JP2016088004A - Method for manufacturing three-dimensional molded article, apparatus for manufacturing three-dimensional 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 having a broad selection range of tones and designs and having physical properties matching its appearance can be manufactured with high productivity, and a three-dimensional molded article having excellent designing property and physical properties matching its appearance.SOLUTION: The method for manufacturing a three-dimensional molded article comprises stacking layers 1 to manufacture a three-dimensional molded article, in which a first portion 2 as a region including at least a part of an outer surface of the three-dimensional molded article is formed by discharging a liquid by an inkjet process and then curing, and a second portion as at least a partial region of other portion than the first portion in the three-dimensional molded article is formed by injecting a thermoplastic composition containing a fused thermoplastic resin from a nozzle M81 and then solidifying.SELECTED DRAWING: Figure 1

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.

  Conventionally, for example, a method of forming a three-dimensional structure based on a model of a three-dimensional object generated by three-dimensional CAD software or the like is known.

  As a method of forming a three-dimensional structure, a lamination method (three-dimensional structure method) is known. In the laminating method, in general, after a model of a three-dimensional object is divided into a number of two-dimensional cross-sectional layers, the cross-sectional members corresponding to each two-dimensional cross-sectional layer are sequentially formed, and the cross-sectional members are sequentially laminated to obtain the tertiary. Form the original model.

  The lamination method can be formed immediately as long as there is a model of the 3D model to be modeled, and there is no need to create a mold prior to modeling. It is possible to form a shaped object. In addition, since thin plate-like cross-sectional members are laminated one by one, for example, even a complex object having an internal structure can be formed as an integrated shaped object without being divided into a plurality of parts. .

  As such a laminating method, a technique is known in which gypsum particles are bonded by applying water to gypsum powder to produce a three-dimensional structure (see, for example, Patent Document 1).

  However, with such a technique, it is difficult to obtain a three-dimensional structure having a desired color tone, and as a result, it has been difficult to sufficiently improve the design of the three-dimensional structure. In addition, in such a method, since the range of selection of materials that can be used is relatively narrow, the manufactured three-dimensional structure has various physical properties such as specific gravity, hardness, elastic modulus, and flexibility. The user of the three-dimensional structure sometimes felt uncomfortable, unlike what was imagined from the appearance of the three-dimensional structure.

JP-T-2003-531220 gazette

  An object of the present invention is to provide a method for producing a three-dimensional structure, a method for producing a three-dimensional structure, which can produce a three-dimensional structure having a wide range of color tone and design properties and having properties corresponding to the appearance with high productivity. It is to provide an apparatus, and to provide a three-dimensional structure that is excellent in design and has physical properties according to the appearance.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure by producing a three-dimensional structure by laminating layers,
Forming a first portion which is a region including at least a part of the outer surface of the three-dimensional structure by discharging a liquid by an inkjet method and then curing the first portion;
By injecting a thermoplastic composition containing a molten thermoplastic resin from a nozzle into a second part that is at least a part of a part other than the first part of the three-dimensional structure, and then solidifying the second part. It is characterized by forming.

  Accordingly, it is possible to provide a method for manufacturing a three-dimensional structure that can produce a three-dimensional structure having a wide range of choices in color tone and design properties and having properties corresponding to the appearance with high productivity.

  In the method for producing a three-dimensional structure of the present invention, the liquid is applied to a layer formed using a particle-containing composition containing particles by an ink jet method, and the liquid is infiltrated into the gaps between the particles and then cured. It is preferable to form the first part.

  As a result, a solidified portion can be formed inside the layer, and as a result, a bonded portion in which particles are bonded by the solidified portion can be formed. Since the bonding portion formed in this way includes particles and a solidified portion (cured portion), it is particularly excellent in hardness and mechanical strength. Therefore, the finally obtained three-dimensional structure is particularly excellent in mechanical strength, and is more reliable in which unintentional deformation is more reliably prevented.

In the method for producing a three-dimensional structure according to the present invention, the particle-containing composition contains a solvent,
When the liquid is applied to the layer, the solvent is preferably removed from the layer.

  Thereby, the handleability (ease of handling) of the particle-containing composition can be made particularly excellent, the productivity of the three-dimensional structure can be made particularly excellent, and finally The dimensional accuracy, mechanical strength, and reliability of the obtained three-dimensional structure are particularly excellent.

  In the three-dimensional structure manufacturing method of the present invention, the particle-containing composition preferably includes an aqueous solvent as the solvent.

  Thereby, the fluidity of the particle-containing composition and the uniformity of the composition of the layer formed using the particle-containing composition can be made particularly excellent. Moreover, water is easy to remove after the formation of the layer, and even when it remains in the three-dimensional structure, it is difficult to adversely affect water. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the particle-containing composition further includes a binder.

  Thereby, the further improvement of the operator's safety at the time of manufacture of a three-dimensional structure and the dimensional accuracy of the manufactured three-dimensional structure can be aimed at.

  In the three-dimensional structure manufacturing method of the present invention, after forming the second portion using the thermoplastic composition, at least a part of the second portion is embedded using the particle-containing composition. It is preferable to form the layer as described above.

  Thereby, the dimensional accuracy of the three-dimensional structure becomes particularly excellent. In addition, the productivity of the three-dimensional structure can be made particularly excellent.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that the liquid contains a photocurable resin.

  As a result, the mechanical strength of the obtained three-dimensional structure and the productivity of the three-dimensional structure can be made particularly excellent, and unintentional deformation during the production of the three-dimensional structure can be more effectively performed. Can be prevented.

In the method for producing a three-dimensional structure of the present invention, the thermoplastic resin contains polycarbonate,
The liquid preferably contains an acrylic polymerizable compound.

  Thereby, the adhesiveness of the solidification part formed using the said thermoplastic resin and the solidification part formed using the said liquid can be made especially excellent, and durability and reliability of a three-dimensional structure The property can be made particularly excellent.

  In the three-dimensional structure manufacturing method of the present invention, the thickness of the first part is preferably 0.01 mm or more and 1.0 mm or less.

  Thereby, the width | variety of selection of the color tone of the three-dimensional structure and the design property can be made wider, while making the three-dimensional structure have physical properties according to the appearance more reliably. Further, the adhesion between the first part and the second part can be made particularly excellent, and the durability of the three-dimensional structure can be made particularly excellent.

  In the three-dimensional structure manufacturing method of the present invention, the thermoplastic composition preferably includes a filler in addition to the thermoplastic resin.

  Thereby, the mechanical strength and reliability as the whole three-dimensional structure can be made particularly excellent. Moreover, the adjustment of the hardness of the finally obtained three-dimensional structure can also be suitably performed. In addition, the specific gravity and the like of the second part can be easily adjusted, and a physical property of the three-dimensional structure can be adjusted more suitably, such as a three-dimensional structure having a high specific gravity can be manufactured.

The three-dimensional structure manufacturing apparatus of the present invention is a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
Liquid ejection means for ejecting the liquid used for forming the cured portion by an inkjet method;
And a thermoplastic composition imparting means for imparting a thermoplastic composition containing a molten thermoplastic resin.

  Accordingly, it is possible to provide a three-dimensional structure manufacturing apparatus capable of manufacturing a three-dimensional structure having a wide range of color tone and design properties and having physical properties according to the appearance with high productivity.

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

  Thereby, it is excellent in the designability and can provide the three-dimensional structure which has the physical property according to the external appearance.

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

  Thereby, it is excellent in the designability and can provide the three-dimensional structure which has the physical property according to the external appearance.

The three-dimensional structure of the present invention is a three-dimensional structure manufactured using a three-dimensional modeling method,
The first part which is a region including at least a part of the outer surface is made of a material including a cured product of a curable resin, and is a part of at least a part of a part other than the first part. The second portion is composed of a material containing a thermoplastic resin.

  Thereby, it is excellent in the designability and can provide the three-dimensional structure which has the physical property according to the external appearance.

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 method of manufacturing the three-dimensional structure 10 according to the present embodiment includes a particle-containing composition (layer-forming composition) 1 ′ including particles 11 and a solvent 12. A layer forming step (1b, 1c, 1d, 1h, 1i, 1j, 1n, 1o) for forming the layer 1 using, and infiltrating the liquid 2 ′ into the layer 1 and then curing the layer 1; From the nozzle M81, a first solidified part forming step (1e, 1f, 1k, 1l) for forming the solidified part 2 (first solidified part 2A) and a thermoplastic composition 2 ″ containing a molten thermoplastic resin are obtained from the nozzle M81. And a second solidified portion forming step (1a, 1g, 1m) for injecting and forming the solidified portion 2 (second solidified portion 2B). These steps are sequentially repeated (1p), and thereafter Next, among the particles 11 constituting each layer 1, those not bonded by the solidified portion 2 are removed. And a coupling particle removal step (1q).

  And the 1st site | part which is an area | region containing at least one part of the outer surface of the three-dimensional structure 10 is solidified by forming the 1st solidification part 2A (liquid 2 'is ejected by the inkjet method, and is hardened after that. Part 2), and a second part which is at least a part of the part other than the first part of the three-dimensional structure 10 is formed as a second solidified part 2B (molten thermoplastic composition 2). '' Is formed as a solidified portion 2) formed by injecting from the nozzle M81 and then solidifying (see 1q).

  Thus, in this embodiment, each part of the three-dimensional structure 10 is not formed by the same method, but the solidified portion 2 is formed by a different method depending on the part of the three-dimensional structure 10.

  Thereby, the characteristics according to each method act synergistically, the range of selection of color tone and design property is wide, and the three-dimensional structure 10 having physical properties according to the appearance can be manufactured with high productivity.

  More specifically, the part (first part) corresponding to the outer surface of the finally obtained three-dimensional structure 10 is formed by ejecting the liquid 2 ′ by the ink jet method and then curing it, thereby forming the tertiary. The productivity of the original shaped article 10 can be made excellent. Further, in the ink jet method, for example, liquids containing various colorants can be suitably used as the liquid 2 ′ to be ejected, so that the range of selection of the color tone and design properties of the three-dimensional structure 10 can be expanded. . In addition, in the ink jet method, the liquid 2 ′ can be applied with high reproducibility even in a fine pattern, so that the dimensional accuracy of the finally obtained three-dimensional structure 10 can be increased. In particular, the texture of the outer surface (color tone, surface flatness, surface roughness, uneven shape, etc.) that greatly affects the appearance of the three-dimensional structure 10 can be made excellent. When an object is a model (including a doll, a figure, etc.), it is possible to express a texture like the actual object (an object imitated by the model).

  In addition, at least a part of the region other than the first region (second region) is formed by injecting the molten thermoplastic composition 2 ″ from the nozzle M81 and then solidifying the three-dimensional modeling. Various physical properties (for example, specific gravity, hardness, elastic modulus, flexibility, etc.) of the entire object 10 can be suitably adjusted to desired conditions.

  This is because the method of forming the solidified portion 2 by injecting and solidifying the molten thermoplastic composition 2 ″ from the nozzle M81 is compared with the method of forming the solidified portion 2 using the inkjet method. This is because the solidified portion 2 can be stably formed even when various additives are included in the material for use (particularly when the additive is included at a high content).

  More specifically, in the ink jet method, when various additives are added to the liquid 2 ′ to be ejected, the influence on the ejection of droplets is large, and it is necessary to set the ejection conditions according to the composition of the liquid 2 ′. In addition, there is a problem that the dispersion of the droplet amount becomes large, the positional accuracy of the droplet discharge is lowered, and in some cases, the droplet discharge itself becomes impossible. In the method of forming the solidified portion 2 by injecting and solidifying the composition 2 ″ from the nozzle M81, when the thermoplastic composition 2 ″ includes various additives (particularly, when the additive is included at a high content rate) ), The material (thermoplastic composition 2 ″) can be stably supplied to the target site. Further, as will be described in detail later, the thermoplastic composition 2 ″ is usually stored in a solid state such as a filament before injection, and therefore has a higher specific gravity than, for example, a thermoplastic resin. In the case where the thermoplastic composition 2 ″ is in a solid state, the dispersed state of the filler or the like can be improved even when the filler (for example, a metal material or the like) is included. Further, such a thermoplastic composition 2 ″ is usually melted immediately before injection and extruded from the nozzle M81, and has a relatively high viscosity even at the time of injection, and is applied to a target site. After that, it solidifies in a relatively short time. For this reason, even in the solidified part 2 (second solidified part 2B) at the time of injection or after injection, the dispersed state of the filler or the like can be maintained in a good state. Therefore, the unintentional variation in composition in the second part can be effectively prevented, and the physical properties of the three-dimensional structure 10 can be surely satisfied.

Hereinafter, each step will be described.
«Second solidified portion forming step»
In the second solidified portion forming step, the molten thermoplastic composition 2 ″ is injected from the nozzle M81 to form the solidified portion 2 (second solidified portion 2B) (see 1a, 1g, and 1m).

  In particular, in the first second solidified portion forming step, the molten thermoplastic composition 2 ″ is injected from the nozzle M81 onto the surface of the stage (support) M41, and the solidified portion 2 (second second) having a predetermined pattern is injected. The solidified portion 2B) is formed (see 1a), and in the second and subsequent second solidified portion forming steps, the layer 1 provided with the solidified portion 2 (the first solidified portion 2A and the second solidified portion 2B). On top, the molten thermoplastic composition 2 ″ is injected from the nozzle M81 to form a solidified portion 2 (second solidified portion 2B) having a predetermined pattern (see 1 g and 1 m).

  The molten thermoplastic composition 2 ″ is applied to a predetermined part, and then solidifies when the temperature is lowered to become a solidified part 2 (second solidified part 2 B).

  In this step, as the second solidified portion 2B, a second part that is at least a part of a part other than the first part of the three-dimensional structure 10 is formed.

  As described above, by having the solidified portion 2 (second solidified portion 2B) formed by injecting the molten thermoplastic composition 2 ″ from the nozzle M81 and then solidifying it, the physical properties of the three-dimensional structure 10 are obtained. (For example, specific gravity, hardness, elastic modulus, flexibility, etc.) can be suitably adjusted, and the three-dimensional structure 10 can be obtained as having physical properties according to its appearance.

  In the present embodiment, the second and subsequent second solidified portion forming steps (the step of forming the second solidified portion 2B on the layer 1) should be in contact with the layer 1 (the second solidified portion 2B). It is carried out with the solvent 12 removed from the layer 1).

  Thereby, the unintentional deformation | transformation of the layer 1 in this process can be prevented more effectively, and the unintentional deformation | transformation of the 2nd solidification part 2B is also prevented more effectively. As a result, the dimensional accuracy and reliability of the finally obtained three-dimensional structure 10 are particularly excellent.

In this step, the filament-like (thread-like) thermoplastic composition 2 ″ is heated and melted and injected from the nozzle M81.
The thermoplastic composition 2 ″ will be described in detail later.

  In this step, the molten thermoplastic composition 2 is also applied to the second region M412, which is a region different from the first region M411, which is a region for manufacturing the target three-dimensional structure 10 of the stage M41. '' And solidified to form a solidified product 6 having the same height as the second solidified portion 2B formed in the same process (see 1a, 1g, and 1m). The solidified product 6 is used to determine the thickness of the layer 1 to be formed in the layer forming step, as will be described in detail later.

  In particular, in the present embodiment, the solidified product 6 is formed so as to be stacked over a plurality of times (see 1a, 1g, 1m, and 1p) so as to correspond to the plurality of layers 1.

  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.

  In the present embodiment, the plurality of solidified products 6 formed so as to be stacked over several steps have the same shape and the same area. In other words, among the plurality of solidified products 6 formed so as to be stacked over a plurality of steps, the one formed in an arbitrary step is defined as a first solidified product, and a step subsequent to the first solidified product. When the second solidified product is formed from the above, the second solidified product does not have a region that does not overlap the first solidified product when viewed in plan.

  By such a configuration, unintentional deformation (so-called drooling) of the solidified product 6 can be more effectively prevented, and the difference between the thickness of the solidified portion 2 and the thickness of the solidified product 6 can be further increased. It can be made small, and the dimensional accuracy and mechanical strength of the three-dimensional structure 10 as a whole can be further improved.

≪Layer formation process≫
In the layer formation step, a layer 1 having a predetermined thickness is formed using a particle-containing composition (layer-forming composition) 1 ′ containing particles 11 and a solvent 12 (1b, 1c, 1d, 1h, 1i). 1j, 1n, 1o).

In particular, in the first layer formation step, the layer forming composition 1 ′ containing the particles 11 and the solvent 12 is used on the stage (support) M41 provided with the solidified portion 2 (second solidified portion 2B). Then, the layer 1 having a predetermined thickness is formed (see 1b, 1c, and 1d). In the second and subsequent layer formation steps, the layer 1 (in the configuration shown, the layer 1 on which the coupling portion 3 is formed) is formed. Then, a new layer 1 having a predetermined thickness is formed using the layer-forming composition 1 ′ containing the particles 11 and the solvent 12 (see 1h, 1i, 1j, 1n, and 1o).
The layer forming composition (particle-containing composition) 1 ′ will be described in detail later.

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

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

  Further, in the present embodiment, at least a part of the solidified portion 2 (second solidified portion 2B) previously formed is buried in the layer 1 formed in this step (1c, 1i, 1o).

  Thereby, for example, the stability of the shape of the solidified portion 2 formed in a later step is improved on the upper surface side of the solidified portion 2 (the solidified portion 2 buried in the layer 1 in this step). Moreover, the height adjustment of the layer 1 formed at this process can be performed suitably. As a result, the dimensional accuracy of the three-dimensional structure 10 is particularly excellent. Moreover, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Further, for example, in a later step, the solidified portion 2 (solidified portion 2 buried in the layer 1 in this step) is contacted with the solidified portion 2 (second solidified portion 2B) of the layer 1 to be buried. In the case of forming the first solidified portion 2A (see 1e, 1f, 1k, 1l), an unintentional elevation between the solidified portion 2 buried in the layer 1 in this step and the second solidified portion 2B. It can prevent more effectively that a difference arises. As a result, the dimensional accuracy of the three-dimensional structure 10 is particularly excellent.

  In this step, it is preferable that the layer forming composition 1 ′ (particularly the particles 11) is not left on the upper surface of the solidified portion 2 (second solidified portion 2 </ b> B) buried in the present step.

  Thereby, the fall of the adhesiveness of the said solidification part 2 and the solidification part 2 (1st solidification part 2A) formed at the 1st solidification part formation process after that can be prevented. Moreover, it can prevent that an aesthetic appearance is impaired.

  In order to prevent the layer forming composition 1 ′ (particularly, the particles 11) from remaining on the upper surface of the solidified portion 2 (second solidified portion 2B) buried in this step, the above-described solidified product 6 is used. be able to.

  That is, the thickness of the layer 1 formed in this step can be determined based on the height of the upper surface of the solidified product 6 formed using the molten thermoplastic composition 2 ''.

  Thereby, the constituent components (for example, the particles 11) of the layer forming composition 1 ′ are unintentionally formed on the upper surface of the solidified portion 2 (second solidified portion 2B) buried in this step at the end of this step. It can be prevented from remaining. As a result, in the subsequent steps, the adhesion between the solidified portion 2 and the solidified portion 2 newly formed on the solidified portion 2 can be reliably improved. As a result, the mechanical strength of the finally obtained three-dimensional structure 10 can be made particularly excellent. Further, three-dimensional due to the unintentional presence of the particles 11 constituting the layer forming composition 1 ′ between the arbitrary solidified portion 2 and the solidified portion 2 formed on the solidified portion 2. A decrease in the dimensional accuracy of the shaped article 10 can be more effectively prevented.

  In particular, in this embodiment, in the layer forming process, the flattening means M42 is brought into contact with the upper surface of the solidified product 6, and the height (contacting surface) at which the flattening means M42 comes into contact with the solidified product 6 is used as a reference. The layer 1 having a predetermined thickness is formed (see 1b, 1h, and 1n).

  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.

  In the illustrated configuration, the thickness of the layer 1 formed in this step is the same as the thickness of the solidified portion 2 to be buried (second solidified portion 2B), but the thickness of the layer 1 formed in this step is the same. May be smaller than the thickness of the solidified portion 2 to be buried (second solidified portion 2B). For example, by adjusting the height of the flattening means M42 so as to press the solidified product 6 with a predetermined pressing force, the stress applied to the flattening means M42 is a portion where the solidified portion 2 and the solidified product 6 do not exist. Then, the height of the layer 1 formed by the flattening means M42 may be lower than that of the solidified portion 2 buried in this step, as compared with the portion where the solidified portion 2 and the solidified product 6 are present. it can. Thereby, the pressing force by the flattening means M42 applied to the upper surface of the solidified portion 2 buried in this step can be made relatively large, and the layer forming layer is formed on the upper surface of the solidified portion 2 buried in this step. It can prevent more effectively that composition 1 '(especially particle | grains 11) remain | survives.

  In addition, the solidified product 6 may be formed in a region (first region M411) in which a part constituting the substantial part of the target three-dimensional structure 10 on the stage M41 is formed. In the present embodiment, it is formed in a second region M412 different from the first region M411.

  Thereby, when the flattening means M42 is brought into contact (when the thickness of the newly formed layer 1 is determined), the solidified portion 2 or the layer 1 related to the modeling of the target three-dimensional structure 10 is not affected. Intentional deformation or the like can be prevented more reliably. 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.

  In the present embodiment, the layer forming composition 1 ′ is applied to the first region M411 with a predetermined thickness, and then the solvent 12 contained in the layer forming composition 1 ′ is removed (1d, 1j).

  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 subsequent first solidification part forming step.

  The removal of the solvent 12 may be performed under any conditions, but can be performed by, for example, heat treatment, pressure reduction treatment, air blowing, or the like.

  When the solvent 12 is removed by heating, the heating temperature is preferably, for example, 30 ° C. or more and 100 ° C. or less, although it varies depending on the constituent material of the layer 1 and the like (types of particles 11, solvent 12 and the like). More preferably, the temperature is from 95 ° C to 95 ° C. The upper limit of the temperature range is preferably not more than the boiling point of the solvent 12 in order to prevent shape change due to rapid vaporization.

  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.

  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 solidified part forming process≫
In the first solidified portion forming step, the liquid 2 ′ is applied by an ink jet method (see 1e and 1k), and then the liquid 2 ′ is cured (see 1f and 1l) to form the first solidified portion 2A. To do.

  By applying the liquid 2 'by the 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 increased. In general, the liquid 2 ′ ejected using an ink jet method can suitably contain various colorants and the like. For this reason, the color tone of the solidification part 2 (1st solidification part 2A) formed using liquid 2 'can be controlled easily and reliably. Further, for example, by using a plurality of different types of liquids 2 ′ for forming the solidified part 2 (first solidified part 2A), for example, the color tone at each part is different, or the landing position of the liquid 2 ′ By adjusting the mixing ratio of the plurality of types of liquids 2 ′, the color reproduction region that can be expressed using the limited types of liquids 2 ′ can be widened (for example, full color expression). Moreover, although the 1st site | part containing the outer surface of the three-dimensional structure 10 is a part which is especially easy to affect the external appearance of the three-dimensional structure 10, forming such a 1st part by an inkjet method. Thus, the aesthetics of the three-dimensional structure 10 can be easily and reliably improved.

  In particular, in the present embodiment, the liquid 2 ′ used for forming the solidified portion 2 (first solidified portion 2A) is formed on the layer 1 in a state where the solvent 12 is removed and the spaces 4 are present between the plurality of particles 11 by the inkjet method. And the liquid 2 'penetrates into the layer 1 (see 1e and 1k), and then the liquid 2' penetrated into the layer 1 is cured (see 1f and 1l).

  Thereby, the solidification part 2 (1st solidification part 2A) can be formed in the inside of the layer 1 (part which was the space 4 between the particle | grains 11), As a result, the said solidification part 2 (1st solidification part) Part 2A) can form the joint part 3 in which the particles 11 are joined. Since the joint part 3 formed in this way includes the particles 11 and the solidified part 2 (first solidified part 2A), the joint part 3 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.

  The thickness of the first part (the first solidified portion 2A provided as the region including the outer surface of the three-dimensional structure 10) is preferably 0.01 mm or more and 1.0 mm or less, and 0.02 mm or more. More preferably, it is 0.5 mm or less.

  Thereby, the function of the 2nd part can be more effectively exhibited, controlling the property of the surface of three-dimensional structure 10 more suitably. As a result, the range of selection of the color tone and design of the three-dimensional structure 10 can be increased while ensuring that the three-dimensional structure 10 has physical properties according to the appearance. Further, the adhesion between the first part and the second part can be made particularly excellent, and the durability of the three-dimensional structure 10 can be made particularly excellent.

  In the present embodiment, the three-dimensional structure 10 has a bottom surface that is not visually recognized in a normal usage pattern (for example, the three-dimensional structure 10 is used by being fixed on a support base, or the three-dimensional structure 10 is used. The entire outer surface of the three-dimensional structure 10 that can be visually recognized in a normal usage form is the first portion configured by the first solidified portion 2A (1q). reference).

  With such a configuration, the effects as described above are more remarkably exhibited, and the aesthetic properties of the three-dimensional structure 10 as a whole can be made particularly excellent.

≪Unbound particle removal process≫
Then, after repeating the series of steps as described above (see 1p), as a post-processing step, among the particles 11 constituting each layer 1, those not bound by the solidified portion 2 (unbound particles) are removed. An unbound particle removing step (see 1q) 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 manufacture a three-dimensional structure having a wide range of selection of color tone and design properties and having physical properties according to the appearance with high productivity.

  In particular, according to the three-dimensional structure manufacturing method of the present embodiment, a three-dimensional structure excellent in dimensional accuracy and the like can be efficiently manufactured.

[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 the present embodiment, the height measurement unit M9 measures the height (thickness) of the solidified product 6 formed using the molten thermoplastic composition 2 ″, and based on the measurement result, The thickness of the layer 1 newly formed after the formation of the solidified product 6 is determined.

  With such a configuration, for example, since it is not necessary to bring the flattening means M42 into contact with the solidified 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 when the area of the solidified product 6 is relatively small, the height (thickness) of the solidified 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 the thermoplastic composition 2 '' used for formation of the solidified product 6 can be reduced, which is preferable from the viewpoint of reducing the production cost of the three-dimensional structure 10 and saving resources.

<Thermoplastic composition (second solidified part forming material)>
Next, the thermoplastic composition (second solidified portion forming material) used for producing the three-dimensional structure of the present invention will be described in detail.

  The thermoplastic composition 2 '' used for forming the second solidified portion 2B is melted by heating and injected from the nozzle M81.

(Thermoplastic resin)
The thermoplastic composition 2 '' includes at least a thermoplastic resin.

  Examples of the thermoplastic resin constituting the thermoplastic composition 2 ″ include acrylonitrile-butadiene-styrene (ABS), polyacrylate, polyolefin, cyclic olefin polymer, polycarbonate, polyamide, polyimide, polyethylene, polybutylene terephthalate, and liquid crystal polymer. Resin (LCP), polyether ether ketone (PEEK), thermoplastic elastomer (TPE), polystyrene, polyvinyl chloride, polysulfone, polyurethane, polyester, epoxy resin, silicone resin, diallyl phthalate resin, cellulose plastic, rosin-modified maleic acid Resin, polycaprolactone, poly (lactide-co-glycolide), polylactide, poly (lactide-co-caprolactone), nylon 12, PPSF (polyphen Rusarufon) and PLA (polylactic acid) resins, copolymers thereof, and the like, may be used alone or in combination of two or more selected from these.

  Among these, polycarbonate is preferable as the thermoplastic resin. By using polycarbonate, the impact resistance, heat resistance, flame retardancy, and the like of the second solidified portion 2B can be made particularly excellent. Also, polycarbonate is excellent in dispersion stability of fillers (particularly fillers composed of high specific gravity materials such as metal materials) even in a molten state. In addition, polycarbonate has excellent characteristics as described above, but is relatively inexpensive and excellent in cost performance as a raw material for the three-dimensional structure 10.

  Further, since the polycarbonate is excellent in affinity with the polymer of the acrylic polymerizable compound, the first solidified portion 2A is composed of a polymer of the acrylic polymerizable compound (liquid 2 ′ Can include an acrylic polymerizable compound), the adhesion between the first solidified portion 2A and the second solidified portion 2B can be particularly excellent, and the durability of the three-dimensional structure 10 can be improved. The reliability can be made particularly excellent.

(Other ingredients)
The thermoplastic composition 2 '' may contain components other than the thermoplastic resin (other components). For example, various colorants such as pigments and dyes; wetting agents (humectants); fixing agents; antifungal agents; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; It may be included.

  In particular, when the thermoplastic composition 2 ″ contains a filler, the mechanical strength of the second solidified portion 2B formed using the thermoplastic composition 2 ″ can be made particularly excellent. The mechanical strength and reliability of the finally obtained three-dimensional structure 10 as a whole can be made particularly excellent. Moreover, since the hardness of the 2nd solidification part 2B formed using thermoplastic composition 2 '' can be raised, the adjustment of the hardness of the three-dimensional structure 10 finally obtained can also be performed suitably. it can. Further, if the thermoplastic composition 2 ″ contains a filler, the specific gravity of the second solidified portion 2B formed using the thermoplastic composition 2 ″ and the thermoplastic composition 2 ″ is easily adjusted. be able to. For example, in the solidified portion 2 (first solidified portion 2A) formed using the liquid 2 ′ ejected by the ink jet method, a high specific gravity solidified portion (second solidified portion 2B) that is difficult to be realized is used. It can be formed easily. Thus, the physical property of the three-dimensional structure 10 can be adjusted more suitably.

  As the filler, for example, various metal materials (including alloys), metal compounds (for example, metal oxides, metal nitrides, metal carbides, etc.), carbon materials (graphite, carbon nanotubes, etc.) and the like can be used. In the case of forming a solidified portion having a high specific gravity as described above, a metal material is preferable. Since the metal material generally has high specific gravity and excellent strength, the effect is more remarkably exhibited.

  On the other hand, when it is desired to reduce the weight, it is desirable to use a hollow material such as a silica balloon, a glass balloon, or a shirasu balloon.

  Furthermore, conductivity can be imparted by using carbon black, carbon fiber, metal powder, metal foil, etc., or magnetism can be imparted by using ferrite-based particles, magnetic iron oxide, or the like.

  Thereby, desired characteristics can be easily imparted to the second solidified portion 2 </ b> B formed using the thermoplastic composition 2 ″, and the above-described effects can be exhibited more remarkably.

  The shape of the filler is not particularly limited, and may be any shape such as a spherical shape, a spindle shape, a needle shape, a cylindrical shape, a scale shape, or an indefinite shape.

  The filler content in the thermoplastic composition 2 ″ is preferably 30% by volume or more and 90% by volume or less, and more preferably 52% by volume or more and 74% by volume or less.

  As a result, it is possible to more effectively prevent the undesired compositional variation in the second solidified portion 2B formed by using the thermoplastic composition 2 ″, and to make the above-described effects more prominent. It can be demonstrated.

  In the second solidified part forming step, the viscosity of the thermoplastic composition 2 ″ when applying the thermoplastic composition 2 ″ to a desired site is preferably 10 Pa · s or more and 2000 Pa · s or less, More preferably, it is 50 Pa · s or more and 1000 Pa · s or less.

  Thereby, the thermoplastic composition 2 '' can be more reliably applied to a desired site in a desired shape and pattern, and the dimensional accuracy of the three-dimensional structure 10 can be more reliably improved. it can. Moreover, the productivity of the three-dimensional structure 10 can be made particularly excellent.

  Further, the heating temperature of the thermoplastic composition 2 ″ when injecting the thermoplastic composition 2 ″ from the nozzle M81 in the second solidified portion forming step depends on the composition of the thermoplastic composition 2 ″. The temperature is preferably from 100 ° C. to 400 ° C., more preferably from 150 ° C. to 300 ° C.

  Thereby, the viscosity of the thermoplastic composition 2 ″ when the thermoplastic composition 2 ″ is injected from the nozzle M81 can be made suitable, and the thermoplastic composition can be more reliably formed in a desired shape and pattern. The product 2 '' can be applied to a desired site, and the time until the melted thermoplastic composition 2 '' is cooled and solidified after being applied to the target site is shortened. It can prevent more reliably that thermoplastic composition 2 '' exerts a bad influence on other site | parts (for example, already formed solidified part 2 etc.). As a result, the dimensional accuracy and reliability of the three-dimensional structure 10 can be more reliably improved, and the productivity of the three-dimensional structure 10 can be particularly improved.

  The thermoplastic composition 2 '' is injected from the nozzle M81 in a state of being heated and melted, but is preferably in the form of a filament (yarn) before being heated and melted.

  Thereby, it is easy to control the amount of the thermoplastic composition 2 '' that is heated and melted when necessary. Also, the thermoplastic composition 2 "can be efficiently melted by heating the thermoplastic composition 2" from the outer peripheral direction of the filament. Therefore, it is preferable from the viewpoint of energy saving. Further, for example, by winding a filament-like (thread-like) thermoplastic composition 2 ″ around the outer periphery of a roll-shaped member, an operation for feeding out a desired amount of the thermoplastic composition 2 ″ can be easily performed when necessary. It can be carried out. In addition, the thermoplastic composition 2 "can be easily stored.

  The thickness (when the cross-sectional shape is circular) of the filamentous thermoplastic composition 2 ″ is preferably 0.1 mm or more and 5 mm or less, and preferably 0.5 mm or more and 3 mm or less. More preferred.

Moreover, you may use multiple types of thermoplastic composition 2 '' for manufacture of the three-dimensional molded item 10. FIG.
For example, the physical properties of the three-dimensional structure 10 as a whole can be more suitably adjusted by using a plurality of types of thermoplastic compositions 2 ″ having different physical properties such as specific gravity. In addition, for example, when a plurality of types of three-dimensional structure 10 are manufactured, by appropriately using a plurality of types of thermoplastic composition 2 ″, it is possible to suitably cope with multi-product production.

<Liquid (first solidified portion forming liquid)>
Next, the liquid (first solidified portion forming liquid) used for manufacturing the three-dimensional structure of the present invention will be described in detail.

  The liquid (first solidified part forming liquid) 2 ′ includes at least a constituent component (including a precursor) of the first solidified part (cured part) 2 </ b> A.

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

  As a result, the strength, shape stability, and the like of the first solidified portion (cured portion) 2A to be formed can be made particularly excellent. In the bonding portion 3, the reaction product (cured product) of the resin material (polymerizable compound) can function as a bonding agent that bonds the particles 11. Further, the bonding force between the solidified portions 2 between the adjacent layers 1 can be made sufficiently large. For this reason, the mechanical strength of the three-dimensional structure 10 can be made excellent, and unintentional deformation of the three-dimensional structure 10 can be effectively prevented. In addition, since the heat resistance of the first solidified portion 2A (particularly, the first portion constituting the outer surface of the three-dimensional structure 10) becomes excellent, unintentional deformation in the three-dimensional structure 10, Unintentional modification and deterioration of the material can be more effectively prevented, and 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.

  In particular, when the liquid 2 ′ contains a photocurable resin as the curable resin material (polymerizable compound), the mechanical strength of the obtained three-dimensional structure 10 and the productivity of the three-dimensional structure 10 are particularly excellent. In addition, it is possible to more effectively prevent unintentional deformation at the time of manufacturing the three-dimensional structure 10.

  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, the strength (particularly the surface strength) of the finally obtained three-dimensional structure 10 can be made particularly excellent. In addition, since a polymer formed by reaction of an acrylic polymerizable compound generally has high transparency, for example, the color developability when a three-dimensional structure is manufactured using a material containing a colorant. It can be made especially excellent, and the aesthetics of the three-dimensional structure 10 can be made particularly excellent. Further, when the thermoplastic composition 2 ″ contains polycarbonate, the above-described effects can be obtained.

  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.), trifunctional or higher glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc., tetrafunctional or higher glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, cresol novolac resin poly) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2) 21P, Celoxide 2081, Epolide GT-301, Epolide GT-401, EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (eg, 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, and the design of the three-dimensional structure 10 can be improved. it can.

  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.

  Further, the viscosity of the liquid 2 ′ (viscosity when applied to a desired site in the first solidified portion forming step) is preferably 2 mPa · s or more and 30 mPa · s or less, and preferably 5 mPa · s or more and 20 mPa · s. The following is more preferable.

  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, 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 ′. In particular, in the inkjet method, a plurality of types of liquids 2 ′ can be suitably mixed at an arbitrary ratio, so that a desired color tone can be expressed easily and reliably.

  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 (particle-containing 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 layer forming composition (particle-containing 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 and the like of the finally obtained three-dimensional structure 10 can be made particularly excellent. The fluidity is excellent, the aggregation of the particles 11 and the like can be effectively prevented, and the ease of handling (handleability) of the layer-forming composition 1 ′ during production is particularly excellent. be able to.

(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.

  With such a configuration, when the three-dimensional structure 10 is manufactured (in the first solidified portion forming step), the curable resin material (polymerizable compound) constituting the liquid 2 ′ is placed in the pores. The anchor effect can be exhibited, 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 is particularly excellent. Can be. Further, when the curable resin material (polymerizable compound) constituting the liquid 2 ′ enters the pores of the particles 11, the unintentional wetting and spreading of the liquid 2 ′ can be effectively prevented. 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, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-n-propoxysilane, methylisopropoxysilane, methyl-n-butyroxysilane, methyltri-sec-butoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethylisopropoxysilane Silane, ethyl-n-butyroxysilane, ethyltri-sec-butyroxysilane, ethyltri-t-butyloxysilane, n-propyltrimeth Xysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, isobutyltri Ethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] pyridine, 4- [2- (trichloro Silyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, phenylto Methoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, benzylmethyldimethoxysilane, benzyldimethyl Methoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltri Methoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane , Amyltriethoxysilane, benzoxacilepine dimethyl ester, 5- (bicycloheptenyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, Mophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloromethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) Phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyl Trimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- ( -Cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclohexenyltrichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyl Dimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyl Trimethoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane , Cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethyl Norpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N-diethyl-3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) triethoxysilane, 2-hydroxy-4- (3-triethoxypropoxy) diphenylketone, 3- ( p-methoxyphenyl) propylmethyl Chlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyldichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7-hexachloro-6-triethoxysilyl-2-norbornene, 3-iodopropyltrimethoxylane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyl Methoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) Ethylamino} -3-propionate, RN-α-phenethyl-N′-triethoxysilylpropylurea, SN-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxy Silane, phenethyldimethylmethoxysilane, phenethyldimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-fluoro Phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxysilane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5 -Dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, (S) -N-triethoxysilylpropyl-O-mentcarbamate, 3- (triethoxysilylpropyl) -p-nitro Benzamide, 3- (triethoxysilyl) propylsuccinic anhydride, N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (Trimethoxysilylethyl) benzi -N, N, N-trimethylammonium chloride, phenylvinyldiethoxysilane, 3-thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3 -(Triethoxysilyl) propyl} phthalamic acid, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 1-trimethoxysilyl-2 -(Chloromethyl) phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N -Trimethoxysilylop Lopyl-N, N, N-tributylammonium bromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxy Run, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenyl Methylchlorosilane, vinyltriphenoxysilane, vinyltris-t-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, 3 Aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldichlorosilane, 5- (Bicycloheptenyl) trichlorosilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane 3-phenoxypropyltrichlorosilane, t-butylphenylchlorosilane , T-butylphenylmethoxysilane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilylmethyl) heptacosane, ((Chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenylethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyldimethylethoxysilane, 3-cyanopropyltrichlorosilane, fluorinated alkylsilane, and the like can be mentioned, and one or more selected from these can be used in combination.

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 resin material (binder) has a sufficient space (holes) into which the resin material (binder) enters, and the mechanical strength of the particles 11 itself can be made excellent. The mechanical strength of the three-dimensional structure 10 having the joint portion 3 into which the agent) has entered can be made 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.

  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. 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 polyvinylpyrrolidone shows high solubility also to an aqueous solvent (especially water), a binder (liquid) among the particles 11 constituting each layer 1 in the unbound particle removal step (after completion of modeling). Those that are not bound by the reaction product of the resin material (polymerizable compound) constituting 2 ′ can be easily and reliably removed. Moreover, since polyvinyl pyrrolidone is excellent in affinity with various colorants, when the liquid 2 ′ containing the colorant is used in the first solidified portion forming 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 uses the liquid 2 ′, the thermoplastic composition 2 ″, and the layer forming composition (particle-containing composition) 1 ′ to repeatedly form and laminate the layer 1 to obtain the tertiary. The original model 10 is manufactured. 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 is supplied from the control unit M2, the particle-containing composition supply unit M3 that houses the layer forming composition 1 ′, and the particle-containing composition supply unit M3. The layer forming part M4 for forming the layer 1 using the layer forming composition 1 ′ and the liquid discharging part (liquid applying means) M5 for discharging the liquid (first solidified part forming liquid) 2 ′ to the layer 1 And an energy ray irradiating means (curing means) M6 for irradiating energy rays for curing the liquid 2 ′ and a thermoplastic composition 2 ″ for forming the second solidified portion 2B in a molten state. Thermoplastic composition applying means M8, and a height measuring means M9 for measuring the height of the solidified product 6 formed using the thermoplastic composition 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. . Further, when the height of the upper surface of the solidified product 6 is measured by the height measuring means M9 described in detail later, and the thickness of the layer 1 is adjusted based on the height, the thickness of the layer 1 is adjusted. 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 thermoplastic composition applying unit M8, the height measuring unit M9, and the like. Specifically, for example, the discharge pattern and discharge amount of the liquid 2 ′ by the liquid discharge unit M5, the heating temperature and injection pattern of the thermoplastic composition 2 ″ by the thermoplastic composition applying means M8, the injection amount, and the particle-containing composition The supply amount of the layer forming composition 1 ′ from the material supply unit M3, the lowering amount of the stage (elevating stage) M41, and the like are controlled.

  The particle-containing 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 (part to which the layer forming composition 1 ′, liquid 2 ′, and thermoplastic composition 2 ″ are applied. The part including the first region M411 and the second region M412). It is. Thereby, the layer 1 with high uniformity of thickness can be formed easily and reliably. Moreover, the thickness of the newly formed layer 1 can be suitably adjusted based on the height of the upper surface of the solidified product 6.

  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, on the surface of the stage M41 (the portion to which the layer forming composition 1 ′, the liquid 2 ′, and the thermoplastic composition 2 ″ are applied. The portion including the first region M411 and the second region M412) Surface treatment may be performed. 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 Y 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 solidified product 6 by the height measuring means M9. Accordingly, the constituent component (for example, the particles 11) of the layer forming composition 1 ′ is unintentionally left on the upper surface of the solidified portion 2 at the end of the layer forming step. Can be prevented.

  The blade may include 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) M <b> 42.

  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 solidified 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 solidified product 6, a state in which the predetermined stress becomes a predetermined value on the flattening means M42 is changed to the leveling means M42 when the layer 1 is formed. It can be determined as the height.

  The abutment of the flattening means M42 on the solidified product 6 can be suitably performed by relatively moving the stage M41 and the flattening means M42 in the Z direction. It may be performed by moving in the direction, or may be performed by moving the stage M41 upward.

  The liquid discharge unit (liquid application unit) M5 discharges the liquid 2 'to the layer 1 by an 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.

  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 in each layer 1 and the amount of liquid 2 'applied in each unit of the layer 1 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 liquid 2 ′ can be applied, the first solidified portion 2A having a desired pattern can be reliably formed, and the dimensional accuracy 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 ray irradiating means (curing means) M6 irradiates energy rays for curing the liquid 2 'applied to the layer 1.

  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 thermoplastic composition applying means M8 is for injecting the molten thermoplastic composition 2 ''. By providing such a thermoplastic composition applying means M8, the solidified portion 2 (second solidified portion 2B) having a desired shape can be formed. In particular, when the solidified portion 2 is formed on the layer 1, the material for forming the solidified portion 2 (thermoplastic composition 2 ″) is prevented from unintentionally penetrating into the layer 1 and solidified in a desired shape. Part 2 (second solidified part 2B) can be formed. Further, the second solidified portion 2B and the solidified product 6 can be suitably formed under the same conditions (for example, the same thickness and the same density).

  The thermoplastic composition applying means M8 is wound around the outer periphery of a roll-shaped member (not shown), and the filament-shaped thermoplastic composition 2 '' fed from the roll-shaped member is heated and melted by a heating means (not shown). The molten thermoplastic composition 2 ″ is configured to be injected from the nozzle M81.

  The thermoplastic composition applying means M8 controls the pattern to be formed and the amount of the thermoplastic composition 2 ″ to be applied in accordance with a command from the drive control unit M22. The injection pattern, the injection amount, and the like of the thermoplastic composition 2 ″ by the thermoplastic composition applying unit M8 are determined based on the slice data. Thereby, a necessary and sufficient amount of the thermoplastic composition 2 '' can be applied, the second solidified portion 2B having a desired pattern can be reliably formed, and the dimensional accuracy of the three-dimensional structure 10 can be improved. The mechanical strength can be more reliably improved.

The height measuring means M9 measures the height of the upper surface of the solidified product 6.
Information on the height of the upper surface of the solidified product 6 is transmitted from the height measuring means M9 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. .

  In the configuration shown in FIG. 9, the height measuring means M <b> 9 obtains the height of the solidified product 6 by obtaining the focal distance from above the solidified product 6. With such a configuration, the height of the solidified product 6 can be measured without moving the height measuring means M9, so that the time required for measuring the height of the solidified 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, it is possible to manufacture a three-dimensional structure having a wide range of selection of color tone and design property and having physical properties according to the appearance with high productivity.

  In particular, according to the three-dimensional structure manufacturing apparatus of this embodiment, a three-dimensional structure excellent in dimensional accuracy and the like can be efficiently manufactured.

《Three-dimensional structure》
The three-dimensional structure of the present invention is manufactured using the three-dimensional structure forming method (particularly, the manufacturing method of the present invention) as described above, and is a first region that includes at least a part of the outer surface. The part is made of a material containing a cured product of a curable resin, and the second part, which is at least a part of the part other than the first part, is made of a material containing a thermoplastic resin. It is a thing.

  Thereby, it is excellent in the designability and can provide the three-dimensional structure which has the physical property according to the external appearance.

  Such a three-dimensional structure can be suitably manufactured using the three-dimensional structure manufacturing apparatus of the present invention as described above.

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

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

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

  For example, in the three-dimensional structure manufacturing apparatus and the three-dimensional structure of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits the same function, and an arbitrary configuration is added. You can also. For example, the three-dimensional structure manufacturing apparatus of the present invention may include a heating means and a decompression means (not shown). Thereby, for example, the solvent can be efficiently removed from the layer forming composition, and the productivity of the three-dimensional structure can be made particularly excellent. Moreover, the three-dimensional structure manufacturing apparatus of the present invention may include a cooling means (not shown). Thereby, for example, the molten thermoplastic composition applied from the thermoplastic composition applying means can be quickly made into a solidified part having sufficient shape stability, and the productivity of the three-dimensional structure is particularly improved. It can be excellent.

  In the above-described embodiment, the solidified portion is formed for all layers. However, a layer in which the solidified portion is not formed may be included. For example, a solidified portion may not be formed with respect to a layer formed immediately above the stage and may function as a sacrificial layer.

  In the above-described embodiment, the case where the layer forming step, the first solidified portion forming step, and the second solidified portion forming step are repeatedly performed as a series of steps has been mainly described. May be different in each cycle. For example, among the above steps, the first solidified portion forming step may be omitted, or the second solidified portion forming step may be performed. It may have an omitted cycle.

  Moreover, in the manufacturing method of the three-dimensional structure of this invention, the order of a process and a process is not limited to the thing mentioned above, You may carry out by exchanging at least one part. For example, in the above-described embodiment, the second solidified portion forming step after the second time (when n is an integer of 1 or more, the second solidified portion 2B buried in the (n + 1) th layer 1 from the bottom is formed. The second solidified part forming step) has been described as being performed after the first solidified part 2A is formed in the lower layer (the nth layer 1 from the bottom). However, the second and subsequent second solidified part forming steps are described. (The second solidified portion forming step for forming the second solidified portion 2B buried in the n + 1th layer 1 from the bottom) forms the first solidified portion 2A in the lower layer (the nth layer 1 from the bottom) It may be performed before.

  In addition, for example, the curing process performed for forming each first solidified portion (cured portion) may not be repeated every time a pattern corresponding to each first solidified portion (cured portion) is formed. Alternatively, it may be one that is performed in a lump after forming a laminate in which an uncured pattern is provided in a plurality of layers.

  Moreover, although embodiment mentioned above typically demonstrated the case where the composition for layer formation contains a solvent, the composition for layer formation may not contain a solvent.

  Moreover, in embodiment mentioned above, although the case where a three-dimensional structure was what consists of a 1st site | part and a 2nd site | part was demonstrated typically, for example, other than a 1st site | part and a 2nd site | part It may have a part.

  Moreover, although embodiment mentioned above demonstrated typically the case where a three-dimensional molded item consists of a 1st solidification part and a 2nd solidification part, for example, a 1st solidification part, a 2nd solidification part, A solidified part other than the solidified part may be formed. For example, a solidified part (third solidified part) may be formed by applying a liquid (solidified part forming liquid) on a layer containing a solvent (a layer containing a plurality of particles). In this way, by applying a liquid (solidified portion forming liquid) on the layer containing the solvent, the liquid is prevented from penetrating in the layer, and the solidified portion having a desired shape on the layer. The (third solidified portion) can be easily and reliably formed.

  In the above-described embodiment, the case where the first portion is formed by applying a liquid by an ink jet method in a layer composed of a plurality of particles has been representatively described. The part 1 may be formed by discharging a liquid by an ink jet method and then curing the liquid. For example, the part may be formed by applying to a part not containing particles.

  Moreover, in embodiment mentioned above, in addition to the molten thermoplastic composition and the liquid discharged by the inkjet method, a three-dimensional structure is formed using the layer forming composition (particle-containing composition) containing a plurality of particles. Although the case where it manufactures was demonstrated, in this invention, it is not necessary to use the composition for layer formation (particle-containing composition) containing several particle | grains. In such a case, the three-dimensional structure is formed by laminating a solidified part formed by using a molten thermoplastic composition and a layer including a solidified part (cured part) formed by a liquid ejected by an inkjet method. Is obtained as a result.

  In the above-described embodiment, the case where a part of the outer surface of the three-dimensional structure (the entire outer surface excluding a part of the bottom surface of the three-dimensional structure) is the first portion is representatively described. In the present invention, the first portion may be the entire outer surface of the three-dimensional structure. Moreover, in embodiment mentioned above, although the whole outer surface which can be visually recognized in a normal usage pattern among the outer surfaces of a three-dimensional structure was demonstrated as a 1st site | part, among the outer surfaces of a three-dimensional structure A part of the outer surface that can be visually recognized in a normal usage pattern may be a part other than the first part (for example, the second part).

  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-treatment process include a cleaning process, a shape adjustment process for performing deburring, a coloring process, a coating layer forming process, and a light irradiation process for reliably curing an uncured polymerizable compound (curable resin material). And a curing completion step in which heat treatment is performed.

  In the above-described embodiment, the solidified material used for determining the thickness of the layer is the first region on the modeling stage where the portion constituting the substantial part of the target three-dimensional structure is formed. Although the case where it is formed in a different second region has been described, the solidified material 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 solidified material used for determining the thickness of the layer is typically determined by observation from the upper surface of the solidified material. The thickness may be obtained by observation from the side of the solidified 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 solidified product can be measured at a plurality of points.

Further, in the above-described embodiment, the case where a plurality of solidified products formed so as to be stacked over several steps has the same shape and the same area is representatively described. The plurality of solidified products that are sequentially reduced in area toward the upper side, and the laminate formed by stacking the plurality of solidified products may have a pyramid shape or the like, for example. Even in such a case, the same effect as described above can be obtained.
In the present invention, the solidified material used for determining the layer thickness may not be formed.

  Moreover, the three-dimensional structure manufacturing apparatus of this invention is for collect | recovering what was not used for formation of a layer among the composition for layer formation (particle-containing composition) supplied from the particle-containing composition supply part. A recovery mechanism (not shown) may be provided. Accordingly, a sufficient amount of the layer forming composition (particle-containing composition) can be supplied while preventing excessive layer-forming composition (particle-containing composition) from accumulating in the layer forming portion. Therefore, the three-dimensional structure can be manufactured more stably while preventing the generation of defects in the layer more effectively. Moreover, since the collected layer forming composition (particle-containing composition) can be used again for the production of a three-dimensional structure, it can contribute to the reduction of the manufacturing cost of the three-dimensional structure, It is also preferable from the viewpoint of resource saving.

  Moreover, the three-dimensional structure manufacturing apparatus of this invention may be equipped with the collection | recovery mechanism for collect | recovering the composition for layer formation (particle-containing composition) removed by the unbound particle removal process.

DESCRIPTION OF SYMBOLS 10 ... Three-dimensional structure 1 ... Layer 1 '... Particle-containing composition (composition for layer formation)
DESCRIPTION OF SYMBOLS 11 ... Particle | grains 12 ... Solvent 2 ... Solidification part 2A ... 1st solidification part (hardening part)
2B ... 2nd solidification part 2 '... Liquid (1st solidification part formation liquid)
2 '' ... thermoplastic composition (second solidified portion forming material)
DESCRIPTION OF SYMBOLS 3 ... Coupling part 4 ... Space 6 ... Solidified material M100 ... Three-dimensional structure manufacturing apparatus M2 ... Control part M21 ... Computer M22 ... Drive control part M3 ... Particle content composition supply part M4 ... Layer formation part M41 ... Stage (elevating stage) , Support)
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)
M8 ... thermoplastic composition applying means M81 ... nozzle M9 ... height measuring means

Claims (14)

It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
Forming a first portion which is a region including at least a part of the outer surface of the three-dimensional structure by discharging a liquid by an inkjet method and then curing the first portion;
By injecting a thermoplastic composition containing a molten thermoplastic resin from a nozzle into a second part that is at least a part of a part other than the first part of the three-dimensional structure, and then solidifying the second part. A method for producing a three-dimensional structure characterized by forming.   The liquid is applied to a layer formed using a particle-containing composition containing particles by an ink jet method, and the first portion is formed by allowing the liquid to penetrate into the gaps between the particles and then curing the liquid. Item 3. A method for manufacturing a three-dimensional structure according to Item 1. The particle-containing composition contains a solvent,
The method for producing a three-dimensional structure according to claim 2, wherein when the liquid is applied to the layer, the solvent is removed from the layer.   The method for producing a three-dimensional structure according to claim 3, wherein the particle-containing composition contains an aqueous solvent as the solvent.   The method for producing a three-dimensional structure according to claim 3 or 4, wherein the particle-containing composition further contains a binder.   The said layer is formed so that at least one part of the said 2nd site | part may be embedded using the said particle | grain containing composition after forming the said 2nd site | part using the said thermoplastic composition. The manufacturing method of the three-dimensional structure according to any one of the above.   The method for producing a three-dimensional structure according to any one of claims 1 to 6, wherein the liquid contains a photocurable resin. The thermoplastic resin contains polycarbonate,
The method for producing a three-dimensional structure according to any one of claims 1 to 7, wherein the liquid contains an acrylic polymerizable compound.   The method for manufacturing a three-dimensional structure according to any one of claims 1 to 8, wherein a thickness of the first part is 0.01 mm or more and 1.0 mm or less.   The method for producing a three-dimensional structure according to any one of claims 1 to 9, wherein the thermoplastic composition includes a filler in addition to the thermoplastic resin. A three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
Liquid ejection means for ejecting the liquid used for forming the cured portion by an inkjet method;
A three-dimensional structure manufacturing apparatus comprising: a thermoplastic composition applying unit that applies a thermoplastic composition containing a molten thermoplastic resin.   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. A three-dimensional structure manufactured using a three-dimensional modeling method,
The first part which is a region including at least a part of the outer surface is made of a material including a cured product of a curable resin, and is a part of at least a part of a part other than the first part. A three-dimensional structure characterized in that the second portion is made of a material containing a thermoplastic resin.

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