JP2015202613A - Method for manufacturing three-dimensional molded article, apparatus for manufacturing three-dimensional molded article, and three-dimensional molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a three-dimensional molded article by which a three-dimensional molded article excellent in dimensional accuracy can be stably manufactured, to provide an apparatus for manufacturing a three-dimensional molded article, which can stably manufacture a three-dimensional molded article with excellent dimensional accuracy, and to provide a three-dimensional molded article manufactured by using the above method for manufacturing a three-dimensional molded article.SOLUTION: The method for manufacturing a three-dimensional molded article of the present invention is carried out by repeating a series of steps including: a layer forming step of forming a layer by using a composition containing a granular material; and a binder liquid imparting step of imparting a binder liquid into the layer to bind the granular material. An amount of the binder liquid to be imparted is controlled depending on the compatibility of the granular material and the binder liquid.

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.

  However, conventionally, it has been difficult to obtain a three-dimensional structure with excellent dimensional accuracy.

JP 2003-53847 A

  An object of the present invention is to provide a manufacturing method of a three-dimensional structure that can stably manufacture a three-dimensional structure excellent in dimensional accuracy, and to stably manufacture a three-dimensional structure excellent in dimensional accuracy. An object of the present invention is to provide an apparatus for manufacturing a three-dimensional structure, and to provide a three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention includes a layer forming step of forming a layer using a composition containing granules,
A series of steps including a binding liquid application step of applying a binding liquid for binding the particles to the layer,
The amount of the binding liquid applied is adjusted according to the compatibility between the particles and the binding liquid.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture the three-dimensional structure excellent in dimensional accuracy stably can be provided.

In the method for producing a three-dimensional structure according to the present invention, it is preferable that the amount of the binding liquid applied increases as the compatibility between the particles and the binding liquid increases.
Thereby, the dimensional accuracy of the three-dimensional structure can be made particularly excellent.

  In the method for producing a three-dimensional structure of the present invention, it is preferable that the granules are made of an organic material.

  Thereby, the adhesiveness of the said granule and the said binding liquid goes up, and the mechanical strength of a molded article improves.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the composition is a paste that includes a solvent for dispersing the particles in addition to the particles.

  Thereby, the fluidity | liquidity of a composition can be improved and the workability | operativity at the time of layer formation can be improved, and the unintentional scattering of the powder (granule) at the time of layer formation etc. can be prevented effectively.

  In the three-dimensional structure manufacturing method of the present invention, the series of steps preferably include a solvent removal step of removing the solvent between the layer formation step and the binding liquid application step. .

  Thereby, the mechanical strength of the three-dimensional structure can be further improved.

  In the three-dimensional structure manufacturing method of the present invention, the solvent removal step is preferably performed by heating.

  Thereby, the further improvement of the mechanical strength of a three-dimensional structure can be aimed at. In addition, the productivity of the three-dimensional structure can be made particularly excellent.

In the method for producing a three-dimensional structure of the present invention, the binding liquid contains an ultraviolet curable resin,
In the series of steps, it is preferable to have a curing step of irradiating ultraviolet rays to cure the ultraviolet curable resin after the binding liquid applying step.

  Thereby, the mechanical strength of the three-dimensional structure and the productivity of the three-dimensional structure can be made particularly excellent. It is also advantageous from the viewpoint of storage stability of the binding liquid and production cost of the three-dimensional structure.

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 composition containing granules,
A stage to which the composition is applied and the layer is formed;
A binding liquid applying means for applying a binding liquid for binding the particles to the layer;
The amount of the binding liquid applied is adjusted according to the compatibility between the particles and the binding liquid.

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

In the three-dimensional structure manufacturing apparatus of the present invention, it is preferable that a plurality of types of binding liquids having different compatibility with the predetermined particles can be applied.
Thereby, it can respond suitably to manufacture of various three-dimensional modeling objects.

In the three-dimensional structure manufacturing apparatus of the present invention, it is preferable that a plurality of types of the particles having different compatibility with the predetermined binding liquid can be supplied.
Thereby, it can respond suitably to manufacture of various three-dimensional modeling objects.

In the three-dimensional structure manufacturing apparatus of the present invention, the binding liquid contains an ultraviolet curable resin,
It is preferable that the three-dimensional structure manufacturing apparatus includes ultraviolet irradiation means.

  Thereby, the mechanical strength of the three-dimensional structure and the productivity of the three-dimensional structure can be made particularly excellent. It is also advantageous from the viewpoint of the production cost of the three-dimensional structure.

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

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

It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is sectional drawing which shows typically suitable 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.

  1, 2, and 3 are cross-sectional views schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure according to the present invention.

  As shown in FIGS. 1, 2, and 3, the manufacturing method of the present embodiment uses a composition 11 containing particles to form a layer 1 having a predetermined thickness (1 a, 1 e). ), A solvent removing step (layer heating step) (1b, 1f) for removing the solvent from the layer 1, and a binding liquid applying step (1c, 1g) for applying the binding liquid 12 to the layer 1 by an inkjet method. ) And a binder contained in the binding liquid 12 applied to the layer 1 to cure the binder and bond the granules, thereby forming a cured portion (bonded portion) 13 in the layer 1 (1d, 1h), and sequentially repeating these steps (1i), and then removing unbound particles that are not bound by the binder among the particles constituting each layer 1 ( 1j).

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 (a composition for three-dimensional modeling) 11 including particles (1a, 1e).

  When the composition 11 includes particles, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be improved. Moreover, the heat resistance, mechanical strength, etc. of the three-dimensional structure 10 can be made excellent.

  Although the composition (composition for three-dimensional modeling) 11 should just contain a granule, it is preferable that it is a paste-like thing containing the solvent which disperse | distributes a granule.

  Thereby, the fluidity | liquidity of the composition 11 can be improved and the workability | operativity at the time of layer 1 formation can be improved. In addition, it is possible to effectively prevent unintentional scattering of the powder (particles) when the layer 1 is formed.

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

  Since the aqueous solvent generally has appropriate volatility, the workability (ease of work, work efficiency) in the layer formation process is particularly excellent, and the finally obtained three-dimensional structure 10 It is possible to reliably prevent the solvent from remaining unintentionally.

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

  In addition, the aqueous solvent is generally highly safe. For this reason, it is preferable also when aiming at a worker's safety at the time of manufacture of the three-dimensional structure 10.

  In the present invention, the aqueous solvent means water or a liquid having a high affinity with water, and specifically means 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 a solvent (particularly an aqueous solvent) will be mainly described.
The 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 of 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 (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 or more and 20000 mPa. -More preferably, it is 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 made particularly excellent. Moreover, the solvent removal in a solvent removal process (layer heating process) can also be performed efficiently in a short time, and the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent.

≪Solvent removal process (layer heating process) ≫
After forming the layer 1 in the layer forming step, the solvent contained in the layer 1 is removed (1b, 1f).
Thereby, the content rate of the solvent in the finally obtained three-dimensional structure 10 can be made particularly low, and the bonding force between the particles and the binder can be made particularly high. Moreover, in the binding liquid application | coating process explained in full detail behind, the effect by adjusting the application quantity of the binding liquid 12 according to the compatibility of a granule and the binding liquid 12 is more reliably exhibited. From the above, the mechanical strength of the three-dimensional structure 10 can be further improved.

  This step may be performed by any method, for example, by placing the layer 1 in a reduced pressure environment or by spraying a dry gas (a gas having a low content of solvent component). It is preferable to perform the heat treatment (layer heat treatment).

  Thereby, the content rate of the solvent in the layer 1 can be made particularly low efficiently. As a result, the mechanical strength of the finally obtained three-dimensional structure 10 can be further improved, and the productivity of the three-dimensional structure can be particularly improved.

  In particular, in this step, it is preferable to perform the first heat treatment and the second heat treatment that is heated at a higher temperature than the first heat treatment.

  Thus, when the composition 11 (layer 1) contains an aqueous solvent by combining the first heat treatment and the subsequent second heat treatment, the content of the aqueous solvent in the layer 1 Can be efficiently reduced, and the content of the aqueous solvent in the three-dimensional structure 10 can be reliably reduced while the productivity of the three-dimensional structure 10 is excellent. Therefore, the strength of the bonding by the binding liquid 12 applied in the subsequent step can be surely excellent, and the mechanical strength of the finally obtained three-dimensional structure 10 is easily and reliably excellent. Can be.

It is considered that such an effect is obtained for the following reason.
That is, in the first heat treatment, the evaporation rate of the aqueous solvent from the outer surface of the layer 1 and the transfer rate of the aqueous solvent existing in the inside (deep part) of the layer 1 to the vicinity of the outer surface of the layer 1 Can be kept relatively large, and as a result, the aqueous solvent as a whole of the layer 1 can be contained while preventing the aqueous solvent from being trapped inside the layer 1 (deep part). The rate can be reduced efficiently. Further, in the second heat treatment, by increasing the heating temperature, the aqueous solvent remaining in the layer 1 is efficiently removed, and the content of the aqueous solvent as the entire layer 1 is sufficiently low. It can be. Therefore, it is possible to effectively prevent the aqueous solvent from remaining in the layer 1 from inhibiting the binding of the particles by the binding liquid. As a result, it is considered that the mechanical strength of the finally obtained three-dimensional structure 10 can be easily and reliably made excellent.

<First heat treatment>
In the layer heating step, first, a first heat treatment is performed.

  In the first heat treatment, mainly the aqueous solvent present in the vicinity of the outer surface of the layer 1 formed in the layer forming step is evaporated at an appropriate speed and is present in the layer 1 (in the deep part). The purpose is to move the aqueous solvent to the vicinity of the outer surface of the layer 1.

  Although the heating temperature of the layer 1 in the first heat treatment may be lower than the heating temperature in the second heat treatment, it is preferably 30 ° C. or higher and 70 ° C. or lower, preferably 35 ° C. or higher and 60 ° C. The following is more preferable.

  Thereby, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent while the productivity of the three-dimensional structure 10 is particularly excellent.

  The first heat treatment may be performed by any method. For example, the first heat treatment may be performed by a method using a hot plate, a method using an infrared heater, a method using hot air, or the like. Preferred method.

  Thereby, the evaporation of the aqueous solvent from the outer surface of the layer 1 and the movement of the aqueous solvent from the inside (deep part) of the layer 1 to the outer surface can be progressed more efficiently, and the productivity of the three-dimensional structure 10 is increased. Can be made particularly excellent.

  The wind speed of the hot air in the first heat treatment is preferably 1.0 m / sec or more and 30 m / sec or less, and more preferably 2.0 m / sec or more and 20 m / sec or less.

  Thereby, productivity of the three-dimensional structure 10 can be made particularly excellent while preventing unintentional deformation or the like of the layer 1 more reliably.

  The treatment time (heating time) of the first heat treatment is preferably 0.1 second or longer and 60 seconds or shorter, and more preferably 1 second or longer and 45 seconds or shorter.

  Thereby, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent while the productivity of the three-dimensional structure 10 is particularly excellent.

  Note that the first heat treatment may be performed collectively for the entire layer 1 or sequentially for each portion of the layer 1. When the first heat treatment is sequentially performed on each part of the layer 1, it is preferable that the treatment time for each part satisfies the above-described conditions.

  When the first heat treatment is performed using hot air, it is preferable to blow the hot air from an oblique direction on the outer surface side of the layer 1 (a direction inclined by a predetermined angle from the normal direction of the layer 1).

  Thereby, the evaporation of the aqueous solvent from the outer surface of the layer 1 and the movement of the aqueous solvent from the inside (deep part) of the layer 1 to the outer surface can be further efficiently advanced, and the productivity of the three-dimensional structure 10 is increased. Can be further improved.

The angle θ formed by the normal of the layer 1 and the hot air blowing direction is preferably 10 ° to 85 °, and more preferably 30 ° to 80 °.
Thereby, the effect mentioned above is exhibited more notably.

  Moreover, the blowing direction of hot air may be constant or may change with time.

<Second heat treatment>
After the first heat treatment described above, a second heat treatment is performed.
In the second heat treatment, the layer 1 is heated at a temperature higher than the heating temperature in the first heat treatment.

  In the second heat treatment, the productivity of the three-dimensional structure 10 is mainly obtained by performing the heat treatment at a higher temperature on the layer in which the content of the aqueous solvent is lowered by the first heat treatment described above. The purpose is to sufficiently reduce the content of the aqueous solvent in the layer 1 as a whole without incurring a decrease in the thickness.

  The heating temperature of the layer 1 in the second heat treatment is preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 45 ° C. or higher and 90 ° C. or lower.

  Thereby, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent while the productivity of the three-dimensional structure 10 is particularly excellent.

  The second heat treatment may be performed by any method. For example, the second heat treatment may be performed by a method using a hot plate, a method using an infrared heater, a method using hot air, or the like. Preferred method.

  Thereby, the evaporation of the aqueous solvent from the outer surface of the layer 1 and the movement of the aqueous solvent from the inside (deep part) of the layer 1 to the outer surface can be progressed more efficiently, and the productivity of the three-dimensional structure 10 is increased. Can be made particularly excellent.

  The wind speed of the hot air in the second heat treatment is preferably 1.0 m / sec or more and 30 m / sec or less, and more preferably 2.0 m / sec or more and 20 m / sec or less.

  Thereby, productivity of the three-dimensional structure 10 can be made particularly excellent while preventing unintentional deformation or the like of the layer 1 more reliably.

  The treatment time (heating time) of the second heat treatment is preferably from 0.1 second to 60 seconds, and more preferably from 1 second to 45 seconds.

  Thereby, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent while the productivity of the three-dimensional structure 10 is particularly excellent.

  Note that the second heat treatment may be performed collectively for the entire layer 1, or may be sequentially performed for each part of the layer 1. When the second heat treatment is sequentially performed on each part of the layer 1, it is preferable that the processing time for each part satisfies the above-described conditions.

  When the second heat treatment is performed using hot air, it is preferable to blow the hot air from an oblique direction on the outer surface side of the layer 1 (a direction inclined by a predetermined angle from the normal direction of the layer 1).

  Thereby, the evaporation of the aqueous solvent from the outer surface of the layer 1 and the movement of the aqueous solvent from the inside (deep part) of the layer 1 to the outer surface can be further efficiently advanced, and the productivity of the three-dimensional structure 10 is increased. Can be further improved.

The angle θ formed by the normal of the layer 1 and the hot air blowing direction is preferably 10 ° to 85 °, and more preferably 30 ° to 80 °.
Thereby, the effect mentioned above is exhibited more notably.

  Moreover, the blowing direction of hot air may be constant or may change with time.

≪Binding liquid application process≫
Next, the binding liquid 12 for binding the 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 part of the layer 1 corresponding to the real part (substantial part) of the three-dimensional structure 10.

  Thereby, the granule which comprises the layer 1 can be firmly couple | bonded, and the hardening part (joint part) 13 of a desired shape can be finally formed. Moreover, the mechanical strength of the finally obtained three-dimensional structure 10 can be made excellent.

  In this step, the application amount of the binding liquid 12 (application amount per unit volume) is adjusted according to the compatibility between the particles constituting the layer 1 and the binding liquid 12.

  Specifically, the higher the compatibility between the granules and the binding liquid 12, the larger the application amount of the binding liquid 12 (application amount per unit volume) in this step, and the granules and the binding liquid 12. The lower the compatibility with is, the smaller the applied amount of the binding liquid 12 (applied amount per unit volume) in this step.

  Thus, by adjusting the application amount of the binding liquid 12 according to the compatibility between the particles and the binding liquid 12, the gap between the particles can be suitably filled with the binding liquid 12, The mechanical strength and dimensional accuracy of the finally obtained three-dimensional structure 10 can be made excellent.

This is considered to be due to the following reasons.
That is, the absorbability of the binding liquid 12 of the granules constituting the layer 1 varies depending on the compatibility between the granules and the binding liquid 12. For this reason, for example, when the compatibility between the particles and the binding liquid 12 is high, the amount of the binding liquid 12 to be applied is increased in consideration of an increase in the amount of the binding liquid 12 absorbed by the particles. By increasing the amount, it is possible to prevent the amount of the binding liquid 12 existing between the granules from being insufficient. In addition, when the compatibility between the granules and the binding liquid 12 is low, the amount of the binding liquid 12 to be applied is reduced in consideration of the fact that the amount of the binding liquid 12 absorbed by the granules is reduced. By doing so, it is possible to prevent the excessive binding liquid 12 from being supplied to the layer 1, and to allow the binding liquid 12 to selectively exist at a desired portion of the layer 1.

  From the above, by adjusting the application amount of the binding liquid 12 according to the compatibility between the granules and the binding liquid 12, the mechanical strength of the finally obtained three-dimensional structure 10 and The dimensional accuracy can be made excellent.

  On the other hand, in the case where the amount of the binding liquid applied according to the compatibility between the particles and the binding liquid is not adjusted, the excellent effects as described above cannot be obtained.

  For example, when the compatibility between the particles and the binding liquid is high, the particles generally absorb the binding liquid and swell at a relatively high rate. For this reason, in the case where the amount of binding liquid applied is not adjusted despite the high compatibility between the particles and the binding liquid, the proportion of the binding liquid applied that is absorbed by the granules Since the amount of the binding liquid existing between the particles (particles) increases, the bonding force between the particles (particles) decreases, and the mechanical strength of the three-dimensional structure becomes low.

  In addition, when the compatibility between the particles and the binding liquid is low, generally, the ratio of the binding liquid absorbed by the particles is low. For this reason, even when the compatibility between the particles and the binding liquid is low, when the amount of the binding liquid applied is not adjusted, the applied binding liquid is suitably held between the particles (particles). The binding liquid overflows to a desired part in the layer (for example, the outside of the layer or a part where the binding liquid in the layer should not be applied (a part that should not be a binding part)). It's out. As a result, the dimensional accuracy of the finally obtained three-dimensional structure is low.

  As described above, in this step, the application amount of the binding liquid 12 is adjusted according to the compatibility between the particles constituting the layer 1 and the binding liquid 12, but the granules and the binding liquid 12 As the compatibility index, for example, an SP (solubility parameter) value can be adopted. That is, it can be said that the smaller the absolute value of the difference between the SP value of the granule and the SP value of the binding solution 12 is, the higher the compatibility is, and the absolute value of the difference between the SP value of the granule and the SP value of the binding solution 12 is. It can be said that compatibility is so low that is large.

  When the layer 1 includes a plurality of types of granules, these weighted average values can be adopted as the SP values of the granules, and the binding liquid 12 includes a plurality of types of components. As the SP value of the binding liquid 12, a weighted average value of these components can be adopted as the SP value of the binding liquid.

  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 particularly high. Moreover, adjustment of the application amount of the binder liquid 12 can be performed more suitably.

  As a specific example of the application amount of the binding liquid 12 (application amount per unit volume), when the thickness of the layer 1 is 10 μm or more and 100 μm or less and the binding liquid 12 is ejected at 720 dpi, it is per dot. The amount of the binding liquid 12 applied is preferably adjusted in the range of 0.5 ng to 80 ng depending on the combination of the granules and the binding liquid 12.

For example, the thickness of the layer 1 is 50 μm, the binding liquid 12 is applied at 720 dpi, and the amount of the binding liquid 12 applied per dot is such that the absolute value of the difference in SP value between the particles and the binding liquid 12 is 2. In the following, it is preferable to adjust in the range of 5 ng or more and 60 ng or less. Further, when the absolute value of the difference in SP value between the granule and the binding liquid 12 is larger than 2, it is preferably adjusted in the range of 1 ng to 10 ng.
Thereby, the effect mentioned above is exhibited more reliably.
The binding liquid 12 will be described in detail later.

≪Curing process (bonding 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).

  As described above, in the binding liquid application step, the application amount of the binding liquid 12 is adjusted according to the compatibility between the particles and the binding liquid 12, and therefore in the region where the bonding portion 13 is to be formed. An appropriate amount of the binding liquid 12 exists between the adjacent particles. As a result, the bonding portion 13 formed in this step has excellent bonding strength between particles. As a result, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent. In addition, since the binding liquid 12 is selectively applied to a desired part of the layer 1 and the outflow of the binding liquid to the unintentional part is reliably prevented, the coupling part 13 having a desired shape is obtained. Is reliably formed. As a result, the finally obtained three-dimensional structure 10 has excellent dimensional accuracy.

  Although this step varies depending on the type of binder, for example, when the binder is a thermosetting resin, it can be performed by heating, and when the binder is a photocurable resin, it can be performed by irradiation with the corresponding light. (For example, when the binder is an ultraviolet curable resin, it can be performed by irradiation with ultraviolet rays).

  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.

  For example, when the binder is not a curable component, this step can be omitted. In this case, the binding liquid application process described above also serves as the bonding process.

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

  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.

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

  FIG. 4 is a cross-sectional view schematically showing a preferred 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 the composition (composition for three-dimensional structure) 11 including the particles. .

As shown in FIG. 4, the three-dimensional structure manufacturing apparatus 100 includes a control unit 2, a composition supply unit 3 that contains a composition 11 that includes particles, and a composition 11 that is supplied from the composition supply unit 3. A layer forming unit 4 that forms the layer 1 using heat, a heating unit (layer heating unit) 7 that heats the layer 1, and a binding liquid discharge unit (binding liquid applying unit) that discharges the binding liquid 12 to the layer 1 ) 5 and energy beam irradiation means (curing means) 6 for irradiating energy beams for curing the binding liquid 12.
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 layer heating unit 7, the binding liquid discharge unit 5, the energy beam irradiation unit 6, and the like. 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 descending amount of the stage 41, the layer heating means 7 The heating conditions (heating temperature, warm air speed, etc.) 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.

  In particular, in the illustrated configuration, in order to supply different types of compositions 11, a composition supply unit 3 A, a composition supply unit 3 B, a composition supply unit 3 C, and a composition are provided as a plurality of composition supply units 3. The product supply unit 3D is provided.

  And the composition 11 accommodated in these composition supply part 3A, 3B, 3C, 3D contains the granule from which compatibility with the predetermined | prescribed binding liquid 12 mutually differs. More specifically, for example, the composition supply unit 3A contains a composition 11 containing granules composed of polyethyl methacrylate, and the composition supply unit 3B contains granules composed of polystyrene. In the composition supply unit 3C, the composition 11 containing granules composed of nylon 6 is accommodated, and in the composition supply unit 3D, granules composed of silica are contained. The composition 11 to be contained can be accommodated.

  With such a configuration, the composition contained in the composition supply unit can be replaced according to the characteristics (physical properties) and the like required for the three-dimensional structure 10 to be manufactured without performing the replacement of the composition accommodated in the composition supply unit. Eleven types can be suitably selected. In addition, the compatibility between the particles and the binding liquid 12 can be suitably adjusted. From the above, it can respond suitably for the manufacture of various three-dimensional structures 10.

  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 forming a new layer 1 on the previously formed layer 1, the previously formed layer 1 is moved downward relative to the side surface support portion 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 is preferably composed of a high-strength material. Examples of the constituent material of the stage 41 include various metal materials such as stainless steel.

  Further, the surface of the stage 41 (site 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 binding liquid 12 are more effectively prevented from adhering to the stage 41, or the durability of the stage 41 is made particularly excellent. 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.

  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 part 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.

  In addition, the surface of the side surface support portion 45 (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 are more effectively prevented from adhering to the side surface support portion 45, and the durability of the side surface support portion 45 is particularly excellent. 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 made particularly excellent. As a material used for the surface treatment of the surface of the side support part 45, for example, a fluorine-based resin such as polytetrafluoroethylene can be cited.

The layer heating means 7 performs a heat treatment (layer heat treatment) on the layer 1.
In particular, in the present embodiment, the layer heating means 7 performs the first heat treatment and the second heat treatment described above.

  Thus, since the single layer heating means 7 can perform the first heat treatment and the second heat treatment, the configuration of the three-dimensional structure manufacturing apparatus 100 can be simplified. .

  The conditions for the heat treatment may be controlled based on the detection result of detecting the temperature of the layer 1 or the content of the solvent in the layer 1 with a sensor (not shown), for example. Moreover, you may change a heating condition with a timer.

  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. Further, the discharge amount (discharge amount per unit volume) of the binding liquid 12 is adjusted according to the compatibility with the particles contained in the layer 1 (the layer 1 to which the binding liquid 12 is to be applied). Is controlled.

  Thereby, the space | gap between granule can be filled with the binder liquid 12 suitably, and the mechanical strength and dimensional accuracy of the three-dimensional structure 10 finally obtained can be made excellent.

  In particular, the present embodiment includes a plurality of binding liquid storage portions (not shown) for storing a plurality of types of binding liquids 12 so that different types of binding liquids 12 can be applied. The type of the binding liquid 12 supplied to the binding liquid discharge unit (binding liquid applying means) 5 can be changed.

  And the binding liquid 12 accommodated in these binding liquid accommodating parts mutually differs in compatibility with a predetermined granule.

  With such a configuration, according to the characteristics (physical properties) and the like required for the three-dimensional structure 10 to be manufactured without performing the replacement of the binding liquid 12 stored in the binding liquid storage unit. The type of the binding liquid 12 can be suitably selected. In addition, the compatibility between the particles and the binding liquid 12 can be suitably adjusted. From the above, it can respond suitably for the manufacture of various three-dimensional structures 10.

  Further, in the present embodiment, the binding liquid application unit 5 is a binding liquid discharge unit that discharges the binding liquid 12 by an ink jet 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 particularly with high 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 energy ray irradiating means (curing means) 6 irradiates energy rays for curing the binding liquid 12 applied to the layer 1.

The type of energy beam irradiated by the energy beam irradiation unit 6 varies depending on the constituent material of the binding liquid 12, and examples thereof include ultraviolet rays, visible rays, infrared rays, X-rays, γ rays, electron beams, and ion beams. Among these, from the viewpoint of cost and productivity of the three-dimensional structure, it is preferable to use ultraviolet rays.
According to the three-dimensional structure manufacturing apparatus of the present invention as described above, a three-dimensional structure excellent in mechanical strength and dimensional accuracy can be stably manufactured.

<Composition (Composition for 3D modeling)>
Next, the composition (composition for three-dimensional modeling) 11 used for manufacturing the three-dimensional modeled object of the present invention will be described in detail.

  The composition (three-dimensional modeling composition) 11 includes at least a three-dimensional modeling powder including 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.

  As an inorganic material which comprises a granule, various metals, a metal compound, etc. are mentioned, for example. 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 organic materials constituting the granules include synthetic resins and natural polymers. More specifically, polyethylene resins; polypropylene; polyethylene oxide; polypropylene oxide, polyethyleneimine; polystyrene; polyurethane; polyurea; A silicone resin; an acrylic silicone resin; a polymer having a (meth) acrylic acid ester such as polymethyl methacrylate as a constituent monomer; a cross polymer having a (meth) acrylic acid ester as a constituent monomer such as a methyl methacrylate crosspolymer (ethylene Acrylic acid copolymer resin, etc.); polyamide resin such as nylon 12, nylon 6, copolymer nylon; polyimide; carboxymethyl cellulose; gelatin; starch; chitin;

Especially, it is preferable that a granule is comprised with the organic material.
Thereby, compatibility with the binding liquid containing the ultraviolet curable resin is increased, the adhesion between the particles and the binding liquid is increased, and the mechanical strength of the molded article is improved.

  Specific examples of the SP value of the constituent material of the granule include, for example, 9.7 for polyethyl methacrylate, 9.1 to 9.5 for polymethyl methacrylate, and 9. for ethylene-acrylic acid copolymer. 5. Nylon 12 is 9.9, polystyrene is 10.3, nylon 6 is 11.6, and polyacrylonitrile is 14.8.

  The average particle diameter of the particles constituting the three-dimensional modeling powder 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 10 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 can be more effectively prevented. The dimensional accuracy of the molded article 10 can be made particularly excellent. In addition, the fluidity of the powder for three-dimensional modeling and the fluidity of the composition (three-dimensional modeling composition) 11 including the powder for three-dimensional modeling are particularly excellent, and the productivity of the three-dimensional model 10 is particularly excellent. Can be.

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

  The Dmax of the particles constituting the three-dimensional modeling powder 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 10 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 can be more effectively prevented. The dimensional accuracy of the molded article 10 can be made particularly excellent. In addition, the fluidity of the powder for three-dimensional modeling and the fluidity of the composition (three-dimensional modeling composition) 11 including the powder for three-dimensional modeling are particularly excellent, and the productivity of the three-dimensional model 10 is particularly excellent. Can be.

  The particles constituting the powder for three-dimensional modeling may have any shape, but preferably have a spherical shape. Thereby, the fluidity of the powder for three-dimensional modeling and the fluidity of the composition (three-dimensional modeling composition) 11 including the powder for three-dimensional modeling are particularly excellent, and the productivity of the three-dimensional model 10 is particularly improved. While being able to be excellent, it is possible to more effectively prevent the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 and to make the dimensional accuracy of the three-dimensional structure 10 particularly excellent. Can do.

  The content of the three-dimensional modeling powder in the composition (three-dimensional modeling composition) 11 is preferably 5% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. preferable. Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent while the fluidity of the composition (composition for three-dimensional structure) 11 is sufficiently excellent. .

(solvent)
The composition 11 may contain a solvent in addition to the granules.

  Thereby, the composition 11 can be suitably paste-like, the fluidity of the composition 11 should be stably excellent, and the productivity of the three-dimensional structure 10 should be particularly excellent. Can do.

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

  Examples of the aqueous solvent constituting the composition 11 include water; alcoholic solvents such as methanol, ethanol and isopropanol; ketone solvents such as methyl ethyl ketone and acetone; glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether. Solvent; 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 two selected from these A combination of the above can be used.

  Especially, it is preferable that the composition 11 contains water. Thereby, water-soluble resin can be dissolved more reliably and the fluidity of the composition 11 and the uniformity of the composition of the layer 1 formed using the composition 11 can be made particularly excellent. Moreover, water is easy to remove in the layer heating step. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems.

  The content of the solvent in the composition 11 is preferably 5% by mass or more and 88% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. Thereby, while the effect as mentioned above is exhibited more notably, the productivity of the three-dimensional structure 10 can be made particularly excellent.

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.

(Water-soluble resin)
The composition 11 may contain a water-soluble resin together with a plurality of granules.

  By including the water-soluble resin, the particles can be bonded (temporarily fixed) to each other at the portion where the binding liquid 12 of the layer 1 is not applied, and unintentional scattering of the particles can be more effectively prevented. it can. Thereby, the further improvement of the operator's safety and the dimensional accuracy of the manufactured three-dimensional structure 10 can be aimed at.

  Any water-soluble resin may be used as long as at least a part thereof is soluble in water. For example, the solubility in water at 25 ° C. (mass soluble in 100 g of water) is 5 [g / 100 g water] or more. It is preferable that it is more than 10 [g / 100g water].

  Examples of the water-soluble resin include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactam 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, and modified starch 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.

  Among these, when the water-soluble resin is polyvinyl alcohol, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent. Further, by adjusting the degree of saponification and the degree of polymerization, the characteristics of the water-soluble resin (for example, water solubility, water resistance, etc.) and the characteristics of the composition 11 (for example, viscosity, fixing force of granules, wettability, etc.) are further improved. It can control suitably. For this reason, it can respond suitably by manufacture of the various three-dimensional structure 10. Polyvinyl alcohol is inexpensive and stable in supply among various water-soluble resins. For this reason, the stable three-dimensional structure 10 can be manufactured while suppressing the production cost.

  When the water-soluble resin contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is preferably 75 or more and 98 or less. Thereby, the fall of the solubility of the polyvinyl alcohol with respect to water can be suppressed. Therefore, when the composition 11 contains water, the adhesive fall between the adjacent layers 1 can be suppressed more effectively.

  When the water-soluble resin contains polyvinyl alcohol, the degree of polymerization of the polyvinyl alcohol is preferably 300 or more and 2500 or less. Thereby, when the composition 11 contains water, the mechanical strength of each layer 1 and the adhesiveness between adjacent layers 1 can be made particularly excellent.

  Further, when the water-soluble resin is polyvinyl pyrrolidone (PVP), the following effects can be obtained. That is, since polyvinylpyrrolidone is excellent in adhesiveness to various materials such as glass, metal, and plastic, the strength and shape stability of the portion to which the binder 12 is not applied in the layer 1 are particularly excellent. The dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly excellent. Moreover, since polyvinylpyrrolidone shows high solubility with respect to various organic solvents, when the composition 11 contains an organic solvent, the fluidity of the composition 11 can be made particularly excellent. Thus, the layer 1 in which the variation in thickness is more effectively prevented can be suitably formed, and the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly excellent. Moreover, since polyvinylpyrrolidone shows high solubility also to water, in the unbonded particle removal process (after the completion of modeling), among the particles constituting each layer 1, those that are not bound by a binder are easy. And it can be removed reliably. Moreover, since polyvinylpyrrolidone is excellent in affinity with various colorants, when the binding liquid 12 containing the colorant is used in the binding liquid application step, the colorant diffuses unintentionally. Can be effectively prevented. Moreover, when the paste-like composition 11 contains polyvinylpyrrolidone, it is possible to effectively prevent bubbles from being entrained in the composition 11, and defects due to entrainment of bubbles occur in the layer forming step. This can be effectively prevented.

  When the water-soluble resin contains polyvinyl pyrrolidone, the weight average molecular weight of the polyvinyl pyrrolidone 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.

  The content of the water-soluble resin in the composition 11 is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 15% by mass or less. Thereby, while the effect as mentioned above is exhibited more notably, the productivity of the three-dimensional structure 10 can be made particularly excellent.

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

<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 12 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 mechanical strength of the three-dimensional structure 10 obtained, and productivity of the three-dimensional structure 10. Among various curable resins, in particular, from the viewpoint of the mechanical strength of the obtained three-dimensional structure 10, the productivity of the three-dimensional structure 10, the storage stability of the binding liquid 12, in particular, an ultraviolet curable resin ( Polymerizable compounds) are 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.), tetra- or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, poly of cresol novolac resin) 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 12 is preferably 80% by mass or more, and more preferably 85% by mass or more. Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent.

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

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

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

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

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

  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 and the like.

  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 liquid 12 contains a pigment, the average particle diameter of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less. Thereby, the discharge stability of the binding liquid 12 and the dispersion stability of the pigment in the binding liquid 12 can be made particularly excellent, and an image with better 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. Directed 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 12 contains a colorant, the content of the colorant in the binder liquid 12 is preferably 1% by mass or more and 20% by mass or less. Thereby, particularly excellent concealability and color reproducibility can be obtained.

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

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

  When the binding liquid 12 contains a surfactant, the three-dimensional structure 10 can have better abrasion resistance. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used. 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 binding liquid 12 may include a solvent. Thereby, the viscosity of the binding liquid 12 can be suitably adjusted, and even when the binding liquid 12 includes a high-viscosity component, the discharge stability of the binding liquid 12 by the inkjet method is particularly excellent. It can be.

  Examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 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 12 is preferably 10 mPa · s or more and 30 mPa · s or less, and more preferably 15 mPa · s or more and 25 mPa · s or less. Thereby, the discharge stability of the binding liquid 12 by the inkjet method can be made particularly excellent. In the present specification, the viscosity means a value measured at 25 ° C. using an E-type viscometer (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 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.

In the illustrated configuration, the three-dimensional structure manufacturing apparatus includes one heating unit as a heating unit (layer heating unit) for heating the layer, but includes two or more layer heating units. Also good. Thereby, for example, the conditions of the first heat treatment and the second heat treatment can be adjusted more suitably. Moreover, the unintentional dispersion | variation in the heating conditions in each site | part of a layer can be suppressed more effectively.
In addition, the three-dimensional structure manufacturing apparatus may not include a heating unit.

  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.

  Further, in the above-described embodiment, the case where the amount of binding liquid applied is adjusted so that the higher the compatibility between the particles and the binding liquid, the larger the amount of binding liquid applied. As described above, in the present invention, the adjustment method is not limited to the above as long as the amount of the binding liquid applied is adjusted according to the compatibility between the particles and the binding liquid.

  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 curing process is described as being repeatedly performed together with the layer forming process and the binding liquid applying process in addition to the layer forming process and the binding liquid applying process. However, the curing process is repeatedly performed. It doesn't have to be a thing. For example, it may be performed collectively after forming a laminate including a plurality of uncured layers.

  Further, in the above-described embodiment, the case where the binding liquid application process and the bonding process are performed after performing the layer heating process in the series of repeated processes is described. It may be performed before the layer heating step.

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

Examples of the pretreatment process include a stage cleaning process.
Examples of the post-processing step include a cleaning step, a shape adjustment step for performing deburring, a coloring step, a coating layer forming step, and a binder curing completion step for performing a light irradiation process for reliably curing the uncured binder. Etc.

  In the above-described embodiment, the method having the binding liquid application process and the curing process (bonding process) has been mainly described. For example, the binding liquid includes a thermoplastic resin as a binder. In some cases, it is not necessary to provide a curing step (bonding step) after the binding liquid applying step (the binding liquid applying step can be combined with the bonding step). In such a case, the three-dimensional structure manufacturing apparatus may not include the energy beam irradiation unit (curing unit).

  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.

In the embodiment described above, the case where the composition (composition for three-dimensional modeling) includes a solvent (particularly an aqueous solvent) has been mainly described. However, in the present invention, the composition includes a solvent. It may not be.
Further, the composition may not be in the form of a paste.

DESCRIPTION OF SYMBOLS 10 ... Three-dimensional modeling thing 1 ... Layer 11 ... Composition (Composition for three-dimensional modeling)
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, 3A, 3B, 3C, 3D ... Composition supply part 4 ... Layer formation part 41 ... Stage 42 ... Squeegee (flattening means)
43 ... Guide rail 44 ... Composition temporary placement part 45 ... Side support part (frame)
5: Binding liquid discharge part (binding liquid applying means)
6. Energy beam irradiation means (curing means)
7. Heating means (layer heating means)

Claims (13)

A layer forming step of forming a layer using a composition containing granules,
A series of steps including a binding liquid application step of applying a binding liquid for binding the particles to the layer,
A method for producing a three-dimensional structure, wherein the amount of the binding liquid applied is adjusted in accordance with the compatibility between the particles and the binding liquid.   The method for producing a three-dimensional structure according to claim 1, wherein the higher the compatibility between the particles and the binding liquid, the greater the amount of the binding liquid applied.   The method for producing a three-dimensional structure according to claim 1 or 2, wherein the particles are made of an organic material.   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the composition is a paste that includes a solvent that disperses the particles in addition to the particles.   5. The method for producing a three-dimensional structure according to claim 4, wherein the series of steps includes a solvent removal step of removing the solvent between the layer formation step and the binding liquid application step.   The method for producing a three-dimensional structure according to claim 5, wherein the solvent removing step is performed by heating. The binding liquid contains an ultraviolet curable resin,
7. The three-dimensional according to claim 1, further comprising a curing step of irradiating ultraviolet rays to cure the ultraviolet curable resin after the binding liquid applying step in the series of steps. Manufacturing method of a model. A three-dimensional structure manufacturing apparatus that manufactures a three-dimensional structure by laminating layers using a composition containing granules,
A stage to which the composition is applied and the layer is formed;
A binding liquid applying means for applying a binding liquid for binding the particles to the layer;
The three-dimensional structure manufacturing apparatus characterized by adjusting the application amount of the binding liquid according to the compatibility between the particles and the binding liquid.   The three-dimensional structure manufacturing apparatus according to claim 8, wherein the three-dimensional structure manufacturing apparatus is configured to be able to apply a plurality of types of the binding liquids having different compatibility with the predetermined particles.   The three-dimensional structure manufacturing apparatus according to claim 8 or 9, wherein the three-dimensional structure manufacturing apparatus is configured to be able to supply a plurality of types of the particles having different compatibility with the predetermined binding liquid. The binding liquid contains an ultraviolet curable resin,
The three-dimensional structure manufacturing apparatus according to any one of claims 8 to 10, wherein the three-dimensional structure manufacturing apparatus includes ultraviolet irradiation means.   A three-dimensional structure manufactured using the manufacturing method according to any one of claims 1 to 7.   A three-dimensional structure manufactured using the apparatus according to any one of claims 8 to 11.

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