JP2017031490A - Method for manufacturing three-dimensional molded object, apparatus for manufacturing three-dimensional molded object, three-dimensional molded object, and composition for manufacturing three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a three-dimensional molded object by which a three-dimensional molded object excellent in dimensional accuracy can be efficiently manufactured while suppressing waste in materials.SOLUTION: The method for manufacturing a three-dimensional molded object aims to laminate layers formed into predetermined patterns to manufacture a three-dimensional molded object by repeating a sequence of steps including: a discharge step of discharging a composition comprising particles and a thixotropic material while applying external force to the composition to reduce the viscosity of the composition; and a joining step of, after the composition comes into contact with a target portion, imparting energy to the composition to join the particles.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a three-dimensional structure, a three-dimensional structure manufacturing apparatus, a three-dimensional structure, and a composition for manufacturing a three-dimensional structure.

  Conventionally, for example, a method of forming a three-dimensional structure based on model data of a three-dimensional object generated by three-dimensional CAD software, a three-dimensional scanner, or the like is known.

  As a method of forming a three-dimensional structure, a lamination method (three-dimensional structure method) is known. In the laminating method, generally, after the model data of the three-dimensional object is divided into a large number of two-dimensional cross-sectional layer data (slice data), the cross-sectional members corresponding to each two-dimensional cross-sectional layer data are sequentially formed, Are sequentially laminated to form a three-dimensional structure.

  The layering method can be formed immediately as long as there is model data of the 3D model to be modeled, and there is no need to create a mold prior to modeling, so it is quick and inexpensive. It is possible to form an original model. In addition, since thin plate-like cross-sectional members are laminated one by one, for example, even a complex object having an internal structure can be formed as an integrated shaped object without being divided into a plurality of parts. .

  As such a laminating method, there is a technique for forming a three-dimensional structure by forming a material layer using a material containing metal powder and a solvent, irradiating the material layer with a light beam, and joining the metal powder. It is known (see, for example, Patent Document 1).

  However, in such a technique, only a part of the material constituting the material layer is irradiated with the light beam and sintered, so that the material layer constituting the portion not irradiated with the light beam is only removed. It was a useless part. In addition, there is a problem that the dimensional accuracy of the three-dimensional structure is lowered because the metal powder is sintered in the vicinity of the irradiation region of the predetermined light beam, although it is incomplete in the vicinity thereof.

  In addition, it is conceivable to apply a material containing a metal powder and a solvent in a predetermined pattern. In such a case, if the material has a high viscosity, it becomes difficult to discharge the material itself, and the viscosity of the material If it is low, there is a problem that the discharged material unwillingly spreads out and the desired shape cannot be maintained.

JP 2008-184622 A

  An object of the present invention is to provide a manufacturing method of a three-dimensional structure that can efficiently manufacture a three-dimensional structure that is excellent in dimensional accuracy while suppressing the generation of waste of the material. To provide a three-dimensional structure manufacturing apparatus that can efficiently manufacture a three-dimensional structure excellent in dimensional accuracy, to provide a three-dimensional structure excellent in dimensional accuracy, An object of the present invention is to provide a composition for manufacturing a three-dimensional structure that can be suitably used for manufacturing a three-dimensional structure excellent in accuracy.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention includes an ejection step in which an external force is applied to a composition containing particles and a thixotropic material, and the composition is ejected in a state where the viscosity is reduced,
A bonding step of applying energy and bonding the particles after the composition contacts a target site;
By repeating a series of steps including the above, a layer formed in a predetermined pattern is laminated to produce a three-dimensional structure.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture efficiently the three-dimensional structure excellent in dimensional accuracy can be provided, suppressing generation | occurrence | production of the waste of material.

  In the method for producing a three-dimensional structure of the present invention, it is preferable that the viscosity of the composition is reduced by stirring during the discharging step.

  Thereby, according to the kind of composition etc., the provision conditions of external force can be adjusted suitably. Also, an external force can be suitably applied to a relatively large amount of the composition. Further, even when the dispersion stability of the particles in the composition is low, the dispersion state of the particles at the time of ejection can be improved by stirring.

  In the method for producing a three-dimensional structure of the present invention, it is preferable that the viscosity of the composition is reduced by applying vibration during the discharging step.

  Thereby, simplification of the structure of the apparatus used for manufacture of a three-dimensional structure can be achieved. Moreover, the maintenance of the apparatus used for manufacture of a three-dimensional structure becomes easy. Moreover, mixing of bubbles into the composition can be more effectively prevented, and the ejection stability of the composition can be further improved.

  In the three-dimensional structure manufacturing method of the present invention, the composition preferably contains a polysaccharide as the thixotropic material.

  Thereby, the dimensional accuracy and productivity of a three-dimensional structure can be made compatible at a higher level. In addition, the storage stability of the composition can be improved, and a three-dimensional structure can be manufactured stably over a longer period of time. In addition, the storage conditions of the composition are relaxed, and storage and management become easy.

  In the three-dimensional structure manufacturing method of the present invention, the composition preferably further contains a binder.

  Thereby, the dimensional accuracy of a three-dimensional structure can be made more excellent. Moreover, adjustment of the porosity (porosity) in a three-dimensional structure, the density of a three-dimensional structure, etc. can be performed suitably.

  In the three-dimensional structure manufacturing method of the present invention, the composition preferably contains a curable resin as the binder.

  Accordingly, even a three-dimensional structure having a complicated shape or a fine structure can be more suitably manufactured. In addition, the productivity of the three-dimensional structure can be improved.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the composition includes the particles composed of a material including at least one of a metal material and a ceramic material.

  Thereby, the texture (a high-class feeling), mechanical strength, durability, etc. of a three-dimensional structure can be made more excellent.

  In the three-dimensional structure manufacturing method of the present invention, the composition preferably contains a volatile solvent.

  Thereby, the viscosity adjustment of a composition can be performed suitably and the discharge stability of a composition can be made more excellent. In addition, since volatile solvents can be efficiently removed in the manufacturing process of a three-dimensional structure, it is effective to prevent harmful effects caused by unintentionally remaining in the finally obtained three-dimensional structure. Can be prevented.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable to further include a step of removing the solvent.

  Thereby, the productivity of the three-dimensional structure can be further improved. In addition, for example, unintentional deformation of the layer due to rapid volatilization (e.g. bumping) of the solvent in the joining process can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure is more reliably improved. can do.

  In the three-dimensional structure manufacturing method of the present invention, the joining step is preferably performed by laser irradiation.

  Thereby, the productivity of the three-dimensional structure can be further improved. Moreover, since energy efficiency can be made excellent, it is advantageous also from an energy-saving viewpoint.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the viscosity of the composition in the discharging step is 1 mPa · s or more and 30 mPa · s or less.

  Thereby, the discharge stability of a composition can be made more excellent, and the productivity of a three-dimensional structure can be made more excellent.

  In the method for producing a three-dimensional structure of the present invention, it is preferable that the viscosity when the discharged composition comes into contact with a target site is 5 mPa · s or more and 100 mPa · s or less.

  Thereby, the dimensional accuracy, mechanical strength, etc. of a three-dimensional structure can be made more excellent.

The three-dimensional structure manufacturing apparatus of the present invention applies an external force to the composition containing particles and a thixotropic material, and a viscosity reducing means for reducing the viscosity,
Discharge means for discharging the composition in a state of reduced viscosity;
And a bonding energy applying means for applying energy for bonding the particles after the composition contacts a target site.

  Accordingly, it is possible to provide a three-dimensional structure manufacturing apparatus that can efficiently manufacture a three-dimensional structure excellent in dimensional accuracy while suppressing the generation of waste of material.

The three-dimensional structure of the present invention is manufactured using the method for manufacturing a three-dimensional structure of the present invention.
Thereby, the three-dimensional structure excellent in dimensional accuracy can be provided.

The three-dimensional structure of the present invention is manufactured using the three-dimensional structure manufacturing apparatus of the present invention.
Thereby, the three-dimensional structure excellent in dimensional accuracy can be provided.

The composition for producing a three-dimensional structure of the present invention is a composition used for producing a three-dimensional structure by laminating layers formed in a predetermined pattern.
It contains particles and a thixotropic material, and is characterized in that the viscosity is lowered by the addition of external force.

  Thereby, the composition for three-dimensional structure manufacture which can be used suitably for manufacture of the three-dimensional structure excellent in dimensional accuracy can be provided.

It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is a flowchart which shows an example of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows typically suitable embodiment of the three-dimensional structure manufacturing apparatus of this invention.

Hereinafter, preferred embodiments will be described in detail with reference to the accompanying drawings.
<Method for producing three-dimensional structure>
First, the manufacturing method of the three-dimensional structure according to the present invention will be described.

  FIGS. 1-10 is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the three-dimensional structure of this invention, FIG. 11 is an example of the manufacturing method of the three-dimensional structure of this invention. It is a flowchart which shows.

  As shown in FIG. 1 to FIG. 10 and FIG. 11, in the manufacturing method of the three-dimensional structure 10 of this embodiment, an external force is applied to the composition 1 ′ containing the particles 11 and the thixotropic material to reduce the viscosity. The discharge process (see FIGS. 1 and 5) for discharging the composition 1 ′ and the bonding process (FIGS. 4 and 5) for applying energy and bonding the particles 11 after the composition 1 ′ has contacted the target site. 8), and sequentially repeating these steps, the layers 1 formed in a predetermined pattern are stacked (see FIG. 9) to obtain the target three-dimensional structure 10 (see FIG. 10). ).

  In this way, the composition 1 ′ containing the thixotropic material is used for the production of the three-dimensional structure 10 (formation of the joint portion 2), and the composition 1 ′ in a state where the viscosity is reduced by applying external force is discharged. By this, the viscosity (fluidity) at the time of discharge of composition 1 'and the viscosity (fluidity) at the time of contacting the target site | part (adherence) can be made different. Thereby, it is possible to effectively prevent the composition from spreading unintentionally when the composition 1 ′ comes into contact with the target site while ensuring excellent dischargeability of the composition 1 ′. . As a result, it is possible to efficiently manufacture the three-dimensional structure 10 having excellent dimensional accuracy while suppressing generation of waste of material.

Hereinafter, each step will be described in detail.
≪Discharge process≫
In the discharging step, a composition (a composition for manufacturing a three-dimensional structure) 1 ′ containing particles 11 and a thixotropic material is discharged (see FIGS. 1 and 5). In particular, in the present embodiment, a composition 1 ′ including particles 11 as a dispersoid and at least a part of other components as a dispersion medium 12 for dispersing the particles (dispersoid) 11 is discharged. In particular, in this step, the composition 1 ′ is discharged in a state where an external force is applied in advance to the composition 1 ′ containing the thixotropic material. As described above, by applying an external force to the composition 1 ′ containing the thixotropic material prior to discharge, the viscosity of the composition 1 ′ can be reduced. For this reason, discharge of composition 1 'at this process can be performed smoothly.

The composition 1 ′ will be described in detail later.
The external force applied to the composition 1 ′ during this step may be given by any method, but can be given, for example, by stirring.

  Thereby, external force application conditions (for example, stirring speed, stirring force, stirring energy, stirring blade shape (for example, propeller, paddle, turbine, anchor, helical ribbon shape, etc.), etc.) depending on the type of composition 1 ′, etc. Can be suitably adjusted. Also, an external force can be suitably applied to a relatively large amount of the composition 1 '. Further, even when the dispersion stability of the particles 11 in the composition 1 ′ is low, the dispersion state of the particles 11 at the time of ejection can be improved by stirring.

  Agitation of the composition 1 ′ prior to the discharging step can be performed, for example, at an agitation speed of 100 rpm to 200 rpm.

  As a result, the effect of lowering the viscosity of the composition 1 ′ due to external force is more significantly exhibited while preventing the apparatus from becoming large. Moreover, the dispersion state of the particles 11 at the time of discharge can be made better.

In addition, an external force applied to the composition 1 ′ during this step can be applied by vibration.
Thereby, simplification of the structure of the apparatus (three-dimensional structure manufacturing apparatus) used for manufacture of the three-dimensional structure 10 can be achieved. Moreover, the maintenance of the three-dimensional structure manufacturing apparatus becomes easy. Moreover, mixing of bubbles into the composition 1 ′ can be more effectively prevented, and the ejection stability of the composition 1 ′ can be further improved.

  The frequency of vibration applied to the composition 1 ′ prior to the discharging step is not particularly limited, but is preferably 15 kHz to 1000 kHz, and more preferably 25 kHz to 950 kHz.

  Thereby, the effect of reducing the viscosity of the composition 1 ′ due to external force is more remarkably exhibited. In addition, widely used ultrasonic transducers can be suitably applied.

  The viscosity of the composition 1 ′ in this step (viscosity in a state where the viscosity is reduced by applying an external force) is preferably 1 mPa · s or more and 45 mPa · s or less, and preferably 3 mPa · s or more and 40 mPa · s or less. Is more preferable.

  Thereby, the discharge stability of the composition 1 ′ can be further improved, and the productivity of the three-dimensional structure 10 can be further improved.

  In this specification, the viscosity means a value measured using an E-type viscometer (for example, VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.) unless otherwise specified.

  In addition, the amount of decrease in the composition 1 ′ due to the application of external force (the difference between the viscosity in a state where the external force was not applied and the viscosity in the state where the external force was applied) was 5 mPa · s or more and 30 mPa · s. It is preferably s or less, more preferably 10 mPa · s or more and 25 mPa · s or less.

  Thereby, the effect of the present invention by using the composition containing the thixotropic material is more remarkably exhibited, improving the discharge stability of the composition, improving the productivity of the three-dimensional structure, and the dimensions of the three-dimensional structure. The effect such as improvement in accuracy becomes more remarkable.

  The composition 1 ′ can be discharged using, for example, various discharge devices such as an ink jet device and various dispensers. In this step, it is preferable to discharge the composition 1 ′ as droplets.

  Thereby, for example, it is possible to more suitably cope with the production of the three-dimensional structure 10 having a fine structure, and the dimensional accuracy of the three-dimensional structure 10 can be further improved.

  In general, for example, when a composition containing particles is discharged as droplets compared to a case where a paste-like composition containing particles is continuously supplied, the composition has a lower viscosity (more High fluidity) is required, but simply applying a composition adjusted to a low viscosity (for example, a composition adjusted for viscosity by dilution with a solvent, etc.) to the intended site There is a problem in that the discharged material unintentionally wets and spreads, and a desired shape cannot be maintained. On the other hand, in the present invention, a composition containing a thixotropic material is used, and the viscosity is reduced by an external force when the composition is discharged. The fluidity at the time of contact with the body is different. Therefore, by discharging the composition 1 ′ as droplets in this step, the above-described problems are effectively generated while enjoying the benefits of discharging the composition 1 ′ as droplets as described above. Therefore, the effect of the present invention is more remarkably exhibited.

  The droplets of the composition 1 ′ ejected in this step preferably have a volume per droplet of 1 pL or more and 100 pL or less, and more preferably 2 pL or more and 80 pL or less.

  Thereby, for example, it is possible to more suitably cope with the manufacture of the three-dimensional structure 10 having a fine structure, the dimensional accuracy of the three-dimensional structure 10 can be made more excellent, and three-dimensional The productivity of the shaped article 10 can be further improved.

  In particular, in the first discharge step, the composition 1 ′ is discharged in a predetermined pattern toward the surface of the stage (support) M41 (see FIG. 1). In the second and subsequent discharge steps, the composition 1 is first discharged. The composition 1 ′ is discharged in a predetermined pattern toward the layer 1 having the joint portion 2 formed using “(see FIG. 5). That is, in the first discharge step, the stage (support) M41 is an adherend of the composition 1 ′ (see FIG. 2), and in the second and subsequent discharge steps, the previously formed layer 1 is the composition. 1 ′ adherend (see FIG. 6).

  As described above, the composition 1 ′ is in a state in which the viscosity is lowered by applying an external force during the discharging process, but after discharging, such an external force acts on the composition 1 ′. Therefore, the viscosity of composition 1 ′ after ejection increases. That is, the fluidity of the composition 1 ′ when the composition 1 ′ contacts the target site (see FIGS. 2 and 6) is lower than the fluidity of the composition 1 ′ in the discharging process. be able to. Therefore, it is possible to effectively prevent unintentional deformation (wetting spread, etc.) after the composition 1 ′ contacts the target site while making the discharge property of the composition 1 ′ excellent. It is possible to achieve both high productivity of the original shaped article 10 and excellent dimensional accuracy.

  The viscosity at the time when the discharged composition 1 ′ is in contact with the target site (adherent) is preferably 5 mPa · s or more and 100 mPa · s or less, and preferably 10 mPa · s or more and 80 mPa · s or less. More preferred.

  Thereby, the dimensional accuracy, mechanical strength, etc. of the three-dimensional structure 10 can be made more excellent.

  Further, when the viscosity of the composition 1 ′ in the discharging step is η0 [mPa · s] and the viscosity of the composition 1 ′ at the time of contact with the adherend is η1 [mPa · s], 4 ≦ η1− It is preferable to satisfy the relationship of η0 ≦ 80, and it is more preferable to satisfy the relationship of 7 ≦ η1−η0 ≦ 60.

  Thereby, productivity of the three-dimensional structure 10 and dimensional accuracy of the three-dimensional structure 10 can be made compatible at a higher level.

  In the case where the composition 1 ′ used in the discharging process contains a volatile solvent, a solvent removing process for removing the solvent may be performed prior to the joining process described in detail later.

  Thereby, the productivity of the three-dimensional structure 10 can be further improved. In addition, for example, unintentional deformation of the layer 1 due to rapid volatilization (such as bumping) of the solvent in the joining process can be prevented more effectively, and the dimensional accuracy of the three-dimensional structure 10 is more reliably improved. Can be.

  When performing a solvent removal process, the said process can be performed by heat processing or pressure reduction processing, for example.

  Even when the solvent removal step is performed, it is not necessary to completely remove the solvent from the composition 1 ′ used in the bonding step. Even in such a case, the remaining solvent can be removed by the energy applied in the joining step.

≪Support material application process≫
In the present embodiment, the support material (support portion) 5 is formed using the support material forming composition 5 ′ together with the composition 1 ′ described above (see FIGS. 3 and 7).

  Thereby, in the case where a plurality of layers 1 are stacked, even if the portion where the joint portion 2 is to be newly formed is not in contact with the joint portion 2 of the previously formed layer 1, the newly joined portion The site | part which should form the part 2 can be supported suitably. From such a thing, the three-dimensional structure 10 of various shapes can be manufactured with the outstanding dimensional accuracy.

  The support material forming composition 5 ′ can be discharged, for example, by the same method as that for the composition 1 ′ described above.

≪Join process≫
After the composition 1 ′ contacts the target site (adhered body), energy is applied to the composition 1 ′ (see FIGS. 4 and 8).

  Thereby, the particle | grains 11 contained in the composition 1 'join, and the junction part 2 is formed. By forming the joint portion 2 in this way, the subsequent unintentional movement of the particles 11 is prevented, and the dimensional accuracy of the three-dimensional structure 10 can be improved. In addition, the joint portion 2 formed in this manner is generally one in which the particles 11 are firmly joined. In addition, in this step, when the layer 1 having the bonding portion 2 formed on the lower side of the layer 1 to which energy is applied, generally, the bonding portion 2 of the lower layer 1 is newly added. The formed joint portion 2 is firmly joined. For this reason, the mechanical strength of the finally obtained three-dimensional structure 10 can be made excellent.

  Further, in this step, by applying energy, the particles 11 can be joined and unnecessary components other than the particles 11 can be removed. For example, binders, solvents and the like can be removed, and these components can be effectively prevented from remaining in the joint 2 where they are formed.

  The form of joining varies depending on the constituent material of the particles 11, and examples thereof include fusion, sintering, and melting.

  Application of energy to the composition 1 ′ in this step may be performed by any method, but is preferably performed by irradiation with energy rays.

  Thereby, energy can be selectively given to the composition 1 ′, and the energy efficiency of the formation of the joint portion 2 can be further improved.

  In this step, the energy rays irradiated to the composition 1 ′ vary depending on the constituent material of the particles 11, but for example, ultraviolet rays, visible rays, infrared rays, X-rays, γ rays, electron beams, ion beams, neutrons. Line, alpha ray, arc discharge, plasma discharge, and the like. Of these, infrared is preferable.

  Thereby, joining of particle | grains 11, removal of the binder etc. which are mentioned later can be performed more efficiently, and the productivity of the three-dimensional structure 10 can be made more excellent. Moreover, since energy efficiency can be made excellent, it is advantageous also from an energy-saving viewpoint. Moreover, the unintentional modification | denaturation of the constituent material of the particle | grains 11 can be prevented more effectively.

In this step, laser irradiation is preferable.
Thereby, joining of particle | grains 11, removal of the binder etc. which are mentioned later can be performed more efficiently, and the productivity of the three-dimensional structure 10 can be made more excellent. Moreover, since energy efficiency can be made excellent, it is advantageous also from an energy-saving viewpoint.

  Examples of lasers that can be used in this step include solid lasers such as ruby lasers, YAG lasers, Nd: YAG lasers, titanium sapphire lasers, and semiconductor lasers; liquid lasers such as dye lasers; neutral atom lasers (helium neon lasers) Etc.), ion laser (argon ion laser, etc.), molecular laser (carbon dioxide laser, nitrogen laser, etc.), excimer laser, metal vapor laser (helium cadmium laser, etc.), etc .; free electron laser; oxygen-iodine chemical laser And chemical lasers such as hydrogen fluoride laser; fiber lasers and the like.

  When this step is performed by laser irradiation, the beam diameter of the laser irradiated on the composition 1 ′ is preferably 0.5 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less.

  Thereby, the joining part 2 can be formed more efficiently while making the dimensional accuracy of the three-dimensional structure 10 more excellent, and the productivity of the three-dimensional structure 10 can be made more excellent. .

The output of the laser is not particularly limited, but is preferably 50 W or more and 100 W or less.
Thereby, the junction part 2 can be formed efficiently, preventing the enlargement of an apparatus.

  Although the thickness of the layer 1 in which the junction part 2 was formed in this process is not specifically limited, It is preferable that they are 10 micrometers or more and 500 micrometers or less, and it is more preferable that they are 20 micrometers or more and 250 micrometers or less.

  Thereby, while making the productivity of the three-dimensional structure 10 excellent, the dimensional accuracy of the three-dimensional structure 10 can be made more excellent.

≪Support material (support part) removal process≫
Then, after repeating the series of steps as described above (see FIG. 9), the support material 5 is removed as a post-processing step (see FIG. 10). Thereby, the three-dimensional structure 10 is taken out.

  Specific methods of this step include, for example, a method of removing the support material 5 with a brush, a method of removing the support material 5 by suction, a method of blowing a gas such as air, and a method of applying a liquid such as water ( Examples thereof include a method of immersing the laminate obtained as described above in a liquid, a method of spraying a liquid, and a method of applying vibration such as ultrasonic vibration. Moreover, it can carry out combining 2 or more types of methods selected from these.

  According to the manufacturing method of the present invention as described above, a three-dimensional structure excellent in dimensional accuracy can be efficiently manufactured while suppressing the generation of waste of material.

  In the illustrated configuration, the above-described steps are described as being sequentially performed for easy understanding. However, different steps are performed simultaneously in each part of the modeling region (space on the stage). Also good.

《Three-dimensional structure manufacturing device》
Next, the three-dimensional structure manufacturing apparatus of this invention is demonstrated.

  FIG. 12 is a cross-sectional view schematically showing a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention.

  As shown in FIG. 12, the three-dimensional structure manufacturing apparatus M100 applies the external force to the control unit M2, the composition 1 ′ containing the particles 11 and the thixotropic material, and reduces the viscosity, and the viscosity is reduced. A composition supply unit (discharge unit) M3 that discharges the lowered composition 1 ′ and a bonding energy applying unit that applies energy for bonding the particles 11 after the composition 1 ′ has contacted the target site. M6 and a support material forming composition supply unit (support material forming composition discharging means) M8 that discharges the support material forming composition 5 ′ used for forming the support material (supporting portion) 5 are provided.

The control unit M2 includes a computer M21 and a drive control unit M22.
The computer M21 is a general desktop computer configured with a CPU, a memory, and the like inside. The computer M21 converts the shape of the three-dimensional structure 10 as model data, and outputs cross-sectional data (slice data) obtained by slicing the shape into parallel thin layers of slices to the drive control unit M22. .

  The drive control unit M22 includes a viscosity reducing unit M1, a composition supply unit (discharge unit) M3, a layer forming unit M4, a bonding energy applying unit M6, and a support material forming composition supply unit (support material forming composition discharge unit). It functions as a control means for driving M8 and the like. Specifically, for example, the external force (energy) applied to the composition 1 ′ by the viscosity reducing unit M1, the discharge pattern and discharge amount of the composition 1 ′ by the composition supply unit (discharge unit) M3, the composition for forming the support material Discharge pattern and discharge amount of the support material forming composition 5 ′ by the material supply unit (support material forming composition discharge unit) M8, energy application pattern and application amount by the bonding energy application unit M6, stage (elevating stage) M41 Controls the amount of descent, etc.

  The viscosity lowering means M1 applies an external force to the composition 1 'in response to a command from the drive control unit M22 to reduce the viscosity of the composition 1'.

  As the viscosity reducing means M1, for example, a stirring means for stirring the composition 1 'can be used.

  Thereby, according to the kind etc. of composition 1 ', the provision conditions (for example, stirring speed, stirring force, stirring energy, etc.) of external force can be adjusted suitably. Also, an external force can be suitably applied to a relatively large amount of the composition 1 '. Further, even when the dispersion stability of the particles 11 in the composition 1 ′ is low, the dispersion state of the particles 11 at the time of ejection can be improved by stirring.

  Further, as the viscosity reducing unit M1, for example, a vibrating unit that applies vibration to the composition 1 'can be used.

  Thereby, simplification of the structure of the three-dimensional structure manufacturing apparatus M100 can be achieved. In addition, maintenance of the three-dimensional structure manufacturing apparatus M100 is facilitated. In addition, it is possible to more effectively prevent bubbles from being mixed into the composition 1 ′, and the ejection stability of the composition 1 ′ can be further improved.

  As the vibration means, for example, an ultrasonic vibrator that applies ultrasonic vibration can be suitably used.

  Since the ultrasonic vibrator can generate vibrations having a frequency that more effectively causes a decrease in the viscosity of the composition 1 ′, the use of the ultrasonic vibrator has the effects described above. It is more prominent. In addition, various types of ultrasonic vibrators are widely distributed, are easily available, and are advantageous from the viewpoint of cost reduction of the three-dimensional structure manufacturing apparatus M100 and the three-dimensional structure 10.

  The layer forming part M4 is supplied with the composition 1 ′ and the support material forming composition 5 ′, and is composed of the composition 1 ′ (joining part 2) and the support material forming composition 5 ′ (support material 5). It has a stage (elevating stage) M41 that supports the layer 1 and a frame M45 that surrounds the elevating stage M41.

  When the new layer 1 is formed on the previously formed layer 1, the elevating stage M41 is sequentially lowered by a predetermined amount according to a command from the drive control unit M22. The thickness of the newly formed layer 1 is defined by the descending amount of the elevating stage M41.

  The stage M41 has a flat surface (site to which the composition 1 'and the support material forming composition 5' are applied). Thereby, the layer 1 with high uniformity of thickness can be formed easily and reliably.

  Stage M41 is preferably made of a high-strength material. Examples of the constituent material of the stage M41 include various metal materials such as stainless steel.

  Further, the surface of the stage M41 (site to which the composition 1 'and the support material forming composition 5' are applied) may be subjected to a surface treatment. Thereby, for example, the constituent material of the composition 1 ′ and the constituent material of the support material forming composition 5 ′ can be more effectively prevented from firmly attaching to the stage M41, or the durability of the stage M41 can be improved. In particular, the three-dimensional structure 10 can be produced stably over a longer period of time. Examples of the material used for the surface treatment of the surface of the stage M41 include fluorine resins such as polytetrafluoroethylene.

  The composition supply unit (discharge means) M3 is moved by a command from the drive control unit M22, and the composition 1 'accommodated therein is supplied to the stage M41.

  The composition supply unit (discharge means) M3 is configured to discharge the composition 1 '.

  Examples of the composition supply unit (discharge means) M3 include an ink jet head and various dispensers, and it is particularly preferable to discharge the composition 1 'as droplets. Thereby, the composition 1 ′ can be applied in a fine pattern, and even the three-dimensional structure 10 having a fine structure can be manufactured with particularly high productivity.

  As a droplet discharge method using an inkjet method, for example, a piezo method, a method in which the composition 1 ′ is discharged with bubbles generated by heating the composition 1 ′, or the like can be used.

  The composition supply unit (ejection means) M3 controls the pattern of the bonding portion 2 to be formed in each layer 1 and the amount of the composition 1 ′ applied in each portion of the layer 1 according to a command from the drive control unit M22. . A discharge pattern, a discharge amount, and the like of the composition 1 ′ by the composition supply unit (discharge unit) M <b> 3 are determined based on slice data. As a result, a necessary and sufficient amount of the composition 1 ′ can be applied, the joint portion 2 having a desired pattern can be reliably formed, and the dimensional accuracy of the three-dimensional structure 10 is more reliably improved. Can be.

  The distance between the tip of the composition supply unit (discharge means) M3 (discharge surface of the composition 1 ′) and the surface of the adherend that the composition 1 ′ contacts is preferably 1 mm or more and 20 mm or less. It is preferably 15 mm or less.

  Thereby, the position accuracy of the composition 1 ′ with respect to the adherend (for example, the landing position accuracy when the composition 1 ′ is applied as a droplet) is further improved, and in contact with the adherend. The viscosity of composition 1 ′ can be greater. As a result, the dimensional accuracy of the three-dimensional structure 10 can be further improved.

  The size (nozzle diameter) of the discharge portion of the composition supply portion (discharge means) M3 is not particularly limited, but is preferably 20 μm or more and 150 μm or less.

  Thereby, while making the dimensional accuracy of the three-dimensional structure 10 more excellent, the productivity of the three-dimensional structure 10 can be made more excellent.

  The bonding energy applying means M6 applies energy for bonding the particles 11 contained in the composition 1 'after the composition 1' has contacted the target site.

  Thereby, the particle | grains 11 contained in the composition 1 'can join, and the junction part 2 can be formed.

  Moreover, it is preferable that the joining energy provision means M6 irradiates an energy ray.

  Thereby, energy can be selectively given to the composition 1 ′, and the energy efficiency of the formation of the joint portion 2 can be further improved.

Moreover, it is preferable that the joining energy provision means M6 irradiates a laser.
Thereby, joining of the particle | grains 11, removal of a binder, etc. can be performed more efficiently, and the productivity of the three-dimensional structure 10 can be made more excellent. Moreover, since energy efficiency can be made excellent, it is advantageous also from an energy-saving viewpoint.

  The support material forming composition supply section (support material forming composition discharging means) M8 is configured to discharge the support material forming composition 5 'used for forming the support material (support section) 5.

  As the support material forming composition supply unit (support material forming composition discharge unit) M8, for example, as in the case of the composition supply unit (discharge unit) M3 described above, an inkjet head, various dispensers, and the like can be given. In particular, the composition 1 ′ is preferably ejected as droplets.

  Accordingly, the support material forming composition 5 ′ can be applied in a fine pattern, the amount of use of the support material forming composition 5 ′ can be suppressed, and the three-dimensional structure having a fine structure. Even if it is 10, it can be manufactured with particularly high productivity.

  The support material forming composition supply unit (support material forming composition discharging means) M8 is provided with a pattern of the support material 5 to be formed in each layer 1 and a support applied to each part of the layer 1 according to a command from the drive control unit M22. The amount of the material forming composition 5 ′ is controlled. The discharge pattern, the discharge amount, and the like of the support material forming composition 5 ′ by the support material forming composition supply unit (support material forming composition discharging means) M <b> 8 are determined based on the slice data. As a result, a necessary and sufficient amount of the support material forming composition 5 ′ can be applied, and the support material (support portion) 5 having a desired pattern can be reliably formed. The accuracy and the like can be more reliably improved.

  According to the three-dimensional structure manufacturing apparatus of the present invention as described above, a three-dimensional structure excellent in dimensional accuracy can be efficiently manufactured while suppressing the generation of waste of material.

<< Composition (Composition for manufacturing a three-dimensional structure) >>
Next, the composition of the present invention (a composition for producing a three-dimensional structure) will be described.

  The composition (composition for producing a three-dimensional structure) of the present invention is a composition used for producing a three-dimensional structure by laminating layers formed in a predetermined pattern, and particles, thixo And a tropic material, and the viscosity is lowered by the addition of external force.

  Such a composition (a composition for producing a three-dimensional structure) can be suitably used for the production of a three-dimensional structure excellent in dimensional accuracy.

  The composition (composition for producing a three-dimensional structure) of the present invention can be suitably applied to a method for producing a three-dimensional structure as described above and a three-dimensional structure production apparatus.

(particle)
The composition 1 ′ includes a plurality of particles 11.

  Since the composition (composition for producing a three-dimensional structure) 1 ′ includes the particles 11, the selection of the constituent material of the three-dimensional structure 10 can be widened, and desired physical properties and textures can be obtained. The three-dimensional structure 10 having the above can be suitably obtained. For example, when a three-dimensional structure is manufactured using a material dissolved in a solvent, there are restrictions on the materials that can be used, but such restrictions are eliminated by using the composition 1 ′ including the particles 11. be able to. Further, for example, the mechanical strength, toughness, durability, and the like of the three-dimensional structure 10 can be further improved, and the three-dimensional structure 10 can be applied not only as a trial use but also as an actual product.

  Examples of the constituent material of the particles 11 include metal materials, metal compounds (ceramics, etc.), resin materials, pigments, and the like.

  In particular, if the composition 1 ′ includes particles 11 that are composed of a material including at least one of a metal material and a ceramic material, for example, the texture (high-quality feeling) and mechanical strength of the three-dimensional structure 10. Further, durability and the like can be improved.

  In particular, when the particles 11 are made of a material containing a metal material, the three-dimensional structure 10 can have a particularly high-class feeling, weight feeling, mechanical strength, toughness, and the like. Moreover, since the heat dissipation after applying the energy for joining the particles 11 proceeds efficiently, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Examples of the metal material constituting the particles 11 include magnesium, iron, copper, cobalt, titanium, chromium, nickel and alloys containing at least one of these (for example, maraging steel, stainless steel, cobalt chromium molybdenum, titanium alloy). , Nickel based alloys, aluminum alloys, etc.).

  Examples of the metal compound constituting the particles 11 include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; magnesium hydroxide, aluminum hydroxide, water Various metal hydroxides such as calcium oxide; various metal nitrides such as silicon nitride, titanium nitride and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; calcium carbonate and magnesium carbonate Carbonate of various metals such as calcium sulfate, sulfate of various metals such as magnesium sulfate, silicate of various metals such as calcium silicate and magnesium silicate, phosphate of various metals such as calcium phosphate, aluminum borate Borate salts of various metals such as magnesium borate, and composites thereof. .

  Examples of the resin material constituting the particles 11 include polybutylene terephthalate, polyethylene terephthalate, polypropylene, polystyrene, syndiotactic polystyrene, polyacetal, modified polyphenylene ether, polyether ether ketone, polycarbonate, acrylonitrile-butadiene-styrene copolymer. (ABS resin), polyether nitrile, polyamide (nylon, etc.), polyarylate, polyamide imide, polyether imide, polyimide, liquid crystal polymer, polysulfone, polyether sulfone, polyphenylene sulfide, fluorine resin and the like.

  As the pigment constituting the particles 11, both inorganic pigments and organic pigments can be used.

Examples of the inorganic pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, titanium oxide, and the like, and one kind selected from these. Alternatively, two or more kinds can be used in combination.
Among the inorganic pigments, titanium oxide is preferable in order to exhibit a preferable white color.

  Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments and the like can be mentioned, and one or more selected from these can be used in combination.

  The shape of the particle 11 is not particularly limited, and may be any shape such as a spherical shape, a spindle shape, a needle shape, a cylindrical shape, and a scale shape, and may be an indefinite shape, but has a spherical shape. It is preferable.

  The average particle diameter of the particles 11 is not particularly limited, but is preferably 0.5 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less.

  Thereby, the fluidity | liquidity of the composition 1 'can be made suitable, a discharge process can be performed more smoothly, and joining of the particle | grains 11 in a joining process can be performed more suitably. Further, for example, it is possible to efficiently remove the binder and the like in the joining process, and more effectively prevent constituent materials other than the particles 11 from remaining in the final three-dimensional structure 10 unintentionally. can do. Therefore, the productivity and the mechanical strength of the three-dimensional structure 10 to be manufactured can be further improved while the productivity of the three-dimensional structure 10 is more excellent. It is possible to more effectively prevent the occurrence of unintentional unevenness in the three-dimensional structure 10 and to improve the dimensional accuracy of the three-dimensional structure 10.

  In the present invention, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser (Coulter counter method particle size distribution analyzer ( It can be determined by measuring with a 50 μm aperture using COULTER ELECTRONICS INS TA-II type).

  The Dmax of the particles 11 is preferably 1 μm or more and 40 μm or less, and more preferably 3 μm or more and 30 μm or less.

  Thereby, the fluidity | liquidity of the composition 1 'can be made suitable, a discharge process can be performed more smoothly, and joining of the particle | grains 11 in a joining process can be performed more suitably. As a result, the mechanical strength of the manufactured three-dimensional structure 10 can be further improved while the productivity of the three-dimensional structure 10 is improved, and the manufactured three-dimensional structure 10 is manufactured. It is possible to more effectively prevent the occurrence of unintentional irregularities in, and to improve the dimensional accuracy of the three-dimensional structure 10.

  The content of the particles 11 in the composition 1 ′ is preferably 50% by mass or more and 99% by mass or less, and more preferably 55% by mass or more and 98% by mass or less.

  Thereby, the amount of components removed in the manufacturing process of the three-dimensional structure 10 can be made smaller while making the composition 1 ′ easier to handle, and the three-dimensional structure can be reduced. This is particularly advantageous from the viewpoint of 10 productivity, production cost, and resource saving. Moreover, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be further improved.

The particles 11 are made of a material that undergoes a chemical reaction (for example, an oxidation reaction) in the manufacturing process (for example, a joining step) of the three-dimensional structure 10 and is included in the composition 1 ′. The composition may be different between the composition of the particles 11 and the constituent material of the final three-dimensional structure 10.
The composition 1 ′ may include two or more kinds of particles.

(Thixotropic material)
The composition 1 ′ includes a thixotropic material (thixotropic agent).

  Since the composition (composition for producing a three-dimensional structure) 1 ′ contains a thixotropic material, the viscosity (fluidity) at the time of discharging the composition 1 ′ and the composition 1 ′ is a target site (covered). The viscosity (fluidity) at the time of contact with the (adhering body) can be made different. Thereby, it is possible to effectively prevent the composition from spreading unintentionally when the composition 1 ′ comes into contact with the target site while ensuring excellent dischargeability of the composition 1 ′. . As a result, it is possible to efficiently manufacture the three-dimensional structure 10 having excellent dimensional accuracy while suppressing generation of waste of material.

  Examples of thixotropic materials include monosaccharides such as glucose, fructose and N-acetylglucosamine, various saccharides such as polysaccharides such as pectin, amylose, cellulose, dextrin and glucan; fatty acids such as fatty acid amide and polyhydroxycarboxylic acid amide. Amides; Fatty acid esters such as polyhydroxycarboxylic acid esters; Oxidized polyolefins such as oxidized polyethylene; Oxidized polyolefin amides such as oxidized polyethylene amide; Hydrogenated castor oil; Ureas such as modified urea, urea-modified urethane, urea-modified polyamide Materials; polyurethane; bentonite and the like.

  Among them, as the thixotropic material, polysaccharides are preferable, and pectin is more preferable.

  Thereby, the difference in the viscosity of the composition 1 ′ due to the presence or absence of external force can be made larger, and the dimensional accuracy and productivity of the three-dimensional structure 10 can be compatible at a higher level. In addition, such a thixotropic material is excellent in chemical stability during storage of the composition 1 ′, and therefore, unintentional modification and deterioration of the composition 1 ′ can be more effectively prevented, and the tertiary is maintained for a longer period of time. It can be suitably used for manufacturing the original shaped article 10. Further, the storage conditions of the composition 1 'are relaxed, and storage and management are facilitated. In addition, since such a thixotropic material has a function of improving the dispersion stability of the particles 11 (particularly, the particles 11 made of a metal material or a metal compound), the discharge stability of the composition 1 ′ is improved. This is also advantageous for further improving the dimensional accuracy and productivity of the three-dimensional structure 10.

  In composition 1 ', the thixotropic material may be contained in any form, but is preferably in a liquid state (for example, a molten state, a dissolved state, etc.). That is, it is preferably contained as a constituent component of the dispersion medium 12.

  Thereby, the viscosity change of the composition 1 'by an external force can be increased. In addition, unintentional variations in the composition and characteristics of each part of the composition 1 ′ can be suppressed.

  The content of the thixotropic material in the composition 1 ′ is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.2% by mass or more and 5% by mass or less.

  Thereby, the amount of change in the viscosity of the composition 1 ′ by applying an external force can be made larger, and the effects of the present invention as described above are more remarkably exhibited. Moreover, since the content rate of the particles 11 in the composition 1 ′ can be made higher, the shrinkage rate of the composition 1 ′ in the joining step can be made smaller. Therefore, the dimensional accuracy of the three-dimensional structure 10 can be further improved, and the amount of components to be removed in the manufacturing process of the three-dimensional structure 10 can be further reduced. This is particularly advantageous from the viewpoint of the productivity, production cost, and resource saving of the product 10.

(binder)
The composition 1 ′ may further contain a binder in addition to the components described above.

  Thereby, for example, unintentional deformation of the composition 1 ′ after the discharged composition 1 ′ contacts the target portion can be more effectively prevented. As a result, the dimensional accuracy of the three-dimensional structure 10 can be further improved. Moreover, adjustment of the porosity (porosity) in the three-dimensional structure 10, the density of the three-dimensional structure 10, etc. can be performed suitably.

  Any binder may be used as long as it has a function of temporarily fixing the particles 11 in the composition 1 ′ before being subjected to the joining step. For example, various resin materials such as thermoplastic resins and curable resins are used. However, it is preferable to include a curable resin.

Thereby, for example, the timing before the bonding step with respect to the discharged composition 1 ′ (for example, after the discharge of the composition 1 ′, the composition 1 ′ comes into contact with the target portion (the adherend). The flow of the composition 1 ′ is performed by performing a curing treatment at a timing before (before landing) or at a timing after the discharged composition 1 ′ contacts (landed) the target portion (adhered body). Therefore, the composition 1 ′ can be suitably arranged even in the case of a more complicated pattern or a pattern having a fine structure. Therefore, even the three-dimensional structure 10 having a complicated shape or a fine structure can be more suitably manufactured. Further, the viscosity of the composition 1 ′ at the time of discharge and the viscosity in a state where the composition 1 ′ is in contact with the target portion (adhered body) (viscosity of the composition 1 ′ when the curable resin is cured) Therefore, the dischargeability of the composition 1 ′ and the productivity of the three-dimensional structure 10 can be further improved.
The curing treatment can be performed by irradiation with energy rays such as ultraviolet rays.

Hereinafter, the case where a curable resin is included as a binder is demonstrated typically.
As the curable resin, for example, various thermosetting resins and photocurable resins can be suitably used.

  As the curable resin (polymerizable compound), for example, various monomers, various oligomers (including dimers, trimers, etc.), prepolymers, and the like can be used, but the composition 1 ′ is a curable resin (polymerizable compound). ) Preferably contains at least a monomer component. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous for improving the discharge stability of the curable resin (polymerizable compound).

  As the curable resin (polymerizable compound), a resin that generates a polymer by addition polymerization or ring-opening polymerization by radical species or cationic species generated from a polymerization initiator by irradiation of energy rays is preferably used. . Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

  Examples of the addition polymerizable compound include compounds having at least one ethylenically unsaturated double bond. As the addition polymerizable compound, a compound having at least one, preferably two or more terminal ethylenically unsaturated bonds can be preferably used.

  The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound, or a mixture thereof. Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

  In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like, addition products of isocyanates and epoxies, dehydration condensation products of carboxylic acids, etc. Can be used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines and thiols, as well as removal of halogen groups, tosyloxy groups, etc. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasing substituent and an alcohol, amine or thiol can also be used.

  Specific examples of the radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, (meth) acrylic acid ester, which is either monofunctional or polyfunctional. Can also be used.

  In the present invention, a cationic ring-opening polymerizable compound having at least one cyclic ether group such as an epoxy group or an oxetane group in the molecule can be suitably used as the curable resin (polymerizable compound).

  Examples of the cationic polymerizable compound include a curable compound containing a ring-opening polymerizable group, and among them, a heterocyclic group-containing curable compound is particularly preferable. Such curable compounds include, for example, epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, vinyl ethers, etc. Among them, epoxy derivatives, oxetanes, etc. Derivatives and vinyl ethers are preferred.

  The composition 1 ′ may contain an oligomer (including a dimer, trimer, etc.), a prepolymer, etc. in addition to the monomer as a curable resin (polymerizable compound). As the oligomer and prepolymer, for example, those having the above-described monomer as a constituent component can be used.

  In the composition 1 ′, the binder may be contained in any form, but is preferably in a liquid form (for example, a molten state, a dissolved state, etc.). That is, it is preferably contained as a constituent component of the dispersion medium 12.

  Thereby, a binder can function as the dispersion medium 12 which disperse | distributes the particle | grains 11, and can make the discharge property of the composition 1 'more excellent. In addition, the binder can suitably coat the particles 11 during the joining process, and the stability of the shape of the layer 1 during the joining process can be further improved, and each component in the layer 1 can be improved. Unintentional variation can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure 10 can be further improved.

  The content of the binder in the composition 1 ′ is preferably 0.5% by mass or more and 48% by mass or less, and more preferably 1% by mass or more and 43% by mass or less.

  Thereby, the function of temporarily fixing the particles 11 by the binder is more effectively exhibited while making the fluidity of the composition 1 ′ more appropriate in the discharging step. Further, the binder can be removed more reliably in the joining step. Thus, the dimensional accuracy and reliability of the manufactured three-dimensional structure 10 can be further improved while making the productivity of the three-dimensional structure 10 more excellent.

(solvent)
The composition 1 ′ may contain a volatile solvent.

  Thereby, the viscosity of the composition 1 ′ can be suitably adjusted, and the ejection stability of the composition 1 ′ can be further improved. Further, the solvent can function as the dispersion medium 12 in which the particles 11 are dispersed in the composition 1 ′, and the dispersion state of the composition 1 ′ can be improved. In addition, since the volatile solvent can be efficiently removed in the manufacturing process of the three-dimensional structure 10, the occurrence of harmful effects caused by unintentionally remaining in the finally obtained three-dimensional structure 10 is avoided. It can be effectively prevented.

  Examples of the solvent include water; (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ethyl acetate, n-propyl acetate, acetic acid acetates such as iso-propyl, n-butyl acetate and iso-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl n-butyl ketone, diisopropyl ketone, acetylacetone Ketones such as ethanol; alcohols such as ethanol, propanol, butanol; tetraalkylammonium acetates; dimethyl sulfoxide, diethyl sulfoxide, etc. One type selected from these, including phosphine solvents; pyridine solvents such as pyridine, γ-picoline, and 2,6-lutidine; and ionic liquids such as tetraalkylammonium acetate (for example, tetrabutylammonium acetate). Alternatively, two or more kinds can be used in combination.

  In particular, by using a mixture of a tetraalkylammonium acetate and an aprotic organic solvent (such as a sulfoxide solvent or a pyridine solvent), the polysaccharide as the thixotropic material described above can be suitably dissolved.

  When the composition 1 ′ includes particles 11 made of a metal material, it is preferable to use an aprotic solvent as the solvent. Thereby, the unintentional oxidation reaction of the constituent material of the particle | grains 11 etc. can be prevented effectively.

  The content of the solvent in the composition 1 ′ is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 25% by mass or less.

  Thereby, the amount of components removed in the manufacturing process of the three-dimensional structure 10 can be made smaller while making the composition 1 ′ easier to handle, and the three-dimensional structure can be reduced. This is particularly advantageous from the viewpoint of 10 productivity, production cost, and resource saving. Moreover, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be further improved.

(Other ingredients)
Moreover, composition 1 'may contain components other than having mentioned above. Examples of such components include a polymerization initiator; a dispersant; a surfactant; a thickener; an agglomeration inhibitor; an antifoaming agent; a slip agent (leveling agent); a dye; a polymerization inhibitor; Accelerators; humectants (humectants); fixing agents; antifungal agents; antiseptics; antioxidants; ultraviolet absorbers; chelating agents;

  As the polymerization initiator, for example, a radical polymerization initiator or a cationic polymerization initiator can be used, but it is preferable to use a radical polymerization initiator. The radical polymerization initiator preferably has an absorption peak in the ultraviolet region.

  Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, keto Examples thereof include oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  When the composition 1 ′ includes a polymerization initiator, the polymerization initiator may be included in any form in the composition 1 ′, but a liquid (eg, a molten state, a dissolved state, etc.) It is preferable that That is, it is preferably contained as a constituent component of the dispersion medium 12.

  Thereby, a polymerization initiator can function as the dispersion medium 12 which disperse | distributes the particle | grains 11, and can make the discharge property of composition 1 'more excellent. Moreover, the hardened | cured material of a binder (curable resin) can coat | cover the particle | grains 11 suitably in a joining process, and it can make the stability of the shape of the layer 1 in the joining process more excellent. The unintentional variation of each component in the layer 1 can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure 10 can be further improved.

  The content of the polymerization initiator in the composition 1 'is preferably 0.5% by mass or more and 10% by mass or less.

  Thereby, the function of temporarily fixing the particles 11 with the binder (cured product of the curable resin) is more effectively exhibited while making the fluidity of the composition 1 ′ in the discharging process more appropriate. Further, the binder can be removed more reliably in the joining step. Thus, the dimensional accuracy and reliability of the manufactured three-dimensional structure 10 can be further improved while making the productivity of the three-dimensional structure 10 more excellent.

  When composition 1 'contains pectin as a thixotropic material, the pH of the composition is preferably 2.8 or more and 3.5 or less.

  Thereby, the difference in the viscosity of the composition 1 ′ due to the presence or absence of external force can be made larger, and the dimensional accuracy and productivity of the three-dimensional structure 10 can be compatible at a higher level.

《Three-dimensional structure》
The three-dimensional structure of the present invention can be manufactured using the manufacturing method and the three-dimensional structure manufacturing apparatus of the present invention as described above.

  Thereby, the three-dimensional structure excellent in dimensional accuracy can be provided. Further, according to the manufacturing method and the manufacturing apparatus as described above, since particles having various compositions can be used, the range of selection of the constituent material of the three-dimensional structure can be widened. The object can have desired physical properties, texture, and the like.

  The use of the three-dimensional structure of the present invention is not particularly limited, and examples thereof include appreciation objects / exhibits such as dolls and figures; medical devices such as implants.

  Moreover, the three-dimensional structure of the present invention may be applied to any of prototypes, mass-produced products, and custom-made products.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the three-dimensional structure manufacturing apparatus of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits the same function, and an arbitrary configuration can be added.

  For example, the three-dimensional structure manufacturing apparatus of the present invention may include a heating means and a decompression means (not shown). Thereby, for example, the solvent can be efficiently removed from the composition for manufacturing a three-dimensional structure and the composition for forming a support material, and the productivity of the three-dimensional structure can be made particularly excellent.

  In the present invention, the composition may be discharged from a plurality of discharge portions. Thereby, according to each site | part of the three-dimensional structure to be manufactured, for example, a plurality of types of compositions can be used in combination.

  Moreover, in this invention, you may manufacture a three-dimensional molded item in the chamber where the composition etc. of atmosphere were managed. Thereby, for example, the bonding step can be performed in an inert gas, and unintentional modification of particles can be more effectively prevented. In addition, for example, by performing the bonding step in an atmosphere containing a reactive gas, a three-dimensional structure formed of a material having a composition different from the composition of the particles used as the raw material can be suitably manufactured.

  Moreover, the three-dimensional structure manufacturing apparatus of this invention may be equipped with the heating means which heats the discharged composition. Thereby, the discharge property of a composition can be made more excellent. Moreover, by heating the composition before discharge, the composition after discharge is cooled, and the difference in viscosity before and after discharge can be increased. Thereby, productivity and dimensional accuracy of a three-dimensional structure can be made compatible at a higher level.

  Moreover, the three-dimensional structure manufacturing apparatus of the present invention may include a cooling means (not shown). Thereby, for example, the layer can be rapidly cooled after the joining of the particles, and the subsequent steps can be suitably performed. As a result, the productivity, dimensional accuracy, reliability, etc. of the three-dimensional structure can be made particularly excellent.

  Further, in the above-described embodiment, the case where the viscosity reducing unit is provided in the discharge unit has been representatively described. However, the viscosity reducing unit left the viscosity of the composition at the time of discharge for a sufficiently long time. The installation site is not limited as long as it can be lower than the viscosity of the composition in the state. For example, the viscosity reducing means may be disposed in a tank that contains the composition or in a channel such as a tube.

  In the embodiment described above, the case where the layer is directly formed on the surface of the stage has been representatively described. For example, a modeling plate is arranged on the stage, and the layer is stacked on the modeling plate to perform three-dimensional modeling. You may manufacture things. In such a case, in the manufacturing process of the three-dimensional structure, the modeling plate and the particles constituting the lowermost layer may be joined, and then the modeling plate may be removed from the target three-dimensional structure by post-processing. . Thereby, for example, it is possible to more effectively prevent the occurrence of warping of the layer (laminated body) in the process of laminating a plurality of layers, and the dimensional accuracy of the finally obtained three-dimensional structure can be further increased. It can be excellent.

  Moreover, although embodiment mentioned above demonstrated as what forms a junction part with respect to all the layers, you may have the layer in which a junction part is not formed. For example, a layer (for example, a layer made of a support material) where a joint portion is not formed may be formed on a contact surface with the stage (immediately above the stage), and the layer may function as a sacrificial layer.

  Moreover, in the manufacturing method of the three-dimensional structure of this invention, the order of a process and a process is not limited to what was mentioned above, You may replace and carry out at least one part. For example, in the above-described embodiment, the case where the support material application process is performed between the discharge process and the bonding process is representatively described. However, the support material application process is performed after the bonding process, for example. Also good. Further, the support material forming composition may be discharged in the same process as the discharge of the composition (composition for producing a three-dimensional structure) used for forming the joint.

  In the above-described embodiment, the case where the composition for forming the support material is used together with the composition used for forming the joint portion is representatively described. However, in the present invention, the shape of the three-dimensional structure to be manufactured, etc. Depending on the case, the composition for forming a support material may not be used.

  Moreover, in the manufacturing method of this invention, you may perform a pre-processing process, an intermediate processing process, and a post-processing process as needed.

Examples of the pretreatment process include a stage cleaning process.
Examples of the post-processing step include a cleaning step, a shape adjustment step for performing deburring, a coloring step, a coating layer forming step, a heat treatment step for improving the bonding strength of particles, and the like.

  DESCRIPTION OF SYMBOLS 10 ... Three-dimensional structure, 1 ... Layer, 1 '... Composition (Composition for three-dimensional structure manufacture), 11 ... Particle | grain (dispersoid), 12 ... Dispersion medium, 2 ... Joint part, 5 ... Support material ( Support part), 5 '... support material forming composition, M100 ... three-dimensional structure manufacturing apparatus, M1 ... viscosity reducing means, M2 ... control part, M21 ... computer, M22 ... drive control part, M3 ... composition supply part (Discharge means), M4 ... layer forming part, M41 ... stage (elevating stage, support), M45 ... frame, M6 ... joining energy applying means, M8 ... composition supply part for supporting material formation (composition for supporting material formation) Material discharge means)

Claims (16)

A discharge step of applying an external force to the composition containing the particles and the thixotropic material, and discharging the composition in a state where the viscosity is reduced;
A bonding step of applying energy and bonding the particles after the composition contacts a target site;
A method for producing a three-dimensional structure, characterized by laminating layers formed in a predetermined pattern by repeatedly performing a series of steps including:   The method for producing a three-dimensional structure according to claim 1, wherein the viscosity of the composition is reduced by stirring during the discharging step.   The manufacturing method of the three-dimensional structure according to claim 1 or 2, wherein the viscosity of the composition is reduced by applying vibration during the discharging step.   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the composition contains a polysaccharide as the thixotropic material.   The method for producing a three-dimensional structure according to any one of claims 1 to 4, wherein the composition further contains a binder.   The method for producing a three-dimensional structure according to claim 5, wherein the composition contains a curable resin as the binder.   The method of manufacturing a three-dimensional structure according to any one of claims 1 to 6, wherein the composition includes, as the particles, a material composed of a material including at least one of a metal material and a ceramic material.   The method for producing a three-dimensional structure according to any one of claims 1 to 7, wherein the composition contains a volatile solvent.   The method for producing a three-dimensional structure according to claim 8, further comprising a step of removing the solvent.   The method for manufacturing a three-dimensional structure according to any one of claims 1 to 9, wherein the joining step is performed by laser irradiation.   The method for producing a three-dimensional structure according to any one of claims 1 to 10, wherein the viscosity of the composition in the discharging step is 1 mPa · s or more and 30 mPa · s or less.   The method for producing a three-dimensional structure according to any one of claims 1 to 11, wherein a viscosity when the discharged composition comes into contact with a target site is 5 mPa · s or more and 100 mPa · s or less. A viscosity reducing means for applying an external force to the composition containing the particles and the thixotropic material to reduce the viscosity;
Discharge means for discharging the composition in a state of reduced viscosity;
An apparatus for producing a three-dimensional structure, comprising: a joining energy imparting unit that imparts energy for joining the particles after the composition contacts a target site.   A three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure according to any one of claims 1 to 12.   A three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus according to claim 13. It is a composition used to laminate a layer formed in a predetermined pattern and produce a three-dimensional structure,
A composition for producing a three-dimensional structure, comprising particles and a thixotropic material, wherein the viscosity is reduced by applying an external force.

Images