JP2019025725A - Three-dimensional modeling material set, three-dimensional modeling material cartridge set, three-dimensional modeling apparatus, and manufacturing method of three-dimensional modeled article - Google Patents

Abstract

To provide a three-dimensional modeled material set capable of manufacturing a three-dimensional modeled article with both improved strength and suppressed stickiness on the surface.SOLUTION: The three-dimensional modeling material set includes: a first three-dimensional modeled material which includes a first photopolymerizable compound and a first photopolymerization initiator, in which a content of the first photopolymerization initiator is 0.5 to 3.0% by mass with respect to the first three-dimensional modeled material; and a second three-dimensional modeled material which includes a second photopolymerizable compound and a second photopolymerization initiator, in which a content of the second photopolymerization initiator with respect to the second three-dimensional modeled material is 1.2 to 20 times the content of the first photopolymerization initiator.SELECTED DRAWING: Figure 6

Description

  The present invention relates to a three-dimensional modeling material set, a three-dimensional modeling material cartridge set, a three-dimensional modeling apparatus, and a method for manufacturing a three-dimensional modeling object.

  The three-dimensional modeling apparatus is also called a 3D printer. As a three-dimensional modeling apparatus, for example, according to the three-dimensional cross-sectional shape data, a three-dimensional modeling material is arranged using an inkjet method, and cured by ultraviolet rays or the like, and a three-dimensional modeled object (for example, a product such as an industrial product) , A toy such as a doll) is known.

  Here, various proposals have been made regarding a three-dimensional modeling apparatus and a method for manufacturing a three-dimensional model.

  For example, Patent Document 1 discloses that “a layer forming step of forming a modeling material layer by applying a modeling material, a semi-curing step of semi-curing the modeling material layer, and binder particles on the semi-cured modeling material layer. An addition step of adding, and performing the addition step on at least one of the plurality of modeling material layers laminated by repeating the layer formation step and the semi-curing step. A three-dimensional modeling method characterized by forming a three-dimensional modeled object has been proposed.

  Further, in Patent Document 2, “when forming a laminated flat plate by the photo-curing modeling method, a step of forming a layer leaving an uncured part by irradiating at a distance, and at the time of curing the upper layer And a step of curing the uncured portion, and forming a laminated flat plate while offsetting distortion caused by curing, and proposes a laminated flat plate forming method in a photo-curing forming method. Yes.

  Further, Patent Document 3 states that “in a region corresponding to one of the cross-sections of the cross-sectional group of the liquid surface of the photocurable liquid, based on the data of the cross-sectional groups obtained by slicing the desired shaping shape into a plurality of layers. Repeating the step of irradiating and the step of coating the surface of the cross-section cured layer formed in the light irradiation step with an uncured photocurable liquid while switching the cross section handled in the light irradiation step to an adjacent cross section. In the photo-curing modeling method of modeling a three-dimensional object that exhibits a desired modeling shape as a whole by laminating and integrating cross-section hardened layers, the contour portion of the cross-sectional group is irradiated with light on all layers, and the contour inner region is divided into a plurality of layers. The photo-curing modeling method for reducing the internal stress is characterized in that the light irradiation step for the inner region of the contour is omitted for the predetermined layer so that the light is irradiated once.

JP2015-476 JP-A-5-154924 Japanese Patent Application Laid-Open No. 7-100937

The three-dimensional structure is produced, for example, by laminating a cured product of a layer of a three-dimensional structure. Specifically, for example, after forming a cured product of the layer of the three-dimensional modeling material by discharging the three-dimensional modeling material and irradiating light, the three-dimensional modeling material is further discharged on the obtained cured product to emit light. By repeating the irradiation, a cured product of the layer of the three-dimensional modeling material is laminated, and a three-dimensional modeling product is obtained.
Since the three-dimensional structure obtained by the above method has a layer of the three-dimensional structure on the cured product, the adhesive force at the interface is weak and it is difficult to obtain the strength.
On the other hand, when the 3D modeling material is not sufficiently cured, stickiness may occur on the surface of the obtained 3D model.

  The problem of the present invention is that the content of the first photopolymerization initiator exceeds 3.0% by mass, and the content of the second photopolymerization initiator is the same as the content of the first photopolymerization initiator. Compared with the case where it is, it is providing the three-dimensional modeling material set from which the three-dimensional modeling thing in which the improvement in intensity | strength and suppression of the stickiness in the surface were compatible was obtained.

  The above problem is solved by the following means.

The invention according to claim 1
It contains a first photopolymerizable compound and a first photopolymerization initiator, and the content of the first photopolymerization initiator is 0.5% by mass or more and 3.0% by mass with respect to the first three-dimensional modeling material. % First 3D modeling material,
It contains a second photopolymerizable compound and a second photopolymerization initiator, and the content of the second photopolymerization initiator relative to the second three-dimensional modeling material is the content of the first photopolymerization initiator. A second three-dimensional modeling material that is 1.2 times to 20 times the amount;
3D modeling material set with

The invention according to claim 2
The first three-dimensional modeling material further includes a first oxygen scavenger,
The second three-dimensional modeling material further includes a second oxygen scavenger,
The content of the second oxygen scavenger with respect to the second three-dimensional modeling material is 1.2 to 20 times the content of the first oxygen scavenger with respect to the first three-dimensional modeling material. The three-dimensional modeling material set according to claim 1.

The invention according to claim 3
A first three-dimensional modeling material comprising a first photopolymerizable compound, a first photopolymerization initiator, and a first oxygen scavenger;
A second photopolymerizable compound, a second photopolymerization initiator, and a second oxygen scavenger, wherein a content of the second oxygen scavenger with respect to a second three-dimensional modeling material is the first A second 3D modeling material that is 1.2 to 20 times the content of the first oxygen scavenger relative to the 3D modeling material;
3D modeling material set with

The invention according to claim 4
A first three-dimensional modeling material cartridge containing a first three-dimensional modeling material in the three-dimensional modeling material set according to any one of claims 1 to 3,
A second 3D modeling material cartridge containing a second 3D modeling material in the 3D modeling material set;
3D modeling material cartridge set with

The invention according to claim 5
A first discharge unit that accommodates the first three-dimensional modeling material in the three-dimensional modeling material set according to any one of claims 1 to 3, and discharges the first three-dimensional modeling material;
Containing a second 3D modeling material in the 3D modeling material set, and discharging a second 3D modeling material;
A light irradiation unit for irradiating light that cures the discharged first three-dimensional modeling material and the second three-dimensional modeling material;
3D modeling device.

The invention according to claim 6
A coating film is formed by discharging the first three-dimensional modeling material in the three-dimensional modeling material set according to any one of claims 1 to 3, and the coating film is irradiated with light. A first step of semi-curing the film to form a semi-cured layer having a semi-cured surface;
The first three-dimensional modeling material is discharged onto the semi-cured surface of the semi-cured layer to form a coating film, and the coating film is irradiated with light to cure the semi-cured layer to form a cured layer. A second step of semi-curing the coating film to form a semi-cured layer having a semi-cured surface;
Discharging the second three-dimensional modeling material in the three-dimensional modeling material set onto the semi-cured surface of the semi-cured layer formed on the cured layer to form a coating film, and irradiating the coating film with light; A third step of curing the semi-cured layer and curing the coating film while forming a cured layer to form a cured layer constituting the outer peripheral surface of the three-dimensional structure;
The manufacturing method of the three-dimensional structure which has this.

  According to the invention according to claim 1, the content of the first photopolymerization initiator exceeds 3.0% by mass, and the content of the second photopolymerization initiator is that of the first photopolymerization initiator. Compared to the case where the content is the same, there is provided a three-dimensional modeling material set from which a three-dimensional modeled object in which improvement in strength and suppression of stickiness on the surface are compatible is obtained.

  According to the invention of claim 2, compared with the case where the content of the second oxygen scavenger is the same as the content of the first oxygen scavenger, both improvement in strength and suppression of stickiness on the surface are achieved. A three-dimensional modeling material set from which a three-dimensional modeling object can be obtained is provided.

  According to the invention of claim 3, compared with the case where the content of the second oxygen scavenger is the same as the content of the first oxygen scavenger, both improvement in strength and suppression of stickiness on the surface are compatible. A three-dimensional modeling material set from which a three-dimensional modeling object can be obtained is provided.

  According to the invention according to claim 4, 5 or 6, the content of the second photopolymerization initiator is the same as the content of the first photopolymerization initiator, and the second oxygen scavenger The tertiary that provides a three-dimensional structure that is both improved in strength and less sticky on the surface than when a three-dimensional structure set with the same content as the first oxygen scavenger is applied. An original modeling material cartridge set, a three-dimensional modeling apparatus, or a method for manufacturing a three-dimensional model is provided.

It is process drawing which shows an example of the manufacturing method of the three-dimensional molded item using the three-dimensional modeling material set which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional molded item using the three-dimensional modeling material set which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional molded item using the three-dimensional modeling material set which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional molded item using the three-dimensional modeling material set which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional molded item using the three-dimensional modeling material set which concerns on this embodiment. It is a schematic block diagram which shows an example of the three-dimensional modeling apparatus which concerns on this embodiment.

  Embodiments that are examples of the present invention will be described below.

[Three-dimensional modeling material set according to the first embodiment]
The three-dimensional modeling material set according to the first embodiment includes a first photopolymerizable compound and a first photopolymerization initiator, and the content of the first photopolymerization initiator is the first three-dimensional. A first tertiary dimensional material that is 0.5% by mass to 3.0% by mass with respect to the modeling material, a second photopolymerizable compound, and a second photopolymerization initiator, and a second tertiary The second three-dimensional modeling material, wherein the content of the second photopolymerization initiator with respect to the original modeling material is 1.2 to 20 times the content of the first photopolymerization initiator. Prepare.
Since the three-dimensional modeling material set according to the first embodiment has the above-described configuration, a three-dimensional modeling object in which improvement in strength and suppression of stickiness on the surface are compatible is obtained. The reason is not clear, but is estimated as follows.

The three-dimensional structure is produced, for example, by laminating a cured product of a layer of a three-dimensional structure. Specifically, for example, after forming a cured product of the layer of the three-dimensional modeling material by discharging the three-dimensional modeling material and irradiating light, the three-dimensional modeling material is further discharged on the obtained cured product to emit light. By repeating the irradiation, a cured product of the layer of the three-dimensional modeling material is laminated, and a three-dimensional modeling product is obtained.
However, when a layer of 3D modeling material is stacked on top of the cured product and cured, the adhesive force at the interface between the lower layer cured product and the newly formed upper layer cured product becomes weak, and the resulting tertiary It may be difficult to obtain the strength (particularly the strength in the stacking direction) of the original model.
On the other hand, stickiness on the surface of the obtained three-dimensional structure may occur if the curability of the layer of the three-dimensional structure material is simply lowered in order to increase the adhesion at the interface.

On the other hand, in the three-dimensional modeling material set, as described above, the content of the first photopolymerization initiator is 0.5% by mass or more and 3.0% by mass or less, and the second photopolymerization is started. The content of the agent is 1.2 to 20 times the content of the first photopolymerization initiator. Therefore, if the first 3D modeling material layer is irradiated with light under conditions where the second 3D modeling material layer is appropriately cured, the first 3D modeling material layer is not completely cured and half It becomes a cured state. Thereby, a semi-cured layer having a semi-cured surface is formed. Here, the “semi-cured state” refers to a state in which a curing reaction has occurred but is not completely cured, and there is a room for increasing the hardness by further curing. The “semi-cured layer having a semi-cured surface” means a layer having at least a semi-cured surface, and is completely cured inside the layer (ie, there is no room for increasing the hardness). You may have the area | region. Hereinafter, the “semi-cured layer having a semi-cured surface” may be simply referred to as “semi-cured layer”.
That is, in the 3D modeling material set, when conditions such as light irradiation are the same, a semi-cured layer is formed by using the first 3D modeling material and cured by using the second 3D modeling material. A highly cured layer is formed. Therefore, for example, by producing a three-dimensional structure by the following method, a three-dimensional structure having a high strength and a reduced surface stickiness can be obtained.

  FIGS. 1-5 is process drawing which shows an example of the manufacturing method of the three-dimensional structure using the said three-dimensional structure material set.

First, as shown in FIG. 1, the first three-dimensional modeling material is discharged onto the modeling table 20 to form a first coating film 22A (coating film P) that is a layer of the first three-dimensional modeling material. To do. And as shown in FIG. 1, light is irradiated with respect to surface 22AS of the side which is not in contact with the modeling base 20 among the 1st coating films 22A.
The first coating film 22A is semi-cured by the light irradiation. Thereby, as shown in FIG. 2, the first coating film 22A becomes the first semi-cured layer 22B (semi-cured layer P). The first semi-cured layer 22B has a semi-cured surface 22BS.

Next, as shown in FIG. 2, the first three-dimensional modeling material is further discharged onto the semi-cured surface 22BS of the first semi-cured layer 22B to apply the first coating film 24A (coating film Q). Form. And as shown in FIG. 2, light is irradiated with respect to surface 24AS of the side which is not in contact with 1st semi-hardened layer 22B among 1st coating films 24A.
By the light irradiation, the first coating film 24A in contact with the semi-cured surface 22BS of the first semi-cured layer 22B is semi-cured while the first semi-cured layer 22B is further cured. Thereby, as shown in FIG. 3, the first semi-cured layer 22B becomes the first cured layer 22C (cured layer P), and the first coating film 24A becomes the first semi-cured layer 24B (semi-cured layer Q). ) The first semi-cured layer 24B has a semi-cured surface 24BS.

Next, the process of discharging a 1st three-dimensional modeling material further on the surface of a semi-hardened state in a semi-hardened layer, forming a 1st coating film, and irradiating light to a 1st coating film is repeated.
Thereby, as shown in FIG. 4, the first cured layer obtained by a plurality of light irradiation steps is laminated, and the first semi-cured layer is the outermost surface layer not in contact with the modeling table 20. The formed semi-cured laminate 26B (laminate R) is obtained. The semi-cured laminate 26B includes a first cured layer laminate including the first cured layer 22C and the first cured layer obtained by curing the first semi-cured layer 24B by light irradiation, and the surface of the laminate. And a first semi-cured layer formed by discharging the first three-dimensional modeling material and irradiating with light. The semi-cured laminate 26B has a semi-cured surface 26BS.

Finally, as shown in FIG. 4, a second coating film 28A (coating film T) is formed by discharging the second three-dimensional modeling material onto the semi-cured surface 26BS of the semi-curing laminate 26B. Light is irradiated to the surface 28AS on the side of the second coating film 28A that is not in contact with the modeling table 20.
By the light irradiation, the second coating 28A in contact with the semi-cured surface 26BS is cured while the semi-cured surface 26BS of the semi-cured laminate 26B is further cured. Thereby, the semi-cured surface 26BS in the semi-cured laminate 26B is cured to become a cured layer (cured layer R), and the second coating film 28A is cured to constitute the outer peripheral surface of the three-dimensional structure. It becomes a hardened layer (hardened layer T). And as shown in FIG. 5, the three-dimensional structure 40C which the semi-hardened laminated body 26B and the 2nd coating film 28A hardened | cured integrally is obtained.
In addition, the layer which comprises the surface of the side which is not in contact with the modeling stand 20 among the outer peripheral surfaces of the three-dimensional structure 40C is a hardened layer (which is formed last in the manufacturing process of the three-dimensional structure 40C, as described above. That is, it is a cured layer in which the second coating film 28A is cured. In the present embodiment, the second 3D modeling material is used only for the formation of the last layer (hereinafter also referred to as “final layer”) formed in the manufacturing process of the 3D structure, and for the formation of the other layers. The first three-dimensional modeling material is used.

  Thus, if a three-dimensional structure is manufactured using the three-dimensional structure set, the three-dimensional structure is not formed on the cured product, but on the semi-cured surface. The coating film is formed. And since light is irradiated in the state where the semi-cured layer of the three-dimensional modeling material and the coating film of the three-dimensional modeling material are in contact, the curing reaction proceeds in both the semi-cured layer and the coating film, A covalent bond is also formed at the interface between the semi-cured layer and the coating film, and the strength of the interface is improved. Therefore, it is estimated that a three-dimensional structure with high strength can be obtained.

In addition, in the 3D modeling material set, the content of the photopolymerization initiator in the second 3D modeling material used for forming the final layer of the 3D modeling object is larger than that of the first 3D modeling material. Therefore, a three-dimensional structure in which the stickiness of the surface is suppressed is obtained.
When the content of the photopolymerization initiator in the second three-dimensional modeling material is the same as that of the first three-dimensional modeling material, the final layer also becomes a semi-cured layer, and thus the surface of the three-dimensional modeling object becomes sticky. Sometimes. However, in the 3D modeling material set, the content of the photopolymerization initiator in the first 3D modeling material is 0.5% by mass or more and 3.0% by mass or less, and the second 3D modeling material is used. The content of the photopolymerization initiator in is from 1.2 times to 20 times the content of the photopolymerization initiator in the first three-dimensional modeling material. Therefore, in the manufacturing process of the 3D model, both the improvement of the interface strength and the curing of the final layer are realized by light irradiation in the state where the coating film of the semi-cured layer and the 3D model material is in contact. It is speculated that a three-dimensional structure having both high strength and suppression of surface stickiness can be obtained.

Moreover, if a three-dimensional structure is manufactured using the three-dimensional structure material set, a three-dimensional structure with high transparency can be easily obtained.
Specifically, when the cured product of the layer of the three-dimensional modeling material is laminated, the transmittance decreases due to light reflection or the like at the interface between the cured product and the cured product, and the interfaces with low light transmittance overlap. In some cases, a three-dimensional structure having low transparency as a whole is obtained.
On the other hand, when the 3D modeling material set is used, light is irradiated in a state where the semi-cured layer of the 3D modeling material and the coating film of the 3D modeling material are in contact, and the semi-cured layer and the coating film And are integrally cured, and in addition to improving the interfacial strength, a decrease in light transmittance is also suppressed.

Moreover, when laminating | curing the hardened | cured material of the layer of a three-dimensional modeling material, in order to raise the adhesive force in the interface of hardened | cured material and hardened | cured material, the method of providing an additive (for example, binder particle | grains) to an interface can be considered. And in the three-dimensional structure that has increased the adhesive strength at the interface by adding an additive to the interface, the light transmittance is further lowered by the additive of the interface, the interface to which the additive has been applied overlaps, A three-dimensional structure with low transparency as a whole may be obtained.
On the other hand, when the 3D modeling material set is used, as described above, the strength of the interface is improved without adding an additive to the interface, so that the 3D model is compatible with both high strength and high transparency. Is obtained.

  Hereinafter, the details of the three-dimensional modeling material set according to the first embodiment will be described.

In the three-dimensional modeling material set, the content of the photopolymerization initiator is 0.5% by mass or more and 3.0% by mass or less, and the content of the photopolymerization initiator is the first tertiary. And a second three-dimensional modeling material that is 1.2 times or more and 20 times or less of the original modeling material.
The first three-dimensional modeling material and the second three-dimensional modeling material each include a photopolymerizable compound and a photopolymerization initiator, and may include other components such as additives as necessary.

The first three-dimensional modeling material and the second three-dimensional modeling material may be the same or different in the type and content of each component, except that the content of the photopolymerization initiator is different. May be. However, from the viewpoint of the affinity between the semi-cured layer of the first three-dimensional modeling material and the coating film of the second three-dimensional modeling material, the first three-dimensional modeling material and the second three-dimensional modeling material are: It is preferable that the components of the same kind are included in each other, and it is more preferable that they are composed of the same components.
For example, the three-dimensional modeling material set includes a first three-dimensional modeling material including a photopolymerizable compound and a photopolymerization initiator, and a second three-dimensional modeling including the photopolymerizable compound and the photopolymerization initiator. It is preferable to have a material.

<Content of photopolymerization initiator>
As described above, the content of the photopolymerization initiator in the first three-dimensional modeling material is 0.5% by mass or more and 3.0% by mass or less with respect to the total mass of the first three-dimensional modeling material. Moreover, 0.7 mass% or more and 3.0 mass% or less are preferable with respect to the total mass of a 1st three-dimensional modeling material, and content of a photoinitiator is 1.0 mass% or more and 2.5 mass%. The following is more preferable.
When the content of the photopolymerization initiator in the first three-dimensional modeling material is in the above range, a three-dimensional modeled object having a higher internal hardness than that in the above range is obtained. A three-dimensional structure with higher strength can be obtained.

As for content of the photoinitiator in a 2nd three-dimensional modeling material, 0.6 mass% or more and 30 mass% or less are mentioned with respect to the total mass of a 2nd three-dimensional modeling material, for example, 3.5 mass % To 10% by mass is preferable, and 4.0% to 8.0% by mass is more preferable.
When the content of the photopolymerization initiator in the second three-dimensional modeling material is in the above range, a three-dimensional modeling object in which the stickiness of the surface is suppressed as compared with the case where the content is smaller than the above range is obtained, which is larger than the above range. A three-dimensional structure having a higher surface strength than the case can be obtained.

  In addition, the content of the photopolymerization initiator in the second three-dimensional modeling material is 1.2 to 20 times the content of the photopolymerization initiator in the first three-dimensional modeling material, as described above. From the viewpoint of coexistence of improvement in strength of the three-dimensional structure and suppression of stickiness of the surface, it is preferably 3 times or more and 15 times or less, more preferably 5 times or more and 10 times or less.

  In addition, each of the first three-dimensional modeling material and the second three-dimensional modeling material may include only one type of photopolymerization initiator, or may include two or more types. However, the “content of photopolymerization initiator” in the three-dimensional modeling material containing two or more photopolymerization initiators means the total amount of the two or more photopolymerization initiators.

  Hereinafter, among the details of the components of each three-dimensional modeling material, matters common to the first three-dimensional modeling material and the second three-dimensional modeling material will be described.

(Photopolymerizable compound)
The photopolymerizable compound is a compound that polymerizes when irradiated with light, and may be any of a monomer, an oligomer, and a prepolymer, and examples thereof include a compound having a photopolymerizable group.
As the photopolymerizable compound, compounds having a photopolymerizable group may be used singly or in combination of two or more.

Examples of the photopolymerizable group include a radical polymerizable group and a cationic polymerizable group.
The photopolymerizable compound may have only one photopolymerizable group in one molecule, or may have two or more. The compound having a photopolymerizable group may have both a radical polymerizable group and a cationic polymerizable group.

Examples of the radically polymerizable group include an ethylenically unsaturated double bond. Examples of the ethylenically unsaturated double bond include (meth) acryloyl group, N-vinyl group, vinyl ether group and the like.
Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl group.

Examples of the compound having a radical polymerizable group include a compound having a (meth) acryloyl group. Moreover, as a compound which has a (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate etc. are mentioned suitably.
In the present specification, (meth) acrylate means both acrylate and methacrylate, and (meth) acryl means both acrylic and methacrylic. (Meth) acryloyl means both an acryloyl group and a methacryloyl group.
As the compound having a cationic polymerizable group, for example, an epoxy compound, an oxetane compound, and a vinyl ether compound are preferably mentioned from the viewpoint of curability.
Examples of the compound having a radical polymerizable group and a cationic polymerizable group include a compound having a (meth) acryloyl group as a radical polymerizable group and a vinyl ether group as a cationic polymerizable group.

  Among these, the photopolymerizable compound is preferably a compound having a radical polymerizable group, more preferably a compound having a (meth) acryloyl group, and further preferably urethane (meth) acrylate.

-Urethane (meth) acrylate-
Urethane (meth) acrylate is a compound having a urethane structure and two or more (meth) acryloyl groups in one molecule. The urethane (meth) acrylate may be a monomer or an oligomer, but is preferably an oligomer.
The functional number of urethane (meth) acrylate (number of (meth) acryloyl groups) is preferably 2 or more and 20 or less (preferably 2 or more and 15 or less).

  Examples of the urethane (meth) acrylate include a reaction product using a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth) acrylate. Specific examples of urethane (meth) acrylates include, for example, a reaction product of a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound and having an isocyanate group at the terminal, and a hydroxyl group-containing (meth) acrylate. Is mentioned. Moreover, the reaction product of a polyisocyanate compound and a hydroxyl group containing (meth) acrylate is also mentioned as urethane (meth) acrylate.

-Polyisocyanate compound As a polyisocyanate compound, chain | strand-shaped saturated hydrocarbon isocyanate, cyclic saturated hydrocarbon isocyanate, aromatic polyisocyanate etc. are mentioned, for example. Among these, the polyisocyanate compound is preferably a chain saturated hydrocarbon isocyanate having no light absorption band in the near ultraviolet region and a cyclic saturated hydrocarbon isocyanate having no light absorption band in the near ultraviolet region.
Examples of the chain saturated hydrocarbon isocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
Examples of the cyclic saturated hydrocarbon isocyanate include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate.
Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1, Examples include 3-phenyl diisocyanate and 1,5-naphthalene diisocyanate.

-Polyol compound As a polyol compound, diol, a polyhydric alcohol, etc. are mentioned, for example.
Examples of the diol include alkylene glycol (for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanedio Le, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, etc.) and the like.
Examples of the polyhydric alcohol include alkylene polyhydric alcohols containing three or more hydroxyl groups (for example, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol). Erythritol, sorbitol, pentaerythritol, dipentaerythritol, mannitol, etc.).

  Examples of the polyol compound include polyether polyol, polyester polyol, and polycarbonate polyol.

Examples of polyether polyols include multimers of polyhydric alcohols, adducts of polyhydric alcohols and alkylene oxides, and ring-opening polymers of alkylene oxides.
Here, as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 1, 2-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

Examples of the polyester polyol include a reaction product of a polyhydric alcohol and a dibasic acid, a ring-opening polymer of a cyclic ester compound, and the like.
Here, as a polyhydric alcohol, the polyhydric alcohol illustrated by description of polyether polyol is mentioned, for example.
Examples of the dibasic acid include carboxylic acids (for example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.), carboxylic acid anhydrides, and the like.
Examples of the cyclic ester compound include ε-caprolactone, β-methyl-δ-valerolactone, and the like.

Examples of the polycarbonate polyol include a reaction product of glycol and alkylene carbonate, a reaction product of glycol and diaryl carbonate, a reaction product of glycol and dialkyl carbonate, and the like.
Here, examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like.
Examples of the diaryl carbonate include diphenyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4′-dimethyldiphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4 ′. -Diethyl diphenyl carbonate, 4,4'-dipropyl diphenyl carbonate, phenyl toluyl carbonate, bischlorophenyl carbonate, phenyl chlorophenyl carbonate, phenyl naphthyl carbonate, dinaphthyl carbonate and the like.
Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, and diisoamyl carbonate. Etc.

-Hydrogen group-containing (meth) acrylate Examples of the hydrogen group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy -3-Phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Examples of the hydrogen group-containing (meth) acrylate include an adduct of a glycidyl group-containing compound (for example, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, etc.) and (meth) acrylic acid.

-Urethane (meth) acrylate weight average molecular weight-
The weight average molecular weight of the urethane (meth) acrylate is preferably 500 or more and 5000 or less, and more preferably 1000 or more and 3000 or less.
The weight average molecular weight of urethane (meth) acrylate is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

Urethane (meth) acrylate may be used alone or in combination of two or more. When two or more urethane (meth) acrylates are used in combination, it is preferable to use at least one of a polyester-based urethane (meth) acrylate having a polyester skeleton and a polyether-based urethane (meth) acrylate having a polyether skeleton.
As content of the polyester-type urethane (meth) acrylate and polyether-type urethane (meth) acrylate with respect to the whole urethane (meth) acrylate, 1 mass% or more and 99 mass% or less are mentioned, for example, 2 mass% or more and 98 mass% or less are mentioned. Is preferred. A compounding quantity is adjusted according to the viscosity of a desired three-dimensional modeling material.

Moreover, you may use together a urethane (meth) acrylate and the other photopolymerizable compound mentioned later as a photopolymerizable compound.
When urethane (meth) acrylate and other photopolymerizable compound are used in combination, the content of urethane (meth) acrylate with respect to the entire photopolymerizable compound is, for example, from 1% by mass to 99% by mass, and 2% by mass. % To 98% by mass is preferable. A compounding quantity is adjusted according to the viscosity of a desired three-dimensional modeling material.

-Other photopolymerizable compounds-
The other photopolymerizable compound is not particularly limited, and examples thereof include other (meth) acrylates other than urethane (meth) acrylate.
Examples of other (meth) acrylates include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.

Monofunctional (meth) acrylates include, for example, linear, branched, or cyclic alkyl (meth) acrylates, hydroxyl-containing (meth) acrylates, heterocyclic (meth) acrylates, and (meth) acrylamide compounds. Etc.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl. Examples include (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.

  As the (meth) acrylate having a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, Examples thereof include polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol block polymer mono (meth) acrylate.

Examples of the (meth) acrylate having a heterocyclic ring include tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, and 4- (meth) acryloyloxy. Examples include methyl-2-cyclohexyl-1,3-dioxolane, adamantyl (meth) acrylate, and the like.
Examples of the (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and N, N. Examples include '-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide and N-hydroxybutyl (meth) acrylamide.

  Among the polyfunctional (meth) acrylates, examples of the bifunctional (meth) acrylate include 1,10-decanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,7-heptanediol Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, Neopentyl glycol di (meth) acrylate, hydroxypivalate Rate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, EO (ethylene Oxide) modified bisphenol A di (meth) acrylate, PO (propylene oxide) modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, EO (ethylene oxide) modified bisphenol F di (meth) acrylate Etc.

  Among polyfunctional (meth) acrylates, trifunctional or higher (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, EO (ethylene oxide) modified diglycerin tetra (meth) ) Acrylate, ditrimethylolpropane tetra (meth) acrylate modified acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Meth) acrylate.

Other photopolymerizable compounds may be used alone or in combination of two or more.
When urethane (meth) acrylate is used in combination with another photopolymerizable compound, the other photopolymerizable compound is preferably a monofunctional alkyl (meth) acrylate from the viewpoint of reaction rate, and more preferably methyl (meth) acrylate. preferable.

-Content of photopolymerizable compound-
The content of the photopolymerizable compound (in the case where a plurality of types of photopolymerizable compounds are used in combination), the total content of the plurality of types of photopolymerizable compounds) is, for example, 70% by mass with respect to the entire three-dimensional modeling material. The content is 96% by mass or less and preferably 80% by mass or more and 96% by mass or less.

  As described above, the type and content of the photopolymerizable compound included in the first three-dimensional modeling material and the type and content of the photopolymerizable compound included in the second three-dimensional modeling material are the same. May be different. However, from the viewpoint of the affinity between the semi-cured layer of the first three-dimensional modeling material and the coating film of the second three-dimensional modeling material, the first three-dimensional modeling material and the second three-dimensional modeling material are: It is preferable to contain the same kind of photopolymerizable compounds, and it is more preferable that the types and contents of the photopolymerizable compounds are the same.

(Photopolymerization initiator)
The photopolymerization initiator is a compound that generates an active species (for example, radical, cation, etc.) that initiates the photopolymerization reaction of the photopolymerizable compound by light irradiation. Examples of the photopolymerization initiator include a photoradical polymerization initiator that generates radicals as active species, a photocationic polymerization initiator that generates cations as active species, and the like. It is selected according to the type. That is, when a compound having a radical polymerizable group is used as the photopolymerizable compound, a photo radical polymerization initiator is used as the photo polymerization initiator. Moreover, when using the compound which has a cationically polymerizable group as a photopolymerizable compound, a photocationic polymerization initiator is used as a photoinitiator. In addition, you may use together a radical photopolymerization initiator and a photocationic polymerization initiator.

-Photo radical polymerization initiator-
Examples of radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums.
Among the above compounds, phosphine oxides are preferable from the viewpoint of curability.

  Examples of acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2- And benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.

  Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, IRGACURE TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE). 819).

  Further, as the radical polymerization initiator, various compounds described in “Application and Market of UV / EB Curing Technology (CMC Publishing Co., Ltd., edited by Yoneho Tabata / edited by Radtech Research Association)” are also used.

In addition, when using a photoradical polymerization initiator as a photoinitiator, in addition to the said photoradical polymerization initiator, you may use a photosensitizer. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, and thioxanthone.
When using a photosensitizer, as content of the photosensitizer with respect to the whole three-dimensional modeling material, 0.1 mass% or more and 10 mass% or less are mentioned, for example, and it is 0 from a viewpoint of the hardness control of a three-dimensional molded item. 2 mass% or more and 5 mass% or less are preferable, and 0.3 mass% or more and 3 mass% or less are more preferable.

-Photocationic polymerization initiator-
Examples of the photocationic polymerization initiator include diazonium salts, iodonium salts (such as diaryl iodonium salts), sulfonium salts (such as triarylsulfonium salts), iron arene complexes, and organic polyhalogen compounds. Among these, as diazonium salt, iodonium salt and sulfonium salt, JP-B Nos. 54-14277, 54-14278, JP-A No. 51-56885, US Pat. No. 3,708,296, No. 3, And compounds described in No. 853,002.

Particularly suitable compounds, diazonium, ammonium, iodonium, sulfonium, _B aromatic onium compounds such as phosphonium ^{_{(C 6 F 5) 4 -}} , PF 6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 - Among them, those having a borate compound as a counter anion are preferable because of their high acid generation ability. Also suitable are sulfonates that generate sulfonic acid, halides that generate hydrogen halide, iron allene complexes, and the like. Furthermore, as for the photocationic polymerization initiator, the photoacid generator compound described in pages 55 to 78 of Joe Tsuda “Molecular design of ultra-LSL resist” (Kyoritsu Shuppan, 1990) is used.

  Commercially available compounds are also used as the cationic photopolymerization initiator. As a commercially available compound, the product made from BASF, IRGACURE250, 270, and 290 are preferable.

  As described above, the type of photopolymerization initiator contained in the first three-dimensional modeling material and the type of photopolymerization initiator contained in the second three-dimensional modeling material may be the same or different. It may be. However, from the viewpoint of the affinity between the semi-cured layer of the first three-dimensional modeling material and the coating film of the second three-dimensional modeling material, the first three-dimensional modeling material and the second three-dimensional modeling material are: It is preferable that the same kind of photopolymerization initiators be included, and it is more preferable that the types of the photopolymerizable compounds contained are the same.

On the other hand, when the first 3D modeling material layer is irradiated with light under the condition that the second 3D modeling material layer is appropriately cured, the first 3D modeling material layer is in a semi-cured state. In order to facilitate, the first three-dimensional modeling material and the second three-dimensional modeling material may include different types of photopolymerization initiators.
As a different kind of photopolymerization initiator, for example, there is a ratio (Ai / Ap) between the absorbance (Ai) at the wavelength of light irradiated to the three-dimensional structure and the absorbance (Ap) at the maximum absorption wavelength in the absorption spectrum. Different photopolymerization initiators may be mentioned. For example, a compound having a smaller value of the ratio (Ai / Ap) than the photopolymerization initiator contained in the second three-dimensional modeling material is used as the photopolymerization initiator contained in the first three-dimensional modeling material. May be. Specifically, for example, a compound having a ratio (Ai / Ap) of less than 1/5 is used as a photopolymerization initiator contained in the first three-dimensional modeling material, and is included in the second three-dimensional modeling material. Examples of the photopolymerization initiator include a method using a compound having the above ratio (Ai / Ap) of 1/5 or more.
The absorption spectrum was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model number: U-4100) as a measuring device, temperature: 25 ° C., measurement speed: 600 nm / min, slit width: 2 nm. The measurement interval is 1 nm.

  In addition, when the first 3D modeling material layer is light-irradiated under the condition that the second 3D modeling material layer is appropriately cured, the first 3D modeling material layer is in a semi-cured state. In order to facilitate, the photosensitizer may be contained only in the second three-dimensional modeling material.

(Other ingredients)
-Oxygen scavenger-
As described above, the three-dimensional modeling material may include an oxygen scavenger as necessary.
Examples of the oxygen scavenger include amine-based oxygen scavengers and organic phosphorus-based oxygen scavengers.
An amine-based oxygen scavenger is an oxygen scavenger having an amino group, and examples thereof include ethyl 4- (dimethylamino) benzoate.
The organic phosphorus-based oxygen scavenger is an oxygen scavenger having a phosphorus atom, and examples thereof include triphenylphosphine (TPP) and triethylphosphite (TEP).

  Note that each of the first three-dimensional modeling material and the second three-dimensional modeling material may include only one type of oxygen scavenger or two or more types. However, the “content of oxygen scavenger” in the three-dimensional modeling material containing two or more oxygen scavengers means the total amount of the two or more oxygen scavengers.

  When both the first three-dimensional modeling material and the second three-dimensional modeling material contain an oxygen scavenger, the type and content of the oxygen scavenger contained in the first three-dimensional modeling material, and the second three-dimensional The type and content of the oxygen scavenger contained in the modeling material may be the same or different. However, from the viewpoint of the affinity between the semi-cured layer of the first three-dimensional modeling material and the coating film of the second three-dimensional modeling material, the first three-dimensional modeling material and the second three-dimensional modeling material are: It is preferable that the same kind of oxygen scavengers be included, and it is more preferable that the types and contents of the oxygen scavengers are the same.

On the other hand, when the first 3D modeling material layer is irradiated with light under the condition that the second 3D modeling material layer is appropriately cured, the first 3D modeling material layer is in a semi-cured state. In order to make it easy, content of the oxygen scavenger in the first three-dimensional modeling material and the second three-dimensional modeling material may be different.
Specifically, the content of the oxygen scavenger in the second three-dimensional modeling material is preferably 1.2 to 20 times the content of the oxygen scavenger in the first three-dimensional modeling material, and preferably 3 times or more. It is preferably 15 times or less, more preferably 5 times or more and 10 times or less.

The content of the oxygen scavenger in the first three-dimensional modeling material is, for example, 0.05% by mass to 3% by mass with respect to the total mass of the first three-dimensional modeling material, and 0.1% by mass or more. 1 mass% or less is preferable and 0.2 mass% or more and 0.5 mass% or less are more preferable.
When the content of the oxygen scavenger in the first three-dimensional modeling material is in the above range, a three-dimensional modeling object having a higher internal hardness than in the case where the content is smaller than the above range is obtained, and compared with the case where the content is larger than the above range. And high strength 3D objects can be obtained.

The content of the oxygen scavenger in the second three-dimensional modeling material is, for example, 0.1% by mass or more and 10% by mass or less, and 0.5% by mass with respect to the total mass of the second three-dimensional modeling material. The content is preferably 5.0% by mass or less and more preferably 1.0% by mass or more and 3.0% by mass or less.
When the content of the oxygen scavenger in the second three-dimensional modeling material is in the above range, a three-dimensional modeling object in which the stickiness of the surface is suppressed compared to the case where the content is smaller than the above range is obtained, and is larger than the above range. As a result, a three-dimensional structure having a higher surface strength can be obtained.

-Polymerization inhibitor-
The three-dimensional modeling material may include a polymerization inhibitor as necessary.
Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (that is, polymerization inhibitors having a phenol structure such as p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4- Hydroxytoluene, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-butylphenol), 4,4′-thiobis (3-methyl-6- t-butylphenol)), hindered amines, hydroquinone monomethyl ether (MEHQ), and hydroquinone.
The content of the polymerization inhibitor is, for example, preferably from 0.1 parts by weight to 30 parts by weight, and more preferably from 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the photopolymerizable compound.
In addition, a polymerization inhibitor may be used individually by 1 type, and may be used together 2 or more types.

-Surfactant-
The three-dimensional modeling material may include a surfactant as necessary.
Examples of the surfactant include silicone surfactants, acrylic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine surfactants. Well-known surfactant is mentioned.
0.05 mass% or more and 15 mass% or less are preferable with respect to the whole three-dimensional modeling material, and, as for content of surfactant, 0.1 mass% or more and 10 mass% or less are more preferable.
In addition, surfactant may be used individually by 1 type and may be used together 2 or more types.

-Colorant-
The three-dimensional modeling material may include a colorant as necessary.
Examples of the colorant include various conventionally known colorants such as pigments and dyes, and pigments are particularly preferable from the viewpoint of improving the weather resistance of the three-dimensional structure.

  The pigment is not particularly limited, and is generally a commercially available organic pigment and inorganic pigment, those obtained by dispersing these pigments in a dispersion medium (for example, resin), those obtained by grafting a resin on the pigment surface, The thing etc. which dye | stained the resin particle with dye are mentioned.

The color of the colorant is appropriately selected according to the color of the target three-dimensional structure, and is not particularly limited, and examples thereof include a white colorant.
Examples of the white colorant include white pigments such as titanium dioxide, zirconium oxide, calcium carbonate, barium sulfate, silicon oxide, magnesium oxide, aluminum oxide, tin oxide, kaolin, and talc.
Examples of the colorant other than white include a yellow colorant, a magenta colorant, and a cyan colorant. Specific examples of the colorant other than white include azo pigments such as azo lake pigments, polycyclic pigments such as azo dyes and phthalocyanine pigments, organic pigments such as nitro pigments, and inorganic pigments such as carbon black.

As for content of a coloring agent, 0.01 mass% or more and 50 mass% or less are mentioned, for example with respect to the total mass of a three-dimensional modeling material, and 0.1 mass% or more and 20 mass% or less are preferable.
However, in the three-dimensional modeling material used for manufacturing a three-dimensional modeled object with high transparency, the content of the colorant with respect to the entire three-dimensional modeling material is preferably 0.1% by mass or less, and 0.05% by mass or less. It is more preferable that it is 0.01 mass% or less.

-Others-
Other components other than the above that may be included in the three-dimensional modeling material include, for example, solvents, fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents, thickeners, dispersants, polymerization accelerators, and penetration agents. Well-known additives such as accelerators and wetting agents (humectants) can be mentioned.

(Characteristics of 3D modeling materials)
Examples of the viscosity of the three-dimensional modeling material include a range of 3 mPa · s to 100 mPa · s, and preferably 5 mPa · s to 30 mPa · s.
Here, the viscosity is a value measured using Rheomat 115 (manufactured by Contraves) as a measuring device under the conditions of a measurement temperature of 55 ° C. and a shear rate of 1400 s ⁻¹ .

Examples of the surface tension of the three-dimensional modeling material include a range of 18 mN / m to 70 mN / m, and preferably 20 mN / m to 40 mN / m.
Here, the surface tension is a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

[Three-dimensional modeling material set according to the second embodiment]
The three-dimensional modeling material set according to the second embodiment includes a first three-dimensional modeling material including a first photopolymerizable compound, a first photopolymerization initiator, and a first oxygen scavenger, and a second A second photopolymerization compound, a second photopolymerization initiator, and a second oxygen scavenger, wherein the content of the second oxygen scavenger with respect to the second three-dimensional modeling material is the first three-dimensional And a second three-dimensional modeling material that is 1.2 times or more and 20 times or less the content of the first oxygen scavenger with respect to the modeling material.

The three-dimensional modeling material set according to the second embodiment has the above-described configuration, so that the strength of the second oxygen scavenger is higher than that of the first oxygen scavenger. A high three-dimensional structure can be obtained.
Specifically, similarly to the case of the three-dimensional modeling material set according to the first embodiment, the layer of the second three-dimensional modeling material is appropriately used by using the three-dimensional modeling material set according to the second embodiment. When the first three-dimensional modeling material layer is irradiated with light under the curing condition, the first three-dimensional modeling material layer is in a semi-cured state. Therefore, the coating of the 3D modeling material is formed on the surface of the semi-cured state, and light is irradiated in a state where the semi-cured layer of the 3D modeling material and the coating of the 3D modeling material are in contact with each other. It is estimated that the strength of the three-dimensional structure is improved and a high-strength three-dimensional structure is obtained.

Similarly to the case of the 3D modeling material set according to the first embodiment, when the 3D modeling material set according to the second embodiment is used, the 3D modeling achieves both high strength and suppression of surface stickiness. A thing is obtained.
Furthermore, as in the case of the three-dimensional modeling material set according to the first embodiment, when the three-dimensional modeling material set according to the second embodiment is used, the strength of the interface is increased even without adding an additive to the interface. In order to improve, a three-dimensional structure in which high strength and high transparency are compatible is obtained.

  In the three-dimensional modeling material set according to the second embodiment, the content of the photopolymerization initiator is not limited, and the content of the oxygen scavenger in the second three-dimensional modeling material is the first three-dimensional. Except for being 1.2 times or more and 20 times or less of the content of the oxygen scavenger in the modeling material, it is the same as the three-dimensional modeling material set according to the first embodiment.

<Three-dimensional modeling material cartridge set, three-dimensional modeling apparatus, and three-dimensional modeling manufacturing method>
The three-dimensional modeling apparatus according to the present embodiment includes a three-dimensional modeling material, a discharge unit that discharges the three-dimensional modeling material, and a light irradiation unit that emits light that cures the discharged three-dimensional modeling material. . And each 3D modeling material (namely, 1st 3D modeling material and 2nd 3D modeling material) in the said 3D modeling material set is applied to a 3D modeling material.

  The three-dimensional modeling apparatus may include a three-dimensional modeling material cartridge that accommodates a three-dimensional modeling material and is formed into a cartridge so as to be attached to and detached from the three-dimensional modeling apparatus. That is, the 3D modeling apparatus includes a first 3D modeling material cartridge containing the first 3D modeling material, a second 3D modeling material cartridge containing the second 3D modeling material, You may provide the three-dimensional modeling material cartridge set which has.

In the three-dimensional modeling apparatus, for example, a three-dimensional structure is manufactured by repeating a discharge process for discharging a three-dimensional modeling material and a light irradiation process for curing the discharged three-dimensional modeling material by light irradiation. .
For example, the first three-dimensional modeling material is discharged to form the coating film P, and the coating film P is irradiated with light so that the coating film P is semi-cured and has a semi-cured surface P. The first three-dimensional modeling material is discharged onto the semi-cured surface of the semi-cured layer P to form a coating film Q, and the coating film Q is irradiated with light to form the semi-cured layer P. Is cured to form a cured layer P, and the coating layer Q is semi-cured to form a semi-cured layer Q having a semi-cured surface, and the second step is repeated, whereby the cured layer P and the semi-cured layer Q are repeated. 3rd process of forming the laminated body R which has the semi-hardened layer R in which the coating film R of the 1st three-dimensional modeling material was semi-hardened in the laminated body of the hardened layer containing the hardened layer Q which the hardened layer Q hardened | cured. Then, the second three-dimensional modeling material is discharged onto the semi-cured surface of the laminate R to form a coating film T, and the coating film T is irradiated with light to form the semi-cured layer R. Through a fourth step of forming a cured layer T constituting the outer peripheral surface of the 3D object, the curing the coating film T with a cured layer R by reduction, the 3D object is produced.

  The three-dimensional modeling apparatus accommodates the first three-dimensional modeling material and discharges the first three-dimensional modeling material, and the second three-dimensional modeling material stores the second three-dimensional modeling material. You may provide the 2nd discharge part which discharges material, and the light irradiation part which irradiates the light which hardens the discharged 1st three-dimensional modeling material and 2nd three-dimensional modeling material.

Hereinafter, as an example of the three-dimensional modeling apparatus according to the present embodiment, a three-dimensional modeling apparatus including a first discharge unit, a second discharge unit, and a light irradiation unit will be described with reference to the drawings.
FIG. 6 is a schematic configuration diagram illustrating an example of a three-dimensional modeling apparatus including a first discharge unit, a second discharge unit, and a light irradiation unit among the three-dimensional modeling apparatus according to the present embodiment.

  The three-dimensional modeling apparatus 101 according to the present embodiment is an inkjet three-dimensional modeling apparatus. As shown in FIG. 6, the three-dimensional modeling apparatus 101 includes, for example, a modeling unit 10 and a modeling table 20. Further, the three-dimensional modeling apparatus 101 has a first three-dimensional modeling material cartridge 30 that accommodates the first three-dimensional modeling material and a second that accommodates the second three-dimensional modeling material so as to be attached to and detached from the apparatus. And a three-dimensional modeling material cartridge 32.

  The modeling unit 10 includes, for example, a first three-dimensional modeling material discharge head 12 (an example of a first discharge unit) that discharges a first three-dimensional modeling material droplet, and a second three-dimensional modeling material droplet. Is provided with a second three-dimensional modeling material discharge head 14 (an example of a second discharge unit) and a light irradiation device 16 that emits light. In addition, the modeling unit 10 includes a control unit that controls the light irradiation intensity in the light irradiation device 16, for example, although not illustrated. In addition, although not illustrated, the modeling unit 10 may include, for example, a rotating roller that removes and flattens an excess of the three-dimensional modeling material discharged from the modeling table 20.

  The modeling unit 10 is, for example, a system (so-called carriage system) that moves on the modeling area of the modeling table 20 in the main scanning direction and the sub-scanning direction intersecting (for example, orthogonal) with the driving device (not shown). It has become.

  As the first three-dimensional modeling material discharge head 12 and the second three-dimensional modeling material discharge head 14, piezo type (piezoelectric type) discharge heads that discharge droplets of each material by pressure are applied. Each discharge head is not limited to this, and may be a discharge head that discharges each material by pressure from a pump.

The first 3D modeling material discharge head 12 is connected to the first 3D modeling material cartridge 30 through a supply pipe (not shown), for example. Then, the three-dimensional modeling material is supplied to the first three-dimensional modeling material discharge head 12 by the first three-dimensional modeling material cartridge 30.
The second 3D modeling material discharge head 14 is connected to the second 3D modeling material cartridge 32 through a supply pipe (not shown), for example. Then, the second 3D modeling material cartridge 32 supplies the 3D modeling material to the second 3D modeling material discharge head 14.

The first three-dimensional modeling material discharge head 12 and the second three-dimensional modeling material discharge head 14 each have an effective discharge area (a nozzle for discharging the first three-dimensional modeling material and the second three-dimensional modeling material. The arrangement area) is a short ejection head smaller than the modeling area of the modeling table 20.
The first three-dimensional modeling material discharge head 12 and the second three-dimensional modeling material discharge head 14 each have an effective discharge area (for example, the first three-dimensional modeling material and the second three-dimensional modeling material). As a long head in which the nozzle arrangement area to be discharged is equal to or greater than the modeling area width on the modeling table 20 (the length in the direction intersecting (for example, orthogonal to) the moving direction (main scanning direction) of the modeling unit 10) Also good. In this case, the modeling unit 10 is configured to move only in the main scanning direction.

As the light irradiation device 16, for example, an ultraviolet irradiation device that irradiates ultraviolet light of 350 nm or more and 400 nm or less is used. Examples of the ultraviolet irradiation device include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deep ultraviolet lamp, a lamp that uses a microwave to excite a mercury lamp from the outside without an electrode, an ultraviolet laser, a xenon lamp, and a UV-LED (ultraviolet light emitting diode). A device having a light source such as) is applied. Among these, the ultraviolet irradiation device is preferably an ultraviolet laser or a UV-LED (ultraviolet light emitting diode) from the viewpoint of suppressing a temperature rise during the production of the three-dimensional structure.
The light irradiation device 16 may include one type of light source, or may include two or more types of light sources having different emission wavelengths.

  The modeling table 20 has a surface having a modeling area where a three-dimensional modeling material and a support material are discharged to form a modeled object. And the modeling stand 20 is raised / lowered by a drive device (not shown).

  Next, using the three-dimensional modeling apparatus 101, a method of manufacturing a three-dimensional model 40C that is a cured product of the first three-dimensional model material and the second three-dimensional model material (manufacturing method of the three-dimensional model) Will be described.

  First, for example, in order to form a three-dimensional modeling data, for example, from three-dimensional CAD (Computer Aided Design) data of a three-dimensional modeling object to be modeled with a three-dimensional modeling material by a computer (not shown). 2D shape data (slice data) is generated.

Next, based on the two-dimensional shape data for forming the modeled object, the first three-dimensional modeling material is discharged from the first three-dimensional modeling material discharge head 12 while moving the modeling unit 10, and the modeling table On 20, a layer of the first three-dimensional modeling material (first coating film 22 </ b> A) is formed. Then, the light irradiation device 16 irradiates light to the first three-dimensional modeling material layer (first coating film 22A), and semi-cures the three-dimensional modeling material to form a semi-cured layer (first semi-cured layer). 22B).
At this time, the intensity of light applied to the first three-dimensional modeling material layer (first coating film 22A) is controlled by a control unit (not shown). The intensity of the light is not particularly limited, for example, 50 mW / cm ² or more 5000 mW / cm ² or less. Moreover, the irradiation amount of light is not particularly limited, and examples thereof include 50 mJ / cm ² or more and 1000 mJ / cm ² or less.

  In addition, you may perform the process of forming the layer of a 1st three-dimensional modeling material, and performing light irradiation, supplying the gas containing oxygen to the surface of the layer of a 1st three-dimensional modeling material. By adjusting the oxygen concentration of the gas to be supplied, the degree of cure of the first three-dimensional modeling material layer after light irradiation is controlled. Specifically, the higher the oxygen concentration of the supplied gas, the lower the degree of cure of the first three-dimensional modeling material layer after light irradiation, and the higher the oxygen concentration of the supplied gas, the first tertiary after light irradiation. The degree of cure of the original modeling material layer is increased.

Next, the modeling table 20 is lowered. The lowering of the modeling table 20 is the thickness of the layer to be formed next.
And while moving the modeling unit 10 to the surface (semi-cured surface 22BS) of the semi-cured layer (first semi-cured layer 22B) based on the two-dimensional shape data for forming the modeled object, the first The first 3D modeling material is discharged from the 3D modeling material discharge head 12. Furthermore, the light irradiation device 16 irradiates light to the first three-dimensional modeling material layer (first coating film 24 </ b> A) formed by discharging the first three-dimensional modeling material. Thereby, the semi-cured layer is cured to become a cured layer (first cured layer 22C), and the first three-dimensional modeling material layer (first coating film 24A) is semi-cured and semi-cured layer ( The first semi-cured layer 24B).

  If necessary, by repeating the descending of the modeling table 20, the discharge of the first three-dimensional modeling material, and the irradiation of light, the cured product of the first three-dimensional modeling material layer is laminated, A laminated body (semi-cured laminated body 26B) in which a semi-cured layer obtained by semi-curing a layer of the three-dimensional modeling material 1 is obtained.

  Finally, after lowering the modeling table 20, a final layer is formed on the surface (semi-cured surface 26BS) of the laminate (semi-cured laminate 26B). Specifically, while moving the modeling unit 10 based on the two-dimensional shape data for forming the modeled object, the second three-dimensional modeling material is discharged from the second three-dimensional modeling material discharge head 14, A layer of the second three-dimensional modeling material (second coating film 28A) is formed. Then, the light irradiation device 16 irradiates the second three-dimensional modeling material layer (second coating film 28 </ b> A) with light. Thereby, the surface (semi-cured surface 26BS) of the laminate (semi-cured laminate 26B) and the second three-dimensional modeling material layer (second coating film 28A) are integrally cured, and the tertiary An original model 40C is obtained.

In addition, the wavelength of the light irradiated to the layer of the 2nd three-dimensional modeling material may be the same as the wavelength of the light irradiated to the 1st three-dimensional modeling material, and may differ. For example, when the light irradiation device 16 includes two or more types of light sources having different emission wavelengths, the light irradiated to the first three-dimensional structure is obtained in order to obtain a three-dimensional structure that achieves both strength improvement and suppression of surface stickiness. The second three-dimensional modeling material may be irradiated with light having a different wavelength.
Specifically, for example, in the first three-dimensional modeling material, in the photopolymerization initiator included in the first three-dimensional modeling material, light having a wavelength at which the ratio (Ai / Ap) is less than 1/5. Irradiate. In the second 3D modeling material, the ratio (Ai / Ap) is 1/5 or more in the photopolymerization initiator included in the second 3D modeling material and the photosensitizer included as necessary. Irradiate light with a wavelength of As a result, it is considered that a three-dimensional structure having both improved strength and reduced surface stickiness can be easily obtained.

  The step of forming the second three-dimensional modeling material layer and performing the light irradiation may be performed while supplying a gas containing oxygen to the surface of the second three-dimensional modeling material layer. In the manufacturing process of the three-dimensional structure, when supplying gas in both the step of irradiating the layer of the first three-dimensional structure and the step of irradiating the layer of the second three-dimensional structure, supply The oxygen concentration of the gas may be the same or different. For the purpose of obtaining a three-dimensional structure that achieves both improvement in strength and suppression of stickiness on the surface, the oxygen concentration of the gas supplied in the process of irradiating the layer of the first three-dimensional structure is changed to the second three-dimensional structure. You may make it higher than the oxygen concentration of the gas supplied in the process of light-irradiating the layer of material. Specifically, for example, the oxygen concentration of the gas supplied in the process of irradiating the first three-dimensional modeling material layer is 25% or more, and the second three-dimensional modeling material is supplied in the process of irradiating light. A method of setting the oxygen concentration of the gas to be 21% or less.

As described above, a three-dimensional structure 40C that is a cured product of the first three-dimensional structure material and the second three-dimensional structure material is obtained.
Note that the obtained three-dimensional structure may be subjected to post-processing such as polishing.

  Hereinafter, although an example and a comparative example are given and this embodiment is described more concretely, this embodiment is not limited to the following examples. Unless otherwise specified, “part” and “%” are based on mass.

[Example A]
<Preparation of 3D modeling material>
Each component described in Table 1 below was mixed to prepare a three-dimensional modeling material.
In addition, the numerical value in Table 1 means content (mass part) of an applicable component.

Abbreviations described in Table 1 are as follows.
U-15HA: photopolymerizable compound (urethane acrylate oligomer, weight average molecular weight: 2300), manufactured by Shin-Nakamura Chemical Co., Ltd. IBXA: photopolymerizable compound (compound name: isobornyl acrylate) manufactured by Tokyo Chemical Industry Co., Ltd.

Irgacure 819: photopolymerization initiator (compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), manufactured by BASF Ltd. EDB: oxygen scavenger (compound name: 4- (dimethylamino) benzoic acid Ethyl acid), manufactured by Tokyo Chemical Industry Co., Ltd., MEHQ: polymerization inhibitor (compound name: 4-methoxyphenol), manufactured by Sigma-Aldrich

<Production and evaluation of 3D modeling material set>
As the first three-dimensional modeling material and the second three-dimensional modeling material in the three-dimensional modeling material set, the three-dimensional modeling material set shown in Table 2 below was used to obtain a three-dimensional modeling material set.

(Production of 3D modeling equipment)
Select a Polaris head (model number: PQ512 / 85) manufactured by Fuji Film Dimatics as the ejection head, and Subzero-055 (intensity of 100 w / cm) manufactured by INTEGRATION TECHNOLOGY LTD as the ultraviolet light source (light irradiation device). Was installed in a modeling apparatus consisting of a drive unit and a control unit, and this was used as a test modeling apparatus. The modeling apparatus is a system in which the ejection head and the light source both reciprocate, and is configured to perform formation by performing lamination of a modeling material layer having a thickness of 20 μm and curing treatment by ultraviolet irradiation for each scan. . Further, in the modeling apparatus, the modeling material is passed through a Tygon 2375 chemical-resistant tube made by Saint-Gobain Co., Ltd. by a liquid pump from a storage tank under a light-shielding condition, and passed through a profile star A050 filter (filtering accuracy 5 μm) made by Nippon Pole. After removing the liquid, the liquid was fed to the ink jet head.

(Production of 3D objects)
Using the obtained three-dimensional modeling apparatus, using a three-dimensional modeling material set that combines the three-dimensional modeling materials shown in Table 2, the dumbbell type in which the stacking direction is vertical (that is, the cross-sectional area at the center in the stacking direction is a stack) A test piece having a dumbbell shape smaller than the cross-sectional area at both ends in the direction) was formed.
Specifically, the first three-dimensional modeling material in the three-dimensional modeling material set shown in Table 2 is used to form a layer other than the final layer of the three-dimensional modeling object, and the tertiary shown in Table 2 is used to form the final layer. The second 3D modeling material in the original modeling material set was used.
In addition, the cross-sectional area of the center part of the lamination direction in the obtained test piece was 0.05 cm < ² >, the cross-sectional area in the both ends of the lamination direction was 0.1 cm < ² >, and the thickness of the lamination direction was 0.1 cm.

(Evaluation of strength (tensile strength))
About the obtained test piece, when it was pulled and ruptured by a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Strograph VE1D) at room temperature (25 ° C.) and a pulling speed of 50 mm / min. The strength was measured and taken as the tensile strength. The results are shown in Table 2.

(Evaluation of surface stickiness)
The surface of the obtained test piece was touched with a finger, and the stickiness of the surface was evaluated according to the following criteria. The results are shown in Table 2.
A: Stickiness on the surface was not felt B: Stickiness on the surface was felt

(Measurement of transmittance)
The transmittance in the stacking direction of the obtained test piece was measured with a spectrophotometer (U-4000, manufactured by Hitachi). The results are shown in Table 2. Note that the transmittance values shown in Table 2 are the maximum transmittance values in the wavelength range of 400 nm to 700 nm.

  From the above results, it can be seen that, in this example, a three-dimensional structure that achieves both improvement in strength and suppression of stickiness on the surface can be obtained as compared with the comparative example.

[Example B]
<Preparation of 3D modeling material>
Each component described in Table 3 below was mixed to prepare a three-dimensional modeling material.
In addition, the numerical value in Table 3 means content (mass part) of applicable component.
Moreover, the abbreviations described in Table 3 are as described above.

<Production and evaluation of 3D modeling material set>
As the first three-dimensional modeling material and the second three-dimensional modeling material in the three-dimensional modeling material set, the three-dimensional modeling material shown in the following Table 4 was used to obtain a three-dimensional modeling material set.
Using the same 3D modeling apparatus as in Example A and using a 3D modeling material set in combination with the 3D modeling materials shown in Table 4, the same test piece as in Example A was modeled.
Moreover, the same evaluation as an Example was performed about the obtained test piece. The results are shown in Table 4.

  From the above results, Reference Example B1 and Reference in which the content of the oxygen scavenger in the second three-dimensional modeling material is 1.2 to 20 times the content of the oxygen scavenger in the first three-dimensional modeling material In Example B2, the strength is improved compared to Reference Example B3 and Reference Example B4 in which the content of the oxygen scavenger in the second three-dimensional modeling material is the same as the content of the oxygen scavenger in the first three-dimensional modeling material. It can be seen that a three-dimensional structure that achieves both suppression of stickiness on the surface can be obtained.

DESCRIPTION OF SYMBOLS 10 Modeling unit 12 1st 3D modeling material discharge head 14 2nd 3D modeling material discharge head 16 Light irradiation apparatus 20 Modeling table 22A, 24A 1st coating film 22B, 24B 1st semi-hardened layer 22C 1st Cured layer 26B semi-cured laminate 28A second coating film 30 first three-dimensional modeling material cartridge 32 second three-dimensional modeling material cartridge 40C three-dimensional modeling object 101 three-dimensional modeling apparatus

Claims (6)

It contains a first photopolymerizable compound and a first photopolymerization initiator, and the content of the first photopolymerization initiator is 0.5% by mass or more and 3.0% by mass with respect to the first three-dimensional modeling material. % First 3D modeling material,
It contains a second photopolymerizable compound and a second photopolymerization initiator, and the content of the second photopolymerization initiator relative to the second three-dimensional modeling material is the content of the first photopolymerization initiator. A second three-dimensional modeling material that is 1.2 times to 20 times the amount;
3D modeling material set with The first three-dimensional modeling material further includes a first oxygen scavenger,
The second three-dimensional modeling material further includes a second oxygen scavenger,
The content of the second oxygen scavenger with respect to the second three-dimensional modeling material is 1.2 to 20 times the content of the first oxygen scavenger with respect to the first three-dimensional modeling material. The three-dimensional modeling material set according to claim 1. A first three-dimensional modeling material comprising a first photopolymerizable compound, a first photopolymerization initiator, and a first oxygen scavenger;
A second photopolymerizable compound, a second photopolymerization initiator, and a second oxygen scavenger, wherein a content of the second oxygen scavenger with respect to a second three-dimensional modeling material is the first A second 3D modeling material that is 1.2 to 20 times the content of the first oxygen scavenger relative to the 3D modeling material;
3D modeling material set with A first three-dimensional modeling material cartridge containing a first three-dimensional modeling material in the three-dimensional modeling material set according to any one of claims 1 to 3,
A second 3D modeling material cartridge containing a second 3D modeling material in the 3D modeling material set;
3D modeling material cartridge set with A first discharge unit that accommodates the first three-dimensional modeling material in the three-dimensional modeling material set according to any one of claims 1 to 3, and discharges the first three-dimensional modeling material;
Containing a second 3D modeling material in the 3D modeling material set, and discharging a second 3D modeling material;
A light irradiation unit for irradiating light that cures the discharged first three-dimensional modeling material and the second three-dimensional modeling material;
3D modeling device. By discharging the 1st three-dimensional modeling material in the three-dimensional modeling material set of any one of Claims 1-3, forming the coating film P, and irradiating the coating film P with light. A first step of semi-curing the coating film P to form a semi-cured layer P having a semi-cured surface;
The first three-dimensional modeling material is ejected onto the semi-cured surface of the semi-cured layer P to form a coating film Q, and the coating film Q is irradiated with light to cure the semi-cured layer P. A second step of semi-cured layer Q having a semi-cured surface by semi-curing the coating film Q while forming a cured layer P;
By repeating the second step, the coating layer R of the first three-dimensional modeling material is semi-finished on a laminate of the cured layer including the cured layer P and the cured layer Q obtained by curing the semi-cured layer Q. Forming a laminate R having a cured semi-cured layer R; and
The second three-dimensional modeling material in the three-dimensional modeling material set is ejected onto the semi-cured surface of the laminate R to form a coating film T, and the coating film T is irradiated with light. A fourth step of curing the cured layer R to form the cured layer R that forms the outer peripheral surface of the three-dimensional structure by curing the coating film T while forming the cured layer R;
The manufacturing method of the three-dimensional structure which has this.