WO2015072155A1 - Manufacturing method of three-dimensional structure, three-dimensional structure, manufacturing program of three-dimensional structure, color correction control method of three-dimensional structure, and three-dimensional structure manufacturing apparatus - Google Patents

Manufacturing method of three-dimensional structure, three-dimensional structure, manufacturing program of three-dimensional structure, color correction control method of three-dimensional structure, and three-dimensional structure manufacturing apparatus Download PDF

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Publication number
WO2015072155A1
WO2015072155A1 PCT/JP2014/005760 JP2014005760W WO2015072155A1 WO 2015072155 A1 WO2015072155 A1 WO 2015072155A1 JP 2014005760 W JP2014005760 W JP 2014005760W WO 2015072155 A1 WO2015072155 A1 WO 2015072155A1
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Prior art keywords
dimensional structure
manufacturing
ink
unit
layer
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PCT/JP2014/005760
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English (en)
French (fr)
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Eiji Okamoto
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Seiko Epson Corporation
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Publication of WO2015072155A1 publication Critical patent/WO2015072155A1/en

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    • 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
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber

Definitions

  • the present invention relates to a manufacturing method of a three-dimensional structure, a three-dimensional structure, a manufacturing program of a three-dimensional structure, a color correction control method of a three-dimensional structure, and a three-dimensional structure manufacturing apparatus.
  • the laminating method generally, the three-dimensional object model is divided into a plurality of two-dimensional cross-sectional layers, and then a cross-sectional member corresponding to each of the two-dimensional cross-sectional layers is sequentially formed, and the three-dimensional structure is formed by sequentially laminating the cross-sectional members.
  • the laminating method is able to directly form the three-dimensional structure, and there is no need to prepare a mold before forming the three-dimensional structure, and thus it is possible to rapidly and inexpensively form the three-dimensional object.
  • the three-dimensional structure is formed by laminating the thin plate-like cross-sectional members one by one, and thus, for example, even when the object is a complicated object including an internal structure, it is possible to form the three-dimensional structure as an integrated structure without being divided into a plurality of components.
  • coloring properties at the time of being viewed from a side surface of each layer and coloring properties at the time of being viewed from a laminating direction may be different from each other even in a portion to which the same color is applied.
  • An object of the invention is to provide a three-dimensional structure in which a variation in coloring properties is suppressed even when it is observed from various angles, to provide a manufacturing method of a three-dimensional structure which is able to suppress a variation in coloring properties even when it is observed from various angles, to provide a manufacturing program of a three-dimensional structure, and to provide a color correction control method of a three-dimensional structure and a three-dimensional structure manufacturing apparatus.
  • a manufacturing method of a three-dimensional structure for manufacturing the three-dimensional structure having unit layers onto which a coloring ink is discharged laminated thereon in which color correction is performed according to an angle theta of an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure in a plurality of portions on a surface of the three-dimensional structure on the basis of three-dimensional shape data of the three-dimensional structure.
  • the manufacturing method of a three-dimensional structure may include a layer forming process in which a layer of a predetermined thickness is formed by using a three-dimensional structure forming composition including a three-dimensional structure forming powder which is configured of a plurality of particles, and a water soluble resin; and an ink discharging process in which the ink is discharged onto the layer.
  • a three-dimensional structure which is manufactured by the manufacturing method of a three-dimensional structure according to the invention.
  • a three-dimensional structure having unit layers onto which a coloring ink is discharged laminated thereon, in which when an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure is an angle theta, in two regions of which the angles theta are different from each other, and colors are identical to each other, discharge patterns of the coloring ink are different from each other.
  • a manufacturing program of a three-dimensional structure used for manufacturing the three-dimensional structure having unit layers onto which a coloring ink is discharged laminated thereon in which color correction data is prepared according to an angle theta of an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure in a plurality of portions on a surface of the three-dimensional structure on the basis of three-dimensional shape data of the three-dimensional structure, and a discharge pattern of the coloring ink is determined on the basis of the color correction data.
  • a color correction control method used for manufacturing a three-dimensional structure having unit layers onto which a coloring ink is discharged laminated thereon, in which color correction data is prepared according to an angle theta of an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure in a plurality of portions on a surface of the three-dimensional structure on the basis of three-dimensional shape data of the three-dimensional structure, and a color of the surface of the three-dimensional structure is controlled on the basis of the color correction data.
  • a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure having unit layers onto which a coloring ink is discharged laminated thereon, in which color correction is performed according to an angle theta of an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure in a plurality of portions on a surface of the three-dimensional structure on the basis of three-dimensional shape data of the three-dimensional structure.
  • Fig. 1A is a perspective view illustrating a three-dimensional structure.
  • Fig. 1B is a longitudinal cross-sectional view illustrating the three-dimensional structure.
  • Fig. 2 is a schematic view illustrating a three-dimensional structure manufacturing apparatus for manufacturing the three-dimensional structure.
  • Fig. 3 is a block diagram of a control unit provided in the three-dimensional structure manufacturing apparatus illustrated in Fig. 2.
  • Fig. 4A is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • Fig. 4B is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • FIG. 4C is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • Fig. 4D is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • Fig. 5E is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • Fig. 5F is a schematic view illustrating a process in a preferred embodiment of a manufacturing method of a three-dimensional structure according to the invention.
  • Fig. 6 is a cross-sectional view schematically illustrating a state of a layer (a three-dimensional structure forming composition) immediately before an ink applying process.
  • Fig. 7 is a cross-sectional view schematically illustrating a state where particles are bound by a curable resin.
  • Fig. 1A is a perspective view illustrating the three-dimensional structure
  • Fig. 1B is a longitudinal cross-sectional view illustrating the three-dimensional structure
  • Fig. 2 is a schematic view illustrating a three-dimensional structure manufacturing apparatus for manufacturing the three-dimensional structure.
  • Figs. 1A and 1B an upper side of Figs. 1A and 1B is described as “Upper”, a lower side is described as “Lower”, a right side is described as “Right”, and a left side is described as “Left”.
  • a three-dimensional structure 1 illustrated in Fig. 1A is in the shape of a sphere.
  • the three-dimensional structure 1 is obtained by laminating a plurality of thin film-like unit layers 7 as illustrated by a dotted line in Fig. 1B.
  • the unit layer 7 is obtained from curing an ink 4 (refer to Fig. 2) including a curable resin.
  • Fig. 1B 25 unit layers 7 are illustrated, but the number of laminated unit layers 7 is not particularly limited, and in general, is approximately several dozen to several tens of thousands.
  • the three-dimensional structure 1 includes a core portion 2 positioned on a side of a central portion, and an outer circumferential portion 3 which covers an entire outer surface of the core portion 2.
  • the core portion 2 is formed by using a core portion forming ink.
  • the outer circumferential portion 3 is formed by using an outer circumferential portion forming ink.
  • the core portion forming ink, and the outer circumferential portion forming ink are collectively referred to as the "ink 4" (refer to Fig. 2).
  • a color of the core portion 2 may be any color. That is, the color of the core portion 2 may be transparent, and may be a chromatic color such as red, blue, and yellow, an achromatic color such as white, black, and gray, and a metallic luster color such as gold, and silver. It is preferable that the color of the core portion 2 be white. Accordingly, it is possible to improve coloring properties of the entire outer circumferential portion 3.
  • a color of the outer circumferential portion 3 may be any color insofar as it is not transparent.
  • chromaticness or brightness of the core portion 2 and the outer circumferential portion 3 are not particularly limited, respectively.
  • an inside region of the core portion 2 may be entirely the same color, or may be different colors.
  • an average thickness of the outer circumferential portion 3 is not particularly limited.
  • the average thickness of the outer circumferential portion 3 is, preferably greater than or equal to 30 micrometers and less than or equal to 200 micrometers, and more preferably greater than or equal to 50 micrometers and less than or equal to 150 micrometers.
  • the average thickness is less than the lower limit, it is difficult to form the three-dimensional structure 1 which is relatively dark.
  • the average thickness exceeds the upper limit, the coloring properties of the outer circumferential portion 3 may deteriorate.
  • the three-dimensional structure of the invention is manufactured by a manufacturing method described later.
  • the three-dimensional structure of the invention when an acute angle formed by a plane direction A of the unit layer and a surface direction B of the three-dimensional structure is set to an angle theta (theta of Fig. 1B), in two regions of which the angles theta are different from each other, and the colors are identical to each other, discharge patterns of the ink are different from each other. Accordingly, even when the three-dimensional structure is observed from various angles, the variation in the coloring properties of the three-dimensional structure is suppressed.
  • an intended purpose of the three-dimensional structure according to the invention is not particularly limited, but for example, an aesthetic object and an exhibit such as a doll, or a figure; a medical instrument such as an implant, and the like are included.
  • the three-dimensional structure of the invention may be applied to any one of a prototype, a mass-produced product, and a tailor-made product.
  • Fig. 2 is a schematic view illustrating the three-dimensional structure manufacturing apparatus for manufacturing the three-dimensional structure.
  • Fig. 3 is a block diagram of a control unit provided in the three-dimensional structure manufacturing apparatus illustrated in Fig. 2.
  • the three-dimensional structure manufacturing apparatus 100 is an apparatus which creates a model of the unit layer 7, sequentially forms each of the unit layers 7 on the basis of the model, and forms the three-dimensional structure 1 by sequentially laminating each of the unit layers 7.
  • the three-dimensional structure manufacturing apparatus 100 includes a computer 20 for performing creation of the model of the unit layer 7 or the like, and a three-dimensional structure forming unit 30 for forming the three-dimensional structure 1.
  • the three-dimensional structure forming unit 30 includes an ink discharge unit 40 electrically connected to the computer 20, a powder supply unit 50, a powder control unit 60, a light source 70, and a three-dimensional structure forming stage 80.
  • the ink discharge unit 40 a liquid droplet discharging head 41 for discharging liquid droplets of the ink 4 by an ink jet method is installed.
  • the ink discharge unit 40 includes an ink supply unit (not illustrated).
  • a so-called piezoelectric drive type liquid droplet discharging head 41 is adopted.
  • the ink discharge unit 40 includes an X direction movement unit 42 and a Y direction movement unit 43 for moving the liquid droplet discharging head 41 in an XY plane.
  • the powder supply unit 50 has a function of supplying a three-dimensional structure forming powder (hereinafter, simply referred to as a "powder") to the three-dimensional structure forming stage 80 described later.
  • the powder supply unit 50 is configured to be driven by a powder supply unit drive section (not illustrated).
  • the powder control unit 60 includes a blade 61, and a guide rail 62 which regulates an operation of the blade 61.
  • the powder control unit 60 has a function of controlling the powder supplied from the powder supply unit 50 by the blade 61, and forming a layer of a predetermined thickness which is configured of the powder on the three-dimensional structure forming stage 80.
  • the blade 61 is elongated in a Y direction, and a tip of a lower portion thereof is in the shape of a sharp knife.
  • the blade 61 is configured to be driven in an X direction along the guide rail 62 by a blade drive section (not illustrated).
  • the light source 70 has a function of curing the ink 4 applied onto the layer of the powder which is formed by the powder control unit.
  • the light source 70 is configured to emit ultraviolet light.
  • a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and the like are able to be adopted.
  • the three-dimensional structure forming stage 80 is in the shape of a rectangle in an XY cross section. On the three-dimensional structure forming stage 80, the unit layer 7 is formed by binding the powder with the ink 4.
  • the three-dimensional structure forming stage 80 is able to be moved in a Z direction by a three-dimensional structure forming stage drive section (not illustrated).
  • the three-dimensional structure forming unit 30 includes a drive control unit (not illustrated).
  • the drive control unit includes a motor control unit, a position detection control unit, a powder supply control unit, a discharge control unit, and an exposure control unit.
  • the motor control unit individually controls driving of the liquid droplet discharging head 41 in an XY direction, driving of the blade 61, and driving of the three-dimensional structure forming stage 80 on the basis of a command from a CPU provided in the computer 20 described later.
  • the position detection control unit individually controls a position of the liquid droplet discharging head 41, a position of the blade 61, and a position of the three-dimensional structure forming stage 80 on the basis of a command from the CPU.
  • the powder supply control unit controls driving of the powder supply unit 50 (a supply of the powder) on the basis of a command from the CPU.
  • the discharge control unit controls driving of the liquid droplet discharging head 41 (discharge of the liquid droplets) on the basis of a command from the CPU.
  • the exposure control unit controls a light-emitting state of the light source 70 on the basis of a command from the CPU.
  • the computer 20 includes a control unit 21 for controlling an operation of each unit of the three-dimensional structure forming unit 30, a reception unit 24, and an image creation unit 25.
  • the control unit 21 includes the Central Processing Unit (CPU) 22, and a storage unit 23.
  • CPU Central Processing Unit
  • the CPU 22 performs various arithmetic processings as a processor in order to execute a control program 231.
  • the storage unit 23 includes a Read Only Memory (ROM), a Random Access Memory (RAM), or the like.
  • a data developing unit 232 which is a region for storing the control program 231 in which a control procedure of an operation of the three-dimensional structure forming unit 30 is described or a region for temporarily developing various data items, or the like is set.
  • the storage unit 23 is connected to the CPU 22 through a data bus 29.
  • the image creation unit 25 and the reception unit 24 are connected to the control unit 21 through the data bus 29.
  • the drive control unit of the three-dimensional structure forming unit 30 is connected to the control unit 21 through an input and output interface 28 and the data bus 29.
  • the powder supply unit drive section, the three-dimensional structure forming stage drive section, the blade drive section, the liquid droplet discharging head, and the light source described above are connected to the drive control unit through the input and output interface 28 and the data bus 29, respectively.
  • the image creation unit 25 has a function of creating the model of the three-dimensional structure 1, or the like.
  • the image creation unit 25 includes software for creating a three-dimensional object such as three-dimensional computer-aided design (CAD), or the like.
  • CAD computer-aided design
  • the image creation unit 25 has a function of creating a three-dimensional structure model with which the model of the three-dimensional structure 1 is created, and a function of creating a two-dimensional model which shows the outer surface of the model of the three-dimensional structure 1 such as in a Standard Triangulated Language (STL) or the like by a two-dimensional model in the shape of a polygon such as a triangle or a quadrangle. That is, the image creation unit 25 also has a function of creating three-dimensional shape data of the three-dimensional structure 1.
  • STL Standard Triangulated Language
  • the image creation unit 25 has a function of creating a model of the unit layer 7 by cutting the model of the three-dimensional structure 1 in the shape of a layer.
  • Unit layer data created by the image creation unit 25 is stored in the storage unit 23, and is transmitted to the drive control unit of the three-dimensional structure forming unit 30 through the input and output interface 28 and the data bus 29.
  • the three-dimensional structure forming unit 30 is driven on the basis of the transmitted unit layer data.
  • the reception unit 24 includes a Universal Serial BUS (USB) port, a LAN port, or the like.
  • the reception unit 24 has a function of receiving an original object for creating the model of the three-dimensional structure 1 from an external device (not illustrated) such as a scanner, or the like.
  • a monitor (a display device) and a keyboard (an input device) are connected to the computer 20 (not illustrated).
  • the monitor and the keyboard are connected to the control unit 21 through the input and output interface and the data bus, respectively.
  • the monitor includes a function of displaying an image file acquired by the reception unit 24 on an image display region. By including the monitor, an operator is able to visually understand the image file or the like.
  • the input device is not limited to the keyboard, but a mouse, a trackball, a touch panel, or the like may be used.
  • the unit layer data is created on the basis of the three-dimensional shape data
  • the layer of the three-dimensional structure forming powder (the three-dimensional structure forming composition including the three-dimensional structure forming powder) is formed on the three-dimensional structure forming stage 80 on the basis of the unit layer data
  • the unit layer 7 is formed by applying the ink 4, and the formed unit layer 7 is sequentially laminated multiple times, and thus the three-dimensional structure 1 is obtained.
  • the angle theta (refer to Fig. 1B) of the acute angle formed by the plane direction A of the unit layer 7 and the surface direction B of the three-dimensional structure 1 in the plurality of portions on the surface of the three-dimensional structure is obtained on the basis of the three-dimensional shape data of the three-dimensional structure created as described above, and color correction is performed according to the obtained angle theta. Accordingly, it is possible to manufacture the three-dimensional structure 1 in which the variation in the coloring properties is suppressed even when it is observed from the various angles.
  • a manufacturing program of a three-dimensional structure in which the angle theta of the acute angle formed by the plane direction A of the unit layer 7 and the surface direction B of the three-dimensional structure 1 in the plurality of portions on the surface of the three-dimensional structure 1 is obtained on the basis of the three-dimensional shape data of the three-dimensional structure 1, color correction data is prepared according to the angle theta, and a discharge pattern of the ink 4 is determined on the basis of the color correction data is stored.
  • the unit layer 7 is formed as an aggregate of a plurality of minimum discharge units.
  • the minimum discharge unit is a unit into which the unit layer 7 is divided, and a minimum unit to be formed by discharge.
  • the density correction coefficient is multiplied by color density of the minimum discharge unit in each position, and thus the color density of each minimum discharge unit is determined, and the discharge pattern is determined on the basis of the determined color density. Accordingly, it is possible to more efficiently suppress the variation in the coloring properties even when it is observed from the various angles.
  • the manufacturing program of a three-dimensional structure is configured to calculate the density correction coefficient by applying two formulas described above according to the three-dimensional shape data and the size of the minimum discharge unit which is regulated in advance, to determine the ink discharge pattern of a portion corresponding to the outer circumferential portion 3 side of the respective unit layers 7, and to transmit a signal to the drive control unit.
  • the angle theta of the acute angle formed by the plane direction A of the unit layer 7 and the surface direction B of the three-dimensional structure in the plurality of portions is obtained on the basis of the three-dimensional shape data of the three-dimensional structure created as described above, and the color correction is performed according to the obtained angle theta. Accordingly, it is possible to suppress the variation in the coloring properties even when it is observed from the various angles.
  • Figs. 4A to 4D and Figs. 5E and 5F are schematic views illustrating each process in a preferred embodiment of the manufacturing method of a three-dimensional structure according to the invention
  • Fig. 6 is a cross-sectional view schematically illustrating a state of the layer (the three-dimensional structure forming composition) immediately before an ink applying process
  • Fig. 7 is a cross-sectional view schematically illustrating a state where particles are bound by the curable resin.
  • the manufacturing method of this embodiment includes a layer forming process (Figs. 4A and 4D) which forms a layer 6 having a predetermined thickness on the three-dimensional structure forming stage 80 by using the three-dimensional structure forming composition including the three-dimensional structure forming powder, an ink applying process (Fig. 4B and Fig. 5E) which applies the ink 4 including the curable resin onto the layer 6 by an ink jet method, and a curing process (Fig. 4C and Fig. 5F) which cures the curable resin included in the ink 4 applied onto the layer 6, and repeats the processes in sequence, and then further includes an unbound particle removing process which removes particles which are not bound by the curable resin among the particles configuring each layer 6.
  • a layer forming process Figs. 4A and 4D
  • an ink applying process Fig. 4B and Fig. 5E
  • a curing process Fig. 4C and Fig. 5F
  • the layer 6 having a predetermined thickness is formed on the three-dimensional structure forming stage 80 by using the three-dimensional structure forming composition including the three-dimensional structure forming powder (Fig. 4A).
  • the three-dimensional structure forming composition is supplied from the powder supply unit 50 onto the three-dimensional structure forming stage 80, and the layer 6 of a predetermined thickness is formed by the blade 61.
  • the three-dimensional structure forming composition includes a plurality of particles 63 and a water soluble resin 64.
  • the water soluble resin 64 By including the water soluble resin 64, it is possible to effectively prevent the particles 63 from being bound (temporarily fixed) (refer to Fig. 6), and to effectively prevent the unintended scattering of the particles or the like. Accordingly, it is possible to improve safety of the operator and dimensional accuracy of the three-dimensional structure 1 to be manufactured.
  • the thickness of the layer 6 formed in this process is not particularly limited, but the thickness is, preferably greater than or equal to 30 micrometers and less than or equal to 500 micrometers, and more preferably greater than or equal to 70 micrometers and less than or equal to 150 micrometers. Accordingly, it is possible to make productivity of the three-dimensional structure 1 sufficiently excellent, and it is possible to make dimensional accuracy of the three-dimensional structure 1 to be manufactured especially excellent by more effectively preventing occurrence of unintended concavities and convexities of the three-dimensional structure 1.
  • the ink 4 including a curable resin 44 is applied onto the layer 6 by the ink jet method (Fig. 4B).
  • the angle theta of the acute angle formed by the plane direction A of the unit layer and the surface direction B of the three-dimensional structure in the plurality of portions on the surface of the three-dimensional structure is obtained, the color correction is performed according to the obtained angle theta, and the ink 4 (the core portion forming ink and the outer circumferential portion forming ink) is discharged in a pattern according to the condition.
  • the ink 4 is selectively applied onto only a portion corresponding to a real portion (a substantive portion) of the three-dimensional structure 1 in the layer 6.
  • the ink 4 is applied by the ink jet method, and thus it is possible to apply the ink 4 with high reproducibility even when an applying pattern of the ink 4 is a fine pattern. As a result, it is possible to especially increase dimensional accuracy of the finally obtained three-dimensional structure 1.
  • the curable resin 44 applied onto the layer 6 is cured by radiating ultraviolet rays from the light source 70, and a cured portion (the unit layer 7) is formed (Fig. 4C). Accordingly, it is possible to make binding strength between the curable resin 44 and the particle 63 especially excellent. As a result, it is possible to make mechanical strength of the finally obtained three-dimensional structure 1 especially excellent.
  • the ink applying process and the curing process may be simultaneously progressively performed. That is, before forming the entire pattern of one entire layer 6, a curing reaction may be allowed to sequentially progress from the portion onto which the ink 4 is applied.
  • the ink 4 applied onto the layer 6 by the ink applying process after a second ink applying process (refer to Fig. 4D) is used for binding the particles 63 configuring the layer 6, and a part of the applied ink 4 seeps through the layer 6 which is lower than that of the applied ink 4. For this reason, the ink 4 binds not only the particles 63 in each of the layers 6, but also the particles 63 between adjacent layers. As a result, the entire finally obtained three-dimensional structure 1 has excellent mechanical strength.
  • this process for example, a method for cleaning away the unbound particles by a brush or the like, a method for removing the unbound particles by suction, a method for spraying gas such as air, a method for applying liquid such as water (for example, a method for immersing the laminated body obtained as described above in the liquid, a method for spraying the liquid, or the like), a method for applying vibration such as ultrasonic vibration, and the like are included.
  • this process is able to be performed by combining two or more methods selected therefrom.
  • a method for immersing the laminated body in the liquid such as water after spraying the gas such as air, a method for applying the ultrasonic vibration in a state where the laminated body is immersed in the liquid such as water, and the like are included.
  • a method for applying the liquid including water onto the laminated body obtained as described above is preferably adopted.
  • the particles which are not bound by the curable resin 44 among the particles 63 configuring each of the layers 6 are temporarily fixed by the water soluble resin 64, but the temporary fixing is released by dissolving the water soluble resin 64 with the liquid including water, and thus it is possible to more easily and more reliably remove the unbound particles from the three-dimensional structure 1.
  • the three-dimensional structure forming composition includes the three-dimensional structure forming powder, and the water soluble resin 64.
  • the three-dimensional structure forming powder is configured of a plurality of particles 63.
  • the particle 63 any particle is able to be used, but it is preferable that the particle 63 be configured by porous particles (porous particles). Accordingly, it is possible to allow the curable resin 44 to preferably enter inside the pores at the time of manufacturing the three-dimensional structure 1. As a result, it is possible to be preferably used for manufacturing the three-dimensional structure with excellent mechanical strength.
  • an inorganic material for example, an organic material, a complex thereof, and the like are included.
  • the inorganic material configuring the porous particles for example, various metals, a metallic compound, and the like are included.
  • the metallic compound for example, 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 silicone nitride, titanium nitride, and aluminum nitride; various metal carbides such as silicone 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; various metal borates such as aluminum borate, and magnesium borate; a complex compound thereof, and the metallic
  • a synthetic resin, a natural polymer, and the like are included, and more specifically, a polyethylene resin; poly propylene; polyethylene oxide; polypropylene oxide; polyethylene imine; polystyrene; polyurethane; polyurea; polyester; a silicone resin; an acrylic silicone resin; a polymer such as polymethyl methacrylate having (meth)acrylic ester as a constituent monomer; a cross polymer (an ethylene acrylic acid copolymer resin or the like) such as methyl methacrylate cross polymer having (meth)acrylic ester as a constituent monomer; a polyamide resin such as nylon 12, nylon 6, and copolymer nylon; polyimide; carboxymethyl cellulose; gelatin; a starch; chitin; chitosan, and the like are included.
  • a polyethylene resin such as polymethyl methacrylate having (meth)acrylic ester as a constituent monomer
  • a cross polymer an ethylene acrylic acid copolymer resin or the like
  • porous particles are, preferably configured of an inorganic material, more preferably configured of a metal oxide, and further preferably configured of silica. Accordingly, it is possible to make properties such as mechanical strength, and light resistance of the three-dimensional structure especially excellent. In addition, particularly, when the porous particles are configured of silica, the effects described above are more remarkably realized. In addition, since silica has excellent fluidity, it is advantageous for forming a layer with high uniformity in thickness, and thus it is possible to make productivity and dimensional accuracy of the three-dimensional structure 1 especially excellent.
  • silica it is possible to preferably use commercially available silica.
  • Siloid 63, Siloid 65, Siloid 66, Siloid 77, Siloid 74, Siloid 79, Siloid 404, Siloid 620, Siloid 800, Siloid 150, Siloid 244, and Siloid 266 (manufactured by Fuji Silysia Chemical Ltd.), 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), and the like are included.
  • the porous particles be subjected to a hydrophobization treatment.
  • the curable resin 44 included in the ink 4 tends to have hydrophobicity. Therefore, the porous particles are subjected to the hydrophobization treatment, and thus it is possible to allow the curable resin 44 to preferably enter inside the pores of the porous particles. As a result, an anchor effect is more remarkably realized, and thus it is possible to make mechanical strength of the three-dimensional structure 1 to be obtained more excellent.
  • the porous particles are subjected to the hydrophobization treatment, it is possible to be preferably reused.
  • any treatment may be used insofar as hydrophobicity of the porous particle increases, and a treatment which introduces a hydrocarbon group is preferable. Accordingly, it is possible to further increase hydrophobicity of the particle. In addition, it is possible to more easily and reliably increase uniformity of the degree of the hydrophobization treatment in each portion (including a surface inside the pores) of each particle or particle surface.
  • a silane compound having a silyl group is preferable.
  • the compound which is able to be used for the hydrophobization treatment for example, hexamethyl disilazane, dimethyl dimethoxysilane, diethyl diethoxysilane, 1-propenyl methyl dichlorosilane, propyl dimethyl chlorosilane, propyl methyl dichlorosilane, propyl trichlorosilane, propyl triethoxysilane, propyl trimethoxysilane, styryl ethyl trimethoxysilane, tetradecyl trichlorosilane, 3-thiocyanate propyl triethoxysilane, p-tolyl dimethyl chlorosilane, p-tolyl methyl dichlorosilane, p-tolyl trichlorosilane, p-
  • hexamethyl disilazane be used for the hydrophobization treatment. Accordingly, it is possible to further increase hydrophobicity of the particles. In addition, it is possible to more easily and reliably increase uniformity of the degree of the hydrophobization treatment in each of the portions (including the surface inside the pores) of each of the particles or the particle surfaces.
  • the particles to be subjected to the hydrophobization treatment are immersed in liquid including the silane compound, and thus it is possible to preferably allow a desired reaction to proceed, and it is possible to form a chemical adsorption film of the silane compound.
  • the particles 63 to be subjected to the hydrophobization treatment are exposed to vapor of the silane compound, and thus it is possible to preferably allow a desired reaction to be proceeded, and it is possible to form the chemical adsorption film of the silane compound.
  • An average particle diameter of the particles 63 configuring the three-dimensional structure forming powder is not particularly limited, but is preferably greater than or equal to 1 micrometer and less than or equal to 25 micrometers, and more preferably greater than or equal to 1 micrometer and less than or equal to 15 micrometers. Accordingly, it is possible to make mechanical strength of the three-dimensional structure 1 especially excellent, and it is possible to make dimensional accuracy of the three-dimensional structure 1 especially excellent by more effectively preventing the occurrence of the unintended concavities and convexities of the three-dimensional structure 1 to be manufactured.
  • the average particle diameter is a volume-based average particle diameter, and for example, the average particle diameter is able to be obtained by adding a sample to methanol, and by analyzing a dispersion liquid dispersed by an ultrasonic dispersion instrument for 3 minutes using an aperture of 50 micrometers in a particle size distribution measuring instrument (TA-II Type manufactured by COULTER ELECTRONICS INS) using a Coulter counter method.
  • TA-II Type manufactured by COULTER ELECTRONICS INS
  • Dmax of the particles 63 configuring the three-dimensional structure forming powder is, preferably greater than or equal to 3 micrometers and less than or equal to 40 micrometers, and more preferably greater than or equal to 5 micrometers and less than or equal to 30 micrometers. Accordingly, it is possible to make mechanical strength of the three-dimensional structure 1 especially excellent, and it is possible to make dimensional accuracy of the three-dimensional structure 1 especially excellent by more effectively preventing the occurrence of the unintended concavities and convexities of the three-dimensional structure 1 to be manufactured.
  • porosity of the porous particle is, preferably greater than or equal to 50%, and more preferably greater than or equal to 55% and less than or equal to 90%. Accordingly, the curable resin has sufficient penetrating space (the pores), and it is possible to make mechanical strength of the porous particle itself excellent. As a result, it is possible to make mechanical strength of the three-dimensional structure 1 which is formed by allowing the binding resin to enter inside the pores especially excellent.
  • the porosity of the particle indicates a ratio (a volume fraction) of the pores existing in the particle with respect to an apparent volume of the particle, and when density of the particle is rho [g/cm 3 ], and real density of the constituent material of the particle is rho 0 [g/cm 3 ], the porosity is a value shown by ⁇ (rho 0 - rho) / rho 0 ⁇ * 100.
  • an average pore diameter (a fine pore diameter) of the porous particle is, preferably greater than or equal to 10 nm, and more preferably greater than or equal to 50 nm and less than or equal to 300 nm. Accordingly, it is possible to make mechanical strength of the finally obtained three-dimensional structure 1 especially excellent.
  • the pigment preferably being kept in the pores of the porous particles is possible. For this reason, it is possible to prevent unintended diffusion of the pigment, and thus it is possible to more reliably form a high-definition image.
  • the particle 63 configuring the three-dimensional structure forming powder may have any shape, and it is preferable that the particle be in the shape of a sphere. Accordingly, it is possible to make fluidity of the three-dimensional structure forming powder and fluidity of the three-dimensional structure forming composition including the three-dimensional structure forming powder especially excellent, and thus it is possible to make productivity of the three-dimensional structure 1 especially excellent, and it is possible to make dimensional accuracy of the three-dimensional structure 1 especially excellent by more effectively preventing the occurrence of the unintended concavities and convexities of the three-dimensional structure 1 to be manufactured.
  • the three-dimensional structure forming powder may include a plurality of types of particles of which conditions (for example, a constituent material of the particles, a type of hydrophobization treatment, or the like) as described above are different from each other.
  • Voidage of the three-dimensional structure forming powder is, preferably greater than or equal to 70% and less than or equal to 98%, and more preferably greater than or equal to 75% and less than or equal to 97.7%. Accordingly, it is possible to make mechanical strength of the three-dimensional structure especially excellent. In addition, it is possible to make fluidity of the three-dimensional structure forming powder and fluidity of the three-dimensional structure forming composition including the three-dimensional structure forming powder especially excellent, and thus it is possible to make productivity of the three-dimensional structure especially excellent, and it is possible to make dimensional accuracy of the three-dimensional structure especially excellent by more effectively preventing the occurrence of the unintended concavities and convexities of the three-dimensional structure to be manufactured.
  • the voidage of the three-dimensional structure forming powder indicates a ratio of a sum of a volume of the pores of the entire particles configuring the three-dimensional structure forming powder to a capacity of a container and a volume of voids existing between the particles when the container with a predetermined capacity (for example, 100 mL) is filled with the three-dimensional structure forming powder, and when bulk density of the three-dimensional structure forming powder is P [g/cm 3 ], and real density of a constituent material of the three-dimensional structure forming powder is P 0 [g/cm 3 ], the voidage is a value shown by ⁇ (P 0 - P) / P 0 ⁇ * 100.
  • a content ratio of the three-dimensional structure forming powder in the three-dimensional structure forming composition is, preferably greater than or equal to 10 mass% and less than or equal to 90 mass%, and more preferably greater than or equal to 15 mass% and less than or equal to 58 mass%. Accordingly, it is possible to make fluidity of the three-dimensional structure forming composition sufficiently excellent, and it is possible to make mechanical strength of the finally obtained three-dimensional structure 1 especially excellent.
  • the three-dimensional structure forming composition includes the water soluble resin 64 together with a plurality of particles 63.
  • the particles 63 are bound (temporarily fixed) (refer to Fig. 3), and thus it is possible to effectively prevent the unintended scattering of the particles 63 or the like. Accordingly, it is possible to improve safety of the operator and dimensional accuracy of the three-dimensional structure 1 to be manufactured.
  • the water soluble resin may be soluble in water, and for example, solubility with respect to water (mass dissolvable in the 100 g of water) at 25 degrees Celsius is preferably greater than or equal to 5 [g/100 g of water], and is more preferably greater than or equal to 10 [g/100 g of water].
  • the water soluble resin 64 for example, a synthetic polymer such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), sodium polyacrylate, polyacrylamide, modified polyamide, polyethylene imine, and polyethylene oxide, a natural polymer such as corn starch, mannan, pectin, agar, alginic acid, dextran, glue, and gelatin, a semi-synthetic polymer such as carboxymethyl cellulose, hydroxyethyl cellulose, oxidized starch, and modified starch, and the like are included, and a combination of at least one selected therefrom is able to be used.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • sodium polyacrylate sodium polyacrylate
  • polyacrylamide modified polyamide
  • polyethylene imine polyethylene imine
  • polyethylene oxide a natural polymer such as corn starch, mannan, pectin, agar, alginic acid, dextran,
  • the water soluble resin product for example, methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metolose SM-15), hydroxyethyl cellulose (manufactured by Fuji Chemical Co., AL-15), hydroxy propyl cellulose (manufactured by Nippon Soda Co., Ltd., HPC-M), carboxymethyl cellulose (manufactured by Nichirin Chemical Co., Ltd., CMC-30), starch phosphate ester sodium (I) (manufactured by Matsutani Chemical Co., Hosta 5100), polyvinyl pyrrolidone (manufactured by Tokyo Chemical Co., PVP K-90), methyl vinyl ether/a maleic acid copolymer (manufactured by GAF Gauntlet Inc.
  • methyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd., Metolose SM-15
  • hydroxyethyl cellulose manufactured by Fuji Chemical Co., AL-15
  • polyacrylamide manufactured by Wako Pure Chemical Industries, Ltd.
  • modified polyamide modified nylon
  • polyethylene oxide manufactured by Steel Chemical Co., Ltd., PEO-1, manufactured by Meisei Chemical Works, Ltd., Alkox
  • a random copolymer of ethylene oxide and propylene oxide manufactured by Meisei Chemical Works, Ltd., Alkox EP
  • sodium polyacrylate manufactured by Wako Pure Chemical Industries, Ltd.
  • carboxy vinyl polymer/a cross-linked acryl-based water soluble resin manufactured by Sumitomo Seika Chemicals Co., Ltd., Aqupec
  • the water soluble resin 64 is polyvinyl alcohol
  • by adjusting a saponification degree or polymerization degree it is possible to more preferably control properties (for example, water solubility, water resistance, or the like) of the water soluble resin 64 or properties (for example, viscosity, fixing force of the particles 63, wettability, or the like) of the three-dimensional structure forming composition. For this reason, it is possible to more preferably respond to manufacturing of various three-dimensional structures 1.
  • polyvinyl alcohol is inexpensive, and there is a stable supply thereof. For this reason, it is possible to reduce the production cost and to perform stable manufacturing of the three-dimensional structure 1.
  • the saponification degree of polyvinyl alcohol is, preferably greater than or equal to 85 and less than or equal to 90. Accordingly, it is possible to inhibit solubility of polyvinyl alcohol with respect to water from being decreased. For this reason, when the three-dimensional structure forming composition includes water, it is possible to more effectively inhibit adhesiveness between adjacent unit layers 7 from being decreased.
  • the polymerization degree of polyvinyl alcohol is, preferably greater than or equal to 300 and less than or equal to 1000. Accordingly, when the three-dimensional structure forming composition includes the water, it is possible to make mechanical strength of each unit layer 7 or adhesiveness between the adjacent unit layers 7 especially excellent.
  • the water soluble resin 64 is polyvinyl pyrrolidone (PVP)
  • PVP polyvinyl pyrrolidone
  • the following effects are obtained. That is, polyvinyl pyrrolidone has excellent adhesiveness with respect to various materials such as glass, metal, and plastic, and thus it is possible to make strength and shape stability of a portion onto which the ink is not applied in the layer 6 especially excellent, and it is possible to make dimensional accuracy of the finally obtained three-dimensional structure 1 especially excellent.
  • polyvinyl pyrrolidone exhibits high solubility with respect to various organic solvents, and thus when the three-dimensional structure forming composition includes an organic solvent, it is possible to make fluidity of the three-dimensional structure forming composition especially excellent.
  • polyvinyl pyrrolidone exhibits high solubility with respect to water, and thus it is possible to easily and reliably remove the particles which are not bound by the curable resin 44 among the particles 63 configuring each layer 6 in the unbound particle removing process (after the formation is ended).
  • polyvinyl pyrrolidone has suitable affinity with the three-dimensional structure forming powder, and thus it is difficult to sufficiently cause polyvinyl pyrrolidone to penetrate into a pore 611 as described above.
  • polyvinyl pyrrolidone has relatively high wettability with respect to the surface of the particles 63. For this reason, it is possible to more effectively realize a function of temporary fixing as described above.
  • polyvinyl pyrrolidone has excellent affinity with various colorants, and thus when the ink 4 including the colorant is used in the ink applying process, it is possible to effectively prevent the colorant from unintentionally diffusing.
  • polyvinyl pyrrolidone has an antistatic function, and thus when a powder which is not fixed is used as the three-dimensional structure forming composition in the layer forming process, it is possible to effectively prevent the powder from being scattered.
  • the three-dimensional structure forming composition when a powder which is fixed is used as the three-dimensional structure forming composition in the layer forming process, it is possible to effectively prevent bubbles from being entrained into the three-dimensional structure forming composition when the paste-like three-dimensional structure forming composition includes polyvinyl pyrrolidone, and it is possible to more effectively prevent occurrence of a defect due to the rolled-in bubbles in the layer forming process.
  • a weight average molecular weight of the polyvinyl pyrrolidone is, preferably greater than or equal to 10000 and less than or equal to 1700000, and more preferably greater than or equal to 30000 and less than or equal to 1500000. Accordingly, it is possible to more effectively realize the functions described above.
  • the water soluble resin 64 be in a liquid state (for example, a dissolved state, a melted state, or the like) at least in the layer forming process. Accordingly, it is possible to more easily and reliably increase uniformity in thickness of the layer 6 formed by using the three-dimensional structure forming composition.
  • a content ratio of the water soluble resin 64 in the three-dimensional structure forming composition with respect to bulk volume of the three-dimensional structure forming powder is, preferably less than or equal to 15 vol%, and more preferably greater than or equal to 2 vol% and less than or equal to 5 vol%. Accordingly, it is possible to sufficiently realize a function of the water soluble resin 64 as described above and to secure a wider space that the ink 4 enters, and thus it is possible to make mechanical strength of the three-dimensional structure 1 especially excellent.
  • the three-dimensional structure forming composition may include a solvent in addition to the water soluble resin 64 and the three-dimensional structure forming powder as described above. Accordingly, it is possible to make fluidity of the three-dimensional structure forming composition especially excellent, and it is possible to make productivity of the three-dimensional structure 1 especially excellent.
  • the solvent dissolve the water soluble resin 64. Accordingly, it is possible to make fluidity of the three-dimensional structure forming composition excellent, and it is possible to more effectively prevent the unintended variation in the thickness of the layer 6 formed by using the three-dimensional structure forming composition.
  • the water soluble resin 64 it is possible to attach the water soluble resin 64 to the particles 63 with higher uniformity over the entire layer 6, and it is possible to more effectively prevent occurrence of unintended unevenness in a composition. For this reason, it is possible to more effectively prevent occurrence of an unintended variation in mechanical strength of each portion of the finally obtained three-dimensional structure 1, and it is possible to further increase reliability of the three-dimensional structure 1.
  • the solvent configuring the three-dimensional structure forming composition for example, water; an alcoholic solvent such as methanol, ethanol, and isopropanol; a ketone-based solvent such as methyl ethyl ketone, and acetone; a glycol ether-based solvent such as ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; a glycol ether acetate-based solvent such as propylene glycol-1-monomethylether-2-acetate, and propylene glycol-1-monoethylether-2-acetate; polyethylene glycol, poly propylene glycol, and the like are included, and a combination of at least one selected therefrom is able to be used.
  • an alcoholic solvent such as methanol, ethanol, and isopropanol
  • a ketone-based solvent such as methyl ethyl ketone, and acetone
  • a glycol ether-based solvent such as ethylene glycol monoeth
  • the three-dimensional structure forming composition include water. Accordingly, it is possible to more reliably dissolve the water soluble resin 64, and it is possible to make fluidity of the three-dimensional structure forming composition and uniformity of the composition of the layer 6 formed by using the three-dimensional structure forming composition especially excellent.
  • the water is easily removed after forming the layer 6, and even when the water remains in the three-dimensional structure 1, it is difficult for the water to exert a negative effect.
  • it is advantageous from a viewpoint of safety with respect to the human body, and environmental concerns.
  • a content ratio of the solvent in the three-dimensional structure forming composition is, preferably greater than or equal to 5 mass% and less than or equal to 75 mass%, and more preferably greater than or equal to 35 mass% and less than or equal to 70 mass%. Accordingly, it is possible to more remarkably realize an effect which is obtained by including the solvent described above, and it is possible to easily remove the solvent in the manufacturing process of the three-dimensional structure 1 in a short period of time, and thus it is advantageous from a viewpoint of further improving productivity of the three-dimensional structure 1.
  • a content ratio of the water in the three-dimensional structure forming composition is, preferably greater than or equal to 20 mass% and less than or equal to 73 mass%, and more preferably greater than or equal to 50 mass% and less than or equal to 70 mass%. Accordingly, it is possible to more remarkably realize the effect as described above.
  • the three-dimensional structure forming composition may include a component in addition to the components described above.
  • a component for example, a polymerization initiator; a polymerization accelerator; a penetration enhancer; a wetting agent (a moisturizing agent); a fixing agent; an antifungal agent; an antiseptic agent; an antioxidizing agent; an ultraviolet ray absorber; a chelating agent; a pH adjuster, and the like may be included.
  • the ink 4 includes at least the curable resin 44.
  • the curable resin 44 is a component having a function of binding the particles 63 by curing.
  • the curable resin 44 is not particularly limited, but it is preferable that the curable resin 44 have hydrophobicity (lipophilicity). Accordingly, it is possible to increase affinity between the ink 4 and the particles 63 subjected to the hydrophobization treatment, and the ink 4 is able to preferably enter the pores 611 of the particles 63 subjected to the hydrophobization treatment by applying the ink 4 onto the layer 6. As a result, the anchor effect is preferably realized by the curable resin 44, and thus it is possible to make mechanical strength of the finally obtained three-dimensional structure 1 excellent.
  • the hydrophobic curable resin may have sufficiently low affinity with the water, and for example, it is preferable that solubility of the hydrophobic curable resin with respect to water at 25 degrees Celsius be less than or equal to 1 g/100 g of water.
  • the curable resin 44 for example, a thermoplastic resin; various photocurable resins such as a visible light curable resin (in the narrow sense, a photocurable resin) which is cured by light in a visible light region, an ultraviolet ray curable resin, and an infrared ray curable resin; an X-ray curable resin, and the like are included, and a combination of at least one selected therefrom is able to be used.
  • a visible light curable resin in the narrow sense, a photocurable resin
  • an ultraviolet ray curable resin infrared ray curable resin
  • an X-ray curable resin and the like
  • the curable resin 44 be a curable resin.
  • the ultraviolet ray curable resin (a polymerizable compound) is especially preferable.
  • the ultraviolet ray curable resin (the polymerizable compound)
  • a material in which addition polymerization or ring-opening polymerization is started by radical species, cationic species, and the like which are generated from a photopolymerization initiator by irradiation of ultraviolet rays, and thus a polymer is generated is preferably used.
  • radicals, cations, anions, metathesis, and coordination polymerization are used.
  • cations, anions, radicals, metathesis, and coordination polymerization are used as a polymerization method of the ring-opening polymerization.
  • an addition polymerizable compound for example, a compound having at least one ethylenically unsaturated double bond and the like are included.
  • a compound having at least one, preferably at least two terminal ethylenically unsaturated bonds is able to be preferably used.
  • An ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a multifunctional polymerizable compound, or a mixture thereof.
  • a monofunctional polymerizable compound for example, an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, or the like), esters thereof, amides thereof, and the like are included.
  • esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
  • an addition reaction product of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, and a mercapto group with isocyanates and epoxies, a product of a dehydration condensation reaction with a carboxylic acid, and the like are able to be used.
  • an addition reaction product of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines, and thiols, and a substitution reaction product with unsaturated carboxylic acid esters or amides having a releasing substituent such as a halogen group or a tosyloxy group with alcohols, and amines or thiols are able to be used.
  • (meth)acrylic ester is representative, and either monofunctional (meth)acrylic ester or multifunctional (meth)acrylic ester is able to be used.
  • a monofunctional (meth)acrylate for example, tolyloxyethyl (meth)acrylate, phenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like are included.
  • bifunctional (meth)acrylate for example, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and the like are included.
  • trifunctional (meth)acrylate for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene oxide-modified tri(meth)acrylate of trimethylol propane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxy propyl) 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, sorbitol tri(meth)acrylate, and the like are included.
  • a tetrafunctional (meth)acrylate for example, pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylol propane tetra(meth)acrylate, propionic acid dipentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and the like are included.
  • a pentafunctional (meth)acrylate for example, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like are included.
  • a hexafunctional (meth)acrylate for example, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like are included.
  • a polymerizable compound in addition to a (meth)acrylate for example, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and the like are included.
  • an itaconic acid ester for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, and the like are included.
  • a crotonic acid ester for example, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, and the like are included.
  • isocrotonic acid ester for example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like are included.
  • maleic acid ester for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate, and the like are included.
  • esters for example, aliphatic alcohol-based esters disclosed in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231, esters having an aromatic skeleton disclosed in JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149, esters containing an amino group disclosed in JP-A-1-165613 and the like are able to be used.
  • a monomer of an amide from an unsaturated carboxylic acid and an aliphatic polyvalent amine compound for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine tris-acrylamide, xylylene bis-acrylamide, xylylene bis-methacrylamide, and the like are included.
  • amide-based monomers for example, an amide-based monomer having a cyclohexylene structure disclosed in JP-B-54-21726, and the like are included.
  • a urethane-based addition polymerizable compound manufactured by using an addition reaction between isocyanate and a hydroxyl group is also preferable, and as a specific example thereof, for example, a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule in which a vinyl monomer containing a hydroxyl group shown in the following Formula (1) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule disclosed in JP-B-48-41708, and the like are included.
  • CH 2 C(R 1 )COOCH 2 CH(R 2 )OH (1) (Where, in Formula (1), R 1 and R 2 independently indicate H or CH 3 , respectively.)
  • a cationic ring-opening polymerizable compound having one or more cyclic ether groups such as an epoxy group, and an oxetane group in the molecule is able to be preferably used as the ultraviolet ray curable resin (the polymerizable compound).
  • a curable compound containing a ring-opening polymerizable group, and the like are included, and among them, a curable compound containing a heterocyclic group is especially preferable.
  • a curable compound containing a heterocyclic group is especially preferable.
  • cyclic imino ethers such as an epoxy derivative, an oxetane derivative, a tetrahydrofuran derivative, a cyclic lactone derivative, a cyclic carbonate derivative, and an oxazoline derivative, vinyl ethers, and the like are included, and among them, an epoxy derivative, an oxetane derivative, and vinyl ethers are preferable.
  • epoxy derivative for example, monofunctional glycidyl ethers, multifunctional glycidyl ethers, monofunctional alicyclic epoxies, multifunctional alicyclic epoxies, and the like are included.
  • Examples of specific glycidyl ether compounds include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, or the like), trifunctional or higher glycidyl ethers (for example, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl tris-hydroxyethyl isocyanurate, or the like), tetrafunctional or more glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, a polyglycidyl ether of a cresol novolac resin, polyglycidyl ethers of a phenol novolac resin, or the like), alicyclic epoxie
  • an alicyclic epoxy derivative is able to be preferably used as the polymerizable compound.
  • the "alicyclic epoxy group” indicates a structure of a portion in which a double bond of a cycloalkene ring such as a cyclopentene group, and cyclohexene group is epoxidized by a suitable oxidizing agent such as hydrogen peroxide, and a peracid.
  • alicyclic epoxy compound multifunctional alicyclic epoxies having two or more cyclopentene oxide groups or cyclohexene oxide groups in one molecule is preferable.
  • the alicyclic epoxy compound for example, 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate, di(3,4-epoxycyclohexyl) adipate, di(3,4-epoxycyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, di(2,3-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide, and the like are included.
  • a glycidyl compound having a general epoxy group which does not have an alicyclic structure in the molecule is able to be independently used, or is able to be used together with the alicyclic epoxy compound.
  • a glycidyl ether compound for example, a glycidyl ether compound, a glycidyl ester compound, and the like are able to be included, and a combination including a glycidyl ether compound is preferable.
  • the glycidyl ether compound for example, an aromatic glycidyl ether compound such as 1,3-bis(2,3-epoxy propyloxy) 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, an aliphatic glycidyl ether compound such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether, and the like are included.
  • a glycidyl ester for example, a glycidyl ester of a linoleic acid dimer and the like are able to be included.
  • a compound (hereinafter, simply referred to as an "oxetane compound") having an oxetanyl group which is a cyclic ether of a four-membered ring is able to be used.
  • a compound containing an oxetanyl group is a compound having one or more oxetanyl groups in one molecule.
  • a content ratio of the curable resin 44 in the ink 4 is, preferably greater than or equal to 80 mass%, and more preferably greater than or equal to 85 mass%. Accordingly, it is possible to make mechanical strength of the finally obtained three-dimensional structure 1 especially excellent.
  • the ink 4 may include other components in addition to the components described above.
  • various colorants such as a pigment, and a dye; a dispersant; a surfactant agent; a polymerization initiator; a polymerization accelerator; a solvent; a penetration enhancer; a wetting agent (a moisturizing agent); a fixing agent; an antifungal agent; an antiseptic agent; an antioxidizing agent; an ultraviolet ray absorber; a chelating agent; a pH adjuster; a thickener; a filler; an aggregation prevention agent; an antifoaming agent, and the like are included.
  • the colorant in the ink 4 it is possible to obtain the three-dimensional structure 1 which is colored with a color corresponding to a color of the colorant.
  • the colorant by including a pigment as the colorant, it is possible to make light resistance of the ink 4 and the three-dimensional structure 1 excellent.
  • a pigment either an inorganic pigment or an organic pigment is able to be used.
  • carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, titanium oxide, and the like are included, and a combination of at least one selected therefrom is able to be used.
  • titanium oxide is preferable.
  • an azo pigment such as an insoluble azo pigment, a condensed azo pigment, an azo lake, and an azo chelate pigment
  • a polycyclic pigment such as a phthalocyanine pigment, a perylene or perynone 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, basic dye-type chelate, acid dye-type chelate, or the like
  • a dyeing lake basic dye-type lake, or acid dye-type lake
  • a nitro pigment a nitroso pigment, aniline black, a daylight fluorescent pigment, and the like
  • the carbon black used as a black-colored (black) pigment for example, No. 2300, No. 900, MCF 88, No. 33, No. 40, No. 45, No. 52, MA 7, MA 8, MA 100, No. 2200B, or the like (manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, or the like (manufactured by Carbon Columbia), Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, or the like(manufactured by CABOT JAPAN K.K.), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U
  • white-colored (white) pigment for example, C.I. Pigment White 6, 18, and 21, and the like are included.
  • yellow-colored (yellow) pigment for example, 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, and the like are included.
  • 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,
  • magenta-colored (magenta) pigment for example, 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, and the like are included.
  • cyan-colored (cyan) pigment for example, 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, C.I. Vat Blue 4, and 60, and the like are included.
  • pigments for example, C.I. Pigment Green 7, and 10, C.I. Pigment Brown 3, 5, 25, and 26, C.I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, and 63, and the like are included.
  • an average particle diameter of the pigment is, preferably less than or equal to 300 nm, and more preferably greater than or equal to 50 nm and less than or equal to 250 nm. Accordingly, it is possible to make discharge stability of the ink 4 or dispersion stability of the pigment in the ink 4 especially excellent, and it is possible to form an image with more excellent image quality.
  • the ink 4 includes a pigment, and the particle 63 is porous
  • a relationship of d1 / d2 > 1 be satisfied when an average pore diameter of the particles 63 is d1 [nm], and an average pore diameter of the pigment is d2 [nm], and it is more preferable that a relationship of 1.1 less than or equal to d1 / d2 less than or equal to 6 be satisfied.
  • the pigment preferably being kept in the pores of the particle 63 is possible. For this reason, it is possible to prevent unintended diffusion of the pigment, and thus it is possible to more reliably form a high-definition image.
  • the dye for example, an acid dye, a direct dye, a reactive dye, a basic dye, and the like are included, and a combination of at least one selected therefrom is able to be used.
  • the dye for example, 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, C.I. Reactive Black 3, 4, and 35, and the like are included.
  • a content ratio of the colorant in the ink 4 is, preferably greater than or equal to 1 mass% and less than or equal to 20 mass%. Accordingly, it is possible to obtain especially excellent shielding properties and color reproducibility.
  • a content ratio of titanium oxide in the ink 4 is, preferably greater than or equal to 12 mass% and less than or equal to 18 mass%, and more preferably greater than or equal to 14 mass% and less than or equal to 16 mass%. Accordingly, it is possible to obtain especially excellent shielding properties.
  • the ink 4 includes a pigment
  • the dispersant is not particularly limited, but for example, includes a dispersant which is commonly used for manufacturing a pigment dispersion liquid such as a polymeric dispersant.
  • a polymeric dispersant for example, a polymeric dispersant containing at least one of polyoxyalkylene polyalkylene polyamine, a vinyl-based polymer and copolymer, an acryl-based polymer and copolymer, polyester, polyamide, polyimide, polyurethane, an amino-based polymer, a silicone-containing polymer, a sulfur-containing polymer, a fluorine-containing polymer, and an epoxy resin as a main component is included.
  • Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc. Solsperse series (Solsperse 36000 or the like) manufactured by Noveon Company, Disperbyk series manufactured by BYK company, Disparon series manufactured by Kusumoto Chemicals, Ltd., and the like are included.
  • the surfactant agent is not particularly limited, but for example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant agent is able to be used, and among them, it is preferable that polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane be used.
  • the surfactant agent for example, BYK-347, BYK-348, BYK-UV 3500, 3510, 3530, and 3570 (trade names of BYK company), and the like are included.
  • the ink 4 may include a solvent. Accordingly, it is possible to preferably perform viscosity adjustment of the ink 4, and thus when the ink 4 includes a component of high viscosity, it is possible to make discharge stability of the ink 4 with the ink jet method especially excellent.
  • (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ester acetates 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 acetylacetone; alcohols such as ethanol, propanol, and butanol, and the like are included, and a combination of at least one selected therefrom is able to be used
  • viscosity of the ink 4 is, preferably greater than or equal to 10 mPa x s and less than or equal to 25 mPa x s, and more preferably greater than or equal to 15 mPa x s and less than or equal to 20 mPa x s. Accordingly, it is possible to make discharge stability of the ink with the ink jet method especially excellent. Furthermore, herein, “viscosity” indicates a value measured at 25 degrees Celsius by using an E-type viscometer (VISCONIC ELD manufactured by Tokyo Keiki INC).
  • a plurality of types of ink 4 may be used for manufacturing the three-dimensional structure 1.
  • an ink 4 (a color ink) which includes a colorant, and an ink 4 (a clear ink) which does not include a colorant may be used.
  • the ink 4 which includes the colorant may be used as the ink 4 applied onto a region affecting a color tone
  • the ink 4 which does not include the colorant may be used as the ink 4 applied onto a region not affecting the color tone.
  • a plurality of types of ink 4 may be used together such that a region (a coat layer) is disposed on an outer surface of the region formed by the ink 4 which includes the colorant by using the ink 4 which does not include the colorant.
  • ink 4 including colorants of different compositions may be used. Accordingly, it is possible to broaden a color reproduction region which is able to be shown according to a combination of the inks 4.
  • a cyan-colored (cyan) ink 4 When a plurality of types of ink 4 is used, it is preferable that at least a cyan-colored (cyan) ink 4, a magenta-colored (magenta) ink 4 and a yellow-colored (yellow) ink 4 be used. Accordingly, it is possible to broaden the color reproduction region which is able to be shown according to the combination of the inks 4.
  • the finally obtained three-dimensional structure 1 to include a first region onto which the white-colored (white) ink 4 is applied, and a region (a second region) overlapped with the first region and disposed on an outer surface side of the first region, onto which the colored ink 4 other than the white-colored ink is applied. Accordingly, it is possible to realize shielding properties of the first region onto which the white-colored (white) ink 4 is applied, and thus it is possible to further increase chromaticness of the three-dimensional structure 1.
  • the three-dimensional structure of the invention may be manufactured by using the three-dimensional structure forming composition described above, but is not limited to being manufactured by using the method described above.
  • the curing process in addition to the layer forming process and the ink applying process, is also repeated along with the layer forming process and the ink applying process is described, but the curing process may not be repeated.
  • the laminated body may be collectively cured.
  • the curing process is able to be omitted.
  • a pre-processing process an intermediate-processing process, and a post-processing process may be performed.
  • a sweeping process of the three-dimensional structure forming stage is included.
  • a cleaning process for example, a cleaning process, a shape adjusting process for performing deburring or the like, a coloring process, a covering layer forming process, a curable resin curing completion process for performing light irradiation processing which reliably cures uncured curable resin or heat processing, and the like are included.
  • the ink may not be applied onto a layer formed immediately on the three-dimensional structure forming stage, and this layer may function as a sacrificial layer.
  • the ink applying process is performed by the ink jet method, but the ink applying process may be performed by using other methods (for example, other printing methods).

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PCT/JP2014/005760 2013-11-18 2014-11-17 Manufacturing method of three-dimensional structure, three-dimensional structure, manufacturing program of three-dimensional structure, color correction control method of three-dimensional structure, and three-dimensional structure manufacturing apparatus WO2015072155A1 (en)

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JP2013237650A JP2015098091A (ja) 2013-11-18 2013-11-18 三次元造形物の製造方法、三次元造形物、三次元造形物の製造用プログラム、三次元造形物の色補正制御方法および三次元造形物製造装置

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US20180186090A1 (en) * 2017-01-05 2018-07-05 Xyzprinting, Inc. Method for compensating color of colored 3d object
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US20220324164A1 (en) * 2019-03-15 2022-10-13 Hewlett-Packard Development Company, L.P. Coloured objects in additive manufacturing

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JP6657601B2 (ja) * 2014-08-08 2020-03-04 株式会社リコー 立体造形用粉末材料、立体造形材料セット、及び立体造形物の製造方法
TWI571714B (zh) * 2015-06-15 2017-02-21 Printing Tech Res Inst Method of making multi - angle color guide table
CN110869196A (zh) * 2017-07-28 2020-03-06 惠普发展公司，有限责任合伙企业 变换属性数据以补偿属性值偏移

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CN107580546A (zh) * 2015-07-30 2018-01-12 惠普发展公司，有限责任合伙企业 用于三维打印的颜色校准
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US20180186090A1 (en) * 2017-01-05 2018-07-05 Xyzprinting, Inc. Method for compensating color of colored 3d object
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US10587774B2 (en) 2017-01-27 2020-03-10 Hewlett-Packard Development Company, L.P. 3D printed object halftone image generation containing updated voxel data
US20220324164A1 (en) * 2019-03-15 2022-10-13 Hewlett-Packard Development Company, L.P. Coloured objects in additive manufacturing

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