WO2021153637A1

WO2021153637A1 - Three-dimensional molding filament

Info

Publication number: WO2021153637A1
Application number: PCT/JP2021/002921
Authority: WO
Inventors: 亜希子平野
Original assignee: 三菱ケミカル株式会社
Priority date: 2020-01-28
Filing date: 2021-01-27
Publication date: 2021-08-05
Also published as: JPWO2021153637A1

Abstract

The present invention addresses the problem of obtaining a three-dimensional molding filament having a multilayer structure, with which all the properties of each layer can be expressed efficiently, and can coexist. A three-dimensional molding filament according to the present invention has a sea-island structure in a cross section perpendicular to the longitudinal direction, wherein the sea of the sea-island structure contains a thermoplastic resin (A), the islands of the sea-island structure contain a thermoplastic resin (B), and the sea-island structure is continuous in the longitudinal direction of the filament.

Description

Filament for 3D modeling

The present invention relates to a three-dimensional modeling material, particularly a three-dimensional modeling filament used in a material extrusion method (ME method).
The present invention also relates to a filament for three-dimensional modeling, a wound body, and a cartridge for three-dimensional modeling.

Additional modeling technology (additive manufacturing), a system commonly referred to today as a three-dimensional printer (3D printer) (for example, a Fused Deposition Modeling (FDM) system manufactured by Stratasys Incorporated in the United States), is a computer. It is used to build three-dimensional objects in layers based on a CAD model. Among them, the material extrusion method (ME method) inserts the raw material into the extrusion head as a filament made of a thermoplastic resin, and continuously heats and melts the raw material from the nozzle portion provided in the extrusion head onto the XY plane substrate in the chamber. It has become widely used because it is a simple system in which the extruded resin is deposited on a resin laminate that has already been deposited and fused, and this is integrally solidified as it cools. In the ME method, a three-dimensional object similar to a CAD model is usually constructed by repeating the extrusion process while the nozzle position with respect to the substrate rises in the Z-axis direction perpendicular to the XY plane (for example,). See Patent Documents 1 and 2).

In recent years, 3D printers are expected to be used not only for design confirmation but also for industrial applications such as modeling of final products and manufacturing tools. Therefore, the above filaments also have various high functions. Is required. Therefore, a technique for imparting a plurality of functions to the filament by forming the filament into a multilayer structure is disclosed (see, for example, Patent Document 3).

For example, as one of the multi-layered structures, a method of improving the adhesiveness between the layers of the molded molded product by forming the filament into a core-sheath structure is also being studied (see, for example, Patent Documents 4 to 5).

Japan Special Table 2003-502184 Japan Special Table 2003-534159 Japanese Patent Application Laid-Open No. 2016-193602 International Publication No. 2019/151235 International Publication No. 2019/235104

Here, in filaments having a core-sheath structure as described in Patent Documents 3 to 5, when resins having different physical properties are used as the resins constituting the core and the sheath, the physical characteristics of the respective resins are the physical properties of the filament. It is expected that the expression will greatly depend on the volume fraction of each resin (that is, the volume ratio of the core and the sheath) in the entire filament. That is, when the volume fraction of the core is large (the diameter of the core is large with respect to the filament diameter), the physical characteristics of the filament itself are closer to the physical characteristics of the core, and conversely, the volume fraction of the core is small (the volume fraction of the core with respect to the filament diameter). (Small diameter), the physical properties of the filament itself are considered to be closer to those of the sheath. On the other hand, as a result of detailed examination by the present inventor, the functions of the resin constituting the core and the functions of the resin constituting the sheath have contradictory characteristics in the entire core-sheath filament, and both functions are at a high level. It turned out to be difficult to maintain in.

For example, in Patent Documents 4 to 5, the filament is formed into a core-sheath structure, and the Tg of the resin constituting the sheath or the crystallization temperature (Tc) in the temperature lowering process is made lower than that of the resin constituting the core. It is disclosed that the adhesiveness between layers can be improved while maintaining the heat resistance of the resin. However, if the volume ratio of the sheath is increased in order to improve the adhesiveness between layers, the volume ratio of the core becomes smaller and the modeled product Heat resistance is low. That is, since the interlayer adhesiveness secured by the sheath layer and the heat resistance secured by the core layer have contradictory characteristics depending on the respective volume ratios, both the interlayer adhesiveness and the heat resistance are high as the core sheath filament as a whole. It is difficult to maintain at the level.

The present invention solves the above problems, and provides a three-dimensional modeling filament having a multi-layer structure, which can efficiently express and coexist with all the characteristics of each layer. The purpose.

As a result of diligent studies, the present inventor has a sea-island structure in a cross section perpendicular to the longitudinal direction, the sea part of the sea-island structure contains a thermoplastic resin (A), and the island part of the sea-island structure is thermoplastic. It was considered that the above-mentioned problems could be solved by using a filament for three-dimensional modeling containing the resin (B).

That is, the present invention relates to the following <1> to <14>.
<1>
It has a sea-island structure in a cross section perpendicular to the longitudinal direction,
The sea part of the sea island structure contains the thermoplastic resin (A),
The island portion of the sea island structure contains a thermoplastic resin (B),
A three-dimensional modeling filament in which the sea-island structure is continuous in the longitudinal direction of the filament.

<2>
The three-dimensional modeling filament according to <1>, wherein the glass transition temperature of the thermoplastic resin (A) is lower than the glass transition temperature of the thermoplastic resin (B).
<3>
The three-dimensional modeling according to <1> or <2>, wherein the crystallization temperature of the thermoplastic resin (A) in the temperature lowering process is lower than the crystallization temperature of the thermoplastic resin (B) in the temperature lowering process. For filament.
<4>
The amount of heat of crystallization of the thermoplastic resin (A) in the process of lowering the temperature is lower than the amount of heat of crystallization of the thermoplastic resin (B) in the process of lowering the temperature, to any one of the above <1> to <3>. The described three-dimensional modeling filament.

<5>
The group in which the thermoplastic resin (A) is composed of an acrylonitrile-butadiene-styrene copolymer resin, a methyl methacrylate-butadiene-styrene copolymer resin, a polycarbonate, a polyetherimide, a polyolefin, a polyamide, a polyetheretherketone, and a polyetherketoneketone. The three-dimensional modeling filament according to any one of <1> to <4>, which comprises at least one selected from.
<6>
The group in which the thermoplastic resin (B) is composed of an acrylonitrile-butadiene-styrene copolymer resin, a methyl methacrylate-butadiene-styrene copolymer resin, a polycarbonate, a polyetherimide, a polyolefin, a polyamide, a polyetheretherketone, and a polyetherketoneketone. The three-dimensional modeling filament according to any one of <1> to <5>, which comprises at least one selected from.

<7>
The three-dimensional modeling filament according to any one of <1> to <6>, wherein the island portion of the sea-island structure is divided into two or more and ten or less in a cross section perpendicular to the longitudinal direction of the filament.
<8>
When the filament diameter is D, the area ratio of the island part in the circle with a diameter of 9 / 10D from the cross-sectional center of the cross section perpendicular to the longitudinal direction of the filament is 35% or more with respect to the area of the circle with a diameter of 9 / 10D. The filament for three-dimensional modeling according to any one of <1> to <7>, which is 99% or less.
<9>
The above-mentioned <1> to <8>, wherein when the filament diameter is D, the entire circle outside the circle having a diameter of 98 / 100D from the cross-sectional center of the cross section perpendicular to the longitudinal direction of the filament is the sea part. Filament for 3D modeling.

<10>
The glass transition temperature (Tg) of the thermoplastic resin (A) in the sea portion of the sea island structure is 5 to 100 ° C. lower than the glass transition temperature (Tg) of the thermoplastic resin (B). The filament for three-dimensional modeling according to any one of the above.
<11>
The three-dimensional modeling filament according to any one of <1> to <10>, wherein the island portion has a diameter d of 50 μm or more and 1500 μm or less.

<12>
A resin molded body made of the three-dimensional modeling filament according to any one of <1> to <11>.
<13>
The wound body of the filament for three-dimensional modeling according to any one of <1> to <11>.
<14>
A three-dimensional modeling cartridge made of the three-dimensional modeling filament according to any one of <1> to <11>.

According to the present invention, in a three-dimensional modeling filament having a multi-layer structure, it is possible to provide a three-dimensional modeling filament capable of efficiently expressing and coexisting all the characteristics of each layer.

FIG. 1 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 2 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 3 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 4 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 5 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 6 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 7 is a schematic view illustrating an example of a sea-island structure in a cross section of a filament for three-dimensional modeling of the present invention. FIG. 8 is a schematic view illustrating an example of a core-sheath structure in a three-dimensional modeling filament cross section. FIG. 9 is an overall perspective view of the dumbbell-shaped sample for explaining a state in which the dumbbell-shaped sample formed by using the three-dimensional modeling filament is erected with the tension direction vertical. FIG. 10 is a schematic view illustrating a cross section in the tensile direction of a dumbbell-shaped sample formed by using a three-dimensional modeling filament. FIG. 11 is a schematic diagram illustrating the degree of change in the shape of the dumbbell-shaped sample formed by using the three-dimensional modeling filament. FIG. 12 is a photographic view showing a cross-sectional observation result of the three-dimensional modeling filament obtained in Example 1. FIG. 13 is a photographic view showing a cross-sectional observation result of the three-dimensional modeling filament obtained in Example 2. FIG. 14 is a photographic view showing a cross-sectional observation result of the three-dimensional modeling filament obtained in Example 3. FIG. 15 is a photographic view showing a cross-sectional observation result of the three-dimensional modeling filament obtained in Comparative Example 1. FIG. 16 is a photographic view showing a cross-sectional observation result of the three-dimensional modeling filament obtained in Comparative Example 2.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist thereof.
In addition, in this specification, "mass" is synonymous with "weight".

The present invention has a sea-island structure in a cross section perpendicular to the longitudinal direction, the sea portion of the sea-island structure contains a thermoplastic resin (A), and the island portion of the sea-island structure contains a thermoplastic resin (B). The sea-island structure is a three-dimensional modeling filament that is continuous in the longitudinal direction of the filament.

<Filament for 3D modeling>
1. 1. Shape of sea-island structure The filament for three-dimensional modeling of the present invention has a sea-island structure including a sea part composed of a sea component and an island part composed of an island component. The sea part and the island part are regions having different compositions in a cross section (diametrical cross section) perpendicular to the long axis of the filament. Further, in the sea-island structure, a plurality of island components (island parts) are scattered within the sea component (sea part).

Here, the sea-island structure in the three-dimensional modeling filament of the present invention will be described with reference to FIGS. 1 to 5. 1 to 5 are cross-sectional views of the filament, and is a view obtained by cutting an arbitrary portion of the filament perpendicular to the longitudinal direction of the filament and observing the cross section.
In the three-dimensional modeling filaments shown in FIGS. 1 to 3, the sea portion 1 containing the thermoplastic resin (A) is interspersed with the island portions 2 containing the thermoplastic resin (B). The number of islands is not particularly limited in the cross section, but for example, FIG. 1 shows that the number of islands 2 is three, and FIG. 2 shows that the number of islands 2 is larger. Further, the shape of the island portion 2 does not have to be circular, and examples thereof include a fan shape as shown in FIG. 3, a star shape, a quadrangle, and a polygon.

Further, the island portion may be composed of only the thermoplastic resin (B), but as shown by reference numeral 3 in FIGS. 4 and 5, a part of the island portion is formed of the thermoplastic resin (A) and the thermoplastic resin (A). It may be composed of a thermoplastic resin (C) having different physical properties from both of the thermoplastic resin (B). As the thermoplastic resin (C), the same thermoplastic resin (A) and the same as those exemplified below can be used as the thermoplastic resin (B).

Here, the filament for 3D modeling of the present invention has a sea island in a vertical cross section from the viewpoint of efficiently expressing and coexisting all the characteristics of each layer and from the viewpoint of unifying the physical properties in the 3D model. The structure is preferably continuous in the longitudinal direction without significantly changing its shape.

Further, the filament for three-dimensional molding of the present invention prevents voids from being mixed into the resin molded body to be molded, and from the viewpoint of improving the strength and appearance of the resin molded body, a gap in a cross section perpendicular to the long axis of the filament. The rate is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, particularly preferably 0.1% or less, and 0.01% or less. Is most preferable.

For example, by using the thermoplastic resin (A) described in detail below as the sea component constituting the sea part and containing the thermoplastic resin (B) as the island component constituting the island part, high-performance three-dimensional modeling is performed. Filament can be provided.
The reason why the three-dimensional modeling filament of the present invention exerts the effect of the present invention is not yet clear, but it is presumed as follows.

That is, the three-dimensional modeling filament of the present invention has a sea-island structure including a sea part and an island part, so that even if the volume of the thermoplastic resin (A) constituting the sea part is increased, the thermoplastic resin constituting the island part is formed. By arranging (B) evenly in the cross section of the filament, the characteristics of the thermoplastic resin (B) can be efficiently reflected in the entire filament. As a result, it is considered that the three-dimensional modeling filament of the present invention can efficiently express and coexist all the characteristics of each layer.

In a cross section perpendicular to the long axis direction of the three-dimensional modeling filament, when the filament diameter is D, the area occupied by the island portion is 9 / 10D in diameter within a circle with a diameter of 9 / 10D from the center of the cross section. It is preferably 35% or more and 99% or less with respect to the area of the circle. As described above, when the proportion of the island portion containing the thermoplastic resin (B) is present in the filament in a certain amount, the characteristics of both the thermoplastic resin (A) and the thermoplastic resin (B) can be improved at a high level of 3 It is considered that this can be reflected in the filament for dimensional modeling. Further, from the viewpoint of coordinating the characteristics of both resins at a high level, the area ratio is preferably 40% or more, more preferably 43% or more, further preferably 45% or more, and 50%. % Or more is particularly preferable, and 54% or more is most preferable. Further, it is preferably 95% or less, more preferably 90% or less, further preferably 88% or less, particularly preferably 80% or less, and most preferably 75% or less.

In the three-dimensional modeling filament of the sea-island structure of the present invention, all the islands may be covered with the sea as shown in FIGS. 1 to 5, and some of the islands may be exposed on the filament surface as shown in FIG. It may have a portion to be formed, or as shown in FIG. 7, all the island portions may have a portion exposed on the filament surface. However, if the sea area is to be provided with a function to improve the adhesiveness between layers and to modify the surface characteristics (surface smoothness, surface tactile sensation, etc.) of other shaped objects, all the island areas are as shown in FIGS. 1 to 5. It is preferable that the sea part is covered with the sea part because the retention rate of the functional sea part is increased.

In the present invention, in the cross section perpendicular to the long axis direction of the three-dimensional modeling filament, it is preferable that the entire circle with a diameter of 98 / 100D from the cross-sectional center of the cross section perpendicular to the longitudinal direction of the filament is the sea portion. That is, it is preferable that the filament surface is covered with a sea component. Since the filament surface is covered with a sea component, when the sea part has an interlayer adhesiveness improving function and a surface property modifying function, the effect is likely to be exhibited. For example, interlayer adhesiveness, surface smoothness, surface tactile sensation, and the like can be improved. Further, from the viewpoint of maximizing the function of the sea part, it is more preferable that the outside of the circle having a diameter of 95 / 100D is the sea part from the center of the cross section, and it is further preferable that the outside of the circle of 90 / 100D is the sea part. It is particularly preferable that all the outside of the circle of 85 / 100D is the sea part, and most preferably all the outside of the circle of 79 / 100D is the sea part.

2. Other Physical Properties, etc. The diameter (filament diameter D) of the filament for three-dimensional molding of the present invention depends on the specifications of the system used for molding the resin molded product by the material extrusion method (ME method), but is 1.0 mm or more. It is preferably 1.5 mm or more, more preferably 1.6 mm or more, particularly preferably 1.7 mm or more, while the upper limit is preferably 5.0 mm or less, more preferably 4 It is 0.0 mm or less, more preferably 3.5 mm or less, and particularly preferably 3.0 mm or less. Further, it is preferable that the accuracy of the filament diameter D is within ± 5% with respect to an arbitrary measurement point of the filament from the viewpoint of stability of raw material supply. In particular, in the three-dimensional modeling filament of the present invention, the standard deviation of the filament diameter D is preferably 0.07 mm or less, and particularly preferably 0.06 mm or less.

Further, the outer shape of the three-dimensional modeling filament of the present invention is not particularly specified, and shapes such as a quadrangle, a polygon, and a star shape can be mentioned even if the cross section perpendicular to the longitudinal direction is not circular, but from the viewpoint of formability. It is preferable that the cross section is circular with high roundness. The roundness of the outer shape of the filament cross section is preferably 0.93 or more, and particularly preferably 0.95 or more. The upper limit of roundness is 1.0. The roundness is obtained by measuring the major axis and the minor axis in the filament cross section and calculating the minor axis / major axis ratio. The closer the ratio is to 1.0, the closer the cross-sectional shape of the filament is to a perfect circle.

The number of islands in the cross section perpendicular to the longitudinal direction of the three-dimensional modeling filament of the present invention is not particularly limited, but it is preferably divided into 2 or more and 10 or less. When the number of islands is two or more, the characteristics of the thermoplastic resin (B) constituting the islands can be more efficiently reflected in the three-dimensional modeling filament. The number of islands is more preferably 3 or more. On the other hand, in order to increase the ratio of the sea part to the island part, the number of islands in the cross section of the filament is preferably 10 or less, more preferably 9 or less, further preferably 8 or less, particularly preferably 7 or less, and 6 or less. Is the most preferable.

The cross-sectional shape of the island part of the filament for three-dimensional modeling is not limited to a circular shape, but is called a so-called multi-lobal cross section such as a polygonal cross section, a flat cross section, a lens type cross section, a three-leaf cross section, and a six-leaf cross section. A deformed cross section having the same number of concave portions as the number of convex portions at 8 places, a hollow cross section, or a known deformed cross section may be used. The degree of deformation of the multi-roval cross section is preferably 1.2 or more and 6.0 or less. The degree of deformation referred to here is the circumscribed circle diameter of the cross-sectional shape divided by the inscribed circle diameter of the cross-sectional shape. When the degree of deformation is 1.2 or more, the unevenness of the deformed cross section is large, so that the contact area between the island component and the sea component is large, and peeling is suppressed. On the other hand, when the degree of deformation is 6.0 or less, the strength is high.

From the viewpoint of productivity, the diameter d of the island portion is preferably 50 μm or more, more preferably 100 μm or more, further preferably 200 μm or more, still more preferably 300 μm or more, particularly preferably 400 μm or more, and particularly preferably 500 μm or more. Is the most preferable. When the lower limit of the diameter d is within the above range, the characteristics of the thermoplastic resin (B) in the three-dimensional modeling filament can be more efficiently reflected in the three-dimensional modeling filament. The upper limit of the diameter d is preferably 1500 μm or less, more preferably 1200 μm or less, further preferably 1000 μm or less, still more preferably 900 μm or less, and particularly preferably 800 μm or less. , 700 μm or less is most preferable. When the upper limit of the diameter d is within the above range, the characteristics of the resin and the thermoplastic resin (A) can be more efficiently reflected in the filament for three-dimensional modeling. The diameter d of the island portion can be measured from the cross-sectional image by observing the cross section of the three-dimensional modeling filament with a microscope. In the present invention, the longest diameter of each island is defined as the diameter of the island, and the average value of the number of islands is defined as the diameter d of the island.

3. 3. Thermoplastic resin (A) and thermoplastic resin (B)
In the present invention, the thermoplastic resin (A) and the thermoplastic resin (B) have one or more different physical characteristics. Here, the physical characteristics include resin composition, molecular weight, additive composition, color, thermal characteristics (melting point, glass transition temperature, crystallization temperature at temperature rise, crystallization temperature at temperature decrease, heat of crystal melting, heat of crystallization, etc.). , Melt characteristics (MFR, melt viscosity, shear storage elasticity, etc.), mechanical properties (tensile storage elasticity, tensile strength, impact resistance, linear expansion coefficient, thermal conductivity, water absorption, surface hardness, etc.) And any one or more of these are different.

The thermoplastic resin (A) and the thermoplastic resin (B) may be any material that can be extruded by thermal melting, and can be appropriately selected according to the function to be imparted to the molded product to be molded. For example, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), polystyrene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, modified polyphenylene ether, polyetherimide, etc. Crystalline resins such as amorphous resins, polyolefins, polyesters, polyamides, polyvinyl alcohols, polyetherketones, polyetheretherketones, polyetherketoneketones, olefin-based, styrene-based, polyester-based thermoplastic elastomers, and mixtures thereof. Is preferably used.

More specifically, the thermoplastic resin (A) is preferably an amorphous resin such as acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, polycarbonate, polyetherimide, or polyester. , Polyethylene, Polyamide, Polyether Ether Ketone, Polyether Ketone Ketone and other crystalline resins, preferably acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, polycarbonate and other amorphous resins. It is more preferable to contain a resin or a crystalline resin such as polyester, polyamide or polyolefin, and an amorphous resin such as acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, polycarbonate, polyester, etc. It is more preferable to contain crystalline resins such as polyamide and polyolefin, and amorphous resins such as acrylonitrile-butadiene-styrene copolymer resin and methyl methacrylate-butadiene-styrene copolymer resin, and crystalline resins such as polyester and polyamide are used. It is particularly preferable to contain, and it is most preferable to contain an amorphous resin such as an acrylonitrile-butadiene-styrene copolymer resin and a methyl methacrylate-butadiene-styrene copolymer resin.
Two or more of these resins may be mixed and used as appropriate.

The thermoplastic resin (B) includes amorphous resins such as acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, polycarbonate and polyetherimide, and polyolefins, polyamides and polyether ether ketones. , Polyether Ketone It is preferable to contain a crystalline resin such as ketone, and an amorphous resin such as acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, polycarbonate, etc., polyamide, polyether ether, etc. It is preferable to contain crystalline resins such as ketones and polyether ketone ketones, and amorphous resins such as acrylonitrile-butadiene-styrene copolymer resins and methyl methacrylate-butadiene-styrene copolymer resins, polyamides and polyether ether ketones, Polyether Ketone It is preferable to contain a crystalline resin such as ketone, and most preferably it contains an amorphous resin such as acrylonitrile-butadiene-styrene copolymer resin and polycarbonate.
Two or more of these resins may be mixed and used as appropriate.

Further, the thermoplastic resin (A) and the thermoplastic resin (B) include fillers such as carbon black, carbon fiber, glass fiber, talc, mica, nanoclay and magnesium, and additives such as antioxidants, lubricants and colorants. Can be mixed as appropriate.

<Preferable examples of different physical characteristics>
(Different thermal characteristics)
In one embodiment, it is preferable that the thermoplastic resin (A) and the thermoplastic resin (B) have different thermal characteristics. As a result, the molded product formed by using the three-dimensional molding filament of the present invention has two functions, such as heat resistance and interlayer adhesiveness, and heat resistance and formability (suppression of warpage during molding). It is thought that it can be maintained at the level.
Among the thermal characteristics, it is preferable that the glass transition temperature of the thermoplastic resin (A) is lower than the glass transition temperature of the thermoplastic resin (B).
Further, it is preferable that the crystallization temperature of the thermoplastic resin (A) in the temperature lowering process is lower than the crystallization temperature of the thermoplastic resin (B) in the temperature lowering process.
Further, it is preferable that the amount of heat of crystallization of the thermoplastic resin (A) in the process of lowering the temperature is lower than the amount of heat of crystallization of the thermoplastic resin (B) in the process of lowering the temperature.

For example, when both the thermoplastic resin (A) and the thermoplastic resin (B) are amorphous resins, the glass transition temperature (Tg) of the thermoplastic resin (A) is the glass transition temperature of the thermoplastic resin (B). It is preferably lower than (Tg). Here, from the viewpoint of interlayer adhesion, the Tg of the thermoplastic resin (A) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and 15 ° C. or higher lower than the Tg of the thermoplastic resin (B). More preferably, it is particularly preferably 20 ° C. or higher, and most preferably 25 ° C. or higher. From the viewpoint of productivity, the Tg of the thermoplastic resin (A) is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and 60 ° C. or lower lower than the Tg of the thermoplastic resin (B). It is more preferable, and it is particularly preferable that the temperature is 50 ° C. or lower. The glass transition temperature can be adjusted by adjusting the composition, molecular weight, blending with a plasticizer or a compatible resin, and the like. The glass transition temperature can be measured by the method described in Examples.

Further, for example, when both the thermoplastic resin (A) and the thermoplastic resin (B) are crystalline resins, the crystallization of the thermoplastic resin (A) is measured at a cooling rate of 10 ° C./min in the differential scanning calorimetry. It is preferable that the temperature (Tc) is lower than the crystallization temperature (Tc) measured at a cooling rate of 10 ° C./min in the differential scanning calorimetry of the thermoplastic resin (B). Here, from the viewpoint of interlayer adhesiveness, the Tc of the thermoplastic resin (A) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and 20 ° C. or higher lower than the Tc of the thermoplastic resin (B). More preferably, it is particularly preferably 40 ° C. or higher, and most preferably 50 ° C. or higher. From the viewpoint of productivity, the Tc of the thermoplastic resin (A) is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and 110 ° C. or lower lower than the Tc of the thermoplastic resin (B). Further preferably, it is particularly preferably 90 ° C. or lower, and most preferably 80 ° C. or lower. The crystallization temperature (Tc) in the temperature lowering process can be adjusted by adjusting the composition, molecular weight, addition of a nucleating agent, blending with a compatible resin, and the like. The crystallization temperature in the temperature lowering process is raised from room temperature to the crystal melting temperature (melting point Tm) + 20 ° C. at a heating rate of 10 ° C./min by using a differential scanning calorimeter according to JIS K7121. Then, after holding the temperature for 1 minute, the temperature can be measured from the temperature lowering process when the temperature is lowered to 30 ° C. at a cooling rate of 10 ° C./min.

Further, for example, when either the thermoplastic resin (A) or the thermoplastic resin (B) is a crystalline resin and one of them is an amorphous resin, the thermoplastic resin (A) can be used from the viewpoint of interlayer adhesion. Of the glass transition temperature (Tg) and the crystallization temperature (Tc) in the temperature lowering process, the one with the highest observable temperature is the glass transition temperature (Tg) and the temperature lowering process of the thermoplastic resin (B). Of the crystallization temperature (Tc) in the above, the temperature is preferably 1 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher than the lowest observable temperature. It is particularly preferable that the temperature is as low as 15 ° C. or higher, and most preferably as low as 20 ° C. or higher. From the viewpoint of productivity, it is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, further preferably 110 ° C. or lower, particularly preferably 90 ° C. or lower, and most preferably 80 ° C. or lower. preferable.

Further, for example, the crystallization calorie (ΔHc) measured at a cooling rate of 10 ° C./min in the differential scanning calorimetry of the thermoplastic resin (A) is the cooling rate of 10 ° C. in the differential scanning calorimetry of the thermoplastic resin (B). It is preferably lower than the amount of heat of crystallization (ΔHc) measured at / min. Here, from the viewpoint of interlayer adhesion, the ΔHc of the thermoplastic resin (A) is preferably 1 J / g or more lower than the ΔHc of the thermoplastic resin (B), more preferably 5 J / g or more, and 10 J / g. It is more preferably lower by g or more, particularly preferably lower by 15 J / g or more, and most preferably 20 J / g or more. Further, from the viewpoint of heat resistance of the resin molded product described later, it is preferably as low as 100 J / g or less, more preferably as low as 90 J / g or less, further preferably as low as 80 J / g or less, and as low as 70 J / g or less. It is particularly preferable, and most preferably it is as low as 60 J / g or less.

Furthermore, the heat resistance and the interlayer are that the crystallization heat quantity (ΔHc) measured at a cooling rate of 10 ° C./min in the differential scanning calorimetry of the thermoplastic resin (A) is 0 J / g or more and less than 60 J / g. It is preferable from the viewpoint of adhesiveness. From the viewpoint of heat resistance of the resin molded product described later, the amount of heat of crystallization (ΔHc) of the thermoplastic resin (A) is preferably 1 J / g or more, more preferably 5 J / g or more, and 10 J / g. It is more preferably g or more. Further, from the viewpoint of adhesiveness between layers of the resin molded product described later, it is preferably 60 J / g or less, more preferably 50 J / g or less, and further preferably 45 J / g or less.

Here, the calorific value for crystallization (ΔHc) can be adjusted by adjusting the composition and molecular weight of the thermoplastic resin, the addition of a nucleating agent, blending with compatible and incompatible amorphous resins, and the like. The amount of heat of crystallization (ΔHc) is measured by using a differential scanning calorimeter to raise the temperature of about 10 mg of the sample from room temperature to the crystal melting temperature (melting point Tm) + 20 ° C. at a heating rate of 10 ° C./min. It can be obtained from the thermogram measured in the temperature lowering process when the temperature is kept at the temperature for 1 minute and then lowered to 30 ° C. at a cooling rate of 10 ° C./min.

(The formulation of additives is different)
In one embodiment, it is preferable that the thermoplastic resin (A) and the thermoplastic resin (B) have different additive formulations. The different formulations may mean that the type of additive to be added is different, the amount of the additive to be added may be different, or both of them may be different. Here, examples of the additive include fillers such as carbon black, carbon fiber, glass fiber, glass wool, cellulose nanofiber, talc, mica, nanoclay, and magnesium, antioxidants, lubricants, and colorants.

In particular, it is preferable that the amount of the filler compounded differs between the thermoplastic resin (A) and the thermoplastic resin (B). Generally, by adding a filler, the strength of the molded molded product is increased, but there is a problem that the interlayer adhesiveness is lowered. However, according to the embodiment of the present invention, the strength and interlayer adhesiveness are increased. It is considered that these two functions can be maintained at a high level. Here, it is preferable that the amount of the filler of the thermoplastic resin (A) is smaller than the amount of the filler of the thermoplastic resin (B). Here, from the viewpoint of interlayer adhesion, the blending amount of the filler of the thermoplastic resin (A) is preferably 1% by weight or more lower than the blending amount of the filler of the thermoplastic resin (B), and is 5% by weight or more lower. Is more preferable, 10% by weight or more is more preferable, 15% by weight or more is particularly preferable, and 20% by weight or more is most preferable. Further, from the viewpoint of the strength of the modeled object and the difference in physical properties between the thermoplastic resin (A) and the thermoplastic resin (B), it is preferably 100% by weight or less, and more preferably 80% by weight or less. , 70% by weight or less is more preferable, 60% by weight or less is particularly preferable, and 50% by weight or less is most preferable.

Further, the blending amount of the filler of the thermoplastic resin (A) is preferably 20% by weight or less, more preferably 10% by weight or less from the viewpoint of adhesiveness. Further, from the viewpoint of strength and physical properties of the thermoplastic resin (B) not being too wide, 0% by weight or more is preferable, and 1% by weight or more is more preferable. The filler content of the thermoplastic resin (B) is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, and the viscosity at the time of melting is too high from the viewpoint of strength. 50% by weight or less is preferable, and 40% by weight or less is more preferable, from the viewpoint of not having a large difference in physical properties from the thermoplastic resin (A).

(Different melting characteristics)
In one embodiment, it is preferable that the thermoplastic resin (A) and the thermoplastic resin (B) have different melting characteristics. As a result, it is possible to suppress the deformation due to stringing and heat during molding while improving the surface smoothness of the molded molded product. At this time, it is preferable that the melt viscosity of the thermoplastic resin (A) is lower than the melt viscosity of the thermoplastic resin (B) under the molding temperature (nozzle temperature) at the time of molding, that is, the MFR is high. That is, the smoothness of the surface of the molded product is improved by the flow of the thermoplastic resin (A) during molding, while the difficulty of flowing the thermoplastic resin (B) suppresses stringing and deformation due to heat during molding. It is considered that the surface smoothness and the formability can be maintained at a high level by adopting the embodiment of the present invention. Here, from the viewpoint of surface smoothness, the MFR of the thermoplastic resin (A) is preferably 0.5 g / 10 minutes or more higher than the MFR of the thermoplastic resin (B), and is preferably 1 g / 10 minutes or more higher. More preferably, it is more preferably 2 g / 10 minutes or more, and most preferably 5 g / 10 minutes or more. Further, from the viewpoint of formability and productivity, it is preferably 50 g / 10 minutes or less, more preferably 40 g / 10 minutes or less, and even more preferably 30 g / 10 minutes or less. Here, the MFR can be measured with a load of 2.16 kgf under the nozzle temperature at the time of modeling according to JIS K7210.

(Manufacturing method of filament for 3D modeling)
The filament for three-dimensional modeling of the present invention uses a thermoplastic resin (A) contained in the sea portion and a thermoplastic resin (B) (and, if necessary, a thermoplastic resin (C)) contained in the island portion. Manufactured. The method for producing the three-dimensional modeling filament of the present invention is not particularly limited, but it is preferably produced by the melt extrusion method.

For example, the sea-island structure of the three-dimensional modeling filament of the present invention may be formed by blending and melt-kneading the thermoplastic resin (A) and the thermoplastic resin (B) as a combination of incompatible resins. With this method, the size and number of islands can be easily adjusted according to the blend ratio and melt-kneading conditions.
Further, for example, the above-mentioned sea-island structure can be produced by melting the thermoplastic resin (A) and the thermoplastic resin (B) separately and performing melt deposition extrusion. In this case, the sea-island structure becomes a three-dimensional modeling filament that is continuous in the length direction of the filament. In this method, since the sea-island structure in the cross section mainly depends on the laminated shape of the co-extruded base and the nozzle, the influence of the resin type on the sea-island structure is relatively small, and there is an advantage that the selection range of the resin type is wide.
Among them, the above-mentioned thermoplastic resin (A), the thermoplastic resin (B), and the above-mentioned thermoplastic resin (C), if necessary, are melted by different extruders to form a laminated block having the above-mentioned sea-island structure. A method of forming a filament by melt-laminating extrusion using a laminated base is preferable.

<Filament winding body for 3D modeling and cartridge for 3D modeling>
When modeling a resin molded body with a 3D modeling printer using the 3D modeling filament of the present invention, the 3D modeling filament should be stably stored, and the 3D modeling filament should be used in the 3D modeling printer. Is required to be stably supplied. Therefore, the filament for 3D modeling of the present invention is hermetically packaged as a winding body wound around a bobbin, or the winding body is a cartridge for mounting a printer for 3D modeling (hereinafter, simply "3D modeling"). It is preferable that it is stored in a "cartridge for use") from the viewpoints of long-term storage, stable feeding, protection from environmental factors such as moisture, and prevention of twisting. As the cartridge for 3D modeling, in addition to the winding body wound around the bobbin, a cartridge that uses a moisture-proof material or a moisture-absorbing material inside and has a structure in which at least the orifice part that feeds out the filament for 3D modeling is sealed. Can be mentioned.
Usually, a winding body in which a filament for 3D modeling is wound around a bobbin, or a cartridge for 3D modeling including the winding body is installed in or around a 3D modeling printer, and is always for 3D modeling during molding. From the cartridge, the 3D modeling filament continues to be introduced into the 3D modeling printer.

<Resin molded product>
(Molding method of resin molded body)
In the method for molding a resin molded product of the present invention, a resin molded product is obtained by molding with a three-dimensional molding printer using the three-dimensional molding filament of the present invention. As a modeling method using a three-dimensional modeling printer, a material extrusion method (ME method), a powder bed melt bonding method (PBF method), a multi-jet fusion method, a material injection method (MJ method), and a liquid tank photopolymerization method (VP method) ) And so on. The three-dimensional modeling filament of the present invention can be suitably used for a material extrusion method (ME method). Hereinafter, the case of the material extrusion method (ME method) will be described as an example.

The ME type three-dimensional modeling printer generally has a chamber, and in the chamber, a heatable substrate, an extrusion head installed in a gantry structure, a heating melter, a filament guide, a filament cartridge installation portion, etc. It is equipped with a raw material supply unit. In some 3D modeling printers, the extrusion head and the heating / melting device are integrated.
By installing the extrusion head in the gantry structure, it can be arbitrarily moved on the XY plane of the base. The base is a platform for constructing a target three-dimensional object, a support material, etc., and by heating and heat-retaining it, adhesiveness with a resin molded body can be obtained, and the obtained resin molded body can be used as a desired three-dimensional object for dimensional stability. It is preferable that the specifications can be improved. Further, in order to improve the adhesiveness between the base and the resin molded product, an adhesive glue may be applied onto the base, or a sheet or the like having good adhesiveness to the resin molded product may be attached. Here, examples of the sheet having good adhesiveness to the resin molded body include a sheet having fine irregularities on the surface such as an inorganic fiber sheet, and a sheet made of the same type of resin as the resin molded body. Normally, at least one of the extrusion head and the substrate is movable in the Z-axis direction perpendicular to the XY plane.

The three-dimensional modeling filament is unwound from the raw material supply unit, fed to the extrusion head by a pair of opposing rollers or gears, heated and melted by the extrusion head, and extruded from the tip nozzle. According to the signal transmitted based on the CAD model, the extrusion head moves its position and supplies the raw material onto the substrate for stacking and deposition. After this step is completed, the laminated deposit can be taken out from the substrate, and if necessary, the support material or the like can be peeled off or the excess portion can be cut off to obtain a resin molded body as a desired three-dimensional object. ..

The means for continuously supplying the raw material to the extrusion head is a method of feeding out filaments or fibers, a method of supplying powder or liquid from a tank or the like via a quantitative feeder, and a method of plastically supplying pellets or granules with an extruder or the like. An example is an example of a method of extruding and supplying the material. Among these, from the viewpoint of simplicity of the process and supply stability, the method of feeding and supplying the filament, that is, the method of feeding and supplying the above-mentioned three-dimensional modeling filament of the present invention is the most preferable.

When supplying filaments to a 3D modeling printer, it is common to engage the filaments with drive rolls such as nip rolls and gear rolls and supply them to the extrusion head while taking them back. Here, in order to stabilize the raw material supply by strengthening the grip by the engagement between the filament and the drive roll, the minute uneven shape is transferred to the surface of the filament, and the frictional resistance with the engaging portion is increased. It is also preferable to add an inorganic additive, a spreading agent, an adhesive, rubber, or the like for increasing the size to the thermoplastic resin (A). If the filament has uneven thickness, gripping may not be possible due to engagement between the filament and the drive roll, and the drive roll may idle and the filament may not be supplied to the extrusion head.

(Use of resin molded product)
The resin molded product of the present invention is excellent in various properties such as strength, surface appearance, heat resistance, and durability. The use is not particularly limited, but stationery; toys; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for OA equipment, various parts such as automobiles, motorcycles, and bicycles. It can be suitably used for applications such as electric / electronic equipment materials, agricultural materials, horticultural materials, fishery materials, civil engineering / building materials, and medical supplies.

Although the following will be described in more detail in Examples, the present invention is not limited by these. The various measured values and evaluations displayed in this example were performed as follows.

(1) Glass transition temperature (Tg)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name "Pyris1 DSC", about 10 mg of the resin raw material was heated from room temperature to 250 ° C. at a heating rate of 10 ° C./min according to JIS K7121. It was held at temperature for 1 minute. After that, the temperature was lowered to 30 ° C. at a cooling rate of 10 ° C./min, and the glass transition temperature (Tg) (° C.) (re-) was taken from each thermogram measured when the temperature was raised to 250 ° C. at a heating rate of 10 ° C./min again. The temperature rise process) was determined. In addition, each value is rounded down to the second place in the minority.

(2) Observation of the area ratio of each layer in the cross section, the diameter of the island part, the island area ratio within the 9 / 10D circle, and the sea part outside the specific particle size circle. The cross section was observed with a microscope and measured from the cross section image. The diameter of the islands was calculated by averaging the number of islands, with the longest diameter of each island as the diameter of the islands.

(3) Interlayer Adhesive Strength It was evaluated by measuring the tensile strength of a molded product formed by using the three-dimensional modeling filaments obtained in Examples and Comparative Examples in accordance with JIS K 7161. As a sample for the tensile test, a dumbbell-shaped sample having a sample length of 75 mm, a width of 10 mm, and a thickness of 5 mm was formed. The axial direction (tensile direction) of the dumbbell-shaped sample is the Z-axis direction (stacking direction), and a three-dimensional printer (manufactured by 3Dgene, product name INDUSTRY F340) is used, the printing speed is 60 mm / sec, and the internal filling rate is 100%. The molding was performed at a substrate temperature of 100 ° C. and a nozzle temperature of 265 ° C. The chamber temperature at the time of modeling was carried out under two conditions of 75 ° C. and 85 ° C. The molten resin was discharged from the extrusion nozzle in the form of a strand having a diameter of 0.4 mm.
A tensile test was performed on the above-mentioned dumbbell-shaped molded product at an initial chuck-to-chuck distance of 45 mm, a speed of 50 mm / min, and 23 ° C., and the interlayer adhesive strength was evaluated from the tensile elongation at break as follows.
Good: Tensile breaking elongation is 6% or more OK: Tensile breaking elongation is 5% or more and less than 6% NG: Tensile breaking elongation is less than 5%

(4) Heat resistance Using the three-dimensional modeling filaments obtained in Examples and Comparative Examples, as shown in FIGS. 9 and 10, 5 mm on both sides of a dumbbell having a sample length of 75 mm, a width of 10 mm, and a thickness of 5 mm. A dumbbell-shaped sample 4 having a rib 5 was formed. The molding conditions were the same as those for the interlayer adhesion evaluation except that the chamber temperature was set to 40 ° C. The modeled product thus obtained was allowed to stand in an oven at 100 ° C. for 6 hours in a state where the dumbbell-shaped sample 4 was erected with the tensile direction perpendicular to it, and the change in shape was observed. Regarding the degree of change in shape, as shown in FIG. 11, the central axis (a) of the initial dumbbell-shaped sample 4 and the upper handle portion 4a of the dumbbell-shaped sample 4 after standing at 100 ° C. for 6 hours. The heat resistance was evaluated according to the following criteria from the angle α formed by the central axis (b).
OK: Deformation at high temperature is small (angle α is 5 ° or less)
NG: Large deformation at high temperature (angle 5α is larger than °)

<Raw materials used>
ABS resin: Chi Mei Corp. Manufactured, trade name: PA757, Tg: 104 ° C
PBS resin: manufactured by Mitsubishi Chemical Corporation, product name: Bio PBS FD92, Tg: less than 0 ° C, Tm: 86 ° C

<Examples and Comparative Examples>
[Example 1]
(Preparation of raw materials for each layer)
The above ABS resin is mixed at a ratio of 90 parts by mass and PBS resin at a ratio of 10 parts by mass, and melt-kneaded and extruded at 250 ° C. with a 25 mmφ twin-screw extruder to prepare the raw material (A) for the sea part (or for the sheath layer). And said. The raw material (A) had a Tg of about 80 ° C. Further, as the raw material (B) for the island part (or for the core layer), the above ABS resin was used as it was.
At this time, according to JIS K7210 of the raw material (A), the MFR of each temperature measured at each temperature with a load of 2.16 kgf was 2.2 (g / 10 min) at 220 ° C. and 5.4 (g / 10 min) at 240 ° C. It was 9.3 (g / 10min) at 260 ° C. (g / 10min).
Further, according to JIS K7210 of the raw material (B), the MFR of each temperature measured at each temperature with a load of 2.16 kgf was 1.7 (g / 10 min) at 220 ° C. and 5.0 (g / g) at 240 ° C. It was 7.4 (g / 10min) at 260 ° C. (/ 10min).
(Filament production)
A filament for three-dimensional modeling having a sea-island structure having a cross section similar to that of FIG. A filament having a diameter of 1.75 mm was obtained by co-extruding at a melting temperature of 230 to 250 ° C. and then cooling in cooling water at 40 ° C. with a ratio of extrusion amount to the raw material (B) of 1: 1.
The cross-sectional observation results of this filament are shown in FIG. 12, and the various evaluation results are shown in Table 1. In addition, as a result of cross-section inspection, it was observed that the entire area outside the circle of 97 / 100D was the sea area.

[Example 2]
The three-dimensional modeling filament having a sea-island structure having a sea-island structure similar to that in FIG. 1 was made in the same manner as in Example 1 except that the extrusion amount ratio of the raw material (A) and the raw material (B) was 1.7: 1. A filament having a diameter of 1.75 mm was obtained.
The cross-sectional observation results of this filament are shown in FIG. 13, and the various evaluation results are shown in Table 1. In addition, as a result of cross-section inspection, it was observed that the entire 80 / 100D circle was the sea area.

[Example 3]
A filament for three-dimensional modeling having a sea-island structure having a sea-island structure similar to that in FIG. A filament having a diameter of 1.75 mm was obtained.
The cross-sectional observation results of this filament are shown in FIG. 14, and the various evaluation results are shown in Table 1. In addition, as a result of cross-section inspection, it was observed that the entire outside of the circle of 78 / 100D was the sea area.

[Comparative Example 1]
A filament for three-dimensional modeling having a core-sheath structure whose cross section is shown in FIG. The extrusion amount ratio was 1: 1 and the mixture was coextruded at a melting temperature of 230 to 250 ° C. and then cooled in cooling water at 40 ° C. to obtain a filament having a diameter of 1.75 mm.
The cross-sectional observation results of this filament are shown in FIG. 15, and the various evaluation results are shown in Table 1.

[Comparative Example 2]
A filament having a diameter of 1.75 mm was obtained by the same method as in Comparative Example 1 except that the extrusion amount ratio between the raw material (A) and the raw material (B) was changed to 2: 1.
The cross-sectional observation results of this filament are shown in FIG. 16, and the various evaluation results are shown in Table 1.

In the above Examples and Comparative Examples, the Tg of the raw material (A) used for the sea part or the sheath layer is lower than the Tg of the raw material (B) used for the island part or the core layer. This is intended to impart interlayer adhesiveness to the three-dimensional modeling filament with the raw material (A) and heat resistance with the raw material (B).
Here, when Comparative Example 1 and Comparative Example 2 are compared, Comparative Example 2 has a larger sheath volume than Comparative Example 1, and Comparative Example 2 has higher interlayer adhesiveness than Comparative Example 1, but the heat resistance is higher. Comparative Example 2 is lower than Comparative Example 1. That is, the interlayer adhesiveness and heat resistance are contradictory characteristics when viewed as a filament as a whole.
On the other hand, in the examples, by adopting the sea-island structure of the present invention in the cross section, the volume ratio of the raw material (A) in the filament is in the same range as in Comparative Examples 1 and 2, but compared with Comparative Example 1. The interlayer adhesiveness is equal to or higher than that of Comparative Example 2, and the heat resistance is equal to or higher than that of Comparative Example 2.

More specifically, in Example 1 and Comparative Example 1, the content ratios of the raw material (A) and the raw material (B) are the same, but the tensile elongation at break on the Z axis is improved. It is considered that this is because the sea part fills the space between the laminated objects more efficiently than the core-sheath structure, thereby reducing the voids (defects) that trigger the fracture.
Further, when Example 2 and Comparative Example 1 are compared, the heat resistance of Example 2 is equal to or higher than that of Comparative Example 1 even though the content ratio of the raw material (B) is smaller in Example 2. It is considered that this is because even if the total area of the island part is small, the island part efficiently suppresses the softening of the sea part at high temperature by efficiently arranging it in the filament.

From the above, the filament having the sea-island structure of the present invention can maintain both the interlayer adhesiveness of the raw material (A) and the heat resistance of the raw material (B) at a higher level than that of the core-sheath filament. It can be said that there is.
It should be noted that Examples 1 and 2 have slightly better heat resistance than Example 3. It is considered that this is because the island ratio within the 9 / 10D circle is higher than that in Example 3, and the island portion made of the raw material (B) is slightly more likely to exhibit heat resistance. Further, Examples 1 and 2 have slightly better interlayer adhesiveness at 75 ° C. as compared with Example 3. It is considered that this is because the heat resistance is good as described above, the modeled object is less likely to be deformed during modeling, and the modeled object is less likely to have a defect that triggers breakage.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 28, 2020 (Japanese Patent Application No. 2020-011790), the contents of which are incorporated herein by reference.

The three-dimensional modeling filament having the sea-island structure of the present invention can efficiently express all the characteristics of each layer and can coexist, and in particular, the heat resistance of the modeled object in three-dimensional modeling can be obtained. It is preferably used to improve the interlayer adhesiveness.

1: Sea part (sea part made of thermoplastic resin (A))
2: Island part (island part made of thermoplastic resin (B))
3: Island part (island part made of thermoplastic resin (C))
4: Dumbbell-shaped sample 4a: Handle part 5: Rib

Claims

It has a sea-island structure in a cross section perpendicular to the longitudinal direction,
The sea part of the sea island structure contains the thermoplastic resin (A),
The island portion of the sea island structure contains a thermoplastic resin (B),
A three-dimensional modeling filament in which the sea-island structure is continuous in the longitudinal direction of the filament.
The three-dimensional modeling filament according to claim 1, wherein the glass transition temperature of the thermoplastic resin (A) is lower than the glass transition temperature of the thermoplastic resin (B).
The three-dimensional modeling filament according to claim 1 or 2, wherein the crystallization temperature of the thermoplastic resin (A) in the temperature lowering process is lower than the crystallization temperature of the thermoplastic resin (B) in the temperature lowering process.
The three-dimensional according to any one of claims 1 to 3, wherein the amount of heat of crystallization of the thermoplastic resin (A) in the process of lowering the temperature is lower than the amount of heat of crystallization of the thermoplastic resin (B) in the process of lowering the temperature. Filament for modeling.
The group in which the thermoplastic resin (A) is composed of an acrylonitrile-butadiene-styrene copolymer resin, a methyl methacrylate-butadiene-styrene copolymer resin, a polycarbonate, a polyetherimide, a polyolefin, a polyamide, a polyetheretherketone, and a polyetherketoneketone. The three-dimensional modeling filament according to any one of claims 1 to 4, which comprises at least one selected from.
The group in which the thermoplastic resin (B) is composed of an acrylonitrile-butadiene-styrene copolymer resin, a methyl methacrylate-butadiene-styrene copolymer resin, a polycarbonate, a polyetherimide, a polyolefin, a polyamide, a polyetheretherketone, and a polyetherketoneketone. The three-dimensional modeling filament according to any one of claims 1 to 5, which comprises at least one selected from.
The three-dimensional modeling filament according to any one of claims 1 to 6, wherein the island portion of the sea-island structure is divided into 2 or more and 10 or less in a cross section perpendicular to the longitudinal direction of the filament.
When the filament diameter is D, the area ratio of the island part in the circle with a diameter of 9 / 10D from the cross-sectional center of the cross section perpendicular to the longitudinal direction of the filament is 35% or more with respect to the area of the circle with a diameter of 9 / 10D. The three-dimensional modeling filament according to any one of claims 1 to 7, which is 99% or less.
The three-dimensional modeling according to any one of claims 1 to 8, wherein when the filament diameter is D, the entire circle outside the circle having a diameter of 98 / 100D from the cross-sectional center of the cross section perpendicular to the longitudinal direction of the filament is the sea portion. Filament for.
Any of claims 1 to 9, wherein the glass transition temperature (Tg) of the thermoplastic resin (A) in the sea portion of the sea island structure is 5 to 100 ° C. lower than the glass transition temperature (Tg) of the thermoplastic resin (B). The filament for three-dimensional modeling according to item 1.
The three-dimensional modeling filament according to any one of claims 1 to 10, wherein the diameter d of the island portion is 50 μm or more and 1500 μm or less.
A resin molded body made of the three-dimensional molding filament according to any one of claims 1 to 11.
The wound body of the filament for three-dimensional modeling according to any one of claims 1 to 11.
A three-dimensional modeling cartridge made of the three-dimensional modeling filament according to any one of claims 1 to 11.