JP2016087810A - Method for manufacturing three-dimensional molded article, apparatus for manufacturing three-dimensional molded article, and three-dimensional molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a three-dimensional molded article and an apparatus for manufacturing a three-dimensional molded article, by which a three-dimensional molded article excellent in dimensional accuracy and mechanical strength can be efficiently manufactured, and a three-dimensional molded article having excellent dimensional accuracy and mechanical strength.SOLUTION: The method for manufacturing a three-dimensional molded article comprises repeating processes of forming a layer and discharging a liquid to the layer to manufacture a three-dimensional molded article. The method includes: a layer forming step of forming a layer having a desired thickness by using a composition for layer formation containing particles; a liquid imparting step of imparting a liquid to the layer; and a curing step of curing the liquid to form a cured part. The thickness of a layer to be newly formed after the cured products formed is determined based on the height of an upper surface of the cured product formed using the liquid.SELECTED DRAWING: None

Description

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

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

  However, with repeated layer formation, the flattening member such as a squeegee used for layer formation wears and deforms, and due to fluctuations in the amount of liquid applied, etc. Deviations from the desired design values may occur. If the thickness of such a layer shifts, the dimensional accuracy of the finally obtained three-dimensional structure decreases, or the bonding force between the bonding portions formed in the adjacent layers decreases. There was a problem that the mechanical strength of the obtained three-dimensional structure was lowered.

JP-A-6-218712

  An object of the present invention is to provide a three-dimensional structure manufacturing method and a three-dimensional structure manufacturing apparatus capable of efficiently manufacturing a three-dimensional structure excellent in dimensional accuracy and mechanical strength, and to provide a dimensional accuracy. Another object is to provide a three-dimensional structure excellent in mechanical strength.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure, in which a layer is formed, a process of discharging liquid to the layer is repeated, and a three-dimensional structure is manufactured.
A layer forming step of forming the layer having a predetermined thickness using a composition for forming a layer containing particles;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
The thickness of the layer to be newly formed after the formation of the cured product is determined based on the height of the upper surface of the cured product formed using the liquid.

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

The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure, in which a layer is formed, a process of discharging liquid to the layer is repeated, and a three-dimensional structure is manufactured.
A layer forming step of forming the layer having a predetermined thickness using a composition for forming a layer containing particles;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
The height of the cured product formed using the liquid is measured, and the thickness of the layer to be newly formed after the formation of the cured product is determined based on the measurement result.

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

The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure, in which a layer is formed, a process of discharging liquid to the layer is repeated, and a three-dimensional structure is manufactured.
A layer forming step of flattening the layer forming composition containing particles by using a flattening means to form the layer having a predetermined thickness;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
The flattening means is brought into contact with an upper surface of a cured product formed using the liquid, and the layer having a predetermined thickness is formed on the basis of the contact surface.

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

  In the three-dimensional structure manufacturing method of the present invention, the cured product is different from the first region on the modeling stage in which the portion constituting the substantial part of the target three-dimensional structure is formed. It is preferable that it is formed in this area.

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

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

  Thereby, the dimensional accuracy and reliability of the finally obtained three-dimensional structure can be further improved, and the productivity of the three-dimensional structure can be particularly improved.

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

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

  In the three-dimensional structure manufacturing method of the present invention, the cured product is preferably formed so as to be stacked over a plurality of steps so as to correspond to the plurality of layers.

  Thereby, the dimensional accuracy and mechanical strength as a whole three-dimensional structure can be made particularly excellent.

  In the method for producing a three-dimensional structure according to the present invention, among the plurality of cured products formed so as to be stacked over a plurality of steps, a product formed in an arbitrary step is a first cured product, the first When the second cured product is a product formed in a later process than the cured product, the second cured product has a region that does not overlap with the first cured product when viewed in plan. It is preferable that it is not.

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

In the method for producing a three-dimensional structure of the present invention, the layer forming step is performed using the layer forming composition containing the particles and a solvent.
After the layer forming step, a first liquid applying step of applying the liquid onto the layer containing the solvent;
A first curing step for curing the liquid applied on the layer;
It is preferable to have a solvent removal step of removing the solvent from the layer.

  Thereby, unintentional permeation of the liquid into the inside of the layer can be suitably prevented, and a cured portion having a desired shape can be more reliably formed on the upper surface of the layer. As a result, the dimensional accuracy of the finally obtained three-dimensional structure can be made particularly excellent.

In the three-dimensional structure manufacturing method of the present invention, after the solvent removal step, the liquid is applied to the layer in a state where the solvent is removed, and the second liquid is applied to permeate the liquid into the layer. Process,
It is preferable to further include a second curing step of curing the liquid that has penetrated into the layer.

  As a result, a hardened part can be formed inside the layer, and the finally obtained three-dimensional structure is particularly excellent in mechanical strength and more reliable in which unintentional deformation is more reliably prevented. It becomes.

The three-dimensional structure manufacturing apparatus of the present invention is a three-dimensional structure manufacturing apparatus that forms a layer, repeats the process of discharging liquid to the layer, and manufactures a three-dimensional structure,
A stage for forming the layer using a layer-forming composition containing particles;
A liquid applying means for applying a liquid to the layer;
A curing means for curing the liquid,
The thickness of the layer to be newly formed after the formation of the cured product is determined based on the height of the upper surface of the cured product formed using the liquid.

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

  The three-dimensional structure of the present invention is manufactured using the method for manufacturing a three-dimensional structure of the present invention.

  Thereby, the three-dimensional structure excellent in dimensional accuracy and mechanical strength can be provided.

  The three-dimensional structure of the present invention is manufactured using the three-dimensional structure manufacturing apparatus of the present invention.

  Thereby, the three-dimensional structure excellent in dimensional accuracy and mechanical strength can be provided.

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

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

<Method for producing three-dimensional structure>
First, the manufacturing method of the three-dimensional structure according to the present invention will be described.
[First Embodiment]
1, 2, 3, and 4 are cross-sectional views schematically showing each step in the first embodiment of the method for manufacturing a three-dimensional structure of the present invention.

  As shown in FIGS. 1, 2, 3, and 4, the manufacturing method of the three-dimensional structure 10 of the present embodiment uses a layer-forming composition 1 ′ containing particles 11 and a layer 1 having a predetermined thickness. A layer forming step (1d, 1k, 1r) for forming a liquid, and a liquid applying step for applying a liquid (cured portion forming liquid) 2 ′ used for forming the cured portion 2 (first cured portion 2A) to the layer 1 ( 1e, 1h, 1l, 1o) and a curing step (1f, 1i, 1m, 1p) for curing the liquid 2 ′ to form the cured portion 2.

  In the liquid application step, the target three-dimensional structure 10 is configured in the second region M412 that is a region different from the first region M411 that is a region in which the target three-dimensional structure 10 is manufactured. The liquid 2 ′ used for forming the cured portion 2 is applied, and in the curing step, the liquid 2 ′ applied to the first region M411 is cured to form the cured portion 2 and applied to the second region M412. The cured liquid 2 ′ is cured to form a cured product 6 having the same height as the cured portion 2.

  Further, in the layer formation step (for example, the step (1k) performed after the step (1f) or the step (1r) performed after the step (1m)) performed after the formation of the cured product 6, Based on the height of the upper surface, the thickness of the layer 1 is determined (1j, 1q).

  Thus, by determining the thickness of the layer 1 based on the height of the upper surface of the cured product 6, the constituent components (for example, the particles 11) of the layer forming composition 1 ′ It is possible to prevent unintentional remaining on the upper surface of the cured portion 2 at times.

  Thereby, in the subsequent process, the adhesiveness of the said hardening part 2 and the hardening part 2 newly formed on the said hardening part 2 can be made excellent reliably. As a result, the mechanical strength of the finally obtained three-dimensional structure 10 can be made excellent.

  In addition, three-dimensional due to the unintentional presence of the particles 11 constituting the layer-forming composition 1 ′ between the arbitrary cured part 2 and the cured part 2 formed on the cured part 2. A decrease in the dimensional accuracy of the shaped article 10 can be prevented.

  In particular, in the present embodiment, in the layer forming step, the flattening means M42 is brought into contact with the upper surface of the cured product 6, and the height (contact surface) at which the flattening means M42 comes into contact with the cured product 6 is used as a reference. The layer 1 having a predetermined thickness is formed (see 1j and 1q).

  Thereby, it is possible to more effectively prevent the above problems from occurring with a simple configuration, and to manufacture the three-dimensional structure 10 having excellent mechanical strength and dimensional accuracy with excellent productivity. it can.

  As described above, in the present embodiment, the cured product 6 is different from the first region M411 on the stage M41 where the portion constituting the substantial part of the target three-dimensional structure 10 is formed. It is formed in the region M412.

  Thereby, when the flattening means M42 is brought into contact (when the thickness of a layer to be newly formed is determined) or the like, the hardened part 2 or the layer 1 relating to the modeling of the target three-dimensional structure 10 is reluctant. Can be more reliably prevented from occurring. As a result, the dimensional accuracy and reliability of the finally obtained three-dimensional structure 10 can be made particularly excellent.

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

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

  In particular, in the illustrated configuration, a second region M412 is provided upstream of the first region M411 in the relative movement direction of the flattening means M42 with respect to the stage M41.

  Thereby, following the relative height adjustment of the flattening means M42, the layer 1 can be efficiently formed by the flattening means M42, and the productivity of the three-dimensional structure 10 is particularly excellent. be able to.

  The discharge pattern density of the liquid 2 'in the second region M412 is preferably equal to the discharge pattern density of the liquid 2' in the first region M411. For example, when the liquid 2 'is discharged at 720 dpi in the first region M411, the liquid 2' is preferably discharged at 720 dpi also in the second region M412.

  Thereby, the difference between the thickness of the cured portion 2 and the thickness of the cured product 6 can be made smaller, the effects as described above can be exhibited more significantly, and the finally obtained three-dimensional modeling The dimensional accuracy and mechanical strength of the object 10 can be made particularly excellent.

  Moreover, in this embodiment, the hardened | cured material 6 is formed so that it may pile up over several processes (refer 1b, 1f, 1m, 1s) so that it may respond | correspond to the some layer 1. FIG.

  Thereby, suitable thickness can be determined for each of the plurality of layers 1, and the dimensional accuracy and mechanical strength of the three-dimensional structure 10 as a whole can be made particularly excellent.

  Moreover, in this embodiment, the some hardened | cured material 6 formed so that it may pile up over several processes has all the same shape and the same area. In other words, among the plurality of cured products 6 formed so as to be stacked over a plurality of steps, a product formed in an arbitrary step is defined as a first cured product, and a step subsequent to the first cured product. When the second cured product is formed as the second cured product, the second cured product does not have a region that does not overlap with the first cured product when viewed in plan.

  By such a configuration, unintentional deformation (so-called drooling, etc.) of the cured product 6 can be more effectively prevented, and the difference between the thickness of the cured part 2 and the thickness of the cured product 6 can be further increased. It can be made small, and the effects as described above can be exhibited more remarkably. As a result, the dimensional accuracy and mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent.

  Although the manufacturing method of the three-dimensional structure according to the present invention only needs to have a layer forming process, a liquid application process, and a curing process, the manufacturing method of the three-dimensional structure 10 according to the present embodiment includes particles 11. And a layer forming step (1c, 1d, 1j, 1k, 1q, 1r) for forming layer 1 using layer forming composition 1 ′ containing solvent 12 and curing on layer 1 containing solvent 12 On the layer 1 in a state containing the first liquid application step (1e, 1l) for applying the liquid (cured part forming liquid) 2 ′ used for forming the part 2 (first cured part 2A) and the solvent 12 The applied liquid (cured part forming liquid) 2 ′ is cured to form a cured part 2 (first cured part 2A), a first curing step (1f, 1m), and the solvent 12 is removed from the layer 1 The solvent removal step (1g, 1n), and the cured portion 2 (second cured) in the layer 1 where the solvent 12 has been removed. 2B) a liquid (curing part forming liquid) 2 ′ used for formation, and a second liquid application step (1h, 1o) for infiltrating the liquid 2 ′ into the layer 1, and infiltrated into the layer 1 A second curing step (1i, 1p) for curing the liquid (curing portion forming liquid) 2 ′ and forming the curing portion 2 (second curing portion 2B), and sequentially repeating these steps. (1s) Furthermore, it has the unbonded particle removal process (1t) which removes what is not couple | bonded by the hardening part 2 among the particles 11 which comprise each layer 1 after that.

  Thus, in the first liquid application step, the liquid (cured part forming liquid) 2 ′ used for forming the cured part 2 (first cured part 2A) is applied on the layer 1 containing the solvent 12. By doing this, it is possible to prevent the liquid 2 ′ used for forming the cured portion 2 from inadvertently penetrating into a site other than the intended site. As a result, the cured portion 2 (first cured portion 2A) having a desired shape can be easily and reliably formed. Then, based on the height of the upper surface of the cured product 6 as described above, combined with the effect of determining the thickness of the layer 1 to be newly formed after the formation of the cured product, the finally obtained three-dimensional modeling The dimensional accuracy of the object 10 can be made particularly excellent.

  Further, in the present embodiment, prior to the first layer forming step, the cured portion 2 (the third portion is formed on the stage M41 where the layer 1 (the layer 1 formed using the layer forming composition 1 ′) is not formed. A third liquid application step (1a) for applying a liquid (cured part forming liquid) 2 ′ used for forming the cured part 2C), and curing the liquid 2 ′ to cure the second part (third cured part 2C). ) Forming a third curing step (1b).

  Thereby, the hardening part 2 (hardening part 2 which does not contain the particle | grains 11) buried in the lowermost layer 1 can be formed, and the layer 1 which does not contain the hardening part 2 which does not contain the particle 11 is not formed. Therefore, the productivity of the three-dimensional structure 10 can be made particularly excellent. Further, in the finally obtained three-dimensional structure 10, since the hardened portion 2 that constitutes the outer surface when viewed from the side can be unified with a portion made of a material that does not include the particles 11, The aesthetic appearance of the molded article 10 as a whole can be made particularly excellent.

  In the third liquid application step, the liquid 2 ′ is applied to the first region M411, and the liquid 2 ′ is applied to the second region M412. In the third curing step, the first region M411 is applied. The liquid 2 ′ applied to is cured to form a cured part 2 (third cured part 2 </ b> C), and the liquid 2 ′ applied to the second region M <b> 412 is cured to form a cured product 6.

  Thereby, not only the hardening part 2 formed on the upper surface of the layer 1, but also the hardening part 2 (third hardening part 2C) formed on the surface of the stage M41 (first region M411) is a layer forming step. It is possible to prevent unintentional remaining on the upper surface of the hardened portion 2 (third hardened portion 2C) at the end of the (first layer forming step). As a result, it is possible to more effectively prevent the above-described problem from occurring, and it is possible to particularly improve the dimensional accuracy and mechanical strength of the finally obtained three-dimensional structure.

Hereinafter, each step will be described.
≪Third liquid application process≫
In the third liquid application step, the liquid 2 ′ used for forming the cured portion 2 (third cured portion 2C) is applied by the ink jet method on the first region M411 of the stage M41 where the layer 1 is not formed ( 1a).

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

  Thereby, for example, in the finally obtained three-dimensional structure 10, the hardened portion 2 that constitutes the outer surface when viewed from the side can be unified with a portion made of a material that does not include the particles 11. The aesthetic appearance of the three-dimensional structure 10 as a whole can be made particularly excellent.

In particular, in this step, since the liquid 2 ′ is applied by an ink jet method, the liquid 2 ′ can be applied with good reproducibility even if the application pattern of the liquid 2 ′ has a fine shape. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly high.
In this step, the liquid 2 ′ is also applied to the second region M412 of the stage M41.

The liquid 2 ′ includes at least a polymerizable compound (uncured curable resin material) (liquid 2 ′ applied in the first liquid application process described later, liquid applied in the second liquid application process) The same applies to 2 ').
The liquid 2 ′ will be described in detail later.

≪Third curing process≫
The liquid 2 ′ applied to the first region M411 of the stage M41 becomes a curing unit 2 (third curing unit 2C) by performing a predetermined curing process thereafter (see 1b).

  For example, when the liquid 2 ′ contains a thermosetting polymerizable compound (thermosetting resin), the liquid 2 ′ can be cured by heating, and the liquid 2 ′ can be converted into a photocurable polymerizable compound (photocurable resin). When it is included, it can be cured by light irradiation.

  In the present step, the liquid 2 ′ applied to the second region M <b> 412 of the stage M <b> 41 is also subjected to the curing process as described above to form the cured product 6.

  Moreover, in order to form the hardening part 2 of predetermined thickness, before performing the process demonstrated later, a series including application | coating of liquid 2 '(liquid application process) and hardening of liquid 2' (hardening process). This process may be repeated.

≪Layer formation process≫
In the layer forming step, a layer 1 having a predetermined thickness is formed using a composition (layer forming composition) 1 ′ containing particles 11 and a solvent 12 (1c, 1d, 1j, 1k, 1q, 1r). reference).

In particular, in the first layer formation step, a composition containing the particles 11 and the solvent 12 on the stage (support) M41 provided with the cured portion 2 (third cured portion 2C) (layer forming composition). 1 ′ is used to form the layer 1 having a predetermined thickness (1c, 1d), and in the second and subsequent layer formation steps, the layer 1 (the layer 1 in which the coupling portion 3 is formed in the illustrated configuration) On top of this, a new layer 1 having a predetermined thickness is formed (1j, 1k, 1q, 1r) using a composition (layer-forming composition) 1 ′ containing particles 11 and a solvent 12.
The composition (layer forming composition) 1 ′ will be described in detail later.

  In addition, this step is performed so that at least a part of the hardened portion 2 previously formed is buried in the layer 1 newly formed in this step.

  That is, in the layer formation process performed in a state where the cured portion 2 (third cured portion 2C) formed in the third liquid application step described above is exposed on the outer surface, the cured portion 2 (third cured portion). Part 2C) is buried (see 1d), and the hardened part 2 (first hardened part 2A) formed in the first liquid application step described later is exposed on the outer surface. In the layer forming step performed in step (b), at least a part of the cured portion 2 (first cured portion 2A) is buried (see 1k and 1r).

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

  Further, for example, the second cured portion 2B is formed in a later step in a portion of the layer 1 in which the cured portion 2 (the cured portion 2 buried in the layer 1 in this step) is buried, in contact with the cured portion 2. (1h, 1i, 1o, 1p), it is more effective that an unintentional height difference occurs between the hardened part 2 buried in the layer 1 in this step and the second hardened part 2B. Can be prevented. As a result, the dimensional accuracy of the three-dimensional structure 10 is particularly excellent.

  In this step, the layer 1 is formed with the surface flattened using a squeegee as the flattening means M42.

  Further, in this step, when the layer 1 is formed in the first region M411 using the flattening means M42, the layer 1 is newly formed after the cured product 6 is formed based on the height of the upper surface of the cured product 6. The thickness of layer 1 is determined. That is, the flattening means M42 is brought into contact with the upper surface of the cured product 6, and the layer 1 having a predetermined thickness is formed on the basis of the height (contact surface) at which the flattening means M42 contacts the cured product 6. To do.

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

  In this step, the composition 1 ′ (particularly, the particles 11) is not left on the upper surface of the cured portion 2 buried in this step.

  Thereby, the fall of the adhesiveness of the said hardening part 2 and the hardening part 2 (1st hardening part 2A) formed at the 1st liquid provision process after that can be prevented, and finally obtained. The mechanical strength of the three-dimensional structure 10 can be made excellent. Moreover, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made excellent.

  In the illustrated configuration, the thickness of the layer 1 formed in this step is the same as the thickness of the buried hardened portion 2 (third hardened portion 2C, first hardened portion 2A), but formed in this step. The thickness of the layer 1 to be formed may be smaller than the thickness of the buried hardened part 2 (third hardened part 2C, first hardened part 2A). For example, by adjusting the height of the flattening means M42 so as to press the cured product 6 with a predetermined pressing force, the stress applied to the flattening means M42 is a portion where the cured portion 2 and the cured product 6 do not exist. Then, the height of the layer 1 formed by the flattening means M42 is lower than that of the hardened portion 2 buried in this step, as compared with the portion where the hardened portion 2 and the hardened product 6 exist. Can do. Thereby, the pressing force by the flattening means M42 applied to the upper surface of the hardened portion 2 buried in this step can be made relatively large, and the composition 1 is formed on the upper surface of the hardened portion 2 buried in this step. It is possible to more effectively prevent (particularly, the particles 11) from remaining.

  Although the thickness of the layer 1 formed at this process is not specifically limited, For example, it is preferable that they are 20 micrometers or more and 500 micrometers or less, and it is more preferable that they are 30 micrometers or more and 150 micrometers or less.

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

  The viscosity of the layer forming composition 1 ′ in the layer forming step is preferably 500 mPa · s or more and 1,000,000 mPa · s or less.

  Thereby, this process can be performed more efficiently and the productivity of the three-dimensional structure 10 can be made particularly excellent. In addition, in this specification, a viscosity means the value measured in 25 degreeC using an E-type viscosity meter (Tokyo Keiki Co., Ltd. VISCONIC ELD).

≪First liquid application process≫
In the first liquid application step, the liquid 2 used for forming the hardened portion 2 (first hardened portion 2A) in a region including the surface (upper surface) of the layer 1 containing the solvent 12 formed in the layer forming step. 'Is given (see 1e, 1l).

  Thus, when the liquid 2 ′ is applied, the layer 1 to which the liquid 2 ′ is applied is in a state containing the solvent 12, in other words, the gap between the particles 11 in the layer 1 is filled with the solvent. By being in the state, unintentional penetration of the liquid 2 ′ into the inside of the layer 1 can be suitably prevented. As a result, in the subsequent first curing step, the desired upper surface of the layer 1 can be obtained. The cured portion 2 (first cured portion 2A) can be formed in the shape of

  In particular, in this embodiment, when the layer 1 is viewed in plan among the surfaces of the layer 1 including the embedded cured part 2 (first cured part 2A, third cured part 2C), the cured part 2 ( It has the 1st liquid application process as a process of providing liquid 2 'to the field including the portion which does not overlap with the 1st hardening part 2A and the 3rd hardening part 2C (refer to 1e and 1l) ).

  Conventionally, when a new layer (upper layer) is formed on the surface of an already formed layer (lower layer) and a bonding portion (cured portion) is formed on the layer (upper layer), it should be formed on the layer (upper layer) When the joint (cured part) has a region that does not overlap with the joint (cured part) formed in the lower layer, the joint part (cured part) having the desired shape cannot be formed. Although it was easy to cause the problem that the dimensional accuracy of the finally obtained three-dimensional structure is lowered, by applying the liquid 2 ′ to the layer 1 containing the solvent 12, the cured portion to be formed in the upper layer Even if it has a region that does not overlap with the cured portion formed in the lower layer, the occurrence of the above problems can be reliably prevented. Therefore, among the surfaces of the layers including the buried cured portion (first cured portion, third cured portion), when the layer is viewed in plan, the cured portion (first cured portion, third cured portion) When the first liquid application process as the process of applying the liquid is performed on the region including the portion that does not overlap with the above-described region, the effects as described above are more remarkably exhibited.

  Further, in this step, since the liquid 2 'is applied by an ink jet method, the liquid 2' can be applied with good reproducibility even if the application pattern of the liquid 2 'has a fine shape. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly high.

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

≪First curing process≫
In the first curing step, a predetermined amount of liquid 2 ′ (liquid 2 ′ applied to the region including the surface (upper surface) of the layer 1 in a state including the solvent 12) applied in the first liquid applying step is determined. A curing process is performed to form a 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 applying step (in the illustrated configuration, applied to the upper surface of the cured product 6 formed in the third curing step). The cured liquid 2 ′) is also subjected to the curing treatment as described above to form a cured product 6.

≪Solvent removal process≫
In the solvent removal step, the solvent 12 is removed from the layer 1 (see 1g and 1n).

  Thereby, a space 4 in which the solvent 12 or the like does not exist is formed between the particles 11 constituting the layer 1. This space 4 functions as an absorption part that absorbs the liquid 2 ′ in the second liquid application step.

  This step may be performed under any conditions as long as it removes the solvent 12 from the layer 1, but can be performed by, for example, heat treatment, pressure reduction treatment, air blowing, or the like.

  When this step is performed by heating, the heating temperature is preferably, for example, 30 ° C. or more and 100 ° C. or less, and preferably 60 ° C. or more, although it varies depending on the constituent materials of the layer 1 and the like (types of particles 11, solvent 12, etc. More preferably, the temperature is 95 ° C. or lower.

  Thereby, the solvent 12 can be efficiently removed while preventing unintentional modification of the constituent material of the layer 1 and unintentional deformation of the layer 1 and the like, and the productivity of the three-dimensional structure 10 is improved. Can be made particularly excellent.

  Even if the liquid 2 ′ is applied to the upper surface of the layer 1 from which the solvent 12 is removed in this step in the previous step (first liquid application step), the liquid 2 ′ is not cured in the first step. Since the curing process is performed in the curing process and the cured part 2 (the first cured part 2A) has high shape stability, even if the solvent 12 is removed in this process, unintentional deformation occurs. That is effectively prevented.

≪Second liquid application process≫
In the second liquid application step, the liquid 2 ′ used for forming the cured part 2 (second cured part 2B) is applied to the layer 1 from which the solvent 12 has been removed, and the liquid 2 ′ is added to the layer 1. Infiltrate (see 1h, 1o).

  Thereby, the hardening part 2 (2nd hardening part 2B) can be formed in the inside of the layer 1 (site | part which was the space 4 between the particles 11) in the 2nd hardening process after that.

  Further, in this step, since the liquid 2 'is applied by an ink jet method, the liquid 2' can be applied with good reproducibility even if the application pattern of the liquid 2 'has a fine shape. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly high.

≪Second curing process≫
In the second curing step, a predetermined curing is applied to the liquid 2 ′ (liquid 2 ′ that has penetrated into the inside of the layer 1 (the portion that was the space 4 between the particles 11)) applied in the second liquid applying step. The treatment is performed to form the cured portion 2 (second cured portion 2B) (see 1i and 1p).

  Thereby, the coupling | bond part 3 which the particle | grains 11 couple | bonded by the said hardening part 2 (2nd hardening part 2B) can be formed. Since the bonding part 3 formed in this way includes the particles 11 and the cured part 2 (second cured part 2B), it is particularly excellent in hardness and mechanical strength. Therefore, the finally obtained three-dimensional structure 10 is particularly excellent in mechanical strength, and is more reliable in which unintentional deformation is more reliably prevented.

≪Unbound particle removal process≫
Then, after repeating the series of steps as described above (see 1 s), as a post-processing step, among the particles 11 constituting each layer 1, those not bound by the cured portion 2 (unbound particles) are removed. An unbound particle removing step (see 1t) is performed. Thereby, the three-dimensional structure 10 is taken out.

  As a specific method of this step, for example, a method of removing unbound particles with a brush, a method of removing unbound particles by suction, a method of blowing a gas such as air, a method of applying a liquid such as water ( Examples thereof include a method of immersing the laminate obtained as described above in a liquid, a method of spraying a liquid, and a method of applying vibration such as ultrasonic vibration. Moreover, it can carry out combining 2 or more types of methods selected from these. More specifically, there are a method of immersing in a liquid such as water after blowing a gas such as air, a method of applying ultrasonic vibration in a state of immersing in a liquid such as water, and the like. Especially, it is preferable to employ | adopt the method (especially the method of immersing in the liquid containing water) which provides the liquid containing water with respect to the laminated body obtained as mentioned above.

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

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

  5, FIG. 6, FIG. 7, and FIG. 8 are cross-sectional views schematically showing each step in the second embodiment of the method for manufacturing a three-dimensional structure of the present invention. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.

  As shown in FIGS. 5, 6, 7, and 8, the manufacturing method of the three-dimensional structure 10 of the present embodiment includes the same steps as those of the above-described embodiment, but is formed in the layer forming step. The method for determining the thickness of the layer 1 is different from that of the above-described embodiment.

  That is, in this embodiment, the height (thickness) of the cured product 6 formed using the liquid 2 ′ is measured by the height measuring means M7, and the formation of the cured product 6 is performed based on the measurement result. The thickness of the layer 1 to be newly formed later is determined.

  With such a configuration, for example, since it is not necessary to bring the flattening means M42 into contact with the cured product 6, unintentional wear and deformation of the flattening means M42 can be prevented, and the life of the flattening means M42 can be extended. And the effect of facilitating maintenance of the manufacturing apparatus of the three-dimensional structure 10 can be obtained. Even if 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 is appropriately determined. be able to. For this reason, the usage-amount of liquid 2 'used for formation of the hardened | cured material 6 can be reduced, and it is preferable from a viewpoint of reduction of the production cost of the three-dimensional structure 10, and resource saving.

<Liquid (Liquid for forming cured portion)>
Next, the liquid (hardening part formation liquid) used for manufacture of the three-dimensional structure according to the present invention will be described in detail.

  The liquid (cured portion forming liquid) 2 ′ includes at least the constituent components (including the precursor) of the cured portion 2.

(Curable resin material (polymerizable compound))
The liquid 2 ′ contains a resin material (polymerizable compound) that can undergo a curing reaction.

  Thereby, especially the intensity | strength etc. of the hardening part 2 formed can be made excellent. Moreover, in the 2nd hardening part 2B, it can function suitably as a binder which couple | bonds the particle | grains 11, and can make the mechanical strength of the three-dimensional structure 10 and the stability of a shape excellent. . In addition, since the heat resistance of the hardened portion 2 is excellent, it is more effective that unintentional deformation, unintentional modification, and deterioration of the material occur in the hardened portion 2 that receives a cumulative heat history with lamination. Therefore, the reliability of the three-dimensional structure 10 can be improved.

  Examples of the curable resin material (polymerizable compound) include a thermosetting resin; a visible light curable resin (narrowly defined photocurable resin) that is cured by light in the visible light region, an ultraviolet curable resin, and an infrared curable resin. And various photo-curable resins; X-ray curable resins and the like can be used, and one or more selected from these can be used in combination.

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

  As the ultraviolet curable resin (polymerizable compound), a resin in which addition polymerization or ring-opening polymerization is initiated by irradiation with ultraviolet rays by radical species or cationic species generated from a photopolymerization initiator, and a polymer is preferably used. . Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

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

  The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound, or a mixture thereof. Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

  In particular, the liquid 2 ′ preferably contains an acrylic polymerizable compound such as acrylic acid, methacrylic acid or a derivative thereof (for example, an ester compound) as the polymerizable compound.

  Thereby, especially the intensity | strength of the three-dimensional structure 10 obtained finally can be made excellent.

  In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like, addition products of isocyanates and epoxies, dehydration condensation products of carboxylic acids, etc. Can be used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines and thiols, as well as removal of halogen groups, tosyloxy groups, etc. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasing substituent and an alcohol, amine or thiol can also be used.

  Specific examples of the radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, (meth) acrylic acid ester, which is either monofunctional or polyfunctional. Can also be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of glycidyl ethers include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.), tri- or more functional glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, poly of cresol novolac resin) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2) 21P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), polycyclohexyl epoxy methyl ether of phenol novolac resin, etc. Oxetanes (for example, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.)) and the like.

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

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

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

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

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

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

  Further, the liquid 2 ′ may include a silicone-based polymerizable compound (which becomes a silicone-based resin by polymerization) as the polymerizable compound.

  Thereby, for example, the three-dimensional structure 10 made of a rubber-like elastic material can be suitably manufactured. As a result, it is possible to suitably manufacture a three-dimensional structure having a movable part and a deformed part by elastic deformation.

  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 of the three-dimensional structure 10 finally obtained can be made particularly excellent.

(Other ingredients)
Further, the liquid 2 ′ may contain components other than those described above. Examples of such components include various colorants such as pigments and dyes; dispersants; surfactants; polymerization initiators; polymerization accelerators; solvents; penetration enhancers; wetting agents (humectants); Examples include glazes; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; pH adjusters; thickeners; fillers;

  In particular, when the liquid 2 ′ contains a colorant, the three-dimensional structure 10 colored in a color corresponding to the color of the colorant can be obtained.

  In particular, by including a pigment as the colorant, the light resistance of the liquid 2 ′ and the three-dimensional structure 10 can be improved. As the pigment, either an inorganic pigment or an organic pigment can be used.

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

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

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

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

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

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

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

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

  When the liquid 2 'contains a pigment, the average particle size of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less. Thereby, the discharge stability of the liquid 2 ′ and the dispersion stability of the pigment in the liquid 2 ′ can be made particularly excellent, and an image with better image quality can be formed.

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

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

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

  When the liquid 2 'includes a colorant, the content of the colorant 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 ′ contains titanium oxide as a colorant, the content of titanium oxide in the liquid 2 ′ is preferably 12% by mass to 18% by mass, and more preferably 14% by mass to 16% by mass. The following is more preferable. Thereby, a particularly excellent concealing property can be obtained.

  When the liquid 2 ′ contains a pigment, the dispersibility of the pigment can be further improved by further containing a dispersant. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples of the polymer dispersant include, for example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, and sulfur-containing polymer. , Fluorine-containing polymers, and epoxy resins having one or more types as main components. Commercially available polymer dispersants include, for example, Ajinomoto Fine Techno's Ajisper series, Solsperse series (Solsperse 36000, etc.) available from Noveon, BYK's Dispervic series, Enomoto Kasei The company's Disparon series, etc. are listed.

  When the liquid 2 ′ contains a surfactant, the three-dimensional structure 10 can have better abrasion resistance. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used. Specific examples of the surfactant include, for example, BYK-347, BYK-348, BYK-UV3500, 3510, 3530, 3570 (above, trade names manufactured by BYK).

  Further, the liquid 2 'may contain a solvent. Thereby, the viscosity of the liquid 2 ′ can be suitably adjusted, and even when the liquid 2 ′ contains a high-viscosity component, the ejection stability of the liquid 2 ′ by the ink jet method is particularly excellent. Can do.

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

  The viscosity of the liquid 2 ′ is preferably 2 mPa · s or more and 30 mPa · s or less, and more preferably 5 mPa · s or more and 20 mPa · s or less. Thereby, the discharge stability of the liquid 2 'by the ink jet method can be made particularly excellent.

Moreover, you may use multiple types of liquid 2 'for manufacture of the three-dimensional molded item 10. FIG.
For example, the liquid 2 ′ used in the first liquid application step (liquid 2 ′ used in the formation of the first cured portion 2A), the liquid 2 ′ used in the second liquid application step (in the formation of the second cured portion 2B). The liquid 2 ′ to be used and the liquid 2 ′ to be used in the third liquid application step (the liquid 2 ′ used to form the third cured portion 2C) may be the same as or different from each other. Also good.

  Further, a liquid 2 '(color ink) containing a colorant and a liquid 2' (clear ink) containing no colorant may be used. Thereby, for example, the liquid 2 ′ containing a colorant is used as the liquid 2 ′ to be applied to the area that affects the color tone on the appearance of the three-dimensional structure 10, and the color tone is affected on the appearance of the three-dimensional structure 10. A liquid 2 ′ that does not contain a colorant may be used as the liquid 2 ′ that is applied to the region that is not provided. Further, in the finally obtained three-dimensional structure 10, a region (coat) formed using the liquid 2 ′ not containing the colorant on the outer surface of the region formed using the liquid 2 ′ containing the colorant. A plurality of types of liquids 2 ′ may be used in combination so as to provide a layer.

  Further, for example, a plurality of types of liquids 2 ′ containing colorants having different compositions may be used. Thereby, the color reproduction region that can be expressed can be widened by combining these liquids 2 ′.

  When a plurality of types of liquids 2 ′ are used, it is preferable to use at least a violet (cyan) liquid 2 ′, a reddish violet (magenta) liquid 2 ′, and a yellow (yellow) liquid 2 ′. Thereby, the color reproduction region which can be expressed can be made wider by the combination of these liquids 2 '.

  Further, when the white liquid 2 'is used in combination with another colored liquid 2', for example, the following effects can be obtained. That is, the finally obtained three-dimensional structure 10 overlaps the first region to which the white (white) liquid 2 ′ is applied and the first region, and is on the outer surface side of the first region. And a region (second region) to which a colored liquid 2 ′ other than white is applied. Thereby, the 1st area | region to which white (white) liquid 2 'was provided can exhibit concealment property, and the chroma of the three-dimensional structure 10 can be improved more.

<Layer forming composition>
Next, the layer forming composition used for the production of the three-dimensional structure of the present invention will be described in detail.

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

  By using such a layer forming composition 1 ′, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent, and the fluidity of the composition 1 ′ can be improved. As a result, the particles 11 can be effectively prevented from agglomerating and the like, and the ease of handling (handleability) of the composition 1 ′ during production can be made particularly excellent. In addition, as described above, the first cured portion 2A and the second cured portion 2B, which are different from each other in the positional relationship with the layer 1 formed using the composition 1 ', can be easily and reliably formed. The three-dimensional structure 10 to be manufactured can be excellent in mechanical strength and the like and also in dimensional accuracy.

(particle)
The layer forming composition 1 ′ includes a plurality of particles 11.
The particles 11 are preferably high in hardness.

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

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

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

  Due to such a configuration, when the three-dimensional structure 10 is manufactured (in the second liquid application step), the curable resin material or the reaction product (hereinafter, these are collectively referred to as the liquid 2 ′). And also simply referred to as “resin material”) can be suitably penetrated into the pores, exhibiting an anchor effect, and as a result, the binding force of the particles 11 can be made particularly excellent. As a result, the mechanical strength of the three-dimensional structure 10 as a whole can be made particularly excellent. Further, since the resin material constituting the liquid 2 ′ enters the pores of the particles 11, it is possible to effectively prevent unintentional wetting and spreading of the liquid 2 ′. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made higher.

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

  As an inorganic material which comprises the particle | grains 11, various metals, a metal compound, etc. are mentioned, for example. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; various kinds such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Metal hydroxides; various metal nitrides such as silicon nitride, titanium nitride and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metals such as calcium carbonate and magnesium carbonate Carbonates; sulfates of various metals such as calcium sulfate and magnesium sulfate; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; aluminum borate, magnesium borate, etc. And various metal borates and composites thereof.

  Examples of the organic material constituting the particles 11 include synthetic resins and natural polymers. More specifically, polyethylene resin; polypropylene; polyethylene oxide; polypropylene oxide, polyethyleneimine; polystyrene; polyurethane; polyurea; A silicone resin; an acrylic silicone resin; a polymer having a (meth) acrylic acid ester such as polymethyl methacrylate as a constituent monomer; a cross polymer having a (meth) acrylic acid ester as a constituent monomer such as a methyl methacrylate crosspolymer (ethylene Acrylic acid copolymer resin, etc.); polyamide resin such as nylon 12, nylon 6, copolymer nylon; polyimide; carboxymethyl cellulose; gelatin; starch; chitin;

  Especially, it is preferable that the particle | grains 11 are comprised by the metal oxide, and it is more preferable that it is comprised by the silica.

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

  In particular, when the particles 11 are made of silica, the effects described above are more remarkably exhibited. In addition, since silica is excellent in fluidity, it is advantageous for forming a layer with higher uniformity of thickness, and also in making the productivity and dimensional accuracy of the three-dimensional structure particularly excellent. It is advantageous.

The particles 11 may be subjected to a surface treatment such as a hydrophobic treatment.
The hydrophobization treatment applied to the particles 11 may be any treatment that increases the hydrophobicity of the particles (mother particles), but is preferably a hydrocarbon group-introducing one.

  Thereby, the hydrophobicity of the particle | grains 11 can be made higher. In addition, the degree of hydrophobic treatment at each particle 11 and each part of the surface of the particle 11 (including the surface inside the hole in the case where the particle 11 has a hole open to the outside) is uniformly uniform. The property can be made higher.

As a compound used for the hydrophobizing treatment, a silane compound containing a silyl group is preferable. Specific examples of compounds that can be used in the hydrophobization treatment include, for example, hexamethyldisilazane, dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, and propyltrichlorosilane. , Propyltriethoxysilane, propyltrimethoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p -Tolyltrimethoxysilane, p-tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n- Tildi-n-butyroxysilane, di-sec-butyldi-sec-butyroxysilane, di-t-butyldi-t-butyloxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyldimethylchlorosilane, Octadecylmethyldichlorosilane, octadecylmethoxydichlorosilane, 7-octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyl Dimethylchlorosilane, undecyltrichlorosilane, vinyldimethylchlorosilane, methyloctadecyldimethoxy Orchid, methyldodecyldiethoxysilane, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, Methyl triethoxysilane, methyl tri-n-propoxy silane, methyl isopropoxy silane, methyl-n-butoxy silane, methyl tri-sec-butoxy silane, methyl tri-t-butoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tri-n-propoxy Silane, ethyl isopropoxy silane, ethyl-n-butyroxy silane, ethyl tri-sec-butyloxy silane, ethyl tri-t-butyl Tyroxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n- Propyltriethoxysilane, isobutyltriethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, 2- [2- ( Trichlorosilyl) ethyl] pyridine, 4- [2- (trichlorosilyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane Dibenzyldimethoxysilane, dibenzyldiethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane , Benzyltrimethoxysilane, benzylmethyldimethoxysilane, benzyldimethylmethoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzyltriethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxy Silane, 3-acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane , Allyltrimethoxysilane, allyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepine dimethyl ester, 5 (Bicycloheptenyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyl Trimethoxysilane, 2-chloromethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-silane Noethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyl Triethoxysilane, 3-cyclohexenyltrichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane ,
Cyclohexyldimethylchlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltri Chlorosilane, cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7- Dimethylnorpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) to Ethoxysilane, N, N-diethyl-3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (full Furyloxymethyl) triethoxysilane, 2-hydroxy-4- (3-triethoxypropoxy) diphenylketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p -(Methylphenethyl) methyldichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3 - Sidoxypropyltrimethoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7, -hexachloro-6 Triethoxysilyl-2-norbornene, 3-iodopropyltrimethoxylane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethoxysilane, 3- Mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyl Trimetoki Sisilane, RN-α-phenethyl-N′-triethoxysilylpropylurea, SN-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane Phenethyldimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyl Trimethoxysilane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilyl) Ethyl) -5- (chloroacetoxy) bicycloheptane, (S) -N-triethoxysilylpropyl-O-mentcarbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide, 3- (triethoxysilyl) propyl Succinic anhydride, N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenylvinyldiethoxysilane, 3-thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3- (tri Ethoxysilyl) propyl} phthalamic acid, (3 , 3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) Ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N, N-tributylammonium bromide N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyl Methoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris -T-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane Benzyldimethylchlorosilane, benzylmethyldichlorosilane, Netyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicycloheptenyl) triethoxysilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (Bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-phenoxypropyltrichlorosilane, t-butylphenylchlorosilane, t-butylphenylmethoxy Silane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl ) Phenylethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, Examples include 3-cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyltrichlorosilane, and fluorinated alkylsilane. It can be used alone or in combination are-option.

Among these, hexamethyldisilazane is preferably used for the hydrophobization treatment.
Thereby, the hydrophobicity of the particle | grains 11 can be made higher. In addition, the degree of hydrophobic treatment at each particle 11 and each part of the surface of the particle 11 (including the surface inside the hole in the case where the particle 11 has a hole open to the outside) is uniformly uniform. The property can be made higher.

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

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

  The average particle diameter of the particles 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.

  As a result, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 can be more effectively prevented. The dimensional accuracy of the molded article 10 can be made particularly excellent. Further, the fluidity of the layer forming composition 1 ′ can be made particularly excellent, and the productivity of the three-dimensional structure 10 can be made 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.

  As a result, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 10 can be more effectively prevented. The dimensional accuracy of the molded article 10 can be made particularly excellent. Further, the fluidity of the layer forming composition 1 ′ can be made particularly excellent, and the productivity of the three-dimensional structure 10 can be made particularly excellent.

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

  As a result, the space (holes) into which the resin material (binder) enters can be sufficiently provided, and the mechanical strength of the particles 11 itself can be improved. As a result, the resin material enters the holes. The mechanical strength of the three-dimensional structure 10 having the connecting portion 3 formed can be particularly excellent.

In the present invention, the porosity of the particles 11 refers to the ratio (volume ratio) of the pores existing inside the particles 11 to the apparent volume of the particles 11, and the density of the particles 11 is represented by ρ [ g / cm ³ ] and the true density ρ ₀ [g / cm ³ ] of the constituent material of the particles 11, the value is represented by {(ρ ₀ −ρ) / ρ ₀ } × 100.

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

  Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent. Further, when the liquid 2 ′ (colored ink) containing a pigment is used for manufacturing the three-dimensional structure 10, the pigment can be suitably held in the pores of the particles 11. For this reason, unintentional diffusion of the pigment can be prevented, and a high-definition image can be more reliably formed.

  The particles 11 may have any shape, but preferably have a spherical shape. As a result, the fluidity of the layer forming composition 1 ′ can be made particularly excellent, the productivity of the three-dimensional structure 10 can be made particularly excellent, and the three-dimensional structure 10 to be manufactured can be improved. It is possible to effectively prevent the occurrence of the intentional irregularities and to make the dimensional accuracy of the three-dimensional structure 10 particularly excellent.

The layer forming composition 1 ′ may include a plurality of types 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 or less, and more preferably 10% by mass or more and 53% by mass or less.

  Thereby, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent while sufficiently improving the fluidity of the layer forming composition 1 ′.

(solvent)
The layer forming composition 1 ′ contains a solvent 12.

  Thereby, the handleability (ease of handling) of the layer forming composition 1 ′ can be made particularly excellent, and the layer 1 with higher thickness uniformity can be easily formed. Unintentional deformation of the layer 1 can be prevented more effectively. In addition, in the first liquid application step, it is possible to effectively prevent the liquid 2 ′ from infiltrating into the layer 1 (the layer 1 including the solvent 12) unintentionally. The hardened portion 2 formed by the method can surely have a desired shape. From the above, the dimensional accuracy of the finally obtained three-dimensional structure 10 can be made particularly excellent.

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

  Among these, the layer forming composition 1 ′ preferably contains an aqueous 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 ′ can be made particularly excellent. In addition, water is easy to remove after the formation of the layer 1, and even when it remains in the three-dimensional structure 10, it is difficult to adversely affect water. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems. When the liquid 2 ′ used for forming the first cured portion 2A contains a polymerizable compound as described above (in particular, an acrylic polymerizable compound or a silicone polymerizable compound), the layer 1 (solvent 12 is removed). Involuntary penetration of the liquid 2 'into the containing layer 1) can be more effectively prevented, the first cured portion 2A having a desired shape can be more reliably formed, and three-dimensional The dimensional accuracy and reliability of the shaped article 10 can be made particularly excellent. Further, when the layer forming composition 1 ′ contains a water-soluble resin as a binder described in detail later, the water-soluble resin can be more suitably dissolved in the layer forming composition 1 ′. The effect by including a binder (water-soluble resin) as described in detail is more effectively exhibited.

  The aqueous solvent may be a solvent having high solubility in water. Specifically, for example, the solubility in water at 25 ° C. (mass soluble in 100 g of water) is 30 [g / 100 g water] or more. It is preferable that it is more than 50 [g / 100g water].

  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, and more preferably 29% by mass or more and 89% by mass or less.

  Thereby, while the effect by containing the solvent 12 as mentioned above is exhibited more notably, since the solvent 12 can be easily removed in a short time in the manufacturing process of the three-dimensional structure 10, the three-dimensional structure This is advantageous from the viewpoint of improving the productivity of the article 10.

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, and more preferably 47% by mass or more and 90% by mass or less.
Thereby, the effects as described above are more remarkably exhibited.

(binder)
The layer forming composition 1 ′ may include a binder together with the plurality of particles 11 and the solvent 12.

  Thereby, a plurality of particles 11 can be suitably bonded (temporarily fixed) in the layer 1 formed using the layer-forming composition 1 ′ (particularly, the layer 1 in a state where the solvent 12 is removed). It is possible to effectively prevent the particles 11 from being scattered unintentionally. Thereby, the further improvement of the operator's safety and the dimensional accuracy of the manufactured three-dimensional structure 10 can be aimed at.

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

  Thereby, the fluidity of the layer-forming composition 1 ′ can be made particularly good, and the unintentional variation in the thickness of the layer 1 formed using the layer-forming composition 1 ′ is more effective. Can be prevented. Further, when the layer 1 in a state where the solvent 12 is removed is formed, the binder can be attached to the particles 11 with higher uniformity over the entire layer 1, and unintentional compositional unevenness occurs. It can prevent more effectively. For this reason, generation | occurrence | production of the unintentional dispersion | variation in the mechanical strength in each site | part of the three-dimensional structure 10 finally obtained can be prevented more effectively, and the reliability of the three-dimensional structure 10 is higher. Can be.

  Any binder can be used as long as it has a function of temporarily fixing a plurality of particles 11 in the layer 1 formed using the layer-forming composition 1 ′ (particularly, the layer 1 from which the solvent 12 has been removed). Although it is good, a water-soluble resin can be preferably used.

  By including the water-soluble resin, when the layer-forming composition 1 ′ contains an aqueous solvent (particularly water) as the solvent 12, the binder (water-soluble resin) is dissolved in the layer-forming composition 1 ′. It can be included, and the fluidity and handleability (ease of handling) of the layer-forming composition 1 ′ can be made particularly excellent. As a result, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Moreover, the site | part to which the liquid 2 'of the layer 1 was not provided in the manufacturing process of the three-dimensional structure 10 can be easily and efficiently removed by applying an aqueous solvent (particularly water). As a result, the productivity of the three-dimensional structure 10 can be made particularly excellent. Moreover, since it can prevent easily and reliably that the site | part from which a layer should be removed adheres to and remains in the finally obtained three-dimensional structure 10, the dimensional accuracy of the three-dimensional structure 10 is particularly high. It can be excellent.

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

  Examples of water-soluble resins include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactone diol, sodium polyacrylate, polyacrylamide, modified polyamide, polyethyleneimine, polyethylene oxide, and a random co-polymer of ethylene oxide and propylene oxide. Synthetic polymers such as polymerized polymers, natural polymers such as corn starch, mannan, pectin, agar, alginic acid, dextran, glue, gelatin, semi-synthetic polymers such as carboxymethylcellulose, hydroxyethylcellulose, oxidized starch, modified starch, etc. One or two or more selected can be used in combination.

  Specific examples of the water-soluble resin product include, for example, methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metroise SM-15), hydroxyethyl cellulose (manufactured by Fuji Chemical Co., Ltd., AL-15), hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd., HPC- M), carboxymethyl cellulose (manufactured by Nichirin Chemical Co., Ltd., CMC-30), starch phosphate ester sodium (I) (manufactured by Matsutani Chemical Co., Ltd., Hoster 5100), polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd., PVP K-90), Methyl vinyl ether / maleic anhydride copolymer (manufactured by GAF Gauntlet, AN-139), polyacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.), modified polyamide (modified nylon) (manufactured by Toray Industries, Inc., AQ nylon), polyethylene oxide (steel chemical company) Made by PEO-1, Meisei Chemical Industries, Arco ), Random copolymer of ethylene oxide and propylene oxide (manufactured by Meisei Chemical Co., Ltd., Alcox EP), sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), carboxyvinyl polymer / crosslinked acrylic water-soluble resin ( Sumitomo Seika Co., Ltd., Akpec).

  Especially, when the water-soluble resin as a binder is polyvinyl alcohol, the mechanical strength of the three-dimensional structure 10 can be made particularly excellent. Further, by adjusting the degree of saponification and the degree of polymerization, characteristics of the binder (for example, water solubility, water resistance, etc.) and characteristics of the layer forming composition 1 ′ (for example, viscosity, fixing force of the particles 11, wettability, etc.) Can be controlled more suitably. For this reason, it can respond suitably by manufacture of the various three-dimensional structure 10. Polyvinyl alcohol is inexpensive and stable in supply among various water-soluble resins. For this reason, the stable three-dimensional structure 10 can be manufactured while suppressing the production cost.

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

  When the water-soluble resin as a binder contains polyvinyl alcohol, the polymerization degree of the polyvinyl alcohol is preferably 300 or more and 1000 or less. Thereby, when the layer forming composition 1 ′ contains an aqueous solvent (particularly water), the mechanical strength of each layer 1 and the adhesion between adjacent layers 1 can be made particularly excellent.

  Moreover, when the water-soluble resin as a binder is polyvinylpyrrolidone (PVP), the following effects are acquired. That is, since polyvinylpyrrolidone is excellent in adhesion to various materials such as glass, metal, and plastic, the strength and shape stability of the layer 1 to which the liquid 2 ′ is not applied are particularly excellent. In particular, the dimensional accuracy of the three-dimensional structure 10 obtained can be made particularly excellent. Moreover, since polyvinylpyrrolidone shows high solubility with respect to various organic solvents, when the layer forming composition 1 ′ contains an organic solvent, the fluidity of the layer forming composition 1 ′ is particularly excellent. It is possible to suitably form the layer 1 ′ in which the unintentional thickness variation is more effectively prevented, and the dimensional accuracy of the finally obtained three-dimensional structure 10 is particularly excellent. Can be. Moreover, since polyvinyl pyrrolidone shows high solubility also to an aqueous solvent (especially water), in the unbonded particle removal step (after the completion of shaping), among the particles 11 constituting each layer 1, a resin material (bonded) Those not bound by the agent can be removed easily and reliably. Moreover, since polyvinylpyrrolidone is excellent in affinity with various colorants, when the liquid 2 ′ containing the colorant is used in the second liquid application step, the colorant diffuses unintentionally. Can be effectively prevented.

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

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

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

  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, and 1.0% by mass. More preferably, it is 10 mass% or less.

  As a result, the effects of including the binder as described above are more remarkably exhibited, and the content of the particles 11 and the like in the layer-forming composition 1 ′ can be made sufficiently high and manufactured. In particular, the mechanical strength of the three-dimensional structure 10 can be made excellent.

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

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

  FIG. 9 is a cross-sectional view schematically showing a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention.

  The three-dimensional structure manufacturing apparatus M100 manufactures the three-dimensional structure 10 by repeatedly forming and laminating the layer 1 using the layer forming composition 1 '. In particular, the three-dimensional structure manufacturing apparatus M100 manufactures the three-dimensional structure 10 by performing the three-dimensional structure manufacturing method of the present invention as described above.

  As shown in FIG. 9, the three-dimensional structure manufacturing apparatus M100 includes a control unit M2, a composition supply unit M3 that stores the layer forming composition 1 ′, and a layer forming unit that is supplied from the composition supplying unit M3. Irradiating a layer forming part M4 for forming the layer 1 using the composition 1 ', a liquid discharging part (liquid applying means) M5 for discharging the liquid 2' to the layer 1, and an energy ray for curing the liquid 2 ' Energy beam irradiating means (curing means) M6, and height measuring means M7 for measuring the height of the cured product 6 formed using the liquid 2 ′.

The control unit M2 includes a computer M21 and a drive control unit M22.
The computer M21 is a general desktop computer configured with a CPU, a memory, and the like inside. The computer M21 converts the shape of the three-dimensional structure 10 as model data, and outputs cross-sectional data (slice data) obtained by slicing the shape into parallel thin layers of slices to the drive control unit M22. . Moreover, when measuring the height of the upper surface of the hardened | cured material 6 with the height measurement means M7 explained in full detail behind and adjusting the thickness of the layer 1 based on the said height, based on the thickness of the layer 1 Then, rewriting (correction / correction) of the sectional data (slice data) is performed.

  The drive control unit M22 functions as a control unit that drives the layer forming unit M4, the liquid discharge unit M5, the energy beam irradiation unit M6, the height measurement unit M7, and the like. Specifically, for example, the discharge pattern and discharge amount of the liquid 2 ′ by the liquid discharge unit M5, the supply amount of the layer forming composition 1 ′ from the composition supply unit M3, the lowering amount of the stage (elevating stage) M41, and the like To control.

  The composition supply unit M3 is configured to move in response to a command from the drive control unit M22, and the layer forming composition 1 'accommodated therein is supplied to the stage M41.

  The layer forming part M4 is supplied with the layer forming composition 1 ′, and supports a layer (lifting stage) M41 that supports the layer 1 formed by the layer forming composition 1 ′, and the layer forming part M4 held by the stage M41. A flattening means (squeegee) M42 that forms the layer 1 while flattening the composition 1 ', a guide rail M43 that regulates the operation of the flattening means M42, and the elevating stage M41 are surrounded and are in close contact with the elevating stage M41. And a provided frame M45.

  When the new layer 1 is formed on the previously formed layer 1, the elevating stage M41 is sequentially lowered by a predetermined amount according to a command from the drive control unit M22. The thickness of the newly formed layer 1 is defined by the descending amount of the elevating stage M41 and the height of the flattening means M42 described in detail later.

  The stage M41 has a flat surface (a portion to which the layer forming composition 1 'and the liquid 2' are applied; a portion including the first region M411 and the second region M412). Thereby, the layer 1 with high uniformity of thickness can be formed easily and reliably. Moreover, based on the height of the upper surface of the hardened | cured material 6, the thickness of the layer 1 newly formed can be adjusted suitably.

  Stage M41 is preferably made of a high-strength material. Examples of the constituent material of the stage M41 include various metal materials such as stainless steel.

  Further, the surface of the stage M41 (the portion to which the layer forming composition 1 ′ and the liquid 2 ′ are applied. The portion including the first region M411 and the second region M412) may be subjected to surface treatment. Good. Thereby, for example, the constituent material of the layer forming composition 1 ′ and the constituent material of the liquid 2 ′ can be more effectively prevented from sticking firmly to the stage M <b> 41, or the durability of the stage M <b> 41 is particularly excellent. It is possible to achieve stable production of the three-dimensional structure 10 over a longer period of time. Examples of the material used for the surface treatment of the surface of the stage M41 include fluorine resins such as polytetrafluoroethylene.

  The squeegee as the flattening means M42 has a longitudinal shape extending in the X direction, and includes a blade having a blade-like shape with a pointed lower end.

  The layer 1 formed by flattening the layer forming composition 1 ′ by the flattening means M42 is necessary based on information such as the height of the upper surface of the cured product 6 by the height measuring means M7. Therefore, the constituent component (for example, the particles 11) of the layer forming composition 1 ′ remains unintentionally left on the upper surface of the cured portion 2 at the end of the layer forming step. Can be prevented.

  The length of the blade in the Y direction is provided with a vibration mechanism (not shown) that applies minute vibrations to the blade so that the layer forming composition 1 ′ can be smoothly diffused by the flattening means (squeegee) M42. It may be.

  The three-dimensional structure manufacturing apparatus M100 detects, for example, the stress applied to the flattening means M42 when the flattening means M42 comes into contact with the upper surface of the cured product 6 formed in the second region M412 of the stage M41. There may be provided stress detecting means (not shown).

  Thereby, for example, when the flattening means M42 is brought into contact with the upper surface of the cured product 6, the state in which the predetermined stress is given to the flattening means M42 at a predetermined value is reduced by the flattening means M42 when the layer 1 is formed. It can be determined as the height.

  The contact of the flattening means M42 with the cured product 6 can be suitably performed by relatively moving the stage M41 and the flattening means M42 in the Z direction. For example, the flattening means M42 is moved downward. It may be performed by moving in the direction, or may be performed by moving the stage M41 upward.

  The liquid discharge part (liquid applying means) M5 discharges the liquid 2 'by the ink jet method. By providing such a liquid discharge part (liquid applying means) M5, the liquid 2 ′ can be applied in a fine pattern, and even a three-dimensional structure 10 having a fine structure is manufactured with particularly high productivity. can do. Moreover, the hardening part 2 and the hardened | cured material 6 can be suitably formed as what has the same conditions (for example, the same thickness, the same density).

  As a droplet discharge method (inkjet method), a piezo method, a method in which the liquid 2 ′ is discharged by bubbles generated by heating the liquid 2 ′, and the like can be used. The piezo method is preferred from the standpoint of difficulty in altering the constituent components.

  The liquid ejection unit (liquid application unit) M5 controls the pattern to be formed and the amount of liquid 2 'to be applied according to a command from the drive control unit M22. A discharge pattern, a discharge amount, and the like of the liquid 2 ′ by the liquid discharge unit (liquid application unit) M <b> 5 are determined based on slice data. As a result, a necessary and sufficient amount of the liquid 2 ′ can be applied, the cured portion 2 having a desired pattern can be reliably formed, and the dimensional accuracy and mechanical strength of the three-dimensional structure 10 can be more reliably ensured. It can be excellent. In addition, when the liquid 2 ′ contains a colorant, a desired color tone can be obtained with certainty, and the change in the thickness of the layer 1 can cause an undesired change in color tone, and the color balance can be unintentionally lost. Can be reliably prevented.

  The energy beam irradiation means (curing means) M6 irradiates energy rays for curing the applied liquid 2 '.

  The type of energy beam irradiated by the energy beam irradiation unit M6 varies depending on the constituent material of the liquid 2 ', and examples thereof include ultraviolet rays, visible rays, infrared rays, X rays, γ rays, electron beams, ion beams, and the like. Among these, from the viewpoint of cost and the productivity of the three-dimensional structure 10, it is preferable to use ultraviolet rays.

The height measuring means M7 measures the height of the upper surface of the cured product 6.
Information on the height of the upper surface of the cured product 6 is transmitted from the height measuring means M7 to the control unit M2, and is used to adjust the thickness of the formed layer 1 and the relative height of the flattening means M42. .

  Further, in the configuration shown in FIG. 9, the height measuring means M <b> 7 obtains the height of the cured product 6 by obtaining the focal distance from above the cured product 6. With such a configuration, the height of the cured product 6 can be measured without moving the height measuring means M7, so that the time required for measuring the height of the cured product 6 is shortened. The productivity of the three-dimensional structure 10 can be made particularly excellent.

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

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

  The use of the three-dimensional structure of the present invention is not particularly limited, and examples thereof include appreciation objects / exhibits such as dolls and figures; medical devices such as implants.

  Moreover, the three-dimensional structure of the present invention may be applied to any of prototypes, mass-produced products, and custom-made products.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

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

  Further, in the above-described embodiment, the first region in which the cured product used for determining the layer thickness is formed on the modeling stage and the part constituting the substantial part of the target three-dimensional modeled object is formed. Although the case where it is formed in a different second region has been described, the cured product used for determining the layer thickness is the one formed in the first region, in particular, the substantial part of the three-dimensional structure. It may be a part of

  In the above-described embodiment, the case where the height of the upper surface of the cured product used for determining the layer thickness is determined by observation from the upper surface of the cured product is representatively described. The thickness may be obtained by observation from the side surface of the cured product.

  In the above-described embodiment, the case where a fixed height measuring unit is used has been described as a representative example. However, the height measuring unit is movable (for example, movable in the XY direction of the stage). May be. Thereby, for example, the height of the upper surface of the cured product can be measured at a plurality of points.

  Further, in the above-described embodiment, the case where a solvent-containing composition is used as the layer-forming composition is representatively described. However, the layer-forming composition only needs to include at least a plurality of particles. It may not be included.

  Further, in the above-described embodiment, a plurality of cured products formed so as to be stacked over several steps are typically described as having the same shape and the same area. The plurality of cured products that are sequentially reduced in area toward the upper side, and the laminate formed by stacking the plurality of cured products may have, for example, a pyramid shape or the like. Even in such a case, the same effect as described above can be obtained.

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

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

  Moreover, in embodiment mentioned above, when performing a layer formation process, a 1st liquid provision process, a 1st hardening process, a solvent removal process, a 2nd liquid provision process, and a 1st hardening process as a series of processes. However, the series of steps to be repeated may be different in each cycle. For example, the first liquid application step and the first curing step are omitted from the above steps. It may have a cycle, or may have a cycle in which the second liquid application step and the second curing step are omitted.

  Further, for example, the curing process performed for forming each cured part may not be repeated every time a pattern corresponding to each cured part is formed, and an uncured pattern is provided in a plurality of layers. It may be performed in a lump after forming the laminated body.

  In the above-described embodiment, the liquid used for forming the cured portion and the cured product has been mainly described with respect to the case where the liquid is applied by an inkjet method. However, the liquid used for forming the cured portion and the cured product may be other methods (for example, Or other printing method).

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

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

DESCRIPTION OF SYMBOLS 10 ... Three-dimensional structure 1 ... Layer 1 '... Composition (Composition for layer formation)
DESCRIPTION OF SYMBOLS 11 ... Particle 12 ... Solvent 2 ... Curing part 2A ... 1st hardening part 2B ... 2nd hardening part 2C ... 3rd hardening part 2 '... Liquid (Liquid for hardening part formation)
DESCRIPTION OF SYMBOLS 3 ... Coupling part 4 ... Space 6 ... Hardened material M100 ... Three-dimensional structure manufacturing apparatus M2 ... Control part M21 ... Computer M22 ... Drive control part M3 ... Composition supply part M4 ... Layer formation part M41 ... Stage (lifting stage, support) body)
M411 ... 1st area | region M412 ... 2nd area | region M42 ... Flattening means (squeegee)
M43 ... guide rail M45 ... frame M5 ... liquid discharge part (liquid applying means)
M6 ... Energy beam irradiation means (curing means)
M7: Height measuring means

Claims (13)

Forming a layer, repeating the process of discharging the liquid to the layer, and manufacturing a three-dimensional structure,
A layer forming step of forming the layer having a predetermined thickness using a composition for forming a layer containing particles;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
Based on the height of the upper surface of the cured product formed using the liquid, the thickness of the layer to be newly formed after the formation of the cured product is determined. Forming a layer, repeating the process of discharging the liquid to the layer, and manufacturing a three-dimensional structure,
A layer forming step of forming the layer having a predetermined thickness using a composition for forming a layer containing particles;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
The three-dimensional modeling characterized by measuring the height of a cured product formed using the liquid and determining the thickness of the layer to be newly formed after the cured product is formed based on the measurement result Manufacturing method. Forming a layer, repeating the process of discharging the liquid to the layer, and manufacturing a three-dimensional structure,
A layer forming step of flattening the layer forming composition containing particles by using a flattening means to form the layer having a predetermined thickness;
A liquid application step of applying the liquid to the layer;
A curing step of curing the liquid and forming a cured portion;
The flattening means is brought into contact with an upper surface of a cured product formed using the liquid, and the layer having a predetermined thickness is formed on the basis of the contact surface. Production method.   2. The cured product is formed in a second region different from a first region in which a part constituting a substantial part of the target three-dimensional modeled object is formed on a modeling stage. The manufacturing method of the three-dimensional structure of any one of thru | or 3.   The method for manufacturing a three-dimensional structure according to claim 4, wherein the second region is provided on an outer peripheral side of the first region.   The method for manufacturing a three-dimensional structure according to claim 4 or 5, wherein a discharge pattern density of the liquid in the second region is equal to a discharge pattern density of the liquid in the first region.   The method of manufacturing a three-dimensional structure according to any one of claims 1 to 6, wherein the cured product is formed so as to be stacked over a plurality of steps so as to correspond to the plurality of layers.   Among the plurality of cured products formed so as to be stacked over a plurality of steps, a product formed in an arbitrary step is formed in a first cured product, a step after the first cured product. 8. The three-dimensional image according to claim 7, wherein when the second cured product is used, the second cured product does not have a region that does not overlap the first cured product when viewed in plan. Manufacturing method of a model. Performing the layer forming step using the layer forming composition containing the particles and a solvent,
After the layer forming step, a first liquid applying step of applying the liquid onto the layer containing the solvent;
A first curing step for curing the liquid applied on the layer;
The method for producing a three-dimensional structure according to claim 1, further comprising a solvent removal step of removing the solvent from the layer. After the solvent removal step, a second liquid application step of applying the liquid to the layer in a state where the solvent is removed and allowing the liquid to penetrate into the layer;
The method for producing a three-dimensional structure according to claim 9, further comprising a second curing step of curing the liquid that has penetrated into the layer. A three-dimensional structure manufacturing apparatus that forms a layer and repeats the process of discharging liquid to the layer to manufacture a three-dimensional structure,
A stage for forming the layer using a layer-forming composition containing particles;
A liquid applying means for applying a liquid to the layer;
A curing means for curing the liquid,
The three-dimensional structure manufacturing apparatus characterized by determining the thickness of the layer to be newly formed after forming the cured product based on the height of the upper surface of the cured product formed using the liquid.   A three-dimensional structure manufactured using the method for manufacturing a three-dimensional structure according to any one of claims 1 to 10.   A three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus according to claim 11.

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