JP2016078437A - Liquid for stereoscopic molding, liquid set for stereoscopic molding, method for producing stereoscopic molding and stereoscopic molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a stereoscopic molding that can simply and efficiently produce a complicated and high definition stereoscopic molding represented by an organ model or the like.SOLUTION: The method for producing a stereoscopic molding comprises repeating a plurality of times a first step of applying a first liquid as a hydrogel precursor including at least a polyfunctional monomer to form a film and a second step of curing the film formed in the first step. Alternatively, the method for producing a stereoscopic molding comprises repeating a plurality of times a first step of applying a first liquid as a hydrogel precursor including at least a polyfunctional monomer to form a film, a third step of applying a second liquid including a hydrogel precursor and having a composition different from that of the first liquid to a position different from that to which the first liquid is applied to form a film, and a fourth step of curing the films formed each in the first step and the third step.SELECTED DRAWING: None

Description

  The present invention relates to a three-dimensional modeling liquid, a three-dimensional modeling liquid set, a method for manufacturing a three-dimensional model, and a three-dimensional model.

  2. Description of the Related Art In recent years, an inkjet optical modeling method has been proposed 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 the inkjet optical modeling method, a method has been proposed in which a support made of a material different from that of a three-dimensional model is formed at the same time to prevent the three-dimensional model from being deformed or dropped during the three-dimensional model (for example, Patent Document 1). And 2).

  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. In particular, organ models used for surgical practice etc. have complex internal structures such as blood vessel structures inside the organ and tumor parts, and it is extremely difficult to produce the organ model using a mold. It is.

  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 according to the present invention as a means for solving the above-described problems includes a first step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer,
A second step of curing the film formed in the first step;
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 three-dimensional modeling apparatus used in the method for manufacturing a three-dimensional modeled object of the present invention. FIG. 3 is a schematic view showing another example of the three-dimensional modeling apparatus used in the method for manufacturing a three-dimensional modeled object of the present invention. FIG. 4A is a schematic perspective view illustrating an example of a three-dimensional structure manufactured by the method for manufacturing a three-dimensional structure according to the present invention. 4B is a schematic cross-sectional view of FIG. 4A.

(3D modeling liquid (first liquid))
The liquid for three-dimensional modeling of the present invention, that is, the first liquid used in the method for manufacturing a three-dimensional molded object of the present invention is composed of a hydrogel precursor and further contains other components as necessary.

<Hydrogel precursor>
The hydrogel precursor preferably contains at least a polyfunctional monomer, preferably contains water, an organic solvent, a layered mineral, a monofunctional monomer, and a polymerization initiator, and further contains other components as necessary. .

-Multifunctional monomer-
The polyfunctional monomer is a compound having two or more unsaturated carbon-carbon bonds, and is preferably an active energy ray-curable monomer. Examples thereof include a bifunctional monomer, a trifunctional monomer, and a trifunctional or higher monomer.
The homopolymer of the polyfunctional monomer is preferably water-soluble. In the present invention, the water-solubility of the homopolymer of the polyfunctional monomer means that, for example, when 1 g of the homopolymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more thereof is dissolved.

  Examples of the bifunctional monomer include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and neopentyl glycol hydroxypivalic acid. Ester di (meth) acrylate (MANDA), hydroxypivalate neopentyl glycol ester 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 hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, propoxylated neopentyl glycol di (meta) ) Acrylate, ethoxy modified bisphenol A di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, methylene bisacrylamide and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), triallyl isocyanate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the tri- or higher functional monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, penta ( And (meth) acrylate ester and dipentaerythritol hexa (meth) acrylate (DPHA). These may be used individually by 1 type and may use 2 or more types together.

  The content of the polyfunctional monomer is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the three-dimensional modeling liquid. When the content is in the range of 0.001% by mass to 1% by mass, the elastic modulus and hardness of the obtained hydrogel can be adjusted to an appropriate range.

-Water-
As the water, for example, ion-exchanged water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water can be used. In the water, other components such as an organic solvent may be dissolved or dispersed depending on 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.

-Organic solvent-
The organic solvent is preferably aqueous, and examples thereof include alcohols such as ethanol, ethers, and ketones.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2,6-hexanetriol, 1,2-butanediol, 1,2-hexanediol, 1,2 -Pentanediol, 1,3-dimethyl-2-imidazolidinone, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2-pyrrolidone, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,3-hex Diol, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, β-butoxy-N, N-dimethylpropionamide, β-methoxy-N, N-dimethylpropionamide, γ-butyrolactone, ε-caprolactam, ethylene glycol, Ethylene glycol-n-butyl ether, ethylene glycol-n-propyl ether, ethylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoethyl ether, glycerin, diethylene glycol, diethylene glycol-n-hexyl ether, diethylene glycol methyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diglycol Serine, dipropylene glycol, dipropylene glycol-n-propyl ether, dipropylene glycol monomethyl ether, dimethyl sulfoxide, sulfolane, thiodiglycol, tetraethylene glycol, triethylene glycol, triethylene glycol ethyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol monobutyl ether, triethylene glycol methyl ether, tripropylene glycol, tripropylene glycol-n-propyl ether, tripropylene glycol methyl ether, trimethylolethane, trimethylolpropane, propylpropylene diglycol, propylene glycol (1,2- Propanediol), propylene glycol-n-butyl ether, Propylene glycol -t- butyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, hexylene glycol, polyethylene glycol, and polypropylene glycol. These may be used individually by 1 type and may use 2 or more types together.
The content of the organic solvent is preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the total amount of the three-dimensional modeling liquid.

-Layered minerals-
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.
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 three-dimensional modeling liquid. When the content is in the range of 1% by mass or more and 40% by mass or less, the viscosity of the liquid for three-dimensional modeling is appropriate, and the ejectability by inkjet and the hardness of the three-dimensional modeled object are good.

-Monofunctional monomer-
The monofunctional monomer is a compound having one unsaturated carbon-carbon bond, for example, acrylamide, N-substituted acrylamide derivative, N, N-disubstituted acrylamide derivative, N-substituted methacrylamide derivative, N, N- Examples include di-substituted methacrylamide derivatives and other monofunctional monomers. These may be used individually by 1 type and may use 2 or more types together.

  The N-substituted acrylamide derivative, N, N-disubstituted acrylamide derivative, N-substituted methacrylamide derivative, or N, N-disubstituted methacrylamide derivative is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include N, N-dimethylacrylamide and N-isopropylacrylamide.

  Examples of the other monofunctional monomers include 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), and caprolactone-modified tetrahydroflur. Furyl (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, Isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, urethane (meth) acrylate, etc. It is below. These may be used individually by 1 type and may use 2 or more types together.

By polymerizing the monofunctional monomer, a water-soluble organic polymer having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group or the like can be obtained.
The water-soluble organic polymer having the amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group or the like is an advantageous component for maintaining the strength of the hydrogel.
The content of the monofunctional monomer is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 1% by mass or more and 10% by mass or less, and preferably 1% by mass with respect to the total amount of the three-dimensional modeling liquid. More preferred is 5% by mass or less. When the content is in the range of 1% by mass or more and 10% by mass or less, there is an advantage that the dispersion stability of the layered mineral in the three-dimensional modeling liquid is maintained and the stretchability of the three-dimensional model is improved. The stretchability refers to a property that does not stretch and break when a three-dimensional structure is pulled.

-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.

  Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2-amidinopropane) dihydrochloride ( VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2,2'-azobis-2- Methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), VA-044, VA-46B, V-50, VA- 057, VA-061, VA-067, VA-086, 2,2′-azobis (2-cyclopropylpropionitrile), 2, '- azobis (methyl isobutyrate - DOO) (V-601) (both available from Wako Pure Chemical Industries, Ltd.) and the like.

  Examples of the peroxide initiator include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S). ) (Available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butylperoxy-2-ethyl Hexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

  Examples of the persulfate initiator include potassium persulfate, sodium persulfate, and ammonium persulfate.

  Examples of the redox initiator include a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite, a system based on the organic peroxide and a tertiary amine. (For example, a system based on benzoyl peroxide and dimethylaniline), a system based on an organic hydroperoxide and a transition metal (for example, a system based on cumene hydroperoxide and cobalt naphthate), and the like.

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

  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%-3 mass% are preferable with respect to the monomer whole quantity of the liquid for three-dimensional modeling.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, surfactants, colorants, stabilizers, water-soluble resins, low-boiling alcohols, surface treatment agents, viscosity adjustments Agents, adhesion-imparting agents, antioxidants, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants and the like.

-Physical properties of 3D modeling liquid-
There is no restriction | limiting in particular as surface tension of the said three-dimensional modeling liquid, Although it can select suitably according to the objective, 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 more preferable. .
When the surface tension is 20 mN / m or more, the discharge property of the three-dimensional modeling liquid is good at the time of three-dimensional modeling, and when it is 45 mN / m or less, the three-dimensional modeling liquid is filled into the discharge nozzle or the like. The filling property is good.
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 three-dimensional modeling 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 in the range of 3 mPa · s or more and 20 mPa · s or less, the discharge property of the liquid for three-dimensional modeling is good.
In addition, the said viscosity can be measured in 25 degreeC environment using a rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make) etc., for example.

The 80% strain compressive stress of the hydrogel obtained by curing the three-dimensional modeling liquid is preferably 0.4 MPa or more. When the 80% strain compressive stress is 0.4 MPa or more, there is an advantage that hardness close to a living body texture can be reproduced and a realistic organ model can be provided.
The 80% strain compressive stress can be measured using, for example, a universal testing machine (manufactured by Shimadzu Corporation, AG-I).

  The three-dimensional modeling liquid of the present invention can be suitably used for the production of various three-dimensional models, and the three-dimensional modeling liquid set of the present invention, the three-dimensional model manufacturing method of the present invention, and the three-dimensional modeling of the present invention described later. It can be particularly suitably used as a product.

(3D modeling liquid set)
The three-dimensional modeling liquid set of the present invention includes a first liquid and a second liquid, and preferably includes a third liquid and a fourth liquid, and other components as necessary. Comprising.

<Second liquid>
As said 2nd liquid, the same thing can be used except a hydrogel precursor and a composition different from said 1st liquid.
The composition different from that of the first liquid means that at least one of the types and contents of the components constituting the second liquid is different from that of the first liquid.

  It is preferable that the first liquid and the second liquid become hydrogels having different elastic moduli (80% strain compressive stress or compressive elastic modulus) when cured. Thereby, the three-dimensional molded item which has the area | region where an elasticity modulus differs in one three-dimensional molded item can be manufactured efficiently.

<Third liquid>
The third liquid preferably contains at least a polymerization initiator, preferably contains water and an organic solvent, and may further contain a polyfunctional monomer, a monofunctional monomer, and other components as necessary. . The third liquid does not contain a layered mineral.

-Polymerization initiator-
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Among these, a photopolymerization initiator is preferable from the viewpoint of storage stability.
As the thermal polymerization initiator and the photopolymerization initiator, the same ones as the three-dimensional modeling liquid of the present invention can be used.

By using the photopolymerization initiator independently for a third liquid different from at least one of the first liquid and the second liquid, at least one of the first liquid and the second liquid Than when assuming that a photopolymerization initiator is used in at least one of the first liquid and the second liquid from the aspect of the same storage stability. Many additions are possible. Therefore, the polymerization rate of the three-dimensional structure increases, and it becomes possible to manufacture efficiently.
From the viewpoint of storage stability, the third liquid preferably has a higher content of photopolymerization initiator than at least one of the first liquid and the second liquid. More preferably, at least one of the second liquids does not contain a photopolymerization initiator.

  The polyfunctional monomer, the monofunctional monomer, and the other components can be the same as those in the first liquid, and a more suitable monomer can be appropriately selected in combination with the polymerization initiator. .

-Viscosity change rate-
The third liquid preferably has a viscosity change rate of 20% or less before and after being allowed to stand at 50 ° C. for 2 weeks, more preferably 10% or less.
When the viscosity change rate is 10% or less, the storage stability of the third liquid is appropriate. For example, when the application of the third liquid is performed by an inkjet method, the discharge stability is good. Become.

The viscosity change rate before and after being allowed to stand at 50 ° C. for 2 weeks can be measured as follows.
Place the third liquid in a polypropylene jar (50 mL) and leave it in a thermostatic bath at 50 ° C. for 2 weeks, then remove it from the thermostatic bath and leave it to room temperature (25 ° C.) to measure the viscosity. Do. The viscosity of the third liquid before entering the thermostatic bath is the viscosity before storage, and the viscosity of the third liquid after taking out from the thermostatic bath is the viscosity after storage, and the viscosity change rate is calculated by the following formula. The pre-storage viscosity and the post-storage viscosity can be measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
Viscosity change rate (%) = [(viscosity after storage) − (viscosity before storage)] / (viscosity before storage) × 100

The viscosity before storage of the third liquid at 25 ° C. is preferably 20 mPa · s or less, more preferably 3 mPa · s or more and 20 mPa · s or less, and further preferably 3 mPa · s or more and 12 mPa · s or less. When the viscosity is 20 mPa · s or less, ejection from the ink jet nozzle is stabilized.
The post-storage viscosity of the third liquid is preferably 3 mPa · s or more and 12 mPa · s or less at 25 ° C.

<Fourth liquid>
The fourth liquid is a liquid that becomes a hard molded body for supporting a three-dimensional structure formed of hydrogel (soft body) (also referred to as “material for hard molded body”). The fourth liquid contains a curable material, preferably contains a polymerization initiator, and further contains other components as necessary, but does not contain water or layered minerals.

-Curable material-
The curable material is preferably a compound that causes a polymerization reaction upon irradiation with active energy rays (ultraviolet rays, electron beams, etc.), heating, and the like, and can be appropriately selected depending on the purpose. Examples include energy ray curable compounds and thermosetting compounds. Among these, materials that are liquid at room temperature are preferable.

The active energy ray-curable compound is a relatively low-viscosity monomer having an unsaturated double bond capable of radical polymerization in a molecular structure, and is used in the first liquid and the second liquid. It can be used by appropriately selecting from monomers and monofunctional monomers. These may be used individually by 1 type and may use 2 or more types together.
The content of the curable material is not particularly limited and can be appropriately selected depending on the purpose.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, water-soluble resins, low-boiling alcohols, surfactants, viscosity modifiers, adhesion-imparting agents, oxidation agents, etc. Inhibitors, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants and the like can be mentioned.

The surface tension of the fourth liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mN / m or more and 45 mN / m or less, and more preferably 25 mN / m or more and 34 mN / m or less. .
When the surface tension is 20 mN / m or more, the ejection property at the time of three-dimensional modeling is good, and when it is 45 mN / m or less, when the fourth liquid is filled into the three-dimensional modeling discharge nozzle or the like The filling property is good.
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 fourth liquid is not particularly limited and may be appropriately selected depending on the purpose. It can be appropriately used by adjusting the temperature, but at 25 ° C., it is 3 mPa · s or more and 20 mPa · s. The following is preferable, and 6 mPa · s or more and 12 mPa · s or less is more preferable.
In the range where the viscosity is 3 mPa · s or more and 20 mPa · s or less, the dischargeability of the fourth liquid at the time of three-dimensional modeling is good.
In addition, the said viscosity can be measured in 25 degreeC environment using a rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make) etc., for example.

  The liquid set for three-dimensional modeling of the present invention can be suitably used for the production of various three-dimensional models, and is particularly complex and fine as represented by an organ model, etc., and a region having a different elastic modulus in one three-dimensional model It can be suitably used for the production of a three-dimensional modeled object having the above, and can be particularly suitably used for the method for producing a three-dimensional modeled object of the present invention described later and the three-dimensional modeled object of the present invention.

(Method for manufacturing a three-dimensional model)
<First form>
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 the eighth step, and further if necessary. And other steps.

-First step-
The first step is a step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer.
As the first liquid, the same liquid as the three-dimensional modeling liquid of the present invention can be used.

The method for applying the first liquid is not particularly limited as long as it is a method in which droplets made of the first liquid can be applied to a target location with appropriate accuracy, and can be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned. In order to carry out these methods, a known apparatus can be suitably used.
Among these, the inkjet method is particularly preferable in the present invention. 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. .

-Second step-
The second step is a step of curing the film formed in the first step.

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

As the heating in the heating device, for example, a method of heating the formed film by contacting a heat source, a method of irradiating far infrared rays, near infrared rays, microwaves, or the like, a method of blowing hot air, etc. The method of heating without making it contact is mentioned.
In addition, although the said heating can be performed independently, it can also be performed before ultraviolet irradiation, simultaneously with ultraviolet irradiation, or after ultraviolet irradiation.

  The cured film is composed of water and water in a three-dimensional network structure formed by combining the water-soluble organic polymer obtained by polymerizing the monofunctional monomer and the polyfunctional monomer and the layered mineral. A component that dissolves is included.

-Fifth process-
The fifth step is a step of applying a third liquid containing at least a polymerization initiator to the same position as the first liquid.
The fifth step is preferably performed between the first step and the second step.
As said 3rd liquid, the same thing can be used except a polymerization initiator except that a composition differs from said 1st liquid. The composition different from that of the first liquid means that at least one of the types and contents of components constituting the first liquid is different from that of the third liquid.
Applying the third liquid to the same position as the first liquid means applying the third liquid on the first liquid that has been previously applied. Since the third liquid is compatible with the first liquid, the third liquid is included in the third liquid by applying the third liquid to the same position as the first liquid. The polymerization initiator can act as a polymerization initiator for the monomer contained in the first liquid.

As the third liquid, the same liquid as the third liquid in the three-dimensional modeling liquid set of the present invention can be used.
The method for applying the third liquid is not particularly limited as long as it is a system that can apply droplets made of the third liquid to a target location with appropriate accuracy, and can be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned.

-Eighth process-
The eighth step is a step of forming a film by applying a fourth liquid, which is a hard molded body for supporting the three-dimensional structure formed of the hydrogel, to a position different from the first liquid. It is.

As the fourth liquid, the same liquid as the fourth liquid in the three-dimensional modeling liquid set of the present invention can be used.
Applying to a position different from the first liquid means that the application position of the fourth liquid and the first liquid does not overlap, and the fourth liquid and the first liquid are adjacent to each other. It does not matter. Since the fourth liquid has a composition different from that of the first liquid and is difficult to mix, even when the fourth liquid and the first liquid are adjacent to each other, the boundary between the four liquids after curing becomes clear.
The method for applying the fourth liquid is not particularly limited as long as it is a system that can apply droplets of the fourth liquid to a target location with appropriate accuracy, and may be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned.

-Other processes-
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the data processing process which acquires and processes three-dimensional data, hydrogel and its support body (hard molding) The peeling process to peel, the cleaning process of a three-dimensional molded item, the polishing process of a three-dimensional molded article, etc. are mentioned.

  In the manufacturing method of the three-dimensional structure according to the first 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. 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.

<Second form>
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.

-Third step-
The third step is a step of forming a film containing a hydrogel precursor and applying a second liquid having a composition different from that of the first liquid to a position different from that of the first liquid.
Applying to a position different from the first liquid means that the application position of the first liquid and the second liquid does not overlap, and the first liquid and the second liquid are adjacent to each other. It does not matter. The second liquid has a composition different from that of the first liquid, but is compatible with each other. Therefore, the second liquid and the first liquid are compatible with each other at an adjacent portion and cured. And one hydrogel having different elastic moduli can be formed.
As said 1st liquid and 2nd liquid, the thing similar to said 1st liquid and said 2nd liquid in the liquid set for three-dimensional model | molding of this invention can be used.
The method for applying the second liquid is not particularly limited as long as it is a system that can apply droplets made of the second liquid to a target location with appropriate accuracy, and may be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned.

-Fourth step-
The fourth step is a step of curing the films formed in the first step and the third step, respectively.
Curing of the film formed in the first step and curing of the film formed in the third step may be performed simultaneously or separately, but simultaneously from the viewpoint of production efficiency. Preferably it is done.
There is no restriction | limiting in particular as a means to harden | cure the said film | membrane, According to the objective, it can select suitably, For example, it is the same as that of the said 2nd process in the manufacturing method of the three-dimensional molded item of said 1st form.

-Sixth process-
The sixth step is a step of applying a third liquid containing at least a polymerization initiator to the same position as at least one of the first liquid and the second liquid.
The sixth step is preferably performed between the first step and the third step, or between the third step and the fourth step.
As said 3rd liquid, a polymerization initiator is included, The same thing can be used except said 1st liquid and said 2nd liquid having a different composition. The first liquid and the second liquid are different in composition from each other that at least one of the types and contents of the components constituting the first liquid and the second liquid is different from the third liquid. Means different.
Applying the third liquid to the same position as at least one of the first liquid and the second liquid means that at least one of the first liquid and the second liquid previously applied It means that the third liquid is applied on top of the other. Since the third liquid is compatible with the first liquid and the second liquid, the third liquid is placed at the same position as at least one of the first liquid and the second liquid. By applying, the polymerization initiator contained in the third liquid can act as a polymerization initiator for the monomer contained in the first liquid and the second liquid.

As the third liquid, the same liquid as the third liquid in the three-dimensional modeling liquid set of the present invention can be used.
The method for applying the third liquid is not particularly limited as long as it is a system that can apply droplets made of the third liquid to a target location with appropriate accuracy, and can be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned.

-Seventh process-
The seventh step is different from at least one of the first liquid and the second liquid in a fourth liquid that is a rigid molded body for supporting the three-dimensional structure formed of the hydrogel. This is a step of forming a film by applying it to a position.

As the fourth liquid, the same liquid as the fourth liquid in the three-dimensional modeling liquid set of the present invention can be used.
Applying to a position different from the first liquid and the second liquid means that the application position of the fourth liquid and the first liquid and the second liquid do not overlap, and the fourth liquid The liquid and the first liquid and the second liquid may be adjacent to each other. Since the fourth liquid has a composition different from that of the first liquid and the second liquid and is difficult to mix, the fourth liquid may be adjacent to the first liquid or the second liquid. The boundary between the two after curing becomes clear.
The method for applying the fourth liquid is not particularly limited as long as it is a system that can apply droplets of the fourth liquid to a target location with appropriate accuracy, and may be appropriately selected according to the purpose. For example, a dispenser method, a spray method, an inkjet method, etc. are mentioned.

-Other processes-
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the data processing process which acquires and processes three-dimensional data, hydrogel and its support body (hard molding) The peeling process to peel, the cleaning process of a three-dimensional molded item, the polishing process of a three-dimensional molded article, etc. are mentioned.

  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. 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.

  The data processing step can be performed with reference to, for example, the description of Japanese Patent No. 5239037. In the present invention, for example, from the acquisition of data to the discharge of each liquid using a three-dimensional modeling liquid set Is performed as follows.

  First, various data obtained by converting the surface data or solid data of the 3D shape designed by 3D CAD, or the 3D shape surface data or solid data captured by the 3D canner or digitizer, to the 3D modeling apparatus is input. . Based on the input various data, the modeling direction of the three-dimensional shape to be modeled is determined. In addition, there is no restriction | limiting in particular about a modeling direction, Usually, it is preferable to select the direction where the Z direction (height direction) becomes the lowest.

  After determining the modeling direction, the projection area of the three-dimensional shape onto 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 as an amount to move, Although it changes with shapes, magnitude | sizes, and used materials, it is about 1 mm-about 10 mm. With this, the block shape in which the shape to be shaped is confined (the upper surface is opened) is specified.

  This block shape is cut into slices (slices) in the Z direction with a single layer thickness. The thickness of the one layer varies depending on the material used and cannot be defined unconditionally, but is preferably 10 μm 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 material to be used.

  Next, based on the contour line of the outermost contour of the ring slice data, the inside / outside determination (determining whether each liquid of the three-dimensional modeling liquid set is ejected to a position on the contour line) is performed by using an inkjet method. The position to inject is controlled.

  For example, when the first liquid, the second liquid, and the fourth liquid are used, the fourth liquid forming the support body may be used as the order in which the liquids in the three-dimensional modeling liquid set are ejected. It is preferable to eject at least one of the first liquid and the second liquid forming the three-dimensional structure (hydrogel) after ejecting the liquid. When ejected in this order, a reservoir such as a groove or a weir is formed in the support body first, and at least one of the first liquid and the second liquid is ejected into the reservoir, Even if liquid materials are used as the first liquid and the second liquid at room temperature, there is no concern about “sagging”, and a wide range of photo-curing resins, thermosetting resins, and the like can be used. When a third liquid is further used, after ejecting at least one of the first liquid and the second liquid, the same position as at least one of the first liquid and the second liquid This is the same except that the third liquid is ejected to the first.

  Further, in order to further shorten the modeling time, at least one of the first liquid, the second liquid, and the fourth liquid is ejected and laminated in each of the forward path and the return path of the integrated inkjet head. Is preferred. Furthermore, by making an active energy ray irradiator (for example, an ultraviolet irradiator) or an infrared irradiator adjacent to an inkjet head that ejects each liquid of the three-dimensional modeling liquid set, the time required for the smoothing process can be saved, High-speed modeling is possible.

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 or the dispenser method, and is applied so as to form an image one by one before being cured. At least one of the first liquid and the second liquid and the fourth liquid are in an incompatible state where the contact portions are clearly separated and immiscible.
In the conventional modeling method, a contact portion between at least one of the first liquid and the second liquid and the fourth liquid is compatible, and the boundary becomes unclear during photocuring. As a result, fine irregularities remain on the surface of the three-dimensional structure, but in the method for manufacturing a three-dimensional structure of the present invention, at least one of the first liquid and the second liquid and the fourth liquid. Since the liquid is incompatible with the liquid, the boundary after photocuring becomes clear. Furthermore, peelability improves due to the difference in hardness between the obtained three-dimensional model and the support. Thereby, the surface smoothness of a three-dimensional molded item improves, and it becomes possible to abbreviate | omit or reduce significantly the grinding | polishing process after modeling.

<3D modeling equipment>
FIG. 2 is a schematic view showing an example of a three-dimensional modeling apparatus used in the present invention.
The three-dimensional modeling apparatus 39 in FIG. 2 uses a head unit in which inkjet heads are arranged to transfer at least one of the first liquid and the second liquid from the modeling-object ejection head unit 30 to a support ejection head. The third liquid is ejected from the units 31 and 32, and the liquids in the three-dimensional modeling liquid set are stacked while being cured by the adjacent ultraviolet irradiators or infrared irradiators 33 and 34.
In FIG. 2, only one modeling object ejection head unit 30 is provided, but two or more modeling object ejection head units 30 may be provided. It is also possible to add an infrared irradiator (not shown) at a position adjacent to the ultraviolet irradiators 33 and 34 and stack the liquids of the three-dimensional modeling liquid set while heat curing.
The fourth liquid is ejected from the support jet head units 31 and 32 and solidified to form a first support layer having a reservoir, and the first support layer has a first support layer formed on the first support layer. At least one of the liquid and the second liquid is ejected from the ejection head unit 30 for the modeled object, and the first modeling is performed by irradiating at least one of the first liquid and the second liquid with active energy rays. Forming a physical layer, spraying and solidifying the fourth liquid on the first support layer, laminating a second support layer having a reservoir, and forming the second support layer At least one of the first liquid and the second liquid is sprayed on the reservoir, and at least one of the first liquid and the second liquid is irradiated with active energy rays, thereby the first modeling. A second three-dimensional object layer is laminated on the object layer to produce a three-dimensional object 35 .

  When the multi-head unit moves in the direction of the arrow A, basically, the support 36, the three-dimensional modeling is performed using the support jet head unit 31, the model jet head unit 30, the ultraviolet irradiator or the infrared irradiator 34. The object 35 is formed on the modeling object support substrate 37. The support jet head unit 32, the ultraviolet irradiator or the infrared irradiator 33 may be used as an auxiliary.

  Further, when the multi-head unit moves in the direction of arrow B, basically, using the support jet head unit 32, the model jet head unit 30, the ultraviolet irradiator or the infrared irradiator 33, the support 36, The three-dimensional model 35 is formed on the model support substrate 37. The support jetting head unit 31, the ultraviolet irradiator, or the infrared irradiator 34 may be used as an auxiliary.

  Furthermore, in order to keep the gap between the injection head unit 30 for the molded object, the injection head units 31 and 32 for the support body, and the ultraviolet irradiator or infrared irradiation device 33 and 34, and the three-dimensional object 35 and the support body 36 constant, Lamination is performed while lowering the stage 36 in accordance with the number of laminations.

  FIG. 3 is a schematic view showing another example of a molded article manufacturing process having a configuration capable of improving the smoothness of each layer as compared with FIG. 2. The basic process is the same as in FIG. 2 except that an ultraviolet irradiator or infrared irradiator 33, 34 is disposed between the molded article ejection head 30 and the support ejection head units 31, 32. Different.

  Further, in the three-dimensional modeling apparatus 39, the ultraviolet irradiator or the infrared irradiators 33 and 34 are used when moving in either direction of arrows A and B, and the layers are laminated by heat generated by the ultraviolet irradiation or infrared irradiation. The surface of at least one of the first liquid and the second liquid is smoothed, and as a result, the dimensional stability of the three-dimensional structure is improved.

  Further, as the three-dimensional modeling apparatus 39, an ink recovery mechanism, a recycling mechanism, or the like can be added. You may provide the detection mechanism of the braid | blade which removes each liquid of the said three-dimensional modeling liquid set adhering to the nozzle surface, or a non-ejection nozzle. It is also preferable to control the environmental temperature in the apparatus during modeling.

(3D objects)
The three-dimensional modeled object of the present invention comprises a hydrogel obtained by curing the three-dimensional modeled liquid of the present invention, and preferably, a first region constituted by the first hydrogel and the first hydrogel. At least a second region composed of a second hydrogel having a different elastic modulus (80% strain compressive stress or compressive elastic modulus), and depending on the application, the first hydrogel and The 80% strain compressive stress of either one of the second hydrogels is preferably 0.4 MPa or more, or the compression elastic modulus is preferably 0.3 MPa or more. Thereby, the three-dimensional molded item (hydrogel) which has the area | region from which an elasticity modulus differs in one three-dimensional molded item is obtained.
The 80% strain compressive stress can be measured using, for example, a universal testing machine (manufactured by Shimadzu Corporation, AG-I). The compressive elastic modulus can be calculated as the slope at the time of 10% displacement by taking the difference between 10% strain compressive stress and 20% strain compressive stress.

  The hydrogel composed of the hydrogel precursor includes a water-soluble organic polymer obtained by polymerizing at least a polyfunctional monomer and a three-dimensional network structure formed by combining a single layer dispersion of a layered mineral with water. It is preferable that it is a hydrogel in which is included.

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.
In the present invention, the water solubility of the water-soluble organic polymer means that, for example, when 1 g of the water-soluble organic polymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more thereof is dissolved.

  As shown to FIG. 4A and 4B, in the three-dimensional molded item of this invention, it is preferable that said 1st area | region (area | region A) includes the said 2nd area | region (area | region B) completely.

  Since the three-dimensional model can have regions with different elastic moduli in one three-dimensional model, it is preferably used as an organ model or the like. The organ model can faithfully reproduce internal structures such as blood vessels and diseased parts with different hardness and elastic modulus, the tactile sensation and sharpness of the organ are very close to the desired organ, and can be opened with a scalpel. Therefore, it is particularly suitable as an organ model for procedure practice.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production Example 1 of Fourth Liquid (Liquid for Hard Molded Body))
-Preparation of liquid 1 for hard molded body-
10 parts by mass of urethane acrylate (Made by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038) as curable material, and neopentyl glycol hydroxypivalate ester dimethacrylate (made by Nippon Kayaku Co., Ltd., trade name: KAYARAD MANDA) as curable material ) 90 parts by mass, 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 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 liquid 1 for hard molded body.
When the surface tension and viscosity of the obtained liquid 1 for 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>
About the obtained liquid 1 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 1 for hard molded objects, the viscosity was measured at 25 degreeC using the rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make).

Example 1
<Preparation of 3D modeling liquid 1 (first liquid or second liquid)>
Based on the composition shown in Table 1, the three-dimensional modeling liquid 1 was produced as follows.

-Preparation of water-
Ion-exchanged water subjected to vacuum degassing for 10 minutes was used as pure water.

-Preparation of initiator solution-
-As a photoinitiator liquid, the photoinitiator (Irgacure 184, BASF company make) was dissolved in the ratio of 2 mass parts with respect to 98 mass parts of ethanol, and it prepared as aqueous solution.
-As thermal-polymerization initiator liquid 1, sodium peroxodisulfate (made by Wako Pure Chemical Industries Ltd.) was dissolved in the ratio of 2 mass parts with respect to 98 mass parts of pure waters, and it prepared as aqueous solution.
-As thermal-polymerization initiator liquid 2, VA-067 (made by Wako Pure Chemical Industries Ltd.) was dissolved in the ratio of 2 mass parts with respect to 98 mass parts of pure waters, and it prepared as aqueous solution.

-Preparation of liquid for solid modeling 1-
First, the pure water while 195 parts by mass was stirred, a layered mineral _{[Mg 5.34 Li 0.66 Si 8 O} 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, 8 parts by mass (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., DMAA) from which the polymerization inhibitor was removed by passing through a column of activated alumina as a monofunctional monomer was added to the obtained dispersion. As a functional monomer, 0.3 part by mass of methylene bisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., MBAA) was added. Furthermore, 2 parts by mass of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed as a surfactant.
Next, while cooling in an ice bath, 0.5 parts by mass of the photopolymerization initiator liquid and 5 parts by mass of the thermal polymerization initiator liquid 1 were added, and after stirring and mixing, vacuum degassing was performed for 10 minutes. . Subsequently, filtration was performed to remove impurities and the like, and a three-dimensional modeling liquid 1 was prepared.
The obtained three-dimensional modeling liquid 1 has a surface tension of 31.1 mN / m measured in the same manner as the hard molded body liquid 1 and a viscosity measured in the same manner as the hard molded body liquid 1 is 25. It was 9.8 mPa · s at ° C. These results are shown in Table 1.

<Production of hydrogel>
Next, the three-dimensional modeling liquid 1 is poured into a mold, covered with quartz glass and sealed, and irradiated with a light amount of 350 mJ / cm ² with an ultraviolet irradiator (SPUSURE SP5-250DB manufactured by USHIO INC.). Then, a hydrogel 1 having a cubic shape of 10 mm × 10 mm × 10 mm was produced.
About the obtained hydrogel 1, the compression test was done as follows. The results are shown in Table 1.

<Compression test>
A universal testing machine (manufactured by Shimadzu Corporation, AG-I) was provided with a compression jig for a load cell of 1 kN and 1 kN, and a hydrogel 1 having a shape of 10 mm × 10 mm × 10 mm was installed. The stress against compression applied to the load cell was recorded in a computer, and the stress against displacement was plotted.
The fractured hydrogel has a maximum compressive stress at the time of fracture, and the hydrogel that did not break shows 80% strain compressive stress.
Moreover, the compression elastic modulus of hydrogel was obtained from the measurement data obtained from the same universal testing machine. As the compressive elastic modulus, the difference between the 10% strain compressive stress and the 20% strain compressive stress was calculated as the slope at the time of 10% displacement.

(Examples 2 to 8 and Comparative Example 1)
<Preparation of 3D modeling liquids 2-9>
In Example 1, three-dimensional modeling liquids 2 to 9 were prepared in the same manner as in Example 1 except that the compositions and contents shown in Tables 1 to 3 below were changed.
About the obtained 3D modeling liquids 2 to 9, the surface tension and the viscosity were measured in the same manner as in Example 1. The results are shown in Tables 1 to 3.
Next, using the obtained three-dimensional modeling liquids 2 to 7 and 9, hydrogels 2 to 7 and 9 were prepared in the same manner as the preparation of the hydrogel 1. Moreover, using the solid modeling liquid 8, the ultraviolet irradiator used when the hydrogel 1 was produced was changed to an infrared irradiator, and heated to 80 ° C. to produce the hydrogel 8.
The obtained hydrogels 2 to 9 were subjected to a compression test in the same manner as the hydrogel 1. The results are shown in Tables 1 to 3.

Details of the materials used in Tables 1 to 3 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)
* Monofunctional monomer 1: DMAA: N, N-dimethylacrylamide (Wako Pure Chemical Industries, Ltd.)
* Monofunctional monomer 2: IPAM: N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Multifunctional monomer: MBAA: Methylenebisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Photopolymerization initiator solution (Irgacure 184 2 parts by mass / ethanol 98 parts by mass)
* Thermal polymerization initiator solution 1 (Na peroxodisulfate 2 parts by mass / 98 parts by mass of water)
* Thermal polymerization initiator liquid 2 (VA-067 is 2 parts by mass / water 98 parts by mass)

Example 9
Using the three-dimensional modeling liquid set shown in Table 4 and the three-dimensional modeling apparatus shown in FIG. 2, a three-dimensional modeled object as shown in FIGS. 4A and 4B was produced.
First, the three-dimensional modeling liquid 1 as the first liquid and the three-dimensional modeling liquid 4 as the second liquid are supplied to two tanks that communicate with an inkjet head (MH2420, manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional modeling apparatus. The two types of three-dimensional modeling liquids were respectively ejected from each ink jet head to form a film. The first liquid and the second liquid were ejected at different positions.
Next, the film was cured by irradiating the film with a light amount of 350 mJ / cm ² with an ultraviolet irradiation machine (SPOT CURE SP5-250DB, manufactured by USHIO INC.). By repeating these series of steps, the three-dimensional structure 1 was formed.
As shown in FIGS. 4A and 4B, the obtained three-dimensional structure 1 had a region B made of the hydrogel 4 inside, and a region A made of the hydrogel 1 outside the region B.
About the obtained three-dimensional molded item 1, the structure of the three-dimensional molded item was evaluated as follows. The results are shown in Table 5.

<Structure of 3D object>
○: Solid object is formed from two regions A and B having different elastic moduli shown in FIGS. 4A and 4B. Δ: Two-dimensional object is two regions A having different elastic moduli shown in FIGS. 4A and 4B. Although it is formed from B, it is easy to collapse at the time of conveyance, and there is a problem as a three-dimensional structure. ×: The three-dimensional structure is not formed from two regions A and B having different elastic moduli shown in FIGS. 4A and 4B.

(Example 10)
In Example 9, as shown in Table 4, the 3D modeling liquid 2 as the first liquid and the 3D modeling liquid 4 as the second liquid were used, and the 3D modeling was performed in the same manner as in Example 9. 3D modeling of the thing 2 was performed and it carried out similarly to Example 9, and evaluated the structure of the 3D modeling object. The results are shown in Table 5.

(Example 11)
In Example 9, as shown in Table 4, the 3D modeling liquid 3 as the first liquid and the 3D modeling liquid 4 as the second liquid were used, and the 3D modeling was performed in the same manner as in Example 9. Three-dimensional modeling of the thing 3 was performed and it carried out similarly to Example 9, and evaluated the structure of the three-dimensional molded article. The results are shown in Table 5.

(Example 12)
In Example 9, as shown in Table 4, the three-dimensional modeling liquid 1 as the first liquid, the three-dimensional modeling liquid 4 as the second liquid, and the rigid molded body liquid 1 as the fourth liquid are used. The three-dimensional object 4 and the support were formed, and the structure of the three-dimensional object was evaluated in the same manner as in Example 9. The results are shown in Table 5.

(Example 13)
In Example 9, as shown in Table 4, the three-dimensional modeling liquid 5 was used as the first liquid and the three-dimensional modeling liquid 4 was used as the second liquid. 3D modeling of the thing 5 was performed and it carried out similarly to Example 9, and evaluated the structure of the three-dimensional molded article. The results are shown in Table 5.

(Example 14)
In Example 9, as shown in Table 4, the 3D modeling liquid 6 as the first liquid and the 3D modeling liquid 4 as the second liquid were used in the same manner as in Example 9, except that the 3D modeling liquid 4 was used. The object 6 was three-dimensionally modeled, and the structure of the three-dimensional object was evaluated in the same manner as in Example 9. The results are shown in Table 5.

(Example 15)
In Example 9, as shown in Table 4, the 3D modeling liquid 7 as the first liquid and the 3D modeling liquid 4 as the second liquid were used in the same manner as in Example 9, except that the 3D modeling liquid 4 was used. Three-dimensional modeling of the thing 7 was performed and it carried out similarly to Example 9, and evaluated the structure of the three-dimensional molded article. The results are shown in Table 5.

(Example 16)
In Example 9, as shown in Table 4, the three-dimensional modeling liquid 1 was used as the first liquid and the three-dimensional modeling liquid 8 was used as the second liquid. Irradiated with an ultraviolet irradiator and cured, and the three-dimensional modeling liquid 8 was cured by heating to 80 ° C. with an infrared irradiator, and three-dimensional modeling of the three-dimensional modeled object 8 was performed by repeating these series of steps. In the same manner as in Example 9, the structure of the three-dimensional structure was evaluated. The results are shown in Table 5.

(Example 17)
In Example 9, as shown in Table 4, the 3D modeling liquid 8 was used as the first liquid and the 3D modeling liquid 1 was used as the second liquid. Irradiate and cure with an ultraviolet irradiator, and the solid modeling liquid 8 is heated and cured at 80 ° C. with an infrared irradiator. By repeating these series of steps, the three-dimensional model 9 is three-dimensionally modeled. In the same manner as in Example 9, the structure of the three-dimensional structure was evaluated. The results are shown in Table 5.

(Comparative Example 2)
In Example 9, as shown in Table 4, the three-dimensional modeling liquid 9 as the first liquid, the three-dimensional modeling liquid 4 as the second liquid, and the hard molded body liquid 1 as the fourth liquid are used. Except for the above, the three-dimensional object 10 was formed and the support was formed in the same manner as in Example 9, and the structure of the three-dimensional object was evaluated in the same manner as in Example 9. The results are shown in Table 5.

(Comparative Example 3)
The solid modeling liquid 4 is used as the second liquid, the internal structure is formed in advance in a mold, and the solid structure is placed in the mold, and the three-dimensional modeling liquid 1 as the first liquid is further poured into the mold. In the same manner as in Example 9, it was photocured in the same manner as in Example 9. However, the central shape, the region B could not be fixed at a predetermined position, dropped to the lower part, and a three-dimensional model was produced. could not.

(Comparative Example 4)
In Example 9, as shown in Table 4, except that only one type of three-dimensional modeling liquid 1 was used, three-dimensional modeling of the three-dimensional model 11 was performed in the same manner as in Example 9, and the same as in Example 9. The structure of the three-dimensional model was evaluated. The results are shown in Table 5.

(Preparation Example 1)
<Preparation of the first liquid or the second liquid (solid modeling liquid) 1-1>
First, the pure water while 195 parts by mass was stirred, a layered mineral _{[Mg 5.34 Li 0.66 Si 8 O} 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, 16 parts by mass (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., DMAA) from which the polymerization inhibitor was removed by passing through a column of activated alumina as a monofunctional monomer was added to the obtained dispersion. As a functional monomer, 0.3 part by mass of methylene bisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., MBAA) was added. Furthermore, after adding 2 parts by mass of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) as a surfactant and mixing, vacuum degassing was performed for 10 minutes. Subsequently, filtration was performed to remove impurities and the like, and a first liquid or a second liquid (solid modeling liquid) 1-1 was prepared.

<Storage stability>
The obtained first liquid or second liquid 1-1 is put into a polypropylene wide-mouth bottle (50 mL), left in a thermostatic bath at 50 ° C. for 2 weeks, taken out from the thermostatic bath and brought to room temperature (25 ° C.). The initial viscosity (viscosity before storage) was measured at 1 atm.
The first liquid or the second liquid 1-1 was put in a polypropylene wide-mouth bottle (50 mL), left in a thermostatic bath at 50 ° C. for 2 weeks, and then taken out from the thermostatic bath. The first liquid or the second liquid 1-1 taken out from the thermostat was allowed to stand until it reached room temperature (25 ° C.), and the viscosity was measured after storage at 1 atm. The pre-storage viscosity and the post-storage viscosity were measured using a rotational viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.).
From the obtained measurement results, the viscosity change rate was calculated by the following formula 1, and the storage stability was evaluated according to the following criteria.
[Formula 1]
Viscosity change rate (%) = [(viscosity after storage) − (viscosity before storage)] / (viscosity before storage) × 100
[Evaluation criteria]
A: The viscosity change rate is 10% or less.
B: The viscosity change rate exceeds 10% and is 20% or less.
C: Viscosity change rate exceeds 20%.
The measurement results of the pre-storage viscosity, the post-storage viscosity, and the storage stability evaluation results are shown in Table 6.

(Preparation Examples 2 and 4-5)
<Preparation of the first liquid or the second liquid (solid modeling liquid) 1-2 and 1-4 to 1-5>
In the said preparation example 1, except having changed into the composition and content shown in following Table 6, it carried out similarly to the said preparation example 1, and made the 1st or 2nd liquid 1-2 and 1-4-1-5. Prepared.
About the obtained 1st liquid or the 2nd liquid 1-2 and 1-4-1-5, it carried out similarly to the preparation example 1, and evaluated storage stability. The results are shown in Table 6.

(Preparation Example 3)
<Preparation of the first liquid or the second liquid (three-dimensional modeling liquid) 1-3>
First, the pure water while 195 parts by mass was stirred, a layered mineral _{[Mg 5.34 Li 0.66 Si 8 O} 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, 8 parts by mass (manufactured by Rockwood) was added little by little and stirred to prepare a dispersion.
Next, 20 parts by mass of N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., IPAM) from which the polymerization inhibitor was removed by passing through a column of activated alumina as the monofunctional monomer 2 was added to the obtained dispersion, and polyfunctional As a monomer, 0.3 part by mass of methylene bisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., MBAA) was added. Furthermore, 2 parts by mass of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed as a surfactant.
Next, while cooling in an ice bath, 1 part by mass of the photopolymerization initiator liquid and 10 parts by mass of the thermal polymerization initiator liquid 1 were added, and after stirring and mixing, vacuum degassing was performed for 10 minutes. Subsequently, filtration was performed to remove impurities and the like, and a first liquid or a second liquid (solid modeling liquid) 1-3 was prepared.
About the obtained 1st liquid or 2nd liquid 1-3, it carried out similarly to the preparation example 1, and evaluated storage stability. The results are shown in Table 6.

(Preparation Examples 6 to 8)
<Preparation of third liquid 3-1 to 3-3>
In Preparation Example 3, third liquids 3-1 to 3-3 were prepared in the same manner as Preparation Example 3, except that the composition and content shown in Table 7 were changed.
The obtained third liquids 3-1 to 3-3 were evaluated for storage stability in the same manner as in Preparation Example 1. The results are shown in Table 7.

Details of the materials used in Tables 6 and 7 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)
* Monofunctional monomer 1: DMAA: N, N-dimethylacrylamide (Wako Pure Chemical Industries, Ltd.)
* Monofunctional monomer 2: IPAM: N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Multifunctional monomer: MBAA: Methylenebisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
* Photopolymerization initiator solution (Irgacure 184 2 parts by mass / ethanol 98 parts by mass)
* Thermal polymerization initiator solution 1 (Na peroxodisulfate 2 parts by mass / 98 parts by mass of water)

(Examples 18 to 20 and 22)
Using the three-dimensional modeling liquid set shown in Table 8, a three-dimensional model was manufactured using the three-dimensional modeling apparatus shown in FIG.
Specifically, the first liquid or the second liquid shown in Table 8 and the third liquid are filled into two tanks that lead to an inkjet head (MH2420 manufactured by Ricoh Industry Co., Ltd.) of the three-dimensional modeling apparatus. Each of the two liquids was ejected from each ink jet head to form a film. The third liquid was ejected at the same position as the first liquid or the second liquid.
Next, the film was cured by irradiating the film with ultraviolet light having a light amount shown in Table 8 with an ultraviolet irradiator (USHIO Corporation, SPOT CURE SP5-250DB). By repeating these series of steps, three-dimensionally shaped objects of Examples 18 to 20 and 22 were produced.

(Example 21)
As shown in Table 8 below, as a three-dimensional modeling liquid set, Examples 18 to 18 were used except that the solid molding liquid 1 was used for the support jetting head unit 31 in FIG. In the same manner as 20 and 22, a three-dimensionally shaped article of Example 21 was produced.

  Next, 80% distortion compressive stress was measured as follows about the obtained three-dimensional molded item of Examples 18-22. The results are shown in Table 8.

<80% strain compression stress evaluation (compression test)>
A universal testing machine (manufactured by Shimadzu Corporation, AG-I) was provided with a compression jig for a load cell of 1 kN and 1 kN, and a three-dimensional modeled object having a shape of 10 mm × 10 mm × 10 mm was installed. The stress against compression applied to the load cell was recorded in a computer, and the stress against displacement was plotted.
The fractured three-dimensional model was set to the maximum compressive stress at the time of rupture, and the three-dimensional model that was not fractured was set to 80% strain compressive stress.
[Evaluation criteria]
◯: 80% strain compression stress of the three-dimensional model is 1.0 MPa or more Δ: 80% strain compression stress of the three-dimensional model is 0.4 MPa or more and less than 1.0 MPa ×: 80% strain compression of the three-dimensional model The stress is less than 0.4 MPa

(Example 23)
Using the same three-dimensional modeling liquid 1, three-dimensional modeling liquid 4, and rigid molding liquid 1 as the three-dimensional modeling liquid set of Example 12, data processing is performed by the three-dimensional modeling apparatus shown in FIG. 2 in Japanese Patent No. 5239037. Based on the three-dimensional model data of the liver obtained according to the description, a pig liver organ model was formed.
The obtained liver organ model approximated the shape, touch and elasticity of an actual pig liver.

Aspects of the present invention are as follows, for example.
<1> a first step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer;
A second step of curing the film formed in the first step;
Is a method for producing a three-dimensional modeled object characterized by repeating a plurality of times.
<2> a first step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer;
A third step that includes a hydrogel precursor and forms a film by applying a second liquid having a composition different from that of the first liquid to a position different from that of the first liquid;
It is a manufacturing method of the three-dimensional molded item characterized by repeating the 4th process of hardening the film formed by said 1st process and said 3rd process in multiple times, respectively.
<3> The method for producing a three-dimensional structure according to <1>, further including a fifth step of applying a third liquid containing at least a polymerization initiator to the same position as the first liquid.
<4> The solid according to <2>, further including a sixth step of applying a third liquid containing at least a polymerization initiator to the same position as at least one of the first liquid and the second liquid. It is a manufacturing method of a molded article.
<5> The solid according to <4>, wherein the content of the polymerization initiator in the third liquid is larger than the content of the polymerization initiator in at least one of the first liquid and the second liquid. It is a manufacturing method of a molded article.
<6> The method for producing a three-dimensional structure according to any one of <2> and <4> to <5>, wherein at least one of the first liquid and the second liquid does not contain a polymerization initiator. It is.
<7> The method for producing a three-dimensional structure according to any one of <2> and <4> to <6>, wherein at least one of the first liquid and the second liquid contains a polymerization initiator. It is.
<8> The method for producing a three-dimensional structure according to any one of <3> to <5> and <7>, wherein the polymerization initiator is any one of a photopolymerization initiator and a thermal polymerization initiator.
<9> The method for producing a three-dimensional structure according to any one of <1> to <8>, wherein the hydrogel precursor includes at least a layered mineral dispersed in water in a single layer state.
<10> The method for producing a three-dimensional structure according to any one of <2> and <4> to <9>, wherein at least one of the first liquid and the second liquid contains a monofunctional monomer.
<11> The method for producing a three-dimensional structure according to any one of <2> and <4> to <10>, wherein the second liquid contains a polyfunctional monomer.
<12> The method for producing a three-dimensional structure according to any one of <9> to <11>, wherein the layered mineral is synthetic hectorite.
<13> The method for producing a three-dimensional structure according to any one of <1> to <12>, wherein the polyfunctional monomer is an active energy ray-curable monomer.
<14> The method for producing a three-dimensional structure according to any one of <10> to <13>, wherein the monofunctional monomer or the polyfunctional monomer has a water-soluble homopolymer.
<15> The method for producing a three-dimensional structure according to any one of <1> to <2>, wherein the application method of the first liquid is one of an inkjet method and a dispenser method.
<16> The method for producing a three-dimensional structure according to <2>, wherein the application method of the second liquid is either an inkjet method or a dispenser method.
<17> The method for producing a three-dimensional structure according to any one of <3> to <4>, wherein the method for applying the third liquid is any one of an inkjet method and a dispenser method.
<18> a first step of applying a first liquid to form a film;
A third step of forming a film by applying the second liquid to a position different from the first liquid;
A method for producing a three-dimensional structure that repeats the fourth step of curing the film formed in each of the first step and the third step, a plurality of times,
The first liquid and the second liquid are hydrogels having different elastic moduli from each other when cured.
<19> The solid according to <18>, further including a sixth step of applying a third liquid containing at least a polymerization initiator to the same position as at least one of the first liquid and the second liquid. It is a manufacturing method of a molded article.
<20> The method for producing a three-dimensional structure according to any one of <18> to <19>, wherein one 80% strain compression stress of the hydrogel is 0.4 MPa or more.
<21> A fourth liquid serving as a hard molded body for supporting the three-dimensional structure formed of the hydrogel is provided at a position different from at least one of the first liquid and the second liquid. The method for producing a three-dimensional structure according to any one of <18> to <20>, further including a seventh step of forming a film.
<22> A three-dimensional modeling liquid, which is a hydrogel precursor containing at least a polyfunctional monomer.
<23> For three-dimensional modeling according to <22>, wherein the viscosity is 3 mPa · s to 20 mPa · s at 25 ° C., and the 80% strain compression stress of the hydrogel obtained by curing is 0.4 MPa or more. It is liquid.
<24> A first liquid as a hydrogel precursor containing at least a polyfunctional monomer, and a second liquid containing a hydrogel precursor and having a composition different from that of the first liquid. It is a liquid set for three-dimensional modeling.
<25> The three-dimensional modeling liquid set according to <24>, further including a third liquid having a polymerization initiator content higher than at least one of the first liquid and the second liquid.
<26> The liquid set for three-dimensional modeling according to <25>, wherein the viscosity change rate of the third liquid before and after being allowed to stand at 50 ° C. for 2 weeks is 20% or less.
<27> The three-dimensional modeling liquid set according to any one of <24> to <26>, wherein at least one of the first liquid and the second liquid does not contain a polymerization initiator.
<28> The three-dimensional modeling liquid set according to any one of <24> to <26>, wherein at least one of the first liquid and the second liquid contains a polymerization initiator.
<29> The three-dimensional modeling liquid set according to any one of <25> to <26> and <28>, wherein the polymerization initiator is any one of a photopolymerization initiator and a thermal polymerization initiator.
<30> The three-dimensional modeling liquid set according to any one of <24> to <29>, wherein the first liquid and the second liquid are hydrogels having different elastic moduli from each other when cured. It is.
<31> having at least a first region composed of the first hydrogel and a second region composed of the second hydrogel having an elastic modulus different from that of the first hydrogel. ,
The three-dimensional structure is characterized in that the 80% strain compressive stress of either the first hydrogel or the second hydrogel is 0.4 MPa or more.
<32> The three-dimensional structure according to <31>, wherein one of the first hydrogel and the second hydrogel has a compression elastic modulus of 0.3 MPa or more.
<33> The three-dimensional structure according to any one of <31> to <32>, wherein the first region completely includes the second region.
<34> From the above <31>, wherein the hydrogel is 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. <33> A three-dimensional structure according to any one of the above.
<35> The three-dimensional structure according to any one of <31> to <34>, which is used as an organ model.

  The method for producing a three-dimensional structure according to any one of <1> to <21>, the liquid for three-dimensional structure according to any one of <22> to <23>, any one of <24> to <30> The three-dimensional modeling liquid set described above and the three-dimensional modeling object described in any one of <31> to <35> are intended to solve the above-described problems and achieve the following objects. . That is, the manufacturing method of the three-dimensional modeled object, the three-dimensional modeled liquid, the three-dimensional modeled liquid set, and the three-dimensional modeled object easily and efficiently manufacture a complicated and fine three-dimensional modeled object represented by an organ model or the like. It aims at providing the manufacturing method of the possible three-dimensional molded item, the liquid for three-dimensional modeling, the liquid set for three-dimensional modeling, and the three-dimensional molded item.

Japanese Patent No. 4366538 Japanese Patent No. 4908679

DESCRIPTION OF SYMBOLS 30 Injection head unit for modeling objects 31, 32 Injection head unit for support bodies 33, 34 Ultraviolet irradiation machine or infrared irradiation apparatus 35 Three-dimensional modeling object 36 Support body 37 Modeling object support substrate 38 Stage 39 Three-dimensional modeling apparatus

Claims (20)

A first step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer;
A second step of curing the film formed in the first step;
A method for producing a three-dimensional modeled object characterized by repeating a plurality of times. A first step of forming a film by applying a first liquid as a hydrogel precursor containing at least a polyfunctional monomer;
A third step that includes a hydrogel precursor and forms a film by applying a second liquid having a composition different from that of the first liquid to a position different from that of the first liquid;
The method for producing a three-dimensional structure, wherein the fourth step of curing the films formed in the first step and the third step is repeated a plurality of times.   The manufacturing method of the three-dimensional molded item of Claim 1 which further includes the 5th process of providing the 3rd liquid which contains a polymerization initiator at least to the same position as said 1st liquid.   The three-dimensional structure according to claim 2, further comprising a sixth step of applying a third liquid containing at least a polymerization initiator to the same position as at least one of the first liquid and the second liquid. Method.   5. The three-dimensional structure according to claim 4, wherein the content of the polymerization initiator in the third liquid is greater than the content of the polymerization initiator in at least one of the first liquid and the second liquid. Method.   The manufacturing method of the three-dimensional molded item according to any one of claims 1 to 5, wherein the hydrogel precursor includes at least a layered mineral dispersed in water in a single layer state.   The method for producing a three-dimensional structure according to claim 2, wherein at least one of the first liquid and the second liquid contains a monofunctional monomer.   The manufacturing method of the three-dimensional molded item in any one of Claim 2 and 4 to 7 in which said 2nd liquid contains a polyfunctional monomer. A first step of applying a first liquid to form a film;
A third step of forming a film by applying the second liquid to a position different from the first liquid;
A method for producing a three-dimensional structure that repeats the fourth step of curing the film formed in each of the first step and the third step, a plurality of times,
The method for producing a three-dimensional structure, wherein the first liquid and the second liquid become hydrogels having different elastic moduli from each other when cured.   The three-dimensional structure according to claim 9, further comprising a sixth step of applying a third liquid containing at least a polymerization initiator to the same position as at least one of the first liquid and the second liquid. Method.   A film is formed by applying a fourth liquid, which is a rigid molded body for supporting the three-dimensional structure composed of the hydrogel, to a position different from at least one of the first liquid and the second liquid. The manufacturing method of the three-dimensional molded item in any one of Claim 9 to 10 which further contains a 7th process.   A three-dimensional modeling liquid, which is a hydrogel precursor containing at least a polyfunctional monomer.   The liquid for three-dimensional modeling according to claim 12, wherein the viscosity is 3 mPa · s or more and 20 mPa · s or less at 25 ° C, and the 80% strain compressive stress of the hydrogel obtained by curing is 0.4 MPa or more.   For three-dimensional modeling, comprising: a first liquid as a hydrogel precursor containing at least a polyfunctional monomer; and a second liquid containing a hydrogel precursor and having a composition different from that of the first liquid. Liquid set.   The three-dimensional modeling liquid set according to claim 14, further comprising a third liquid having a polymerization initiator content higher than at least one of the first liquid and the second liquid. Having at least a first region composed of a first hydrogel and a second region composed of a second hydrogel having an elastic modulus different from that of the first hydrogel;
The three-dimensional structure characterized by the 80% strain compressive stress of either one of said 1st hydrogel and said 2nd hydrogel being 0.4 Mpa or more.   The three-dimensional modeled object according to claim 16, wherein the compression elastic modulus of one of the first hydrogel and the second hydrogel is 0.3 MPa or more.   The three-dimensional structure according to any one of claims 16 to 17, wherein the first region completely includes the second region.   The hydrogel is 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. The three-dimensional structure described in 2.   The three-dimensional structure according to any one of claims 16 to 19, which is used as an organ model.