JP2017024260A - Method for manufacturing three-dimensional molded object and apparatus for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a three-dimensional molded object, by which a complicated and precise three-dimensional molded object represented by an organic model or the like can be easily and efficiently manufactured.SOLUTION: The method for manufacturing a three-dimensional molded object includes a step of imparting a first liquid comprising at least water and a hydrogel precursor to form a film and a second step of curing the film formed in the first step by use of a UV light-emitting diode, wherein these steps are repeated a plurality of times.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a three-dimensional structure and an apparatus for manufacturing the same.

Conventionally, as a three-dimensional 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 inkjet optical modeling method, a method has been proposed in which a member support different from the three-dimensional model is formed at the same time to prevent deformation or dropping of the three-dimensional model during the three-dimensional modeling (for example, Patent Document 2). And 3).

  Recently, there is an increasing need for gel-like or soft three-dimensional objects with three-dimensional and fine structures such as medical organ models and cell scaffold materials used in regenerative medicine. A method for manufacturing a three-dimensional structure that can be reproduced from data has not yet been provided.

  An object of this invention is to provide the manufacturing method of the three-dimensional molded item which can manufacture the complicated and fine three-dimensional molded item represented by the organ model etc. simply and efficiently.

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 with an ultraviolet light emitting diode is repeated a plurality of times.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the three-dimensional molded item which can manufacture the complicated and fine three-dimensional molded item represented by the organ model etc. simply and efficiently can be provided.

FIG. 1 is a schematic diagram showing an example of a layered mineral and a state in which the layered mineral is dispersed in water. FIG. 2 is a schematic diagram illustrating an example of a manufacturing apparatus for a three-dimensional structure according to the present invention. FIG. 3 is a schematic diagram illustrating another example of the manufacturing apparatus for a three-dimensional structure according to the present invention. FIG. 4 is a schematic view showing still another example of the three-dimensional object manufacturing apparatus of the present invention. FIG. 5 is a diagram illustrating a state of an intermediate body (before support peeling) manufactured by the manufacturing method of a three-dimensional structure. Drawing 6 is a figure showing the state after exfoliation manufactured by the manufacturing method of a solid fabrication thing. FIG. 7 is a diagram for explaining the measurement of the error in the vertical direction and the error in the horizontal direction of the shaped body after peeling.

(Manufacturing method of three-dimensional structure and manufacturing apparatus of three-dimensional structure)
The manufacturing method of the three-dimensional structure according to the first embodiment of the present invention includes the first step and the second step, preferably includes the fifth step, and further includes other steps as necessary. Comprising.
The manufacturing apparatus for a three-dimensional structure according to the first aspect of the present invention preferably includes a first means and a second means, preferably a fifth means, and further means as required. It has.

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

The means for applying the first liquid as the first means 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. Examples thereof include a dispenser method, a spray method, and an ink jet method. 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, As a said inkjet nozzle, GEN4 by Ricoh Industry Co., Ltd. etc. are mentioned suitably, for example. This ink jet nozzle is preferable in that the amount of liquid that can be dropped from the head portion at a time is large and the coating area is large, so that the coating 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 “a liquid material for a soft molded body”.

-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.
There is no restriction | limiting in particular as content of the said water, According to the objective, it can select suitably.

-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 layered mineral etc. are mentioned.
The layered mineral is preferably a layered mineral dispersed in water in a single layer state.
Here, as shown in the upper diagram of FIG. 1, the layered mineral presents a state in which two-dimensional disk-shaped crystals having a unit cell in the crystal are stacked, and when the layered mineral is dispersed in water, As shown in the lower diagram of FIG. 1, each single layer is separated into a disk-like crystal.
There is no restriction | limiting in particular as said layered mineral, According to the objective, it can select suitably, For example, a water swelling layered clay mineral etc. are mentioned.
Examples of the water-swellable layered clay mineral 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.
The water swellability means that water molecules are inserted between layers of a layered mineral and dispersed in water as shown in FIG.
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.). Among these, synthetic hectorite is preferable.
1 mass% or more and 40 mass% or less are preferable with respect to the whole quantity of a 1st liquid, and, as for content of the said layered mineral, 1 mass% or more and 15 mass% or less are more preferable. When the content is in the range of 1% by mass or more and 40% by mass or less, the viscosity of the first liquid is appropriate, and the ejectability at the inkjet nozzle and the hardness of the three-dimensional modeled object are good.

--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. Examples include acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N-acryloylmorpholine and the like. These may be used individually by 1 type and may use 2 or more types together.
By polymerizing the polymerizable monomer, a 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 polymer having an 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 hydrogel.
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 or more and 20% by mass or less with respect to the total amount of the first liquid.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected depending on the purpose.
For example, surfactants, stabilizers, surface treatment agents, polymerization initiators, colorants, viscosity modifiers, adhesion promoters, antioxidants, anti-aging agents, crosslinking accelerators, UV absorbers, plasticizers, antiseptics Agents, organic solvents, dispersants and the like.

-Physical properties of the first liquid-
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 or more and 45 mN / m or less are preferable, and 25 mN / m or more and 34 mN / m or less are preferable. More preferred.
When the surface tension is 20 mN / m or more and 45 mN / m or less, good discharge of the first liquid can be performed during three-dimensional modeling.
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.).

The viscosity of the first liquid is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 3 mPa · s or more and 20 mPa · s or less at 25 ° C., and 6 mPa · s or more and 12 mPa · s or less. Is more preferable.
When the viscosity is 3 mPa · s or more and 20 mPa · s or less, the first liquid can be favorably ejected during three-dimensional modeling.
The viscosity can be measured in a 25 ° C. environment using, for example, a rotational viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.).

<Second step and second means>
The second step is a step of curing the film formed in the first step with an ultraviolet light emitting diode (UV-LED), and can be performed by a second means.

As a means for curing the film as the second means, an ultraviolet light emitting diode (UV-LED) is used.
There is no restriction | limiting in particular as the light emission wavelength of the said ultraviolet light emitting diode, Although it can select suitably according to the objective, Generally there exists a thing of 365nm, 375nm, 385nm, 395nm, 405nm, In consideration of the influence of color, it is advantageous to emit light at a short wavelength so that the absorption of the polymerization initiator is increased.
The ultraviolet light emitting diode (UV-LED) has a smaller thermal energy applied to the film during curing than a commonly used ultraviolet irradiation lamp (for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp), an electron beam, and the like. Thermal damage to the film is reduced.
In particular, since the hydrogel modeled by the present invention is present in a state where water is stored, its characteristics are manifested, so that the effect is remarkable.
Amount of film hardening of the ultraviolet light emitting diode (UV-LED) may, 100 mJ / cm ² or more 1,000 mJ / cm ² is preferred.

The cured film is an organic-inorganic composite hydrogel in which water and a component dissolved in the water are included in a three-dimensional network structure formed by combining a water-soluble organic polymer and a layered mineral. It is preferable that
The organic-inorganic composite hydrogel has improved extensibility, can be peeled off without breaking, and the processing after modeling is greatly simplified.

<Fifth step and fifth means>
The fifth step is a step of smoothing the film cured in the second step, and can be performed by a fifth means.
There is no restriction | limiting in particular as said 5th means, According to the objective, it can select suitably, For example, a roller, a blade, etc. are mentioned.

-Roller-
The shape, structure, size, material and the like of the roller are not particularly limited and may be appropriately selected depending on the purpose. Examples of the shape include a cylindrical solid body and a hollow inside. The structure may be a single-layer structure or a laminated structure, and the size is appropriately selected depending on the size of the three-dimensional object. can do. Examples of the material include resin, rubber, metal, or a combination thereof.
Examples of the roller include a cored bar, a rubber roller having a rubber layer on the cored bar, a rubber roller made only of rubber without a cored bar, a core material, and a foam layer formed on the outer periphery of the core material. Examples thereof include a foam roller and a metal roller.

-Blade-
The shape, structure, size, material and the like of the blade are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a flat plate shape, a strip shape, and a sheet shape. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size of the three-dimensional structure. . Examples of the material include metal, plastic, rubber, or a combination thereof.
Examples of the blade include a support member and an elastic member partially fixed to the support member and having a free end, a blade made of only an elastic member, a doctor blade, and the like.

The film formed in the first step and cured in the second step does not necessarily have a target film thickness (layer thickness) in all regions. That is, in the case of the ink jet method, there may be non-ejection, and a step between dots may occur in both the ink jet method and the dispenser method, which may be insufficient to form a highly accurate three-dimensional object.
In order to compensate for this, for example, the layer is mechanically smoothed (equalized) immediately after the layer is formed, mechanically scraped off, the smoothness is detected, and the film formation amount is set to the dot level when the next layer is laminated. It is possible to make adjustments using the
The hydrogel used in the present invention has a relatively soft hardness because the target three-dimensional model is an organ model such as an internal organ. For this reason, in smoothing, a smoothing method of mechanically leveling immediately after forming the layer can be used effectively.
Examples of the mechanical smoothing method include a method of leveling with a blade-shaped smoothing member, a method of leveling with a roller-shaped smoothing member, and the like.
When the roller-shaped smoothing member is used, the effect of smoothing is more effectively exhibited when the roller is rotated in the direction of reversing the operation direction.
The blade-shaped smoothing member is more effective when the surface of the shaped body is smoothed than the roller-shaped smoothing member.

<Other processes and other means>
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, It implements by other means. be able to.

  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 manufactured, and cannot be specified unconditionally. However, if the thickness per layer is in the range of 10 μm or more and 50 μm or less, the peeling can be performed accurately. Therefore, it is necessary to repeat the stacking by the height of the three-dimensional model to be produced.

The manufacturing method of the three-dimensional structure according to the second aspect of the present invention includes the first step, the third step, and the fourth step, and includes the sixth step and the seventh step. Is preferable, and further includes other steps as necessary.
An apparatus for manufacturing a three-dimensional structure according to the second aspect of the present invention includes the first means, the third means, and the fourth means, and includes sixth means and seventh means. It is preferable to have other means as required.

<Third step and third means>
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, and can be performed by a third means.
The means for applying the second liquid as the third means is the same as the first means in the three-dimensional structure manufacturing apparatus of the first embodiment, and therefore the description thereof is omitted.

  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 The liquid application position may be adjacent. Since the second liquid has a composition different from that of the first liquid and is difficult to mix, even when the second liquid and the first liquid are adjacent to each other, the boundary between the two after the curing becomes clear.

<< Second liquid >>
Said 2nd liquid is a liquid used as the hard molded object for supporting the three-dimensional molded item comprised with hydrogel (soft body) (it is also called "the liquid material for hard molded bodies").
The second liquid contains at least a curable material, and further contains other components as necessary.

-Curable material-
The curable material is preferably a compound that undergoes a polymerization reaction by UV light-emitting diode (UV-LED) light and is cured, for example, an active energy ray-curable compound, a photopolymerizable prepolymer, or an emulsion type light. Examples thereof include curable resins and thermosetting compounds. 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 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 or more and 1% by mass or less with respect to the total amount of the second liquid.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a polymerization initiator, a colorant, a water-soluble resin, water, a low-boiling alcohol, a surfactant, a viscosity modifier, Adhesiveness imparting agents, antioxidants, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants and the like can be mentioned.

--Polymerization initiator--
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

--- Thermal polymerization initiator ---
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an azo initiator, a peroxide initiator, a persulfate initiator, or a redox (oxidation reduction) initiator. Etc.

--- Photopolymerization initiator ---
As said photoinitiator, the arbitrary substances which produce | generate a radical by irradiation of ultraviolet light emitting diode (UV-LED) light 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.

  There is no restriction | limiting in particular in content of the said polymerization initiator, Although it can select suitably according to the objective, 0.01 mass% or more and 3 mass% or less are preferable with respect to the whole quantity of curable material.

In addition, when irradiating ultraviolet light emitting diode (UV-LED) light, the second liquid pigment prevents the ultraviolet light emitting diode (UV-LED) light from being absorbed or concealed, thereby preventing a decrease in curing speed. For the purpose, a sensitizer can also be used.
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.

-Physical properties of the second liquid-
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 or more and 45 mN / m or less are preferable, and 25 mN / m or more and 34 mN / m or less are preferable. More preferred.
When the surface tension is 20 mN / m or more and 45 mN / m or less, the second liquid can be favorably discharged during three-dimensional modeling.
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.).
The viscosity of the second liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mPa · s or more and 20 mPa · s or less at 25 ° C., and 6 mPa · s or more and 12 mPa · s or less. Is more preferable.
When the viscosity is 3 mPa · s or more and 20 mPa · s or less, the second liquid can be favorably discharged during the three-dimensional modeling.
The viscosity can be measured in a 25 ° C. environment using, for example, a rotational viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.).

<Fourth step and fourth means>
The fourth step is a step of curing the films formed in the first step and the third step with an ultraviolet light emitting diode, and can be performed by a fourth means.
Since the fourth step and the fourth means are the same as the second step and the second means in the manufacturing method and manufacturing apparatus of the three-dimensional structure according to the first embodiment, the description thereof is omitted. Omitted.
The curing of the film formed in the first step and the curing of the film formed in the fourth step may be performed simultaneously or separately.
The cured film is an organic-inorganic composite hydrogel in which water and a component dissolved in the water are included in a three-dimensional network structure formed by combining a water-soluble organic polymer and a layered mineral. When the support is removed after modeling, it is suitably used for natural peeling simply by drying and shrinking the support.
The organic-inorganic composite hydrogel has improved extensibility, can be peeled off without breaking, and the processing after three-dimensional modeling is greatly simplified.

<Sixth step and sixth means>
The sixth step is a step of smoothing the film cured in the fourth step, and can be performed by a sixth means.
Since the sixth step and the sixth means are the same as the fifth step and the fifth means in the manufacturing method and manufacturing apparatus of the three-dimensional structure of the first embodiment, the description thereof is omitted. Omitted.

<Seventh step and seventh means>
The seventh step is a step of peeling a portion made of the hydrogel formed from the hydrogel precursor and a portion made of the polymer formed of the curable material, and is performed by the seventh means. be able to.
There is no restriction | limiting in particular as said 7th means, According to the objective, it can select suitably, For example, various peeling apparatuses etc. are mentioned.

There is no restriction | limiting in particular in the rubber hardness of the part which consists of said hydrogel, Although it can select suitably according to the objective, 6 or more and 60 or less are preferable, and 8 or more and 20 or less are more preferable.
When the rubber hardness is 6 or more and 60 or less, the shape is not lost during the three-dimensional modeling, and the peeling after the three-dimensional modeling can be performed satisfactorily.
In addition, the said rubber hardness can be measured by the method based on ISO7691 (type A), for example, can be measured using a durometer (the TC-718N made from a teclock company) etc.
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 and other means>
The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a discharge stabilization step, a shaped body cleaning step, a shaped body polishing step, and the like, and a discharge stabilization means. It can be carried out by means for cleaning the shaped body, polishing means for the shaped body, and the like.

−Discharge stabilization process and discharge stabilization means−
When an inkjet head is used as a means for ejecting liquid, drying of the nozzles during non-ejection becomes a major issue for stable operation.
For this reason, the discharge stabilization step and the discharge stabilization means are (1) by covering (capping) the discharge port with a member having a shape covering at least the tip of the head when the inkjet head does not continuously discharge for a long time. , Preventing drying of the discharge port tip, (2) the viscosity of the internal liquid near the discharge port is increased by drying,
Alternatively, the discharge formed state can be maintained for a long time by discharging the film formed by drying by suction, and (3) wiping the discharge port or the discharge port and its periphery.
These are extremely difficult when using a liquid containing a low-boiling solvent such as water when modeling a three-dimensional model that requires continuous discharge for 24 hours or longer, especially when modeling a soft material. is important.

--Capping process--
In the capping step, when a suction instruction is issued after the discharge operation is completed, the inkjet head moves to the cap portion and comes into contact with the cap. After completion of the cap contact, the pump starts a suction operation, and discharges liquid from all the discharge ports including the defective discharge portion. After completion of the suction operation, the inkjet head moves along the wiping member, and the capping process is completed.

--- Discharge failure recovery process--
In the ejection failure recovery step, the inkjet head is then moved to the ejection position in order to resume the ejection operation. When the ejection is finished and the modeling is finished, the nozzle moves again to the cap contact position, and the ejection failure recovery process is completed.
When manufacturing a large three-dimensional object, it is necessary to perform continuous discharge for a long period of time, and therefore it is preferable that the discharge failure recovery step is periodically performed.
There is no particular limitation on the timing of ejection failure recovery, and it can be appropriately selected according to the purpose. However, from the viewpoint of ejection failure recovery, it is preferable to perform it periodically every continuous operation within 2 hours. .

  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 material is used as the liquid forming the support.
On the contrary, when it is desired to manufacture a hard modeled body, a second liquid containing at least a curable material is used as the liquid for forming the three-dimensional modeled object, and water and hydrogel are used as the liquid for forming the support. A first liquid containing at least a precursor 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 body.
Further, which of the first step and the third step may be performed first, it is preferable that the third step is performed first because the support can be formed first.

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 three-dimensional modeling.

Hereinafter, specific embodiment of the manufacturing method of the three-dimensional molded item of this invention and the manufacturing apparatus of a three-dimensional molded item is described.
A liquid material for a soft molded body was used as the first liquid, and a liquid material for a hard molded body was used as the second liquid to obtain a modeled product of a soft hydrogel.
As described above, in order to obtain a soft three-dimensional modeled object, the liquid material for the soft molded body is disposed in the molded body portion, and the liquid material for the hard molded body is disposed in the support body portion. In order to obtain a hard three-dimensional modeled object, conversely, a liquid material for a hard molded body is disposed in the molded body portion, and a liquid material for a soft molded body 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, a three-dimensional shape designed by three-dimensional CAD, or three-dimensional surface data or solid data captured by a three-dimensional scanner or digitizer is converted into an STL format and input to a three-dimensional structure 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 about the quantity to move, Although it changes with shapes, magnitude | sizes, and liquid materials to be used, 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 or more and 50 μm or less.
When there is one three-dimensional model to be modeled, this 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 at a time for each model). 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 designating the liquid material to be used.

  Next, it becomes a modeling process. Soft molding based on the contour of the outermost contour of the loop cutting data, by determining whether it is inside or outside (determining whether liquid material for soft molding or liquid material for hard molding is injected at a position on the contour) The position for injecting the body liquid material and the position for injecting the rigid molded body liquid material are controlled.

  As the order of injection, the liquid material for the hard molded body forming the support layer is sprayed, and then the liquid material for the soft molded body forming the shaped body layer is sprayed.

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

  In order to further shorten the modeling time, a method of laminating the liquid material for the soft molded body and the liquid material for the hard molded body in each of the forward path and the return path of the integrated inkjet head is preferable.

Furthermore, high-speed modeling is possible by placing an ultraviolet light emitting diode (UV-LED) light irradiator adjacent to an inkjet head that ejects a liquid material for a soft molded body.
Moreover, in order to smooth the three-dimensionally modeled layer, the smoothing process is performed immediately after performing the curing process.
In the smoothing process, for example, a smoothing member such as a roller or a blade is used to smooth the surface of the cured film. Thereby, the precision for every layer improves and the whole three-dimensional molded item can be produced precisely.
At this time, in order to shorten the lamination time and to improve the smoothness of the layer, the smoothing member is preferably disposed adjacent to the UV-LED light irradiator.

FIG. 2 is a schematic diagram illustrating an example of a molded body manufacturing process in the method for manufacturing a three-dimensional object according to the present invention using the manufacturing apparatus for a three-dimensional object according to the present invention.
The three-dimensional structure manufacturing apparatus 10 uses the head unit in which the inkjet heads are arranged, the liquid material for the soft molded body from the liquid material ejection head unit 11 for the shaped body, and the liquid material ejection head units 12 and 13 for the support. The liquid material for hard molded bodies is ejected and laminated while curing the liquid material for soft molded bodies with the adjacent ultraviolet light emitting diode (UV-LED) light irradiators 14 and 15.
That is, the liquid material for the hard molded body is ejected from the ink jet head (the liquid material ejecting head units 12 and 13 for the support body) and solidified to form the first support layer having the reservoir, and the first support body. The liquid material for the soft molded body is ejected from the inkjet head (the liquid material ejecting head unit 11 for the molded body) to the reservoir of the layer, and the soft material for liquid material is irradiated with UV-LED light to be cured. Forming a model body layer.
Next, a molten liquid material for a hard molded body is sprayed and solidified on the first support layer to laminate a second support layer having a reservoir, and the reservoir of the second support layer A liquid material for a soft molded body is sprayed onto the liquid material, and the liquid material for the soft molded body is irradiated with UV-LED light, and a second modeling body layer is laminated on the first modeling body layer, and three-dimensional three-dimensional modeling is performed. An object 19 is produced.

  When the multi-head unit moves in the direction of the arrow A, the support 18 is basically formed by using the support liquid material ejection head unit 12, the shaped body liquid material ejection head unit 11, and the UV-LED light irradiator 15. Then, the model body 19 is formed on the model body support substrate 16. The support liquid material ejecting head unit 13 and the UV-LED light irradiator 14 may be used supplementarily.

  When the multi-head unit moves in the direction of arrow B, it is basically supported using the liquid material ejecting head unit 13 for supporting body, the liquid material ejecting head unit 11 for modeling body, and the UV-LED light irradiator 14. The body 18 and the modeling body 19 are formed on the modeling body support substrate 16. The support liquid material jet head unit 12 and the UV-LED light irradiator 15 may be used supplementarily.

  Furthermore, in order to keep the gap between the liquid material ejection head units 11, 12, 13 and the UV-LED light irradiators 14, 15, the shaped body 19, and the support body 18, the stage 17 is lowered according to the number of laminations. Laminate while.

  FIG. 3 is a schematic diagram illustrating another example of the three-dimensional structure manufacturing process in the method for manufacturing a three-dimensional structure according to the present invention using the three-dimensional structure manufacturing apparatus according to the present invention. The basic process is the same as that in FIG. 2, but the UV-LED light irradiators 14 and 15 are arranged between the liquid material ejecting head 11 for forming body and the liquid material ejecting heads 12 and 13 for support. The point is different.

FIG. 4 is a schematic view showing another example of a three-dimensional object manufacturing process in the three-dimensional object manufacturing method of the present invention using the three-dimensional object manufacturing apparatus provided with the smoothing member.
Smoothing members 20 and 21 capable of smoothing the cured film surfaces are disposed at both ends of the UV-LED light irradiators 14 and 15 in FIG. As the smoothing member, a roller shape or a blade shape is used.
When the multi-head unit moves in the direction of arrow A, the support 18 is basically formed by using the support liquid material jet head unit 12, the shaped body liquid material jet head unit 11, and the UV-LED light irradiator 14. And the modeling body 19 are formed on the modeling body support substrate 16. At the same time, the support 18 and the model 19 are smoothed by the smoothing member 20. The support liquid material ejection head unit 13 and the UV-LED light irradiator 15 may be used supplementarily.
When the multi-head unit moves in the direction of arrow B, it is basically supported using the liquid material ejecting head unit 13 for supporting body, the liquid material ejecting head unit 11 for modeling body, and the UV-LED light irradiator 14. The body 18 and the model body 19 are formed on the model body support substrate 16. At the same time, the support 18 and the model 19 are smoothed by the smoothing member 20. The support liquid material ejecting head unit 12 and the UV-LED light irradiator 15 may be used supplementarily.

  In addition, as the three-dimensional structure device 10, a liquid recovery mechanism, a recycling mechanism, and the like can be added. A blade for removing the liquid material adhering to the nozzle surface and a non-ejection nozzle detection mechanism may be provided. Furthermore, it is also preferable to control the environmental temperature in the manufacturing apparatus of the three-dimensional molded item at the time of three-dimensional modeling.

<Solid modeling liquid set>
The three-dimensional modeling liquid set used in the present invention includes the first liquid and the second liquid, and further includes other components as necessary.
The liquid set for three-dimensional modeling can be suitably used for manufacturing various three-dimensional models, and can be particularly preferably used for manufacturing complicated and fine three-dimensional models represented by organ models and the like.

<3D objects>
The three-dimensional structure used in the present invention is composed of a hydrogel formed from a hydrogel precursor, and the rubber hardness of the hydrogel is 6 or more and 60 or less. When the rubber hardness is 6 or more and 60 or less, elasticity and strength required for the organ model can be obtained.
The rubber hardness can be measured, for example, by a method based on ISO7691 (type A).

The hydrogel is preferably a hydrogel in which water is contained in a three-dimensional network structure formed by combining a water-soluble organic polymer and a single layer dispersion of a layered mineral.
Examples of the water-soluble organic polymer include organic polymers having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group, and the like.
The water-soluble organic polymer is an advantageous component for maintaining the strength of the aqueous gel.
The organic polymer may be a homopolymer (homopolymer), a heteropolymer (copolymer), or may be modified as long as it exhibits water solubility. These functional groups may be introduced, and may be in the form of a salt, but a homopolymer is preferred.
The water solubility of the water-soluble organic polymer means that, for example, when 1 g of the organic polymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more thereof is dissolved.
The three-dimensional model is preferably used as an organ model. The organ model is particularly suitable as an organ model for practicing a technique because the tactile sensation and sharpness of the organ are very close to the desired organ and can be opened with a scalpel.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
Specific examples of the three-dimensional modeling in which the liquid material for the soft molded body as the first liquid and the liquid material for the hard molded body as the second liquid are laminated one layer at a time will be described below.

Example 1
<Preparation of second liquid (liquid material for rigid molded body)>
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 mass of KAYARAD MANDA), 3 parts by mass of a photopolymerization initiator (manufactured by BASF, trade name: Irgacure 184), and 2 parts by mass of a blue pigment (manufactured by Toyo Ink Co., Ltd., trade name: Lionol Blue 7400G) as a colorant 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 uniform liquid material for a hard molded body.
About the obtained liquid 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 liquid 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 liquid 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).

<Preparation of first liquid (liquid material for soft molded body)>
Ion-exchanged water subjected to vacuum degassing for 10 minutes was used 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 liquid material for flexible molded body-
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 uniform liquid material for a flexible molded body.
About the obtained liquid material for flexible molded bodies, the surface tension measured in the same manner as the liquid material for hard molded bodies was 34.4 mN / m, and the viscosity measured in the same manner as the liquid material for hard molded bodies was It was 10.1 mPa · s at 25.0 ° C.

<3D modeling>
Fill the two tanks leading to the inkjet head (GEN4, manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional structure manufacturing apparatus 10 shown in FIG. 2 with the liquid material for the hard molded body and the liquid material for the soft molded body, The liquid material for a hard molded body and the liquid material for a soft molded body were respectively ejected from an inkjet head to form a film. In addition, the liquid material for hard molded bodies and the liquid material for soft molded bodies were sprayed at different positions.
Next, the film is irradiated with a light amount of 350 mJ / cm ² with a UV-LED (Integration, SubZero-LED, wavelength: 365 nm) light irradiator, so that the liquid material for the hard molded body and the soft molded body are irradiated. While the liquid material for use was cured, a modeled body and a support were formed as a three-dimensional modeled object.

  Next, about the obtained three-dimensional molded item, various characteristics were evaluated as follows. The results are shown in Table 3.

<Moldability of 3D objects>
As shown in FIG. 5, the stepped shaped body 30 and the supports 31 and 32 covering the stepped shaped body 30 were three-dimensionally shaped using the three-dimensionally shaped manufacturing apparatus shown in FIG. 2. The moldability of the three-dimensional structure at this time was evaluated based on the following criteria.
[Evaluation criteria]
○: Target modeling was possible (good)
×: The target modeling was not possible (defect)

<Measurement of “horizontal error” and “vertical error” of the model>
Regarding the “horizontal error” and “vertical error” of the shaped body 30, as shown in FIG. 7, the horizontal and vertical dimensions of the shaped body 30 were measured at 10 locations respectively using calipers. Ten variations were determined as follows and evaluated according to the following criteria.
-10 variations
The horizontal and vertical lengths of the shaped body 30 shown in FIG. 7 are measured at 10 places with calipers, and the obtained measurement values at 10 places and input signals for shaping (the target length in the horizontal direction or the vertical direction). The maximum value and the minimum value of the error were obtained. Select the larger of the maximum and minimum values of the obtained error and divide the selected absolute value of the error by the input signal (target length in the horizontal direction or target length in the vertical direction). The ratio (%) multiplied by 100 was obtained, and the variation was 10 locations.
[Evaluation criteria]
A: Variation at 10 locations is less than 2% (good)
○: Variation at 10 locations is 2% or more and less than 5% (normal)
X: Variation at 10 locations is 5% or more (defect)

<Tensile peeling>
Immediately after modeling the three-dimensional model, the model body 30 was obtained by pulling and peeling the support 31 in the horizontal direction as shown in FIG. Based on the following criteria, tensile peeling was evaluated.
[Evaluation criteria]
A: The support was peeled off as a unit, and a molded body was obtained without further processing (good)
○: Most of the support could be peeled off, and the remaining support could be completely peeled off by simply rubbing with a brush (normal)
X: The support cannot be peeled off (defective)

<Peeling after drying>
After performing the tensile peeling test on one support 31 shown in FIG. 6, the other support 32 was allowed to stand at room temperature (25 ° C.) for 5 hours, and then a test was performed to peel the support 32. Based on the criteria, peeling after drying was evaluated.
[Evaluation criteria]
A: After peeling, the shaped body and the dried and contracted support were completely separated, and the support was also able to peel as a single piece (good)
○: Most of the support could be peeled off, and the remaining support could be completely peeled off by simply rubbing with a brush (normal)
X: The support cannot be peeled off (defective)

<Surface property of the molded body after peeling>
The surface of the shaped body (interface with the support) 33 after the tensile peel test was observed, and the surface property of the shaped body after peeling was evaluated based on the following criteria.
[Evaluation criteria]
○: A smooth surface was obtained with no residual microscopic support on the surface of the modeled body (good)
X: The support remains and a smooth surface cannot be obtained (defect).

<Rubber hardness of the model>
Separately, the liquid material for the soft molded body is poured into a mold, covered with glass and sealed, and irradiated with ultraviolet rays (USHIO Corporation, SPOT CURE SP5-250DB) 14 and 15 with a light intensity of 350 mJ / cm ² . Was irradiated and cured to produce a columnar pellet-shaped sample piece (hydrogel, shaped body) having a diameter of 20 mm and a thickness of 4 mm.
The obtained sample piece was measured with a durometer (GS-718N, manufactured by Teclock Co., Ltd.) by pressing the probe into the center of the 20 mm diameter surface and measuring the rubber hardness after 15 seconds by a method based on ISO 7691 (type A). The rubber hardness was 16.

(Example 2)
In Example 1, the content of the synthetic hectorite (Laponite XLG, manufactured by Nippon Silica Co., Ltd.) in the liquid material for the flexible molded body was changed to 4 parts by mass, and the dispersion was prepared. Then, a liquid material for a soft molded body was produced, and three-dimensional modeling was performed in the same manner as in Example 1.
About the obtained liquid material for flexible molded objects, the viscosity measured in the same manner as the liquid material for hard molded bodies of Example 1 was 6.8 mPa · s at 25.0 ° C., and the surface tension was the same as Example 1. .4 mN / m.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

(Example 3)
In Example 1, the content of the synthetic hectorite (Laponite XLG, manufactured by Nippon Silica Co., Ltd.) in the liquid material for the flexible molded body was changed to 12 parts by mass, and a dispersion was produced. Then, a liquid material for a soft molded body was produced, and three-dimensional modeling was performed in the same manner as in Example 1.
About the obtained liquid material for flexible molded objects, the viscosity measured in the same manner as the liquid material for hard molded bodies of Example 1 was 17.6 mPa · s at 25.0 ° C., and the surface tension was the same as in Example 1. .4 mN / m.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

Example 4
A liquid material for a soft molded body was prepared in the same manner as in Example 1 except that the polymerizable monomer in the liquid material for a soft molded body was changed to N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.). Then, three-dimensional modeling was performed in the same manner as in Example 1.
About the obtained liquid material for flexible molded objects, the viscosity measured in the same manner as the liquid material for hard molded bodies of Example 1 was 10.3 mPa · s at 25.0 ° C., and the surface tension was the same as in Example 1. .4 mN / m.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

(Example 5)
Three-dimensional modeling was performed in the same manner as in Example 1 using the same liquid material for soft molded bodies and liquid material for hard molded bodies as in Example 1.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.
In addition, about the peeling after drying of Example 5, when it dried by heating and drying at 50 degreeC for 2 hours, the support body peeled completely in about 10 minutes, and was favorable.

(Comparative Example 1)
In Example 1, the synthetic hectorite in the liquid material for soft molded bodies 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. Produced a liquid material for a soft molded body in the same manner as in Example 1, and three-dimensional modeling 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 liquid material for flexible molded objects, the viscosity measured in the same manner as the liquid material for hard molded bodies of Example 1 was 8.0 mPa · s at 25.0 ° C., and the surface tension was the same as Example 1. .4 mN / m.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.
In Comparative Example 1, it was found that a part of the modeling body could not withstand the weight of the support and was crushed during the three-dimensional modeling, and the target modeling body could not be obtained.

(Comparative Example 2)
In Example 1, in the case of the three-dimensional modeling, instead of using the UV-LED light irradiation machine, an ultraviolet irradiation machine (USHIO Corporation, SPOT CURE SP5-250DB) was used, and a light amount of 350 mJ / cm ² was irradiated. The three-dimensional modeling was performed in the same manner as in Example 1.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

(Example 6)
In Example 1, three-dimensional modeling was performed in the same manner as in Example 1 except that the three-dimensional model manufacturing apparatus shown in FIG.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

(Example 7)
In Example 1, three-dimensional modeling was performed in the same manner as in Example 1 except that the three-dimensional model manufacturing apparatus shown in FIG.
Specifically, two tanks that lead the liquid material for the hard molded body and the liquid material for the soft molded body to the inkjet head (GEN4, manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional structure manufacturing apparatus 10 shown in FIG. And the liquid material for the hard molded body and the liquid material for the soft molded body were respectively ejected from the inkjet head to form a film. In addition, the liquid material for hard molded bodies and the liquid material for soft molded bodies were sprayed at different positions.
Next, the film was irradiated with a light amount of 350 mJ / cm ² with a UV-LED (Integration, SubZero-LED, wavelength: 365 nm) light irradiation machine to cure the film, and then the cured film was applied to the film. Then, a smoothing process was performed with the rollers 20 and 21 to form a modeled body and a support as a three-dimensional modeled object.
As the roller, a metal roller made of an aluminum alloy with a diameter of 25 mm whose surface was anodized was used.
Next, about the obtained three-dimensional molded item, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 3.

  Next, details of the liquid material for the soft molded body and the liquid material for the hard molded body are summarized in Tables 1 and 2.

The details of the liquid material for soft moldings and the liquid material for hard moldings shown in Tables 1 and 2 are as follows.
* Layered Mineral _{XLG: [Mg 5.34 Li 0.66 Si} 8 O 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, manufactured by RockWood Co.)
* Polymerizable monomer DMA: N, N-dimethylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Polymerizable monomer IPAM: N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Curable material UK6038: Urethane acrylate (Made by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038)
* Curable material MANDA: Neopentyl glycol hydroxypivalate ester di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD MANDA)
* Photopolymerization initiator (BASF, Irgacure 184)
* Blue pigment: Toyo Ink Co., Ltd., trade name: Lionol Blue 7400G

表３の結果から、実施例１から７は、比較例１と比べて造形体の成型性に優れ、比較例１及び２と比べて造形体の「水平方向の誤差」及び「垂直方向の誤差」のバラツキが小さいことがわかった。

From the results of Table 3, Examples 1 to 7 are superior in moldability of the shaped body compared to Comparative Example 1, and the “horizontal error” and “vertical direction error” of the shaped body compared to Comparative Examples 1 and 2. "It was found that there was little variation.

As an aspect of this invention, it is 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;
The method for producing a three-dimensional object characterized by repeating the second step of curing the film formed in the first step with an ultraviolet light emitting diode 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;
A fourth step of curing the films respectively formed in the first step and the third step with an ultraviolet light emitting diode;
Is a method for producing a three-dimensional modeled object characterized by repeating a plurality of times.
<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 layered mineral dispersed in a single layer in water.
<5> The method for producing a three-dimensional structure according to any one of <1> and <3> to <4>, further including a fifth step of smoothing the film cured in the second step. It is.
<6> The method for producing a three-dimensional structure according to any one of <2> to <4>, further including a sixth step of smoothing the film cured in the fourth step.
<7> The method for producing a three-dimensional structure according to any one of <4> to <6>, wherein the layered mineral is synthetic hectorite.
<8> The <3> to <7>, wherein the polymerizable monomer is at least one selected from acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and N-acryloylmorpholine. It is the manufacturing method of three-dimensional molded item.
<9> The above <2> to <4>, further including a seventh 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, and <4> It is a manufacturing method of the three-dimensional molded item in any one of <6> to <8>.
<10> The method for producing a three-dimensional structure according to <9>, wherein the rubber hardness of the portion made of the hydrogel is 6 or more and 60 or less.
<11> The method for producing a three-dimensional structure according to any one of <9> to <10>, wherein the portion made of the hydrogel and the portion made of the polymer are separated by drying shrinkage.
<12> First means for forming a film by applying a first liquid containing at least water and a hydrogel precursor;
And a second means for curing the film formed of the first member with an ultraviolet light-emitting diode.
<13> The three-dimensional structure manufacturing apparatus according to <12>, further including fifth means for smoothing the film cured by the second means.
<14> first means for forming a film by applying a first liquid containing at least water and a hydrogel precursor;
A third means for forming a film by applying a second liquid containing at least a curable material to a position different from the first liquid;
A fourth means for curing the film respectively formed by the first member and the third member with an ultraviolet light emitting diode;
It is the manufacturing apparatus of the three-dimensional molded item characterized by having.
<15> The three-dimensional structure manufacturing apparatus according to <14>, further including sixth means for smoothing the film cured by the fourth means.
<16> The apparatus for producing a three-dimensional structure according to any one of <12> to <15>, wherein the hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer.
<17> The three-dimensional structure manufacturing apparatus according to <16>, wherein the mineral dispersible in water is a layered mineral dispersed in water in a single layer state.
<18> The three-dimensional structure manufacturing apparatus according to <17>, wherein the layered mineral is synthetic hectorite.
<19> The <16> to <18>, wherein the polymerizable monomer is at least one selected from acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and N-acryloylmorpholine. It is a manufacturing apparatus of three-dimensional molded item.
<20> Any one of the items <14> to <19>, further including a seventh means for peeling the portion made of the hydrogel formed from the hydrogel precursor and the portion made of the polymer formed from the curable material. It is a manufacturing apparatus of the three-dimensional molded item of description.

  The manufacturing method for a three-dimensional structure according to any one of <1> to <11> and the manufacturing apparatus for a three-dimensional structure according to any one of <12> to <20> The problem is to solve and achieve the following objectives. That is, the manufacturing method of the three-dimensional structure, and the manufacturing apparatus of the three-dimensional structure, a manufacturing method of a three-dimensional structure that can easily and efficiently manufacture a complicated and fine three-dimensional structure represented by an organ model, and the like, and It aims at providing the manufacturing apparatus of a three-dimensional molded item.

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

DESCRIPTION OF SYMBOLS 10 Manufacturing apparatus of three-dimensional molded item 11 Liquid material injection head unit 12 for modeling objects 12, 13 Liquid material injection head unit 14 for support bodies UV-LED light irradiation machine 16 Modeling object support substrate 17 Stage 18 Support body 19 Modeling object 20 , 21 Smoothing member 30 Model body 31, 32 Support body 33 Model body surface (interface with support body)

Claims (14)

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 in that the second step of curing the film formed in the first step with an ultraviolet light emitting diode is repeated a plurality of times. 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;
A fourth step of curing the films respectively formed in the first step and the third step with an ultraviolet light emitting diode;
A method for producing a three-dimensional modeled object characterized by repeating a plurality of times.   The manufacturing method of the three-dimensional molded item in any one of Claim 1 to 2 in which the said hydrogel precursor contains the mineral and polymerizable monomer which can be disperse | distributed to water.   The method for producing a three-dimensional structure according to claim 3, wherein the mineral dispersible in water is a layered mineral dispersed in a single layer in water.   The manufacturing method of the three-dimensional molded item in any one of Claim 1 and 3 to 4 which further includes the 5th process of smoothing the film | membrane hardened | cured by said 2nd process.   The manufacturing method of the three-dimensional molded item in any one of Claim 2 to 4 which further includes the 6th process of smoothing the film | membrane hardened | cured at the said 4th process.   7. The method according to claim 2, further comprising a seventh 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. Manufacturing method of a three-dimensional molded item.   The method for producing a three-dimensional structure according to claim 7, wherein a rubber hardness of a portion made of the hydrogel is 6 or more and 60 or less.   The manufacturing method of the three-dimensional molded item in any one of Claim 7 to 8 from which the part which consists of the said hydrogel, and the part which consists of the said polymer peels by dry shrinkage. A first means for forming a film by applying a first liquid containing at least water and a hydrogel precursor;
And a second means for curing the film formed of the first member with an ultraviolet light emitting diode.   The apparatus for producing a three-dimensional structure according to claim 10, further comprising fifth means for smoothing the film cured by the second means. A first means for forming a film by applying a first liquid containing at least water and a hydrogel precursor;
A third means for forming a film by applying a second liquid containing at least a curable material to a position different from the first liquid;
A fourth means for curing the film respectively formed by the first member and the third member with an ultraviolet light emitting diode;
An apparatus for producing a three-dimensional structure, characterized by comprising:   The manufacturing apparatus of the three-dimensional molded item of Claim 12 which further contains the 6th means which smoothes the film | membrane hardened | cured by the said 4th means. The three-dimensional structure according to any one of claims 12 to 13, further comprising a seventh means for peeling a portion made of a hydrogel formed from the hydrogel precursor and a portion made of a polymer formed from a curable material. Manufacturing equipment.

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