WO2016067584A1

WO2016067584A1 - Method for manufacturing three-dimensional structure, three-dimensional structure manufacturing apparatus, and three-dimensional structure

Info

Publication number: WO2016067584A1
Application number: PCT/JP2015/005357
Authority: WO
Inventors: Tomoaki Takahashi; Toshimitsu Hirai
Original assignee: Seiko Epson Corp
Current assignee: Seiko Epson Corp
Priority date: 2014-10-30
Filing date: 2015-10-26
Publication date: 2016-05-06
Anticipated expiration: 2017-04-30
Also published as: JP2016087810A; TW201618938A

Abstract

A method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, includes a layer forming step of forming the layer having a predetermined thickness using a layer forming composition including particles, a liquid applying step of applying the liquid to the layer, and a curing step of forming a cured portion by curing the liquid, in which based on a height of an upper surface of a cured product formed using the liquid, a thickness of the layer to be newly formed after formation of the cured product is determined.

Description

METHOD FOR MANUFACTURING THREE-DIMENSIONAL STRUCTURE, THREE-DIMENSIONAL STRUCTURE MANUFACTURING APPARATUS, AND THREE-DIMENSIONAL STRUCTURE

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 technology for forming a three-dimensional structure by forming powder layers (layers) using a composition including powder (particles) and by stacking these layers is known (for example, refer to PTL 1). In this technology, a three-dimensional structure is formed by repeating the following operations.
First, powder is spread thinly in a uniform thickness to form a powder layer, a binder material (liquid) is applied to only a desired portion of the powder layer, and powder (particles) is bound to each other, whereby a bound portion (cured portion) is formed. As a result, a member having a thin plate-shape (hereinafter, referred to as a "cross-section member") is formed at the bound portion formed by binding of the powder to each other. Thereafter, a thin powder layer is further formed on the powder layer, and powder is selectively bound to each other only at a desired portion, whereby a bound portion is formed. As a result, a new cross-section member is formed even in the newly formed powder layer. At this time, the newly formed cross-section member is also bound to the cross-section member formed previously. A three-dimensional structure can be formed by stacking cross-section members (bound portions) having a thin plate-shape layer by layer by repeating such operations.

However, along with repeatedly performing layer formation, a flattening member such as a squeegee or the like used at the time of layer formation is worn or deformed, or by fluctuation or the like in the applied amount of liquid, deviation from the desired designed value occurs in the thickness of the layer formed in some cases. When such deviation occurs in the thickness of the layer, there is a problem in that the dimensional accuracy of a finally obtained three-dimensional structure is reduced, the binding force between the bound portions formed in the adjacent layers is reduced, the mechanical strength of a finally obtained three-dimensional structure is reduced, or the like.

JP-A-6-218712

An advantage of some aspects of the invention is to provide a method for manufacturing a three-dimensional structure and a three-dimensional structure manufacturing apparatus, capable of efficiently manufacturing a three-dimensional structure which has excellent dimensional accuracy and mechanical strength, and a three-dimensional structure which has excellent dimensional accuracy and mechanical strength.

The advantage is achieved by the following aspects of the invention.
A method for manufacturing a three-dimensional structure according to an aspect of the invention is a method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, including: a layer forming step of forming the layer having a predetermined thickness using a layer forming composition including particles; a liquid applying step of applying the liquid to the layer; and a curing step of forming a cured portion by curing the liquid, in which based on a height of an upper surface of a cured product formed using the liquid, a thickness of the layer to be newly formed after formation of the cured product is determined.

With this configuration, it is possible to provide a method for manufacturing a three-dimensional structure, capable of efficiently manufacturing a three-dimensional structure which has excellent dimensional accuracy and mechanical strength.

A method for manufacturing a three-dimensional structure according to another aspect of the invention is a method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, including: a layer forming step of forming the layer having a predetermined thickness using a layer forming composition including particles; a liquid applying step of applying the liquid to the layer; and a curing step of forming a cured portion by curing the liquid, in which a height of a cured product formed using the liquid is measured, and based on the measurement result, a thickness of the layer to be newly formed after formation of the cured product is determined.

A method for manufacturing a three-dimensional structure according to still another aspect of the invention is a method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, including: a layer forming step of forming the layer having a predetermined thickness by flattening a layer forming composition including particles, using a flattening device; a liquid applying step of applying the liquid to the layer; and a curing step of forming a cured portion by curing the liquid, in which the flattening device is brought into contact with an upper surface of a cured product formed using the liquid, and based on the contact surface, the layer having a predetermined thickness is formed.

In the method for manufacturing a three-dimensional structure of the aspect of the invention, it is preferable that the cured product is formed at a second region different from a first region where a portion configuring an entity portion of the three-dimensional structure of interest on the forming stage is formed.

With this configuration, it is possible to make the dimensional accuracy and the reliability of a finally obtained three-dimensional structure particularly excellent.

In the method for manufacturing a three-dimensional structure of the aspect of the invention, it is preferable that the second region is provided on the outer peripheral side of the first region.

With this configuration, it is possible to make the dimensional accuracy and the reliability of a finally obtained three-dimensional structure more excellent, and it is possible to make the productivity of a three-dimensional structure particularly excellent.

In the method for manufacturing a three-dimensional structure of the aspect of the invention, it is preferable that a discharge pattern density of the liquid in the second region is equal to a discharge pattern density of the liquid in the first region.

With this configuration, it is possible to make the dimensional accuracy and the mechanical strength of a finally obtained three-dimensional structure particularly excellent.

In the method for manufacturing a three-dimensional structure of the aspect of the invention, it is preferable that the cured product is formed so as to be stacked over a plurality of steps, to correspond to the plurality of layers.

With this configuration, it is possible to make the dimensional accuracy and the mechanical strength of the overall three-dimensional structure particularly excellent.

In the method for manufacturing a three-dimensional structure of the aspect of the invention, it is preferable that, when a cured product formed in any step, of a plurality of the cured products formed by being stacked over a plurality of steps, is defined as a first cured product, and a cured product formed in a later step than the first cured product is defined as a second cured product, the second cured product does not have a region not overlapping with the first cured product, when seen in a plan view.

It is preferable that the method for manufacturing a three-dimensional structure of the aspect of the invention further includes a first liquid applying step of applying the liquid to the layer in a state of including a solvent after the layer forming step is performed using the layer forming composition including the particles and the solvent; a first curing step of curing the liquid applied to the layer; and a solvent removing step of removing the solvent from the layer.

With this configuration, it is possible to suitably prevent the unintended penetration of a liquid into the inside of a layer, and it is possible to more reliably form a cured portion having a desired shape on the upper surface of the layer. As a result, it is possible to make the dimensional accuracy of a finally obtained three-dimensional structure particularly excellent.

It is preferable that the method for manufacturing a three-dimensional structure of the aspect of the invention further includes a second liquid applying step of applying the liquid to the layer in a state in which the solvent is removed after the solvent removing step and penetrating the liquid into the layer; and a second curing step of curing the liquid penetrated into the layer.

With this configuration, it is possible to form a cured portion in the inside of the layer, a finally obtained three-dimensional structure has particularly excellent mechanical strength, unintended deformation thereof is more reliably prevented, and thus, the reliability thereof becomes higher.

A three-dimensional structure manufacturing apparatus according to yet another aspect of the invention is a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, including: a stage that forms the layer using a layer forming composition including particles; a liquid applying device that applies a liquid to the layer; and a curing device that cures the liquid, in which based on a height of an upper surface of a cured product formed using the liquid, a thickness of the layer to be newly formed after formation of the cured product is determined.

With this configuration, it is possible to provide a three-dimensional structure manufacturing apparatus capable of efficiently manufacturing a three-dimensional structure which has excellent dimensional accuracy and mechanical strength.

A three-dimensional structure according to still yet another aspect of the invention is a three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure of the aspect of the invention.

With this configuration, it is possible to provide a three-dimensional structure which has excellent dimensional accuracy and mechanical strength.

A three-dimensional structure according to further another aspect of the invention is manufactured using the three-dimensional structure manufacturing apparatus of the aspect of the invention.

Fig. 1A is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1B is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1C is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1D is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1E is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1F is a cross-sectional view schematically showing a step in a first embodiment of a method for manufacturing a three-dimensional structure according to the invention. Fig. 1G is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1H is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1I is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1J is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1K is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1L is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1M is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1N is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1O is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1P is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1Q is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1R is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1S is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 1T is a cross-sectional view schematically showing a step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2A is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2B is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2C is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2D is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2E is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2F is a cross-sectional view schematically showing a step in a second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2G is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2H is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2I is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2J is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2K is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2L is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2M is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2N is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2O is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2P is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2Q is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2R is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2S is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 2T is a cross-sectional view schematically showing a step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention. Fig. 3 is a cross-sectional view schematically showing a preferred embodiment of a three-dimensional structure manufacturing apparatus according to the invention.

Hereinafter, preferred embodiments of the invention will be described in detail with reference to the accompanying drawings.
Method for Manufacturing Three-Dimensional Structure

First, the method for manufacturing a three-dimensional structure according to the invention will be described.
First Embodiment
Figs. 1A to 1T are cross-sectional views schematically showing each step in the first embodiment of the method for manufacturing a three-dimensional structure according to the invention.

As shown in Figs. 1A to 1T, the method for manufacturing a three-dimensional structure 10 of the embodiment has a layer forming step (Fig. 1D, Fig. 1K, and Fig. 1R) of forming a layer 1 having a predetermined thickness using a layer forming composition 1' including particles 11, a liquid applying step (Fig. 1E, Fig. 1H, Fig. 1L, and Fig. 1O) of applying a liquid (cured portion forming liquid) 2' used in formation of a cured portion 2 (a first cured portion 2A) to the layer 1, and a curing step (Fig. 1F, Fig. 1I, Fig. 1M, and Fig. 1P) of forming the cured portion 2 by curing the liquid 2'.

In the liquid applying step, the liquid 2' used in formation of the cured portion 2 configuring an intended three-dimensional structure 10 is applied to a second region M412 which is a region different from a first region M411 which is a region at which the intended three-dimensional structure 10 is manufactured; and in the curing step, the cured portion 2 is formed by curing the liquid 2' applied to the first region M411, and a cured product 6 having the same height as that of the cured portion 2 is formed by curing the liquid 2' applied to the second region M412.

When the layer forming step (for example, a step of (Fig. 1K) performed after a step of (Fig. 1F) or a step of (Fig. 1R) performed after a step of (Fig. 1M)) is performed after the cured product 6 is formed, the thickness of the layer 1 is determined based on the height of the upper surface of the cured product 6 (Fig. 1J and Fig. 1Q).

In this manner, by determining the thickness of the layer 1 based on the height of the upper surface of the cured product 6, it is possible to prevent the constituent (for example, the particles 11) of the layer forming composition 1' from unintentionally remaining on the upper surface of the cured portion 2 at the time when the layer forming step ends.

Thereby, in a subsequent step, it is possible to reliably make the adhesion between the cured portion 2 and the cured portion 2 newly formed on the cured portion 2 excellent. As a result, it is possible to make the mechanical strength of the finally obtained three-dimensional structure 10 excellent.

In addition, it is possible to prevent the reduction in the dimensional accuracy of the three-dimensional structure 10, caused by the unintentional presence of the particles 11 configuring the layer forming composition 1' between any cured portion 2 and the cured portion 2 formed on the cured portion 2.

In particular, in the embodiment, in the layer forming step, the flattening device M42 is brought into contact with the upper surface of the cured product 6, and, based on the height (contact surface) at which the flattening device M42 is in contact with the cured product 6, the layer 1 having a predetermined thickness is formed (refer to Fig. 1J and Fig. 1Q).

Thereby, with the simple configuration, it is possible to more effectively prevent an occurrence of the problem described above, and it is possible to manufacture the three-dimensional structure 10 having excellent mechanical strength and dimensional accuracy with excellent productivity.

As described above, in the embodiment, the cured product 6 is formed at the second region M412 different from the first region M411 where a portion configuring an entity portion of an intended three-dimensional structure 10 is formed, on the stage M41.

Thereby, when the flattening device M42 is brought into contact with the upper surface of the cured product 6 (when the thickness of the layer to be newly formed is determined), it is possible to more reliably prevent an occurrence of unintended deformation in the layer 1 according to the cured portion 2 or forming of the intended three-dimensional structure 10. As a result, it is possible to make the dimensional accuracy and the reliability of the finally obtained three-dimensional structure 10 particularly excellent.

In the configuration in the figures, the second region M412 is provided on the outer peripheral side of the first region M411.

Thereby, effects as described above are more significantly exhibited, it is possible to make the dimensional accuracy and the reliability of a finally obtained three-dimensional structure 10 more excellent, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent.

In particular, in the configuration in the figures, regarding the relative moving direction with respect to the stage M41 of the flattening device M42, the second region M412 is provided on the upstream side of the first region M411.

Thereby, the relative height of the flattening device M42 can be adjusted, and due to this, it is possible to efficiently perform formation of the layer 1 by the flattening device M42, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent.

The discharge pattern density of the liquid 2' in the second region M412 is preferably equal to the discharge pattern density of the liquid 2' in the first region M411. For example, in a case where the liquid 2' is discharged at 720 dpi in the first region M 411, the liquid 2' is preferably discharged at 720 dpi even in the second region M 412.

Thereby, it is possible to make the difference between the thickness of the cured portion 2 and the thickness of the cured product 6 smaller, effects as described above are more significantly exhibited, and it is possible to make the dimensional accuracy and the mechanical strength of a finally obtained three-dimensional structure 10 particularly excellent.

In the embodiment, the cured product 6 is preferably formed so as to be stacked over a plurality of steps (Fig. 1B, Fig. 1F, Fig. 1M, and Fig. 1S), to correspond to the plurality of layers 1.

Thereby, it is possible to determine a suitable thickness for each of the plurality of layers 1, and it is possible to make the dimensional accuracy and the mechanical strength of the overall three-dimensional structure 10 particularly excellent.

In addition, in the embodiment, all of the plurality of cured products 6 formed by being stacked over several steps have the same shape and the same area. In other words, when a cured product formed in any step, of the plurality of cured products 6 formed by being stacked over a plurality of steps, is defined as a first cured product, and a cured product formed in a later step than the first cured product, of the plurality of cured products 6 formed by being stacked over a plurality of steps, is defined as a second cured product, the second cured product does not have a region not overlapping with the first cured product, when seen in a plan view.

Thereby, by such a configuration, it is possible to more effectively prevent the unintended deformation (so-called sagging or the like) of the cured product 6, it is possible to make the difference between the thickness of the cured portion 2 and the thickness of the cured product 6 smaller, and effects as described above can be more significantly exhibited. As a result, it is possible to make the dimensional accuracy and the mechanical strength of the finally obtained three-dimensional structure 10 particularly excellent.

The method for manufacturing a three-dimensional structure according to the invention may have a layer forming step, a liquid applying step, and a curing step, and the method for manufacturing the three-dimensional structure 10 of the embodiment has a layer forming step of forming the layer 1 using the layer forming composition 1' including the particles 11 and the solvent 12 (Fig. 1C, Fig. 1D, Fig. 1J, Fig. 1K, Fig. 1Q, and Fig. 1R), a first liquid applying step (Fig. 1E and Fig. 1L) of applying the liquid (cured portion forming liquid) 2' used in formation of the cured portion 2 (first cured portion 2A) on the layer 1 in a state of including the solvent 12, a first curing step (Fig. 1F and Fig. 1M) of forming the cured portion 2 (first cured portion 2A) by curing the liquid (cured portion forming liquid) 2' applied on the layer 1 in a state of including the solvent 12, a solvent removing step of removing the solvent 12 from the layer 1 (Fig. 1G and Fig. 1N), a second liquid applying step (Fig. 1H and Fig. 1O) of applying the liquid (cured portion forming liquid) 2' used in formation of the cured portion 2 (second cured portion 2B) to the layer 1 in a state in which the solvent 12 is removed, and penetrating the liquid 2' into the layer 1, and a second curing step (Fig. 1I and Fig. 1P) of forming the cured portion 2 (second cured portion 2B) by curing the liquid (cured portion forming liquid) 2' penetrated into the layer 1, and these steps are sequentially repeatedly performed (Fig. 1S), and, thereafter, the method for manufacturing the three-dimensional structure 10 of the embodiment further has an unbound particle removing step (Fig. 1T) of removing particles which are not bound by the cured portion 2, of the particles 11 configuring each layer 1.

In this manner, by applying the liquid (cured portion forming liquid) 2' used in formation of the cured portion 2 (first cured portion 2A) to the layer 1 in a state of including the solvent 12, in the first liquid applying step, it is possible to prevent the liquid 2' used in formation of the cured portion 2 from unintentionally penetrating into a portion other than the intended portion. As a result, it is possible to easily and reliably form the cured portion 2 (first cured portion 2A) having a desired shape. Effects by determining the thickness of the layer 1 to be newly formed after formation of the cured product are obtained based on the height of the upper surface of the cured product 6 as described above, and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly excellent.

The embodiment has a third liquid applying step (Fig. 1A) of applying the liquid (cured portion forming liquid) 2' used in formation of the cured portion 2 (third cured portion 2C) to the stage M41 on which the layer 1 (layer 1 formed using a layer forming composition 1') is not formed before the first layer forming step, and a third curing step (Fig. 1B) of forming the cured portion 2 (third cured portion 2C) by curing the liquid 2'.

Thereby, since it is possible to form the cured portion 2 (cured portion 2 not including the particles 11) buried in the lowermost layer 1, and the layer 1 not including the cured portion 2 not including the particles 11 is not formed, it is possible to make the productivity of the three-dimensional structure 10 particularly excellent. Since, in the finally obtained three-dimensional structure 10, the cured portion 2 configuring an outer surface when viewed from the side can be unified with a portion configured of a material not containing the particles 11, it is possible to make an aesthetic appearance of the overall three-dimensional structure 10 particularly excellent.

In the third liquid applying step, the liquid 2' is applied to the first region M411, and the liquid 2' is also applied to the second region M412, and in the third curing step, the cured portion 2 (third cured portion 2C) is formed by curing the liquid 2' applied to the first region M411, and the cured product 6 is formed by curing the liquid 2' applied to the second region M412.

Thereby, it is possible to prevent the particles 11 from unintentionally remaining on the upper surface of the cured portion 2 (third cured portion 2C) at the time when the layer forming step (first layer forming step) ends, for not only the cured portion 2 formed on the upper surface of the layer 1 but also the cured portion 2 (third cured portion 2C) formed on the surface of the stage M41 (first region M411). As a result, it is possible to more effectively prevent an occurrence of the problem described above, and it is possible to make the dimensional accuracy and the mechanical strength of the finally obtained three-dimensional structure particularly excellent.

Hereinafter, each step will be described.
Third Liquid Applying Step
In the third liquid applying step, the liquid 2' used in formation of the cured portion 2 (third cured portion 2C) on the first region M411 of the stage M41 on which the layer 1 is not formed is applied by an ink jet method (refer to Fig. 1A).

In the step, the liquid 2' is applied to a portion corresponding to a part of the finally obtained three-dimensional structure 10. In the configuration in the figures, the liquid 2' is applied to a portion corresponding to a region near the outer surface where the finally obtained three-dimensional structure 10 can be visually recognized when viewed from the side.

Thereby, for example, since, in the finally obtained three-dimensional structure 10, the cured portion 2 configuring an outer surface when viewed from the side can be unified with a portion configured of a material not containing the particles 11, it is possible to make an aesthetic appearance of the overall three-dimensional structure 10 particularly excellent.

In particular, in the step, the liquid 2' is applied by an ink jet method, and thus, it is possible to reproducibly apply the liquid 2' even in a case where the applying pattern of the liquid 2' has a fine shape. As a result, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly high.
In addition, in the step, the liquid 2' is also applied to the second region M412 of the stage M41.

The liquid 2' includes at least a polymerizable compound (uncured curable resin material) (same is also applied with respect to the liquid 2' applied in the first liquid applying step described below and the liquid 2' applied in the second liquid applying step).
The liquid 2' will be described below in detail.

Third Curing Step
The liquid 2' applied to the first region M411 of the stage M41 becomes the cure portion 2 (third cured portion 2C) by being subjected to a subsequent predetermined curing treatment (refer to Fig. 1B).

For example, in a case where the liquid 2' includes a thermosetting polymerizable compound (thermosetting resin), it is possible to cure by heating, and in a case where the liquid 2' includes a photocurable polymerizable compound (photocurable resin), it is possible to cure by light irradiation.

In the step, the liquid 2' applied to the second region M412 of the stage M41 is also subjected to the curing treatment as described above, and as a result, the cured product 6 is formed.

In addition, in order to form the cured portion 2 having a predetermined thickness, a series of steps including application of the liquid 2' (liquid applying step) and curing of the liquid 2' (curing step) may be repeatedly performed before performing the step described below.
Layer Forming Step

In the layer forming step, the layer 1 having a predetermined thickness is formed using the composition (layer forming composition) 1' including the particles 11 and the solvent 12 (refer to Fig. 1C, Fig. 1D, Fig. 1J, Fig. 1K, Fig. 1Q, and Fig. 1R).

In particular, in the first layer forming step, the layer 1 having a predetermined thickness is formed on the stage (support) M41 provided with the cured portion 2 (third cured portion 2C) using the composition (layer forming composition) 1' including the particles 11 and the solvent 12 (Fig. 1C and Fig. 1D), and in the second and subsequent layer formation steps, the new layer 1 having a predetermined thickness is formed on the layer 1 (in the configuration in the figures, the layer 1 in which a bound portion 3 is formed) using the composition (layer forming composition) 1' including the particles 11 and the solvent 12 (Fig. 1J, Fig. 1K, Fig. 1Q, and Fig. 1R).
The composition (layer forming composition) 1' will be described below in detail.

In addition, in the step, at least a part of the cured portion 2 formed previously is buried in the layer 1 newly formed in the step.

That is, in the layer forming step which is performed in a state in which the cured portion 2 (third cured portion 2C) formed in the third liquid applying step described above is exposed on the outer surface, at least a part of the cured portion 2 (third cured portion 2C) is buried (refer to Fig. 1D), and in the layer forming step which is performed in a state in which the cured portion 2 (first cured portion 2A) formed in the first liquid applying step described below is exposed on the outer surface, at least a part of the cured portion 2 (first cured portion 2A) is buried (refer to Fig. 1K and Fig. 1R).

Thereby, for example, stability of the shape of the cured portion 2 to be formed in a subsequent step on the upper surface side of the cured portion 2 (cured portion 2 buried in the layer 1 in the step) is improved. As a result, the dimensional accuracy of the three-dimensional structure 10 becomes particularly excellent.

For example, in a case where the second cured portion 2B is formed in a subsequent step on the portion in contact with the cured portion 2 of the layer 1 in which the cured portion 2 (cured portion 2 which is buried in the layer 1 in the step) is buried (refer to Fig. 1H, Fig. 1I, Fig. 1O, and Fig. 1P), it is possible to more effectively prevent an occurrence of an unintended difference of elevation between the cured portion 2 buried in the layer 1 in the step and the second cured portion 2B. As a result, the dimensional accuracy of the three-dimensional structure 10 becomes particularly excellent.

In the step, the layer 1 of which the surface is flattened is formed using a squeegee as the flattening device M42.

In the embodiment, when the layer 1 is formed at the first region M411 using the flattening device M42, the thickness of the layer 1 to be newly formed after formation of the cured product 6 is determined based on the height of the upper surface of the cured product 6. That is, the flattening device M42 is brought into contact with the upper surface of the cured product 6, and, based on the height (contact surface) at which the flattening device M42 is in contact with the cured product 6, the layer 1 having a predetermined thickness is formed.

In the step, a flattening device (for example, a roller or the like) other than a squeegee may be used.

In the step, the composition 1' (in particular, particles 11) should not remain on the upper surface of the cured portion 2 buried in the step.

Thereby, it is possible to prevent the reduction in the adhesion between the cured portion 2 and the cured portion 2 (first cured portion 2A) formed in the subsequent first liquid applying step, and it is possible to make the mechanical strength of the finally obtained three-dimensional structure 10 excellent. In addition, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 excellent.

In the configuration in the figures, the thickness of the layer 1 formed in the step is the same as the thickness of the buried cured portion 2 (third cured portion 2C, the first cured portion 2A), however, the thickness of the layer 1 formed in the step may be smaller than the thickness of the buried cured portion 2 (third cured portion 2C, the first cured portion 2A). For example, the height adjustment of the flattening device M42 is performed so as to press the cured product 6 with a predetermined pressure force, and as a result, the stress applied to the flattening device M42 at a portion where the cured portion 2 or cured product 6 is not present becomes lower compared to the stress at a portion where the cured portion 2 or cured product 6 is present, and it is possible to make the height of the layer 1 formed by the flattening device M42 lower than that of the cured portion 2 buried in the step. Thereby, it is possible to make the pressure force by the flattening device M42, applied to the upper surface of the cured portion 2 buried in the step, relatively large, and it is possible to more effectively prevent the composition 1' (in particular, particles 11) on the upper surface of the cured portion 2 buried in the step from remaining.

Though the thickness of the layer 1 formed in the step is not particularly limited, for example, the thickness of the layer 1 is preferably 20 micrometers to 500 micrometers, and more preferably 30 micrometers to 150 micrometers.

Thereby, it is possible to more effectively prevent an occurrence of unintended unevenness in the three-dimensional structure 10 to be manufactured, and it is possible to make the dimensional accuracy of the three-dimensional structure 10 particularly excellent, while making productivity of the three-dimensional structure 10 sufficiently excellent.

The viscosity of the layer forming composition 1' in the layer forming step is preferably 500 mPa*s to 1000000 mPa*s.

Thereby, it is possible to more efficiently perform the step, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent. Moreover, in the specification, the viscosity refers to a value measured at 25 degrees centigrade using an E type viscometer (VISCONIC ELD manufactured by Tokyo Keiki Inc.).
First Liquid Applying Step

In the first liquid applying step, the liquid 2' used in formation of the cured portion 2 (first cured portion 2A) is applied to a region including the surface (upper surface) of the layer 1 in a state of including the solvent 12 formed in the layer forming step (refer to Fig. 1E and Fig. 1L).

In this manner, in a case where the liquid 2' is applied, when the layer 1 to which the liquid 2' is applied is in a state of including the solvent 12, in other words, voids of the particles 11 in the layer 1 are in a state of being filled with a solvent, it is possible to suitably prevent unintended penetration of the liquid 2' into the inside of the layer 1, and as a result, in the subsequent first curing step, it is possible to form the cured portion 2 (first cured portion 2A) having a desired shape on the upper surface of the layer 1.

In particular, the embodiment has the first liquid applying step as a step of applying the liquid 2' to a region including a non-overlapping portion with the cured portion 2 (first cured portion 2A and the third cured portion 2C) when the layer 1 is seen in a plan view, of the surface of the layer 1 including the cured portion 2 (first cured portion 2A and the third cured portion 2C) buried (refer to Fig. 1E and Fig. 1L).

In the related art, in a case where a new layer (upper layer) is formed on the surface of the already formed layer (lower layer), and a bound portion (cured portion) is formed on the layer (upper layer), if the bound portion (cured portion) to be formed on the layer (upper layer) has a non-overlapping region with the bound portion (cured portion) formed on the lower layer, it is not possible to form a bound portion (cured portion) having an intended shape, and a problem in that the dimensional accuracy of the finally obtained three-dimensional structure is reduced is likely to occur, however, by applying the liquid 2' to the layer 1 in a state of including the solvent 12, even in a case where the cured portion to be formed on the upper layer has a region not overlapping with the cured portion which is formed on the lower layer, it is possible to more reliably prevent an occurrence of the problem as described above. Therefore, in the case of having the first liquid applying step as a step of applying the liquid to a region including a non-overlapping portion with the cured portion (first cured portion and the third cured portion) when the layer is seen in a plan view, of the surface of the layer including the cured portion (first cured portion and the third cured portion) buried, effects as described above are more significantly exhibited.

In addition, in the step, the liquid 2' is applied by an ink jet method, and thus, it is possible to reproducibly apply the liquid 2' even in a case where the applying pattern of the liquid 2' has a fine shape. As a result, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly high.

In addition, in the step, the liquid 2' is also applied to the second region M412 (in the configuration in the figures, the upper surface of the cured product 6 formed in the third curing step) of the stage M41.
First Curing Step

In the first curing step, a predetermined curing treatment is performed on the liquid 2' (liquid 2' applied to a region including the surface (upper surface) of the layer 1 in a state of including the solvent 12) applied in the first liquid applying step, and as a result, the cured portion 2 (first cured portion 2A) is formed (refer to Fig. 1F and Fig. 1M).

In addition, in the step, a curing treatment as described above is also performed on the liquid 2' (in the configuration in the figures, the liquid 2' applied to the upper surface of the cured product 6 formed in the third curing step) applied to the second region M412 of the stage M41 in the first liquid applying step, and as a result, the cured product 6 is formed.
Solvent Removing Step

In the solvent removing step, the solvent 12 is removed from the layer 1 (refer to Fig. 2A and Fig. 1N).

Thereby, a space 4 in which the solvent 12 is not present is formed between the particles 11 configuring the layer 1. The space 4 functions as an absorbing portion absorbing the liquid 2' in the subsequent second liquid applying step.

The step may be performed under any condition as long as the solvent 12 is removed from the layer 1, and for example, a heat treatment, a pressure reduction treatment, blowing, or the like can be performed in the step.

In the case of performing the step by heating, although the heating temperature varies depending on the constituent material or the like (type or the like of the particles 11, the solvent 12, or the like) of the layer 1, for example, the heating temperature is preferably 30 degrees centigrade to 100 degrees centigrade, and more preferably 60 degrees centigrade to 95 degrees centigrade.

Thereby, it is possible to efficiently remove the solvent 12, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent, while preventing unintended denaturation of the constituent material of the layer 1 or unintended deformation of the layer 1 or the like.

Moreover, even in a case where the liquid 2' is applied in the previous step (first liquid applying step) on the upper surface of the layer 1 in which the solvent 12 is removed in this step, the liquid 2' is subjected to a curing treatment in the curing step (first curing step), and as a result, the cured portion 2 (first curing portion 2A) having high stability of the shape is obtained. Therefore, even in a case where the solvent 12 is removed in the step, an occurrence of unintended deformation is effectively prevented.
Second Liquid Applying Step

In the second liquid applying step, the liquid 2' used in formation of the cured portion 2 (second cured portion 2B) is applied, in the layer 1 in a state in which the solvent 12 is removed and the liquid 2' is penetrated into the layer 1 (refer to Fig. 1H and Fig. 1O).

Thereby, in the subsequent second curing step, it is possible to form the cured portion 2 (second cured portion 2B) in the inside (portion which is the space 4 between the particles 11) of the layer 1.

In addition, in the step, the liquid 2' is applied by an ink jet method, and thus, it is possible to reproducibly apply the liquid 2' even in a case where the applying pattern of the liquid 2' has a fine shape. As a result, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly high.
Second Curing Step

In the second curing step, a predetermined curing treatment is performed on the liquid 2' (liquid 2' which penetrates into the inside (portion which is the space 4 between the particles 11) of the layer 1) applied in the second liquid applying step, and as a result, the cured portion 2 (second cured portion 2B) is formed (refer to Fig. 1I and Fig. 1P).

Thereby, it is possible to form the bound portion 3 in which the particles 11 are bound by the cured portion 2 (second curing portion 2B). Since the bound portion 3 formed in this manner includes the particles 11 and the cured portion 2 (second cured portion 2B), the bound portion 3 has particularly excellent hardness and mechanical strength. Therefore, the finally obtained three-dimensional structure 10 has particularly excellent mechanical strength, unintended deformation thereof is more reliably prevented, and thus, the reliability thereof becomes higher.
Unbound Particle Removing Step

After the series of steps as described above is repeatedly performed (refer to Fig. 1S), as a post-treatment step, the unbound particle removing step (refer to Fig. 1T) of removing particles (unbound particles) which are not bound by the cured portion 2, of the particles 11 configuring each layer 1 is performed. Thereby, the three-dimensional structure 10 is obtained.

Examples of the specific method of the step include a method of removing unbound particles with a brush or the like, 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 (for example, a method of immersing the layered product obtained in the same manner as described above in a liquid, and a method of spraying a liquid), and a method of applying vibration such as ultrasonic vibration. In addition, two or more methods selected from these can be performed in combination. More specifically, a method of immersing into a liquid such as water after blowing a gas such as air, and a method of applying ultrasonic vibration in a state of being immersed into a liquid such as water are exemplified. Among these, a method of applying a liquid including water (in particular, a method of immersing into a liquid including water) is preferably employed with respect to the layered product obtained in the same manner as described above.

According to the manufacturing method according to the invention described above, it is possible to efficiently manufacture a three-dimensional structure which has excellent dimensional accuracy, mechanical strength, and durability. In addition, since the yield of the three-dimensional structure can be improved, the invention is also advantageous from the viewpoint of reducing the manufacturing cost of a three-dimensional structure.
Second Embodiment

Next, a second embodiment of the method for manufacturing a three-dimensional structure according to the invention will be described.

Figs. 2A to 2T are cross-sectional views schematically showing each step in the second embodiment of the method for manufacturing a three-dimensional structure according to the invention.
In the following description, the second embodiment will be described while focusing on the difference from the embodiment described above, and the description of the same contents will not be repeated.

As shown in Figs. 2A to 2T, although the method for manufacturing the three-dimensional structure 10 of the embodiment has the same steps as those in the embodiment described above, the thickness determining method of the layer 1 to be formed in the layer forming step is different from that in the embodiment described above.

That is, in the embodiment, the height (thickness) of the cured product 6 formed using the liquid 2' is measured by a height measuring device M7, and, based on the measurement result, the thickness of the layer 1 to be newly formed after formation of the cured product 6 is determined.

By such a configuration, for example, the flattening device M42 does not need to be brought into contact with the cured product 6, and thus, it is possible to prevent the unintended wear and deformation of the flattening device M42, and an effect in which extension of the life of the flattening device M42 is achieved, or the maintenance of the apparatus for manufacturing the three-dimensional structure 10 becomes easy is obtained. In addition, even in a case where the area of the cured product 6 is relatively small, it is possible to accurately measure the height (thickness) of the cured product 6, and it is possible to properly determine the thickness of the layer 1 to be newly formed. For this reason, it is possible to reduce the amount of the liquid 2', used in formation of the cured product 6, and from the viewpoint of reduction of the production cost of the three-dimensional structure 10 and resource saving, such a configuration is preferable.
Liquid (Cured portion Forming Liquid)

Next, the liquid (cured portion forming liquid) used in manufacturing the three-dimensional structure according to the invention will be described in detail.

The liquid (cured portion forming liquid) 2' includes at least a constituent (including a precursor) of the cured portion 2.
Curable Resin Material (Polymerizable Compound)

The liquid 2' includes a resin material (polymerizable compound) in which a curing reaction can be proceeded.

Thereby, it is possible to make the strength or the like of the cured portion 2 formed particularly excellent. In addition, in the second curing portion 2B, it is possible to suitably function as a binder to bind the particles 11 to each other, and it is possible to make the mechanical strength and the stability of shape of the three-dimensional structure 10 excellent. In addition, since the heat resistance of the cured portion 2 becomes excellent, it is possible to more effectively prevent unintended deformation in the cured portion 2 which receives a cumulative thermal history due to the stacking, or unintended denaturation or deterioration of the material and it is possible to make the reliability of the three-dimensional structure 10 excellent.

Examples of the curable resin material (polymerizable compound) include a thermosetting resin; various photocurable resins such as a visible light curable resin which is cured by light in the visible light region (photocurable resin in the narrow sense), a ultraviolet ray curable resin, and an infrared ray curable resin; and an X-ray curable resin, and one type or two or more types selected from these can be used singly or in combination.

Among these, from the viewpoint of the mechanical strength of the obtained three-dimensional structure 10, the productivity of the three-dimensional structure 10, and the storage stability of the liquid 2', in particular, an ultraviolet ray curable resin (polymerizable compound) is preferable.

As the ultraviolet ray curable resin (polymerizable compound), a resin in which an addition polymerization or a ring-opening polymerization is initiated by radical species or cationic species generated from a photopolymerization initiator by irradiation of ultraviolet rays, and a polymer is generated is preferably used. As the polymerization mode of addition polymerization, a radical, a cationic, an anionic, a metathesis, and a coordination polymerization can be exemplified. In addition, as the polymerization mode of ring-opening polymerization, a cationic, an anionic, a radical, a metathesis, and a coordination polymerization can be exemplified.

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 terminal ethylenically unsaturated bond, and preferably two or more terminal ethylenically unsaturated bonds can be preferably used.

The ethylenically unsaturated polymerizable compound has a monofunctional polymerizable compound, a polyfunctional polymerizable compound, or a chemical form of mixture of these.
Examples of the monofunctional polymerizable compound include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters thereof, and amides. As the polyfunctional polymerizable compound, esters of an unsaturated carboxylic acid and an aliphatic polyol compound, or an amides of an unsaturated carboxylic acid and an aliphatic polyamine compound are used.

In particular, the liquid 2' preferably includes an acryl-based polymerizable compound such as acrylic acid, methacrylic acid, or a derivative thereof (for example, an ester compound) as the polymerizable compound.

Thereby, it is possible to make the strength of the finally obtained three-dimensional structure 10 particularly excellent.

In addition, a product of an addition reaction between unsaturated carboxylic acid esters or amides, which have a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, and isocyanates or epoxies, a product of a dehydration condensation reaction between the above unsaturated carboxylic acid esters or amides and carboxylic acids, and the like also can be used. Moreover, a product of an addition reaction between unsaturated carboxylic acid esters or amides, which have an electrophilic substituent such as an isocyanate group or an epoxy group, and alcohols, amines, or thiols, and a product of a substitution reaction between unsaturated carboxylic acid esters or amides, which have a leaving substituent such as a halogen group or a tosyloxy group, and alcohols, amines, or thiols also can be used.

As specific examples of the radical polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, (meth)acrylic acid ester is representatively exemplified, and any of a monofunctional compound and polyfunctional compound can be used.

Specific examples of a monofunctinoal (meth)acrylate include tolyloxyethyl (meth)acrylate, phenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, isobornyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

Specific examples of a bifunctional (meth)acrylate include 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, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate.

Specific examples of a trifunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionic acid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri(meth)acrylate, and sorbitol tri(meth)acrylate.

Specific examples of a tetrafunctional (meth)acrylate include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic acid dipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

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

Specific examples of a hexafunctional (meth)acrylate include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

Examples of polymerizable compounds other than (meth)acrylates include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, and maleic acid ester.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetraitaconate.

Examples of the crotonic acid ester 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 the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

In addition, specific examples of the amide monomer of an unsaturated carboxylic acid and an aliphatic amine compound include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene-bis-acrylamide, 1,6-hexamethylene-bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bis-acrylamide, and xylylene bis-methacrylamide.

In addition, a urethane-based addition polymerizable compound manufactured by an addition reaction between isocyanate and a hydroxyl group is also suitable, and as such a specific example thereof, a vinyl urethane compound containing two or more polymerizable vinyl groups in a 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 in a molecule can be exemplified.

CH₂=C(R1)COOCH₂CH(R2)OH (1)
(Here, in Formula (1), each of R1 and R2 independently represents H or CH₃.)

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

As the cationic polymerizable compound, curable compounds including a ring-opening polymerizable group can be exemplified, and among these, a heterocyclic group-containing curable compound is particularly preferable. Examples of such curable compounds include cyclic imino ethers such as epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, and oxazoline derivatives, and vinyl ethers, and among these, epoxy derivatives, oxetane derivatives, and vinyl ethers are preferable.

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

Examples of the specific compounds of glycidyl ethers include diglycidyl ethers (for example, ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether), tri- or higher functional glycidyl ethers (for example, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether, and triglycidyl trishydroxyethyl isocyanurate), tetra- or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of a cresol novolac resin, and polyglycidyl ether of a phenolic novolac resin), alicyclic epoxies (for example, polycyclohexyl epoxymethyl ether of a phenolic novolac resin), and oxetanes.

As the polymerizable compound, alicyclic epoxy derivatives can be preferably used. An "alicyclic epoxy group" refers to a substructure obtained by epoxidizing the double bond in the cycloalkene ring of a cyclopentene group, a cyclohexene group, or the like with a suitable oxidant such as hydrogen peroxide, peroxy acid, or the like.

As the alicyclic epoxy compound, polyfunctional alicyclic epoxy compounds having two or more cyclohexene oxide groups or cyclopentene oxide groups in a molecule is preferable. Specific examples of the alicyclic epoxy compound include 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, di(3,4-epoxycyclohexyl)adipate, di(3,4-epoxycyclohexylmethyl)adipate, bis(2,3-epoxycyclopentyl)ether, di(2,3-epoxy-6-methylcyclohexylmethyl)adipate, and dicyclopentadiene dioxide.

A glycidyl compound having an ordinary epoxy group which does not have an alicyclic structure in the molecule may be used alone or in combination with the above alicyclic epoxy compounds.

As such an ordinary glycidyl compound, a glycidyl ether compound and a glycidyl ester compound can be exemplified, and the glycidyl ether compound is preferably used in combination.

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

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

In addition, the liquid 2' may include a silicone-based polymerizable compound (silicone-based resin obtained by polymerization) as the polymerizable compound.

Thereby, for example, it is possible to suitably manufacture the three-dimensional structure 10 which is configured of a rubber-like material having elasticity. As a result, it is possible to suitably manufacture a three-dimensional structure having a movable portion and a deforming portion by elastic deformation.

The content of the curable resin material in the liquid 2' is preferably equal to or greater than 80% by mass, and more preferably equal to or greater than 85% by mass. Thereby, it is possible to make the mechanical strength or the like of the finally obtained three-dimensional structure 10 particularly excellent.

Other Components
In addition, the liquid 2' may include components other than the components described above. Examples of such components include various colorants such as a pigment and a dye; a dispersant; a surfactant; a polymerization initiator; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; an ultraviolet absorbent; a chelating agent; a pH adjusting agent; a thickener; a filler; an aggregation preventing agent; and a defoamer.

In particular, in a case where the liquid 2' includes a colorant, it is possible to obtain the three-dimensional structure 10 which is colored in the color corresponding to the color of the colorant.

In particular, by including a pigment as a colorant, it is possible to make the light resistance of the liquid 2' and the three-dimensional structure 10 favorable. Both an inorganic pigment and an organic pigment can be used as the pigment.

Examples of the inorganic pigment include carbon blacks (C. I. Pigment Black 7) such as a furnace black, a lamp black, an acetylene black, and a channel black, iron oxide, and titanium oxide, and one type or two or more types selected from these can be used singly or in combination.
Among the inorganic pigments, titanium oxide is preferable in order to exhibit a preferred white color.

Examples of the organic pigments include azo pigments such as an insoluble azo pigment, a condensed azo pigment, an azo lake, and a chelate azo pigment, polycyclic pigments such as a phthalocyanine pigment, a perylene and a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxane pigment, a thioindigo pigment, an isoindolinone pigment, and a quinophthalone pigment, a dye chelate (for example, a basic dye type chelate, an acidic dye type chelate, and the like), a dyeing lake (a basic dye type lake and an acidic dye type lake), a nitro pigment, a nitroso pigment, an aniline black, and a daylight fluorescent pigment, and one type or two or more types selected from these can be used singly or in combination.

In a case where the liquid 2' includes a pigment, the average particle diameter of the pigment is preferably equal to or less than 300 nm, and more preferably 50 nm to 250 nm. Thereby, it is possible to be make the discharge stability of the liquid 2' and the dispersion stability of the pigment in the liquid 2' particularly excellent, and it is possible to form an image having more excellent image quality.

Moreover, in the specification, the average particle diameter refers to an average particle diameter based on volume, and for example, after a sample is added to methanol, the mixture is dispersed for 3 minutes with an ultrasonic wave disperser, and the average particle size of the obtained dispersion is measured using an aperture of 50 micrometers by a Coulter counter method particle size distribution measuring instrument (TA-II type manufactured by COULTER ELECTRONICS INS.).

In addition, examples of the dyes include an acidic dye, a direct dye, a reactive dye, and a basic dye, and one type or two or more types selected from these can be used singly or in combination.

In a case where the liquid 2' includes a colorant, the content of the colorant in the liquid 2' is preferably 1% by mass to 20% by mass. Thereby, particularly excellent concealing properties and color reproducibility are obtained.

In particular, in a case where the liquid 2' includes titanium oxide as a colorant, the content of the titanium oxide in the liquid 2' is preferably 12% by mass to 18% by mass, and more preferably 14% by mass to 16% by mass. Thereby, particularly excellent concealing properties are obtained.

In a case where the liquid 2' includes a pigment, if the liquid 2' further includes a dispersant, it is possible to make the dispersibility of the pigment more favorable. Examples of the dispersant, which are not particularly limited, include dispersants which are commonly used in the preparation of pigment dispersions such as a polymer dispersant. Specific examples of the polymer dispersant include dispersants containing one or more types among polyoxyalkylene polyalkylene polyamine, a vinyl-based polymer and copolymer, an acryl-based polymer and copolymer, polyester, polyamide, polyimide, polyurethane, an amino-based polymer, a silicon-containing polymer, a sulfur-containing polymer, a fluorine-containing polymer, and an epoxy resin, as a main component.

If the liquid 2' includes a surfactant, it is possible to make the abrasion resistance of the three-dimensional structure 10 more favorable. The surfactant is not particularly limited, and for example, silicone-based surfactants such as polyester-modified silicone or polyether-modified silicone can be used, and among these, polyether-modified polydimethyl siloxane or polyester-modified polydimethyl siloxane is preferably used.

In addition, the liquid 2' may include a solvent. Thereby, it is possible to suitably adjust the viscosity of the liquid 2', and even in a case where the liquid 2' includes a component having a high viscosity, it is possible to make the discharge stability of the liquid 2' by an ink jet method excellent.

Examples of the solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; acetic acid esters such as ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and iso-butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl-n-butyl ketone, diisopropyl ketone, and acetyl acetone; and alcohols such as ethanol, propanol, and butanol, and one type or two or more types selected from these can be used singly or in combination.

In addition, the viscosity of the liquid 2' is preferably 2 mPa^.s to 30 mPa^.s, and more preferably 5 mPa^.s to 20 mPa^.s.
Thereby, it is possible to make the discharge stability of the liquid 2' by an ink jet method particularly excellent.

In addition, in manufacturing the three-dimensional structure 10, plural types of the liquid 2' may be used.
For example, the liquid 2' used in the first liquid applying step (liquid 2' used in formation of the first cured portion 2A), the liquid 2' used in the second liquid applying step (liquid 2' used in formation of the second cured portion 2B), and the liquid 2' used in the third liquid applying step (liquid 2' used in formation of the third cured portion 2C) may be the same as or different from each other.

In addition, the liquid 2' (color ink) including a colorant and the liquid 2' (clear ink) not including a colorant may be used. Thereby, for example, regarding an appearance of the three-dimensional structure 10, the liquid 2' including a colorant as the liquid 2' applied to a region that affects the color may be used, and regarding an appearance of the three-dimensional structure 10, the liquid 2' not including a colorant as the liquid 2' applied to a region that does not affect the color may be used. In addition, in the finally obtained three-dimensional structure 10, plural types of the liquid 2' may be used in combination such that a region (coating layer) formed using the liquid 2' not including a colorant is provided to the outer surface of a region formed using the liquid 2' including a colorant.

In addition, for example, plural types of the liquid 2' including colorants having different constitutions may be used. Thereby, by combination of these liquids 2', it is possible to widen a color reproduction region that can be expressed.

In a case of using plural types of the liquid 2', it is preferable to use at least the liquid 2' having a cyan color, the liquid 2' having a magenta color, and the liquid 2' having a yellow color. Thereby, by combination of these liquids 2', it is possible to further widen a color reproduction region that can be expressed.

In addition, using the liquid 2' having a white color and other liquid 2' having a color in combination, for example, the following effect is obtained. That is, it is possible to make the finally obtained three-dimensional structure 10 have a first region where the liquid 2' having a white color is applied and a region (second region) where the liquid 2' having a color other than a white color is applied, and which is overlapped with the first region and provided on the outer surface than the first region. Thereby, the first region where the liquid 2' having a white color is applied can exhibit a concealing properties, and it is possible to further increase color saturation of the three-dimensional structure 10.

Layer Forming Composition
Next, the layer forming composition used in manufacturing the three-dimensional structure according to the invention will be described in detail.

The composition (layer forming composition) 1' includes the particles 11 as a filler, and the solvent 12 as a dispersion medium dispersing the particles 11.

By using the layer forming composition 1', it is possible to make the mechanical strength or the like of the finally obtained three-dimensional structure 10 particularly excellent, it is possible to make the fluidity of the composition 1' excellent and to also effectively prevent aggregation or the like of the particles 11, and it is possible to make ease of handling (handleability) of the composition 1' during manufacture particularly excellent. In addition, as described above, it is possible to easily and reliably form separately the first cured portion 2A and the second curing portion 2B which have different positional relationships with the layer 1 formed using the composition 1' from each other, and it is possible to make the mechanical strength or the like of the manufactured three-dimensional structure 10 excellent and the dimensional accuracy thereof excellent.

Particles
The layer forming composition 1' includes a plurality of particles 11.
The particle 11 has preferably a high hardness.

Thereby, it is possible to make the mechanical strength or the like of the finally obtained three-dimensional structure 10 particularly excellent.

The hardness of the particles 11 can be determined, for example, by particle compression strength evaluation using MCT-210 (manufactured by Shimadzu Corporation).

The particles 11 are preferably porous particles having pores which open to the outside and subjected to a hydrophobization treatment.

By such a configuration, it is possible to make the curable resin material configuring the liquid 2' or the reaction product (hereinafter, also collectively simply referred to as "resin material") suitably penetrate into the pores when the three-dimensional structure 10 is manufactured (in the second liquid applying step), and an anchoring effect is exhibited. As a result, it is possible to make the bonding force of the particles 11 particularly excellent, and as a result, it is possible to make the mechanical strength of the overall three-dimensional structure 10 particularly excellent. In addition, when the resin material configuring the liquid 2' enters into the space of the particles 11, it is possible to effectively prevent unintended wet-spreading of the liquid 2'. As a result, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 higher.

Examples of the constituent material of the particles 11 include an inorganic material, an organic material, and a complex of these.

Examples of the inorganic material configuring the particles 11 include various metals and metal compounds. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zirconium oxide, tin oxide, magnesium oxide, and potassium titanate; various metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; 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 metal carbonates such as calcium carbonate and magnesium carbonate; various metal sulfates such as calcium sulfate and magnesium sulfate; various metal silicates such as calcium silicate and magnesium silicate; various metal phosphates such as calcium phosphate; and various metal borates such as aluminum borate and magnesium borate, or composite compounds of these.

As the organic material configuring the particles 11, synthetic resins and natural polymers can be exemplified, and more specific examples thereof include a polyethylene resin; polypropylene; polyethylene oxide; polypropylene oxide, polyethylene imine; polystyrene; polyurethane; polyurea; polyester; a silicone resin; an acrylic silicone resin; polymers having (meth)acrylic acid ester as a constituent monomer such as polymethyl methacrylate; cross polymers having (meth)acrylic acid ester as a constituent monomer such as methyl methacrylate cross polymer (ethylene acrylic acid copolymer resin or the like); polyamide resins such as Nylon 12, Nylon 6, and copolymer nylon; polyimide; carboxymethyl cellulose; gelatin; starch; chitin; and chitosan.

Among these, the particles 11 are preferably configured of a metal oxide, and more preferably configured of silica.

Thereby, it is possible to make characteristics such as mechanical strength and light resistance of the three-dimensional structure particularly excellent.

In addition, in particular, in a case where the particles 11 are configured of silica, the effect as described above is more significantly exhibited. In addition, since silica has also excellent fluidity, silica is useful for forming a layer having higher thickness uniformity, and silica is also advantageous from the viewpoint of making the productivity and dimensional accuracy of the three-dimensional structure particularly excellent.

The particles 11 may be subjected to a surface treatment such as a hydrophobization treatment.
As the hydrophobization treatment performed to the particles 11, any treatment may be used as long as it increases hydrophobicity of the particles (base particles), and it is preferable to introduce a hydrocarbon group.

Thereby, it is possible to further increase hydrophobicity of the particles 11. In addition, it is possible to easily and reliably further increase uniformity of the degree of the hydrophobization treatment at each portion (including the surface of the inside of a pore in the case of having a pore which opens to the outside) of each particle 11 or the surface of the particle 11.

As a compound used in the hydrophobization treatment, a silane compound including a silyl group is preferable. Specific examples of the compound which can be used in the hydrophobization treatment include hexamethyldisilazane, dimethyl dimethoxysilane, diethyl diethoxysilane, 1-propenylmethyl dichlorosilane, propyldimethyl chlorosilane, propylmethyl dichlorosilane, propyl trichlorosilane, propyl triethoxysilane, propyl trimethoxysilane, styrylethyl trimethoxysilane, tetradecyl trichlorosilane, 3-thiocyanatopropyl triethoxysilane, p-tolyldimethyl chlorosilane, p-tolylmethyl dichlorosilane, p-tolyl trichlorosilane, p-tolyl trimethoxysilane, p-tolyl triethoxysilane, di-n-propyl di-n-propoxysilane, diisopropyl diisopropoxysilane, di-n-butyl di-n-butyroxysilane, di-sec-butyl di-sec-butyroxysilane, di-t-butyl di-t-butyroxysilane, octadecyl trichlorosilane, octadecylmethyl diethoxysilane, octadecyl triethoxysilane, octadecyl trimethoxysilane, octadecyldimethyl chlorosilane, octadecylmethyl dichlorosilane, octadecyl methoxydichlorosilane, 7-octenyldimethyl chlorosilane, 7-octenyl trichlorosilane, 7-octenyl trimethoxysilane, octylmethyl dichlorosilane, octyldimethyl chlorosilane, octyl trichlorosilane, 10-undecenyldimethyl chlorosilane, undecyl trichlorosilane, vinyldimethyl chlorosilane, methyloctadecyl dimethoxysilane, methyldodecyl diethoxysilane, methyloctadecyl dimethoxysilane, methyloctadecyl diethoxysilane, n-octylmethyl dimethoxysilane, n-octylmethyl diethoxysilane, triacontyldimethyl chlorosilane, triacontyl trichlorosilane, methyl trimethoxysilane, methyl triethoxysilane, methyl tri-n-propoxysilane, methyl isopropoxysilane, methyl-n-butyroxysilane, methyl tri-sec-butyroxysilane, methyl tri-t-butyroxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, ethyl tri-n-propoxysilane, ethyl isopropoxysilane, ethyl-n-butyroxysilane, ethyl tri-sec-butyroxysilane, ethyl tri-t-butyroxysilane, n-propyl trimethoxysilane, isobutyl trimethoxysilane, n-hexyl trimethoxysilane, hexadecyl trimethoxysilane, n-octyl trimethoxysilane, n-dodecyl trimethoxysilane, n-octadecyl trimethoxysilane, n-propyl triethoxysilane, isobutyl triethoxysilane, n-hexyl triethoxysilane, hexadecyl triethoxysilane, n-octyl triethoxysilane, n-dodecyl trimethoxysilane, n-octadecyl triethoxysilane, 2-[2-(trichlorosilyl)ethyl]pyridine, 4-[2-(trichlorosilyl)ethyl]pyridine, diphenyl dimethoxysilane, diphenyl diethoxysilane, 1,3-(trichlorosilylmethyl)heptacosane, dibenzyl dimethoxysilane, dibenzyl diethoxysilane, phenyl trimethoxysilane, phenylmethyl dimethoxysilane, phenyldimethyl methoxysilane, phenyl dimethoxysilane, phenyl diethoxysilane, phenylmethyl diethoxysilane, phenyldimethyl ethoxysilane, benzyl triethoxysilane, benzyl trimethoxysilane, benzylmethyl dimethoxysilane, benzyldimethyl methoxysilane, benzyl dimethoxysilane, benzyl diethoxysilane, benzylmethyl diethoxysilane, benzyldimethyl ethoxysilane, benzyl triethoxysilane, dibenzyl dimethoxysilane, dibenzyl diethoxysilane, 3-acetoxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, 4-aminobutyl triethoxysilane, (aminoethylaminomethyl)phenethyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 6-(aminohexylaminopropyl) trimethoxysilane, p-aminophenyl trimethoxysilane, p-aminophenyl ethoxysilane, m-aminophenyl trimethoxysilane, m-aminophenyl ethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, omega-aminoundecyl trimethoxysilane, amyl triethoxysilane, benzoxasilepine dimethylester, 5-(bicycloheptenyl) triethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane, 8-bromooctyl trimethoxysilane, bromophenyl trimethoxysilane, 3-bromopropyl trimethoxysilane, n-butyl trimethoxysilane, 2-chloromethyl triethoxysilane, chloromethylmethyl diethoxysilane, chloromethylmethyl diisopropoxysilane, p-(chloromethyl)phenyl trimethoxysilane, chloromethyl triethoxysilane, chlorophenyl triethoxysilane, 3-chloropropylmethyl dimethoxysilane, 3-chloropropyl triethoxysilane, 3-chloropropyl trimethoxysilane, 2-(4-chlorosulfonylphenyl)ethyl trimethoxysilane, 2-cyanoethyl triethoxysilane, 2-cyanoethyl trimethoxysilane, cyanomethylphenethyl triethoxysilane, 3-cyanopropyl triethoxysilane, 2-(3-cyclohexenyl)ethyl trimethoxysilane, 2-(3-cyclohexenyl)ethyl triethoxysilane, 3-cyclohexenyl trichlorosilane, 2-(3-cyclohexenyl)ethyl trichlorosilane, 2-(3-cyclohexenyl)ethyldimethyl chlorosilane, 2-(3-cyclohexenyl)ethylmethyl dichlorosilane, cyclohexyldimethyl chlorosilane, cyclohexylethyl dimethoxysilane, cyclohexylmethyl dichlorosilane, cyclohexylmethyl dimethoxysilane, (cyclohexylmethyl)trichlorosilane, cyclohexyl trichlorosilane, cyclohexyl trimethoxysilane, cyclooctyl trichlorosilane, (4-cyclooctenyl)trichlorosilane, cyclopentyl trichlorosilane, cyclopentyl trimethoxysilane, 1,1-diethoxy-1-silacyclopenta-3-en, 3-(2,4-dinitrophenylamino)propyl triethoxysilane, (dimethylchlorosilyl)methyl-7,7-dimethylnorpinane, (cyclohexylaminomethyl)methyl diethoxysilane, (3-cyclopentadienylpropyl)triethoxysilane, N,N-diethyl-3-aminopropyl)trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, (furfuryloxymethyl)triethoxysilane, 2-hydroxy-4-(3-triethoxypropoxy)diphenyl ketone, 3-(p-methoxyphenyl)propylmethyl dichlorosilane, 3-(p-methoxyphenyl)propyl trichlorosilane, p-(methylphenethyl)methyl dichlorosilane, p-(methylphenethyl)trichlorosilane, p-(methylphenethyl)dimethyl chlorosilane, 3-morpholinopropyl trimethoxysilane, (3-glycidoxypropyl)methyl diethoxysilane, 3-glycidoxypropyl trimethoxysilane, 1,2,3,4,7,7,-hexachloro-6-methyl diethoxysilyl-2-norbornene, 1,2,3,4,7,7,-hexachloro-6-triethoxysilyl-2-norbornene, 3-iodopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, (mercaptomethyl)methyl diethoxysilane, 3-mercaptopropylmethyl dimethoxysilane, 3-mercaptopropyl dimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxypropyl trimethoxysilane, methyl {2-(3-trimethoxysilylpropylamino)ethylamino}-3-propionate, 7-octenyl trimethoxysilane, R-N-alpha-phenethyl-N'-triethoxysilylpropyl urea, S-N-alpha-phenethyl-N'-triethoxysilylpropyl urea, phenethyl trimethoxysilane, phenethylmethyl dimethoxysilane, phenethyldimethyl methoxysilane, phenethyl dimethoxysilane, phenethyl diethoxysilane, phenethylmethyl diethoxysilane, phenethyldimethyl ethoxysilane, phenethyl triethoxysilane, (3-phenylpropyl)dimethyl chlorosilane, (3-phenylpropyl)methyl dichlorosilane, N-phenylaminopropyl trimethoxysilane, N-(triethoxysilylpropyl)dansylamide, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, 2-(triethoxysilylethyl)-5-(chloroacetoxy)bicycloheptane, (S)-N-triethoxysilylpropyl-O-menthocarbamate, 3-(triethoxysilylpropyl)-p-nitrobenzamide, 3-(triethoxysilyl)propyl succinic anhydride, N-[5-(trimethoxysilyl)-2-aza-1-oxo-pentyl]caprolactam, 2-(trimethoxysilylethyl)pyridine, N-(trimethoxysilylethyl)benzyl-N,N,N-trimethyl ammonium chloride, phenylvinyl diethoxysilane, 3-thiocyanatopropyl triethoxysilane, (tridecafluoro-1,1,2,2,-tetrahydrooctyl)triethoxysilane, N-{3-(triethoxysilyl)propyl}phthalamic acid, (3,3,3-trifluoropropyl)methyl dimethoxysilane, (3,3,3-trifluoropropyl)trimethoxydisilane, 1-trimethoxysilyl-2-(chloromethyl)phenyl ethane, 2-(trimethoxysilyl)ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylene triamine, N-(3-trimethoxysilylpropyl)pyrrole, N-trimethoxysilylpropyl-N,N,N-tributyl ammonium bromide, N-trimethoxysilylpropyl-N,N,N-tributyl ammonium chloride, N-trimethoxysilylpropyl-N,N,N-trimethyl ammonium chloride, vinylmethyldiethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinylmethyl dimethoxysilane, vinyldimethyl methoxysilane, vinyldimethyl ethoxysilane, vinylmethyl dichlorosilane, vinylphenyl dichlorosilane, vinylphenyl diethoxysilane, vinylphenyl dimethyl silane, vinylphenylmethyl chlorosilane, vinyl triphenoxysilane, vinyl tris-t-butoxysilane, adamantylethyl trichlorosilane, allylphenyl trichlorosilane, (aminoethylaminomethyl)phenethyl trimethoxysilane, 3-aminophenoxydimethylvinyl silane, phenyl trichlorosilane, phenyldimethyl chlorosilane, phenylmethyl dichlorosilane, benzyl trichlorosilane, benzyldimethyl chlorosilane, benzylmethyl dichlorosilane, phenethyldiisopropyl chlorosilane, phenethyl trichlorosilane, phenethyldimethyl chlorosilane, phenethylmethyl dichlorosilane, 5-(bicycloheptenyl)trichlorosilane, 5-(bicycloheptenyl)triethoxysilane, 2-(bicycloheptyl)dimethyl chlorosilane, 2-(bicycloheptyl)trichlorosilane, 1,4- bis(trimethoxysilylethyl)benzene, bromophenyl trichlorosilane, 3-phenoxypropyldimethyl chlorosilane, 3-phenoxypropyl trichlorosilane, t-butylphenyl chlorosilane, t-butylphenyl methoxysilane, t-butylphenyl dichlorosilane, p-(t-butyl)phenethyldimethyl chlorosilane, p-(t-butyl)phenethyl trichlorosilane, 1,3-(chlorodimethylsilylmethyl)heptacosane, ((chloromethyl)phenylethyl)dimethyl chlorosilane, ((chloromethyl)phenylethyl)methyl dichlorosilane, ((chloromethyl)phenylethyl)trichlorosilane, ((chloromethyl)phenylethyl)trimethoxysilane, chlorophenyl trichlorosilane, 2-cyanoethyl trichlorosilane, 2-cyanoethylmethyl dichlorosilane, 3-cyanopropylmethyl diethoxysilane, 3-cyanopropylmethyl dichlorosilane, 3-cyanopropylmethyl dichlorosilane, 3-cyanopropyldimethyl ethoxysilane, 3-cyanopropylmethyl dichlorosilane, 3-cyanopropyl trichlorosilane, and fluorinated alkyl silanes, and one type or two or more types selected from these can be used singly or in combination.

Among these, hexamethyl disilazane is preferably used in the hydrophobization treatment. Thereby, it is possible to further increase hydrophobicity of the particles 11. In addition, it is possible to easily and reliably further increase uniformity of the degree of the hydrophobization treatment at each portion (including the surface of the inside of a pore in the case of having pores which open to the outside) of each particle 11 or the surface of the particle 11.

In a case where the hydrophobization treatment using a silane compound is performed in a liquid phase, by immersing the particles (base particles) to be subjected to the hydrophobization treatment in the liquid including the silane compound, it is possible to make a suitable desired reaction proceed, and it is possible to form a chemical adsorption film of the silane compound.

In addition, in a case where the hydrophobization treatment using a silane compound is performed in a gas phase, by exposing the particles (base particles) to be subjected to the hydrophobization treatment to the vapor of the silane compound, it is possible to make a suitable desired reaction proceed, and it is possible to form a chemical adsorption film of the silane compound.

Though the average particle diameter of the particles 11 is not particularly limited, the average particle diameter of the particles 11 is preferably 1 micrometer to 25 micrometers, and more preferably 1 micrometer to 15 micrometers.

Thereby, it is possible to make the mechanical strength of the three-dimensional structure 10 particularly excellent, it is possible to more effectively prevent an occurrence of unintended unevenness in the three-dimensional structure 10 to be manufactured, and it is possible to make the dimensional accuracy of the three-dimensional structure 10 particularly excellent. In addition, it is possible to make the fluidity of the layer forming composition 1' particularly excellent, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent.

D_max of the particles 11 is preferably 3 micrometers to 40 micrometers, and more preferably 5 micrometers to 30 micrometers.

The porosity of the particles 11 is preferably equal to or greater than 50%, and more preferably 55% to 90%.

Thereby, the particles can have sufficient space (pores) into which the resin material (binder) enters, and it is possible to make the mechanical strength of the particles 11 excellent, and as a result, it is possible to make the mechanical strength of the three-dimensional structure 10 having the bound portion 3 obtained by penetration of the resin material into pores particularly excellent.

Moreover, in the present, the porosity of the particles 11 refers to a proportion (volume ratio) of pores which are present in the inside of the particles 11, with respect to the apparent volume of the particles 11, and when the density of the particles 11 is defined as rho [g/cm³] and the true density of the constituent material of the particles 11 is defined as rho0 [g/cm³], the porosity of the particles 11 is a value represented by {(rho0 - rho)/rho0} x 100.

The average pore diameter (fine pore diameter) of the particles 11 is preferably equal to or greater than 10 nm, and more preferably 50 nm to 300 nm.

Thereby, it is possible to make the mechanical strength of the finally obtained three-dimensional structure 10 particularly excellent. In addition, in the case of using the liquid 2' (color ink) including a pigment in manufacturing the three-dimensional structure 10, it is possible to suitably hold the pigment in pores of the particles 11. Therefore, it is possible to prevent unwanted diffusion of the pigment, and it is possible to more reliably form a high-definition image.

Although the particles 11 may have any shape, the particles 11 preferably have a spherical shape. Thereby, it is possible to make the fluidity of the layer forming composition 1' particularly excellent and make the productivity of the three-dimensional structure 10 particularly excellent, and it is possible to more effectively prevent an occurrence of unintended unevenness in the three-dimensional structure 10 to be manufactured and make the dimensional accuracy of the three-dimensional structure 10 particularly excellent.

The layer forming composition 1' may include plural types of particles 11. The content of the particles 11 in the layer forming composition 1' is preferably 8% by mass to 91% by mass, and more preferably 10% by mass to 53% by mass.

Thereby, it is possible to make the mechanical strength of the finally obtained three-dimensional structure 10 excellent, while making the fluidity of the layer forming composition 1' particularly excellent.

Solvent
The layer forming composition 1' includes the solvent 12.

Thereby, it is possible to make handleability (ease of handling) of the layer forming composition 1' particularly excellent, it is possible to easily form the layer 1 having higher thickness uniformity, and it is possible to more effectively prevent unintended deformation of the layer 1.
In addition, it is possible to more effectively prevent unintended penetration of the liquid 2' into the layer 1 (layer 1 including the solvent 12) in the first liquid applying step, and it is possible to make the cured portion 2 formed in the first liquid applying step reliably have a desired shape. As described above, it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly excellent.

Examples of the solvent configuring the layer forming composition 1' include water; alcoholic solvents such as methanol, ethanol, and isopropanol; ketone-based solvents such as methyl ethyl ketone and acetone; glycol ether-based solvents such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, glycol ether acetate-based solvents such as propylene glycol 1-monomethyl ether 2-acetate and propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, and polypropylene glycol, and one type or two or more types selected from these can be used singly or in combination.

Among these, the layer forming composition 1' preferably includes an aqueous solvent, and more preferably includes water.

Thereby, it is possible to make the fluidity of the layer forming composition 1' and the uniformity of the constitution of the layer 1 formed using the layer forming composition 1' particularly excellent. Water is easily removed after the layer 1 is formed, and does not exercise adverse effects even in a case where water remains in the three-dimensional structure 10. Water is also advantageous from the viewpoint of safety with respect to human body and environmental issues. In a case where the liquid 2' used in formation of the first cured portion 2A includes a polymerizable compound (in particular, an acryl-based polymerizable compound or a silicone-based polymerizable compound) as described above, it is possible to more effectively prevent unintended penetration of the liquid 2' into the layer 1 (layer 1 including the solvent 12), it is possible to more reliably form the first cured portion 2A having a desired shape, and it is possible to make the dimensional accuracy and the reliability of the three-dimensional structure 10 particularly excellent. In addition, in a case where the layer forming composition 1' includes a water-soluble resin as a binder described below in detail, it is possible to make the water-soluble resin be in a more suitable dissolved state in the layer forming composition 1', and effects due to including a binder (water-soluble resin) as described below in detail are more effectively exhibited.

The aqueous solvent is not limited as long as it has a high solubility in water, and specifically, for example, an aqueous solvent having a solubility (mass dissolvable in 100g of water) of equal to or greater than 30 [g/100 g water] in water at 25 degrees centigrade is preferable, and an aqueous solvent having a solubility of equal to or greater than 50 [g/100 g water] in water at 25 degrees centigrade is more preferable.

The content of the solvent 12 in the layer forming composition 1' is preferably 9% by mass to 92% by mass, and more preferably 29% by mass to 89% by mass.

Thereby, since effects due to including the solvent 12 as described above can be more significantly exhibited, and it is possible to easily remove the solvent 12 in a short period of time in the manufacturing step of the three-dimensional structure 10, including a solvent is advantageous from the viewpoint of productivity improvement of the three-dimensional structure 10.

In particular, the content of the water in the layer forming composition 1' is preferably 18% by mass to 92% by mass, and more preferably 47% by mass to 90% by mass. Thereby, effects as described above are more significantly exhibited.

Binder
The layer forming composition 1' may include a plurality of particles 11, the solvent 12, and a binder.

Thereby, in the layer 1 (in particular, the layer 1 in a state in which the solvent 12 is removed) formed using the layer forming composition 1', it is possible to suitably bind (temporarily fix) a plurality of particles 11, and it is possible to effectively prevent unintended scattering of the particles 11. Thereby, it is possible to further improve safety of a worker and the dimensional accuracy of the three-dimensional structure 10 to be manufactured.

In a case where the layer forming composition 1' includes a binder, it is preferable that the binder is dissolved in the solvent 12, in the layer forming composition 1'.

Thereby, it is possible to make the fluidity of the layer forming composition 1' particularly favorable, and it is possible to more effectively prevent unintended variations in the thickness of the layer 1 formed using the layer forming composition 1'. In addition, when the layer 1 in a state in which the solvent 12 is removed is formed, it is possible to attach the binder to the particles 11 with higher uniformity over the entire layer 1, and it is possible to more effectively prevent an occurrence of unintended constitution unevenness. For this reason, it is possible to more effectively prevent an occurrence of unintended variations in the mechanical strength at each portion of the finally obtained three-dimensional structure 10, and it is possible to further increase the reliability of the three-dimensional structure 10.

Although the binder may have a function of temporarily fixing the plurality of particles 11 in the layer 1 (in particular, the layer 1 in a state in which the solvent 12 is removed) formed using the layer forming composition 1', it is possible to suitably use a water-soluble resin.

In a case where the layer forming composition 1' includes an aqueous solvent (in particular, water) as the solvent 12 by including a water-soluble resin, it is possible to make the binder (water-soluble resin) be included in the layer forming composition 1' in a dissolved state, and it is possible to make the fluidity, and the handleability (ease of handling) of the layer forming composition 1' particularly excellent.
As a result, it is possible to make the productivity of the three-dimensional structure 10 particularly excellent.

It is possible to easily and efficiently remove the portion where the liquid 2' of the layer 1 is not applied in the manufacturing step of the three-dimensional structure 10, by applying an aqueous solvent (in particular, water). As a result, it is possible to make the productivity of the three-dimensional structure 10 particularly excellent. In addition, since it is possible to easily and reliably prevent the portion where the layer should be removed from attaching to or remaining in the finally obtained three-dimensional structure 10, it is possible to make the dimensional accuracy of the three-dimensional structure 10 particularly excellent.

Hereinafter, the water-soluble resin as a binder will be described mainly. The water-soluble resin is not limited as long as at least a part thereof is soluble in an aqueous solvent, and for example, a water-soluble resin having a solubility of equal to or greater than 5 [g/100 g water] in water at 25 degrees centigrade is preferable, and a water-soluble resin having a solubility of equal to or greater than 10 [g/100 g water] in water at 25 degrees centigrade is more preferable.

Examples of the water-soluble resin include synthetic polymers such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactonediol, sodium polyacrylate, polyacryl amide, modified polyamide, polyethylene imine, polyethylene oxide, and a random copolymer of ethylene oxide and propylene oxide, natural polymers such as cornstarch, mannan, pectin, agar, alginic acid, dextran, glues, and gelatin, and semi-synthetic polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, oxidized starch, and modified starch, and one type or two or more types selected from these can be used singly or in combination.

Specific examples of the water-soluble resin product include methyl cellulose (manufactured by Shin-Etsu Chemicals Co., Ltd., Metolose SM-15), hydroxyethyl cellulose (manufactured by Fuji Chemical Industry Co., Ltd., AL-15), hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd., HPC-M), carboxymethyl cellulose (Nichirin Chemical Co., Ltd., CMC-30), sodium (I) starch phosphate (manufactured by Matsutani Chemical Industry Co., Ltd., Hoster 5100), polyvinyl pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd., PVP K-90), a methyl vinyl ether/maleic anhydride copolymer (manufactured by GAF Gantrez, AN-139), polyacryl amide (manufactured by Wako Pure Chemical Industries, Ltd.), modified polyamide (modified nylon) (manufactured by Toray Industries, Inc., AQ nylon), polyethylene oxide (PEO-1 manufactured by Steel Chemical Co., Ltd., Alkox manufactured by Meisei Chemical Works, Ltd.), an ethylene oxide/propylene oxide random copolymer (manufactured by Meisei Chemical Works, Ltd., Alkox EP), sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), and a carboxyvinyl polymer/cross-linked acryl-based water-soluble resin (manufactured by Sumitomo Seika Chemicals Co., Ltd., AQUPEC).

Among these, in a case where the water-soluble resin as a binder is polyvinyl alcohol, it is possible to make the mechanical strength of the three-dimensional structure 10 particularly excellent. In addition, by adjusting the saponification degree and the polymerization degree, it is possible to more suitably control characteristics (for example, water solubility and water resistance) of the binder or characteristics (for example, viscosity, fixing force of the particles 11, and wettability) of the layer forming composition 1'. Therefore, it is possible to more suitably cope with according to manufacture of the various three-dimensional structures 10. In addition, among various water-soluble resins, polyvinyl alcohol is inexpensive and a supply thereof is stable. Therefore, it is possible to manufacture the stable three-dimensional structure 10 while reducing the production cost.

In a case where the water-soluble resin as a binder includes polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is preferably 85 to 90. Thereby, it is possible to suppress decrease in the solubility of the polyvinyl alcohol in an aqueous solvent (in particular, water). For this reason, in a case where the layer forming composition 1' includes an aqueous solvent (in particular, water), it is possible to more effectively suppress reduction in the adhesion between the layers 1 which are adjacent.

In a case where the water-soluble resin as a binder includes polyvinyl alcohol, the polymerization degree of the polyvinyl alcohol is preferably 300 to 1000. Thereby, in a case where the layer forming composition 1' includes an aqueous solvent (in particular, water), it is possible to make the mechanical strength of each layer 1 or the adhesion between the layers 1 which are adjacent particularly excellent.

In addition, in a case where the water-soluble resin as a binder is polyvinyl pyrrolidone (PVP), the following effects are obtained. That is, since polyvinyl pyrrolidone has excellent adhesion with respect to various materials such as glass, metal, and plastic, it is possible to make the strength and stability of the shape of the portion where the liquid 2' in the layer 1 particularly excellent, and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly excellent. Since polyvinyl pyrrolidone shows high solubility in various organic solvents, in a case where the layer forming composition 1' includes an organic solvent, it is possible to make the fluidity of the layer forming composition 1' excellent, it is possible to suitably form the layer 1' in which unintentional variations in the thickness are more effectively prevented, and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 10 particularly excellent. Since polyvinyl pyrrolidone shows high solubility also in an aqueous solvent (in particular, water), in the unbound particle removing step (after forming ends), it is possible to easily and reliably remove the particles unbound by a resin material (binder) of the particles 11 configuring each layer 1. In addition, since polyvinyl pyrrolidone has excellent affinity with various colorants, in the case of using the liquid 2' including a colorant in the second liquid applying step, it is possible to effectively prevent the colorant from being unintentionally spread.

In a case where the water-soluble resin includes polyvinyl pyrrolidone as a binder, the weight average molecular weight of the polyvinyl pyrrolidone is preferably 10000 to 1700000, and more preferably 30000 to 1500000. Thereby, it is possible to more effectively exhibit the function described above.

In a case where the water-soluble resin includes polycaprolactonediol as a binder, the weight average molecular weight of the polycaprolactonediol is preferably 10000 to 1700000, and more preferably 30000 to 1500000. Thereby, it is possible to more effectively exhibit the function described above.

In the layer forming composition 1, the binder is preferably in a liquid state (for example, a dissolved state or a molten state) in the film forming step. Thereby, it is possible to easily and reliably further increase uniformity in the thickness of the layer 1 formed using the layer forming composition 1'.

In a case where the layer forming composition 1' includes a binder, the content of the binder in the layer forming composition 1' is preferably 0.5% by mass to 25% by mass, and more preferably 1.0% by mass to 10% by mass.

Thereby, effects due to including a binder as described above are more significantly exhibited, it is possible to sufficiently increase the content of the particles 11 in the layer forming composition 1', and it is possible to make the mechanical strength of the manufactured three-dimensional structure 10 particularly excellent.

Other Components
The layer forming composition may include components other than the components described above. Examples of such components include a polymerization initiator; a polymerization accelerator; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; a ultraviolet absorbent; a chelating agent; and a pH adjusting agent.

Three-Dimensional Structure Manufacturing Apparatus
Next, the three-dimensional structure manufacturing apparatus according to the invention will be described.

Fig. 3 is a cross-sectional view schematically showing a preferred embodiment of the three-dimensional structure manufacturing apparatus according to the invention.

A three-dimensional structure manufacturing apparatus M100 is an apparatus for manufacturing the three-dimensional structure 10 by repeatedly forming and stacking the layers 1 using the layer forming composition 1'. In particular, the three-dimensional structure manufacturing apparatus M100 is an apparatus for manufacturing the three-dimensional structure 10 by performing the method for manufacturing a three-dimensional structure according to the invention as described above.

As shown in Fig. 3, the three-dimensional structure manufacturing apparatus M100 has a control portion M2, a composition supply portion M3 which accommodates the layer forming composition 1', a layer forming portion M4 which forms the layer 1 using the layer forming composition 1' supplied from the composition supply portion M3, a liquid discharge portion (liquid applying device) M5 which discharges the liquid 2' to the layer 1, an energy ray irradiation device (curing device) M6 which applies an energy rays to cure the liquid 2', and a height measuring device M7 which measures the height of the cured product 6 formed using the liquid 2'.

The control portion M2 has a computer M21 and a drive control portion M22. The computer M21 is a general desk type computer which is configured to equip a CPU and a memory therein. The computer M21 converts the shape of the three-dimensional structure 10 to model data, and a cross-sectional data (slice data) obtained by slicing the model data into several parallel layers of a thin cross-sectional body is output to the drive control portion M22. In addition, the height of the upper surface of the cured product 6 is measured by the height measuring device M7 descried below, and in the case of adjusting the thickness of the layer 1 based on the height, rewriting (correction and revision) of the cross-sectional data (slice data) is performed based on the thickness of the layer 1.

The drive control portion M22 functions as a control device which drives the layer forming portion M4, the liquid discharge portion M5, the energy ray irradiation device M6, the height measuring device M7, or the like, respectively. Specifically, for example, the drive control portion M22 controls a discharge pattern or discharge amount of the liquid 2' by the liquid discharge portion M5, the supply amount of the layer forming composition 1' from the composition supply portion M3, and the extent of descent of the stage (lifting stage) M41.

The composition supply portion M3 is moved by the instructions from the drive control portion M22, and configured such that the layer forming composition 1' contained therein is supplied to the stage M41.

The layer forming portion M4 has, the stage (lifting stage) M41 to which the layer forming composition 1' is supplied and supports the layer 1 formed of the layer forming composition 1', the flattening device (squeegee) M42 which forms the layer 1 while flattening the layer forming composition 1' held on the stage M41, a guide rail M43 which regulates the operation of the flattening device M42, and a frame body M45 which surrounds the lifting stage M41 and is provided so as to be in close contact with the lifting stage M41.

The lifting stage M41 descends sequentially by only a predetermined extent by the instructions from the drive control portion M22 when forming a new layer 1 on the layer 1 formed previously. By the extent of descent of the lifting stage M41 and the height of the flattening device M42 described below in detail, the thickness of the layer 1 newly formed is defined.

The stage M41 has the flat surface (a portion to which the layer forming composition 1' and the liquid 2' are applied, a portion including the first region M411 and the second region M412). Thereby, it is possible to easily and reliably form the layer 1 having high thickness uniformity. In addition, on the basis of the height of the upper surface of the cured product 6, it is possible to suitably adjust the thickness of the layer 1 newly formed.

The stage M41 is preferably configured of a material having high strength. Examples of the constituent material of the stage M41 include various metal materials such as stainless steel.

A surface treatment may be performed on the surface (a portion to which the layer forming composition 1' and the liquid 2' are applied, a portion including the first region M411 and the second region M412) of the stage M41. Thereby, for example, it is possible to more effectively prevent the constituent material of the layer forming composition 1' or the constituent material of the liquid 2' from being strongly attached to the stage M41, it is possible to make the durability of the stage M41 particularly excellent, or it is possible to stably produce the three-dimensional structure 10 over a long period of time. Examples of the material used in the surface treatment of the surface of the stage M41 include fluorine-based resins such as polytetrafluoroethylene.

The squeegee as the flattening device M42 has a long shape extending in the X direction, and is equipped with a blade having a blade-like shape in which the lower tip is sharp.

Since the layer 1 formed by flattening of the layer forming composition 1' is suitably adjusted as necessary based on information such as the height of the upper surface of the cured product 6 by the height measuring device M7, by the flattening device M42, it is possible to prevent the constituent (for example, the particles 11) of the layer forming composition 1' from unintentionally remaining on the upper surface of the cured portion 2 at the time when the layer forming step ends.

The blade may equipped with a vibration mechanism (not shown) which applies fine vibration to the blade such that diffusion of the layer forming composition 1' by the flattening device (squeegee) M42 is smoothly performed.

For example, the three-dimensional structure manufacturing apparatus M100 may be equipped with a stress detecting device (not shown) which detects stress applied to the flattening device M42 when the flattening device M42 is in contact with the upper surface of the cured product 6 formed at the second region M412 of the stage M41.

Thereby, for example, in a case where the flattening device M42 is in contact with the upper surface of the cured product 6, it is possible to determine the state where a predetermined stress becomes a predetermined value with respect to the flattening device M42 as the height of the flattening device M42 at the time of formation of the layer 1.

Moreover, bringing the flattening device M42 into contact with the cured product 6 can be more suitably performed by relatively moving the stage M41 and the flattening device M42 in the Z direction, and for example, it may be performed by moving the flattening device M42 in the downward direction, or may be performed by moving the stage M41 in the upward direction.

The liquid discharge portion (liquid applying device) M5 discharges the liquid 2' by an ink jet method. By equipping such a liquid discharge portion (liquid applying device) M5, it is possible to apply the liquid 2' in fine patterns, and it is even possible to manufacture the three-dimensional structure 10 having a fine configuration with particularly excellent productivity. In addition, it is possible to suitably form the cured portion 2 and the cured product 6 under the same conditions (for example, the same thickness, the same density).

As a liquid droplet discharge system (system of an ink jet method), a piezo system or a system for discharging the liquid 2' by bubbles generated by heating the liquid 2' can be used, and from the viewpoint of the difficulty in changing in quality of the constituent of the liquid 2', the piezo system is preferable.

In the liquid discharge portion (liquid applying device) M5, a pattern to be formed or the amount of the liquid 2' to be applied is controlled by the instructions from the drive control portion M22. The discharge pattern, the discharge amount, or the like of the liquid 2' by the liquid discharge portion (liquid applying device) M5 is determined based on the slice data. Thereby, it is possible to apply the necessary and sufficient amount of the liquid 2', it is possible to reliably form the cured portion 2 having a desired pattern, and it is possible to more reliably make the dimensional accuracy and the mechanical strength of the three-dimensional structure 10 excellent. In addition, in a case where the liquid 2' includes a colorant, it is possible to reliably obtain a desired color, and it is possible to reliably prevent an occurrence of an unintentional color change and unintentional collapse of the color balance, due to the change in the thickness of the layer 1.

The energy ray irradiation device (curing device) M6 applies energy rays to cure the liquid 2' applied.

The type of energy rays that the energy ray irradiation device M6 applies varies depending on the constituent materials of the liquid 2', and examples thereof include ultraviolet rays, visible rays, infrared rays, X-rays, gamma-rays, an electron beam, and an ion beam. Among these, ultraviolet rays are preferably used from the viewpoint of cost and productivity of the three-dimensional structure 10.

The height measuring device M7 measures the height of the upper surface of the cured product 6. Information on the height of the upper surface of the cured product 6 is transmitted to the control protion M2 from the height measuring device M7, and is used in adjusting the thickness of the layer 1 to be formed and the relative height of the flattening device M42.

In addition, in the configuration shown in Fig. 3, the height measuring device M7 determines the height of the cured product 6 by determining the focal length from the upper direction of the cured product 6. Since it is possible to measure the height of the cured product 6 without moving the height measuring device M7 by such a configuration, it is possible to shorten the time required for measuring the height of the cured product 6, and it is possible to make the productivity of the three-dimensional structure 10 particularly excellent.

By the three-dimensional structure manufacturing apparatus according to the invention described above, it is possible to efficiently manufacture a three-dimensional structure which has excellent dimensional accuracy and mechanical strength.

Three-Dimensional Structure
The three-dimensional structure according to the invention is manufactured using the manufacturing method according to the invention. Thereby, it is possible to provide a three-dimensional structure which has the dimensional accuracy and the mechanical strength.

Use of the three-dimensional structure according to the invention is not particularly limited, and examples thereof include items for appreciation and articles on exhibition such as a doll and a figure; and medical devices such as an implant.

In addition, the three-dimensional structure according to the invention may be applied to any of a prototype, mass-produced products, and tailor made products.

Hereinabove, the preferred embodiments of the invention have been described, but the invention is not limited to these embodiments.

For example, in the above-described embodiments, it has been described that for all of the layers, a cured portion is formed, however, the embodiments may have a layer in which a cured portion is not formed. For example, a layer formed just on the stage may be functioned as a sacrificial layer without forming a cured portion thereon.

In the above-described embodiments, a case where a cured product used in determining the thickness of a layer is formed at the second region different from the first region where a portion configuring an entity portion of an intended three-dimensional structure on the forming stage is formed has been described, however, the cured product used in determining the thickness of a layer may be a cured product formed at the first region, in particular, a part of an entity portion of the three-dimensional structure.

In the above-described embodiments, a case where the height of the upper surface of a cured product used in determining the thickness of a layer is determined by an observation from the upper surface of the cured product has been representatively described, however, the height of the upper surface of a cured product may be determined by an observation from the side surface of the cured product.

In the above-described embodiments, the case of using a fixed height measuring device has been representatively described, however, the height measuring device may be movable (for example, movable in the XY direction of the stage). Thus, for example, it is possible to measure the height of the upper surface of the cured product at a plurality of points.

In the above-described embodiments, the case of using a layer forming composition including a solvent has been representatively described, however, the layer forming composition may include at least a plurality of particles, or may not include a solvent.

In addition, in the above-described embodiments, a case where all of a plurality of cured products formed by being stacked over several steps have the same shape and the same area has been representatively described, however, for example, each area of the plurality of cured products to be stacked decreases sequentially towards the upper side, and the layered product with a plurality of cured products formed by being stacked, for example, may have a shape such as a pyramid shape or the like. Even in such a case, the same effects as described above are obtained.

The three-dimensional structure manufacturing apparatus according to the invention may be equipped with a recovery mechanism not shown for recovering the composition unused in formation of a layer of the composition supplied from the composition supply portion. Thereby, since it is possible to supply a sufficient amount of the composition while preventing the excessive composition from being accumulated in a layer forming portion, it is possible to manufacture a more stable three-dimensional structure while more effectively preventing an occurrence of defects in layers. In addition, since it is possible to use the recovered composition in manufacturing a three-dimensional structure again, it is possible to contribute to reduction in the manufacturing cost of the three dimensional structure, and the three-dimensional structure manufacturing apparatus according to the invention is preferable from the viewpoint of resource saving.

The three-dimensional structure manufacturing apparatus according to the invention may be equipped with a recovery mechanism for recovering the composition removed in the unbound particle removing step.

In the above-described embodiments, description has been made focused on the case of repeatedly performing the layer forming step, the first liquid applying step, the first curing step, the solvent removing step, the second liquid applying step, and the first curing step as a series of steps, however, the series of steps repeatedly performed may be different in each cycle, and for example, the series of steps repeatedly performed may have a cycle in which the first liquid applying step and the first curing step of the above steps are omitted, or may have a cycle in which the second liquid applying step and the second curing step of the above steps are omitted.

The curing treatment performed for formation of each curing portion may not repeatedly performed each time a pattern corresponding to each curing portion is formed, and may be collectively performed after a layered product in which uncured patterns are provided on the plurality of layers is formed.

In the embodiment described above, description has been made focused on a case where the liquid used in formation of the cured portion and the cured product are applied by an ink jet method, however, the liquid used in formation of the cured portion and the cured product may be applied using other methods (for example, other printing methods).

In addition, in the manufacturing method according to the invention, a pretreatment step, an intermediate treatment step, or a post-treatment step may be performed, as necessary.

Examples of the pretreatment step include a cleaning step of the stage or the like. Examples of the post-treatment step include a cleaning step, a shape adjusting step of performing deburring or the like, a coloring step, a coating layer forming step, and a resin material curing completion step of performing a light irradiation treatment or a heating treatment to reliably cure an uncured resin material.

10: Three-dimensional structure
1: Layer
1': Composition (layer forming composition)
11: Particles
12: Solvent
2: Cured portion
2A: First cured portion
2B: Second cured portion
2C: Third cured portion
2': Liquid (cured portion forming liquid)
3: Bound portion
4: Space
6: Cured product
M100: Three-dimensional structure manufacturing apparatus
M2: Control portion
M21: Computer
M22: Drive control portion
M3: Composition supply portion
M4: Layer forming portion
M41: Stage (lifting stage, support)
M411: First region
M412: Second region
M42: Flattening device (squeegee)
M43: Guide rail
M45: Frame body
M5: Liquid discharge portion (liquid applying device)
M6: Energy ray irradiation device (curing device)
M7: Height measuring device

Claims

A method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, comprising:
a layer forming step of forming the layer having a predetermined thickness using a layer forming composition including particles;
a liquid applying step of applying the liquid to the layer; and
a curing step of forming a cured portion by curing the liquid,
wherein based on a height of an upper surface of a cured product formed using the liquid, a thickness of the layer to be newly formed after formation of the cured product is determined.
A method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, comprising:
a layer forming step of forming the layer having a predetermined thickness using a layer forming composition including particles;
a liquid applying step of applying the liquid to the layer; and
a curing step of forming a cured portion by curing the liquid,
wherein a height of a cured product formed using the liquid is measured, and based on the measurement result, a thickness of the layer to be newly formed after formation of the cured product is determined.
A method for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, comprising:
a layer forming step of forming the layer having a predetermined thickness by flattening a layer forming composition including particles, using a flattening device;
a liquid applying step of applying the liquid to the layer; and
a curing step of forming a cured portion by curing the liquid,
wherein the flattening device is brought into contact with an upper surface of a cured product formed using the liquid, and based on the contact surface, the layer having a predetermined thickness is formed.
The method for manufacturing a three-dimensional structure according to any one of Claims 1 to 3,
wherein the cured product is formed at a second region different from a first region where a portion configuring an entity portion of the three-dimensional structure of interest on the forming stage is formed.
The method for manufacturing a three-dimensional structure according to Claim 4,
wherein the second region is provided on an outer peripheral side of the first region.
The method for manufacturing a three-dimensional structure according to Claim 4 or 5,
wherein a discharge pattern density of the liquid in the second region is equal to a discharge pattern density of the liquid in the first region.
The method for manufacturing a three-dimensional structure according to any one of Claims 1 to 6,
wherein the cured product is formed so as to be stacked over a plurality of steps, to correspond to a plurality of the layers.
The method for manufacturing a three-dimensional structure according to Claim 7,
wherein, when a cured product formed in any step, of a plurality of the cured products formed by being stacked over a plurality of steps, is defined as a first cured product, and a cured product formed in a later step than the first cured product is defined as a second cured product, the second cured product does not have a region not overlapping with the first cured product, when seen in a plan view.
The method for manufacturing a three-dimensional structure according to any one of Claims 1 to 8, comprising:
a first liquid applying step of applying the liquid to the layer in a state of including a solvent after the layer forming step is performed by using the layer forming composition including the particles and the solvent;
a first curing step of curing the liquid applied to the layer; and
a solvent removing step of removing the solvent from the layer.
The method for manufacturing a three-dimensional structure according to Claim 9, further comprising:
a second liquid applying step of applying the liquid to the layer in a state in which the solvent is removed after the solvent removing step and penetrating the liquid into the layer; and
a second curing step of curing the liquid penetrated into the layer.
A three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by repeating a treatment of forming a layer and discharging a liquid to the layer, comprising:
a stage that forms the layer using a layer forming composition including particles;
a liquid applying device that applies a liquid to the layer; and
a curing device that cures the liquid,
wherein based on a height of an upper surface of a cured product formed using the liquid, a thickness of the layer to be newly formed after formation of the cured product is determined.
A three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure according to any one of Claims 1 to 10.
A three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus according to Claim 11.