JP2017132110A - Molding material, molding and method for producing three-dimensional object - Google Patents

Abstract

To provide a modeling material capable of shortening the manufacturing time of a three-dimensional object manufactured by AM technology.
A molding material comprising a thermoplastic resin and a disintegrant that expands by contact with water.
[Selection figure] None

Description

  The present invention relates to a modeling material, a modeled object, and a method for manufacturing a three-dimensional object.

The three-dimensional modeling technology called additive manufacturing (AM) technology is different from the modeling technology that has been widely used in the past, and can create a three-dimensional object modeled by a computer without the need for a mold. There is a feature.
In the AM technology, when manufacturing a three-dimensional object in which a cavity or a bowl-shaped part exists, a material that assists the shaping of the part, that is, a support material is required, but this support material needs to be finally removed. There is. Here, a material constituting a three-dimensional object for modeling is referred to as a structural material, and when it is not necessary to distinguish between a support material and a modeling material, these are collectively referred to as a modeling material. Moreover, what was comprised with the modeling apparatus and comprised from the structural material and the support material is called a modeled object, but when producing the solid object which does not require a support material, a structure and a modeled object correspond.
As a method for removing a support material from a modeled object, a mechanical removal method (Patent Document 1) and a dissolution removal method (Patent Document 2) in which a support material is dissolved and removed in a solvent are known.

Special table 2010-521339 JP 2012-111226 A

However, the mechanical removal method has a problem that it takes time and labor to remove the support material because it is necessary to remove the support material manually. In addition, the dissolution and removal method has a problem that it takes time to remove because the portion made of the support material is gradually dissolved from the contact portion with the solvent.
Thus, in any method, it took a considerable time to remove the support material included in the modeled object. The present invention is made in order to solve the above-described problems, and an object of the present invention is to use a modeling material capable of shortening the manufacturing time of a three-dimensional object, which is a modeling object, in the AM technology and the same. It is in providing the manufacturing method of a solid thing.

  The modeling material of the present invention is characterized by having a thermoplastic resin and a disintegrant that expands in volume by contact with water.

  ADVANTAGE OF THE INVENTION According to this invention, providing the modeling material which makes it possible to shorten the manufacturing time required in order to manufacture the solid object which is a modeling objective with AM technology, and the manufacturing method of a solid object using the same. it can.

It is a schematic diagram which shows the example of a structure of the three-dimensional modeling apparatus used by 1st embodiment. It is a schematic diagram which shows the example of a structure of the three-dimensional modeling apparatus used by 2nd embodiment. It is a figure explaining the specific example of the method of immersing a molded article in water. 3 is a schematic diagram showing a three-dimensional object produced in Example 1. FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below. Further, in the present invention, within the scope not departing from the gist of the invention, based on the ordinary knowledge of a person skilled in the art, the present invention includes those appropriately modified or improved to the embodiments described below. It is.

[Modeling material]
The modeling material of the present invention includes a thermoplastic resin and a disintegrant that expands by volume when contacted with water. In this invention, a modeling material is a modeling material used when manufacturing a molded article with a three-dimensional modeling technique. The modeling material is classified into a target modeling object, a structural material that forms a three-dimensional object obtained by processing the modeling object, and a support material that supports the lamination of the structural material. The support portion made of the support material is a portion that supports the structural material laminated on the region where no structural material exists, and is a portion that is finally removed. The modeling material of the present invention may be used as a structural material or a support material.
The modeling material of the present invention is a solid substance, and examples of the shape thereof include, but are not limited to, a particle shape, a pellet shape, a rod shape, and a filament shape. In addition, when the modeling material of this invention is a particulate material, it can utilize with the three-dimensional modeling technique by a sheet | seat lamination method.

  When the modeling material of the present invention is a particulate material, the particle size is preferably 1 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less. When the particle size is smaller than 1 μm, it is necessary to form a particle layer in which a plurality of particles are stacked in order to increase the layer thickness for one time in order to increase the stacking speed, and it becomes difficult to control the particle layer. Sometimes. On the other hand, when the particle size is larger than 100 μm, the lamination accuracy tends to deteriorate. In addition, the range of the preferable particle diameter mentioned above is applicable even when using the particle | grains used as the modeling material of this invention as structural material particle | grains, or when using as support material particle | grains.

When the modeling material of the present invention is used in AM technology based on a sheet lamination method in which the modeling material is fused by heat, the modeling material is used regardless of whether the modeling material of the present invention is used as a structural material or a support material. It is necessary to include a thermoplastic resin as one of the constituent materials. The term “thermoplastic” as used herein refers to a property that is difficult to deform at room temperature, but exhibits plasticity when heated at a temperature corresponding to the material and can be freely deformed.
In the present invention, the thermoplastic resin that is one of the constituent materials of the modeling material includes not only a water-insoluble thermoplastic resin generally used as an organic polymer material but also a water-soluble thermoplastic resin. Further, the molecular weight of the thermoplastic resin used as the constituent material of the modeling material of the present invention is not particularly limited, and may be 10,000 or more, or may be a molecular weight of less than 10,000 defined as an oligomer. May be.
Water-insoluble thermoplastic resins include ABS (acrylonitrile butadiene styrene), PP (polypropylene), PE (polyethylene), PS (polystyrene), PMMA (acrylic), PET (polyethylene terephthalate), PPE (polyphenylene ether), PA (Nylon / polyamide), PC (polycarbonate), POM (polyacetal), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), PEEK (polyetheretherketone), LCP (liquid crystal polymer), fluororesin, urethane resin, elastomer Etc. However, the present invention is not limited to these.
Specific examples of water-soluble thermoplastic resins (hereinafter sometimes referred to as water-soluble resins) include carbohydrates that exist widely in nature (for example, monosaccharides such as glucose, xylose, and fructose, sucrose, lactose, and maltose). Disaccharides such as trehalose and isomaltulose (palatinose (registered trademark)), tetrasaccharides such as melezitose, maltotriose, stachyose, nigerotriose, raffinose and kestose, isomaltoligosaccharides, fructooligosaccharides, xylooligosaccharides, soybean oligos Sugar, galactooligosaccharide, nigerooligosaccharide, oligosaccharide such as dairy oligosaccharide, dietary fiber such as polydextrose, inulin, sugar alcohol such as xylitol, sorbitol, mannitol, maltitol, lactitol, oligosaccharide alcohol, erythritol, etc.), polyvinyl Polyols such as alcohol, polyethylene glycol, and a polyether such as polypropylene glycol.
In the present invention, a mixed material obtained by mixing the above-described water-insoluble thermoplastic resin and a water-soluble thermoplastic resin can be used as a constituent material of the modeling material.

In the present invention, the disintegrant, which is one of the materials constituting the modeling material, expands (swells) when contacted with water, and causes a crack in a portion made of a water-soluble thermoplastic resin. When water permeates through the crack, dissolution of the portion made of the water-soluble thermoplastic resin is promoted, and the entire portion made of the modeling material collapses. Therefore, when the modeling material of the present invention is used as a support material, the disintegrant plays a role of causing the shape of the support portion made of the support material to collapse and promoting separation from the structure.
Swelling here refers to swelling of a solid. Specifically, when the solid is immersed in a liquid, the solid absorbs a large amount of liquid and significantly increases its volume. The degree to which the solid swells (swelling degree) is an indicator of the ease with which the shape of the solid collapses (disintegration). At this time, the higher the degree of swelling, the higher the disintegrating property of the solid, but specifically, the solid having its own degree of swelling of 10% or more when water is absorbed is preferable. If the degree of swelling is less than 10%, the effect of promoting the removal of the support material may not appear clearly when the modeling material of the present invention is used as the support material.
Specific examples of the disintegrant material include cellulose derivative salts such as sodium starch glycolate, calcium carboxymethyl cellulose, sodium carboxymethyl cellulose, sodium carboxymethyl starch, natural product derivatives such as alginic acid derivatives, crospovidone ( Cross-linked polyvinyl pyrrolidone) and synthetic polymer derivatives such as vinyl acetate-vinyl pyrrolidone copolymer. Among these materials, cellulose derivatives are preferable. Cellulose derivatives as used herein include cell sources that are not modified but also modified by the introduction of predetermined substituents. The modified cellulose includes a salt of the aforementioned cellulose derivative.
In addition, the term “cellulose” as used herein refers to a state in which a plurality of fibrous cellulose molecules are intertwined in a complicated manner. A plurality of fibrous cellulose molecules are intertwined in a complicated manner, so that hydrophilic liquid molecules can be held in an assembly in which hydrophilic cellulose molecules are intertwined with each other, and a property that the volume swells can be expressed. . On the other hand, cellulose (so-called cellulose nanofibers) dispersed at a monomolecular level by a special method disclosed in “Isogai, Akira .; Saito, Tsuguyuki .; Fukuzumi Hayata. Nanoscale 2011, 3, p71-85.” Not suitable as a disintegrant. In the case of cellulose nanofiber, it shows interaction with hydrophilic liquid, but since it is dispersed to the molecular level in advance, it may form a gel with hydrophilic liquid, but before volume expansion It is because it does not reach.

  When using the modeling material of this invention as a support material, Preferably content of the disintegrating agent contained in a modeling material (support material) is 10 to 90 weight% with respect to the whole modeling material (support material). It is. If the content of the disintegrant is less than 10% by weight with respect to the entire modeling material (support material), the effect of promoting the removal of the support material by including the disintegrant may not clearly appear. On the other hand, when the content of the disintegrant exceeds 90% by weight with respect to the entire modeling material (support material), the moldability of the support material may be hindered. In the present invention, the content of the disintegrant contained in the modeling material (support material) is more preferably 15 wt% or more and 45 wt% or less with respect to the entire modeling material (support material).

[Modeled object]
The shaped article of the present invention has a structure composed of at least a structural material. Examples of the structural material included in the shaped article of the present invention include, but are not limited to, the shaped material of the present invention. However, when the modeled object of the present invention is composed of only the structural material, the structural material includes the modeled material of the present invention. Moreover, when the molded object of this invention is comprised only with a structural material, the molded object of this invention can be handled as a solid object which is a finished product of a three-dimensional modeling technique.
As a material other than the structural material included in the shaped article of the present invention, for example, there is a support material. When a structure material and a support material are included in the modeled object of the present invention, the model material of the present invention is mainly used as a support material. In such a case, a thermoplastic resin, a metal material, or the like can be used as the structural material. The structural material preferably has a thermoplastic resin. The term “having” as used herein is not limited to an embodiment in which the structural material itself is the thermoplastic resin, and a part of the structural material is the thermoplastic resin and is a material other than the thermoplastic resin (metal material). Etc.) are also included in the structural material. In addition, when a structure and a support body are contained in the molded article of this invention, the solid thing comprised with a structural material is obtained by removing a support body from a molded article. A specific method for removing the support material in such a case will be described later.

[Method of manufacturing a three-dimensional object]
Next, the example of the manufacturing method of the three-dimensional object of this invention by the additive manufacturing method is demonstrated.

(1) 1st embodiment 1st embodiment in the manufacturing method of the solid thing of this invention is a manufacturing method which has the process of following [1a] and [2a].
[1a] Material layer forming step in which at least structural material particles are arranged to form a material layer [2a] Modeled object forming step in which a material layer is stacked to form a modeled object This is a process for manufacturing a shaped object using only a structural member. Here, when a modeled object is manufactured only from the structural material particles (particulate structural material) according to the process of the present embodiment, the manufactured modeled object becomes the target three-dimensional object as it is.

Moreover, this embodiment is a manufacturing process using a sheet lamination method. Specifically, a shaped article can be obtained by repeating the steps [1a] and [2a] and laminating a necessary number of material layers.
Hereinafter, each step will be described in detail.

[0a] Structural Material Particles The structural material particles used in the present embodiment have a thermoplastic resin and a disintegrant that expands and disintegrates when contacted with water. In the present invention, the method for obtaining the structural material particles used in the present embodiment is not particularly limited, and examples thereof include the method described below.
Specifically, there is a method (kneading and pulverizing method) in which particles are obtained by melt-kneading a thermoplastic resin and a disintegrant to obtain a solid, and pulverizing the obtained solid. According to this method, it is possible to produce a particulate material that can be used as a structural material at low cost. Other methods include a mechanical pulverization method, a melt dispersion cooling method in which a particulate material is obtained by being dispersed in a medium in a molten state and cooled. In the present invention, since the disintegrant is contained in the structural material particles, a dry granulation method that does not use water, for example, the above-described kneading and pulverization method is preferably used.

[1a] Material layer forming step This step is a step of arranging at least structural material particles according to the cross-sectional data of the target three-dimensional object.
When forming the material layer, modeling material particles such as structural material particles may be drawn with dots to form the material layer, or the material layer may be drawn with lines or surfaces. A method of drawing with a line or a surface is preferable from the viewpoint of modeling speed. Examples of a method for forming a material layer by drawing with lines or surfaces include an electrophotographic method and a method using an ink jet method disclosed in Japanese Patent Application Laid-Open No. 2014-133414. In forming a material layer to be drawn with a line or a surface, a known method such as a method for forming a material layer using an electrostatic action by charging can also be used.

Hereinafter, a process for forming a material layer by an electrophotographic method, which is an example of this process, will be described with reference to the drawings. FIG. 1 is a schematic diagram illustrating an example of a configuration of a three-dimensional modeling apparatus used in the present embodiment (first embodiment). As described above, FIG. 1 is a diagram schematically illustrating a configuration of a three-dimensional modeling apparatus using an electrophotographic method.
1 according to this embodiment (hereinafter referred to as “apparatus 10a”) includes a developing device 11, an image carrier 12, an exposure device 13, an intermediate carrier belt 14, and a stage 15. And temperature control means 16. When manufacturing a three-dimensional object that can be a three-dimensional object by the manufacturing process of the present embodiment, in this step (material layer forming step), first, a particle image of structural material particles is formed on the image carrier 12. Then, the formed particle image is transferred onto the intermediate carrier belt 14 to form a material layer composed of structural material particles.

Hereinafter, the formation process of the material layer in this embodiment is demonstrated in detail. First, the surface of the image carrier 12 is uniformly charged by a charging device (not shown). The charging method is not particularly limited.
Next, using the exposure device 13, the charged image carrier 12 is exposed according to slice data (cross-sectional data) of the three-dimensional object to be produced, and an electrostatic latent image is formed on the surface of the image carrier 12. Specifically, an electrostatic latent image of the structure portion region in the slice data of the modeled object (three-dimensional object) to be produced is formed on the image carrier 12.
Subsequently, the structural material particles 1 are supplied from the developing device 11 to the image carrier 12. As a result, the electrostatic latent image is arranged on either the area where the electrostatic latent image is formed on the surface of the image carrier 12 or the area where the electrostatic latent image is not formed. As a result, the electrostatic latent image can be visualized, and a particle image of the structural material particles 1 can be formed on the surface of the image carrier 12. That is, this step (material layer forming step) includes a step of developing at least the electrostatic latent image formed on the image carrier with the structural material particles 1 to form a particle image.
Thereafter, at least a particle image composed of the structural material particles 1 arranged on the image carrier 12 is transferred onto the intermediate carrier belt 14 at a predetermined timing. Thereby, the material layer which consists of a particle image by the structural material particle | grains 1 can be formed. That is, the material layer is formed by transferring the second layer in which the other particles are arranged to the transfer body in which the first layer in which the structural material particles 1 are arranged is transferred. When transferring to the transfer body, a known transfer method such as electrostatic transfer using electrostatic energy can be used.

[2a] Molded object formation process (lamination process)
This step is a step of repeatedly forming the material layer formed in the previous step to form a shaped article. The material layer can be laminated by forming a separate material layer on the surface of the previously formed material layer, or by forming a new material layer directly on the surface of the previously formed material layer. May be laminated. In addition, when laminating the material layer formed separately on the surface of the previously formed material layer, the material layer is once formed on the substrate and then transferred to the surface of the previously formed material layer. Good. The base material used at this time is called a transfer body. When transferring the material layer to the transfer body, a known transfer method such as electrostatic transfer using electrostatic energy can be used.

Hereinafter, an example of this process will be described with reference to FIG. The method of the previous step (material layer forming step) is not particularly limited, but here it will be described as being performed by the above-described electrophotographic method.
The material layer formed on the intermediate carrier belt 14 is moved to the stacking position by the rotation of the intermediate carrier belt 14. When the material layer is moved to the stacking position, it is heated by the temperature control means 16 and the particles constituting the material layer are fused together. And it is transcribe | transferred and laminated | stacked on the modeling object in the middle of manufacture on the upper surface of the stage 15, or the stage 15. FIG. At this time, regions (structure portions 17) constituting the three-dimensional object are formed by laminating the regions made of the structural material particles constituting the material layer. That is, the lamination process in the manufacturing method of the three-dimensional object (three-dimensional object) according to the present embodiment includes a heat fusion process in which thermal energy is applied to the material layer to fuse the structural material particles in the material layer.
The timing for heating the material layer and fusing the particles constituting the material layer to each other is not particularly limited, and may be performed before, simultaneously with, or after the lamination. It may be performed at the timing.
In the present embodiment, in the heat fusion process, the structural material particles in the material layer are heated by the temperature control means 16, and the heated structural material particles are temperature-controlled at substantially the same temperature. At this time, the temperature control means 16 is preferably heated at a temperature at which the structural material particles soften.

[3a] Modeled object (three-dimensional object)
A model is obtained through the above steps. Here, when only a structural material particle is used to obtain a modeled object in the above process, the modeled object is used as it is as a target three-dimensional object without being processed in a subsequent process, although it depends on the obtained modeled object. Can do. Moreover, when processing the said modeling thing at a next process, surface processings, such as grinding | polishing, etc. are mentioned as a specific processing method of the said modeling thing, for example.

(2) Second Embodiment The second embodiment of the method for producing a three-dimensional object of the present invention is a production method having the following steps [1b] to [3b].
[1b] Material layer forming step of forming a material layer by arranging water-insoluble structural material particles and support material particles [2b] Modeled object forming step of forming a modeled object by stacking the material layers [3b The removal process which removes the part comprised by the said support material particle | grains of a modeling object by making it contact with water When producing the target solid object using the modeling material of this invention as a support material, process [3b] (removal Although the point that the process is essential is different from the first embodiment, the process shown in the first embodiment can be used for other points. Hereinafter, each process will be described in detail with a focus on differences from the first embodiment.

[0b] Support Material Particles The support material particles used in the present embodiment expand as a result of contact with a thermoplastic resin and water, like the particulate matter used as the structural material particles in the first embodiment. And a disintegrant that disintegrates. For this reason, support material particle | grains can be manufactured by the method similar to the manufacturing method of the structural material which is a particulate matter shown by 1st embodiment. In addition, the manufacturing method of the structural material particle | grains used in this embodiment can employ | adopt the method conventionally used when making the material used as a structural material into a particulate form.

[1b] Material layer forming step This step is a step of arranging the structural material particles and the support material particles according to the cross-sectional data of the target three-dimensional object.
As described in the first embodiment, when forming a material layer, a known method such as a method for forming a material layer using an electrostatic action by charging can be used. When forming a material layer including a plurality of types of modeling material particles (structural material particles, support material particles) as in this embodiment, electrostatic force is used from the viewpoint of high arrangement accuracy of different types of modeling material particles. An electrophotographic system using is preferable.
FIG. 2 is a schematic diagram illustrating an example of a configuration of a three-dimensional modeling apparatus used in the present embodiment (second embodiment). Hereinafter, this process will be described with reference to FIG. In addition, in the three-dimensional modeling apparatus 10b of FIG. 2, the same code | symbol may be attached | subjected about the member which is common with the three-dimensional modeling apparatus 10a of FIG.
The three-dimensional modeling apparatus 10b in FIG. 2 (hereinafter referred to as “apparatus 10b”) forms a particle image by the support material particles 1b in addition to the image carrier 12a for forming a particle image by the structural material particles 1a. Image carrier 12b. Except for this, the 3D modeling apparatus 10a of FIG. In the present embodiment, in this step, first, a particle image of the structural material particles is formed on the image carrier 12a, and a particle image of the support material particles is formed on the image carrier 12b. These particle images are transferred onto the intermediate carrier belt 14 to form a material layer composed of structural material particles and support material particles.

Hereinafter, the material layer forming step will be described in detail, but in the description common to the formation of each particle image, the subscripts “a” and “b” of the constituent members are omitted, and the developing device 11, the image carrier 12, etc. It describes.
First, the surface of the image carrier 12 is uniformly charged by a charging device (not shown). The charging method is not particularly limited.
Next, using the exposure device 13, the charged image carrier 12 is exposed according to slice data (cross-sectional data) of the three-dimensional object to be produced, and an electrostatic latent image is formed on the surface of the image carrier 12. Specifically, the electrostatic latent image of the structure part region in the slice data of the three-dimensional object to be produced is formed on the image carrier 12a, and the electrostatic latent image of the support part region is formed on the image carrier 12b.
Subsequently, the modeling material particles are supplied from the developing device 11 to the image carrier 12. As a result, the electrostatic latent image on the surface of the image carrier 12 is disposed in either the region where the electrostatic latent image is formed or the region where the electrostatic latent image is not formed. As a result, the electrostatic latent image is visualized, and a particle image by the structural material particles 1a is formed on the surface of the image carrier 12a, and a particle image by the support material particles 1b is formed on the surface of the image carrier 12b. be able to. In other words, in the present embodiment, this step includes a step of developing the electrostatic latent image formed on the image carrier with the structural material particles 1a and the support material particles 1b to form a particle image.
Thereafter, the respective particle images respectively arranged on the image carriers (12a, 12b) are transferred onto the intermediate carrier belt 14 at a predetermined timing. Thereby, the material layer which consists of the particle image by the structural material particle | grains 1a and the particle image by the support material particle | grains 1b can be formed. That is, the second layer in which the other particle is arranged is transferred to the transfer body on which the first layer in which either the structural material particle 1a or the support material particle 1b is arranged is transferred, and the material Form a layer. When transferring to the transfer body, a known transfer method such as electrostatic transfer using electrostatic energy can be used. The order of transferring the particle image to the intermediate carrier belt 14 is not particularly limited, and the particle image made of the support material particles 1b may be transferred after the particle image made of the structural material particles 1a is transferred, You may transfer in the reverse order.

[2] Molded object formation process (lamination process)
This step is a step of repeatedly forming the material layer formed in the previous step to form a shaped article. Hereinafter, an example of this process will be described with reference to FIG. In the present invention, the method of the pre-process is not particularly limited, but here it will be described as being performed by the above-described electrophotographic method.
The material layer formed on the intermediate carrier belt 14 is moved to the stacking position by the rotation of the intermediate carrier belt 14. When the material layer is moved to the stacking position, it is heated by the temperature control means 16 and the particles constituting the material layer are fused together. And it is transcribe | transferred and laminated | stacked on the modeling object in the middle of manufacture on the upper surface of the stage 15, or the stage 15. FIG. At this time, a region (structure portion 17a) constituting a three-dimensional object is formed by laminating regions made of structural material particles in the material layer, and a support portion 17b is formed by laminating regions made of support material particles. That is, in the method of manufacturing a three-dimensional object according to the present embodiment, this step is a heating process in which thermal energy is applied to the material layer to fuse the modeling material particles (structural material particles 1a and support material particles 1b) in the material layer. Includes a fusing process.
In this embodiment, in the heat fusion process, both the structural material particles and the support material particles in the material layer are heated by the temperature control means 16, and these particles are temperature-controlled to substantially the same temperature. At this time, it is preferable that the temperature control means 16 performs heating at a temperature at which both the structural material particles and the support material particles soften. Therefore, when the softening temperatures of the structural material particles and the support material particles are different, it is preferable that the temperature control means 16 performs heating at a temperature equal to or higher than the higher temperature.

[3b] Removal Step This step is a step of removing a portion (support portion) made of the support material particles from the molded article. The support part is removed by bringing the model into contact with water. In this embodiment, the disintegrant mentioned above is contained in the support material particle 1b which comprises a support part. Here, when the support portion comes into contact with water, the disintegrant contained in the support portion absorbs water and swells and expands. When the disintegrant swells and expands in this manner, the form of the disintegrant is deformed. As a result, more water enters the disintegrant, and as a result, the disintegrant disintegrates. Due to the swelling (expansion) and disintegration of the disintegrant described above, the support portion having the disintegrant is deformed and finally detached from the modeled object.

  In this embodiment, the support particles constituting the support portion contain a thermoplastic resin. Here, it is preferable that the thermoplastic resin is a water-soluble resin, because the water-soluble resin is dissolved by the contact of the water-soluble resin and water, and the removal of the support portion becomes easier. However, when the support material is composed only of the water-soluble resin, it may take time to remove the support portion from the modeled object, particularly when a three-dimensional object having a complicated structure is manufactured. Specifically, when the support portion exists deep in the modeled object, it may take a long time to remove the support portion by allowing water to penetrate deep into the support portion. Further, the water-soluble resin contained in the support part may take in water and produce a gel-like substance at the time of contact between water and the support part. This gel-like substance hinders the removal of the support part by water, and can be one of the causes of increasing the time required to remove the support part. On the other hand, when the disintegrant described above is included in the support material as in the present invention, the water-soluble resin constituting the support portion is dissolved inside the support portion by swelling and disintegration of the disintegrant due to contact with water. It is possible to form a space for taking in water necessary for the generation. As a result, the water required to dissolve the water-soluble resin can flow quickly and in large quantities into the back of the support material, resulting in a reduction in the time required for this step (removal step) compared to the conventional method. Can be made.

In this step, the specific method is not particularly limited as long as the support portion can be removed by bringing the support portion into contact with water. As such a method, for example, a method of immersing a shaped article in water can be mentioned. In addition, the solvent used for the removal of a support part is not limited to water, The material which has little influence on a structural material other than water may be included.
FIG. 3 is a diagram illustrating a specific example of a method of immersing a shaped article in water. FIG. 3 is also a schematic diagram showing a configuration of a removing device that removes the support portion 17b from the molded article 17. 3 includes a pedestal 21 on which the model 17 is placed, a magnetic stirrer main body 22, and a magnetic stirrer agitator 23.

  The magnetic stirrer main body 22 rotates the magnetic stirrer stirrer 23 to stir the water 25 filled in the container 24 of the removing device. Since the support part 17b of the molded article 17 has a disintegrant, the disintegrant is disintegrated by contacting the water 25. Then, the support portion 17b is detached from the modeling material 17 and removed by the collapse of the disintegrant. The stage portion 21a of the pedestal 21 is preferably formed in a net shape so that water flows uniformly against the molded article 17. Further, in the removal step, for the purpose of speeding up the removal of the support portion 17b from the molded article 17, temperature control (heating, etc.) of the water 25, ultrasonic vibration may be applied to the water 25, and the like. . In addition, the support part 17b can be removed even if the molded article 17 is simply immersed in the water 25 and left standing for a certain period of time.

  The temperature of the water 25 used in the removing device 3 in FIG. 3 is not particularly limited, but the dissolution rate increases in the heated state, and the support portion 17b can be removed faster. The temperature of the water 25 is preferably about 60 ° C. to 80 ° C., but the upper limit temperature is appropriately adjusted depending on the heat resistance temperature of the structural material. For example, when the structural material is ABS or PP, if the temperature is raised to 100 ° C., the three-dimensional object may be deformed by heat, so it is preferable to suppress the water temperature below the deflection temperature under load of the structural material.

  The output of the ultrasonic vibration is preferably adjusted according to the shape of the target three-dimensional object. If there is a lot of fine modeling, if the output is not lowered and applied, the modeling part may be damaged by ultrasonic waves, so it is preferable to suppress the output to the extent that the three-dimensional object is not damaged.

  Moreover, when removing the support part 17b still more rapidly, the water 25 may be sprayed from nozzles (not shown), such as a spray, and sprayed on the molded article 17. In that case, it is preferable to spray the water 25 at a water pressure or a flow rate that does not damage the structural portion 17a. In order to spray water 25 evenly on the modeled object 17, a plurality of nozzles may be used, or the nozzles may be movable with respect to the modeled object 17. As the nozzle, a general spray nozzle can be used. The diameter and the number of nozzles may be appropriately selected depending on the size of the target model 17 and the type of support material particles.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following description, “%” means weight% unless otherwise specified.

[Example 1]
The material used in the present embodiment and a specific method for forming a model will be described below. FIG. 4 is a schematic diagram showing a three-dimensional object produced in this example (Example 1). 4A is a diagram showing a planar pattern of a material layer formed when producing a three-dimensional object, and FIG. 4B is a perspective view showing a modeled object produced in this example. FIG. 4C is a perspective view showing the three-dimensional object produced in this example.

(1) Constituent material In the present Example, particulate ABS (average particle diameter 50 micrometers) was used as a structural material.

(2) Support material In the present Example, the support material which has the thermoplastic resin (water-soluble resin) shown below and a disintegrating agent was used.
Thermoplastic resin (water-soluble resin): Fujioligo # 450P (composition: starch sugar composed of glucose and various oligosaccharides, mainly composed of maltotetraose), disintegrant made by Nippon Food Chemical Co., Ltd .: carboxymethylcellulose calcium, Daicel Finechem In the present Example, the support material was prepared by kneading and pulverizing a mixture of the thermoplastic resin and the disintegrant in a ratio of thermoplastic resin: disintegrant = 20: 80. . The average particle size of the particulate support material used in this example is 50 μm.

(3) Material Layer Formation Step A material layer was formed using a particulate constituent material and a particulate support material. Specifically, first, the particles of the support material are arranged in the plane region indicated by the symbol B in FIG. 4A, and the particles of the structural material are arranged in the plane region indicated by the symbol A in FIG. Thus, a material layer was formed. In FIG. 4A, d ₁ was 2 cm and d ₂ was 1 cm. Next, the material layer was transferred to a polyimide base material to form a sheet-like material layer on the base material.

(4) Manufacturing process of modeling object The process of said (3) is performed 100 times, and the support part 17b and structure part 17a which are shown by FIG.4 (b) are shown by laminating | stacking 100 material layers on the said base material. A shaped object consisting of In FIG. 4B, d ₃ (lamination thickness) was 2 mm. Moreover, in order to perform the evaluation test mentioned later, five shaped objects were produced.

(5) Evaluation of the removal performance of the support part by water About the modeling thing obtained at the process of said (4), the removal performance of the support part contained in a modeling thing was evaluated.
Specifically, first, after putting a model (five pieces) into a 200 mL beaker containing 150 mL of water, applying ultrasonic waves with an ultrasonic cleaner (output: 110 W, combined frequency of 24 kHz and 31 kHz) It was immersed for 5 minutes. This evaluated whether the support material contained in the molded article was removed from the structural material. Here, specific evaluation criteria are shown below.
○: As shown in FIG. 4C, the support part was completely peeled from the structural material.
X: A part of support part was adhering to the structure (peeling of the support material from the structural material was incomplete).
The evaluation results are shown in Table 1. At the time of evaluation, an evaluation experiment is performed for each of the five manufactured objects, and when more than half of the structures have been evaluated as “◯”, “○” is displayed in Table 1 and “×” is displayed. When more than half of the structures were evaluated as “x”, “x” was displayed in Table 1.

[Example 2]
In Example 1 (2), a molded article was produced in the same manner as in Example 1 except that PEG 20000 (manufactured by Sanyo Chemical Co., Ltd.) was used as the thermoplastic resin (water-soluble resin) instead of Fujioligo # 450P. did. Moreover, the removal performance of the support part 17b contained in the obtained molded article was evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 1]
In Example 1 (3), the same method as in Example 1 except that particulate Fujioligo # 450P (average particle size: 50 μm) was used instead of the support material prepared in Example 1 (2). A modeled object was prepared. Moreover, the removal performance of the support part 17b contained in the obtained molded article was evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
In Example 2, a shaped article was produced in the same manner as in Example 2 except that particulate PEG 20000 (average particle size: 50 μm) was used instead of the support material prepared in Example 2. Moreover, the removal performance of the support part 17b contained in the obtained molded article was evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
In Example 1 (2), a molded article was produced in the same manner as in Example 1 except that the mixing ratio of the thermoplastic resin and the disintegrant was thermoplastic resin: disintegrant = 5: 95. Moreover, the removal performance of the support part 17b contained in the obtained molded article was evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]
In Example 2, a molded article was produced in the same manner as in Example 2 except that the mixing ratio of the thermoplastic resin and the disintegrant was thermoplastic resin: disintegrant = 5: 95. Moreover, the removal performance of the support part 17b contained in the obtained molded article was evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

  From Table 1, it was confirmed that the removability of the support part was remarkably improved by including a disintegrant having the property of expanding and disintegrating by contact with water. In addition, from Table 1, it was confirmed that the support portion formed of the support material with a very small ratio (5% or less) of the thermoplastic resin (water-soluble resin) does not exhibit the effect by the disintegrant.

  The modeling material of this invention can be utilized when producing the solid thing produced by a three-dimensional modeling technique.

  1 (1a): structural material particles, 1b: support material particles, 17a: structural part, 17b: support part

Claims (15)

  A molding material comprising a thermoplastic resin and a disintegrant that expands in volume by contact with water.   The molding material according to claim 1, wherein the molding material is a particulate material having the thermoplastic resin and the disintegrant.   The molding material according to claim 1, wherein the thermoplastic resin is a water-soluble resin.   The modeling material according to any one of claims 1 to 3, wherein the disintegrant is a cellulose derivative containing a plurality of cellulose molecules.   The modeling material according to claim 1, wherein the modeling material is used as a support material.   6. The modeling material according to claim 1, wherein a content of the disintegrant is 10% by weight or more and 90% by weight or less with respect to the entire modeling material. A shaped object having at least a structure,
The said structure is comprised with the modeling material as described in any one of Claims 1 thru | or 4, The molded article characterized by the above-mentioned. A shaped object having a structure and a support body,
A modeled article, wherein the support body is composed of the modeled material according to claim 5 or 6.   The shaped article according to claim 8, wherein the structure is made of a water-soluble thermoplastic resin. A material layer forming step in which at least structural material particles are arranged to form a material layer; and
A modeled object forming step of forming the modeled object by laminating the material layers,
A method for producing a three-dimensional object, wherein the structural material particles include a thermoplastic resin and a disintegrant that expands by contact with water.   The three-dimensional object according to claim 10, wherein the modeled object forming step includes a heat-fusing step of applying thermal energy to the material layer to fuse the structural material particles contained in the material layer. Production method.   The three-dimensional image according to claim 10 or 11, wherein the material layer forming step includes a step of developing a latent electrostatic image formed on an image carrier with the structural material particles to form a particle image. Manufacturing method. A material layer forming step of forming a material layer by arranging water-insoluble structural material particles and support material particles;
A shaped article forming step of forming a shaped article by laminating the material layers;
A removal step of removing the portion formed of the support material particles of the modeled object by contacting with water, and
The method for producing a three-dimensional object, wherein the support material particles have a thermoplastic resin and a disintegrant that expands by contact with water.   The said modeling thing formation process includes the heat-fusion process which gives a thermal energy to the said material layer, and fuse | melts the structural material particle and support material particle which are contained in the said material layer, It is characterized by the above-mentioned. The manufacturing method of three-dimensional thing.   14. The material layer forming step includes a step of developing a latent electrostatic image formed on an image carrier with the structural material particles and the support material particles to form a particle image. 14. A method for producing a three-dimensional object according to 14.

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