JP2016112793A - Three-dimensional molding composition, manufacturing method of three-dimensional molding, three-dimensional molding manufacturing apparatus and three-dimensional molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensional molding composition capable of manufacturing a three-dimensional molding excellent in mechanical strength, and further to provide a manufacturing method of the three-dimensional molding capable of manufacturing the three-dimensional molding excellent in the mechanical strength, a three-dimensional molding manufacturing apparatus and the three-dimensional molding excellent in the mechanical strength.SOLUTION: A three-dimensional molding composition of the present invention includes: particles; a surface treatment agent modifying surfaces of the particles; and solvent. It is preferable that the surface treatment agent be at least one agent selected from a group consisting of a silane coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent and a zirconate-based coupling agent. It is preferable that each of the particles be at least one element selected from a group consisting of silica, calcium carbonate, alumina and titanium oxide.SELECTED DRAWING: None

Description

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

  A technique for modeling a three-dimensional object while solidifying powder with a binding liquid is known (see, for example, Patent Document 1). In this technique, a three-dimensional object is formed by repeating the following operations. First, the powder is thinly spread with a uniform thickness to form a powder layer, and the powder is bonded to each other by discharging a binding liquid to a desired portion of the powder layer. As a result, in the powder layer, only the portion where the binding liquid is discharged is bonded to form a thin plate-like member (hereinafter referred to as “cross-sectional member”). Thereafter, a thin powder layer is formed on the powder layer, and a binding liquid (curable ink) is discharged to a desired portion. As a result, a new cross-sectional member is also formed in the portion of the newly formed powder layer where the binding liquid has been discharged. At this time, since the binding liquid discharged onto the powder layer soaks and reaches the previously formed cross-sectional member, the newly formed cross-sectional member is also bonded to the previously formed cross-sectional member. By repeating such operations and laminating thin plate-like cross-sectional members one by one, a three-dimensional object can be formed.

  With such 3D modeling technology, as long as there is 3D shape data of the object to be modeled, it is possible to immediately model by combining powder, and there is no need to create a mold prior to modeling. It is possible to form a three-dimensional object quickly and inexpensively. In addition, since thin plate-like cross-sectional members are layered one by one and shaped, for example, even a complex object having an internal structure can be formed as an integrated shaped object without being divided into a plurality of parts. .

  However, conventionally, the binding force by the binding liquid cannot be made sufficiently high, and the strength of the three-dimensional structure cannot be made sufficiently high.

JP-A-6-218712

  An object of the present invention is to provide a composition for three-dimensional modeling that can produce a three-dimensional modeled object with excellent mechanical strength, and a tertiary that can produce a three-dimensional modeled article with excellent mechanical strength. An object of the present invention is to provide an original modeled object manufacturing method and a three-dimensional modeled object manufacturing apparatus, and to provide a three-dimensional modeled object excellent in mechanical strength.

Such an object is achieved by the present invention described below.
The composition for three-dimensional modeling of the present invention includes particles,
A surface treatment agent for modifying the surface of the particles;
And a solvent.
Thereby, the three-dimensional structure excellent in mechanical strength can be manufactured.

  In the three-dimensional structure forming composition of the present invention, the surface treatment agent is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. It is preferable that

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

In the three-dimensional structure forming composition of the present invention, the silane coupling agent is preferably an amino silane coupling agent and / or an acrylic silane coupling agent.
Thereby, the mechanical strength of the obtained three-dimensional structure can be improved more effectively.

In the three-dimensional structure forming composition of the present invention, the titanate coupling agent preferably includes isopropyl triisostearoyl titanate.
Thereby, the mechanical strength of the obtained three-dimensional structure can be improved more effectively.

In the three-dimensional structure forming composition of the present invention, the particles are preferably at least one selected from the group consisting of silica, calcium carbonate, alumina, and titanium oxide.
Thereby, the mechanical strength of the obtained three-dimensional structure can be made more excellent.

The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure by producing a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a composition for three-dimensional modeling including particles, a surface treatment agent for modifying the surface of the particles, and a solvent;
Heating the layer to remove the solvent; and
A discharge step of discharging a binding liquid containing a binder that binds the plurality of particles to the layer.
Thereby, the three-dimensional structure excellent in mechanical strength can be manufactured efficiently.

In the method for producing a three-dimensional structure of the present invention, the surface treatment agent is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. Preferably it is a seed.
Thereby, the mechanical strength of the obtained three-dimensional structure can be made more excellent.

In the three-dimensional structure manufacturing method of the present invention, in the heating step, the layer is preferably heated to a temperature of 40 ° C. or higher and 180 ° C. or lower.
Thereby, the three-dimensional structure excellent in mechanical strength can be manufactured more efficiently.

In the method for producing a three-dimensional structure according to the present invention, it is preferable to include a removal step of removing the particles that are not bound by the binder after repeatedly performing the layer forming step, the heating step, and the discharging step. .
Thereby, the three-dimensional structure excellent in mechanical strength can be manufactured more efficiently.

The three-dimensional structure manufacturing apparatus of the present invention is a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
A layer forming means for forming the layer using a three-dimensional modeling composition comprising particles, a surface treatment agent for modifying the surface of the particles, and a solvent;
Heating means for heating the layer and removing the solvent;
The layer includes discharge means for discharging a binding liquid containing a binder that bonds the plurality of particles to each other.
Thereby, the three-dimensional structure excellent in mechanical strength can be manufactured efficiently.

The three-dimensional structure of the present invention is manufactured by the method for manufacturing a three-dimensional structure of the present invention.
Thereby, the three-dimensional structure excellent in mechanical strength can be provided.

The three-dimensional structure of the present invention is manufactured by the three-dimensional structure manufacturing apparatus of the present invention.
Thereby, the three-dimensional structure excellent in mechanical strength can be provided.

It is a schematic diagram which shows each process about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is a schematic diagram which shows each process about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is the top view which planarly viewed suitable embodiment of the three-dimensional structure manufacturing apparatus of this invention from the top. It is a side view of the three-dimensional structure manufacturing apparatus shown in FIG. It is a perspective view which shows the shape of the three-dimensional structure (three-dimensional structure A) manufactured by each Example and each comparative example. It is a perspective view which shows the shape of the three-dimensional structure (three-dimensional structure B) manufactured by each Example and each comparative example.

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

1. First, a method for manufacturing a three-dimensional structure according to the present invention will be described.

  FIG. 1 and FIG. 2 are schematic views showing each step in a preferred embodiment of the method for producing a three-dimensional structure of the present invention.

  As shown in FIGS. 1 and 2, the manufacturing method of the present embodiment forms the layer 1 using a three-dimensional modeling composition containing particles, a surface treatment agent that modifies the surface of the particles, and a solvent. A layer forming step (1a, 1d) to be performed, a heating step in which the formed layer 1 is heated to remove at least part of the solvent, and a binding liquid 2 containing a binder is applied to the layer 1 by an inkjet method. A discharge step (1b, 1e) and a curing step (1c, 1f) for curing the binder contained in the binding liquid 2 applied to the layer 1, and sequentially repeating these steps; In addition, an unbound particle removal step (1h) for removing particles that are not bound by the binder among the particles constituting each layer 1 is included.

Hereinafter, each step will be described in detail.
<Layer formation process>
First, the layer 1 is formed on the modeling stage 102 using the composition for three-dimensional modeling (1a).

  This step can be performed, for example, by using a method such as a squeegee method, a screen printing method, a doctor blade method, or a spin coating method.

  The thickness of the layer 1 formed in this step is not particularly limited, but is preferably 10 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. Thereby, generation | occurrence | production of the unintentional unevenness | corrugation etc. in the three-dimensional structure 1000 manufactured can be prevented more effectively, making the productivity of the three-dimensional structure 1000 sufficiently excellent.

<Heating process>
Next, the formed layer 1 is heated.

  Thereby, at least one part of the solvent contained in the composition for three-dimensional modeling which comprises the layer 1 is removed.

  Further, in this step, the particle surface is modified by the surface treatment agent contained in the three-dimensional structure forming composition along with the removal of the solvent. By modifying the particle surface in this way, the affinity between the particle surface and a binding liquid (binder) described later is increased, and the mechanical strength of the finally obtained three-dimensional structure is excellent. can do.

  In addition, before preparing as a composition for three-dimensional modeling, it is also conceivable to subject the particles to a surface treatment with a surface treatment agent in advance, but there is a problem that the number of steps increases and the manufacturing method becomes complicated. In addition, although it is conceivable to purchase and use particles that have been subjected to surface treatment, there is a problem that the cost increases. Furthermore, particles that have not undergone time since surface treatment tend to have a higher affinity with the binder, and the surface of the particles is modified immediately before discharging the binding liquid as in the present invention. Thus, the mechanical strength of the obtained three-dimensional structure 1000 can be further increased.

In this step, the layer 1 is preferably heated to a temperature of 40 ° C. or higher and 180 ° C. or lower, more preferably heated to a temperature of 80 ° C. or higher and 150 ° C. or lower. As a result, the dehydration condensation reaction between the functional group of the particle surface and the functional group of the surface treatment agent can easily occur, and the removal of the solvent and the modification of the particle surface can proceed more efficiently at a temperature where the surface treatment agent does not decompose Can do.
The three-dimensional modeling composition will be described in detail later.

<Discharge process>
Thereafter, a binding liquid 2 containing a binder is discharged onto the layer 1 by an ink jet method (1b).

  In this step, the binding liquid 2 is selectively applied only to the part of the layer 1 corresponding to the real part (the part with the substance) of the three-dimensional structure 1000.

In this step, since the binding liquid 2 is applied by an ink jet method, the binding liquid 2 can be applied with good reproducibility even if the application pattern of the binding liquid 2 has a fine shape.
The binding liquid 2 will be described in detail later.

<Curing process>
Next, the binder applied to the layer 1 is cured to form the cured part 3 (1c). Thereby, the bond strength between the particles can be made particularly excellent, and as a result, the mechanical strength and water resistance of the finally obtained three-dimensional structure 1000 can be made particularly excellent.

  This step varies depending on the type of the curing component (binder). For example, when the curing component (binder) is thermosetting, it can be performed by heating, and when the curing component (binder) is photocurable. , Can be performed by irradiation with the corresponding light (for example, when the curing component is ultraviolet curable, it can be performed by irradiation with ultraviolet light).

  The discharge process and the curing process may be performed simultaneously. That is, before the entire pattern of one layer 1 is formed, the curing reaction may be sequentially advanced from the portion to which the binding liquid 2 is applied.

  Thereafter, the series of steps described above is repeated (see 1d, 1e, and 1f). Thereby, it becomes the state which the particle | grains of the site | part to which the coupling | bonding liquid 2 was provided among each said layer 1 couple | bonded, and the three-dimensional structure 1000 as a laminated body by which the layer 1 of such a state was laminated | stacked is obtained ( 1g).

  In addition, the binding liquid 2 applied to the layer 1 in the second and subsequent ejection steps (see 1d) is used for bonding particles constituting the layer 1, and part of the applied binding liquid 2 is , Penetrates the lower layer 1. For this reason, the binding liquid 2 is used not only for bonding particles in each layer 1 but also for bonding particles between adjacent layers. As a result, the finally obtained three-dimensional structure 1000 has excellent mechanical strength as a whole.

<Unbound particle removal step>
Then, after repeating the series of steps as described above, as a post-treatment step, among the particles constituting each layer 1, unbound particle removal step of removing particles not bound by the binder (unbound particles) (1h) is performed. Thereby, the three-dimensional structure 1000 is taken out.

  As a specific method of this step, for example, a method of removing unbound particles with a brush, a method of removing unbound particles by suction, a method of blowing a gas such as air, a method of applying a liquid such as water ( Examples thereof include a method of immersing the laminate obtained as described above in a liquid, a method of spraying a liquid, and a method of applying vibration such as ultrasonic vibration. Moreover, it can carry out combining 2 or more types of methods selected from these. More specifically, there are a method of immersing in a liquid such as water after blowing a gas such as air, a method of applying ultrasonic vibration in a state of immersing in a liquid such as water, and the like. Especially, it is preferable to employ | adopt the method (especially the method of immersing in the liquid containing water) which provides the liquid containing water with respect to the laminated body obtained as mentioned above. Thereby, unbound particles can be removed from the three-dimensional structure 1000 more easily and more reliably. In addition, it is possible to more reliably prevent a defect such as a scratch from occurring in the three-dimensional structure 1000 when removing the unbound particles. In addition, by adopting such a method, the three-dimensional structure 1000 can be washed.

2. Next, the three-dimensional modeling composition will be described in detail.

  The three-dimensional modeling composition includes a plurality of particles, a surface treatment agent that modifies the surface of the particles, and a solvent.

Hereinafter, each component will be described in detail.
<Particle>
The three-dimensional structure forming composition contains particles.

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

  Examples of the inorganic material constituting the particles include various metals and metal compounds. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; various kinds such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Metal hydroxides; various metal nitrides such as silicon nitride, titanium nitride and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metals such as calcium carbonate and magnesium carbonate Carbonates; sulfates of various metals such as calcium sulfate and magnesium sulfate; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; aluminum borate, magnesium borate, etc. And boric salts of various metals, and composites thereof such as talc and mica.

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

  Among these, the particles are preferably composed of an inorganic material, more preferably composed of a metal oxide, and at least selected from the group consisting of silica, calcium carbonate, alumina, and titanium oxide. More preferably, it is one. Thereby, the characteristics such as mechanical strength and light resistance of the three-dimensional structure can be made particularly excellent. In addition, silica, calcium carbonate, alumina, and titanium oxide are excellent in fluidity, which is advantageous for forming a layer with higher thickness uniformity and productivity and dimensional accuracy of the three-dimensional structure 1000. Can be made particularly excellent.

  The average particle diameter of the particles is not particularly limited, but is preferably 1 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less. As a result, the mechanical strength of the three-dimensional structure 1000 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 1000 can be more effectively prevented. The dimensional accuracy of the shaped object 1000 can be made particularly excellent. Moreover, the fluidity of the composition for three-dimensional modeling can be made particularly excellent, and the productivity of the three-dimensional modeling thing can be made particularly excellent. In the present invention, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser (Coulter counter method particle size distribution analyzer ( It can be determined by measuring with a 50 μm aperture using COULTER ELECTRONICS INS TA-II type).

  The Dmax of the particles is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less. As a result, the mechanical strength of the three-dimensional structure 1000 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 1000 can be more effectively prevented. The dimensional accuracy of the shaped object 1000 can be made particularly excellent. Moreover, the fluidity of the composition for three-dimensional modeling can be made particularly excellent, and the productivity of the three-dimensional modeling object 1000 can be made particularly excellent. Moreover, the scattering of the light by particle | grains in the surface of the three-dimensional structure 1000 manufactured can be prevented more effectively.

  The particles may have any shape, but preferably have a spherical shape. Thereby, the fluidity of the composition for three-dimensional modeling can be made particularly excellent, the productivity of the three-dimensional model 1000 can be made particularly excellent, and the unwillingness in the manufactured three-dimensional model 1000 can be achieved. Generation of unevenness and the like can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure 1000 can be made particularly excellent. Moreover, the scattering of the light by particle | grains in the surface of the three-dimensional structure 1000 manufactured can be prevented more effectively.

The content of the particles in the three-dimensional modeling composition is preferably 10% by mass or more and 90% by mass or less, and more preferably 15% by mass or more and 58% by mass or less. The particles may be porous, the range of the bulk density of approximately 0.1g ^/ cm ³ ~1.0g ^/ cm 3 is suitably in the ^range of 0.15g / cm ³ ~0.5g / cm 3 A porous powder is more preferable. Thereby, the mechanical strength of the finally obtained three-dimensional structure 1000 can be made particularly excellent while sufficiently improving the fluidity of the three-dimensional structure forming composition.

≪Surface treatment agent≫
The composition for three-dimensional modeling contains a surface treatment agent that modifies the particle surface.

  The surface treatment agent has a function of modifying the particle surface so as to improve the affinity with the binder.

  As such a surface treatment agent, it is preferable to use at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. Thereby, the affinity between the particle surface and the binder can be made higher. As a result, the bonding force between the particles by the binder can be made higher, and the mechanical strength of the obtained three-dimensional structure 1000 can be made more excellent.

  Examples of silane coupling agents include amino silane coupling agents, ureido silane coupling agents, vinyl silane coupling agents, methacrylic silane coupling agents, epoxy silane coupling agents, and mercapto silane coupling agents. And isocyanate-based silane coupling agents. Among these, it is particularly preferable to use an amino silane coupling agent and / or an acrylic silane coupling agent as the silane coupling agent. Thereby, the affinity between the particle surface and the binder can be further increased.

  Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, 3- (acryloxy) propyltrimethoxysilane, N-2-aminoethyl-3-amino. Propylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltris (β-methoxy-ethoxy) silane, β- (3 , 4-epoxycyclohexyl) -ethyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like. .

  Examples of titanate coupling agents include titanate coupling agents having an alkyl phosphite group, titanate coupling agents having an alkyl phosphate group, titanate coupling agents having an alkyl pyrophosphate group, tetraalkyl type, mono Examples include an alkoxy type, a coordination type, a chelate type, a quaternary salt type, a neoalkoxy type, and a cycloheteroatom type.

  Specific examples of the titanate coupling agent include, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetraoctyl bis (ditrityl). Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphat titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctai Nortitanate, isopropyl dimethacrylisostearoyl titanate, isopropylisostearoyl Acrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumyl phenyloxyacetate titanate diisostearoyl ethylene titanate, neopentyl (diaryl) oxy- ( Tri) dioctyl phosphato titanate, dineopentyl (diaryl) oxy-di (paraamino) benzoyl titanate, neopentyl (diaryl) oxy-tri (N-ethylenediamino) ethyl titanate, dineopentyl (diaryl) oxy-tri (m-amino) phenyl titanate Etc. Among these, it is particularly preferable to use isopropyl triisostearoyl titanate. Thereby, the affinity between the particle surface and the binder can be further increased.

  Specific examples of the aluminate coupling agent include, for example, alkyl acetoacetate aluminum diisopropylate, diisobutyl (oleyl) acetoacetyl aluminate, diisopropyl (oleyl) acetoacetyl aluminate, amino zircoaluminate, carboxyl zircoaluminate, Examples include methacryloxy zirco aluminate, fatty acid zirco aluminate, mercapto zirco aluminate and the like.

  Specific examples of the zirconate coupling agent include, for example, zirconium stearate, tetra (2,2-diallyloxymethyl) butyl-di (ditridecyl) phosphitozirconate, neopentyl (diaryl) oxy- (tri) dioctylphos Fattyzirconate, Dineopentyl (diaryl) oxy-di (paraamino) benzoyl zirconate, Neopentyl (diaryl) oxy-tri (N-ethylenediamino) ethyl zirconate, Dineopentyl (diaryl) oxy-tri (m-amino) phenylzirconate Etc.

  The content of the surface treatment agent in the composition for three-dimensional modeling is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. Thereby, the mechanical strength of the finally obtained three-dimensional structure 1000 can be made particularly excellent.

≪Solvent≫
The three-dimensional structure forming composition contains a solvent. Thereby, the fluidity | liquidity of the composition for three-dimensional modeling can be made especially excellent, and the productivity of the three-dimensional modeling thing 1000 can be made especially excellent.

  Although it does not specifically limit as a solvent which comprises the composition for three-dimensional modeling, It is preferable to use an aqueous solvent. The aqueous solvent is composed of water and / or a liquid having excellent compatibility with water, but is preferably composed mainly of water, and particularly the water content is 70 wt% or more. It is preferable that it is 90 wt% or more. Thereby, the water-soluble resin can be more reliably dissolved, and the fluidity of the three-dimensional modeling composition and the uniformity of the composition of the layer 1 formed using the three-dimensional modeling composition are particularly excellent. It can be. In addition, water is easy to remove after the formation of the layer 1, and even when it remains in the three-dimensional structure 1000, it is difficult to adversely affect water. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems.

  The content of the solvent in the three-dimensional modeling composition is preferably 5% by mass or more and 75% by mass or less, and more preferably 35% by mass or more and 70% by mass or less. Thereby, while the effect by including a solvent as mentioned above is exhibited more notably, since a solvent can be easily removed in a short time in the manufacturing process of the three-dimensional structure 1000, the three-dimensional structure 1000 This is advantageous from the viewpoint of improving productivity.

  In particular, when the three-dimensional modeling composition contains water as a solvent, the content of water in the three-dimensional modeling composition is preferably 20% by mass to 73% by mass, and more preferably 50% by mass to 70% by mass. It is more preferable that the amount is not more than mass%. Thereby, the effects as described above are more remarkably exhibited.

≪Water-soluble resin≫
The composition for three-dimensional modeling may contain a water-soluble resin together with the above components. By including the water-soluble resin, the particles can be bonded (temporarily fixed), and the particles can be effectively prevented from being unintentionally scattered. Thereby, the improvement of a worker's safety and the dimensional accuracy of the three-dimensional structure 1000 manufactured can be aimed at. Further, since the water-soluble resin has high affinity with the particle surface, the particle surface can be easily coated.

  It is preferable that at least a part of the water-soluble resin is soluble in water. For example, the solubility in water at 25 ° C. (mass soluble in 100 g of water) is 5 [g / 100 g water] or more. It is more preferable that it is 10 [g / 100 g water] or more. Thereby, the affinity with the particle surface can be made higher, and unbound particles can be more easily removed in the unbound particle removal step.

  In the composition for three-dimensional modeling, the water-soluble resin is preferably in a liquid state (for example, a dissolved state, a molten state, etc.) at least in the layer forming step. Thereby, the uniformity of the thickness of the layer 1 formed using the composition for three-dimensional modeling can be made higher easily and reliably.

  The water-soluble resin includes at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, ammonium polyacrylate, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene oxide, polyethylene glycol, polyacrylamide, and polyethyleneimine. It is preferable to use what is included. Thereby, the affinity between the water-soluble resin and the particles (hydrogen bond between the water-soluble functional group of the water-soluble resin and the hydroxyl group, carboxyl group, or amino group on the particle surface) can be made particularly high. .

  In addition, since the water-soluble resin has a hydroxyl group and has high affinity (solubility) with an aqueous solvent, it can be easily and uniformly dissolved. The content of the water-soluble resin in the three-dimensional modeling composition is preferably 15% by volume or less, and more preferably 2% by volume or more and 5% by volume or less with respect to the bulk volume of the particles. This makes it possible to ensure a wider space for the binding liquid to enter while sufficiently exerting the function of the water-soluble resin as described above, and to make the mechanical strength of the three-dimensional structure 1000 particularly excellent. be able to.

≪Other ingredients≫
Further, the three-dimensional modeling composition may include components other than those described above. Examples of such components include a polymerization initiator; a polymerization accelerator; a penetration accelerator; a wetting agent (humectant); a fixing agent; an antifungal agent; an antiseptic; an antioxidant; an ultraviolet absorber; Examples include regulators.

3. Next, the binding liquid will be described in detail.

<< Binder >>
The binding liquid contains at least a binder.
The binder is a component having a function of binding particles by curing.

  Examples of the binder include various kinds of materials such as thermoplastic resins; thermosetting resins; visible light curable resins (narrowly defined photocurable resins) that are cured by light in the visible light region, ultraviolet curable resins, and infrared curable resins. Photocurable resin; X-ray curable resin and the like can be mentioned, and one or more selected from these can be used in combination. Among these, from the viewpoint of the mechanical strength of the obtained three-dimensional structure, the productivity of the three-dimensional structure, and the like, the binder is preferably a curable resin. Among various curable resins, in particular, from the viewpoint of mechanical strength of the obtained three-dimensional structure, productivity of the three-dimensional structure, storage stability of the binding liquid, etc., in particular, an ultraviolet curable resin (polymerizable compound). Is preferred.

  As the ultraviolet curable resin, a resin which is polymerized by addition polymerization or ring-opening polymerization by radical species or cationic species generated from a photopolymerization initiator by ultraviolet irradiation is preferably used. Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

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

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

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

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

  Specific examples of the monofunctional (meth) acrylate include, for example, phenoxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl ( And (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

  Specific examples of the bifunctional (meth) acrylate include, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, penta Erythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, dipropylene glycol diacrylate, tripropylene Recall diacrylate and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the binder in the binding liquid is preferably 80% by mass or more, and more preferably 85% by mass or more. Thereby, the mechanical strength of the finally obtained three-dimensional structure 1000 can be made particularly excellent.

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

  In particular, when the binding liquid contains a colorant, the three-dimensional structure 1000 colored in a color corresponding to the color of the colorant can be obtained.

  In particular, the light resistance of the binding liquid and the three-dimensional structure 1000 can be improved by including a pigment as the colorant. As the pigment, either an inorganic pigment or an organic pigment can be used.

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

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

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

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

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

  In particular, when the binding liquid contains titanium oxide as a colorant, the content of titanium oxide in the binding liquid is preferably 12% by mass or more and 18% by mass or less, and is 14% by mass or more and 16% by mass or less. More preferably. Thereby, a particularly excellent concealing property can be obtained.

  When the binding liquid contains a pigment, the dispersibility of the pigment can be further improved if it further contains a dispersant. As a result, a partial decrease in mechanical strength due to pigment bias can be more effectively suppressed.

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

  When the binding liquid contains a surfactant, the three-dimensional structure 1000 can have better abrasion resistance. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used. Specific examples of the surfactant include, for example, BYK-UV3500, 3510, 3530, 3570 (above, trade names manufactured by BYK).

  The binding liquid may contain a solvent. Thereby, the viscosity of the binding liquid can be suitably adjusted, and even when the binding liquid contains a high-viscosity component, the discharge stability of the binding liquid by the inkjet method can be made particularly excellent.

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

Further, the viscosity of the binding liquid is preferably 7 mPa · s or more and 25 mPa · s or less, and more preferably 10 mPa · s or more and 20 mPa · s or less. Thereby, the discharge stability of the ink by the inkjet method can be made particularly excellent. In addition, in this specification, a viscosity means the value measured in 25 degreeC using an E-type viscosity meter (Tokyo Keiki Co., Ltd. VISCONIC ELD).
Moreover, you may use multiple types of binding liquid for manufacture of the three-dimensional structure 1000.

  For example, a binding liquid containing a colorant (color ink) and a binding liquid not containing a colorant (clear ink) may be used. Accordingly, for example, a binding liquid containing a colorant is used as a binding liquid to be applied to a region that affects the color tone on the appearance of the three-dimensional structure 1000, and the color tone is not affected on the appearance of the three-dimensional structure 1000. A binding liquid that does not contain a colorant may be used as the binding liquid applied to the region. Further, in the finally obtained three-dimensional structure 1000, an area (coat layer) using a binding liquid not containing a colorant is provided on the outer surface of the area formed using the binding liquid containing a colorant. In addition, a plurality of types of binding liquids may be used in combination.

  Further, for example, a plurality of types of binding liquids containing different colorants may be used. Thereby, the color reproduction area which can be expressed can be made wide by the combination of these binding liquids.

  When a plurality of types of binding liquids are used, it is preferable to use at least a cyan binding liquid, a magenta binding liquid, and a yellow binding liquid. Thereby, the color reproduction area which can be expressed can be made wider by the combination of these binding liquids.

  Further, by using the white (white) binding liquid in combination with other colored binding liquids, for example, the following effects can be obtained. That is, the finally obtained three-dimensional structure 1000 is overlapped with the first region to which the white (white) binding liquid is applied, and the first region, and on the outer surface side of the first region. And a region to which a colored binding liquid other than white is provided. Thereby, the 1st area | region to which the white (white) binding liquid was provided can exhibit concealment property, and the chroma of the three-dimensional structure 1000 can be improved more.

4). Next, a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention will be described.

  FIG. 3 is a plan view of a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention viewed from above, and FIG. 4 is a side view of the three-dimensional structure manufacturing apparatus shown in FIG.

  The three-dimensional structure manufacturing apparatus 100 has a three-dimensional structure by laminating a layer 1 formed using a composition for three-dimensional structure including particles, a surface treatment agent that modifies the surface of the particles, and a solvent. It is an apparatus for manufacturing a modeled object.

  As shown in FIGS. 3 and 4, the three-dimensional structure manufacturing apparatus 100 includes a modeling unit 10 on which a three-dimensional structure is modeled, a supply unit 11 that supplies a composition for three-dimensional modeling, and a supplied tertiary. A squeegee (layer forming means) 12 that forms the layer 1 of the three-dimensional modeling composition on the modeling unit 10 using the original modeling composition, and the surplus three-dimensional modeling composition is recovered when the layer 1 is formed. A recovery unit 13 for heating, a heating unit 14 for heating the layer 1, a discharge unit 15 for discharging a binding liquid containing a binder to the layer 1, an ultraviolet irradiation unit 16 for irradiating the layer 1 with ultraviolet rays, have.

  As shown in FIGS. 3 and 4, the modeling unit 10 includes a frame body 101 and a modeling stage 102 provided inside the frame body 101.

The frame body 101 is composed of a frame-shaped member.
The modeling stage 102 has a rectangular shape on the XY plane.

  The modeling stage 102 is configured to move (lift) in the Z-axis direction by a driving unit (not shown).

The layer 1 is formed in a region formed by the inner wall surface of the frame body 101 and the modeling stage 102.
The modeling unit 10 can be driven in the X-axis direction by a driving unit (not shown).

  Then, when the modeling unit 10 moves in the X-axis direction, that is, to a drawing region of the discharge unit 15 to be described later, the binding liquid is discharged to the layer 1 by the discharge unit 15.

  The supply unit 11 has a function of supplying a 3D modeling composition into the 3D model manufacturing apparatus 100.

  The supply unit 11 includes a supply region 111 to which the three-dimensional modeling composition is supplied, and a supply unit 112 that supplies the three-dimensional modeling composition to the supply region 111.

  The supply region 111 has a long rectangular shape in the X-axis direction, and is provided in contact with one side of the frame body 101. The supply region 111 is provided so as to be flush with the upper surface of the frame body 101.

  The composition for three-dimensional modeling supplied to the supply region 111 is conveyed to the modeling stage 102 by the squeegee 12 described later, and forms the layer 1.

  The squeegee (layer forming means) 12 has a long plate shape in the X-axis direction. Further, the squeegee 12 is configured to be driven in the Y-axis direction by a driving unit (not shown). Further, the squeegee 12 is configured such that the tip in the short axis direction is in contact with the upper surface of the frame body 101 and the supply region 111.

  The squeegee 12 moves the composition for three-dimensional modeling supplied to the supply region 111 to the modeling stage 102 while moving in the Y-axis direction, and forms the layer 1 on the modeling stage 102.

  In this embodiment, the moving direction of the squeegee 12 and the moving direction of the modeling unit 10 are configured to intersect (orthogonal). By adopting such a configuration, it is possible to prepare for the formation of the next layer 1 when the discharge of the binding liquid by the discharge unit 15 is performed, and to improve the production efficiency of the three-dimensional structure. Can do.

  The collection unit 13 is a box-shaped member whose upper surface is opened, and is provided separately from the modeling unit 10. The collection unit 13 has a function of collecting the composition for three-dimensional modeling that has become excessive due to the formation of the layer 1.

  The collection unit 13 is in contact with the frame body 101 and is provided to face the supply unit 11 through the frame body 101.

  The surplus composition for three-dimensional modeling carried by the squeegee 12 is recovered by the recovery unit 13, and the recovered three-dimensional modeling composition is reused.

The heating means 14 has a function of heating the layer 1 and drying the layer 1. That is, it has a function of removing at least a part of the solvent contained in the layer 1. Further, the surface of the particles contained in the layer 1 is modified by the surface treatment agent by the heating of the heating means 14.
The discharge unit 15 has a function of discharging the binding liquid to the formed layer 1.

  Specifically, when the modeling unit 10 in which the layer 1 is formed on the modeling stage 102 moves in the X-axis direction and reaches the drawing area below the ejection unit 15, the coupling unit 15 is coupled to the layer 1 from the ejection unit 15. Liquid is discharged.

  The discharge unit 15 is mounted with a droplet discharge head that discharges a droplet of a binding liquid by an inkjet method. Moreover, the discharge part 15 is provided with the coupling liquid supply part which is not illustrated. In the present embodiment, a so-called piezo drive type droplet discharge head is employed.

  Two ultraviolet irradiation means 16 are provided at both ends in the moving direction (X-axis direction) of the discharge unit 15.

  The ultraviolet irradiation means 16 has a function of curing the binder in the layer 1 by irradiating the layer 1 with ultraviolet rays and bonding the particles in the layer 1 together.

  In the above description, the case where the squeegee 12 is used as the layer forming unit has been described. However, the squeegee 12 is not limited to the squeegee and may be a roller, for example.

  Further, the collection unit 13 may be provided with a removing unit that removes the three-dimensional modeling composition attached to the squeegee 12. As the removing means, ultrasonic waves, wiping, static electricity or the like can be used.

  Further, when the three-dimensional modeling composition does not contain a solvent, the heating means 17 may not be provided.

  Moreover, although it demonstrated as having the ultraviolet irradiation means 16 in the said description, it is not limited to this. For example, when the binder contains a thermosetting resin, it may be a heating means.

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

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

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

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

  For example, in the above-described embodiment, the configuration in which the recovery unit and the modeling unit are separate from each other has been described. However, the configuration is not limited thereto, and the recovery unit and the modeling unit may be configured integrally. In this case, the layer 1 may be formed by moving the modeling part and the recovery part without moving the squeegee.

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

As a pre-processing process, the cleaning process of a modeling stage etc. are mentioned, for example.
As the post-treatment process, for example, a cleaning process, a shape adjustment process for deburring, a coloring process, a coating layer forming process, a light irradiation process or a heat treatment for surely curing an uncured ultraviolet curable resin is performed. Examples include an ultraviolet curable resin curing completion step.

  Moreover, although embodiment mentioned above demonstrated as what provides a binding liquid with respect to all the layers, you may have the layer to which a binding liquid is not provided. For example, the binding liquid may not be applied to the layer formed immediately above the modeling stage, and the layer may function as a sacrificial layer.

  In the above-described embodiment, the case where the ejection step is performed by the ink jet method has been mainly described, but the ejection step may be performed using another method (for example, another printing method).

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. In the following description, the processing that does not particularly indicate the temperature condition is performed at room temperature (25 ° C.). Moreover, what does not show temperature conditions in particular also about various measurement conditions is a numerical value in room temperature (25 degreeC).

[1] Production of three-dimensional structure (Example 1)
1. Preparation of Composition for Three-Dimensional Modeling First, a powder composed of silica particles having a large number of hydroxyl groups on the surface (trade name “Nipsil E-75” manufactured by Tosoh Silica Co., Ltd .: average particle size 2.4 μm) was prepared.

  Next, powder: 30.00 mass%, water: 59.00 mass%, ammonium polyacrylate as a water-soluble resin: 10.00 mass%, and 3-aminopropyltriethoxysilane as a coupling agent 1.00 mass% was mixed and the composition for three-dimensional modeling was obtained.

2. Manufacture of three-dimensional structure Using the obtained composition for three-dimensional structure, the shape as shown in FIG. 5, that is, thickness: 4 mm × length: 150 mm, both ends indicated by hatched portions (see FIG. A three-dimensional structure A having a width of 20 mm and a length of 35 mm provided in the upper and lower sides), a width of 10 mm between the areas, and a length of 80 mm. And the three-dimensional structure B which is a shape as shown in FIG. 6, ie, the cube shape of thickness: 4 mm × width: 10 mm × length: 80 mm, was manufactured as follows.

  First, a three-dimensional modeling apparatus was prepared, and a layer having a thickness of 50 μm was formed on the surface of the support (stage) using the three-dimensional modeling composition by a squeegee method (layer forming step).

  Next, after the layer formation, the layer was heated to 150 ° C. and allowed to stand for 2 minutes to remove water contained in the three-dimensional modeling composition and to modify the surface of the silica particles.

  Next, ink was applied in a predetermined pattern to the layer constituted by the three-dimensional modeling composition by an inkjet method (ink ejection step). As the ink, an ink having the following composition and a viscosity at 25 ° C. of 22 mPa · s was used.

<UV curable resin>
・ Phenoxyethyl acrylate: 20.00% by mass
Isobornyl acrylate: 20.00% by mass
・ 2- (2-vinyloxyethoxy) ethyl acrylate: 50.00% by mass

<Polymerization initiator>
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 5.00% by mass
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: 4.50% by mass

<Polymerization inhibitor>
・ P-methoxyphenol: 0.10% by mass

<Surfactant>
-BYK3500 (trade name manufactured by BYK): 0.40 mass%

  Next, the layer was irradiated with ultraviolet rays to cure the ultraviolet curable resin contained in the three-dimensional modeling composition (curing step).

  Thereafter, a series of steps from the layer formation step to the curing step were repeated so that a plurality of layers were stacked while changing the ink application pattern according to the shape of the three-dimensional structure to be manufactured.

Thereafter, the laminate obtained as described above is immersed in water and subjected to ultrasonic vibration, whereby particles constituting each layer are not bound by an ultraviolet curable resin (unbound particles). Was removed, and two three-dimensional structures A and two three-dimensional structures B were obtained.
Then, the drying process was performed on the conditions of 60 degreeC * 20 minutes.

(Examples 2-7, Comparative Examples 1-3)
The composition of the three-dimensional modeling composition is changed as shown in Table 1 by changing the type of raw materials used for the preparation of the three-dimensional modeling composition and the mixing ratio of each component, and the conditions in the heating process are shown in Table 1. A three-dimensional structure was manufactured in the same manner as in Example 1 except that the change was made as shown in FIG.

Table 1 shows the configurations of the three-dimensional modeling compositions of the examples and the comparative examples. In the table, the surface-treated silica indicates Nipsil E-75 wet-treated with 3-aminopropyltriethoxysilane, and alumina indicates a product name “AEROXIDE Alu 65” manufactured by Nippon Aerosil Co., Ltd., and titanium oxide. Indicates a product name “AEROXIDE TIO ₂ P25” manufactured by Nippon Aerosil Co., Ltd.

[2] Evaluation [2.1] Tensile strength and tensile modulus About the three-dimensional structure A of each Example and each Comparative Example, in accordance with JIS K 7161: 1994 (ISO 527: 1993), tensile yield stress: Measurement was performed under the conditions of 50 mm / min and tensile modulus: 1 mm / min, and the tensile strength and tensile modulus were evaluated according to the following criteria.

(Tensile strength)
A: Tensile strength is 30 MPa or more.
B: Tensile strength is 20 MPa or more and less than 30 MPa.
C: Tensile strength is 10 MPa or more and less than 20 MPa.
D: Tensile strength is less than 10 MPa.

(Tensile modulus)
A: The tensile elastic modulus is 1.5 GPa or more.
B: Tensile modulus is 1.0 GPa or more and less than 1.5 GPa.
C: Tensile modulus is 0.5 GPa or more and less than 1.0 GPa.
D: Tensile modulus is less than 0.5 GPa.

[2.2] Flexural strength and flexural modulus About the three-dimensional structure B of each of the above Examples and Comparative Examples, the distance between fulcrums of 64 mm and the test speed are in accordance with JIS K 7171: 1994 (ISO 178: 1993). Measurement was performed under the condition of 2 mm / min, and bending strength and flexural modulus were evaluated according to the following criteria.

(Bending strength)
A: Bending strength is 60 MPa or more.
B: Bending strength is 45 MPa or more and less than 60 MPa.
C: Bending strength is 30 MPa or more and less than 45 MPa.
D: Bending strength is less than 30 MPa.

(Flexural modulus)
A: Bending elastic modulus is 2.4 GPa or more.
B: The flexural modulus is 2.2 GPa or more and less than 2.4 GPa.
C: Flexural modulus is 2.0 GPa or more and less than 2.2 GPa.
D: Flexural modulus is less than 2.0 GPa.

These results are summarized in Table 1.
As is apparent from Table 1, in the present invention, a three-dimensional structure excellent in mechanical strength was obtained. On the other hand, in the comparative example, sufficient results were not obtained.

DESCRIPTION OF SYMBOLS 1 ... Layer 2 ... Binding liquid 3 ... Curing part 10 ... Modeling part 11 ... Supply part 12 ... Squeegee (layer formation means)
DESCRIPTION OF SYMBOLS 13 ... Recovery part 14 ... Heating means 15 ... Discharge part 16 ... Ultraviolet irradiation means 100 ... Three-dimensional structure manufacturing apparatus 101 ... Frame body 102 ... Modeling stage 111 ... Supply area 112 ... Supply means 1000 ... Three-dimensional structure

Claims (12)

Particles,
A surface treatment agent for modifying the surface of the particles;
A composition for three-dimensional modeling, comprising a solvent.   The three-dimensional modeling according to claim 1, wherein the surface treatment agent is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. Composition.   The three-dimensional structure forming composition according to claim 2, wherein the silane coupling agent is an amino silane coupling agent and / or an acrylic silane coupling agent.   The three-dimensional structure forming composition according to claim 2 or 3, wherein the titanate coupling agent includes isopropyl triisostearoyl titanate.   The three-dimensional structure forming composition according to any one of claims 1 to 4, wherein the particles are at least one selected from the group consisting of silica, calcium carbonate, alumina, and titanium oxide. It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a composition for three-dimensional modeling including particles, a surface treatment agent for modifying the surface of the particles, and a solvent;
Heating the layer to remove the solvent; and
A method for producing a three-dimensional structure, comprising: a step of discharging a binding liquid containing a binder that binds the plurality of particles to the layer.   The three-dimensional modeling according to claim 6, wherein the surface treatment agent is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. Manufacturing method.   The method for producing a three-dimensional structure according to claim 1, wherein in the heating step, the layer is heated to a temperature of 40 ° C. or higher and 180 ° C. or lower.   The method for producing a three-dimensional structure according to claim 1, further comprising a removal step of removing the particles that are not bound by the binder after repeatedly performing the layer forming step, the heating step, and the discharging step. . A three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
A layer forming means for forming the layer using a three-dimensional modeling composition comprising particles, a surface treatment agent for modifying the surface of the particles, and a solvent;
Heating means for heating the layer and removing the solvent;
The three-dimensional structure manufacturing apparatus characterized by having discharge means for discharging a binding liquid containing a binder that binds the plurality of particles to the layer.   A three-dimensional structure manufactured by the method for manufacturing a three-dimensional structure according to any one of claims 7 to 9.   A three-dimensional structure manufactured by the three-dimensional structure manufacturing apparatus according to claim 10.

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