JP2016179561A - Method for manufacturing three-dimensional molded object, apparatus for manufacturing three-dimensional molded object, composition for surface treatment, composition set for manufacturing three-dimensional molded object, and three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensional molded object excellent in mechanical strength, a method for manufacturing a three-dimensional molded object by which the three-dimensional molded object can be efficiently manufactured, an apparatus for manufacturing a three-dimensional molded object, a composition for surface treatment, and a composition set for manufacturing a three-dimensional molded object.SOLUTION: The method for manufacturing a three-dimensional molded object aims to manufacture a three-dimensional molded object by stacking layers 1, and the method includes: a layer formation step of forming the layer 1 by using a layer-forming composition 111 comprising a plurality of particles; a surface treatment composition imparting step of imparting a surface treatment composition 14' comprising a surface treating agent that modifies surfaces of the particles constituting the layer 1, to the layer 1; and a binder liquid imparting step of imparting a binder liquid 12 to the layer 1.SELECTED DRAWING: Figure 1

Description

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

  A technique for modeling a three-dimensional object while solidifying a powder with a binding liquid is known (see, for example, Patent Document 1). In this technique, a three-dimensional object is formed by repeating the following operations. First, the powder is thinly spread with a uniform thickness to form a powder layer, and the powder is bonded to each other by discharging a binding liquid to a desired portion of the powder layer. As a result, in the powder layer, only the portion where the binding liquid is discharged is bonded to form a thin plate-like member (hereinafter referred to as “cross-sectional member”). Thereafter, a thin powder layer is formed on the powder layer, and a binding liquid (curable ink) is discharged to a desired portion. As a result, a new cross-sectional member is also formed at the portion where the binding liquid of the newly formed powder layer is discharged. At this time, the binding liquid discharged onto the powder layer soaks and reaches the previously formed cross-sectional member, so that the newly formed cross-sectional member is also coupled to the previously formed cross-sectional member. By repeating such operations and laminating thin plate-like cross-sectional members one by one, a three-dimensional object can be formed.

  With such 3D modeling technology, as long as there is 3D shape data of the object to be modeled, it is possible to immediately model by combining powder, and there is no need to create a mold prior to modeling. It is possible to form a three-dimensional object quickly and inexpensively. In addition, since thin plate-like cross-sectional members are layered one by one and shaped, 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. .

  However, conventionally, the binding force by the binding liquid cannot be made sufficiently high, and the strength of the three-dimensional structure cannot be made sufficiently high.

JP-A-6-218712

  An object of the present invention is to provide a three-dimensional structure that is excellent in mechanical strength, and a method for producing a three-dimensional structure that can efficiently manufacture a three-dimensional structure that is excellent in mechanical strength. The object is to provide an original model manufacturing apparatus, a composition for surface treatment, and a composition set for manufacturing a three-dimensional model.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure by producing a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a layer forming composition containing a plurality of particles;
A surface treatment composition applying step for applying a surface treatment composition containing a surface treatment agent for modifying the surface of the particles constituting the layer to the layer;
And a binding liquid application step for applying a binding liquid to the layer.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture the three-dimensional structure excellent in mechanical strength efficiently can be provided.

  In the three-dimensional structure manufacturing method of the present invention, the layer forming composition preferably includes a solvent in addition to the particles.

  As a result, the fluidity of the layer forming composition can be increased, the workability during layer formation can be improved, and a layer with high surface flatness can be formed easily and reliably. In addition, it is possible to more effectively prevent unintentional scattering of particles during formation of the layer.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable to have a solvent removal step of removing the solvent from the layer between the layer formation step and the surface treatment composition application step.

  Thereby, the composition for surface treatment can easily more suitably penetrate into the gaps between the plurality of particles constituting the layer, and the surface treatment for the particles can be performed more efficiently.

In the three-dimensional structure manufacturing method of the present invention, it is preferable to have a solvent removal step of removing the solvent from the layer between the surface treatment composition application step and the binding liquid application step.
Thereby, the productivity of the three-dimensional structure can be made particularly excellent.

  In the method for producing a three-dimensional structure of the present invention, the surface treatment composition preferably includes a coupling agent.

  Thereby, the bonding force between the particles by the binder can be made higher, and the mechanical strength of the obtained three-dimensional structure can be made more excellent.

  In the three-dimensional structure manufacturing method of the present invention, the coupling agent is selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. Or it is preferable that they are 2 or more types.

  Thereby, the bonding force between the particles by the binder can be further increased, and the mechanical strength of the obtained three-dimensional structure can be further improved.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the surface treatment composition is selectively applied to at least a part of the portion to which the binding liquid is to be applied by an inkjet method.

  Thereby, the surface treatment composition can be selectively applied to a desired site, the amount of the surface treatment composition used can be suppressed, the production cost of the three-dimensional structure can be reduced, and resource saving can be achieved. It is preferable from the viewpoint. Moreover, the particle | grains which comprise the area | region in which a connection part is not formed among layers can be collect | recovered, and it can reuse suitably for manufacture of a three-dimensional structure.

In the method for producing a three-dimensional structure of the present invention, the binding liquid contains a polymerizable compound,
It is preferable to have the hardening process of superposing | polymerizing and hardening the said polymeric compound after the said binding liquid provision process.

  Thereby, the mechanical strength, water resistance, etc. of the three-dimensional structure can be made particularly excellent.

The three-dimensional structure manufacturing apparatus of the present invention is an apparatus for manufacturing a three-dimensional structure by laminating layers using a layer forming composition including a plurality of particles.
A stage to which the layer forming composition is applied and the layer is formed;
A surface treatment composition applying means for applying a surface treatment composition containing a surface treatment agent for modifying the surface of the particles constituting the layer to the layer;
And a binding liquid applying means for applying a binding liquid to the layer.

  Thereby, the three-dimensional structure manufacturing apparatus which can manufacture the three-dimensional structure excellent in mechanical strength efficiently can be provided.

The composition for surface treatment of the present invention is a composition used for producing a three-dimensional structure by laminating layers using a layer forming composition containing a plurality of particles,
Prior to forming a bonding portion by applying a binding liquid to the layer, the layer is applied to the layer,
It contains a surface treatment agent for modifying the surface of the particles constituting the layer.

  Thereby, the composition for surface treatment which can manufacture efficiently the three-dimensional structure excellent in mechanical strength can be provided.

The composition set for manufacturing a three-dimensional structure of the present invention is used to manufacture a three-dimensional structure,
A layer forming composition comprising a plurality of particles;
A composition for surface treatment of the present invention;
And a binding liquid that binds the particles subjected to the surface treatment with the surface treatment agent.

  Thereby, the composition set for three-dimensional structure manufacture which can manufacture the three-dimensional structure excellent in mechanical strength efficiently can be provided.

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 mechanical strength 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 mechanical strength can be provided.

The three-dimensional structure of the present invention is manufactured using the composition for surface treatment of the present invention.
Thereby, the three-dimensional structure excellent in mechanical strength can be provided.

The three-dimensional structure of the present invention is manufactured using the composition set for manufacturing a three-dimensional structure of the present invention.
Thereby, the three-dimensional structure excellent in mechanical strength can be provided.

It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows each process typically about 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. It is the top view which planarly viewed the stage vicinity of the three-dimensional structure manufacturing apparatus of this invention shown in FIG. 5, (a) is a figure which shows an example of arrangement | positioning of each member at the time of layer formation, (b) It is a figure which shows an example of arrangement | positioning of each member at the time of providing the composition for surface treatment. It is the top view which planarly viewed the stage vicinity of the three-dimensional structure manufacturing apparatus of this invention shown in FIG. 5, (c) is a figure which shows an example of arrangement | positioning of each member at the time of heating a layer, (d (A) is a figure which shows an example of arrangement | positioning of each member at the time of forming a hardening part, when providing a binding liquid to a layer. It is a perspective view which shows the shape of the three-dimensional structure (three-dimensional structure A) manufactured by each Example and each comparative example. It is a perspective view which shows the shape of the three-dimensional structure (three-dimensional structure B) manufactured by each Example and each comparative example.

  Hereinafter, preferred embodiments of the present invention 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.

  1, 2, and 3 are cross-sectional views schematically showing each step in a preferred embodiment of the method for producing a three-dimensional structure of the present invention, and FIG. 4 is a production of the three-dimensional structure of the present invention. It is a flowchart which shows an example of a method.

  As shown in FIGS. 1, 2, and 3, the manufacturing method of the present embodiment forms a layer 1 using a layer-forming composition (particle-containing composition) 11 including a plurality of particles 111. (1a, 1f) and a surface treatment composition 14 ′ containing a surface treatment agent are applied to the layer 1, and a surface treatment process for modifying the surface of the particles 111 constituting the layer 1 (application of the surface treatment composition) Step) (1b, 1c, 1g, 1h), a binding liquid application step (1d, 1i) for applying the binding liquid 12 to the layer 1, and a binding contained in the binding liquid 12 applied to the layer 1 A curing step (1e, 1j) for curing the agent to form a cured portion (bonding portion) 13 in the layer 1, and sequentially repeating these steps (1k). Of unbound particles that remove particles that are not bound by a binder from among particles 111 constituting It has a 1l).

  Thus, by modifying the surface of the particles 111, the bonding force between the particles 111 and the binding liquid 12 (binder) can be improved, and the mechanical strength of the three-dimensional structure 10 can be increased. It can be excellent.

Hereinafter, each step will be described in detail.
≪Layer formation process≫
In the layer forming step, the layer 1 having a predetermined thickness is formed using the layer forming composition 11 including a plurality of particles 111 (1a, 1f).

  When the layer forming composition 11 includes the particles 111, the mechanical strength and the like of the finally obtained three-dimensional structure 10 can be improved.

  The layer-forming composition 11 will be described in detail later, but preferably contains a solvent in addition to the particles 111.

Thereby, for example, the layer-forming composition 11 can be made into a paste-like material, the fluidity of the layer-forming composition 11 can be improved, and workability at the time of forming the layer 1 can be improved. The layer 1 having a high surface flatness can be easily and reliably formed. In addition, unintentional scattering of the powder (particles 111) during formation of the layer 1 can be more effectively prevented.
In this step, the layer 1 is formed with a flattened surface using a flattening means.

  In the first layer formation step, the layer 1 is formed with a predetermined thickness on the surface of the stage 41 (1a). At this time, the side surface of the stage 41 and the side surface support portion (frame body) 45 are in close contact (contact), and the layer forming composition is formed between the stage 41 and the side surface support portion (frame body) 45. The object 11 is prevented from falling.

  In the second and subsequent layer formation steps, a new layer 1 (second layer) is formed on the surface of the layer 1 (first layer) formed in the previous step (1f). At this time, the side surface of the layer 1 on the stage 41 (at least the uppermost layer 1 when there are a plurality of layers 1 on the stage 41) and the side surface support portion (frame body) 45 are in close contact with each other. The layer forming composition 11 is prevented from falling from between the stage 41 and the layer 1 on the stage 41.

  The viscosity of the layer-forming composition 11 in this step (value measured using an E-type viscometer (for example, VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.)) is preferably 500 mPa · s or more and 60000 mPa · s or less. It is more preferably 1000 mPa · s or more and 20000 mPa · s or less. Thereby, generation | occurrence | production of the unintentional dispersion | variation in the film thickness in the layer 1 formed can be prevented more effectively.

  The thickness of the layer 1 formed in this step is not particularly limited, but is preferably, for example, 5 μm or more and 500 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 10 μm or more and 50 μm or less. .

  Thereby, while making the productivity of the three-dimensional structure 10 sufficiently excellent, the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 is more effectively prevented, and the three-dimensional structure 10 The dimensional accuracy can be further improved.

≪Surface treatment process (surface treatment composition application process) ≫
Thereafter, the surface treatment composition 14 ′ containing the surface treatment agent is applied to the layer 1 (1b, 1g), and the surfaces of the particles 111 constituting the layer 1 are modified (1c, 1h).

  By modifying the surface of the particle 111 in this way, the affinity between the surface of the particle 111 and a binding liquid 12 (binding agent) and a cured product of the binding agent, which will be described later, is increased, and finally obtained tertiary. The mechanical strength of the original shaped article 10 can be made excellent.

  Application of the surface treatment composition 14 ′ (modification of the particles 111) is performed by at least a part of the layer 1 to which the binding liquid 12 is to be applied (in particular, at least the real part of the three-dimensional structure 10 to be manufactured) (Part corresponding to the surface of the substance) (1b, 1g).

  In the above description, the “site to which the binding liquid 12 is to be applied” includes not only the area where the droplet of the binding liquid 12 having a predetermined size has landed but also the area where the liquid has spread after landing.

  In addition, when the surface treatment composition 14 ′ is applied to a part of the layer 1 to which the binding liquid 12 is to be applied, the surface treatment composition 14 ′ is at least three-dimensional to be manufactured. It is preferable that it is an area | region including the site | part which should become the surface (especially outer surface) of the molded article 10. FIG.

  Since the surface (particularly the outer surface) of the three-dimensional structure 10 is a region that greatly affects the mechanical strength of the three-dimensional structure, the surface treatment composition 14 ′ is applied to such a part. As a result, the effects as described above are more remarkably exhibited.

  The application of the surface treatment composition 14 ′ can be performed by, for example, a spray method, a method using a dispenser, an ink jet method, or the like, but is preferably performed by an ink jet method.

  Thereby, composition 14 'for surface treatment can be selectively given to a desired part, the amount of surface treatment composition 14' can be controlled, and the production cost of three-dimensional structure 10 can be reduced. It is preferable from the viewpoint of reduction and resource saving. Moreover, the particle | grains 111 which comprise the area | region in which the coupling | bond part 13 is not formed among the layers 1 can be collect | recovered, and can be reused suitably for manufacture of the three-dimensional structure 10.

  The modification of the particles 111 can be suitably performed, for example, by applying the surface treatment composition 14 ′ to the layer 1 and then performing a heat treatment (1 c, 1 h).

  Thereby, the surface of the particle 111 can be efficiently modified, and the productivity of the three-dimensional structure 10 and the mechanical strength of the three-dimensional structure 10 can be made particularly excellent. Moreover, when the layer 1 contains a solvent, the removal of the solvent from the layer 1 can also be performed efficiently. Further, when the layer 1 to be heat-treated contains water, the chemical reaction for modifying the particles 111 by the surface treatment agent can be more efficiently advanced.

  When performing heat processing at this process, it is preferable that heating temperature is 40 degreeC or more and 180 degrees C or less, and it is more preferable that it is 80 degreeC or more and 150 degrees C or less.

  Thereby, the effects as described above are more remarkably exhibited while effectively preventing unintended reactions such as unintentional decomposition of the surface treatment agent.

  In addition, instead of modifying the surface of the particles after forming the layer, it is possible to use a layer-forming composition that has been previously surface-treated with a surface treatment agent. During storage or the like, the surface state of the particles may deteriorate, and the adhesion between the particles and the binder may not be sufficiently improved. In addition, since the surface state of the particles varies depending on the storage period and storage state of the layer forming composition, for example, when a plurality of three-dimensional structures are manufactured, There is a problem that the mechanical strength is different and the quality and stability of the three-dimensional structure are low.

On the other hand, by modifying the surface of the particles after forming the layer, the above problems can be effectively prevented.
The surface treatment composition 14 ′ will be described in detail later.

≪Binding liquid application process≫
Thereafter, a binding liquid 12 for binding the particles 111 constituting the layer 1 is applied to the layer 1 (1d, 1i).

  In this step, the binding liquid 12 is selectively applied only to a part of the layer 1 corresponding to the real part (substantial part) of the three-dimensional structure 10.

  As a result, the particles 111 constituting the layer 1 can be firmly bonded to each other, and finally a bonded portion (cured portion) 13 having a desired shape can be formed. In particular, since the surface-modified particles 111 are bonded, the bonding force at the bonding portion 13 can be increased, and the mechanical strength of the finally obtained three-dimensional structure 10 should be excellent. Can do.

  In addition, the binding liquid 12 applied to the layer 1 in the second and subsequent binding liquid application steps (see 1 i) is used for bonding the particles 111 constituting the layer 1, and in the layer 1. It is also used for coupling between the coupling portion 13 and the lower layer 1 adjacent to the layer 1 (coupling between the coupling portions 13 of each layer 1). As a result, the finally obtained three-dimensional structure 10 has excellent mechanical strength as a whole.

  In addition, by forming the coupling portion 13 using the binding liquid 12, the amount of energy required to form the coupling portion 13 can be reduced.

  In the present embodiment, the binding liquid 12 is applied to the layer 1 by an ink jet method.

  Thereby, even if the application pattern of the binding liquid 12 has a fine shape, the binding liquid 12 can be applied with good reproducibility. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made higher.

  In addition, the binding liquid 12 only needs to include a binder having a function of binding the particles 111. However, in the present embodiment, the binding liquid 12 includes a curable resin as a binder. It is preferable to contain a curable resin (particularly, an ultraviolet curable resin).

Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 and the productivity of the three-dimensional structure 10 can be further improved. Further, it is advantageous from the viewpoint of storage stability of the binding liquid 12 and production cost of the three-dimensional structure 10.
The binding liquid 12 will be described in detail later.

≪Curing process≫
After the binding liquid 12 is applied to the layer 1 in the binding liquid application step, the binder contained in the binding liquid 12 applied to the layer 1 is cured to form a cured portion (bonding portion) 13 in the layer 1. (1e, 1j).

  In the present embodiment, the binding liquid 12 contains a curable resin (polymerizable compound) as a binder, and this step is performed by performing a treatment according to the type of the curable resin, etc. A coupling portion) 13 is formed. For example, when the curable resin (polymerizable compound) is a thermosetting polymerizable compound (thermosetting resin), it can be cured by heating, and the curable resin (polymerizable compound) is photocurable polymerization. In the case of a curable compound (photo-curable resin), it can be cured by light irradiation.

  Thereby, the mechanical strength, water resistance, etc. of the three-dimensional structure 10 can be made particularly excellent. In particular, the adhesion and bonding force with the particles 111 subjected to the surface treatment with the surface treatment agent can be made particularly excellent, and the mechanical strength of the three-dimensional structure 10 is particularly excellent. Can do.

  In addition, you may perform a binding liquid provision process and a hardening process simultaneously. That is, before the entire pattern of one layer 1 is formed, the curing reaction may proceed sequentially from the portion to which the binding liquid 12 is applied.

  By repeatedly performing the series of steps described above, the particles 111 in the portion to which the binding liquid 12 is applied are combined in each layer 1, and a stacked body in which a plurality of layers 1 in such a state are stacked. A three-dimensional structure 10 is obtained (1k).

  When the layer forming composition 11 contains a solvent in addition to the particles 111, the solvent may be removed at any timing. In the series of steps, the layer forming step and the surface treatment composition are performed. The following effects are acquired as it is removed at the timing between the product application step.

  That is, the surface treatment composition 14 ′ is more preferably easily penetrated into the gaps between the plurality of particles 111 constituting the layer 1, and the surface treatment (formation of the surface treatment portion 14) on the particles 111 can be performed more efficiently. . Further, when the particles 111 are made of a porous material, the surface treatment of the particles 111 with the surface treatment agent into the pores can be performed efficiently. As a result, even in the pores where the binder is difficult to penetrate, it can be firmly bonded to the binder, the anchor effect is more prominently exhibited, and the mechanical strength of the three-dimensional structure 10 is particularly excellent. Can be.

  Moreover, the following effects will be acquired if it is removed in the series of said process at the timing between the surface treatment composition provision process and the binding liquid provision process.

  That is, when the solvent contained in the layer 1 is removed by heating, the surface treatment of the particles 111 with the surface treatment agent can be suitably advanced along with the removal of the solvent by heating. Therefore, the productivity of the three-dimensional structure 10 can be made particularly excellent.

≪Unbound particle removal process≫
Then, after repeating a series of steps as described above, as a post-processing step, among the particles 111 constituting each layer 1, those that are not bound by the binder (unbound particles) are removed. Step (1l) is performed. Thereby, the three-dimensional structure 10 is taken out.

  As a specific method of this step, for example, a method of removing unbound particles with a brush, a method of removing unbound particles by suction, a method of blowing a gas such as air, 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. More specifically, there are a method of immersing in a liquid such as water after blowing a gas such as air, a method of applying ultrasonic vibration in a state of immersing in a liquid such as water, and the like. Especially, it is preferable to employ | adopt the method (especially the method of immersing in the liquid containing water) which provides the liquid containing water with respect to the laminated body obtained as mentioned above.

  Thereby, unbound particles can be removed more easily and more reliably. In addition, it is possible to more reliably prevent a defect such as a scratch from occurring in the three-dimensional structure 10 when removing the unbound particles.

  The manufacturing method of the three-dimensional structure as described above is summarized in a flowchart as shown in FIG.

  According to the manufacturing method of the present invention as described above, a three-dimensional structure excellent in mechanical strength can be efficiently manufactured.

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

  FIG. 5 is a sectional view schematically showing a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention. FIGS. 6 and 7 show the vicinity of the stage of the three-dimensional structure manufacturing apparatus of the present invention shown in FIG. It is the top view seen from the top, and in FIG. 6, (a) is a figure which shows an example of arrangement | positioning of each member at the time of layer formation, (b) is each member at the time of providing the composition for surface treatment. FIG. 7C is a diagram showing an example of the arrangement of each member when the layer is heated, and FIG. 7D is a diagram showing a binding liquid applied to the layer. In the meantime, it is a figure which shows an example of arrangement | positioning of each member at the time of forming a hardening part. 6 (a), 6 (b), and FIG. 7 (d), the heating means 9 is not shown, and in FIG. 7 (c), the heating means 9 is shown.

  The three-dimensional structure manufacturing apparatus 100 manufactures the three-dimensional structure 10 by repeatedly forming and laminating the layer 1 using the layer forming composition 11 including a plurality of particles 111.

  The three-dimensional structure manufacturing apparatus 100 of the present embodiment includes a control unit 2, a layer forming composition supply unit 3 that contains a layer forming composition 11 including a plurality of particles 111, and a layer forming composition supply unit. A layer forming unit 4 for forming the layer 1 using the layer forming composition 11 supplied from 3, a binding liquid discharging unit (binding liquid applying means) 5 for discharging the binding liquid 12 to the layer 1, and Ultraviolet irradiation means (curing means) 6 for irradiating the binding liquid 12 with ultraviolet rays, surface treatment composition applying means 8 for applying the surface treatment composition 14 ′ to the layer 1, and layer 1 Heating means 9 for heating the.

The control unit 2 includes a computer 21 and a drive control unit 22.
The computer 21 is a general desktop computer configured with a CPU, a memory, and the like inside. The computer 21 converts the shape of the three-dimensional structure 10 as model data, and outputs cross-section data (slice data) obtained by slicing the shape into parallel thin layers of slices to the drive control unit 22. .

  The drive control unit 22 functions as a control unit that drives the layer forming unit 4, the binder discharge unit 5, the ultraviolet irradiation unit 6, the surface treatment composition applying unit 8, the heating unit 9, and the like. Specifically, for example, the supply amount of the layer forming composition 11 from the layer forming composition supply unit 3, the descending amount of the stage 41, the surface treatment composition 14 ′ from the surface treatment composition applying means 8. Supply amount, supply pattern, discharge pattern and discharge amount of the binding liquid 12 by the binding liquid discharge unit 5, heating timing by the heating means 9, heating temperature, and the like are controlled.

  The layer forming composition supply unit 3 is moved by a command from the drive control unit 22, and the layer forming composition 11 accommodated therein is supplied to the layer forming composition temporary placement unit 44. Has been.

  The layer forming unit 4 includes a layer forming composition temporary storage unit 44 that temporarily holds the layer forming composition 11 supplied from the layer forming composition supply unit 3 and a layer forming composition temporary storage unit 44. A squeegee (flattening means) 42 that forms the layer 1 while flattening the layer-forming composition 11 held on the guide, a guide rail 43 that regulates the operation of the squeegee 42, and a stage 41 that supports the formed layer 1 And a side support part (frame body) 45 surrounding the stage 41.

  When the new layer 1 is formed on the previously formed layer 1, the previously formed layer 1 is moved downward relative to the side support portion (frame body) 45. Thereby, the thickness of the newly formed layer 1 is defined.

  In particular, in the present embodiment, when the new layer 1 is formed on the previously formed layer 1, the stage 41 is sequentially lowered by a predetermined amount according to a command from the drive control unit 22. Thus, since the stage 41 is configured to be movable in the Z-axis direction (vertical direction), the number of members to be moved in order to adjust the thickness of the layer 1 when the new layer 1 is formed. Since it can reduce, the structure of the three-dimensional structure manufacturing apparatus 100 can be made simpler.

The stage 41 has a flat surface (part to which the layer forming composition 11 is applied).
Thereby, the layer 1 with high uniformity of thickness can be formed easily and reliably. Moreover, in the three-dimensional structure 10 to be manufactured, it is possible to effectively prevent unintentional deformation or the like from occurring.

The stage 41 has a rectangular shape on the XY plane.
The stage 41 is configured to move (lift) in the Z-axis direction by a driving unit (not shown).

  The stage 41 is preferably composed of a high-strength material. Examples of the constituent material of the stage 41 include various metal materials such as stainless steel.

  Further, the surface of the stage 41 (part to which the layer forming composition 11 is applied) may be subjected to surface treatment. As a result, for example, the constituent material of the layer forming composition 11 can be more effectively prevented from adhering to the stage 41, or the durability of the stage 41 can be further improved. It is possible to achieve stable production over a longer period of time. Examples of the material used for the surface treatment of the surface of the stage 41 include fluorine-based resins such as polytetrafluoroethylene.

  The squeegee 42 has a longitudinal shape extending in the Y-axis direction, and includes a blade having a blade-like shape with a pointed lower end.

  The length of the blade in the Y-axis direction is greater than or equal to the width of the stage 41 (modeling region) (the length in the Y-axis direction).

  The squeegee 42 is configured to be driven in the X-axis direction by a driving unit (not shown). Further, the squeegee 42 is configured such that the tip in the short axis direction is in contact with the upper surface of the layer forming composition temporary placement portion 44 and the upper surface of the frame body 45.

  While moving in the X-axis direction, the squeegee 42 transports the layer forming composition 11 supplied to the layer forming composition temporary placement portion 44 to the space on the stage 41 to form the layer 1.

  The three-dimensional structure manufacturing apparatus 100 may include a vibration mechanism (not shown) that applies minute vibrations to the blade so that the squeegee 42 can smoothly diffuse the layer forming composition 11.

  The side surface support portion (frame body) 45 has a function of supporting the side surface of the layer 1 formed on the stage 41. Further, when the layer 1 is formed, it also has a function of defining the area of the layer 1.

The frame body 45 is composed of a frame-shaped member.
The frame body 45 is preferably made of a high-strength material. Examples of the constituent material of the frame body 45 include various metal materials such as stainless steel.

In addition, the surface of the frame body 45 (part that can come into contact with the layer forming composition 11) may be subjected to surface treatment. Thereby, for example, the constituent material of the layer forming composition 11 can be more effectively prevented from adhering to the side surface support portion 45, or the durability of the side surface support portion 45 can be further improved. It is possible to achieve stable production of the original shaped article 10 over a longer period of time. Further, when the previously formed layer 1 is moved downward relative to the side support 45, it is possible to effectively prevent the layer 1 from being disturbed unintentionally. As a result, the dimensional accuracy and reliability of the finally obtained three-dimensional structure 10 can be further improved. As a material used for the surface treatment of the surface of the side support part 45, for example, a fluorine-based resin such as polytetrafluoroethylene can be cited.
The layer 1 is formed in a region formed by the inner wall surface of the frame 45 and the stage 41.

  The binding liquid applying means (binding liquid discharge unit) 5 applies the binding liquid 12 supplied from a binding liquid storage unit (not shown) to the layer 1.

  The binding liquid discharge section (binding liquid applying means) 5 controls the application pattern of the binding liquid 12 and the like according to the pattern to be formed in each layer 1 according to a command from the drive control section 22.

  Specifically, the binding liquid discharge part 5 is configured so that the relative positional relationship with the layer 1 can be changed, and the binding liquid discharge part 5 is a part of the portion where the coupling part 13 is to be formed. When located in the upper part, the binder liquid 12 is discharged.

  Further, in the present embodiment, the binding liquid discharge unit 5 overlaps the area on the stage 41 (area that overlaps the stage 41 when viewed in plan) and the area other than the area on the stage 41 (when viewed in plan, overlaps with the stage 41). It is configured to be movable between the two areas (see FIG. 6 and FIG. 7).

  Thereby, the binding liquid discharge part 5 is retracted from the area on the stage 41 except when the binding liquid 12 is applied (see FIG. 7D), and the binding liquid discharge part 5 is moved to the area on the stage 41. Occurrence of problems due to the existence can be effectively prevented. More specifically, for example, when the layer 1 is formed (see FIG. 6A), it is effective that the particles 111 contained in the layer forming composition 11 fly up and adhere to the binding liquid discharge unit 5. Therefore, stable droplet discharge can be performed over a long period of time. Further, during heating by the heating means 9 (see FIG. 7C), it is possible to effectively prevent the binding liquid discharge part 5 from drying, the solid matter from being deposited on the binding liquid discharge part 5, and the like. Therefore, stable droplet discharge can be performed over a long period of time. Further, when the surface treatment composition 14 ′ is applied by the surface treatment composition application means 8 (see FIG. 6B), mist, vaporized material, etc. of the surface treatment composition 14 ′ are discharged from the binding liquid. Adhering to the part 5 can be effectively prevented.

  In the present embodiment, the binding liquid application unit 5 is a binding liquid discharge unit that discharges the binding liquid 12 by an inkjet method.

  Thereby, the binding liquid 12 can be applied in a fine pattern, and even the three-dimensional structure 10 having a fine structure can be manufactured with higher productivity.

  As a droplet discharge method (inkjet method), a piezo method, a method of discharging the binding liquid 12 with bubbles generated by heating the binding liquid 12, and the like can be used. The piezo method is preferred from the standpoint of difficulty in altering the constituent components of the liquid 12.

In the configuration shown in the figure, the binding liquid applying means 5 is a line head having a length equal to or larger than the width in the Y-axis direction of the modeling region (stage 41).
Thereby, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  The ultraviolet irradiation means (curing means) 6 irradiates ultraviolet rays for curing the binding liquid 12 applied to the layer 1.

In the configuration shown in the drawing, the ultraviolet irradiation means 6 has an irradiation area having a length equal to or greater than the width of the modeling area (stage 41) in the Y-axis direction.
Thereby, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Further, two ultraviolet irradiation means 6 are provided at both ends in the moving direction (X-axis direction) of the binding liquid applying means 5.

  Thereby, in both the positive and negative movements of the binding liquid applying unit 5 and the ultraviolet irradiation unit 6 in the X-axis direction, the treatment of the binding liquid 12 and the curing of the binding liquid 12 are preferably performed simultaneously. The productivity of the three-dimensional structure 10 can be made particularly excellent.

  The surface treatment composition applying means 8 applies a surface treatment composition 14 ′ supplied from a surface treatment composition container (not shown) to the layer 1.

  The surface treatment composition applying means 8 may be anything as long as it can apply the surface treatment composition 14 ′ to the layer 1, for example, a liquid or gaseous surface treatment. A spray for spraying the composition 14 ′ or a dispenser for supplying the liquid surface treatment composition 14 ′ may be used, but in this embodiment, droplets of the surface treatment composition 14 ′ are ejected. It is the droplet discharge part which does.

  Thereby, a necessary and sufficient amount of the surface treatment composition 14 ′ can be suitably applied to a desired site, which is advantageous from the viewpoint of resource saving and production cost reduction.

  The surface treatment composition application means (surface treatment composition discharge unit) 8 is provided with an application pattern of the surface treatment composition 14 ′ according to a pattern to be formed in each layer 1 according to a command from the drive control unit 22. It is controlled.

  Specifically, the surface treatment composition applying means (surface treatment composition discharge portion) 8 is configured so that the relative positional relationship with the layer 1 can be changed, and the surface treatment composition discharge is performed. When the portion 8 is positioned above the portion to which the surface treatment composition 14 ′ is to be applied, the surface treatment composition 14 ′ is discharged.

  In the present embodiment, the surface treatment composition discharge unit 8 includes an area on the stage 41 (an area overlapping the stage 41 when viewed in plan) and an area other than the stage 41 (when viewed in plan the stage 41 And a region that does not overlap) (see FIGS. 6 and 7).

  Thereby, the surface treatment composition discharge part 8 is retracted from the region on the stage 41 except when the surface treatment composition 14 ′ is applied (see FIG. 6B), and the surface treatment composition discharge part 8. Can be effectively prevented from occurring due to the presence of the in the region on the stage 41. More specifically, for example, when the layer 1 is formed (see FIG. 6A), the particles 111 contained in the layer-forming composition 11 fly up and adhere to the surface treatment composition 14 ′. This can be effectively prevented, and stable droplet discharge can be performed over a long period of time. Further, when heated by the heating means 9 (see FIG. 7C), it is effective that the surface treatment composition discharge unit 8 is dried, and a solid substance is deposited on the surface treatment composition discharge unit 8. Therefore, stable droplet discharge can be performed over a long period of time. In addition, when the binding liquid 12 is applied by the binding liquid applying means 5 (see FIG. 7D), it is effective that mist, vaporized material, etc. of the binding liquid 12 adhere to the binding liquid discharge part 5. Can be prevented.

  In the present embodiment, the surface treatment composition applying unit 8 is a binding liquid discharge portion that discharges the surface treatment composition 14 ′ by an ink jet method.

  Thereby, the selectivity of the region to which the surface treatment composition 14 ′ is applied can be made higher, which is particularly advantageous from the viewpoint of saving resources and reducing the manufacturing cost of the three-dimensional structure 10.

  As a droplet discharge method (inkjet method), a piezo method, a method in which the surface treatment composition 14 ′ is discharged by bubbles generated by heating the binding liquid 12, and the like can be used. The piezo method is preferred from the standpoint of difficulty in altering the constituent components of the surface treatment composition 14 ′.

In the illustrated configuration, the surface treatment composition applying means 8 is a line head having a length equal to or greater than the width of the modeling region (stage 41) in the Y-axis direction.
Thereby, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Two surface treatment composition applying means 8 are provided at both ends of the binding liquid applying means 5 in the moving direction (X-axis direction).

  Thus, in both the positive and negative movements in the X-axis direction of the surface treatment composition application unit 8, after the surface treatment composition application unit 8 provides the surface treatment composition 14 ′, the binding liquid application unit 5 performs the treatment. The process of providing the binding liquid 12 can be performed smoothly, and the productivity of the three-dimensional structure 10 can be made particularly excellent.

  In particular, in the present embodiment, the moving direction (X-axis direction) of the binding liquid application unit 5 and the surface treatment composition application unit 8 is provided outside the ultraviolet irradiation unit (curing unit) 6. In other words, ultraviolet irradiation means (curing means) 6 and surface treatment composition applying means 8 are provided in this order on both positive and negative sides of the binding liquid applying means 5 in the X-axis direction.

  Thus, in both the positive and negative movements in the X-axis direction of the surface treatment composition application unit 8, after the surface treatment composition application unit 8 provides the surface treatment composition 14 ′, the binding liquid application unit 5 performs the treatment. The application of the binding liquid 12 and the curing process of the binding liquid 12 can be performed smoothly, and the productivity of the three-dimensional structure 10 can be made particularly excellent.

  In the present embodiment, the surface treatment composition application unit 8 is configured to be movable independently of the binding liquid application unit 5.

  As a result, the mist, vaporized substance, etc. of the surface treatment composition 14 ′ adhere to the binding liquid discharge part 5, and the mist, vaporized substance, etc. of the binder liquid 12 adhere to the surface treatment composition discharge part 8. It can prevent more effectively. Moreover, the unnecessary movement of a member can be suppressed at the time of manufacture of the three-dimensional structure 10. Because of this, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  The heating means 9 has a function of heating the layer 1. By having such a heating means, for example, the modification of the particles 111 with the surface treatment agent can be suitably advanced, or the solvent contained in the layer 1 can be suitably removed.

  The heating means 9 may be anything as long as it can heat the layer 1 (the uppermost layer 1 when the layer 1 is laminated), for example, heating wire, seeds, etc. A heater, a warm air heater, an infrared heater or the like can be used.

  When the heating means 9 is an infrared heater, the surface facing the layer 1 of the heating means 9 may be made of a material having infrared transparency (for example, quartz). Thereby, the solvent evaporated from the layer 1 can be prevented from directly adhering to the infrared lamp.

  In the illustrated configuration, the heating means 9 can heat the entire layer 1 at the same time. For example, the heating means 9 is configured to be movable. You may be comprised so that an area | region can be changed.

  According to the manufacturing apparatus of the present invention as described above, a three-dimensional structure excellent in mechanical strength can be efficiently manufactured.

<Layer forming composition>
Next, the layer forming composition will be described in detail.
The layer forming composition 11 includes at least a plurality of particles 111.

(particle)
Examples of the constituent material of the particles 111 include inorganic materials, organic materials, and composites thereof.

  Examples of the inorganic material constituting the particles 111 include various metals and metal compounds. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; various kinds such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Metal hydroxides; 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; various metals such as calcium carbonate and magnesium carbonate Carbonates; sulfates of various metals such as calcium sulfate and magnesium sulfate; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; aluminum borate, magnesium borate, etc. Various metal borates, their composites, gypsum (calcium sulfate hydrates) Include anhydrides) such as calcium sulfate.

  Examples of the organic material constituting the particles 111 include synthetic resins, natural polymers, and the like. More specifically, polyethylene resin; polypropylene; polyethylene oxide; polypropylene oxide, polyethyleneimine; polystyrene; polyurethane; polyurea; A silicone resin; an acrylic silicone resin; a polymer having a (meth) acrylic acid ester such as polymethyl methacrylate as a constituent monomer; a cross polymer having a (meth) acrylic acid ester as a constituent monomer such as methyl methacrylate crosspolymer (ethylene Acrylic acid copolymer resins, etc.); polyamide resins such as nylon 12, nylon 6, copolymer nylon, etc .; polyimides; carboxymethyl cellulose; gelatin; starch; chitin;

  Among these, the particle 111 is preferably composed of a metal oxide, and more preferably composed of silica.

  Since the metal oxide is generally excellent in its own mechanical strength, light resistance, and the like, this makes it possible to make the properties of the three-dimensional structure 10 such as mechanical strength and light resistance more excellent. . In addition, the metal oxide has a particularly favorable chemical reaction for surface modification by the surface treatment agent constituting the surface treatment composition 14 ′, and has particularly excellent bond strength and bond reliability with the binder. Is a material that can be. For this reason, the mechanical strength and reliability of the three-dimensional structure 10 can be made particularly excellent.

  In particular, when the particles 111 are made of silica, the effects described above are more remarkably exhibited. Moreover, the silica is excellent also in the fluidity | liquidity of itself, and can make the fluidity | liquidity of the composition 11 for layer formation containing a silica more excellent. This is advantageous for forming the layer 1 having higher thickness uniformity, and is also advantageous for improving the productivity and dimensional accuracy of the three-dimensional structure 10.

  The average particle diameter of the particles 111 is not particularly limited, but is preferably 1 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less.

  Thereby, while being able to make the mechanical strength of the three-dimensional structure 10 more excellent, generation | occurrence | production of the unintentional unevenness | corrugation etc. in the three-dimensional structure 10 manufactured more effectively is prevented, and three-dimensional The dimensional accuracy of the shaped article 10 can be further improved. Moreover, the fluidity | liquidity of the composition 11 for layer formation can be made more excellent, and the productivity of the three-dimensional structure 10 can be made more excellent.

  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 ( For example, it can obtain | require by measuring using a 50 micrometer aperture in COULTER ELECTRONICS INC type TA-II.

  The Dmax of the particles 111 is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less.

  Thereby, while being able to make the mechanical strength of the three-dimensional structure 10 more excellent, generation | occurrence | production of the unintentional unevenness | corrugation etc. in the three-dimensional structure 10 manufactured more effectively is prevented, and three-dimensional The dimensional accuracy of the shaped article 10 can be further improved. Moreover, the fluidity | liquidity of the composition 11 for layer formation can be made more excellent, and the productivity of the three-dimensional structure 10 can be made more excellent.

  The particles 111 may be dense, but are preferably those having pores (particularly porous particles).

  Thereby, for example, not only on the surface visible from the outside of the particle 111 but also in the pores, it can come into contact with the binder, and the contact area with the binder can be increased. In addition, since the surface treatment with the surface treatment agent is also performed in the pores of the particles 111, it can be firmly bonded to the binder even in the pores that are difficult for the binder to infiltrate. Prominently demonstrated. For this reason, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent.

  The porosity of the particles 111 is preferably 50% or more, and more preferably 55% or more and 90% or less.

  As a result, there is sufficient space (holes) for the binder to enter, and the mechanical strength of the particles 111 itself can be made excellent. As a result, the bond is formed by the binder entering the pores. The mechanical strength of the three-dimensional structure 10 having the portion 13 can be further improved.

In the present invention, the porosity of the particles 111 refers to the ratio (volume ratio) of vacancies existing inside the particles 111 to the apparent volume of the particles 111, and the density of the particles 111 is expressed by ρ [ g / cm ³ ], and the true density ρ ₀ [g / cm ³ ] of the constituent material of the particles 111 is a value represented by {(ρ ₀ −ρ) / ρ ₀ } × 100.

  The average pore diameter (pore diameter) of the particles 111 is preferably 10 nm or more, and more preferably 50 nm or more and 300 nm or less.

  Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be further improved. In addition, in the case of using the binder liquid 12 (colored ink) containing a pigment for manufacturing the three-dimensional structure 10, the pigment can be suitably held in the pores of the particles 111. For this reason, unintentional diffusion of the pigment can be prevented, and a high-definition image can be more reliably formed.

  The particles 111 may have any shape, but preferably have a spherical shape. As a result, the fluidity of the layer-forming composition 11 can be improved, the productivity of the three-dimensional structure 10 can be improved, and the unwillingness in the manufactured three-dimensional structure 10 can be obtained. Generation of unevenness and the like can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure 10 can be further improved.

The layer forming composition 11 may include a plurality of types of particles 111.
The content of the particles 111 in the layer-forming composition 11 is preferably 8% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 90% by mass or less.

  Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be further improved while sufficiently improving the fluidity of the layer forming composition 11.

(solvent)
The layer forming composition 11 may contain a solvent in addition to the particles 111.

  Thereby, for example, the layer-forming composition 11 can be made into a paste-like material, the fluidity of the layer-forming composition 11 can be improved, and workability at the time of forming the layer 1 can be improved. The layer 1 having a high surface flatness can be easily and reliably formed. In addition, unintentional scattering of the powder (particles 111) during formation of the layer 1 can be more effectively prevented.

  In particular, when the layer forming composition 11 includes an aqueous solvent as a solvent, the following effects are obtained.

  That is, since the aqueous solvent has a high affinity with water, a water-soluble resin described later can be suitably dissolved. Thereby, the fluidity | liquidity of the composition 11 for layer formation can be made favorable, and the unintentional dispersion | variation in the thickness of the layer 1 formed using the composition 11 for layer formation is prevented more effectively. can do. In addition, when the layer 1 in a state where the aqueous solvent is removed is formed, the water-soluble resin can be adhered to the particles 111 with higher uniformity over the entire layer 1, and unintentionally uneven composition occurs. Can be more effectively prevented. For this reason, generation | occurrence | production of the unintentional dispersion | variation in the mechanical strength in each site | part of the three-dimensional structure 10 finally obtained can be prevented more effectively, and the reliability of the three-dimensional structure 10 is higher. Can be.

  In the present invention, the aqueous solvent refers to water or a liquid having a high affinity with water, and specifically refers to a solvent having a solubility in 100 g of water at 25 ° C. of 50 g or more.

  Examples of the aqueous solvent constituting the layer forming composition 11 include water; alcoholic solvents such as methanol, ethanol, and isopropanol; ketone solvents such as methyl ethyl ketone and acetone; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and the like. Glycol ether solvents: Glycol ether acetate solvents such as propylene glycol 1-monomethyl ether 2-acetate, propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, polypropylene glycol, etc., one selected from these Alternatively, two or more kinds can be used in combination.

  Especially, as an aqueous solvent which comprises the composition 11 for layer formation, water is preferable. When the layer-forming composition 11 contains water, when the layer-forming composition 11 contains a water-soluble resin as described in detail later, the water-soluble resin can be more reliably dissolved, and layer formation The fluidity of the composition 11 and the uniformity of the composition of the layer 1 formed using the layer forming composition 11 can be made more excellent. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems. In the case where the layer-forming composition 11 contains water and the layer 1 is provided with the surface treatment composition 14 ′, when the layer-forming composition 11 contains water, the particles 111 are modified by the surface treatment agent. The chemical reaction can be made to proceed more efficiently, and the productivity of the three-dimensional structure 10 and the reliability of the three-dimensional structure 10 can be made particularly excellent.

  The content of the solvent in the layer-forming composition 11 is preferably 1% by mass or more and 92% by mass or less, and more preferably 2% by mass or more and 89% by mass or less.

  Thereby, while the effect by including a solvent as mentioned above is exhibited more notably, since a solvent can be easily removed in a short time in the manufacturing process of the three-dimensional structure 10, the three-dimensional structure The productivity of 10 can be made more excellent. Further, the layer 1 in a state where the solvent is removed can include voids at an appropriate ratio, and the permeability of the binding liquid 12 can be further improved. The mechanical strength, dimensional accuracy, and the like of the molded article 10 can be further improved.

When the aqueous solvent contains water, the proportion of water in the aqueous solvent is preferably 80% by mass or more, and more preferably 90% by mass or more.
Thereby, the effects as described above are more remarkably exhibited.

(binder)
The layer forming composition 11 may contain a binder.

  Thereby, in the layer 1 formed using the layer-forming composition 11, a plurality of particles 111 can be suitably bonded (temporarily fixed), and the unwanted scattering of the particles 111 can be effectively prevented. can do. Thereby, the further improvement of the operator's safety and the dimensional accuracy of the manufactured three-dimensional structure 10 can be aimed at.

  In the case where the layer forming composition 11 includes a solvent and a binder, in the layer forming composition 11, the binder is preferably dissolved in the solvent.

  Thereby, the fluidity | liquidity of the composition 11 for layer formation can be made more favorable, and the unintentional dispersion | variation in the thickness of the layer 1 formed using the composition 11 for layer formation is made more effective. Can be prevented. Further, when the layer 1 in a state where the solvent is removed is formed, the binder can be attached to the particles 111 with higher uniformity over the entire layer 1, and unintentional unevenness of the composition is more likely to occur. It can be effectively prevented. For this reason, generation | occurrence | production of the unintentional dispersion | variation in the mechanical strength in each site | part of the three-dimensional structure 10 finally obtained can be prevented more effectively, and the reliability of the three-dimensional structure 10 is higher. Can be.

  Any binder may be used as long as it has a function of temporarily fixing the plurality of particles 111 in the layer 1 formed using the layer forming composition 11, and a water-soluble resin can be preferably used.

  By including a water-soluble resin, when the layer-forming composition 11 includes an aqueous solvent (particularly water) as a solvent, the layer-forming composition 11 includes a binder (water-soluble resin) in a dissolved state. Thus, the fluidity and handleability (ease of handling) of the layer-forming composition 11 can be further improved. As a result, the productivity of the three-dimensional structure 10 can be further improved.

  Moreover, the site | part to which the binding liquid 12 of the layer 1 was not provided in the manufacturing process of the three-dimensional structure 10 can be easily and efficiently removed by applying an aqueous solvent (particularly water). As a result, the productivity of the three-dimensional structure 10 can be further improved. Moreover, since it can prevent easily and reliably that the site | part which should be removed of the layer 1 adheres and remains | survives in the finally obtained three-dimensional structure 10, the dimensional accuracy of the three-dimensional structure 10 is improved. It can be made better.

Hereinafter, the water-soluble resin as the binder will be mainly described.
The water-soluble resin may be at least partly soluble in an aqueous solvent. For example, the solubility in water (mass that can be dissolved in 100 g of water) at 25 ° C. is 5 [g / 100 g water] or more. It is preferable that it is more than 10 [g / 100g water].

  Examples of water-soluble resins include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactone diol, sodium polyacrylate, ammonium polyacrylate, polyacrylamide, modified polyamide, polyethyleneimine, polyethylene oxide, ethylene oxide and propylene. Synthetic polymers such as random copolymer with oxide, natural polymers such as corn starch, mannan, pectin, agar, alginic acid, dextran, glue, gelatin, semi-synthetic polymers such as carboxymethylcellulose, hydroxyethylcellulose, oxidized starch, modified starch, etc. 1 type selected from these, or 2 or more types can be used in combination.

  Especially, when the water-soluble resin as a binder is polyvinyl alcohol, the mechanical strength of the three-dimensional structure 10 can be further improved. Further, by adjusting the degree of saponification and the degree of polymerization, the properties of the binder (for example, water solubility, water resistance, etc.) and the properties of the layer forming composition 11 (for example, viscosity, fixing force of the particles 111, wettability, etc.) It can control more suitably. For this reason, it can respond suitably by manufacture of the various three-dimensional structure 10. Polyvinyl alcohol is inexpensive and stable in supply among various water-soluble resins. For this reason, the stable three-dimensional structure 10 can be manufactured while suppressing the production cost.

  When the water-soluble resin as the binder contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is preferably 85 or more and 90 or less. Thereby, the fall of the solubility of polyvinyl alcohol with respect to an aqueous solvent (especially water) can be suppressed. Therefore, when the layer forming composition 11 contains an aqueous solvent (particularly water), it is possible to more effectively suppress the decrease in adhesiveness between the adjacent layers 1.

  When the water-soluble resin as the binder contains polyvinyl alcohol, the degree of polymerization of the polyvinyl alcohol is preferably 300 or more and 2000 or less. Thereby, when the composition 11 for layer formation contains an aqueous solvent (especially water), the mechanical strength of each layer 1 and the adhesiveness between the adjacent layers 1 can be made more excellent.

  Moreover, when the water-soluble resin as a binder is polyvinylpyrrolidone (PVP), the following effects are acquired. That is, since polyvinylpyrrolidone is excellent in adhesiveness to various materials such as glass, metal, and plastic, it is assumed that the strength and shape stability of the layer 1 to which the binding liquid 12 is not applied are more excellent, The dimensional accuracy of the finally obtained three-dimensional structure 10 can be further improved. Moreover, since polyvinylpyrrolidone shows high solubility with respect to various organic solvents, when the composition 11 for layer formation contains the organic solvent, the fluidity | liquidity of the composition 11 for layer formation is made more excellent. It is possible to suitably form the layer 1 in which the unintentional thickness variation is more effectively prevented, and to improve the dimensional accuracy of the finally obtained three-dimensional structure 10. be able to. Moreover, since polyvinylpyrrolidone shows high solubility also to an aqueous solvent (especially water), in the unbonded particle removal process (after the completion of modeling), it binds with a binder among the particles 111 constituting each layer 1. What is not done can be removed easily and reliably. Moreover, since polyvinylpyrrolidone is excellent in affinity with various colorants, when the binding liquid 12 containing the colorant is used in the binding liquid application step, the colorant diffuses unintentionally. Can be effectively prevented.

When the water-soluble resin as the binder contains polyvinyl pyrrolidone, the polyvinyl pyrrolidone preferably has a weight average molecular weight of 10,000 to 170,000, and more preferably 30,000 to 1500,000.
Thereby, the function mentioned above can be exhibited more effectively.

When the water-soluble resin as the binder contains polycaprolactone diol, the weight average molecular weight of the polycaprolactone diol is preferably 10,000 or more and 170,000 or less, and more preferably 30,000 or more and 1500,000 or less.
Thereby, the function mentioned above can be exhibited more effectively.

  In the layer forming composition 11, the binder is preferably in a liquid state (for example, a dissolved state, a molten state, etc.) in the layer forming step. Thereby, the uniformity of the thickness of the layer 1 formed using the layer forming composition 11 can be made higher and easier.

  When the layer forming composition 11 includes a binder, the content of the binder in the layer forming composition 11 is preferably 0.5% by mass or more and 25% by mass or less, and 1.0% by mass or more and 10% by mass. It is more preferable that the amount is not more than mass%.

  Thereby, while the effect by including a binder as mentioned above is exhibited more notably, the content rate of the particle | grains 111 etc. in the composition 11 for layer formation can be made high enough, and three-dimensional modeling The productivity of the object 10 and the mechanical strength of the manufactured three-dimensional structure 10 can be further improved.

(Other ingredients)
Further, the layer forming composition 11 may contain components other than those described above. Examples of such components include a polymerization initiator; a polymerization accelerator; a penetration accelerator; a wetting agent (humectant); a fixing agent; an antifungal agent; an antiseptic; an antioxidant; an ultraviolet absorber; Examples include regulators.

  Further, the layer forming composition 11 may contain a surface treating agent as described in detail later as a constituent component of the surface treating composition 14 ′. Thereby, the further improvement of the mechanical strength of the three-dimensional structure 10 can be aimed at.

<Surface treatment composition>
Next, the surface treatment composition will be described in detail.

The surface treatment composition 14 ′ is applied to the layer 1 prior to forming the bonding portion 13 by applying the binding liquid 12 to the layer 1, and at least the particles 111 constituting the layer 1. It contains a surface treatment agent that modifies the surface.
Thereby, the three-dimensional structure 10 excellent in mechanical strength can be efficiently manufactured.

(Surface treatment agent)
The surface treatment agent may be any as long as it has a function of modifying the surface of the particles 111 so as to improve the affinity with the binder, but is preferably a coupling agent.

  Thereby, the affinity between the surface of the particle 111 and the binder can be made higher. As a result, the bonding force between the particles 111 by the binder can be made higher, and the mechanical strength of the obtained three-dimensional structure 10 can be made more excellent.

  Various types of coupling agents can be used, but one or two selected from the group consisting of silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents. It is preferable to use more than one species.

  Thereby, the affinity between the surface of the particle 111 and the binder can be further increased. As a result, the bonding force between the particles 111 by the binder can be further increased, and the mechanical strength of the obtained three-dimensional structure 10 can be further improved.

  Examples of silane coupling agents include amino silane coupling agents, acrylic silane coupling agents, ureido silane coupling agents, vinyl silane coupling agents, methacrylic silane coupling agents, and epoxy silane coupling agents. , Mercapto silane coupling agents, isocyanate silane coupling agents and the like. Among these, it is particularly preferable to use an amino silane coupling agent and / or an acrylic silane coupling agent as the silane coupling agent. Thereby, the affinity between the particle 111 surface and the binder can be further increased.

  Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, 3- (acryloxy) propyltrimethoxysilane, N-2-aminoethyl-3-amino. Propylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltris (β-methoxy-ethoxy) silane, β- (3 , 4-epoxycyclohexyl) -ethyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like. .

  Examples of titanate coupling agents include titanate coupling agents having an alkyl phosphite group, titanate coupling agents having an alkyl phosphate group, titanate coupling agents having an alkyl pyrophosphate group, tetraalkyl type, mono Examples include an alkoxy type, a coordination type, a chelate type, a quaternary salt type, a neoalkoxy type, and a cycloheteroatom type.

  Specific examples of the titanate coupling agent include, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetraoctyl bis (ditrityl). Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphat titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctai Nortitanate, isopropyl dimethacrylisostearoyl titanate, isopropylisostearoyl Acrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumyl phenyloxyacetate titanate diisostearoyl ethylene titanate, neopentyl (diaryl) oxy- ( Tri) dioctyl phosphato titanate, dineopentyl (diaryl) oxy-di (paraamino) benzoyl titanate, neopentyl (diaryl) oxy-tri (N-ethylenediamino) ethyl titanate, dineopentyl (diaryl) oxy-tri (m-amino) phenyl titanate Etc. Among these, it is particularly preferable to use isopropyl triisostearoyl titanate. Thereby, the affinity between the particle 111 surface and the binder can be further increased.

  Specific examples of the aluminate coupling agent include, for example, alkyl acetoacetate aluminum diisopropylate, diisobutyl (oleyl) acetoacetyl aluminate, diisopropyl (oleyl) acetoacetyl aluminate, amino zircoaluminate, carboxyl zircoaluminate, Examples include methacryloxy zirco aluminate, fatty acid zirco aluminate, mercapto zirco aluminate and the like.

  Specific examples of the zirconate coupling agent include, for example, zirconium stearate, tetra (2,2-diallyloxymethyl) butyl-di (ditridecyl) phosphitozirconate, neopentyl (diaryl) oxy- (tri) dioctylphos Fattyzirconate, Dineopentyl (diaryl) oxy-di (paraamino) benzoyl zirconate, Neopentyl (diaryl) oxy-tri (N-ethylenediamino) ethyl zirconate, Dineopentyl (diaryl) oxy-tri (m-amino) phenylzirconate Etc.

  The content of the surface treatment agent in the surface treatment composition 14 ′ is preferably 0.5% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.

  As a result, a necessary and sufficient amount of the surface treatment agent can be efficiently attached to the particles 111 at the site to which the surface treatment composition 14 ′ has been applied, and the mechanically obtained finally obtained three-dimensional structure 10 is obtained. The strength can be made particularly excellent. In addition, since it is not necessary to use an excessive amount of the surface treatment agent, it is preferable from the viewpoint of saving resources and reducing the profitability of the three-dimensional structure 10. In addition, the storage stability and ejection stability of the surface treatment composition 14 ′ can be made particularly excellent.

(solvent)
The surface treatment composition 14 ′ may contain a solvent in addition to the surface treatment agent.

  Thereby, for example, the surface treatment composition 14 ′ can be made into a liquid composition having an appropriate viscosity and fluidity, and the surface treatment composition 14 ′ can be more smoothly applied to the layer 1. Can do. In addition, since the surface treatment agent is diluted with a solvent, it is easy to adjust the amount of the surface treatment agent supplied to the layer 1, and it is possible to more effectively prevent application of an excess surface treatment agent.

  As the solvent constituting the surface treatment composition 14 ', any solvent may be used as long as it can dissolve or disperse the surface treatment agent described above. For example, water; methanol, ethanol, isopropanol, etc. Alcoholic solvents; ketone solvents such as methyl ethyl ketone and acetone; glycol ether solvents such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; propylene glycol 1-monomethyl ether 2-acetate, propylene glycol 1-monoethyl ether 2-acetate Examples include glycol ether acetate solvents such as polyethylene glycol and polypropylene glycol, and one or more selected from these can be used in combination.

  The content of the solvent in the surface treatment composition 14 ′ is preferably 50% by mass or more and 99.5% by mass or less, and more preferably 80% by mass or more and 99% by mass or less.

  Thereby, while the effect by including a solvent as mentioned above is exhibited more notably, since a solvent can be easily removed in a short time in the manufacturing process of the three-dimensional structure 10, the three-dimensional structure The productivity of 10 can be made more excellent.

(Other ingredients)
Further, the surface treatment composition 14 ′ may contain components other than those described above. Examples of such components include a dispersant, a surfactant, a polymerization initiator, a polymerization accelerator, a penetration accelerator, a wetting agent (humectant), a fixing agent, an antifungal agent, an antiseptic, an antioxidant, and an ultraviolet ray. Absorbers; chelating agents; pH adjusters; thickeners; fillers; anti-aggregation agents;

  Further, the viscosity of the surface treatment composition 14 ′ is preferably 1 mPa · s or more and 30 mPa · s or less, and more preferably 3 mPa · s or more and 25 mPa · s or less. Thereby, the discharge stability of the surface treatment composition 14 ′ by the ink jet method can be further improved. In the present specification, the viscosity means a value measured at 25 ° C. using an E-type viscometer (for example, VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.) unless otherwise specified.

<Binding liquid>
Next, the binding liquid will be described in detail.
The binding liquid 12 contains at least a binder.

(Binder)
The binding liquid 12 contains at least a curable resin as a binder.

  Examples of the curable resin include a thermosetting resin; various photo-curing properties such as a visible light curable resin (a photocurable resin in a narrow sense) that is cured by light in the visible light region, an ultraviolet curable resin, and an infrared curable resin. Resin; X-ray curable resin etc. are mentioned, It can use combining 1 type (s) or 2 or more types selected from these. Among these, from the viewpoint of the mechanical strength of the three-dimensional structure 10 to be obtained, the productivity of the three-dimensional structure 10, the storage stability of the binder liquid 12, an ultraviolet curable resin (polymerizable compound) is particularly preferable.

  In particular, by using an ultraviolet curable resin (polymerizable compound), the effect obtained by subjecting the particles 111 to the surface treatment with the surface treatment agent is more remarkably exhibited, and the mechanical strength of the three-dimensional structure 10 is particularly enhanced. It can be excellent.

  As the ultraviolet curable resin (polymerizable compound), a resin in which addition polymerization or ring-opening polymerization is initiated by irradiation with ultraviolet rays by radical species or cationic species generated from a photopolymerization initiator, and a polymer 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.

  Specific examples of the monofunctional (meth) acrylate include, for example, tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. are mentioned.

  Specific examples of the bifunctional (meth) acrylate include, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, penta Examples include erythritol di (meth) acrylate and dipentaerythritol di (meth) acrylate.

  Specific examples of the trifunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri ( Data) acrylate, and the like.

  Specific examples of the tetrafunctional (meth) acrylate include, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate.

  Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Specific examples of the hexafunctional (meth) acrylate include, for example, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa ( And (meth) acrylate.

  Examples of the polymerizable compound other than (meth) acrylate include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester and the like.

  Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diesterate. Examples include itaconate and sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate.

  Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Specific examples of the amide monomer of unsaturated carboxylic acid and aliphatic polyvalent amine compound include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  A urethane-based addition polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable.

  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 ultraviolet 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.

  Examples of preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxies, polyfunctional alicyclic epoxies, and the like.

  Specific examples of glycidyl ethers include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.), trifunctional or higher glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc., tetra- or more functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cresol novolac resin poly) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, ceroxide) 021P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), polycyclohexyl epoxy methyl ether of phenol novolac resin, etc.) Oxetanes (for example, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.)) and the like.

  As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. The “alicyclic epoxy group” refers to a partial structure obtained by epoxidizing a double bond of a cycloalkene ring such as a cyclopentene group or a cyclohexene group with an appropriate oxidizing agent such as hydrogen peroxide or peracid.

  The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy having two or more cyclohexene oxide groups or cyclopentene oxide groups in one molecule. Specific examples of the alicyclic epoxy compound include, for example, 4-vinylcyclohexylene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, Examples include di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3-epoxy-6-methylcyclohexylmethyl) adipate, and dicyclopentadiene dioxide.

  The glycidyl compound which has a normal epoxy group which does not have an alicyclic structure in a molecule | numerator can be used independently, or can also be used together with the said alicyclic epoxy compound.

  Examples of such normal glycidyl compounds include glycidyl ether compounds and glycidyl ester compounds, but it is preferable to use glycidyl ether compounds in combination.

  Specific examples of the glycidyl ether compound include 1,3-bis (2,3-epoxypropyloxy) benzene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac. Glycidyl ether compounds such as epoxy resin, trisphenolmethane epoxy resin, 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, and aliphatic glycidyl ether such as trimethylolpropane triglycidyl ether Compounds and the like. Examples of the glycidyl ester include a glycidyl ester of linolenic acid dimer.

  As the polymerizable compound, a compound having an oxetanyl group which is a 4-membered cyclic ether (hereinafter, also simply referred to as “oxetane compound”) can be used. An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in one molecule.

  The content of the binder in the binding liquid 12 is preferably 80% by mass or more, and more preferably 85% by mass or more. Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent.

(Other ingredients)
Further, the binding liquid 12 may contain components other than those described above. Examples of such components include various colorants such as pigments and dyes; dispersants; surfactants; polymerization initiators; polymerization accelerators; solvents; penetration enhancers; wetting agents (humectants); Examples include glazes; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; pH adjusters; thickeners; fillers;

  In particular, when the binding liquid 12 contains a colorant, the three-dimensional structure 10 colored in a color corresponding to the color of the colorant can be obtained.

  In particular, the light resistance of the binding liquid 12 and the three-dimensional structure 10 can be improved by including a pigment as the colorant. As the pigment, either an inorganic pigment or an organic pigment 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 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.

  When the binder liquid 12 contains a colorant, the content of the colorant in the binder liquid 12 is preferably 1% by mass or more and 20% by mass or less. Thereby, more excellent concealment and color reproducibility can be obtained.

  In particular, when the binding liquid 12 contains titanium oxide as a colorant, the content of titanium oxide in the binding liquid 12 is preferably 12% by mass or more and 30% by mass or less, and more preferably 14% by mass or more and 25% by mass. It is more preferable that the amount is not more than mass%. Thereby, the more excellent concealment property is obtained.

  When the binder liquid 12 contains a pigment, the dispersibility of the pigment can be further improved if it further contains a dispersant. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples of the polymer dispersant include, for example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, and sulfur-containing polymer. , Fluorine-containing polymers, and epoxy resins having one or more types as main components.

  When the binding liquid 12 contains a surfactant, the three-dimensional structure 10 can have better abrasion resistance. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used.

  Further, the binding liquid 12 may contain a solvent. Thereby, the viscosity of the binding liquid 12 can be suitably adjusted, and even when the binding liquid 12 includes a high-viscosity component, the discharge stability of the binding liquid 12 by the ink jet system is more excellent. It can be.

  Examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ethyl acetate, n-propyl acetate, iso-acetate Acetates such as 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, etc. Ketones: Examples include alcohols such as ethanol, propanol, and butanol, and one or more selected from these can be used in combination.

  Further, the binding liquid 12 may contain a surface treatment agent as described as a constituent of the surface treatment composition 14 ′. Thereby, the further improvement of the mechanical strength of the three-dimensional structure 10 can be aimed at.

  The viscosity of the binding liquid 12 is preferably 1 mPa · s or more and 30 mPa · s or less, and more preferably 3 mPa · s or more and 25 mPa · s or less. Thereby, the discharge stability of the binding liquid 12 by an inkjet method can be made more excellent.

In addition, a plurality of types of binding liquids 12 may be used for manufacturing the three-dimensional structure 10.
For example, a binder liquid 12 (color ink) containing a colorant and a binder liquid 12 (clear ink) not containing a colorant may be used. Thereby, for example, the binding liquid 12 containing the colorant is used as the binding liquid 12 to be applied to the area that affects the color tone on the appearance of the three-dimensional structure 10, and the color tone is adjusted on the appearance of the three-dimensional structure 10. A binding liquid 12 that does not contain a colorant may be used as the binding liquid 12 that is applied to a region that does not have an influence. Further, in the finally obtained three-dimensional structure 10, an area (coat layer) using the binding liquid 12 not containing the colorant on the outer surface of the area formed using the binding liquid 12 containing the colorant. ) May be used in combination.

  For example, you may use the multiple types of binding liquid 12 containing the coloring agent of a different composition. Thereby, the color reproduction area which can be expressed by the combination of these binding liquids 12 can be widened.

  When a plurality of types of binding liquids 12 are used, it is preferable to use at least a cyan binding liquid 12, a magenta binding liquid 12, and a yellow binding liquid 12. Thereby, the color reproduction area which can be expressed by the combination of these binder liquids can be made wider.

  Further, by using the white binding liquid 12 in combination with other colored binding liquids 12, for example, the following effects can be obtained. That is, the finally obtained three-dimensional structure 10 is overlapped with the first region to which the white binding liquid 12 is applied and the first region, and the outer surface is more than the first region. And a region provided with a colored binding liquid 12 other than white provided on the side. Thereby, the 1st area | region to which the white (white) binding liquid was provided can exhibit concealment property, and can improve the chroma of the three-dimensional structure 10 more.

<< Composition set for manufacturing 3D objects >>
Next, the composition set for producing a three-dimensional structure of the present invention will be described in detail.

  The composition set for producing a three-dimensional structure of the present invention combines a composition for forming a layer containing a plurality of particles, a composition for surface treatment of the present invention, and particles subjected to surface treatment with a surface treatment agent. And a binding liquid.

  Thereby, the composition set for three-dimensional structure manufacture which can manufacture the three-dimensional structure excellent in mechanical strength efficiently can be provided.

  The composition set for producing a three-dimensional structure of the present invention may be obtained by roughening two or more kinds of compositions for at least one of the layer forming composition, the surface treatment composition and the binding liquid. Good.

《Three-dimensional structure》
The three-dimensional structure of the present invention can be manufactured using the above-described method for manufacturing a three-dimensional structure, a three-dimensional structure manufacturing apparatus, a composition for surface treatment, and a composition set for manufacturing a three-dimensional structure. it can.
Thereby, the three-dimensional structure excellent in mechanical strength can be provided.

  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, in the above-described embodiment, the configuration for lowering the stage has been representatively described. However, in the manufacturing method of the present invention, for example, the side support portion may be configured to move upward.

  Further, a roller or the like may be used as the flattening means instead of the squeegee as described above.

Moreover, although embodiment mentioned above demonstrated the case where a binding liquid provision means was a line head, a binding liquid provision means may be a serial head, for example.
Similarly, the surface treatment layer composition applying means may be, for example, a serial head.

  In addition, the three-dimensional structure manufacturing apparatus of the present invention is a recovery mechanism (not shown) for recovering a layer forming composition supplied from a layer forming composition supply unit that was not used for forming a layer. May be provided. As a result, a sufficient amount of the layer forming composition can be supplied while preventing an excessive amount of the layer forming composition from accumulating in the layer forming portion. It is possible to manufacture a three-dimensional structure more stably while preventing it. In addition, since the collected layer forming composition can be used again for the production of the three-dimensional structure, it can contribute to the reduction of the manufacturing cost of the three-dimensional structure, and also from the viewpoint of resource saving. preferable.

  Moreover, the three-dimensional structure manufacturing apparatus of this invention may be equipped with the collection | recovery mechanism for collect | recovering the composition for layer formation removed by the unbound particle removal process.

  In addition, when a material containing a solvent (for example, a composition for forming a layer or a binding liquid) is used for manufacturing a three-dimensional structure, the three-dimensional structure manufacturing apparatus of the present invention collects the solvent removed from the layer. Solvent recovery means may be provided.

  In the above-described embodiment, the case where the binding liquid application process is performed by the ink jet method has been mainly described. However, the binding liquid application process is performed using another method (for example, another printing method). There may be.

  In the above-described embodiment, subsequent to the application of the surface treatment composition to the layer, the particle modification treatment with the applied surface treatment composition (surface treatment agent) (specifically, heat treatment, etc.) However, another treatment may be performed between the application of the surface treatment composition to the layer and the particle modification treatment (specifically, heat treatment, etc.). . For example, after the surface treatment composition is applied to the layer, a binding solution may be applied, and then a particle modification process (specifically, a heat treatment or the like) may be performed. In such a case, for example, the particle modification process may be performed before the binder liquid curing process or may be performed after the binder liquid curing process. The particle modification treatment may be performed simultaneously with the binder solution curing treatment. Thereby, the productivity of the three-dimensional structure can be made particularly excellent.

In the above-described embodiment, the case where the particle modification process is performed in a series of steps performed for each layer (a series of steps performed repeatedly) is typically described. However, the particle modification process is performed for each layer. It may not be performed, and may be performed collectively for a plurality of layers.
The particle modification treatment may be performed in a plurality of stages.

  Further, the application of the surface treatment composition and the particle modification treatment may not be performed on all layers, and may be performed on some of the plurality of layers constituting the three-dimensional structure. You may only do it.

  In the above-described embodiment, the flattening means is described as moving on the stage. However, the movement of the stage changes the positional relationship between the stage and the squeegee, and flattening is performed. Also good.

  Further, in the above-described embodiment, it has been described that the coupling portion is formed for all layers, but a layer in which the coupling portion is not formed may be included. For example, a coupling portion may not be formed with respect to a layer formed immediately above the stage, and may function as a sacrificial layer.

  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 post-processing steps include a cleaning step, a shape adjustment step for performing deburring, a coloring step, a coating layer forming step, and a binder curing completion step for performing an ultraviolet irradiation treatment for surely curing an uncured binder. Etc.

  In the above-described embodiment, the case where the binding liquid includes a curable resin (polymerizable compound) has been mainly described. However, the binding liquid is, for example, instead of the curable resin (polymerizable compound). It may contain a thermoplastic resin. Even in such a case, the thermoplastic resin is changed from a molten state to a solidified state, or the solvent (solvent for dissolving the thermoplastic resin) contained in the binding liquid is removed to solidify the thermoplastic resin. By doing so, a coupling portion can be formed, and the same effect as described above can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. In the following description, the processing that does not particularly indicate the temperature condition is performed at room temperature (25 ° C.). Moreover, what does not show temperature conditions in particular also about various measurement conditions is a numerical value in room temperature (25 degreeC).

[1] Production of three-dimensional structure (Example 1)
1. 1. Preparation of composition set for manufacturing a three-dimensional structure 1-1. Preparation of Layer-Forming Composition First, a powder composed of silica particles having a large number of hydroxyl groups on the surface (trade name “Nipsil E-75” manufactured by Tosoh Silica Co., Ltd .: average particle size 2.4 μm) was prepared.

  Next, powder: 30.00 mass%, water: 60.00 mass%, and ammonium polyacrylate as a water-soluble resin: 10.00 mass% were mixed to obtain a layer forming composition.

1-2. Preparation of composition for surface treatment 3-aminopropyltriethoxysilane as a surface treatment agent (coupling agent): 10% by mass and water as a solvent: 90% by mass are mixed to obtain a composition for surface treatment. It was.

1-3. Preparation of binding solution The following components were mixed to obtain a binding solution.

<UV curable resin>
・ Phenoxyethyl acrylate: 20.00% by mass
Isobornyl acrylate: 20.00% by mass
・ 2- (2-vinyloxyethoxy) ethyl acrylate: 50.00% by mass

<Polymerization initiator>
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 5.00% by mass
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: 4.50% by mass

<Polymerization inhibitor>
・ P-methoxyphenol: 0.10% by mass

<Surfactant>
-BYK3500 (trade name manufactured by BYK): 0.40 mass%

2. Manufacture of a three-dimensional structure Using the composition set for manufacturing a three-dimensional structure obtained as described above (a composition for forming a layer, a composition for surface treatment, and a binding liquid), as shown in FIG. The shape, that is, thickness: 4 mm × length: 150 mm, the width of the region provided at both ends (upper and lower sides in the figure) indicated by the hatched portion is 20 mm, and the length is 35 mm. A three-dimensional structure A having a width of 10 mm and a length of 80 mm, and a shape as shown in FIG. 9, that is, thickness: 4 mm × width: 10 mm × length: A three-dimensional structure B having a rectangular parallelepiped shape of 80 mm was manufactured as follows.

  First, a three-dimensional structure manufacturing apparatus as shown in FIGS. 5 to 7 is prepared, and a layer having a thickness of 50 μm is formed on the surface of the support (stage) by using the layer forming composition by the squeegee method. Formed (layer forming step).

  Next, after the layer formation, the layer was heated to 150 ° C. and allowed to stand for 2 minutes to remove water contained in the layer forming composition.

  Next, the composition for surface treatment was provided by the ink jet method in a pattern corresponding to the region in the layer where the bonding portion should be formed (surface treatment composition applying step).

  Thereafter, heat treatment was performed under the condition of 100 ° C. × 10 minutes, and surface modification of the particles constituting the layer was performed.

  Next, a binding liquid was applied in a predetermined pattern (application pattern of the layer forming composition) to the layer to which the surface treatment composition was applied by an ink jet method (binding liquid application process).

  Next, the layer was irradiated with ultraviolet rays to cure the ultraviolet curable resin contained in the layer (curing step).

  Thereafter, a series of steps from the layer formation step to the curing step were repeated so that a plurality of layers were stacked while changing the ink application pattern according to the shape of the three-dimensional structure to be manufactured.

  Thereafter, the laminate obtained as described above is immersed in water and subjected to ultrasonic vibration, whereby particles constituting each layer are not bound by an ultraviolet curable resin (unbound particles). Was removed, and two three-dimensional structures A and two three-dimensional structures B were obtained (unbound particle removal step).

(Examples 2 to 7)
Types of raw materials used for the preparation of the layer forming composition, compounding ratios of each component, types of raw materials used for preparing the composition for surface treatment, compounding ratios of each component, and conditions for heat treatment for surface modification of the particles A three-dimensional structure was manufactured in the same manner as in Example 1 except that the values were set as shown in Table 1.

(Example 8)
After the layer formation step, the surface treatment composition application step is performed without performing the heat treatment, and then the third treatment is performed in the same manner as in Example 1 except that the heat treatment is performed at 100 ° C. for 15 minutes. An original model was manufactured.

(Examples 9 to 14)
Types of raw materials used for the preparation of the layer forming composition, compounding ratios of each component, types of raw materials used for preparing the composition for surface treatment, compounding ratios of each component, and conditions for heat treatment for surface modification of the particles A three-dimensional structure was manufactured in the same manner as in Example 8 except that Table 1 was shown.

(Comparative Example 1)
A three-dimensional structure was manufactured in the same manner as in Example 1 except that the surface treatment composition application step was omitted.

(Comparative Example 2)
Comparative Example 1 except that the surface-treated silica (Nipsil E-75 wet-treated with 3-aminopropyltriethoxysilane) that had been surface-treated in advance was used as the particles constituting the layer forming composition. In the same manner, a three-dimensional structure was manufactured.

Table 1 shows the conditions for the layer forming composition and the surface treatment composition used in the above Examples and Comparative Examples, and the conditions for the heat treatment for the surface treatment (surface modification) of the particles with the surface treatment agent. It was. In the table, alumina indicates a product name “AEROXIDE Alu 65” manufactured by Nippon Aerosil Co., Ltd., and titanium oxide indicates a product name “AEROXIDE TIO ₂ P25” manufactured by Nippon Aerosil Co., Ltd. In the table, ammonium polyacrylate is "PAA", polyvinyl alcohol is "PVA", 3-aminopropyltriethoxysilane is "APTES", 3- (acryloxy) propyltrimethoxysilane "AOPTMS", isopropyltriiso Stearoyl titanate “IPT”. The viscosities of the layer forming compositions used in each of the examples are values in the range of 1000 mPa · s to 20000 mPa · s, and the viscosity of the surface treatment composition used in each of the examples is The viscosities were all in the range of 3 mPa · s to 25 mPa · s.

[2] Evaluation [2.1] Scattering of particles The degree of occurrence of scattering of particles during the production of the three-dimensional structure of each Example and each Comparative Example was evaluated according to the following criteria.

A: No scattering of particles is observed.
B: Scattering of particles is hardly observed.
C: Slight scattering of particles is observed.
D: Scattering of particles is clearly recognized.
E: Scattering of particles is noticeable.

[2.2] Tensile strength and tensile modulus About the three-dimensional structure A of each of the above Examples and Comparative Examples, in accordance with JIS K 7161: 1994 (ISO 527: 1993), tensile yield stress: 50 mm / min, Measurement was performed under the condition of tensile elastic modulus: 1 mm / min, and the tensile strength and tensile elastic modulus were evaluated according to the following criteria.

(Tensile strength)
A: Tensile strength is 20 MPa or more.
B: Tensile strength is 10 MPa or more and less than 20 MPa.
C: Tensile strength is less than 10 MPa.

(Tensile modulus)
A: Tensile elastic modulus is 1.0 GPa or more.
B: Tensile modulus is 0.5 GPa or more and less than 1.0 GPa.
C: Tensile modulus is less than 0.5 GPa.

[2.3] Flexural strength and flexural modulus About the three-dimensional structure B of each of the examples and comparative examples, the distance between fulcrums of 64 mm and the test speed are based on JIS K 7171: 1994 (ISO 178: 1993). Measurement was performed under the condition of 2 mm / min, and bending strength and flexural modulus were evaluated according to the following criteria.

(Bending strength)
A: Bending strength is 45 MPa or more.
B: Bending strength is 30 MPa or more and less than 45 MPa.
C: Bending strength is less than 30 MPa.

(Flexural modulus)
A: The flexural modulus is 2.2 GPa or more.
B: The flexural modulus is 2.0 GPa or more and less than 2.2 GPa.
C: Flexural modulus is less than 2.0 GPa.
These results are summarized in Table 2.

  As is clear from Table 2, in the present invention, a three-dimensional structure excellent in mechanical strength was obtained. On the other hand, in the comparative example, sufficient results were not obtained.

DESCRIPTION OF SYMBOLS 10 ... Three-dimensional structure 1 ... Layer 11 ... Composition for layer formation (particle-containing composition)
111 ... Particles 12 ... Binding liquid 13 ... Curing part (bonding part)
DESCRIPTION OF SYMBOLS 14 '... Composition for surface treatment 14 ... Surface treatment part 100 ... Three-dimensional structure manufacturing apparatus 2 ... Control part 21 ... Computer 22 ... Drive control part 3 ... Composition supply part for layer formation 4 ... Layer formation part 41 ... Stage 42 ... Squeegee (flattening means)
43 ... guide rail 44 ... layer forming composition temporary placement portion 45 ... side surface support portion (frame)
5: Binding liquid discharge part (binding liquid applying means)
6 ... UV irradiation means (curing means)
8 ... Surface treatment composition applying means (surface treatment composition discharge part)
9. Heating means

Claims (15)

It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a layer forming composition containing a plurality of particles;
A surface treatment composition applying step for applying a surface treatment composition containing a surface treatment agent for modifying the surface of the particles constituting the layer to the layer;
The manufacturing method of the three-dimensional structure characterized by having a binding liquid provision process which provides a binding liquid to the said layer.   The method for producing a three-dimensional structure according to claim 1, wherein the layer forming composition includes a solvent in addition to the particles.   The method for producing a three-dimensional structure according to claim 2, further comprising a solvent removal step of removing the solvent from the layer between the layer formation step and the surface treatment composition application step.   4. The method for producing a three-dimensional structure according to claim 2, further comprising a solvent removal step of removing the solvent from the layer between the surface treatment composition application step and the binding liquid application step. 5.   The method for producing a three-dimensional structure according to any one of claims 1 to 4, wherein the composition for surface treatment includes a coupling agent.   The said coupling agent is 1 type, or 2 or more types selected from the group which consists of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. A manufacturing method of a three-dimensional structure.   The method for producing a three-dimensional structure according to any one of claims 1 to 6, wherein the surface treatment composition is selectively applied to at least a part of the portion to which the binding liquid is to be applied by an inkjet method. . The binding liquid contains a polymerizable compound,
The method for producing a three-dimensional structure according to any one of claims 1 to 7, further comprising a curing step of polymerizing and curing the polymerizable compound after the binding liquid application step. A three-dimensional structure manufacturing apparatus that manufactures a three-dimensional structure by laminating layers using a layer forming composition containing a plurality of particles,
A stage to which the layer forming composition is applied and the layer is formed;
A surface treatment composition applying means for applying a surface treatment composition containing a surface treatment agent for modifying the surface of the particles constituting the layer to the layer;
A three-dimensional structure manufacturing apparatus comprising: a binding liquid applying unit that applies a binding liquid to the layer. A composition used for manufacturing a three-dimensional structure by laminating layers using a layer forming composition containing a plurality of particles,
Prior to forming a bonding portion by applying a binding liquid to the layer, the layer is applied to the layer,
A surface treatment composition comprising a surface treatment agent for modifying the surface of the particles constituting the layer. It is a composition set for manufacturing a three-dimensional structure used to manufacture a three-dimensional structure,
A layer forming composition comprising a plurality of particles;
The surface treatment composition according to claim 10;
A composition set for producing a three-dimensional structure, comprising: a binding liquid that binds the particles subjected to the surface treatment with the surface treatment agent.   A three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure according to any one of claims 1 to 8.   A three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus according to claim 9.   A three-dimensional structure manufactured using the composition for surface treatment according to claim 10.   A three-dimensional structure manufactured using the composition set for manufacturing a three-dimensional structure according to claim 11.

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