JP2020152118A - Production device of hydrogel three-dimensional model - Google Patents

Abstract

To provide a method for producing a three-dimensional model, in which the method can easily and efficiently produce a complicated and detailed three-dimensional model represented by an organ model.SOLUTION: There is provided a method for producing a three-dimensional model in which a first step of applying a first liquid containing at least water and a hydrogel precursor to form a film, and a second step of curing the film formed in the first step with an ultraviolet light emitting diode are multiply repeated.SELECTED DRAWING: None

Description

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

Conventionally, as a three-dimensional modeling method, a method of irradiating a liquid photocurable resin with laser light, particularly ultraviolet light one layer at a time, to produce a three-dimensional three-dimensional model has been proposed (for example, Patent Document 1). reference). However, in the 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. Further, there is a problem that it is necessary to control the temperature and the like in order to stabilize the quality of the liquid photocurable resin.
Further, in recent years, an inkjet stereolithography method has been disclosed in which a liquid photocurable resin is formed into an image at a required portion of a modeled object by an inkjet method, and a three-dimensional modeled object is formed by forming a multi-layered image thereof. In such an inkjet stereolithography method, a method has been proposed in which a member support different from the three-dimensional model is simultaneously formed to prevent the three-dimensional object from being deformed or dropped during the three-dimensional model (for example, Patent Document 2). And 3).

Recently, there is an increasing need for gel-like or soft three-dimensional shaped objects with three-dimensional and fine structures such as organ models for medical use and scaffolding materials for cells used in regenerative medicine, but complicated and fine structures are three-dimensional. A method for manufacturing a three-dimensional model that can be reproduced from the data has not yet been provided.

An object of the present invention is to provide a method for manufacturing a three-dimensional model that can easily and efficiently manufacture a complicated and fine three-dimensional model represented by an organ model or the like.

The method for producing a three-dimensional object of the present invention as a means for solving the above-mentioned problems includes a first step of applying a first liquid containing at least water and a hydrogel precursor to form a film.
The second step of curing the film formed in the first step with an ultraviolet light emitting diode is repeated a plurality of times.

According to the present invention, it is possible to provide a method for manufacturing a three-dimensional model that can easily and efficiently manufacture a complicated and fine three-dimensional model represented by an organ model or the like.

FIG. 1 is a schematic view showing an example of a layered mineral and a state in which the layered mineral is dispersed in water. FIG. 2 is a schematic view showing an example of a three-dimensional model manufacturing apparatus of the present invention. FIG. 3 is a schematic view showing another example of the three-dimensional model manufacturing apparatus of the present invention. FIG. 4 is a schematic view showing still another example of the three-dimensional model manufacturing apparatus of the present invention. FIG. 5 is a diagram showing a state of an intermediate (before peeling of the support) manufactured by the method for manufacturing a three-dimensional model. FIG. 6 is a diagram showing a state after peeling manufactured by a method for manufacturing a three-dimensional model. FIG. 7 is a diagram for explaining the measurement of the vertical error and the horizontal error of the modeled body after peeling.

(Manufacturing method of three-dimensional model and equipment for manufacturing three-dimensional model)
The method for producing a three-dimensional model according to the first embodiment of the present invention includes a first step and a second step, preferably includes a fifth step, and further includes other steps as necessary. Including.
The apparatus for manufacturing a three-dimensional object according to the first aspect of the present invention preferably has a first means, a second means, and a fifth means, and further, if necessary, other means. Must have.

<First step and first means>
The first step is a step of applying a first liquid containing water and a hydrogel precursor to form a film, and can be carried out by the first means.

The means for applying the first liquid as the first means is not particularly limited as long as the droplets can be applied to a 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 and the like can be mentioned. A known device can be preferably used to carry out these methods.
Among these, the dispenser method is excellent in quantification of droplets, but the coating area is narrow, and the spray method can easily form fine ejected substances, has a wide coating area, and is excellent in coating property. The quantification of the droplets is poor, and scattering occurs due to the spray flow. Therefore, in the present invention, the above-mentioned inkjet method is particularly preferable. The inkjet method has the advantages of better quantification of droplets than the spray method, a wider coating area than the dispenser method, and is preferable in that a complicated three-dimensional shape can be formed accurately and efficiently. ..

In the case of the above-mentioned inkjet method, it has a nozzle capable of ejecting the first liquid. As the nozzle, a nozzle from a known inkjet printer can be preferably used, and as the nozzle, for example, GEN4 manufactured by Ricoh Industry Co., Ltd. is preferably used. This inkjet nozzle is preferable because the amount of liquid that can be dropped from the head portion at one time is large and the coating area is large, so that the coating speed can be increased.

<< First liquid >>
The first liquid comprises water and a hydrogel precursor, and further comprises other components as needed. The first liquid is also referred to as a "liquid material for a soft molded article".

-Water-
As the water, for example, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used.
Other components such as an organic solvent may be dissolved or dispersed in the water depending on the purpose of imparting moisturizing property, antibacterial property, conductivity, hardness adjustment and the like.
The content of the water is not particularly limited and may be appropriately selected depending on the intended purpose.

-Hydrogel precursor-
The hydrogel precursor contains minerals and polymerizable monomers that are dispersible in water, and further contains other components as needed.

--Minerals that can be dispersed in water ---
The mineral that can be dispersed in water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include layered minerals.
The layered mineral is preferably a layered mineral dispersed in water in a single layer state.
Here, as shown in the upper figure 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 figure of FIG. 1, each single layer state is separated into disk-shaped crystals.
The layered mineral is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water-swellable layered clay minerals.
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 swelling property means that water molecules are inserted between layers of layered minerals and dispersed in water as shown in FIG.
As the water-swellable layered clay mineral, one of the above-exemplified ones may be used alone, two or more of them may be used in combination, or a synthetic one may be appropriately synthesized. It may be a commercially available product.
Examples of the commercially available product include synthetic hectorite (Raponite XLG, manufactured by RockWood), SWN (manufactured by Coop Chemical Ltd.), fluorinated hectorite SWF (manufactured by Coop Chemical Ltd.), and the like. Of these, synthetic hectorite is preferred.
The content of the layered mineral is preferably 1% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total amount of the first liquid. 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 ejection property of the inkjet nozzle and the hardness of the three-dimensional model are good.

--Polymerizable monomer ---
Specific examples of the polymerizable monomer include acrylamide, N-substituted acrylamide derivative, N, N-di-substituted acrylamide derivative, N-substituted methacrylicamide derivative, and N, N-di-substituted methacrylicamide derivative. Examples include acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N-acryloylmorpholin and the like. These may be used alone or in combination of two or more.
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 and the like can be obtained.
The polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group and the like is an advantageous constituent 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 may be appropriately selected depending on the intended purpose.
For example, surfactants, stabilizers, surface treatment agents, polymerization initiators, colorants, viscosity modifiers, adhesion-imparting agents, antioxidants, anti-aging agents, cross-linking accelerators, UV absorbers, plasticizers, preservatives. Agents, organic solvents, dispersants and the like can be mentioned.

-Physical properties of the first liquid-
The surface tension of the first liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 20 mN / m or more and 45 mN / m or less is preferable, and 25 mN / m or more and 34 mN / m or less is 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 at the time of 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.) or the like.

The viscosity of the first 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, and 6 mPa · s or more and 12 mPa · s or less at 25 ° C. Is more preferable.
When the viscosity is 3 mPa · s or more and 20 mPa · s or less, good discharge of the first liquid can be performed at the time of three-dimensional modeling.
The viscosity can be measured in an environment of 25 ° C. 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 carried out by the second means.

An ultraviolet light emitting diode (UV-LED) is used as a means for curing the film as the second means.
The emission wavelength of the ultraviolet light emitting diode is not particularly limited and may be appropriately selected depending on the intended purpose. Generally, there are 365 nm, 375 nm, 385 nm, 395 nm, and 405 nm, but the wavelength of the ultraviolet light emitting diode can be selected. Considering the influence of color, short wavelength light emission is more advantageous so that the absorption of the polymerization initiator is increased.
The ultraviolet light emitting diode (UV-LED) has a smaller thermal energy given to the film during curing than a commonly used ultraviolet irradiation lamp (for example, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp), electron beam, or the like. Reduced thermal damage to the membrane.
In particular, the hydrogel formed in the present invention has a remarkable effect because it exhibits its characteristics when it exists in a state where water is stored.
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 components that dissolve in water are contained in a three-dimensional network structure formed by combining a water-soluble organic polymer and layered minerals. Is preferable.
The organic-inorganic composite hydrogel has improved extensibility and can be integrally peeled off without breaking, which greatly simplifies the post-modeling process.

<Fifth step and fifth means>
The fifth step is a step of smoothing the film cured in the second step, and can be carried out by the fifth means.
The fifth means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include rollers and blades.

-Roller-
The shape, structure, size, material, etc. of the roller are not particularly limited and may be appropriately selected depending on the intended purpose. The shape includes, for example, a cylindrical medium body and a hollow inside. 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 model and the like. can do. Examples of the material include resin, rubber, metal, or a combination thereof.
The rollers include a core metal, a rubber roller having a rubber layer on the core metal, a rubber roller composed of only rubber without a core metal, a core material, and a foam layer formed on the outer periphery of the core material. Examples include foaming rollers and metal rollers having the above.

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

The film formed in the first step and cured in the second step does not necessarily have the target film thickness (layer thickness) in all regions. That is, in the case of the inkjet method, there may be non-ejection, and in both the inkjet method and the dispenser method, a step between dots may occur, which may be insufficient for forming a highly accurate three-dimensional model.
To compensate for this, for example, immediately after forming a layer, it is mechanically smoothed (leveled), mechanically scraped off, smoothness is detected, and the amount of film formed is set at the dot level when the next layer is laminated. A method such as adjusting with is conceivable.
The hardness of the hydrogel used in the present invention is relatively soft because the target three-dimensional model is an organ model such as an internal organ. Therefore, in smoothing, a smoothing method that mechanically smoothes immediately after forming the layer can be effectively used.
Examples of the mechanical smoothing method include a method of smoothing with a blade-shaped smoothing member and a method of leveling with a roller-shaped smoothing member.
When the roller-shaped smoothing member is used, the smoothing effect is more effectively exhibited by rotating the roller in the direction opposite to the operation direction.
The blade-shaped smoothing member is more effective when the surface of the modeled object is scraped and smoothed as compared with the roller-shaped smoothing member.

<Other processes and other means>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a peeling step, a polishing step of the modeled body, a cleaning step of the modeled body, and the like, which are carried out by other means. be able to.

In the method for manufacturing a three-dimensional model of the first aspect, each of the above steps is repeated a plurality of times. The number of repetitions varies depending on the size, shape, structure, etc. of the three-dimensional model to be produced and cannot be unconditionally specified, but if the thickness per layer is in the range of 10 μm or more and 50 μm or less, it can be peeled off with high accuracy. Since it is possible to model without doing so, it is necessary to repeatedly stack the three-dimensional model to be produced by the height of the model.

The method for producing a three-dimensional model according to the second embodiment 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 other steps are included as necessary.
The three-dimensional model manufacturing apparatus according to the second aspect of the present invention has the first means, the third means, and the fourth means, and includes the sixth means and the seventh means. It is preferable, and other means are provided as needed.

<Third step and third means>
The third step is a step of applying a second liquid containing at least a curable material to a position different from that of the first liquid to form a film, and can be carried out by a third means.
The means for applying the second liquid as the third means is the same as the first means in the apparatus for manufacturing the three-dimensional model of the first form, and thus the description thereof will be omitted.

The "position different from the first liquid" means that the second liquid application position and the first liquid application position do not overlap, and the second liquid application position and the first liquid application position do not overlap. The liquid application position may be adjacent to the liquid. Since the second liquid has a different composition from 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 curing becomes clear.

<< Second liquid >>
The second liquid is a liquid that becomes a hard molded body for supporting a three-dimensional model composed of a hydrogel (soft body) (also referred to as a "liquid material for a hard molded body").
The second liquid contains at least a curable material and, if necessary, other components.

-Curable material-
The curable material is preferably a compound that undergoes a polymerization reaction by ultraviolet 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 include curable resins and thermosetting compounds. Among these, a material that is liquid 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 by irradiating with active energy rays.
Examples of the compound that undergoes radical polymerization include a compound having an ethylenically unsaturated group.
Examples of the cation-polymerizing compound include a compound 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, for example, a monofunctional group 2-ethylhexyl (meth) acrylate (EHA), 2-Hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), caprolactone-modified tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydro Flufuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol ( Meta) acrylate, difunctional tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalic acid ester di (Meta) acrylate (MANDA), Neopentyl glycol hydroxypivalate di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4-butanediol di (meth) acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate ( NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalate neopentyl glycol ester di (meth) acrylate, propoxylated 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 trimethylol propanetri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), dipentaerythritol hexa (Meta) acrylate (DPHA), diol Reallyl isocyanate, (meth) acrylate of ε-caprolactone-modified dipentaerythritol, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropanthry (meth) acrylate, propoxylated trimethylolpropanthry (meth) Meta) acrylate, propoxylated glyceryltri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, Penta (meth) acrylate ester and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of commercially available products of the active energy ray-curable compound include KAYARAD TC-110S, KAYARAD R-128H, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R-167, KAYARAD HX-220. 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-320, KAYARAD TPA KAYARAD RP-1040, KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-60, 0075, KAYARAD DN-2475, KAYAMER PM-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, 295, 355, 399E494, 9041203, 208, 242. , 313, 604, 205, 206, 209, 210, 214, 231E239, 248, 252, 297, 348, 365C, 480, 9036, 350 (all manufactured by Nippon Kayaku Co., Ltd.), Beam Set 770 (Arakawa Chemical Industry Co., Ltd.) (Made by Co., Ltd.), etc. These may be used alone or in combination of two or more.

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

Examples of the emulsion type photocurable resin include polyester (meth) acrylate, bisphenol-based epoxy (meth) acrylate, bisphenol A-based epoxy (meth) acrylate, propylene oxide-modified bisphenol A-based epoxy (meth) acrylate, and alkali. Molten epoxy (meth) acrylate, acrylic-modified epoxy (meth) acrylate, phosphate-modified epoxy (meth) acrylate, polycarbonate-based urethane (meth) acrylate, polyester-based urethane (meth) acrylate, alicyclic urethane (meth) acrylate, fat Examples thereof include group urethane (meth) acrylate, polybutadiene (meth) acrylate, and polystyryl (meth) acrylate.

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 (all manufactured by Mitsubishi Rayon Co., Ltd.), Orestar 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 (all manufactured by Nippon Kayaku Co., Ltd.), Beam Set 700, 710, 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 (The above is manufactured by Arakawa Chemical Industry Co., 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, 4501TA, 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, MT408-42, 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 (all manufactured by Taisei Kako Co., Ltd.) and the like.

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 intended purpose. For example, a polymerization initiator, a colorant, a water-soluble resin, water, a low boiling point alcohol, a surfactant, a viscosity modifier, etc. Adhesive-imparting agents, antioxidants, antioxidants, cross-linking accelerators, UV 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-based initiator, a peroxide initiator, a persulfate initiator, and a redox (oxidation-reduction) initiator. And so on.

--- Photopolymerization initiator ---
As the photopolymerization initiator, any substance that generates radicals by irradiation with 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, and Michler ketone. , Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2 -Methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 1-hydroxycyclohexylphenylketone, azobisisobutyronitrile , Benzoyl peroxide, di-tert-butyl peroxide and the like. These may be used alone or in combination of two or more.

The content of the polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01% by mass or more and 3% by mass or less with respect to the total amount of the curable material.

When irradiating the ultraviolet light emitting diode (UV-LED) light, the second liquid pigment prevents the curing speed from being lowered due to the absorption or concealment of the ultraviolet light emitting diode (UV-LED) light. A sensitizer can also be used for the purpose.
Examples of the sensitizer include cyclic amine compounds such as aliphatic amines, amines having aromatic groups, and piperidine; urea compounds such as o-tolylthiourea; and soluble salts of sodium diethylthiophosphate and aromatic sulfinic acid. Sulfur compounds such as: N, N'-di-substituted-p-Aminobenzonitrile and other nitrile compounds; Tri-n-butylphosphine, sodium diethyldithiophosfeed and other phosphorus compounds; Michler ketone, N-nitrosohydroxylamine derivatives, oxazolidine Examples thereof include compounds, tetrahydro-1,3-oxazine compounds, formaldehyde, nitrogen compounds such as condensates of acetaldehyde and diamine, and the like. These may be used alone or in combination of two or more.

--Colorant ---
As the colorant, dyes and pigments that are dissolved or stably dispersed in the second liquid and have excellent thermal stability are suitable. Among these, a soluble dye (Solvent Dye) is preferable. Further, it is possible to mix two or more kinds of colorants in a timely manner for the purpose of color adjustment and the like.

-Physical properties of the second liquid-
The surface tension of the second liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 20 mN / m or more and 45 mN / m or less is preferable, and 25 mN / m or more and 34 mN / m or less is preferable. More preferred.
When the surface tension is 20 mN / m or more and 45 mN / m or less, a good discharge of the second liquid can be performed at the time of 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.) or the like.
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, and 6 mPa · s or more and 12 mPa · s or less at 25 ° C. Is more preferable.
When the viscosity is 3 mPa · s or more and 20 mPa · s or less, a good discharge of the second liquid can be performed at the time of three-dimensional modeling.
The viscosity can be measured in an environment of 25 ° C. 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 by the ultraviolet light emitting diode, and can be carried out by the fourth means.
Since the fourth step and the fourth means are the same as the second step and the second means in the method for manufacturing the three-dimensional model of the first form and the manufacturing apparatus thereof, the description thereof will be described. Omit.
The curing of the film formed in the first step and the curing of the film formed in the fourth step may be performed at the same time or separately.
The cured film is an organic-inorganic composite hydrogel in which water and components that dissolve in water are contained in a three-dimensional network structure formed by combining a water-soluble organic polymer and layered minerals. Is preferably used for spontaneous peeling of the support simply by drying and shrinking when the support is removed after molding.
The organic-inorganic composite hydrogel has improved extensibility and can be integrally peeled off without breaking, which greatly simplifies the treatment after three-dimensional modeling.

<Sixth step and sixth means>
The sixth step is a step of smoothing the film cured in the fourth step, and can be carried out by the sixth means.
Since the sixth step and the sixth means are the same as the fifth step and the fifth means in the method for manufacturing the three-dimensional model of the first form and the manufacturing apparatus thereof, the description thereof will be described. Omit.

<Seventh step and seventh means>
The seventh 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, and is carried out by the seventh means. be able to.
The seventh means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include various peeling devices.

The rubber hardness of the portion made of the hydrogel is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 6 or more and 60 or less, and more preferably 8 or more and 20 or less.
When the rubber hardness is 6 or more and 60 or less, the shape does not collapse during the three-dimensional modeling, and peeling after the three-dimensional modeling can be performed satisfactorily.
The rubber hardness can be measured by a method conforming to ISO7691 (Type A), and can be measured using, for example, a durometer (manufactured by Teclock Co., Ltd., GS-718N).
The portion made of the hydrogel and the portion made of the polymer can be peeled off by drying shrinkage.
The drying shrinkage can be performed by various methods such as a method of leaving the product 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 intended purpose. Examples thereof include a discharge stabilization step, a model cleaning step, a model polishing step, and the like. , It can be carried out by cleaning means of the modeled body, polishing means of the modeled body, or the like.

-Discharge stabilization process and discharge stabilization means-
When an inkjet head is used as a means for ejecting a liquid, drying of the nozzle at the time of non-ejection becomes a big problem for stable operation.
Therefore, in the ejection stabilizing step and the ejection stabilizing means, when continuous ejection is not performed from the inkjet head for a long time, (1) the ejection port is covered (capped) with a member having a shape that at least covers the tip of the head. , Preventing the tip of the discharge port from drying out, (2) The viscosity of the internal liquid near the discharge port increases due to drying.
Alternatively, the stable discharge state can be maintained for a long time by discharging the film formed by drying by a suction action, and (3) wiping the discharge port or the discharge port and its surroundings.
These things are extremely important in the process of modeling a three-dimensional model that requires continuous discharge for a long time of 24 hours or more, especially when a liquid containing a low boiling point solvent such as water is used when modeling a soft material. is important.

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

−− Discharge defect recovery process −−
In the ejection defect recovery step, the inkjet head is then moved to the ejection position in order to restart the ejection operation. When the discharge is completed and the modeling is completed, the process is moved to the cap contact position again, and the discharge defect recovery step is completed.
In the case of manufacturing a large three-dimensional model, it is necessary to continuously discharge for a long period of time, so it is preferable that the discharge defect recovery step is carried out regularly.
The timing of recovery from defective discharge is not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of recovery of defective discharge, it is preferable to periodically perform every continuous operation within 2 hours. ..

In the method for manufacturing a three-dimensional model of the second aspect, each of the above steps is repeated a plurality of times. The number of repetitions varies depending on the size, shape, structure, etc. of the three-dimensional model to be produced and cannot be unconditionally specified, but if the thickness per layer is in the range of 10 μm to 50 μm, it can be peeled off with high accuracy. Since it is possible to model without any need, it is necessary to repeatedly stack the three-dimensional model to be produced by the height of the model.

In the method for producing a three-dimensional model of the second form, when a soft model of hydrogel formed from a hydrogel precursor is produced, water and water are used as liquids for forming the soft model. 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 produce a hard model, a second liquid containing at least a curable material is used as the liquid for forming the three-dimensional model, and water and hydrogel are used as the liquid for forming the support. A first liquid containing at least the precursor is used.
Therefore, in the method for producing a three-dimensional model of the second form, it is possible to separately produce a three-dimensional model by simply changing the liquid to be applied according to the hardness of the desired model. Further, in any case, the difference in hardness between the support and the modeled body makes it possible to peel off very easily.
Further, it does not matter which of the first step and the third step is performed first, and it is preferable to perform the third step first because the support can be formed first.

As described above, in the method for producing a three-dimensional model of the present invention, a liquid is ejected from pores such as an inkjet method and a dispenser method so that an image of each layer can be formed and cured. The former first liquid and the second liquid are in an immiscible incompatible state in which the parts in contact with each other are clearly separated.
In the conventional molding method, the contact portion between the first liquid and the second liquid is compatible with each other, and the boundary becomes unclear during photocuring. As a result, minute irregularities remain on the surface of the modeled object, but in the method for producing a three-dimensional modeled object of the present invention, the first liquid and the second liquid are in an incompatible state, so that after photocuring. Boundary becomes clear. Further, the peelability is improved due to the difference in hardness between the obtained modeled body and the support. As a result, the surface smoothness of the modeled body is improved, and it is possible to omit or significantly reduce the polishing step after the three-dimensional modeling.

Hereinafter, a method for manufacturing a three-dimensional model and a specific embodiment of an apparatus for manufacturing a three-dimensional model will be described.
A liquid material for a soft molded product was used as the first liquid, and a liquid material for a hard molded product was used as the second liquid to obtain a molded product of a soft hydrogel.
As described above, in order to obtain a soft three-dimensional model, a liquid material for a soft molded body is arranged in a modeled body portion, and a liquid material for a hard molded body is arranged in a support portion. On the contrary, in order to obtain a hard three-dimensional model, a liquid material for a hard molded body is arranged on a molded body portion, and a liquid material for a soft molded body is arranged on a support portion.
As a method of applying the liquid, an inkjet method or a dispenser method can also 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 all cases, the embodiment using the inkjet method as the liquid application method will be mainly described below.

First, the surface data or solid data of the three-dimensional shape designed by the three-dimensional CAD or the three-dimensional shape captured by the three-dimensional scanner or digitizer is converted into the STL format and input to the three-dimensional model 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.

After determining the modeling direction, the projected area of the three-dimensional shape on the XY plane, the XY plane, and the YY plane is obtained. In order to reinforce the obtained block shape, each other surface is moved outward by an appropriate amount except for the upper surface of the XY surface. The amount to be moved is not particularly limited and varies depending on the shape, size and liquid material used, but is about 1 mm to 10 mm. With this, the block shape in which the shape to be modeled is confined (the upper surface is open) is specified.

This block shape is sliced in the Z direction with a single layer thickness. The thickness of the layer varies depending on the material used and cannot be unconditionally specified, 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 come to the center of the Z stage (a table on which the model object that descends by one layer for each layer model). Further, when a plurality of block shapes are formed at the same time, the block shapes are arranged on the Z stage, but it is also possible to stack the block shapes. These block shaping, round slice data (slice data: contour data), and arrangement on the Z stage can be automatically created by specifying the liquid material to be used.

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

The order of injection is as follows: the liquid material for a hard molded body forming the support layer is injected, and then the liquid material for a soft molded body forming the molded body layer is injected.

When the injection is performed in such an order, a reservoir such as a groove or a dam 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 concern about "dripping", and a wide range of photocurable resins, thermosetting resins and the like can be used.

Further, in order to further shorten the molding time, a method of injecting and laminating a liquid material for a soft molded body and a liquid material for a hard molded body on each of the outward and return paths of the integrated inkjet head is preferable.

Further, high-speed modeling is possible by adjoining an ultraviolet light emitting diode (UV-LED) light irradiator to an inkjet head that injects a liquid material for a soft molded body.
Further, in order to smooth the three-dimensionally formed layer, a smoothing treatment is performed immediately after the curing treatment is performed.
In the smoothing treatment, for example, a smoothing member such as a roller or a blade is used to smooth the surface of the cured film. As a result, the accuracy of each layer is improved, and the entire three-dimensional model can be precisely manufactured.
At this time, in order to shorten the stacking time and improve the smoothness of the layer, it is preferable to arrange the smoothing member adjacent to the UV-LED light irradiator.

FIG. 2 is a schematic view showing an example of a modeled body manufacturing process in the method for manufacturing a three-dimensional modeled object of the present invention using the device for manufacturing a three-dimensional modeled object of the present invention.
The three-dimensional model manufacturing apparatus 10 uses a head unit in which the inkjet heads are arranged to supply the liquid material for the soft molded body from the liquid material injection head unit 11 for the model and the liquid material injection head units 12 and 13 for the support. The liquid material for a hard molded body is injected, and the liquid material for a soft molded body is laminated while being cured by adjacent ultraviolet light emitting diode (UV-LED) light irradiators 14 and 15.
That is, the liquid material for a hard molded body is injected from an inkjet head (liquid material injection head units for supports 12 and 13) and solidified to form a first support layer having a reservoir, and the first support thereof. A liquid material for a soft molded body is sprayed onto the reservoir of the layer from an inkjet head (liquid material injection head unit 11 for a modeled body), and the liquid material for the soft molded body is irradiated with UV-LED light to be cured. Form the model layer of.
Next, a molten liquid material for a hard molded body is sprayed onto the first support layer to solidify it, and a second support layer having a reservoir is laminated, and the reservoir of the second support layer is laminated. A liquid material for a soft molded body is sprayed onto the body, and the liquid material for a soft molded body is irradiated with UV-LED light to laminate a second modeled body layer on the first modeled body layer for three-dimensional three-dimensional modeling. Manufacture thing 19.

When the multi-head unit moves in the direction of arrow A, the support 18 is basically used by using the liquid material injection head unit 12 for the support, the liquid material injection head unit 11 for the model, and the UV-LED light irradiator 15. And the model 19 is formed on the model support substrate 16. The liquid material injection head unit 13 for the support and the UV-LED light irradiator 14 may be used as an auxiliary.

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

Further, in order to keep the gap between the liquid material injection head units 11, 12, 13 and the UV-LED light irradiators 14, 15 and the model 19 and the support 18 constant, the stage 17 is lowered according to the number of times of stacking. While stacking.

FIG. 3 is a schematic view showing another example of the three-dimensional model manufacturing process in the method for manufacturing the three-dimensional model of the present invention using the device for manufacturing the three-dimensional model of the present invention. The basic process is the same as in FIG. 2, but the UV-LED light irradiators 14 and 15 are arranged between the liquid material injection head 11 for the model and the liquid material injection heads 12 and 13 for the support. The point is different.

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

Further, as the three-dimensional modeling device 10, it is also possible to add a liquid recovery mechanism, a recycling mechanism, and the like. It may be provided with a blade for removing the liquid material adhering to the nozzle surface or a detection mechanism for a non-ejection nozzle. Further, it is also preferable to control the environmental temperature in the manufacturing apparatus of the three-dimensional model at the time of three-dimensional modeling.

<Liquid set for 3D modeling>
The liquid set for three-dimensional modeling used in the present invention comprises the first liquid and the second liquid, and further contains other components and the like as necessary.
The liquid set for three-dimensional modeling can be suitably used for producing various three-dimensional objects, and in particular, can be suitably used for producing complex and fine three-dimensional objects represented by an organ model or the like.

<Three-dimensional model>
The three-dimensional model used in the present invention is made 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, the elasticity and strength required for the organ model can be obtained.
The rubber hardness can be measured, for example, by a method conforming to ISO7691 (Type A).

The hydrogel is preferably a hydrogel in which water is contained in a three-dimensional network structure formed by complexing a water-soluble organic polymer and a single-layer dispersion of layered minerals.
Examples of the water-soluble organic polymer include an organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group and the like.
The water-soluble organic polymer is an advantageous component for maintaining the strength of an aqueous gel.
The organic polymer may be a homopolymer (homopolymer), a heteropolymer (copolymer), or may be modified as long as it exhibits water solubility, and is known. The functional group of the above may be introduced, or it may be in the form of a salt, but a homopolymer is preferable.
The water-soluble property of the water-soluble organic polymer means, for example, that when 1 g of the organic polymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more of the organic polymer 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 procedures because the tactile sensation and sharpness of the organ are extremely close to the desired organ and the incision can be made with a surgical scalpel.

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

(Example 1)
<Preparation of second liquid (liquid material for hard molded parts)>
Urethane acrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038) 10 parts by mass as a curable material, neopentyl glycol hydroxypivalate di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: 90 parts by mass of KAYARAD MANDA), 3 parts by mass of photopolymerization initiator (manufactured by BASF, trade name: Irgacure 184), and 2 parts by mass of 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 rotation speed of 2,000 rpm until a homogeneous mixture was obtained. Subsequently, filtration was performed to remove impurities and the like, and finally vacuum degassing was carried out for 10 minutes to obtain a homogeneous liquid material for a hard molded body.
The surface tension and viscosity of the obtained liquid material for a hard molded body 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]
The surface tension of the obtained liquid material for a hard molded body was measured by a suspension method using a surface tension meter (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

[Measurement of viscosity]
The obtained liquid material for a hard molded body was measured with a rotational viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.) in an environment of 25.0 ° C.

<Preparation of the first liquid (liquid material for soft molded parts)>
Ion-exchanged water that had been degassed under reduced pressure for 10 minutes was used as pure water.

-Preparation of initiator solution-
(A) As the initiator solution 1, a photopolymerization initiator (Irgacure 184, manufactured by BASF) was dissolved in 98 parts by mass of methanol at a ratio of 2 parts by mass to prepare a solution.

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

-Preparation of liquid materials for soft moldings-
First, while stirring the pure water 195 parts by mass, as a water-swellable layered clay mineral _{[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) 8 parts by mass 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.) from which the polymerization inhibitor had been removed by passing through a column of activated alumina was added to the obtained dispersion as a polymerizable monomer. Further, 0.2 parts 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 parts by mass of the (A) initiator solution 1 is added, 5 parts by mass of the (B) initiator solution 2 is added, and after stirring and mixing, deaeration under reduced pressure is performed by 10. Performed for minutes. Subsequently, filtration was performed to remove impurities and the like to obtain a homogeneous liquid material for a soft molded product.
With respect to the obtained liquid material for a soft molded body, the surface tension measured in the same manner as the liquid material for a hard molded body was 34.4 mN / m, and the viscosity measured in the same manner as the liquid material for a hard molded body was 34.4 mN / m. It was 10.1 mPa · s at 25.0 ° C.

<Three-dimensional modeling>
The liquid material for a hard molded product and the liquid material for a soft molded product are filled into two tanks leading to an inkjet head (GEN4 manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional molded product manufacturing apparatus 10 shown in FIG. 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. The liquid material for the hard molded body and the liquid material for the soft molded body were sprayed at different positions.
Next, the film is irradiated with a light amount of 350 mJ / cm ² with a UV-LED (SubZero-LED manufactured by Integration Co., Ltd., wavelength: 365 nm) light irradiator to obtain the liquid material for the hard molded body and the soft molded body. While curing the liquid material for use, a modeled body and a support as a three-dimensional modeled object were formed.

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

<Moldability of 3D model>
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 by using the three-dimensional model manufacturing apparatus shown in FIG. The moldability of the three-dimensional model at this time was evaluated based on the following criteria.
[Evaluation criteria]
◯: Aimed modeling was possible (good)
×: The target modeling could not be performed (defective)

<Measurement of "horizontal error" and "vertical error" of the model>
Regarding the "horizontal error" and "vertical error" of the obtained model 30, as shown in FIG. 7, the horizontal and vertical dimensions of the model 30 were measured at 10 points each with a caliper. The variations at 10 points were obtained as follows, and evaluated according to the following criteria.
-10 variations-
The horizontal and vertical lengths of the model 30 shown in FIG. 7 were measured at 10 points with a caliper, and the obtained measured values at 10 points and an input signal for modeling (target length in the horizontal direction or vertical direction). The maximum and minimum values of the error from the target length) were obtained. Select the larger absolute value of the maximum and minimum values of the obtained error, and divide the absolute value of the selected 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 set at 10 points.
[Evaluation criteria]
⊚: The variation at 10 points is less than 2% (good)
◯: The variation at 10 points is 2% or more and less than 5% (normal)
X: The variation at 10 points is 5% or more (defective)

<Pulling peeling>
Immediately after modeling the three-dimensional model, the support 31 was pulled and peeled off in the horizontal direction as shown in FIG. 6 to obtain the model 30. Tension peeling was evaluated based on the following criteria.
[Evaluation criteria]
⊚: The support was peeled off as a unit, and a modeled body was obtained without any further treatment (good).
◯: Most of the supports could be peeled off, and some of the remaining supports could be completely peeled off by simply rubbing with a brush (normal).
X: Support cannot be peeled off (defective)

<Peel after drying>
After performing the tensile peeling test on one of the supports 31 shown in FIG. 6, the other support 32 was left at room temperature (25 ° C.) for 5 hours, and then the support 32 was peeled off. Detachment after drying was evaluated based on the criteria.
[Evaluation criteria]
⊚: After peeling, the modeled body and the support that had dried and shrunk were completely separated, and the support could also be peeled together (good).
◯: Most of the supports could be peeled off, and some of the remaining supports could be completely peeled off by simply rubbing with a brush (normal).
X: Support cannot be peeled off (defective)

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

<Rubber hardness of modeled body>
Separately, the liquid material for the soft molded body is poured into a mold, covered with glass, and sealed, and the amount of light of 350 mJ / cm ² with an ultraviolet irradiator (SPOT CURE SP5-250DB, manufactured by Ushio, Inc.) 14 and 15. Was irradiated and cured to prepare a columnar pellet-shaped sample piece (hydrogel, modeled body) having a diameter of 20 mm and a thickness of 4 mm.
The obtained sample piece was pressed into the center of a surface having a diameter of 20 mm using a durometer (manufactured by Teclock Co., Ltd., GS-718N), and the rubber hardness 15 seconds later was measured by a method conforming to ISO7691 (Type A). , The rubber hardness was 16.

(Example 2)
In Example 1, the same as in Example 1 except that the content of synthetic hectorite (Raponite XLG, manufactured by Nippon Silica Co., Ltd.) in the liquid material for a soft molded body was changed to 4 parts by mass to prepare a dispersion. A liquid material for a soft molded body was produced, and three-dimensional modeling was performed in the same manner as in Example 1.
Regarding the obtained liquid material for soft molded products, the viscosity measured in the same manner as the liquid material for hard molded products of Example 1 was 6.8 mPa · s at 25.0 ° C., and the surface tension was the same as in Example 134. It was .4 mN / m.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 3)
In Example 1, the same as in Example 1 except that the content of synthetic hectorite (Raponite XLG, manufactured by Nippon Silica Co., Ltd.) in the liquid material for a soft molded body was changed to 12 parts by mass to prepare a dispersion. A liquid material for a soft molded body was produced, and three-dimensional modeling was performed in the same manner as in Example 1.
Regarding the obtained liquid material for soft molded products, the viscosity measured in the same manner as the liquid material for hard molded products of Example 1 was 17.6 mPa · s at 25.0 ° C., and the surface tension was the same as in Example 134. It was .4 mN / m.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 4)
A liquid material for a soft molded product was prepared in the same manner as in Example 1 except that the polymerizable monomer in the liquid material for a soft molded product was changed to N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) in Example 1. Then, three-dimensional modeling was performed in the same manner as in Example 1.
Regarding the obtained liquid material for soft molded products, the viscosity measured in the same manner as the liquid material for hard molded products of Example 1 was 10.3 mPa · s at 25.0 ° C., and the surface tension was the same as in Example 134. It was .4 mN / m.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 5)
Using the same liquid material for soft molded products and liquid material for hard molded products as in Example 1, three-dimensional modeling was performed in the same manner as in Example 1.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.
Regarding the peeling after drying in Example 5, when the product was peeled by heating and drying at 50 ° C. for 2 hours, the support was completely peeled off in about 10 minutes, which was good.

(Comparative Example 1)
In Example 1, except that synthetic hectorite in the liquid material for soft molded bodies was not added, and an equal amount of N, N'-methylenebisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added instead of synthetic hectorite. Made 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.
Regarding the obtained liquid material for a soft molded product, the viscosity measured in the same manner as the liquid material for a hard molded product of Example 1 was 8.0 mPa · s at 25.0 ° C., and the surface tension was the same as that of Example 1.34 It was .4 mN / m.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.
In Comparative Example 1, it was found that a part of the modeled body could not bear the weight of the support and was crushed in the middle of the three-dimensional modeling, and the desired modeled body could not be obtained.

(Comparative Example 2)
In Example 1, a light amount of 350 mJ / cm ² was irradiated by using an ultraviolet irradiator (SPOT CURE SP5-250DB, manufactured by Ushio, Inc.) instead of the UV-LED light irradiator at the time of three-dimensional modeling. Performed three-dimensional modeling in the same manner as in Example 1.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. 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. 3 was used for the three-dimensional modeling.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. 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. 4 was used for forming the three-dimensional model.
Specifically, two tanks that connect the liquid material for a hard molded product and the liquid material for a soft molded product to the inkjet head (GEN4 manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional molded product manufacturing apparatus 10 shown in FIG. And the liquid material for a hard molded body and the liquid material for a soft molded body were respectively ejected from the inkjet head to form a film. The liquid material for the hard molded body and the liquid material for the soft molded body were sprayed at different positions.
Next, the film is irradiated with a light amount of 350 mJ / cm ² with a UV-LED (SubZero-LED manufactured by Integration Co., Ltd., wavelength: 365 nm) light irradiator to cure the film, and then the cured film is subjected to. The rollers 20 and 21 were used to perform smoothing treatment 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 having a diameter of 25 mm whose surface was anodized was used.
Next, various characteristics of the obtained three-dimensional model were evaluated in the same manner as in Example 1. The results are shown in Table 3.

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

Details of the liquid material for soft molded products and the liquid material for hard molded products shown in Tables 1 and 2 are as follows.
* Layered mineral XLG: [Mg _5.34 Li _0.66 Si ₈ O ₂₀ (OH) ₄ ] Synthetic hectorite having a composition of Na ⁻ _0.66 (Laponite XLG, manufactured by RockWood)
* 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 (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Diamond Beam UK6038)
* Curable material MANDA: Neopentyl glycol hydroxypivalic acid ester di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD MANDA)
* Photopolymerization initiator (BASF, Irgacure 184)
* Blue pigment: manufactured by Toyo Ink Co., Ltd., product 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 in Table 3, Examples 1 to 7 are superior in moldability of the modeled body as compared with Comparative Example 1, and "horizontal error" and "vertical error" of the modeled body as compared with Comparative Examples 1 and 2. It turned out that the variation was small.

Examples of aspects of the present invention are as follows.
<1> The first step of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
This is a method for manufacturing a three-dimensional model, which comprises repeating the second step of curing the film formed in the first step with an ultraviolet light emitting diode a plurality of times.
<2> The first step of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
A third step of applying a second liquid containing at least a curable material to a position different from that of the first liquid to form a film.
A fourth step of curing the films formed in the first step and the third step with an ultraviolet light emitting diode, and
This is a method for manufacturing a three-dimensional model, which is characterized by repeating the above steps a plurality of times.
<3> The method for producing a three-dimensional model 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 model according to <3>, wherein the mineral dispersible in water is a layered mineral dispersed in water in a single layer state.
<5> The method for producing a three-dimensional model according to any one of <1> and <3> to <4>, further comprising a fifth step of smoothing the film cured in the second step. Is.
<6> The method for producing a three-dimensional model according to any one of <2> to <4>, further comprising a sixth step of smoothing the film cured in the fourth step.
<7> The method for producing a three-dimensional model according to any one of <4> to <6>, wherein the layered mineral is synthetic hectorite.
<8> The above-mentioned <3> to <7>, wherein the polymerizable monomer is at least one selected from acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and N-acryloyl morpholine. This is a method for manufacturing a three-dimensional model.
<9> The above <2> to <4> and <9> further comprising a seventh step of 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 the method for manufacturing a three-dimensional model according to any one of 6> to <8>.
<10> The method for producing a three-dimensional model 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 model according to any one of <9> to <10>, wherein the portion made of the hydrogel and the portion made of the polymer are peeled off by drying shrinkage.
<12> A first means for applying a first liquid containing at least water and a hydrogel precursor to form a film, and
It is a three-dimensional model manufacturing apparatus characterized by having a second means for curing a film formed of the first member with an ultraviolet light emitting diode.
<13> The apparatus for manufacturing a three-dimensional model according to <12>, further comprising a fifth means for smoothing the film cured by the second means.
<14> A first means for applying a first liquid containing at least water and a hydrogel precursor to form a film, and
A third means of applying a second liquid containing at least a curable material to a position different from that of the first liquid to form a film.
A fourth means of curing the film formed by the first member and the third member by an ultraviolet light emitting diode, and
It is a three-dimensional model manufacturing apparatus characterized by having.
<15> The apparatus for manufacturing a three-dimensional model according to <14>, further including a sixth means for smoothing a film cured by the fourth means.
<16> The apparatus for producing a three-dimensional model according to any one of <12> to <15>, wherein the hydrogel precursor contains a mineral and a polymerizable monomer that can be dispersed in water.
<17> The apparatus for producing a three-dimensional model according to <16>, wherein the mineral dispersible in water is a layered mineral dispersed in water in a single layer state.
<18> The apparatus for producing a three-dimensional model according to <17>, wherein the layered mineral is synthetic hectorite.
<19> The above-mentioned <16> to <18>, wherein the polymerizable monomer is at least one selected from acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and N-acryloyl morpholine. It is a manufacturing device for three-dimensional shaped objects.
<20> Any of the above <14> to <19> further comprising 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 an apparatus for manufacturing a three-dimensional model described in 1.

The method for manufacturing a three-dimensional model according to any one of <1> to <11> and the apparatus for manufacturing a three-dimensional model according to any one of <12> to <20> have the above-mentioned problems in the prior art. The task is to solve the problem and achieve the following objectives. That is, the method for manufacturing the three-dimensional model and the apparatus for manufacturing the three-dimensional model are a method for manufacturing a three-dimensional model that can easily and efficiently produce a complicated and detailed three-dimensional model represented by an organ model or the like. An object of the present invention is to provide an apparatus for manufacturing a three-dimensional object.

Special Table 2009-591143 Japanese Patent No. 4366538 Japanese Patent No. 4908679

10 Three-dimensional model manufacturing equipment 11 Liquid material injection head unit for model body 12, 13 Liquid material injection head unit for support 14, 15 UV-LED light irradiator 16 Model body support substrate 17 Stage 18 Support body 19 Model body 20 , 21 Smoothing member 30 Modeled body 31, 32 Support 33 Modeled body surface (interface with support)

Claims (14)

The first step of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
A method for producing a three-dimensional model, which comprises repeating a second step of curing a film formed in the first step with an ultraviolet light emitting diode a plurality of times. The first step of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
A third step of applying a second liquid containing at least a curable material to a position different from that of the first liquid to form a film.
A fourth step of curing the films formed in the first step and the third step with an ultraviolet light emitting diode, and
A method for manufacturing a three-dimensional model, which comprises repeating the above steps a plurality of times. The method for producing a three-dimensional model according to any one of claims 1 to 2, wherein the hydrogel precursor contains a mineral dispersible in water and a polymerizable monomer. The method for producing a three-dimensional model according to claim 3, wherein the mineral dispersible in water is a layered mineral dispersed in water in a single layer state. The method for producing a three-dimensional model according to any one of claims 1 and 3 to 4, further comprising a fifth step of smoothing the film cured in the second step. The method for producing a three-dimensional model according to any one of claims 2 to 4, further comprising a sixth step of smoothing the film cured in the fourth step. The invention according to any one of claims 2 to 4, and 6, 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. A method for manufacturing a three-dimensional model. The method for producing a three-dimensional model according to claim 7, wherein the rubber hardness of the portion made of the hydrogel is 6 or more and 60 or less. The method for producing a three-dimensional model according to any one of claims 7 to 8, wherein the portion made of the hydrogel and the portion made of the polymer are peeled off by drying shrinkage. A first means of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
An apparatus for manufacturing a three-dimensional model, which comprises a second means for curing a film formed of the first member with an ultraviolet light emitting diode. The apparatus for manufacturing a three-dimensional model according to claim 10, further comprising a fifth means for smoothing the film cured by the second means. A first means of applying a first liquid containing at least water and a hydrogel precursor to form a film, and
A third means of applying a second liquid containing at least a curable material to a position different from that of the first liquid to form a film.
A fourth means of curing the film formed by the first member and the third member by an ultraviolet light emitting diode, and
A device for manufacturing a three-dimensional object, which is characterized by having. The apparatus for manufacturing a three-dimensional model according to claim 12, further comprising a sixth means for smoothing a film cured by the fourth means. The three-dimensional model 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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