TW201618938A - Method for manufacturing three-dimensional structure, three-dimensional structure manufacturing apparatus, and three-dimensional structure - Google Patents

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 shaped object, three-dimensional shaped object manufacturing device and three-dimensional shaped object

The present invention relates to a method of manufacturing a three-dimensional shaped object, a three-dimensional shaped object manufacturing apparatus, and a three-dimensional shaped object.

A technique of forming a powder layer (layer) using a composition containing powder (particles) and laminating them to form a three-dimensional shaped object is known (for example, see Patent Document 1). In this technique, a three-dimensional shaped object is shaped by repeatedly performing the following operations. First, the powder is thinly spread with a uniform thickness to form a powder layer, and only a desired portion of the powder layer is coated with a binder material (liquid), and the powders (particles) are bonded to each other to form a joint portion (hardened portion). . As a result, a member having a thin plate shape (hereinafter referred to as a "section member") is formed at a joint portion where the powders are bonded to each other. Thereafter, a powder layer is further formed thinly on the powder layer, and the powders are selectively bonded to each other only at a desired portion to form a joint. As a result, a new cross-sectional member is also formed in the newly formed powder layer. At this time, the newly formed sectional member is also bonded to the previously formed sectional member. By repeating such an operation, a thin plate-like cross-section member (joining portion) is laminated one by one to shape a three-dimensional shaped object.

However, as the layer formation is repeated, there is a need for the flattening member such as a squeegee used for layer formation to be worn, deformed, or the thickness of the formed layer is deviated due to variations in the amount of liquid imparted or the like. The case of the design value. If the thickness of such a layer occurs When the deviation occurs, there is a problem that the dimensional accuracy of the finally obtained three-dimensional shaped object is lowered, or the bonding force formed between the joint portions of the adjacent layers is lowered, and the mechanical strength of the finally obtained three-dimensional shaped object is lowered.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-218712

An object of the present invention is to provide a method for producing a three-dimensional shaped object which can efficiently produce a three-dimensional shaped object excellent in dimensional accuracy and mechanical strength, a three-dimensional shaped object producing apparatus, and a three-dimensional shaped object excellent in dimensional accuracy and mechanical strength.

This object is achieved by the present invention described below.

The method for producing a three-dimensional shaped article of the present invention is a method of repeatedly forming a layer and ejecting a liquid to the layer, and producing a three-dimensional shaped article, comprising: a layer forming step of using a layer-forming composition containing particles. Forming the above-mentioned layer of a specific thickness; a liquid imparting step of imparting the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and based on the upper surface of the cured product formed using the liquid The height depends on the thickness of the above-mentioned layer newly formed after the formation of the cured product.

Thereby, it is possible to provide a method for producing a three-dimensional shaped article capable of efficiently producing a three-dimensional shaped article excellent in dimensional accuracy and mechanical strength.

The method for producing a three-dimensional shaped article of the present invention is a method of repeatedly forming a layer and ejecting a liquid to the layer, and producing a three-dimensional shaped article, comprising: a layer forming step of using a layer-forming composition containing particles. Form a specific thickness The liquid layer imparting step of imparting the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and measuring a height of the cured product formed using the liquid, based on the measurement result Determined by the thickness of the above layer newly formed after the formation of the cured product.

Thereby, it is possible to provide a method for producing a three-dimensional shaped article capable of efficiently producing a three-dimensional shaped article excellent in dimensional accuracy and mechanical strength.

The method for producing a three-dimensional shaped article of the present invention is a method for repeatedly forming a layer and ejecting a liquid to the layer, and producing a three-dimensional shaped article, comprising: a layer forming step of using a flattening mechanism to cause a particle-containing material The layer forming composition is planarized to form the layer having a specific thickness; the liquid imparting step of applying the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and planarizing the layer The mechanism abuts against the upper surface of the cured product formed by using the liquid, and forms the above-mentioned layer of a specific thickness based on the abutting surface.

Thereby, it is possible to provide a method for producing a three-dimensional shaped article capable of efficiently producing a three-dimensional shaped article excellent in dimensional accuracy and mechanical strength.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the cured product is formed on the forming platform in a second region different from the first region in which the solid portion of the three-dimensional shaped object that constitutes the target is formed.

Thereby, the dimensional accuracy and reliability of the finally obtained three-dimensional shaped object can be made particularly excellent.

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

Thereby, the dimensional accuracy and reliability of the finally obtained three-dimensional shaped object can be further improved, and the productivity of the three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the discharge pattern density of the liquid in the second region is equal to the density of the discharge pattern of the liquid in the first region.

Thereby, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the cured product is formed by laminating a plurality of steps in a manner corresponding to a plurality of the layers.

Thereby, the dimensional accuracy and mechanical strength of the entire three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the plurality of cured products formed by laminating in a plurality of steps are formed into a first cured product by any step. When the step formed by the step of the first cured product is the second cured product, the second cured product does not have a region that does not overlap the first cured product in plan view.

Thereby, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferred that the layer forming step is carried out using the layer forming composition containing the particles and the solvent, and the first liquid applying step is performed on the layer After the forming step, the liquid is applied to the layer containing the solvent; the first curing step is to cure the liquid applied to the layer; and the solvent removing step is to remove the solvent from the layer.

Thereby, it is possible to preferably prevent accidental penetration of the liquid into the interior of the layer, and it is possible to more reliably form the hardened portion of the desired shape on the upper surface of the layer. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable to further include a second liquid application step after the solvent removal step, after removing the solvent The layer of the above state imparts the liquid to allow the liquid to penetrate into the layer; and the second hardening step of hardening the liquid permeating into the layer.

Thereby, the hardened portion can be formed inside the layer, so that the finally obtained three-dimensional shaped object is particularly excellent in mechanical strength, and more reliable in preventing accidental deformation.

The three-dimensional shaped object manufacturing apparatus of the present invention is a method of repeatedly forming a layer and discharging a liquid to the layer, and manufacturing a three-dimensional shaped object, comprising: a platform for forming the layer using a composition for forming a layer containing particles; a liquid imparting mechanism that imparts a liquid to the layer; and a hardening mechanism that hardens the liquid; and the height of the upper surface of the cured product formed based on the use of the liquid is determined by the layer newly formed after the formation of the cured product The thickness.

Thereby, it is possible to provide a three-dimensional shaped object manufacturing apparatus capable of efficiently manufacturing a three-dimensional shaped object excellent in dimensional accuracy and mechanical strength.

The three-dimensional shaped article of the present invention is characterized in that it is manufactured by using the method for producing a three-dimensional shaped article of the present invention.

Thereby, it is possible to provide a three-dimensional shape excellent in dimensional accuracy and mechanical strength.

The three-dimensional shaped article of the present invention is characterized in that it is manufactured by using the three-dimensional shaped article manufacturing apparatus of the present invention.

Thereby, it is possible to provide a three-dimensional shape excellent in dimensional accuracy and mechanical strength.

1 story

1'‧‧‧Composition (layer formation composition)

2‧‧‧ Hardening Department

2A‧‧‧1st hardening department

2B‧‧‧2nd hardening department

2C‧‧‧3rd hardening department

2'‧‧‧Liquid (liquid for hardening formation)

3‧‧‧Combination Department

4‧‧‧ Space

6‧‧‧ hardened material

10‧‧‧Three-dimensional shape

11‧‧‧ particles

12‧‧‧Solvent

M2‧‧‧Control Department

M3‧‧‧Composition Supply Department

M4‧‧‧ Formation Department

M5‧‧‧Liquid ejecting unit (liquid dispensing mechanism)

M6‧‧‧Energy ray irradiation mechanism (hardening mechanism)

M7‧‧‧ Height measuring agency

M21‧‧‧ computer

M22‧‧‧Drive Control Department

M41‧‧‧ platform (lifting platform, support)

M42‧‧‧Flating mechanism (scraping board)

M43‧‧‧ rail

M45‧‧‧shell

M100‧‧‧Three-dimensional shaped object manufacturing device

M411‧‧‧1st area

M412‧‧‧2nd area

Fig. 1 (1a) to (1f) are cross-sectional views schematically showing respective steps in the first embodiment of the method for producing a three-dimensional shaped article of the present invention.

2(1g) to (1k) are cross-sectional views schematically showing respective steps in the first embodiment of the method for producing a three-dimensional shaped article of the present invention.

3(1l) to (1p) are cross-sectional views schematically showing respective steps in the first embodiment of the method for producing a three-dimensional shaped article of the present invention.

4(1q) to (1t) are cross-sectional views schematically showing respective steps in the first embodiment of the method for producing a three-dimensional shaped article of the present invention.

Fig. 5 (2a) to (2f) are schematic cross-sectional views showing the second embodiment of the method for producing a three-dimensional shaped article of the present invention.

6(2g) to (2k) are cross-sectional views schematically showing the second embodiment of the method for producing a three-dimensional shaped article of the present invention.

7(21) to (2p) are cross-sectional views schematically showing the second embodiment of the method for producing a three-dimensional shaped article of the present invention.

8(2q) to (2t) are cross-sectional views schematically showing the second embodiment of the method for producing a three-dimensional shaped article of the present invention.

Fig. 9 is a cross-sectional view schematically showing a preferred embodiment of the apparatus for manufacturing a three-dimensional shaped article of the present invention.

Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

"Manufacturing method of three-dimensional shaped objects"

First, a method of manufacturing a three-dimensional shaped article of the present invention will be described.

[First Embodiment]

1, 2, 3, and 4 are cross-sectional views schematically showing respective steps in the first embodiment of the method for producing a three-dimensional shaped article of the present invention.

As shown in Fig. 1, Fig. 2, Fig. 3, and Fig. 4, the method for producing a three-dimensional shaped article 10 of the present embodiment includes a layer forming step (1d, 1k, 1r) using a layer forming composition containing particles 11. The material 1' is formed into a layer 1 having a specific thickness; the liquid is supplied to the step (1e, 1h, 1l, 1o), and the liquid for forming the hardened portion 2 (the first cured portion 2A) is applied to the layer 1 (the liquid for forming the hardened portion) 2'; and a hardening step (1f, 1i, 1m, 1p) which hardens the liquid 2' to form the hardened portion 2.

In the liquid application step, the second region M412, which is a region different from the first region M411 which is the region in which the target three-dimensional shaped object 10 is manufactured, is provided for formation. The liquid 2' of the hardened portion 2 of the three-dimensional shaped object 10 is targeted, and in the hardening step, the liquid 2' applied to the first region M411 is cured to form the hardened portion 2, and is applied to the second region M412. The liquid 2' is hardened to form a cured product 6 having the same height as the hardened portion 2 described above.

Further, in the layer forming step performed after the formation of the cured material 6 (for example, the step of (1k) performed after the step (1f) or the step (1r) after the step (1m), based on The height of the upper surface of the cured material 6 determines the thickness (1j, 1q) of the layer 1.

By determining the thickness of the layer 1 based on the height of the upper surface of the cured material 6, it is possible to prevent the constituent components (for example, the particles 11) of the layer forming composition 1' from remaining unexpectedly at the end of the layer forming step. The upper surface of the hardened portion 2.

Thereby, in the subsequent step, the adhesion between the hardened portion 2 and the hardened portion 2 newly formed on the cured portion 2 can be made to be excellent. As a result, the mechanical strength of the finally obtained three-dimensional shaped article 10 can be made excellent.

Further, it is possible to prevent the dimensional accuracy of the three-dimensional shaped object 10 from being caused by accidentally presenting the particles 11 constituting the layer forming composition 1' between the hardened portion 2 and the hardened portion 2 formed on the cured portion 2. reduce.

In particular, in the present embodiment, in the layer forming step, the flattening mechanism M42 is brought into contact with the upper surface of the cured product 6, and the flattening mechanism M42 is in contact with the height (contact surface) of the cured product 6 as a reference. A layer 1 of specific thickness is formed (refer to 1j, 1q).

Thereby, the above-described problem can be prevented more effectively with a simple configuration, and the three-dimensional shaped article 10 excellent in mechanical strength and dimensional accuracy can be manufactured with excellent productivity.

As described above, in the present embodiment, the cured product 6 is formed on the stage M41 in the second region M412 which is different from the first region M411 in which the solid portion of the three-dimensional shaped object 10 is formed.

Thereby, it is possible to more reliably prevent the layer 1 occurring in the hardened portion 2 or the formation of the target three-dimensional shaped object 10 when the flattening mechanism M42 is brought into contact (when the thickness of the newly formed layer is determined) or the like. Unexpected deformation, etc. As a result, the finally obtained three-dimensional shape 10 can be obtained. The dimensional accuracy and reliability have been particularly excellent.

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

As a result, the above-described effects can be exhibited more remarkably, and the dimensional accuracy and reliability of the three-dimensional shaped object 10 finally obtained can be further improved, and the productivity of the three-dimensional shaped object 10 can be made particularly excellent.

In particular, in the configuration shown in the drawing, the second region M412 is disposed on the upstream side of the first region M411 in the relative movement direction of the flattening mechanism M42 with respect to the stage M41.

Thereby, after the relative height adjustment of the flattening mechanism M42 is performed, the formation of the layer 1 by the flattening mechanism M42 can be performed efficiently, and the productivity of the three-dimensional shaped object 10 can be made particularly excellent.

It is preferable that the discharge pattern density of the liquid 2' in the second region M412 is equal to the discharge pattern density of the liquid 2' in the first region M411. For example, when the liquid 2' is ejected at 720 dpi in the first region M411, it is preferable that the liquid 2' is also ejected at 720 dpi in the second region M412.

Thereby, the difference between the thickness of the hardened portion 2 and the thickness of the cured product 6 can be made smaller, and the above-described effects can be exhibited more remarkably, and the dimensional accuracy and mechanical strength of the finally obtained three-dimensional shaped object 10 can be obtained. Become a particularly good person.

Further, in the present embodiment, the cured product 6 is formed by laminating a plurality of steps (see 1b, 1f, 1m, 1s) in a manner corresponding to the plurality of layers 1.

Thereby, a preferable thickness can be determined for each of the plurality of layers 1, and the dimensional accuracy and mechanical strength of the entire three-dimensional shaped object 10 can be made particularly excellent.

Further, in the present embodiment, the plurality of cured products 6 formed by stacking in a plurality of steps have the same shape and the same area. In other words, when any one of the plurality of cured products 6 formed by laminating in a plurality of steps is formed as a first cured product, the step formation after the first cured product is set. For the second hardening In the case of the object, the second cured product does not have a region that does not overlap the first cured product in a plan view.

With such a configuration, it is possible to more effectively prevent the unexpected deformation (so-called collapse, etc.) of the cured product 6, and the difference between the thickness of the hardened portion 2 and the thickness of the cured product 6 can be made smaller, thereby making it more remarkable. The effect is as described above. As a result, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional shaped object 10 can be made particularly excellent.

The method for producing a three-dimensional shaped article of the present invention may be a layer forming step, a liquid applying step, and a curing step, and the method for producing the three-dimensional shaped article 10 of the present embodiment includes a layer forming step (1c, 1d, 1j, 1k, 1q, 1r), the layer 1 is formed using the layer forming composition 1' containing the particles 11 and the solvent 12, and the first liquid is supplied to the layer (1e, 1l), which is the layer 1 in the state containing the solvent 12. The liquid (hardened portion forming liquid) 2' for forming the cured portion 2 (first cured portion 2A) is applied thereto, and the first curing step (1f, 1m) is applied to the layer 1 in a state containing the solvent 12. The upper liquid (hardened portion forming liquid) 2' is cured to form the cured portion 2 (first cured portion 2A); the solvent removing step (1g, 1n) is for removing the solvent 12 from the layer 1, and the second liquid imparting step (1h, 1o), the liquid 1 (hardened portion forming liquid) 2' for forming the cured portion 2 (second hardened portion 2B) is applied to the layer 1 in a state in which the solvent 12 is removed, and the liquid 2' is infiltrated to In the layer 1 and the second hardening step (1i, 1p), the liquid (hardened portion forming liquid) permeating into the layer 1 is hardened 2' to form a hard Part 2 (second hardened portion 2B); the steps (1s) are repeated in sequence, and thereafter there is an unbound particle removing step (1t) which is formed by the hardened portion of the particles 11 constituting each layer 1 2 combine remover.

In the first liquid application step, the liquid (hardened portion forming liquid) 2' for forming the cured portion 2 (first cured portion 2A) is provided on the layer 1 in the state containing the solvent 12, thereby preventing it from being prevented. The liquid 2' for forming the hardened portion 2 is accidentally infiltrated into a portion other than the target portion. As a result, the hardened portion 2 (first cured portion 2A) having a desired shape can be easily and surely formed. Further, the effect of the thickness of the layer 1 newly formed after the formation of the cured product based on the height of the upper surface of the cured material 6 as described above is complemented, and the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made special. Excellent.

Further, in the present embodiment, before the first sub-layer forming step, the third liquid supply step (1a) is performed, and the layer 1 (layer 1 formed using the layer forming composition 1') is not formed. A liquid (hardened portion forming liquid) 2' for forming the hardened portion 2 (third hardened portion 2C) and a third hardening step (1b) for curing the liquid 2' are formed on the stage M41. Hardened portion 2 (third hardened portion 2C).

Thereby, the hardened portion 2 (the cured portion 2 not containing the particles 11) embedded in the lowermost layer 1 can be formed, and the layer 1 not including the hardened portion 2 not containing the particles 11 can be formed, so that three-dimensionality can be obtained. The productivity of the shaped object 10 is particularly excellent. Further, in the three-dimensional shaped object 10 finally obtained, the cured portion 2 which constitutes the outer surface when the portion including the material containing no particles 11 is unified can be used in a side view, so that the appearance of the three-dimensional shaped object 10 as a whole can be particularly excellent. By.

Further, in the third liquid supply step, the liquid 2' is applied to the first region M411, and the liquid 2' is also applied to the second region M412. In the third curing step, the liquid 2' is applied to the first region M411. The hardened portion 2 (the third hardened portion 2C) is formed to be hardened, and the liquid 2' applied to the second region M412 is cured to form the cured product 6.

Thereby, not only the hardened portion 2 formed on the upper surface of the layer 1 can prevent the composition 1' from being accidentally left, but also the hardened portion 2 (the third hardened portion 2C) formed on the surface of the stage M41 (first region M411). Further, it is also possible to prevent the composition 1' from accidentally remaining on the upper surface of the hardened portion 2 (third hardened portion 2C) at the end of the layer forming step (first layer forming step). As a result, it is possible to more effectively prevent the occurrence of the above-described problem, and it is possible to make the dimensional accuracy and mechanical strength of the finally obtained three-dimensional shaped object particularly excellent.

Hereinafter, each step will be described.

≪3rd liquid imparting step≫

In the third liquid supply step, the liquid 2' for forming the cured portion 2 (the third cured portion 2C) is applied to the first region M411 of the stage M41 in which the layer 1 is not formed by the inkjet method (see 1a). ).

In this step, the liquid 2' is imparted to a portion corresponding to one of the finally obtained three-dimensional shaped articles 10. In the configuration shown in the drawing, the liquid 2' is given to a portion corresponding to the region near the outer surface when the three-dimensional shaped object 10 finally obtained is viewed from the side.

In this way, for example, in the three-dimensional shaped object 10 finally obtained, the cured portion 2 which constitutes the outer surface when the portion including the material containing no particles 11 is used in a unified view can be used, so that the appearance of the entire three-dimensional shaped object 10 can be improved. Particularly excellent.

In particular, in this step, since the liquid 2' is provided by the inkjet method, even if the pattern of the liquid 2' is given a fine shape, the liquid 2' can be imparted with good reproducibility. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made particularly high.

Further, in this step, the liquid 2' is also applied to the second region M412 of the stage M41.

The liquid 2' contains at least a polymerizable compound (unhardened curable resin material) (the liquid 2' given in the first liquid application step and the liquid 2' given in the second liquid application step) ).

Further, the liquid 2' will be described in detail later.

≪3rd hardening step≫

The liquid 2' applied to the first region M411 of the stage M41 is subjected to a specific hardening treatment thereafter to become the cured portion 2 (third cured portion 2C) (see 1b).

For example, when the liquid 2' contains a thermosetting polymerizable compound (thermosetting resin), it can be cured by heating, and the photocurable polymerizable compound (photocurable resin) is contained in the liquid 2'. In the case of the person, it can be hardened by irradiation of light.

Further, in this step, the liquid 2' applied to the second region M412 of the stage M41 is also subjected to the hardening treatment as described above to form the cured product 6.

Further, in order to form the hardened portion 2 having a specific thickness, a series of treatments including the application of the liquid 2' (liquid application step) and the curing of the liquid 2' (hardening step) may be repeated before the step described later. .

≪ layer formation step≫

In the layer forming step, a layer 1 (see 1c, 1d, 1j, 1k, 1q, 1r) having a specific thickness is formed using a composition (layer forming composition) 1' containing the particles 11 and the solvent 12.

In the first layer forming step, a composition containing the particles 11 and the solvent 12 (the composition for layer formation) is used on the platform (support) M41 in which the cured portion 2 (the third cured portion 2C) is provided. 1', forming a layer 1 (1c, 1d) having a specific thickness, in the layer forming step after the second and subsequent layers, in the layer 1 (in the configuration shown, the layer 1 of the bonding portion 3 is formed) A composition (layer-forming composition) 1' containing the particles 11 and the solvent 12 is used to form a new layer 1 (1j, 1k, 1q, 1r) having a specific thickness.

In addition, the composition (layer formation composition) 1' will be described in detail later.

Further, this step is carried out by embedding at least a part of the previously formed hardened portion 2 into the layer 1 newly formed in this step.

In other words, in the layer forming step in which the cured portion 2 (third cured portion 2C) formed in the third liquid application step is exposed on the outer surface, the cured portion 2 (third cured portion 2C) is used. In the layer formation step in which the hardened portion 2 (first cured portion 2A) formed in the first liquid application step is exposed to the outer surface, the layer is formed by embedding at least a part of the method (see 1d). The hardened portion 2 (first cured portion 2A) is embedded in at least a portion thereof (see 1k, 1r).

Thereby, for example, the stability of the shape of the hardened portion 2 formed on the upper surface side of the hardened portion 2 (the hardened portion 2 embedded in the layer 1 in this step) in the subsequent step is improved. As a result, the dimensional accuracy of the three-dimensional shaped object 10 is particularly excellent.

Further, for example, a second hardened portion is formed in a portion of the layer 1 in which the hardened portion 2 (the cured portion 2 embedded in the layer 1 is buried in this step) is in contact with the hardened portion 2 by a subsequent step. In the case of 2B (refer to 1h, 1i, 1o, 1p), it is possible to more effectively prevent an unexpected height difference between the hardened portion 2 and the second hardened portion 2B buried in the layer 1 in this step. As a result, the dimensional accuracy of the three-dimensional shaped object 10 is particularly excellent.

In this step, the squeegee as the planarization mechanism M42 is used to form the layer 1 as a watch. Face flattened.

Further, in this step, when the layer 1 is formed in the first region M411 by using the planarizing mechanism M42, the thickness of the layer 1 newly formed after the formation of the cured material 6 is determined based on the height of the upper surface of the cured material 6. . In other words, the flattening mechanism M42 is brought into contact with the upper surface of the cured product 6, and the layer 1 having a specific thickness is formed with the flattening mechanism M42 abutting on the height (abutting surface) of the cured product 6.

Further, in this step, a flattening mechanism (for example, a roller or the like) other than the squeegee may be used.

This step is carried out so as not to leave the composition 1' (especially the particles 11) on the upper surface of the hardened portion 2 buried in this step.

Thereby, the adhesion between the cured portion 2 and the cured portion 2 (first cured portion 2A) formed in the subsequent first liquid application step can be prevented from being lowered, and the mechanical strength of the finally obtained three-dimensional shaped article 10 can be prevented. Excellent. Moreover, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made excellent.

In the configuration shown in the figure, the thickness of the layer 1 formed in this step is the same as the thickness of the embedded hardened portion 2 (the third cured portion 2C and the first cured portion 2A), but may be used in this step. The thickness of the layer 1 to be formed is smaller than the thickness of the embedded hardened portion 2 (the third cured portion 2C and the first cured portion 2A). For example, by adjusting the height adjustment of the flattening mechanism M42 by pressing the cured material 6 with a specific pressing force, the stress applied to the flattening mechanism M42 can be hardened in the portion where the hardened portion 2 or the hardened material 6 is not present. The portion of the portion 2 or the cured material 6 is low, so that the height of the layer 1 formed by the flattening mechanism M42 is lower than the height of the hardened portion 2 buried in this step. Thereby, the pressing force applied to the upper surface of the hardened portion 2 embedded in this step by the flattening mechanism M42 can be made relatively large, so that the composition 1' (especially the particle 11) can be more effectively prevented. ) remains on the upper surface of the hardened portion 2 buried in this step.

The thickness of the layer 1 formed in this step is not particularly limited, and is, for example, preferably 20 μm or more and 500 μm or less, and more preferably 30 μm or more and 150 μm or less.

Thereby, the productivity of the three-dimensional shaped object 10 can be made sufficiently excellent, and the occurrence of unexpected unevenness in the three-dimensional shaped object 10 to be produced can be more effectively prevented, so that the dimensional accuracy of the three-dimensional shaped object 10 is particularly excellent. By.

The viscosity of the layer forming composition 1' in the layer forming step is preferably 500 mPa. Above s and 1000000mPa. s below.

Thereby, this step can be performed more efficiently, so that the productivity of the three-dimensional shaped object 10 can be made particularly excellent. In the present specification, the viscosity refers to a value measured at 25 ° C using an E-type viscometer (VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.).

≪1st liquid imparting step≫

In the first liquid application step, a liquid for forming the hardened portion 2 (first hardened portion 2A) is applied to a region including the surface (upper surface) of the layer 1 in a state in which the solvent 12 is formed in the layer forming step. 2' (refer to 1e, 1l).

Thus, when the liquid 2' is imparted, the layer 1 to which the liquid 2' is imparted is in a state containing the solvent 12, in other words, the gap of the particles 11 in the layer 1 is filled with a solvent, whereby the liquid can be preferably prevented. 2, the inside of the layer 1 is accidentally infiltrated, and as a result, in the first hardening step, the hardened portion 2 (first cured portion 2A) can be formed on the upper surface of the layer 1 in a desired shape.

In particular, in the present embodiment, the first liquid application step is performed as follows in the surface of the layer 1 including the hardened portion 2 (the first cured portion 2A and the third cured portion 2C) which are embedded; The liquid 2' is provided in a region where the layer 1 is not overlapped with the hardened portion 2 (the first cured portion 2A and the third cured portion 2C) (see 1e and 1l).

Previously, when a new layer (upper layer) was formed on the surface of the already formed layer (lower layer), and a joint portion (hardened portion) was formed in the layer (upper layer), the combination should be formed in the layer (upper layer). When the portion (hardened portion) has a region that does not overlap with the joint portion (hardened portion) formed in the lower layer, the joint portion (hardened portion) of the target shape cannot be formed, and the dimensional accuracy of the finally obtained three-dimensional shape is likely to occur. The problem of lowering, but by imparting the liquid 2' to the layer 1 containing the solvent 12, even if it is formed in the hardened portion of the upper layer, it is not formed in the lower layer. In the case where the hardened portions overlap, it is possible to surely further prevent the occurrence of the above problem. Therefore, when the first liquid application step is provided, the above-described effects are exhibited more remarkably, and the first liquid application step is a step of including the hardened portion (the first hardened portion, the third portion). Among the surfaces of the layer of the hardened portion, a liquid is provided in a region where the layer is not overlapped with the hardened portion (the first cured portion and the third cured portion) when the layer is viewed in plan.

Moreover, in this step, since the liquid 2' is provided by the inkjet method, even if the pattern of the liquid 2' is given a fine shape, the liquid 2' can be imparted with good reproducibility. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made particularly high.

Further, in this step, the liquid 2' is also applied to the second region M412 of the stage M41 (in the configuration shown in the figure, the surface of the cured material 6 formed in the third curing step).

≪The first hardening step≫

In the first hardening step, specific hardening is applied to the liquid 2' (the liquid 2' to the region containing the surface (upper surface) of the layer 1 containing the solvent 12 in the first liquid application step). The treatment is performed to form the cured portion 2 (first cured portion 2A) (see 1f and 1m).

Further, in this step, the liquid 2' applied to the second region M412 of the stage M41 in the first liquid application step is also applied to the cured product formed in the third curing step in the configuration shown in the figure. The liquid 2') on the upper surface of the surface 6 is subjected to a hardening treatment as described above to form a cured product 6.

≪ Solvent removal step≫

In the solvent removal step, the solvent 12 is removed from the layer 1 (see 1g, 1n).

Thereby, a space 4 in which the solvent 12 or the like is not present is formed between the particles 11 constituting the layer 1. This space 4 functions as an absorbing portion that absorbs the liquid 2' in the subsequent second liquid application step.

This step may be carried out under any conditions as long as the solvent 12 is removed from the layer 1, and may be carried out, for example, by heat treatment, reduced pressure treatment, air blowing, or the like.

When the step is performed by heating, the constituent material of the layer 1 or the like (particles 11. The type of the solvent 12 or the like is different, and the heating temperature is, for example, preferably 30 ° C or more and 100 ° C or less, more preferably 60 ° C or more and 95 ° C or less.

Thereby, it is possible to prevent the unexpected modification of the constituent materials of the layer 1 or the like, or the unexpected deformation of the layer 1 or the like, and to remove the solvent 12 efficiently, and the productivity of the three-dimensional shaped object 10 can be made particularly excellent.

Further, even in the previous step (first liquid application step), the liquid 2' is applied to the upper surface of the layer 1 from which the solvent 12 is to be removed in this step, and the liquid 2' is also subjected to the hardening step (first hardening step). The hardened portion 2 (the first cured portion 2A) having a high shape stability is subjected to the hardening treatment, and even if the solvent 12 is removed in this step, the accidental deformation is effectively prevented.

≪Second liquid application step≫

In the second liquid application step, the liquid 2' for forming the cured portion 2 (second cured portion 2B) is applied to the layer 1 in a state in which the solvent 12 is removed, and the liquid 2' is infiltrated into the layer 1 (refer to 1h, 1o).

Thereby, in the second hardening step thereafter, the hardened portion 2 (the second cured portion 2B) can be formed inside the layer 1 (the portion which is originally the space 4 between the particles 11).

Moreover, in this step, since the liquid 2' is provided by the inkjet method, even if the pattern of the liquid 2' is given a fine shape, the liquid 2' can be imparted with good reproducibility. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made particularly high.

≪The second hardening step≫

In the second hardening step, the liquid 2' (the liquid 2' which penetrates into the inside of the layer 1 (the portion which is originally the space 4 between the particles 11) is subjected to a specific hardening treatment in the second liquid application step. The hardened portion 2 (second hardened portion 2B) is formed (see 1i, 1p).

Thereby, the joint portion 3 in which the particles 11 are joined by the hardened portion 2 (the second cured portion 2B) can be formed. Since the joint portion 3 formed in this manner contains the particles 11 and the cured portion 2 (second cured portion 2B), it is particularly excellent in hardness or mechanical strength. Therefore, the final three-dimensional The shape 10 is particularly excellent in mechanical strength and more reliable in preventing accidental deformation.

≪Unbound particle removal step≫

Then, after repeating one of the series of steps as described above (refer to 1s), as a post-processing step, an unbound particle removing step is performed, which removes the unbonded portion of the particles 11 constituting each layer 1 which is not bonded by the hardened portion 2. (unbound particles) (see 1t). Thereby, the three-dimensional shaped object 10 is taken out.

Specific examples of the method include a method of removing unbound particles by a brush or the like, a method of removing unbound particles by suction, a method of blowing a gas such as air, and a method of applying a liquid such as water (for example). A method of immersing a layered body obtained in the above manner in a liquid, a method of blowing a liquid, or the like, a method of imparting vibration such as ultrasonic vibration, or the like. Further, two or more methods selected from the group consisting of these may be combined. More specifically, a method of immersing in a liquid such as water after blowing a gas such as air, or a method of imparting ultrasonic vibration in a state of being immersed in a liquid such as water may be mentioned. Among them, a method of imparting a liquid containing water to the layered body obtained as above (especially, a method of immersing in a liquid containing water) is preferably employed.

According to the manufacturing method of the present invention as described above, it is possible to efficiently manufacture a three-dimensional shaped article excellent in dimensional accuracy, excellent in mechanical strength and durability. Moreover, since the yield of the three-dimensional shaped object is improved, it is also advantageous from the viewpoint of reducing the manufacturing cost of the three-dimensional shaped object.

[Second Embodiment]

Next, a second embodiment of the method for producing a three-dimensional shaped article of the present invention will be described.

Fig. 5, Fig. 6, Fig. 7, and Fig. 8 are cross-sectional views schematically showing the second embodiment of the method for producing a three-dimensional shaped article of the present invention. In the following description, differences from the above-described embodiments will be mainly described, and the description of the same matters will be omitted.

As shown in FIG. 5, FIG. 6, FIG. 7, and FIG. 8, the manufacture of the three-dimensional shaped object 10 of the present embodiment The method has the same steps as those of the above embodiment, but the method of determining the thickness of the layer 1 formed in the layer forming step is different from that of the above embodiment.

That is, in the present embodiment, the height (thickness) of the cured product 6 formed by using the liquid 2' is measured by the height measuring means M7, and based on the measurement result, it is determined that the cured product 6 is newly formed after formation. The thickness of layer 1.

With such a configuration, for example, it is not necessary to bring the flattening mechanism M42 into contact with the cured material 6, so that accidental wear or deformation of the flattening mechanism M42 can be prevented, and the life of the flattening mechanism M42 or the three-dimensional shape can be obtained. The maintenance of the manufacturing apparatus of 10 becomes easy and the like. Further, even when the area of the cured product 6 is relatively small, the height (thickness) of the cured product 6 can be accurately measured, and the thickness of the newly formed layer 1 can be appropriately and accurately determined. Therefore, the amount of the liquid 2' used for forming the cured product 6 can be reduced, and it is preferable from the viewpoint of reducing the production cost of the three-dimensional shaped object 10 and saving resources.

<Liquid (liquid for forming a hardened portion)>

Next, the liquid (the liquid for forming a hardened portion) for producing the three-dimensional shaped article of the present invention will be described in detail.

The liquid (liquid for forming a hardened portion) 2' contains at least a constituent component (including a precursor) of the cured portion 2.

(curable resin material (polymerizable compound))

The liquid 2' is a resin material (polymerizable compound) which can carry out a hardening reaction.

Thereby, the strength and the like of the formed hardened portion 2 can be made particularly excellent. Further, in the second curing portion 2B, the bonding agent for bonding the particles 11 can function as a good function, and the mechanical strength and shape stability of the three-dimensional shaped object 10 can be excellent. Further, since the heat resistance of the hardened portion 2 is excellent, it is possible to more effectively prevent the occurrence of accidental deformation of the hardened portion 2 of the heat history accumulated with the buildup, or accidental modification or deterioration of the material. The reliability of the three-dimensional shaped object 10 is excellent.

Examples of the curable resin material (polymerizable compound) include a thermosetting tree. a variety of photocurable resins such as a visible light curable resin (narrow photohardenable resin), an ultraviolet curable resin, and an infrared curable resin which are cured by light in the visible light region; and an X-ray curable resin; One type or a combination of two or more types selected from the group consisting of these may be used.

Among these, an ultraviolet curable resin (polymerizable compound) is particularly preferable from the viewpoints of the mechanical strength of the three-dimensional shaped article 10, the productivity of the three-dimensional shaped article 10, and the storage stability of the liquid 2'.

As the ultraviolet curable resin (polymerizable compound), it is preferred to use a radical species or a cationic species generated by a photopolymerization initiator by ultraviolet irradiation to initiate addition polymerization or ring-opening polymerization to cause polymerization. Object. Examples of the polymerization pattern of the addition polymerization include a radical, a cation, an anion, a metathesis, and a coordination polymerization. Further, examples of the polymerization pattern of the ring-opening polymerization include cation, anion, radical, metathesis, and coordination polymerization.

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

The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound, a polyfunctional polymerizable compound, or a mixture thereof. Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.), or esters thereof, guanamines, and the like. . As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound can be used.

In particular, the liquid 2' is preferably an acrylic polymerizable compound such as acrylic acid, methacrylic acid or the like (for example, an ester compound).

Thereby, the strength of the finally obtained three-dimensional shaped object 10 can be made particularly excellent.

Further, an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group may also be used. An addition reaction product of an acid ester or a guanamine with an isocyanate or an epoxy, a dehydration condensation reaction product with a carboxylic acid, or the like. Further, an addition reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an oxime amine with an alcohol, an amine or a thiol may be used, and further, a halogen group or A substituted carboxylic acid ester such as a toluenesulfoxy group or a substituted substituent of a decylamine and an alcohol, an amine or a thiol.

Specific examples of the radically polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyol compound are, for example, a (meth) acrylate, and any of a monofunctional group and a polyfunctional group can be used.

Specific examples of the monofunctional (meth) acrylate include toluyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ethyl methyl acrylate, methyl (meth) acrylate, (meth) acrylate Ester, tetrahydrofurfuryl (meth)acrylate, and the like.

Specific examples of the difunctional (meth) acrylate include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and 1,3-butanediol II ( Methyl) acrylate, tetramethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, hexane diol di(meth) acrylate Ester, 1,4-cyclohexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and the like.

Specific examples of the trifunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolpropane. Alkylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloxypropylpropyl Ether, isocyanuric acid alkylene oxide modified tri(meth)acrylate, dipentaerythritol tris(meth)acrylate, tris((meth)propenyloxyethyl) isocyanurate, hydroxyl Neopentaldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, and the like.

Specific examples of the tetrafunctional (meth) acrylate include, for example, pentaerythritol. Tetra(meth)acrylate, sorbitol tetra(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol tetrakis(meth)acrylate, and pentaerythritol ethoxylate Tetra (meth) acrylate or the like.

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

Specific examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate, and phosphazene alkylene oxide-modified hexamethyl group. Acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Examples of the polymerizable compound other than the (meth) acrylate include an itaconate, a crotonate, a methacrylate, a maleate, and the like.

Examples of the itaconate include ethylene glycol diconconate, propylene glycol diconconate, 1,3-butylene glycol diconconate, and 1,4-butanediol diconiconic acid. Ester, tetramethylene glycol diconconate, pentaerythritol diconconate, sorbitol tetraconate, and the like.

Examples of the butenoic acid ester include ethylene glycol dimethyl acrylate, tetramethylene glycol dimethyl acrylate, pentaerythritol dimethyl acrylate, and sorbitol tetradicrotonate. )Wait.

Examples of the methacrylate include ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, and sorbitol tetramethacrylate.

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

Further, specific examples of the monomer of the decylamine of the unsaturated carboxylic acid and the aliphatic polyamine compound include methylene bis-acrylamide, methylene bis-methyl acrylamide, and 1,6. - hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, diethylidene triamine methacrylamide, benzodimethyl bis decylamine, phthalic acid Bis-methyl methacrylamide and the like.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferable, and as such a specific example, for example, it is 2 for one molecule. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule of a polyisocyanate compound having one or more isocyanate groups added to a vinyl monomer having a hydroxyl group represented by the following formula (1) Compounds, etc.

CH ₂ =C(R1)COOCH ₂ CH(R2)OH (1)

(wherein, in the formula (1), R1 and R2 each independently represent H or CH ₃ )

In the present invention, a cationic ring-opening polymerizable compound having one or more cyclic ether groups such as an epoxy group or an oxetanyl group in the molecule is preferably used as the ultraviolet curable resin (polymerizable property). Compound).

The cationically polymerizable compound may, for example, be a curable compound containing a ring-opening polymerizable group. Among them, a curable compound containing a heterocyclic group is particularly preferred. Examples of such a curable compound include an epoxy derivative, an oxetane derivative, a tetrahydrofuran derivative, a cyclic lactone derivative, and a cyclic carbonate derivative. A cyclic imine ether such as an oxazoline derivative or a vinyl ether is preferable, and among them, an epoxy derivative, an oxetane derivative, and a vinyl ether are preferable.

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

Specific examples of the specific compound of the glycidyl ethers include diglycidyl ethers (for example, ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether), and trifunctional or higher glycidyl ethers (for example, three). Hydroxymethylethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trihydroxyethyl isocyanurate, etc.), tetrafunctional or higher glycidyl ethers (eg sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxy (phenol novolac resin) Polycyclohexyl epoxy methyl ether or the like), oxetane or the like.

As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. "alicyclic The epoxy group means a partial structure in which a double bond of a cycloolefin ring such as a cyclopentenyl group or a cyclohexenyl group is epoxidized by a suitable oxidizing agent such as hydrogen peroxide or a peracid.

The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy compound having two or more epoxycyclohexane groups or epoxycyclopentyl groups in one molecule. Specific examples of the alicyclic epoxy compound include 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl)methyl ester, and hexane. Di(3,4-epoxycyclohexyl) acid, bis(3,4-epoxycyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl)ether, adipic acid (2,3-epoxy-6-methylcyclohexylmethyl) ester, dicyclopentadiene dioxide, and the like.

The glycidyl compound having a usual epoxy group which does not have an alicyclic structure in the molecule may be used alone, or may be used in combination with the above alicyclic epoxy compound.

Examples of such a usual glycidyl compound include a glycidyl ether compound or a glycidyl ester compound, and a glycidyl ether compound is preferably used in combination.

Specific examples of the glycidyl ether compound include 1,3-bis(2,3-epoxypropoxy)benzene, bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol. . Novolak type epoxy resin, cresol. An aromatic glycidyl ether compound such as a novolak type epoxy resin or a trisphenol methane type epoxy resin; 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane An aliphatic glycidyl ether compound such as triglycidyl ether. Examples of the glycidyl ester include glycidyl esters of a secondary linoleic acid dimer.

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

Further, the liquid 2' may be a polymerizable compound containing an anthrone-based polymerizable compound (an oxime-based resin by polymerization).

Thereby, a three-dimensional shaped object 10 composed of, for example, a rubber-like elastic material can be preferably produced. As a result, the movable portion and the deformation based on the elastic deformation can be preferably manufactured. The three-dimensional shape of the Ministry.

The content of the curable resin material in the liquid 2' is preferably 80% by mass or more, and more preferably 85% by mass or more. Thereby, the mechanical strength and the like of the finally obtained three-dimensional shaped article 10 can be made particularly excellent.

(other ingredients)

Further, the liquid 2' may be a component other than the above. Examples of such a component include various coloring agents such as a pigment and a dye; a dispersing agent; a surfactant; a polymerization initiator; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (humectant); Mold inhibitor; preservative; antioxidant; UV absorber; chelating agent; pH adjuster; tackifier; filler; anti-agglomerating agent; defoamer.

In particular, by allowing the liquid 2' to contain a coloring agent, a three-dimensional shaped object 10 colored in a color corresponding to the color of the coloring agent can be obtained.

In particular, by containing a pigment as a coloring agent, the light resistance of the liquid 2' and the three-dimensional shaped article 10 can be improved. As the pigment, any of an inorganic pigment and an organic pigment can be used.

Examples of the inorganic pigments include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and black, iron oxide, and titanium oxide, and one type or a combination of them can be used. 2 or more types.

Among the above inorganic pigments, in order to exhibit a preferable white color, titanium oxide is preferred.

Examples of the organic pigment include an azo pigment such as an insoluble azo pigment, a condensed azo pigment, an azo lake, and a chelating azo pigment; a phthalocyanine pigment, an anthraquinone and a purple ketone pigment, an anthraquinone pigment, and a quinone. Ketone pigment, two a polycyclic pigment such as an alkane pigment, a thioindigo pigment, an isoindolinone pigment, or a quinacridone pigment; a dye chelate (for example, a basic dye type chelate compound, an acid dye type chelate compound, etc.); dyed color Precipitation (basic dye type lake, acid dye type lake); nitro pigment; nitroso pigment; aniline black; luminescent pigment; etc.; can be used in one or a combination of two selected from More than one species.

In the case where the liquid 2' is a pigment-containing one, the average particle diameter of the pigment is preferably 300. Below nm, more preferably 50 nm or more and 250 nm or less. Thereby, the discharge stability of the liquid 2' or the dispersion stability of the pigment in the liquid 2' can be made particularly excellent, and an image excellent in image quality can be formed.

Further, in the present specification, the average particle diameter means an average particle diameter based on a volume, and can be obtained, for example, by using a Coulter counter size distribution analyzer (TA-manufactured by COULTER ELECTRONICS INS) Type II), a dispersion obtained by adding a sample to methanol and dispersing it for 3 minutes using an ultrasonic disperser was measured using an aperture of 50 μm.

In addition, as the dye, for example, an acid dye, a direct dye, a reactive dye, a basic dye, or the like can be used, and one type or a combination of two or more types selected from the group consisting of these may be used.

When the liquid 2' is a coloring agent, the content of the coloring agent in the liquid 2' is preferably 1% by mass or more and 20% by mass or less. Thereby, particularly excellent concealability and color reproducibility can be obtained.

In particular, when the liquid 2' is a coloring agent containing titanium oxide, the content of the titanium oxide in the liquid 2' is preferably 12% by mass or more and 18% by mass or less, and more preferably 14% by mass or more. And 16% by mass or less. Thereby, particularly excellent concealability can be obtained.

When the liquid 2' contains a pigment, if the dispersant is further contained, the dispersibility of the pigment can be further improved. The dispersing agent is not particularly limited, and examples thereof include a dispersing agent conventionally used for preparing a pigment dispersion liquid such as a polymer dispersing agent. Specific examples of the polymer dispersant include, for example, one or more of the following components: a polyoxyalkylene alkyl polyalkyleneamine, a vinyl polymer and a copolymer, and an acrylic polymer. And copolymers, polyesters, polyamines, polyimines, polyurethanes, amine polymers, cerium-containing polymers, sulfur-containing polymers, fluoropolymers, and epoxy resins.

If the liquid 2' is a surfactant, the friction resistance of the three-dimensional shaped object 10 can be made even better. The surfactant is not particularly limited, and for example, a polyester-modified anthrone or a polyether-modified anthrone such as an anthrone-based surfactant can be used. The polydimethylsiloxane or polyester modified polydimethyloxane is modified with a polyether.

Further, the liquid 2' may also be a solvent-containing one. Thereby, the viscosity adjustment of the liquid 2' can be preferably performed, and even if the liquid 2' is a component containing a high viscosity, the discharge stability of the liquid 2' by the inkjet method can be made particularly 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; ethyl acetate and n-propyl acetate; Acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl a ketone such as n-butyl ketone, diisopropyl ketone or acetonitrile; or an alcohol such as ethanol, propanol or butanol; or a combination of two or more selected from the group consisting of the above-mentioned ones.

Moreover, the viscosity of the liquid 2' is preferably 2 mPa. Above s and 30mPa. Below s, more preferably 5mPa. Above s and 20mPa. s below. Thereby, the discharge stability of the liquid 2' by the inkjet method can be made particularly excellent.

Further, a plurality of liquids 2' may be used in the production of the three-dimensional shaped object 10.

For example, the liquid 2' used in the first liquid application step (the liquid 2' for forming the first cured portion 2A) and the liquid 2' used in the second liquid application step (for forming the second hardened portion 2B) The liquid 2') and the liquid 2' (the liquid 2' used to form the third cured portion 2C) used in the third liquid application step may be the same or different.

Further, a liquid 2' (color ink) containing a coloring agent and a liquid 2' (transparent ink) containing no coloring agent may be used. Thereby, for example, a liquid 2' containing a coloring agent can be used as the liquid 2' imparted to a region which affects the color tone in the appearance of the three-dimensional shaped object 10, and a liquid 2' not containing a coloring agent can be used as the three-dimensional shaped object. The appearance of 10 does not affect the liquid 2' of the area of the hue. Further, it is also possible to use a plurality of liquids 2' in the following manner, that is, in the finally obtained three-dimensional shaped object 10, a liquid containing no coloring agent is provided on the surface other than the region formed using the liquid 2' containing the coloring agent. The area formed by 2' (coating).

Further, for example, a plurality of liquids 2' containing coloring agents of different compositions may be used. With this, By the combination of these liquids 2', the color reproduction area that can be expressed can be made wider.

In the case of using a plurality of liquids 2', it is preferred to use at least a liquid blue 2', a reddish purple (dark red) liquid 2', and a yellow liquid 2'. Thereby, by combining these liquids 2', the color reproduction area which can be expressed can be made wider.

Further, by using a white liquid 2' in combination with other colored liquids 2', for example, the following effects can be obtained. In other words, the three-dimensional shaped object 10 finally obtained can be made to have a first region having a liquid 2' to which white is applied, and a white region which is overlapped with the first region and which is disposed on the outer surface side of the first region. It is the area (the second area) of the liquid 2' other than the colored liquid. Thereby, the first region of the liquid 2' to which white is imparted can exhibit concealability, and the chroma of the three-dimensional shaped object 10 can be further improved.

<Composition for layer formation>

Next, the layer forming composition used in the production of the three-dimensional shaped article of the present invention will be described in detail.

The composition (layer forming composition) 1' contains the particles 11 as a filler and the solvent 12 as a dispersion medium in which the particles 11 are dispersed.

By using the layer forming composition 1', the mechanical strength and the like of the finally obtained three-dimensional shaped article 10 can be particularly excellent, and the fluidity of the composition 1' can be excellent, and the particles can be effectively prevented. The agglomeration of 11 or the like makes the handling (operability) of the composition 1' at the time of manufacture particularly excellent. Further, as described above, the first curing portion 2A and the second curing portion 2B which are different from each other in the positional relationship between the layers 1 formed using the composition 1' can be easily and surely produced, and the three-dimensional shape can be produced. The object 10 is excellent in mechanical strength and the like and is excellent in dimensional accuracy.

(particle)

The layer forming composition 1' contains a plurality of particles 11.

The particles 11 are preferably of higher hardness.

Thereby, the mechanical strength and the like of the finally obtained three-dimensional shaped object 10 can be made particularly excellent. By.

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

The particles 11 are preferably porous having a pore open to the outside and subjected to a hydrophobic treatment.

With this configuration, when the three-dimensional shaped object 10 is produced (in the second liquid application step), the curable resin material constituting the liquid 2' or the reaction product thereof (hereinafter, collectively referred to as "etc." The resin material ") is preferably infiltrated into the pores to exert an anchoring effect. As a result, the bonding strength of the particles 11 is particularly excellent, and as a result, the mechanical strength of the entire three-dimensional shaped article 10 can be particularly excellent. Further, by allowing the resin material constituting the liquid 2' to enter the pores of the particles 11, the unexpected wetting and diffusion of the liquid 2' can be effectively prevented. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made higher.

Examples of the constituent material of the particles 11 include inorganic materials, organic materials, composites thereof, and the like.

Examples of the inorganic material constituting the particles 11 include various metals or metal compounds. Examples of the metal compound include various metal oxides such as cerium oxide, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide, magnesium oxide, and potassium titanate; magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and the like. Various metal hydroxides; various metal nitrides such as tantalum nitride, titanium nitride, aluminum nitride; various metal carbides such as tantalum carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metals such as calcium carbonate and magnesium carbonate Carbonate; sulfates of various metals such as calcium sulfate and magnesium sulfate; citrates of various metals such as calcium citrate and magnesium citrate; phosphates of various metals such as calcium phosphate; boric acid of various metals such as aluminum borate and magnesium borate a salt; or a compound thereof or the like.

Examples of the organic material constituting the particles 11 include a synthetic resin and a natural polymer, and more specifically, a polyethylene resin; polypropylene; polyethylene oxide; polypropylene oxide; polyethyleneimine; Polystyrene; polyurethane; polyurea; polyester; anthrone Resin; fluorenone acrylate resin; polymethyl methacrylate or the like using (meth) acrylate as a polymer constituting a monomer; methyl methacrylate crosspolymer or the like using (meth) acrylate as a constituent monomer Crosslinked polymer (ethylene-acrylic copolymer resin, etc.); nylon 12, nylon 6, polyamine resin such as copolymerized nylon; polyimine, carboxymethyl cellulose, gelatin, starch, chitin, chitosan, etc. .

Among them, the particles 11 preferably contain a metal oxide, and more preferably contain cerium oxide.

Thereby, characteristics such as mechanical strength and light resistance of the three-dimensional shaped article can be made particularly excellent.

Further, in particular, if the particles 11 are those containing cerium oxide, the above effects can be exhibited more remarkably. Further, since the flowability of the cerium oxide is also excellent, it is advantageous in the formation of a layer having a higher uniformity of thickness, and is also advantageous in that the productivity and dimensional accuracy of the three-dimensional shaped article are particularly excellent.

The particles 11 may also be surface treated by performing a hydrophobization treatment or the like.

The hydrophobization treatment applied to the particles 11 may be any treatment for improving the water repellency of the particles (parent particles), but it is preferably a hydrocarbon group.

Thereby, the water repellency of the particles 11 can be made higher. Further, it is possible to easily and surely make the uniformity of the degree of dehydration treatment of each of the surfaces of the respective particles 11 or the surface of the particles 11 (when the pores are open to the outside, the surface including the inside of the pores) becomes higher. By.

The compound used for the hydrophobization treatment is preferably a decane compound containing a decyl group. Specific examples of the compound which can be used for the hydrophobization treatment include hexamethyldiazepine, dimethyldimethoxydecane, diethyldiethoxydecane, and 1-propenylmethyldichloride. Decane, propyldimethylchlorodecane, propylmethyldichlorodecane, propyltrichlorodecane, propyltriethoxydecane, propyltrimethoxydecane, styrylethyltrimethoxydecane, ten Tetraalkyl trichlorodecane, 3-thiocyanate propyl triethoxy decane, p-tolyl dimethyl chlorodecane, p-tolyl methyl dichloro decane, p-tolyl trichloro decane, p-tolyl Trimethoxydecane, p-tolyltriethoxydecane, di-n-propyldi-n-propoxyoxydecane, diisopropyldiisopropoxydecane, di-n-butyldi-n-butoxydecane , di-t-butyldi-second butoxydecane, di-t-butyldi-t-butoxydecane, octadecyltrichlorodecane, octadecylmethyldiethoxydecane , octadecyltriethoxydecane, octadecyltrimethoxydecane, octadecyldimethylchlorodecane, octadecylmethyldichlorodecane, octadecyl Oxydichlorosilane, 7-octenyldimethylchloromethane, 7-octenyltrichlorodecane, 7-octenyltrimethoxydecane, octylmethyldichlorodecane, octyldimethyl chloride Decane, octyltrichlorodecane, 10-undecenyldimethylchlorodecane, undecyltrichlorodecane, vinyldimethylchlorodecane, methyloctadecyldimethoxydecane, methyl Dodecyldiethoxydecane, methyloctadecyldimethoxydecane, methyloctadecyldiethoxydecane, n-octylmethyldimethoxydecane, n-octylmethyl Diethoxydecane, tridecyldimethylchlorodecane, tridecyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, A Isopropoxydecane, methyl-n-butoxydecane, methyltri-t-butoxydecane, methyltri-t-butoxydecane, ethyltrimethoxydecane, ethyltriethoxy Base decane, ethyl tri-n-propoxy decane, ethyl isopropoxy decane, ethyl-n-butoxy decane, ethyl tri-second butoxy decane, ethyl tri-tert-butoxy Decane, n-propyl trimethyl Oxydecane, isobutyltrimethoxydecane, n-hexyltrimethoxydecane, cetyltrimethoxydecane, n-octyltrimethoxydecane, n-dodecyltrimethoxynonane, n-octadecane Trimethoxy decane, n-propyl triethoxy decane, isobutyl triethoxy decane, n-hexyl triethoxy decane, cetyl triethoxy decane, n-octyl triethoxy decane , n-dodecyltrimethoxydecane, n-octadecyltriethoxydecane, 2-[2-(trichlorodecylalkyl)ethyl]pyridine, 4-[2-(trichlorodecanealkyl)B Pyridine, diphenyldimethoxydecane, diphenyldiethoxydecane, 1,3-(trichlorodecylmethyl)heptadecane, dibenzyldimethoxydecane, dibenzyl Diethoxy decane, phenyl trimethoxy decane, phenylmethyl dimethoxy decane, phenyl dimethyl methoxy decane, phenyl dimethoxy decane, phenyl diethoxy decane, Phenylmethyldiethoxydecane, phenyldimethylethoxydecane, benzyltriethoxydecane, benzyltrimethoxydecane, benzylmethyldimethoxydecane, benzyldimethyl Methoxy Alkane, benzyl dimethoxydecane, benzyl diethoxy decane, benzyl methyl diethoxy decane, benzyl dimethyl ethoxy decane, benzyl triethoxy decane, dibenzyl Methoxydecane, dibenzyldiethoxydecane, 3-ethoxymethoxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, allyltrimethoxydecane, allyl Triethoxy decane, 4-aminobutyl triethoxy decane, (aminoethylaminomethyl) phenethyltrimethoxy decane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 6-(aminohexylaminopropyl)trimethoxynonane, P-aminophenyl trimethoxy decane, p-aminophenyl ethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl ethoxy decane, 3-aminopropyl trimethoxy decane , 3-aminopropyltriethoxydecane, ω-aminoundecyltrimethoxydecane, pentyltriethoxydecane, Benzoxasilepine dimethyl ester, 5-(bicycloheptenyl)triethoxy Decane, bis(2-hydroxyethyl)-3-aminopropyltriethyl Oxydecane, 8-bromooctyltrimethoxydecane, bromophenyltrimethoxydecane, 3-bromopropyltrimethoxydecane, n-butyl ester trimethoxydecane, 2-chloromethyltriethoxydecane , chloromethyl methyl diethoxy decane, chloromethyl methyl diisopropoxy decane, p-(chloromethyl)phenyl trimethoxy decane, chloromethyl triethoxy decane, chlorophenyl three Ethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 2-(4-chlorosulfonylphenyl) Ethyltrimethoxydecane, 2-cyanoethyltriethoxydecane, 2-cyanoethyltrimethoxydecane, cyanomethylphenethyltriethoxydecane, 3-cyanopropyltriethoxy Decane, 2-(3-cyclohexenyl)ethyltrimethoxydecane, 2-(3-cyclohexenyl)ethyltriethoxydecane, 3-cyclohexenyltrichlorodecane, 2-( 3-cyclohexenyl)ethyltrichlorodecane, 2-(3-cyclohexenyl)ethyldimethylchlorodecane, 2-(3-cyclohexenyl)ethylmethyldichlorodecane, ring Hexyl dimethyl chlorodecane, cyclohexylethyl dimethoxy decane, cyclohexyl methyl dichloro decane, cyclohexyl methyl dimethyl Oxoxane, (cyclohexylmethyl)trichlorodecane, cyclohexyltrichlorodecane, cyclohexyltrimethoxydecane, cyclooctyltrichlorodecane, (4-cyclooctenyl)trichlorodecane, cyclopentyl Chlorodecane, cyclopentyltrimethoxydecane, 1,1-diethoxy-1-indanyl-3-ene, 3-(2,4-dinitrophenylamino)propyltriethyl Oxydecane, (dimethylchloroindolyl)methyl-7,7-dimethylnorbornane, (cyclohexylaminomethyl)methyldiethoxydecane, (3-cyclopentadienyl) Propyl)triethoxydecane, N,N-diethyl-3-aminopropyl)trimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2- (3,4-epoxycyclohexyl)ethyltriethoxydecane, (decyloxymethyl)triethoxydecane, 2-hydroxy-4-(3-triethoxypropoxy)diphenyl Ketone, 3-(p-methoxyphenyl)propylmethyldichlorodecane, 3-(p-methoxyphenyl)propyltrichlorodecane, p-(methylphenethyl)methyldichlorodecane , p-(methylphenethyl)trichlorodecane, p-(methylphenethyl)dimethylchlorodecane, 3-morpholinylpropyltrimethoxydecane, (3-glycidoxypropyl) A Diethoxy decane, 3 - glycidoxypropyltrimethoxydecane, 1,2,3,4,7,7,-hexachloro-6-methyldiethoxydecyl-2-derivative Alkene, 1,2,3,4,7,7,-hexachloro-6-triethoxydecyl-2-derivative Alkene, 3-iodopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, (decylmethyl)methyldiethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyldimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, methyl {2-(3-trimethoxydecylpropylamino)ethylamino}-3-propionate, 7-octenyltrimethoxydecane, RN-α-benzene Ethyl-N'-triethoxydecyl propyl urea, SN-α-phenethyl-N'-triethoxydecyl propyl urea, phenethyl trimethoxy decane, phenethyl methyl Dimethoxydecane, phenethyl dimethyl methoxy decane, phenethyl dimethoxy decane, phenethyl diethoxy decane, phenethyl methyl diethoxy decane, phenethyl Methyl ethoxy decane, phenethyl triethoxy decane, (3-phenylpropyl) dimethyl chlorodecane, (3-phenylpropyl) methyl dichloro decane, N-phenylamino Propyltrimethoxydecane, N-(triethoxydecylpropyl)dansylamine, N-(3-triethoxydecane Propyl)-4,5-dihydroimidazole, 2-(triethoxydecylethyl)-5-(chloroethenyloxy)bicycloheptane, (S)-N-triethoxydecyl propyl-O-menthylcarbamate, 3-(triethoxydecylpropyl)-p-nitrobenzamide, 3-(triethoxydecyl)propyl succinic anhydride, N -[5-(trimethoxydecyl)-2-aza-1-oxo-pentyl]caprolactam, 2-(trimethoxydecylethyl)pyridine, N-(trimethoxy)矽alkylethyl)benzyl-N,N,N-trimethylammonium chloride, phenylvinyldiethoxydecane, 3-thiocyanatepropyltriethoxydecane, (tridecafluoro -1,1,2,2,-tetrahydrooctyl)triethoxydecane, N-{3-(triethoxydecyl)propyl}benzamide, (3,3,3 -trifluoropropyl)methyldimethoxydecane, (3,3,3-trifluoropropyl)trimethoxynonane, 1-trimethoxydecyl-2-(chloromethyl)phenylethane, 2-(trimethoxydecyl)ethylphenylsulfonyl azide, β-trimethoxydecylethylethyl-2-pyridine, trimethoxydecylpropyl diethylidene triamine, N-( 3-trimethoxydecylpropyl)pyrrole, N-trimethoxydecylpropyl-N,N,N-tributyl bromide Ammonium, N-trimethoxydecylpropyl-N,N,N-tributylammonium chloride, N-trimethoxydecylpropyl-N,N,N-trimethylammonium chloride, vinyl Methyl diethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, vinyl methyl dimethoxy decane, vinyl dimethyl methoxy decane, vinyl dimethyl ethoxy Base decane, vinyl methyl dichloro decane, vinyl phenyl dichloro decane, vinyl phenyl diethoxy decane, vinyl phenyl dimethyl decane, vinyl phenyl methyl chloro decane, vinyl three Phenoxydecane, vinyl tri-t-butoxydecane, adamantylethyltrichlorodecane, allylphenyltrichloromethane, (aminoethylaminomethyl)phenethyltrimethoxy Decane, 3-aminophenoxydimethylvinyldecane, phenyltrichlorodecane, phenyldimethylchlorodecane, phenylmethyldichlorodecane, benzyltrichlorodecane, benzyldimethyl chloride Decane, benzylmethyldichlorodecane, phenethyldiisopropylchlorodecane, phenethyltrichlorodecane, phenethyldimethylchlorodecane, phenethylmethyldichlorodecane, 5-(bicycloheptane Alkene Trichlorodecane, 5-(bicycloheptenyl)triethoxydecane, 2-(bicycloheptyl)dimethylchlorodecane, 2-(bicycloheptyl)trichlorodecane, 1,4-bis(trimethyl) Oxidylalkylethyl)benzene, bromophenyltrichlorodecane, 3-phenoxypropyldimethylchlorodecane, 3-phenoxypropyltrichlorodecane, tert-butylphenylchlorodecane, Tributylphenylmethoxydecane, tert-butylphenyldichlorodecane, p-(t-butyl)phenethyldimethylchlorodecane, p-(t-butyl)phenethyltrichloromethane, 1,3-(Chlorodimethyldecylmethyl)heptadecane, ((chloromethyl)phenylethyl)dimethylchlorodecane, ((chloromethyl)phenylethyl)methyldi Chlorodecane, ((chloromethyl)phenylethyl)trichlorodecane, ((chloromethyl)phenylethyl)trimethoxynonane, chlorophenyltrichlorodecane, 2-cyanoethyltrichloromethane, 2-cyanoethylmethyldichlorodecane, 3-cyanopropylmethyldiethoxydecane, 3-cyanopropylmethyldichlorodecane, 3-cyanopropylmethyldichlorodecane, 3-cyanopropane Dimethyl ethoxy decane, 3-cyanopropyl methyl dichloro decane, 3-cyanopropyl trichloro decane, fluorinated alkyl decane, etc., may be selected from the group consisting of In one kind or in combination of two or more kinds.

Among them, hexamethyldioxane is preferably used for the hydrophobization treatment.

Thereby, the water repellency of the particles 11 can be made higher. Further, it is possible to easily and surely make the uniformity of the degree of dehydration treatment of each of the surfaces of the respective particles 11 or the surface of the particles 11 (when the pores are open to the outside, the surface including the inside of the pores) becomes higher. By.

When the hydration treatment using a decane compound is carried out in a liquid phase, the desired reaction can be preferably carried out by immersing the particles (parent particles) to be subjected to the hydration treatment in a liquid containing a decane compound. Thereby, a chemisorption film of a decane compound can be formed.

Further, when the hydration treatment using a decane compound is carried out in the vapor phase, the desired reaction can be preferably carried out by exposing the particles (parent particles) to be subjected to the hydration treatment to the vapor of the decane compound. Thereby, a chemisorption film of a decane compound can be formed.

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

Thereby, the mechanical strength of the three-dimensional shaped object 10 can be made particularly excellent, and the occurrence of accidental irregularities in the three-dimensional shaped object 10 to be manufactured can be more effectively prevented, so that the dimensional accuracy of the three-dimensional shaped object 10 becomes special. Excellent. Moreover, the fluidity of the layer forming composition 1' can be made particularly excellent, and the productivity of the three-dimensional shaped object 10 is particularly excellent.

The Dmax of the particles 11 is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less.

Thereby, the mechanical strength of the three-dimensional shaped object 10 can be made particularly excellent, and The occurrence of unexpected concavities and the like in the three-dimensional shaped object 10 to be produced is effectively prevented, so that the dimensional accuracy of the three-dimensional shaped object 10 is particularly excellent. Moreover, the fluidity of the layer forming composition 1' can be made particularly excellent, and the productivity of the three-dimensional shaped object 10 is particularly excellent.

The porosity of the particles 11 is preferably 50% or more, more preferably 55% or more and 90% or less.

Thereby, the space (pore) into which the resin material (bonding agent) enters can be sufficiently obtained, and the mechanical strength of the particles 11 itself is excellent, and as a result, the bonding portion in which the resin material penetrates into the pores can be obtained. The mechanical strength of the three-dimensional shaped object 10 is particularly excellent.

Further, in the present invention, the porosity of the particles 11 means the ratio (volume ratio) of the pores existing inside the particles 11 to the apparent volume of the particles 11, and when the density of the particles 11 is set to ρ [g /cm ³ ], when the true density of the constituent material of the particles 11 is ρ0 [g/cm ³ ], the value expressed by {(ρ0-ρ)/ρ0}×100.

The average pore diameter (pore diameter) of the particles 11 is preferably 10 nm or more, more preferably 50 nm or more and 300 nm or less.

Thereby, the mechanical strength of the finally obtained three-dimensional shaped article 10 can be made particularly excellent. Further, in the case where the pigment-containing liquid 2' (colored ink) is used in the production of the three-dimensional shaped article 10, the pigment can be preferably held in the pores of the particles 11. Therefore, the diffusion of the unexpected pigment can be prevented, so that a high-definition image can be formed more surely.

The particles 11 may be of any shape, preferably in the shape of a sphere. Thereby, the fluidity of the layer forming composition 1' can be made particularly excellent, so that the productivity of the three-dimensional shaped object 10 is particularly excellent, and the accident in the manufactured three-dimensional shaped object 10 can be more effectively prevented. The occurrence of irregularities or the like makes the dimensional accuracy of the three-dimensional shaped object 10 particularly excellent.

The layer forming composition 1' may also be a compound containing a plurality of kinds of particles 11.

The content of the particles 11 in the layer forming composition 1' is preferably 8% by mass or more and 91% by mass. The amount is not more than 5% by mass, more preferably 10% by mass or more and 53% by mass or less.

Thereby, the fluidity of the layer forming composition 1' can be sufficiently excellent, and the mechanical strength of the finally obtained three-dimensional shaped article 10 is particularly excellent.

(solvent)

The layer forming composition 1' contains a solvent 12 as it is.

Thereby, the operability (ease of handling) of the layer forming composition 1' can be made particularly excellent, and the layer 1 having a higher uniformity of thickness can be easily formed, and the accident of the layer 1 can be more effectively prevented. The deformation. Further, in the first liquid supply step, the liquid 2' can be prevented from being inadvertently infiltrated into the layer 1 (layer 1 containing the solvent 12), and the cured portion 2 formed in the first liquid application step can be made true. The ground has the shape you want. Therefore, the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made particularly excellent.

Examples of the solvent for constituting the composition for forming a layer 1' include water; an alcoholic solvent such as methanol, ethanol or isopropyl alcohol; a ketone solvent such as methyl ethyl ketone or acetone; ethylene glycol monoethyl ether or ethylene glycol; a glycol ether solvent such as an alcohol monobutyl ether; a glycol ether acetate solvent such as propylene glycol 1-monomethyl ether 2-acetate or propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, polypropylene glycol For example, one type or a combination of two or more types selected from the group consisting of these may be used.

Among them, the layer forming composition 1' preferably contains a water-based solvent, and more preferably contains water.

Thereby, the fluidity of the layer forming composition 1' and the uniformity of the composition of the layer 1 formed using the layer forming composition 1' are particularly excellent. Further, after the formation of the layer 1, water can be easily removed, and even when water remains in the three-dimensional shaped article 10, adverse effects are less likely to occur. Moreover, it is also advantageous from the viewpoints of human safety and environmental issues. In addition, when the liquid 2' for forming the first cured portion 2A contains the polymerizable compound (especially an acrylic polymerizable compound or an anthrone-based polymerizable compound) as described above, it can be more effectively prevented. The unexpected penetration of the liquid 2' into the layer 1 (layer 1 containing the solvent 12) can more reliably form the first hardened portion 2A having a desired shape, thereby allowing The dimensional accuracy and reliability of the three-dimensional shaped object 10 are particularly excellent. Further, in the case where the layer-forming composition 1' contains a water-soluble resin as a binder to be described later in detail, the layer-forming composition 1' can make the water-soluble resin more soluble. The effect produced by containing a binder (water-soluble resin) as described in detail later is more effectively exhibited.

The solvent of the aqueous solvent may be a solvent having a high solubility in water. Specifically, for example, it is preferably a solubility of water at 25 ° C (a mass which can be dissolved in 100 g of water) is 30 [g/100 g of water] or more. More preferably, it is 50 [g/100 g water] or more.

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

Thereby, the effect produced by containing the solvent 12 as described above can be exhibited more remarkably, and the solvent 12 can be easily removed in a short period of time in the manufacturing process of the three-dimensional shaped object 10, so that the production from the three-dimensional shaped object 10 is produced. It is advantageous from the viewpoint of sexual improvement.

In particular, the content of water in the layer forming composition 1' is preferably 18% by mass or more and 92% by mass or less, more preferably 47% by mass or more and 90% by mass or less.

Thereby, the effects as described above are more significantly exerted.

(adhesive)

The layer forming composition 1' may be a one containing not only a plurality of particles 11 and a solvent 12 but also a binder.

Thereby, in the layer 1 formed by using the layer forming composition 1' (in particular, the layer 1 in a state in which the solvent 12 is removed), a plurality of particles 11 can be preferably bonded (temporarily fixed), so that The accidental splashing of the particles 11 and the like is effectively prevented. Thereby, the safety of the operator or the dimensional accuracy of the manufactured three-dimensional shaped object 10 can be further improved.

In the case where the layer forming composition 1' is a binder-containing composition, in the layer forming composition 1', the binder is preferably dissolved in the solvent 12.

Thereby, the fluidity of the layer forming composition 1' can be made particularly excellent, and thus The unexpected unevenness of the thickness of the layer 1 formed by using the layer forming composition 1' is more effectively prevented. Further, when the layer 1 in the state in which the solvent 12 is removed is formed, the binder can be adhered to the particles 11 over the entire layer 1 with higher uniformity, and the uneven composition of the composition can be more effectively prevented. Therefore, it is possible to more effectively prevent the occurrence of an unexpected unevenness in the mechanical strength of each portion of the finally obtained three-dimensional shaped object 10, and the reliability of the three-dimensional shaped object 10 can be made higher.

The binder may be a member having a function of temporarily laminating a plurality of particles 11 in the layer 1 formed by using the layer forming composition 1' (in particular, the layer 1 in a state in which the solvent 12 is removed). A water-soluble resin can be preferably used.

When the layer-forming composition 1' contains an aqueous solvent (particularly water) as the solvent 12, the layer-forming composition 1' can be contained in a dissolved state in a solvent-soluble resin (water-soluble resin). Therefore, the fluidity and workability (ease of handling) of the layer forming composition 1' can be made particularly excellent. As a result, the productivity of the three-dimensional shaped object 10 can be made particularly excellent.

Further, by imparting an aqueous solvent (especially water), the portion of the layer 1 which is not imparted with the liquid 2' during the production of the three-dimensional shaped article 10 can be easily and efficiently removed. As a result, the productivity of the three-dimensional shaped object 10 can be made particularly excellent. Moreover, the portion to be removed of the layer can be easily and surely prevented from adhering to and remaining in the finally obtained three-dimensional shaped object 10, so that the dimensional accuracy of the three-dimensional shaped object 10 can be made particularly excellent.

Hereinafter, the description will be given focusing on a water-soluble resin as a binder.

The water-soluble resin may be at least a part of which is soluble in an aqueous solvent. For example, it is preferably a solubility in water of 25 ° C (a mass which can be dissolved in 100 g of water) is 5 [g/100 g of water] or more, more preferably 10 [g/100g water] or more.

Examples of the water-soluble resin include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polycaprolactone diol, sodium polyacrylate, polyacrylamide, modified polyamine, and polyethylene. Amine, polyethylene oxide, random copolymer of ethylene oxide and propylene oxide Polymers; natural polymers such as corn starch, mannan, pectin, agar, alginic acid, dextran, bone glue, gelatin; carboxymethyl cellulose, hydroxyethyl cellulose, oxidized starch, modified starch, etc. A semi-synthetic polymer or the like may be used alone or in combination of two or more kinds selected from the group consisting of them.

Specific examples of the water-soluble resin product include methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metolose SM-15), hydroxyethyl cellulose (manufactured by FUJI Chemical Co., Ltd., AL-15), and hydroxypropyl cellulose. (manufactured by Japan Soda Co., Ltd., HPC-M), carboxymethyl cellulose (manufactured by Nichirin Chemical Co., Ltd., CMC-30), sodium starch phosphate (I) (manufactured by Matsutani Chemical Co., Ltd., Hoster 5100), polyvinylpyrrole Pyridone (manufactured by Tokyo Chemical Co., Ltd., PVP K-90), methyl vinyl ether/maleic anhydride copolymer (manufactured by GAF Gantrez Co., Ltd., AN-139), polypropylene decylamine (manufactured by Wako Pure Chemical Industries, Ltd.), modified poly Indoleamine (modified nylon) (manufactured by Toray Industries, AQ nylon), polyethylene oxide (PEO-1 manufactured by Iron Chemical Co., Ltd., ALKOX manufactured by Mingcheng Chemical Industry Co., Ltd.), ethylene oxide and propylene oxide Random copolymer (manufactured by Mingcheng Chemical Industry Co., Ltd., ALKOX EP), sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), carboxyvinyl polymer/crosslinked acrylic water-soluble resin (manufactured by Sumitomo Seika Co., Ltd., Aqupec )Wait.

In the case where the water-soluble resin as the binder is polyvinyl alcohol, the mechanical strength of the three-dimensional shaped article 10 can be made particularly excellent. Further, by the adjustment of the degree of saponification or the degree of polymerization, the properties of the binder (for example, water solubility, water resistance, etc.) or the properties of the layer-forming composition 1' (for example, viscosity, particle 11) can be further preferably controlled. Fixing force, wettability, etc.). Therefore, the manufacture of the various three-dimensional shaped objects 10 can be further preferably handled. Further, polyvinyl alcohol is a low-cost and stable supply of various water-soluble resins. Therefore, the production cost can be suppressed, and the manufacture of the stable three-dimensional shaped object 10 can be performed.

In the case where the water-soluble resin as the binder contains polyvinyl alcohol, the degree of saponification of the polyvinyl alcohol is preferably 85 or more and 90 or less. Thereby, the decrease in the solubility of the polyvinyl alcohol to the aqueous solvent (especially water) can be suppressed. Therefore, the layer forming composition 1' contains water. In the case of a solvent (especially water), the decrease in the adhesion between the adjacent layers 1 can be more effectively suppressed.

In the case where the water-soluble resin as the binder contains polyvinyl alcohol, the degree of polymerization of the polyvinyl alcohol is preferably 300 or more and 1,000 or less. Therefore, when the layer forming composition 1' contains an aqueous solvent (particularly water), the mechanical strength of each layer 1 or the adhesion between the adjacent layers 1 can be made particularly excellent.

Further, in the case of a water-soluble resin-based polyvinylpyrrolidone (PVP) as a binder, the following effects can be obtained. That is, since polyvinylpyrrolidone is excellent in adhesion to various materials such as glass, metal, and plastic, the strength of the portion of layer 1 which is not imparted to the liquid 2' can be obtained. The stability of the shape is particularly excellent, so that the dimensional accuracy of the finally obtained three-dimensional shaped object 10 is particularly excellent. Further, since polyvinylpyrrolidone exhibits high solubility in various organic solvents, when the layer forming composition 1' contains an organic solvent, the fluidity of the layer forming composition 1' can be made special. Preferably, the layer 1' which is more effective in preventing the uneven thickness unevenness can be preferably formed, so that the dimensional accuracy of the finally obtained three-dimensional shaped object 10 can be made particularly excellent. Further, since polyvinylpyrrolidone exhibits high solubility to an aqueous solvent (especially water), the particles constituting each layer 1 can be easily and surely formed in the unbound particle removal step (after completion of formation). 11 is not removed by the binder by the resin material (binding agent). Further, since the polyvinylpyrrolidone is excellent in affinity with various coloring agents, when the liquid 2' containing the coloring agent is used in the second liquid application step, the coloring agent can be effectively prevented from being accidentally diffused.

When the water-soluble resin as the binder contains polyvinylpyrrolidone, the weight average molecular weight of the polyvinylpyrrolidone is preferably 10,000 or more and 1,700,000 or less, more preferably 30,000 or more and 1,500,000 or less.

Thereby, the above functions can be performed more effectively.

When the water-soluble resin as the binder contains polycaprolactone diol, the weight average molecular weight of the polycaprolactone diol is preferably 10,000 or more and 700,000 or less. Good is more than 30,000 and less than 1.500000.

Thereby, the above functions can be performed more effectively.

In the layer forming composition 1', the binder is preferably in a liquid state (for example, a dissolved state, a molten state, or the like) in the layer forming step. Thereby, the uniformity of the thickness of the layer 1 formed by the layer forming composition 1' can be easily and surely made higher.

When the layer forming composition 1' contains a binder, the content of the binder in the layer forming composition 1' is preferably 0.5% by mass or more and 25% by mass or less, more preferably 1.0% by mass. The above and 10% by mass or less.

In this way, the effect of the binder as described above can be more remarkably exhibited, and the content ratio of the particles 11 and the like in the layer forming composition 1' can be sufficiently high, and the three-dimensionally produced can be produced. The mechanical strength and the like of the shaped article 10 are particularly excellent.

(other ingredients)

Further, the layer-forming composition may be one containing the components other than the above. As such a component, for example, a polymerization initiator; a polymerization accelerator; a penetration enhancer; a wetting agent (humectant); a fixative; an antifungal agent; a preservative; an antioxidant; a UV absorber; a chelating agent; pH adjuster, etc.

"Three-dimensional shape manufacturing equipment"

Next, a three-dimensional shaped object manufacturing apparatus of the present invention will be described.

Fig. 9 is a cross-sectional view schematically showing a preferred embodiment of the apparatus for manufacturing a three-dimensional shaped article of the present invention.

The three-dimensional shaped object manufacturing apparatus M100 is manufactured by using the layer forming composition 1', and the layer 1 is overmolded and laminated to produce a three-dimensional shaped object 10. In particular, the three-dimensional shaped object manufacturing apparatus M100 is manufactured by manufacturing the three-dimensional shaped object of the present invention as described above.

As shown in Fig. 9, the three-dimensional shaped object manufacturing apparatus M100 includes a control unit M2, a composition supply unit M3 that accommodates a layer forming composition 1', and a layer forming unit M4 that uses a self-composition The layer forming composition 1' supplied to the supply portion M3 forms the layer 1; the liquid ejecting portion (liquid applying means) M5 ejects the liquid 2' to the layer 1, and the energy ray irradiation means (curing means) M6 is irradiated to make The liquid 2' hardened energy ray; and a height measuring mechanism M7 which measures the height of the hardened material 6 formed using the liquid 2'.

The control unit M2 has a computer M21 and a drive control unit M22.

The computer M21 is a general desktop computer including a CPU (Central Processing Unit) or a memory. The computer M21 records the shape of the three-dimensional shaped object 10 as model data, and outputs the sectional data (slice data) obtained by cutting the plurality of thin sections which are cut into parallel to the drive control unit M22. Further, the height of the upper surface of the cured material 6 is measured by the height measuring mechanism M7 described later in detail, and when the thickness of the layer 1 is adjusted based on the height, the cross-sectional data (slice data) is performed based on the thickness of the layer 1. Overwrite (correction. Correction).

The drive control unit M22 functions as a control unit such as the drive layer forming unit M4, the liquid ejecting unit M5, the energy ray irradiation unit M6, and the height measuring unit M7. Specifically, for example, the discharge pattern or the discharge amount of the liquid 2' by the liquid discharge portion M5, the supply amount of the layer formation composition 1' from the composition supply portion M3, the amount of drop of the platform (elevation platform) M41, and the like are controlled. .

The composition supply unit M3 is configured to be moved by the command from the drive control unit M22, and the layer forming composition 1' accommodated inside is supplied to the stage M41.

The layer forming portion M4 includes a platform (elevating platform) M41, a layer 1 composition for supplying the layer, a layer 1 formed by the layer forming composition 1', and a flattening mechanism (scraper) M42. It planarizes the layer forming composition 1' held on the stage M41, and forms the layer 1; the guide rail M43 which regulates the action of the flattening mechanism M42; and the housing M45 which surrounds the lifting platform M41 and is in close contact with the lifting platform Set by the way of M41.

When the lifting platform M41 forms a new layer 1 on the previously formed layer 1, by driving from the drive The command of the motion control unit M22 is sequentially decreased by a specific amount. The thickness of the newly formed layer 1 is defined by the amount of drop of the lifting platform M41 and the height of the flattening mechanism M42 which will be described later in detail.

The surface of the platform M41 is a flat portion for providing the layer forming composition 1' and the liquid 2'. The portion including the first region M411 and the second region M412 is flat. Thereby, the layer 1 having a higher uniformity of thickness can be formed easily and surely. Further, the thickness of the newly formed layer 1 can be preferably adjusted based on the height of the upper surface of the cured material 6.

The platform M41 is preferably a material containing high strength. As a constituent material of the stage M41, various metal materials, such as stainless steel, etc. are mentioned, for example.

Further, the surface of the stage M41 (the portion for providing the layer forming composition 1' and the liquid 2', and the portion including the first region M411 and the second region M412) may be subjected to surface treatment. Thereby, for example, the constituent material of the layer forming composition 1' or the constituent material of the liquid 2' can be more effectively prevented from being firmly adhered to the stage M41, or the durability of the stage M41 can be made particularly excellent, and a three-dimensional shape can be realized. 10 more stable production in the long run. The material for the surface treatment of the surface of the stage M41 is, for example, a fluorine-based resin such as polytetrafluoroethylene.

The squeegee as the flattening mechanism M42 has a long shape extending in the X direction, and has a blade having a sharp-edged blade shape at the lower end.

The layer 1 formed by flattening the layer forming composition 1' by the flattening mechanism M42 is based on information such as the height of the upper surface of the cured material 6 measured by the height measuring mechanism M7, and is preferably as needed. Since it is adjusted, it is possible to prevent the constituent components (for example, the particles 11) of the layer forming composition 1' from remaining unexpectedly on the upper surface of the hardened portion 2 at the end of the layer forming step.

In addition, a vibration mechanism (not shown) that imparts a slight vibration to the blade may be provided so that the layer forming composition 1 using the flattening mechanism (scraper) M42 can be smoothly performed in the Y direction of the blade. 'The spread.

Further, the three-dimensional shaped object manufacturing apparatus M100 may be provided with, for example, a stress detecting mechanism (not As shown in the figure, the stress detecting means detects the stress applied to the flattening mechanism M42 when the flattening mechanism M42 is brought into contact with the upper surface of the cured material 6 formed on the second region M412 of the stage M41.

Therefore, for example, when the flattening mechanism M42 is brought into contact with the upper surface of the cured material 6, the state in which the specific stress applied to the planarizing mechanism M42 is a specific value can be determined as the flattening at the time of formation of the layer 1. The height of the mechanism M42.

Further, the abutting of the cured material 6 by the flattening mechanism M42 can be preferably performed by relatively moving the stage M41 and the flattening mechanism M42 in the Z direction, for example, by moving the flattening mechanism M42 downward. This can also be done by moving the platform M41 upward.

The liquid ejecting unit (liquid applying means) M5 is a person who ejects the liquid 2' by an inkjet method. By providing such a liquid ejecting unit (liquid supply means) M5, the liquid 2' can be provided in a fine pattern, and even if it is a three-dimensional shaped object 10 having a fine structure, it can be manufactured with particularly good productivity. Further, the cured portion 2 and the cured product 6 can be preferably formed under the same conditions (for example, the same thickness and the same density).

As the droplet discharge method (the method of the inkjet method), a piezoelectric method or a bubble generated by heating the liquid 2' can be used to eject the liquid 2', and the constituents of the liquid 2' can be used. From the viewpoint of not easily deteriorated, etc., it is preferably a piezoelectric method.

The liquid ejecting unit (liquid applying means) M5 controls the pattern to be formed and the amount of liquid 2' to be supplied by an instruction from the drive control unit M22. The discharge pattern and the discharge amount of the liquid 2' by the liquid ejecting unit (liquid supply means) M5 are determined based on the slice data. Thereby, it is possible to provide a sufficient amount of the liquid 2', and it is possible to reliably form the cured portion 2 of the desired pattern, and the dimensional accuracy and mechanical strength of the three-dimensional shaped object 10 can be made more excellent. Further, when the liquid 2' is a coloring agent-containing one, the desired color tone can be surely obtained, and it is possible to surely prevent an unexpected color tone change and color balance accidentally with the change of the thickness of the layer 1. Being broken and so on.

The energy ray irradiation means (curing means) M6 illuminates an energy ray for hardening the supplied liquid 2'.

The type of the energy ray to be irradiated by the energy ray irradiation means M6 differs depending on the constituent material of the liquid 2', and examples thereof include ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, electron beams, and ion beams. Among them, ultraviolet rays are preferably used from the viewpoint of cost and productivity of the three-dimensional shaped article 10.

The height measuring mechanism M7 measures the height of the upper surface of the hardened material 6.

The information on the height of the upper surface of the cured material 6 is sent from the height measuring mechanism M7 to the control portion M2 for adjustment of the thickness of the formed layer 1 and the relative height of the flattening mechanism M42.

Further, in the configuration shown in FIG. 9, the height measuring means M7 determines the height of the cured product 6 by determining the focal length from the upper side of the cured product 6. With this configuration, the height of the cured product 6 can be measured without moving the height measuring mechanism M7, so that the time required for the measurement of the height of the cured product 6 can be shortened, so that the productivity of the three-dimensional shaped object 10 can be made special. Excellent.

According to the three-dimensional shaped object manufacturing apparatus of the present invention as described above, it is possible to efficiently manufacture a three-dimensional shaped article excellent in dimensional accuracy and mechanical strength.

"Three-dimensional shape"

The three-dimensional shaped article of the present invention is produced by using the production method of the present invention as described above.

Thereby, it is possible to provide a three-dimensional shape excellent in dimensional accuracy and mechanical strength.

The use of the three-dimensional shaped article of the present invention is not particularly limited, and examples thereof include a puppet, a figurine, and the like. Display materials; medical equipment such as implants.

Further, the three-dimensional shaped article of the present invention may be applied to any of a prototype, a quantity product, and a fixed product.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

For example, in the above embodiment, it is said that the hardened portion is formed in all the layers. However, it is also possible to have a layer in which a hardened portion is not formed. For example, a layer formed directly above the stage may be used as a sacrificial layer without forming a hardened portion.

Further, in the above-described embodiment, the cured region for determining the thickness of the layer is formed on the forming platform and is different from the first region in which the first region of the solid portion forming the target three-dimensional shaped object is formed. Although the case has been described, the hardened material for determining the thickness of the layer may be one of the solid portions formed in the first region, particularly the three-dimensional shaped object.

Further, in the above embodiment, the case where the height of the upper surface of the cured material for determining the thickness of the layer is determined by the observation of the upper surface of the cured material is representatively described, but the cured product is used. The height of the surface can also be determined by observation from the side of the cured material.

In the above embodiment, the case where the fixer is used as the height measuring mechanism is typically described. However, the height measuring mechanism may be a movable person (for example, a person who can move in the XY direction of the platform). Thereby, for example, the height of the upper surface of the hardened material can be measured for a plurality of points.

In the above-described embodiment, the case where the solvent-containing composition is used as the layer-forming composition is typically described. However, the layer-forming composition may be any one containing at least a plurality of particles. Do not contain solvents.

Further, in the above-described embodiment, a case where a plurality of cured products formed by laminating in a plurality of steps and having the same shape and the same area are representatively described, but for example, The plurality of hardened materials in the laminate are sequentially reduced in size toward the upper side, and the laminated body in which a plurality of hardened materials are laminated is, for example, in the shape of a pyramid. That is, in the case of this case, the same effects as described above can be obtained.

Moreover, the apparatus for manufacturing a three-dimensional shaped article of the present invention may be provided with a recovery mechanism (not shown) for recovering the unformed layer formed in the composition supplied from the composition supply unit. Thereby, the remaining composition can be prevented from accumulating in the layer forming portion, and a sufficient amount of the composition can be supplied, so that generation of defects in the layer can be more effectively prevented, and the three-dimensional shaped article can be more stably produced. Also, the recovered composition can be reused for three-dimensional shapes The manufacture is therefore advantageous in reducing the manufacturing cost of the three-dimensional shaped object, and is also preferable from the viewpoint of saving resources.

Further, the apparatus for manufacturing a three-dimensional shaped article of the present invention may further include a recovery mechanism for recovering the composition removed in the unbound particle removal step.

Further, in the above embodiment, 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 are repeated as a series of steps. Although the description has been made for the center, a series of steps may be performed differently in each cycle. For example, the cycle of the first liquid application step and the first curing step in the above steps may be omitted, or the first step may be omitted. 2 The cycle of the liquid imparting step and the second hardening step.

Further, for example, the curing treatment for forming the respective cured portions may not be repeated every time the pattern corresponding to each of the cured portions is formed, or may be formed after the formation of the unhardened pattern in a plurality of layers. In general, etc.

Further, in the above-described embodiment, the liquid for forming the cured portion and the cured product is mainly described by the inkjet method. However, the liquid for forming the cured portion and the cured product may be used. The method (eg, other printing methods) is given to the person.

Further, in the manufacturing method of the present invention, the pretreatment step, the intermediate treatment step, and the post-treatment step may be performed as needed.

As the pretreatment step, for example, a cleaning step of the platform or the like can be cited.

Examples of the post-treatment step include a washing step, a shape adjusting step of removing burrs, a coloring step, a coating layer forming step, and a light irradiation treatment or a heat treatment for reliably curing the uncured resin material. The resin material hardening end step or the like.

Claims (13)

A method for producing a three-dimensional shaped object, which is a method of repeatedly forming a layer and ejecting a liquid to the layer, and producing a three-dimensional shaped article, comprising: a layer forming step of using a layer-forming composition containing particles Forming the above-mentioned layer of a specific thickness; a liquid imparting step of imparting the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and based on the upper surface of the cured product formed using the liquid The height depends on the thickness of the above-mentioned layer newly formed after the formation of the cured product. A method for producing a three-dimensional shaped object, which is a method of repeatedly forming a layer and ejecting a liquid to the layer, and producing a three-dimensional shaped article, comprising: a layer forming step of using a layer-forming composition containing particles Forming the above-mentioned layer of a specific thickness; a liquid imparting step of imparting the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and measuring a height of the cured product formed using the liquid, based on The measurement result is determined by the thickness of the layer newly formed after the formation of the cured product. A method for producing a three-dimensional shaped object, which is a method of repeatedly forming a layer and ejecting a liquid to the layer, and manufacturing a three-dimensional shaped object, comprising: a layer forming step of using a flattening mechanism to cause a particle-containing material The layer forming composition is planarized to form the layer having a specific thickness; the liquid imparting step of applying the liquid to the layer; and a hardening step of hardening the liquid to form a hardened portion; and planarizing the layer The mechanism abuts against the upper surface of the cured product formed by using the liquid, and forms the above-mentioned layer of a specific thickness based on the abutting surface. The method for producing a three-dimensional shaped article according to any one of claims 1 to 3, wherein the hardened material is formed on the forming platform different from the first region for forming a portion of the solid portion of the three-dimensional shaped object that constitutes the target The second area of the person. The method of manufacturing a three-dimensional shaped article according to claim 4, wherein the second region is provided on an outer circumference side of the first region. A method of producing a three-dimensional shaped article according to claim 4 or 5, wherein the discharge pattern density of the liquid in the second region is equal to the density of the discharge pattern of the liquid in the first region. The method for producing a three-dimensional shaped article according to any one of claims 1 to 6, wherein the hardened material is formed by laminating a plurality of steps in a manner corresponding to a plurality of the layers. The method for producing a three-dimensional shaped article according to claim 7, wherein the plurality of hardened materials formed by laminating in a plurality of steps are formed into a first cured product by any step, and When the step after the first cured product is formed as the second cured product, the second cured product does not have a region that does not overlap the first cured product in plan view. The method for producing a three-dimensional shaped article according to any one of claims 1 to 8, wherein the layer forming step is carried out using the layer forming composition containing the particles and the solvent, and the first liquid applying step is performed After the layer forming step, the liquid is applied to the layer containing the solvent; the first curing step is to cure the liquid applied to the layer; and the solvent removing step is performed from the layer The above solvent. The method for producing a three-dimensional shaped article according to claim 9, further comprising: a second liquid supply step of applying the liquid to the layer in a state in which the solvent is removed after the solvent removal step, and allowing the liquid to permeate This layer And a second hardening step of hardening the liquid permeating into the layer. A three-dimensional shaped object manufacturing apparatus for repeatedly forming a layer and discharging a liquid to the layer to produce a three-dimensional shaped object, comprising: a platform for forming the layer using a layer-forming composition containing particles; a liquid imparting mechanism that imparts a liquid to the layer; and a hardening mechanism that hardens the liquid; and the height of the upper surface of the cured product formed based on the use of the liquid is determined by the layer newly formed after the formation of the cured product The thickness. A three-dimensional shaped article, which is manufactured by using the method for producing a three-dimensional shaped article according to any one of claims 1 to 10. A three-dimensional shaped article, which is manufactured by using a three-dimensional shaped article manufacturing apparatus as claimed in claim 11.