JP6733305B2 - Method for producing three-dimensional object, apparatus for modeling gel structure, and liquid set for modeling gel structure used therein - Google Patents

Description

The present invention relates to a method and an apparatus for manufacturing a three-dimensional object, and a liquid set for three-dimensional object used therein.

Conventionally, as a layered modeling method, a method has been proposed in which a liquid photo-curable resin is irradiated with laser light, particularly ultraviolet light, one layer at a time to produce a three-dimensional solid object (for example, Patent Document 1). reference).

Further, in recent years, there has been disclosed an inkjet stereolithography method in which a liquid photo-curable resin is imaged on a required portion of the molded article by an inkjet method, and a three-dimensional molded article is formed by stacking the images.

Furthermore, in recent years, high-strength hydrogels have been actively developed, and for example, nanocomposite gels, double network gels, slide ring gels, etc. are used, and these high-strength hydrogels are extremely difficult to obtain in conventional gel members. It has the advantage of being tough and flexible.

The high-strength hydrogel has flexibility due to its high solvent content, and is expected to be applied to various fields including medical treatment. The high-strength hydrogel has a complicated and precise structure and is free from the hardness in the shaped object when it is applied to, for example, a preliminary simulation in biological surgery or a substitute for a living body (cartilage, vitreous body of the eyeball, etc.). Is required to be controlled.

It is an object of the present invention to provide a method for producing a three-dimensional object which is excellent in modeling accuracy and which can easily and efficiently produce a complicated and precise three-dimensional object.

The method for producing a three-dimensional structure of the present invention as a means for solving the above-mentioned problems, a first liquid containing a solvent and a curable material is applied to form a film, and the formed film contains a solvent. A film forming step of forming a film by applying the second liquid in an applied amount corrected for the evaporation amount of the solvent in the film, and a curing step of hardening the formed film are repeated a plurality of times. ..

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a three-dimensional molded object which is excellent in modeling accuracy and can manufacture a complicated and fine three-dimensional molded object simply and efficiently can be provided.

FIG. 1 is a schematic diagram showing an example of an apparatus for manufacturing a three-dimensional object according to the present invention.

(Method for manufacturing three-dimensional object and apparatus for manufacturing three-dimensional object)
The method for producing a three-dimensional model according to the present invention, a first liquid containing a solvent and a curable material is applied to form a film, and the formed liquid film contains a second liquid containing a solvent in the film. A film forming step of forming a film by applying a corrected application amount of the evaporation amount of the solvent;
The curing step of curing the formed film is repeated a plurality of times, and further includes other steps as necessary.
The method for producing a three-dimensional molded article of the present invention, in the conventional high-hardness hydrogel, most of it is composed of a solvent component, and particularly when a volatile solvent is used, the shape and strength are likely to change and are high. It is based on the finding that there is a problem that it is difficult to obtain accuracy.
Further, in the method for producing a three-dimensional object of the present invention, in the method for producing a three-dimensional three-dimensional object by the conventional layered modeling method, it is necessary to store a large amount of liquid photocurable resin, It is based on the finding that there is a problem that the size of the liquid photocurable resin needs to be increased and the temperature and the like for stabilizing the quality of the liquid photocurable resin are required to be controlled.

The manufacturing apparatus for a three-dimensional molded object of the present invention applies a first liquid containing a solvent and a curable material to form a film, and forms a second liquid containing a solvent in the film on the formed film. It has a film forming means for forming a film by applying a corrected application amount of the evaporation amount of the solvent, and a curing means for curing the formed film, and further has other means as necessary. ..
The method for producing a three-dimensional object according to the present invention can be suitably implemented by the apparatus for producing a three-dimensional object according to the present invention.

<Film forming process and film forming means>
In the film forming step, a first liquid containing a solvent and a curable material is applied to form a film, and a second liquid containing a solvent is added to the formed film to evaporate the solvent in the film. This is a step of forming a film by applying a corrected amount of the minute portion, and further includes other processing as necessary.
The film forming means applies a first liquid containing a solvent and a curable material to form a film, and forms a second liquid containing a solvent on the formed film by an evaporation amount of the solvent in the film. It is a means for forming a film by applying the corrected amount, and further includes other members as necessary.
The film forming step can be preferably performed by the film forming means.

In the film forming step and the film forming means, a film formed by applying the first liquid is treated with a first liquid in order to supplement a solvent component that is volatilized from the film during ejection and curing reaction. By applying a second liquid from a different head to the same position as the first liquid at a deposition amount corrected for the evaporation amount of the solvent in the film, thereby forming a film by the first liquid. It is possible to prevent the obtained three-dimensional object from shrinking due to the evaporation of the solvent from the formed film, so that a three-dimensional object having high strength can be obtained.
In addition, when a mixed liquid material (ink) with a solvent component added in advance is used, the viscosity changes, which impairs ejection stability. However, additional ejection of the second liquid in this way causes evaporation of water during flight. By doing so, it is possible to compensate for the water lost during ultraviolet curing.

As a method of correcting the amount of evaporation, a test pattern is formed, and a difference from the amount of a forming substance expected from the data is measured to determine the applied amount of the second material.
By imparting the first liquid and the second liquid to the same position, it is possible to supplement water at any time during modeling, and in the obtained three-dimensional model, volume contraction due to drying, strain, mass change, It is possible to prevent reduction of modeling accuracy such as peeling and cracking due to stress generation, and to achieve extremely high-definition and stable modeling.
By exposing the film formed by the first liquid and the second liquid to UV and stacking the cured films, a three-dimensional object can be formed.
The film after curing contains water and a component soluble in the water in a three-dimensional network structure formed by compositing an organic polymer and a water-swellable layered clay mineral, organic-inorganic It is preferably a composite hydrogel.

The three-dimensional model manufactured by the method for manufacturing a three-dimensional model of the present invention is preferably a gel structure.
The three-dimensional model preferably contains the solvent in an amount of 10% by mass or more.
The amount of the solvent in the three-dimensional molded object should be stored in a drying oven (DV240S, manufactured by Yamato Scientific Co., Ltd.) set at a temperature of boiling point or higher for 6 hours or more, and measured by the weight change after sufficient solvent volatilization. You can

The compression strength of the three-dimensional molded article is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.02 MPa or more and 4 MPa or less, more preferably 0.1 MPa or more and 2 MPa or less. The compressive strength should be measured using a dynamic ultra-micro hardness meter (DUH-W201S, manufactured by Shimadzu Corporation) equipped with software for a micro compression tester (MCT-W, manufactured by Shimadzu Corporation). You can

-First liquid-
The first liquid (hereinafter, also referred to as “material for soft molded body”) contains a solvent and a curable material, preferably contains a mineral, and further contains other components as necessary.
The first liquid is preferably a gel material.
The gel material means a gel in which a solvent is incorporated in a network structure composed of a polymer. When the solvent taken in is water, it is called a hydrogel, and when it is an organic solvent taken in, it is called an organogel. The organic solvent means an organic substance that is in a liquid state at room temperature.

---Curable material---
The curable material is not particularly limited as long as it has curability and can be appropriately selected depending on the purpose, and examples thereof include polymerizable monomers such as monofunctional monomers and polyfunctional monomers, and oligomers.

--- Polymerizable monomer ---
Examples of the polymerizable monomer include monofunctional monomers and polyfunctional monomers. Further, an oil gel forming monomer and the like can also be mentioned. These may be used alone or in combination of two or more.

----- Monofunctional monomer ---
Examples of the monofunctional monomer include acrylamide, N-substituted acrylamide derivatives, N,N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, N,N-disubstituted methacrylamide derivatives, and acrylic acid. These may be used alone or in combination of two or more. Among these, acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, hydroxyethylacrylamide and isobornyl (meth)acrylate are preferable.

An organic polymer can be obtained by polymerizing the monofunctional monomer.

The content of the monofunctional monomer is preferably 0.5% by mass or more and 20% by mass or less based on the total amount of the first liquid.

The monofunctional monomer other than the above is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include 2-ethylhexyl (meth)acrylate (EHA), 2-hydroxyethyl (meth)acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), caprolactone-modified tetrahydrofurfuryl (meth)acrylate, 3-methoxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, lauryl (meth)acrylate, 2-phenoxyethyl ( Examples thereof include (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, tridecyl (meth)acrylate, caprolactone (meth)acrylate, and ethoxylated nonylphenol (meth)acrylate.

-----Polyfunctional monomer ---
The polyfunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include bifunctional monomers and trifunctional or higher functional monomers. These may be used alone or in combination of two or more.

Examples of the bifunctional monomer include tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polypropylene glycol di(meth). Acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate (MANDA), hydroxypivalic acid 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 pentyl glycol di(meth)acrylate, Ethoxy-modified bisphenol A di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the trifunctional or higher functional monomers include trimethylolpropane tri(meth)acrylate (TMPTA), pentaerythritol tri(meth)acrylate (PETA), dipentaerythritol hexa(meth)acrylate (DPHA), triallyl isocyanurate. , Ε-caprolactone modified dipentaerythritol tri(meth)acrylate, ε-caprolactone modified dipentaerythritol tetra(meth)acrylate, (meth)acrylate, ε-caprolactone modified dipentaerythritol penta(meth)acrylate, ε-caprolactone modified di Pentaerythritol hexa(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, propoxylated glyceryl tri( (Meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, penta(meth)acrylate ester and the like. To be These may be used alone or in combination of two or more.

----- Oil gel forming monomer ---
The oil gel forming monomer is not particularly limited as long as it is a monomer that dissolves in the organic solvent and forms a polymerization network during gelation.
Examples of the oil gel-forming monomer include acrylamide derivatives (acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, acryloylmorpholine, etc.), methacrylamide derivatives (methacrylamide, dimethylmethacrylamide, N-isopropyl). Methacrylamide, N-methylolmethacrylamide, methacryloylmorpholine, etc.), acrylate (hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, alkyl acrylate (methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate) Lauryl acrylate, etc.), methacrylate (hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, alkyl methacrylate (methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc., glycidyl methacrylate, etc.) Etc.), acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, vinyl acetate, acrylic acid, methacrylic acid and the like. These may be used alone or in combination of two or more.

Further, a low molecular weight oil gelling agent which gels due to electrostatic interaction with a solvent, hydrogen bond, van der Waals force, π-π interaction or the like without constructing a polymerization network may be used.
Examples of the low molecular weight oil gelling agent include 3,2,4-dibenzylidene-D-sorbitol, N-lauroyl-L-glutamic acid-α,γ-bis-n-butylamide, benzoylgluconamide derivative and O-methyl-4. ,6-benzylidene-D-galactose, 2,3-O-isopropylideneglyceraldehyde derivative, L-isoleucine derivative, L-valyl-11-valine derivative, diamide and diamide synthesized from trans-1,2-cyclohexanediamine Examples thereof include urea derivatives, double-headed amino acid derivatives, L-lysine derivatives, and the like.

--- Oligomer ---
As the oligomer, a low polymer of the above-mentioned monomer or a polymer having a reactive unsaturated bond group at the terminal may be used alone or in combination of two or more.

−−Solvent−−
The solvent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include water and organic solvents. These may be used alone or in combination of two or more.

--- Water ---
As the water, for example, deionized water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water can be used.
As the water, for example, other components such as an organic solvent may be dissolved or dispersed depending on the purpose of imparting moisturizing properties, imparting antibacterial properties, imparting conductivity, adjusting compression stress and elastic modulus, and the like.

--- Organic solvent ---
As the organic solvent, for example, various solvents retained in the polymer network can be used.
The organic solvent is appropriately selected depending on the intended purpose without any limitation, provided that it is an organic substance that is in a liquid state at room temperature. For example, alcohols such as methanol and ethanol, oleyl alcohol (boiling point: 207°C), Higher alcohols such as dodecanol, stearyl alcohol, hexanol and hexyldecanol, diols such as ethylene glycol and propylene glycol, amines such as dimethylformamide and dimethylacetamide, ketones such as acetone and methyl ethyl ketone, dimethyl sulfoxide and tetrahydrofuran, benzene and toluene, Examples include xylene, acetic acid, ethyl acetate, butyl acetate, acetic anhydride and the like. These may be used alone or in combination of two or more.
The organic solvent may contain water as long as it does not adversely affect the physical properties of the organogel.

Since the solvent forms a gel structure, it is preferable that the solvent does not polymerize with the curable material.
The boiling point of the solvent is preferably 250° C. or lower.

The content of the solvent is preferably 10% by mass or more, more preferably 10% by mass or more and 99% by mass or less, further preferably 60% by mass or more and 98% by mass or less, and 70% by mass with respect to the total amount of the first liquid. % To 97% by mass is particularly preferable.

−− Minerals −−
The mineral is appropriately selected depending on the intended purpose without any limitation, and examples thereof include layered minerals.
The layered mineral is preferably a dispersed mineral dispersed in water in a single layer state.
The layered mineral is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a water-swellable layered clay mineral.

Examples of the water-swellable layered clay mineral include water-swellable smectite and water-swellable mica. More specific examples include water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, and water-swellable synthetic mica.
The water swelling property means that water molecules are inserted between layers of the layered mineral and absorb water to expand the volume.
As the water-swellable layered clay mineral, the above-exemplified compounds may be used alone or in combination of two or more, or may be appropriately synthesized. It may be a commercially available product.

Examples of the commercially available product 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 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, based on the total amount of the first liquid. When the content is 1% by mass or more and 40% by mass or less, the viscosity of the first liquid is appropriate, and the ejection property with an inkjet nozzle and the hardness of the three-dimensional object become good.

−−Other ingredients−−
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include stabilizers, surface treatment agents, polymerization initiators, colorants, viscosity modifiers, adhesion promoters, and oxidation agents. Examples include anti-aging agents, anti-aging agents, cross-linking accelerators, UV absorbers, plasticizers, preservatives and dispersants.

--- Stabilizer ---
The stabilizer is used for dispersing and stabilizing the mineral and maintaining the sol state. Further, in the inkjet method, a stabilizer is used as necessary to stabilize the characteristics of the liquid.
Examples of the stabilizer include high-concentration phosphates, glycols, nonionic surfactants, and the like.

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

---Polymerization initiator---
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Among these, the photopolymerization initiator is preferable from the viewpoint of storage stability.
As the photopolymerization initiator, any substance that generates radicals upon irradiation with light (especially 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, methylbenzoylformate, 1-hydroxycyclohexylphenylketone, azobisisobutyronitrile , Benzoyl peroxide, di-tert-butyl peroxide and the like. These may be used alone or in combination of two or more.

The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include azo initiators, peroxide initiators, persulfate initiators and redox (redox) initiators. And so on.

Examples of the azo initiator include VA-044, VA-46B, V-50, VA-057, VA-061, VA-067, VA-086, 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) (manufactured by DuPont Chemical Co., Ltd.), 2,2′-azobis(2-cyclopropylpropionitrile), 2,2′-azobis(methylisobutyrate) (V-601) (manufactured by Wako Pure Chemical Industries, Ltd.) Yaku Kogyo Co., 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). , Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11, Elf Atochem), t-butyl peroxy-2-ethylhexanoate (Trigonox 21). -C50, manufactured by Akzo Nobel), dicumyl peroxide and the like.

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

Examples of the redox initiator include, for example, a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite, based on the organic peroxide and a tertiary amine. Examples thereof include a system (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.

The content of the polymerization initiator is preferably 1% by mass or less, and more preferably 0.1% by mass or less, based on the total amount of the first liquid. When the content is 1% by mass or less, it is possible to prevent the curing reaction from being hindered.

-Colorant-
As the colorant, dyes and pigments that are dissolved or stably dispersed in the curable material and have excellent thermal stability are suitable. Among these, a soluble dye (Solvent Dye) is preferable. Further, it is possible to appropriately mix two or more kinds of colorants by adjusting the color.
Examples of the dye include those described below.
Examples of black dyes include MS BLACK VPC (manufactured by Mitsui Toatsu Co., Ltd.),
AIZEN SOT BLACK-1, AIZEN SOT BLACK-5 (manufactured by Hodogaya Chemical Co., Ltd.), RESORIN BLACK GSN 200%, RESOLIN BLACK BS (manufactured by Bayer Japan), KAYASET BLACK A-N (manufactured by Nippon Kayaku Co., Ltd.), DAIWA BLACK MSC (manufactured by Daiwa Kasei Co., Ltd.), HSB-202 (manufactured by Mitsubishi Chemical Co., Ltd.), NEPTUNE BLACK X60, NEOPEN BLACK X58 (manufactured by BASF Japan Co., Ltd.), Oleosol Fast BLACK RL (manufactured by Taoka Chemical Industry Co., Ltd.), Chuo. BLACK80, Chuo BLACK80-15 (made by Chuo Gosei Kagaku Co., Ltd.), etc. are mentioned.
As a magenta dye, for example, MS Magenta VP, MS Magenta HM-1450, MS Magenta Hso-147 (manufactured by Mitsui Toatsu Co., Ltd.), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOT Red-3, AIZEN SOT. Pink-1, SPIRON Red GEHSPE CIAL (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MAC ROLEX Red Violet R, MACROLEX ROT 5B (manufactured by Bayer Japan Co., Ltd.), KAYASET RedB, KAYAKASET Red 130. (Manufactured by Nippon Kayaku Co., Ltd.), PHLOXIN, ROSE BENG AL, ACID Red (manufactured by Daiwa Kasei Co., Ltd.), HSR-31, DIARESIN RedK (manufactured by Mitsubishi Chemical Corporation), Oil Red (manufactured by BASF Japan Co., Ltd.), Oil Pink330. (Manufactured by Chuo Synthetic Chemical Co., Ltd.) and the like.
As the cyan dye, for example, MS Cyan HM-1238, MS Cyan HSo-16, Cyan Hso-144, MS Cyan VPG (manufactured by Mitsui Toatsu Co., Ltd.), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES BlueGN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIU S SUPRA TURQ. Blue FB-LL 330% (manufactured by Bayer Japan Ltd.), KAYASET Blue Fr, KAYASET Blue N, KAYASET Blue 814, Turq. Blue GL-5 200, Light Blue BGL-5 200 (manufactured by Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Oleosol Fast Blue GL (manufactured by Daiwa Kasei Co., Ltd.), DIARESIN Blue P (manufactured by Mitsubishi Chemical Co., Ltd.), SUDAN Blue. Examples include NEOPEN Blue 808 and ZAPON Blue 806 (manufactured by BASF Japan Ltd.).
Examples of the yellow dye include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (manufactured by Mitsui Toatsu Co., Ltd.), AIZENSOT Yellow-1, AIZEN SOT Yellow-3, AIZEN SOT Yellow-6 (Hodogaya). CHEMICAL CO., LTD., MACROLEX Yellow 6G, MACROLEX FLUOR, Yellow 10GN (manufactured by Bayer Japan KK), KAYASET Yellow SF-G, KAYASET Yellow2G, KAYASET Yellow A-G, KAYASET YAG (Japan) Yellow. , DAIWA Yellow 330HB (manufactured by Daiwa Kasei Co., Ltd.), HSY-68 (manufactured by Mitsubishi Chemical Co., Ltd.), SUDAN Yellow 146, NEOPEN Yellow 075 (manufactured by BASF Japan), Oil Yellow 129 (manufactured by Chuo Synthetic Chemical Co., Ltd.), and the like. Can be mentioned.
As the pigment, various organic and inorganic pigments can be used, for example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments and chelate azo pigments, phthalocyanine pigments, perylene pigments, anthecenone pigments, quinacridone pigments, dioxazine. Examples thereof include pigments, thioindigo pigments, isoindolinone pigments, and polycyclic pigments such as quinophthalone pigments. As the pigment, specifically, organic or inorganic pigments having the following numbers described in the color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53. : 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment. Orange 13, 16, 20, 36 and the like.
As the blue or cyan pigment, for example, pigment blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like.
Examples of the green pigment include Pigment Green 7, 26, 36, 50 and the like.
Examples of the yellow pigment include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137. , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like.
Examples of the black pigment include Pigment Black 7, 28, and 26.
As the pigment, a commercially available product can be used, and examples of the commercially available product include Chromophine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromophine Orange 3700L, 6730, Chromophine Scarlet 6750, Chromophine. Magenta 6880, 6886, 6891N, 6790, 6887, Chromo Fine Violet RE, Chromo Fine Red 6820, 6830, Chromo Fine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromo Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromo Fine Black A-1103, Seika Fast Yellow 10GH. , A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Seika Fast Red 8040, C405(F), CA120, LR-116. , 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose. R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seica Fast Orange 900, 2900, Seica Light Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (above, Dainichi Seika Kogyo Co., Ltd.) KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338. 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (above, manufactured by DIC Corporation); Colortex Yellow 301, 314, 315, 316, P-624, 314. , U10GN, U3GN, UNN, UA-414 , U263, Finecol Yellow T-13, T-05, Pigment Yellow 1705, Colortex Orange 202, Colortex Red 101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN. , URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex BrownB610N, Colortex Violet600, Pigment Red 122, 5403, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, 518, Color tex Black 702, U905 (above, Sanyo Pigment Co., Ltd.); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (above, Toyo Ink Mfg. Co., Ltd.); Toner Magenta E. Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapeam Blue B2G (above, Hoechst Industries Ltd.); carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #980. , #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, Examples include #33, #32, #30, #25, #20, #10, #5, #44, CF9 (above, manufactured by Mitsubishi Chemical Corporation).

-Second liquid-
The second liquid contains a solvent and optionally other components.
The second liquid preferably does not include the curable material, and preferably does not include a material component that causes a polymerization reaction with the curable material in the first liquid.
The same solvent as the solvent in the first liquid can be used as the solvent.
As the solvent, it is preferable to use the same solvent as that used in the first liquid.

−−Other ingredients−−
As the other components, those similar to the other components in the first liquid can be used.

The first liquid and the second liquid are not particularly limited, and the surface tension, viscosity, droplet amount, etc. can be appropriately selected according to the purpose.

The surface tension of the first liquid and the second liquid is appropriately selected depending on the intended purpose without any limitation, but it is preferably 20 mN/m or more and 45 mN/m or less, and 25 mN/m or more and 34 mN or more. /M or less is more preferable. When the surface tension is 20 mN/m or more, the ejection property can be improved during modeling, and when the surface tension is 45 mN/m or less, the ejection nozzle for molding can be easily filled with liquid. You can
The surface tension can be measured using, for example, a surface tension meter (device name: automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

-Viscosity-
The viscosity of the first liquid and the second liquid is not particularly limited and can be appropriately selected depending on the purpose, and can be appropriately used by adjusting the temperature, but at 25° C., It is preferably 3 mPa·s or more and 20 mPa·s or less, and more preferably 6 mPa·s or more and 12 mPa·s or less. When the viscosity is 3 mPa·s or more and 20 mPa·s or less, dischargeability can be improved during modeling.
The viscosity can be measured, for example, using a rotational viscometer (device name: VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.) in an environment of 25°C.

The viscosity can be adjusted by the mixing ratio of the curable material and the solvent for the first liquid, and can be adjusted by the mixing ratio of solvent components having different viscosities for the second liquid. it can.

-Droplet amount-
The droplet amount of the first liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 pL or more and 60 pL or less, more preferably 15 pL or more and 30 pL or less. When the droplet amount is 2 pL or more, the ejection property can be improved at the time of modeling, and when it is 60 pL or less, the ejection nozzle for modeling can be easily filled with the liquid.
The droplet amount of the second liquid can be adjusted by the amount of water evaporation of the film made of the first liquid.

-Viscosity change rate-
The first liquid and the second liquid preferably have a viscosity change rate of ±20% or less, and more preferably ±10% or less with respect to the viscosity before storage (initial viscosity) after being left at 50° C. for 2 weeks. preferable.
When the viscosity change rate is ±20% or less, the storage stability of the first liquid and the second liquid is appropriate, and for example, when the second liquid is applied by an inkjet method. The ejection stability becomes good.
The rate of change in viscosity before and after being left at 50° C. for 2 weeks can be measured as follows.
The second liquid was placed in a polypropylene wide-mouth bottle (50 mL), left in a constant temperature bath at 50° C. for 2 weeks, then taken out from the constant temperature bath and allowed to reach room temperature (25° C.) to measure viscosity. To do. The viscosity of the second liquid before being put into the constant temperature bath is the viscosity before storage, and the viscosity of the second liquid after being taken out from the constant temperature bath is the viscosity after storage, and the rate of change in viscosity can be calculated by the following formula. The viscosity before storage and the viscosity after storage 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 of the first liquid and the second liquid before storage at 25° C. is preferably 25 mPa·s or less, more preferably 3 mPa·s or more and 20 mPa·s or less, and 3 mPa·s or more and 10 mPa·s or less. Is particularly preferable. When the viscosity is 25 mPa·s or less, ejection from the inkjet nozzle is stabilized.
The viscosity of the first liquid and the second liquid after storage is preferably 3 mPa·s or more and 10 mPa·s or less at 25°C.

The method for applying the first liquid and the second liquid is not particularly limited as long as it is a method in which droplets 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. can be mentioned. In addition, in order to carry out these methods, it is possible to preferably use the applying means in the apparatus for producing a three-dimensional object of the present invention.
Among these, the dispenser method is excellent in the quantitativeness of droplets, but the applied area is narrow. In the spray method, fine ejected substances can be easily formed, the application area is wide, and the application property is excellent, but the quantitative property of the liquid droplet is deteriorated and the spray flow may cause scattering. The inkjet method has an advantage that the quantitativeness of liquid droplets is better than the spray method, and has an advantage that the applied area can be made wider than the dispenser method, so that a complicated three-dimensional shape can be formed accurately and efficiently. be able to. Therefore, in the present invention, it is preferable to use the inkjet method.

Examples of the ink jet system applying means include a nozzle capable of ejecting the curable liquid and the non-curable material. A nozzle in a known inkjet printer can be preferably used as the nozzle, and examples of the inkjet printer include MH5420/5440 manufactured by Ricoh Industry Co., Ltd. This inkjet printer is preferable in that the amount of liquid droplets that can be dripped at one time from the head portion is large and the application area is wide, so that the application speed can be increased.
As the plurality of applying means, two or more applying means are preferable, and two applying means are more preferable.

<Curing step and curing means>
The curing step is a step of curing the film formed in the film forming step.
The curing means is means for curing the film formed by the film forming means.
The curing step can be preferably carried out by the curing means.

Examples of the curing means include an ultraviolet (UV) irradiation lamp and an electron beam. The means for curing the film is preferably equipped with a mechanism for removing ozone.
Examples of the type of the ultraviolet (UV) irradiation lamp include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide, and an LED.
The ultra-high pressure mercury lamp is a point light source, but the DeepUV type, which has a 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 region, it is effective as a coloring matter, and halides of metals such as Pb, Sn, and Fe are used, and can be selected according to the absorption spectrum of the polymerization initiator.
The lamp used for curing is not particularly limited and may be appropriately selected depending on the purpose. For example, commercially available products such as H lamp, D lamp and V lamp manufactured by Fusion System can be used.

<Other steps and other means>
The other steps are appropriately selected depending on the intended purpose without any limitation, and examples thereof include a support forming step, a removing step, a molded body polishing step, and a molded body cleaning step.
The other means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a support forming means, a removing means, a molded body polishing means, and a molded body cleaning means.
The support forming step can be suitably carried out by the support forming means, the removing step can be suitably carried out by the removing means, and the step of polishing the molded body may be performed by It can be preferably carried out by a polishing means, and the step of cleaning the molded body can be preferably carried out by a cleaning means of the molded body.

<<Support forming step and support forming means>>
The support-forming step is a step of forming a support by applying a support-forming liquid containing a curable material to a position different from the first liquid and the second liquid. It can be performed by forming means.
As the method and means for applying the support-forming liquid, the same methods and means as those for applying the first liquid and the second liquid can be used.

The support-forming liquid contains a curable material and, if necessary, a polymerization initiator, a coloring material, and other components. The support forming liquid is also referred to as a "material for a hard molded body".

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

-Polymerization initiator-
As the polymerization initiator, the same one as the polymerization initiator in the first liquid can be used.

The liquid for forming the support is not particularly limited, and the surface tension, the viscosity and the like can be appropriately selected according to the purpose.
The surface tension of the support-forming liquid can be the same as the surface tension of the first liquid.
The viscosity of the support-forming liquid may be the same as the viscosity of the first liquid.

<<Removal process and removal means>>
The removing step and removing means are performed by immersing in a bath filled with water or an organic solvent to remove, a method and means for applying temperature, a method and means for ultrasonically vibrating, a method and means for applying energy by stirring, etc. Can be used, or a combination thereof can be appropriately used.

In the method for producing a three-dimensional molded item, the above steps are repeated a plurality of times. The number of repetitions depends on the size, shape, etc. of the three-dimensional object to be produced and cannot be specified unconditionally, but the average thickness per layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 50 μm or less. preferable. When the average thickness is 5 μm or more and 50 μm or less, it is possible to accurately perform modeling without peeling, and it is possible to stack only the height of the three-dimensional shaped object.

As described above, in the method for producing a three-dimensional object of the present invention, the first liquid and the second liquid are discharged from the pores of the ink jet system or the dispenser system to form an image of each layer. Granted to be able to.

Hereinafter, specific embodiments of the method for producing a three-dimensional object of the present invention and the apparatus for producing a three-dimensional object of the present invention will be described.
First, the surface data or solid data of the three-dimensional shape designed by the three-dimensional CAD or the three-dimensional shape captured by the three-dimensional canner or digitizer is converted into the STL format and input to the additive manufacturing apparatus.

Next, a modeling process is implemented. FIG. 1 is a schematic diagram showing an example of an apparatus for manufacturing a three-dimensional object according to the present invention. As shown in FIG. 1, a plurality of heads 1, 2, and 3 in a three-dimensional object manufacturing apparatus 10 are moved bidirectionally to bring a first liquid, a second liquid, and a support-forming liquid to a predetermined area. The dots are formed by ejecting a predetermined amount. At that time, it is possible to mix the first liquid and the second liquid in the dots and correct the evaporation amount of the solvent in the first liquid.
Then, the formed film can be cured by irradiating it with ultraviolet rays (UV) to form a film that forms the model part 5 and the support part 4.

After forming one layer of film, the modeling stage 6 descends by the height of one layer. Again, continuous dots are formed on the film, and the film is cured by irradiating the film with ultraviolet rays (UV) to form a film. By repeating these laminations, it becomes possible to form a three-dimensional object.
The physical strength and the solubility of the three-dimensional object thus three-dimensionally adjusted can be partially adjusted.

In addition, by adhering an ultraviolet (UV) irradiator to the jetting inkjet head, the time required for the smoothing process can be omitted, and high-speed modeling is possible.

(3D modeling liquid set)
The three-dimensional modeling liquid set of the present invention includes a first liquid and a second liquid used in the method for producing a three-dimensional molded article of the present invention, and further includes other liquids as necessary.

As the first liquid, the same liquid as the first liquid in the method for producing a three-dimensional molded item can be used.
As the second liquid, the same liquid as the second liquid in the method for producing a three-dimensional molded item can be used.

The solvent in the first liquid preferably does not undergo a polymerization reaction with the curable material in the first liquid.
The first liquid preferably contains a polymerization initiator that generates radicals or cations by irradiation with active energy rays.
The content of the solvent in the first liquid is preferably 10% by mass or more based on the total amount of the first liquid.
It is preferable that the second liquid does not include a curable material that undergoes a polymerization reaction with the curable material in the first liquid.
The boiling point of the solvent in the first liquid and the second liquid is preferably 250° C. or lower.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

(Preparation Example 1 of the first liquid)
<Preparation of first liquid A>
While stirring the pure water 20.0 parts by weight solvent, synthetic hectorite having a composition of _{[Mg 5.34 Li 0.66 Si 8 O} 20 (OH) 4] -0.66 Na +0.66 as a layered clay mineral 0.8 parts by mass of light (Laponite XLG, manufactured by Rockwood) was added little by little and stirred to prepare a dispersion liquid.
Next, 4.0 mass of N,N-dimethylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) in which the polymerization inhibitor was removed by passing through a column of activated alumina as a curable material (polymerizable monomer) in the dispersion liquid. Added in parts. Next, 0.01 parts by mass of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) as a surfactant was added and mixed.
Next, 0.015 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184) was added as a photopolymerization initiator and mixed to obtain a mixed liquid.
Next, 0.1 part by mass of tetramethylethylenediamine (TEMED, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization accelerator while cooling the obtained mixed liquid in an ice bath, and mixed and stirred for hydrogel modeling. A first liquid A consisting of the hydrogel forming liquid was obtained. The composition is shown in Table 1 below.

(Preparation example 2 of the first liquid)
<Preparation of first liquid B>
To 16.0 parts by mass of oleyl alcohol as a solvent, 4.0 parts by mass of stearyl acrylate as a curable material (polymerizable monomer) and 0.4 parts by mass of ethylene glycol dimethacrylate were added and mixed.
Next, 0.2 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184) was mixed as a photopolymerization initiator to obtain a mixed solution.
Next, while cooling the obtained mixed solution in an ice bath, 0.02 parts by mass of tetramethylethylenediamine (TEMED, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization accelerator, mixed and stirred, and under a nitrogen atmosphere. After bubbling for 3 hours, a first liquid B containing an organogel-forming material and oleyl alcohol as a solvent was obtained. The composition is shown in Table 1 below.

(Preparation example 1 of the second liquid)
<Preparation of Second Liquid A>
80 parts by mass of pure water as a solvent, 3 parts by mass of glycerin as a viscosity modifier, and 17 parts by mass of 3-methyl-1,3-butanediol were added to obtain a second liquid A for solvent compensation. The composition is shown in Table 2 below.

(Preparation example 2 of the second liquid)
<Preparation of second liquid B>
16.0 parts by mass of oleyl alcohol as a solvent and 4.0 parts by mass of glycerin as a viscosity modifier were stirred to obtain a second liquid B for solvent compensation. The composition is shown in Table 2 below.

(Preparation Example 1 of Support Forming Liquid)
<Preparation of Support Forming Liquid A>
10.0 parts by mass of urethane acrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038) as a curable material (polymerizable monomer), neopentyl glycol hydroxypivalate ester di(meth)acrylate (manufactured by Nippon Kayaku Co., Ltd., Trade name: KAYARAD, MANDA) 90.0 parts by mass, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184) 3.0 parts by mass as a polymerization initiator, and a blue pigment (Toyochem Co., Ltd.) as a colorant. (Product name: Lionol Blue 7400G) 2.0 parts by mass in total 105 parts by mass was dispersed using a homogenizer (HG30 manufactured by Hitachi Koki Co., Ltd.) at a rotation speed of 2,000 rpm until a homogeneous mixture was obtained. .. Subsequently, filtration was performed to remove impurities and the like, and finally vacuum deaeration was performed for 10 minutes to obtain a homogeneous support-forming liquid A. The composition is shown in Table 3 below.

(Example 1)
[Measurement of correction amount]
An ink jet head (Ricoh) of a gel three-dimensional molded article manufacturing apparatus 10 shown in FIG. 1 is used to transfer a first liquid A, a second liquid A, and a support-forming liquid to the three-dimensional molded object manufacturing apparatus shown in FIG. It was filled in each of three tanks leading to GEN4) manufactured by Industry Co., Ltd.
First, as a test pattern for measuring the amount of supplemented water, the first liquid A was discharged onto the modeling stage to form a film. Next, an LED lamp head (1.6 W/cm ² , manufactured by integration technology, subzeroLED060) was irradiated to cure the film, and by repeating coating and curing, a 100 mm×100 mm×10 mm modeled object was produced. When all the discharged first liquid becomes a modeled object, the mass of the modeled object becomes 100 g because the density of the first liquid is about 1 g/cm ³ . Next, when the mass of the shaped object was measured using an electronic balance (device name: ASP64, manufactured by As One Co., Ltd.), it was 80 g, which was 80 when the solvent in the first liquid was considered not to evaporate. It became mass%. Therefore, the solvent reduction amount during modeling is considered to be 20% by mass, and 20% by mass of the ejection amount of the first liquid ejected from the inkjet head 1 in advance is used as the first amount of the second liquid from the inkjet head 2. When the liquid was ejected at the same position as the applying position, the amount of evaporation was the corrected amount of the solvent in the film.

[3D modeling]
The first liquid A is ejected from the inkjet head 1 at 3×10 ⁻³ g/cm ² , and the second liquid A is ejected from the inkjet head 2 to the same position as the landing position of the first liquid 3×10 ^{−. 3} g/cm ² and the support-forming liquid was ejected from the inkjet head 3 at a position different from the first liquid and the second liquid at 6×10 ⁻³ g/cm ² . , A film was formed.

Then, the formed film was irradiated with an fvLED lamp head (1.6 W/cm ² ) to cure the film to obtain a cured film, and then the obtained cured film was rolled using a roller. Smoothing processing was performed. This was repeated as an inkjet film for each layer to produce a modeled object.
As the roller, a metal roller made of an aluminum alloy having a diameter of 25 mm, the surface of which was anodized, was used.
The support-forming liquid functions as a support material that supports a modeled object formed by film formation of the first liquid and the second liquid.
Finally, the structure formed by the liquid for forming a support and the molded object formed by the film formation of the first liquid and the second liquid were physically peeled by hand to obtain a hydrogel three-dimensional molded object. .. When the solvent amount of the obtained hydrogel three-dimensional model was measured by a drying method, the solvent amount was 80% by mass.

(Example 2)
[Measurement of correction amount]
Measurement of the correction amount of Example 1 except that the first liquid A was changed to the first liquid B and the second liquid A was changed to the second liquid B in the measurement of the correction amount of Example 1. The correction amount was measured in the same manner as in. As a result, the correction amount was 5% by mass.

[3D modeling]
In the three-dimensional modeling of Example 1, the first liquid A was changed to the first liquid B, the second liquid A was changed to the second liquid B, and the discharge amount of the second liquid B was 3×10. An organogel three-dimensional modeled product was obtained in the same manner as in the three-dimensional modeled product of Example 1, except that the setting was ^-3 g/cm ² . When the solvent amount of the obtained organogel three-dimensional model was measured by a drying method, the solvent amount was 80% by mass.

(Comparative Example 1)
[3D modeling]
In the three-dimensional model of Example 1, a hydrogel three-dimensional model was obtained in the same manner as the three-dimensional model of Example 1, except that the second liquid A was not used. When the solvent amount of the obtained hydrogel gel three-dimensional model was measured by a drying method, the solvent amount was 78% by mass.

(Comparative example 2)
[3D modeling]
In the three-dimensional modeling of Example 2, an organogel three-dimensional molded article was obtained in the same manner as the three-dimensional modeling of Example 1, except that the second liquid B was not used. When the solvent amount of the obtained organogel three-dimensional model was measured by a drying method, the solvent amount was 30% by mass.

With respect to the obtained three-dimensional molded item, "modeling accuracy ("difference from theoretical mass", "strength ratio", and "difference from theoretical value in thickness direction")" was evaluated as follows. The results are shown in Table 4 below.

[Preparation of control three-dimensional object]
Each first liquid was poured into a 100 mm×100 mm×10 mm mold, and UV-cured gel three-dimensional molded article was obtained using an LED lamp head (1.6 W/cm ² , manufactured by integration technology, subzero LED060).

(Difference from theoretical mass)
The solvent (theoretical mass) of the control three-dimensional model and the mass (measured mass) of the obtained three-dimensional model are dried in a drying oven to remove the solvent, and an electronic balance (device name: ASP64, manufactured by As One Co., Ltd.) is used. The change in weight was confirmed, the difference between the theoretical mass and the measured mass was calculated, and the “difference (%) from the theoretical mass” was obtained.

(Strength ratio)
The compression strength of the control three-dimensional model and the compression strength of the obtained three-dimensional model are measured, and the strength ratio (%) of the compression strength of the three-dimensional model to the compression strength of the control three-dimensional model is calculated. The strength multiplication factor (%)" was determined. When the strength magnification is closer to 1, it means that the three-dimensional model is not hardened due to the evaporation of the solvent.
The compressive strength is measured using a device in which a dynamic ultra-micro hardness meter (DUH-W201S, manufactured by Shimadzu Corporation) is equipped with software for a micro compression tester (MCT-W, manufactured by Shimadzu Corporation). did.

(Difference from the theoretical value in the thickness direction)
The average thickness of the control three-dimensional model and the average thickness of the obtained three-dimensional model are measured using a three-dimensional microscope (device name: KEYENCE VR-3000, manufactured by KEYENCE CORPORATION), and the control three-dimensional model is compressed. The difference between the average thickness of the three-dimensional molded item and the strength was calculated, and the "difference from the theoretical value in the thickness direction" was obtained. The closer the difference is to 0%, the higher the modeling accuracy is.

As shown in Table 4, the three-dimensional molded products of Examples 1 and 2 have a small difference from the theoretical mass of 2% by mass to 5% by mass, and have a solvent content close to that of the control three-dimensional molded product (bulk molded product). You know you have.
Further, it can be seen that the three-dimensional molded products of Examples 1 and 2 have a small strength magnification of 1.1 to 1.2 times, and have a compressive strength close to that of the control three-dimensional molded product (bulk molded product).
Further, it can be seen that the three-dimensional objects of Examples 1 and 2 have a small difference from the theoretical value in the thickness direction of 10% to 13%, and the control three-dimensional object (bulk object) has an average thickness.
On the other hand, in Comparative Examples 1 and 2, the difference from the theoretical mass is 11% to 30%, the strength magnification is 2.4 to 3.0 times, and the difference from the theoretical value in the thickness direction is 13% to 33%. It can be seen that the obtained three-dimensional model has a higher value than the control three-dimensional model.

Aspects of the present invention are as follows, for example.
<1> A first liquid containing a solvent and a curable material is applied to form a film, and a second liquid containing the solvent is added to the formed film to correct the amount of evaporation of the solvent in the film. A film forming step of forming a film by applying the applied amount,
The method for producing a three-dimensional object is characterized in that the curing step of curing the formed film is repeated a plurality of times.
<2> The method for producing a three-dimensional object according to <1>, which is used for producing a three-dimensional object having a gel structure.
<3> The method for producing a three-dimensional object according to any one of <1> to <2>, wherein the content of the solvent in the three-dimensional object is 10% by mass or more.
<4> The first liquid is the method for producing a three-dimensional object according to any one of <1> to <3>, further including a mineral.
<5> The method for producing a three-dimensional object according to <4>, wherein the mineral is a layered mineral.
<6> The method for producing a three-dimensional object according to <5>, wherein the layered mineral is a water-swellable layered clay mineral.
<7> The method for producing a three-dimensional structure according to <6>, wherein the water-swellable layered clay mineral is water-swellable hectorite, water-swellable montmorillonite, water-swellable saponite, and water-swellable synthetic mica. is there.
<8> The method for producing a three-dimensional object according to any one of <4> to <7>, wherein the content of the mineral is 1% by mass or more and 40% by mass or less with respect to the total amount of the first liquid. is there.
<9> The method for producing a three-dimensional object according to any one of <4> to <8>, wherein the content of the mineral is 1% by mass or more and 15% by mass or less with respect to the first liquid total amount. is there.
<10> The method for producing a three-dimensional object according to any one of <1> to <9>, in which the first liquid further contains a polymerization initiator.
<11> The method for producing a three-dimensional object according to any one of <1> to <10>, wherein the first liquid further contains a colorant.
<12> The method for producing a three-dimensional object according to any one of <1> to <11>, in which the solvent in the second liquid does not contain a curable material.
<13> The method for producing a three-dimensional object according to any one of <1> to <12>, wherein the solvent in the second liquid is the same as the solvent in the first liquid.
<14> The method for producing a three-dimensional object according to any one of <1> to <13>, wherein the surface tension of the first liquid is 20 mN/m or more and 45 mN/m or less.
<15> A liquid set for three-dimensional modeling, comprising the first liquid and the second liquid in the method for producing a three-dimensional molded article according to any one of <1> to <14>. ..
<16> The solvent in the first liquid does not undergo a polymerization reaction with the curable material in the first liquid,
It is the three-dimensional modeling liquid set according to <15>, in which the content of the solvent is 10% by mass or more.
<17> The three-dimensional modeling liquid according to any one of <15> to <16>, in which the second liquid does not contain a curable material that polymerizes with the curable material in the first liquid. It is a set.
<18> The liquid set for three-dimensional modeling according to any one of <15> to <17>, wherein the first liquid further contains a polymerization initiator that generates radicals or cations by irradiation with active energy rays. is there.
<19> The liquid set for three-dimensional modeling according to any one of <15> to <18>, wherein the boiling points of the solvents in the first liquid and the second liquid are 250° C. or less.
<20> A first liquid containing a solvent and a curable material is applied to form a film, and a second liquid containing the solvent is added to the formed film to correct the evaporation amount of the solvent in the film. A film forming means for forming a film by applying the applied amount,
And a curing unit configured to cure the formed film.
<21> The manufacturing apparatus for a three-dimensional object according to <20>, further including an inkjet head.

<3> The method for producing a three-dimensional object according to any one of <1> to <14>, the three-dimensional modeling liquid set according to any one of <15> to <19>, and <20> to <21>. The manufacturing apparatus for a three-dimensional molded item according to any one of the items 1 to 3 can solve the above-mentioned problems in the related art and achieve the object of the present invention.

Japanese Patent Publication No. 2009-915143

1, 2, 3 head 6 modeling stage

Claims (5)

A first liquid containing a solvent and a curable material is applied to form a film, and the second film containing the solvent is applied to the formed film so that the amount of evaporation of the solvent in the film is corrected. A film forming process of applying and forming a film,
A method of manufacturing a three-dimensional object , comprising: a curing step of curing the formed film ;
The method for producing a three-dimensional object, wherein the three-dimensional object is a gel structure . The method for producing a three-dimensional object according to claim 1, wherein the content of the solvent in the three-dimensional object is 10% by mass or more. Having a first liquid containing a solvent and a curable material, and a second liquid containing a solvent,
The gel structure modeling liquid set, wherein the second liquid does not contain a curable material that undergoes a polymerization reaction with the curable material in the first liquid. A first liquid containing a solvent and a curable material is applied to form a film, and the second film containing the solvent is applied to the formed film so that the amount of evaporation of the solvent in the film is corrected. And a film forming means for forming a film,
And a curing unit configured to cure the formed film. The apparatus for modeling a gel structure according to claim 4, further comprising an inkjet head.