TW201527064A - Method for manufacturing three-dimensional structure and three-dimensional structure - Google Patents

Abstract

The present invention relates to a method for manufacturing a three-dimensional structure by stacking layers, and which includes an ink discharge step of discharging an ink for forming an outermost layer to a region to become the outermost layer of the three-dimensional structure of the layer and discharging an ink for forming a sacrificial layer for forming a sacrificial layer to a region on a surface side of the layer which is adjacent to the region to become the outermost layer of the layer, a curing step of curing the ink for forming an outermost layer and the ink for forming a sacrificial layer discharged, and a filling step of filling a region surrounded by a cured product of the ink for forming an outermost layer with a composition for forming a three-dimensional object including powder for forming a three-dimensional object configured of a plurality of particles and forming a composition layer for forming a three-dimensional object.

Description

Three-dimensional shape forming method and three-dimensional shape forming object

The present invention relates to a method of manufacturing a three-dimensional shaped object and a three-dimensional shaped article.

Since the prior art, a method of forming a three-dimensional shaped object based on, for example, a model of a three-dimensional object generated by a three-dimensional CAD (computer-aided design) software or the like has been known.

As one of methods for forming a three-dimensional shaped object, a laminate method is known. Regarding the layering method, after the model of the three-dimensional object is divided into a plurality of two-dimensional section layers, the section members corresponding to the two-dimensional section layers are sequentially formed, and the section members are sequentially laminated to form a three-dimensional shape.

The layering method can be formed directly as long as there is a model of a three-dimensional shaped object to be shaped, and it is not necessary to produce a model or the like before forming, so that a three-dimensional shaped object can be formed quickly and inexpensively. Further, since a three-dimensional shaped object is formed by laminating a thin plate-shaped cross-section member layer by layer, even if it is a complicated object having an internal structure, for example, it can be formed into an integrated shape without being divided into a plurality of parts.

As one of such a lamination method, a technique of forming a three-dimensional shaped object by hardening a powder by a bonding liquid is known (for example, refer to Patent Document 1). In this technique, when each layer is formed, an ink containing a coloring agent is ejected to a portion corresponding to the outer surface side of the three-dimensional shaped object, thereby imparting color to the three-dimensional shaped object.

However, the above method of hardening the powder has a problem that the outer surface is brittle due to the use of the powder. Further, it is difficult to express a fine color on the outer surface due to irregularities or the like caused by the powder.

On the other hand, as one of the lamination methods, a technique of forming a three-dimensional shaped object by ejecting ink and hardening the ink itself is known (for example, see Patent Document 2). In this technique, the layers can be formed thinner, and a colorful color representation can be performed on the outer surface. Further, since the powder is not used, it exhibits high strength as a whole.

However, the above method of hardening the ink has a problem that although it is not problematic for producing a small three-dimensional shaped object, it is too time consuming to manufacture a three-dimensional shaped object which is large to some extent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-150556

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-280354

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a three-dimensional shaped object which can stably and efficiently produce a three-dimensional shaped object having a high mechanical strength of an outer surface and realizing a fine color expression, and provides a mechanical strength of the outer surface which is high and A three-dimensional shape that achieves a subtle color expression.

The above object is achieved by the present invention described below.

The method for producing a three-dimensional shaped article of the present invention is a method for producing a three-dimensional shaped object by laminating a layer formed using an ink containing a curable resin, and is characterized in that the ink ejecting step is performed to the layer Should be the outermost of the above three-dimensional shape The outer layer forming ink is ejected from the layer region, and the sacrificial layer forming ink for the sacrificial layer is ejected to a region on the surface side of the outermost layer adjacent to the region of the layer to be the outermost layer; and the hardening step is performed The outermost layer forming ink to be ejected and the sacrificial layer forming ink are cured; and a filling step of filling a three-dimensional shape containing the three-dimensional shaped powder containing the particles in a region surrounded by the cured product of the outermost layer forming ink. The composition is used to form a three-dimensional shaped composition layer.

Thereby, it is possible to stably and efficiently manufacture a three-dimensional shape in which the outer surface has high mechanical strength and realizes fine color expression.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the three-dimensional forming composition to be filled is planarized based on the height of the cured product of the outermost layer forming ink in the filling step. deal with.

Thereby, the dimensional accuracy of the finally obtained three-dimensional shaped object can be made particularly high, and the surface shape and appearance of the three-dimensional shaped object can be better controlled.

In the method for producing a three-dimensional shaped article of the present invention, it is preferred to have a powder bonding step of ejecting a binding ink containing a curable resin onto the three-dimensional forming composition layer to form a powder bonding layer.

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

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the powder bonding step and the k+1 layer in the formation of the layer of the kth layer (k is an integer of 1 or more) (k is 1 or more) The ink ejecting step in the formation of the above layer of the integer) is performed together.

Thereby, the formation of the powder bonding layer can be performed substantially simultaneously with the formation of the outermost layer of the unit layer of the upper layer and the sacrificial layer, and the three-dimensional shaped article can be manufactured more efficiently.

In the method for producing a three-dimensional shaped article of the present invention, it is preferred that the ink is ejected. In the step, the outermost layer forming ink is ejected to a region of the plurality of layers which is to be the outermost layer of the three-dimensional shaped object, and is adjacent to the outermost layer adjacent to a region of the plurality of layers which is to be the outermost layer. The region on the surface side ejects the sacrificial layer forming ink for forming the sacrificial layer.

Thereby, the thinner outermost layer can be formed without being affected by the particle size of the three-dimensional shaped powder constituting the three-dimensional forming composition. As a result, it is possible to form a three-dimensional shaped object having a finer color and texture on the outer surface.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the ink for forming the outermost layer contains a solvent selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and a polyether aliphatic group. One of a group consisting of (meth)acrylic acid urethane oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate Or two or more types.

Thereby, the outermost layer forming ink can be hardened at a more appropriate curing speed, and the productivity of the three-dimensional shaped article can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the ink for forming a sacrificial layer contains a selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, and poly One of a group consisting of ethylene glycol di(meth)acrylate and (meth)acryloylmorpholine and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate or Two or more types.

Thereby, the sacrificial layer forming ink can be cured at a more appropriate curing speed, and the appearance of the fine texture can be more reliably obtained, and the productivity of the three-dimensional shaped object can be made particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable that the outermost layer forming ink and the sacrificial layer forming ink contain bis(2,4,6-trimethylbenzylidene)-phenyl group. Phosphine oxide and/or 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide as a polymerization initiator.

Thereby, the outermost layer forming ink and the sacrificial layer forming ink can be cured at a more appropriate curing rate, and the productivity of the three-dimensional shaped article can be particularly excellent.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable to use the above-mentioned colorless ink as the above-mentioned outermost layer forming ink, in addition to a coloring ink containing a coloring agent, and a colorless ink containing no coloring agent. The formation of the region near the outer surface of the outermost three-dimensional shaped object of the outermost layer is such that the colored ink is used for the formation of the region inside the region.

The portion containing the coloring agent (especially the pigment) is more brittle than the portion not containing the coloring agent, and is liable to cause damage or defects, but is formed by using the outermost layer containing no coloring agent in the vicinity of the surface other than the three-dimensional shaped object. The area formed by the ink can effectively prevent the above problems.

In the method for producing a three-dimensional shaped article of the present invention, it is preferable to use a colored ink containing a coloring agent as the outermost layer forming ink, a color ink and a white ink as the colored ink, and the white ink to use the color. The formation of the area inside the area where the ink is formed.

Thereby, the area (first area) to which the white ink is applied can exhibit concealability, and the chroma of the three-dimensional shape can be further improved.

The three-dimensional shaped article of the present invention is characterized in that it is manufactured by using the method for producing a three-dimensional shaped article of the present invention.

Thereby, it is possible to provide a three-dimensional shape in which the outer surface has high mechanical strength and realizes fine color expression.

1‧‧‧Three-dimensional shape

1'‧‧‧Preform

4A‧‧‧Inner outer layer forming ink

4B‧‧‧Sacrificial layer forming ink

4C‧‧‧Ink combined with ink

6‧‧‧ powder binding layer

6'‧‧‧Three-dimensional forming composition layer

7‧‧‧ outermost layer

8‧‧‧sacrificial layer

20‧‧‧ computer

21‧‧‧Control Department

22‧‧‧CPU

23‧‧‧Memory Department

24‧‧‧ Receiving Department

25‧‧‧Image Generation Department

28‧‧‧Input and output interface

29‧‧‧ data bus

30‧‧‧Shaping Department

40‧‧‧Ink ejector

41‧‧‧Drop ejection head

42‧‧‧X direction moving department

43‧‧‧Y direction moving department

44‧‧‧ hardening resin

50‧‧‧Powder Supply Department

60‧‧‧Powder Control Department

61‧‧‧blade

62‧‧‧rails

63‧‧‧ particles

64‧‧‧Water-soluble resin

70‧‧‧Light source

80‧‧‧ Forming platform

100‧‧‧Three-dimensional shaped object manufacturing device

231‧‧‧Control program

232‧‧‧Information Development Department

611‧‧‧ pores

26‧‧‧Display (display section)

27‧‧‧Keyboard (input device)

301‧‧‧Drive Control Department

302‧‧‧Motor Control Department

303‧‧‧Location Detection Control Department

304‧‧‧Powder Supply Control Department

305‧‧‧Spray Control Department

306‧‧‧Exposure Control Department

307‧‧‧Powder supply drive mechanism

308‧‧‧Shaping platform drive mechanism

309‧‧‧blade drive mechanism

Fig. 1 (1a) to (1d) are cross-sectional views schematically showing respective steps in a preferred embodiment of the method for producing a three-dimensional shaped article of the present invention.

2(1e) to (1g) are cross-sectional views schematically showing respective steps in a preferred embodiment of the method for producing a three-dimensional shaped article of the present invention.

Fig. 3 (1a) and (1b) are cross-sectional views schematically showing a part of steps in another embodiment of the method for producing a three-dimensional shaped article of the present invention.

Fig. 4 is a cross-sectional view schematically showing a state in a layer (a composition for three-dimensional forming) before the ink ejecting step.

Fig. 5 is a cross-sectional view schematically showing a state in which particles are bonded to each other by a curable resin.

Fig. 6 is a schematic view showing a three-dimensional shaped object manufacturing apparatus for manufacturing a three-dimensional shaped object.

Fig. 7 is a block diagram showing a control unit of the apparatus for manufacturing a three-dimensional object shown in Fig. 6.

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

1. Method for manufacturing three-dimensional shaped object

First, a method of manufacturing a three-dimensional shaped article of the present invention will be described.

1 and 2 are cross-sectional views schematically showing respective steps in a preferred embodiment of a method for producing a three-dimensional shaped article of the present invention, and FIG. 3 is a view schematically showing another method for producing a three-dimensional shaped article of the present invention. FIG. 4 is a cross-sectional view schematically showing a state in a layer before the ink ejecting step (a composition for three-dimensional forming), and FIG. 5 is a view schematically showing a particle using a curable resin. A cross-sectional view of the state of being combined with each other.

As shown in Fig. 1 and Fig. 2, the method for producing a three-dimensional shaped article 1 of the present embodiment has a step of forming an outermost layer forming ink 4A containing a curable resin and a sacrificial layer containing a curable resin by an inkjet method. The ink ejecting step (1a, 1c, 1e) for ejecting the ink 4B in a specific pattern; forming the outermost layer forming ink 4A and the sacrificial layer for ejecting The hardening resin contained in the ink 4B is hardened to form a hardening step (1a, 1c, 1e) of the outermost layer 7 and the sacrificial layer 8; and the region surrounded by the outermost layer 7 is filled with a powder containing a three-dimensional shape comprising a plurality of particles. a three-dimensional forming composition to form a three-dimensional forming composition layer 6' filling step (1b, 1d); and a three-dimensional forming composition layer 6' to eject a binding ink containing a curable resin to bind a powder (1c) And 1e); the steps are repeated in this order, and thereafter, the outermost layer forming ink 4A is further ejected to a region where the outermost layer of the three-dimensional shaped object 1 is to be formed. Further, the sacrificial layer forming ink 4B is ejected toward the surface side of the outermost layer adjacent to the region of the outermost layer of the three-dimensional shaped object 1.

The method of manufacturing the three-dimensional shaped article 1 of the present embodiment is characterized in that the region surrounded by the outermost layer 7 and the sacrificial layer 8 formed of the outermost layer forming ink 4A and the sacrificial layer forming ink 4B as described above is filled with a three-dimensional shape. A composition for three-dimensional shaping of a powder.

By forming the outermost layer 7 only from the outermost layer forming ink 4A as described above, the mechanical strength of the outer surface can be made higher than that of the three-dimensional shaped article obtained by hardening the powder. Moreover, it is possible to perform fine color expression.

Further, since the inside of the three-dimensional shaped object 1 is formed by using the three-dimensional forming composition containing the powder for three-dimensional forming, the three-dimensional shaped object can be stably and efficiently produced as compared with the method of producing the three-dimensional shaped object 1 using only the ink. 1.

Further, since the sacrificial layer 8 is formed on the outer side of the outermost layer 7 of the three-dimensional shaped object 1, the outflow of the outermost layer forming ink 4A can be prevented, and a finer color or texture can be exhibited on the outer surface of the three-dimensional shaped object 1.

Hereinafter, each step will be described.

≪Ink ejection step (ink imparting step)≫

In the ink ejecting step, the outermost layer forming ink 4A containing the curable resin and the sacrificial layer forming ink 4B containing the curable resin are ejected in a specific pattern on the forming platform 80 by the ink jet method (1a, 1c). ).

More specifically, the area to be the outermost layer 7 of the three-dimensional shaped object 1 is given the most The outer layer forming ink 4A is provided with a sacrificial layer forming ink 4B in a region adjacent to a region to be the outermost layer 7 of the three-dimensional shaped object 1, that is, a region on the surface side of the outermost layer 7.

In the first ink ejecting step, the ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) (1a) is ejected onto the forming platform 80, and the outermost layer is ejected in the second and subsequent ink ejecting steps. The ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) (1c, 1e) is ejected from the sacrificial layer 8.

As described above, in the present invention, the outermost layer forming ink 4A is applied to the portion to be the outermost layer of the three-dimensional shaped article 1 to form the outermost layer 7, and the outermost layer of the outermost layer 7 is provided with the sacrificial layer forming ink 4B. The sacrificial layer 8 is formed.

According to the above configuration, the mechanical strength of the outer surface can be made higher than that of the three-dimensional shaped article obtained by hardening the powder. Moreover, it is possible to perform fine color expression. Further, it is possible to prevent the outflow of the outermost layer forming ink 4A, and to exhibit a finer color or texture on the outer surface of the three-dimensional shaped object 1.

In this step, the ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) is supplied by the ink jet method. Therefore, even the ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) When the pattern is given a fine shape, the ink can be imparted with good reproducibility. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 1 can be made particularly high, and the surface shape and appearance of the three-dimensional shaped object 1 can be more preferably controlled.

The outermost layer forming ink 4A and the sacrificial layer forming ink 4B will be described in detail below.

≪ Hardening step ≫

After the ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) is supplied (discharged) in the ink ejecting step, the hardening component contained in the ink (the outermost layer forming ink 4A and the sacrificial layer forming ink 4B) is contained ( The curable resin) is cured (1b, 1d). Thereby, the outermost layer 7 and the sacrificial layer 8 can be obtained.

In this step, by hardening the hardening component (curable resin) contained in the ink, the outer surface of the three-dimensional shaped object 1 finally obtained becomes a cured product, and thus, for example, a three-dimensional shape containing a thermoplastic resin. Mechanical strength, durability, and the like are excellent as compared with each other.

This step differs depending on the type of the curing component (curable resin). For example, when the curing component (curable resin) is a thermosetting resin, it can be heated by heating, and the curing component (curable resin) is light. In the case of a curable resin, it can be carried out by irradiating the corresponding light (for example, when the hardening component (curable resin) is an ultraviolet curable resin, it can be performed by irradiating ultraviolet rays).

In the above description, the ink is applied to the outer layer 7 and the sacrificial layer 8 in a shape or pattern corresponding to the outermost layer 7 and the sacrificial layer 8, and the entire layer including the ink is cured. However, in the present invention, at least In a part of the area, the ink is ejected and the ink is hardened at the same time. In other words, before the entire outer layer 7 of the first layer and the entire pattern of the sacrificial layer 8 are formed, at least a part of the region corresponding to the outermost layer 7 and the sacrificial layer 8 may be sequentially hardened from the portion to which the ink is applied. .

Further, in this step, it is not necessary to completely harden the hardening component contained in the ink. For example, at the end of this step, the sacrificial layer forming ink 4B can be incompletely cured, and the outermost layer forming ink 4A can be cured at a higher degree of hardening than the sacrificial layer forming ink 4B.

Thereby, the sacrificial layer removal step described in detail below can be easily performed, and the productivity of the three-dimensional shaped object 1 can be further improved.

also. At the end of this step, the outermost layer forming ink 4A may be hardened in an incomplete state. That is, in the case of facilitating such a case, for example, after performing the subsequent steps (for example, "ink ejection step" after forming the outermost layer 7 of the lower layer and the sacrificial layer 8 in the hardening step, etc.), it is in an incompletely hardened state. The outermost layer forming ink 4A is subjected to a formal hardening treatment for improving the degree of hardening, whereby the resulting three-dimensional fabric can be obtained. The mechanical strength and the like of the shape 1 become excellent. In addition, in the state in which the outermost layer forming ink 4A (lower layer) is cured in an incomplete state, the ink for forming the upper layer is provided, whereby the adhesion between the layers is particularly excellent.

≪fill step≫

Next, a three-dimensional forming composition containing a three-dimensional forming powder containing a plurality of particles is filled in a region surrounded by the cured product of the outermost layer forming ink 4A, that is, a region surrounded by the outermost layer 7 to form a three-dimensional forming composition. Layer 6'.

As described above, since the inside of the three-dimensional shaped object 1 is formed by using the three-dimensional forming composition containing the powder for three-dimensional forming, the three-dimensional shape can be stably and efficiently produced as compared with the method of manufacturing the three-dimensional shaped object 1 using only the ink. Matter 1.

This step can be carried out by, for example, a doctor blade method, a screen printing method, a doctor blade method, a spin coating method, or the like.

In the present step, the composition for three-dimensional forming which has been applied to the region surrounded by the outermost layer 7 is subjected to a planarization treatment based on the height of the cured product of the outermost layer forming ink. Thereby, a unit layer having a more uniform thickness (a layer including the outermost layer 7 and the powder bonding layer 6 described later) can be formed. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 1 can be made particularly high, and the surface shape and appearance of the three-dimensional shaped object 1 can be more preferably controlled.

The three-dimensional forming composition contains a plurality of particles 63 and a water-soluble resin 64 as described in detail below. By including the water-soluble resin 64, the particles 63 are bonded to each other (temporarily fixed) (see FIG. 4), and the unintentional scattering of the particles or the like can be effectively prevented. Thereby, it is possible to improve the safety of the worker or the dimensional accuracy of the manufactured three-dimensional shaped object 1.

In the case where the composition for three-dimensional forming is solid (granular), for example, the composition for three-dimensional forming contains a water-soluble resin which is solid at a storage temperature (for example, room temperature (25 ° C)). (a case of a thermoplastic resin) of 64 and a state in which a plurality of particles 63 are bonded by the water-soluble resin), or before the formation of the layer as described above, The three-dimensional forming composition is melted by heating to be in a fluid state. Thereby, the filling can be performed efficiently by the simple method as described above. As a result, the three-dimensional shape 1 having higher dimensional accuracy can be manufactured with higher productivity.

≪ powder combination step ≫

Next, the binding ink 4C (1c, 1e) containing the curable resin 44 is discharged to the three-dimensional forming composition layer 6' formed in the above-described filling step. The powder bonding layer 6 is formed by curing the curable resin of the discharged bonding ink 4C, thereby forming a unit layer including the outermost layer 7 and the powder bonding layer 6.

Moreover, in this step, the particles 63 constituting the three-dimensional forming composition layer 6 can be firmly bonded to each other by the curable resin 44, and the mechanical strength of the three-dimensional shaped article 1 finally obtained can be particularly excellent. Further, when the three-dimensional forming composition constituting the three-dimensional forming composition layer 6 contains a plurality of porous particles 63, the curable resin 44 enters the pores 611 of the particles 63 to exert an anchoring effect, and as a result, The bonding force of the particles 63 to each other (the bonding force by the curable resin 44) becomes excellent, and the mechanical strength of the finally obtained three-dimensional shaped object 1 can be made excellent (refer to FIG. 5).

This step is preferably the outermost layer forming ink 4A and the sacrificial layer forming ink in the formation of the unit layer higher than the unit layer formed as shown in FIG. 1 (1c) and FIG. 2 (1e). The ink ejection step of 4B is performed together. In other words, the powder bonding step in the formation of the unit layer of the kth layer (k is an integer of 1 or more) is preferably an ink ejection step in the formation of the unit layer of the k+1th layer (k is an integer of 1 or more). Go together. Thereby, the formation of the powder bonding layer 6 can be performed substantially simultaneously with the formation of the outermost layer 7 of the unit layer of the upper layer and the sacrificial layer 8, and the three-dimensional shaped object 1 can be manufactured more efficiently.

Further, as the bonding ink 4C, the same ink as the outermost layer forming ink 4A described in detail below can be used.

The above-described series of steps are repeated, and the outermost layer 7 is formed by the outermost layer forming ink 4A on the upper surface of the three-dimensional shaped object 1 in the unit layer direction. By this, it becomes a neighboring list The bit layer (including the layer of the outermost layer 7 and the powder bonding layer 6) is bonded to each other, and can be obtained by providing a pre-formed body of the sacrificial layer 8 on the surface of the layered body in which the unit layers of the state are laminated in plural. 1' (see 1f).

≪ sacrifice layer removal step≫

Then, after repeating one of the series of steps as described above, the sacrificial layer 8 (1 g) is removed from the preform 1'.

Thereby, the three-dimensional shaped object 1 can be obtained.

As a method of removing the sacrificial layer 8, for example, a method of selectively dissolving and removing the sacrificial layer 8 using a liquid that selectively dissolves the sacrificial layer 8 may be cited; or absorption of the sacrificial layer 8 is used as compared with the outermost layer 7. The higher the liquid, the sacrificial layer 8 selectively absorbs the liquid, thereby causing the sacrificial layer 8 to swell, or the mechanical strength of the sacrificial layer 8 to be lowered, and then the sacrificial layer 8 is peeled or broken.

The liquid to be used in the present step varies depending on the constituent materials of the outermost layer 7 and the sacrificial layer 8, and examples thereof include water, alcohols such as methanol, ethanol, and isopropyl alcohol, glycerin, ethylene glycol, and diethyl phthalate. A diol such as an alcohol, a triethylene glycol, a propylene glycol or a dipropylene glycol, or the like, which contains one or more selected from the group consisting of sodium hydroxide and hydrogen in order to improve the solubility of the sacrificial layer. A water-soluble substance which generates hydroxide ions such as potassium oxide, sodium hydrogencarbonate or an organic amine, and a surfactant which facilitates separation of the sacrificial sacrificial layer.

The method of imparting the liquid is not particularly limited, and examples thereof include a dipping method, a spraying method (blowing method), a coating method, various printing methods, and the like.

Further, in the above description, the liquid user has been described, but a substance having the same function (for example, a solid, a gas, a supercritical fluid, or the like) may be used.

Further, when the liquid is applied to the preform 1' or after the liquid is supplied, ultrasonic vibration can be imparted. Thereby, the removal of the sacrificial layer 8 can be promoted, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Furthermore, in the above embodiment, the outermost layer 7 is formed in the amount of one unit unit layer. After the sacrificial layer 8 and the region surrounded by the outermost layer 7, the composition for filling the three-dimensional shape is described. However, the present invention is not limited to the above. For example, the composition may be formed as shown in FIG. After the outermost layer 7 and the sacrificial layer 8 of the unit layer amount, the three-dimensional forming composition is filled in a region surrounded by the outermost layer 7 of the plurality of layers. Thereby, the thinner outermost layer 7 can be formed without being affected by the particle size of the three-dimensional shaped powder constituting the three-dimensional forming composition. As a result, the three-dimensional shaped object 1 having an outer surface having a finer color and texture can be formed.

2. Three-dimensional shaped object manufacturing device

Next, the three-dimensional shaped object manufacturing apparatus 100 of the present embodiment will be described.

Fig. 6 is a schematic view showing a three-dimensional shaped object manufacturing apparatus for manufacturing a three-dimensional shaped object. Fig. 7 is a block diagram showing a control unit of the apparatus for manufacturing a three-dimensional object shown in Fig. 6.

The three-dimensional shaped object manufacturing apparatus 100 is a device suitable for the above-described method for manufacturing a three-dimensional shaped object, and is a model for generating a unit layer (the outermost layer 7, the powder bonded layer 6) and the sacrificial layer 8, and sequentially forms based on the models. Each layer, and each unit layer is sequentially laminated, thereby forming a three-dimensional shaped object 1 device.

As shown in FIG. 6 and FIG. 7, the three-dimensional shaped object manufacturing apparatus 100 includes a computer 20 and a forming unit 30, and the computer 20 is configured to generate a model such as a unit layer, and the forming unit 30 forms a three-dimensional shaped object 1.

Hereinafter, each part constituting the three-dimensional shaped object manufacturing apparatus 100 will be described in detail.

[Forming Department 30]

As shown in FIG. 6, the forming unit 30 includes an ink ejecting unit (ink ejecting mechanism) 40, a powder supply unit 50, a powder control unit 60, a light source 70, and a forming platform 80 that are electrically connected to the computer 20.

The ink ejecting unit 40 is provided with a liquid droplet ejecting head 41 that ejects the outermost layer forming ink 4A, the sacrificial layer forming ink 4B, and the droplets of the bonded ink 4C by an inkjet method. Further, the ink ejecting unit 40 includes an ink supply unit (not shown). In this embodiment, the so-called pressure is employed. The liquid droplet ejection head 41 is electrically driven. The droplet discharge head 41 is configured to change the discharge amount of the outermost layer forming ink 4A and the sacrificial layer forming ink 4B in accordance with an instruction from the control unit 21 to be described later.

Further, the ink ejecting portion 40 has an X-direction moving portion 42 and a Y-direction moving portion 43 that move the droplet ejecting head 41 in the XY plane.

The powder supply unit 50 has a function of supplying a three-dimensional forming powder (a three-dimensional forming composition) to the following forming platform 80. The powder supply unit 50 is configured to be driven by a powder supply unit drive mechanism (not shown).

The powder control unit 60 includes a blade 61 and a guide rail 62 that controls the operation of the blade 61. The powder control unit 60 has a function of controlling the three-dimensional forming composition supplied from the powder supply unit 50 by the blade 61, and forming a composition for three-dimensional forming on the region surrounded by the outermost layer 7 on the forming platform 80. Composition layer 6' for three-dimensional forming.

The blade 61 has an elongated shape in the Y direction and has a sharp edge shape of a lower tip. The blade 61 is configured to be driven in the X direction along the guide rail 62 by a blade driving mechanism (not shown).

The layer supply mechanism is constituted by the powder supply unit 50 and the powder control unit 60.

The light source 70 has a function of curing the discharged outermost layer forming ink 4A, the sacrificial layer forming ink 4B, and the bonded ink 4C.

The light source 70 is constructed to emit ultraviolet light. As the light source 70, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp or the like can be used.

The forming platform 80 has a rectangular shape in the XY section. On the forming platform 80, a unit layer (outermost layer 7, powder bonding layer 6) and a sacrificial layer 8 are formed.

The forming platform 80 is movable in the Z direction by a forming platform driving mechanism (not shown).

The forming platform 80 is moved downward by the thickness of the outermost layer 7 formed. Here, the powder supply unit 50 and the powder control unit 60 form a three-dimensional forming composition layer 6' in a region surrounded by the outermost layer 7. .

Further, the shaping unit 30 includes a drive control unit (not shown).

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 controls the driving of the droplet discharge head 41 in the XY direction, the driving of the blade 61, and the driving of the forming platform 80 based on commands from the CPU of the computer 20 described below.

The position detection control unit controls the position of the droplet discharge head 41, the position of the blade 61, and the position of the forming platform 80 based on commands from the CPU.

The powder supply control unit controls the driving of the powder supply unit 50 (supply of powder) based on an instruction from the CPU.

The discharge control unit controls the driving of the droplet discharge head 41 (discharge of the droplets) based on an instruction from the CPU.

The exposure control unit controls the light emission state of the light source 70 based on an instruction from the CPU.

[computer 20]

As shown in FIG. 7, the computer 20 has a control unit 21, a receiving unit 24, and an image generating unit 25 that control the operations of the respective portions of the shaping unit 30.

The control unit 21 includes a CPU (Central Processing Unit) 22 and a storage unit 23.

The CPU 22 performs various arithmetic processing as a processor and executes the control program 231.

The memory unit 23 has a ROM (Read Only Memory), a RAM (Random Access Memory), and the like. The memory unit 23 is provided with an area for storing the control program 231 indicating the control program of the operation in the shaping unit 30, or a data development unit 232 as an area for temporarily expanding various materials. The memory unit 23 is connected to the CPU 22 via the data bus 29 .

Further, the control unit 21 connects the image generating unit 25 and receives via the data bus 29 Department 24. Further, the control unit 21 connects the drive control unit of the shaping unit 30 via the input/output interface 28 and the data busbar 29. Further, the drive control unit connects the above-described powder supply unit drive mechanism, the forming platform drive mechanism, the blade drive mechanism, the droplet discharge head, and the light source via the input/output interface 28 and the data busbar 29, respectively.

The image generating unit 25 has a function of manufacturing a model or the like of the three-dimensional shaped object 1. The image generating unit 25 includes a software for generating a three-dimensional object such as a three-dimensional CAD (computer-aided design).

The image generating unit 25 has a three-dimensional shape model generating function for generating a model of the three-dimensional shaped object 1, or a STL (Standard Trianguking Language) or the like for generating a polygon such as a triangle or a quadrangle on the outer surface of the model of the three-dimensional shaped object 1. A two-dimensional model performs the function of a two-dimensional model. That is, the image generating unit 25 has a function of generating three-dimensional shape data of the three-dimensional shaped object 1.

Further, the image generating unit 25 has a function of cutting the model of the three-dimensional shaped object 1 in a layered manner to generate data of the unit layer (the outermost layer 7 and the powder bonded layer 6). Further, it has a function of generating sacrificial layer data based on the unit layer data.

The unit layer data and the sacrificial layer data generated by the image generating unit 25 are stored in the storage unit 23, and are transmitted to the drive control unit of the forming unit 30 via the input/output interface 28 and the data bus bar 29. Based on the transmitted unit layer data and the sacrificial layer data, the shaping unit 30 is driven.

The receiving unit 24 includes a USB (Universal Serial BUS) port, a LAN port, and the like. The receiving unit 24 has a function of receiving an original object for generating a model of the three-dimensional shaped object 1 from an external device (not shown) such as a scanner.

Further, the computer 20 is connected to a display (display device) or a keyboard (input device) (not shown). The display and the keyboard are respectively connected to the control unit 21 via an input/output interface and a data bus.

The display has a function of displaying the receiving portion 24 in the image display area. Image file. By providing a display, the operator can visually grasp the image file and the like.

Furthermore, the input device is not limited to a keyboard, and may be a mouse, a trackball, a touch panel, or the like.

3. Ink set (outermost layer forming ink 4A, sacrificial layer forming ink 4B, and bonding ink 4C)

Next, the ink set will be described.

The ink set of the present embodiment includes at least one of the outermost layer forming ink 4A, the sacrificial layer forming ink 4B, and the bonded ink 4C. The ink set of the present embodiment is applied to the method for producing a three-dimensional shaped article of the present invention and the three-dimensional shaped article manufacturing device as described above.

In addition, since the outermost layer forming ink 4A and the binder ink 4C contain ink of the same composition, only the outermost layer forming ink 4A will be described, and the description of the bonding ink 4C will be omitted.

<The outermost layer forming ink (in combination with ink)>

The outermost layer forming ink 4A contains at least a curable resin (hardening component).

(curable resin)

Examples of the curable resin (hardening component) include a thermosetting resin, a visible light curable resin (narrow photocurable resin) which is cured by light in a visible light region, an ultraviolet curable resin, an infrared curable resin, and the like. For each of the photocurable resins and the X-ray curable resin, one type of these may be used, or two or more types may be used in combination.

Among them, the ultraviolet curable resin (polymerizable compound) is particularly preferable from the viewpoints of the mechanical strength of the three-dimensional shaped article 1 or the productivity of the three-dimensional shaped article 1 and the storage stability of the outermost layer forming ink 4A.

The ultraviolet curable resin (polymerizable compound) is preferably used in which radical polymerization or ring-opening polymerization is started by using a radical species or a cationic species generated from a photopolymerization initiator by ultraviolet irradiation. Produce polymers. As an aggregate of addition polymerization The formula includes a radical, a cation, an anion, a metathesis, and a coordination polymerization. Moreover, as a polymerization method of ring-opening polymerization, a cation, an anion, a radical, a metathesis, and a coordination polymerization are mentioned.

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

The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound, 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, methacrylic acid, maleic acid, etc.) or esters thereof and guanamines. Wait.

As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound can be used.

Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction product of an isocyanate or an epoxy group, a dehydration condensation reaction product with a carboxylic acid, or the like may be used. . Further, an addition reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an oxime amine with an alcohol, an amine or a thiol may be used, and a halogen may be used. A substituted reactant of an unsaturated carboxylic acid ester or a guanamine of a cleavable substituent such as a sulfonyloxy group or an alcohol, an amine or a thiol.

Specific examples of the radically polymerizable compound of the ester of the unsaturated carboxylic acid and the aliphatic polyol compound include, for example, a monofunctional or polyfunctional group represented by (meth) acrylate.

Specific examples of the monofunctional (meth) acrylate include toluyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ethyl methyl acrylate, methyl (meth) acrylate, (meth) acrylate Ester, dipropylene glycol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-(2-vinyloxyethyl)(meth)acrylate Oxy)ethyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

Specific examples of the difunctional (meth) acrylate include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and 1,3-butanediol II ( Methyl) acrylate, 1,4-butanediol di(meth) acrylate, propylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, hexane diol di(methyl) Acrylate, 1,4-cyclohexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, etc. .

Specific examples of the trifunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolpropane. Alkylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloxypropylpropyl Ether, iso-cyanuric acid alkylene oxide modified tri(meth)acrylate, dipentaerythritol tris(meth)acrylate, isocyanuric acid tris((meth)propenyloxyethyl) ester Hydroxytrimethylacetaldehyde modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, and the like.

Specific examples of the tetrafunctional (meth) acrylate include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, and di-trimethylolpropane tetra(methyl). Acrylate, dipentaerythritol tetra(meth)acrylate, pentoxide tetraol tetra(meth)acrylate, and the like.

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 dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate, and phosphazene alkylene oxide modified hexa Acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Examples of the polymerizable compound other than the (meth) acrylate include, for example, itaconic acid. Esters, crotonates, methacrylates, maleates, and the like.

Examples of the itaconate include ethylene glycol diconconate, propylene glycol diconconate, 1,3-butylene glycol diconconate, and 1,4-butanediol diconiconic acid. Ester, 1,4-butanediol diconconate, pentaerythritol diconconate, sorbitol tetraconcanate, and the like.

Examples of the butenoate include ethylene glycol dimethyl acrylate, 1,4-butanediol bis acrylate, pentaerythritol dimethyl acrylate, sorbitol tetra- bis crotonate, and the like. .

Examples of the methacrylate include ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, and sorbitol tetramethacrylate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol di maleate, and sorbitol tetradecyl. Oleic acid esters and the like.

For example, the aliphatic alcohol-based esters described in JP-A-57-196231, and the Japanese Patent Publication No. Sho 57-196231, and the Japanese Patent Publication No. Sho 57-196231 Or an aromatic skeleton as described in Japanese Laid-Open Patent Publication No. Hei 59-5241, Japanese Patent Application Laid-Open No. Hei No. Hei. The amine group or the like described in the publication.

Further, specific examples of the monomer of the decylamine of the unsaturated carboxylic acid and the aliphatic polyamine compound include methylene bis-acrylamide, methylene bis-methyl acrylamide, and 1,6. - hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, diethylidene triamine methacrylamide, benzodimethyl bis decylamine, phthalic acid Bis-methyl methacrylamide, (meth) propylene decyl morpholine and the like.

Other preferred examples of the amide-based monomer include those having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate group and a hydroxyl group is also preferable, and specific examples thereof include a Japanese patent. In the polyisocyanate compound having two or more isocyanate groups in one molecule, a vinyl group-containing monomer having a hydroxyl group represented by the following formula (1) is contained in one molecule, and two of them are contained in one molecule, which is described in JP-A-48-41708. The above polymerizable vinyl urethane compound or the like.

CH ₂ =C(R ¹ )COOCH ₂ CH(R ² )OH (1)

(wherein, in the 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 one or more cyclic ether groups such as an epoxy group or an oxetanyl group in the molecule can be preferably used as the ultraviolet curable resin (polymerizable compound).

The cationically polymerizable compound may, for example, be a curable compound containing a ring-opening polymerizable group, and among them, a hardening compound containing a heterocyclic group is particularly preferable. Examples of such a curable compound include an epoxy derivative, an oxetane derivative, a tetrahydrofuran derivative, a cyclic lactone derivative, and a cyclic carbonate derivative. A cyclic imine ether such as an oxazoline derivative or a vinyl ether is preferable, and among them, an epoxy derivative, an oxetane derivative, and a vinyl ether are preferable.

Examples of preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxy resins, and polyfunctional alicyclic epoxy resins.

Specific examples of the glycidyl ether-based compound include diglycidyl ethers (for example, ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether) and trifunctional or higher glycidyl ethers (for example). For example, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl isocyanurate trihydroxyethyl ester, etc., and tetrafunctional or higher glycidyl ethers (eg sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenolic novolac resin, etc.), alicyclic epoxy (eg Celloxide 2021P) , Celloxide 2081, Epolead GT-301, Epolead GT-401 (above manufactured by Daicel Chemical Industry Co., Ltd.), EHPE (Daisai Chemical Industry Co., Ltd.) (manufactured by the company), phenolic novolac resin polycyclohexyl epoxide methyl ether, etc., oxetane (for example, OX-SQ, PNOX-1009 (manufactured by Toagosei Co., Ltd.), etc.).

As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. The "alicyclic epoxy group" refers to a partial structure in which a double bond of a cycloolefin ring such as a cyclopentenyl group or a cyclohexenyl group is epoxidized with a suitable oxidizing agent such as hydrogen peroxide or a peracid.

The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy compound having two or more epoxycyclohexane groups or epoxycyclopentyl groups in one molecule. Specific examples of the alicyclic epoxy compound include 4-vinylcyclohexene dioxide and carboxylic acid (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl ester. , bis(3,4-epoxycyclohexyl) adipate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl)ether, Di(2,3-epoxy-6-methylcyclohexylmethyl) dicarboxylate, dicyclopentadiene dioxide, and the like.

A glycidyl compound having an epoxy group which does not have an alicyclic structure in the molecule may be used alone or in combination with the above alicyclic epoxy compound.

Examples of such a usual glycidyl compound include a glycidyl ether compound or a glycidyl ester compound, and a glycidyl ether compound is preferably used in combination.

Specific examples of the glycidyl ether compound include 1,3-bis(2,3-epoxypropoxy)benzene, bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol. An aromatic glycidyl ether compound such as a novolak type epoxy resin, a cresol novolak type epoxy resin, or a trisphenol methane type epoxy resin, 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol An aliphatic glycidyl ether compound such as diglycidyl ether or trimethylolpropane triglycidyl ether. Examples of the glycidyl ester include a glycidyl ester of a linolenic acid dimer.

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

The outermost layer forming ink 4A preferably contains the above-mentioned hardening component, particularly selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and polyether aliphatic (meth)acrylic acid. One or more of a group consisting of a urethane oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate . Thereby, the outermost layer forming ink 4A can be hardened at a more appropriate curing speed, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Moreover, the mechanical strength and shape stability of the outermost layer 7 formed by curing the outermost layer forming ink 4A can be particularly excellent. As a result, the strength, durability, and reliability of the three-dimensional shaped article 1 can be made particularly excellent.

In addition, by containing these hardening components, the cured product of the outermost layer forming ink 4A can be made to have particularly low solubility and swelling property against various solvents (for example, water). As a result, in the sacrificial layer removing step, the sacrificial layer 8 can be more reliably removed with higher selectivity, and the unintended deformation caused by the defect or the like of the outermost layer 7 can be prevented. As a result, the dimensional accuracy of the three-dimensional shaped object 1 can be made more sure.

Moreover, since the swellability (absorbability of the solvent) of the cured product of the outermost layer forming ink 4A can be made low, for example, the drying treatment after the sacrificial layer removing step and the subsequent processing can be omitted or simplified. Moreover, since the solvent resistance of the three-dimensional shaped object 1 finally obtained is also improved, the reliability of the three-dimensional shaped object 1 is extremely high.

In particular, when the outermost layer forming ink 4A contains 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, the following effects can be obtained: it is difficult to be inhibited by oxygen and can be hardened with low energy, and is promoted. The copolymerization of other monomers is included to increase the strength of the shaped object.

In addition, when the outermost layer forming ink 4A contains a polyether aliphatic (meth) acrylate urethane oligomer, the effect of increasing the strength and the high toughness of the shaped article can be obtained.

In addition, when the outermost layer forming ink 4A contains 2-hydroxy-3-phenoxypropyl (meth)acrylate, the effect of having flexibility and improving the elongation at break can be obtained.

Further, if the outermost layer forming ink 4A contains 4-hydroxybutyl (meth)acrylate, The effect of improving the adhesion to PMMA (polymethyl methacrylate), PEMA (polyethylmethacrylate) particles, cerium oxide particles, metal particles, and the like is improved. The strength of the object.

The outermost layer forming ink 4A contains the above specific hardening component (selected from 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, polyether aliphatic (meth)acrylic acid amide. When one or two or more of the group consisting of an ester oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, The ratio of the specific hardening component to the entire hardening component constituting the outermost layer forming ink 4A is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass. Thereby, the effects as described above are more prominently exhibited.

The content of the hardening component in the outermost layer forming ink 4A is preferably 80% by mass or more and 97% by mass or less, more preferably 85% by mass or more and 95% by mass or less.

Thereby, the mechanical strength of the three-dimensional shaped object 1 finally obtained can be made particularly excellent. Moreover, the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

(polymerization initiator)

Further, the outermost layer forming ink 4A preferably contains a polymerization initiator.

Thereby, the curing speed of the outermost layer forming ink 4A when the three-dimensional shaped object 1 is produced can be improved, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

As the polymerization initiator, for example, a photoradical polymerization initiator (aromatic ketone, fluorenylphosphine oxide compound, aromatic sulfonium compound, organic peroxide, thio compound (9-oxygen sulphur) can be used. a compound, a thienyl-containing compound, etc., a hexaarylbiimidazole compound, a ketoxime compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, an alkane The base amine compound or the like) or a photocationic polymerization initiator or the like, specifically, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy group -2-phenylacetophenone, Ketone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4 , 4'-diaminobenzophenone, mischrone, benzoin propyl ether, benzoin ethyl ether, benzoin dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2 -methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 9-oxosulfur Diethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, bis(2,4,6-trimethylbenzylidene)-benzene Phosphine oxide, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, 2,4-diethyl 9-oxosulfur And bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, etc., one type selected from these, or two or more types can be used. Use in combination.

Among them, as the polymerization initiator constituting the outermost layer forming ink 4A, it is preferred to contain bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethyl. Benzobenzyl-diphenyl-phosphine oxide.

By containing such a polymerization initiator, the outermost layer forming ink 4A can be cured at a more appropriate curing speed, and the productivity of the three-dimensional shaped article 1 can be made particularly excellent.

Moreover, the mechanical strength and shape stability of the outermost layer 7 formed by curing the outermost layer forming ink 4A can be particularly excellent. As a result, the strength, durability, and reliability of the three-dimensional shaped object 1 can be made particularly excellent.

In particular, if the outermost layer forming ink 4A and the sacrificial layer forming ink 4B described in detail each contain bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide as a polymerization initiator, The outermost layer forming ink 4A and the sacrificial layer forming ink 4B can more preferably control the curing rate. As a result, the productivity of the three-dimensional shaped object 1 can be further improved.

When the outermost layer forming ink 4A and the sacrificial layer forming ink 4B described below each contain bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide as a polymerization initiator, It is preferable that the content of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide in the outermost layer forming ink 4A is higher than that in the sacrificial layer forming ink 4B (2, 4) , the content of 6-trimethyl benzhydryl)-phenylphosphine oxide.

Thereby, the outermost layer forming ink 4A and the sacrificial layer forming ink 4B can be hardened at a higher speed.

The content of the polymerization initiator in the outermost layer forming ink 4A is not particularly limited, and is preferably higher than the content of the polymerization initiator in the sacrificial layer forming ink 4B.

Thereby, the outermost layer forming ink 4A and the sacrificial layer forming ink 4B can be hardened at a higher speed.

Further, for example, by adjusting the processing conditions of the hardening step, the degree of hardening of the outermost layer 7 can be sufficiently increased after the completion of the hardening step, and the degree of polymerization of the sacrificial layer 8 can be relatively lowered. As a result, it becomes possible to more easily remove the sacrificial layer 8 in the sacrificial layer removing step, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Further, since it is not necessary to increase the amount of the energy line to be irradiated more than necessary, it is also preferable from the viewpoint of energy saving.

In particular, the content ratio of the polymerization initiator in the outermost layer forming ink 4A is X ₁ [% by mass], and the content ratio of the polymerization initiator in the sacrificial layer forming ink 4B is set to X ₂ [quality] In the case of %], it is preferable to satisfy the relationship of 1.05 ≦ X ₁ / X ₂ ≦ 2.0, and it is more preferable to satisfy the relationship of 1.1 ≦ X ₁ / X ₂ ≦ 1.5.

Thereby, the outermost layer forming ink 4A and the sacrificial layer forming ink 4B can be hardened at a higher speed, and the productivity of the three-dimensional shaped object 1 can be further improved.

The specific value of the content ratio of the polymerization initiator in the outermost layer forming ink 4A is preferably 3.0% by mass or more and 18% by mass or less, more preferably 5.0% by mass or more and 15% by mass or less.

Thereby, the outermost layer forming ink 4A can be hardened at a more appropriate curing speed, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Moreover, the mechanical strength and shape stability of the outermost layer 7 formed by curing the outermost layer forming ink 4A can be particularly excellent. As a result, the strength, durability, and reliability of the three-dimensional shaped object 1 can be made particularly excellent.

The preferred embodiment of the blending ratio of the curable resin and the polymerization initiator in the outermost layer forming ink 4A (except for the "other components" described below) is, of course, the most preferred embodiment of the present invention. The composition of the ink for forming the outer layer is not limited to the one described below.

"Assembling ratio example"

. 2-(2-vinyloxyethoxy)ethyl acrylate: 32 parts by mass

. Polyether aliphatic urethane oligomer: 10 parts by mass

. 2-hydroxy-3-phenoxypropyl acrylate: 13.75 parts by mass

. Dipropylene glycol diacrylate: 15 parts by mass

. 4-hydroxybutyl acrylate: 20 parts by mass

. Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide: 5 parts by mass

. 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide: 4 parts by mass

In the case of the above-described blending, the effects as described above are more prominently exhibited.

(other ingredients)

Further, the outermost layer forming ink 4A may contain components other than the above.

Examples of such a component include various coloring agents such as pigments and dyes; dispersing agents; surfactants; sensitizers; polymerization accelerators; solvents; penetration promoters; wetting agents (humectants); Mold; preservative; antioxidant; UV absorber; chelating agent; pH adjuster; tackifier; filler; anti-agglomerating agent; defoamer.

In particular, by including the coloring agent in the outermost layer forming ink 4A, the three-dimensional shaped object 1 colored in a color corresponding to the color of the coloring agent can be obtained.

In particular, by containing a pigment as a coloring agent, the light resistance of the outermost layer forming ink 4A and the three-dimensional shaped article 1 can be improved. As the pigment, any of an inorganic pigment and an organic pigment can be used.

Examples of the inorganic pigment include carbon black (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, titanium oxide, and the like, and one selected from the group consisting of, or Two or more types are used in combination.

Among the above inorganic pigments, in order to exhibit a preferable white color, titanium oxide is preferred.

Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelating azo pigments, phthalocyanine pigments, anthraquinone and anthraquinone pigments, anthraquinone pigments, and quinacridone. Pigment, two Polycyclic pigments such as alkane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, dye chelate compounds (eg basic dye type chelate, acid dye type chelate, etc.), dyed color a lake (basic dye type lake, acid dye type lake), a nitro pigment, a nitroso pigment, a nigrosine, a fluorescent pigment, or the like, which may be selected from one of these, or 2 Use in combination of the above.

More specifically, examples of the carbon black used as the black pigment include No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, and MA8. , MA100, No. 2200B, etc. (above, manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, 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, etc. (above CABOT JAPAN KK), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (above made by Degussa) and so on.

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

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

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

As the pigment of cyan, for example, CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, 66, CI reduction blue 4, 60, etc.

Further, examples of the pigment other than the above include CI Pigment Green 7, 10, CI Pigment Brown 3, 5, 25, and 26, and CI Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, and 24 , 34, 36, 38, 40, 43, 63, etc.

When the outermost layer forming ink 4A contains a pigment, the average particle diameter of the pigment is preferably 300 nm or less, more preferably 50 nm or more and 250 nm or less.

Thereby, the discharge stability of the outermost layer forming ink 4A or the dispersion stability of the pigment in the outermost layer forming ink 4A can be particularly excellent, and an image excellent in image quality can be formed.

In addition, as the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye may be used, and one type of these may be used, or two or more types may be used in combination.

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

When the outermost layer forming ink 4A contains a coloring agent, the content of the coloring agent in the outermost layer forming ink 4A 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 outermost layer forming ink 4A contains titanium oxide as a coloring agent, the content of titanium oxide in the outermost layer forming ink 4A is preferably 12% by mass or more and 18% by mass or less, more preferably 14%. The mass% or more and 16 mass% or less. Thereby, particularly excellent concealability can be obtained.

When the outermost layer forming ink 4A contains a pigment, the dispersing agent is further contained, whereby the dispersibility of the pigment can be further improved.

The dispersing agent is not particularly limited, and examples thereof include a dispersing agent conventionally used in the preparation of a pigment dispersion liquid such as a polymer dispersing agent.

Specific examples of the polymer dispersant include polyoxyalkylene alkyl polyalkyleneamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamines, and polycondensates. One or more of the quinone imine, the polyurethane, the amine-based polymer, the ruthenium-containing polymer, the sulfur-containing polymer, the fluoropolymer, and the epoxy resin are the main components.

Examples of the commercial product of the polymer dispersant include Ajisper Series manufactured by Ajinomoto Fine-Techno Co., Ltd., and Solsperse available from Noveon Corporation. Series (Solsperse 36000, etc.), Disperbyk Series manufactured by BYK, and Disparlon Series manufactured by Nanben Chemical Co., Ltd.

When the outermost layer forming ink 4A contains a surfactant, the rubbing resistance of the three-dimensional shaped object 1 can be further improved.

The surfactant is not particularly limited, and for example, a polyester-modified polyfluorene or a polyether-modified polyfluorene or the like which is a polyfluorene-based surfactant can be used. Among them, a polyether-modified polydimethylene is preferably used. A dimethyl oxane or a polyester modified polydimethyl siloxane.

Specific examples of the surfactant include BYK-347, BYK-348, BYK-UV3500, 3510, 3530, and 3570 (the above are trade names of BYK Corporation).

Further, the outermost layer forming ink 4A may contain a solvent.

By this, the viscosity adjustment of the outermost layer forming ink 4A can be preferably performed. Even if the outermost layer forming ink 4A is a component having a high viscosity, the ejection of the outermost layer forming ink 4A by the ink jet method can be stabilized. Sex becomes 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 and n-propyl acetate; Acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl A ketone such as n-butyl ketone, diisopropyl ketone or etidyl acetone; or an alcohol such as ethanol, propanol or butanol, or the like, may be used alone or in combination of two or more. .

Moreover, the viscosity of the outermost layer forming ink 4A is preferably 10 mPa. Above s and 30mPa. Below s, more preferably 15mPa. Above s and 25mPa. s below.

Thereby, the discharge stability of the outermost layer forming ink 4A by the inkjet method can be made particularly excellent. In the present specification, the viscosity refers to a value measured at 25 ° C using an E-type viscometer (VISCONIC ELD manufactured by Tokyo Keiki Co., Ltd.).

Further, when manufacturing the three-dimensional shaped object 1, a plurality of outermost layer forming inks 4A may be used.

For example, the outermost layer forming ink 4A (color ink) containing a coloring agent and the outermost layer forming ink 4A (clear ink) containing no coloring agent may be used.

By this, for example, the outermost layer forming ink 4A containing a coloring agent can be used as the outermost layer forming ink 4A applied to the region which affects the appearance and color tone of the three-dimensional shaped article 1, and the most coloring-free ink can be used. The outer layer forming ink 4A is advantageous as the outermost layer forming ink 4A which is applied to a region which does not affect the appearance and color tone of the three-dimensional shaped article 1, and the production cost of the three-dimensional shaped article 1 is lowered.

Further, in the three-dimensional shaped article 1 finally obtained, a plurality of outermost layer forming inks 4A may be used in combination as follows, that is, the outer surface of the region formed using the outermost layer forming ink 4A containing the coloring agent may be used. A region (coating layer) formed by the ink for forming the outermost layer containing the coloring agent.

The portion containing the coloring agent (especially the pigment) is more brittle than the portion not containing the coloring agent, and is liable to cause damage or defects, but is formed by using the outermost layer containing no coloring agent in the vicinity of the surface other than the three-dimensional shaped object. The area formed by the ink can effectively prevent the above problems.

Further, for example, a plurality of outermost layer forming inks 4A containing coloring agents having different compositions may be used.

Thereby, the color reproduction region which can be expressed can be enlarged by the combination of the outermost layer forming inks 4A.

When a plurality of outermost layer forming inks 4A are used, it is preferable to use at least the cyan outermost layer forming ink 4A, the reddish (magenta) outermost layer forming ink 4A, and yellow (yellow). The outermost layer forming ink 4A.

Thereby, the color reproduction region which can be expressed can be further enlarged by the combination of the outermost layer forming inks 4A.

Further, by using the white outermost layer forming ink 4A in combination with the other colored outermost layer forming ink 4A, for example, the following effects can be obtained.

In other words, the three-dimensional shaped object 1 finally obtained can have a first region which is provided with white for the outermost layer forming ink 4A, and a white region which is provided on the outer surface side of the first region and which is provided with white. A region (second region) of the colored outermost layer forming ink 4A. Thereby, the first region of the white ink-forming outermost layer forming ink 4A can be made to be concealed, and the saturation of the three-dimensional shaped object 1 can be further improved.

Further, as described above, the effect of obtaining a fine texture and the effect of improving the saturation can be synergistic, and the aesthetic appearance (aesthetic) of the three-dimensional shaped object 1 is particularly excellent.

Further, as the bonding ink 4C, a clear ink containing no coloring agent may be used, and a white ink may be used.

<Sacrificial layer forming ink>

The sacrificial layer forming ink 4B contains at least a curable resin (hardening component).

(curable resin)

The curable resin (hardening component) constituting the sacrificial layer forming ink 4B is, for example, the same as the curable resin (hardening component) exemplified as the constituent component of the outermost layer forming ink 4A.

In particular, the curable resin (hardening component) constituting the sacrificial layer forming ink 4B and the curable resin (hardening component) constituting the outermost layer forming ink 4A described above are preferably cured by the same kind of energy ray.

Thereby, the configuration of the three-dimensional shaped object manufacturing apparatus can be effectively prevented from being complicated, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent. Moreover, the surface shape of the three-dimensional shaped object 1 can be more reliably controlled.

The sacrificial layer forming ink 4B preferably contains various hardening components, particularly selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, and polyethylene glycol (a) One or two or more of the group consisting of acrylate and (meth)acryl decylmorpholine and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

Thereby, the sacrificial layer forming ink 4B can be hardened by a more appropriate hardening speed, and The productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Further, the sacrificial layer 8 formed by curing the sacrificial layer forming ink 4B can be particularly excellent in mechanical strength and shape stability. As a result, when the three-dimensional shaped object 1 is manufactured, the lower layer (first layer) of the sacrificial layer 8 can more preferably support the outermost layer forming ink 4A for forming the upper layer (the second layer). Therefore, it is possible to more preferably prevent unintended deformation (especially sag, etc.) of the outermost layer 7 (the sacrificial layer 8 of the first layer functions as a supporting material), and the resulting three-dimensional shaped object 1 can be obtained. The dimensional accuracy has become even more excellent.

In particular, when the sacrificial layer forming ink 4B contains (meth) acryloyl morpholine, the following effects can be obtained.

That is, the (meth) propylene hydrazinomorpholine is in a state of not being completely hardened even when the hardening reaction proceeds (a polymer of (meth) acryloyl morpholine which is not completely cured), and It has a higher solubility in various solvents such as water. Therefore, in the sacrificial layer removing step as described above, it is possible to more effectively prevent the occurrence of defects in the outermost layer 7, and to selectively and surely remove the sacrificial layer 8 with high efficiency. As a result, the three-dimensional shaped object 1 of a desired form can be obtained with high reliability and productivity.

Further, when the sacrificial layer forming ink 4B contains tetrahydrofurfuryl (meth) acrylate, the following effects can be obtained: the flexibility after curing is maintained, and the gel is easily formed by the treatment of removing the liquid of the sacrificial layer 8. Shape, thus improving the removal.

In addition, when the sacrificial layer forming ink 4B contains ethoxyethoxyethyl (meth)acrylate, the following effects can be obtained: even after curing, the tackiness is likely to remain, and the liquid using the sacrificial layer 8 can be improved. Removal.

Further, when the sacrificial layer forming ink 4B contains polyethylene glycol di(meth)acrylate, the effect of improving the solubility in the liquid when the liquid in which the sacrificial layer 8 is removed is mainly composed of water is obtained. And make removal easy.

The sacrificial layer forming ink 4B contains the above specific hardening component (selected from tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol (a) In the case of one or two or more of the group consisting of acrylate and (meth)acryl hydrazinomorpholine, the specific hardening component is all the hardening component with respect to the ink for forming the sacrificial layer forming ink 4B. The ratio is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass. Thereby, the effects as described above are more prominently exhibited.

The content of the hardening component in the sacrificial layer forming ink 4B is preferably 83% by mass or more and 98.5% by mass or less, more preferably 87% by mass or more and 95.4% by mass or less.

Thereby, the stability of the shape of the formed sacrificial layer 8 can be made particularly excellent, and the unit layer of the lower side can be more unintentionally deformed when the unit layer is overlapped when the three-dimensional shaped object 1 is manufactured. The upper unit layer can be preferably supported. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 1 can be made particularly excellent. Moreover, the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

(polymerization initiator)

Further, the sacrificial layer forming ink 4B preferably contains a polymerization initiator.

Thereby, the curing speed of the sacrificial layer forming ink 4B when the three-dimensional shaped object 1 is produced can be appropriately increased, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Further, the stability of the shape of the sacrificial layer 8 to be formed can be particularly excellent, and the unit layer on the lower side can be more unintentionally deformed when the unit layer is overlapped when the three-dimensional shaped object 1 is produced. The unit layer on the upper side can be preferably supported. As a result, the dimensional accuracy of the finally obtained three-dimensional shaped object 1 can be made particularly excellent.

The polymerization initiator which constitutes the sacrificial layer forming ink 4B is, for example, the same as the polymerization initiator which is exemplified as the constituent component of the outermost layer forming ink 4A.

Among them, the sacrificial layer forming ink 4B preferably contains bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl. Base-phosphine oxide as a polymerization initiator.

By containing such a polymerization initiator, the sacrificial layer can be more suitably hardened. The formation ink 4B is hardened, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Further, the sacrificial layer 8 formed by curing the sacrificial layer forming ink 4B can be particularly excellent in mechanical strength and shape stability. As a result, when the three-dimensional shaped object 1 is manufactured, the lower layer (first layer) of the sacrificial layer 8 can more preferably support the outermost layer forming ink 4A for forming the upper layer (the second layer). Therefore, it is possible to more preferably prevent unintended deformation (especially sag, etc.) of the outermost layer 7 (the sacrificial layer 8 of the first layer functions as a supporting material), and the resulting three-dimensional shaped object 1 can be obtained. The dimensional accuracy has become even more excellent.

The specific value of the content ratio of the polymerization initiator in the sacrificial layer forming ink 4B is preferably 1.5% by mass or more and 17% by mass or less, more preferably 4.6% by mass or more and 13% by mass or less.

Thereby, the sacrificial layer forming ink 4B can be hardened at a more appropriate curing speed, and the productivity of the three-dimensional shaped object 1 can be made particularly excellent.

Further, the sacrificial layer 8 formed by curing the sacrificial layer forming ink 4B can be particularly excellent in mechanical strength and shape stability. As a result, when the three-dimensional shaped object 1 is manufactured, the lower layer (first layer) of the sacrificial layer 8 can more preferably support the outermost layer forming ink 4A for forming the upper layer (the second layer). Therefore, it is possible to more preferably prevent unintended deformation (especially sag, etc.) of the outermost layer 7 (the sacrificial layer 8 of the first layer functions as a supporting material), and the resulting three-dimensional shaped object 1 can be obtained. The dimensional accuracy has become even more excellent.

The preferred embodiment of the blending ratio of the curable resin and the polymerization initiator in the sacrificial layer forming ink 4B (the ink composition excluding the "other components" described below) is, of course, the sacrifice in the present invention. The composition of the layer forming ink is not limited to the one described below.

"Preparation ratio example 1"

. Tetrahydrofurfuryl acrylate: 36 parts by mass

. Ethoxyethoxyethyl acrylate: 55.75 parts by mass

. Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide: 3 parts by mass

. 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide: 5 parts by mass

"Preparation ratio example 2"

. Dipropylene glycol diacrylate: 37 parts by mass

. Polyethylene glycol (400) diacrylate: 55.85 parts by mass

. Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide: 3 parts by mass

. 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide: 4 parts by mass

"Preparation ratio example 3"

. Tetrahydrofurfuryl acrylate: 36 parts by mass

. Propylene decylmorpholine: 55.75 parts by mass

. Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide: 3 parts by mass

. 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide: 5 parts by mass

"Preparation ratio example 4"

. 2-(2-vinyloxyethoxy)ethyl acrylate: 36 parts by mass

. Polyethylene glycol (400) diacrylate: 55.75 parts by mass

. Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide: 3 parts by mass

. 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide: 5 parts by mass

In the case of the above-described blending, the effects as described above are more prominently exhibited.

(other ingredients)

Further, the sacrificial layer forming ink 4B may contain components other than the above. Examples of such a component include various coloring agents such as pigments and dyes; dispersing agents; surfactants; sensitizers; polymerization accelerators; solvents; penetration promoters; wetting agents (humectants); Mold; preservative; antioxidant; UV absorber; chelating agent; pH adjuster; tackifier; filler; anti-agglomerating agent; defoamer.

In particular, by causing the sacrificial layer forming ink 4B to contain a coloring agent, the visibility of the sacrificial layer 8 is improved, and it is possible to more reliably prevent at least a part of the sacrificial layer 8 from being unintentionally in the finally obtained three-dimensional shaped object 1. Residual.

The coloring agent constituting the sacrificial layer forming ink 4B is, for example, the same as the coloring agent exemplified as the constituent component of the outermost layer forming ink 4A, but preferably, it is the surface of the self-made three-dimensional shaped object 1 When viewed in the normal direction, the coloring agent of a color different from the color of the outermost layer 7 (the color to be visually recognized in the appearance of the three-dimensional shaped object 1) which is overlapped with the sacrificial layer 8 formed of the sacrificial layer forming ink 4B is different. Thereby, the effects as described above are more prominently exhibited.

When the sacrificial layer forming ink 4B contains a pigment, the dispersing agent is further contained, whereby the dispersibility of the pigment can be further improved. The dispersing agent constituting the sacrificial layer forming ink 4B is, for example, the same as the dispersing agent exemplified as the constituent component of the outermost layer forming ink 4A.

Moreover, the viscosity of the sacrificial layer forming ink 4B is preferably 10 mPa. Above s and 30mPa. Below s, more preferably 15mPa. Above s and 25mPa. s below.

Thereby, the discharge stability of the sacrificial layer forming ink 4B by the inkjet method can be made particularly excellent.

In addition, the ink set may include at least one of the outermost layer forming ink 4A, at least one of the sacrificial layer forming ink 4B, and the bonded ink 4C, but may have a fourth color different from the above. Ink.

4. Three-dimensional forming composition

Next, the composition for three-dimensional forming will be described in detail.

The three-dimensional forming composition contains a three-dimensional forming powder and a water-soluble resin 64.

Hereinafter, each component will be described in detail.

≪Three-dimensional shape powder ≫

The three-dimensional shape forming powder includes a plurality of particles 63.

As the particles 63, any particles may be used, but it is preferable to contain porous particles (porous particles). Thereby, when the three-dimensional shaped object 1 is manufactured, the ink contained in the bonded ink 4C can be contained. The curable resin 44 is preferably infiltrated into the pores, and as a result, it can be preferably used for the production of a three-dimensional shaped article excellent in mechanical strength.

Examples of the constituent material of the porous particles constituting the powder for three-dimensional forming include an inorganic material, an organic material, and a composite of the above.

Examples of the inorganic material constituting the porous particles include various metals or metal compounds. Examples of the metal compound include various metal oxides such as cerium oxide, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide, magnesium oxide, and potassium titanate; magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Various metal hydroxides, various metal nitrides such as tantalum nitride, titanium nitride, and aluminum nitride; various metal carbides such as tantalum carbide and titanium carbide; various metal sulfides such as zinc sulfide; various types such as calcium carbonate and magnesium carbonate. Metal carbonate; sulfate of various metals such as calcium sulfate and magnesium sulfate; citrate of various metals such as calcium citrate and magnesium citrate; phosphate of various metals such as calcium phosphate; various metals such as aluminum borate and magnesium borate Borate or such composites and the like.

Examples of the organic material constituting the porous particles include a synthetic resin, a natural polymer, and the like, and more specifically, a polyethylene resin, polypropylene, polyethylene oxide, polypropylene oxide, and poly(ethylene) Polyimide; polyurethane; polyurea; polyester; polyoxyl resin; acrylic polyoxyl resin; polymethyl methacrylate and the like (meth) acrylate as a constituent a polymer; a methyl methacrylate cross-linking polymer such as a (meth) acrylate as a cross-linking polymer constituting a monomer (ethylene-acrylic copolymer resin, etc.); nylon 12, nylon 6, copolymerized nylon Isoguanamine resin; polyimine; carboxymethyl cellulose; gelatin; starch; chitin;

Among them, the porous particles preferably contain an inorganic material, more preferably a metal oxide, and more preferably contain cerium oxide. Thereby, characteristics such as mechanical strength and light resistance of the three-dimensional shaped article can be made particularly excellent. Further, in particular, if the porous particle contains cerium oxide, the above effects can be exhibited more remarkably. Further, since the cerium oxide is also excellent in fluidity, it is advantageous for forming a layer having a higher uniformity of thickness, and can be made into three The productivity and dimensional accuracy of the dimensional shape are particularly excellent.

As the cerium oxide, a commercially available one can be preferably used. Specifically, for example, Mizukasil P-526, Mizukasil P-801, Mizukasil NP-8, Mizukasil P-802, Mizukasil P-802Y, Mizukasil C-212, Mizukasil P-73, Mizukasil P-78A, Mizukasil P -78F, Mizukasil P-87, Mizukasil P-705, Mizukasil P-707, Mizukasil P-707D, Mizukasil P-709, Mizukasil C-402, Mizukasil C-484 (above manufactured by Mizusawa Chemical Industry Co., Ltd.); Tokusil U, Tokusil UR, Tokusil GU, Tokusil AL-1, Tokusil GU-N, Tokusil N, Tokusil NR, Tokusil PR, Solex, Finesil E-50, Finesil T-32, Finesil X-30, Finesil X-37, Finesil X-37B, Finesil X-45, Finesil X-60, Finesil X-70, Finesil RX-70, Finesil A, Finesil B (above, manufactured by Tokuyama), Sipernat, Carplex FPS-101, Carplex CS-7 ,Carplex 22S,Carplex 80,Carplex 80D,Carplex XR,Carplex 67 (above DSL.Japan); Syloid 63, Syloid 65, Syloid 66, Syloid 77, Syloid 74, Syloid 79, Syloid 404, Syloid 620 , Syloid 800, Syloid 150, Syloid 244, Syloid 266 (above manufactured by Fuji Silysia Chemical); Nipsil AY-200, Nipsil AY-6A2, Nipsil AZ-200, Nipsil AZ-6A0, Nipsil BY-200, Nipsil BY-200, Nipsil CX-200, Nipsil CY-200, Nipsil E-150J, Nipsil E-220A, Nipsil E-200A (above is manufactured by Tosoh Silica) and the like.

Further, the porous particles are preferably subjected to a hydrophobic treatment. However, in general, the curable resin 44 contained in the binder ink 4C tends to be hydrophobic. Therefore, the curable resin 44 can be more preferably infiltrated into the pores of the porous particles by the porous particles being hydrophobized. As a result, the anchoring effect can be more significantly exerted, and the mechanical strength of the obtained three-dimensional shaped object 1 becomes more excellent. Further, if the porous particles are hydrophobized, they can be preferably reused. If more detailed, if the porous particles are In the hydrophobized treatment, the affinity of the water-soluble resin and the porous particles described below is lowered, and thus it becomes possible to prevent the water-soluble resin from entering the pores. As a result, in the production of the three-dimensional shaped article 1, the porous particles in the region where the ink is not supplied can be easily removed by washing with water or the like, and can be recovered with high purity. Therefore, by mixing the collected three-dimensional shaped powder with a water-soluble resin or the like at a specific ratio, a three-dimensional shaped powder which is surely controlled to a desired composition can be obtained.

The hydrophobization treatment for the porous particles constituting the powder for three-dimensional shape formation may be any one as long as it is a treatment for improving the hydrophobicity of the porous particles, and it is preferred to introduce a hydrocarbon group. Thereby, the hydrophobicity of the particles can be made higher. Moreover, the uniformity of the degree of hydrophobization treatment of each particle or the surface of each particle surface (including the surface inside the pore) can be easily and surely made higher.

As the compound for the hydrophobizing treatment, a decane compound containing a decyl group is preferable. Specific examples of the compound which can be used for the hydrophobizing treatment include hexamethyldiazepine, dimethyldimethoxydecane, diethyldiethoxydecane, and 1-propenylmethyldichloride. Decane, propyldimethylchlorodecane, propylmethyldichlorodecane, propyltrichlorodecane, propyltriethoxydecane, propyltrimethoxydecane, styrylethyltrimethoxydecane, ten Tetraalkyl trichlorodecane, 3-thiocyanate propyl triethoxy decane, p-tolyl dimethyl chlorodecane, p-tolyl methyl dichloro decane, p-tolyl trichloro decane, p-tolyl Trimethoxy decane, p-tolyl triethoxy decane, di-n-propyl di-n-propoxy decane, diisopropyl diisopropoxy decane, di-n-butyl di-n-butoxy decane, second Butyl di-butoxy decane, di-tert-butyl di-t-butoxy decane, octadecyl trichloro decane, octadecyl methyl diethoxy decane, octadecyl triethoxy Baseline, octadecyltrimethoxydecane, octadecyldimethylchlorodecane, octadecylmethyldichlorodecane, octadecylmethoxy Dichlorodecane, 7-octenyldimethylchloromethane, 7-octenyltrichlorodecane, 7-octenyltrimethoxydecane, octylmethyldichlorodecane, octyldimethylchlorodecane, Octyl trichlorodecane, 10-undecyl alkenyl dimethyl chlorodecane, undecyl trichloro decane, vinyl dimethyl chlorodecane, methyl octadecyl dimethoxy decane, methyl ten Dialkyldiethoxydecane, methyloctadecyldimethoxydecane, methyloctadecyldiethoxydecane, n-octylmethyldimethoxydecane, n-octylmethyldi Ethoxy decane, tridecyl dimethyl chlorodecane, tridecyl trichloro decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl Propoxy decane, methyl n-butoxy decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl Tri-n-propoxy decane, ethyl isopropoxy decane, ethyl n-butoxy decane, ethyl tri-tert-butoxy decane, ethyl tri-tert-butoxy decane, n-propyl trimethoxy decane Isobutyltrimethoxydecane, n-hexyltrimethoxydecane, cetyltrimethoxydecane, n-octyltrimethoxydecane, n-dodecyltrimethoxynonane, n-octadecyltrimethoxy Decane, n-propyltriethoxydecane, isobutyltriethoxydecane, n-hexyltriethoxydecane, cetyltriethoxydecane, n-octyltriethoxydecane, plus twelve Alkyltrimethoxydecane, n-octadecyltriethoxydecane, 2-[2-(trichlorodecylalkyl)ethyl]pyridine, 4-[2-(trichlorodecylalkyl)ethyl]pyridine, Diphenyldimethoxydecane, diphenyldiethoxydecane, 1,3-(trichlorodecylmethyl)heptadecane, dibenzyldimethoxydecane, dibenzyldiethoxy Baseline, phenyltrimethoxydecane, phenylmethyldimethoxydecane, phenyldimethylmethoxydecane, phenyldimethoxydecane, phenyldiethoxydecane, phenylmethyl Diethoxydecane, phenyldimethylethoxydecane, benzyltriethoxydecane, benzyltrimethoxydecane, benzylmethyldimethoxydecane, benzyldimethylmethoxydecane Benzyl Methoxy decane, benzyl diethoxy decane, benzyl methyl diethoxy decane, benzyl dimethyl ethoxy decane, benzyl triethoxy decane, dibenzyl dimethoxy decane, Dibenzyldiethoxydecane, 3-ethoxymethoxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, allyltrimethoxydecane, allyltriethoxy Decane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 6-(aminohexylaminopropyl)trimethoxynonane, p-aminophenyl Trimethoxy decane, p-aminophenyl ethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl ethoxy decane, 3-aminopropyl trimethoxy decane, 3-amino group Propyl triethoxy decane, ω-aminoundecyltrimethoxy decane, pentyl triethoxy decane, benzoxepane dimethylene, 5-(bicycloheptenyl) three Ethoxy decane, bis(2-hydroxyethyl)-3-aminopropyltriethoxy Alkane, 8-bromooctyltrimethoxydecane, bromophenyltrimethoxydecane, 3-bromopropyltrimethoxydecane, n-butyltrimethoxydecane, 2-chloromethyltriethoxydecane, chlorine Methyl methyl diethoxy decane, chloromethyl methyl diisopropoxy decane, p-(chloromethyl)phenyl trimethoxy decane, chloromethyl triethoxy decane, chlorophenyl triethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 2-(4-chlorosulfonylphenyl)B Trimethoxy decane, 2-cyanoethyltriethoxy decane, 2-cyanoethyltrimethoxydecane, cyanomethylphenethyltriethoxydecane, 3-cyanopropyltriethyl Oxydecane, 2-(3-cyclohexenyl)ethyltrimethoxynonane, 2-(3-cyclohexenyl)ethyltriethoxydecane, 3-cyclohexenyltrichloromethane, 2 -(3-cyclohexenyl)ethyltrichlorodecane, 2-(3-cyclohexenyl)ethyldimethylchlorodecane, 2-(3-cyclohexenyl)ethylmethyldichlorodecane , cyclohexyldimethylchlorodecane, cyclohexylethyldimethoxydecane, cyclohexylmethyldichlorodecane, cyclohexylmethyl Methoxydecane, (cyclohexylmethyl)trichlorodecane, cyclohexyltrichlorodecane, cyclohexyltrimethoxydecane, cyclooctyltrichlorodecane, (4-cyclooctenyl)trichlorodecane, cyclopentyl Trichlorodecane, cyclopentyltrimethoxydecane, 1,1-diethoxy-1-indanyl-3-ene, 3-(2,4-dinitrophenylamino)propyl Ethoxy decane, (dimethylchloroindolyl)methyl-7,7-dimethylnorbornane, (cyclohexylaminomethyl)methyldiethoxydecane, (3-cyclopentadiene) Propyl)triethoxydecane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, (decyloxymethyl)triethoxydecane, 2-hydroxy-4-(3-triethoxypropoxy) Diphenyl ketone, 3-(p-methoxyphenyl)propylmethyldichlorodecane, 3-(p-methoxyphenyl)propyltrichloromethane, p-(methylphenethyl)methyldi Chlorodecane, p-(methylphenethyl)trichlorodecane, p-(methylphenethyl)dimethylchlorodecane, 3-morpholinylpropyltrimethoxydecane, (3-glycidoxypropyl) Methyldiethoxydecane , 3-glycidoxypropyltrimethoxydecane, 1,2,3,4,7,7-hexachloro-6-methyldiethoxynonanyl-2-decane Alkene, 1,2,3,4,7,7-hexachloro-6-triethoxydecyl-2-derivative Alkene, 3-iodopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, (decylmethyl)methyldiethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyldimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, {2-(3-trimethoxydecylpropylamino)ethylamino}-3-propionic acid methyl ester, 7-octenyltrimethoxydecane, RN-α-phenylethyl -N'-triethoxydecyl propyl urea, SN-α-phenethyl-N'-triethoxydecyl propyl urea, phenethyl trimethoxy decane, phenethyl methyl two Methoxy decane, phenethyl dimethyl methoxy decane, phenethyl dimethoxy decane, phenethyl diethoxy decane, phenethyl methyl diethoxy decane, phenethyl dimethyl Ethoxy decane, phenethyltriethoxy decane, (3-phenylpropyl)dimethylchlorodecane, (3-phenylpropyl)methyldichlorodecane, N-phenylaminopropyl Trimethoxy decane, N-(triethoxydecylpropyl) dansylamine, N-(3-triethoxydecyl) -4,5-dihydroimidazole, 2-(triethoxydecylethyl)-5-(chloroethenyloxy)bicycloheptane, (S)-N-triethoxydecyl-propyl Benzyl-O-menthylcarbamate, 3-(triethoxydecylpropyl)-p-nitrobenzamide, 3-(triethoxydecyl)propyl succinic anhydride, N- [5-(Trimethoxydecyl)-2-aza-1-yloxy-pentyl]caprolactam, 2-(trimethoxydecylethyl)pyridine, N-(trimethoxydecane Benzyl)benzyl-N,N,N-trimethylammonium chloride, phenylvinyldiethoxydecane, 3-thiocyanatepropyltriethoxydecane, (tridecafluoro- 1,1,2,2-tetrahydrooctyl)triethoxydecane, N-{3-(triethoxydecyl)propyl}benzamide, (3,3,3-three Fluoropropyl)methyldimethoxydecane, (3,3,3-trifluoropropyl)trimethoxydecane, 1-trimethoxydecyl-2-(chloromethyl)phenylethane, 2- (trimethoxydecyl)ethylbenzenesulfonium azide, β-trimethoxydecylethyl-2-pyridine, trimethoxydecylpropyl diethyltriamine, N-(3-trimethoxy Base hydroxypropyl)pyrrole, N-trimethoxydecylpropyl-N,N,N-tributylammonium bromide, N- Methoxydecylpropyl-N,N,N-tributylammonium chloride, N-trimethoxydecylpropyl-N,N,N-trimethylammonium chloride, vinylmethyldiethyl Oxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, vinyl methyl dimethoxy decane, vinyl dimethyl methoxy decane, vinyl dimethyl ethoxy decane, ethylene Methyl dichloromethane, vinyl phenyl dichloro decane, vinyl phenyl diethoxy decane, vinyl phenyl dimethyl decane, vinyl phenyl methyl chloro decane, vinyl triphenoxy decane , vinyl tri-tert-butoxydecane, adamantylethyltrichlorodecane, allylphenyl trichlorodecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, 3-amine Phenoxy dimethyl vinyl decane, phenyl trichloro decane, phenyl dimethyl chloro decane, phenyl methyl dichloro decane, benzyl trichloro decane, benzyl dimethyl chloro decane, benzyl Dichlorodecane, phenethyldiisopropylchlorodecane, phenethyltrichlorodecane, phenethyldimethylchlorodecane, phenethylmethyldichlorodecane, 5-(bicycloheptenyl)trichloro Alkanes, 5-(bicycloheptenyl)triethoxydecane, 2-(bicycloheptyl)dimethylchlorodecane, 2-(bicycloheptyl)trichlorodecane, 1,4-bis(trimethoxydecane) Benzyl)benzene, bromophenyltrichlorodecane, 3-phenoxypropyldimethylchlorodecane, 3-phenoxypropyltrichlorodecane, tert-butylphenylchlorodecane, tert-butyl Phenylmethoxydecane, tert-butylphenyldichlorodecane, p-(t-butyl)phenethyldimethylchlorodecane, p-(t-butyl)phenethyltrichloromethane, 1,3 -(Chlorodimethyldecylmethyl)heptadecane, ((chloromethyl)phenylethyl)dimethylchlorodecane, ((chloromethyl)phenylethyl)methyldichloromethane, ((Chloromethyl)phenylethyl)trichlorodecane, ((chloromethyl)phenylethyl)trimethoxynonane, chlorophenyltrichlorodecane, 2-cyanoethyltrichlorodecane, 2- Cyanoethylmethyldichlorodecane, 3-cyanopropylmethyldiethoxydecane, 3-cyanopropylmethyldichlorodecane, 3-cyanopropylmethyldichlorodecane, 3- Cyanopropyl dimethyl ethoxy decane, 3-cyanopropyl methyl dichloro decane, 3-cyanopropyl trichloro decane, fluorinated alkyl decane, etc. In one kind of those selected from, or used in combination of two or more.

Among them, hexamethyldioxane is preferably used for the hydrophobizing treatment. By doing this, The particles are more hydrophobic. Moreover, the uniformity of the degree of hydrophobization treatment of each particle or the surface of each particle surface (including the surface inside the pore) can be easily and surely made higher.

When the hydrophobization treatment using a decane compound is carried out in a liquid phase, by subjecting the particles containing the decane compound to the particles to be subjected to the hydrophobization treatment, the desired reaction can be preferably carried out, and the chemisorption of the decane compound can be formed. membrane.

Further, in the case where the hydrophobization treatment using a decane compound is carried out in the vapor phase, by subjecting the particles 63 to be subjected to the hydrophobization treatment to the vapor of the decane compound, the desired reaction can be preferably carried out, and a decane compound can be formed. Chemical adsorption film.

The average particle diameter of the particles 63 constituting the three-dimensional shaped powder 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. Thereby, the mechanical strength of the three-dimensional shaped object 1 can be made particularly excellent, and the dimensional accuracy of the three-dimensional shaped object 1 can be made particularly excellent. Moreover, the fluidity of the powder for three-dimensional forming and the fluidity of the three-dimensional forming composition containing the powder for three-dimensional forming are particularly excellent, and the productivity of the three-dimensional shaped article is particularly excellent. Further, in the present invention, the average particle diameter means an average particle diameter based on a volume, and can be, for example, 50 μm by using a Coulter counter size analyzer (TA-II type manufactured by COULTER ELECTRONICS INS). The mesh was obtained by measuring a dispersion obtained by adding a sample to methanol and dispersing it for 3 minutes using an ultrasonic disperser.

The Dmax of the particles 63 constituting the three-dimensional shaped powder is preferably 3 μm or more and 40 μm or less, more preferably 5 μm or more and 30 μm or less. Thereby, the mechanical strength of the three-dimensional shaped object 1 can be made particularly excellent, and the dimensional accuracy of the three-dimensional shaped object 1 can be made particularly excellent. Moreover, the fluidity of the powder for three-dimensional forming and the fluidity of the three-dimensional forming composition containing the powder for three-dimensional forming are particularly excellent, and the productivity of the three-dimensional shaped article 1 is particularly excellent. Further, scattering of light by the particles 63 on the surface of the manufactured three-dimensional shaped object 1 can be more effectively prevented.

In the case where the particles 63 are porous particles, the porosity of the porous particles is preferably 50% or more, more preferably 55% or more and 90% or less. Thereby, the space (void) into which the curable resin enters is sufficiently obtained, and the mechanical strength of the porous particles themselves can be made excellent, and as a result, the mechanical strength of the three-dimensional shaped article 1 in which the bonding resin is infiltrated into the pores can be changed. It is particularly excellent. Further, in the present invention, the porosity of the particles means the ratio (volume ratio) of the pores existing inside the particles to the apparent volume of the particles, and the density of the particles is set to ρ [g/cm. ³ ] The value represented by {(ρ _{0 -} ρ) / ρ ₀ } × 100 when the true density of the constituent materials of the particles is ρ _{0 [} g / cm ³ ].

In the case where the particles 63 are porous particles, the average pore diameter (pore diameter) of the porous particles is preferably 10 nm or more, more preferably 50 nm or more and 300 nm or less. Thereby, the mechanical strength of the three-dimensional shaped object 1 finally obtained can be made particularly excellent.

The particles 63 constituting the three-dimensional shaped powder may have any shape, and preferably have a spherical shape. In this way, the fluidity of the powder for three-dimensional forming and the fluidity of the three-dimensional forming composition containing the powder for three-dimensional forming are particularly excellent, and the productivity of the three-dimensional shaped article 1 is particularly excellent, and three-dimensionality can be obtained. The dimensional accuracy of the shaped object 1 is particularly excellent.

The powder for three-dimensional forming may be a plurality of particles containing different conditions as described above (for example, the constituent materials of the particles described above, the type of the hydrophobization treatment, and the like).

The void ratio of the powder for three-dimensional forming is preferably 70% or more and 98% or less, more preferably 75% or more and 97.7% or less. Thereby, the mechanical strength of the three-dimensional shaped object can be made particularly excellent. In addition, the fluidity of the powder for three-dimensional forming and the fluidity of the three-dimensional forming composition containing the powder for three-dimensional forming are particularly excellent, and the productivity of the three-dimensional shaped article is particularly excellent, and the three-dimensional shape can be made. The dimensional accuracy is particularly excellent. In the present invention, the void ratio of the powder for three-dimensional forming refers to a case where all of the particles constituting the three-dimensional forming powder are contained in a container in which a powder having a three-dimensional shape is filled in a specific capacity (for example, 100 mL). The ratio of the volume of the pores to the volume of the voids existing between the particles with respect to the capacity of the container is set to the bulk density of the powder for three-dimensional forming, P [g/cm ³ ], and the powder for three-dimensional forming. The value represented by {(P _{0 -} P) / P ₀ } × 100 when the true density of the constituent material is P ₀ [g/cm ³ ].

The content of the three-dimensional forming powder in the three-dimensional forming composition is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 58% by mass or less. Thereby, the fluidity of the three-dimensional shaped composition can be sufficiently excellent, and the mechanical strength of the three-dimensional shaped article 1 finally obtained can be particularly excellent.

≪Water-soluble resin ≫

The three-dimensional forming composition contains a plurality of particles 63 and a water-soluble resin 64. By containing the water-soluble resin 64, the particles 63 can be bonded (temporarily fixed) to each other (see FIG. 4), and the unintentional scattering or the like of the particles 63 can be effectively prevented. Thereby, it is possible to improve the safety of the worker or the dimensional accuracy of the manufactured three-dimensional shaped object 1.

In the present invention, the water-soluble resin may be at least a part of which is soluble in water. For example, the solubility in water at 25 ° C (the mass of water soluble in 100 g) is 5 [g/ 100 g of water or more, more preferably 10 [g/100 g of water] or more.

Examples of the water-soluble resin 64 include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactam diol, sodium polyacrylate, polypropylene decylamine, and modified polyamine. Synthetic polymers such as polyethyleneimine, polyethylene oxide, random copolymer of ethylene oxide and propylene oxide, corn starch, mannan, pectin, agar, alginic acid, dextran, A natural polymer such as bone glue or gelatin, a semi-synthetic polymer such as carboxymethyl cellulose, hydroxyethyl cellulose, oxidized starch or modified starch, or the like, or one or more selected from the group consisting of And use.

Examples of the water-soluble resin product include methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "Metolose SM-15"), and hydroxyethyl cellulose (manufactured by Fuji Chemical Co., Ltd.: trade name "AL-15" ”, hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.: trade name “HPC-M”), carboxymethyl cellulose (manufactured by Nichirin Chemical Co., Ltd.: trade name “CMC-30”), sodium starch phosphate (I) (Songgu Chemical Company manufacture: trade name "Hoster 5100"), polyvinylpyrrolidone (manufactured by Tokyo Chemical Co., Ltd.: trade name "PVPK-90"), methyl vinyl ether/maleic anhydride copolymer (manufactured by GAF Gantrez Co., Ltd.) : Product name "AN-139"), Polyacrylamide (made by Wako Pure Chemical Industries, Ltd.), Modified Polyamide (modified nylon) (manufactured by Toray Industries, Inc., trade name "AQ Nylon"), Polyepoxy Alkane (manufactured by Steel Chemical Co., Ltd.: trade name "PEO-1", manufactured by Mingcheng Chemical Industry Co., Ltd.: trade name "Alkox"), ethylene oxide/propylene oxide random copolymer (manufactured by Mingcheng Chemical Industry Co., Ltd.: trade name "Alkox EP"), sodium polyacrylate (Wako Pure Chemicals), carboxyvinyl polymer/crosslinked acrylic water-soluble resin (manufactured by Sumitomo Seiko Co., Ltd.: trade name "Aqupec").

In the case where the water-soluble resin 64 is polyvinyl alcohol, the mechanical strength of the three-dimensional shaped article 1 can be made particularly excellent. Further, by adjusting the degree of saponification or the degree of polymerization, the characteristics (e.g., water solubility, water resistance, etc.) of the water-soluble resin 64 or the characteristics of the three-dimensional forming composition can be more preferably controlled (e.g., viscosity, fixing force of the particles 63, wetting Sex, etc.). Therefore, it is possible to better cope with the manufacture of a plurality of three-dimensional shaped objects 1. Further, among various water-soluble resins, polyvinyl alcohol is inexpensive and stable in supply. Therefore, it is possible to suppress the production cost and to manufacture the stable three-dimensional shaped object 1.

When the water-soluble resin 64 contains polyvinyl alcohol, the degree of saponification of the polyvinyl alcohol is preferably 85 or more and 90 or less. Thereby, the decrease in the solubility of polyvinyl alcohol to water can be suppressed. Therefore, when the composition for three-dimensional forming contains water, the decrease in the adhesion between the adjacent unit layers can be more effectively suppressed.

When the water-soluble resin 64 contains polyvinyl alcohol, the degree of polymerization of the polyvinyl alcohol is preferably 300 or more and 1,000 or less. Therefore, when the composition for three-dimensional forming contains water, the mechanical strength of each unit layer or the adhesion between adjacent unit layers can be made particularly excellent.

Further, in the case where the water-soluble resin 64 is polyvinylpyrrolidone (PVP), the following effects can be obtained. That is, polyvinylpyrrolidone is used for various materials such as glass, metal, and plastic. Since the adhesiveness of the three-dimensional shaped composition layer 6' is particularly excellent in the strength and shape stability of the portion in which the ink is not provided, the dimensional accuracy of the finally obtained three-dimensional shaped article 1 is particularly excellent. . Further, since polyvinylpyrrolidone exhibits high solubility in various organic solvents, when the three-dimensional forming composition contains an organic solvent, the fluidity of the three-dimensional forming composition can be particularly excellent. It is preferable to form the three-dimensional forming composition layer 6' which is more effective in preventing undesired thickness unevenness, and the dimensional accuracy of the finally obtained three-dimensional shaped object 1 can be made particularly excellent. Further, since polyvinylpyrrolidone has a moderate affinity with the powder for three-dimensional forming, it is difficult to sufficiently cause entry into the pores 611 as described above, and on the other hand, the wettability to the surface of the particles 63 is relatively high. . Therefore, the function of temporarily fixing as described above can be more effectively exerted. Further, since the polyvinylpyrrolidone has an antistatic function, when the ungelatinized powder is used as the three-dimensional forming composition 1 in the filling step, the powder can be effectively prevented from scattering. Further, when a gelatinized composition is used as a three-dimensional forming composition in the filling step, if the paste-form three-dimensional forming composition contains polyvinylpyrrolidone, it can be effectively prevented from being used in a three-dimensional forming composition. Entrained air bubbles can more effectively prevent defects caused by entrained air bubbles in the filling step.

When the water-soluble resin 64 contains polyvinylpyrrolidone, the weight average molecular weight of the polyvinylpyrrolidone is preferably 10,000 or more and 700,000 or less, more preferably 30,000 or more and 1,500,000 or less. Thereby, the above functions can be performed more effectively.

In the three-dimensional forming composition, the water-soluble resin 64 is preferably in a state of being in a liquid state (for example, a dissolved state, a molten state, or the like) at least in the filling step. Thereby, the uniformity of the thickness of the three-dimensional forming composition layer 6' formed by the three-dimensional forming composition can be easily and surely made higher.

The content of the water-soluble resin 64 in the three-dimensional forming composition is preferably 15% by volume or less, more preferably 2% by volume or more and 5% by volume or less based on the bulk of the powder for three-dimensional forming. Thereby, the function of the water-soluble resin 64 as described above can be sufficiently developed The mechanical strength of the three-dimensional shaped article 1 is particularly excellent in that the space for infiltrating the ink 4C can be more widely ensured.

≪Solvent ≫

The three-dimensional forming composition may contain a solvent in addition to the water-soluble resin 64 and the three-dimensional forming powder as described above. Thereby, the fluidity of the three-dimensional shaped composition can be particularly excellent, and the productivity of the three-dimensional shaped article 1 can be made particularly excellent.

The solvent is preferably one which dissolves the water-soluble resin 64. Thereby, the fluidity of the three-dimensional forming composition can be improved, and the unintended unevenness of the thickness of the three-dimensional forming composition layer 6' formed by using the three-dimensional forming composition can be more effectively prevented. Further, when the three-dimensional forming composition layer 6' in which the solvent has been removed is formed, the water-soluble resin 64 can be attached to the particles 63 with higher uniformity over the entire three-dimensional forming composition layer 6'. It is more effective to prevent unintended compositional inequality. Therefore, it is possible to more effectively prevent unintentional unevenness in mechanical strength of each portion of the three-dimensional shaped object 1 finally obtained, and the reliability of the three-dimensional shaped object 1 can be made higher.

Examples of the solvent constituting the composition for three-dimensional forming include water; alcoholic solvents such as methanol, ethanol, and isopropyl alcohol; ketone solvents such as methyl ethyl ketone and acetone; ethylene glycol monoethyl ether and ethylene glycol. a glycol ether solvent such as butyl ether; a glycol ether acetate solvent such as propylene glycol 1-monomethyl ether 2-acetate or propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, polypropylene glycol, etc. One type of these may be used, or two or more types may be used in combination.

Among them, the composition for three-dimensional shape formation preferably contains water. Thereby, the water-soluble resin 64 can be more reliably dissolved, and the fluidity of the three-dimensional forming composition and the uniformity of the composition of the three-dimensional forming composition layer 6' formed by using the three-dimensional forming composition can be made. Particularly excellent. Further, the removal of water after the formation of the three-dimensional shaped composition layer 6' is easy, and it is less likely to cause adverse effects even when it remains in the three-dimensional shaped article 1. Moreover, it is also advantageous in terms of the safety of the human body and the viewpoint of environmental issues.

In the case where the composition for three-dimensional forming contains a solvent, the composition for three-dimensional forming The content of the solvent is preferably 5% by mass or more and 75% by mass or less, more preferably 35% by mass or more and 70% by mass or less. Thereby, the effect by the solvent as described above can be exhibited more remarkably, and the solvent can be easily removed in a short period of time in the manufacturing process of the three-dimensional shaped article 1, so that the productivity of the three-dimensional shaped article 1 is improved. It is advantageous from the point of view.

In particular, when the composition for three-dimensional forming contains water as a solvent, the water content in the three-dimensional forming composition is preferably 20% by mass or more and 73% by mass or less, more preferably 50% by mass or more and 70% by mass. %the following. Thereby, the effects as described above can be exhibited more remarkably.

≪Other ingredients≫

Further, the composition for three-dimensional forming may contain components other than the above. As such a component, for example, a polymerization initiator; a polymerization accelerator; a penetration enhancer; a wetting agent (humectant); a fixative; an antifungal agent; a preservative; an antioxidant; a UV absorber; a chelating agent; pH adjuster, etc.

The three-dimensional shaped article of the present invention can be produced by using the above-described production method, three-dimensional shaped article manufacturing apparatus, and ink set. Thereby, it is possible to provide a three-dimensional shape in which the outer surface has high mechanical strength and realizes fine color expression.

The use of the three-dimensional shaped article of the present invention is not particularly limited, and examples thereof include an appreciator such as a doll or a portrait, a display, and a medical device such as an implant.

Further, the three-dimensional shaped article of the present invention can also be applied to any of a prototype, a quantity product, and a fixed product.

Further, the three-dimensional shape of the present invention may also be a model (for example, a vehicle such as an automobile, a locomotive, a ship, or an airplane; a building; an animal, a plant, or the like; a natural object such as a stone (a non-biological); a model of various foods, etc.).

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

For example, in the above embodiment, the ink for forming the outermost layer is ejected by an inkjet method. Although the water, the sacrificial layer forming ink, and the ink are combined, the ink may be applied by other methods (for example, other printing methods).

Further, in the manufacturing method of the present invention, the pretreatment step, the intermediate treatment step, and the post-treatment step may be carried out as needed.

As the pretreatment step, for example, a cleaning step of the platform or the like can be cited.

Examples of the post-treatment step include a washing step, a shape adjustment step of performing deburring, and the like, and an additional hardening treatment for increasing the degree of hardening of the curable resin constituting the outermost layer.

Further, in the above embodiment, the case where the ink ejecting step is performed by the ink jet method has been mainly described. However, the ink ejecting step may be performed by another method (for example, another printing method).

Further, in the above embodiment, the particles in the three-dimensional forming composition layer are bonded by the bonding ink, but the bonding may be performed without using the bonding ink.

Claims (11)

A method for producing a three-dimensional shaped object by laminating a layer formed using an ink containing a curable resin to produce a three-dimensional shaped article, comprising the steps of: an ink ejecting step to the layer The outermost layer forming ink is ejected from the outermost layer of the three-dimensional shaped object, and a sacrificial layer for forming a sacrificial layer is formed in a region on the surface side of the outermost layer adjacent to the region of the layer which is to be the outermost layer. An ink; a hardening step of curing the discharged outermost layer forming ink and the sacrificial layer forming ink; and a filling step of filling the region surrounded by the cured product of the outermost layer forming ink. The three-dimensional forming composition for powders for three-dimensional forming of particles forms a three-dimensional forming composition layer. The method for producing a three-dimensional shaped article according to claim 1, wherein in the filling step, the three-dimensional forming composition to be filled is subjected to a flattening treatment based on the height of the cured product of the outermost layer forming ink. The method for producing a three-dimensional shaped article according to claim 1 or 2, which has a powder bonding step of ejecting a binding ink containing a curable resin to the three-dimensional forming composition layer to form a powder binding layer. The method for producing a three-dimensional shaped article according to claim 3, wherein the powder bonding step in the formation of the layer of the kth layer (k is an integer of 1 or more) and the k+1th layer (k is an integer of 1 or more) The above-described ink ejection step in the formation of the above layer is performed together. The method for producing a three-dimensional shaped article according to any one of claims 1 to 3, wherein in the ink ejecting step, the outermost layer is formed by ejecting the plurality of layers of the layer to be the outermost layer of the three-dimensional shaped article. Ink, to the above plural The sacrificial layer forming ink for forming the sacrificial layer is ejected from a region on the surface side of the outermost layer adjacent to the region of the outermost layer. The method for producing a three-dimensional shaped article according to any one of claims 1 to 5, wherein the outermost layer forming ink contains a polymer selected from the group consisting of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. a group consisting of an ether aliphatic methacrylate oligomer, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate One or more of them. The method for producing a three-dimensional shaped article according to any one of claims 1 to 6, wherein the sacrificial layer forming ink contains an ethoxyethoxy group selected from the group consisting of tetrahydrofurfuryl (meth) acrylate and (meth) acrylate. Ethyl ester, polyethylene glycol di(meth)acrylate, and (meth)acryloylmorpholine, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate One or two or more types. The method for producing a three-dimensional shaped article according to any one of claims 1 to 7, wherein the outermost layer forming ink and the sacrificial layer forming ink each contain bis(2,4,6-trimethylbenzylidene group) -Phenylphosphine oxide and / or 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide as a polymerization initiator. The method for producing a three-dimensional shaped article according to any one of claims 1 to 8, wherein, as the outermost layer forming ink, a colorless ink containing a coloring agent is used, and a colorless ink containing no coloring agent is used, and the colorless ink is used. The ink is used for forming a region in the vicinity of the outer surface of the three-dimensional shaped article of the outermost layer, and the colored ink is used for forming a region on the inner side of the region. The method for producing a three-dimensional shaped article according to any one of claims 1 to 9, wherein a colored ink containing a coloring agent is used as the outermost layer forming ink, and a color ink and a white ink are used as the colored ink, and the white ink is used. Inside the area formed by using the above color ink The formation of the area. A three-dimensional shaped article, which is manufactured by using the method of any one of claims 1 to 10.