JP2018052126A - Molding device and molding body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding device capable of easily and efficiently manufacturing complicated and fine solid molded objects.SOLUTION: A molding device 39 at least has a head unit 31 which jets a material containing at least water and a hydrogel precursor and curing means for curing said material. The hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer. In the molding device 39, it is preferable that the water-dispersible mineral is a water-swellable laminar clay.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a modeling apparatus capable of easily and efficiently manufacturing a complicated three-dimensional modeled object, and a modeled body.

Conventionally, as a layered modeling method, a method of producing a three-dimensional three-dimensional model by irradiating a liquid photocurable resin with laser light, particularly ultraviolet light, layer by layer has been proposed (for example, Patent Document 1). reference). However, in this proposed method, it is necessary to store a large amount of liquid photocurable resin, and it is necessary to increase the size of the apparatus. In addition, there is a problem that it is necessary to manage the temperature and the like for stabilizing the quality of the liquid photocurable resin.
In recent years, there has been disclosed an inkjet optical modeling method in which a liquid photocurable resin is imaged at a necessary portion of a modeled object by an inkjet method, and a three-dimensional modeled object is formed by multilayering this. In such an ink jet optical modeling method, a method has been proposed in which a member support different from a modeled object is formed at the same time to prevent deformation and dropping of the three-dimensional modeled object during modeling (for example, Patent Documents 2 and 3). reference).

  In addition, as an additive manufacturing method using an ink jet method, a method of laminating and bonding a binder (binder) with an ink jet to a starch or gypsum powder layer developed at the Massachusetts Institute of Technology (this is called “powder lamination method”) And a method of directly injecting and laminating a resin for a molded article (this is classified as a “molten resin deposition method”).

The powder laminating method using powder requires removal of unbound residual powder by suction or brush after completion of modeling, and the modeled body is also fragile, so the modeled body is damaged during the removal operation and difficult to handle. Met.
On the other hand, the method of directly injecting and laminating the resin for a modeled object requires a step of removing the support material from the modeled intermediate body taken out after modeling. Such a process includes a process of scraping with a brush, a process of removing by immersing in a special solvent or water for a long time, and in the case of a molded article with a complicated shape, it is performed by combining the above processes, The reality is that a lot of time and effort is spent, and a dedicated device for removal is also required.
In recent years, there has been a growing need for three-dimensional, finely structured gels and soft shaped objects such as medical organ models and cell scaffold materials used in regenerative medicine. The manufacturing method of the three-dimensional molded item that can be reproduced from the data has not yet been provided.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a manufacturing method of a three-dimensional structure that can easily and efficiently manufacture a complicated and fine three-dimensional structure.

The method for producing a three-dimensional structure of the present invention as a means for solving the above problems includes a first step of forming a film by applying a first liquid containing at least water and a hydrogel precursor,
The second step of curing the film formed in the first step is repeated a plurality of times.
Moreover, the manufacturing method of the three-dimensional molded item of the present invention includes a first step of forming a film by applying a first liquid containing at least water and a hydrogel precursor,
A third step of forming a film by applying a second liquid containing at least a curable material to a position different from the first liquid;
The fourth step of curing the films respectively formed in the first step and the third step is repeated a plurality of times.

  ADVANTAGE OF THE INVENTION According to this invention, the said various problems in the past can be solved, and the manufacturing method of the three-dimensional molded item which can manufacture a complicated and detailed three-dimensional molded item simply and efficiently can be provided.

Drawing 1 is a schematic diagram showing an example of a fabrication object manufacturing process in a manufacturing method of a three-dimensional fabrication thing of the present invention. FIG. 2 is a schematic diagram illustrating another example of a shaped body manufacturing process in the method for manufacturing a three-dimensional structure according to the present invention. FIG. 3 is a diagram illustrating an intermediate manufactured by the method for manufacturing a three-dimensional model and a state after peeling.

[Method for producing a three-dimensional structure of the first form]
The manufacturing method of the three-dimensional molded item which concerns on the 1st form of this invention includes a 1st process and a 2nd process, and also includes another process as needed.
In the manufacturing method of the three-dimensional structure according to the first aspect, the steps are repeated a plurality of times. The number of repetitions varies depending on the size, shape, structure, etc. of the three-dimensional structure to be produced, and cannot be specified unconditionally. However, if the thickness per layer is in the range of 10 μm to 50 μm, the separation is performed with high accuracy. Since it is possible to form without any problem, it is necessary to repeat the stacking for the height of the three-dimensional structure to be manufactured.

In the manufacturing method of the three-dimensional structure according to the first aspect, it is possible to efficiently manufacture a soft shaped body made of a hydrogel formed from a hydrogel precursor.
Each process in the manufacturing method of the three-dimensional molded item of the said 1st form is demonstrated in detail.

<First step>
The first step is a step of forming a film by applying a first liquid containing water and a hydrogel precursor.

The method for applying the first liquid is not particularly limited as long as the droplet can be applied to the target location with appropriate accuracy, and can be appropriately selected according to the purpose. For example, a dispenser method, A spray method, an inkjet method, etc. are mentioned. In order to carry out these methods, a known apparatus can be suitably used.
Among these, the dispenser method is excellent in the quantitative property of droplets, but the application area is narrowed, and the spray method can easily form a fine discharge, the application area is wide, and the application property is excellent. The quantitative property of the droplets is poor and scattering due to the spray flow occurs. For this reason, in the present invention, the ink jet method is particularly preferable. The ink jet method is advantageous in that the quantitative property of droplets is better than the spray method, and there is an advantage that the coating area can be widened compared to the dispenser method, and a complicated three-dimensional shape can be formed accurately and efficiently. .

  In the case of the ink jet method, a nozzle capable of discharging the first liquid is provided. In addition, the nozzle in a well-known inkjet printer can be used suitably as this nozzle, For example, GEN4 by Ricoh Industry Co., Ltd. etc. are mentioned suitably as said inkjet printer. This ink jet printer is preferable in that the amount of ink that can be dropped from the head portion at a time is large and the application area is large, so that the application speed can be increased.

<< first liquid >>
The first liquid contains water and a hydrogel precursor, and further contains other components as necessary. The first liquid is also referred to as “soft molding material”.

-Water-
As said water, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used, for example.
In the water, other components such as an organic solvent may be dissolved or dispersed in accordance with purposes such as imparting moisture retention, imparting antibacterial properties, imparting conductivity, and adjusting hardness.

-Hydrogel precursor-
The hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer, and further contains other components as necessary.

-Minerals that can be dispersed in water-
There is no restriction | limiting in particular as a mineral dispersible in the said water, According to the objective, it can select suitably, For example, a water swelling layered clay mineral etc. are mentioned.
The water-swellable layered clay mineral is a layered clay mineral that can be uniformly dispersed at a primary crystal level in water, and examples thereof include water-swellable smectite and water-swellable mica. More specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, water-swellable synthetic mica and the like can be mentioned.
As the water-swellable layered clay mineral, those exemplified above may be used singly or in combination of two or more, or may be appropriately synthesized, Commercial products may be used.
Examples of the commercially available products include synthetic hectorite (Laponite XLG, manufactured by Rockwood), SWN (manufactured by Coop Chemical Ltd.), and fluorinated hectorite SWF (manufactured by Coop Chemical Ltd.).
There is no restriction | limiting in particular in content of the mineral dispersible in the said water, Although it can select suitably according to the objective, 1 mass%-40 mass% are preferable with respect to 1st liquid whole quantity.

--Polymerizable monomer--
Examples of the polymerizable monomer include acrylamide, N-substituted acrylamide derivatives, N, N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, N, N-disubstituted methacrylamide derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polymerizable monomer include acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and the like.
By polymerizing the polymerizable monomer, a water-soluble organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group, or the like is obtained. The water-soluble organic polymer having the amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group or the like is an advantageous component for maintaining the strength of the aqueous gel.
The content of the polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass to 20% by mass with respect to the total amount of the first liquid.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, stabilizers, surface treatment agents, photopolymerization initiators, colorants, viscosity modifiers, adhesion promoters, Antioxidants, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants and the like can be mentioned.

The stabilizer is used to disperse and stabilize the water-swellable layered clay mineral and maintain a sol state. In addition, in the ink jet system, a stabilizer is used as necessary to stabilize the characteristics as a liquid.
Examples of the stabilizer include high-concentration phosphates, glycols, and nonionic surfactants.

  Examples of the surface treatment agent include polyester resin, polyvinyl acetate resin, silicone resin, coumarone resin, fatty acid ester, glyceride, and wax.

There is no restriction | limiting in particular as surface tension of said 1st liquid, Although it can select suitably according to the objective, For example, 20 mN / m-45 mN / m are preferable, and 25 mN / m-34 mN / m are more preferable. .
When the surface tension is less than 20 mN / m, the discharge may become unstable (the discharge direction bends or does not discharge) during modeling. When the surface tension exceeds 45 mN / m, the discharge nozzle for modeling, etc. When filling the liquid, it may not be completely filled.
The surface tension can be measured using, for example, a surface tension meter (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).
There is no restriction | limiting in particular as a viscosity of said 1st liquid, According to the objective, it can select suitably, Although it can utilize suitably by adjusting temperature, For example, at 25 degreeC, 3 mPa * s-20 mPa -S is preferable and 6mPa * s-12mPa * s are more preferable.
When the viscosity is less than 3 mPa · s, the discharge may become unstable (the discharge direction bends or does not discharge) during modeling, and when it exceeds 20 mPa · s, the discharge may not occur.
In addition, the said viscosity can be measured in 25 degreeC environment using a rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make) etc., for example.

<Second step>
The second step is a step of curing the film formed in the first step.
The cured film includes water and a component that dissolves in water in a three-dimensional network structure formed by combining a water-soluble organic polymer and a water-swellable layered clay mineral. An inorganic composite hydrogel is preferred.
The organic-inorganic composite hydrogel has improved extensibility, can be peeled off without breaking, and the processing after modeling is greatly simplified.

6-60 are preferable and, as for the rubber hardness of the said organic-inorganic composite hydrogel, 8-20 are more preferable.
If the rubber hardness is less than 6, the shape may be lost during modeling, and if it exceeds 60, the rubber hardness may be broken during post-modeling peeling.
The rubber hardness can be measured using a durometer (GS-718N, manufactured by Teclock Co.).

Examples of the means for curing the film include an ultraviolet (UV) irradiation lamp and an electron beam. The means for curing the film is preferably provided with a mechanism for removing ozone.
Examples of the ultraviolet (UV) irradiation lamp include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide.
The ultra-high pressure mercury lamp is a point light source, but the Deep UV type, which has high light utilization efficiency in combination with an optical system, can irradiate in a short wavelength region.
The metal halide is effective as a colored product because of its wide wavelength range, and metal halides such as Pb, Sn, and Fe are used, and can be selected according to the absorption spectrum of the photopolymerization initiator. There is no restriction | limiting in particular as a lamp | ramp used for hardening, According to the objective, it can select suitably, For example, using what is marketed like H lamp, D lamp, or V lamp etc. made from Fusion System. can do.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, a peeling process, the grinding | polishing process of a molded object, the cleaning process of a molded object, etc. are mentioned.

[Method for producing a three-dimensional structure of the second form]
The manufacturing method of the three-dimensional structure according to the second embodiment of the present invention preferably includes the first step, the third step, and the fourth step, and preferably includes the fifth step. According to other steps.
In the manufacturing method of the three-dimensional structure according to the second aspect, the above steps are repeated a plurality of times. The number of repetitions varies depending on the size, shape, structure, etc. of the three-dimensional structure to be produced, and cannot be specified unconditionally. However, if the thickness per layer is in the range of 10 μm to 50 μm, the separation is performed with high accuracy. Since it is possible to form without any problem, it is necessary to repeat the stacking for the height of the three-dimensional structure to be manufactured.

In the manufacturing method of the three-dimensional modeled object of the second form, when producing a soft modeled body of a hydrogel formed from a hydrogel precursor, as a liquid that forms a soft modeled body, water, and A first liquid containing at least a hydrogel precursor is used, and a second liquid containing at least a curable monomer is used as a liquid for forming a support.
On the contrary, when it is desired to produce a hard model body, the liquid that forms at least the curable monomer is used as the liquid that forms the model body, and water and the hydrogel precursor are used as the liquid that forms the support body. A first liquid containing at least is used.
Therefore, in the manufacturing method of the three-dimensional molded item of the said 2nd form, it can be made separately only by changing the liquid to apply with the hardness of the desired molded object. Moreover, in any case, it becomes possible to peel off very easily due to the difference in hardness between the support and the shaped object.
In addition, which of the first step and the second step may be performed first, it is preferable that the second step is performed first because the support can be formed first.
Hereinafter, each process in the manufacturing method of the three-dimensional molded item of the said 2nd form is demonstrated in detail.

<First step>
Since it is the same as that of said 1st process in the manufacturing method of the three-dimensional molded item of a said 1st form, the description is abbreviate | omitted.

<Third step>
The third step is a step of forming a film by applying a second liquid containing at least a curable material to a position different from the first liquid.

  The “position different from the first liquid” means that the application position of the second liquid and the application position of the first liquid do not overlap, and the application position of the second liquid and the first liquid May be adjacent to each other.

The method for applying the second liquid is not particularly limited as long as the droplet can be applied to the target place with appropriate accuracy, and can be appropriately selected according to the purpose. For example, a dispenser method, A spray method, an inkjet method, etc. are mentioned. In order to carry out these methods, a known apparatus can be suitably used.
Among these, the dispenser method is excellent in the quantitative property of droplets, but the application area is narrowed, and the spray method can easily form a fine discharge, the application area is wide, and the application property is excellent. The quantitative property of the droplets is poor and scattering due to the spray flow occurs. For this reason, in the present invention, the ink jet method is particularly preferable. The ink jet method is advantageous in that the quantitative property of droplets is better than the spray method, and there is an advantage that the coating area can be widened compared to the dispenser method, and a complicated three-dimensional shape can be formed accurately and efficiently. .

  In the case of the ink jet method, a nozzle capable of discharging the second liquid is provided. In addition, the nozzle in a well-known inkjet printer can be used suitably as this nozzle, For example, GEN4 by Ricoh Industry Co., Ltd. etc. are mentioned suitably as said inkjet printer. This ink jet printer is preferable in that the amount of ink that can be dropped from the head portion at a time is large and the application area is large, so that the application speed can be increased.

<< Second liquid >>
The second liquid preferably contains at least a curable material, preferably contains a photopolymerization initiator and a colorant, and further contains other components as necessary. The second liquid is also referred to as a “hard molding material”.

  The curable material is not particularly limited as long as it is a compound that is cured by active energy ray irradiation, heating, or the like, and can be appropriately selected according to the purpose. For example, the active energy ray curable compound and the photopolymerizable prepolymer can be selected. Examples include polymers, emulsion-type photocurable resins, thermosetting compounds, and the like. Among these, a liquid material at room temperature is preferable from the viewpoint of preventing nozzle clogging.

The active energy ray-curable compound is a compound that undergoes radical polymerization or cationic polymerization upon irradiation with active energy rays.
Examples of the radical polymerizing compound include compounds having an ethylenically unsaturated group.
Examples of the compound that undergoes cationic polymerization include compounds having an alicyclic epoxy group or an oxetane ring.

  The active energy ray-curable compound is a relatively low-viscosity monomer having an unsaturated double bond capable of radical polymerization in the molecular structure, such as monofunctional 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), caprolactone-modified tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate Rate, ethoxylated nonylphenol (meth) acrylate, bifunctional tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neo Pentyl glycol hydroxypivalate ester di (meth) acrylate (MANDA), hydroxypivalate neopentyl glycol ester di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4-butane Diol di (meth) acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate, diethylene Recall di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, propoxylation Opentyl glycol di (meth) acrylate, ethoxy modified bisphenol A di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyfunctional trimethylolpropane tri (meth) acrylate ( TMPTA), pentaerythritol tri (meth) acrylate (PETA), dipentaerythritol hexa (meth) acrylate (DPHA), Real alkyl isocyanate, (meth) acrylate of ε-caprolactone modified dipentaerythritol, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri ( (Meth) acrylate, propoxylated glyceryl tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, Examples include penta (meth) acrylate esters. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products of the active energy ray-curable compound include, for example, KAYARAD TC-110S, KAYARAD R-128H, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R-167, KAYARAD HAR-AD, HX-620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD TPA-330 KAYARADRP-1040, KAYARAD T-1420, KA YARAD DPHA, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYAARAD DPCA-60, KAYAARAD DPCA-120, KAYARAD DNAR 24AM, KAYARAD DNAR -2, KAYAMER PM-21, KS series HDDA, TPGDA, TMPTA, SR series 256, 257, 285, 335, 339A, 395, 440, 495, 504, 111, 212, 213, 230, 259, 268, 272, 344, 349, 601, 602, 610, 9003, 368, 415, 444, 454, 492, 499, 502, 9020, 9035, 2 5, 355, 399E494, 9041203, 208, 242, 313, 604, 205, 206, 209, 210, 214, 231E239, 248, 252, 297, 348, 365C, 480, 9036, 350 (Nippon Kayaku Co., Ltd.) Company-made), beam set 770 (made by Arakawa Chemical Industries, Ltd.), and the like. These may be used individually by 1 type and may use 2 or more types together.

  As said photopolymerizable prepolymer, the photopolymerizable prepolymer used for manufacture of an ultraviolet curable resin can be used. Examples of the photopolymerizable prepolymer include polyester resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, ether resins, and acrylates or methacrylates such as polyhydric alcohols.

  Examples of the emulsion-type photocurable resin include polyester (meth) acrylate, bisphenol epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, propylene oxide modified bisphenol A epoxy (meth) acrylate, and alkali. Soluble epoxy (meth) acrylate, acrylic modified epoxy (meth) acrylate, phosphoric acid modified epoxy (meth) acrylate, polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, alicyclic urethane (meth) acrylate, fat Group urethane (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate and the like.

  Commercially available products of the emulsion-type photocurable resin include, for example, Diamond Beam UK6105, Diamond Beam UK6038, Diamond Beam UK6055, Diamond Beam UK6063, Diamond Beam UK4203 (above, manufactured by Mitsubishi Rayon Co., Ltd.), Olestar Ra1574 (Mitsui). KAYARAD UX series 2201, 2301, 3204, 3301, 4101, 6101, 7101, 8101, KAYARAD R & EX series, 011, 300, 130, 190, 2320, 205, 131, 146, 280, KAYARAD MAX series 1100, 2100, 2101, 2102, 2203, 2104, 3100, 3101, 3510, 3661 (Nippon Kayaku Co., Ltd.), beam set 700, 7 0, 720, 750, 502H, 504H, 505A-6, 510, 550B, 551B, 575, 261, 265, 267, 259, 255, 271, 243, 101, 102, 115, 207TS, 575CB, AQ-7, AQ-9, AQ-11, EM-90, EM-92 (manufactured by Arakawa Chemical Industries, Ltd.), 0304TB, 0401TA, 0403KA, 0404EA, 0404TB, 0502TI0502TC, 102A, 103A, 103B, 104A, 1312MA, 1403EA, 1422TM, 1428TA, 1438MG, 1551MB, IBR-305, 1FC-507, 1SM-012, 1AN-202, 1ST-307, 1AP-201, 1PA-202, 1XV-003, 1KW-430, 1KW-501, 4 01TA, 4502MA, 4503MX, 4517MB, 4512MA, 4523TI, 4537MA, 4557MB, 6501MA, 6508MG, 6513MG, 6416MA, 6421MA, 6560MA, 6614MA, 717-1, 856-5, QT701-45, 6522MA, 6479MA, 6519MB, 6535MA, 724-65A, 824-65, 6540MA, 6RI-350, 6TH-419, 6HB-601, 6543MB, 6AZ-162, 6AZ-309, 6AZ-215, 6544MA, 6AT-203B, 6BF-203, 6AT-113, 6HY316, 6RL-505, 7408MA, 7501TE, 7511MA, 7505TC, 7529MA, MT408-13, MT408-15, MT40 8-42, 7CJ-601, 7PN-302, 7541MB, 7RZ-011, 7613MA, 8DL-100, 8AZ-103, 5YD-420, 9504MNS, Acryt WEM-202U, 030U, 321U, 306U, 162, WBR-183U 601U, 401U, 3DR-057, 829, 828 (manufactured by Taisei Kako Co., Ltd.).

  The content of the curable material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.001% by mass to 1% by mass with respect to the total amount of the second liquid.

-Photopolymerization initiator-
As the photopolymerization initiator, any substance that generates radicals upon irradiation with light (particularly, ultraviolet rays having a wavelength of 220 nm to 400 nm) can be used.
Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone, Michler's ketone , Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2 -Methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoylfo Formate, 1-hydroxycyclohexyl phenyl ketone, azobisisobutyronitrile, benzoyl peroxide, and di -tert- butyl peroxide. These may be used individually by 1 type and may use 2 or more types together.

In addition, when irradiating light (especially ultraviolet rays), a sensitizer is used for the purpose of preventing a decrease in curing speed due to absorption or concealment of light (especially ultraviolet rays) by the second liquid pigment. You can also
Examples of the sensitizer include aliphatic amines, amines having aromatic groups, cyclic amine compounds such as piperidine; urea compounds such as o-tolylthiourea; sodium diethyl thiophosphate, soluble salts of aromatic sulfinic acid Sulfur compounds such as N, N′-disubstituted-p-aminobenzonitrile, etc .; phosphorus compounds such as tri-n-butylphosphine and sodium diethyldithiophosphide; Michler's ketone, N-nitrosohydroxylamine derivative, oxazolidine And nitrogen compounds such as compounds, tetrahydro-1,3-oxazine compounds, formaldehyde, condensates of acetaldehyde and diamines, and the like. These may be used individually by 1 type and may use 2 or more types together.

-Colorant-
As the colorant, dyes and pigments that are dissolved or stably dispersed in the second liquid and further excellent in thermal stability are suitable. Among these, a soluble dye (Solvent Dye) is preferable. In addition, two or more kinds of colorants can be mixed in a timely manner for the purpose of color adjustment and the like.

Examples of the dye include those described below.
Examples of the black dye include MS BLACK VPC (manufactured by Mitsui Chemicals), AIZEN SOT BLACK-1, AIZEN SOT BLACK-5 (manufactured by Hodogaya Chemical Co., Ltd.), RESRIN BLACK GSN 200%, and RESOLIN BLACK BS (Bayer Japan). KAYASET BLACK A-N (manufactured by Nippon Kayaku Co., Ltd.), DAIWA BLACK MSC (manufactured by Daiwa Kasei Co., Ltd.), HSB-202 (manufactured by Mitsubishi Kasei Co., Ltd.), NEPTUNE BLACK X60, NEOPEN BLACK X58 (BASF Japan) Oleosol Fast BLACK RL (manufactured by Taoka Chemical Co., Ltd.), Chuo BLACK80, Chuo BLACK80-15 (manufactured by Chuo Synthetic Chemical Co., Ltd.), and the like.

  Examples of the magenta dye include MS Magenta VP, MS Magenta HM-1450, MS Magenta Hso-147 (manufactured by Mitsui Chemicals), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOT Red-3, and AIZEN SOT Pink. -1, SPIRON Red GEHSSPECIAL (Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT 5B (manufactured by Bayer Japan), KAYASET RedB, KAYASET Red 130, KAYAS 80 Japan Co., Ltd.), PHLOXIN, ROSE BENGAL, ACID Red (Daiwa Kasei Co., Ltd.), SR-31, DIARESIN RedK (manufactured by Mitsubishi Kasei Co., Ltd.), Oil Red (manufactured by BASF Japan Co., Ltd.), Oil Pink330 (made by the central Synthetic Chemical Co., Ltd.), and the like.

  Examples of cyan dyes include MS Cyan HM-1238, MS Cyan HSo-16, Cyan Hso-144, MS Cyan VPG (manufactured by Mitsui Chemicals), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), and RESOLIN. BR. Blue BGLN 200%, MACROLEX Blue RR, CERES BlueGN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (manufactured by Bayer Japan), KAYASET Blue Fr, KAYASET Blue N, KAYASET Blue 814, Turq. Blue GL-5 200, LightBlue BGL-5 200 (manufactured by Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (manufactured by Daiwa Kasei Co., Ltd.), DIARESINBlue P (manufactured by Mitsubishi Kasei Co., Ltd.), SUDAN Blue 6 NEOPEN Blue 808, ZAPON Blue 806 (manufactured by BASF Japan) and the like can be mentioned.

  Examples of the yellow dye include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (manufactured by Mitsui Chemicals), AIZENSOT Yellow-1, AIZEN SOT YellowW-3, and AIZEN SOT Yellow-6 (Hodogaya Chemical). Manufactured by Co., Ltd.), MACROLEX Yellow 6G, MACROLEX FLUOR, Yellow 10GN (manufactured by Bayer Japan), KAYASET Yellow SF-G, KAYASET Yellow 2G, KAYASET Yellow AG, KAYASET Y. DAIWA Yellow 330HB (manufactured by Daiwa Kasei Co., Ltd.), HSY-68 (manufactured by Mitsubishi Kasei Co., Ltd.), SUDAN Yellow 146, NEOPEN Yellow 075 (manufactured by BASF Japan), Oil Yellow 129 (manufactured by Chuo Synthetic Chemical Co., Ltd.) and the like.

As the pigment, various organic and inorganic pigments can be used, for example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene pigments, anthosequinone pigments, quinacridone pigments, dioxazines. Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments.
Specifically, as the pigment, organic or inorganic pigments having the following numbers described in the color index can be used.

  Examples of the red or magenta pigment include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, and 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36 etc. are mentioned.

Examples of the blue or cyan pigment include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like.
Examples of the green pigment include Pigment Green 7, 26, 36, and 50.
Examples of the yellow pigment include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, and 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like.
Examples of the black pigment include Pigment Black 7, 28, 26, and the like.

  Commercially available products can be used as the pigment. Examples of the commercially available products include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine. Magenta 6880, 6886, 6891N, 6790, 6887, Chromofine Violet RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-55 D, 5310, 5370, 6830, Chromo Fine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY-260, 2700 (B ), 2770, Seika Fast Red 8040, C405 (F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T -7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 9 00, 2900, Seikalite Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (above, manufactured by DIC Corporation); Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U26 Finecol Yellow T-13, T-05, Pigment Yellow 1705, Colortex Orange 202, Colortex Red 101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, U3BN, U3BN , UGN, UG276, U456, U457, 105C, USN, Colortex Maroon 601, Colortex Brown B610N, Colortex violet 600, Pigment Red 122, Colortex Blue 516, 517, 518, 518, 518, 519, A818P 702, U905 (above, mountain Pigment Co., Ltd.); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink Manufacturing Co., Ltd.); Toner Magenta E02, Permanent RubinF6B, TonerYell G -02, Hostapeam Blue B2G (manufactured by Hoechst Industry); carbon black # 2600, # 2400, # 2350, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 850, MCF88, # 750, # 650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, # 52, # 50, # 47, # 45, # 45L, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 44, CF9 (above, manufactured by Mitsubishi Chemical Corporation) .

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose.For example, a water-soluble resin, a low boiling alcohol, a surfactant, a viscosity modifier, an adhesion promoter, an antioxidant, Antiaging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants and the like can be mentioned.

-Water-soluble resin-
Examples of the water-soluble resin include polyvinyl alcohol resin, polyacrylic acid resin, cellulose resin, starch, gelatin, vinyl resin, amide resin, imide resin, acrylic resin, and polyethylene glycol.

--Low boiling alcohol--
As the low boiling alcohol, an aliphatic alcohol having 1 to 4 carbon atoms is preferable.
Examples of the aliphatic alcohol having 1 to 4 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol. . These may be used individually by 1 type and may use 2 or more types together.
The content of the low-boiling alcohol is preferably 1% by mass to 30% by mass and more preferably 10% by mass to 20% by mass with respect to the total amount of the second liquid. When the content is more than 30% by mass, there may be a problem in ejection properties. When the content is less than 1% by mass, the effect of increasing the drying speed may not be obtained.

There is no restriction | limiting in particular as surface tension of said 2nd liquid, Although it can select suitably according to the objective, For example, 20 mN / m-45 mN / m are preferable, and 25 mN / m-34 mN / m are more preferable. .
When the surface tension is less than 20 mN / m, the discharge may become unstable (the discharge direction bends or does not discharge) during modeling. When the surface tension exceeds 45 mN / m, the discharge nozzle for modeling, etc. When filling the liquid, it may not be completely filled.
The surface tension can be measured using, for example, a surface tension meter (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).
There is no restriction | limiting in particular as a viscosity of said 2nd liquid, Although it can select suitably according to the objective, It can use suitably by adjusting temperature, For example, at 25 degreeC, 3 mPa * s-20 mPa -S is preferable and 6mPa * s-12mPa * s are more preferable.
When the viscosity is less than 3 mPa · s, the discharge may become unstable (the discharge direction bends or does not discharge) during modeling, and when it exceeds 20 mPa · s, the discharge may not occur.
In addition, the said viscosity can be measured in 25 degreeC environment using a rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make) etc., for example.

<Fourth process>
The fourth step is a step of curing the films formed in the first step and the third step, respectively.
Curing of the film formed in the first step and curing of the film formed in the third step may be performed simultaneously or separately.
The cured film includes water and a component that dissolves in water in a three-dimensional network structure formed by combining a water-soluble organic polymer and a water-swellable layered clay mineral. The inorganic composite hydrogel is preferably used for natural peeling by simply drying and shrinking the support when the support is removed after shaping.
The organic-inorganic composite hydrogel has improved extensibility, can be peeled off without breaking, and the processing after modeling is greatly simplified.

Examples of the means for curing the film include an ultraviolet (UV) irradiation lamp and an electron beam. The means for curing the film is preferably provided with a mechanism for removing ozone.
Examples of the ultraviolet (UV) irradiation lamp include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide.
The ultra-high pressure mercury lamp is a point light source, but the Deep UV type, which has high light utilization efficiency in combination with an optical system, can irradiate in a short wavelength region.
The metal halide is effective as a colored product because of its wide wavelength range, and metal halides such as Pb, Sn, and Fe are used, and can be selected according to the absorption spectrum of the photopolymerization initiator. There is no restriction | limiting in particular as a lamp | ramp used for hardening, According to the objective, it can select suitably, For example, using what is marketed like H lamp, D lamp, or V lamp etc. made from Fusion System. can do.

<Fifth process>
The fifth step is a step of peeling a portion made of a hydrogel formed from the hydrogel precursor and a portion made of a polymer formed from the curable material.
6-60 are preferable and, as for the rubber hardness of the part which consists of said hydrogel, 8-20 are more preferable.
If the rubber hardness is less than 6, the shape may be lost during modeling, and if it exceeds 60, the rubber hardness may be broken during post-modeling peeling.
The rubber hardness can be measured using a durometer (GS-718N, manufactured by Teclock Co.).
The portion made of the hydrogel and the portion made of the polymer can be separated by drying shrinkage.
The drying shrinkage can be performed by various methods such as a method of leaving in an atmosphere of 50 ° C. and a method of reducing the pressure.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the cleaning process of a molded object, the grinding | polishing process of a molded object, etc. are mentioned.

As described above, in the method for producing a three-dimensional structure according to the present invention, the liquid is ejected from the pores such as the ink jet method and the dispenser method, and applied and cured so that an image of each layer can be formed. The previous first liquid and the second liquid are in an incompatible state where the contact portions are clearly separated and are immiscible.
In the conventional modeling method, the contact portion between the first liquid and the second liquid is compatible, and the boundary becomes unclear during photocuring. As a result, fine irregularities remain on the surface of the modeled body. However, in the method of manufacturing a three-dimensional modeled object of the present invention, the first liquid and the second liquid are incompatible with each other, and thus after photocuring. The boundary of becomes clear. Furthermore, peelability is improved by the difference in hardness between the obtained shaped body and the support. Thereby, the surface smoothness of a modeling body improves and it becomes possible to abbreviate | omit or reduce significantly the grinding | polishing process after modeling.

<Embodiment>
Hereinafter, specific embodiment of the manufacturing method of the three-dimensional molded item of this invention is described.
Using a soft molding material as the first liquid (ink composition ink) and using a hard molding material as the second liquid (ink composition for the support), a soft hydrogel molding is obtained. It was.
As described above, in order to obtain a soft three-dimensional object, a material for a soft molded body is disposed in the molded object portion, and a material for the hard molded body is disposed in the support body portion. In order to obtain a hard three-dimensional object, conversely, a hard molded body material is disposed in the molded body portion, and a soft molded body material is disposed in the support body portion.
As a method for applying the liquid, an inkjet method or a dispenser method can be applied as long as the droplets can be applied to a target place with appropriate accuracy. Since the embodiments are almost the same in any case, the following description will mainly focus on an embodiment using an ink jet method as a method for applying a liquid.

  First, the three-dimensional shape designed by the three-dimensional CAD, or the three-dimensional surface data or solid data captured by the three-dimensional canner or digitizer is converted into the STL format and input to the additive manufacturing apparatus.

  Based on this input data, the modeling direction of the three-dimensional shape to be modeled is determined. The modeling direction is not particularly limited, but usually the direction in which the Z direction (height direction) is the lowest is selected.

  When the modeling direction is determined, the projection area of the three-dimensional shape on the XY plane, XZ plane, and YZ plane is obtained. In order to reinforce the obtained block shape, the other surfaces are moved outward by an appropriate amount except for the upper surface of the XY plane. There is no restriction | limiting in particular in the quantity to move, Although it changes with shapes, sizes, and used materials, it is about 1 mm-about 10 mm. With this, the block shape in which the shape to be shaped is confined (the upper surface is opened) is specified.

  This block shape is cut into slices (slices) in the Z direction with a single layer thickness. The thickness of the one layer varies depending on the material used and cannot be defined unconditionally, but is preferably 10 μm to 50 μm. When there is one model to be modeled, the block shape is arranged so as to be in the middle of the Z stage (a table on which a model that descends one layer for each model) is placed. In addition, when a plurality of models are formed simultaneously, the block shape is arranged on the Z stage, but the block shapes can be stacked. These block shaping, circular cut data (slice data: contour data), and arrangement on the Z stage can be automatically created by specifying the material to be used.

  Next, it becomes a modeling process. Based on the contour of the outermost contour of the ring cut data, it is used for soft molding by internal / external judgment (determining whether to inject soft molding material or hard molding material at a position on the contour line) The position for injecting the material and the position for injecting the material for the hard molded body are controlled.

  As an order of injection, after ejecting the hard molded body material forming the support layer, the soft molded body material forming the molded body is ejected.

  When sprayed in this order, a reservoir such as a groove or a weir is first formed in the support, and the soft molding material is injected into the reservoir, and the soft molding material is liquid at room temperature. Even if the material is used, there is no fear of sagging, and a wide range of photo-curing resins, thermosetting resins, and the like can be used.

  Further, in order to further shorten the modeling time, a method of injecting and laminating a soft molding material and a hard molding material in each of the forward path and the return path of the integrated head is preferable.

  Furthermore, by placing an active energy ray irradiator adjacent to an inkjet head that injects a material for a soft molded body, the time required for the smoothing process can be saved, and high-speed modeling is possible.

<Modeling equipment>
The modeling apparatus 39 uses the head unit in which the inkjet heads are arranged to eject the soft molded material from the modeled ink jet head unit 30 and the hard molded material from the support ink jet head units 31 and 32. Then, the materials for the soft molded body are laminated while being cured by the adjacent ultraviolet irradiators 33 and 34.
That is, a material for a hard molded body is ejected from an ink jet head (support ink ejecting head units 31 and 32 for support) and solidified to form a first support layer having a reservoir, and the first support layer A liquid flexible molded material made of an active energy ray-curable compound is ejected from the inkjet head (the ink jet head unit 30 for a molded article) into the reservoir, and the active molding material is irradiated with active energy rays. 1 is formed, and a second support layer having a reservoir is laminated by spraying and solidifying a molten material for a hard molded body on the first support layer, and the second support layer is laminated. A liquid flexible molding material made of an active energy ray-curable compound is sprayed on the reservoir portion of the support layer, and the soft molding material is irradiated with active energy rays on the first shaped article layer. Laminating the second model layer To produce a three-dimensional stacked shaped object 35 to obtain a dimension laminated molded product.

  When the multi-head unit moves in the direction of arrow A, basically, the support body 36 and the model body 35 are moved using the support ink jet head unit 31, the model ink jet head unit 30, and the ultraviolet irradiation machine 34. Formed on the model body support substrate 37. The support ink jet head unit 32 and the ultraviolet irradiator 33 may be used supplementarily.

  Further, when the multi-head unit moves in the direction of arrow B, basically, the support body 36, the model body is used by using the support body ink jet head unit 32, the model ink jet head unit 30, and the ultraviolet irradiator 33. 35 is formed on the modeling body support substrate 37. The support ink jet head unit 31 and the ultraviolet irradiator 34 may be used supplementarily.

  Furthermore, in order to keep the gap between the ink jet head units 30, 31, 32 and the ultraviolet irradiators 33, 34, the shaped body 35 and the support 36, the layers are stacked while the stage 36 is lowered according to the number of times of stacking.

  FIG. 2 is a schematic view showing another example of a molded article manufacturing process having a configuration capable of improving the smoothness of each layer as compared with FIG. 1. The basic steps are the same as in FIG. 1 except that the ultraviolet irradiators 33 and 34 are disposed between the molded object material ejecting head 30 and the support material ejecting heads 31 and 32.

  Moreover, in the modeling apparatus 39 of this system, the ultraviolet irradiators 33 and 34 are used when moving in either direction of the arrows A and B, and for the laminated hard molded body by heat generated by the ultraviolet irradiation. The material surface is smoothed, and as a result, the dimensional stability of the shaped body can be improved.

  Further, as the modeling apparatus 39, it is possible to add an ink collection and recycling mechanism. A blade for removing the ink composition adhering to the nozzle surface and a non-ejection nozzle detection mechanism may be provided. It is also preferable to control the environmental temperature in the apparatus during modeling.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
A specific example of the layered manufacturing in which the soft molded body material as the first liquid and the hard molded body material as the second liquid are stacked one by one will be described.
In the following examples, a soft molded material is used as the first liquid (ink composition ink), and a hard molded material is used as the second liquid (support ink composition). A gel body was obtained.
In the fifth step, from the viewpoint of releasability, the hard moldable material is the first liquid (ink body ink composition), and the soft mold body material is the second liquid (support body ink composition). The result was exactly the same.

Example 1
<Manufacture of hard molded material>
10 parts by mass of urethane acrylate (Made by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038) as a curable material, and neopentyl glycol hydroxypivalate ester di (meth) acrylate (made by Nippon Kayaku Co., Ltd., trade name: 90 parts by weight of KAYARAD MANDA), 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name: Irgacure 184), and 2 parts by weight of a blue pigment (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name: Lionol Blue 7400G) A total of 300 g was dispersed using a homogenizer (manufactured by Hitachi Koki Co., Ltd., HG30) at a rotational speed of 2,000 rpm until a homogeneous mixture was obtained. Subsequently, filtration was performed to remove impurities and the like, and finally vacuum deaeration was performed for 10 minutes to obtain a homogeneous material for a hard molded body.
About the obtained material for hard molded bodies, the surface tension and the viscosity were measured as follows. The surface tension was 27.1 mN / m and the viscosity was 10.1 mPa · s at 25 ° C.

[Measurement of surface tension]
About the obtained material for hard molded bodies, surface tension was measured by a hanging drop method using a surface tension meter (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

[Measurement of viscosity]
About the obtained material for hard molded objects, it measured in the environment of 25.0 degreeC with the rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make).

<Manufacture of flexible molded material>
Hereinafter, ion-exchanged water that has been degassed for 10 minutes is referred to as pure water.

-Preparation of initiator solution-
(A) As initiator solution 1, a photopolymerization initiator (Irgacure 184, manufactured by BASF) was dissolved at a ratio of 2 parts by mass with respect to 98 parts by mass of methanol, and prepared as a solution.

  (B) As initiator solution 2, sodium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved at a ratio of 2 parts by mass with respect to 98 parts by mass of pure water to prepare an aqueous solution.

-Preparation of materials for flexible moldings-
First, a synthetic hectorite having a composition of [Mg _5.34 Li _0.66 Si ₈ O ₂₀ (OH) ₄ ] Na ⁻ _0.66 as a water-swellable layered clay mineral while stirring 195 parts by mass of pure water ( 8 parts by mass of Laponite XLG (manufactured by Rockwood) was added little by little and stirred to prepare a dispersion.
Next, 20 parts by mass of N, N-dimethylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.), which was passed through an activated alumina column and removed the polymerization inhibitor, was added as a polymerizable monomer to the obtained dispersion. Further, 0.2 part by mass of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a surfactant and mixed.
Next, while cooling in an ice bath, 0.5 part by mass of the (A) initiator liquid 1 is added, 5 parts by mass of the (B) initiator liquid 2 is added, and after stirring and mixing, degassing under reduced pressure is performed 10 times. Conducted for a minute. Subsequently, filtration was performed to remove impurities and the like to obtain a homogeneous material for a flexible molded body.
About the obtained material for flexible molded objects, the surface tension measured in the same manner as the material for hard molded bodies was 34.4 mN / m, and the viscosity measured in the same manner as the material for hard molded bodies was 25.0. It was 12.2 mPa · s at ° C.

<Laminated modeling and peeling>
Each of the hard molded material and the soft molded material was filled in two inkjet heads (GEN4 manufactured by Ricoh Industry Co., Ltd.) and injected.
A molded body and a support while curing the material for a hard molded body and the material for a soft molded body by irradiating a light amount of 350 mJ / cm ^{2 with} an ultraviolet irradiation machine (SPUS CURE SP5-250DB manufactured by USHIO INC.) Was formed.
Specifically, as a modeled object, as shown in FIG. 3A, a stepped model body 21 and support bodies 22 and 23 covering the modeled object 21 are modeled using the inkjet optical modeling apparatus shown in FIG. Immediately after modeling, the model body 21 was pulled and peeled in the horizontal direction. As a result, the support body 22 was peeled off as a unit, and the model body 21 was completed without the need for further processing.
Moreover, the other support body 23 was left to stand at room temperature for 5 hours, and the test which peels the support body 23 was implemented. After peeling, the shaped body 21 and the dried and contracted support 23 were completely separated, and the support was also peeled off as a unit. It was possible to peel off by simply leaving it to stand and drying.
When the model body surface 24 after peeling was confirmed, there was no residue of a minute support and a smooth surface was formed.

Separately, the material for the soft molded body is poured into a mold, covered with glass and sealed, and photocured in the same manner as above to produce a cylindrical pellet sample piece (hydrogel) having a diameter of 20 mm and a thickness of 4 mm. did.
About the obtained sample piece, when the rubber hardness was measured as follows, the rubber hardness was 16.

[Measurement of rubber hardness]
Using a durometer (GS-718N, manufactured by Teclock Co., Ltd.), the rubber hardness 15 seconds after the probe was pushed into the center of the 20 mm diameter surface was measured by a method based on ISO 7691 (type A).

(Example 2)
In Example 1, the same procedure as in Example 1 was conducted, except that the amount of synthetic hectorite (Laponite XLG, manufactured by Nippon Silica Co., Ltd.) in the flexible molded material was changed to 4 parts by mass to prepare a dispersion. Then, a material for a soft molded body was prepared, layered modeling was performed in the same manner as in Example 1, and peeling was performed in the same manner as in Example 1.
About the obtained material for flexible molded objects, the viscosity measured in the same manner as the material for hard molded bodies of Example 1 was 6.8 mPa · s at 25.0 ° C., and the surface tension was 34.4 mN as in Example 1. / M.
A sample piece (hydrogel) was produced in the same manner as in Example 1 for the material for flexible molded body, and the rubber hardness was measured to be 24.
In Example 2, as in Example 1, the modeled body and the support were completely separated after being pulled and peeled, and the modeled body was also separated without being disassembled. Further, the film was allowed to stand at room temperature for 5 hours and peeled off normally after drying.
When the surface of the modeled body after peeling was confirmed, there was no residue of a minute support and a smooth surface was formed.

(Example 3)
In Example 1, except that the amount of synthetic hectorite (Laponite XLG, manufactured by Nippon Silica Co., Ltd.) in the soft molded material was changed to 12 parts by mass, and a dispersion was produced, the same as in Example 1. Then, a material for a soft molded body was prepared, layered modeling was performed in the same manner as in Example 1, and peeling was performed in the same manner as in Example 1.
The viscosity of the obtained flexible molding material measured in the same manner as that of the hard molding material of Example 1 was 17.6 mPa · s at 25.0 ° C., and the surface tension was 34.4 mN as in Example 1. / M.
About the said flexible molded object material, it carried out similarly to Example 1, the sample piece (hydrogel) was produced, and it was 10 when the rubber hardness was measured.
Also in Example 3, as in Example 1, the modeled body and the support were completely separated after the tensile peeling, and the modeled body was also peeled off as a unit. Further, the film was allowed to stand at room temperature for 5 hours and peeled off normally after drying.
When the surface of the modeled body after peeling was confirmed, there was no residue of a minute support and a smooth surface was formed.

Example 4
In Example 1, except that the polymerizable monomer in the soft molding material was changed to N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.), a soft molding material was produced in the same manner as in Example 1, Laminated modeling was performed in the same manner as in Example 1, and peeling was performed in the same manner as in Example 1.
The obtained soft molding material was measured in the same manner as the hard molding material of Example 1 with a viscosity of 10.3 mPa · s at 25.0 ° C. and a surface tension of 34.4 mN as in Example 1. / M.
A sample piece (hydrogel) was produced in the same manner as in Example 1 for the material for flexible molded body, and the rubber hardness was measured to be 14.
In Example 4, as in Example 1, the molded body and the support were completely separated after the tensile peeling, and the molded body was also peeled off as a unit. Further, the film was allowed to stand at room temperature for 5 hours and peeled off normally after drying.
When the surface of the modeled body after peeling was confirmed, there was no residue of a minute support and a smooth surface was formed.

(Example 5)
Using the same soft molding material and hard molding material as in Example 1, layered modeling was performed in the same manner as in Example 1, and peeling was performed in the same manner as in Example 1.
In Example 5, as in Example 1, the molded body and the support were completely separated after the tensile peeling, and the molded body was also peeled off as a unit. Separately, it was dried by heating at 50 ° C. for 2 hours, and the support was completely peeled off in about 10 minutes.
When the surface of the modeled body after peeling was confirmed, there was no residue of a minute support and a smooth surface was formed.

(Comparative Example 1)
In Example 1, the synthetic hectorite in the material for a flexible molded body was not added, but an equivalent amount of N, N′-methylenebisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added instead of the synthetic hectorite. In the same manner as in Example 1, a material for a flexible molded body was produced, and layered modeling was performed in the same manner as in Example 1. The peeling was performed in the same manner as in Example 1. In Comparative Example 1, no hydrogel precursor was obtained, and no hydrogel was obtained.
About the obtained material for flexible molded objects, the viscosity measured in the same manner as the material for hard molded bodies of Example 1 is 8.0 mPa · s at 25.0 ° C., and the surface tension is 34.4 mN as in Example 1. / M.
With respect to the material for a soft molded body, a sample piece was produced in the same manner as in Example 1, and the rubber hardness was measured.
In Comparative Example 1, the support body collapsed brittlely when it was pulled and peeled, but it was completely peeled off simply by rubbing with a brush. Further, after leaving it to stand at room temperature for 5 hours and drying, most of the support could be peeled off, and the remaining part of the support was completely peeled off by simply rubbing with a brush. However, it was found that a part of the soft molded body could not withstand the weight of the support and was crushed in the middle of the layered modeling, and the target modeled body could not be obtained.

  Next, in Tables 1 to 3, performance evaluation of the soft molded body material, the hard molded body material, and the soft molded body is shown collectively.

* DMA: N, N-dimethylacrylamide (Wako Pure Chemical Industries, Ltd.)
* IPAM: N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)

* UK6038: Urethane acrylate (Made by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038)
* MANDA: Neopentyl glycol hydroxypivalate ester di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD MANDA)

* In Table 3, the evaluation criteria in “Tensile peeling”, “Peeling after drying”, “Surface property of shaped body after peeling”, and “Formability of shaped body” are all ◎: Good, ○: Normal, X: Indicates a defect.

Aspects of the present invention are as follows, for example.
<1> a first step of forming a film by applying a first liquid containing at least water and a hydrogel precursor;
A method for producing a three-dimensional structure characterized by repeating the second step of curing the film formed in the first step a plurality of times.
<2> a first step of forming a film by applying a first liquid containing at least water and a hydrogel precursor;
A third step of forming a film by applying a second liquid containing at least a curable material to a position different from the first liquid;
It is a manufacturing method of the three-dimensional molded item characterized by repeating the 4th process of hardening the film formed by said 1st process and said 3rd process in multiple times, respectively.
<3> The method for producing a three-dimensional structure according to any one of <1> to <2>, wherein the hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer.
<4> The method for producing a three-dimensional structure according to <3>, wherein the mineral dispersible in water is a water-swellable layered clay mineral.
<5> The method according to any one of <2> to <4>, including a fifth step of peeling a portion made of a hydrogel formed from the hydrogel precursor and a portion made of a polymer formed from a curable material. It is a manufacturing method of the three-dimensional molded item of description.
<6> The method for producing a three-dimensional structure according to <5>, wherein the rubber hardness of the portion made of the hydrogel is 6 to 60.
<7> The method for producing a three-dimensional structure according to any one of <1> to <6>, wherein the liquid application method is any one of an inkjet method and a dispenser method.
<8> The method for producing a three-dimensional structure according to any one of <5> to <7>, wherein the portion made of the hydrogel and the portion made of the polymer are separated by drying shrinkage.

Special table 2009-519143 gazette Japanese Patent No. 4366538 Japanese Patent No. 4908679

DESCRIPTION OF SYMBOLS 21 Model body 22, 23 Support body 24 Model body surface 30 Model body ink jet head unit 31, 32 Support body ink jet head unit 33, 34 UV irradiation machine 35 Model body 36 Support body 37 Model body support substrate 38 Stage 39 Modeling equipment

Claims (9)

A head unit for ejecting water and a material containing at least a hydrogel precursor;
A curing means for curing the material,
The modeling apparatus characterized in that the hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer.   The modeling apparatus according to claim 1, wherein the mineral dispersible in water is a water-swellable layered clay mineral. A first head unit for ejecting a first liquid containing at least water and a hydrogel precursor;
A second head unit that ejects a second liquid containing at least a curable material to a position different from the first liquid;
A curing means for curing the first liquid and the second liquid, and
A modeling apparatus for modeling a three-dimensional modeled object capable of peeling a portion made of a hydrogel formed from the hydrogel precursor and a portion made of a polymer formed from the curable material.   The modeling apparatus according to claim 3, wherein the hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer.   The modeling apparatus according to claim 4, wherein the mineral dispersible in water is a water-swellable layered clay mineral.   The modeling apparatus according to any one of claims 3 to 5, wherein a rubber hardness of a portion made of the hydrogel is 6 to 60.   The modeling apparatus according to claim 3, wherein the portion made of the hydrogel and the portion made of the polymer are peeled off by drying shrinkage.   The modeling apparatus according to claim 3, wherein the liquid ejecting method is one of an inkjet method and a dispenser method.   A shaped body comprising at least water, a mineral dispersible in water, and a polymer.