin is a modified thermoplastic resin that contains a butene-based polyolefin in the skeleton. The modified thermoplastic resin that contains a butene-based polyolefin in the skeleton is a modified resin obtained by modifying a thermoplastic resin that contains a butene-based polyolefin in the skeleton with a polymer that has a reactive group and has a nonpolar molecular chain. The present invention was created based on such findings.

[0017] In addition, by blending a polymer having a reactive group exhibiting hydrophilicity in a specific ratio range with the base resin (thermoplastic resin) of the resin composition for a three-dimensional modeling apparatus, moldability can be improved and an appropriate adhesive strength can be exhibited. Here, improving moldability means that warping and shrinkage occurring in the model can be reduced and a model consisting of a predetermined number of layers can be modeled. In addition, the appropriate adhesive strength means that the adhesive strength of the resin composition for a three-dimensional modeling apparatus to the stage and / or protective sheet of the three-dimensional modeling apparatus is in a range where a model made of the resin composition for a three-dimensional modeling apparatus can be fixed to the stage and / or protective sheet, and the model can be removed from the stage and / or protective sheet after modeling without causing damage to the protective sheet and the model.

[0018] <Outline of Resin Composition for Three-Dimensional Modeling Device> The resin composition for a three-dimensional modeling apparatus according to the embodiment of the present invention is modified by a polymer having a reactive group and a molecular chain that is a non-polar polymer, and is configured to include a material for a three-dimensional modeling apparatus containing a modified thermoplastic resin containing a butene-based polyolefin in the skeleton. Specifically, the resin composition for a three-dimensional modeling apparatus according to the present embodiment contains (A) a thermoplastic resin and (B) a modified thermoplastic resin which is modified by a polymer having a reactive group and a molecular chain that is a non-polar polymer, and contains a butene-based polyolefin in the skeleton. This resin composition for a three-dimensional modeling apparatus can ensure adhesion to the stage without using a protective sheet (such as a PP sheet or platform tape) or adhesive used in the three-dimensional modeling apparatus, so that even if a three-dimensional object having an edge (for example, a box-shaped object) is molded, warping at the bottom surface can be significantly suppressed.

[0019] In this embodiment, the term "molecular chain" refers to a structure including all or a part of a polymer, oligomer molecule, or block composed of structural units linked in a linear or branched manner between terminal groups, branching points, or boundary structural units specific to a polymer.

[0020] <Details of Resin Composition for Three-Dimensional Modeling Apparatus> [(A) Thermoplastic resin] Examples of the (A) thermoplastic resin (hereinafter, sometimes referred to as "component (A)") include styrene-based resins, acrylic-based resins, aromatic polycarbonate-based resins, aliphatic polycarbonate-based resins, aromatic polyester-based resins, aliphatic polyester-based resins, olefin-based resins (e.g., aliphatic polyolefin-based resins, cyclic olefin-based resins), polyamide-based resins, polyphenylene ether-based resins, thermoplastic polyimide-based resins, polyacetal-based resins, polysulfone-based resins, and amorphous fluorine-based resins.

[0021] In this embodiment, the thermoplastic resin (A) is preferably an olefin resin, more preferably polypropylene, from the viewpoint of properties such as water absorption, post-processability, impact resistance, chemical resistance, and / or heat resistance. In addition, either homopolypropylene or random polypropylene can be used as the polypropylene. The polypropylene is preferably random polypropylene (random copolymer), from the viewpoint of being less likely to crystallize than homopolypropylene and being able to further reduce warping of the molded object.

[0022] (Amount of component (A)) The blending amount of component (A) is 40 wt% or more, optionally 50 wt% or more, optionally 60 wt% or more, and is 90 wt% or less, optionally 80 wt% or less, optionally 70 wt% or less.

[0023] [(B) Modified thermoplastic resin] The modified thermoplastic resin (B) (hereinafter sometimes referred to as "component (B)"), which is modified with a polymer having a reactive group and a molecular chain of a nonpolar polymer and contains a butene-based polyolefin in the skeleton, may be a modified resin obtained by modifying a thermoplastic resin containing a butene-based polyolefin in the skeleton with a polymer (C) (hereinafter sometimes referred to as "component (C)") having a reactive group and a molecular chain of a nonpolar polymer, which will be described later. Specific examples of component (B) include modified ethylene-propylene-butene copolymers and / or modified propylene-butene copolymers.

[0024] In this embodiment, the (B) component is preferably a modified resin when the (C) component is maleic anhydride modified polypropylene (MAPP). That is, the (B) component is preferably an ethylene-propylene-butene copolymer modified with MAPP (hereinafter, sometimes referred to as "maleic acid modified ethylene-propylene-butene copolymer") and / or a propylene-butene copolymer modified with MAPP (hereinafter, sometimes referred to as "maleic acid modified propylene-butene copolymer").

[0025] (Molecular weight of component (B)) From the viewpoint of reducing warpage of the molded product and ensuring adhesion, the molecular weight (weight average molecular weight) of component (B) is 50,000 or more, preferably 60,000 or more, and 100,000 or less, preferably 95,000 or less. The weight average molecular weight can be determined using high-temperature gel permeation chromatography (high-temperature GPC) in terms of polystyrene, and then calculated in terms of polypropylene using the Q factor.

[0026] (Amount of component (B)) From the viewpoint of reducing warping of the molded object and ensuring adhesion, the blending amount of the (B) component is preferably 2.0 wt% or more, more preferably 5.0 wt% or more, even more preferably 8.0 wt% or more, preferably 20 wt% or less, also preferably 18 wt% or less, and even more preferably 15 wt% or less.

[0027] [(C) Polymer having reactive groups and non-polar molecular chains] The component (C) is a polymer having a reactive group capable of reacting with other substituents, and the molecular chain is substantially non-polar or hydrophobic. The component (C) only needs to have a reactive group in the molecular chain, and the chain length of the reactive group does not need to be controlled. In addition, other structural units may be included in a part of the molecular chain. Furthermore, the non-polar polymer in the molecular chain may have other groups different from the reactive group. In addition, it is particularly preferable that the component (C) is a graft type polymer.

[0028] (Reactive group) The reactive group includes at least one hydrophilic group selected from the group consisting of a succinic anhydride group, a carbonyl group (eg, a methoxycarbonyl group), and a carboxyl group.

[0029] (Nonpolar polymer) A non-polar polymer is a polymeric substance that does not have a permanent dipole, and is considered a non-polar polymer even if it contains a permanent dipole derived from impurities that are mixed in under normal use conditions or from additives that are normally added, etc. Examples of non-polar polymers include polyethylene resin, polypropylene resin, and tetrafluoroethylene resin.

[0030] In this embodiment, the non-polar polymer, which is a molecular chain, may be a substantially non-polar or hydrophobic olefin-based resin, such as polypropylene, polyethylene, a resin obtained by homopolymerizing or copolymerizing two or more kinds of α-olefins (e.g., propylene, 1-butene, 1-pentene, etc.), ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer resin, propylene-α-olefin copolymer, etc.

[0031] In addition, when the molecular chain is an ethylene-vinyl acetate copolymer resin, a (meth)acrylic resin, or the like, the reactive group may be a methoxycarbonyl group or the like contained in the molecular chain. In this case, the non-polar polymer in this embodiment refers to the molecular structure of the portion containing a methoxycarbonyl group or the like (in this case, the molecular chain refers to a structure in which the molecular chain itself contains a reactive group. In this case, if the molecular chain portion excluding the reactive group is non-polar, it is considered to be a non-polar polymer). In addition, another reactive group (a reactive group different from a methoxycarbonyl group) may be separately introduced into the ethylene-vinyl acetate copolymer resin, the (meth)acrylic resin, or the like by graft polymerization or the like.

[0032] The non-polar polymer is preferably at least one non-polar polymer selected from the group consisting of polypropylene, ethylene-vinyl acetate copolymer resin, and acrylic resin, from the viewpoints of availability, low specific gravity, versatility, physical properties, and / or processability. Among these, polypropylene is more preferable from the viewpoint of physical properties. Note that these olefin resins may contain other copolymerizable units. Moreover, these olefin resins may be used alone or in combination of two or more kinds.

[0033] (polymer) Examples of the polymer containing the above molecular chain and reactive group include various polymers that combine the above molecular chain and the above reactive group. Examples include polypropylene, ethylene-vinyl acetate copolymer resin, and acrylic resin that have at least one of the above reactive groups. As the polymer, a polymer in which the reactive group is bonded to the molecular chain like a pendant group is more preferable, and for example, a graft copolymer is preferable. Among the above polymers, it is most preferable to use maleic anhydride-modified polypropylene (MAPP), which has maleic anhydride groups as reactive groups and has polypropylene molecular chains, from the viewpoint of imparting hydrophilicity to the resin composition for a three-dimensional modeling apparatus.

[0034] (molecular weight) The weight average molecular weight of the (C) component may be lower than the weight average molecular weight of the (A) component from the viewpoint of ease of handling. From the viewpoint of reducing the warpage of the molded object without increasing it, the weight average molecular weight of the (C) component is preferably 100,000 or less, more preferably 90,000 or less, even more preferably 70,000 or less, more preferably 65,000 or less, and even more preferably 60,000 or less. From the viewpoint of ensuring the effect of reducing the warpage of the molded object, the weight average molecular weight of the (C) component is preferably 20,000 or more, even more preferably 25,000 or more, even more preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more. The weight average molecular weight can be calculated as a polystyrene equivalent using high-temperature gel permeation chromatography (high-temperature GPC) and then calculated as a polypropylene equivalent using a Q factor.

[0035] (Graft ratio in component (B)) When the component (C) is a graft type polymer (i.e., a graft copolymer), the adhesive strength of the resin composition for a three-dimensional modeling apparatus is improved by having a reactive group. However, from the viewpoint of further improving the adhesive strength of the resin composition for a three-dimensional modeling apparatus, it is preferable to increase the graft ratio in the component (B). In other words, even if the graft ratio is low, the adhesive strength is improved, but the adhesive strength tends to be further improved when the graft ratio is increased. In addition, the warping of the object formed using the resin composition for a three-dimensional modeling apparatus also tends to be reduced when the component (C) has a reactive group. This is partly because the adhesive strength is improved by the presence of the reactive group. However, from the viewpoint of further reducing the warping of the resin composition for a three-dimensional modeling apparatus, it is preferable to increase the graft ratio. In other words, even if the graft ratio is low, the warping is reduced, but the warping tends to be further reduced when the graft ratio is increased. However, if the adhesive strength is increased too much, the object made of the resin composition for a three-dimensional modeling apparatus and the stage of the three-dimensional modeling apparatus or the resin sheet placed on the stage are strongly adhered to each other, and it may be difficult to remove the object from the stage or the resin sheet. Therefore, from the viewpoint of facilitating removal of the shaped object from the stage or the resin sheet, it is preferable to set upper and lower limits for the graft ratio.

[0036] In this embodiment, when component (C) is a graft copolymer (for example, when MAPP), from the viewpoint of improving adhesive strength and / or reducing warpage, and from the viewpoint of ease of forming a three-dimensional object having edges, the graft ratio in component (B) is 1.0% or more, and preferably 1.1% or more, and is 2.5% or less, and preferably 2.0% or less.

[0037] (Amount of reactive group introduced) By including a predetermined ratio of component (C) (component (C) introduced into component (B)) in component (A), the adhesive strength of the resin composition for a three-dimensional modeling apparatus is improved and warping of the resin composition for a three-dimensional modeling apparatus (and / or the modeled object) is reduced. Furthermore, by setting the ratio of the reactive groups of component (C) introduced into component (B) contained in the resin composition for a three-dimensional modeling apparatus within a predetermined range, the adhesive strength of the resin composition for a three-dimensional modeling apparatus is improved and warping is reduced. The present inventors have found that when a modified resin containing a butene-based polyolefin in the skeleton is used as component (B), it is possible to achieve both improved adhesive strength and reduced warping of the resin composition for a three-dimensional modeling apparatus even when the amount of reactive groups introduced is small.

[0038] That is, when the (C) component is a graft copolymer, the value obtained by multiplying the mass ratio of the (B) component to the total mass of the resin composition for a three-dimensional modeling apparatus by the graft ratio in the (B) component (hereinafter, sometimes referred to as the "amount of reactive groups introduced") can be set within a predetermined range, thereby improving the adhesive strength of the resin composition for a three-dimensional modeling apparatus and reducing warpage. For example, when the mass ratio of the (B) component to the total mass of the resin composition for a three-dimensional modeling apparatus is 10 wt%, and the graft ratio of the (C) component in the (B) component is 2.0%, the amount of reactive groups introduced is calculated as 10 x 2.0 / 100 = 0.200 (%). Specifically, when a modified thermoplastic resin containing a butene-based polyolefin in its skeleton, that is, the (B) component according to this embodiment, is used, the amount of reactive groups introduced is 0.020% or more, may be 0.022% or more, may be 0.030% or more, may be 0.3% or less, and may be 0.2% or less. In this embodiment, since component (B) contains a butene-based polyolefin in the skeleton, even if the amount of reactive groups introduced is as small as 0.020% or more and 0.3% or less, it is possible to achieve both improved adhesive strength and reduced warping of the resin composition for three-dimensional modeling apparatus and then perform modeling. Note that the amount of reactive groups introduced must be at least less than 0.57%, and when it is 0.51% or less, it is possible to achieve both improved adhesive strength and reduced warping of the resin composition for three-dimensional modeling apparatus and perform modeling.

[0039] [(D) Low crystalline polypropylene] The resin composition for a three-dimensional object forming apparatus according to this embodiment may further contain (D) low crystalline polypropylene (hereinafter, sometimes referred to as "component (D)"). By containing component (D), warping of the resin composition for a three-dimensional object forming apparatus can be further reduced. Component (D) is preferably a low crystalline homopolypropylene.

[0040] (D) Low crystalline polypropylene has a melting point (T m ) is 0° C. or more and 120° C. or less. The weight average molecular weight of component (D) is preferably 10,000 or more, more preferably 30,000 or more, and even more preferably 50,000 or more, and is preferably 200,000 or less, and more preferably 150,000 or less. The weight average molecular weight can be determined using high temperature gel permeation chromatography (high temperature GPC) in terms of polystyrene, and then calculated in terms of polypropylene using the Q factor.

[0041] Examples of the (D) component include low-elasticity, low-molecular-weight polyolefins, such as low-elasticity, low-molecular-weight polyolefins having a melt flow rate (MFR) of 500 (g / 10 min) (230°C, 2.16 kg) or less (trade name: L-MODU S600, L-MODU S901, manufactured by Idemitsu Kosan Co., Ltd.) and low-elasticity, low-molecular-weight polyolefins having a melt flow rate (MFR) of 100 (g / 10 min) (230°C, 2.16 kg) or less (trade name: L-MODU S901, manufactured by Idemitsu Kosan Co., Ltd.). Also, examples of the (D) component that can be used include low-elasticity, low-molecular-weight polyolefins having a melt viscosity at 170°C of 5000 to 7000 mPa s (trade name: Licocene, manufactured by Clariant).

[0042] (Amount of component (D)) Increasing the amount of component (D) tends to reduce warping of the molded object, and increasing the amount further may reduce the rigidity of the resin composition for a three-dimensional modeling apparatus. Therefore, the amount of component (D) may be 1 wt% or more, 3 wt% or more, 5 wt% or more, less than 10 wt%, or 7 wt% or less. When component (B) is used, the amount of component (D) is 1 wt% or more and less than 10 wt%, thereby improving the effect of suppressing warping of the resin composition for a three-dimensional modeling apparatus and / or the molded object.

[0043] [Filler] The resin composition for a three-dimensional modeling apparatus according to the present embodiment may contain a filler in order to improve strength. The filler is not particularly limited as long as it has a size that allows it to pass through the nozzle of a three-dimensional modeling apparatus. Examples of the filler include glass fiber, carbon fiber, calcium carbonate, and / or talc.

[0044] <Other compounding substances> Various compounding substances such as bulking agents, plasticizers, moisture absorbents, property adjusters, reinforcing agents, colorants, flame retardants, antioxidants, antiaging agents, conductive agents, antistatic agents, UV absorbers, UV dispersants, solvents, fragrances, deodorizers, pigments, dyes, diluents, etc. may be added to the resin composition for use in a 3D modeling apparatus according to this embodiment, as necessary, within the scope that does not impair the physical properties, etc., of the resin composition for use in a 3D modeling apparatus.

[0045] <Crystallization temperature and crystallization heat value of resin composition for 3D modeling apparatus> From the viewpoint of realizing easy modeling and / or reducing warpage in a resin composition for a three-dimensional modeling device, the present inventors focused on the crystallization temperature of the resin and the amount of heat generated by crystallization. That is, a lower crystallization temperature allows the temperature at which the resin is kept warm after melting to be lower. Also, a higher crystallization temperature and a larger amount of heat generated by crystallization mean that a larger amount of resin crystallizes. When a resin crystallizes, the resin is packed more densely (resin molecules come into contact with each other) than before crystallization, and the volume shrinks. As a result, warpage occurs in an object made of crystallized resin, and it is believed that the greater the degree of crystallization, the greater the warpage that occurs.

[0046] From this viewpoint, the present inventors have investigated the crystallization temperature by adjusting the composition of the resin composition for a three-dimensional modeling apparatus, and have found that the crystallization temperature is preferably 110° C. or lower, and more preferably 107° C. or lower.

[0047] The present inventor also found that it is preferable to use the (B) component according to the present embodiment in order to prevent the packing of the resin crystals due to the crystallization of the (A) component, which is the base of the resin composition for a three-dimensional modeling device, from becoming dense. That is, the (B) component is preferably a resin that has a bulkier molecular structure than the (A) component and has a low density, which makes it difficult to crystallize. In addition, from the viewpoint of improving compatibility with the (A) component, it was found that it is preferable to use the (B) component whose base structure (i.e., skeletal structure) contains at least a part of the same structure as the (A) component. For example, when PP is used as the (A) component, it is preferable to use a butene-based polyolefin resin containing propylene in the skeleton as the (B) component. By using such a (B) component, the (B) component is uniformly dispersed in the (A) component, and volume shrinkage due to crystallization can be suppressed. As a result, it is considered that the warping of the molded object can also be reduced.

[0048] From the above viewpoint, the present inventor has discovered that the crystallization heat value of the resin composition for a three-dimensional modeling apparatus according to this embodiment is preferably 40 mJ / mg or less when cooled at a rate of 20°C / min as measured by a differential scanning calorimeter (DSC).

[0049] <Application Areas> The resin composition for a three-dimensional modeling apparatus according to the present embodiment can be used for various applications. Specifically, it can be used for various products such as various structures, various parts (electrical and electronic parts, automotive parts, etc.), home appliances, housing and building materials, and packaging materials. Since the resin composition for a three-dimensional modeling apparatus according to the present embodiment has an appropriate adhesive strength to the stage of the three-dimensional modeling apparatus and / or the resin sheet placed on the stage, it can be used as a filament for a three-dimensional modeling apparatus that does not require the use of adhesives that have been used in the past. Using this filament for a three-dimensional modeling apparatus, a modeled object of a desired shape can be manufactured by a three-dimensional modeling apparatus.

[0050] The resin composition for a three-dimensional modeling apparatus according to the present embodiment can also be molded into a pellet shape and used as pellets for a three-dimensional modeling apparatus. As with the filament for a three-dimensional modeling apparatus, the pellets for a three-dimensional modeling apparatus can also be used in a three-dimensional modeling apparatus that models by feeding a pellet-shaped material. Furthermore, the resin composition for a three-dimensional modeling apparatus according to the present embodiment can significantly reduce warping of a modeled object when it is melted and then hardened, and can therefore also be used as a resin composition for a fused deposition modeling (FDM) modeling apparatus.

[0051] Furthermore, the resin composition for a three-dimensional modeling apparatus according to this embodiment can also be used as a resin composition for injection molding. Usually, in injection molding, shrinkage occurs in the molded body due to volumetric shrinkage caused by crystallization of the resin composition. On the other hand, the resin for a three-dimensional modeling apparatus according to this embodiment can be used as a resin composition for injection molding because it can suppress crystallization of component (A) and reduce warping of the molded object. By forming a resin composition for injection molding using the resin for a three-dimensional modeling apparatus according to this embodiment, effects such as reduction in volumetric shrinkage and deformation of the molded product during injection molding can be obtained, and molded products with high-precision dimensions can be obtained.

[0052] <Method of manufacturing resin composition for three-dimensional modeling device> There is no particular limitation on the method for producing the resin composition for a three-dimensional modeling apparatus according to the present embodiment. For example, the resin composition can be produced by blending a predetermined amount of the (A) component and the (B) component, and further blending the (D) component and other blending substances as necessary, and stirring the mixture. The order of blending the components and other blending substances is not particularly limited and can be determined appropriately. In addition, the resin composition for a three-dimensional modeling apparatus according to the present embodiment can improve the modeling properties even when the amount of the (B) modified thermoplastic resin containing a butene-based polyolefin in its skeleton is about 2.0 wt%. Therefore, the resin composition for a three-dimensional modeling apparatus according to the present embodiment obtained by blending a predetermined amount of the (A) component and the (B) component, and further blending the (D) component and other blending substances as necessary, and kneading the blend, can be used as a master batch, and a composition obtained by adding this master batch to various base materials can be used to form a model.

[0053] <Manufacturing method for molded objects> A resin filament for use in a three-dimensional modeling device (3D printer) is produced using the resin composition for a three-dimensional modeling device according to the present embodiment, using a known technique. The produced resin filament is then set in the three-dimensional modeling device, and a model is produced under predetermined conditions. In producing a model, a resin filament made of the resin composition for a three-dimensional modeling device according to the present embodiment may be directly applied to the stage of the three-dimensional modeling device. However, from the viewpoint of preventing wear and tear on the stage, it is preferable to place a protective sheet on the stage. There is no particular limitation on the protective sheet as long as it can be attached to the stage. For example, the protective sheet may be a polyimide sheet, an acrylic resin sheet, a PP sheet, a masking tape, a masking tape, and / or a cellophane tape. Note that, for these protective sheets, the amount of reactive groups introduced is preferably within the range described above. In addition, when a random polymer (e.g., random polypropylene) is used as the (A) component, a model can be produced without a protective sheet.

[0054] <Effects of the embodiment> The resin composition for a three-dimensional modeling apparatus according to the present embodiment contains component (A) and component (B), which is a modified resin capable of suppressing the crystallization of component (A) and contains a butene-based polyolefin in its skeleton, and therefore can ensure adhesion to the stage of the three-dimensional modeling apparatus without placing a dedicated PP sheet on the stage of the three-dimensional modeling apparatus and without improving the adhesion between the model and the stage with an adhesive. Furthermore, the resin composition for a three-dimensional modeling apparatus according to the present embodiment can form a model with significantly reduced warping of the bottom surface, even if the model is a box-shaped object with edges.

[0055] In addition, since the resin composition for a three-dimensional object according to the present embodiment has good adhesion and can significantly reduce warping of the object, it can form an object on a stage of a modeling apparatus made of a material that has poor adhesion to PP. For example, in a modeling apparatus, an object can be formed on a base material that has poor adhesion to PP, such as an xyz platform sheet, an xyz platform plate on which no sheet is placed, a glass plate, and / or a polyimide sheet.

[0056] <Experimental Example> The present invention will be described in more detail below with reference to experimental examples. It should be noted that these experimental examples are merely illustrative and should not be construed as limiting.

[0057] (Preparation of Experimental Examples 1 to 20 and Comparative Examples 1 to 13) Each compounding material was mixed and stirred at the mixing ratio shown in Table 1 to prepare resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20. Also, each compounding material was mixed and stirred at the mixing ratio shown in Table 2 to prepare resin compositions for Comparative Examples 1 to 13.

[0058] [Table 1]

[0059] [Table 2]

[0060] Details of the compounded substances in Tables 1 and 2 are as follows. (Component A: Thermoplastic resin) PM940M (Sunallomer Co., Ltd., random polypropylene) PM731M (Sunallomer Co., Ltd., random polypropylene) (Component B: Modified thermoplastic resin) PMA-F2 (Toyobo MC Co., Ltd., maleic anhydride modified ethylene-propylene-butene copolymer, weight average molecular weight 70,000, graft ratio 1.5%) PMA-F6 (Toyobo MC Co., Ltd., maleic anhydride modified ethylene-propylene-butene copolymer, weight average molecular weight 60,000, graft ratio 2.0%) PMA-T (Toyobo MC Co., Ltd., maleic anhydride modified propylene-butene copolymer, weight average molecular weight 75,000, graft ratio 1.5%) PMA-TE (Toyobo MC Co., Ltd., maleic anhydride modified propylene-butene copolymer, weight average molecular weight 60,000, graft ratio 1.8%) PMA-TH (Toyobo MC Co., Ltd., maleic anhydride modified propylene-butene copolymer, weight average molecular weight 95,000, graft ratio 1.1%) (B' component: modified thermoplastic resin) MG250P (manufactured by Riken Vitamin Co., Ltd., maleic anhydride modified polypropylene, weight average molecular weight: 58,000, graft ratio: 1.1%) (Component D: Low crystalline homopolypropylene) · L-MODU (Idemitsu Kosan Co., Ltd., L-MODU S901, low crystalline polypropylene, MFR (g / 10min) (230℃, 2.16kg) = 50) LICOCENE (Clariant, LICOCENE PP 1602) (talc) Talc (Takehara Chemical Industry Co., Ltd., P-talc) (Elastomer) DF605 (Tafmer (registered trademark) DF605, ethylene-butene copolymer, manufactured by Mitsui Chemicals, Inc.) DF640 (Mitsui Chemicals, Toughmer (registered trademark) DF640, ethylene-butene copolymer) H1221 (Tuftec (registered trademark) H1221, manufactured by Asahi Kasei Corporation, hydrogenated styrene-based thermoplastic elastomer (SEBS)) C5025 (Asahi Kasei Corporation, Tuftec (registered trademark) C5025, maleic anhydride modified SEBS (SEBS-MA modified))

[0061] [Formability evaluation] The resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13 were evaluated for modeling properties under the following conditions. <3D printer used for modeling evaluation> 3D printer: Da Vinci Jr. Pro.X+ (manufactured by xyz printing) <Modeling conditions> - Modeling stage: XYZ Printing genuine platform plate A platform tape (acrylic resin sheet) made specifically for the xyzprinting Da Vinci Pro series was attached to the modeling stage. Nozzle temperature: 220℃ Stage temperature: 80℃ -Formability evaluation item: Warping

[0062] [Warpage measurement procedure] For the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13, modeling was carried out in the following shapes and under the following conditions. Shape: Rectangular box shape Bottom thickness: 1mm Width x Depth x Height: 50mm x 50mm x 30mm Thickness of the box wall: 2mm ·Building speed: 15mm / s

[0063] (Warpage evaluation method) The above shape, that is, a box-shaped shape, was molded, and the warpage of the four corners of the bottom surface was measured. Specifically, the molded object was left at 23°C for 24 hours without being peeled off from the stage of the three-dimensional molding device from the time when the molding was stopped. Thereafter, the bottom surface of the box-shaped molded object was placed on the top side, and the molded object was scanned with a 3D scanner (Keyence Corporation, 3D scanner VL-500) to measure the minimum height of the four corners of the molded object. Then, the difference between the average height of the highest point on the diagonal line of the four corners and the lowest point on both ends was measured with two diagonals, and the average value was taken as the value of the warpage. That is, the height of the stage was set to 0 in the measurement data of the 3D scanner, and the points where the height was the smallest within a range of 50 mm x 50 mm of the four corners of the molded object were measured. Then, a diagonal line was drawn with the four points obtained by this measurement. Next, the highest point on the diagonal was designated C, and the two points used to draw the diagonal were designated A and B, and the warpage was calculated using the following formula.

[0064] (Calculation formula) Warpage = C-(A+B) / 2

[0065] The warpage was calculated for each of the two diagonals, and the average value was used as the warpage of the molded object. The warpage was calculated as the average value of N3. The warpage (mm) values ​​for each experimental example and each comparative example are shown in Tables 1 and 2.

[0066] (Measurement of crystallization temperature and heat generation amount of crystallization) For each of the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13, a differential scanning calorimeter (DSC) (DSC7000X, manufactured by Hitachi High-Tech Corporation) was used to measure the crystallization temperature (°C) and the amount of heat generated during crystallization (mJ / mg) when the temperature was lowered from 260°C to 30°C at a rate of 20°C / min. The crystallization temperature and amount of heat generated during crystallization in each of the Experimental Examples and Comparative Examples are shown in Tables 1 and 2. The measurement conditions were as follows: 1) Sample: Place approximately 5 mg of sample in an aluminum pan and insert into the testing machine. 2) Temperature conditions (heat up, then cool down) Temperature increase: Increase temperature from 30℃ to 260℃ at a rate of 20℃ / min. Temperature reduction: Reduce temperature from 260℃ to 30℃ at a rate of 20℃ / min. 3) Among the measurement data, the area of ​​the exothermic peak obtained during cooling and the temperature of the highest point of the peak were measured as the amount of heat generated by crystallization and the crystallization temperature, respectively.

[0067] FIG. 1 shows the relationship between the crystallization temperature and warpage of the resin compositions for a three-dimensional object-forming apparatus according to each of the experimental examples and comparative examples.

[0068] In Fig. 1, the horizontal axis shows the area of ​​the crystallization heat peak (i.e., the amount of crystallization heat [mJ / mg]) obtained when the temperature is lowered from 260°C to 30°C at 20°C / min in the measurement using DSC, and the vertical axis shows the measurement results of the warpage of the bottom surface when the above box shape is molded (the warpage value in the above explanation). In each experimental example, a tendency was observed that the warpage became smaller as the amount of crystallization heat became smaller.

[0069] Here, it was observed that the resin compositions for 3D modeling apparatus according to Experimental Examples 1 to 8 (resin compositions containing maleic acid modified ethylene-propylene-butene copolymer) and the resin compositions for 3D modeling apparatus according to Experimental Examples 9 to 20 (resin compositions containing maleic acid modified propylene-butene copolymer) tended to exhibit significantly reduced warping compared to the resin compositions according to Comparative Examples 1 to 13. From this result, it is assumed that the addition of component (B) makes the packing of crystals of the base component (A) (polypropylene in the experimental examples) less dense.

[0070] 1, the resin compositions according to Comparative Examples 1 to 6 (compositions containing only MAPP added) and the resin compositions according to Comparative Examples 11 to 13 (compositions containing SEBS elastomer added) showed warpage of more than 1.5 mm. In Comparative Example 10, the warpage was 1.35 mm, but the crystallization heat value exceeded 40.0 (mJ / mg).

[0071] Here, in the resin compositions according to Comparative Examples 7 and 8 (compositions in which MAPP was added to ethylene-butene copolymer-containing polyolefin), the warpage itself was shown to be 1.0 mm to 1.5 mm. However, it was confirmed that the resin compositions according to Comparative Examples 7 and 8 contain an elastomer, which reduces the rigidity of the resin composition and impairs the properties of component (A). In other words, it was confirmed that the inclusion of an elastomer makes the composition unsuitable for three-dimensional modeling applications. This point was also true in Comparative Example 9 (not shown in FIG. 1) and Comparative Examples 10 to 13.

[0072] In addition, the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 all had a crystallization temperature of 107°C or less and a crystallization heat value of 40.0mJ / mg or less. In other words, the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 ensured ease of modeling and reduced volumetric shrinkage during hardening after melting of the resin compositions for a three-dimensional modeling apparatus, thereby effectively reducing warpage. On the other hand, the resin compositions (systems not containing elastomer) according to Comparative Examples 1 to 6 could not achieve compositions having a crystallization temperature of 107°C or less and a crystallization heat value of 40.0mJ / mg or less. Among the resin compositions according to Comparative Examples 7 to 13, there are compositions (Comparative Examples 11 to 13) in which the crystallization temperature is 107°C or lower and the crystallization heat value is 40.0 mJ / mg or lower. However, since these compositions do not contain the (B) or (B') component, they do not provide the same effects as the resin compositions for three-dimensional modeling apparatus according to each experimental example (the effect of exhibiting good adhesion and significantly reducing warping while maintaining the characteristics of the (A) component).

[0073] It was confirmed that while Comparative Examples 1 to 10 required a high addition amount of component (B') of 15 wt%, the warpage reduction effect was achieved even with a low addition amount of component (B) of 2.0 wt% in Experimental Examples 1, 5, 9, 13, and 17. Therefore, it was demonstrated that the resin compositions for 3D modeling apparatus according to Experimental Examples 1 to 20 can provide resin compositions for 3D modeling apparatus that can reduce warpage while maintaining the properties of the base component (A) to the maximum extent possible.

[0074] Fig. 2 shows the relationship between the amount of maleic acid introduced in the resin composition for a 3D modeling apparatus and warpage in each experimental example, and Fig. 3 shows the relationship between the amount of component (B) added in the resin composition for a 3D modeling apparatus and warpage in each experimental example.

[0075] In Fig. 2, the horizontal axis indicates the amount of maleic acid introduced in the resin compositions for use in a three-dimensional modeling apparatus according to Experimental Examples 1 to 20, and the vertical axis indicates the measurement results of the warpage of the bottom surface when a box shape is molded (the warpage value in the above explanation). Also, in Fig. 3, the horizontal axis indicates the amount of component (B) added in the resin compositions for use in a three-dimensional modeling apparatus according to Experimental Examples 1 to 20, and the vertical axis indicates the measurement results of the warpage of the bottom surface when a box shape is molded (the warpage value in the above explanation). In Figs. 2 and 3, markers are defined for each grade of component (B).

[0076] 2 and 3, the resin compositions for 3D modeling apparatus according to Experimental Examples 1 to 20 showed less warpage than Comparative Example 6 (composition containing 15 wt% MG250P, warpage of 1.84 mm). Although there is a tendency for warpage to decrease as the amount of maleic acid introduced or the amount of component (B) added increases, it was shown that warpage can be sufficiently reduced even when the amount of maleic acid introduced or the amount of component (B) added is small. Note that each of the Experimental Examples did not contain an elastomer, and the effect of reducing warpage was observed, demonstrating that the resin compositions for 3D modeling apparatus according to each of the Experimental Examples can be put to practical use.

[0077] In addition, it was shown that although the amount of maleic acid introduced was 0.20% or less in Experimental Examples 1 to 20, it was possible to form an object with reduced warping. Here, the following two main causes can be considered as the causes of the object peeling off from the stage of the modeling apparatus. (1) The stage is incompatible with the resin composition, resulting in insufficient adhesion. This is because PP, a hydrophobic resin, is inherently incompatible with hydrophilic materials, resulting in insufficient adhesion. (2) The molded object peels off from the stage due to warping caused by the volumetric shrinkage of the resin composition used in the molding.

[0078] In the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20, warpage can be significantly reduced. This makes it possible to prevent peeling from the stage due to warpage based on the above (2), and it was also shown that it is possible to reduce the amount of maleic acid introduced. In addition, warpage can be further reduced by increasing the amount of maleic acid introduced compared to the amount of maleic acid introduced in the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20. However, from the viewpoint of achieving a good balance between improving the adhesive strength of the resin composition for a three-dimensional modeling apparatus and reducing warpage, it is preferable that the amount of maleic acid introduced is 0.51% or less. Also, referring to FIG. 3, it was confirmed that when the amount of the (B) component added exceeds about 10 wt%, the warpage approaches a substantially constant value. Therefore, even if the amount of the (B) component added is further increased, the effect of reducing warpage may not increase dramatically, and the strength of the resin composition for a three-dimensional modeling apparatus may decrease due to the decrease in the proportion of the (A) component, which is the base. For example, when forming a three-dimensional object having edges or a three-dimensional object larger than a certain size, warping is likely to occur, so it was shown that it is preferable to add the (B) component in an amount of approximately 20 wt% or less.

[0079] It was also confirmed that the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 could be used to model a flat plate measuring 150 mm×150 mm×2 mm without warping.

[0080] From the above, it was shown that the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 can reduce warping of objects with edges without using a specific sheet or adhesive during modeling. That is, the resin compositions for a three-dimensional modeling apparatus according to Experimental Examples 1 to 20 contain the modified thermoplastic resin (B) that contains a butene-based polyolefin in its skeleton, and therefore have excellent adhesion and a large warping reduction effect, and therefore can be used to model objects with edges with reduced warping.

[0081] Although the embodiments and experimental examples of the present invention have been described above, the embodiments and experimental examples described above do not limit the invention according to the claims. It should be noted that not all of the combinations of features described in the embodiments and experimental examples are essential to the means for solving the problems of the invention.

Claims

1. (A) a thermoplastic resin; (B) a modified thermoplastic resin having a reactive group and a nonpolar molecular chain, the modified thermoplastic resin including a butene-based polyolefin in its skeleton; A resin composition for a three-dimensional modeling apparatus comprising:

2. the reactive group is at least one hydrophilic reactive group selected from the group consisting of a succinic anhydride group, a carbonyl group, and a carboxyl group, 2. The resin composition for a three-dimensional object forming apparatus according to claim 1, wherein the non-polar polymer is at least one non-polar polymer selected from the group consisting of polypropylene, ethylene-vinyl acetate copolymer resin, and acrylic resin.

3. 2. The resin composition for a three-dimensional object forming apparatus according to claim 1, wherein the polymer having reactive groups and a non-polar molecular chain is maleic anhydride modified polypropylene (MAPP).

4. The resin composition for a three-dimensional object forming apparatus according to claim 1 , wherein the modified thermoplastic resin (B) is contained in an amount of 2.0 wt % or more and 20 wt % or less.

5. 2. The resin composition for a three-dimensional object forming apparatus according to claim 1, wherein the resin composition for a three-dimensional object forming apparatus has a crystallization heat value of 40 mJ / mg or less.

6. The resin composition for a three-dimensional object forming apparatus according to claim 1 , wherein the resin composition for a three-dimensional object forming apparatus has a crystallization temperature of 107° C. or lower.

7. The modified thermoplastic resin (B) is a maleic acid-modified ethylene-propylene-butene copolymer or a maleic acid-modified propylene-butene copolymer, The weight average molecular weight of the maleic acid modified ethylene-propylene-butene copolymer or the weight average molecular weight of the maleic acid modified propylene-butene copolymer is 60,000 or more and 95,000 or less, 2. The resin composition for a three-dimensional object forming apparatus according to claim 1, wherein the graft ratio of the maleic acid modified ethylene-propylene-butene copolymer or the graft ratio of the maleic acid modified propylene-butene copolymer is 1.1% or more and 2.0% or less.

8. 8. The resin composition for a three-dimensional object forming apparatus according to claim 7, comprising 2.0 wt % or more and 20 wt % or less of the maleic acid modified ethylene-propylene-butene copolymer or the maleic acid modified propylene-butene copolymer.

9. (D) Low crystalline polypropylene The resin composition for a three-dimensional object forming apparatus according to claim 1 , further comprising:

10. A filament for a three-dimensional object forming apparatus, comprising the resin composition for a three-dimensional object forming apparatus according to any one of claims 1 to 9.

11. A molded object comprising the resin composition for a three-dimensional object molding apparatus according to any one of claims 1 to 9.

12. A pellet for a three-dimensional object forming apparatus, comprising the resin composition for a three-dimensional object forming apparatus according to any one of claims 1 to 9.

13. A master batch comprising the resin composition for a three-dimensional object forming apparatus according to any one of claims 1 to 9.

14. (A) a thermoplastic resin; (B) a modified thermoplastic resin having a reactive group and a nonpolar molecular chain, the modified thermoplastic resin including a butene-based polyolefin in its skeleton; A resin composition for injection molding comprising:

15. A material for a three-dimensional modeling device, comprising a modified thermoplastic resin having a reactive group and a molecular chain that is modified with a non-polar polymer, the modified thermoplastic resin including a butene-based polyolefin in the skeleton.

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