JP2019084815A - Powder for solid molding, resin powder, and manufacturing method of solid molded article - Google Patents

Abstract

To provide a powder for solid molding capable of disposing particle more closely, and enhancing strength of a resulting solid molded article.SOLUTION: There is provided a powder for solid molding contains a particle (A) 10 consisting volume most frequent particle diameter and a particle (B) 20 having smaller volume average particle diameter than that of the particle (A), in which at least one of the particle (A) and the particle (B) has a columnar body shape, a ratio of a volume average particle diameter Mv of the particle (A) and a number average particle diameter Mn of the particle (A) (volume average particle diameter/number average particle diameter) (Mv/Mn) is 2.0 or less, and total of a specific area of the particle (A) and a specific area of the particle (B) is 110 m/kg or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a powder for three-dimensional shaping, a resin powder, and a method for producing a three-dimensional object.

  The powder bed fusion (PBF) method is a selective laser sintering (SLS) method of selectively irradiating a laser to form a three-dimensional object, or an SMS (selective mask sintering) that applies a laser in a planar manner using a mask. ) Method is known.

  In the PBF method, a powder is melted and adhered by selectively irradiating a thin layer of metal, ceramic or resin with a laser beam to form a film, and then another layer is formed on the formed film. Can be sequentially laminated by repeating the same operation to obtain a three-dimensional object (see, for example, Patent Documents 1 to 3).

  An object of the present invention is to provide a powder for three-dimensional shaping which can pack particles more densely and can improve the strength of the resulting three-dimensional object.

The powder for three-dimensional shaping | molding of this invention as a means for solving the said subject has a volume average particle diameter smaller than the volume average particle diameter of particle | grains (A) which comprise volume mode particle diameter, and the said particle (A). Particles (B) having at least one of the particles (A) and the particles (B) in the form of a column, and the volume average particle diameter Mv of the particles (A) and the particles (A) The ratio (volume average particle diameter / number average particle diameter) (Mv / Mn) of the number average particle diameter Mn to the number average particle diameter Mn) is 2.0 or less, and the specific surface area of the particles (A) and the particles (B) The total specific surface area is 110 m ² / kg or less.

  According to the present invention, it is possible to provide a powder for three-dimensional shaping, in which particles can be packed more densely and the strength of the resulting three-dimensional object can be improved.

FIG. 1 is a schematic view showing an example of a layer formation state of a powder for three-dimensional shaping in the present invention. FIG. 2A is a schematic perspective view showing an example of a substantially cylindrical particle (A). FIG. 2B is a side view of the substantially cylindrical particle (A) of FIG. 2A. FIG. 2C is a side view showing an example of a shape having no apex of the substantially cylindrical particle (A). FIG. 2D is a side view showing another example of the shape having no apex of the substantially cylindrical particle (A). FIG. 2E is a side view showing another example of the shape having no vertex of the substantially cylindrical particle (A). FIG. 2F is a side view showing another example of the shape having no vertex of the substantially cylindrical particle (A). FIG. 2G is a side view showing another example of the shape having no vertex of the substantially cylindrical particle (A). FIG. 2H is a side view showing another example of the shape having no apex of the substantially cylindrical particle (A). FIG. 2I is a side view showing another example of the shape having no apex of the substantially cylindrical particle (A). FIG. 3 is a photograph showing an example of a column. FIG. 4 is a graph showing the frequency (number) of the particles of the powder for three-dimensional shaping of the present invention with respect to the particle diameter (μm). FIG. 5 is a graph showing the frequency (% by volume) with respect to the particle diameter (μm) of the particles of the powder for stereolithography of the present invention. FIG. 6 is a schematic view showing an example of a layer formation state of a conventional powder for three-dimensional shaping. FIG. 7 is a graph showing the frequency (number of particles) relative to the particle size (μm) of the particles of the commercially available powder for stereolithography of Comparative Example 3. FIG. 8 is a graph showing the frequency (volume%) relative to the particle size (μm) of the particles of the commercially available powder for stereolithography of Comparative Example 3. FIG. 9 is a schematic explanatory view showing an example of a three-dimensional object manufacturing apparatus.

(Powder for 3D modeling)
The powder for three-dimensional shaping of the present invention includes particles (A) constituting the volume mode particle diameter and particles (B) having a volume average particle diameter smaller than the volume average particle diameter of the particles (A). And at least one of the particles (A) and the particles (B) has a columnar shape, and the ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (Volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 or less, and the total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg It is the following and contains other components as needed.
In the present invention, the volume mode particle size means the particle size with the highest particle size (frequency) distribution for each particle size.

  In the powder for three-dimensional shaping of the present invention, when powder having particles having a relatively uniform volume average particle diameter is used in the powder for three-dimensional shaping in the prior art, as shown in FIG. This is based on the finding that there is a problem that it is difficult to secure the strength of the three-dimensional object since the void tends to be generated in the resulting three-dimensional object.

When the total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less, the surface of the particles becomes smooth and the fluidity (slip) of the particles themselves is high. As a result, aggregation of the particles (A) and the particles (B) is less likely to occur, making it difficult to form secondary particles. As shown in FIG. 1, in the powder for three-dimensional shaping having the particles (A) and the particles (B), the small-diameter particles (B) enter the voids between the large-diameter particles (A). Since the filling rate of the obtained three-dimensional object is further improved as compared with the case where the volume average particle diameter is uniform, the strength of the three-dimensional object can be improved.

The sum of the specific surface area of the specific surface area and the particles (B) of the particles (A), or less 110m ² / kg, preferably from ^{50 m} 2 / kg or more 100 m ² / kg or less, ^{60 m} 2 / kg or more 80 m ² / Kg or less is more preferable. If the total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 50 m ² / kg or more, the particle size is substantially reduced, it is preferable as a powder for three-dimensional shaping. When the total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less, the flowability (slidability) of the particles (A) is increased. ) Are hard to aggregate, and the particles (B) easily enter the voids of the particles (A).

The total of the specific surface area of the particles (A) and the specific surface area of the particles (B) can be determined, for example, as follows.
In the present invention, the specific surface area of particles is defined as the following formula (1).
The total surface area of the particles can be calculated by obtaining the surface area for each particle and summing the surface area of each particle for the number of particles.
The determination of the total volume of particles and the density of particles will be described later.

The surface area S of one particle is represented by the following formula (2), assuming that the shape of the particle is spherical and the particle diameter of the particle is d.
S = πd ² equation (2)
The total surface area of the particles can be calculated by finding the surface area for each particle from the above equation (2) and summing the surface areas of the particles for the number of particles.

The particle diameter d of the particles can be measured, for example, using a flow type particle size distribution measuring device (device name: FPIA 3000, manufactured by Malvern Co., Ltd.) as follows.
First, after adding a few drops of nonionic surfactant to 10 mL of water from which fine dust has been removed by passing through a filter, the particle size range (for example, equivalent circle diameter: 0.50 μm or more but less than 200.00 μm) The powder for three-dimensional modeling is added so that the number of particles to be measured which is specified is 20 or less per 1 × 10 ⁻³ cm ^{3 of} water. In addition, as said nonionic surfactant, brand name: Contaminone N (made by Wako Pure Chemical Industries Ltd.) is preferable. Next, the water containing the powder for three-dimensional modeling was subjected to a dispersion treatment for 1 minute under the conditions of 20 kHz and 50 W / 10 cm ³ using an ultrasonic disperser (device name: UH-50, manufactured by STM). After that, the dispersion process is performed for 4 minutes. The flow type is obtained by using the powder dispersion for three-dimensional shaping having a particle concentration of 3,000 / 1 × 10 ⁻³ cm ³ or more and 7,000 / 1 × 10 ⁻³ cm ³ or less of the powder for three-dimensional shaping. The particle size distribution of the particles in the defined particle size range is measured using a particle size distribution analyzer.
In the flow type particle size distribution measuring device, the powder dispersion for three-dimensional modeling passes through a flow path in a flat and flat transparent flow cell which spreads along the flow direction. Here, a strobe and a CCD camera are disposed at positions sandwiching the transparent flow cell. When the strobe irradiates light in a direction intersecting the flow direction of the flow path in the transparent flow cell, the light passes through the transparent flow cell, and an optical path is formed in the transparent flow cell.
While the powder dispersion liquid for three-dimensional modeling flows through the flow path in the transparent flow cell, light is emitted from the strobe at an interval of 1/60 seconds, and the CCD is synchronized with the timing when the strobe emits the light. When the camera captures an image of the transparent flow cell, the powder is in the range of the defined particle diameter of the powder for three-dimensional modeling flowing in the transparent flow cell, and in a direction parallel to the direction in which the transparent flow cell is flat. Certain particles are taken as two-dimensional images. Thereby, the number of particles based on the distribution of the equivalent circle diameter and the number of particles having the defined equivalent circle diameter can be measured. Further, the number of particles obtained can be divided into 1,024 channels according to the range of the particle diameter of 0.50 μm to 200 μm.
The particle number can be calculated as n by defining the particle diameter as d and defining the median value of each channel as the particle diameter.

As the particle diameter of the particles, number average particle diameter Mn and volume average particle diameter Mv can be used.
The number average particle diameter Mn can be calculated from d obtained by measurement and the number n of particles using the following equation (3).
The volume average particle diameter Mv can be calculated using the following equation (4), similarly to the number average particle diameter Mn.
The method of calculating the number average particle diameter Mn and the volume average particle diameter Mv is basically in accordance with the calculation contents of calculation software attached to a flow type particle size distribution measuring device (device name: FPIA 3000, manufactured by Malvern Co., Ltd.).

  The particle number distribution can be obtained by defining the particle diameter as d, defining the mean value of each channel as the particle diameter, and graphing the number of particles for each channel (FIG. 4).

The particle volume distribution can be measured, for example, using a flow type particle size distribution measuring device (device name: FPIA 3000, manufactured by Malvern Co., Ltd.).
The volume V of one particle can be determined from the following equation (5).
V = 1 / 6πd ³ equation (5)
Here, the total volume of the particles can be calculated by calculating the volume V for each particle and summing the volume of each particle for the number of particles using the particle diameter of each channel described above and the data of the number .
The particle volume distribution can be obtained by calculating the volume ratio (%) of each channel and graphing the volume ratio (%) for each channel (FIG. 5).

4 and 5 show an example of the measurement results of the powder for three-dimensional shaping according to the present invention, but the particle number distribution and the particle volume distribution of the powder for three-dimensional shaping according to the present invention Existence is recognized.
On the other hand, the existence of two clear particle size distribution peaks is not recognized in the particle number distribution and the particle volume distribution of the commercially available powder for stereolithography of Comparative Example 3, and the powder for stereolithography of the present invention is It turns out that it is a completely different powder (FIG. 7 and FIG. 8).

Examples of the method of determining the density of the particles, that is, the density of the substance constituting the powder include a method of measuring and determining the density of the particles, a method of examining using a chemical manual, and the like.
As a method of measuring and determining the density of the substance that constitutes the powder, for example, using a substance that constitutes the powder, a heat-formed product having a mass of about several g is prepared without bubbles, and the Archimedes method is used. By using, it can measure.

The Archimedes method uses the Archimedes principle that, when a solid is submerged in a liquid, the solid receives buoyancy from the liquid by a weight equal to the weight of the liquid equal to the volume of the submerged solid, It is a method to determine the density of the solid that has sunk.
Assuming that the mass of the solid is m and the volume of the solid is V, the apparent density ρ _{a of the} solid is represented by the following formula (6).
_{a a} = m / V equation (6)
The mass _ml of the solid in the liquid is represented by the following formula (7), where D is the density of the liquid.
m _l = m-DV equation (7)
Therefore, the apparent density _{a a} of _a solid is represented by the following equation (8) from the above equation (6) and the above equation (7).

The apparent density _{a a} of _a solid can also be determined by using a spring and a weight having a spring constant k and fixed in the direction of gravity.
First, the position of the lower end of the spring without hanging the weight is S ₀ , the position of the lower end of the spring when hanging the weight in the direction of gravity in air is S _A , when the weight is suspended in the direction of gravity in the liquid Assuming that the position of the lower end of the spring is S _B , the mass of the solid is m, and the mass of the solid in the liquid _ml is expressed as the following formula (9) and formula (10).
m = k (S _A −S ₀ ) formula (9)
m _l = k (S _B −S ₀ ) formula (10)
Therefore, the apparent density _{a a} of _a solid can be expressed as in the following equation (11) using S ₀ , S _A , S _B , and D.
That is, since the apparent density _{a a of the} solid does not depend on the spring constant k, the apparent density _{a a of the} solid can be obtained regardless of the spring constant k.

When using a solid having an open pore, the solid is immersed in a liquid and the density is measured, then the solid is returned to the air, the liquid adhering to the surface of the solid is wiped off, and the measurement is made in the air. Assuming that the position of the spring is S _A ′, the density ρ of the solid can be obtained by the following equation (12).

<Particle (A)>
The particles (A) constitute, in the powder for three-dimensional shaping, a volume mode particle diameter, and further contain other components as necessary.

  There is no restriction | limiting in particular as a volume average particle diameter of the said particle (A), Although it can select suitably according to the objective, 20 micrometers or more and 120 micrometers or less are preferable, 20 micrometers or more 110 micrometers or less are more preferable, 20 micrometers or more 100 micrometers or less More preferably, in view of dimensional stability, 50 μm or more and 100 μm or less is particularly preferable. The volume average particle diameter of the particles (A) is, for example, a particle size distribution measuring device of flow type (apparatus for separating the particles (A) and the particles (B) and separating the particles (A) in the powder for three-dimensional shaping) Name: FPIA 3000, manufactured by Malvern, Inc.) can be used.

  There is no restriction | limiting in particular as a separation means of the particle | grains (A) in the powder for three-dimensional shaping | molding, According to the objective, it can select suitably, For example, a sieve, a classifier, etc. are mentioned. Among these, the sieve in which the surface of particle (A) is not easily affected is preferable.

The powder for three-dimensional shaping has at least two peaks of the particles (A) and the particles (B) in a particle size distribution. The particle size distribution can be determined, for example, using a flow type particle size distribution measuring device (device name: FPIA 3000, manufactured by Malvern Co., Ltd.).
FIG. 4 is a graph showing the frequency (number) with respect to the particle size (μm). FIG. 5 is a graph showing the frequency (volume%) with respect to the particle size (μm). It can be seen from FIGS. 4 and 5 that the powder for stereolithography of the present invention has two peaks in the particle size distribution.

There is no restriction | limiting in particular as a shape of the said particle | grain (A), According to the objective, it can select suitably, For example, column shape, a sphere, etc. are mentioned. Among these, a cylindrical shape is preferable in that particles can be packed more densely.
It is preferable that the said powder for three-dimensional shaping | molding is a columnar shape which the shape of each particle | grain (A) became independent.

There is no restriction | limiting in particular as said column shape, Although it can select suitably according to the objective, A substantially cylindrical body, a rectangular parallelepiped, etc. are mentioned. By being in the columnar shape, the particles (A) can be packed without gaps, and the strength of the three-dimensional object to be obtained can be improved.
It is preferable that the column shape have opposing surfaces. The facing surfaces may be inclined, and in terms of productivity and stability of laser shaping, parallel and non-inclined ones are more preferable. The shape of the particles may be, for example, a scanning electron microscope (device name: S4200, manufactured by Hitachi, Ltd.), a wet flow particle diameter / shape analyzer (device name: FPIA-3000, manufactured by Sysmex Corporation), etc. Can be observed. The obtained particles may be spheroidized or treated with an external additive to further improve powder flowability.

The ratio of the height to the diameter or the long side of the bottom of the column shape is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.5 times or more and 5 times or less, 0.7 It is more preferably twice or more and twice or less and particularly preferably 0.8 times or more and 1.5 times or less.
The diameter at the bottom of the column shape and the height relative to the long side are, for example, at least 20 images of particles (A) and particles (B) at 300 × magnification using a scanning electron microscope. The diameter or the long side of the bottom of the column and the height of the column can be measured based on the reference length, and can be calculated from the average value thereof.
As the scanning electron microscope, for example, an apparatus name: S4200 (manufactured by Hitachi, Ltd.) can be used.

-Almost cylindrical body-
There is no restriction | limiting in particular as said substantially cylindrical body, According to the objective, it can select suitably, For example, a true cylinder body, an elliptical cylinder body, etc. are mentioned. Among these, a true cylinder is preferable. The circular portion of the substantially cylindrical body may be partially missing. In addition, the substantially circular means that the ratio of the major axis to the minor axis (major axis / minor axis) is 1 to 10.

Moreover, it is preferable that the said substantially cylindrical body has the surface where a substantially circle faces.
The sizes of the circles on the facing surfaces may be somewhat different, but the ratio of the diameter of the circle between the large surface and the small surface (large surface / small surface) is preferably 1.5 times or less, and the shape is unified In order to reduce the density, it is more preferable to use 1.1 times or less.

There is no restriction | limiting in particular as a diameter of the said substantially cylindrical body, Although it can select suitably according to the objective, 5 micrometers or more and 200 micrometers or less are preferable. In addition, when the circular part of a substantially cylindrical body is elliptical, the said diameter means a long diameter.
There is no restriction | limiting in particular as height (distance between both surfaces) of the said substantially cylindrical body, Although it can select suitably according to the objective, 5 micrometers or more and 200 micrometers or less are preferable.

-Rectangular solid-
There is no restriction | limiting in particular as said rectangular parallelepiped, According to the objective, it can select suitably, For example, a rectangle, a cube, etc. are mentioned. Among these, a cube is preferable. Although the rectangular parallelepiped may be partially missing, it is preferably a square whose sides are close in length, from the viewpoint that the degree of dispersion narrows and is densely packed.
Further, it is preferable that the rectangular parallelepiped has a rectangular or square facing surface.

There is no restriction | limiting in particular as each side in the bottom face of the said rectangular parallelepiped, Although it can select suitably according to the objective, 5 micrometers or more and 200 micrometers or less are preferable. The long side in each side is the longest side when one face of the rectangular parallelepiped is the bottom, and when the rectangular parallelepiped is a cube, it is one of the sides having the same length in the bottom. .
There is no restriction | limiting in particular as height of the said rectangular parallelepiped, Although it can select suitably according to the objective, 5 micrometers or more and 200 micrometers or less are preferable. The height means the height direction with respect to the bottom of the rectangular parallelepiped.

  The sides forming the height between the faces of the column are softened at the time of cutting, and the crushed state (cylindrical in a cylindrical shape) is also included in the scope of the present invention. In order to space the space, it is preferable that the side is linear since the powder can be packed densely. As described above, a polygonal column having a surface pressed against the powder side is more preferable because it can be densely packed because the gap at the contact surface becomes narrow.

The height of the column shape is preferably such a length that the volume average particle diameter is 20 μm or more and 100 μm, and in particular, the height is uniform, there is no bias in the shape and size of the powder, and they are formed as an identical aggregate Those close to monodispersion are more preferable.
Among the substantially cylindrical bodies, those close in diameter and height are preferable from the viewpoint of reproducibility, and for the same reason, cubes having equal sides and heights are more preferable for a rectangular parallelepiped.

FIG. 3 is a photograph showing an example of a column.
In addition, FIG. 3 is a photograph by SEM (scanning electron microscope) observation.

  As shown in FIG. 3, the column body 21 has a first surface 22, a second surface 23 and a side surface 24. The first surface 22 has a first opposing surface 22 a and an outer peripheral region 22 b of the first surface which is shaped so as to extend along the side surface 24. The outer peripheral region 22b of the first surface is a surface that is continuous with the first opposing surface 22a via a curved surface, and is substantially orthogonal to the first opposing surface 22a. The second surface 23 has a second opposing surface 23 a facing the first opposing surface 22 a and an outer peripheral region 23 b of the second surface which is a shape extended along the side surface 24. The outer peripheral region 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. In addition, an outer peripheral region 22b of the first surface and an outer peripheral region 23b of the second surface extend on the side surface 24.

The shapes 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 "the outer peripheral region") may be any shape that can be distinguished on the side surface 24 and the SEM image. It includes a shape in which a part of the region is integrated with the side surface 24, a shape in which the outer peripheral region is in contact with the side surface 24, and a shape in which a space exists between the outer peripheral region and the side surface 24. The outer peripheral region 22 b of the first surface and the outer peripheral region 23 b of the second surface are preferably provided in the same surface direction as the surface direction of the side surface 24.
As shown in FIG. 3, the outer peripheral region 22 b of the first surface and the outer peripheral region 23 b of the second surface extend along the side surface 24 and are located on the side surface 24. Further, the characteristic structure 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 is a bottle cap shape Also called.

It is more preferable that the columnar particle (A) has a bottom surface and an upper surface, but the end of the particle (A) has a shape having no apex. The vertex refers to a portion of a corner present in the cylindrical shape. For example, a side view of the cylinder shown in FIG. 2A is represented in FIG. 2B. In this case, it has a rectangular shape, and there are four corner parts, that is, four vertices. An example of the shape having no vertex is shown in FIGS. 2C to 2I. In order to actually confirm the presence or absence of the apex, it can be determined from the projection image on the side surface of the cylindrical particle. For example, the side surface of the columnar particle is observed using a scanning electron microscope (device name: S4200, manufactured by Hitachi, Ltd.) or the like to obtain a two-dimensional image. In this case, the projected image is a quadrilateral, and if a portion formed by two adjacent sides is an end, if formed by only two adjacent straight lines, a corner is formed and has an apex. In the case where the end is formed by a circular arc as shown in FIGS. 2C to 2I, it has no vertex.
As described above, by forming the columnar particles (A) so as not to have an apex, the flowability is improved, the packing density can be further enhanced, and the strength of the three-dimensional object is enhanced. It is very effective.

  In all the columnar particles (A) of the powder for three-dimensional modeling, it is most preferable not to have the apex, which is a portion of a corner existing in the columnar shape, and a columnar particle having no apex It is more preferable that the ratio of (A) is high. Specifically, the content ratio of column-shaped particles (A) having no apex to all column-shaped particles (A) is preferably 30% or more, more preferably 50% or more, and 75% or more. More preferably, 90% or more is particularly preferable. Thereby, the flowability of the powder is enhanced, and the effect of the present invention is further enhanced.

As a method of determining the presence or absence of the apex, for example, as described above, the powder is observed using a scanning electron microscope (apparatus name: S4200, manufactured by Hitachi, Ltd.) or the like, and all obtained two-dimensional images The determination can be made by determining the proportion of columnar particles having no vertex with respect to the columnar particles of. For example, a two-dimensional image of 10 fields of view is photographed by the above method, and the ratio of columnar-shaped particles (A) having no vertex to the total columnar-shaped particles (A) is determined and averaged. it can.
In the cylindrical particle (A) having no apexes, it is not necessary to have a substantially cylindrical or polygonal cylinder, but the projected image of the side has a shape with a constriction or the end portion is elongated. It may include a shape or a shape which is crushed or bent.

  Thus, as a method of making the shape of columnar-shaped particles (A) in the powder not have an apex, any method can be used as long as the apex of the columnar-shaped particles (A) can be rounded. Methods known in the art may also be used, for example, conventionally known spheronizing apparatus, such as high-speed rotary mechanical grinding, high-speed impact mechanical grinding, or surface melting by mechanical friction.

  The melting point of the particles (A) as measured according to ISO 3146 is preferably 100 ° C. or higher because it is within the heat resistant temperature range that can be used for the exterior of a product, etc., and is 150 ° C. or higher Is more preferable, and particularly preferably 200.degree. C. or more. The melting point can be measured using differential scanning calorimetry (DSC) in accordance with ISO 3146 (plastic transition temperature measurement method, JIS K 7121), and when a plurality of melting points exist, the high temperature side Use the melting point of

The specific gravity of the particles (A) is preferably 0.8 or more. When the specific gravity is 0.8 or more, secondary aggregation of particles at the time of recoating can be suppressed, which is preferable. Further, the specific gravity of the particles (A) is preferably 3.0 or less from the needs of weight reduction to replace metal. The specific gravity can be determined by measuring the true specific gravity.
For the measurement of the true specific gravity, for example, the volume of a sample containing the particles (A) is obtained in advance, and a dry-type automatic densitometer using a vapor phase displacement method (apparatus name: Accupic 1330, manufactured by Shimadzu Corporation) By changing the volume and pressure of gas (He gas) at a constant temperature using the above, the mass can be measured from the volume of the sample, and the density of the sample can be determined.

  The average circularity of the particles (A) is preferably 0.7 or more and 0.98 or less, and more preferably 0.83 or more and 0.98 or less, in the particle diameter range of 0.5 μm or more and 200 μm or less. The average degree of circularity can be measured, for example, using a wet flow type particle size and shape analyzer (apparatus name: FPIA-3000, manufactured by Sysmex Corporation), and the degree of circularity of the powder for three-dimensional shaping is measured The value obtained by arithmetically averaging them is expressed as an average circularity. The method of simply determining the circularity can be quantified, for example, by measurement using a wet flow type particle size and shape analyzer (apparatus name: FPIA-3000, manufactured by Malvern Co., Ltd.). This device can rapidly capture particle images in a suspension flowing in a glass cell with a CCD, analyze each particle image in real time, and capture such particles and perform an image analysis. It is effective in determining the average circularity of the present invention. The measurement count number is not particularly limited, but is preferably 3,000 or more and 7,000 or less.

As the particles (A) in the present invention, a thermoplastic resin can be used. The thermoplastic resin means one that is plasticized and melted when heat is applied. Among the thermoplastic resins, crystalline thermoplastic resins may be used. In addition, when the said crystalline resin is measured by ISO 3146 (the plastic transition temperature measuring method, JISK7121), it means what has a melting peak.
Further, the particles (A) in the present invention are not limited to crystalline resins, but may be non-crystalline resins.

  As the crystalline thermoplastic resin, an error occurs when the crystalline thermoplastic resin whose crystal size and crystal orientation are controlled by a method of external stimulation such as heat treatment, drawing, a crystal nucleus material, ultrasonic treatment, etc. is subjected to high temperature recoating It is preferable because it does not easily occur.

-Crystalline thermoplastic resin-
There is no restriction | limiting in particular as said crystalline thermoplastic resin, According to the objective, it can select suitably, For example, polyolefin, polyamide, polyester, polyaryl ketone, polyphenylene sulfide, liquid crystal polymer (LCP), polyacetal (POM,) Melting point: 175 ° C.), and polymers such as polyimide and fluorine resin. These may be used alone or in combination of two or more.

  Examples of the polyolefin include polyethylene and polypropylene (PP, melting point: 180 ° C.). These may be used alone or in combination of two or more.

  Examples of the polyamide include polyamide 410 (PA410), polyamide 6 (PA6), polyamide 66 (PA 66, melting point: 265 ° C.), polyamide 610 (PA 610), polyamide 612 (PA 612), polyamide 11 (PA 11), 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. These may be used alone or in combination of two or more. Among these, PA9T is also called polynonamethylene terephthalamide, is composed of terephthalic acid monomers with carbon having nine diamines, and is generally called semiaromatic because the carboxylic acid side is aromatic. Furthermore, the polyamide of the present invention includes what is called aramid which is formed from p-phenylenediamine and a terephthalic acid monomer as a wholly aromatic which is also aromatic on the diamine side.

  Examples of the polyester include polyethylene terephthalate (PET, melting point: 260 ° C.), polybutylene terephthalate (PBT, melting point: 218 ° C.), polylactic acid (PLA) and the like. Polyesters containing aromatics partially containing terephthalic acid and isophthalic acid to impart heat resistance can also be suitably used in the present invention.

  Examples of the polyaryl ketones include polyetheretherketone (PEEK, melting point: 343 ° C.), polyetherketone (PEK), polyetherketoneketone (PEKK), polyaryletherketone (PAEK), polyetheretherketone ketone (PEEKK), polyether ketone ether ketone ketone (PEKEKK), etc. are mentioned. Other than the polyaryl ketone, any crystalline polymer may be used, and examples thereof include polyacetal, polyimide, and polyether sulfone. As in PA9T, one having two melting point peaks may be used (it is necessary to raise the resin temperature above the second melting point peak to completely melt).

  The powder for three-dimensional shaping is preferably composed of only particles, but may be generally combined with pulverized one.

  There is no restriction | limiting in particular as a manufacturing method of the said crystalline thermoplastic resin, According to the objective, it can select suitably, For example, it heats at the temperature more than the glass transition temperature of each resin with respect to powder, The annealing treatment may be performed, or a method in which a crystal nucleating agent is added to increase crystallinity and then annealing treatment may be mentioned. In addition, a method of enhancing crystallinity by applying ultrasonic waves, a method of enhancing crystallinity by dissolving in a solvent and evaporating slowly, a method of undergoing a process such as crystalline growth by external electric field application treatment, or stretching A method of processing such as pulverization, cutting, etc., which has high orientation and high crystals depending on the conditions, can be mentioned.

  The 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.

  The stretching can be performed by extruding and stretching a three-dimensional modeling resin melt into a fiber shape while stirring at a temperature higher by 30 ° C. or more than the melting point using an extrusion processing machine. At this time, the resin melt for three-dimensional shaping is stretched to about 1 to 10 times to form fibers. At this time, the shape of the fiber cross section can be determined by the shape of the nozzle port of the extrusion machine, but in the present invention, when the column shape is a substantially cylindrical body, the nozzle port also preferably has a circular shape. When the shape is a rectangular solid, the nozzle opening may be rectangular or square. The greater the number of nozzle openings, the more suitable for productivity. Stretching can change the maximum draw ratio for each melt viscosity of the resin.

  As the ultrasonic wave, after adding glycerin (a reagent grade made by Tokyo Chemical Industry Co., Ltd., reagent grade) solvent to the powder about 5 times with respect to the resin, the powder is heated to a temperature 20 ° C. higher than the melting point, ultrasonic wave generator Name: Ultrasonicator UP200S (manufactured by Hielscher) can be used by applying ultrasonic waves with an amplitude of 60% for 24 hours for 24 hours. After washing with a solvent of isopropanol at room temperature, vacuum drying is preferred.

  The external electric field application treatment can be performed by heating the powder above the glass transition temperature and then applying an alternating electric field of 600 V / cm (500 Hz) for 1 hour and then slowly cooling it.

  In the PBF method, it is preferable that the temperature width (temperature window) with respect to the crystal layer change is large because the warpage can be suppressed. It is preferable that the crystalline layer change be different because the resin powder that has a large difference between the melting start temperature and the recrystallization point at the time of cooling has better formability.

The ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (volume average particle diameter / number average particle diameter) (Mv / Mn) is from the viewpoint of improvement in shaping accuracy 2.0 or less, preferably 1.75 or less, and more preferably 1.5 or less.
In addition, said (Mv / Mn) is a parameter | index showing the uniformity of a particle size distribution, and the value of said (Mv / Mn) shows a uniform particle | grain, as it approaches one. The particle (B) can regularly enter the space of the particle (A) of the present invention as the value of (Mv / Mn) approaches 1 and the particle size distribution becomes uniform, and a three-dimensional object obtained The physical properties of can be stabilized.

The particles (A) preferably satisfy at least one selected from the following (1) to (3).
(1) In differential scanning calorimetry, let Tmf1 (° C.) be the melting start temperature of the endothermic peak when the temperature is raised to a temperature 30 ° C. higher than the melting point at 10 ° C./min. When the melting start temperature of the endothermic peak when the temperature is lowered to -30 ° C or less at 10 ° C / min and the temperature is raised to 30 ° C higher than the melting point at 10 ° C / min is Tmf2 (° C) Since (Tmf1-Tmf2) ≧ 3 ° C., (Tmf1-Tmf2) ≧ 5 ° C. is preferable, and (Tmf1-Tmf2) ≧ 10 ° C. is more preferable. The melting start temperature of the endothermic peak draws a straight line parallel to the x-axis from the place where the heat quantity becomes constant to the low temperature side after the endothermic at the melting point is completed, and drops by -15 mW from the straight line Temperature.
(2) In differential scanning calorimetry, the degree of crystallinity determined from the energy amount of the endothermic peak when heated to a temperature 30 ° C. higher than the melting point at 10 ° C./min according to ISO 3146 is Cd1 (% The crystal is obtained from the energy amount of the endothermic peak when the temperature is lowered to −30 ° C. or less at 10 ° C./min and the temperature is further raised to 30 ° C. higher than the melting point at 10 ° C./min. When the conversion degree is Cd2 (%), (Cd1-Cd2)) 3%, so (Cd1-Cd2) ≧ 5% is preferable, and (Cd1-Cd2) ≧ 10% is more preferable.
(3) The degree of crystallinity obtained by X-ray diffraction measurement is Cx1 (%), and the temperature is raised to a temperature 30 ° C. higher than the melting point at 10 ° C./min in a nitrogen atmosphere, and then at 10 ° C./min When the degree of crystallinity obtained by X-ray diffraction measurement when the temperature is lowered to −30 ° C. or lower and the temperature is raised to 30 ° C. higher than the melting point at 10 ° C./min is Cx 2 (% Since Cx1-Cx2) ≧ 3%, (Cx1-Cx2) ≧ 5% is preferable, and (Cx1-Cx2) ≧ 10% is more preferable.

  The (1) to (3) define characteristics of the same particle (A) from different viewpoints, and the (1) to (3) are related to each other, and the (1) to (3) If it can measure by at least 1 sort (s) selected from 3), the powder for three-dimensional shaping | molding of this invention can be identified.

[Method of measuring dissolution start temperature by differential scanning calorimetry of condition (1)]
As a method of measuring the melting start temperature by differential scanning calorimetry (DSC) of the condition (1), a differential scanning calorimeter (for example, a measuring method of plastic transition temperature, JIS K 7121) according to the measuring method. The melting start temperature (Tmf1) of the endothermic peak when the temperature is raised to a temperature 30 ° C. higher than the melting point at 10 ° C./min using a Shimadzu Co., Ltd. product, DSC-60A, etc.). Then, lower the temperature to -30 ° C or lower at 10 ° C / min, and measure the melting start temperature (Tmf2) of the endothermic peak when the temperature is raised to 30 ° C higher than the melting point at 10 ° C / min. . The melting start temperature of the endothermic peak draws a straight line parallel to the x-axis from the place where the heat quantity becomes constant to the low temperature side after the endothermic at the melting point is completed, and drops by -15 mW from the straight line Temperature.

[Method of measuring crystallinity by differential scanning calorimetry of condition (2)]
As a measuring method of the crystallinity degree by the differential scanning calorimetry (DSC) of the said conditions (2), it is 30 from melting | fusing point at 10 degrees C / min. Based on ISO 3146 (the plastic transition temperature measuring method, JISK7121) The energy amount (heat of fusion) of the endothermic peak when the temperature is raised to a high temperature can be measured, and the degree of crystallization (Cd1) can be determined from the heat of fusion relative to the heat of complete crystallization. Thereafter, the temperature is lowered to -30 ° C. or lower at 10 ° C./min, and the energy amount of the endothermic peak when the temperature is raised to 30 ° C. higher than the melting point is further measured at 10 ° C./min. The degree of crystallization (Cd2) can be determined from the heat of fusion for.

[Method of measuring degree of crystallinity by X-ray analyzer of condition (3)]
As a method of measuring the crystallinity degree by the X-ray analyzer under the condition (3), an X-ray analyzer (for example, an apparatus name: Discover 8 manufactured by Bruker) having a two-dimensional detector is used at room temperature The 2θ range can be set to 10 to 40, and the obtained powder can be placed on a glass plate to measure the degree of crystallinity (Cx1). Next, in DSC, the sample is heated at 10 ° C / min in a nitrogen atmosphere, heated to a temperature 30 ° C higher than the melting point, kept warm for 10 minutes, and then cooled to 10 ° C / min and -30 ° C. Can be returned to room temperature, and the degree of crystallinity (Cx2) can be measured in the same manner as Cx1.

The particles (A) may contain, in addition to the thermoplastic resin, flame retardants, plasticizers, heat-stable additives, additives such as crystal nucleating agents, and polymer particles such as non-crystalline resins. These may be used alone or in combination of two or more.
As the polymer particle, a mixture of the polymer particle may be used, or a polymer particle coated on the surface of the polymer particle may be used.

<< Other ingredients >>
The other components may contain any fluidizing agent, sizing agent, toughening agent, antioxidant, flame retardant and the like.

<<< fluidizer >>>
The fluidizing agent refers to one having an effect of enhancing the flowability of the powder for three-dimensional shaping by covering a part or all of the surface of the powder for three-dimensional shaping.
There is no restriction | limiting in particular as said fluidizer, Although it can select suitably according to the objective, The spherical particle which consists of inorganic materials is preferable.
The inorganic material is preferably a metal oxide, and examples thereof include silicon dioxide, aluminum oxide, titanium oxide, zinc oxide, magnesium oxide, tin oxide, iron oxide, copper oxide and the like. These may be used alone or in combination of two or more. Among these, silicon dioxide and titanium oxide are preferable.

As the fluidizing agent, a particulate inorganic material having a volume average particle size of less than 10 μm can be suitably used.
When the fluidizing agent is added as an external additive, the particle diameter of the external additive is preferably 0.1 μm or less. When the particle size of the external additive is 0.1 μm or less, it is smaller than the particle sizes of the particles (A) and the particles (B), so the peak of the external additive in the particle size distribution and the particles (A) And the peaks of the particles (B).

The content of the fluidizing agent may be an amount sufficient to cover the particle surface, and is preferably 0.05% by mass or more and 10% by mass or less with respect to the total amount of the three-dimensional powder. More preferably, it is from 3 to 3% by mass, and particularly preferably from 0.1 to 1.5% by mass.
When the content is 0.05% by mass or more and 10% by mass or less, the flowability of the powder for three-dimensional shaping can be improved, and at the same time, the influence of the decrease in packing density due to the increase of voids can be minimized.

<<< particle size agent >>>
The sizing agent is not particularly limited and may be appropriately selected according to the purpose. For example, alumina, talc, glass-like silica, titania, hydrated silica, or silica surface modified with a silane coupling agent And those using one or more kinds of magnesium silicate.

<<< Toughener >>>
The reinforcing agent is not particularly limited and may be appropriately selected according to the purpose. From the viewpoint of improving the strength, for example, a fiber filler or bead filler, a glass filler described in WO 2008/057844 pamphlet, Glass beads, carbon fiber, aluminum balls and the like can be mentioned. These may be used alone or in combination of two or more.
As a powder for three-dimensional shaping | molding of this invention, what is dried suitably is preferable, and you may make it dry before use by putting a vacuum dryer and a silica gel.

There is no restriction | limiting in particular as said fiber filler, Although it can select suitably according to the objective, A carbon fiber, an inorganic glass fiber, and a metal fiber are preferable.
There is no restriction | limiting in particular as said bead filler, Although it can select suitably according to the objective, A carbon bead, an inorganic glass bead, and a metal bead are preferable.

  In general, when the fiber filler or the bead filler is mixed with the powder for three-dimensional shaping having no sharp melt property, the accuracy of the shaped article tends to deteriorate. This is because the thermal conductivity of the fiber filler and the bead filler to be added is higher than that of the powder for three-dimensional shaping, therefore, when the powder surface is irradiated with laser at the time of SLS shaping, the heat given to the irradiated portion goes out of the irradiated portion. It is a cause that the resin powder is diffused and the temperature of the resin powder outside the irradiation becomes equal to or higher than the melting point and is excessively shaped. On the other hand, the mixed powder of the powder for three-dimensional shaping (the crystalline thermoplastic resin composition having the above-mentioned sharp melt property) and the above-mentioned fiber filler or bead filler of the present invention is a thermal powder because the resin powder has the sharp melt property. Even if the resin temperature outside the laser irradiation part rises due to diffusion, it is difficult to melt, so it is possible to suppress the excessive shaping and to maintain high shaping accuracy.

  The fiber filler preferably has an average fiber diameter of 1 μm to 30 μm and an average fiber length of 30 μm to 500 μm. By using a fiber filler having the above-mentioned average fiber diameter and the above-mentioned average fiber length in the range of this range, it is possible to realize the improvement of the strength of a shaped object, and the surface of the shaped object is a surface of a shaped object to which no fiber filler is added. It is possible to maintain the same degree of roughness.

The bead filler preferably has a circularity of 0.8 or more and 1.0 or less and a volume average particle diameter of 10 μm or more and 200 μm or less. When the area (number of pixels) is S and the perimeter is L, the circularity can be obtained by the following equation.
Circularity = 4πS / L ² ... (formula)
The volume average particle diameter can be measured, for example, using a particle size distribution measuring device (device name: microtrac MT3300EXII, manufactured by Microtrac Bell Inc.).

As content of the said fiber filler, 5 mass% or more and 60 mass% or less are preferable with respect to the powder whole amount for three-dimensional shaping | molding. If it is less than this range, the effect of strength improvement which is the original purpose of the fiber filler addition is small, and if it is more than this range, shaping becomes difficult.
As content of the said bead filler, 5 mass% or more and 60 mass% or less are preferable with respect to the powder whole quantity for three-dimensional shaping | molding. When the content is 5% by mass or more, strength can be improved, which is the original purpose of the bead filler addition, and when it is 60% by mass or less, shaping can be facilitated.

<<< Antioxidant >>>
The particles (A) preferably contain an antioxidant from the viewpoint of suppressing resin deterioration.
There is no restriction | limiting in particular as said antioxidant, According to the objective, it can select suitably, For example, hydrazide type as a metal chelating agent, triazine type as a ultraviolet absorber, hindered phenol type as a radical trapping agent, oxidation The inhibitors include phosphates and sulfurs. These may be used alone or in combination of two or more.

  As content of the said antioxidant, 0.05 mass% or more and 5 mass% or less are preferable with respect to the powder whole quantity for three-dimensional shaping | molding, 0.1 mass% or more and 3 mass% or less are more preferable, and 0.2 mass % Or more and 2% by mass or less is particularly preferable. When the content is in the above range, the effect of preventing thermal deterioration is obtained, and it becomes possible to reuse the resin powder used for shaping. In addition, the effect of preventing discoloration due to heat can be obtained.

<<< Flame retardant >>>
There is no restriction | limiting in particular as said flame retardant, According to the objective, it can select suitably, For example, a halogen type, phosphorus type, inorganic hydration metal compound type, nitrogen type, silicone type etc. are mentioned. These may be used alone or in combination of two or more. When 2 or more types of the said flame retardant are used together, the combination of a halogen type and an inorganic hydrated metal compound type is preferable at the point which can make a flame-retardant performance high.

  As the flame retardant, for example, an inorganic fibrous material such as glass fiber, carbon fiber or aramid fiber, or an inorganic reinforcing agent such as inorganic layered silicate such as talc, mica or montmorillonite improves the flame retardancy. be able to. In this case, it is possible to achieve both of the enhancement of physical properties and the enhancement of flame retardancy.

  As said flame retardant, it can use suitably, for example, for materials which require fire prevention measures, such as a construction material, a vehicle material, and a ship fitting material.

  The flame retardancy of the particles (A) can be evaluated by, for example, JIS K6911, JIS L1091 (ISO 6925), JIS C3005, a heat generation test (corn calorimeter) or the like.

  As content of the said flame retardant, 1 mass% or more and 50 mass% or less are preferable with respect to whole particle (A), and 10 mass% or more and 30 mass% or less from the point which can improve a flame retardance more More preferable. When the content is 1% by mass or more, sufficient flame retardancy can be realized. Moreover, it can suppress that the melting-solidification characteristic of the powder for three-dimensional shaping | molding changes that the said content is 50 mass% or less, and it can prevent that shaping | molding precision fall and physical property deterioration of a modeling thing generate | occur | produce.

The content of the particles (A) is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, with respect to the total amount of three-dimensional shaping powder. % Or more is particularly preferred. When the content is 30% by mass or more, the particles (A) can be closely packed.
The content of the particles (A) can be determined from, for example, the number of particles (A) relative to the number of all particles in the obtained SEM image by collecting a powder for three-dimensional shaping and performing SEM observation .

<Particle (B)>
The particles (B) have a volume average particle size smaller than the volume average particle size of the particles (A).

The volume average particle diameter of the particles (B) is preferably 0.3 times to 0.5 times the volume average particle diameter of the particles (A).
Between the particles (A) having a large diameter when the volume average particle diameter of the particles (B) is 0.3 times or more and 0.5 times or less the volume average particle diameter of the particles (A) When the small-diameter particles (B) enter the voids, the filling rate of the obtained three-dimensional object is improved as compared with the case where the volume average particle diameter is uniform.

  There is no restriction | limiting in particular as a separation means of the particle | grains (B) in the powder for three-dimensional shaping | molding, According to the objective, it can select suitably, For example, a sieve, a classifier, etc. are mentioned. Among these, the sieve in which the surface of particle (B) is not easily affected is preferable.

  There is no restriction | limiting in particular as a shape of the said particle | grain (B), According to the objective, it can select suitably, For example, a column shape, a sphere, etc. are mentioned. Among these, a cylindrical shape is preferable in that particles can be packed more densely.

The particles (B) may have the same shape as the particles (A). When the particles (B) have the same shape as the shape of the particles (A), the same shape as the shape of the particles (A) can be used.
The particles (B) may have a shape different from the shape of the particles (A).

There is no restriction | limiting in particular as said particle | grain (B), According to the objective, it can select suitably, For example, a crystalline thermoplastic resin etc. are mentioned.
As the crystalline thermoplastic resin, the same as the particles (A) can be used.

  The particles (B) may have the same composition as the particles (A) or may have a different composition from the particles (A).

  There is no restriction | limiting in particular as a number average particle diameter of the said particle | grain (B), Although it can select suitably according to the objective, 15 micrometers or more and 50 micrometers or less are preferable.

The ratio of the volume average particle diameter Mv of the particles (B) to the number average particle diameter Mn of the particles (B) (volume average particle diameter / number average particle diameter) (Mv / Mn) is from the viewpoint of improvement in shaping accuracy 2.0 or less is preferable, 1.75 or less is more preferable, and 1.5 or less is especially preferable.
In addition, said (Mv / Mn) is a parameter | index showing the uniformity of a particle size distribution, and the value of said (Mv / Mn) shows a uniform particle | grain, as it approaches one. The particle (B) can regularly enter the space of the particle (A) of the present invention as the value of (Mv / Mn) approaches 1 and the particle size distribution becomes uniform, and a three-dimensional object obtained The physical properties of can be stabilized.
The particle size distribution of the particles (B) is preferably uniform.

<< Other ingredients >>
As the other components, those similar to the other components of the particles (A) can be used.

  As the powder for three-dimensional shaping, although it can be used for SLS method and SMS method, parameters such as appropriate particle size, particle size distribution, heat transfer property, melt viscosity, bulk density, fluidity, melt temperature, and recrystallization temperature It exhibits characteristics that show an appropriate balance.

  The bulk density of the powder for three-dimensional shaping is different in the density possessed by the resin itself from the viewpoint of promoting the degree of laser sintering in the PBF method, but the bulk density is preferably larger, and the tap density is preferably 0. 35 g / mL or more is more preferable, 0.40 g / mL or more is further preferable, and 0.5 g / mL or more is particularly preferable.

[Filling rate]
As a filling rate of the three-dimensional object obtained using the said powder for three-dimensional shaping | molding, 90% or more is preferable, 95% or more is more preferable, and 98% or more is especially preferable.
In the present invention, the filling rate is defined as the following formula (13).
Packing ratio (%) = (density of material−measured density) / density of material × 100 (13)
The density can be measured by the Archimedes method, for example, in the air of a three-dimensional object obtained by using Mettler Toledo, MS 403 S / 02, density measurement kit 0.1 mg, 1 mg balance. And the density can be calculated from the correlation of mass in water.

[Strength]
As for the strength of the three-dimensional object obtained by using the powder for three-dimensional shaping, the bending strength is preferably 80% or more of the bending strength of the material. For example, when a three-dimensional object having a length of 80 mm ± 2 mm, a width of 10 mm ± 0.2 mm, and a thickness of 4 mm ± 0.2 mm is produced, polybutylene terephthalate (PBT) has a bending strength of 35 MPa as the bending strength of each material. As mentioned above, it is preferable that nylon 12 (PA12) is 30 MPa or more, polypropylene (PP) is 20 MPa or more, and polyphenylene sulfide (PPS) is 50 MPa or more.
The bending strength can be measured, for example, using a tensile tester (device name: Autograph, manufactured by Shimadzu Corporation).
The bending strength can be measured under the test conditions of distance between supporting points: 64 mm, test speed: 2 mm / minute according to the method of determining JIS-K 7121 plastic-bending characteristics.
Moreover, the modeling direction in the modeling tank of the three-dimensional molded item obtained shall be distinguished. For example, test pieces generally formed by the SLS method tend to have higher strength in test pieces arranged in the XY direction (horizontal direction) than test pieces formed in the Z direction (lamination direction). In the present invention, the three-dimensional object is measured such that the longitudinal direction thereof is the Z direction (lamination direction).

[Volume ratio (particle (B) / particle (A))]
As a volume ratio (particle (B) / particle (A)) of volume (%) of the particle (A) to volume (%) of the particle (B), particles can be packed more densely Therefore, 0.050 or more and 0.090 or less are preferable, and 0.060 or more and 0.080 or less are more preferable.

[Number ratio (particle (B) / particle (A))]
The number ratio (particles (B) / particles (A)) of the number (particles) of the particles (A) to the number (particles) of the particles (B) is that the particles can be packed more densely Therefore, 1/1 is preferable.

  A particle (A) production step of producing a particle (A) by stretching the material melt for three-dimensional shaping into a fiber and manufacturing the particle (A) as a method of producing the powder for three-dimensional shaping, and the particle (A) And a mixing step of mixing the particles (B), and optionally including other steps.

  As said powder for three-dimensional shaping | molding, the thing similar to the powder for three-dimensional shaping | molding of this invention can be used.

  The particles of the particles (B) may be produced by the same process as the particle (A) production process, or may be produced by a process different from the particle (A) production process.

<Particle (A) Production Process>
As a manufacturing method of the powder for three-dimensional shaping | molding, it has a particle | grain (A) manufacturing process of extending | stretching the material melt for three-dimensional shaping | molding in fiber form, cutting | judgement, and manufacturing particle | grains (A).

As a method of producing the particles (A), a method of producing columnar fibers and then cutting them directly to obtain a substantially cylindrical body or a rectangular solid, a method of obtaining a rectangular solid or a cube from a film shape, or the obtained rectangular solid The particles (A) may be produced into a substantially cylindrical body by post-processing.
As the fiberization, using an extruder, the resin melt for three-dimensional shaping is extruded and stretched into a fiber shape while being stirred at a temperature higher by 30 ° C. or more than the melting point. At this time, the resin melt for three-dimensional shaping is stretched to about 1 to 10 times to form fibers. At this time, the shape of the fiber cross section can be determined according to the shape of the nozzle port of the extrusion machine, but if the shape of the particles (A) is a substantially cylindrical body, the nozzle port should be circular and rectangular. In some cases, the nozzle orifices may be rectangular or square in shape. The higher the dimensional accuracy, the better, and the circular shape of the surface portion is preferably at least 10% or less in the radius. The greater the number of nozzle openings, the more suitable for productivity. Stretching can change the maximum draw ratio for each melt viscosity of the resin.

The above-mentioned cutting is performed using a cutting device such as a guillotine type cutter in which the upper blade and the lower blade are both blades, or a cutting device called a push-off type using a plate instead of the cutter. be able to. There is a method of cutting directly to 0.005 mm or more and 0.2 mm or less using the above-mentioned apparatus or cutting using a CO ₂ laser or the like. The particles (A) can be obtained directly by these methods.

  As the particles (A), after adjusting from several tens of μm to several hundred μm by stretching several times from the form of pellets etc., cut using a laser cut or a blade so that the fiber becomes several μm to several hundred μm And so on.

  The above-mentioned particles (A) are obtained by pulverizing from the form of pellets etc. as a general pulverizing method, using a pulverizing apparatus at room temperature, and classification operation such as filter filtration other than the target particle diameter It is obtained by It can be obtained by grinding using resin brittleness preferably at a low temperature of 0 ° C. or lower (less than the brittle temperature of each resin itself), more preferably at a cryogenic temperature of -25 ° C. or lower, particularly preferably -100 ° C. or lower .

  As particles (A) obtained under other suitable conditions, it is preferable to carry out a sintering process each time a new powder layer is drawn by a roller or the like. In the sintering process, the powder layer portion is selectively melted. A fresh powder layer is applied to the previously formed layer and remelted selectively, which is repeated and the process is continued until the desired three-dimensional object is produced.

The melting of the particles (A) is typically performed by electromagnetic radiation, but the selectivity of melting is, for example, an inhibitor, an absorber, or electromagnetic radiation (eg, masked or by direct laser beam) And selective application of Any suitable electromagnetic radiation source may be used, such as, for example, a CO ₂ laser, an infrared radiation source, a microwave generator, a radiant heater, an LED lamp, etc., or a combination thereof.

  In some embodiments, selective mask sintering (SMS) techniques can be used to produce the three-dimensional object of the present invention. As the SMS process, for example, those described in US Pat. No. 6,531,086 can be suitably used.

  As the SMS process, a shielding mask is used to selectively block infrared radiation and selectively irradiate a portion of the powder layer. When the SMS process is used to manufacture an article from the powder for stereolithography of the present invention, it is preferable to contain one or more substances in the powder composition that enhances the infrared absorption characteristics of the powder for stereolithography, The shaping powder can contain one or more heat absorbing agents and / or dark substances (carbon fibers, carbon black, carbon nanotubes, carbon fibers, cellulose nanofibers, etc.).

<Particle (B) manufacturing process>
It is preferable to include the particle | grain (B) manufacturing process of extending | stretching the material melt for three-dimensional shaping | molding to a fiber form, cutting | judgement, and manufacturing a particle | grain (B) as a manufacturing method of the said powder for three-dimensional shaping.

The particle (B) production process may be the same process as the particle (A) production process.
The particle (B) production process is a process different from the particle (A) production process, and the particles of the particle (B) are produced by a process different from the particle (A) production process. Good.

<Mixing process>
It is preferable that the manufacturing method of the said powder for three-dimensional shaping | molding includes the mixing process of mixing the said particle | grains (A) and particle | grains (B).
There is no restriction | limiting in particular as a mixing means which performs the said mixing process, According to the objective, it can select suitably, For example, a Henschel mixer (made by Nippon Coke Kogyo Co., Ltd.), V-type mixer (made by Tokuju work place) And the like.

  In order to produce a three-dimensional object by the PBF method using the powder for three-dimensional shaping of the present invention, a suitable method is to include a sintered layer in which a plurality of layers containing a polymer matrix are laminated and adhered. preferable. The sintered layer preferably has a thickness suitable for a shaping process. The average thickness of the plurality of sintered layers is preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more. Moreover, as an average thickness of the said sintering layer, less than 200 micrometers is preferable, less than 150 micrometers is more preferable, and less than 120 micrometers is especially preferable.

The powder for stereolithography of the present invention has an appropriate balance of parameters such as particle size, particle size distribution, heat transfer properties, melt viscosity, bulk density, flowability, melt temperature, and recrystallization temperature. Therefore, it is suitably used in various three-dimensional modeling methods using three-dimensional modeling powder such as SLS system, PBF system such as SMS system, MJF (Multi Jet Fusion) system, or BJ (Binder Jetting) method.
Further, the resin powder of the present invention is used as a resin powder for three-dimensional modeling, and suitably used in, for example, surface shrinking agents, spacers, lubricants, paints, grinding wheels, additives, secondary battery separators, foods, cosmetics, clothes, etc. It is used. Furthermore, the resin powder of the present invention can also be used as a material or metal substitute material used in the fields of automobiles, precision instruments, semiconductors, aerospace, medical and the like.
The powder for use in three-dimensional shaping according to the present invention is an article for use in a prototype of an electronic device part or automobile part, a prototype for strength test, a small amount product used for aerospace or a dressing up tool for the automobile industry, etc. Can be suitably used to form The other systems other than the PBF system are expected to be superior in strength as compared with the FDM and the inkjet system, and therefore, they can be used as practical products. Although the production speed is not suitable for mass production such as injection molding, the required production quantity can be obtained, for example, by mass production of small parts in a planar manner. In addition, since the method of manufacturing a three-dimensional object in the PBF method used in the present invention does not require a mold such as injection molding, overwhelming cost reduction and delivery time reduction are achieved in trial production and prototype production. be able to.

(Method for producing three-dimensional object and apparatus for producing three-dimensional object)
The method for producing a three-dimensional object according to the present invention is a method for forming a layer comprising the layer containing the powder for three-dimensional shaping according to the present invention, and a curing step in which the formed layer is cured by electromagnetic irradiation and curing. The product is manufactured and, if necessary, other steps are included.
The apparatus for producing a three-dimensional object has a layer forming means for forming a layer containing the three-dimensional powder according to the present invention, and a powder bonding means for bonding the powders in a selected region of the layer. Furthermore, it has other means as needed.
The method for producing the three-dimensional object can be suitably carried out by the production device for the three-dimensional object.

As said powder for three-dimensional shaping | molding, the thing similar to the powder for three-dimensional shaping | molding of this invention can be used.
As said powder adhesion | attachment means, the electromagnetic wave or the laser is irradiated to the ground powder, for example, The hardening means etc. which fuse | melt resin and it hardens by cooling are mentioned.

As the electromagnetic radiation source used for the electromagnetic radiation, for example, CO ₂ lasers, infrared radiation sources, microwave generator, radiant heater, LED lamp, or combinations thereof, and the like.

  Here, the manufacturing apparatus of the said three-dimensional model is demonstrated using FIG. FIG. 9 is a schematic explanatory view showing an example of a three-dimensional object manufacturing apparatus used in the three-dimensional object manufacturing method of the present invention. As shown in FIG. 9, the powder is stored in the powder supply tank 5 and is supplied to the laser scanning space 6 using the roller 4 according to the amount used. It is preferable that the temperature of the supply tank 5 be adjusted by the heater 3. The laser output from the electromagnetic irradiation source 1 is irradiated to the laser scanning space 6 using the reflecting mirror 2. The powder can be sintered by the heat of the laser to obtain a three-dimensional object.

The temperature of the supply tank 5 is preferably 10 ° C. or more lower than the melting point of the powder.
The component bed temperature in the laser scanning space is preferably 5 ° C. or more lower than the melting point of the powder.
There is no restriction | limiting in particular as an output of the said laser, Although it can select suitably according to the objective, 10 to 150 watt is preferable.

(Three-dimensional object)
The three-dimensional object can be suitably produced by the method for producing a three-dimensional object of the present invention.
Using the resin powder for three-dimensional modeling, a three-dimensional article formed by laser sintering can form a surface that is smooth and exhibits sufficient resolution exhibiting a minimum orange peel or less. Here, the orange peel generally means the presence of an improper rough surface or a surface defect such as a vacancy problem or a distortion problem on the surface of a three-dimensional object formed by laser sintering in a PBF method. Do. The pores may not only impair the appearance but also significantly affect the mechanical strength.

  Furthermore, as the three-dimensional object formed by laser sintering using the above-mentioned resin powder for three-dimensional modeling, warpage, distortion, and smoke due to a phase change which occurs during sintering and after cooling after sintering It is preferred not to exhibit such inappropriate process characteristics.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples.

  For the obtained powder for three-dimensional shaping, “volume average particle diameter and ratio of volume average particle diameter / number average particle diameter (Mv / Mn)”, “height relative to diameter or long side of bottom of particle of column” The ratio "and" specific surface area "were measured as follows. The results are shown in Tables 1 to 3 below.

[Volume average particle diameter, and ratio of volume average particle diameter / number average particle diameter (Mv / Mn)]
First, a few drops of nonionic surfactant (trade name: Contaminone N, manufactured by Wako Pure Chemical Industries, Ltd.) are added to 10 mL of water from which fine dust has been removed by passing through a filter, and then the particle size range ( equivalent circle diameter: 0.50 .mu.m or less 200.00) number of particles measured that defines is such that the water 1 × ¹⁰ -3 cm ³ per 20 or less, was added powder stereolithography. Next, the water containing the powder for three-dimensional modeling was subjected to a dispersion treatment for 1 minute under the conditions of 20 kHz and 50 W / 10 cm ³ using an ultrasonic disperser (device name: UH-50, manufactured by STM). After that, dispersion treatment was performed for 4 minutes. In addition, the flow of the powder by using a powder dispersion for three-dimensional shaping having a particle concentration of 3,000 / 1 × 10 ⁻³ cm ³ or more and 7,000 / 1 × 10 ⁻³ cm ³ or less of the powder for three-dimensional shaping The particle size distribution of particles in the specified particle size range was measured using a formula particle size distribution measuring apparatus (device name: FPIA 3000, manufactured by Malvern Co., Ltd.).
In the flow type particle size distribution measuring device, the powder dispersion for three-dimensional modeling was allowed to pass through a flow path in a flat, flat, transparent flow cell spreading along the flow direction. Here, the strobe and the CCD camera were placed at positions sandwiching the transparent flow cell. The light was emitted in a direction intersecting the flow direction of the flow path in the transparent flow cell, whereby the light passed through the transparent flow cell, and an optical path was formed in the transparent flow cell.
While the powder dispersion liquid for three-dimensional modeling flows through the flow path in the transparent flow cell, light is emitted from the strobe at intervals of 1/60 seconds, and the CCD is synchronized with the timing when the strobe irradiates the light. By causing the camera to photograph the transparent flow cell, the powder in the three-dimensional structure forming powder flowing in the transparent flow cell is in the range of the defined particle diameter and in a direction parallel to the direction in which the transparent flow cell is flat. Certain particles were taken as two-dimensional images. Thereby, the number of particles based on the distribution of the equivalent circle diameter and the number of particles having the defined equivalent circle diameter were measured. Also, the number of particles obtained was obtained by dividing into 1,024 channels according to the range of the particle diameter of 0.50 μm to 200 μm. The diameter of the particles was d, the mean value of each channel was defined as the particle diameter, and the number of particles in the particle diameter range of each channel was calculated as n.
From the diameter d of the obtained particles and the number n of the particles, the number average particle diameter Mn is calculated using the following equation (3).
Further, as in the case of the number average particle diameter Mn, the volume average particle diameter Mv was calculated using the following equation (4).
Furthermore, the ratio (Mv / Mn) of volume average particle diameter / number average particle diameter was determined from the obtained volume average particle diameter and the obtained number average particle diameter.
The calculation method of the number average particle diameter Mn and the volume average particle diameter Mv is according to the calculation contents of calculation software attached to the flow type particle size distribution measuring device (apparatus name: FPIA 3000, manufactured by Malvern Co., Ltd.) .

[A total of the specific surface area of the particles (A) and the specific surface area of the particles (B)]
The total of the specific surface area of the particles (A) and the specific surface area of the particles (B) was determined by using the following formula (1) in the obtained powder for three-dimensional shaping.
The total volume of the particles is calculated by calculating the volume V of one particle using the diameter d of the particles obtained using the flow type particle size distribution analyzer and the number n of the particles and the following equation (5). Using the particle diameter of each channel and the data of the number described above, the volume of each particle was calculated by summing up the volume of each particle.
V = 1 / 6πd ³ equation (5)
In addition, the density of particles was determined by the Archimedes method.

[Ratio at the base of diameter or long side of base of particle of column]
The ratio of the height to the diameter or the long side in the bottom of the particles of the particles of the obtained particles (A) and particles (B) of the column is measured using a scanning electron microscope (apparatus name: S4200, manufactured by Hitachi, Ltd.) The image of the obtained particles (A) and particles (B) at a magnification of 300 times was confirmed, and the diameter or the long side of the bottom of the column and the height were measured based on the reference length. Measure the diameter or long side and height of at least 20 columns in the same manner and use the average value to the diameter or long side of the base of the particles of the particles (A) and particles (B). The ratio of heights was calculated.

Example 1
<Preparation of particles (A)>
Crystalline thermoplastic resin polybutylene terephthalate (PBT) resin (trade name: Novaduran 5020, manufactured by Mitsubishi Engineering Plastics Co., Ltd., melting point: 218 ° C., glass transition temperature: 43 ° C.) Phenolic oxidation to 98.5 mass% 0.5% by mass of an inhibitor (trade name: AO-80, manufactured by ADEKA Co., Ltd.) and 1.0% by mass of a phosphate-based antioxidant (trade name: PEP-36, manufactured by ADEKA) After stirring at a temperature 30 ° C. higher than the melting point using an extruder (manufactured by Japan Steel Works, Ltd.), the melt having a three-dimensional shape was extruded and stretched in a fiber shape using a nozzle whose nozzle shape was circular. The number of threads coming out of the nozzle was 100. After stretching about 4 times to make a fiber with a fiber diameter of 60 μm and an accuracy of ± 4 μm, it is cut using a cutting device with a push-off method at 0.08 mm (80 μm) (NJ series 1200 type made by Kuwano Seiki Co., Ltd.) To obtain substantially cylindrical particles (A).

<Preparation of particles (B)>
Particles (B) of substantially cylindrical bodies were obtained in the same manner as the particles (A) except that fibers having a fiber diameter of 30 μm and precision of ± 5 μm were used and then cut using a 30 μm press-cut type cutting apparatus. .

<Production of Powder 1 for Three-Dimensional Modeling>
The obtained particles (A) and particles (B) were uniformly mixed by means of a Henschel mixer (manufactured by Japan Coke Industry Co., Ltd.) to obtain a powder 1 for three-dimensional shaping. The cross section after cutting was confirmed using a scanning electron microscope (apparatus name: S4200, manufactured by Hitachi, Ltd.) at a magnification of 300 times. As a result, the cross section was finely cut and the cut surfaces were parallel to each other . In addition, when the height of the substantially cylindrical body of the particles (A) was measured, it could be cut with an accuracy of 80 μm ± 10 μm, and when the height of the substantially cylindrical body of the particles (B) was measured, the accuracy of 30 μm ± 5 μm It was able to cut it by. There was little appearance of being crushed at the time of cutting, but it was crushed at the time of cutting at a rate of about 1 in about 100 pieces, and it swelled like a height direction with respect to the surface of a circle or dented on the opposite side The thing which became a dead shape was also included.

(Examples 2 to 13)
In Example 1, powders for three-dimensional shaping of Examples 2 to 13 were obtained in the same manner as in Example 1 except that the materials and the like were changed as shown in Tables 1 to 3 below.

(Comparative example 1)
Phenolic antioxidant (trade name: AO) to 98.5 mass% of polybutylene terephthalate (PBT) resin (trade name: Novadurane 5020, manufactured by Mitsubishi Engineering Plastics Co., Ltd., melting point: 218 ° C., glass transition temperature: 43 ° C.) Add 0.5% by mass of -80, manufactured by ADEKA Co., Ltd., and 1.0% by mass of phosphate-based antioxidant (trade name: PEP-36, manufactured by ADEKA), and add an extrusion processing machine (Japan Co., Ltd.) After stirring at a temperature 30 ° C. higher than the melting point using a steel mill), the stirred product was pressed with a water-cooled roll into a 2 mm thick plate. Thereafter, this was crushed by a blade mill and processed into chips of several mm, and then freeze-ground with a target particle size of 65 μm to obtain a PBT resin powder. Coarse powder was removed from the obtained PBT resin powder with 200 mesh (75 μm mesh) to obtain a powder for three-dimensional shaping of Comparative Example 1.
In addition, freeze grinding is carried out by Osaka Gas Liquid Co., Ltd. (Kashiwa City, Osaka), and freeze grinding conditions are set to grinding outlet temperature: -100 ° C to -120 ° C, grinding device circumferential speed: 80.0 m / s did.

(Comparative example 2)
Trade name: Duraform PA (manufactured by 3D SYSTEMS) was used as a commercially available powder for three-dimensional shaping. The trade name: Duraform PA is shown to be made of nylon 12 (PA12) as the main material.

(Comparative example 3)
As a commercially available powder for three-dimensional modeling, trade name: Asphea-PP (manufactured by Aspect) was used. The trade name: Asphea-PP is shown to be made of polypropylene (PP) as the main material.

(Comparative example 4)
As a commercially available powder for three-dimensional shaping, trade name: Aspex PPS (manufactured by Aspect) was used. The trade name: Aspex PPS is shown to be mainly composed of polyphenylene sulfide (PPS).

  Using the obtained powder for three-dimensional modeling, a three-dimensional object having a length of 80 mm ± 2 mm, a width of 10 mm ± 0.2 mm, and a thickness of 4 mm ± 0.2 mm was produced. Next, "filling rate" and "bending strength" were evaluated as follows. The results are shown in Tables 1 to 3 below.

(Filling rate)
Calculate the density from the correlation of the mass of the obtained three-dimensional object in air and water using the Archimedes method (Metler Toledo, MS 403 S / 02, density measurement kit 0.1 mg, for 1 mg balance) Furthermore, the filling factor of the obtained three-dimensional object was determined using the following formula (13). In addition, 90% or more of the said filling rate is a practicable level.
Packing ratio (%) = (density of material−measured density) / density of material × 100 (13)

(Bending strength)
The bending strength of the produced three-dimensional object was measured using a tensile tester (apparatus name: autograph, manufactured by Shimadzu Corporation), and the "bending strength" of the three-dimensional object was determined. Regarding the measurement of bending strength, the method of determining JIS K 7121 plastic-bending characteristics was followed. The test conditions were: distance between supporting points: 64 mm, testing speed: 2 mm / minute. The bending strength is at a level at which 80% or more of the bending strength of the material can be carried out. Specifically, polybutylene terephthalate (PBT) has a practicable level of 35 MPa or more, nylon 12 (PA12) of 30 MPa or more, polypropylene (PP) of 20 MPa or more, and polyphenylene sulfide (PPS) of 50 MPa or more. .
The bending strength can be measured under the test conditions of distance between supporting points: 64 mm, test speed: 2 mm / minute according to the method of determining JIS-K 7121 plastic-bending characteristics.
Moreover, the modeling direction in the modeling tank of the three-dimensional molded item obtained shall be distinguished. For example, test pieces generally formed by the SLS method tend to have higher strength in test pieces arranged in the XY direction (horizontal direction) than test pieces formed in the Z direction (lamination direction). In the present invention, the three-dimensional object was measured such that the longitudinal direction of the three-dimensional object was in the Z direction (lamination direction).

As an aspect of this invention, it is as follows, for example.
<1> particles (A) constituting the volume mode particle diameter,
Particles (B) having a volume average particle size smaller than the volume average particle size of the particles (A),
At least one of the particles (A) and the particles (B) has a columnar shape,
The ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 or less ,
The total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less.
<2> For three-dimensional modeling according to <1>, wherein the volume average particle diameter of the particles (B) is 0.3 times or more and 0.5 times or less the volume average particle diameter of the particles (A) It is a powder.
<3> The volume ratio (particle (B) / particle (A)) of the volume (%) of the particles (A) to the volume (%) of the particles (B) is 0.050 or more and 0.090 or less It is a powder for three-dimensional shaping | molding in any one of said <1> to <2> which is these.
<4> The ratio of the volume average particle diameter Mv of the particles (B) to the number average particle diameter Mn of the particles (B) (volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 It is a powder for three-dimensional shaping | molding in any one of said <1> to <3> which is the following.
<5> The powder for three-dimensional modeling according to any one of <1> to <4>, wherein the particles (A) have a columnar shape.
<6> The powder for three-dimensional shaping described in any one of <1> to <5>, wherein at least one of the particles (A) and the particles (B) is a substantially cylindrical body.
<7> The ratio of the height to the diameter or the long side of the bottom surface of at least one of the columnar particles (A) and the particles (B) is 0.7 times or more and 2 times or less It is a powder for three-dimensional shaping | molding in any one of <><6>.
<8> The three-dimensional structure according to any one of <1> to <7>, wherein a content of at least one of the columnar particles (A) and the particles (B) is 30% by mass or more. It is a powder for.
The volume average particle diameter of the <9> above-mentioned particle | grains (A) is a powder for three-dimensional shaping | molding in any one of said <1> to <8> which is 20 micrometers or more and 100 micrometers or less.
It is a powder for three-dimensional shaping | molding in any one of said <1> to <9> whose melting | fusing point when it measures based on <10> ISO 3146 is 100 degreeC or more.
<11> The powder for stereolithography according to any one of <1> to <10>, which satisfies at least one selected from the following (1) to (3).
(1) In differential scanning calorimetry, let Tmf1 (° C.) be the melting start temperature of the endothermic peak when the temperature is raised to a temperature 30 ° C. higher than the melting point at 10 ° C./min. When the melting start temperature of the endothermic peak when the temperature is lowered to -30 ° C or less at 10 ° C / min and the temperature is raised to 30 ° C higher than the melting point at 10 ° C / min is Tmf2 (° C) And (Tmf1-Tmf2)) 3 ° C. The melting start temperature of the endothermic peak draws a straight line parallel to the x-axis from the place where the heat quantity becomes constant to the low temperature side after the endothermic at the melting point is completed, and drops by -15 mW from the straight line Temperature.
(2) In differential scanning calorimetry, the degree of crystallinity determined from the energy amount of the endothermic peak when heated to a temperature 30 ° C. higher than the melting point at 10 ° C./min according to ISO 3146 is Cd1 (% The crystal is obtained from the energy amount of the endothermic peak when the temperature is lowered to −30 ° C. or less at 10 ° C./min and the temperature is further raised to 30 ° C. higher than the melting point at 10 ° C./min. When the degree of conversion is Cd2 (%), (Cd1-Cd2) 3 3%.
(3) The degree of crystallinity obtained by X-ray diffraction measurement is Cx1 (%), and the temperature is raised to a temperature 30 ° C. higher than the melting point at 10 ° C./min in a nitrogen atmosphere, and then at 10 ° C./min When the degree of crystallinity obtained by X-ray diffraction measurement when the temperature is lowered to −30 ° C. or lower and the temperature is raised to 30 ° C. higher than the melting point at 10 ° C./min is Cx 2 (% Cx1-Cx2) ≧ 3%.
It is a powder for three-dimensional shaping | molding in any one of said <1> to <11> containing a <12> crystalline thermoplastic resin.
<13> The above-mentioned <12>, wherein the crystalline thermoplastic resin is at least one selected from polyolefin, polyamide, polyester, polyaryl ketone, polyphenylene sulfide, liquid crystal polymer, polyacetal, polyimide and fluorine resin It is a powder for three-dimensional modeling.
<14> The powder for stereolithography according to <13>, wherein the polyester is at least one selected from polyethylene terephthalate, polybutadiene terephthalate, and polylactic acid.
It is a powder for three-dimensional shaping | molding in any one of said <1> to <14> which further contains a <15> external additive.
<16> The powder for three-dimensional modeling according to any one of <1> to <15>, wherein the particles (B) have the same composition as the particles (A).
<17> The powder for three-dimensional modeling according to any one of <1> to <15>, wherein the particles (B) have a different composition from the particles (A).
<18> The powder for three-dimensional modeling according to any one of <1> to <17>, wherein the particles (B) have a shape different from the shape of the particles (A).
<19> A layer forming step of forming a layer containing the powder for three-dimensional shaping described in any one of <1> to <18>,
A curing step of curing the formed layer by electromagnetic irradiation;
And producing a three-dimensional object.
<20> particles (A) constituting the volume mode particle diameter,
Particles (B) having a volume average particle size smaller than the volume average particle size of the particles (A),
At least one of the particles (A) and the particles (B) has a columnar shape,
The ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 or less ,
The total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less.

  The powder for three-dimensional shaping described in any one of <1> to <18>, the method for producing a three-dimensional object described in the above <19>, and the resin powder described in the above <20> To achieve the object of the present invention.

Japanese Patent Application Publication No. 2014-522331 Japanese Patent Application Publication No. 2013-529599 JP-A-2015-515434

10 particles (A)
20 particles (B)

Claims (13)

Particles (A) constituting the volume mode particle diameter,
Particles (B) having a volume average particle size smaller than the volume average particle size of the particles (A),
At least one of the particles (A) and the particles (B) has a columnar shape,
The ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 or less ,
A total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less.   The powder for three-dimensional shaping | molding of Claim 1 which is 0.3 times or more and 0.5 times or less the volume average particle diameter of the said particle | grain (B) with respect to the volume average particle diameter of the said particle (A).   The volume ratio (particle (B) / particle (A)) of the volume (%) of the particles (A) to the volume (%) of the particles (B) is 0.050 or more and 0.090 or less. The powder for three-dimensional shaping | molding in any one of claim | item 1 -2.   The ratio (volume average particle diameter / number average particle diameter) (Mv / Mn) of the volume average particle diameter Mv of the particles (B) to the number average particle diameter Mn of the particles (B) is 2.0 or less The powder for three-dimensional shaping | molding in any one of Claims 1-3.   The powder for three-dimensional shaping according to any one of claims 1 to 4, wherein the particles (A) have a columnar shape.   The ratio of the height to the diameter or the long side of the bottom surface of at least one of the columnar particles (A) and the particles (B) is 0.7 or more and 2 or less. The powder for three-dimensional shaping | molding as described in any.   The powder for three-dimensional shaping | molding in any one of Claim 1 to 6 whose volume average particle diameter of the said particle | grain (A) is 20 micrometers or more and 100 micrometers or less.   The powder for three-dimensional shaping | molding in any one of the Claims 1-7 containing a crystalline thermoplastic resin.   The powder for three-dimensional modeling according to any one of claims 1 to 8, wherein the particles (B) have the same composition as the particles (A).   The powder for three-dimensional modeling according to any one of claims 1 to 9, wherein the particles (B) have a composition different from that of the particles (A).   The powder for three-dimensional modeling according to any one of claims 1 to 10, wherein the particles (B) have a shape different from the shape of the particles (A). A layer forming step of forming a layer containing the powder for three-dimensional shaping according to any one of claims 1 to 11;
A curing step of curing the formed layer by electromagnetic irradiation;
And manufacturing a three-dimensional object. Particles (A) constituting the volume mode particle diameter,
Particles (B) having a volume average particle size smaller than the volume average particle size of the particles (A),
At least one of the particles (A) and the particles (B) has a columnar shape,
The ratio of the volume average particle diameter Mv of the particles (A) to the number average particle diameter Mn of the particles (A) (volume average particle diameter / number average particle diameter) (Mv / Mn) is 2.0 or less ,
A resin powder, wherein the total of the specific surface area of the particles (A) and the specific surface area of the particles (B) is 110 m ² / kg or less.