JP2019137031A - Powder for solid molding, manufacturing apparatus of solid molding, manufacturing method of solid molding, and resin powder - Google Patents

Abstract

To provide a powder for solid molding capable of achieving dimensional accuracy and hardness of a molding in good balance.SOLUTION: The powder contains a first resin particle and a second resin particle and is characterized by that the first resin particle and the second resin particle are a resin of the same kind, and when MFR (melt mass flow rate) of the first resin particle is shown as MFR1 and MFR of the second resin particle is shown as MFR2, these satisfy MFR2>MFR1, and a rate of MFR shown by MFR2/MFR1 is 2-5.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a powder for three-dimensional modeling, a manufacturing apparatus for three-dimensional modeling, a method for manufacturing a three-dimensional modeling, and a resin powder.

  As a method for producing a three-dimensional structure, a powder bed fusion (PBF) method is known. In this method, three-dimensional modeling powders such as metals, inorganic substances, and resins are laminated, and for each layer or multiple layers, three-dimensional modeling powder particles are welded to a set shape pattern by light or a heat source, and three-dimensional modeling powder is welded. This is a method for producing a shaped object.

  PBF methods are classified by means of welding, SLS (selective leser oxidizing) method that selectively irradiates a laser to form a three-dimensional object, SMS (selective mask annealing) method that applies a laser to a flat surface using a mask, There are known HSS (high speed curing) that irradiates a heat source using an ink that enhances heat absorption, a BJ (Binder jetting) system that discharges a binder component and forms a shaped article and then sinters.

  In the above method, the three-dimensional modeling powder particles are melted and fused to form a modeled product, and the fluidity of the resin when the three-dimensional modeling powder is melted is important. For example, Patent Document 1 proposes that two types of resins are melt-mixed and the melt flow rate, which is an index of flowability characteristics in the resin, is 0.5 to 200 g / 10 minutes. Patent Document 2 proposes that the intrinsic viscosity [η] of the polymer be 0.1 to 1.5 dl / g.

However, Patent Document 1 and Patent Document 2 only control the fluidity of the resin powder itself, and this makes it difficult to achieve both dimensional accuracy and strength of the modeled object.
Therefore, an object of this invention is to provide the powder for three-dimensional modeling which can make compatible the dimensional accuracy and intensity | strength of a molded article.

  In order to solve the above problems, the three-dimensional modeling powder of the present invention includes first resin particles and second resin particles, and the first resin particles and the second resin particles are the same type of resin. When the MFR (melt mass flow rate) of the first resin particles is MFR1 and the MFR of the second resin particles is MFR2, MFR2> MFR1, and the MFR ratio represented by MFR2 / MFR1 is 2 It is 5, It is characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the powder for three-dimensional modeling which can make compatible the dimensional accuracy and intensity | strength of a molded article can be provided.

It is a SEM image which shows an example of the powder for solid modeling. It is the figure which expanded a part of FIG. It is a schematic diagram which shows an example of the cut material formed by cut | disconnecting columnar resin in the diagonal direction. It is the schematic which shows an example of the manufacturing apparatus of the three-dimensional molded item which concerns on this invention. It is a conceptual diagram for demonstrating an example of the manufacturing method of the three-dimensional molded item which concerns on this invention. It is a conceptual diagram for demonstrating an example of the manufacturing method of the three-dimensional molded item which concerns on this invention. It is a schematic perspective view which shows an example of a cylindrical body. It is a side view of the cylindrical body of FIG. It is a side view which shows an example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder. It is a side view which shows the other example of the shape which does not have a vertex at the edge part of a cylinder.

  Hereinafter, the three-dimensionally shaped powder, the three-dimensionally shaped manufacturing apparatus, the three-dimensionally shaped manufacturing method and the resin powder according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

(Three-dimensional modeling powder and resin powder)
The three-dimensional modeling powder of the present invention includes first resin particles and second resin particles, wherein the first resin particles and the second resin particles are the same kind of resin, and When MFR (melt mass flow rate) is MFR1, and MFR of the second resin particle is MFR2, MFR2> MFR1, and the ratio of MFR represented by MFR2 / MFR1 is 2-5. .

The resin powder of the present invention includes first resin particles and second resin particles, and the first resin particles and the second resin particles are the same kind of resin, and the MFR ( MFR2> MFR1 when the melt mass flow rate) is MFR1 and the MFR of the second resin particles is MFR2, and the ratio of MFR represented by MFR2 / MFR1 is 2-5.
The three-dimensional modeling powder of the present invention is included in the resin powder of the present invention, and unless otherwise specified, the description of the three-dimensional modeling powder of the present invention also applies to the resin powder of the present invention.

<MFR (melt mass flow rate)>
The value of MFR (melt mass flow rate) defined in the present invention is an index representing the viscosity (fluidity) at the time of melting of the resin. It is measured according to JIS7210 (ISO1133) under + 15 ° C. and a load of 2.16 kg. When the MFR value is large, the viscosity at the time of melting is low (easy to flow), and when it is small, the viscosity at the time of melting is high (hard to flow).

The ratio of the MFR values (hereinafter also referred to as “MFR ratio” and “MFR ratio”) is expressed by the following formula when the MFR value of the first resin particles is MFR1 and the MFR value of the second resin particles is MFR2. This is a value obtained by calculating the MFR value.
MFR ratio = MFR2 / MFR1

  The smaller the MFR value ratio, the smaller the difference in melt viscosity between the first resin particles and the second resin particles, and the larger the ratio, the greater the difference.

The reason why the MFR value is an important configuration in the present invention will be described below.
The PBF (powder bed fusion) method forms a modeled object by irradiating a specific print pattern with light and other heat sources on the stacked three-dimensional modeling powder, and melting and fusing the three-dimensional modeling powder at the irradiated part. To go. Therefore, control of the viscosity characteristics of the melted resin is very important.

  In the conventional method, a method of controlling the melt viscosity of the resin itself contained in the three-dimensional modeling powder has been mainstream. However, in order to increase the strength of the modeled article, it is necessary to sufficiently eliminate the voids between the three-dimensional modeled powder particles and increase the adhesion between the particles. For that purpose, when the resin particles are melted, sufficient fluidity to fill the voids is required.

  For this purpose, it is necessary to lower the viscosity at the time of melting of the resin particles. However, the melt oozes out (overflow) from the assumed shape size range, and the dimensional accuracy is lowered. On the other hand, in order to increase the dimensional accuracy, it is necessary to increase the viscosity at the time of melting, but the gap between the resin powder particles cannot be sufficiently filled, and the modeling strength is weakened. For this reason, it has been difficult to achieve both dimensional accuracy and strength of the modeled object.

  That is, when the resin fluidity at the time of melting is increased in order to reduce the voids of the resin powder at the time of melting, the molten resin liquid has a low viscosity, and thus overflows from the assumed shape size and the dimensional accuracy is lowered. On the other hand, if the resin fluidity at the time of melting is lowered in order to increase the dimensional accuracy, the molten resin liquid has a high viscosity, so that the gaps between the resin powder particles cannot be sufficiently filled, and the modeling strength is weakened.

  The present inventors have found that the desired effect can be obtained particularly when the ratio of MFR1 of the first resin particles to MFR2 of the second resin particles (MFR2 / MFR1) is a predetermined value. It came. Melting by combining resin particles (first resin particles) with low fluidity (high melt viscosity) and resin particles (second resin particles) with high fluidity (low melt viscosity) within a desired range Particles having different viscosities are unevenly distributed in the modeling, and both dimensional accuracy and strength can be achieved.

  More specifically, the first resin particles start to be melted by irradiation with light or a heat source, but by setting the MFR ratio as described above, it is prevented from flowing too much and writing of the light or heat source is performed. Traces (molded edges) can be sharpened.

  Further, in the conventional technique, since the melt does not flow up to the voids between the particles, voids are generated between the particles. On the other hand, in the present invention, the second resin particles having good fluidity are provided. Since it penetrates into the voids during melting, the adhesion between the particles is improved, and the strength of the shaped article can be improved.

  Since the melt viscosity of the resin itself varies depending on the output of light or a heat source, the most important characteristic is the ratio of the melt viscosity of the first resin particles to the second resin particles in order to exhibit the above effect. In the present invention, the MFR ratio is set to 2-5. When the MFR ratio is less than 2, the melt viscosity of the first particle and the second particle is too close, so that the void cannot be filled sufficiently. When the MFR ratio is larger than 5, if the output of the light or heat source until the first particles are melted is increased, the melt viscosity of the second particles becomes too low, causing a decrease in accuracy. Moreover, as MFR ratio, 3-4 are preferable.

  The MFR of the first resin particles and the second resin particles can be controlled by selecting a resin grade that constitutes the particles, or by adding an additive such as a plasticizer to the resin.

<Weight ratio of first resin particles and second resin particles>
The three-dimensional modeling powder of the present invention needs to contain at least two kinds of first resin particles and second resin particles. In order to further enhance the effects of the present invention, the first resin particles The mixing weight ratio of the second resin particles is also important.

  The ratio of the weight of the first resin particles to the weight of the second resin particles with respect to the three-dimensional modeling powder is preferably 4: 6 to 9.8: 0.2, and 5: 5 to 9.5: More preferably, it is 0.5. When the weight of the first resin particles is within the above range, it is possible to prevent the strength from being lowered because the voids are not filled with the first resin particles. Moreover, when the second resin particles are within the above range, it is possible to prevent the excessively melted resin liquid from leaking out and reducing the dimensional accuracy.

<Average volume particle diameter of first particles and second particles>
The volume average particle diameter Dv (μm) in the present invention is a resin particle size distribution measuring device (Microtrac MT3300EXII, manufactured by Microtrac Bell Co., Ltd.). Set and measured values.

  In the present invention, the volume average particle diameters of the first resin particles and the second resin particles are also important. The volume average particle diameter of the first resin particles is preferably larger than the volume average particle diameter of the second resin particles. In this case, accuracy and strength are further improved.

  The volume average particle diameter of the first resin particles and the volume average particle diameter of the second resin particles are preferably 5 μm or more and 200 μm or less, and more preferably 20 μm or more and 100 μm or less from the viewpoint of dimensional stability. It is more preferable to set a particle size such that the volume average particle size of the first resin particles is larger than the volume average particle size of the second resin particles within the above range of the volume average particle size.

  Further, the volume average particle size / number average particle size (Mv / Mn) of the three-dimensional modeling powder is preferably 2.00 or less, more preferably 1.50 or less, and particularly preferably 1.20 or less, from the viewpoint of improving modeling accuracy. preferable.

<Shapes of first resin particles and second resin particles>
In the present invention, the shapes of the first resin particles and the second resin particles are also important, and among them, the shape of the first resin particles is important. In particular, the shape of the first resin particles is preferably a vertical column shape (also referred to as “vertical column shape”).

The vertical column shape refers to a first surface, a second surface, and a three-dimensional modeling powder in a SEM image taken at a magnification of 150 times using a scanning electron microscope JSM-7800FPRIME manufactured by JEOL Ltd. In the range observed by the SEM, all of the first surface and the outer peripheral area of the second surface have a shape extending along the side surface.
When it is a vertical pillar shape, when it laminates | stacks with a 3D modeling printer, the packing density of powder becomes high and a molded article with higher intensity | strength can be obtained.

  In addition, regarding the shape of the second resin particles, when the shape of the first resin particles is a vertical column shape, a non-vertical column shape is preferable.

  The first resin particles have a vertical column shape, for example, when about 30 particles are observed from an SEM image and 95% by number or more have a vertical column shape, it can be said that the first resin particles have a vertical column shape. . The same applies to the other shapes, and the same applies to the second resin particles.

  An example of a vertical column shape will be described with reference to FIGS. 1 and 2. 1 and 2 are photographs obtained by SEM (scanning electron microscope) observation. FIG. 1 shows an example in which the resin particles are pillars, and FIG. 2 is an enlarged view of the particles surrounded by a dotted circle in FIG. Hereinafter, the first resin particle and the second resin particle will be described without distinction.

  As shown in FIG. 2, the column 21 has a first surface 22, a second surface 23, and a side surface 24. The first surface 22 includes a first facing surface 22 a and an outer peripheral region 22 b of the first surface having a shape extending along the side surface 24. The outer peripheral region 22b of the first surface is a surface that is continuous with the first facing surface 22a via a curved surface, and is substantially orthogonal to the first facing surface 22a.

  The second surface 23 includes a second facing surface 23 a facing the first facing surface 22 a, and a second surface outer peripheral region 23 b having a shape extending along the side surface 24. The outer peripheral area 23b of the second surface is a surface that is continuous with the second facing surface 23a via a curved surface, and is substantially orthogonal to the second facing surface 23a. The side surface 24 is adjacent to the first surface 22 and the second surface 23.

On the side surface 24, an outer peripheral region 22b of the first surface and an outer peripheral region 23b of the second surface extend. The shape of the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface (hereinafter also referred to as “outer peripheral region”) may be any shape that can be distinguished on the side surface 24 and the SEM image. A shape in which a part is integrated with the side surface 24, a shape in which the outer peripheral region is in contact with the side surface 24, a shape in which a space exists between the outer peripheral region and the side surface 24, and the like are included.
Moreover, it is preferable that the outer peripheral area 22 b of the first surface and the outer peripheral area 23 b of the second surface are provided so as to be substantially the same surface direction as the surface direction of the side surface 24.

As shown in FIG. 2, in the present embodiment, the outer peripheral region 22 b of the first surface and the outer peripheral region 23 b of the second surface are extended along the side surface 24 and located on the side surface 24.
Further, the characteristic structures of the first surface and the second surface covering the vicinity of the connection region between the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface and the side surface 24 are both bottle cap shapes. Called. The bottle cap shape is also included in the category of the vertical column shape.

  In the present invention, the “peripheral region of the first surface” and the “peripheral region of the second surface” mean columnar regions in a range observed with an SEM (scanning electron microscope). That is, the columnar region in the range not observed by the SEM is not included in the “peripheral region of the first surface” and the “peripheral region of the second surface”.

  In the present invention, “the outer peripheral region of the first surface is a shape extending along the side surface” means “all of the outer peripheral region of the first surface (however, limited to the range observed by the SEM). "Means a shape extending along the side surface, and a case where only a part of the outer peripheral region of the first surface extends along the side surface is not included.

  Further, in the present invention, “the outer peripheral region of the second surface is a shape extending along the side surface” means “all of the outer peripheral region of the second surface (however, limited to the range observed by the SEM). "Means a shape extending along the side surface, and a case where only a part of the outer peripheral region of the second surface extends along the side surface is not included.

  In the present embodiment, the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface have shapes in which the first surface 22 and the second surface 23 extend along the side surfaces, respectively. Therefore, between the outer peripheral region 22b of the first surface and the first opposing surface 22a, and between the outer peripheral region 23b of the second surface and the second opposing surface 23a, each continues smoothly via a curved surface. doing.

  By providing the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface so that the columnar body 21 does not have corners, the filling density of the three-dimensional modeling powder including the columnar body 21 is increased. And the tensile strength of the shaped article can be improved.

  Moreover, the fluidity | liquidity of the powder for three-dimensional modeling containing the column 21 can be improved by preventing the column 21 from having a corner | angular part, and the movement defect of the powder for three-dimensional modeling is suppressed at the time of three-dimensional modeling. Therefore, the tensile strength of the shaped article can be improved.

Here, the details of the above “not having a corner” will be described with a specific example.
The substantially cylindrical resin particle has a columnar shape having a bottom surface and an upper surface (first surface 22 and second surface 23), but preferably has no apex in order to increase bulk density. A vertex means a corner portion existing in the column.

  The shape of the columnar particles will be described with reference to FIGS. FIG. 7 is a schematic perspective view showing an example of a cylindrical body. FIG. 8 is a side view of the cylindrical body of FIG. FIG. 9 is a side view showing an example of a shape having no apex at the end of the cylindrical body. 10 to 15 are side views schematically showing other examples of shapes having no apex at the end of the cylindrical body.

  When the cylindrical body shown in FIG. 7 is observed from the side, it has a rectangular shape as shown in FIG. 8, and there are four corner portions, that is, vertices. An example of the shape having no apex at the end is shown in FIGS.

  Confirmation of the presence or absence of the apex of the columnar particles can be determined from the projection image on the side surface of the columnar particles. For example, the side surfaces of the columnar particles are observed using a scanning electron microscope (device name: S4200, manufactured by Hitachi, Ltd.) or the like, and acquired as a two-dimensional image. In this case, the projected image has a quadrilateral shape, and assuming that a portion constituted by two adjacent sides is an end, if it is constituted by only two adjacent straight lines, a corner is formed and has a vertex. 9 to 15, when the end portion is constituted by an arc, the end portion does not have a vertex.

  In addition, at least all of the outer peripheral region 22b of the first surface and all of the outer peripheral region 23b of the second surface in the range observed by the SEM are columnar bodies 21 having a shape extending along the side surface 24. Moreover, the filling density of the column bodies and the fluidity of the column bodies 21 that are required for use in three-dimensional modeling can be exhibited.

  In the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface, the length of the shortest portion in the height direction of the column 21 is preferably 1 μm or more, and more preferably 3 μm or more. More preferably, it is 5 μm or more. When it is 1 μm or more, the curved surface between the outer peripheral region 22b of the first surface and the first opposing surface 22a and between the outer peripheral region 23b of the second surface and the second opposing surface 23a becomes smoother. Therefore, the filling density of the three-dimensional modeling powder including the columnar body 21 can be increased, and the tensile strength of the modeled object can be improved.

  In addition, since the curved surface becomes smoother, the fluidity of the three-dimensional modeling powder including the column can be improved, and the movement failure of the three-dimensional modeling powder during the three-dimensional modeling can be suppressed. The tensile strength can be improved.

The outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface are the length in the height direction of the column 21 and the length of the longest portion is preferably 10 μm or more, preferably 15 μm or more. It is more preferable that
In addition, all said length shall be the length in the range observed by SEM.

  There is no restriction | limiting in particular as a shape of the column 21, Although it can select suitably according to the objective, Solid shapes, such as a substantially cylinder and a substantially prism, are mentioned, It is preferable that it is a substantially prismatic shape. Note that the shapes of the substantially cylinder and the substantially prism include a solid shape having the outer peripheral region 22b of the first surface and the outer peripheral region 23b of the second surface.

  The shape of the first opposing surface 22a and the second opposing surface 23a in the column 21 is determined by the three-dimensional shape of the column 21. For example, when a line (corner) in the height direction of the column 21 can not be observed and a smooth surface can be observed uniformly, the column 21 is a substantially cylinder, and the first opposing surface 22a and the second The shape of the opposed surface 23a is substantially circular. When a plurality of surfaces divided by lines (corners) in the height direction of the column body 21 can be observed, the column body 21 is a substantially rectangular column, and the first facing surface 22a and the second facing surface 23a. The shape is substantially polygonal.

  As described above, the column 21 has the first facing surface 22a and the second facing surface 23a that are facing each other. The first facing surface 22a may be inclined with respect to the second facing surface 23a, but it is preferable that the first facing surface 22a is not substantially inclined but is substantially parallel. By being substantially parallel, the fluidity of the three-dimensional modeling powder including the columnar body 21 can be improved.

  Moreover, the ratio of the length of the longest straight line that can be drawn on the first opposing surface 22a or the second opposing surface 23a of the column body to the height of the column body is 0.5 times or more and 5.0 times or less. Preferably, it is 0.7 times or more and 2.0 times or less, more preferably 0.8 times or more and 1.5 times or less.

  Here, FIG. 3 shows a schematic diagram of an example of a cut product formed by cutting cylindrical resin particles in an oblique direction. As illustrated, the surface direction of the first facing surface and the second facing surface and the surface direction of the side surface may not be perpendicular. Thus, even if it is not vertical, it is included in the standing column shape.

<Resin used for first resin particles and second resin particles>
As the resin used in the first resin particles and the second resin particles in the present invention, a thermoplastic resin can be used. The thermoplastic resin is not particularly limited, but a crystalline resin and a liquid crystal resin (LCP) are preferable. In particular, a resin having a large difference between the melting start temperature and the recrystallization point during cooling is preferable.

  Examples of the crystalline resin include polymers such as polyolefin, polyamide, polyester, polyether, polyphenylene sulfide, polyacetal, and thermoplastic polyimide. These may be used alone or in combination of two or more, but the first resin particles and the second resin particles may use the same type of resin. is important. If the first resin particles and the second resin particles are not the same type of resin, because the melting point is different, because one resin does not melt or the compatibility between the first resin particles and the second resin particles is low, It does not lead to improvement in strength.

  Examples of the polyolefin include polyethylene and polypropylene (PP, melting point: 180 ° C.).

Examples of the polyamide include polyamide 410 (PA410), polyamide 6 (PA6), polyamide 66 (PA66, melting point: 265 ° C.), polyamide 610 (PA610), polyamide 612 (PA612), polyamide 11 (PA11), polyamide 12 (PA12); semi-aromatic polyamide 4T (PA4T), polyamide MXD6 (PAMXD6), polyamide 6T (PA6T), polyamide 9T (PA9T, melting point: 300 ° C.), polyamide 10T (PA10T), and the like.
Among these, PA9T is also called polynonamethylene terephthalamide, which is composed of terephthalic acid monomers in nine diamines, and is generally called semi-aromatic because the carboxylic acid side is aromatic. Furthermore, what is called an aramid made from p-phenylenediamine and a terephthalic acid monomer as a wholly aromatic diamine side is also included in the polyamide of the present invention.

  Examples of the polyester include polyethylene terephthalate (PET, melting point: 260 ° C.), polybutadiene terephthalate (PBT, melting point: 218 ° C.), polylactic acid (PLA), and the like. Polyester containing an aromatic partially containing terephthalic acid or isophthalic acid for imparting heat resistance can also be suitably used in the present invention.

  Examples of the polyether include polyetheretherketone (PEEK, melting point: 343 ° C.), polyetherketone (PEK), polyetherketoneketone (PEKK), polyaryletherketone (PAEK), polyetheretherketoneketone ( PEEKK), polyether ketone ether ketone ketone (PEKEKK) and the like. In addition to the polyether, a crystalline polymer may be used, and examples thereof include polyacetal, polyimide, and polyether sulfone. A material having two melting point peaks such as PA9T may be used.

  In the present invention, the above thermoplastic resin means a material that is plasticized and melted when heated. Of the thermoplastic resins, crystalline resins are preferred. The crystalline resin means one having a melting peak when measured by ISO 3146 (Plastic Transition Temperature Measurement Method, JIS K7121).

  As the crystalline resin, a crystal-controlled crystalline thermoplastic resin is preferable, and the crystalline heat whose crystal size and crystal orientation are controlled by an external stimulation method such as heat treatment, stretching, crystal nucleating agent, ultrasonic treatment, etc. A plastic resin is more preferable.

  There is no restriction | limiting in particular as a manufacturing method of a crystalline thermoplastic resin, According to the objective, it can select suitably. For example, heating at a temperature equal to or higher than the glass transition temperature of the resin, an annealing process for increasing crystallinity, a method for adding a crystal nucleating agent to further increase the crystallinity, and then an annealing process can be given.

  Also, a method of increasing crystallinity by irradiating ultrasonic waves, a method of increasing crystallinity by dissolving in a solvent and slowly volatilizing, a step of crystallinity growth by applying an external electric field, etc., or stretching For example, there may be mentioned a method of subjecting a highly oriented and highly crystallized material to processing such as grinding and cutting.

  Annealing can be performed by heating the resin at a temperature 50 ° C. higher than the glass transition temperature for 3 days and then slowly cooling to room temperature.

  For stretching, for example, the resin solution for three-dimensional modeling is stretched in a fibrous form while stirring at a temperature higher by 30 ° C. or higher than the melting point using an extrusion processing machine. At this time, the melt is preferably drawn to a fiber by stretching about 1 to 10 times. Stretching can change the maximum stretching ratio for each resin and for each melt viscosity.

  As ultrasonic waves, glycerin (manufactured by Tokyo Chemical Industry Co., Ltd., reagent grade) solvent was added about 5 times to the resin, and then heated to a temperature 20 ° C. higher than the melting point, and an ultrasonic generator (produced by Heulshire, ultrasonicator). UP200S) can be performed by applying ultrasonic waves at 24 kHz and amplitude of 60% for 2 hours. Thereafter, it is preferable to vacuum dry after washing with an isopropanol solvent at room temperature.

  The external electric field application treatment can be performed by heating the resin at a glass transition temperature or higher and then applying an AC electric field (500 Hz) of 600 V / cm for 1 hour and then slowly cooling it.

  In the PBF method, it is preferable that the temperature range (temperature window) with respect to the crystal layer change is large because warping during creation of the three-dimensional structure can be suppressed. As for the crystal layer change, the resin powder having a larger difference between the melting start temperature and the recrystallization point at the time of cooling is better because the moldability is improved.

<Other additives>
If necessary, additives such as flame retardants, plasticizers, heat-stable additives, crystal nucleating agents, non-crystalline resins in the resin particles or in addition to the particles as long as the effects of the present invention are not impaired Polymer particles such as the above may be contained.

<Method for producing powder for three-dimensional modeling>
The three-dimensional modeling powder of the present invention can be obtained by producing the first resin particles and the second resin particles, and then mixing them. Mixing can be performed by a known method, for example, a mixer or a shaker.

The first resin particles and the second resin particles can be obtained by powder processing a commercially available resin by a known method. For example, a method of pulverizing resin pellets or powder in a normal temperature or freezing temperature environment, an atomizing method in which a resin is melted and then ejected, a suspension method, and the like can be mentioned. It is also possible to classify the obtained particles to obtain a particle size and particle size distribution suitable for the purpose.
Hereinafter, the powder containing the first resin particles may be referred to as “first particle powder”, “first particle powder”, etc., and the powder containing the second resin particles is referred to as “second particle powder”. , Sometimes referred to as “second particle powder”.

  As a method of obtaining a vertical pillar-shaped powder, a method of directly cutting a resin fiber to obtain a substantially cylindrical body or a rectangular parallelepiped shape, a method of obtaining a rectangular parallelepiped or a cube from a film shape, and post-processing after producing the obtained rectangular solid particles And the like, and the like. Among the above methods, a method of cutting the resin fibers to obtain a powder on the upright column is preferable.

Examples of the method for producing the resin fiber include a method of stretching the resin solution for three-dimensional modeling in a fibrous form while stirring at a temperature higher by 30 ° C. or higher than the melting point using an extrusion processing machine. At this time, the resin solution for three-dimensional modeling is drawn to 1 to 10 times to make a fiber. At this time, the shape of the fiber cross section can be determined by the shape of the nozzle port of the extrusion machine. For example, when the cross section is circular, the nozzle port is preferably circular.
The higher the dimensional accuracy, the better. The circular shape of the surface portion is preferably at least 10% in radius. The greater the number of nozzle openings, the better the productivity.

For the cutting, a cutting device such as a guillotine method in which the upper blade and the lower blade are both blades, or a device called a push-cut method on the lower side, not a blade, and a device that cuts with the upper blade is used. be able to. There are methods of cutting directly to 0.005 mm or more and 0.2 mm or less using the above apparatus or cutting using a CO ₂ laser or the like. By these methods, the powder of the present invention can be obtained directly.

  As a three-dimensional modeling powder obtained under another suitable condition, it is preferable to perform a sintering process each time a new powder layer is drawn with a roller or the like. In the sintering process, the powder layer is selectively melted. A new powder layer is applied to the previously formed layer, selectively melted again, this is repeated, and the above process is continued until a desired three-dimensional model is manufactured.

<Uses of powder for three-dimensional modeling>
The three-dimensional modeling powder of the present invention is suitably used in various three-dimensional modeling methods using resin powder such as an SLS method, an SMS method, an HSS (High Speed Sintering) method, or a BJ (Binder Jetting) method.

<Uses of resin powder>
The resin powder of the present embodiment has an appropriate balance for parameters such as particle size, particle size distribution, heat transfer characteristics, melt viscosity, bulk density, fluidity, melting temperature, and recrystallization temperature, and the SLS method and the SMS method. , MJF (Multi Jet Fusion) method, or BJ (Binder Jetting) method and other three-dimensional modeling methods using resin powder. The resin powder of this embodiment is suitably used in surface shrinkage agents, spacers, lubricants, paints, grindstones, additives, secondary battery separators, foods, cosmetics, clothes, and the like. In addition, it may be used as a material used in the fields of automobiles, precision equipment, semiconductors, aerospace, medicine, and metal substitutes.

(Manufacturing device for 3D objects)
The manufacturing apparatus of the three-dimensional structure according to the present invention includes a supply tank in which the powder for three-dimensional modeling is stored, a layer forming unit that forms a layer containing the powder for three-dimensional modeling, and at least a part of the layer. Melting means for melting, and other means as required.

  Examples of the layer forming means include a roller, a blade, a brush, or a combination thereof.

As a melting means, for example, electromagnetic irradiation is performed to melt. Examples of the electromagnetic radiation source include a CO ₂ laser, an infrared radiation source, a microwave generator, a radiant heater, an LED lamp, or a combination thereof.

  Here, the manufacturing apparatus of the three-dimensional molded item using said three-dimensional modeling powder is demonstrated using FIG. FIG. 4 is a schematic diagram illustrating a manufacturing apparatus for a three-dimensional structure according to an embodiment of the present invention.

  As illustrated in FIG. 4, the modeling apparatus 1 includes a supply tank 11 as an example of a storage unit that stores the resin powder P for modeling, a roller 12 that supplies the resin powder P stored in the supply tank 11, and a roller 12. A laser scanning space 13 in which the resin powder P supplied by the laser beam L is scanned, an electromagnetic irradiation source 18 that is an irradiation source of the laser L as electromagnetic rays, and a laser L irradiated by the electromagnetic irradiation source 18. A reflection mirror 19 that reflects the laser scanning space 13 to a predetermined position is provided. The modeling apparatus 1 also includes heaters 11H and 13H that heat the resin powder P accommodated in the supply tank 11 and the laser scanning space 13, respectively.

  While the electromagnetic irradiation source 18 irradiates the laser L, the reflecting surface of the reflecting mirror 19 moves based on two-dimensional data of a 3D (three-dimensional) model. The two-dimensional data of the 3D model indicates each cross-sectional shape when the 3D model is sliced at a predetermined interval. Thereby, by changing the reflection angle of the laser L, a portion of the laser scanning space 13 indicated by the two-dimensional data is selectively irradiated with the laser L. The resin powder at the laser L irradiation position is melted and welded. That is, the electromagnetic radiation source 18 functions as a melting means for melting the resin powder P.

  Pistons 11 </ b> P and 13 </ b> P are provided in the supply tank 11 and the laser scanning space 13 of the modeling apparatus 1. When the modeling of the layers is completed, the pistons 11P and 13P move the supply tank 11 and the laser scanning space 13 upward or downward with respect to the stacking direction of the modeling object. This makes it possible to supply new resin powder P used for modeling a new layer from the supply tank 11 to the laser scanning space 13.

  Although the modeling apparatus 1 selectively melts the resin powder P by changing the laser irradiation position by the reflecting mirror 19, the present invention is not limited to such an embodiment. The resin powder of the present invention is also preferably used in a selective mask sintering (SMS) type modeling apparatus. In the SMS method, for example, a part of the resin powder is masked with a shielding mask, electromagnetic rays are irradiated, electromagnetic rays such as infrared rays are irradiated to the unmasked portion, and the resin powder is selectively melted to form To do.

  When the SMS process is used, the resin powder P preferably contains one or more heat absorbers that enhance infrared absorption characteristics, dark substances, or the like. Examples of the heat absorbing agent or dark substance include carbon fiber, carbon black, carbon nanotube, and cellulose nanofiber.

  For the SMS process, for example, those described in US Pat. No. 6,531,086 can be suitably used.

(Method for manufacturing a three-dimensional model)
The manufacturing method of the three-dimensional structure according to the present invention includes a layer forming step for forming a layer containing the powder for three-dimensional modeling, and a melting step for melting at least a part of the layer. The melting step is repeated, and further steps are included as necessary.

  Examples of the layer forming step include a step of forming a layer using a roller, a blade, a brush, or a combination thereof.

Examples of the melting step include a step of melting using an electromagnetic irradiation source such as a CO ₂ laser, an infrared irradiation source, a microwave generator, a radiant heater, an LED lamp, or a combination thereof.

  FIG.5 and FIG.6 is a conceptual diagram for demonstrating one Embodiment of the manufacturing method of the three-dimensional molded item of this invention. The manufacturing method of the three-dimensional molded item using the modeling apparatus 1 is demonstrated using FIG.5 and FIG.6.

  The resin powder P accommodated in the supply tank 11 is heated by the heater 11H. The temperature of the supply tank 5 is preferably as high as possible below the melting point of the resin particles P in terms of suppressing warping when the resin particles P are melted by laser irradiation, but the melting of the resin powder P in the supply tank 11 is preferable. It is preferable that the temperature is lower than the melting point of the resin powder P by 10 ° C. or more.

  As shown in FIG. 5 (A), the engine of the modeling apparatus 1 drives the roller 12 as an example of the supply process, and supplies the resin powder P in the supply tank 5 to the laser scanning space 13 to level the ground. A powder layer having a thickness T corresponding to one layer is formed. The resin powder P supplied to the laser scanning space 13 is heated by the heater 13H. The temperature of the laser scanning space 13 is preferably as high as possible in terms of suppressing warping when the resin particles P are melted by laser irradiation, but in terms of preventing the resin powder P from melting in the laser scanning space 13, The melting point of the resin powder P is preferably 5 ° C. or more lower.

  The engine of the modeling apparatus 1 receives input of a plurality of two-dimensional data generated from the 3D model. As shown in FIG. 5B, the engine of the modeling apparatus 1 moves the reflecting surface of the reflecting mirror 19 based on the two-dimensional data on the most bottom surface side among the plurality of two-dimensional data, and the electromagnetic irradiation source 18. Irradiate with laser. There is no restriction | limiting in particular as an output of a laser, Although it selects suitably according to the objective, 10 watts or more and 150 watts or less are preferable.

  By the laser irradiation, the resin powder P at the position corresponding to the pixel indicated by the two-dimensional data on the most bottom surface side of the powder layer is melted. When the laser irradiation is completed, the molten resin is cured, and a sintered layer having a shape indicated by the two-dimensional data on the bottom side is formed.

  Although it does not specifically limit as thickness T of a sintered layer, As an average value, 10 micrometers or more are preferable, 50 micrometers or more are more preferable, and 100 micrometers or more are still more preferable. The thickness T of the sintered layer is not particularly limited, but the average value is preferably less than 200 μm, more preferably less than 150 μm, and still more preferably less than 120 μm.

  As shown in FIG. 6A, when the bottommost sintered layer is formed, the engine of the modeling apparatus 1 seems to form a modeling space having a thickness T of one layer in the laser scanning space 13. Further, the laser scanning space 13 is lowered by the thickness T of one layer by the piston 13P. Further, the engine of the modeling apparatus 1 raises the piston 11 </ b> P so that new resin powder P can be supplied. Subsequently, the engine of the modeling apparatus 1 drives the roller 12 to supply the resin powder P in the supply tank 5 to the laser scanning space 13 to level the ground, thereby forming a powder layer having a thickness T for one layer. To do.

  As shown in FIG. 6 (B), the engine of the modeling apparatus 1 moves the reflecting surface of the reflecting mirror 19 based on the two-dimensional data of the second layer from the bottom surface among the plurality of two-dimensional data, The electromagnetic irradiation source 18 is irradiated with a laser. As a result, the resin powder P at the position corresponding to the pixel indicated by the two-dimensional data of the second layer from the bottom side in the powder layer is melted. When the laser irradiation is completed, the molten resin is cured, and a sintered layer having the shape indicated by the two-dimensional data of the second layer from the bottom surface side is formed in a state of being laminated on the sintered layer on the bottom surface side. The

  The modeling apparatus 1 stacks the sintered layers by repeating the supply process and the layer formation process. When modeling based on all of the plurality of two-dimensional data is completed, a three-dimensional object having the same shape as the 3D model is obtained.

(3D objects)
The three-dimensional modeled object in the present invention is suitably manufactured by the method for manufacturing a three-dimensional modeled object of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

Example 1
<Preparation of first particle powder 1>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 1]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 1>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5010, manufactured by Mitsubishi Engineering Plastics Co., Ltd., melting point: 218 ° C, glass transition temperature: 43 ° C) with a low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [Second Particle Powder 1]. The volume average particle diameter was 40 μm, and the MFR value was 20 g / 10 minutes.

<Preparation of three-dimensional modeling powder 1>
8 kg of [first particle powder 1] and 2 kg of [second particle powder 1] were mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [Powder 1 for 3D modeling].

(Example 2)
<Preparation of first particle powder 2>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Thereafter, in order to melt the surface by mechanical friction, the obtained cut product was treated at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 2]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 2>
Polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5010, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C., glass transition temperature: 43 ° C.) and polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5008, Mitsubishi Engineering Plastics) A melting point: 218 ° C., a glass transition temperature: 43 ° C. was mixed at a ratio of 5: 5 for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises). Thereafter, melting, kneading, and pelletizing were performed at a temperature 30 ° C. higher than the melting point using a table-type kneading extrusion micropellet production apparatus 1AEC (manufactured by Imoto Seisakusho) to prepare PBT pellets. The produced pellets were freeze-pulverized at −200 ° C. using a low-temperature pulverization system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron Corporation) to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [Second Particle Powder 2]. The volume average particle size was 40 μm, and the MFR value was 30 g / 10 min.

<Preparation of three-dimensional modeling powder 2>
8 kg of [first particle powder 2] and 2 kg of [second particle powder 2] were mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 2].

(Example 3)
<Preparation of first particle powder 3>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was treated for 20 minutes at a rotational speed of 9000 rpm using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 3]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 3>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 3]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 3>
8 kg of [first particle powder 3] and 2 kg of [second particle powder 3] were mixed for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 3].

Example 4
<Preparation of first particle powder 4>
After stirring polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5026, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) at a temperature 30 ° C higher than the melting point, resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 4]. . The volume average particle size was 80 μm, and the MFR value was 7 g / 10 min.

<Preparation of second particle powder 4>
Polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5010, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C., glass transition temperature: 43 ° C.) and polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5008, Mitsubishi Engineering Plastics) A melting point: 218 ° C., a glass transition temperature: 43 ° C. was mixed at a ratio of 5: 5 for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises). Thereafter, melting, kneading, and pelletizing were performed at a temperature 30 ° C. higher than the melting point using a table-type kneading extrusion micropellet production apparatus 1AEC (manufactured by Imoto Seisakusho) to prepare PBT pellets. The produced pellets were freeze-pulverized at −200 ° C. using a low-temperature pulverization system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron Corporation) to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [Second Particle Powder 4]. The volume average particle size was 40 μm, and the MFR value was 30 g / 10 min.

<Preparation of three-dimensional modeling powder 4>
8 kg of [first particle powder 4] and 2 kg of [second particle powder 4] were mixed for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 4].

(Example 5)
<Preparation of first particle powder 5>
Polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) and polybutylene terephthalate (PBT) resin (trade name: Nova Duran 5026, Mitsubishi Engineering Plastics) Co., Ltd., melting point: 218 ° C., glass transition temperature: 43 ° C.) was mixed at a ratio of 5: 5 for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises). Then, after stirring at a temperature 30 ° C. higher than the melting point, the resin solution for three-dimensional modeling is used as a three-dimensional modeling resin solution, and the three-dimensional modeling resin solution is formed into a fiber using an extrusion processing machine (manufactured by Nippon Steel Works) with a circular nozzle opening. Stretched out. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 5]. . The volume average particle size was 80 μm, and the MFR value was 8.5 g / 10 minutes.

<Preparation of second particle powder 5>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [Second Particle Powder 5]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 5>
8 kg of [first particle powder 5] and 2 kg of [second particle powder 5] were mixed for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 5].

(Example 6)
<Preparation of first particle powder 6>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 6]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 6>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 6]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 6>
5 kg of [first particle powder 6] and 5 kg of [second particle powder 6] were mixed for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 6].

(Example 7)
<Preparation of first particle powder 7>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Thereafter, in order to melt the surface by mechanical friction, the obtained cut material was treated at 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 7]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 7>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [Second Particle Powder 7]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 7>
[First Particle Powder 7] 9.5 kg and [Second Particle Powder 7] 0.5 kg were mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 7]. It was.

(Example 8)
<Preparation of first particle powder 8>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Thereafter, in order to melt the surface by mechanical friction, the obtained cut product was treated at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 8]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 8>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 8]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 8>
4 kg of [first particle powder 8] and 6 kg of [second particle powder 8] were mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 8].

Example 9
<Preparation of first particle powder 9>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 9]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 9>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 9]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 9>
[First Particle Powder 9] 9.8 kg and [Second Particle Powder 9] 0.2 kg were mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 9]. It was.

(Example 10)
<Preparation of first particle powder 10>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 10]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 10>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [second particle powder 10]. The volume average particle size was 80 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 10>
8.0 kg of [first particle powder 10] and 2.0 kg of [second particle powder 10] are mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 10]. It was.

(Example 11)
<Preparation of the first particle powder 11>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Thereafter, in order to melt the surface by mechanical friction, the obtained cut product was treated at a rotational speed of 9000 rpm for 50 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 11]. . The volume average particle diameter was 40 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 11>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [second particle powder 11]. The volume average particle size was 80 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 11>
8.0 kg of [first particle powder 11] and 2.0 kg of [second particle powder 11] are mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [three-dimensional modeling powder 11]. It was.

Example 12
<Preparation of the first particle powder 12>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [First Particle Powder 12]. The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 12>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 12]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 12>
8.0 kg of [first particle powder 12] and 2.0 kg of [second particle powder 12] are mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [three-dimensional modeling powder 12]. It was.

(Example 13)
<Preparation of the first particle powder 13>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) is stirred at a temperature 30 ° C higher than the melting point, and then a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into the sheet shape is adjusted using a cutting device (Nagino Seiki Seisakusho, NJ series 1200 type) with a cutting width of 50 μm and a cutting speed of 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 13]. . The volume average particle size was 80 μm, and the MFR value was 10 g / 10 min.

<Preparation of second particle powder 13>
After stirring polybutylene terephthalate (PBT) resin (trade name: Novaduran 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) at a temperature 30 ° C higher than the melting point, a resin solution for three-dimensional modeling Then, the resin solution for three-dimensional modeling was stretched into a fibrous shape using an extrusion processing machine (manufactured by Nippon Steel Works) having a circular nozzle opening. The fiber was stretched 4 times to adjust the fiber diameter (diameter) to 55 μm.
Thereafter, the formed fibers were arranged in the same direction and integrated into a sheet by applying a pressure of 10 MPa while heating at a temperature lower by 50 ° C. than the melting point. In addition, the cross-sectional shape of each fiber integrated in a sheet shape was substantially polygonal.
Further, the fiber integrated into a sheet shape is adjusted using a cutting device of a cutting method (manufactured by Kanno Seiki Seisakusho Co., Ltd., NJ series 1200 type) so that the cut width is 30 μm and the cut speed is 280 spm (shots per minute). And cut.
Then, in order to melt the surface by mechanical friction, the obtained cut material was processed at a rotational speed of 9000 rpm for 20 minutes using a multipurpose mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain [First Particle Powder 13]. . The volume average particle size was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 13>
[First particle powder 13] 9.5 kg and [second particle powder 13] 0.5 kg were mixed for 30 minutes using a turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [three-dimensional modeling powder 13]. It was.

(Comparative Example 1)
<Preparation of the first particle powder 14>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5026, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) with low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [first particle powder 14]. The volume average particle size was 80 μm, and the MFR value was 7 g / 10 min.

<Preparation of second particle powder 14>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5020, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 14]. The volume average particle diameter was 40 μm, and the MFR value was 10 g / 10 min.

<Preparation of three-dimensional modeling powder 14>
8.0 kg of [first particle powder 14] and 2.0 kg of [second particle powder 14] are mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [three-dimensional modeling powder 14]. It was.

(Comparative Example 2)
<Preparation of the first particle powder 15>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5026, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) with low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [First Particle Powder 15]. The volume average particle size was 80 μm, and the MFR value was 7 g / 10 min.

<Preparation of second particle powder 15>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained resin powder for three-dimensional modeling was pulverized so as to have a width of 5 μm or more and 100 μm or less to obtain [second particle powder 15]. The volume average particle diameter was 40 μm, and the MFR value was 38 g / 10 min.

<Preparation of three-dimensional modeling powder 15>
8.0 kg of [first particle powder 15] and 2.0 kg of [second particle powder 15] are mixed for 30 minutes using a Turbula mixer (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain [3D modeling powder 15]. It was.

(Comparative Example 3)
<Preparation of three-dimensional modeling powder 16>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5026, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C) with low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained three-dimensional modeling resin powder was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [Three-Dimensional Modeling Powder 16]. The volume average particle size was 80 μm, and the MFR value was 7 g / 10 min.

(Comparative Example 4)
<Preparation of three-dimensional modeling powder 17>
Polybutylene terephthalate (PBT) resin (trade name: NOVADURAN 5008, manufactured by Mitsubishi Engineering Plastics, melting point: 218 ° C, glass transition temperature: 43 ° C), low-temperature grinding system (device name: Linrex Mill LX1, manufactured by Hosokawa Micron) And freeze-pulverized at −200 ° C. to obtain a resin powder for three-dimensional modeling. The obtained three-dimensional modeling resin powder was pulverized so as to have a width of 5 μm or more and 200 μm or less to obtain [three-dimensional modeling powder 17]. The volume average particle size was 80 μm, and the MFR value was 38 g / 10 min.

(Measurement and evaluation)
About the three-dimensional modeling powder obtained in each Example and Comparative Example, measurement of resin particle characteristics and evaluation of modeling quality were performed as follows. The results are shown in Table 1 below.

<Resin particle characteristics>
[MFR (melt mass flow rate) ratio]
MFR (melt mass flow rate) was measured under a load of 2.16 kg using a melt mass flow rate measuring device (manufactured by Dynasco, model D405913) according to JIS7210 (ISO 1133). The melting point was set to + 15 ° C. The measurement was performed after the resin powder was filled and heated for 2 minutes or longer to sufficiently melt the resin. The MFR value of the obtained first resin particles (first particle powder) was MFR1, the MFR value of the second resin particles (second particle powder) was MFR2, and the MFR ratio was calculated by the following formula.
MFR ratio = MFR2 / MFR1

[Volume average particle diameter Dv]
The volume average particle diameter Dv (μm) of the three-dimensional modeling powder was measured using a particle size distribution measuring device (Microtrac MT3300EXII, manufactured by Microtrack Bell). At that time, the particle refractive index for each resin powder was used, and measurement was performed by a dry (atmospheric) method without using a solvent.

[Powder shape]
The obtained three-dimensional modeling powder was photographed at a magnification of 150 times using an SEM (scanning electron microscope JSM-7800FPRIME manufactured by JEOL Ltd.). In the resin powder for three-dimensional modeling in the SEM image obtained by photographing, the first surface, the second surface, and the side surface, and the first surface in the range observed by the SEM, and the first surface It was judged that all of the outer peripheral area of the second surface had a shape extending along the side surface was a vertical column.

<Modeling quality>
[Preparation of test specimen (molded article)]
The resin powder for solid modeling obtained in the supply floor of the SLS modeling apparatus (Ricoh company make, AM S5500P) was added to produce a solid model. As the setting conditions, a laser output of 0.1 mm layer average thickness and 10 watts to 150 watts was set, and a laser scanning space of 0.1 mm and a temperature of −3 ° C. from the melting point was used as the part bed temperature. With the SLS modeling apparatus, five test specimens (XY modeled objects) whose long sides are oriented in the XY plane direction (the plane direction in which the roller 12 in FIG. 4 proceeds) are modeled at the center of the laser scanning space 13. . The interval between the shaped objects is 5 mm or more. The test specimen is an ISO (International Organization for Standardization) 3167 Type 1A multipurpose dogbone-like test specimen (the specimen has a central portion of 80 mm length, 4 mm thickness, 10 mm width). The modeling time was set to 50 hours.

[accuracy]
Each of the obtained five test specimens was measured at five points in the width direction with a digital caliper, and after calculating the average value of the width length, the deviation from the target width length was calculated with the following formula as the accuracy.
Accuracy (mm) = width average value mm-10 mm

The evaluation criteria are as follows.
Very good: 0.1 mm or less Good: larger than 0.1 mm, 0.2 mm or less Inferior: larger than 0.2 mm

[Strength]
The obtained five test specimens were measured for tensile strength (MPa) using a tensile tester (manufactured by Shimadzu Corporation, AGS-5 kN) according to ISO 527, and the average value was defined as “strength”. The tensile test speed was 50 mm / min.

The evaluation criteria are as follows.
Very good: 80 MPa or more Good: 55 MPa or more and less than 80 MPa Inferior: less than 55 MPa

DESCRIPTION OF SYMBOLS 1 Modeling apparatus 11 Supply tank 11H Heater 11P Piston 12 Roller 13 Laser scanning space 13H Heater 13P Piston 18 Electromagnetic irradiation source 19 Reflector 21 Column 22 First surface 22a First opposing surface 22b First surface outer peripheral region 23 2nd surface 23a 2nd opposing surface 23b Outer peripheral area | region of 2nd surface 24 Side surface

JP 2009-40870 A JP 2011-99023 A

Claims (8)

Including first resin particles and second resin particles,
The first resin particles and the second resin particles are the same kind of resin,
When the MFR (melt mass flow rate) of the first resin particles is MFR1 and the MFR of the second resin particles is MFR2, MFR2> MFR1, and the MFR ratio represented by MFR2 / MFR1 is 2 to 5. It is a powder for three-dimensional modeling characterized by being.   2. The ratio of the weight of the first resin particles to the weight of the second resin particles with respect to the three-dimensional modeling powder is 5: 5 to 9.5: 0.5. Three-dimensional modeling powder.   3. The three-dimensional modeling powder according to claim 1, wherein a volume average particle diameter of the first resin particles is larger than a volume average particle diameter of the second resin particles.   The three-dimensional modeling powder according to any one of claims 1 to 3, wherein the first resin particles have a vertical column shape.   The MFR (melt mass flow rate) is measured according to JIS7210, and the three-dimensional modeling powder according to any one of claims 1 to 4.   A supply tank in which the three-dimensional modeling powder according to any one of claims 1 to 5 is stored, and a layer forming means for forming a layer containing the three-dimensional modeling powder according to any one of claims 1 to 5, The manufacturing apparatus of the three-dimensional molded item characterized by having a melting means for melting at least a part of the layer.   Manufacturing of a three-dimensional structure characterized by having a layer formation process which forms the layer containing the powder for three-dimensional modeling in any one of Claims 1-5, and a melting process which fuses at least one part of the said layer. Method. Including first resin particles and second resin particles,
The first resin particles and the second resin particles are the same kind of resin,
When the MFR (melt mass flow rate) of the first resin particles is MFR1 and the MFR of the second resin particles is MFR2, MFR2> MFR1, and the MFR ratio represented by MFR2 / MFR1 is 2 to 5. A resin powder characterized by