JP2018034382A - Production method of three-dimensional molding, three-dimensional molding apparatus, and member subject for molding stand - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a three-dimensional molding excellent detachability between the obtained three-dimensional molding and a molding stand, and also excellent in a surface nature of a joint area between the three-dimensional molding and the molding stand.SOLUTION: A production method of a three-dimensional molding includes steps of: preparing a compound having a mercapto group, and a molding stand having a layer containing a binder polymer at least on a part of the surface; discharging a radical-polymerizable three-dimensional molding material onto a release layer by an inkjet method; and curing the discharged three-dimensional molding material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a three-dimensional structure, a three-dimensional structure forming apparatus, and a member for a forming table.

  The three-dimensional modeling apparatus is also called a 3D printer. For example, in accordance with three-dimensional cross-sectional shape data, a modeling material (model material) is arranged using an ink jet method, and ultraviolet rays (UV) or electron beams (EB) are used. An apparatus for producing a three-dimensional structure (for example, a part such as an industrial product or a toy such as a doll) by repeatedly curing is known.

  In 3D modeling equipment, in order to form a free-form shaped object, when forming an overhang or ceiling, a support material (support) for forming a support part (support part) that supports the lower part of the modeling material Material) is required.

When the discharge head of the apparatus has a single nozzle (discharge portion that discharges only one composition), the same material as the modeling material is used as the support material (support material). In this case, unlike the modeling material that forms the modeled object, a method is adopted in which the density of the modeling material is lowered, the support part (support part) is modeled, and the support part is removed later.
When the ejection head of the apparatus has a multi-nozzle (ejection part that ejects two compositions), a dedicated material that makes the support part (support part) easily come off is used as the support material (support material).
Normally, when forming a three-dimensional structure directly on a modeling table, it is necessary to coat the molding agent and the support agent separately at a certain ratio on the bonding surface in order to balance the adhesion and peelability of the modeling object. For this reason, the surface of the bonding surface becomes rough.

Patent documents 1 thru / or 3 are mentioned as a manufacturing method of the conventional three-dimensional structure.
Patent Document 1 discloses a method for producing a photocurable composition film by exposing a photocurable composition layer to actinic radiation through the surface of a barrier transparent to actinic radiation. A method comprising the step of positioning the surface of the transparent barrier in contact with the composition to form an interface with the composition, wherein the inhibitor layer is in contact with the interface in the photocurable composition A method wherein the photocuring of the composition in the inhibition layer is inhibited during the exposure step so that any photocured composition does not adhere to the barrier, and the following steps: The method includes: moving the film substantially parallel to the interface to form a new layer of a photocurable composition adjacent to the interface, and repeating the creation and exposure steps to previously expose the film. New film in parallel Producing a photocured continuous film of the composition; and selectively performing the exposure step to produce a patterned film, and further comprising the following steps: the film Moving away from the interface in a direction substantially perpendicular to the interface to form a new layer of photocurable composition adjacent to the interface and a series of patterns of photocured material The creation step, the exposure step and the transfer step are repeated to produce an integrated three-dimensional body having a plurality of cross-sectional portions corresponding to the formed film.

Patent document 2 describes slips based on multi-reactive binders, polymerization initiators and fillers, in each case compared to the total mass of the slip: (A) 65 wt% polyreactive binder, (B) 0.001 wt% to 1.0 wt% photoinitiator, and (C) 35 wt% to 90 wt% surface modified ceramic particles, and / or A process for the preparation of ceramic moldings by a rapid prototyping process using slips, characterized by containing, surface-modified glass-ceramic particles, is described.

Patent Document 3 is a method for producing a support used in an inkjet stereolithography method, and contains the following components (A), (B) and (C) with respect to 100% by mass of the total composition. Step 1 of forming a photocurable liquid resin composition layer by injecting the photocurable liquid resin composition to form a photocurable liquid resin composition layer by an inkjet method, and irradiating the photocurable liquid resin composition layer with light. The manufacturing method of the support body which repeats the process 2 which hardens an ionic liquid resin composition layer, and the process containing the process 1 and the process 2 and forms a support body is described.
(A) 15 to 99% by mass of an acrylamide compound having one vinyl group,
(B) Chain transfer agent 0.1-5 mass%,
(C) Photopolymerization initiator 0.5 to 10% by mass

JP-A-4-232728 JP 2010-031279 A JP 2010-155889 A

  The problem to be solved by the present invention is superior to the case in which a three-dimensional structure is directly formed on a modeling table, and is excellent in peelability between the three-dimensional structure and the modeling table. It is providing the manufacturing method of the three-dimensional structure which is excellent in the surface property of the joint surface of this.

  The above problem is solved by the following means.

The invention according to claim 1
A step of preparing a molding table having a compound containing a mercapto group and a layer containing a binder polymer on at least a part of the surface, a step of discharging a radical polymerizable three-dimensional modeling material on the layer by an ink jet method, and And a step of curing the discharged three-dimensional modeling material.

The invention according to claim 2
The method for producing a three-dimensional structure according to claim 1, wherein the compound having a mercapto group is a compound having two or more mercapto groups.

The invention according to claim 3
The method for producing a three-dimensional structure according to claim 1 or 2, wherein the compound having a mercapto group has a molecular weight of 250 or more.

The invention according to claim 4
A molding table having a layer containing a compound having a mercapto group and a binder polymer on at least a part of the surface, and a discharge unit for accommodating the radical polymerizable three-dimensional modeling material and discharging the three-dimensional modeling material by an ink jet method And a light irradiation unit that emits light for curing the discharged three-dimensional modeling material.

The invention according to claim 5
The three-dimensional modeling apparatus according to claim 4, wherein the compound having a mercapto group is a compound having two or more mercapto groups.

The invention according to claim 6
6. The three-dimensional modeling apparatus according to claim 4, wherein the compound having a mercapto group has a molecular weight of 250 or more.

The invention according to claim 7 provides:
It is a member for modeling tables which has a layer containing a compound having a mercapto group and a binder polymer on at least a part of the surface of the substrate.

The invention according to claim 8 provides:
The member for a modeling table according to claim 7, wherein the compound having a mercapto group is a compound having two or more mercapto groups.

The invention according to claim 9 is:
The molecular weight of the compound having the mercapto group is 250 or more.

According to the invention which concerns on Claim 1, it is excellent in the peelability of the obtained three-dimensional structure and a modeling stand compared with the case where a three-dimensional structure is formed directly on a modeling table, A method for producing a three-dimensional structure excellent in surface properties of the joint surface is provided.
According to the second aspect of the present invention, there is provided a method for producing a three-dimensional structure that is superior to the case where a compound having only one mercapto group is used and the peelability between the obtained three-dimensional structure and the forming table is improved. The
According to the invention according to claim 3, it is superior to the case where the molecular weight of the compound having a mercapto group is less than 250, and is excellent in releasability between the obtained three-dimensional structure and the modeling table, and the tertiary in which the mercapto odor is suppressed. A method for manufacturing an original shaped article is provided.

According to the invention which concerns on Claim 4, it is excellent in the peelability of the obtained three-dimensional structure and a modeling stand compared with the case where a three-dimensional structure is formed directly on a modeling table, A three-dimensional modeling apparatus having excellent surface properties of the joint surface is provided.
According to the invention which concerns on Claim 5, compared with the case where the compound which has only one mercapto group is used, the three-dimensional modeling apparatus which is excellent by the peelability of the three-dimensional structure to be obtained and a modeling stand is provided.
According to the invention which concerns on Claim 6, compared with the case where the molecular weight of the compound which has the said mercapto group is less than 250, it is excellent by the peelability of the obtained three-dimensional structure and a modeling stand, and the tertiary which a mercapto odor is suppressed. An original modeling apparatus is provided.

According to the invention which concerns on Claim 7, it is excellent in the peelability of the obtained three-dimensional structure and a modeling stand compared with the case where a three-dimensional structure is formed directly on a modeling table, There is provided a molding table member having excellent surface properties of the joint surface.
According to the invention which concerns on Claim 8, compared with the case where the compound which has only one mercapto group is used, the member for modeling bases which is excellent by the peelability of the obtained three-dimensional molded item and a modeling base is provided.
According to the invention according to claim 9, compared with the case where the molecular weight of the compound having a mercapto group is less than 250, the modeling is excellent in the peelability between the obtained three-dimensional structure and the modeling table, and the mercapto odor is suppressed. A table member is provided.

It is a schematic block diagram which shows an example of the three-dimensional modeling apparatus which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure based on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure based on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure based on this embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

<Method for manufacturing three-dimensional structure>
The manufacturing method of the three-dimensional structure according to the present embodiment prepares a modeling table that has a compound having a mercapto group and a layer containing a binder polymer (hereinafter also referred to as “release layer”) on at least a part of the surface. A step, a step of discharging a radical polymerizable three-dimensional modeling material on the layer by an ink jet method, and a step of curing the discharged three-dimensional modeling material.

  In the manufacturing method of the three-dimensional structure according to the present embodiment, due to the above-described configuration, the peelability between the obtained three-dimensional structure and the modeling table is excellent, and the surface property of the joint surface between the three-dimensional structure and the modeling table is excellent. . The reason is estimated as follows.

Conventionally, when manufacturing a three-dimensional structure, generally a three-dimensional structure is formed on a modeling table, but the peelability between the modeling table and the formed three-dimensional structure is poor, and in the formed three-dimensional structure, There was a case where the surface contacted with the modeling table was transferred to the surface state of the modeling table and the surface property was deteriorated (the surface became rough).
Also, on the modeling table, there is a case where a release layer in which the support material and the model material are mixed is formed, but even in the above case, the peeling property between the modeling table and the formed three-dimensional model is not sufficient, The surface properties were significantly reduced.

  By having a compound containing a mercapto group and a layer (release layer) containing a binder polymer on the surface of the modeling table, the radical polymerizable three-dimensional modeling material discharged onto the release layer is cured, that is, radical polymerization. In doing so, in the vicinity of the interface between the release layer and the three-dimensional modeling material, the generated radical is transferred to a compound having a mercapto group, which is a chain transfer agent, to generate a sulfur radical. The generated sulfur radical draws out hydrogen atoms in the components in the three-dimensional modeling material and starts the radical polymerization reaction in the three-dimensional modeling material again, or the sulfur radical dimerizes and deactivates. Since the component of the release layer and the component in the 3D modeling material do not form a chemical bond, the peeling force between the modeling table having the release layer and the formed 3D model is not high, and the peelability is excellent. .

Moreover, in the manufacturing method of the three-dimensional structure according to the present embodiment, the component of the release layer and the component in the three-dimensional structure do not form a chemical bond, and the three-dimensional structure on the release layer. Since the wettability of the material is also appropriate, and the surface property of the contact portion with the modeling table having the release layer in the obtained three-dimensional structure is excellent, the contact portion with the release layer in the obtained three-dimensional structure and The difference from the non-contact portion is small, and the resulting three-dimensional structure is excellent in appearance and colorability.
In addition, since the difference between the contact portion and the non-contact portion with the release layer in the obtained three-dimensional structure is small, the direction in which the three-dimensional structure is produced is freely selected, for example, the use of a support material is suppressed. The production direction of the three-dimensional structure is selected, and the three-dimensional structure is produced.
Furthermore, specifically, for example, when producing a hemispherical three-dimensional structure, a hemispherical three-dimensional structure is formed by using the sphere cross-section side as a modeling table side without using a support material. Since a three-dimensional shaped object is obtained, ink consumption is suppressed.

  Hereinafter, the manufacturing method of the three-dimensional structure according to the present embodiment will be described in detail.

  In the method for producing a three-dimensional structure according to the present embodiment, a step (preparation step) of preparing a forming table having a compound containing a mercapto group and a layer containing a binder polymer on at least a part of the surface (preparation step) on the layer Then, a three-dimensional structure is manufactured through a step of discharging a radical polymerizable three-dimensional structure material by an ink jet method (discharge process) and a step of curing the discharged three-dimensional structure material (curing step).

(Preparation process)
The manufacturing method of the three-dimensional structure according to the present embodiment includes a step (preparation step) of preparing a forming table having a compound containing a mercapto group and a layer containing a binder polymer on at least a part of the surface.
The release layer is preferably provided on at least a part of a surface of the modeling table forming the three-dimensional modeled object, and is provided so as to exist at least between the three-dimensional modeled object to be formed and the modeling table. More preferably.

  The thickness of the release layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less from the viewpoint of releasability between the obtained three-dimensional structure and the modeling table, and repeated use of the release layer. It is more preferably 2 μm or more and 30 μm or less, and particularly preferably 5 μm or more and 20 μm or less.

There is no restriction | limiting in particular in the formation method of the said peeling layer, What is necessary is just to form by a well-known method.
Among these, from the viewpoint of the surface property of the contact portion with the modeling table having the release layer in the obtained three-dimensional modeled object, there is a method of applying and drying a composition containing a compound having a mercapto group, a binder polymer, and a solvent. Preferably mentioned. The solvent is not particularly limited as long as it is a solvent capable of dissolving a compound having a mercapto group and a binder polymer, and a known solvent is used.

The material of the modeling table is not particularly limited, but is preferably at least one material selected from the group consisting of glass, metal, and resin.
The shape of the modeling table is not particularly limited, and a modeling table having a known shape is used.
Further, the release layer in the method for manufacturing a three-dimensional structure according to the present embodiment may be directly formed on the surface of the modeling table, or provided by installing a modeling table member to be described later on the modeling table. May be.

<Compound having a mercapto group>
The release layer contains a compound having a mercapto group.
The compound having a mercapto group may be a monofunctional mercapto compound (a compound having only one mercapto group) or a polyfunctional mercapto compound (a compound having two or more mercapto groups). It is preferable that it is a polyfunctional mercapto compound from the viewpoint of releasability between the three-dimensional structure to be formed and the modeling table and the repeated use of the release layer.
In addition, the number of mercapto groups in the polyfunctional mercapto compound is preferably 2 or more and 8 or less from the viewpoint of the peelability between the obtained three-dimensional structure and the forming table and the repeated use of the release layer. It is more preferably 6 or less, and particularly preferably 4.
Furthermore, it is preferable that the compound which has a mercapto group is an aliphatic mercapto compound from a peelable viewpoint of the three-dimensional structure to be obtained and the forming table.

The compound having a mercapto group is preferably a compound having a β-mercaptocarboxylic acid ester structure, from the viewpoint of peelability between the obtained three-dimensional structure and the forming table, and two or more β-mercaptocarboxylic acids. More preferably, it is a compound having an ester structure.
The molecular weight of the compound having a mercapto group is preferably 200 or more, more preferably 250 or more, from the viewpoint of the peelability between the obtained three-dimensional structure and the forming table and the suppression of the mercapto odor. It is particularly preferred that it is 350 or more and 1,000 or less.

  Specific examples of the compound having a mercapto group include the following compounds (S-1) to (S-11), but it goes without saying that the compounds are not limited thereto.

  Among these, the compound (S-1) or (S-3) to (S) from the viewpoints of peelability between the obtained three-dimensional structure and the modeling table, suppression of mercapto odor, and repeated use of the release layer. -11) is preferred, compounds (S-7) to (S-11) are more preferred, and compound (S-9) is particularly preferred.

The compound which has a mercapto group may be used individually by 1 type, and may use 2 or more types together.
Content of the compound which has a mercapto group in the said peeling layer is 1 mass% or more and 30 mass% or less with respect to the total mass of the said peeling layer from a peelable viewpoint of the three-dimensional structure to be obtained and a modeling stand. It is preferably 2% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less.

<Binder polymer>
The release layer includes a binder polymer.
The binder polymer is preferably a polymer having no ethylenically unsaturated group.
Specific examples of the binder polymer include polycarbonate resin, polyester resin, acrylic resin, and styrene resin.

A binder polymer may be used individually by 1 type, and may use 2 or more types together.
The content of the binder polymer in the release layer is 70% by mass or more and 99% by mass or less with respect to the total mass of the release layer from the viewpoint of the peelability between the obtained three-dimensional structure and the modeling table. It is preferably 80% by mass or more and 98% by mass or less, more preferably 85% by mass or more and 95% by mass or less.

<Other additives>
The release layer may contain an additive other than the compound having the mercapto group and the binder polymer, but the total content of the other additive is 10 with respect to the total mass of the release layer. It is preferably at most mass%, more preferably at most 5 mass%, particularly preferably at most 1 mass%.
As other additives, known additives are used.
Specifically, a solvent, surfactant, a coloring agent, a fragrance | flavor, etc. are mentioned, for example.
Another additive may be used individually by 1 type and may use 2 or more types together.

(Discharge process)
The manufacturing method of the three-dimensional structure according to the present embodiment includes a step (discharge step) of discharging a radical polymerizable three-dimensional structure material on the release layer by an ink jet method.
The radical polymerizable three-dimensional modeling material used in this embodiment will be described later.
The ink jet head used in the ejection step is not particularly limited, and a known ink jet head is used. For example, a piezo ink jet head can be mentioned.
There is no restriction | limiting in particular in the discharge temperature of the said three-dimensional modeling agent, It can prepare according to the three-dimensional modeling agent to be used.
There is no restriction | limiting in particular also about the discharge amount in the said discharge process, What is necessary is just to discharge the quantity used as the target thickness. Moreover, you may perform the said discharge in multiple times as needed.

In the discharge step, from the viewpoint of peelability between the obtained three-dimensional structure and the modeling table, the three-dimensional modeling is performed on the release layer so that the three-dimensional modeling material and the modeling table are not in direct contact with each other. It is preferable to discharge the material.
What is necessary is just to set suitably the discharge shape of the said three-dimensional modeling material in the said discharge process according to the shape of the three-dimensional structure to form.

Moreover, in the said discharge process, you may discharge a support material not only with the said three-dimensional modeling material but with an inkjet system as needed.
The support material may be discharged onto the release layer or may be directly discharged onto the modeling table. However, in terms of peelability and ease of thickness adjustment with the three-dimensional modeling material, the release layer It is preferable to discharge upward.
The support material used in this embodiment will be described later.

(Curing process)
The manufacturing method of the three-dimensional structure according to the present embodiment includes a step (curing step) of curing the discharged three-dimensional structure.
Curing in the curing step, that is, radical polymerization, may be performed by light (for example, ultraviolet rays or electron beams) or heat, depending on the composition of the three-dimensional modeling material, but is preferably performed by light.
It should be noted that “light” in the present embodiment includes not only visible light but also ultraviolet light, electron beam, infrared light, and the like, unless otherwise specified.
Curing in the curing step is preferably performed by irradiation with ultraviolet rays or electron beams, and more preferably by irradiation with ultraviolet rays.
In the curing step, the discharged support material may be cured as necessary. In the curing step, the three-dimensional modeling material and the support material may be cured at a time or may be separately cured.

There is no restriction | limiting in particular as a light irradiation apparatus used for the said hardening, A well-known thing is used. Among these, an ultraviolet irradiation device and an electron beam irradiation device are preferable, and an ultraviolet irradiation device is more preferable.
Although there is no restriction | limiting in particular as an ultraviolet-ray (UV) irradiation apparatus, The lamp | ramp which excites a mercury lamp by the electrodeless from the outside using a light emitting diode (UV-LED), a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deep ultraviolet lamp, and a microwave, ultraviolet rays A laser, a xenon lamp, a metal halide lamp, etc. are mentioned.
The electron beam (EB) irradiation device is not particularly limited, and examples thereof include scanning type, curtain type, and plasma discharge type electron irradiation devices.

(Other processes)
The manufacturing method of the three-dimensional structure according to the present embodiment includes a radical polymerizable tertiary on a cured material selected from the group consisting of the cured three-dimensional structure material and the cured support material after the curing step. The original modeling material and, if necessary, the step of discharging the support material by an ink jet method, and the discharged three-dimensional modeling material, and, if necessary, the step of curing the discharged support material are tertiary. It is preferable to repeat the number of times necessary to form the original shaped object.
When producing a flat three-dimensional structure, a three-dimensional structure may be produced only by the discharge process and the curing process, but when producing a three-dimensional structure having a certain height. After the discharging step and the curing step, it is preferable to produce the three-dimensional structure by repeating the two steps.
There is no restriction | limiting in particular in the frequency | count of the said repetition, What is necessary is just to set suitably according to the shape of the three-dimensional structure to produce.

When a support material is used, it is preferable that the manufacturing method of the three-dimensional structure according to the present embodiment includes a step of removing the cured support material.
The method for removing the support material is not particularly limited. Depending on the support material used, mechanical removal such as pulverization or water jet may be performed, or chemical removal such as water solution may be performed. May be combined.

Moreover, even if the manufacturing method of the three-dimensional structure according to the present embodiment includes a step of washing the obtained three-dimensional structure and a step of coloring the obtained three-dimensional structure as necessary. Good.
Furthermore, the manufacturing method of the three-dimensional structure according to the present embodiment may include other known processes.

Since the manufacturing method of the three-dimensional structure according to the present embodiment is excellent in the surface property of the contact portion with the modeling table having the release layer in the obtained three-dimensional structure as described above, for example, hemispherical When preparing a three-dimensional structure, the sphere cross-section side is the modeling table side, and even if a hemispherical three-dimensional structure is prepared, an excellent peelability and surface property can be obtained, and a support material is used. A hemispherical three-dimensional structure can be obtained at least.
In addition, the manufacturing method of the three-dimensional structure according to the present embodiment may produce a hemispherical three-dimensional structure using the support material on the side opposite to the cross-section side of the sphere and using a support material. Needless to say.

<Three-dimensional modeling device>
The three-dimensional modeling apparatus according to the present embodiment accommodates a compound base having a mercapto group and a modeling table having a layer containing a binder polymer on at least a part of the surface, and a radical polymerizable three-dimensional modeling material, and the tertiary A discharge unit that discharges the original modeling material by an inkjet method; and a light irradiation unit that irradiates light that cures the discharged three-dimensional modeling material.
The three-dimensional modeling apparatus according to the present embodiment is suitably used for the method for manufacturing a three-dimensional modeled object according to the present embodiment.

  The compound having a mercapto group in the three-dimensional modeling apparatus according to this embodiment, the layer containing the binder polymer, and the modeling table are compounds having a mercapto group in the method for manufacturing a three-dimensional structure according to this embodiment described above. It is synonymous with the layer containing a binder polymer, and a modeling stand, and a preferable aspect is also the same.

The discharge unit in the three-dimensional modeling apparatus according to the present embodiment is not particularly limited as long as it is a discharge apparatus that discharges by an inkjet method, but the above-described inkjet head is preferably exemplified.
The number of ink jet heads and the number of nozzles in the ink jet head are not particularly limited and may be set as appropriate.
Moreover, it is preferable that the three-dimensional modeling apparatus according to the present embodiment includes a support material discharge unit that accommodates the support material and discharges the support material by an inkjet method.
The radical polymerizable three-dimensional modeling material and the support material will be described later.

The light irradiation unit in the three-dimensional modeling apparatus according to the present embodiment may be any apparatus that irradiates light that cures the three-dimensional modeling material, but preferably includes an ultraviolet irradiation apparatus and an electron beam irradiation apparatus.
As the ultraviolet irradiation device and the electron beam irradiation device, those mentioned above are preferably mentioned.
You may have only one said light irradiation part, or may have two or more.
Moreover, it is preferable that the three-dimensional modeling apparatus according to the present embodiment includes a light irradiation unit that emits light for curing the discharged support material.
In addition, the light irradiation part which hardens the said three-dimensional modeling material, and the light irradiation part which hardens the said support material may be the same, and may differ.

Further, the 3D modeling apparatus according to the present embodiment may include a support material removing unit that removes the support material, or the support material removing unit may be provided in a device different from the 3D modeling apparatus according to the present embodiment. May be provided.
Furthermore, the three-dimensional modeling apparatus according to the present embodiment may include other known apparatuses and members.

Hereinafter, the three-dimensional modeling apparatus according to the present embodiment will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram illustrating an example of a 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. 1, the three-dimensional modeling apparatus 101 includes, for example, a modeling unit 10 and a modeling table 20 having a layer 22 containing a compound having a mercapto group and a binder polymer on the surface. In addition, the three-dimensional modeling apparatus 101 includes a model material cartridge 30 that stores a radical polymerizable three-dimensional modeling material (model material) and a support material cartridge 32 that stores a support material so as to be detachable from the apparatus. Yes. In addition, in FIG. 1, MD shows a three-dimensional structure and SP shows a support part.

  The modeling unit 10 includes, for example, a model material ejection head 12 (an example of a first ejection unit) that ejects droplets of a model material and a support material ejection head 14 (an example of a second ejection unit) that ejects droplets of a support material. ) And a light irradiation device 16 (light irradiation device) that emits light. In addition, although not shown, the modeling unit 10 may include, for example, a rotating roller that removes excess model material and support material from the model material and support material discharged onto the modeling table 20 and flattens them. .

  The modeling unit 10 is, for example, a system that can be moved on the modeling region of the modeling table 20 having the layer 22 on the surface in the main scanning direction and the sub-scanning direction intersecting (for example, orthogonal) with the driving unit (not shown). (So-called carriage system).

  Each of the model material discharge head 12 and the support material discharge head 14 is a piezo type (piezoelectric type) discharge head that discharges droplets of each material by pressure. Each discharge head is not limited to this, and may be a discharge head that discharges each material by pressure from a pump.

The model material discharge head 12 is connected to the model material cartridge 30 through a supply pipe (not shown), for example. Then, the model material is supplied to the model material discharge head 12 by the model material cartridge 30.
The support material discharge head 14 is connected to the support material cartridge 32 through a supply pipe (not shown), for example. Then, the support material is supplied to the support material discharge head 14 by the support material cartridge 32.

Each of the model material discharge head 12 and the support material discharge head 14 has an effective discharge area (arrangement area of nozzles for discharging the model material and the support material) smaller than the modeling area of the modeling table 20 having the layer 22 on the surface. It is a short discharge head.
Each of the model material discharge head 12 and the support material discharge head 14 has, for example, an effective discharge region (arrangement region of nozzles for discharging the model material and the support material) on the modeling table 20 having the layer 22 on the surface. It is good also as an elongate head made into the modeling area width | variety (The length of the direction crossing (for example, orthogonal) the moving direction (main scanning direction) of the modeling unit 10) or more. In this case, the modeling unit 10 is configured to move only in the main scanning direction.

The light irradiation device 16 is selected according to the type of model material and support material. Examples of the light irradiation device 16 include an ultraviolet irradiation device and an electron beam irradiation device.
Examples of the ultraviolet irradiation device and the electron beam irradiation device include those described above.

  The modeling table 20 has a surface on which a layer 22 is formed, which has a modeling area where a model material and a support material are discharged to form a modeled object. And the modeling stand 20 which has the layer 22 on the surface can be raised / lowered by the drive device not shown.

  Next, the operation of the 3D modeling apparatus 101 according to the present embodiment (a method for manufacturing a 3D model) will be described.

  First, by using a computer (not shown) or the like, for example, two-dimensional data for forming a model as three-dimensional modeling data from three-dimensional CAD (Computer Aided Design) data of a three-dimensional model formed by a model material. Dimensional shape data (slice data) is generated. At this time, two-dimensional shape data (slice data) for forming the support portion by the support material is also generated. The two-dimensional shape data for forming the support part is such that the width of the modeled object at the upper position is larger than the width of the modeled object at the lower position. A support portion is formed so as to support.

  Next, the model material is ejected from the model material ejection head 12 while moving the modeling unit 10 based on the two-dimensional shape data for forming the modeled object, and the model material layer is formed on the layer 22. To do. Then, the light irradiation device 16 irradiates the model material layer with light, cures the model material, and forms a layer that becomes a part of the modeled object.

If necessary, the support material is discharged from the support material discharge head 14 while moving the modeling unit 10 on the basis of the two-dimensional data for forming the support portion. Adjacent, a layer of support material is formed. Then, the light irradiation device 16 irradiates the support material layer with light, cures the support material, and forms a layer that becomes a part of the support portion.
In this way, the first layer LAY1 including the layer that becomes a part of the modeled object and the layer that becomes a part of the support part is formed as necessary (see FIG. 2A). Here, in FIG. 2A, MD1 shows the layer used as a part of modeling thing in 1st layer LAY1, and SP1 shows the layer used as a part of support part in 1st layer LAY1.

  Next, the modeling table 20 having the layer 22 on the surface is lowered. The lowering of the modeling table 20 is the thickness of the second layer to be formed next (the second layer consisting of a layer that becomes a part of the modeled object and a layer that becomes a part of the support part as necessary). To do.

  Next, similarly to the first layer LAY1, a second layer LAY2 including a layer that becomes a part of the modeled object and, if necessary, a layer that becomes a part of the support part is formed (see FIG. 2B). Here, in FIG. 2B, MD2 shows the layer used as a part of modeling thing in 2nd layer LAY2, and SP2 shows the layer used as a part of support part in 2nd layer LAY2.

  Then, the operation of forming the first layer LAY1 and the second layer LAY2 is repeatedly performed until the nth layer LAYn is formed. As a result, a modeled object at least partially supported by the support part is formed (see FIG. 2C). Here, in FIG. 2C, MDn indicates a layer that is a part of the shaped object in the n-th layer LAYn. MD indicates a shaped object. SP indicates a support unit.

Then, if a support part is removed from a molded article, the target molded article will be obtained. Here, for the removal of the support portion, for example, a method of removing by hand (breakaway method), a method of removing by jetting gas or liquid, and the like are adopted.
In addition, you may give post-processing, such as a grinding | polishing process, for the obtained molded article.

<Modeling table materials>
The modeling table member according to the present embodiment has a layer containing a compound having a mercapto group and a binder polymer on at least a part of the surface of the substrate.
Moreover, the member for modeling stands which concerns on this embodiment is used suitably as a member for modeling stands in a three-dimensional modeling apparatus.
Furthermore, the modeling table member according to the present embodiment may be used by being installed on the modeling table in the three-dimensional modeling apparatus, or may be used as the modeling table itself.
The mercapto in the manufacturing method of the three-dimensional structure according to this embodiment described above, except that the compound having a mercapto group and the layer containing the binder polymer in the member for modeling table according to this embodiment have on the substrate surface. It is synonymous with the layer which contains the compound which has group, and a binder polymer, and its preferable aspect is also the same.

The base material used for the modeling table member according to the present embodiment is not particularly limited, but is preferably at least one material selected from the group consisting of glass, metal and resin, and more preferably from metal and resin. It is more preferable that the material is at least one material selected from the group consisting of:
There is no restriction | limiting in particular as resin, A well-known resin is used.
In addition, the shape of the substrate may be appropriately selected according to the modeling table and the three-dimensional modeling apparatus to be used, but a plate shape or a sheet shape is preferable, and a plate shape is more preferable. In the present embodiment, the difference between the plate shape and the sheet shape is that the plate-like base material is a base material that is not deformed by the weight of the base material when the base material end is fixed. When the base material end is fixed, the base material is deformed by its own weight.
The thickness of the substrate is preferably 10 μm or more and 10 cm or less, and more preferably 10 μm or more and 1 cm or less when the modeling table member according to this embodiment is installed on the modeling table. More preferably, it is 1,000 μm or less. Moreover, when making the modeling stand member which concerns on this embodiment into modeling modeling itself, it is more preferable that they are 0.5 cm or more and 10 cm or less, and it is still more preferable that they are 1 cm or more and 10 cm or less.

The modeling table member according to the present embodiment may further have a protective film on the release layer in order to prevent dirt and scratches in the release layer.
There is no restriction | limiting in particular as a protective film, Although a well-known protective film is used, it is preferable that it is a resin film.
Although there is no restriction | limiting in particular as thickness of a protective film, It is preferable that they are 5 micrometers or more and 500 micrometers or less.

In addition, when the modeling table member according to the present embodiment is installed in the 3D modeling apparatus, the 3D modeling apparatus has a fixture such as a fastener and a jig for fixing the modeling table member according to the present embodiment. It is preferable.
There is no restriction | limiting in particular as a fastener and a jig | tool, A well-known thing is used.

After producing the three-dimensional structure one or more times using the modeling table member according to this embodiment, the used modeling table member according to this embodiment is used as a new modeling table member according to this embodiment. The aspect which replaces | exchanges and also produces a three-dimensional structure is mentioned preferably.
In the three-dimensional modeling apparatus, by exchanging the modeling table member according to the present embodiment, a three-dimensional modeled object having excellent peelability from the modeling table is repeatedly produced.

<< Radically polymerizable three-dimensional modeling material (model material) >>
The three-dimensional modeling material used in the present embodiment is not particularly limited as long as it is radically polymerizable, but preferably contains an ethylenically unsaturated compound, an ethylenically unsaturated compound, and a photopolymerization initiator. It is more preferable to contain.
In addition, the three-dimensional modeling material used in the present embodiment may include other additives such as a polymerization inhibitor and a surfactant.

(Ethylenically unsaturated compounds)
The ethylenically unsaturated compound is not particularly limited as long as it is a compound having an ethylenically unsaturated bond, and may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
Especially, it is preferable that the three-dimensional modeling material used for this embodiment contains urethane (meth) acrylate as an ethylenically unsaturated compound.

-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.
In the present specification, (meth) acrylate means both acrylate and methacrylate. Moreover, (meth) acryloyl means both an acryloyl group and a methacryloyl group.

  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. Specifically, as urethane (meth) acrylate, for example, a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound, and a reaction between a prepolymer having an isocyanate group at the terminal and a hydroxyl group-containing (meth) acrylate Products. Moreover, as urethane (meth) acrylate, the reaction product of a polyisocyanate compound and a hydroxyl-containing (meth) acrylate is mentioned.

-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 from 500 to 5,000, more preferably from 1,000 to 3,000.
The weight average molecular weight of urethane (meth) acrylate is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

-Other ethylenically unsaturated compounds-
Examples of the other ethylenically unsaturated compounds include ethylenically unsaturated compounds having at least one group selected from the group consisting of an N-vinyl group, a vinyl ether group, and a (meth) acryloyl group.

  Specifically, examples of the other ethylenically unsaturated compound include (meth) acrylate (monofunctional (meth) acrylate, polyfunctional (meth) acrylate) and the like.

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 diacrylate, 2-methyl-1,8-octanediol diacrylate, and 2-butyl-2- Ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl-1 , 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, Propylene glycol diacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, EO (ethylene oxide) modified bisphenol A diacrylate, PO (propylene oxide) modified bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, EO ( Ethylene oxide) modified bisphenol F diacrylate and the like.

  Among polyfunctional (meth) acrylates, trifunctional or higher (meth) acrylates include, for example, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, Ethoxylated glycerol triacrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO (ethylene oxide) modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate modified acrylate, dipentaerythritol pentaacrylate, di Examples include pentaerythritol hexaacrylate.

-Content of ethylenically unsaturated compound-
90 mass% or more and 99 mass% or less are preferable with respect to the whole three-dimensional modeling material, and, as for content of an ethylenically unsaturated compound, 93 mass% or more and 97 mass% or less are preferable.
In particular, the ethylenically unsaturated compound is preferably a combination of urethane (meth) acrylate and the other ethylenically unsaturated compound. In this case, the content of urethane (meth) acrylate is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the entire three-dimensional modeling material. On the other hand, the content of the other ethylenically unsaturated compound is preferably 40% by mass or more and 75% by mass or less, and more preferably 50% by mass or more and 65% by mass or less with respect to the entire three-dimensional modeling material.
In addition, an ethylenically unsaturated compound may be used individually by 1 type, and may be used together 2 or more types.

(Photopolymerization initiator)
As the photopolymerization initiator, a radical photopolymerization initiator is preferable.
Examples of radical photopolymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds Ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds, and the like.

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, di Tylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide And well-known photopolymerization initiators.

-Content of photopolymerization initiator-
The content of the photopolymerization initiator is, for example, preferably from 1% by mass to 10% by mass, and more preferably from 3% by mass to 5% by mass with respect to the three-dimensional modeling material.
In addition, a photoinitiator may be used individually by 1 type and may be used together 2 or more types.

(Polymerization inhibitor)
Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (for example, 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-tert-butylphenol), hindered amine, hydroquinone Well-known polymerization inhibitors such as monomethyl ether (MEHQ) and hydroquinone can be mentioned.

-Content of polymerization inhibitor-
The content of the polymerization inhibitor is, for example, preferably 0.1% by mass or more and 1% by mass or less, and more preferably 0.3% by mass or more and 0.5% by mass or less with respect to the three-dimensional modeling material.
In addition, a polymerization inhibitor may be used individually by 1 type, and may be used together 2 or more types.

(Surfactant)
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.

-Surfactant content-
The content of the surfactant is, for example, preferably 0.05% by mass or more and 0.5% by mass or less, and more preferably 0.1% by mass or more and 0.3% by mass or less with respect to the three-dimensional modeling material.
In addition, surfactant may be used individually by 1 type and may be used together 2 or more types.

(Other additives)
In addition to the above, other additives include, for example, colorants, solvents, sensitizers, fixing agents, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, thickeners, dispersants, Well-known additives such as a polymerization accelerator, a penetration accelerator, and a wetting agent (humectant) can be used.

(Characteristics of 3D modeling materials)
The surface tension of the three-dimensional modeling material is preferably in the range of 20 mN / m to 40 mN / m.
In addition, the surface tension of a three-dimensional modeling material and the support material mentioned later is the value measured in the environment of 23 degreeC and 55% RH using the Wilhelmy type surface tension meter (made by Kyowa Interface Science Co., Ltd.).

The viscosity of the three-dimensional modeling material is preferably in the range of 30 mPa · s to 50 mPa · s.
Here, the viscosities of the three-dimensional modeling material and the support material to be described later are values measured using a Rheomat 115 (manufactured by Contraves) as a measuring device, a measurement temperature of 23 ° C., and a shear rate of 1400 s ^−1. .

<< support material >>
There is no restriction | limiting in particular in the support material used for this embodiment, A well-known support material is used.
Moreover, it is preferable that the support material used for this embodiment contains the polymer which does not have an ethylenically unsaturated compound and an ethylenically unsaturated bond, an ethylenically unsaturated compound, a photoinitiator, and ethylenic. It is more preferable to include a polymer having no unsaturated bond.
Furthermore, the support material used in the present embodiment may contain a plasticizer other than the polymer that does not have the ethylenically unsaturated bond, such as water.
In addition to the above, the support material used in the present embodiment may include other additives such as a polymerization inhibitor, a surfactant, and a colorant.

  Regarding preferred embodiments of the ethylenically unsaturated compound, the photopolymerization initiator, and other additives in the support material, except for the content described later, the ethylenically unsaturated compound in the three-dimensional modeling material, photopolymerization described above. It is the same as that of the preferable aspect in an initiator and another additive.

(Polymer without ethylenically unsaturated bond)
Although there is no restriction | limiting in particular as a polymer which does not have an ethylenically unsaturated bond, It is preferable that it is a water-soluble polymer.

The hydroxyl value of the polymer having no ethylenically unsaturated bond is preferably 60 mgKOH / g or more and 300 mgKOH / g or less, more preferably 100 mgKOH / g or more and 290 mgKOH / g or less, and 150 mgKOH / g from the viewpoint of improving the peelability of the support part. More preferably, it is 280 mgKOH / g or less.
The hydroxyl value of a polymer having no ethylenically unsaturated bond is a value measured according to JIS K-0070-1992.

  The polymer having no ethylenically unsaturated bond is preferably at least one selected from the group consisting of polyether polyol, castor oil polyol, and polyester polyol from the viewpoint of improving the peelability of the support portion.

-Polyether polyol Examples of the polyether polyol include multimers of polyhydric alcohols, adducts of polyhydric alcohols and alkylene oxides, and ring-opening polymers of alkylene oxides.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, and 1,2-hexane. Diol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol, 1, Examples include 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.

Castor oil polyol Examples of castor oil polyol include modified castor oil obtained by modifying castor oil with polyhydric alcohol, and modified castor fatty acid obtained by modifying castor oil fatty acid (fatty acid obtained from castor oil) with polyhydric alcohol.
Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyether polyol.

-Polyester polyol As a polyester polyol, the reaction product of a polyhydric alcohol and a dibasic acid, the ring-opening polymer of a cyclic ester compound, etc. are mentioned, for example.
Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyether polyol.
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.

Here, the polymer which does not have an ethylenically unsaturated bond may use a polyhydric alcohol together with the above-mentioned various polyols. In particular, the polyhydric alcohol is preferably used in combination with the polyester polyol. That is, examples of the non-photocurable polymer include a mixture of a polyester polyol and a polyhydric alcohol.
The content of the polyhydric alcohol used in combination with the above-mentioned various polyols is 30% by mass or more and 60% by mass or less (preferably 35% by mass or more and 50% by mass or more) with respect to all monomers used for the production of the polymer having no ethylenically unsaturated bond. (Mass% or less) is preferable. In particular, when a mixture of polyester polyol and polyhydric alcohol is used, the mass ratio (polyester polyol / polyhydric alcohol) is preferably 30/70 or more and 10/90 or less (preferably 25/75 or more and 20/80 or less). .
Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyether polyol.

-Weight average molecular weight of polymer having no ethylenically unsaturated bond-
The weight average molecular weight of the polymer having no ethylenically unsaturated bond is preferably 200 or more and 1000 or less, and more preferably 250 or more and 850 or less, from the viewpoint of improving the peelability of the support portion.
The weight average molecular weight of a polymer having no ethylenically unsaturated bond is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

-Content of polymer having no ethylenically unsaturated bond-
The content of the polymer having no ethylenically unsaturated bond is, for example, preferably 25% by mass or more and 80% by mass or less with respect to the entire support material. In particular, the content of the non-photocurable polymer is preferably 30% by mass or more and 75% by mass or less, and preferably 35% by mass or more and 70% by mass or less with respect to the entire support material from the viewpoint of improving the peelability of the support part. Is more preferable, and 40 mass% or more and 65 mass% or less is still more preferable.
In addition, the polymer which does not have an ethylenically unsaturated bond may be used individually by 1 type, and may be used together 2 or more types.

20 mass% or more and 75 mass% or less are preferable with respect to the whole support material, and, as for content of the ethylenically unsaturated compound in a support material, 30 mass% or more and 65 mass% or less are more preferable.
In particular, also in the support material, it is preferable to use urethane (meth) acrylate and the other ethylenically unsaturated compound in combination as the ethylenically unsaturated compound, similarly to the three-dimensional modeling material. In this case, the content of urethane (meth) acrylate is preferably 5% by mass or more and 45% by mass or less, and more preferably 10% by mass or more and 35% by mass or less with respect to the entire support material. On the other hand, the content of the other ethylenically unsaturated compounds is preferably 10% by mass or more and 70% by mass or less, and more preferably 20% by mass or more and 65% by mass or less with respect to the entire support material.

  The content of the plasticizer other than the polymer having no ethylenically unsaturated bond in the support material is not particularly limited, but is preferably 0.5% by mass or more and 40% by mass or less, and preferably 1% by mass with respect to the entire support material. % To 20% by mass is more preferable.

(Characteristics of support material)
The surface tension of the support material used in the present embodiment is preferably in the range of 20 mN / m to 40 mN / m.
The viscosity of the support material used in this embodiment is preferably in the range of 30 mPa · s to 50 mPa · s.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by the following Example. Unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.

<Preparation of model material MA1>
-Urethane acrylate oligomer: 12.70 parts by mass ("U-200PA" manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Urethane acrylate oligomer: 16.40 parts by mass ("UA-4200" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylate monomer: 50.40 parts by mass (“VEEA” manufactured by Nippon Shokubai Co., Ltd., 2- (2-vinyloxyethoxy) ethyl acrylate)
Acrylate monomer: 14.60 parts by mass (“IBXA”, Osaka Organic Chemical Industry Co., Ltd., isobornyl acrylate)
-Polymerization inhibitor: 0.50 mass part (MEHQ (hydroquinone monomethyl ether))
Polymerization initiator: 3.00 parts by mass (LUCIRIN TPO, manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)
Polymerization initiator: 1.00 parts by mass (Irgacure 379) manufactured by BASF, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -ON)
Sensitizer: 1.00 parts by mass (ITX (2-isopropylthioxanthone))
Cyan pigment: 1.00 parts by mass (“KY410-4B” manufactured by Taisei Kako Co., Ltd.)
Surfactant: 0.20 part by mass (“TEGO Wet 270” manufactured by Evonik, polyether-modified siloxane copolymer)
The above ingredients were mixed to prepare a model material MA1.

<Preparation of support material SA1>
Polyether polyol ("Adeka Polyether P Series P-400" manufactured by ADEKA Co., Ltd.) as a non-photocurable polymer with respect to the prepared model material MA1 is an amount that is 25% by mass with respect to the entire support material The support material SA1 was prepared by mixing.

[Example 1]
<Preparation of composition for layer formation>
To 10 parts of dodecyl mercaptan (S-2), 90 parts of PCZ resin (polycarbonate resin, Iupizeta manufactured by Mitsubishi Gas Chemical Co., Ltd.) and toluene were added to prepare a toluene solution having a solid content of 2%.

<Production of 3D objects>
The three-dimensional modeling apparatus selects a Polaris head (model number: PQ512 / 85) manufactured by Fuji Film Dimatics as an inkjet head, and Subzero-055 (intensity of 100 w / cm) manufactured by INTEGRATION TECHNOLOGY LTD as an ultraviolet irradiation light source, These were installed in the modeling apparatus which consists of a drive part and a control part, and this was made into the modeling apparatus for a test. The modeling apparatus is a system in which the ink jet head and the light source reciprocate together, and each scanning (scanning) is performed by stacking a model material layer having a thickness of 20 μm and, if necessary, a support material layer, and ultraviolet irradiation. It was set as the apparatus which performs a hardening process and forms the support part (support part) by a three-dimensional molded item and a support material as needed. In the modeling apparatus, the model material and the support material are passed through a Tygon 2375 chemical resistant tube manufactured by Saint-Gobain Co., Ltd. by a liquid pump from a storage tank under a light-shielding condition, and profile star A050 filter manufactured by Nippon Pole Co., Ltd. (filtration accuracy 5 μm). ), And after removing foreign matter, the liquid is fed to the ink jet head. The release layer-forming composition was spin-coated at 2,000 rpm on a glass substrate used as a modeling table in the test modeling apparatus.
A layer of about 10 μm was formed on the glass substrate.
A 1 cm square cube was formed on the glass substrate having the release layer using the model material MA1.

<Peelability evaluation>
Peeling that 1 cm square cube formed on the glass substrate having the peeling layer and the glass substrate having the peeling layer are peeled off using a tensile testing machine (FGS-TV manufactured by Nidec Sympo Co., Ltd.) The force was measured.
The smaller the peel force, the better the peelability.
The evaluation results are shown in Table 1.

<Surface property evaluation>
Using a step meter NanoMap-500LS manufactured by AEP Technology, the peel surface center from the glass substrate of a 1 cm square cube for which peelability was evaluated was scanned over a length of 500 μm, and the surface roughness Ra (μm) Was measured.

[Example 2]
90 parts of PCZ resin and toluene are added to 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) (S-9) to prepare a toluene solution having a solid content of 2%. The release layer forming composition was spin-coated at 2,000 rpm on the glass substrate to be used. A layer of about 10 μm was formed on the glass substrate.
In the same manner as in Example 1, a 1 cm square cube was formed on the glass substrate having the release layer by using the model material MA1 and evaluated. The evaluation results are shown in Table 1.

Example 3
90 parts of PCZ resin and toluene were added to 10 parts of tris [(3-mercaptopropionyloxy) ethyl] isocyanurate (S-8) to prepare a toluene solution having a solid content of 2%, and the same molding as in Example 1 was performed. The release layer-forming composition was spin-coated at 2,000 rpm on a glass substrate used as a table. A layer of about 10 μm was formed on the glass substrate.
In the same manner as in Example 1, a 1 cm square cube was formed on the glass substrate having the release layer by using the model material MA1 and evaluated. The evaluation results are shown in Table 1.

Example 4
To 5 parts of pentaerythritol tetrakis (3-mercaptopropionate) (S-9), 95 parts of PCZ resin and toluene were added to prepare a toluene solution with a solid content of 2%. The release layer forming composition was spin-coated at 2,000 rpm on the glass substrate to be used. A layer of about 10 μm was formed on the glass substrate.
In the same manner as in Example 1, a 1 cm square cube was formed on the glass substrate having the release layer by using the model material MA1 and evaluated. The evaluation results are shown in Table 1.

Example 5
80 parts of PCZ resin and toluene are added to 20 parts of pentaerythritol tetrakis (3-mercaptopropionate) (S-9) to prepare a toluene solution with a solid content of 2%. The release layer forming composition was spin-coated at 2,000 rpm on the glass substrate to be used. A layer of about 10 μm was formed on the glass substrate.
In the same manner as in Example 1, a 1 cm square cube was formed on the glass substrate having the release layer by using the model material MA1 and evaluated. The evaluation results are shown in Table 1.

Example 6
To 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) (S-9), 90 parts of cycloolefin resin (ZEONOR manufactured by Nippon Zeon Co., Ltd.) and tetrahydrofuran were added to prepare a tetrahydrofuran solution having a solid content of 2%. The release layer-forming composition was spin-coated at 2,000 rpm on a glass substrate used as a modeling table in the same manner as in Example 1. A layer of about 10 μm was formed on the glass substrate.
In the same manner as in Example 1, a 1 cm square cube was formed on the glass substrate having the release layer by using the model material MA1 and evaluated. The evaluation results are shown in Table 1.

[Comparative Example 1]
A 1 cm square cube was formed and evaluated in the same manner as in Example 1 except that a 1 cm square cube was directly formed on the glass substrate without the release layer. The evaluation results are shown in Table 1.

[Comparative Example 2]
Using the three-dimensional modeling apparatus, instead of the release layer forming composition, the model material MA1 and the support material SA1 are randomly ejected so that the area ratio of the support material SA1 is 1: 1, and cured by ultraviolet irradiation. A 1 cm square cube was formed and evaluated in the same manner as in Example 1 except that a layer (about 10 μm) was formed on the glass substrate. The evaluation results are shown in Table 1.

[Comparative Example 3]
A 1 cm square cube was formed and evaluated in the same manner as in Example 1 except that stearyl alcohol was used instead of dodecyl mercaptan. The evaluation results are shown in Table 1.

[Comparative Example 4]
A 1 cm square cube was formed and evaluated in the same manner as in Example 1 except that dodecyl mercaptan (S-2) was not used and the composition for layer formation was prepared using only PCZ resin. The evaluation results are shown in Table 1.

  From the above, it can be seen from the results of this example that the obtained three-dimensional structure and the forming table are excellent in releasability and the surface property of the three-dimensional structure obtained on the forming table side.

DESCRIPTION OF SYMBOLS 10 Modeling unit 12 Model material discharge head 14 Support material discharge head 16 Light irradiation apparatus 20 Modeling stand 22 Layer containing the compound which has a mercapto group, and a binder polymer 30 Model material cartridge 32 Support material cartridge 101 Three-dimensional modeling apparatus

Claims (9)

Preparing a molding table having a compound having a mercapto group and a layer containing a binder polymer on at least a part of the surface;
On the layer, a step of discharging a radically polymerizable three-dimensional modeling material by an inkjet method, and
Curing the discharged 3D modeling material,
Of manufacturing a three-dimensional structure including   The method for producing a three-dimensional structure according to claim 1, wherein the compound having a mercapto group is a compound having two or more mercapto groups.   The method for producing a three-dimensional structure according to claim 1 or 2, wherein the compound having a mercapto group has a molecular weight of 250 or more. A molding table having a compound having a mercapto group and a layer containing a binder polymer on at least a part of the surface;
Containing a radical polymerizable three-dimensional modeling material, and a discharge unit for discharging the three-dimensional modeling material by an ink jet method;
A light irradiation unit that emits light for curing the discharged three-dimensional modeling material;
3D modeling device.   The three-dimensional modeling apparatus according to claim 4, wherein the compound having a mercapto group is a compound having two or more mercapto groups.   The three-dimensional modeling apparatus according to claim 4 or 5, wherein the compound having a mercapto group has a molecular weight of 250 or more.   A member for a modeling table having a layer containing a compound having a mercapto group and a binder polymer on at least a part of the surface of the substrate.   The member for a modeling table according to claim 7, wherein the compound having a mercapto group is a compound having two or more mercapto groups.   The molding stand member according to claim 7 or 8, wherein the compound having a mercapto group has a molecular weight of 250 or more.