WO2015105047A1 - Procédé de fabrication d'une structure tridimensionnelle et structure tridimensionnelle - Google Patents

Procédé de fabrication d'une structure tridimensionnelle et structure tridimensionnelle Download PDF

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Publication number
WO2015105047A1
WO2015105047A1 PCT/JP2015/000039 JP2015000039W WO2015105047A1 WO 2015105047 A1 WO2015105047 A1 WO 2015105047A1 JP 2015000039 W JP2015000039 W JP 2015000039W WO 2015105047 A1 WO2015105047 A1 WO 2015105047A1
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WO
WIPO (PCT)
Prior art keywords
forming
ink
layer
dimensional structure
outermost layer
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PCT/JP2015/000039
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English (en)
Inventor
Eiji Okamoto
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Seiko Epson Corporation
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Publication date
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Publication of WO2015105047A1 publication Critical patent/WO2015105047A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing

Definitions

  • the present invention relates to a method for manufacturing a three-dimensional structure and a three-dimensional structure.
  • a method for forming a three-dimensional structure is known based on a model of a three-dimensional object, for example, generated by three-dimensional CAD software or the like.
  • a stacking method As one method for forming a three-dimensional structure, a stacking method is known.
  • the stacking method in general, after splitting the model of a three-dimensional object into a large number of two-dimensional cross-sectional layers, a three-dimensional structure is formed by sequentially stacking cross-section members while sequentially forming the cross-section members corresponding to each two-dimensional cross-sectional layer.
  • a three-dimensional structure can be formed immediately as long as there is a model of a three-dimensional structure to be formed, and since there is no need to make a die before forming, it is possible to quickly and inexpensively form a three-dimensional structure.
  • a three-dimensional structure is formed by stacking cross-section members having a thin plate-shape layer by layer, for example, even in a case where the object has a complex internal structure, it is possible to form a formed object as one piece without being divided into a plurality of parts.
  • a technology for forming a three-dimensional structure while hardening a powder with a binding liquid is known (for example, refer to PTL 1).
  • this technique when each layer is formed, by discharging an ink containing a colorant to the location corresponding to the outer surface side of a three-dimensional structure, the three-dimensional structure is colored.
  • An object of the invention is to provide a method for manufacturing a three-dimensional structure in which a three-dimensional structure of which the outer surface has high mechanical strength and on which a fine color expression is performed can be stably and efficiently manufactured, and a three-dimensional structure of which the outer surface has high mechanical strength and on which a fine color expression is performed.
  • a method for manufacturing a three-dimensional structure by stacking layers formed by using an ink containing a curable resin includes an ink discharge step of discharging an ink for forming an outermost layer in a region to become the outermost layer of the three-dimensional structure of the layer and discharging an ink for forming a sacrificial layer in a region on a surface side of the outermost layer which is adjacent to the region to become the outermost layer of the layer, a curing step of curing the ink for forming an outermost layer and the ink for forming a sacrificial layer discharged, and a filling step of filling a region surrounded by a cured product of the ink for forming an outermost layer with a composition for forming a three-dimensional object including powder for forming a three-dimensional object configured of particles and forming a composition layer for forming a three-dimensional object.
  • a planarization treatment is preferably performed with respect to the filled composition for forming a three-dimensional object based on the height of the cured product of the ink for forming an outermost layer.
  • a powder binding step of discharging a binding ink containing a curable resin and forming a powder binding layer is preferably performed with respect to the composition layer for forming a three-dimensional object.
  • the powder binding step in formation of the layer of the kth layer (k is an integer of equal to or greater than 1) is preferably performed together with the ink discharge step in formation of the layer of the (k+1)th layer (k is an integer of equal to or greater than 1).
  • the ink for forming an outermost layer is preferably discharged in a region to become the outermost layer of the three-dimensional structure of the plurality of the layers, and the ink for forming a sacrificial layer is preferably discharged in a region on a surface side of the outermost layer which is adjacent to the region to become the outermost layer of the plurality of the layers.
  • the ink for forming an outermost layer preferably includes one type or two or more types selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, polyether-based aliphatic urethane (meth)acrylate oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • the ink for forming a sacrificial layer preferably includes one type or two or more types selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, (meth)acryloyl morpholine, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.
  • the ink for forming an outermost layer and the ink for forming a sacrificial layer preferably include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and/or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a polymerization initiator.
  • the ink for forming an outermost layer in addition to a coloring ink containing a colorant, a colorless ink not containing a colorant is preferably used, the colorless ink is preferably used for forming a region near the outer surface of the three-dimensional structure, of the outermost surface, and the coloring ink is preferably used for forming a region on the inner side than that region.
  • the portion containing a colorant in particular, a pigment
  • a colorant in particular, a pigment
  • the portion containing a colorant is likely to be brittle, become scratched, or become chipped compared to the portion not containing a colorant, by providing a region formed by using the ink for forming an outermost layer not containing a colorant near the outer surface of a three-dimensional structure, it is possible to effectively prevent the occurrence of such problems.
  • a coloring ink containing a colorant is preferably used, a chromatic color ink and a white ink are preferably used as the coloring ink, and the white ink is preferably used for forming a region on the inner side of the region formed by using the chromatic color ink.
  • a region (first region) where a white ink is applied can exhibit a concealing property, and it is possible to further increase color saturation of a three-dimensional structure.
  • a three-dimensional structure which is manufactured using the method for manufacturing a three-dimensional structure according to the aspect.
  • Fig. 1A is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 1B is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 1C is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 1D is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 2E is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 2F is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 2G is a cross-sectional view schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 3A is a cross-sectional view schematically showing a part of a step in another embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • Fig. 3B is a cross-sectional view schematically showing a part of a step in another embodiment of the method for manufacturing a three-dimensional structure of the invention.
  • FIG. 4 is a cross-sectional view schematically showing a state in a layer (composition for forming a three-dimensional object) immediately before an ink discharge step.
  • Fig. 5 is a cross-sectional view schematically showing a state in which particles are bound to each other by a curable resin.
  • Fig. 6 is a schematic diagram showing a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure.
  • Fig. 7 is a block diagram of a control portion included in the three-dimensional structure manufacturing apparatus shown in Fig. 6.
  • Fig. 1A to Fig. 1D and Fig. 2E to Fig. 2G are cross-sectional views schematically showing each step in a preferred embodiment of the method for manufacturing a three-dimensional structure of the invention
  • Fig. 3A and Fig. 3B are cross-sectional views schematically showing a part of a step in another embodiment of the method for manufacturing a three-dimensional structure of the invention
  • Fig. 4 is a cross-sectional view schematically showing a state in a layer (composition for forming a three-dimensional object) immediately before the ink discharge step
  • Fig. 5 is a cross-sectional view schematically showing a state in which particles are bound to each other by a curable resin.
  • the method for manufacturing a three-dimensional structure 1 of the embodiment has an ink discharge step (Fig. 1A and Fig. 1C, and Fig. 2E) of discharging an ink for forming an outermost layer 4A including a curable resin and an ink for forming a sacrificial layer 4B including a curable resin in a predetermined pattern by an ink jet method, a curing step (Fig. 1A and Fig. 1C, and Fig.
  • a filling step (Fig. 1B and Fig. 1D) of filling a region surrounded by the outermost layer 7 with a composition for forming a three-dimensional object including powder for forming a three-dimensional object configured of a plurality of particles and forming a composition layer for forming a three-dimensional object 6', and a powder binding step (Fig. 1C and Fig.
  • the ink for forming an outermost layer 4A is discharged in a region at which the outermost layer of the three-dimensional structure 1 is to be configured.
  • the ink for forming a sacrificial layer 4B is discharged in a region on the surface side of the outermost layer which is adjacent to the region to become the outermost layer of the three-dimensional structure 1.
  • the method for manufacturing a three-dimensional structure 1 has a characteristic in which a composition for forming a three-dimensional object including powder for forming a three-dimensional object is filled in a region surrounded by the outermost layer 7 and the sacrificial layer 8 formed by the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B as described above.
  • the inside of the three-dimensional structure 1 is formed using a composition for forming a three-dimensional object including powder for forming a three-dimensional object, it is possible to stably and efficiently manufacture the three-dimensional structure 1 compared to a method for manufacturing the three-dimensional structure 1 using only an ink.
  • the sacrificial layer 8 on the outside of the outermost layer 7 of the three-dimensional structure 1, it is possible to prevent the ink for forming an outermost layer 4A from flowing out, and it is possible to express finer colors and textures on the outer surface of the three-dimensional structure 1.
  • the ink for forming an outermost layer 4A including a curable resin and the ink for forming a sacrificial layer 4B including a curable resin are discharged on a forming stage 80 in a predetermined pattern by an ink jet method (Fig. 1A and Fig. 1C).
  • the ink for forming an outermost layer 4A is applied to the region to become the outermost layer 7 of the three-dimensional structure 1
  • the ink for forming a sacrificial layer 4B is applied to the region of the surface side of the outermost layer 7 which is adjacent to the region to become the outermost layer 7 of the three-dimensional structure 1.
  • the ink (the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B) is discharged on the forming stage 80 (Fig. 1A), and in the second or subsequent ink discharge steps, the ink (the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B) is discharged on the outermost layer 7 and the sacrificial layer 8 (Fig. 1C and Fig. 2E).
  • the outermost layer 7 is formed by applying the ink for forming an outermost layer 4A to the portion to become the outermost layer of the three-dimensional structure 1
  • the sacrificial layer 8 is formed by applying the ink for forming a sacrificial layer 4B to the region on the outside of the outermost layer 7.
  • the ink (the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B) is applied by an ink jet method, it is possible to reproducibly apply even in a case where the applying pattern of the ink (the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B) has a fine shape. As a result, it is possible to greatly increase the dimensional accuracy of the finally obtained three-dimensional structure 1, and it is possible to more favorably control the surface shape of the three-dimensional structure 1 and the appearance.
  • the curing component (curable resin) included in the ink (the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B) is cured (Fig. 1B and Fig. 1D). Thereby, the outermost layer 7 and the sacrificial layer 8 are obtained.
  • the outer surface of the three-dimensional structure 1 finally obtained by curing the curing component (curable resin) included in the ink is a surface configured of a cured product. Therefore, the surface has excellent mechanical strength and an excellent durability, for example, compared to a three-dimensional structure configured of a thermoplastic resin.
  • this step can be performed by heating, and in a case where the curing component (curable resin) is a photocurable resin, this step can be performed by irradiation of the corresponding light (for example, in a case where the curing component (curable resin) is an ultraviolet ray curable resin, this step can be performed by irradiation of ultraviolet rays).
  • the ink is applied in the shape and the pattern corresponding to the outermost layer 7 and the sacrificial layer 8, and thereafter, all the layers configured of the ink are cured, however, in the invention, regarding at least a part of a region, discharging of the ink and curing of the ink may be performed at the same time. That is, before the entire patterns of one outermost layer 7 and the entire sacrificial layers 8 are formed, regarding at least a part of the region corresponding to the outermost layer 7 and the sacrificial layer 8, the sequential curing reaction may proceed from the portion to which the ink is applied.
  • the ink for forming a sacrificial layer 4B may be in an incompletely cured state, and the ink for forming an outermost layer 4A may be cured to a higher degree of cure than that of the ink for forming a sacrificial layer 4B.
  • the ink for forming an outermost layer 4A may be in an incompletely cured state.
  • the following step for example, "ink discharge step” or the like after the outermost layer 7 and the sacrificial layer 8 of the lower layer in the curing step are formed
  • the main curing treatment for increasing the degree of cure regarding the ink for forming an outermost layer 4A which is in an incomplete cured state
  • by applying an ink for forming an upper layer in the state in which the ink for forming an outermost layer 4A (lower layer) is in an incompletely cured state it is possible to make the adhesion between the layers excellent.
  • the region surrounded by the cured product of the ink for forming an outermost layer 4A that is, the region surrounded by the outermost layer 7 is filled with the composition for forming a three-dimensional object including powder for forming a three-dimensional object configured of a plurality of particles, whereby the composition layer for forming a three-dimensional object 6' is formed.
  • the inside of the three-dimensional structure 1 is formed using the composition for forming a three-dimensional object including powder for forming a three-dimensional object, it is possible to stably and efficiently manufacture the three-dimensional structure 1 compared to a method for manufacturing the three-dimensional structure 1 using only an ink.
  • This step can be performed by using a method such as a squeegee method, a screen printing method, a doctor blade method, a spin coating method, or the like.
  • a planarization treatment is performed with respect to the composition for forming a three-dimensional object applied to the region surrounded by the outermost layer 7 based on the height of the cured product of the ink for forming an outermost layer.
  • the composition for forming a three-dimensional object includes a water-soluble resin 64 together with a plurality of particles 63.
  • the particles 63 are bound (temporarily fixed) to each other (Fig. 4), and it is possible to effectively prevent unintended scattering of the particles. Thereby, it is possible to improve safety of a worker and the dimensional accuracy of the manufactured three-dimensional structure 1.
  • the composition for forming a three-dimensional object reaches a solid state (pellet form) (for example, a case in which the composition for forming a three-dimensional object includes a water-soluble resin (thermoplastic resin) 64 which reaches a solid state near the storage temperature (for example, room temperature (25 degrees centigrade)), and the plurality of particles 63 reach a state of being bound by the water-soluble resin), before forming the layers as described above, the composition for forming a three-dimensional object is melted by heating, and due to this, the composition for forming a three-dimensional object may be in a state having fluidity. Thereby, it is possible to efficiently fill by a simple method as described above. As a result, it is possible to manufacture the three-dimensional structure 1 having a higher dimensional accuracy, with a higher productivity.
  • a solid state pellet form
  • the composition for forming a three-dimensional object includes a water-soluble resin (thermoplastic resin) 64 which reaches a solid state near the storage temperature (for example, room
  • a binding ink 4C including a curable resin 44 is discharged with respect to the composition layer for forming a three-dimensional object 6 ' formed in the filling step (Fig. 1C and Fig. 2E).
  • the curable resin in the discharge binding ink 4C the powder binding layer 6 is formed, and the unit layer configured of the outermost layer 7 and the powder binding layer 6 is formed.
  • this step it is possible to more strongly bind the particles 63 configuring the composition layer for forming a three-dimensional object 6 to each other by the curable resin 44, and it is possible to make the mechanical strength of the finally obtained three-dimensional structure 1 excellent.
  • the curable resin 44 enters into a pore 611 of the particles 63 and an anchoring effect is exhibited, and as a result, it is possible to make a binding force of the binding of the particles 63 to each other (binding force through the curable resin 44) excellent, and it is possible to make the mechanical strength of the finally obtained three-dimensional structure 1 excellent (see Fig. 5).
  • this step is preferably performed together with the ink discharge step of the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B in formation of the unit layer being one higher than the unit layer formed.
  • the powder binding step in formation of the unit layer of the kth layer (k is an integer of equal to or greater than 1) is preferably performed together with the ink discharge step in formation of the unit layer of the (k+1)th layer (k is an integer of equal to or greater than 1).
  • binding ink 4C the same ink as the ink for forming an outermost layer 4A described below in detail can be used.
  • the outermost layer 7 is formed on the upper surface in the unit layer direction of the three-dimensional structure 1 with the ink for forming an outermost layer 4A.
  • a state in which the adjacent unit layers (layer configured of the outermost layer 7 and the powder binding layer 6) are bound to each other is formed, and a temporarily formed body 1' in which the sacrificial layer 8 is provided on the surface of the laminate in which the unit layers in such a state are multiply stacked is obtained (see Fig. 2F).
  • a method for removing the sacrificial layer 8 a method in which the sacrificial layer 8 is selectively dissolved and removed by using a liquid which selectively dissolves the sacrificial layer 8, a method in which by selectively absorbing the liquid in the sacrificial layer 8 using a liquid which is more strongly absorbed by the sacrificial layer 8 than the outermost layer 7, the sacrificial layer 8 swells, or by reducing the mechanical strength of the sacrificial layer 8, the sacrificial layer 8 is peeled or is destroyed, and the like can be exemplified.
  • the liquid used in this step varies depending on the constituent materials of the outermost layer 7 and the sacrificial layer 8, and for example, water, alcohols such as methanol, ethanol, and isopropyl alcohol, and glycols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol can be used.
  • the liquid contains one type or two or more types selected from these, and into this liquid, a water-soluble substance producing hydroxide ions such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, or an organic amine to increase the solubility of the sacrificial layer and a surfactant to facilitate separation of the peeled sacrificial layer may be mixed.
  • the method for applying the liquid is not particularly limited, and for example, an immersion method, a spraying method, a coating method, various printing methods, or the like can be adopted.
  • ultrasonic vibration when applying the liquid to the temporarily formed body 1' or after applying the liquid, ultrasonic vibration may be applied. Thereby, it is possible to promote the removal of the sacrificial layer 8, and it is possible to make productivity of the three-dimensional structure 1 excellent.
  • the invention is not limited thereto, and for example, as shown in Fig. 3A and Fig. 3B, a constitution in which after the outermost layer 7 and the sacrificial layer 8 of a plurality of the unit layer portions are formed, the region surrounded by a plurality of the outermost layers 7 is filled with the composition for forming a three-dimensional object may be used.
  • Fig. 6 is a schematic diagram showing a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure.
  • Fig. 7 is a block diagram of a control portion included in the three-dimensional structure manufacturing apparatus shown in Fig. 6.
  • the three-dimensional structure manufacturing apparatus 100 is an apparatus which is applied to the method for manufacturing a three-dimensional structure, and is an apparatus in which a model of a unit layer (the outermost layer 7 and the powder binding layer 6) and the sacrificial layer 8 is produced, and by sequentially stacking each unit layer, the three-dimensional structure 1 is formed while sequentially forming each layer based on the model.
  • the three-dimensional structure manufacturing apparatus 100 has a computer 20 for performing production or the like of a model of a unit layer or the like and a forming portion 30 for forming the three-dimensional structure 1.
  • the forming portion 30 is equipped with an ink discharge portion (ink discharge means) 40 which is electrically connected to the computer 20, a powder supply portion 50, a powder control portion 60, a light source 70, and the forming stage 80.
  • ink discharge means ink discharge means
  • the ink discharge portion 40 has a liquid droplet discharge head 41 for discharging liquid droplets of the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B, and the binding ink 4C by an ink jet method.
  • the ink discharge portion 40 is equipped with an ink supply portion which is not shown in the figure.
  • the droplet discharge head 41 which uses a so-called piezoelectric driving method is adopted.
  • the droplet discharge head 41 is configured to be able to change the discharge amount of the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B according to the instructions of a control portion 21 described below.
  • the ink discharge portion 40 has an X-direction moving portion 42 and a Y-direction moving portion 43 for moving the droplet discharge head 41 on an XY plane.
  • the powder supply portion 50 has a function of supplying powder for forming a three-dimensional object (composition for forming a three-dimensional object) to the forming stage 80 described below.
  • the powder supply portion 50 is configured to be driven by powder supply portion driving means which is not shown in the figure.
  • the powder control portion 60 is equipped with a blade 61 and a guide rail 62 for controlling operation of the blade 61.
  • the powder control portion 60 controls the composition for forming a three-dimensional object supplied from the powder supply portion 50 by the blade 61, and has a function of forming the composition for forming a three-dimensional object 6' configured of composition for forming a three-dimensional object in the region surrounded by the outermost layer 7 on the forming stage 80.
  • the blade 61 has a shape elongated in the Y-direction, and has a blade-like shape of which the lower tip is sharp.
  • the blade 61 is configured to be driven in the X-direction along the guide rail 62 by blade driving means which is not shown in the figure.
  • Layer forming means is configured of the powder supply portion 50 and the powder control portion 60.
  • the light source 70 has a function of curing the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B, and the binding ink 4C discharged.
  • the light source 70 is configured to emit ultraviolet light.
  • a mercury lamp, a metal halide lamp, a xenon lamp, or an excimer lamp can be adopted.
  • the forming stage 80 has a rectangular shape in the XY cross section. On this forming stage 80, the unit layer (the outermost layer 7 and the powder binding layer 6) and the sacrificial layer 8 are formed.
  • the forming stage 80 is movable in the Z-direction by a forming stage driving means which is not shown in the figure.
  • the forming stage 80 moves downward by as much as the thickness of the formed outermost layer 7, and by the powder supply portion 50 and the powder control portion 60, the composition layer for forming a three-dimensional object 6' is formed in the region surrounded by the outermost layer 7.
  • the forming portion 30 is equipped with a driving control portion which is not shown in the figure.
  • the driving control portion has a motor control portion, a position detection control portion, a powder supply control portion, a discharge control portion, and an exposure control portion.
  • the motor control portion separately controls driving in the XY-direction of the liquid droplet discharge head 41, driving of the blade 61, and driving of the forming stage 80 based on the instructions from a CPU of the computer 20 described below.
  • the position detection control portion separately controls the position of the liquid droplet discharge head 41, the position of the blade 61, and the position of the forming stage 80 based on the instructions from the CPU.
  • the powder supply control portion controls driving (supply of powder) of the powder supply portion 50 based on the instructions from the CPU.
  • the discharge control portion controls driving (discharge of liquid droplets) of the liquid droplet discharge head 41 based on the instructions from the CPU.
  • the exposure control portion controls the light emitting state of the light source 70 based on the instructions from the CPU.
  • the computer 20 has a control portion 21 for controlling the operation of each portion of the forming portion 30, a receiving portion 24, and an image producing portion 25.
  • the control portion 21 has a CPU (Central Processing Unit) 22 and a memory portion 23.
  • CPU Central Processing Unit
  • the CPU 22 performs various computational processing as a processor, and executes a control program 231.
  • the memory portion 23 has a ROM (Read Only Memory), a RAM (Random Access Memory), and the like. In the memory portion 23, a region where the control program 231 in which the control procedure of operation in the forming portion 30 is recorded is stored, or a data expanding portion 232 which is a region where various types of data is temporarily expanded are set.
  • the memory portion 23 is connected to CPU 22 through a data bus 29.
  • control portion 21 is connected to the image producing portion 25 and the receiving portion 24 through the data bus 29.
  • control portion 21 is connected to the driving control portion of the forming portion 30 through an input/output interface 28 and the data bus 29.
  • driving control portion is connected to the above-described powder supply portion driving means, the forming stage driving means, the blade driving means, the liquid droplet discharge head, and the light source through the input/output interface 28 and the data bus 29, respectively.
  • the image producing portion 25 has a function of manufacturing a model or the like of the three-dimensional structure 1.
  • the image producing portion 25 is configured of software or the like for producing a three-dimensional object such as three-dimensional CAD (computer-aided design).
  • the image producing portion 25 has a three-dimensional structure model producing function of producing a model of the three-dimensional structure 1, or a function of producing a two-dimensional model which expresses an outer surface or the like of a model of the three-dimensional structure 1 by a two-dimensional model of polygons such as a triangle or a quadrangle such as STL (Standard Triangulated Language). That is, the image producing portion 25 has a function of producing three-dimensional shape data of the three-dimensional structure 1.
  • the image producing portion 25 has a function of producing unit layer (the outermost layer 7 and the powder binding layer 6) data by cutting the model of the three-dimensional structure 1 into layers.
  • the image producing portion 25 has a function of producing sacrificial layer data based on the unit layer data.
  • the unit layer data and the sacrificial layer data produced by the image producing portion 25 are stored at the memory portion 23, and transferred to the driving control portion of the forming portion 30 through the input/output interface 28 and the data bus 29.
  • the forming portion 30 is driven based on the transferred unit layer data and sacrificial layer data.
  • the receiving portion 24 is equipped with a USB (Universal Serial BUS) port, a LAN port, and the like.
  • the receiving portion 24 has a function of receiving the original object for producing a model of the three-dimensional structure 1 from an external device (not shown) such as a scanner or the like.
  • the computer 20 is connected to a monitor (display device), and a keyboard (input device) (not shown).
  • the monitor and the keyboard are connected to the control portion 21 through the input/output interface and the data bus, respectively.
  • the monitor has a function of displaying an image file acquired by the receiving portion 24 in an image display region. Via the monitor, a worker can visually grasp the image file or the like.
  • the input device is not limited to a keyboard, and the input device may be a mouse, a trackball, a touch panel, or the like.
  • the ink set of the embodiment is equipped with at least one of the ink for forming an outermost layer 4A, the ink for forming a sacrificial layer 4B, and the binding ink 4C.
  • the ink set of the embodiment is applied to the method for manufacturing a three-dimensional structure of the invention and the three-dimensional structure manufacturing apparatus as described above.
  • the ink for forming an outermost layer 4A and the binding ink 4C are inks configured by the same components, and thus, only the ink for forming an outermost layer 4A will be described, and description of the binding ink 4C will be omitted.
  • the ink for forming an outermost layer 4A includes at least a curable resin (curing component).
  • Example of the curable resin include a thermosetting resin; and various photocurable resins such as a visible light curable resin which is cured by light in the visible light region (photocurable resin in the narrow sense); an ultraviolet ray curable resin; an infrared ray curable resin; and an X-ray curable resin, and one type or two or more types selected from these can be used singly or in combination.
  • various photocurable resins such as a visible light curable resin which is cured by light in the visible light region (photocurable resin in the narrow sense); an ultraviolet ray curable resin; an infrared ray curable resin; and an X-ray curable resin, and one type or two or more types selected from these can be used singly or in combination.
  • an ultraviolet ray curable resin polymerizable compound
  • the ultraviolet ray curable resin polymerizable compound
  • a radical, a cationic, an anionic, a metathesis, and a coordination polymerization can be exemplified.
  • a cationic, an anionic, a radical, a metathesis, and a coordination polymerization can be exemplified.
  • addition polymerizable compound examples include compounds having at least one ethylenically unsaturated double bond.
  • a compound having at least one terminal ethylenically unsaturated bond, and preferably two or more terminal ethylenically unsaturated bonds can be preferably used.
  • the ethylenically unsaturated polymerizable compound has a monofunctional polymerizable compound, a polyfunctional polymerizable compound, or a chemical form of mixture of these.
  • Examples of the monofunctional polymerizable compound include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters thereof, and amides.
  • unsaturated carboxylic acid for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters of an unsaturated carboxylic acid and an aliphatic polyol compound, or an amides of an unsaturated carboxylic acid and an aliphatic amine compound are used.
  • a product of an addition reaction between unsaturated carboxylic acid esters or amides, which have a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, and isocyanates or epoxies, a product of a dehydration condensation reaction between the above unsaturated carboxylic acid esters or amides and carboxylic acids, and the like also can be used.
  • a product of an addition reaction between unsaturated carboxylic acid esters or amides, which have an electrophilic substituent such as an isocyanate group or an epoxy group, and alcohols, amines, and thiols, and a product of a substitution reaction between unsaturated carboxylic acid esters or amides, which have a leaving substituent such as a halogen group or a tosyloxy group, and alcohols, amines, or thiols also can be used.
  • radical polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyol compound
  • (meth)acrylic acid ester is representatively exemplified, and any of a monofunctional compound and a polyfunctional compound can be used.
  • a monofunctinoal (meth)acrylate examples include tolyoxyethyl (meth)acrylate, phenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, isobornyl (meth)acrylate, dipropylene glycol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • bifunctional (meth)acrylate examples include ethylene glycol di(meth)acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate.
  • trifunctional (meth)acrylate examples include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionic acid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri(meth)acrylate, and sorbitol tri(meth)acrylate.
  • tetrafunctional (meth)acrylate examples include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic acid dipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.
  • pentafunctional (meth)acrylate examples include sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
  • hexafunctional (meth)acrylate examples include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
  • polymerizable compounds other than (meth)acrylates examples include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, and maleic acid ester.
  • Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetraitaconate.
  • crotonic acid ester examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid ester examples include ethylene glycol diisocrotonate, pentaerythritol isocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid ester examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters for example, aliphatic alcohol-based esters described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231, esters having an aromatic structure described in JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149, and esters containing an amino group described in JP-A-1-165613 can also be used.
  • amide monomer of an unsaturated carboxylic acid and an aliphatic amine compound examples include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene-bis-acrylamide, 1,6-hexamethylene-bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bis-acrylamide, xylylene bis-methacrylamide, and (meth)acryloyl morpholine.
  • an amide-based monomer having a cyclohexylene structure described in JP-B-54-21726 can be exemplified.
  • a urethane-based addition polymerizable compound manufactured by an addition reaction between isocyanate and a hydroxy group is also suitable, and as the specific example, a vinyl urethane compound containing two or more polymerizable vinyl groups in a molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (1) to a polyisocyanate compound having two or more isocyanate groups in a molecule described in JP-B-48-41708 can be exemplified.
  • CH 2 C(R 1 )COOCH 2 CH(R 2) OH (1) (here, in the formula (1), each of R 1 and R 2 independently represents H or CH 3 .)
  • a cationic ring-opening polymerizable compound having one or more cyclic ether groups such as an epoxy group or an oxetane group in a molecule can be suitably used as an ultraviolet ray curable resin (polymerizable compound).
  • curable compounds including a ring-opening polymerizable group can be exemplified, and among these, a heterocyclic group-containing curable compound is particularly preferable.
  • curable compounds include cyclic imino ethers such as epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, and oxazoline derivatives, and vinyl ethers, and among these, epoxy derivatives, oxetane derivatives and vinyl ethers are preferable.
  • Examples of the preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxy, and polyfunctional alicyclic epoxy.
  • Examples of the specific compounds of glycidyl ethers include diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and the like), tri- or higher functional glycidyl ethers (for example, trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, and the like), tetra or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of a cresol novolac resin, polyglycidyl ether of a phenolic novolac resin, and the like), alicyclic epoxies
  • alicyclic epoxy derivatives can be preferably used as the polymerizable compound.
  • "Alicyclic epoxy group” refers to a substructure obtained by epoxidizing the double bond in the cycloalkene ring of a cyclopentene group, a cyclohexene group, or the like with a suitable oxidant such as hydrogen peroxide, peroxy acid, or the like.
  • alicyclic epoxy compound polyfunctional alicyclic epoxy compounds having two or more cyclohexene oxide groups or cyclopentene oxide groups in a molecule is preferable.
  • Specific examples of the alicyclic epoxy compound include 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, di(3,4-epoxycyclohexyl)adipate, di(3,4-epoxycyclohexylmethyl)adipate, bis(2,3-epoxycyclopentyl)ether, di(2,3-epoxy-6-methylcyclohexylmethyl)adipate, and dicyclopentadiene dioxide.
  • a glycidyl compound having an ordinary epoxy group which does not have an alicyclic structure in the molecule may be used alone or in combination with the above alicyclic epoxy compounds.
  • glycidyl compound As such an ordinary glycidyl compound, a glycidyl ether compound and a glycidyl ester compound can be exemplified, and the glycidyl ether compound is preferably used in combination.
  • the glycidyl ether compound examples include aromatic glycidyl ether compounds such as 1,3-bis(2,3-epoxypropyloxy)benzene, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol-novolac type epoxy resin, a cresol-novolac type epoxy resin, and a trisphenolmethane type epoxy resin, and aliphatic glycidyl ether compounds such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane tritriglycidyl ether.
  • aromatic glycidyl ether compounds such as 1,3-bis(2,3-epoxypropyloxy)benzene, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol-novolac type epoxy resin, a cresol-novolac type epoxy
  • oxetane compound As the polymerizable compound, a compound (hereinafter, simply referred to as "oxetane compound”) having an oxetanyl group which is a cyclic ether having a four-membered ring can be used.
  • An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in a molecule.
  • the ink for forming an outermost layer 4A preferably includes one type or two or more types selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, polyether-based aliphatic urethane (meth)acrylate oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • the ink for forming an outermost layer 4A includes 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, since oxygen inhibition is less likely occur, curing at low energy is possible, and effects in which copolymerization including other monomers is promoted, and the strength of a formed object is increased are obtained.
  • the ink for forming an outermost layer 4A includes a polyether-based aliphatic urethane (meth)acrylate oligomer, an effect in which both high strength and high toughness of a formed object are achieved is obtained.
  • the ink for forming an outermost layer 4A includes 2-hydroxy-3-phenoxypropyl (meth)acrylate, an effect which has flexibility and in which a breaking elongation is improved is obtained.
  • the ink for forming an outermost layer 4A includes 4-hydroxybutyl (meth)acrylate
  • an effect in which strength of a formed object is increased is obtained by improving adhesion to PMMA particles, PEMA particles, silica particles, or metal particles.
  • the ink for forming an outermost layer 4A includes a specific curing component described above (one type or two or more types selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, polyether-based aliphatic urethane (meth)acrylate oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate), the proportion of the specific curing component with respect to the entire curing components configuring the ink for forming an outermost layer 4A is preferably equal to or greater than 80% by mass, more preferably equal to or greater than 90% by mass, and still more preferably 100% by mass. Thereby, effects as described above are more significantly exhibited.
  • a specific curing component described above one type or two or more types selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, polyether-based aliphatic urethane (meth)acrylate oligo
  • the content of the curing component in the ink for forming an outermost layer 4A is preferably 80% by mass to 97% by mass, and more preferably 85% by mass to 95% by mass.
  • the ink for forming an outermost layer 4A preferably includes a polymerization initiator.
  • a photo-radical polymerization initiator for example, a photo-radical polymerization initiator (aromatic ketones, an acyl phosphine oxide compound, an aromatic onium salt compound, an organic peroxide, a thio compound (a thioxanthone compound, a thiophenyl group-containing compound, and the like), a hexaaryl biimidazole compound, a ketooxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, an alkyl amine compound, and the like), or a photo-cationic polymerization initiator can be used, and specific examples thereof include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, xanthone, fluorenone, benzalde
  • a polymerization initiator configuring the ink for forming an outermost layer 4A preferably includes bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the ink for forming an outermost layer 4A together with the ink for forming a sacrificial layer 4B described below in detail, includes bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide as a polymerization initiator, it is possible to more suitably control the curing rate with respect to the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B. As a result, it is possible to make productivity of the three-dimensional structure 1 excellent.
  • the ink for forming an outermost layer 4A together with the ink for forming a sacrificial layer 4B described below in detail, includes bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide as a polymerization initiator
  • the content of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide in the ink for forming an outermost layer 4A is preferably higher than the content of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide in the ink for forming a sacrificial layer 4B.
  • each of the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B is possible to cure at a more suitable rate.
  • the content of a polymerization initiator in the ink for forming an outermost layer 4A is not particularly limited, however, is preferably higher than the content of a polymerization initiator in the ink for forming a sacrificial layer 4B.
  • each of the ink for forming an outermost layer 4A and the ink for forming a sacrificial layer 4B is possible to cure at a more suitable rate.
  • the content of the polymerization initiator in the ink for forming an outermost layer 4A is defined as X 1 [% by mass]
  • the content of the polymerization initiator in the ink for forming a sacrificial layer 4B is defined as X 2 [% by mass]
  • the relationship of 1.05 smaller than or equal to X 1 /X 2 smaller than or equal to 2.0 is preferably satisfied, and the relationship of 1.1 smaller than or equal to X 1 /X 2 smaller than or equal to 1.5 is preferably satisfied.
  • the specific value of the content of the polymerization initiator in the ink for forming an outermost layer 4A is preferably 3.0% by mass to 18% by mass, and more preferably 5.0% by mass to 15% by mass.
  • a preferred specific example of the mixing ratio (ink constitution except for "other components” described below) of a curable resin and a polymerization initiator in the ink for forming an outermost layer 4A is shown below, however, needless to say, the constitution of the ink for forming an outermost layer in the invention is not limited to that described below.
  • the ink for forming an outermost layer 4A may include components other than the components described above.
  • Such components include various colorants such as a pigment and a dye; a dispersant; a surfactant; a sensitizer; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; an ultraviolet absorbent; a chelating agent; a pH adjusting agent; a thickener; a filler; an aggregation preventing agent; and a defoamer.
  • the ink for forming an outermost layer 4A includes a colorant, it is possible to obtain the three-dimensional structure 1 which is colored in the color corresponding to the color of the colorant.
  • a pigment as a colorant, it is possible to make the light resistance of the ink for forming an outermost layer 4A and the three-dimensional structure 1 more favorable.
  • a pigment as a colorant, it is possible to make the light resistance of the ink for forming an outermost layer 4A and the three-dimensional structure 1 more favorable.
  • Both an inorganic pigment and an organic pigment can be used as the pigment.
  • the inorganic pigment examples include carbon blacks (C.I. Pigment Black 7) such as a furnace black, a lamp black, an acetylene black, and a channel black, iron oxide, and titanium oxide, and one type or two or more types selected from these can be used singly or in combination.
  • carbon blacks such as a furnace black, a lamp black, an acetylene black, and a channel black, iron oxide, and titanium oxide, and one type or two or more types selected from these can be used singly or in combination.
  • titanium oxide is preferable in order to exhibit a preferred white color.
  • organic pigments examples include azo pigments such as an insoluble azo pigment, a condensed azo pigment, an azo lake, and a chelate azo pigment, polycyclic pigments such as a phthalocyanine pigment, a perylene, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxane pigment, a thioindigo pigment, an isoindolinone pigment, and a quinophthalone pigment, a dye chelate (for example, a base dye type chelate, an acid dye type chelate, and the like), a dyeing lake (a basic dye type lake and an acidic dye type lake), a nitro pigment, a nitroso pigment, an aniline black, and a daylight fluorescent pigment, and one type or two or more types selected from these can be used singly or in combination.
  • azo pigments such as an insoluble azo pigment, a condensed azo pigment, an azo lake, and a
  • examples of the carbon black used as a black pigment include No. 2300, No. 900, MCF 88, No. 33, No. 40, No. 45, No. 52, MA 7, MA 8, MA 100, No. 2200B, and the like (hereinbefore, manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, and the like (hereinbefore, manufactured by Carbon Columbia, Ltd.), Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, and the like (hereinbefore, manufactured by CABOT JAPAN K.K.), and Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special
  • white pigment examples include C.I. Pigment White 6, 18 and 21.
  • yellow pigment examples include C.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, and 180.
  • magenta pigment examples include C.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, and 245, or C.I. Pigment Violet 19, 23, 32, 33, 36, 38, 43, and 50.
  • Examples of the cyan pigment include C.I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and C.I. Vat Blue 4 and 60.
  • examples of the pigments other than the pigments described above include C.I. Pigment Green 7, 10, C.I. Pigment Brown 3, 5, 25, 26, and C.I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43 and 63.
  • the average particle size of the pigment is preferably equal to or less than 300 nm, and more preferably 50 nm to 250 nm.
  • examples of the dyes include an acid dye, a direct dye, a reactive dye, and a basic dye, and one type or two or more types selected from these can be used singly or in combination.
  • the dye examples include C.I. Acid Yellow 17, 23, 42, 44, 79, and 142, C.I. Acid Red 52, 80, 82, 249, 254, and 289, C.I. Acid Blue 9, 45, and 249, C.I. Acid Black 1, 2, 24, and 94, C.I. Food Black 1 and 2, C.I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, and 173, C.I. Direct Red 1, 4, 9, 80, 81, 225, and 227, C.I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, and 202, C.I. Direct Black 19, 38, 51, 71, 154, 168, 171 and 195, C.I. Reactive Red 14, 32, 55, 79, and 249, and C.I. Reactive Black 3, 4, and 35.
  • the content of the colorant in the ink for forming an outermost layer 4A is preferably 1% by mass to 20% by mass. Thereby, an excellent concealing property and color reproducibility are obtained.
  • the content of the titanium oxide in the ink for forming an outermost layer 4A is preferably 12% by mass to 18% by mass, and more preferably 14% by mass to 16% by mass. Thereby, an excellent concealing property is obtained.
  • the ink for forming an outermost layer 4A includes a pigment
  • the ink for forming an outermost layer 4A further includes a dispersant, it is possible to make the dispersibility of the pigment more favorable.
  • dispersant examples include dispersants which are commonly used in the preparation of pigment dispersions such as a polymer dispersant.
  • polymer dispersant examples include dispersants containing one or more types among polyoxyalkylene polyalkylene polyamine, a vinyl-based polymer and copolymer, an acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, an amino-based polymer, a silicon-containing polymer, a sulfur-containing polymer, a fluorine-containing polymer, and an epoxy resin, as a main component.
  • polymer dispersants examples include Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc., Solsperse series (Solsperse 36000 and the like) available from Noveon Inc., and Disperbyk series manufactured by BYK Chemie, and Disparlon series manufactured by Kusumoto Chemicals, Ltd.
  • the ink for forming an outermost layer 4A includes a surfactant, it is possible to make the abrasion resistance of the three-dimensional structure 1 more favorable.
  • the surfactant is not particularly limited, and for example, silicone-based surfactants such as polyester-modified silicone or polyether-modified silicone can be used, and among these, polyether-modified polydimethyl siloxane or polyester-modified polydimethyl siloxane is preferably used.
  • surfactant examples include BYK-347, BYK-348, BYK-UV3500, 3510, 3530, and 3570 (product names, manufactured by BYK Co., Ltd.).
  • the ink for forming an outermost layer 4A may include a solvent.
  • the solvent examples include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; acetic acid esters such as ethyl acetate, N-propyl acetate, iso-propyl acetate, N-butyl acetate, and iso-butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl-n-butyl ketone, diisopropyl ketone, and acetyl acetone; and alcohols such as ethanol, propanol, and butanol, and one type or two or more types selected from these can be used singly or in combination.
  • the viscosity of the ink for forming an outermost layer 4A is preferably 10 mPa*s to 30 mPa*s, and more preferably 15 mPa*s to 25 mPa*s.
  • the viscosity refers to a value measured at 25 degrees centigrade by using an E type viscometer (VISCONIC ELD manufactured by Tokyo Keiki Inc.).
  • plural types of the ink for forming an outermost layer 4A may be used.
  • an ink (color ink) for forming an outermost layer 4A including a colorant and an ink (clear ink) for forming an outermost layer 4A not including a colorant may be used.
  • the ink for forming an outermost layer 4A including a colorant as the ink for forming an outermost layer 4A applied to a region that affects the color
  • the ink for forming an outermost layer 4A not including a colorant as the ink for forming an outermost layer 4A applied to a region that does not affect the color
  • plural types of the ink for forming an outermost layer 4A may be used in combination such that a region (coating layer) formed by using the ink for forming an outermost layer 4A not including a colorant is provided to the outer surface of a region formed by using the ink for forming an outermost layer 4A including a colorant.
  • the portion containing a colorant in particular, a pigment
  • a colorant in particular, a pigment
  • the portion containing a colorant is likely to be brittle, become scratched, or become chipped compared to the portion not containing a colorant, by providing a region formed by using the ink for forming an outermost layer not containing a colorant near the outer surface of a three-dimensional structure, it is possible to effectively prevent the occurrence of such problems.
  • plural types of the ink for forming an outermost layer 4A including colorants having different constitutions may be used.
  • the ink for forming an outermost layer 4A it is preferable to use at least an ink for forming an outermost layer 4A having a cyan color, an ink for forming an outermost layer 4A having a magenta color, and an ink for forming an outermost layer 4A having a yellow color.
  • the ink for forming an outermost layer 4A having a white color and other inks for forming an outermost layer 4A having another color in combination for example, the following effect is obtained.
  • the finally obtained three-dimensional structure 1 have a first region where the ink for forming an outermost layer 4A having a white color is applied and a region (second region) where the ink for forming an outermost layer 4A having a color other than a white color provided on the outer surface than the first region is applied.
  • the first region where the ink for forming an outermost layer 4A having a white color is applied can exhibit a concealing property, and it is possible to further increase color saturation of the three-dimensional structure 1.
  • binding ink 4C a clear ink not including a colorant may be used, and a white ink may be used.
  • the ink for forming a sacrificial layer 4B includes at least a curable resin (curing component).
  • curable resin (curing component) configuring the ink for forming a sacrificial layer 4B the same resin as the curable resin (curing component) exemplified as a constituent of the ink for forming an outermost layer 4A can be exemplified.
  • the curable resin (curing component) configuring the ink for forming a sacrificial layer 4B and the curable resin (curing component) configuring the ink for forming an outermost layer 4A described above are preferably cured by the same energy rays.
  • the ink 4B for forming a sacrificial layer preferably includes one type or two or more types selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, polyethyleneglycol di(meth)acrylate, (meth)acryloyl morpholine, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.
  • the sacrificial layer 8 which is the lower layer (first layer) can more suitably support the ink for forming an outermost layer 4A for forming the upper layer (second layer). For this reason, it is possible to more suitably prevent unintended deformation (in particular, sagging or the like) of the outermost layer 7 (the sacrificial layer 8 which is the first layer functions as a support material), and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 1 excellent.
  • the ink for forming a sacrificial layer 4B includes (meth)acryloyl morpholine, the following effects are obtained.
  • the ink for forming a sacrificial layer 4B includes tetrahydrofurfuryl (meth)acrylate
  • an effect in which flexibility after curing is maintained, and removability is increased due to a gel state readily being brought about by a treatment with a liquid for removing the sacrificial layer 8 is obtained.
  • the ink for forming a sacrificial layer 4B includes ethoxyethoxyethyl (meth)acrylate, an effect in which tackiness is likely to remain even after curing, and removability by a liquid for removing the sacrificial layer 8 is increased is obtained.
  • the ink for forming a sacrificial layer 4B includes polyethylene glycol di(meth)acrylate
  • a liquid for removing the sacrificial layer 8 has water as a main component, an effect in which solubility in the liquid water is increased, and thus, removal becomes easy is obtained.
  • the ink for forming a sacrificial layer 4B includes a specific curing component described above (one type or two or more types selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, and (meth)acryloyl morpholine),
  • the proportion of the specific curing component with respect to the entire curing components configuring the ink for forming a sacrificial layer 4B is preferably equal to or greater than 80% by mass, more preferably equal to or greater than 90% by mass, and still more preferably 100% by mass.
  • the content of the curing component in the ink 4B for forming a sacrificial layer is preferably 83% by mass to 98.5% by mass, and more preferably 87% by mass to 95.4% by mass.
  • the ink for forming a sacrificial layer 4B preferably includes a polymerization initiator.
  • the same polymerization initiator as the polymerization initiator exemplified as a constituent of the ink for forming an outermost layer 4A can be exemplified.
  • the ink for forming a sacrificial layer 4B preferably includes bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a polymerization initiator.
  • the sacrificial layer 8 which is the lower layer (first layer) can more suitably support the ink for forming an outermost layer 4A for forming the upper layer (second layer). For this reason, it is possible to more suitably prevent unintended deformation (in particular, sagging or the like) of the outermost layer 7 (the sacrificial layer 8 which is the first layer functions as a support material), and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 1 excellent.
  • the specific value of the content of the polymerization initiator in the ink for forming a sacrificial layer 4B is preferably 1.5% by mass to 17% by mass, and more preferably 4.6% by mass to 13% by mass.
  • the sacrificial layer 8 which is the lower layer (first layer) can more suitably support the ink for forming an outermost layer 4A for forming the upper layer (second layer). For this reason, it is possible to more suitably prevent unintended deformation (in particular, sagging or the like) of the outermost layer 7 (the sacrificial layer 8 which is the first layer functions as a support material), and it is possible to make the dimensional accuracy of the finally obtained three-dimensional structure 1 excellent.
  • a preferred specific example of the mixing ratio (ink constitution except for "other components” described below) of a curable resin and a polymerization initiator in the ink for forming a sacrificial layer 4B is shown below, however, needless to say, the constitution of the ink for forming a sacrificial layer in the invention is not limited to that described below.
  • the ink for forming a sacrificial layer 4B may include components other than the components described above.
  • examples of such components include various colorants such as a pigment and a dye; a dispersant; a surfactant; a sensitizer; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; an ultraviolet absorbent; a chelating agent; a pH adjusting agent; a thickener; a filler; an aggregation preventing agent; and a defoamer.
  • various colorants such as a pigment and a dye; a dispersant; a surfactant; a sensitizer; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; an ultraviolet absorbent; a chelating agent;
  • the ink for forming a sacrificial layer 4B includes a colorant
  • the visibility of the sacrificial layer 8 is improved, and in the finally obtained three-dimensional structure 1, it is possible to more reliably prevent at least a part of the sacrificial layer 8 from unintentionally remaining.
  • the same colorant as the colorant exemplified as a constituent of the ink for forming an outermost layer 4A can be exemplified, and the colorant is preferably a colorant which becomes a color different from the color (color to be seen in the appearance of the three-dimensional structure 1) of the outermost layer 7 overlapped with the sacrificial layer 8 formed by the ink for forming a sacrificial layer 4B when observed from the normal direction of the surface of the three-dimensional structure 1.
  • the ink for forming a sacrificial layer 4B includes a pigment
  • the ink for forming an outermost layer 4A further includes a dispersant
  • the dispersant configuring the ink for forming a sacrificial layer 4B the same dispersant as the dispersant exemplified as a constituent of the ink for forming an outermost layer 4A can be exemplified.
  • the viscosity of the ink for forming a sacrificial layer 4B is preferably 10 mPa*s to 30 mPa*s, and more preferably 15 mPa*s to 25 mPa*s.
  • the ink set may be an ink set which is equipped with at least one of the ink for forming an outermost layer 4A, at least one of the ink for forming a sacrificial layer 4B, and the binding ink 4C, and may be equipped with a fourth ink different from these inks.
  • composition for Forming a Three-dimensional object (4. Composition for Forming a Three-dimensional Object) Next, the composition for forming a three-dimensional object will be described in detail.
  • the composition for forming a three-dimensional object includes the powder for forming a three-dimensional object and the water-soluble resin 64.
  • the powder for forming a three-dimensional object is configured of a plurality of particles 63.
  • any particles can be used, and the particles 63 are preferably configured of porous particles.
  • the curable resin 44 included in the binding ink 4C can suitably penetrate into pores, and as a result, porous particles can be suitably used for manufacturing a three-dimensional structure having excellent mechanical strength.
  • Examples of the constituent material of the porous particles configuring the powder for forming a three-dimensional object include an inorganic material, an organic material, and a complex of these.
  • Examples of the inorganic material configuring the porous particles include various metals, a metal compound, and the like.
  • the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zirconium oxide, tin oxide, magnesium oxide, and potassium titanate; various metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; various metal nitrides such as silicon nitride, titanium nitride, and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metal carbonates such as calcium carbonate and magnesium carbonate; various metal sulfates such as calcium sulfate and magnesium sulfate; various metal silicates such as calcium silicate and magnesium silicate; various metal phosphates such as calcium phosphate; and various metal borates such as aluminum borate and magnesium borate, or composite compounds of these.
  • synthetic resins and natural polymers can be exemplified, and more specific examples include a polyethylene resin; polypropylene; polyethylene oxide; polypropylene oxide, polyethylene imine; polystyrene; polyurethane; polyurea; polyester; a silicone resin; an acrylic silicone resin; polymers having (meth)acrylic acid ester as a constituent monomer such as polymethyl methacrylate; cross polymers having (meth)acrylic acid ester as a constituent monomer such as methyl methacrylate cross polymer (ethylene acrylic acid copolymer resin or the like); polyamide resins such as Nylon 12, Nylon 6, and copolymer nylon; polyimide; carboxymethyl cellulose; gelatin; starch; chitin; and chitosan.
  • polyethylene resin polypropylene
  • polyethylene oxide polypropylene oxide
  • polyethylene imine polystyrene
  • polyurethane polyurea
  • polyester a silicone resin
  • an acrylic silicone resin polymers having (meth)acrylic acid
  • the porous particles are preferably configured of an inorganic material, more preferably configured of metal oxide, and still more preferably configured of silica.
  • the porous particles are configured of silica.
  • the effect as described above is more significantly exhibited.
  • silica since silica has also excellent fluidity, silica is useful for forming a layer having higher thickness uniformity, and it is possible to make productivity and dimensional accuracy of the three-dimensional structure 1 excellent.
  • silica commercially available products can be suitably used. Specific examples include Mizukasil P-526, Mizukasil P-801, Mizukasil NP-8, Mizukasil P-802, Mizukasil P-802Y, Mizukasil C-212, Mizukasil P-73, Mizukasil P-78A, Mizukasil P-78F, Mizukasil P-87, Mizukasil P-705, Mizukasil P-707, Mizukasil P-707D, Mizukasil P-709, Mizukasil C-402, and Mizukasil C-484 (manufactured by Mizusawa Industrial Chemicals, Ltd.), Tokusil U, Tokusil UR, Tokusil GU, Tokusil AL-1, Tokusil GU-N, Tokusil N, Tokusil NR, Tokusil PR, SOLEX, Fine Seal E-50, Fine Seal T-32, Fine
  • Syloid 63, Syloid 65, Syloid 66, Syloid 77, Syloid 74, Syloid 79, Syloid 404, Syloid 620, Syloid 800, Syloid 150, Syloid 244, and Syloid 266 (manufactured by Fuji Silysia Chemical Ltd.), and Nipgel AY-200, Nipgel AY-6A2, Nipgel AZ-200, Nipgel AZ-6A0, Nipgel BY-200, Nipgel BY-200, Nipgel CX-200, Nipgel CY-200, Nipsil E-150J, Nipsil E-220A, and Nipsil E-200A (manufactured by Tosoh Silica Corporation).
  • the porous particles are preferably porous particles on which a hydrophobization treatment is performed.
  • the curable resin 44 included in the binding ink 4C tends to have hydrophobicity. Therefore, due to the hydrophobization treatment of porous particles, the curable resin 44 can suitably penetrate into pores of the porous particles. As a result, an anchoring effect is more significantly exhibited, and it is possible to make the mechanical strength of the obtained three-dimensional structure 1 excellent.
  • the porous particles can be suitably reused.
  • any treatment may be used as long as it increases hydrophobicity of the porous particles, and it is preferable to introduce a hydrocarbon group. Thereby, it is possible to further increase hydrophobicity of the particles. In addition, it is possible to easily and reliably further increase uniformity of the degree of the hydrophobic treatment at each portion (including the surface of the inside of a porous) of each particle or the particle surface.
  • a silane compound including a silyl group is preferable.
  • Specific examples of the compound which can be used in the hydrophobization treatment include hexamethyldisilazane, dimethyl dimethoxysilane, diethyl diethoxysilane, 1-propenylmethyl dichlorosilane, propyldimethyl chlorosilane, propylmethyl dichlorosilane, propyl trichlorosilane, propyl triethoxysilane, propyl trimethoxysilane, styrylethyl trimethoxysilane, tetradecyl trichlorosilane, 3-thiocyanatopropyl triethoxysilane, p-tolydimethyl chlorosilane, p-tolymethyl dichlorosilane, p-toly trichlorosilane, p-toly trimethoxysilane, p
  • hexamethyl disilazane is preferably used in the hydrophobization treatment.
  • hydrophobicity of the particles it is possible to further increase hydrophobicity of the particles.
  • the hydrophobization treatment using a silane compound is performed in a liquid phase, by immersing the particles to be subjected to the hydrophobization treatment in the liquid including the silane compound, it is possible to make a suitable desired reaction proceed, and it is possible to form a chemical adsorption film of the silane compound.
  • the average grain size of the particles 63 configuring the powder for forming a three-dimensional object is not particularly limited, the average grain size of the particles 63 is preferably 1 micrometer to 25 micrometers, and more preferably 1 micrometer to 15 micrometers. Thereby, it is possible to make the mechanical strength of the three-dimensional structure 1 excellent, and it is possible to make the dimensional accuracy of the three-dimensional structure 1 excellent. In addition, it is possible to make fluidity of the powder for forming a three-dimensional object and fluidity of the composition for forming a three-dimensional object including the powder for forming a three-dimensional object excellent, and it is possible to make productivity of the three-dimensional structure excellent.
  • the average particle size refers to an average particle size based on volume, and for example, after a sample is added to methanol, the mixture is dispersed for 3 minutes with an ultrasonic wave disperser, and the average particle size of the obtained dispersion is measured using an aperture of 50 micrometers by a Coulter counter method particle size distribution measuring instrument (TA-II type manufactured by COULTER ELECTRONICS INS.).
  • TA-II Coulter counter method particle size distribution measuring instrument
  • D max of the particles 63 configuring the composition for forming a three-dimensional object is not particularly limited, D max of the particles 63 is preferably 3 micrometers to 40 micrometers, and more preferably 5 micrometers to 30 micrometers. Thereby, it is possible to make the mechanical strength of the three-dimensional structure 1 excellent, and it is possible to make the dimensional accuracy of the three-dimensional structure 1 excellent. In addition, it is possible to make fluidity of the powder for forming a three-dimensional object and fluidity of the composition for forming a three-dimensional object including the powder for forming a three-dimensional object excellent, and it is possible to make productivity of the three-dimensional structure excellent. In addition, it is possible to more effectively prevent scattering of light by the particles 63 on the surface of the three-dimensional structure 1 to be manufactured.
  • the porosity of the porous particles is preferably equal to or greater than 50%, and more preferably 55% to 90%.
  • the particles can have sufficient space (pores) into which the curable resin enters, and it is possible to make the mechanical strength of the porous particles themselves excellent, and as a result, it is possible to make the mechanical strength of the three-dimensional structure 1 obtained by penetration of a binding resin into pores excellent.
  • the porosity of particles refers to a proportion (volume ratio) of pores which are present in particles with respect to the apparent volume of particles, and when the density of particles is defined as rho [g/cm 3 ] and the true density of the constituent material of the particles is defined as rho 0 [g/cm 3 ], the porosity of particles is a value represented by ⁇ (rho 0 - rho)/rho 0 ⁇ x 100.
  • the average pore diameter (fine pore diameter) of the porous particles is preferably equal to or greater than 10 nm, and more preferably 50 nm to 300 nm. Thereby, it is possible to make the mechanical strength of the finally obtained three-dimensional structure 1 excellent.
  • the particles 63 configuring the powder for forming a three-dimensional object may be any shape, the particles 63 are preferably a spherical shape. Thereby, it is possible to make fluidity of the powder for forming a three-dimensional object and fluidity of the composition for forming a three-dimensional object including the powder for forming a three-dimensional object excellent, it is possible to make productivity of the three-dimensional structure 1 excellent, and it is possible to make the dimensional accuracy of the three-dimensional structure 1 excellent.
  • the powder for forming a three-dimensional object may be powder including plural types of particles which have the above-described conditions (for example, constituent material of the particles, and type of hydrophobization treatment) different from each other.
  • the percentage of void of the powder for forming a three-dimensional object is preferably 70% to 98%, and more preferably 75% to 97.7%. Thereby, it is possible to make the mechanical strength of the three-dimensional structure excellent.
  • it is possible to make fluidity of the powder for forming a three-dimensional object and fluidity of the composition for forming a three-dimensional object including the powder for forming a three-dimensional object excellent it is possible to make productivity of the three-dimensional structure excellent, and it is possible to make the dimensional accuracy of the three-dimensional structure excellent.
  • the percentage of void of the powder for forming a three-dimensional object refers to a ratio of the volume of pores which all the particles configuring the powder for forming a three-dimensional object have and the sum of the volume of voids which are present between the particles with respect to the capacity of the container, and when the bulk density of the powder for forming a three-dimensional object is defined as P [g/cm 3 ] and the true density of the constituent material of the powder for forming a three-dimensional object is defined as P 0 [g/cm 3 ], the percentage of void is a value represented by ⁇ (P 0 - P)/P 0 ⁇ x 100.
  • the content of the powder for forming a three-dimensional object in the composition for forming a three-dimensional object is preferably 10% by mass to 90% by mass, and more preferably 15% by mass to 58% by mass. Thereby, it is possible to make the fluidity of the composition for forming a three-dimensional object excellent, and it is possible to make the mechanical strength of the finally obtained three-dimensional structure 1 excellent.
  • the composition for forming a three-dimensional object includes a plurality of the particles 63 and the water-soluble resin 64.
  • the particles 63 are bound (temporarily fixed) to each other (see Fig. 4), and it is possible to effectively prevent unintended scattering of the particles 63. Thereby, it is possible to improve safety of a worker and the dimensional accuracy of the manufactured three-dimensional structure 1.
  • the water-soluble resin is not limited as long as at least a part thereof is soluble in water, and for example, a water-soluble resin having a solubility (mass soluble in 100 g water) of equal to or greater than 5 [g/100 g water] in water at 25 degrees centigrade is preferable, and a water-soluble resin having a solubility of equal to or greater than 10 [g/100 g water] in water at 25 degrees centigrade is more preferable.
  • water-soluble resin 64 examples include synthetic polymers such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), sodium polyacrylate, polyacryl amide, modified polyamide, polyethylene imine, and polyethylene oxide, natural polymers such as cornstarch, mannan, pectin, agar, alginic acid, dextran, glues, and gelatin, and semi-synthetic polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, oxidized starch, and modified starch, and one type or two or more types selected from these can be used singly or in combination.
  • synthetic polymers such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), sodium polyacrylate, polyacryl amide, modified polyamide, polyethylene imine, and polyethylene oxide
  • natural polymers such as cornstarch, mannan, pectin, agar, alginic acid, dextran, glues, and gelatin
  • water-soluble resin product examples include methyl cellulose (manufactured by Shin-Etsu Chemicals Co., Ltd.: trade name "Metolose SM-15”), hydroxyethyl cellulose (manufactured by Fuji Chemical Industry Co., Ltd.: trade name "AL-15”), hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.: trade name "HPC-M”), carboxymethyl cellulose (Nichirin Chemical Co., Ltd.: trade name "CMC-30”), sodium (I) starch phosphate (manufactured by Matsutani Chemical Industry Co., Ltd.: trade name "Hoster 5100”), polyvinyl pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.: trade name "PVP K-90”), a methyl vinyl ether/maleic anhydride copolymer (manufactured by GAF Gantrez: trade name "AN-139”), polyacryl amide (manufacture
  • the water-soluble resin 64 is polyvinyl alcohol
  • by adjusting the saponification degree and the polymerization degree it is possible to more suitably control characteristics (for example, water solubility, water resistance, and the like) of the water-soluble resin 64 or characteristics (for example, viscosity, fixing force of the particles 63, wettability, and the like) of the composition for forming a three-dimensional object. Therefore, it is possible to more suitably cope with according to manufacture of the various three-dimensional structures 1.
  • polyvinyl alcohol is inexpensive and a supply thereof is stable. Therefore, it is possible to manufacture the stable three-dimensional structure 1 while reducing the production cost.
  • the saponification degree of the polyvinyl alcohol is preferably 85 to 90. Thereby, it is possible to suppress decrease in the solubility of the polyvinyl alcohol in water. For this reason, in a case where the composition for forming a three-dimensional object includes water, it is possible to more effectively suppress reduction of the adhesion between adjacent unit layers.
  • the polymerization degree of the polyvinyl alcohol is preferably 300 to 1000.
  • the water-soluble resin 64 is polyvinyl pyrrolidone (PVP)
  • PVP polyvinyl pyrrolidone
  • polyvinyl pyrrolidone shows high solubility in various organic solvents
  • the a composition for forming a three-dimensional object includes an organic solvent
  • polyvinyl pyrrolidone since polyvinyl pyrrolidone has a suitable affinity with the powder for forming a three-dimensional object, polyvinyl pyrrolidone does not sufficiently enter into the pore 611 described above, and wettability with respect to the surface of the particles 63 is relatively high. For this reason, it is possible to more effectively exhibit the temporarily fixing function described above.
  • polyvinyl pyrrolidone since polyvinyl pyrrolidone has an antistatic function, in a case where the powder which is not subjected to a pasting treatment is used as the composition for forming a three-dimensional object in the filling step, it is possible to effectively prevent unintended scattering of the powder.
  • the paste-shaped composition for forming a three-dimensional object includes polyvinyl pyrrolidone, it is possible to effectively prevent bubbles from being entrained into the composition for forming a three-dimensional object, and in the filling step, it is possible to more effectively prevent occurrence of defects due to entrainment of bubbles.
  • the weight average molecular weight of the polyvinyl pyrrolidone is preferably 10000 to 1700000, and more preferably 30000 to 1500000. Thereby, it is possible to more effectively exhibit the function described above.
  • the water-soluble resin 64 preferably is in a liquid state (for example, a dissolved state, a molten state, or the like) in at least the filling step. Thereby, it is possible to easily and reliably further increase uniformity in the thickness of the composition layer for forming a three-dimensional object 6' which is formed by using the composition for forming a three-dimensional object.
  • the content of the water-soluble resin 64 in the composition for forming a three-dimensional object is preferably equal to or less than 15% by volume, and more preferably 2% by volume to 5% by volume with respect to a bulk volume of the powder for forming a three-dimensional object.
  • the composition for forming a three-dimensional object may include a solvent in addition to the water-soluble resin 64 as described above and the powder for forming a three-dimensional object. Thereby, it is possible to make fluidity of the composition for forming a three-dimensional object excellent, and it is possible to make productivity of the three-dimensional structure 1 excellent.
  • the solvent is preferably a solvent which can dissolve the water-soluble resin 64.
  • the solvent is preferably a solvent which can dissolve the water-soluble resin 64.
  • Examples of the solvent configuring the composition for forming a three-dimensional object include water; alcoholic solvents such as methanol, ethanol, and isopropanol; ketone-based solvents such as methyl ethyl ketone and acetone; glycol ether-based solvents such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, glycol ether acetate-based solvents such as propylene glycol 1-monomethyl ether 2-acetate and propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, and polypropylene glycol, and one type or two or more types selected from these can be used singly or in combination.
  • alcoholic solvents such as methanol, ethanol, and isopropanol
  • ketone-based solvents such as methyl ethyl ketone and acetone
  • glycol ether-based solvents such as ethylene glycol monoethyl ether and ethylene glycol monobut
  • the composition for forming a three-dimensional object preferably includes water.
  • water is easily removed after the composition layer for forming a three-dimensional object 6' is formed, and does not give adverse effects even in a case where water remains in the three-dimensional structure 1.
  • water is also advantageous from the viewpoint of safety with respect to human body and environmental issues.
  • the content of the solvent in the composition for forming a three-dimensional object is preferably 5% by mass to 75% by mass, and more preferably 35% by mass to 70% by mass.
  • the content of water in the composition for forming a three-dimensional object is preferably 20% by mass to 73% by mass, and more preferably 50% by mass to 70% by mass.
  • composition for forming a three-dimensional object may include components other than the components described above.
  • examples of such components include a polymerization initiator; a polymerization accelerator; a penetration enhancer; a wetting agent (humectant); a fixing agent; a fungicide; a preservative; an antioxidant; an ultraviolet absorbent; a chelating agent; and a pH adjusting agent.
  • the three-dimensional structure of the invention can be manufactured by using the manufacturing method as described above, the three-dimensional structure manufacturing apparatus, and an ink set. Thereby, it is possible to provide a three-dimensional structure of which the outer surface has high mechanical strength and on which a fine color expression may be performed.
  • Use of the three-dimensional structure of the invention is not limited, and items for appreciation and articles for exhibitions such as a doll and a figure; and medical devices such as an implant can be exemplified.
  • the three-dimensional structure of the invention may be applied to any of a prototype, mass-produced products, and tailor made products.
  • the three-dimensional structure of the invention may be a model (for example, models of vehicles such as an automobile, a motorcycle, a ship, and an airplane, buildings, organisms such as an animal and a plant, natural objects (not organism) such as a stone, and various foods).
  • a model for example, models of vehicles such as an automobile, a motorcycle, a ship, and an airplane, buildings, organisms such as an animal and a plant, natural objects (not organism) such as a stone, and various foods).
  • each ink may be applied by other methods (for example, other printing methods).
  • a pretreatment step, an intermediate treatment step, or a post-treatment step may be performed, as necessary.
  • a cleaning step of the stage or the like can be exemplified.
  • a cleaning step As the post-treatment step, a cleaning step, a shape adjusting step of performing deburring or the like, and an additional curing treatment for increasing the degree of cure of a curable resin configuring the outermost layer can be exemplified.
  • the ink discharge step may be performed by using other methods (for example, other printing methods).
  • the particles in the composition layer for forming a three-dimensional object are bound with the binding ink
  • the particles may not be bound with the binding ink.
  • Powder supply portion 60 ... Powder control portion 61 ... Blade 62 ... Guide rail 63 ... Particles 64 ... Water-soluble resin 70 ... Light source 80 ... Forming stage 100 ... Three-dimensional structure manufacturing apparatus 231 ... Control program 232 ... Data expanding portion 611 ... Pore

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Abstract

La présente invention concerne un procédé de fabrication d'une structure tridimensionnelle, par empilement de couches, qui comprend les étapes suivantes : l'éjection d'encre afin de former une couche la plus à l'extérieur sur une région destinée à devenir la couche la plus à l'extérieur de la structure tridimensionnelle de la couche et de former une couche sacrificielle pour une région sur un côté de surface de la couche qui est adjacent à la région destinée à devenir la couche la plus à l'extérieur de la couche; le durcissement de l'encre éjectée pour la formation d'une couche la plus à l'extérieur et pour la formation d'une couche sacrificielle; le remplissage d'une région entourée d'un produit durci de l'encre pour former une couche la plus à l'extérieur avec une composition pour la formation d'un objet tridimensionnel comprenant de la poudre pour la formation d'un objet tridimensionnel constituée d'une pluralité de particules et la formation d'une couche de composition pour la formation d'un objet tridimensionnel.
PCT/JP2015/000039 2014-01-09 2015-01-07 Procédé de fabrication d'une structure tridimensionnelle et structure tridimensionnelle WO2015105047A1 (fr)

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CN106827527A (zh) * 2015-11-12 2017-06-13 精工爱普生株式会社 三维造型物的制造方法
CN107406670A (zh) * 2015-08-04 2017-11-28 瓦克化学股份公司 模制件的制备方法
WO2018218172A1 (fr) * 2017-05-25 2018-11-29 Applied Materials, Inc. Correction de formes fabriquées dans une fabrication additive à l'aide d'une couche initiale
WO2019130292A1 (fr) * 2017-12-28 2019-07-04 Stratasys Ltd. Procédé et système de fabrication additive d'une structure sacrificielle pelable
CN110663102A (zh) * 2017-05-25 2020-01-07 应用材料公司 使用初始层校正增材制造中制造的形状
US10537973B2 (en) 2016-03-09 2020-01-21 Applied Materials, Inc. Correction of fabricated shapes in additive manufacturing
WO2020035456A1 (fr) * 2018-08-15 2020-02-20 DP Polar GmbH Procédé de fabrication d'un objet moulé tridimensionnel par dépôt de couches successives de matière
WO2020094246A3 (fr) * 2018-11-06 2020-08-27 Hans Mathea Procédé de fabrication d'un objet moulé tridimensionnel par dépôt de couches successives de matière
US10882160B2 (en) 2017-05-25 2021-01-05 Applied Materials, Inc. Correction of fabricated shapes in additive manufacturing using sacrificial material
DE102020001068A1 (de) 2020-02-19 2021-08-19 DP Polar GmbH Verfahren zum Herstellen eines dreidimensionalen Formgegenstands mittels schichtweisem Materialauftrag
EP3871859A1 (fr) * 2020-02-26 2021-09-01 Hewlett-Packard Development Company, L.P. Impression tridimensionnelle
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RU2783433C1 (ru) * 2018-11-06 2022-11-14 Дп Полар Гмбх Способ изготовления трехмерного фасонного изделия посредством послойного нанесения материала
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EP3871859A1 (fr) * 2020-02-26 2021-09-01 Hewlett-Packard Development Company, L.P. Impression tridimensionnelle

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