JP2016132245A - Method for producing three-dimensional molded object, apparatus for producing three-dimensional molded object, and three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a three-dimensional molded object and an apparatus for producing a three-dimensional molded object, by which a three-dimensional molded object excellent in dimensional accuracy and mechanical strength can be produced with superior productivity and superior stability, and to provide a three-dimensional molded object excellent in dimensional accuracy and mechanical strength by using the above method for producing a three-dimensional molded object and the above apparatus for producing a three-dimensional molded object.SOLUTION: The method for producing a three-dimensional molded object of the present invention comprises producing a three-dimensional molded object by stacking layers, and the method includes repetition of a series of steps including: a layer formation step of forming the layer by using a composition for forming a layer containing particles; and a bound portion formation step of binding the particles to form a bound portion. While the above series of steps are carried out, a solvent included in a material used for the production of the three-dimensional molded object is recovered by suction.SELECTED DRAWING: None

Description

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

  A technique for forming a three-dimensional structure by forming a material layer (unit layer) using a composition containing powder (particles) and laminating them is known (for example, see Patent Document 1). In this technique, a three-dimensional structure is formed by repeating the following operations. First, powder is spread thinly with a uniform thickness to form a material layer, and the powder is selectively bonded only at a desired portion of the material layer to form a bonded portion. As a result, a thin plate-like member (hereinafter referred to as “cross-sectional member”) is formed at the joint where the powders are joined. Thereafter, a material layer is further thinly formed on the material layer, and the powder is selectively bonded to each other only at a desired portion to form a bonded portion. As a result, a new cross-sectional member is also formed in the newly formed material layer. At this time, the newly formed cross-sectional member is also coupled to the previously formed cross-sectional member. By repeating such an operation and laminating thin plate-like cross-sectional members (joining portions) one by one, a three-dimensional structure can be formed.

  By the way, a material containing a solvent is used for manufacturing a three-dimensional structure, and the solvent is removed in the manufacturing process of the three-dimensional structure (for example, a binding liquid containing a volatile solvent is applied to the layer and bonded) Forming a part).

  In such a case, when the solvent remains when the particles are bonded to form a bonded portion, the dimensional accuracy of the formed bonded portion decreases, or the bond strength of the particles in the bonded portion decreases, There was a problem that the mechanical strength of the three-dimensional structure was lowered. In addition, the volatilized solvent may adversely affect the constituent members of the three-dimensional structure manufacturing apparatus.

JP 2003-53847 A

  An object of the present invention is to provide a manufacturing method of a three-dimensional structure that can manufacture a three-dimensional structure excellent in dimensional accuracy and mechanical strength with excellent productivity and excellent stability. Providing a three-dimensional structure manufacturing apparatus capable of manufacturing a three-dimensional structure excellent in mechanical strength with excellent productivity and excellent stability; and a method for manufacturing the three-dimensional structure, An object of the present invention is to provide a three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus and having excellent dimensional accuracy and mechanical strength.

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 particles;
Repeating a series of steps including a bonding portion forming step of bonding the particles to form a bonding portion,
When performing the series of steps, the solvent contained in the material used for manufacturing the three-dimensional structure is collected by suction.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture the three-dimensional structure excellent in dimensional accuracy and mechanical strength with excellent productivity and excellent stability can be provided.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the stage on which the layer is placed has a hole, and the suction is performed through the hole.

  This makes it possible to more efficiently and more reliably remove the solvent from the layer while preventing the unintentional deformation of the layer more effectively, and the productivity of the three-dimensional structure is particularly excellent. In addition, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional structure can be further improved.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the frame disposed on the outer periphery of the stage on which the layer is placed has a hole, and the suction is performed through the hole. .

  This makes it possible to more efficiently and more reliably remove the solvent from the layer while preventing the unintentional deformation of the layer more effectively, and the productivity of the three-dimensional structure is particularly excellent. In addition, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional structure can be further improved. In addition, even when the number of layers is large, or when the area of the bonding portion formed in the layer provided on the lower surface side of the layer to be subjected to the solvent removal treatment is relatively large, The solvent can be removed efficiently.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the layer forming composition contains the solvent.

  Thereby, for example, 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 effectively prevent unintentional scattering of powder (particles) during layer formation.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable to form the joint by applying a binding liquid to the layer formed using the layer forming composition.

  Thereby, the mechanical strength and dimensional accuracy of the three-dimensional structure can be further improved. Further, the amount of energy required to form the coupling portion can be reduced.

  In the three-dimensional structure manufacturing method of the present invention, the binding liquid preferably contains the solvent.

  Thereby, the viscosity of the binding liquid can be adjusted more suitably, the amount of binding liquid applied, the application pattern can be more accurately controlled, and the dimensional accuracy of the three-dimensional structure is particularly excellent. Can be.

The three-dimensional structure manufacturing apparatus of the present invention is a three-dimensional structure manufacturing apparatus that manufactures a three-dimensional structure by laminating layers using a layer forming composition containing particles,
A stage to which the layer forming composition is applied and the layer is formed;
A coupling portion forming means for coupling the particles to form a coupling portion;
A suction means for sucking a solvent contained in the material used for manufacturing the three-dimensional structure;
And a solvent recovery means for recovering the solvent sucked by the suction means.

  Thereby, the three-dimensional structure manufacturing apparatus which can manufacture the three-dimensional structure excellent in dimensional accuracy and mechanical strength with excellent productivity and excellent stability 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 dimensional accuracy and 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 dimensional accuracy and mechanical strength can be provided.

It is sectional drawing which shows each process typically about 1st Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows each process typically about 1st Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows each process typically about 1st Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows each process typically about 2nd Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows each process typically about 2nd Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows each process typically about 2nd Embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is sectional drawing which shows typically 1st Embodiment of the three-dimensional structure manufacturing apparatus of this invention. It is sectional drawing which shows typically 2nd Embodiment of the three-dimensional structure manufacturing apparatus of this invention.

  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.

[First Embodiment]
FIG.1, FIG.2, FIG.3 is sectional drawing which shows each process typically about 1st Embodiment of the manufacturing method of the three-dimensional structure of this invention.

  As shown in FIGS. 1, 2, and 3, the manufacturing method of the present embodiment forms a layer 1 having a predetermined thickness using a composition (layer forming composition) 11 containing particles and a solvent. A layer forming step (1a, 1e), a solvent removing step (1b, 1f) for removing the solvent from the layer 1 by suction and collecting the solvent removed from the layer 1, and an ink jet method for the layer 1; In the layer 1, the binding liquid application step (1 c, 1 g) for applying the binding liquid 12 and the binder contained in the binding liquid 12 applied to the layer 1 are cured to bond the particles. A curing step (1d, 1h) for forming a cured portion (bonding portion) 13, and sequentially repeating these steps (1i), and then, among the particles constituting each layer 1, with a binder Unbound particle removal step (1j) for removing unbound particles The has.

Hereinafter, each step will be described.
≪Layer formation process≫
In the layer forming step, a layer 1 having a predetermined thickness is formed using a composition (layer forming composition) 11 containing particles (1a, 1e).

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

Moreover, in this embodiment, the composition 11 contains a solvent in addition to the particles.
Thereby, for example, the composition 11 can be made into a paste-like material, the fluidity of the composition 11 can be increased, the workability at the time of forming the layer 1 can be improved, and the layer 1 having a high surface flatness. Can be formed easily and reliably. In addition, unintentional scattering of the powder (particles) during the formation of the layer 1 can be effectively prevented. Further, conventionally, when a composition containing particles and a solvent is used as a composition for layer formation, it is difficult to sufficiently remove the solvent from the solvent layer, and the mechanical strength of the three-dimensional structure is The dimensional accuracy could not be sufficiently improved. Moreover, although heating time may be lengthened in order to make the content rate of the solvent in a layer low enough, in such a case, the productivity of a three-dimensional structure will fall remarkably. Conventionally, when a composition containing particles and a solvent is used as a composition for forming a layer, the solvent is often left at a relatively high content in the finally obtained three-dimensional structure. This has been a cause of lowering the durability and reliability of the three-dimensional structure. On the other hand, in this invention, even if it is a case where the thing containing a solvent is used as a layer forming composition, generation | occurrence | production of the above problems can be prevented reliably. Therefore, when the layer forming composition contains particles and a solvent, the effect of the present invention is more remarkably exhibited.

  The solvent may be any solvent as long as it has a function of dispersing particles (functions as a dispersion medium), but is preferably an aqueous solvent.

  As a result, the workability (ease of work, work efficiency) in the layer forming process is further improved, and more reliably that the solvent remains unintentionally in the finally obtained three-dimensional structure 10. Can be prevented.

  In addition, the aqueous solvent has strong bonding force between molecules due to hydrogen bonding or the like, and the solvent present in the inside (deep part) of the layer 1 with the removal of the solvent molecule (aqueous solvent) from the layer 1 in the solvent removal step. The effect that the molecules move to the outside of the layer 1 is also stronger than that of the non-aqueous solvent. Therefore, by using an aqueous solvent, it is possible to more effectively prevent the solvent from remaining unintentionally in the layer 1.

  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.

  In the following description, the case where the composition 11 includes an aqueous solvent will be mainly described.

The composition (layer forming composition) 11 will be described in detail later.
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 45 are in close contact (contact), and the composition 11 is prevented from falling from between the stage 41 and the side surface support portion 45. .

  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 (1e). 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 45 are in close contact (contact). Thus, the composition 11 is prevented from falling from between the stage 41 and the layer 1 on the stage 41.

  The viscosity of the composition 11 in this step (value measured using an E-type viscometer (eg, VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.)) is preferably 500 mPa · s or more and 60000 mPa · s or less, and preferably 1000 mPa · s. More preferably, it is 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 5 μm or more and 500 μm or less, for example, and more preferably 10 μm or more and 100 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. Moreover, the solvent removal in a solvent removal process can also be performed efficiently in a short time, and the mechanical strength of the three-dimensional structure 10 finally obtained can be made more excellent.

≪Solvent removal process≫
After forming the layer 1 in the layer forming step, the solvent contained in the layer 1 is removed (1b, 1f).

  In particular, in this embodiment, the solvent contained in the layer 1 is removed by suction, and the solvent removed from the layer 1 is recovered by a solvent recovery unit (not shown).

  Thereby, the content rate of the solvent in the finally obtained three-dimensional structure 10 can be reliably reduced, and the bonding force between the particles and the binder can be further increased. In addition, a gap (void) can be reliably formed in the region where the solvent between the particles existed, and the binding liquid can be suitably permeated into the gap (void) in the subsequent binding liquid application step. it can. Also, when removing the solvent by heating, for example, if the heating temperature is increased to increase the productivity of the three-dimensional structure, the layer may be disturbed due to rapid evaporation of the solvent. This problem can be effectively prevented from being removed. From the above, the dimensional accuracy and mechanical strength of the three-dimensional structure 10 can be reliably improved. Furthermore, the solvent can be efficiently removed not only near the surface of the layer 1 but also from the inside of the layer, and energy required for removing the solvent from the layer as compared with the case of removing the solvent by evaporation. The amount can be reduced, and the productivity of the three-dimensional structure 10 can be improved. Moreover, it can prevent that the solvent volatilized from the layer 1 diffuses, for example, the volatilized solvent adheres (for example, dew condensation etc.) to the apparatus for manufacturing the three-dimensional structure 10, and the constituent members of the apparatus It is possible to more reliably prevent adverse effects on the above. Further, since the solvent removed from the layer 1 is recovered by a solvent recovery unit (not shown), the volatilized solvent is prevented from being released to the outside environment, and the load on the environment is small.

  In particular, in the present embodiment, the stage 41 on which the layer 1 is placed has the hole 4121, and the frame body 45 disposed on the outer periphery of the stage 41 has the hole 4521. Then, suction is performed through the hole 4121 and the hole 4521.

  More specifically, the stage 41 includes a base portion 411 made of a dense material and a surface layer 412 made of a porous body having a hole 4121. The frame body 45 is made of a dense material. And a surface layer 452 made of a porous body having a hole 4521. Then, suction is performed through the hole 4121 of the stage 41 (surface layer 412) and the hole 4521 of the frame 45 (surface layer 452).

  Thereby, the solvent can be more efficiently and more reliably removed from the layer 1 while preventing the unintentional deformation or the like of the layer 1 more effectively. Therefore, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional structure 10 can be further improved while the productivity of the three-dimensional structure 10 is particularly excellent.

  In particular, when the stage 41 has the hole 4121, the solvent removal efficiency can be further improved while preventing the unintentional deformation of the layer 1 more effectively.

  Further, since the frame body 45 has the hole 4521, it is formed in the layer 1 provided on the lower surface side of the layer 1 when the number of layers 1 is large or when the solvent removal treatment is to be performed. Even when the area of the coupling portion 13 is relatively large, the solvent can be efficiently removed.

  The solvent removed from the layer 1 by suction through the hole 4121 and the hole 4521 is constituted by a flow path constituted by the groove 4112 provided in the base 411 and a groove 4512 provided in the base 451. It reaches the flow path and is recovered by a solvent recovery means (not shown).

  Thereby, the circulation of the solvent can be made smoother, and the removal efficiency and recovery efficiency of the solvent from the layer 1 can be made more excellent. Therefore, the productivity of the three-dimensional structure 10 can be improved, and the occurrence of harmful effects due to the volatilization of the solvent can be more effectively prevented.

  Note that the hole 4121 and the hole 4521 have a size (diameter) smaller than the size (diameter) of the particles constituting the layer 1.

The suction conditions may be changed as appropriate.
For example, in the initial stage of the solvent removal step, suction is performed through the hole 4121 provided in the stage 41, and then suction is performed through the hole 4121 provided in the stage 41 while the frame 45 is You may control to perform the suction through the provided hole 4521.

  Thereby, the solvent is removed from the layer 1 more efficiently while preventing the unintentional deformation of the layer 1 (for example, the unintentional movement of particles toward the outer peripheral portion of the layer 1) more effectively. The dimensional accuracy and productivity of the three-dimensional structure 10 can be further improved.

  Further, for example, the suction force may be adjusted according to the number of layers 1 (the number of stacked layers) formed on the stage 41. More specifically, for example, when the number of layers 1 formed on the stage 41 is large compared to the case where the number of layers 1 formed on the stage 41 is small, holes provided in the stage 41 are provided. The suction force via the part 4121 may be large. As a result, the suction force applied to the layer 1 provided on the uppermost surface when the solvent is removed from the layer 1 provided on the uppermost surface varies depending on the number of layers 1 (the number of stacked layers) formed on the stage 41. This can be effectively prevented. As a result, the solvent can be removed under stable conditions regardless of the number of stacked layers. Note that even when a plurality of layers 1 are stacked, suction through the holes 4121 can be stably performed due to the presence of voids between particles contained in the layer 1.

  Further, the layer formation step and the solvent removal step may be performed simultaneously. That is, in the layer forming step, the layer forming composition 11 may be applied while sucking.

  Thereby, scattering of the particle | grains at the time of a layer formation process can be prevented more efficiently.

  Thus, when suction is performed in the layer formation step, the suction conditions in the layer formation step may be different from the suction conditions performed thereafter. For example, the suction force of suction performed thereafter may be stronger than the suction force in the layer forming step. Thereby, it is possible to more effectively prevent the unintentional variation in the thickness of the layer 1 formed in the layer forming step, while sufficiently preventing the particles constituting the layer forming composition 11 from being scattered. In addition, the solvent removal efficiency can be further improved, and the productivity of the three-dimensional structure 10 can be further improved.

≪Binding liquid application process≫
Next, a binding liquid 12 for binding particles constituting the layer 1 is applied to the layer 1 (1c, 1g).

  In this step, the binding liquid 12 is selectively applied only to a portion of the layer 1 from which the solvent has been removed that corresponds to the real part (substance with the substance) of the three-dimensional structure 10.

  Thereby, the particles 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. Moreover, the mechanical strength of the finally obtained three-dimensional structure 10 can be made excellent.

  In particular, since the binding liquid 12 is applied to the layer 1 from which the solvent has been removed, the binding liquid 12 can be suitably infiltrated into the gaps between the particles constituting the layer 1, and the intended pattern can be obtained. It can be formed easily and reliably.

  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 particles, but in the present embodiment, the binding liquid 12 includes a curable resin as a binder, and in particular, photocuring as a binder. It is preferable that the resin contains a curable resin (in particular, 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 (bonding part forming 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 (1d, 1h).

  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.

  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.

≪Unbound particle removal process≫
Then, a series of steps as described above are repeated (1i), and then, as a post-processing step, among the particles constituting each layer 1, those that are not bound by the binder (unbound particles) are removed. A particle removal step (1j) 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.

[Second Embodiment]
Next, 2nd Embodiment of the manufacturing method of the three-dimensional structure of this invention is described.

  4, 5 and 6 are cross-sectional views schematically showing each step in the second embodiment of the method for manufacturing a three-dimensional structure of the present invention. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.

  As shown in FIGS. 4, 5, and 6, the manufacturing method of the three-dimensional structure 10 of the present embodiment uses a composition (layer forming composition) 11 containing particles and a solvent to have a predetermined thickness. A layer forming step (2a, 2e) for forming a layer 1 having a first solvent removing step (2b, 2f) for removing the solvent from the layer 1 by suction and recovering the solvent removed from the layer 1; By the ink jet method, the binding liquid application step (2c, 2g) for applying the binding liquid 12 to the layer 1, and the solvent is removed from the layer 1 to which the binding liquid 12 has been applied. 13 and a second solvent removal step (2d, 2h) for recovering the solvent removed from layer 1, these steps are repeated in sequence (2i), and then each layer 1 is Remove the constituent particles that are not bound by the binder. And a coupling particle removal step (2j).

  That is, the binding liquid 12 used for forming the bonding portion 13 contains a solvent, and after applying the binding liquid 12, a step of removing and recovering the solvent from the layer 1 to which the binding liquid 12 has been applied (first step). 2 is the same as that of the above-described embodiment except that the solvent removal step is not included and the curing step is not included.

  Thus, even if the binding liquid 12 contains a solvent, the solvent can be removed and collected by suction. Moreover, since the binding liquid 12 contains a solvent, the viscosity of the binding liquid 12 can be adjusted more suitably, and the application amount and application pattern of the binding liquid 12 can be controlled more accurately. The dimensional accuracy of the three-dimensional structure 10 can be made particularly excellent.

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

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

[First Embodiment]
FIG. 7 is a cross-sectional view schematically showing the first embodiment of the three-dimensional structure manufacturing apparatus of the present invention.

  The three-dimensional structure manufacturing apparatus 100 manufactures the three-dimensional structure 10 by repeatedly forming and laminating the layer 1 using a composition (layer forming composition) 11 containing particles and a solvent. .

  The three-dimensional structure manufacturing apparatus 100 of the present embodiment includes a control unit 2 and a composition supply unit (layer formation composition supply unit) 3 that contains a composition (layer formation composition) 11 containing particles and a solvent. A layer forming unit 4 that forms the layer 1 using the composition 11 supplied from the composition supply unit 3, a suction unit 7 that sucks the solvent contained in the layer 1, and the suction unit 7 from the layer 1. The solvent recovery means 8 for recovering the sucked solvent, the binding liquid discharge section (binding liquid applying means) 5 for discharging the binding liquid 12 to the layer 1 from which the solvent has been removed, and the binding liquid 12 are cured. And ultraviolet irradiation means (curing means) 6 for irradiating ultraviolet rays for the purpose.

  The three-dimensional structure manufacturing apparatus 100 of the present embodiment can be suitably used, for example, in the method for manufacturing a three-dimensional structure of the first embodiment described above.

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 suction unit 7, the solvent recovery unit 8, the binding liquid discharge unit 5, and the ultraviolet irradiation unit 6. Specifically, for example, the discharge pattern and discharge amount of the binding liquid 12 by the binding liquid discharge unit 5, the supply amount of the composition 11 from the composition supply unit 3, the lowering amount of the stage 41, and the suction by the suction means 7 Conditions (suction force, sucked part, etc.), temperature of the solvent recovery means 8 and the like are controlled.

  The composition supply unit 3 is configured to move in response to a command from the drive control unit 22, and the composition 11 accommodated therein is supplied to the composition temporary placement unit 44.

  The layer forming unit 4 includes a composition temporary placement unit 44 that temporarily holds the composition 11 supplied from the composition supply unit 3 and a layer while flattening the composition 11 held in the composition temporary storage unit 44. Squeegee (flattening means) 42 for forming 1, a guide rail 43 for regulating the operation of the squeegee 42, a stage 41 for supporting the formed layer 1, and a side support part (frame body) 45 surrounding the stage 41, have.

  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. As described above, since the stage 41 is configured to be movable in the Z direction (up and down direction), the number of members to be moved in order to adjust the thickness of the layer 1 is reduced when the new layer 1 is formed. Therefore, the configuration of the three-dimensional structure manufacturing apparatus 100 can be made simpler.

The stage 41 has a flat surface (part to which the 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 includes a base 411 made of a dense material and a surface layer 412 made of a porous body having a hole 4121 (see FIGS. 1, 2, and 3).

  As described above, the stage 41 has the hole 4121 and is configured so as to be able to suck the solvent in the layer 1, so that unintentional deformation of the layer 1 (for example, unintentional detachment of particles from the layer 1). It is possible to more efficiently remove the solvent from the layer 1 and more effectively improve the dimensional accuracy and productivity of the three-dimensional structure 10. it can.

  The stage 41 (base 411, surface layer 412) is preferably made of a high-strength material. Examples of the constituent material of the stage 41 include various metal materials such as stainless steel. Further, by setting the stage 41 to be a sintered body of various metal materials such as stainless steel, for example, the stage 41 (surface layer 412) is a porous body having the hole 4121 as described above. It can manufacture suitably.

  Further, the surface of the stage 41 (surface layer 412) (part to which the composition 11 is applied) may be subjected to surface treatment. Thereby, for example, the constituent material of the composition 11 and the constituent material of the binder liquid 12 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 of the original shaped article 10 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.

  Further, a groove 4112 is provided in a portion of the base 411 facing the surface layer 412, and a channel having a semicircular cross-sectional shape (solvent channel) is formed by the groove 4112 (FIG. 1). (See FIGS. 2 and 3). The flow path (groove 4112) is connected to the hole 4121, and the solvent sucked from the layer 1 is recovered by the solvent recovery means 8 through the flow path (groove 4112).

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

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

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

  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 45 includes a base 451 made of a dense material and a surface layer 452 made of a porous body having a hole 4521 (see FIGS. 1, 2, and 3).

  As described above, the frame body 45 has the hole 4521 and is configured to be able to suck the solvent in the layer 1, so that the undesired deformation of the layer 1 (for example, unintentional particles from the layer 1). It is possible to more efficiently remove the solvent from the layer 1 while more effectively preventing deformation due to detachment, etc., and to improve the dimensional accuracy and productivity of the three-dimensional structure 10. Can do.

  The frame 45 (base 451, surface layer 452) 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. Further, by making the frame body 45 made of a sintered body of various metal materials such as stainless steel, for example, the frame body 45 (surface layer 452) is a porous material having the hole 4521 as described above. It can manufacture suitably as a mass.

  In addition, the surface of the frame 45 (surface layer 452) (site that can come into contact with the composition 11) may be subjected to surface treatment. Thereby, for example, the constituent material of the composition 11 and the constituent material of the binding liquid 12 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. As a result, stable production of the three-dimensional structure 10 over a longer period of time can be achieved. 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.

  Further, a groove 4512 is provided in a portion of the base 451 facing the surface layer 452, and the groove 4512 forms a channel having a semicircular cross-sectional shape (solvent channel) (see FIG. 1, see FIG. 2 and FIG. The flow path (groove 4512) is connected to the hole 4521, and the solvent sucked from the layer 1 is recovered by the solvent recovery means 8 through the flow path (groove 4512).

  The suction means 7 has a function of sucking the solvent from the layer 1 and guiding the solvent to the solvent recovery means 8.

As the suction means 7, for example, various pumps can be used.
The solvent recovery means 8 is arranged in the flow path of the fluid (particles containing the solvent) sucked by the suction means 7, and between the layer 1 and the suction means 7 (from the suction means 7) in the flow path. Is also located upstream).

  The solvent recovery means 8 only needs to have a function of recovering the solvent removed from the layer 1, and generally has a function of recovering a liquid solvent. The solvent recovery means 8 may have a function of liquefying (condensing) the solvent at least partially evaporated. As the solvent recovery means 8, for example, a Dewar cooler, an Allen cooler, a Graham cooler, a Dimroth cooler, a Liebig cooler, a Friedrich cooler, a Hopkins cooler, a waist cooler, a cold finger, etc. can be adopted. .

  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.

  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.

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

[Second Embodiment]
Next, 2nd Embodiment of the three-dimensional structure manufacturing apparatus of this invention is described.

  FIG. 8 is a cross-sectional view schematically showing a second embodiment of the three-dimensional structure manufacturing apparatus of the present invention. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.

  As shown in FIG. 8, the three-dimensional structure manufacturing apparatus 100 of the present embodiment includes a control unit 2 and a composition supply unit (layer formation) that contains a composition (layer forming composition) 11 containing particles and a solvent. Composition supply part) 3, layer forming part 4 for forming layer 1 using composition 11 supplied from composition supply part 3, suction means 7 for sucking the solvent contained in layer 1, Solvent recovery means 8 for recovering the solvent sucked from the layer 1 by the suction means 7, and a binding liquid discharge part (binding liquid applying means) 5 for discharging the binding liquid 12 to the layer 1 from which the solvent has been removed. Have. That is, the three-dimensional structure manufacturing apparatus 100 of the present embodiment has the same configuration as that of the above-described embodiment except that the ultraviolet irradiation means (curing means) 6 is not provided.

  Thereby, simplification of the structure of the three-dimensional structure manufacturing apparatus 100 can be achieved. The three-dimensional structure manufacturing apparatus 100 according to the present embodiment is preferably used for, for example, a method that does not require a curing process for forming the coupling portion 13, for example, a method for manufacturing the three-dimensional structure according to the second embodiment described above. Can do.

  According to the three-dimensional structure manufacturing apparatus of the present invention as described above, it is possible to stably manufacture a three-dimensional structure excellent in mechanical strength and dimensional accuracy with excellent productivity.

<Composition (Composition for layer formation)>
Next, the composition (composition for layer formation) used for production of the three-dimensional structure of the present invention will be described in detail.

  The composition (layer-forming composition) includes at least a three-dimensional modeling powder containing a plurality of particles.

(3D modeling powder (particles))
Examples of the constituent material of the particles constituting the three-dimensional modeling powder include inorganic materials, organic materials, and composites thereof.

  Examples of the inorganic material constituting the particles 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. And various metal borates and composites thereof.

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

  Among these, the particles are preferably composed of a metal oxide, and more preferably composed of silica.

  Thereby, characteristics, such as mechanical strength of a three-dimensional structure and light resistance, can be made more excellent.

  In particular, when the particles are composed of silica, the effects described above are more remarkably exhibited. Silica is also excellent in its own fluidity, and the fluidity of the layer-forming composition containing silica can be further improved. This is advantageous for forming a layer having higher thickness uniformity, and is also advantageous for improving the productivity and dimensional accuracy of the three-dimensional structure.

The particles may be subjected to a surface treatment such as a hydrophobic treatment.
The hydrophobizing treatment applied to the particles may be any treatment that increases the hydrophobicity of the particles (mother particles), but is preferably a method for introducing a hydrocarbon group.

  Thereby, the hydrophobicity of the particles can be made higher. In addition, the uniformity of the degree of hydrophobization treatment at each part of each particle or particle surface (including the surface inside the hole in the case of having a hole opening to the outside) easily and reliably. Can be higher.

As a compound used for the hydrophobizing treatment, a silane compound containing a silyl group is preferable. Specific examples of compounds that can be used in the hydrophobization treatment include, for example, hexamethyldisilazane, dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, and propyltrichlorosilane. , Propyltriethoxysilane, propyltrimethoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p -Tolyltrimethoxysilane, p-tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n- Tildi-n-butyroxysilane, di-sec-butyldi-sec-butyroxysilane, di-t-butyldi-t-butyloxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyldimethylchlorosilane, Octadecylmethyldichlorosilane, octadecylmethoxydichlorosilane, 7-octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyl Dimethylchlorosilane, undecyltrichlorosilane, vinyldimethylchlorosilane, methyloctadecyldimethoxy Orchid, methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-n-propoxysilane, methylisopropoxysilane, methyl-n-butyroxysilane, methyltri-sec-butoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethylisopropoxysilane Silane, ethyl-n-butyroxysilane, ethyltri-sec-butyroxysilane, ethyltri-t-butyloxysilane, n-propyltrimeth Xysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, isobutyltri Ethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] pyridine, 4- [2- (trichloro Silyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, phenylto Methoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, benzylmethyldimethoxysilane, benzyldimethyl Methoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltri Methoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, Amyltriethoxysilane, benzoxacilepine dimethyl ester, 5- (bicycloheptenyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromine Phenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloromethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyl Trimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltri Methoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3 Cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclohexenyltrichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethyl Chlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, Cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cycl Lopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethyl Norpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N-diethyl-3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) triethoxysilane, 2-hydroxy-4- (3-triethoxypropoxy) diphenylketone, 3- ( p-Methoxyphenyl) propylmethyldichroic Silane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyldichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7-hexachloro-6-triethoxysilyl-2-norbornene, 3-iodopropyltrimethoxylane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropyl methyl dimeth Sisilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethyl Amino} -3-propionate, RN-α-phenethyl-N′-triethoxysilylpropylurea, S—N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane Phenethyldimethylmethoxysilane, phenethyldimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenyl Propyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxysilane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5- Dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, (S) -N-triethoxysilylpropyl-O-mentcarbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide , 3- (triethoxysilyl) propyl succinic anhydride, N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- ( Trimethoxysilylethyl) benzyl-N N, N-trimethylammonium chloride, phenylvinyldiethoxysilane, 3-thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3- (tri Ethoxysilyl) propyl} phthalamic acid, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 1-trimethoxysilyl-2- (chloromethyl) Phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl -N , N, N-tributylammonium bromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyl Triethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, Vinyltriphenoxysilane, vinyltris-t-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, 3-aminophenyl Roh carboxymethyl dimethylvinylsilane, phenyl trichlorosilane, phenyl dimethylchlorosilane, phenylmethyl dichlorosilane, benzyl trichlorosilane, benzyl dimethyl chlorosilane, benzyl methyl dichlorosilane, phenethyl butyldiisopropylchlorosilane, phenethyl trichlorosilane,
Phenethyldimethylchlorosilane, phenethylmethyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilylethyl) benzene, Bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-phenoxypropyltrichlorosilane, t-butylphenylchlorosilane, t-butylphenylmethoxysilane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, (Chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenylethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane , 3-cyanopropylmethyldiethoxysilane, 3-cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyltrichlorosilane, fluorinated alkylsilane, and the like. Species or a combination of two or more can be used.

Among these, hexamethyldisilazane is preferably used for the hydrophobization treatment.
Thereby, the hydrophobicity of the particles can be made higher. In addition, the uniformity of the degree of hydrophobization treatment at each part of each particle or particle surface (including the surface inside the hole in the case of having a hole opening to the outside) easily and reliably. Can be higher.

  When the hydrophobization treatment using a silane compound is performed in a liquid phase, the desired reaction is suitably advanced by immersing the particles (mother particles) to be hydrophobized in a liquid containing the silane compound. And a silane compound chemisorbed film can be formed.

  In addition, when the hydrophobization treatment using the silane compound is performed in the gas phase, the desired reaction can be suitably advanced by exposing the particles (mother particles) to be hydrophobized to the vapor of the silane compound. It is possible to form a chemical adsorption film of a silane compound.

  The average particle diameter of the particles 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.

  As a result, the mechanical strength of the three-dimensional structure can be made more excellent, and the occurrence of unintentional irregularities in the produced three-dimensional structure can be more effectively prevented. The dimensional accuracy can be made more excellent. Moreover, the fluidity | liquidity of the composition for layer formation can be made more excellent, and the productivity of a three-dimensional structure 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 INS TA-II type | mold).

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

  As a result, the mechanical strength of the three-dimensional structure can be made more excellent, and the occurrence of unintentional irregularities in the produced three-dimensional structure can be more effectively prevented. The dimensional accuracy can be made more excellent. Moreover, the fluidity | liquidity of the composition for layer formation can be made more excellent, and the productivity of a three-dimensional structure can be made more excellent.

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

  As a result, it has a sufficient space (pores) for the binder to enter, and the mechanical strength of the particles themselves can be made excellent. As a result, the binder is formed by the binder entering the pores. It is possible to make the mechanical strength of the three-dimensional structure having the above excellent.

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

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

  Thereby, the mechanical strength of the three-dimensional structure finally obtained can be made more excellent. Further, in the case of using a binding liquid (colored ink) containing a pigment for the production of a three-dimensional structure, the pigment can be suitably held in the pores of the particles. For this reason, unintentional diffusion of the pigment can be prevented, and a high-definition image can be more reliably formed.

  The particles may have any shape, but preferably have a spherical shape. As a result, the fluidity of the layer-forming composition can be made more excellent, the productivity of the three-dimensional structure can be made more excellent, and unintentional unevenness in the manufactured three-dimensional structure can be made. Generation | occurrence | production etc. can be prevented more effectively and the dimensional accuracy of a three-dimensional structure can be made more excellent.

The layer forming composition may include a plurality of types of particles.
The content of the particles in the layer forming composition is preferably 8% by mass or more and 91% by mass or less, and more preferably 10% by mass or more and 60% by mass or less.

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

(solvent)
The layer forming composition preferably contains a solvent in addition to the particles.

  Thereby, for example, the layer-forming composition can be made into a paste-like material, the fluidity of the layer-forming composition can be increased, the workability during layer formation can be improved, and the surface flatness can be improved. A high layer can be easily and reliably formed. In addition, it is possible to effectively prevent unintentional scattering of powder (particles) during layer formation.

  In particular, when the layer forming composition contains an aqueous solvent as a solvent, the following effects can be obtained.

  That is, since the aqueous solvent has a high affinity with water, a water-soluble resin described later can be suitably dissolved. As a result, the fluidity of the layer forming composition can be improved, and unintentional variations in the thickness of the layer formed using the layer forming composition can be more effectively prevented. it can. In addition, when the layer in the state where the aqueous solvent is removed is formed, the water-soluble resin can be adhered to the particles with higher uniformity over the entire layer, and unintentional unevenness of composition is more likely to occur. It can be effectively prevented. For this reason, it is possible to more effectively prevent the occurrence of unintentional variations in mechanical strength at each part of the finally obtained three-dimensional structure, and to improve the reliability of the three-dimensional structure. can do.

  Examples of the aqueous solvent constituting the layer forming composition include water; alcoholic solvents such as methanol, ethanol and isopropanol; ketone solvents such as methyl ethyl ketone and acetone; glycols such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether. 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 and the like, and one or more selected from these Two or more kinds can be used in combination.

  Especially, it is preferable that the composition for layer formation contains water. Thereby, when the layer forming composition contains a water-soluble resin as will be described in detail later, the water-soluble resin can be more reliably dissolved, and the fluidity of the layer forming composition, the layer forming composition The uniformity of the composition of the layer formed using the product can be made more excellent. Water is easy to remove in the solvent removal step. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems.

  The content of the solvent in the layer forming composition is preferably 9% by mass or more and 92% by mass or less, and more preferably 22% by mass or more and 89% by mass or less.

  As a result, the effects of including the solvent as described above are more remarkably exhibited, and the solvent can be easily removed in a shorter time in the manufacturing process of the three-dimensional structure. Productivity can be further improved. In addition, the layer in a state where the solvent has been removed can contain voids at an appropriate ratio, and the permeability of the binding liquid can be further improved, and the finally obtained three-dimensional structure The mechanical strength, dimensional accuracy, etc. 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 may contain a binder.

  Thereby, in the layer formed using the layer forming composition (particularly, the layer from which the solvent has been removed), a plurality of particles can be suitably bonded (temporarily fixed). Can be effectively prevented. Thereby, the further improvement of the operator's safety and the dimensional accuracy of the three-dimensional structure to be manufactured can be achieved.

  When the layer forming composition contains a solvent and a binder, the binder is preferably dissolved in the solvent in the layer forming composition.

  Thereby, the fluidity of the layer forming composition can be made better, and the unintentional variation in the thickness of the layer formed using the layer forming composition can be more effectively prevented. Can do. In addition, when the layer in the state where the solvent is removed is formed, the binder can be attached to the particles with higher uniformity throughout the layer, and it is more effective that unintentional unevenness of composition occurs. Can be prevented. For this reason, it is possible to more effectively prevent the occurrence of unintentional variations in mechanical strength at each part of the finally obtained three-dimensional structure, and to improve the reliability of the three-dimensional structure. can do.

  Any binder may be used as long as it has a function of temporarily fixing a plurality of particles in a layer formed using the layer forming composition (particularly, a layer from which the solvent has been removed). Can be suitably used.

  By including a water-soluble resin, when the layer-forming composition contains an aqueous solvent (particularly water) as a solvent, the layer-forming composition can contain a binder (water-soluble resin) in a dissolved state. The fluidity and handleability (ease of handling) of the composition for forming a layer can be made more excellent. As a result, the productivity of the three-dimensional structure can be improved.

  Moreover, the site | part to which the binding liquid of the layer was not provided in the manufacture process of a three-dimensional structure can be removed easily and efficiently by providing an aqueous solvent (especially water). As a result, the productivity of the three-dimensional structure can be improved. In addition, since it is possible to easily and surely prevent the portion of the layer to be removed from adhering to and remaining on the finally obtained three-dimensional structure, the dimensional accuracy of the three-dimensional structure is superior. Can be.

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.

  Specific examples of the water-soluble resin product include, for example, methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metroise SM-15), hydroxyethyl cellulose (manufactured by Fuji Chemical Co., Ltd., AL-15), hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd., HPC- M), carboxymethyl cellulose (manufactured by Nichirin Chemical Co., Ltd., CMC-30), starch phosphate sodium sodium (I) (manufactured by Matsutani Chemical Co., Ltd., Hoster 5100), polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd., PVP K-90), methyl Vinyl ether / maleic anhydride copolymer (GAF Gauntlet, AN-139), sodium polyacrylate (Toa Gosei, Aron T-50, Aron A-210, Aron AC-103), ammonium polyacrylate (Toa Gosei) Aron A-30SL, Aron AS-110 , Aron AS-1800), polyacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.), modified polyamide (modified nylon) (manufactured by Toray Industries, AQ nylon), polyethylene oxide (manufactured by Steel Manufacturing Chemical Co., Ltd., PEO-1, manufactured by Meisei Chemical Industries, Ltd.) Alcox), random copolymer of ethylene oxide and propylene oxide (manufactured by Meisei Chemical Co., Ltd., Alcox EP), sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), carboxyvinyl polymer / crosslinked acrylic water-soluble resin (Sumitomo Seika Co., Ltd., ACPEC) and the like.

  Especially, when the water-soluble resin as a binder is polyvinyl alcohol, the mechanical strength of a three-dimensional structure can be made more excellent. Also, by adjusting the degree of saponification and degree of polymerization, the properties of the binder (for example, water solubility and water resistance) and the properties of the layer forming composition (for example, viscosity, particle fixing force, wettability, etc.) are more suitable. Can be controlled. For this reason, it can respond suitably by manufacture of various three-dimensional modeling objects. Polyvinyl alcohol is inexpensive and stable in supply among various water-soluble resins. For this reason, a stable three-dimensional structure 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 contains an aqueous solvent (particularly, water), it is possible to more effectively suppress a decrease in adhesiveness between adjacent layers.

  When the water-soluble resin as a binder contains polyvinyl alcohol, the polymerization degree of the polyvinyl alcohol is preferably 300 or more and 1000 or less. Thereby, when the composition for layer formation contains an aqueous solvent (especially water), the mechanical strength of each layer and the adhesiveness between adjacent layers can be made more excellent.

  Moreover, when the water-soluble resin as a binder is polyvinylpyrrolidone (PVP), the following effects are acquired. In other words, since polyvinylpyrrolidone has excellent adhesion to various materials such as glass, metal, and plastic, the strength and shape stability of the portion of the layer to which no binding liquid is applied are further improved. The dimensional accuracy of the three-dimensional structure obtained can be improved. Moreover, since polyvinylpyrrolidone shows high solubility with respect to various organic solvents, when the composition for layer formation contains the organic solvent, the fluidity of the composition for layer formation may be more excellent. It is possible to suitably form a layer in which unintentional thickness variation is effectively prevented, and the dimensional accuracy of the finally obtained three-dimensional structure can be further improved. Moreover, since polyvinylpyrrolidone shows high solubility also to an aqueous solvent (especially water), in the unbonded particle removal step (after completion of modeling), it is bound by a binder among the particles constituting each layer. What is not can be removed easily and reliably. In addition, since polyvinylpyrrolidone is excellent in affinity with various colorants, when a binding liquid containing a colorant is used in the binding liquid application step, the colorant diffuses unintentionally. It 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, 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 formed using the layer forming composition can be made higher and easier.

  When the layer forming composition contains a binder, the content of the binder in the layer forming composition 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. The following is more preferable.

  Thereby, while the effect by including a binder as mentioned above is exhibited more notably, the content rate of the particles etc. in the composition for layer formation can be made sufficiently high, Productivity, mechanical strength of the three-dimensional structure to be manufactured, and the like can be further improved.

(Other ingredients)
Moreover, the layer forming composition 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.

<Binding liquid>
Next, the binding liquid used for manufacturing the three-dimensional structure of the present invention will be described in detail.
The binding liquid contains at least a binder.

(Binder)
Examples of the binder include various kinds of materials such as thermoplastic resins; thermosetting resins; visible light curable resins (narrowly defined photocurable resins) that are cured by light in the visible light region, ultraviolet curable resins, and infrared curable resins. Photocurable resin; X-ray curable resin and the like can be mentioned, and one or more selected from these can be used in combination. Especially, it is preferable that a binder contains curable resin from viewpoints, such as the mechanical strength of the obtained three-dimensional structure, and the productivity of a three-dimensional structure. Among various curable resins, in particular, from the viewpoint of the mechanical strength of the obtained three-dimensional structure, the productivity of the three-dimensional structure, the storage stability of the binding liquid, etc., in particular, an ultraviolet curable resin (polymerizable compound). ) Is preferred.

  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 tetradicrotonate.

  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.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5240, Japanese Patent Application Laid-Open No. 59-5241, Japanese Patent Application Laid-Open No. 2-226149, and those containing an amino group described in Japanese Patent Application Laid-Open No. 1-165613 are also used. be able to.

  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.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, a urethane-based addition polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. As such a specific example, for example, one molecule described in JP-B-48-41708 A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (1) to a polyisocyanate compound having two or more isocyanate groups. Etc.

^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH (1)
(However, in formula (1), R ¹ and R ² each independently represent H or CH ^3. )

  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., tetrafunctional or higher glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, cresol novolac resin poly) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2) 21P, 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, trisphenol methane epoxy resin, aliphatic glycidyl ethers such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane tritriglycidyl 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 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 can be made particularly excellent.

(Other ingredients)
Further, the binding liquid 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 contains a colorant, a three-dimensional structure colored in a color corresponding to the color of the colorant can be obtained.

  In particular, by including a pigment as the colorant, the light resistance of the binding liquid and the three-dimensional structure can be improved. 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.

  More specifically, as carbon black used as a black (black) pigment, for example, No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by Cabot Corp. (CABOL J) Black FW1, Col r Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (made by Degussa).

  Examples of white pigments include C.I. I. Pigment white 6, 18, 21 and the like.

  Examples of yellow (yellow) pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of the violet (cyan) pigment include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4,60 etc. are mentioned.

  Examples of other pigments include C.I. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, and the like.

  When the binder solution contains a pigment, the average particle size of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less. As a result, the discharge stability of the binding liquid and the dispersion stability of the pigment in the binding liquid can be improved, and an image with higher image quality can be formed.

  Examples of the dye include acid dyes, direct dyes, reactive dyes, basic dyes, and the like, and one or more selected from these can be used in combination.

  Specific examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Direct Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, 35 etc. are mentioned.

  When the binder liquid contains a colorant, the content of the colorant in the binder liquid 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 contains titanium oxide as a colorant, the content of titanium oxide in the binding liquid is preferably 12% by mass to 30% by mass, and more preferably 14% by mass to 25% by mass. The following is more preferable. Thereby, the more excellent concealment property is obtained.

  When the binder liquid 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. Commercially available polymer dispersants include, for example, Ajinomoto Fine Techno's Ajisper series, Solsperse series (Solsperse 36000, etc.) available from Noveon, BYK's Dispervic series, Enomoto Kasei The company's Disparon series, etc. are listed.

  If the binding liquid contains a surfactant, the three-dimensional structure 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. Specific examples of the surfactant include, for example, BYK-347, BYK-348, BYK-UV3500, 3510, 3530, 3570 (above, trade names manufactured by BYK).

  Further, the binder liquid may contain a solvent. As a result, the viscosity of the binding liquid can be suitably adjusted, and even when the binding liquid contains a high-viscosity component, the discharge stability of the binding liquid by the ink jet system should be more excellent. Can do.

  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.

  The viscosity of the binding liquid 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 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.

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

  Thereby, the three-dimensional structure excellent in mechanical strength and dimensional accuracy 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, the three-dimensional structure manufacturing apparatus of the present invention includes a recovery mechanism (not shown) for recovering a composition supplied from the composition supply unit that was not used for forming a layer. Also good. Thereby, it is possible to supply a sufficient amount of the composition while preventing the surplus composition from accumulating in the layer forming portion, and thus more effectively preventing the occurrence of defects in the layer. A three-dimensional structure can be manufactured stably. Moreover, since the recovered 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 is also preferable from the viewpoint of resource saving.

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

  The three-dimensional structure manufacturing apparatus may include, for example, a heating unit that heats the layer. Thereby, the fluidity of the solvent in the solvent removal step can be made more excellent, the solvent removal efficiency can be made more excellent, the productivity of the three-dimensional structure, the three-dimensional manufactured The reliability etc. of a molded article can be made more excellent.

  In the above-described embodiment, the case where the layer forming composition includes a solvent in addition to the particles has been mainly described. However, the layer forming composition may not include a solvent. . Even in such a case, for example, when the binding liquid used for forming the joint portion contains a solvent, the above-described effects are exhibited.

  In the above-described embodiment, the surface layer of the stage and the surface layer of the frame body are made of a porous body, and the solvent is sucked through the holes (continuous holes) of these. Although described centrally, these do not have to be made of a porous body, and may have, for example, pores provided linearly in the thickness direction. Such a hole may be provided by machining, for example.

  In the above-described embodiment, the case where the groove functioning as the solvent flow path is provided in the base portion of the stage and the base portion of the frame has been described as a representative example. It may be provided on the surface layer of the layer or frame.

  In the above-described embodiments, the stage and the frame have been described as including the base and the surface layer, respectively, but at least one of them may be configured by a single member.

  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, 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.

  In the above-described embodiment, each of the plurality of layers has been described as being individually subjected to the solvent removal treatment. However, after the plurality of layers are laminated, the solvent removal treatment may be performed on these layers collectively. Good. For example, the layer formed immediately above the stage is not subjected to the solvent removal treatment alone, and the solvent removal treatment is performed on the two-layer laminate in a state where the second layer is superimposed on the surface. May be applied.

  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 embodiments, the solvent is sucked from the side surface direction and the bottom surface direction of the layer. For example, the suction may be performed from only one of the side surface direction and the bottom surface direction of the layer.

  In the above description, the formation of the bonding portion has been mainly described with respect to the case where the binding portion is formed using the binding liquid. However, in the present invention, the bonding portion may be formed by any method. You may perform by irradiating a line | wire and fusing (sintering and joining) particle | grains. In the case of producing a three-dimensional structure by forming a joint by such a method, if a composition containing a solvent in addition to particles is used as the layer forming composition, the solvent remains in the layer when the joint is formed. If this is done, the solvent will rapidly evaporate due to the irradiation of the energy beam, and the layer (bonding part) may be unintentionally deformed, resulting in a decrease in the dimensional accuracy of the finally obtained three-dimensional structure. Is prominently produced. In addition, the problem that the solid bonding of the particles is hindered and the mechanical strength of the three-dimensional structure is lowered also occurs remarkably. On the other hand, in the present invention, even when the bonding portion is formed by fusing (sintering and bonding) the particles constituting the layer by irradiating energy rays, the bonding portion is formed (energy). Since the amount of the solvent contained in the layer can be surely reduced during irradiation of the line, the occurrence of the above-described problems can be reliably prevented.

DESCRIPTION OF SYMBOLS 10 ... Three-dimensional structure 1 ... Layer 11 ... Composition (Composition for layer formation)
12 ... Binding liquid 13 ... Curing part (bonding part)
DESCRIPTION OF SYMBOLS 100 ... Three-dimensional structure manufacturing apparatus 2 ... Control part 21 ... Computer 22 ... Drive control part 3 ... Composition supply part (Composition supply part for layer formation)
DESCRIPTION OF SYMBOLS 4 ... Layer formation part 41 ... Stage 411 ... Base part 4112 ... Groove 412 ... Surface layer 4121 ... Hole part 42 ... Squeegee (flattening means)
43 ... Guide rail 44 ... Composition temporary placement part 45 ... Side support part (frame)
451 ... Base 4512 ... Groove 452 ... Surface layer 4521 ... Hole 5 ... Binding liquid discharge part (binding liquid applying means)
6 ... UV irradiation means (curing means)
7: suction means 8 ... solvent recovery means

Claims (9)

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 particles;
Repeating a series of steps including a bonding portion forming step of bonding the particles to form a bonding portion,
When performing the series of steps, a solvent contained in a material used for manufacturing the three-dimensional structure is collected by suction, and the method for manufacturing a three-dimensional structure is characterized.   The method of manufacturing a three-dimensional structure according to claim 1, wherein the stage on which the layer is placed has a hole, and the suction is performed through the hole.   The manufacturing method of the three-dimensional structure according to claim 1 or 2, wherein a frame disposed on an outer periphery of the stage on which the layer is placed has a hole, and the suction is performed through the hole. .   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the composition for forming a layer contains the solvent.   The manufacturing of the three-dimensional structure according to any one of claims 1 to 4, wherein the joint is formed by applying a binding liquid to the layer formed using the layer forming composition. Method.   The method for producing a three-dimensional structure according to claim 5, wherein the binding liquid contains the solvent. Using a composition for forming a layer containing particles, a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
A stage to which the layer forming composition is applied and the layer is formed;
A coupling portion forming means for coupling the particles to form a coupling portion;
A suction means for sucking a solvent contained in the material used for manufacturing the three-dimensional structure;
A three-dimensional structure manufacturing apparatus comprising: a solvent recovery unit that recovers the solvent sucked by the suction unit.   A three-dimensional structure manufactured using the manufacturing method according to any one of claims 1 to 6.   A three-dimensional structure manufactured using the apparatus according to claim 7.

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