JP7402378B1 - Resin composition for three-dimensional modeling device, filament for three-dimensional modeling device, modeled object, pellet for three-dimensional modeling device, and resin composition for injection molding - Google Patents

Abstract

[Object] A resin composition for a three-dimensional modeling device, a filament for a three-dimensional modeling device, a modeled object, a pellet for a three-dimensional modeling device, which can reduce warping of objects with edges without using a predetermined sheet or adhesive during modeling, and A resin composition for injection molding is provided. [Solution] A resin composition for a three-dimensional modeling device includes (A) a thermoplastic resin, (B) a modified thermoplastic resin containing a butene-based polyolefin in its skeleton, and (B) a modified thermoplastic resin containing a butene-based polyolefin in its skeleton. The thermoplastic resin is (C) a modified resin with a polymer having a reactive group and whose molecular chain is a nonpolar polymer. [Selection diagram] Figure 1

Description

The present invention relates to a resin composition for a three-dimensional modeling device, a filament for a three-dimensional modeling device, a shaped article, 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 article, a pellet for a three-dimensional modeling device, and a resin composition for injection molding containing a butene-based polyolefin.

Conventionally, a molding material contains a thermoplastic resin (A) containing 30 to 80% by mass, a thermoplastic elastomer (B) containing 1 to 45% by mass, and a modifier (containing 0.5 to 15% by mass). C) and a tackifying resin (D) containing 5 to 35% by mass (provided that when the thermoplastic elastomer (B) is a functional group-added thermoplastic elastomer to which a functional group has been added, The modifier (C) may not be included.) Resin molding materials for three-dimensional modeling devices are known (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 three-dimensional modeling has low density, heat resistance, durability, impact resistance, moldability, and low shrinkage. It is possible to provide a resin molding material for a three-dimensional modeling device used in the device.

Japanese Patent Application Publication No. 2020-157609

Here, in the conventional technology including a resin molding material for a three-dimensional modeling device described in Patent Document 1, warpage of the modeled object is reduced by adding an elastomer or rubber to the resin molding material for a three-dimensional modeling device. There is. However, for example, in the resin molding material for a three-dimensional modeling device described in Patent Document 1, although the three-dimensional object to be modeled is only a flat plate with a thickness of 2 mm, a polyimide film is pasted on the stage of the three-dimensional modeling device. Furthermore, applying a 3D stage sealant (water-soluble adhesive) on the polyimide film is an essential requirement for reducing warpage (see paragraph 0075 of Patent Document 1).

This is because, as the number of layers of a modeled object manufactured using a three-dimensional modeling apparatus increases, the warpage of the bottom surface increases. This is due to the inability to secure adhesion to the stage of the modeling device. Therefore, in the conventional technology, the step of applying adhesive to the stage and film cannot be omitted. For example, when manufacturing a model using a crystalline resin such as polypropylene, even if a model with a small number of laminated layers such as a flat plate can be manufactured with a certain degree of warping, if the number of layers such as a box is large. The adhesive application process is an essential step because when a modeled object is modeled, warpage occurs and the modeled object cannot be manufactured.

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 three-dimensional modeling device, a three-dimensional modeling device, a filament for a three-dimensional modeling device, a three-dimensional modeling device, which can reduce warping of objects with edges without using a predetermined sheet or adhesive during modeling. The object of the present invention is to provide pellets for equipment and resin compositions for injection molding.

In order to achieve the above object, the present invention is made by modifying (A) a thermoplastic resin with a polymer having a reactive group and a non-polar molecular chain, and containing a butene-based polyolefin in its skeleton ( B) A resin composition for a three-dimensional modeling device containing a modified thermoplastic resin is provided.

In order to achieve the above object, the present invention also provides a filament for a three-dimensional modeling device comprising the above-mentioned resin composition for a three-dimensional modeling device, a shaped object comprising the above-mentioned resin composition for a three-dimensional modeling device, A pellet for a three-dimensional modeling device comprising a resin composition for a modeling device, and (A) a thermoplastic resin modified with a polymer having a reactive group and a non-polar polymer in the molecular chain, and a butene-based pellet. There is provided an injection molding resin composition containing (B) a modified thermoplastic resin containing a polyolefin in its skeleton.

According to the resin composition for a three-dimensional modeling device, the filament for a three-dimensional modeling device, the modeled object, the pellet for a three-dimensional modeling device, and the resin composition for injection molding according to the present invention, there is no need to use a predetermined sheet or adhesive during modeling. It is possible to provide 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 that can reduce warpage of objects with edges.

It is a figure which shows the relationship between the crystallization temperature and warpage of the resin composition for three-dimensional modeling apparatuses based on each experimental example and each comparative example. It is a figure which shows the relationship between the amount of maleic acid introduced into the resin composition for three-dimensional modeling apparatuses, and warpage based on each experimental example. FIG. 3 is a diagram showing the relationship between the amount of component (B) added and warpage of the resin composition for a three-dimensional modeling apparatus according to each experimental example.

[Embodiment]
Generally, in a modeled object manufactured using a three-dimensional modeling apparatus (3D printer), the warpage of the bottom surface (warpage in the height direction of the model) increases as the number of stacked layers increases. This is because when molten resin is newly layered on top of the bottom of the resin composition that was initially injected and solidified, the newly layered molten resin contracts as it solidifies, causing the upper part of the model to This is due to the generation of a pulling force inward toward the inside of the model. When this tensile force is generated, the bottom of the model is pulled in the height direction, causing warping (in other words, as the model is stacked on the stage of the printer, each stacked layer shrinks). Therefore, it is thought that a force is generated that pulls the bottom of the model upward in the height direction of the model, causing warping.) This warping occurs significantly in three-dimensional objects, for example, three-dimensional objects having edges such as rectangular parallelepiped boxes. This is thought to be due to the fact that in three-dimensional objects having edges, stress due to tensile force is concentrated at the edge portions (that is, corner portions), and large warpage is likely to occur.

Here, the resin composition for 3D modeling equipment used for 3D modeling equipment has extremely low water absorption, good post-processability, excellent impact resistance, chemical resistance, and heat resistance, and can be applied to various uses. It is desired to use a general-purpose resin such as polypropylene (PP). However, for example, PP is a crystalline resin and has a large shrinkage rate of 1% to 2.5%, so that large warpage due to shrinkage tends to occur during modeling (low moldability). Therefore, conventionally, the adhesion between the stage and the modeled object made of the resin composition for the 3D printer has been improved by applying adhesive to the stage of the 3D printer or by placing a special PP sheet or the like on the stage. It is maintained to physically suppress the occurrence of warping. However, PP has extremely weak adhesion to sheets placed on it (protective sheets, platform tapes, etc.), so even if it is modeled on a stage, it will peel off from the stage. Even if it were used, it would not be practical. In addition, when printing large objects or objects with edges, when using conventional resin compositions for three-dimensional modeling devices mainly made of PP, warping occurs even if a specified sheet or adhesive is used. You may become unable to suppress it.

As mentioned above, the adhesiveness of PP is extremely weak, so when manufacturing a modeled object on the stage of a three-dimensional modeling device or a sheet that protects the stage, it is necessary to apply a specified adhesive on the stage or sheet. It is necessary to fix the modeled object to the stage and sheet. If the object is modeled without applying an adhesive, the object will peel off from the stage or sheet due to insufficient adhesive strength or warpage of the PP, making it impossible to model. When applying an adhesive onto a stage or sheet, not only is a step of drying the adhesive after application required, but also the effort of cleaning the bottom surface of the modeled object and the surface of the stage or sheet is required. Furthermore, since a process of cleaning the stage and sheet surface and applying adhesive every time modeling is performed, it is not suitable for continuous production of molded objects.

There is also a method in which a special PP sheet (PP sheet) is used as the sheet and the shaped object is adhered to the sheet. However, when using a PP sheet, the bottom surface of the modeled object and the PP sheet are fused together, and components of the PP sheet remain on the bottom surface of the modeled object. Furthermore, if the PP sheet is fused to the bottom of the modeled object, 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 takes a lot of effort to clean the components (adhesive components) of the PP sheet remaining on the stage. Although the protective sheets used in modeling, such as polylactic acid (PLA), do not have an adhesive effect on the stage, they do not tear easily and can be used multiple times, no adhesive components remain on the stage, and the molded object and the protective sheet are fused. The adhesive component of the protective sheet will not remain on the object. However, since the protective sheet has no adhesive effect, when modeling is performed using a three-dimensional modeling apparatus using a resin filament made of PP, the object formed by the first layer peels off from the protective sheet, making it impossible to print in the first place.

In other words, since adhesives and sheets generally cannot be used repeatedly, it is necessary to reapply the sheet and reapply the adhesive each time a model is created, resulting in the hassle of manufacturing and replacing the sheet. Not only that, but resources such as adhesives and sheets have to be discarded. Therefore, when using a general-purpose resin such as PP as a resin composition for a three-dimensional modeling device, it is necessary to at least improve moldability (improvement in warpage and shrinkage rate corresponds to improvement in moldability); Improved adhesion is required.

Here, the present inventor has developed a resin for a three-dimensional modeling device that can create a three-dimensional object with edges such as a rectangular parallelepiped using a three-dimensional modeling device without using a PP sheet or a special adhesive, and that can reduce warping of the object. In order to obtain a composition, we attempted to further improve the resin composition for three-dimensional modeling apparatus that we had developed so far. As a result of various studies on the formulation of various resin compositions, the present inventors have discovered a resin composition for a three-dimensional modeling device that can significantly reduce the warpage of a model and can produce a three-dimensional object with an edge. . That is, the present inventors have found that by using a resin composition for a three-dimensional modeling device in which a thermoplastic resin contains a specific modified resin, appropriate adhesion to the stage can be ensured (and/or the composition can be easily placed on the stage). The inventors have discovered that it is possible to ensure appropriate adhesion (without damaging the sheet) and to significantly reduce the warping of shaped objects, even for objects with edges such as boxes. The specific modified resin is a modified thermoplastic resin containing a butene-based polyolefin in its skeleton. A modified thermoplastic resin containing a butene-based polyolefin in its skeleton is obtained by modifying a thermoplastic resin containing a butene-based polyolefin in its skeleton with a polymer having a reactive group and a non-polar molecular chain. It is resin. The present invention was created based on this knowledge.

In addition, moldability can be improved by blending a polymer with a reactive group that exhibits hydrophilicity in a specific ratio range into the resin (thermoplastic resin) that is the base of the resin composition for three-dimensional modeling equipment. , and appropriate adhesive strength is exhibited. Here, improvement in moldability refers to being able to reduce warpage and shrinkage occurring in a modeled object, and to be able to model a modeled object consisting of a predetermined number of layers. In addition, appropriate adhesive strength means that the adhesive strength of the resin composition for a stereolithography device to the stage and/or the protective sheet of the stereolithography device is such that the adhesive strength of the resin composition for the stereolithography device to the stage and/or the protection sheet of the stereolithography device is This refers to the adhesive strength within the range that allows a molded object to be fixed and removed from the stage and/or the protective sheet without causing damage to the protective sheet and the molded object after modeling.

<Summary of resin composition for three-dimensional modeling device>
The resin composition for a three-dimensional modeling device according to an embodiment of the present invention is a modified thermoplastic resin composition that is modified with a polymer having a reactive group and whose molecular chain is a nonpolar polymer, and containing a butene-based polyolefin in its skeleton. Contains a resin-containing material for a three-dimensional modeling device. Specifically, the resin composition for a three-dimensional modeling device according to the present embodiment is modified with (A) a thermoplastic resin and a polymer having a reactive group and a non-polar polymer in the molecular chain, and includes butene. (B) modified thermoplastic resin containing polyolefin-based polyolefin in its skeleton. This resin composition for three-dimensional modeling equipment can ensure adhesion to the stage without using a protective sheet (PP sheet, platform tape, etc.) or adhesive used in the three-dimensional modeling equipment, so it can be used for modeling three-dimensional objects with edges. Even objects (for example, box-shaped objects) can be formed with greatly suppressed warpage on the bottom surface.

In this embodiment, "molecular chain" refers to a polymer, oligomer molecule, or oligomer molecule that is composed of structural units connected in a linear or branched manner between terminal groups, branch points, or boundary structural units specific to polymers. Or refers to a configuration that includes all or part of a block.

<Details of resin composition for three-dimensional modeling device>
[(A) Thermoplastic resin]
(A) Thermoplastic resin (hereinafter sometimes referred to as "component (A)") includes styrene resin, acrylic resin, aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic polyester resin, Aliphatic polyester resins, olefin resins (e.g. aliphatic polyolefin resins, cyclic olefin resins), polyamide resins, polyphenylene ether resins, thermoplastic polyimide resins, polyacetal resins, polysulfone resins, and amorphous resins. Examples include fluorine-based resins.

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

(Amount of component (A))
The blending amount of component (A) is 40 wt% or more, may be 50 wt% or more, may be 60 wt% or more, is 90 wt% or less, may be 80 wt% or less, and may be 70 wt% or less. It's okay.

[(B) Modified thermoplastic resin]
(B) modified thermoplastic resin that is modified with a polymer having a reactive group and whose molecular chain is a nonpolar polymer, and contains a butene-based polyolefin in its skeleton (hereinafter sometimes referred to as "component (B)") ), a thermoplastic resin containing a butene-based polyolefin in its skeleton is used as a polymer (hereinafter referred to as "component (C)") which has a reactive group (C) and whose molecular chain is a non-polar polymer. In some cases, modified resins obtained by modification may be mentioned. Specifically, component (B) includes a modified ethylene-propylene-butene copolymer and/or a modified propylene-butene copolymer.

In this embodiment, component (B) is preferably a modified resin in which component (C) is maleic anhydride-modified polypropylene (MAPP). That is, as component (B), an ethylene-propylene-butene copolymer modified with MAPP (hereinafter sometimes referred to as "maleic acid-modified ethylene-propylene-butene copolymer"), and/or MAPP A propylene-butene copolymer modified by (hereinafter sometimes referred to as "maleic acid-modified propylene-butene copolymer") is preferable.

(Molecular weight of component (B))
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, from the viewpoint of reducing warpage of the shaped object and ensuring adhesiveness. , 95,000 or less is preferable. The weight average molecular weight can be determined in terms of polystyrene using high-temperature gel permeation chromatography (high-temperature GPC), and then calculated in terms of polypropylene using a Q factor.

(Amount of component (B))
The blending amount of component (B) is preferably 2.0 wt% or more, preferably 5.0 wt% or more, preferably 8.0 wt% or more, and 20 wt% or more, from the viewpoint of reducing warpage of the modeled object and ensuring adhesiveness. % or less, 18 wt% or less is also preferable, and 15 wt% or less is also preferable.

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

(reactive group)
Examples of the reactive group include at least one hydrophilic group selected from the group consisting of a succinic anhydride group, a carbonyl group (for example, a methoxycarbonyl group), and a carboxyl group.

(Nonpolar polymer)
A non-polar polymer is a polymer substance that does not have a permanent dipole, and does not contain permanent dipoles that come from impurities mixed in under normal usage conditions or additives that are normally added. It is also assumed that the polymer is non-polar. Examples of the nonpolar polymer include polyethylene resin, polypropylene resin, and tetrafluoroethylene resin.

In the present embodiment, the nonpolar polymer that is a molecular chain includes a substantially nonpolar or hydrophobic olefin resin. Examples of olefin resins include polypropylene, polyethylene, resins obtained by homopolymerizing or copolymerizing two or more types of α-olefins (for example, propylene, 1-butene, 1-pentene, etc.), ethylene/α-olefin copolymers, and ethylene/α-olefin copolymers. Examples include vinyl acetate copolymer resin, propylene/α-olefin copolymer, and the like.

Note that when the molecular chain is an ethylene/vinyl acetate copolymer resin, (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 nonpolar polymer in this embodiment refers to the molecular structure of a portion containing a methoxycarbonyl group, etc. (In this case, a molecular chain is 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 nonpolar, it is considered a nonpolar polymer.) Further, other reactive groups (reactive groups different from the methoxycarbonyl group) may be separately introduced into the ethylene/vinyl acetate copolymer resin, (meth)acrylic resin, etc. by graft polymerization or the like.

The non-polar polymer is at least selected from the group consisting of polypropylene, ethylene/vinyl acetate copolymer resin, and acrylic resin from the viewpoint of easy availability, low specific gravity, versatility, physical properties, and/or processability. Preferably, it is one non-polar polymer. Among these, polypropylene is more preferred from the viewpoint of physical properties. Note that these olefin resins may contain other copolymerizable units. Further, these olefin resins can be used alone or in combination of two or more.

(High molecular)
Examples of the polymer containing the above-mentioned molecular chain and reactive group include various polymers in which the above-mentioned molecular chain and the above-described reactive group are combined. Examples include polypropylene, ethylene/vinyl acetate copolymer resin, and acrylic resin, each having at least one reactive group among the above-mentioned reactive groups. As the polymer, a polymer in which a reactive group is bonded to a molecular chain like a pendant group is more preferable, and for example, a graft copolymer is preferable. Among the above polymers, maleic anhydride-modified polypropylene (MAPP), which has a maleic anhydride group as a reactive group and whose molecular chain is polypropylene, is preferred from the viewpoint of imparting hydrophilicity to the resin composition for three-dimensional modeling equipment. It is most preferable to use

(molecular weight)
The weight average molecular weight of component (C) may be lower than that of component (A) from the viewpoint of ease of handling. From the viewpoint of reducing warpage of the modeled object without increasing it, the weight average molecular weight of component (C) is preferably 100,000 or less, preferably 90,000 or less, and also 70,000 or less. It is preferably 65,000 or less, more preferably 60,000 or less. Further, from the viewpoint of ensuring the effect of reducing warpage of the modeled object, the weight average molecular weight of component (C) is preferably 20,000 or more, preferably 25,000 or more, and 30,000 or more. is also preferable, more preferably 40,000 or more, and still more preferably 50,000 or more. The weight average molecular weight can be determined in terms of polystyrene using high-temperature gel permeation chromatography (high-temperature GPC), and then calculated in terms of polypropylene using a Q factor.

(Graft rate in component (B))
When component (C) is a graft type polymer (that is, a graft copolymer), the adhesive force of the resin composition for a three-dimensional modeling device 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 device, it is preferable to increase the grafting rate in the component (B). That is, although the adhesive strength is improved even when the grafting ratio is low, the adhesive strength tends to be further improved when the grafting ratio is increased. Moreover, the warping of a model formed using the resin composition for a three-dimensional modeling apparatus also tends to be reduced because the component (C) has a reactive group. One reason for this is that the presence of reactive groups improves adhesive strength. However, from the viewpoint of further reducing warpage of the resin composition for three-dimensional modeling apparatus, it is preferable to increase the grafting rate. That is, although warpage is reduced even when the grafting ratio is low, warping tends to be further reduced when the grafting ratio is increased. However, if the adhesive strength increases too much, the modeled object made of the resin composition for 3D modeling equipment and the stage of the 3D modeling equipment or the resin sheet placed on the stage will be firmly adhered, and the modeled object will be attached to the stage or the resin sheet. It may be difficult to remove it from the Therefore, it is preferable to set an upper limit and a lower limit for the grafting rate from the viewpoint of facilitating the removal of the shaped object from the stage or resin sheet.

In this embodiment, when component (C) is a graft copolymer (for example, in the case of MAPP), the viewpoints of improving adhesive strength and/or reducing warpage, and ease of modeling a three-dimensional object having edges From this viewpoint, the grafting rate in component (B) is 1.0% or more, preferably 1.1% or more, and 2.5% or less, preferably 2.0% or less.

(Amount of reactive group introduced)
By including component (C) (component (C) introduced into component (B)) in component (A) at a predetermined ratio, the adhesive strength of the resin composition for three-dimensional modeling apparatus is improved, and Warpage of the resin composition (and/or shaped object) is reduced. Furthermore, by adjusting the proportion of the reactive group of component (C) introduced into component (B) in the resin composition for three-dimensional modeling apparatus to a predetermined range, the adhesion of the resin composition for three-dimensional modeling apparatus can be improved. Increased force and reduced warpage. The present inventor has found that when a modified resin containing a butene-based polyolefin in its skeleton is used as component (B), the adhesive strength of the resin composition for three-dimensional modeling equipment can be improved and the warpage can be reduced even if the amount of reactive group introduced is small. We have discovered that it is possible to create a model that achieves both reduction and reduction.

That is, when component (C) is a graft copolymer, the ratio of the mass of component (B) to the entire mass of the resin composition for three-dimensional modeling apparatus is multiplied by the graft ratio in component (B) ( By setting the amount (hereinafter sometimes referred to as "the amount of reactive group introduced") within a predetermined range, it is possible to both improve the adhesive strength and reduce warpage of the resin composition for a three-dimensional modeling device. For example, when the mass ratio of component (B) to the entire mass of the resin composition for three-dimensional modeling apparatus is 10 wt%, and the grafting rate of component (C) in component (B) is 2.0%, the reaction The amount of introduced sexual group is calculated as 10×2.0/100=0.200 (%). Specifically, the amount of reactive group introduced is 0.020% or more, and 0.022% or more when using a modified thermoplastic resin containing a butene-based polyolefin in its skeleton, that is, component (B) according to the present embodiment. It may be 0.030% or more, 0.3% or less, and 0.2% or less. In this embodiment, since the component (B) contains a butene-based polyolefin in its skeleton, even if the amount of reactive group introduced is as small as 0.020% or more and 0.3% or less, the resin composition for three-dimensional modeling equipment It is possible to improve the adhesion of objects and reduce warping while modeling the object. In addition, the amount of reactive group introduced must be at least less than 0.57%, and when it is 0.51% or less, the adhesive strength of the resin composition for three-dimensional modeling apparatus can be improved and the warpage can be reduced. It is possible to achieve both.

[(D) Low crystallinity polypropylene]
The resin composition for a three-dimensional modeling device according to the present embodiment can further include (D) low crystalline polypropylene (hereinafter sometimes referred to as "component (D)"). By including component (D), warping of the resin composition for three-dimensional modeling apparatus can be further reduced. Component (D) is preferably a low-crystalline homopolypropylene.

(D) Low-crystalline polypropylene was measured using a differential scanning calorimeter (DSC) at -10°C for 5 minutes under a nitrogen atmosphere, and then heated at a rate of 10°C/min. It is a homopolypropylene whose melting point (T _m ) defined by the top of the peak observed on the side 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, even more preferably 50,000 or more, preferably 200,000 or less, and more preferably 150,000 or less. The weight average molecular weight can be determined in terms of polystyrene using high-temperature gel permeation chromatography (high-temperature GPC), and then calculated in terms of polypropylene using a Q factor.

Component (D) includes low elasticity, low molecular weight polyolefins, such as low elasticity, low molecular weight polyolefins (products) with a melt flow rate (MFR) of 500 (g/10 min) (230°C, 2.16 kg) or less. Name: L-MODU S600, L-MODU S901, manufactured by Idemitsu Kosan Co., Ltd.) and low elasticity, low molecular weight polyolefins with a melt flow rate (MFR) of 100 (g/10 min) (230°C, 2.16 kg) or less. (Product name: L-MODU S901, manufactured by Idemitsu Kosan Co., Ltd.) can be used. Furthermore, as component (D), a low elasticity, low molecular weight polyolefin (trade name: Licocene, manufactured by Clariant) having a melt viscosity of 5000 to 7000 mPa·s at 170° C. can be used.

(Amount of component (D))
When the amount of component (D) is increased, the warpage of the modeled object tends to be reduced, and when the amount is further increased, the rigidity of the resin composition for a three-dimensional modeling apparatus may be reduced. Therefore, the blending amount of component (D) may be 1 wt% or more, 3 wt% or more, 5 wt% or more, less than 10 wt%, and 7 wt% or less. . When component (B) is used, by setting the blending amount of component (D) to 1 wt% or more and less than 10 wt%, the resin composition for a three-dimensional modeling device and/or the effect of suppressing warpage of a shaped object becomes good.

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

<Other compounded substances>
The resin composition for a three-dimensional modeling device according to the present embodiment may optionally include an extender, a plasticizer, a water absorbent, a physical property regulator, a reinforcing agent, etc., within a range that does not impair the physical properties of the resin composition for a three-dimensional modeling device. Various compounded substances such as colorants, flame retardants, antioxidants, anti-aging agents, conductive agents, antistatic agents, ultraviolet absorbers, ultraviolet dispersants, solvents, fragrances, deodorants, pigments, dyes, diluents, etc. May be added.

<Crystallization temperature and crystallization calorific value of resin composition for three-dimensional modeling device>
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 and crystallization calorific value of the resin. That is, the lower the crystallization temperature, the lower the temperature at which the resin is kept warm after melting. Further, a high crystallization temperature and a large amount of crystallization heat generation mean that a large amount of resin crystallizes. When the resin crystallizes, the resin is packed more densely (resin molecules come into contact with each other) than before crystallization, and its volume shrinks. As a result, warping occurs in the shaped object made of the crystallized resin, and it is thought that the greater the degree of crystallization, the greater the warping that occurs.

From this point of view, the present inventor adjusted the composition of the resin composition for three-dimensional modeling equipment and variously examined the crystallization temperature, and obtained the knowledge that the crystallization temperature is preferably 110 ° C. or lower, and more preferably 107 ° C. or lower. .

In addition, the present inventor uses the component (B) according to the present embodiment in order to prevent the resin crystals from becoming densely packed due to the crystallization of the component (A), which is the base of the resin composition for a three-dimensional modeling device. We found that this is preferable. That is, as component (B), it is preferable to use a resin that has a bulkier molecular structure and lower density than component (A), so that it is less likely to crystallize. In addition, from the viewpoint of improving compatibility with component (A), it is preferable to use component (B) whose base structure (that is, skeleton structure) includes at least a portion of the same structure as component (A). I found out. For example, when PP is used as the component (A), it is preferable to use a resin that is a butene-based polyolefin and contains propylene in its skeleton as the component (B). By using such component (B), component (B) is uniformly dispersed within component (A), and volume shrinkage due to crystallization can be suppressed. As a result, it is thought that warpage of the shaped object can also be reduced.

From the above viewpoint, the present inventor has determined that the crystallization calorific value of the resin composition for a three-dimensional modeling apparatus according to the present embodiment is 40 mJ when the temperature is lowered at a rate of 20°C/min as measured by a differential scanning calorimeter (DSC). It was found that it is preferable that the amount is less than /mg.

<Application field>
The resin composition for a three-dimensional modeling device according to this embodiment can be used for various purposes. Specifically, it can be used for various products such as various structures, various parts (electrical/electronic parts, automobile parts, etc.), home appliances, housing/building materials, packaging materials, etc. The resin composition for a three-dimensional modeling device according to the present embodiment has an appropriate adhesive force for the stage of the three-dimensional modeling device and/or the resin sheet placed on the stage, so It can be used as a filament for three-dimensional modeling devices that do not require the use of agents. Then, using this filament for a three-dimensional modeling device, a modeled object of a desired shape can be manufactured by the three-dimensional modeling device.

Further, the resin composition for a three-dimensional modeling device according to the present embodiment can also be molded into a pellet shape and used as a pellet for a three-dimensional modeling device. Similar to the filament for a three-dimensional modeling device, the pellet for a three-dimensional modeling device can also be used in a three-dimensional modeling device in which a pellet-shaped material is charged and modeled. Furthermore, the resin composition for a three-dimensional modeling device according to the present embodiment can significantly reduce the warping of a modeled object when it is cured after being melted, so it can be used as a resin composition for a modeling device using a fused deposition modeling method (FDM method). It can also be used as

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, the molded article shrinks due to volumetric shrinkage due to crystallization of the resin composition. On the other hand, the resin for a three-dimensional modeling device according to the present embodiment can suppress crystallization of the component (A) and reduce warpage of a modeled object, so it can be used as a resin composition for injection molding. By configuring the resin composition for injection molding using the resin for three-dimensional modeling equipment according to this embodiment, effects such as reduction in volumetric shrinkage and deformation of the molded product can be obtained in injection molding, and molding with highly accurate dimensions can be achieved. You can get the goods.

<Method for producing resin composition for three-dimensional modeling device>
There are no particular restrictions on the method for producing the resin composition for a three-dimensional modeling device according to the present embodiment. For example, component (A) and component (B) are blended in predetermined amounts, and component (D) or other components are added as necessary. It can be manufactured by blending and stirring the blended substances. The mixing order of each component and other compounding substances is not particularly limited and can be determined as appropriate. Moreover, the resin composition for a three-dimensional modeling apparatus according to the present embodiment can improve the moldability even when the amount of the modified thermoplastic resin (B) containing a butene-based polyolefin in its skeleton is about 2.0 wt%. Therefore, the three-dimensional modeling device according to the present embodiment is obtained by blending predetermined amounts of component (A) and component (B), and further blending and kneading component (D) and other blended substances as necessary. It is also possible to form a shaped object using a composition obtained by using a resin composition for use as a masterbatch and adding this masterbatch to various base materials.

<Manufacturing method of modeled object>
Using the resin composition for a three-dimensional modeling device according to this embodiment, a resin filament for use in a three-dimensional modeling device (3D printer) is produced using a known technique. Then, the produced resin filament is set in a three-dimensional modeling device and modeled under predetermined conditions to produce a modeled object. In manufacturing a modeled object, a resin filament made of the resin composition for a three-dimensional modeler according to this embodiment may be used directly on the stage of a three-dimensional modeler to model the object. However, from the viewpoint of preventing wear of 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 curing tape, and/or a cellophane tape. Note that in the case of these protective sheets, the amount of reactive groups introduced is preferably within the range described above. Moreover, when a random polymer (for example, random polypropylene) is used as the component (A), a shaped article can be manufactured without a protective sheet.

<Effects of the embodiment>
The resin composition for a three-dimensional modeling device according to the present embodiment includes component (A) and component (B), which is a modified resin capable of suppressing crystallization of component (A) and contains a butene-based polyolefin in its skeleton. Therefore, the adhesion to the stage of the three-dimensional modeling apparatus can be ensured without placing a dedicated PP sheet on the stage of the three-dimensional modeling apparatus, or without using an adhesive to improve the adhesion between the model and the stage. The resin composition for a three-dimensional modeling apparatus according to the present embodiment can produce a three-dimensional object with significantly reduced warpage on the bottom surface, even if it is a three-dimensional object such as a box shape having an edge.

In addition, the resin composition for a three-dimensional modeling device according to the present embodiment has good adhesion and can significantly reduce warping that occurs in a modeled object, so it can be used in a modeling device made of a material that has poor adhesion to PP. It is also possible to create objects on the stage. For example, in a modeling apparatus, a model can be formed even 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.

<Experiment example>
A more specific explanation will be given below using experimental examples. It goes without saying that these experimental examples are merely illustrative and should not be construed as limiting.

(Preparation of Experimental Examples 1 to 20 and Comparative Examples 1 to 13)
Each compounding substance was blended in the proportions shown in Table 1, and mixed and stirred to prepare resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20. In addition, each compounding substance was blended in the proportions shown in Table 2, mixed and stirred to prepare resin compositions according to Comparative Examples 1 to 13.

Details of the compounded substances in Tables 1 and 2 are as follows.
(Component A: thermoplastic resin)
・PM940M (manufactured by Sun Allomer Co., Ltd., random polypropylene)
・PM731M (manufactured by Sun Allomer Co., Ltd., random polypropylene)
(Component B: modified thermoplastic resin)
・PMA-F2 (manufactured by Toyobo MC Co., Ltd., maleic anhydride-modified ethylene-propylene-butene copolymer, weight average molecular weight 70,000, graft rate 1.5%)
・PMA-F6 (manufactured by Toyobo MC Co., Ltd., maleic anhydride-modified ethylene-propylene-butene copolymer, weight average molecular weight 60,000, graft rate 2.0%)
・PMA-T (manufactured by Toyobo MC Co., Ltd., maleic anhydride-modified propylene-butene copolymer, weight average molecular weight 75,000, graft rate 1.5%)
・PMA-TE (manufactured by Toyobo MC Co., Ltd., maleic anhydride-modified propylene-butene copolymer, weight average molecular weight 60,000, graft rate 1.8%)
・PMA-TH (manufactured by Toyobo MC Co., Ltd., maleic anhydride-modified propylene-butene copolymer, weight average molecular weight 95,000, grafting rate 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 (manufactured by Idemitsu Kosan Co., Ltd., L-MODU S901, low crystallinity polypropylene, MFR (g/10min) (230°C, 2.16kg) = 50)
・LICOCENE (manufactured by Clariant, LICOCENE PP 1602)
(talc)
・Talc (manufactured by Takehara Chemical Industry Co., Ltd., P Talc)
(elastomer)
・DF605 (manufactured by Mitsui Chemicals, Tafmer (registered trademark) DF605, ethylene-butene copolymer)
・DF640 (manufactured by Mitsui Chemicals, Tafmer (registered trademark) DF640, ethylene-butene copolymer)
・H1221 (manufactured by Asahi Kasei Corporation, Tuftec (registered trademark) H1221, hydrogenated styrene thermoplastic elastomer (SEBS))
・C5025 (manufactured by Asahi Kasei Corporation, Tuftec (registered trademark) C5025, maleic anhydride modified SEBS (SEBS-MA modified))

[Moldability evaluation]
Evaluation of the moldability of the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13 was carried out under the following conditions.
<3D printer used for moldability evaluation>
3D printer: da Vinci Jr. Pro. X+ (manufactured by xyz printing)
<Building conditions>
- Modeling stage: XYZ Printing genuine platform plate A platform tape (acrylic resin sheet) exclusively for the XYZ Printing da Vinci Pro series was attached to the model stage.
・Nozzle temperature: 220℃
・Stage temperature: 80℃
・Formability evaluation item: Warpage

[Warpage measurement procedure]
Molding was carried out using the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13 in the following shapes and conditions.
・Shape: Rectangular box shape Bottom thickness: 1mm
Width x depth x height: 50mm x 50mm x 30mm
Box wall thickness: 2mm
・Building speed: 15mm/s

(Warpage evaluation method)
The above shape, that is, a box shape, was modeled, and the warpage at the four corners of the bottom surface was measured. Specifically, from the time when modeling was stopped, the modeled object was allowed to stand still at 23° C. for 24 hours without being removed from the stage of the three-dimensional modeling apparatus. After that, the box-shaped object was placed with the bottom side facing up, and the object was scanned with a 3D scanner (manufactured by Keyence Corporation, 3D Scanner VL-500), and the minimum height of the four corners of the object was measured. . Then, the difference between the average heights of the highest point on the diagonal line at the four corners and the lowest point at both ends was measured on the two diagonal lines, and the average value was taken as the warp value. That is, in the measurement data of the 3D scanner, the height of the stage was set to 0, and the points at which the height was minimum within a range of 50 mm x 50 mm at the four corners of the model were measured. Then, a diagonal line was drawn at the four points obtained through this measurement. Next, the warp was calculated using the following formula, with the highest point on the diagonal as C and the two points used to draw the diagonal as A and B, respectively.

(Calculation formula) Warp = C-(A+B)/2

The warpage was calculated using two diagonal lines, and the average value was taken as the warpage of the modeled object. In addition, in calculating the warpage, the average value of N3 was calculated. Tables 1 and 2 show the values of warpage (mm) in each experimental example and each comparative example.

(Measurement of crystallization temperature and crystallization calorific value)
The resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20 and the resin compositions according to Comparative Examples 1 to 13 were crystallized using a differential scanning calorimeter (DSC) (DSC7000X, manufactured by Hitachi High-Tech Corporation). The temperature (°C) and the amount of heat of crystallization (mJ/mg) when the temperature was lowered from 260°C to 30°C at 20°C/min were measured. Tables 1 and 2 show the crystallization temperature and crystallization calorific value in each experimental example and each comparative example. Note that the measurement conditions are as follows.
1) Sample: Put about 5 mg of sample into an aluminum pan and put it into the test machine.
2) Temperature conditions (after increasing temperature, lowering temperature)
Temperature increase: Temperature increase from 30°C to 260°C at a rate of 20°C/min.
Temperature reduction: Temperature reduction from 260°C to 30°C at a rate of 20°C/min.
3) Among the measurement data, the area of the exothermic peak obtained when the temperature is lowered and the temperature at the highest point of the peak are measured as the crystallization calorific value and crystallization temperature, respectively.

FIG. 1 shows the relationship between crystallization temperature and warpage of resin compositions for three-dimensional modeling apparatuses according to each experimental example and each comparative example.

In FIG. 1, the horizontal axis is the area of the crystallization exothermic peak obtained when the temperature is lowered from 260°C to 30°C at 20°C/min (i.e., the crystallization exothermic amount [mJ/mg]) in the measurement using DSC. ), and the vertical axis shows the measurement results of the warpage of the bottom surface (the warpage value in the above description) when the box shape is formed. In each experimental example, it was observed that as the crystallization heat value decreased, the warpage also decreased.

Here, the resin compositions for stereolithography apparatuses according to Experimental Examples 1 to 8 (resin compositions containing a maleic acid-modified ethylene-propylene-butene copolymer) and the resin compositions for stereolithography apparatuses according to Experimental Examples 9 to 20. (Resin composition containing a maleic acid-modified propylene-butene copolymer) showed a tendency for warpage to be significantly reduced compared to the resin compositions of Comparative Examples 1 to 13. From this result, it is assumed that the crystal packing of the base component (A) (polypropylene in the experimental example) becomes difficult to become dense by adding the component (B).

Further referring to FIG. 1, in the resin compositions according to Comparative Examples 1 to 6 (compositions to which only MAPP was added) and the resin compositions to Comparative Examples 11 to 13 (compositions to which SEBS elastomer was added), The results showed that the warpage was greater than 1.5 mm. In Comparative Example 10, although the warpage was 1.35 mm, the crystallization calorific value exceeded 40.0 (mJ/mg).

Here, in the resin compositions according to Comparative Examples 7 and 8 (compositions in which MAPP was added to polyolefin containing an ethylene-butene copolymer), the warpage itself was shown to be 1.0 mm to 1.5 mm. It was done. However, it was confirmed that in the resin compositions according to Comparative Examples 7 and 8, since the resin compositions contained an elastomer, the rigidity of the resin compositions was reduced, and the properties of component (A) were impaired. In other words, it was confirmed that the elastomer content made it unsuitable for three-dimensional modeling. This point was also the same in Comparative Example 9 (not shown in FIG. 1) and Comparative Examples 10 to 13.

Furthermore, in all of the resin compositions for three-dimensional modeling apparatuses according to Experimental Examples 1 to 20, the crystallization temperature was 107° C. or lower, and the crystallization heat value was 40.0 mJ/mg or lower. In other words, in the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20, ease of modeling can be ensured, and volume shrinkage during curing after melting of the resin compositions for three-dimensional modeling devices can be reduced, and as a result, It was shown that warping can be effectively reduced. On the other hand, in the resin compositions according to Comparative Examples 1 to 6 (systems without elastomer added), the compositions had a crystallization temperature of 107°C or less and a crystallization heat value of 40.0 mJ/mg or less. I couldn't make it happen. 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 less and the crystallization calorific value is 40.0 mJ / mg or less. However, since these compositions do not contain component (B) or component (B'), they do not have the same effect as the resin composition for stereolithography equipment in each experimental example (maintaining the characteristics of component (A)). However, the effect of exhibiting good adhesion and significantly reducing warping cannot be obtained.

In addition, while Comparative Examples 1 to 10 require a high addition amount of component (B') of 15 wt%, in Experimental Example 1, Experimental Example 5, Experimental Example 9, Experimental Example 13, and Experimental Example 17, ) It was confirmed that the effect of reducing warpage was exhibited even when the addition amount of the component was as low as 2.0 wt%. Therefore, in the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20, it is possible to provide resin compositions for three-dimensional modeling devices that can reduce warpage while maintaining the properties of the base component (A) to the maximum extent. It has been shown.

FIG. 2 shows the relationship between the amount of maleic acid introduced into the resin composition for a three-dimensional modeling apparatus and warpage according to each experimental example. Moreover, FIG. 3 shows the relationship between the amount of component (B) added and warpage of the resin composition for a three-dimensional modeling apparatus according to each experimental example.

In FIG. 2, the horizontal axis shows the amount of maleic acid introduced in the resin compositions for three-dimensional modeling apparatuses according to Experimental Examples 1 to 20, and the vertical axis shows the measurement results of the warpage of the bottom surface when a box shape was formed. (value of warpage in the above description). In addition, in FIG. 3, in the resin compositions for three-dimensional modeling apparatuses according to Experimental Examples 1 to 20, the horizontal axis shows the amount of component (B) added, and the vertical axis shows the warpage of the bottom surface when a box shape is formed. The measurement results (warpage values in the above description) are shown. Note that in FIGS. 2 and 3, markers are defined for each grade of component (B).

Referring to FIGS. 2 and 3, in the resin compositions for three-dimensional modeling apparatuses according to Experimental Examples 1 to 20, for example, compared to Comparative Example 6 (a composition containing 15 wt% of MG250P, the warpage was 1.84 mm). It was shown that the warpage was small. Although warpage tends to decrease as the amount of maleic acid introduced or the amount of component (B) added increases, it has been shown that warpage can be sufficiently reduced even if the amount of maleic acid introduced and the amount of component (B) added are small. Ta. In addition, each experimental example did not contain an elastomer, and the effect of reducing warpage was observed, indicating that the resin composition for a three-dimensional modeling apparatus according to each experimental example can be put to practical use.

In addition, in Experimental Examples 1 to 20, although the amount of maleic acid introduced was 0.20% or less, it was shown that a shaped article with reduced warpage could be formed. Here, there are two main reasons why the modeled object comes off from the stage of the modeler.
(1) The stage and the resin composition are not compatible with each other, and adhesion cannot be obtained. This is because PP, which is a hydrophobic resin, is essentially incompatible with hydrophilic materials, and adhesion cannot be obtained.
(2) The modeled object peels off from the stage due to warping due to volumetric shrinkage of the resin composition used for modeling.

In the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20, warpage can be significantly reduced. It was also shown that this makes it possible to prevent peeling from the stage due to warping based on (2) above, and to reduce the amount of maleic acid introduced. Note that warpage can be further reduced by adding a higher amount of maleic acid than the amount of maleic acid introduced in the resin compositions for three-dimensional modeling apparatuses according to Experimental Examples 1 to 20. However, from the viewpoint of achieving both improvement in adhesive strength and reduction in warpage of the resin composition for a three-dimensional modeling device, the amount of maleic acid introduced is preferably 0.51% or less. Further, referring to FIG. 3, it was confirmed that when the amount of component (B) added exceeds around 10 wt%, the warpage approaches a substantially constant value. Therefore, even if the amount of component (B) added is further increased, the effect of reducing warpage may not increase dramatically, and since the proportion of component (A), which is the base, decreases, three-dimensional modeling The strength of the resin composition for devices may decrease. For example, when modeling a three-dimensional object that has edges or a three-dimensional object that is larger than a predetermined size, warping is likely to occur, so it is preferable that the amount of component (B) added is about 20 wt% or less. Shown.

It was also confirmed that using the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20, it was possible to model a flat plate with a size of 150 mm x 150 mm x 2 mm without warping.

From the above, it was shown that the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20 can reduce warping of objects with edges, etc., without using a predetermined sheet or adhesive during modeling. . That is, the resin compositions for three-dimensional modeling devices according to Experimental Examples 1 to 20 have excellent adhesion because they contain (B) a modified thermoplastic resin containing a butene-based polyolefin in the skeleton, and also have an effect of reducing warpage. Because of the large size, it was shown that objects with edges can be formed with reduced warpage.

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. Furthermore, it should be noted that not all combinations of features described in the embodiments and experimental examples are essential for solving the problems of the invention.

Claims (10)

(A) polypropylene which is a thermoplastic resin;
(B) Maleic acid-modified ethylene-propylene-butene copolymer or maleic acid-modified propylene-butene copolymer, which is a modified thermoplastic resin modified with maleic anhydride-modified polypropylene (MAPP) and containing a butene-based polyolefin in the skeleton. Contains a combination of
The blending amount of the thermoplastic resin (A) is 40 wt% or more and 70 wt% or less,
A resin composition for a three-dimensional modeling device , wherein the blending amount of the modified thermoplastic resin (B) is 2.0 wt% or more and 20 wt% or less . The resin composition for a three-dimensional modeling device according to claim 1, wherein the resin composition for a three-dimensional modeling device has a crystallization calorific value of 40 mJ/mg or less. The resin composition for a three-dimensional modeling device according to claim 1, wherein the resin composition for a three-dimensional modeling device has a crystallization temperature of 107° C. or lower. 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,
The three-dimensional modeling apparatus according to claim 1, wherein the grafting ratio of the maleic acid-modified ethylene-propylene-butene copolymer or the grafting ratio of the maleic acid-modified propylene-butene copolymer is 1.1% or more and 2.0% or less. Resin composition for use. The resin composition for a three-dimensional modeling apparatus according to claim 1, further comprising (D) low crystalline polypropylene. A filament for a three-dimensional modeling device, comprising the resin composition for a three-dimensional modeling device according to any one of claims 1 to 5 . A shaped object comprising the resin composition for a three-dimensional modeling apparatus according to any one of claims 1 to 5 . A pellet for a three-dimensional modeling device, comprising the resin composition for a three-dimensional modeling device according to any one of claims 1 to 5 . A masterbatch comprising the resin composition for a three-dimensional modeling apparatus according to any one of claims 1 to 5 . (A) polypropylene which is a thermoplastic resin;
(B) Maleic acid-modified ethylene-propylene-butene copolymer or maleic acid-modified propylene-butene copolymer, which is a modified thermoplastic resin modified with maleic anhydride-modified polypropylene (MAPP) and containing a butene-based polyolefin in the skeleton. Contains a combination of
The blending amount of the thermoplastic resin (A) is 40 wt% or more and 70 wt% or less,
A resin composition for injection molding, wherein the blending amount of the modified thermoplastic resin (B) is 2.0 wt% or more and 20 wt% or less .