WO2019159936A1

WO2019159936A1 - Three-dimensional object manufacturing method and lamination molding system

Info

Publication number: WO2019159936A1
Application number: PCT/JP2019/005015
Authority: WO
Inventors: 健太久保; 谷内　洋
Original assignee: キヤノン株式会社
Priority date: 2018-02-14
Filing date: 2019-02-13
Publication date: 2019-08-22
Also published as: JP2019137061A; JP7301548B2

Abstract

Provided is a method for manufacturing a three-dimensional object by stacking material layers, the method comprising: a material layer formation step S101 for forming a material layer 12 on each of a plurality of base materials 11; a lamination step S102 for forming a laminate 13 by stacking the plurality of base materials 11 each having the material layer 12 formed thereon; and a removal step S103 for removing the base materials 11 from the laminate 13 through heating.

Description

Manufacturing method of three-dimensional object and additive manufacturing system

The present invention relates to a method for manufacturing a three-dimensional object and an additive manufacturing system.

An additive manufacturing method that forms a three-dimensional object having a desired shape by stacking material layers formed of various materials such as metal, ceramic, and resin has attracted attention. In recent years, the field of application of additive manufacturing has expanded, not only to form mockups and parts made of a single type of material, but also to various devices such as batteries, electronic components, and wiring boards made of multiple types of materials. Is being made.

Patent Document 1 describes a method of manufacturing an all-solid battery using a positive electrode ink containing a positive electrode active material, an electrolyte ink containing a polymer electrolyte, and a negative electrode ink containing a negative electrode active material. In the method described in Patent Document 1, each ink is separately applied by an inkjet method to form a layer having a desired shape. After the obtained layer is dried, a layer is formed in the same manner on the layer. By repeating this, an all-solid battery having a structure in which the positive electrode active material, the polymer electrolyte, and the negative electrode active material are precisely arranged three-dimensionally is formed.

Further, in Patent Document 2, a material layer is formed on a sheet material that can be dissolved in a predetermined solvent by using a powder that can be heated and melted, and after the material layers are stacked together with the sheet material, a sheet is formed with the solvent. A method for producing a three-dimensional object by dissolving and removing the material is described.

Japanese Patent Laid-Open No. 2005-116248 JP2015-116710A

According to the method described in Patent Document 1, a three-dimensional object having a structure in which a plurality of kinds of desired materials are arbitrarily arranged three-dimensionally can be formed. However, since the next material layer is directly formed by applying ink directly on the formed material layer, the next layer cannot be formed unless a lower layer is formed. Therefore, as the number of layers increases, the time required to form one solid object increases.

According to the method described in Patent Document 2, a material layer is not directly formed on a three-dimensional object in the middle of formation, but a material layer is formed on a sheet material and then stacked. Can be formed. However, when the sheet material is dissolved and removed with a solvent as in the method described in Patent Document 2, the sheet material sandwiched between the upper and lower material layers cannot be dissolved, and the finally obtained three-dimensional A large amount of sheet material remains in the object. Therefore, the method described in Patent Document 2 cannot form a three-dimensional object in which a desired material is arbitrarily arranged three-dimensionally.

In view of the above-described problems, an object of the present invention is to provide a method for manufacturing a three-dimensional object that can efficiently manufacture a three-dimensional object in which a desired material is arbitrarily arranged three-dimensionally.

The method for producing a three-dimensional object according to one aspect of the present invention includes a material layer forming step of forming a material layer on a plurality of base materials, and a plurality of base materials each having the material layer formed thereon. A stacking step of forming a body, and a removing step of removing the plurality of base materials from the stack by heating.

It is a flowchart of the manufacturing method of a solid object. It is a figure which shows typically the whole structure of an additive manufacturing system. It is a figure which shows the structure of a material layer formation unit typically. It is a figure which shows the structure of a filling apparatus typically. It is a figure which shows typically the filler conveyed on a 1st base material. It is a figure which shows typically the filler conveyed on a 1st base material. It is a figure which shows typically the filler conveyed on a 1st base material. It is an enlarged view near the surface of the 1st substrate in the filling process by the 1st filling device. It is a figure which shows the structure of a transcription | transfer part typically. It is an enlarged view of the surface vicinity of the 2nd base material in the filling process by a 2nd filling apparatus. It is a figure which shows typically the 2nd base material after the 1st particle | grains were transferred by the transfer part, and the 2nd base material after the 2nd particle | grains were transferred by the transfer part. It is a figure which shows typically the 2nd base material after the 1st particle | grains were transferred by the transfer part, and the 2nd base material after the 2nd particle | grains were transferred by the transfer part. It is a figure which shows the structure of a lamination | stacking unit typically. It is a figure which shows the structure of a laminated body typically. It is a figure which shows the structure of a laminated body typically. It is a figure which shows the structure of a removal unit typically. It is a figure which shows typically the structure of the 1st base material which formed the uneven | corrugated pattern on the surface. It is a figure which shows typically the structure of the 1st base material which formed the uneven | corrugated pattern on the surface. It is a figure which shows the thermogravimetric analysis result of the sheet | seats made from polyester.

Hereinafter, embodiments for carrying out the present invention will be exemplarily described in detail with reference to the drawings. However, the dimensions, materials, shapes, relative positions, and the like of each member described in the following embodiments are not intended to limit the scope of the present invention only to those unless otherwise specified. Absent.

<First Embodiment>
A manufacturing method of a three-dimensional object and an additive manufacturing system according to a first embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a flowchart of a method for manufacturing a three-dimensional object according to the first embodiment.

The method for manufacturing a three-dimensional object according to this embodiment includes the following steps (1) to (3). Details of each step will be described later.
Step (1): Material layer forming step (S101) for forming material layers on a plurality of substrates, respectively.
Step (2): Lamination step (S102) in which a plurality of base materials each having a material layer formed thereon are laminated to form a laminate.
Step (3): Removal step of removing a plurality of base materials from the laminate by heating (S103)
In the method for manufacturing a three-dimensional object according to this embodiment, after forming a plurality of material layers on a substrate, the material layers are stacked together with the substrate, and then the plurality of substrates are removed by heating. When the next material layer is directly formed on the formed material layer as in the past, the next material layer cannot be formed on the previous material layer unless the previous material layer is completed. It was necessary to wait for completion of the material layer before forming the next material layer. However, according to the present embodiment, the formation of the previous material layer and the formation of the next material layer can be performed independently. Therefore, even when it takes a long time to form the material layer, a plurality of material layers can be formed efficiently.

For example, if a plurality of material layer forming means are provided, a plurality of material layers can be formed in parallel. Alternatively, even when only one material layer forming means is provided, when it is necessary to dry the formed material layer, etc., the previous material layer is formed on the substrate and then dried. While doing so, it is also possible to start forming the next layer of material on another substrate. Therefore, according to the present embodiment, a three-dimensional object can be efficiently manufactured in a shorter time.

Further, when forming the material layer, the material layer is greatly affected by the surface shape of the underlying layer forming the material layer. When the material layer is formed of a particulate material, the influence of the surface shape of the underlying layer becomes particularly significant. When the surface shape of the underlying layer is not smooth, the density and pattern accuracy of the material layer are reduced. Cheap. When the next material layer is directly formed on the formed material layer as in the prior art, the smoothness of the surface shape of the material layer tends to be lost as the number of stacked layers increases. On the other hand, according to the present embodiment, each material layer is formed on the substrate every time, so that the surface shape of the underlying layer forming the material layer can be aligned every time, and the formation accuracy of each material layer can be improved. Can do. As a result, the density and modeling accuracy of the manufactured three-dimensional object can be increased. Moreover, since each material layer is formed on a base material each time, it is easy to increase the area of the material layer, and there is an advantage that a larger three-dimensional object can be easily manufactured.

Furthermore, in this embodiment, the substrate is removed from the laminate by heating in the removing step. When the substrate is dissolved and removed with a solvent as in the past, or when the substrate is removed mechanically by wind pressure or water pressure, the substrate sandwiched between the upper and lower material layers is sufficient in the laminate. May not be removed. When removing the substrate mechanically, it is particularly difficult to remove the material layer near the center inside the laminate. In addition, when the substrate is mechanically removed, a large force is applied to the upper and lower material layers during the removal, and the structure of the material layer may be destroyed. However, according to this embodiment, since the base material is removed by heating, the base material inside the laminate is easily removed, and the removal rate of the base material is easily increased. In addition, since the force applied to the material layer when removing the base material can be reduced, the density of the material layer can be increased without greatly breaking the structure of the material layer.

In addition, a removal process can also be called the heating process which heats a laminated body at the temperature more than the thermal decomposition temperature of a some base material. In addition, as the plurality of base materials, a single type of base material may be used, or a plurality of types of base materials may be used. When a plurality of types of substrates having different pyrolysis temperatures are used as the plurality of substrates, the heating temperature in the removal step (heating step) is the highest among the respective pyrolysis temperatures of the plurality of substrates. Heating may be performed at a temperature higher than the decomposition temperature.

It should be noted that the method for producing a three-dimensional object according to the present invention is not limited to one having all the above-described steps (1) to (3). For example, in another embodiment of the present invention, the manufacturing method of a three-dimensional object does not have a material layer formation step (step (1)), but a lamination step (step (2)) and a removal step (step (3)). ). That is, for example, a plurality of base materials each having a material layer formed beforehand may be prepared, and the base materials may be laminated together to form a laminated body, and the base material may be removed from the laminated body by heating. Alternatively, in still another embodiment of the present invention, the method for producing a three-dimensional object may include only the removal step (step (3)) among steps (1) to (3). Also according to these embodiments, a three-dimensional object with an increased removal rate of the base material from the laminate can be obtained.

FIG. 2 is a diagram schematically showing the overall configuration of the additive manufacturing system according to the first embodiment.

The additive manufacturing system 1 according to the present embodiment includes a control unit U1, a material layer forming unit U2, a stacked unit U3, a removal unit U4, and a post-processing unit U5. The control unit U1 is responsible for controlling each part of the additive manufacturing system 1. The material layer forming unit U <b> 2 forms the material layer 12 on the base material 11. The stacking unit U3 stacks the plurality of base materials 11 on which the material layers 12 are respectively formed by the material layer forming unit U2, and forms a stacked body 13 including the plurality of material layers 12 and the plurality of base materials 11. The removal unit U4 forms the three-dimensional object 14 by removing the base material 11 by heating from the laminate 13 formed by the laminate unit U3. The post-processing unit U5 performs post-processing of the three-dimensional object 14 formed by the removal unit U4. Note that the unit configuration shown in FIG. 2 is merely an example, and other configurations may be adopted. Hereinafter, the configuration and operation of each unit will be described.

[Controller unit]
The control unit U1 is responsible for controlling each part of the additive manufacturing system 1, specifically, the material layer forming unit U2, the laminate unit U3, the removal unit U4, and the post-processing unit U5.

The control unit U1 accepts input of three-dimensional shape data of a three-dimensional object (hereinafter, sometimes referred to as “modeling object”) formed by the additive manufacturing system 1 from an external device (for example, a personal computer or the like). An input unit may be provided. As the three-dimensional shape data, data created and output by a three-dimensional CAD, a three-dimensional modeler, a three-dimensional scanner, or the like can be used. Although the file format is not ask | required, for example, an STL (Stereolithography) file format can be used preferably.

The control unit U1 calculates the cross-sectional shape of each layer by slicing the three-dimensional shape data at a predetermined pitch, and based on the cross-sectional shape, image data used for image formation in the material layer forming unit U2 (referred to as “slice data”). ) May be provided. Furthermore, the slice data calculation unit analyzes the three-dimensional shape data or the slice data of the upper and lower layers, determines the presence or absence of an overhang portion (portion floating in the air), and if necessary, adds an image for the support material to the slice data. May be added.

As will be described in detail later, the material layer forming unit U2 of the present embodiment uses a plurality of types of materials, and can form a material layer in which each material is patterned. Therefore, data corresponding to each material image may be generated as slice data. As the file format of the slice data, for example, multi-value image data (each value represents a material type) or multi-plane image data (each plane corresponds to a material type) can be used.

Although not shown, the control unit U1 also includes an operation unit, a display unit, and a storage unit. The operation unit is a function that receives an instruction from the user. For example, power on / off, various device settings, operation instructions, and the like can be input. The display unit is a function for presenting information to the user. For example, various setting screens, error messages, operation statuses, and the like can be presented. The storage unit is a function of storing three-dimensional shape data, slice data, various setting values, and the like.

The control unit U1 is configured in hardware by a computer having a CPU (Central Processing Unit), a memory, an auxiliary storage device (hard disk, flash memory, etc.), an input device, a display device, and various I / Fs. Can do. Each function described above is realized by a CPU reading and executing a program stored in an auxiliary storage device or the like, and controlling necessary devices. However, some or all of the functions described above may be configured by a circuit such as an ASIC or FPGA, or may be executed by another computer using technology such as cloud computing or grid computing. Good.

[Material layer forming unit]
The material layer forming unit U <b> 2 is a unit that forms the material layer 12 on the base material 11. Although the method in which the material layer forming unit U2 forms the material layer 12 on the base material 11 is not particularly limited, it is preferable that a plurality of types of materials can be arranged on the base material 11 in an arbitrary pattern. Moreover, although mentioned later in detail, it is preferable that the material layer formation unit U2 forms the material layer 12 which is a particle layer using a particle material. As such a method, specifically, a method in which filling of the material into the concave portion of the concave / convex pattern and transfer of the filled material to the base material are combined, or ink containing a particulate material is ink-jetted. The method including the process of apply | coating on a base material by is mentioned. In addition, a method including a step of sprinkling and adhering a particulate material after applying a liquid onto a substrate by inkjet can be used.

The additive manufacturing system 1 may have a plurality of material layer forming units U2. Thereby, formation of the material layer 12 on the base material 11 can be performed simultaneously, and the throughput of formation of a laminated body and a three-dimensional object can further be improved. In addition, when there are a large number of types of materials constituting the three-dimensional object, the material type in the material layer forming unit U2 is provided by providing the material layer forming unit U2 for each material type or for each group of material types. And process switching can be omitted. Thereby, manufacture of a solid thing can be performed continuously.

Hereinafter, in the case where the material layer forming unit U2 forms the material layer 12 on the base material 11 by a method in which the filling of the material into the concave portions of the concave / convex pattern and the transfer of the filled material to the base material are combined. Will be described.

FIG. 3 is a diagram schematically showing the configuration of the material layer forming unit U2 according to the first embodiment.

The material layer forming unit U2 according to the present embodiment includes a first storage container 21a for storing and supplying the first base material 11a, a first belt device 22a for transporting the first base material 11a, and a first And a pattern forming device 23 that forms a concavo-convex pattern on the substrate 11a. The material layer forming unit U2 includes a first filling device 24a that arranges the first particles P1 in the concave portions of the concave-convex pattern formed on the first base material 11a. The material layer forming unit U2 includes a second storage container 21b for storing and supplying the second base material 11b, and a second belt device 22b for transporting the second base material 11b. The material layer forming unit U2 includes a transfer portion 25a facing the rollers of the first belt device 22a and the second belt device 22b. The first particles P1 are transferred to the substrate 11b. Furthermore, the material layer forming unit U2 includes a second filling device 24b that arranges the second particles P2 in the non-transfer portion on the second base material 11b. In addition, a device that is not highly relevant for explaining the effect of the present case, for example, a separation / recovery device for removing and collecting the first base material 11a after transfer from the first belt device 22a, each cleaning device, and the like are illustrated. Detailed description is omitted.

Hereinafter, the method of forming the material layer 12 on the base material 11 by the material layer forming unit U2 will be described along the flow for each process.

First, the first base material 11a is supplied from the first storage container 21a to the first belt device 22a by supply means (not shown).

The material of the first base material 11a is not particularly limited, but when UV curable ink is applied by a pattern forming device 23 (described later), at least the surface thereof has high wettability with the UV curable ink. It is preferable that it is made of a material. Moreover, it is preferable that the surface of the 1st base material 11a is smooth. Typically, as the first base material 11a, a resin sheet such as polyester that has been subjected to a hydrophilic treatment or an oleophilic treatment in accordance with the ultraviolet curable ink to be used (water-based or oil-based) is used. it can. In addition, the 1st base material 11a may use the base material cut | disconnected separately like cut paper, the continuous base material wound by roll shape like roll paper, and continuous paper like A continuous base material that is alternately folded may be used.

The first belt device 22 a conveys the supplied first base material 11 a to the pattern forming position of the pattern forming device 23. The first belt device 22a includes

drive rollers

221a and 222a, a pressure roller 223a, and a belt-shaped conveying member 224a suspended on them. At this time, the pressure roller 223a rotates by being driven.

The conveying member 224a is preferably selected from resin or metal, and for example, a polyimide resin belt can be used. The

drive rollers

221a and 222a are preferably metal metal rollers. For example, stainless steel metal rollers can be used. As the pressure roller 223a, a soft roller having an elastic layer as a surface layer is preferably used. For example, a soft roller in which an elastic layer of silicone rubber is provided on the surface of a stainless steel core can be used.

In the present embodiment, the first belt device 22a is used as a transport device for transporting the first base material 11a. However, a roller device may be used instead of the belt device. The same applies to the second belt device 21b described later.

The pattern forming device 23 forms a fine concavo-convex pattern on the first base material 11a conveyed to the pattern forming position. The method for forming the concavo-convex pattern is not particularly limited, and a UV imprint method, a thermal imprint method, a UV inkjet method, a printing method, a laser etching method, or the like can be used. When the pattern forming apparatus 23 forms a concavo-convex pattern by the UV imprint method, the pattern forming apparatus 23 has an application unit that applies an ultraviolet curable composition onto the first substrate 11a. The pattern forming apparatus 23 includes a stamping unit that stamps a mold having a concavo-convex pattern formed on the surface of the ultraviolet curable composition on the first substrate 11a, and a light source that irradiates the ultraviolet curable composition with ultraviolet rays. Have. Typically, an ultraviolet curable liquid silicone rubber (PDMS) or resin is used as the ultraviolet curable composition, a film mold is used as the mold, and a UV lamp is used as the light source.

When the first filling device 24a fills the recesses with the first particles P1 using the support material S1 supporting the first particles P1, the recesses of the uneven pattern on the first substrate 11a are It is preferable that the particle P1 can be in contact with the carrier material S1.

In the present embodiment, the pattern forming device 23 forms a concavo-convex pattern on the first substrate 11a. However, the present invention is not limited to this, and a substrate having a concavo-convex pattern previously formed on the surface is used as the first substrate. It may be used as the material 11a. In addition, the pattern forming device 23 may form an uneven pattern directly on the surface of the conveying member 224a of the first belt device 22a, or a conveying member having an uneven pattern on the surface may be used as the conveying member 224a. In this case, in view of durability, it is preferable to form a concavo-convex pattern on the surface using a fine belt such as laser etching, wet etching, or dry etching using a metal belt such as stainless steel or aluminum.

The first substrate 11a having a concavo-convex pattern formed on the surface is conveyed to the filling position of the first filling device 24a by the first belt device 22a.

FIG. 4 is a diagram schematically showing the configuration of the filling apparatus according to the present embodiment. Hereinafter, the configuration of the first filling device 24a will be described, but the same applies to the second filling device 24b.

The first filling device 24a includes a filling container 242a that contains the filler 241a, a stirring screw member 243a that stirs and conveys the filler 241a, a recovery member 244a that collects the filler, and a magnetic member 247a.

The filler 241a includes first particles P1 and a support material S1 that supports the first particles P1. The filler 241a is a mixture of a plurality of powders including a powder composed of a plurality of first particles P1 and a powder composed of a plurality of support materials S1. The filler 241a accommodated in the filling container 242a is sufficiently mixed and frictionally charged when being stirred and conveyed by the stirring screw member 243a. As a result, the first particles P1 are supported on the surface of the support material S1.

The first particles P1 are particles filled in the concave portions of the concavo-convex pattern formed on the first base material 11a, and the material thereof is not particularly limited. The first particles P1 may be particulate inorganic materials such as metal particles, ceramic particles, and glass particles, or may be particulate organic materials such as resin particles. As will be described later, in the present embodiment, when removing the base material 11 in the removing step (step (3)), the base material 11 is removed by heating, and therefore the first particles P1 are the second base material described later. A material having a thermal decomposition temperature higher than 11b is preferred. Since the inorganic material tends to have a high thermal decomposition temperature, the first particles P1 are preferably particulate inorganic materials.

In the present specification, the thermal decomposition temperature is a temperature at which weight reduction of the material starts when the temperature is gradually raised in the atmosphere when heating the removal unit U4. Therefore, by heating the laminate at a temperature equal to or higher than the thermal decomposition temperature of the substrate 11, the substrate 11 in the laminate can be decomposed to reduce its weight, and the substrate 11 is removed from the laminate. Can do. The heating temperature in the removing step is preferably a temperature equal to or higher than the thermal decomposition temperature of the substrate 11, but it is preferable to heat at a temperature higher than the thermal decomposition temperature. Specifically, when the thermogravimetric analysis is performed at a rate of 5 ° C./minute from room temperature (25 ° C.) under the atmosphere (typically air) during heating of the removal unit U4, the initial weight is obtained. It is preferable to heat at a temperature equal to or higher than the temperature at which it becomes 70%. Similarly, when thermogravimetric analysis is performed, it is preferable to heat at a temperature equal to or higher than 50% of the initial weight, and to heat at a temperature equal to or higher than 20% of the initial weight. More preferably. Thereby, the time required for removing the base material 11 can be shortened, or the removal rate of the base material 11 can be increased.

The support material S1 is a magnetic particle. The support material S1 is preferably particles in which the surfaces of resin particles in which ferrite core particles and magnetic materials are dispersed are coated with a resin composition. The particle size and material of the support material S1 are appropriately selected according to the particle size and material of the first particle P1. Thereby, the 1st particle P1 can be carried stably.

Further, in order to improve the chargeability and cohesiveness, particles other than the first particles P1 and the support material S1 are added to the filler 241a, or the surface of the first particles P1 is coated with a resin composition. It doesn't matter. Further, in order to improve the conductivity of the particles P1, as a conductive auxiliary agent, a form containing carbon black such as acetylene black, a metal, or an alloy powder, and the conductive auxiliary agent on the surface of the first particle P1 were coated. A form is included as a modification of this embodiment.

The recovery member 244a includes a roller 245a that can rotate in the direction of arrow d2 in the drawing, and a magnet 246a that is disposed inside the roller 245a and fixed to the filling container 242a. Further, the magnetic member 247a is disposed to face the filling container 242a via the transport member 224a, and has a magnet 248a therein. The magnet 246a has a plurality of N poles and S poles arranged alternately along the rotation direction of the recovery member 244a. The magnet 248a has a plurality of N poles and S poles arranged alternately along the transport direction of the transport member 224a. Further, the magnet 246a has a magnetic pole of a different polarity (N1 pole in the present embodiment) at a position closest to the most downstream magnetic pole (S1 pole in the present embodiment) of the magnet 248a. The N2 pole having the same polarity as the N1 pole is arranged at the position of. Magnet 246a and magnet 248a may be composed of a plurality of magnets, and the types of magnets constituting magnet 246a and magnet 248a are not particularly limited. For example, a means for generating a magnetic field such as a rare earth magnet such as a ferrite magnet, a neodymium magnet, or a samarium cobalt magnet, a permanent magnet such as a plastic magnet, or an electromagnet can be used.

A regulating member that regulates the filler 241a on the first base material 11a or a filler 241a that cannot be collected by the collecting member 244a is again provided upstream or downstream of the collecting member 244a in the conveying direction of the conveying member 224a. A recovery member for recovery may be provided. As a collecting member to be collected again, a collecting member that collects by air blow from a simple member such as a fixed magnet or a regulating member can be used in addition to a member similar to the collecting member 244a.

Next, the process of filling the first particles P1 into the recesses on the first base material 11a by the first filling device 24a will be described with reference to FIGS.

When the first transport member 224a moves in the direction of the solid line arrow d1 in FIG. 4, the first base material 11a carried and transported by the first transport member 224a is transported, and the first filling device 24a It is transported to the filling position.

The filler 241a is conveyed by the stirring screw member 243a and supplied onto the first substrate 11a (dotted line a in FIG. 4). At this time, a magnetic field is formed by the magnetic member 248a and the recovery member 244a, and the filler 241a including the carrier material S1 that is a magnetic particle forms a plurality of magnetic spikes on the first substrate 11a by the magnetic field. The filler 241a supplied onto the first base material 11a is transported on the first base material 11a in a state where magnetic spikes are formed as the first base material 11a moves (dotted line in FIG. 4). b).

FIG. 5 is a schematic diagram of the filler 241a conveyed on the first base material 11a. For the sake of explanation, the filler 241a other than the filler forming one magnetic spike is not shown. As described above, the filler 241a on the first base material 11a forms a magnetic spike along the magnetic field lines of the magnetic field that is formed, and as the first base material 11a moves, FIG. 5A and FIG. 5B and conveyed while changing the shape of the magnetic spike as shown in FIG. 5C. At this time, since a particularly strong magnetic force acts in the vicinity of the magnet 248a, the conveying speed v2 of the filler 241a is smaller than the moving speed v1 of the first base material 11a when the filler 241a moves away from the magnetic pole. In the opposite case, it becomes larger. That is, the filler 241a on the first substrate 11a has a non-zero relative speed with respect to the first substrate 11a.

FIG. 6 is an enlarged view of the vicinity of the surface of the first base material 11a of FIG. Although not shown in FIG. 5, the uneven pattern 111a is formed on the first substrate 11a as shown in FIG. The filler 241a is in contact with the concavo-convex pattern 111a and is zero with respect to the first base material 11a while receiving a magnetic force (solid line Fm in the figure) in a direction perpendicular to the surface of the first base material 11a. It is conveyed with the 1st base material 11a, having a relative speed which is not. Thus, the first particles P1 supported on the support material S1 are conveyed while being rubbed against the uneven pattern 111a on the surface of the first base material 11a. At this time, since the concave portion of the concave / convex pattern 111a is sized so that the first particle P1 can contact but the support material S1 cannot contact, only the first particle P1 is selectively concave in the filler 241a. To touch. The first particles P1 that have come into contact with the recesses are physically restrained by the structure of the concavo-convex pattern 111a, or by electrostatic adhesion and adhesive force with the structural material constituting the first substrate 11a and the concavo-convex pattern 111a. It is strongly restrained and detached from the support material S1.

As shown in FIG. 4, a recovery member 244a is disposed downstream of the magnetic member 247a with a gap from the first transport member 224a. As the first base material 11a moves, the filler 241a conveyed to the vicinity of the most downstream magnetic pole (S1 pole) of the magnet 248a is affected by the magnetic field formed by the magnet 246a, and the first base 11a is moved. It moves from the material 241a to the recovery member 244a and is recovered (dotted line c in FIG. 4).

As described above, in the transport process (dotted lines a, b, and c in FIG. 4), the concave portions of the concave / convex pattern 111a on the surface of the first base material 11a sufficiently come into contact with the plurality of fillers 241a. Therefore, the first particles P1 are selectively and densely arranged in the recesses of the uneven pattern 111a after the filler 241a is recovered by the recovery member 244a.

In FIGS. 5 and 6, all the first particles P1 are illustrated with the same particle size, but there is actually a particle size distribution, and depending on the material, aggregated secondary particles are formed. There is also. Even in such a case, only particles that can contact the concave portions of the concave / convex pattern 111a are selectively densely packed, so that coarse powder, secondary particles, and the like that can adversely affect the formation of the material layer are excluded.

The filler 241a recovered by the recovery member 244a is conveyed by the rotating roller 244a (dotted line d in FIG. 4). The filler 241a conveyed by the roller 244a falls into the filling container 242a due to the influence of the magnetic field and gravity due to two adjacent magnetic poles (N1, N2) repelling each other (dotted line e in FIG. 4). . Thereafter, the mixture is again stirred and conveyed by the stirring screw member 243a, and this is repeated thereafter.

The weight ratio between the first particles P1 in the filler 241a and the support material S1 in the filling container 242a is an inductance sensor that is measured using a magnetic permeability, which is common in electrophotographic apparatuses, or a reflection density on a substrate. Is determined by a patch density sensor or the like that predicts by measuring. Then, if necessary, at least one of the first particles P1 and the support material S1 is supplied by a supply means (not shown). This enables stable filling over a long period of time.

In addition, although the filling apparatus of the type | system | group which fills a recessed part with particle | grain material by forming what is called a magnetic brush using a magnetic particle as a support material was demonstrated here, the system of a filling apparatus is not limited to this. Brush fibers may be used as the support material. Alternatively, an elastic member having at least a surface made of an elastic material may be used as the support material. According to the system in which these particle materials are supported on the support material and rubbed with each other, more dispersed particles can be supplied to the recesses compared to the filling method using a regulating member such as a blade, and the stable and Filling can be performed precisely. This merit becomes more prominent because the particles are more easily aggregated as the particle size of the particles to be filled is smaller.

The first base material 11a in which the first particles 1 are filled in the concave portions of the uneven pattern 111a by the first filling device 24a is conveyed to the transfer unit 25a by the first belt device 22a.

Here, as shown in FIG. 3, the second belt device 22b is similar to the first belt device 22a in that the driving

rollers

221b and 222b, the pressure roller 223b, and a belt-like conveying member suspended on them. 224b. At this time, the pressure roller 223b rotates following. In the transfer unit 25a, the pressure roller 223a of the first belt device 22a and the pressure roller 223b of the second belt device 22b are opposed to each other.

The second substrate 11b is supplied from the second storage container 21b to the second belt device 22b and is conveyed in the direction of the arrow in FIG. The supplied second base material 11b is transported in accordance with the timing at which the first base material 11a is transported to the transfer unit 25a. In the transfer unit 25a, the first particles P1 filled in the first base material 11a are transferred to the second base material 11b. This transfer process will be described with reference to FIG.

FIG. 7 is a diagram schematically showing the configuration of the transfer portion 25a. The transfer unit 25a includes a pressure roller 223a and a conveying member 224a of the first belt device 22a, and a pressure roller 223b and a conveying member 224b of the second belt device 22b. As described above, the

pressure rollers

223a and 223b rotate by being driven, and the two rollers are in contact with each other via the conveying

members

224a and 224b. At least one of the

pressure rollers

223a and 223b is a soft roller having an elastic layer as a surface layer, and a nip portion is formed at a portion where the two rollers are in contact with each other.

The first base material 11a and the second base material 11b filled with the first particles P1 by the first filling device 24a are transported at substantially constant speed by the respective transport members (224a, 224b) and pressurized. The

rollers

223a and 223b enter the nip portion formed by contact. In the nip portion, the first particles P1 on the first substrate 11a come into contact with the second substrate 11b and are transferred onto the second substrate 11b.

The second base material 11b is a base material whose adhesion force to the first particles P1 is larger than the adhesion force of the first base material 11a to the first particles P1. In other words, the adhesion force of the first particles P1 to the second substrate 11b is larger than the adhesion force of the first particles P1 to the first substrate 11a. Thereby, in the nip portion, the first particles P1 on the first base material 11a are transferred onto the second base material 11b.

The material of the second base material 11b is not particularly limited. However, in the present embodiment, the material layer is laminated together with the second base material 11b in a later-described laminating unit U3, and the second base material 11b is removed by heating in the removal unit U4. Therefore, the second base material 11b is preferably made of a material that can be easily removed by heating. In addition, the 2nd base material 11b may be the base material cut | disconnected separately like a cut paper similarly to the 1st base material 11a, or the continuous wound by roll shape like roll paper Or a continuous base material folded alternately like a continuous paper.

It is preferable that the second substrate 11b is subjected to a surface treatment for increasing the adhesive force in order to transfer the first particles P1 that have come into contact therewith. For example, it is preferable that the 2nd base material 11b has the adhesion layer by which the adhesive was apply | coated to the surface. The pressure-sensitive adhesive may be an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a silicone-based pressure-sensitive adhesive, or may be a thermoplastic resin or a photo-curing resin whose adhesive force changes due to disturbance such as heat or light. May be. In addition, you may apply | coat an adhesive to both surfaces of the 2nd base material 11b.

Further, the material layer forming unit U2 may have an application means such as a dispenser or an inkjet head for applying an adhesive to the surface of the second substrate 11b being conveyed.

The type and application amount of the pressure-sensitive adhesive are appropriately adjusted depending on the shape and material of the uneven pattern to be used, the particle size and material of the first particles P1 and the second particles P2, and the like. It is preferable that the adhesive strength is large. The comparison of the adhesive strength can be measured by a general method using a nanoindenter.

In the nip portion, the first particles P1 are constrained by the adhesive force generated between the second particles 11b. When the conveying

members

224a and 224b are separated from each other past the nip portion, the first particles P1 on the first base material 11a are transferred to the second base material 11b.

The second base material 11b to which the first particles P1 have been transferred is transported to the filling position of the second filling device 24b by the transport member 224b.

In the second filling device 24b, a filler 241b having the second particles P2 and the support material S2 is accommodated in the filling container 242a instead of the filler 241a having the first particles P1 and the support material S1. Except for the point, it has the same configuration and function as the first filling device 24a.

The second filling device 24b fills the second particles P2 on the second base material 11b where the first particles P1 are not disposed. As described above, the first particles P1 are arranged on the second base material 11b that has passed through the transfer portion 25a, but a so-called recess is formed in a portion where the first particles P1 are not arranged. Has been. The second filling device 24b fills the recesses with the second particles P2 in the same process as the first filling device 24a.

The filler 241b includes second particles P2 and a support material S2 that supports the second particles P2. The filler 241b is a mixture of a plurality of powders including a powder composed of a plurality of second particles P2 and a powder composed of a plurality of support materials S2. The material of the second particles P2 is not particularly limited, and may be a particulate inorganic material such as metal particles, ceramic particles, glass particles, or particles such as resin particles, like the first particles P1. It may be an organic material having a shape. As will be described later, since the base material 11 is removed by heating when removing the base material 11 in the removing step (step (3)), the second particles P2 are preferably particulate inorganic materials. The first particles P1 and the second particles P2 may be the same material. Also, the support material S2 can be the same as the support material S1. Similarly to the first particles P1, the second particles P2 are preferably made of a material having a higher thermal decomposition temperature than the second base material 11b. Note that the first particles P1 and the second particles P2 are preferably selected from a positive electrode material of a lithium ion battery or an all-solid battery, a material containing a solid electrolyte, and a negative electrode material.

FIG. 8 is an enlarged view of the vicinity of the surface of the second substrate 11b in the filling process by the second filling device 24b. On the second base material 11b, a concavo-convex pattern having a convex portion formed by arranging the first particles P1 and a concave portion in which the first particles P1 are not arranged is formed. The filler 241b is in contact with the concavo-convex pattern and receives a magnetic force (solid line Fm in the figure) in a direction perpendicular to the surface of the second base material 11b, while being zero with respect to the second base material 11b. It is conveyed with the second base material 11b while having no relative speed. Thus, the second particles P2 supported on the support material S2 are conveyed while being rubbed against the uneven pattern on the surface of the second base material 11b. At this time, since the concave portion of the concave / convex pattern has a size that allows the second particles P2 to contact but the support material S2 cannot contact, only the second particles P2 in the filler 241b selectively become concave portions. Contact. The second particles P2 in contact with the recesses are strongly restrained by the physical binding force due to the structure of the concavo-convex pattern and the electrostatic adhesion force and adhesive force between the second base material 11b and the structural material constituting the concavo-convex pattern. And detached from the support material S2.

FIG. 9A is a diagram schematically showing the second substrate 11b after the first particles P1 are transferred by the transfer unit 25a, and the second substrate 11b is viewed from a direction perpendicular to the substrate surface. It is a figure. As shown in FIG. 9A, on the second substrate 11b, a honeycomb pattern is formed in which arrangement regions where the first particles P1 are arranged in a regular hexagonal shape are aligned. The first particles P1 are densely arranged in the regular hexagonal region, and the first particles P1 are not arranged in other portions (the white background portion in FIG. 9A). The surface of the material 11b is exposed. The regular hexagonal region where the first particles P1 are held is the first pattern portion, and the second particle P2 is held, and the honeycomb pattern region corresponding to the gap between the first pattern portions is the second pattern portion. In other words.

FIG. 9B is a diagram schematically showing the second base material 11b after the second particles P2 are filled by the second filling device 24b, and the second base material 11b is perpendicular to the base material surface. It is the figure seen from. As shown in FIG. 9B, the second particles P2 are densely arranged in the region where the first particles P1 are not arranged. Also, the first particles P1 and the second particles P2 are densely arranged at the boundary portion between the region where the first particles P1 are arranged and the region where the second particles P2 are arranged. Has been.

In the present embodiment, in the L × L square region, the first pattern portion and the second pattern portion have the same repetition period L / 5 in the horizontal direction (apparent horizontal direction) of the paper surface. Yes. In the present embodiment, the pattern portion has a first pattern portion in which the first particle group is held and a second pattern portion in which the second particle group is held. In other words. In the present embodiment, particle groups P1 and P2 having different average particle sizes are spread on the first pattern portion and the second pattern portion. For this reason, in the present embodiment, the pattern portion is different from the first particle group P1 and the second particle group P2 in the average particle diameter, and in the area density of the retained particle group, In other words, it is different from the second pattern portion.

In FIG. 9B, the first pattern portion and the second pattern in the directions rotated by + 1 / 3π radians (+60 degrees) and −1 / 3π radians (−60 degrees) with respect to the apparent horizontal direction, respectively. The parts have mutually equal repetition periods L / 5.

Thus, according to the material layer forming unit U2 of the present embodiment, the material layer in which the first particles P1 and the second particles P2 are densely arranged in a pattern is formed on the second base material 11b. can do. Specifically, according to this embodiment, in each of the material layers, the coverage of the base material with particles can be 80% or more. In addition, the coverage of the base material by particles is measured by photographing the region where the material layer is formed with an optical microscope from the vertical direction of the base material, and calculating the area ratio of the particles in the region by image processing software. be able to.

In the present embodiment, the case where the material layer forming unit U2 forms a material layer using two types of particle materials has been described. However, the present invention is not limited to this, and the material layer is formed using one type of particle material. Alternatively, the material layer may be formed using three or more kinds of particulate materials.

When the material layer is formed with one kind of particle material, both the first filling device 24a and the second filling device 24b may be filled with the same particle material. Thereby, it is possible to form a material layer in which one kind of material is arranged more densely. At this time, the first material P1 in the first filling device 24a and the second particle P2 in the second filling device 24b may use the same material but different particle sizes. For example, a finer material layer can be formed by using particles having a smaller particle diameter than the first particles P1 as the second particles P2.

On the other hand, when the material layer is formed of three or more kinds of particle materials, a third filling device may be added on the upstream side of the first filling device 24a or the second filling device 24b. At this time, it is preferable that the particle diameter of the particles filled in the upstream filling apparatus is larger than the particle diameter of the particles filled in the downstream filling apparatus. Moreover, it is preferable to provide a plurality of recesses of different sizes on the base material so that the particles to be filled in the upstream filling device are in contact with only a part of the recesses. Thereby, a material layer in which each particle is densely arranged in a pattern can be formed using three or more kinds of particle materials.

Although complicated in configuration, a plurality of first belt devices 22a may be provided, and different particles may be transferred from the respective devices onto the second base material 11b. Alternatively, a third belt device having a third filling device is provided, and the first and second particles are arranged in the transfer portion formed by the second belt device 22b and the third belt device. The particles may be transferred from the second base material 11b onto the third base material. After that, if the third particle is filled with the third filling device in the portion where neither the first particle nor the second particle is arranged on the third substrate, the material layer is formed with three or more kinds of particle materials. Can be formed.

Thus, according to the material layer forming unit U2 of the present embodiment, a material layer in which a single kind or plural kinds of particles are densely arranged on the base material 11b can be formed.

In the present embodiment, since the material layer forming unit U2 forms each material layer on the base material, it is possible to align the base conditions when forming the material layer. Therefore, the material layer can be formed more stably than in the case where a material layer is further formed on the formed material layer.

In this embodiment, the material layer forming unit U2 forms the material layer by a method in which filling and transfer by two filling devices are combined. However, the present invention is not limited to this. For example, the first particle is applied by a method in which an ink containing a particulate material is applied onto a substrate by ink jet, or a method in which a liquid is applied in a pattern by ink jet on the substrate and then the particulate material is sprinkled and adhered. P1 is arranged. And you may fill the 2nd particle | grains P2 with the above-mentioned filling apparatus in the location where the 1st particle | grains P1 are not arrange | positioned.

Since the particle material that constitutes each material layer and finally constitutes the three-dimensional object is preferably an inorganic material as described above, the material layer formed by the material layer forming unit U2 is an inorganic material. It is preferable to be configured. Thereby, the removal of a base material can be made easy in the removal process in the removal unit U4 mentioned later. However, each material layer may contain an organic material in addition to the inorganic material.

[Laminated unit]
The stacking unit U3 is a unit that stacks a plurality of base materials 11 each having the material layer 12 formed thereon by the material layer forming unit U2 and forms a stacked body 13 including the plurality of material layers 12 and the plurality of base materials 11. is there.

FIG. 10 is a diagram schematically showing the configuration of the laminated unit U3. The stacking unit U3 includes a transport device 31 that transports the base material 11b on which the material layer 12 is formed, and a stage 32 that can be relatively moved in the vertical direction by an actuator (not shown).

The transfer device 31 receives the substrate 11b on which the material layer 12 is formed from the lamination unit U2 and transfers it to the stage 32. The transport device 31 is not particularly limited as long as it is a device capable of transporting the base material 11b, and may be a belt conveyor, a roller, or a robot arm.

When the substrate 11b is conveyed to the stage 32 by the conveying device 31, the stage 32 moves in the vertical direction by the thickness of the substrate 11b and the material layer 12. By repeating the conveyance by the conveyance device 31 and the movement of the stage 32, a plurality of base materials 11b each formed with the material layer 12 are laminated, and the laminated body 13 is formed.

The stacking unit U3 may further include a transport device 33 that transports the formed stacked body 13 to the removal unit U4 and the like, and a pressurizing device (not shown) that pressurizes the stacked body 13 in the stacking direction. The transport device 33 may have the same configuration as the transport device 31.

FIG. 11A is a schematic diagram of a laminate 13 in which four base materials 11b on which a material layer 12 is formed are laminated on a stage 32. FIG. There are a total of three base materials 11b between each of the material layers 12 composed of the first particles P1 and the second particles P2. As described above, it is preferable that the adhesive material for transferring and filling the first particles P1 and the second particles P2 is coated on the upper surface of the base material 11b. Also, an adhesive material may be applied. Thereby, each layer can be more firmly fixed at the time of lamination. At this time, it is preferable not to apply the adhesive material to the lower surface of the base material 11b in contact with the stage 32. Since one base material 11b is always interposed between the adjacent material layers 12, it is difficult to remove the base material in a removing unit described later, but the base material is easily stacked.

FIG. 11B shows a base material 11b (the uppermost base material and the lowermost base material in the figure) in which the material layer 12 is formed on one surface of the base material, and a base material 11b in which the material layer 12 is formed on both surfaces of the base material. FIG. 3 is a schematic diagram of a laminate 13 in which three substrates (center base material in the figure) are laminated on a stage 32; A total of one base material 11b exists between each of the material layers 12 composed of the first particles P1 and the second particles P2. After the material layer is formed on one side of the base material by the material layer forming unit U2, the adhesive layer is applied to the back surface of the base material, and the material layer is formed on the back surface in the same manner. Can be formed. In addition, you may use the double-sided adhesive base material by which the adhesive material was beforehand coated on both surfaces. According to this form, since the ratio of the base material in the laminated body 13 is smaller than in the case of FIG. 11A, the base material is easily lost, but on the other hand, the base material is somewhat difficult to stack.

[Removal unit]
The removal unit U4 is a unit that forms the three-dimensional object 14 by removing the base material 11 by heating from the laminate 13 formed by the laminate unit U3.

FIG. 12 is a diagram schematically showing the configuration of the removal unit U4. The removal unit U <b> 4 includes a transport device 41 that transports the stacked body 13 and a heating furnace 42 that heats the stacked body 13.

The conveying device 41 receives the laminated body 13 from the laminated unit U3 and conveys it to the heating furnace. Similarly to the transport device 31, the transport device 41 is not particularly limited as long as it is a device capable of transporting the stacked body 13, and may be a belt conveyor, a roller, or a robot arm.

The heating furnace 42 is a furnace for heating the laminated body 13. The heating furnace 42 includes a heating unit 421, a pressurizing unit 422, and an atmosphere adjusting unit 423. As the heating furnace 42, a firing furnace used for firing ceramics or the like can be used. The pressurizing unit 422 pressurizes the stacked body 13 being heated in the heating furnace 42 or pressurizes the stacked body 13 before and after heating. In addition, as for the pressurization means 422, it is preferable that the pressurization part which pressurizes the laminated body 13 is formed with the porous body which is easy to let gas pass. The atmosphere adjustment means 423 includes an atmosphere gas supply means 423 a and a decompression means 423 b and adjusts the atmosphere gas in the processing space of the heating furnace 42.

The removal unit U4 is heated at a temperature equal to or higher than the thermal decomposition temperature of the base material (here, the second base material 11b) in the laminated body 13 and lower than the thermal decomposition temperature of each material layer in the laminated body 13. I do. Thereby, the base material in the laminated body 13 can be selectively decomposed and the base material can be removed.

The removal unit U4 preferably loses 90% by weight or more of the base material in the laminate 13 by heating, more preferably 95% by weight or more, and more preferably 97% by weight or more. . At this time, the base material is preferably burned or gasified and released to the outside as a gas. Note that by using a base material formed of an organic material such as a resin as the base material, the base material can be easily removed by heating. As a material constituting the substrate, polyesters such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamides such as nylon, and the like can be used. Among these, it is preferable to use PET from the viewpoint of the decomposition temperature and the low hazard of gas generated at the time of thermal decomposition.

The removal unit U4 preferably exhausts the released gas to the outside of the heating furnace 42 by the decompression means 423b. By setting the inside of the heating furnace 42 to be an oxidizing atmosphere, that is, an atmosphere containing oxygen gas such as air by the atmosphere gas supply means 423a or the like, the substrate can be burned and removed.

When the base material is gasified by thermal decomposition from the laminated body 13 and released as a gas, the material layers in the laminated body 13 may be pushed up to change the shape. Therefore, when heating is performed in the heating furnace 42, it is preferable to pressurize the laminate 13 by the pressurizing unit 422 before or during heating, or during cooling or heat dissipation after heating. Moreover, when pressurizing the laminated body 13 before heating, it is preferable to pressurize in a reduced pressure atmosphere. Thereby, the shape change at the time of removing a base material by heating can be suppressed further, and pressurization during heating can also be omitted. In addition, when pressurizing the laminated body 13 before or after heating, the pressurization may be performed in a portion other than the removal unit U4.

[Post-processing unit]
The post-processing unit U5 is a unit that performs post-processing of the three-dimensional object 14 formed by the removal unit U4.

The type of post-processing performed by the post-processing unit U5 is not particularly limited, and examples thereof include a process in which the three-dimensional object 14 is further heated and baked. In addition, when the post-processing unit U5 performs heat treatment as the post-processing, the removal unit U4 may also serve as the function. By firing the three-dimensional object 14, materials such as the particulate material in each material layer can be sintered together.

In addition, the post-processing unit U5 may also have a pressurizing unit that heats the three-dimensional object 14, similarly to the removal unit U4. The post-processing unit U5 may pressurize the three-dimensional object 14 by a pressurizing unit before or during heating as post-processing, or during cooling or heat dissipation after heating.

Further, the post-processing unit U5 may perform a process of removing at least one kind of material constituting the three-dimensional object 14 from the three-dimensional object 14. For example, when the three-dimensional object 14 is formed of the first particle material P1 and the second particle material P2, after fixing or integrating only the first particle material P1 with each other, Only the second particulate material P2 may be selectively removed by air blowing or the like. At this time, the second particle material P2 functions as a so-called support material in the layered manufacturing method, and has a function of supporting the first particle material P1 during stacking. Thereby, a solid thing can be modeled using the 1st particulate material P1. When only the first particle materials P1 are fixed to each other, for example, a material having a higher sintering temperature than the first particle material P1 is used as the second particle material P2, and the first particle material P1 is used. What is necessary is just to heat at the temperature more than the sintering temperature of this, and the temperature below the sintering temperature of 2nd particle material P2.

As described above, according to this embodiment, it is possible to efficiently manufacture a three-dimensional object in which a desired material is arbitrarily arranged three-dimensionally.

According to the present embodiment, an electrode sheet such as a positive electrode sheet or a negative electrode sheet is formed by forming a material layer on a substrate using a positive electrode material or a negative electrode material of a lithium ion battery or an all-solid battery, or a material containing a solid electrolyte. And a solid electrolyte sheet can be produced. According to the present embodiment, since the particulate material can be densely arranged in an arbitrary pattern, it is possible to provide an electrode sheet or a solid electrolyte sheet having high electrochemical characteristics. In addition, when an electrode sheet is manufactured, a good interface is formed between the positive electrode material or the negative electrode material and the material containing the solid electrolyte by patterning a material containing the solid electrolyte in addition to the positive electrode material or the negative electrode material. be able to. Moreover, an all-solid-state battery can also be manufactured by forming a solid thing using the positive electrode material, the negative electrode material, and the material containing a solid electrolyte.

A three-dimensional object was formed using the additive manufacturing system 1 described above. Specifically, a material layer is formed on a substrate using the material layer forming unit U2 shown in FIG. 3, the substrate on which the material layer is formed is laminated, and the substrate is removed from the laminate by heating. Thus, a three-dimensional electrode sheet, an electrolyte sheet, and an all-solid battery were formed.

In the first belt device 22a and the second belt device 22b, a polyimide resin belt was used as the conveying member 224. Further, as the driving roller 221 and the driving roller 222, stainless steel metal rollers were used, and as the pressure roller 223, a soft roller in which a silicone rubber elastic layer was provided on a stainless steel core was used.

As the first base material 11a, a sheet made of polyester (PET) was used. A concavo-convex pattern having a honeycomb pattern was formed on the first base material 11 a by the pattern forming device 23. First, an ultraviolet curable resin (ultraviolet curable liquid silicone rubber, PDMS, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied on the first substrate 11a. Thereafter, a film mold (standard mold, manufactured by Soken Chemical Co., Ltd.) having a concavo-convex pattern of a honeycomb pattern corresponding to the concavo-convex pattern to be formed was pressed against the ultraviolet curable resin on the first substrate 11a. . With the film mold pressed, the ultraviolet curable resin was cured by irradiating ultraviolet rays with a UV lamp to release the film mold.

FIG. 13 shows the structure of the first base material 11a having the uneven pattern 111a formed on the surface. 13A is a top view of the first base material 11a, and FIG. 13B is a cross-sectional view taken along the line AA of FIG. 13A. As shown in FIG. 13, a honeycomb pattern-shaped uneven pattern having hexagonal frame-shaped protrusions is formed on the surface of the first base material 11 a. Here, as shown in FIG. 13B, the interval between adjacent convex portions (that is, the width of the concave portions) is k (μm), the pitch of the adjacent convex portions is s (μm), and the height of the convex portions (that is, the concave portions). Is d (μm). In the following examples, the shape measurement of the concavo-convex pattern was performed using a non-contact surface / layer cross-sectional shape measurement system (VertScan 2.0 manufactured by Ryoka System Co., Ltd.).

As the second substrate 11b, a sheet made of polyester (PET) having an acrylic adhesive applied on the surface was used.

The first particle P1 and the second particle P2 are LiCoO ₂ (hereinafter LCO), Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ (hereinafter LAGP), Li _6.75 La ₃ Zr _{1. One of 75} Nb _0.25 O ₁₂ (hereinafter referred to as LLZ), Li ₃ BO ₃ (hereinafter referred to as LBO), and graphite was used. Note that lithium cobalt oxide LCO is a positive electrode material, aluminum-substituted germanium lithium lithium LAGP and LLZ, and lithium borate LBO are materials containing a solid electrolyte, and graphite is a negative electrode material. The lithium cobalt oxide LiCoO ₂ can be manufactured by Nippon Chemical Industry Co., Ltd. _Similarly, it is possible to use _{_{_{_{Li 1.5 Al 0.5 Ge 1.5 P 3}}}} O 12. Further, Li _6.75 La ₃ Zr _1.75 Nb _0.25 O ₁₂ can be manufactured by Toyoshima Seisakusho Co., Ltd., and the abbreviation may be LLZNb instead of LLZ. In addition, lithium borate Li ₃ BO ₃ can be manufactured by Toshima Seisakusho Co., Ltd. As graphite, SGP-5 manufactured by SEC Carbon Co., Ltd. can be used.

In addition, as the support material S1 and the support material S2, either a standard carrier (standard carrier P02 manufactured by the Imaging Society of Japan) or an in-house carrier (manufactured by Canon), which is a magnetic particle, was used. The in-house carrier is a particle in which pores of porous ferrite particles are filled with a resin. When forming the material layer 1, the ratio of the first particles P1 in the filler 241a was 17% by weight, and the ratio of the second particles P2 in the filler 241b was 45% by weight.

Based on the first embodiment, the size (interval k, pitch s, depth d) of the uneven pattern 111a formed on the first substrate 11a and the filler are changed as shown in Table 1, and the second Material layers 1 to 7 were formed on the substrate 11b. In forming the material layer 6, a polyester sheet was used as the first substrate 11a, and OP-4003 made by DIC Corporation was used as the ultraviolet curable resin.

The particle diameter of each particle in the filler used when forming each material layer was as shown in Table 2. In Table 2, the particle size (r10, r50, r90) of each particle is the particle size of the cumulative distribution in the particle size distribution on a volume basis, r10 is 10% cumulative, r50 is 50% cumulative, and r90 is 90% cumulative. The particle size. The particle size was measured using a laser diffraction scattering type particle size distribution measuring device (LA-960, manufactured by Horiba, Ltd.).

The density of the formed material layers 1 to 7 was evaluated by the following method. Specifically, the second base material 11b on which each material layer is formed is photographed from the material layer side with an optical microscope, and the coverage of particles in the observation region is determined by image processing software (Adobe Photoshop (registered trademark) manufactured by Adobe Systems). )). As a result, it was found that all the material layers 1 to 4 had a cover rate of 80% or more, and a dense material layer could be formed.

(Examples 1 to 11)
Next, a plurality of second base materials 11b each formed with each material layer were laminated to form a laminate. And the laminated body was transferred to the heating furnace and heated in the heating furnace. The weight of the laminate was measured before and after heating, and the weight ratio (wt%) of the base material before and after heating was evaluated. Further, the upper and lower surfaces of the laminated body after heating were sputtered with gold, and a tester was applied to the upper and lower surfaces to investigate whether or not to leak, and the leaked one was B and the one that did not leak was A. The results are shown in Table 3. In addition, it can be evaluated that what leaks is about 10Ω or less in resistance value.

FIG. 14 is a diagram showing a thermogravimetric analysis result of a polyester (PET) sheet which is the second base material 11b. The thermogravimetric analysis was performed by using a differential thermobalance (TG-DTA manufactured by Rigaku Corporation) and raising the temperature in the air from room temperature (25 ° C.) at a rate of 5 ° C./min. From FIG. 14, the temperature when it was 50% of the initial weight was about 400 ° C., and the temperature when it was 20% of the initial weight was about 500 ° C. In addition, all of LCO, LAGP, LLZ, LBO, and graphite had a thermal decomposition temperature of 510 ° C. or higher.

As shown in Table 3, when the laminated body was formed by changing the material layer, the number of laminated layers, and the heating conditions, a three-dimensional object could be formed in any of the examples. Further, when the temperature of the heat treatment was increased or the heating time was lengthened, the substrate removal rate could be further increased (Examples 3 to 11).

(Examples 12 to 14)
Next, a plurality of second base materials 11b each formed with each material layer were laminated to form a laminate. And the laminated body was transferred to the heating furnace and heated in the heating furnace. Furthermore, the laminate was transferred to a firing furnace and heated and fired in the firing furnace. This produced the all-solid-state battery.

(Example 12)
Four material layers 7 (graphite), two material layers 3 (LAGP), and two material layers 1 (LCO + LAPG) were laminated on the Si substrate with gold sputtered on the surface in order. And the formed laminated body was put into the heating furnace, and it heated for 30 minutes at 500 degreeC under air (atmosphere) in the heating furnace, and the base material was lose | disappeared. Then, it heated at 700 degreeC under vacuum in the sintering furnace for 1 hour. Thereby, the all-solid-state battery 1 was produced.

(Example 13)
On the graphite compact, two material layers 3 (LAGP) and two material layers 1 (LCO + LAPG) were laminated in order for each substrate. And the formed laminated body was put into the heating furnace, and it heated for 30 minutes at 500 degreeC under air (atmosphere) in the heating furnace, and the base material was lose | disappeared. Then, it heated at 700 degreeC under vacuum in the sintering furnace for 1 hour. Thereby, the all-solid-state battery 2 was produced. The graphite compact was formed by pressing graphite powder at 250 MPa with a hydraulic press.

(Example 14)
Four material layers 7 (graphite) were laminated together with the base material under the LLZ compact, and two material layers 5 (LCO + LBO) were laminated together with the base material over the LLZ compact. And the formed laminated body was put into the heating furnace, and it heated for 30 minutes at 500 degreeC under air (atmosphere) in the heating furnace, and the base material was lose | disappeared. After the base material had disappeared, the laminate was pressurized, and then heated in a sintering furnace at 700 ° C. for 1 hour in a vacuum. Thereby, the all-solid-state battery 3 was produced. The LLZ compact was formed by pressurizing LLZ powder with a hydraulic press at 250 MPa, followed by firing at 1150 ° C. for 36 hours in air (atmosphere). The formed LLZ compact was polished with sandpaper on the upper and lower surfaces.

Table 4 shows the evaluation results of the all solid state batteries of Examples 12 to 14.

Each solid state battery was evaluated by performing a charge / discharge test using an electrochemical device (1255WB type manufactured by Solartron). Specifically, A was set when the charge capacity was 10 mAh / g or more and the discharge capacity was 1/10 or more. All the all-solid-state batteries were charged and discharged, and it was confirmed that they operate as secondary batteries.

As described above, according to this example, it was possible to manufacture a battery electrode sheet, an electrolyte sheet, and an all-solid battery. Since the particles constituting each of them can be patterned, a battery having a three-dimensional structure in which the particles are patterned in the plane direction and the stacking direction can be manufactured.

The present invention is not limited to the above embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, in order to make the scope of the present invention public, the following claims are attached.

This application claims priority on the basis of Japanese Patent Application No. 2018-024116 filed on Feb. 14, 2018, the entire contents of which are incorporated herein by reference.

Claims

A material layer forming step of forming a material layer on each of a plurality of substrates,
A stacking step of stacking the plurality of base materials each having the material layer formed thereon to form a stack;
And a removing step of removing the plurality of base materials from the laminate by heating.
The method for producing a three-dimensional object according to claim 1, wherein the removing step is a step of eliminating 90% by weight or more of the base material.
Each of the plurality of material layers is made of the same type of material or a plurality of different types of materials.
The method for producing a three-dimensional object according to claim 1 or 2, wherein the thermal decomposition temperatures of the plurality of base materials are lower than any of the thermal decomposition temperatures of the materials constituting the plurality of material layers.
The method for producing a three-dimensional object according to any one of claims 1 to 3, wherein each of the plurality of base materials is made of an organic material.
The method for producing a three-dimensional object according to claim 4, wherein each of the plurality of material layers is made of an inorganic material.
The method for producing a three-dimensional object according to any one of claims 1 to 5, wherein each of the plurality of material layers is a particle layer in which at least one kind of particles is arranged.
The method for producing a three-dimensional object according to claim 6, wherein at least one of the plurality of material layers constituting the laminate is a particle layer in which a plurality of types of particles are arranged in a pattern. .
The method for producing a three-dimensional object according to claim 6 or 7, wherein a coverage rate of the base material by the particles in each of the plurality of material layers is 80% or more.
The method for producing a three-dimensional object according to any one of claims 1 to 8, wherein each of the plurality of base materials has an adhesive layer on a surface thereof.
The method for producing a three-dimensional object according to any one of claims 1 to 9, further comprising a pressurizing step of pressurizing the laminate after the removing step.
A material layer forming step of forming a material layer on each of a plurality of substrates,
A stacking step of stacking the plurality of base materials each having the material layer formed thereon to form a stack;
And a heating step of heating the laminated body at a temperature equal to or higher than a thermal decomposition temperature of the plurality of base materials.
The plurality of substrates are a single type of substrate or a plurality of types of substrates different from each other,
The method for producing a three-dimensional object according to claim 11, wherein the heating step is a step of heating at a temperature equal to or higher than a highest thermal decomposition temperature among the thermal decomposition temperatures of the plurality of base materials.
The material layer forming step has a step of forming a material layer containing a material containing a solid electrolyte,
The method for producing a three-dimensional object according to any one of claims 1 to 12, wherein the three-dimensional object is a solid electrolyte sheet.
The material layer forming step includes a step of forming a material layer containing a material for forming an electrode,
The method for producing a three-dimensional object according to any one of claims 1 to 12, wherein the three-dimensional object is an electrode sheet.
The material layer forming step includes a step of forming a material layer containing a material containing a solid electrolyte, and a step of forming a material layer containing a positive electrode material or a negative electrode material,
The method for producing a three-dimensional object according to any one of claims 1 to 12, wherein the three-dimensional object is an all-solid battery.
A stacking step of stacking a plurality of base materials each having a material layer formed thereon to form a stack;
And a removing step of removing the plurality of base materials from the laminate by heating.
A method for producing a three-dimensional object having a removing step of removing the plurality of substrates by heating from a laminate in which a plurality of substrates each carrying a material layer is laminated.
A material layer forming unit that respectively forms material layers on a plurality of substrates;
A plurality of the base materials each having the material layer formed thereon, and a laminate unit for forming a laminate;
And a removal unit that removes the base material from the laminate by heating.