JP2022138362A - Molding liquid set, kit for three-dimensional molding, and method for producing three-dimensional molded article - Google Patents

Abstract

To provide a molding liquid set capable of giving a green body having excellent dimensional precision in a lamination direction (Z direction) and having high bending strength.SOLUTION: A molding liquid set comprises: a first molding liquid comprising an epoxy compound; and a second molding liquid comprising an amine compound with an amine group number of 3 or more. The pot life of the second molding liquid is 30 minutes or less.SELECTED DRAWING: None

Description

The present invention relates to a modeling liquid set, a stereolithography kit, and a method of manufacturing a stereolithic object.

Conventionally, in three-dimensional modeling using metal powder, a resin ink obtained by dissolving a resin in a solvent or a reactive ink containing an acrylic monomer or the like is used as a modeling liquid.
In addition, as a non-water-soluble modeling liquid that does not use a solvent and reacts under temperature conditions where the non-aqueous reactive ink does not evaporate, a two-liquid curing type modeling liquid consisting of an epoxy compound and an amine compound is being studied. For example, a three-dimensional modeling material set has been proposed that includes a layered modeling powder containing rod-shaped particles or plate-shaped particles, and two-liquid curable first and second modeling inks (for example, patent Reference 1).

SUMMARY OF THE INVENTION An object of the present invention is to provide a molding liquid set which is excellent in dimensional accuracy in the stacking direction (Z direction) and which can obtain a green body with high bending strength.

A modeling liquid set of the present invention as means for solving the above-mentioned problems has a first modeling liquid containing an epoxy compound and a second modeling liquid containing an amine compound having 3 or more amine groups. and the pot life of the second modeling liquid is 30 minutes or less.

According to the present invention, it is possible to provide a modeling liquid set which is excellent in dimensional accuracy in the stacking direction (Z direction) and which can obtain a green body with high bending strength.

FIG. 1A is a schematic diagram showing an example of the operation of the three-dimensional molded article manufacturing apparatus used in the three-dimensional molded article manufacturing method of the present invention. FIG. 1B is a schematic diagram showing another example of the operation of the three-dimensional molded article manufacturing apparatus used in the three-dimensional molded article manufacturing method of the present invention. FIG. 1C is a schematic diagram showing another example of the operation of the three-dimensional molded article manufacturing apparatus used in the three-dimensional molded article manufacturing method of the present invention. FIG. 1D is a schematic diagram showing another example of the operation of the three-dimensional molded article manufacturing apparatus used in the three-dimensional molded article manufacturing method of the present invention. FIG. 1E is a schematic diagram showing another example of the operation of the three-dimensional molded article manufacturing apparatus used in the three-dimensional molded article manufacturing method of the present invention.

In this specification, "powder" may also be referred to as "powder" or "powder material". A "modeling liquid" may also be referred to as a "curing liquid" or a "reaction liquid." In addition, a three-dimensional object obtained by laminating cured products is sometimes referred to as a "green body", a "sintered body", a "molded body", or a "modeled object". A degreased body obtained by heat-treating a 'green body' is sometimes called a 'degreased body'. A "green body" and a "degreased body" may be collectively referred to as a "sintered precursor".

(Modeling liquid set)
A modeling liquid set of the present invention includes a first modeling liquid containing an epoxy compound and a second modeling liquid containing an amine compound having 3 or more amine groups, and the second modeling liquid can be It has a usage time of 30 minutes or less, and further contains other ingredients as necessary.

Conventional resin ink cures metal powder by distilling off the solvent, so if the solvent contained in the resin ink is a water-soluble solvent, it can be applied to metal powders with a high ionization tendency such as aluminum and magnesium. It is difficult to On the other hand, in the case of non-aqueous solvents, a solvent with a high boiling point that is highly safe is used, so the drying speed of the solvent is slow, and the resin ink seeps out in the opposite direction to the stacking direction (Z direction). quality will decline. Furthermore, since there is a solvent that does not participate in the curing of the metal powder, there is a drawback that the strength of the green body is lower than that of the green body in which the resin ink is completely cured.

Also, conventional reactive inks use low-molecular-weight reactive monomers and thermal polymerization initiators, and harden the metal powder by heat curing. With this reactive ink, it is difficult to control the heating temperature, and there is a problem that if the reaction is performed at a high temperature, the reactive monomer evaporates and hardens the non-modeling portion to which the reactive ink is not applied. In addition, since the reaction of the reactive ink is slow at low temperatures, there is a problem that the reactive ink oozes out in the direction opposite to the stacking direction (Z direction), thereby reducing the dimensional accuracy in the Z direction. Therefore, if the amount of reactive ink used is reduced, there is a problem that the strength of the green body is reduced.

In the prior art (Japanese Patent Application Laid-Open No. 2019-59102), the second modeling ink of the two-liquid curing type first modeling ink and the second modeling ink contains a bifunctional amine compound, There is a problem that a green body having sufficient strength cannot be obtained.

Therefore, the modeling liquid set of the present invention has a first modeling liquid containing an epoxy compound and a second modeling liquid containing an amine compound having 3 or more amine groups, so that the lamination direction (Z direction ), a green body with excellent dimensional accuracy and high bending strength can be obtained.
In the present invention, by using a trifunctional amine compound with a high curing speed, the curing reaction proceeds sufficiently at room temperature, so that the molding liquid can be reduced in the stacking direction (Z direction). Excellent dimensional accuracy (Z direction). In addition, since the second modeling liquid contains a trifunctional amine compound, the bending strength of the green body increases.

<First modeling liquid>
The first modeling liquid contains an epoxy compound, preferably contains a diluent monomer, and further contains other components as necessary.

-epoxy compound-
As the epoxy compound, a liquid epoxy compound having two or more epoxy groups in one molecule and having two or more functional groups is preferable.
Examples of epoxy compounds include glycidyl ether type epoxy resins obtained from polyols, glycidyl amine type epoxy resins obtained from amines having multiple active hydrogens, glycidyl ester type epoxy resins obtained from polycarboxylic acids, and a plurality of 2 A polyepoxide or the like obtained by oxidizing a compound having a heavy bond is used.
Examples of epoxy compounds include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AD-type epoxy resin, bisphenol S-type epoxy resin, epoxy resins having a biphenyl skeleton, and epoxy resins having a naphthalene skeleton. , epoxy resins having a dicyclopentadiene skeleton, phenol novolak type epoxy resins, novolak type epoxy resins such as cresol novolak type epoxy resins; triglycidyl-p-aminophenol, N,N,N',N'-tetraglycidyl-4 , 4′-methylenedianiline and other glycidylamine type epoxy resins, resorcinol diglycidyl ether, triglycidyl isocyanurate, 2,2-bis(4-glycidyloxyphenyl)propane and the like. These may be used individually by 1 type, and may use 2 or more types together.

Commercial products can be used as the epoxy compound, and examples of the commercial products include “jER828,” “jER806,” “jER1001,” “jER801N,” “jER807,” “jER152,” “jER604,” and “jER630.” ”, “jER871”, “YX8000”, “YX8034”, “YX4000” (all manufactured by Mitsubishi Chemical Corporation); “EP-4100”, “EP-4400”, “EP-4901” (all are stock manufactured by the company ADEKA).

- Monomer for dilution -
A liquid epoxy monomer having a molecular weight of 250 or less is used as the diluent monomer.
Examples of diluent monomers include phenyl glycidyl ether, alcohol glycidyl ether, alkyl glycidyl ether, alkyl glycidyl ester, α-olefin epoxide, alkylphenyl glycidyl ether, alkylphenol glycidyl ether and the like. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. These may be used individually by 1 type, and may use 2 or more types together.
Commercially available products can be used as the monomer for dilution, and examples of the commercial products include YED series manufactured by Mitsubishi Chemical Corporation, special epoxy products commercially available as monoepoxy type manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., Japan Oil Co., Ltd. epiol series, ADEKA Corporation ADEKA GLYCIROL ED series, DIC Corporation "EPICLON520" and the like.
The content of the diluent monomer is preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less, relative to the total amount of the first modeling liquid.
When the content of the diluent monomer is 50% by mass or more and 90% by mass or less, there is an advantage that ink jetting can be performed.

-Other ingredients-
Other components of the first modeling liquid are not particularly limited and can be appropriately selected depending on the purpose. Regulators, preservatives, antifungal agents, coloring agents, preservatives, stabilizers and the like are included.

The viscosity of the first modeling liquid at 25° C. is preferably 3 mPa·s or more and 20 mPa·s or less, more preferably 5 mPa·s or more and 10 mPa·s or less. When the viscosity of the first modeling liquid is 3 mPa·s or more and 20 mPa·s or less, ejection of the first modeling liquid from the inkjet nozzle is stabilized.
The viscosity can be measured according to JIS K7117, for example.

The static surface tension of the first modeling liquid is preferably 40 N/m or less, more preferably 10 N/m or more and 30 N/m or less at 25°C. When the static surface tension of the first modeling liquid is 40 N/m or less, ejection from the inkjet nozzle is stabilized.
Static surface tension can be measured, for example, with DY-300 manufactured by Kyowa Interface Science Co., Ltd.

<Second modeling liquid>
The second modeling liquid contains an amine compound, preferably contains a diluent monomer, and further contains other components as necessary.
The pot life of the second modeling liquid is 30 minutes or less, preferably 10 minutes or less. When the pot life of the second modeling liquid is 30 minutes or less, the amine compound and the epoxy compound react and harden in a short period of time. A green body having excellent dimensional accuracy (in the Z direction) can be obtained.

-Method of measuring pot life-
The second modeling liquid and an epoxy resin having an epoxy equivalent of about 190 g/eq (jER828, manufactured by Mitsubishi Chemical Corporation) were blended by equivalent mixing to make 100 g. It is measured with a differential scanning calorimeter (DSC) (device name: DSC Q2000, manufactured by TA Instruments Co., Ltd.), and the pot life can be calculated by multiplying the intersection of the tangent lines in the exothermic curve by 0.7.

-Amine compound-
As the amine compound, a trifunctional or higher functional amine compound having 3 or more amine groups is suitable. By using a trifunctional or higher functional amine compound, a crosslinked structure can be formed, so that the bending strength of the green body can be increased.

Tri- or higher functional amine compounds include, for example, 1,2,3-triaminopropane, triaminohexane, triaminononane, triaminododecane, 1,8-diamino-4-aminomethyloctane, 1,3,6 -triaminohexane, 1,6,11-triaminoundecane, 3-aminomethyl-1,6-diaminohexane, diethylenetriamine, triethylenetetramine, polyoxypropylenetriamine, triaminocyclohexane and the like. These may be used individually by 1 type, and may use 2 or more types together.
Commercially available products can be used as tri- or higher functional amine compounds. Examples of the commercial products include FXH8095 (manufactured by T&K TOKA Co., Ltd.), 8106-A (manufactured by T&K TOKA Co., Ltd.), FXD-821-F ( aliphatic polyamine-based curing agent, manufactured by T&K TOKA Co., Ltd.), polyether triamine T-403 (manufactured by Mitsui Chemicals Fine Co., Ltd.), and the like.

- Monomer for dilution -
As the monomer for dilution, an amine monomer having a molecular weight of 200 or less is used. diethylenetriamine, 2-dimethylaminoethanol, aminobenzylamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis[N-(1-methylpropyl)aniline], aminobenzylamine and the like. These may be used individually by 1 type, and may use 2 or more types together.
The content of the diluting monomer is preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 80% by mass or less, relative to the total amount of the second modeling liquid.
When the content of the diluent monomer is 50% by mass or more and 90% by mass or less, there is an advantage that ink jetting can be performed.

-Other ingredients-
Other components of the second modeling liquid are not particularly limited and can be appropriately selected according to the purpose. , pH adjusters, preservatives, antifungal agents, coloring agents, preservatives, stabilizers, and the like.

Examples of catalysts include dimethylaminopropylamine, triethylenediamine, bis[2-(dimethylamino)ethyl]ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine. , pentamethyldiethylenetriamine, dimorpholinodiethyl ether or bis(2-morpholinoethyl)=ether, 2-dimethylaminoethanol, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The viscosity of the second modeling liquid at 25° C. is preferably 3 mPa·s or more and 20 mPa·s or less, more preferably 5 mPa·s or more and 10 mPa·s or less. When the viscosity is 3 mPa·s or more or 20 mPa·s or less, ejection of the second modeling liquid from the inkjet nozzle is stabilized.
The viscosity can be measured according to JIS K7117, for example.

The static surface tension of the second modeling liquid is preferably 40 N/m or less, more preferably 10 N/m or more and 30 N/m or less at 25°C. When the static surface tension is 40 N/m or less, ejection from the inkjet nozzle is stabilized.
Static surface tension can be measured, for example, with DY-300 manufactured by Kyowa Interface Science Co., Ltd.

(Stereolithography kit)
The three-dimensional modeling kit of the present invention has powder, a first modeling liquid, and a second modeling liquid, and further contains other components as necessary.

<First modeling liquid>
As the first modeling liquid, the first modeling liquid of the present invention containing an epoxy compound is used.

<Second modeling liquid>
As the second modeling liquid, the second modeling liquid of the present invention containing a trifunctional amine compound is used.

<Powder>
As the powder, at least one of the powder of the substrate alone and the powder of the substrate surface coated with an organic material can be used.

-Base material-
The base material is not particularly limited as long as it has the form of powder or particles, and can be appropriately selected according to the purpose. , sand, and magnetic materials. These may be used individually by 1 type, and may use 2 or more types together. Among these, metals and ceramics that can be finally sintered (step) are preferable from the viewpoint of obtaining a three-dimensionally shaped article with extremely high strength.

The metal is not particularly limited as long as it contains a metal as a material, and examples include magnesium (Mg), aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), manganese ( Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), lead ( Pd), silver (Ag), indium (In), tin (Sn), tantalum (Ta), tungsten (W), neodymium (Nd), or alloys thereof. These may be used individually by 1 type, and may use 2 or more types together. Among these, (Fe), copper (Cu), silver (Ag), titanium (Ti), aluminum (Al), or alloys thereof are preferred, and aluminum alloys are more preferred.

Examples of aluminum alloys include _AlSi10Mg , _AlSi12 , _{AlSi7Mg0.6 , AlSi3Mg} , _AlSi9Cu3 , _Scalmalloy , and _ADC12 .

Examples of ceramics include oxides, carbides, nitrides, and hydroxides.
Examples of oxides include metal oxides. Examples of metal oxides include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), and the like.

A commercially available product can be used as the substrate. Commercially available products include, for example, pure Al (manufactured by Toyo Aluminum Co., Ltd., A1070-30BB), pure Ti (manufactured by Osaka Titanium Technologies), SUS316L (manufactured by Sanyo Special Steel Co., Ltd., trade name: PSS316L); Si10MgBB manufactured by Tosoh Corporation); SiO ₂ (manufactured by Tokuyama Corporation, trade name: EXCELICA SE-15K), AlO ₂ (manufactured by Taimei Chemical Industry Co., Ltd., trade name: Taimicron TM-5D), ZrO ₂ (Tosoh Corporation) (trade name: TZ-B53).
In addition, the substrate may be subjected to a known surface treatment (surface modification treatment) for the purpose of improving adhesiveness with organic materials and improving coatability.

The volume average particle diameter of the base material is not particularly limited and can be appropriately selected depending on the intended purpose.
When the volume average particle diameter of the substrate is 2 μm or more, the influence of aggregation is prevented from increasing, and the substrate is easily coated with an organic material, resulting in a decrease in yield, a decrease in the manufacturing efficiency of the model, and a decrease in the substrate. It is possible to prevent deterioration of the handleability and handleability of the material. Moreover, when the volume average particle diameter is 100 μm or less, it is possible to prevent a decrease in contact points between particles and an increase in voids, thereby preventing a reduction in the strength of the three-dimensionally shaped article and its sintered product.
The particle size distribution of the base material is not particularly limited and can be appropriately selected according to the purpose, but a sharper particle size distribution is preferable.
The volume average particle size and particle size distribution of the substrate can be measured using a known particle size measuring device, for example, a particle size distribution measuring device Microtrac MT3000II series (manufactured by Microtrac Bell).

A base material can be manufactured using a conventionally well-known method. Examples of methods for producing a powder or particulate base material include a pulverization method in which a solid is subdivided by applying compression, impact, friction, etc., an atomization method in which a molten metal is sprayed to obtain a rapidly cooled powder, and a method in which a solid is dissolved in a liquid. A precipitation method for precipitating the dissolved components, a gas phase reaction method for vaporizing and crystallizing, and the like can be mentioned.
The substrate is not limited to its manufacturing method, but a more preferable method is, for example, an atomization method because a spherical shape can be obtained and there is little variation in particle size. The atomization method includes a water atomization method, a gas atomization method, a centrifugal atomization method, a plasma atomization method, and the like, all of which are preferably used.

－Organic material－
In the powder obtained by coating the surface of the base material with an organic material, a resin is preferably used as the organic material.
The resin is not limited to the resin that covers the base material, but also includes the resin that covers the base material and is dissolved in the modeling liquid. In addition, the term “coating” refers to a state in which at least a portion of the surface of the base material is covered with a coating resin, and is not limited to a state in which the entire surface of the base material is covered with the resin. Moreover, "dissolving in the modeling liquid" means that, for example, when 1 g of the material of the coating resin is mixed with 100 g of the modeling liquid at 30°C and stirred, 90% by mass or more of the material dissolves.

The resin preferably has low reactivity with respect to highly active metals (highly active metals) that can be used as a base material. In particular, it is more preferable that the resin is soluble in an organic solvent having low solubility in water. As a result, even if the base material is a highly active metal, in other words, a water-repellent material (eg, aluminum, titanium, etc.), it can be applied.

The resin may have a reactive functional group that reacts with the modeling liquid to form a crosslinked structure. Examples of reactive functional groups include acryl groups and vinyl groups. Among these, an acryl group having a high reaction rate is preferable.

In the degreasing process or sintering process, 95% by mass or more of the resin is thermally decomposed when the resin alone is heated at 450°C in order to prevent sintering inhibition due to the resin remaining in the molded product. Preferably.

The resin is preferably a resin having a hydroxyl group. polyester polyol (glass transition temperature: 133° C.), polybutadiene polyol (glass transition temperature: −17° C.), ethyl cellulose (glass transition temperature: 145° C.), nitrocellulose (glass transition temperature: 50° C.) and the like. Other examples include partially saponified vinyl acetate copolymers (vinyl chloride-vinyl acetate, ethylene-vinyl acetate, etc.), polyether polyols, and phenolic polyols. These may be used individually by 1 type, and may use 2 or more types together. Among these, polyacrylic polyols are preferred.

It is preferable that the resin has a large number of hydroxyl groups in the molecule rather than at the ends of the molecules, and has a weight-average molecular weight and a hydroxyl value equal to or higher than a certain level.
The weight average molecular weight is preferably 100,000 or less, more preferably 2,000 or more and 100,000 or less. Also, the resin preferably has a weight average molecular weight of 100,000 or less and is solid at room temperature.
The hydroxyl value is more preferably 10 mgKOH/g or more from the viewpoint of adhesion to the substrate.

A commercially available product may be used as the resin. Commercially available products include, for example, polyacrylic polyol (Acrydic WFU-580 manufactured by DIC Corporation), polyester polyol (Polylite OD-X-668 manufactured by DIC Corporation, ADEKA NEWACE YG-108 manufactured by ADEKA Corporation). , polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., GQ-1000), polyvinyl butyral (manufactured by Kuraray Co., Ltd., Mobital B20H), polyvinyl acetal (manufactured by Sekisui Chemical Co., Ltd., S-LEC BM-2, KS-1), ethyl cellulose (Japanese Shinsei Co., Ltd., ETHOCEL), polyacrylic (Kyoeisha Chemical Co., Ltd., Oricox KC-3000), and the like.

The average thickness of the resin coating the substrate is preferably 5 nm or more and 1,000 nm or less, more preferably 5 nm or more and 500 nm or less, still more preferably 50 nm or more and 300 nm or less, and particularly preferably 100 nm or more and 200 nm or less. When the average thickness is 5 nm or more, the strength of the shaped article is improved. Moreover, when the average thickness is 1,000 nm or less, the dimensional accuracy of the modeled object is improved.
The average thickness can be obtained, for example, by embedding the particles in an acrylic resin or the like and then performing etching or the like to expose the surface of the base material. It can be obtained by measuring the thickness at arbitrary 10 points using an SEM or the like and calculating the average value thereof.

The ratio of the surface area of the resin to the surface area of the particles (surface coverage) is preferably 15% or more, more preferably 50% or more, and even more preferably 80% or more. When the surface coverage is 15% or more, the strength and dimensional accuracy of the model are improved.
In addition, the surface coverage is, for example, obtained by taking a photograph of the powder and measuring 10 arbitrary particles appearing in the two-dimensional photograph. Specifically, the ratio (%) of the area of the portion coated with the resin to the total area of the particle surface is measured, and the average value is calculated as the surface coverage. It should be noted that, for determination of the resin-coated portion, for example, a method of elemental mapping by energy dispersive X-ray spectroscopy such as SEM-EDS can be used.

The method for producing the powder in which the substrate surface is coated with the organic material is not particularly limited and can be appropriately selected according to the purpose. For example, a method of coating the substrate with the organic material according to a known coating method etc. are preferably mentioned.
The method for coating the surface of the base material with the organic material is not particularly limited, and can be appropriately selected from known coating methods. , a stirring and mixing addition method, a dipping method, a kneader coating method, and the like are preferably used. Moreover, these coating methods can be carried out using various known commercially available coating apparatuses, granulating apparatuses, and the like.

－Physical properties of powder－
The volume average particle diameter of the powder is not particularly limited and can be appropriately selected according to the purpose. 10 μm or more and 85 μm or less is particularly preferable.
When the volume average particle diameter is 3 μm or more, the fluidity of the powder is improved, the powder (layer) is easy to form, and the smoothness of the surface of the laminated layers is improved. There is a tendency for dimensional accuracy to improve as well as handling and handleability to improve. Further, when the volume average particle diameter is 250 μm or less, the size of the space between the particles of the powder becomes small, so the porosity of the three-dimensional object becomes small, which contributes to the improvement of the strength. Therefore, it is preferable that the volume average particle diameter is 3 μm or more and 250 μm or less in order to achieve both dimensional accuracy and strength.
The particle size distribution of the powder is not particularly limited and can be appropriately selected according to the purpose.

As for the properties of the powder, the angle of repose, when measured, is preferably 60° or less, more preferably 50° or less, and even more preferably 40° or less.
When the angle of repose is 60° or less, the powder can be efficiently and stably arranged at a desired location on the support.
The angle of repose can be measured using, for example, a powder property measuring device (Powder Tester PT-N type, manufactured by Hosokawa Micron Corporation).

-Other ingredients-
Other components in the stereolithography kit are not particularly limited and can be appropriately selected according to the purpose. be done.

A fluidizing agent is preferable in that a layer or the like made of powder can be easily and efficiently formed.
A filler is a material that is effective mainly for adhering to the surface of powder or for filling voids between powders. As an effect, for example, it is possible to improve the fluidity of the powder, increase the contact points between the powders, and reduce the voids, so that the strength and the dimensional accuracy of the three-dimensional object can be improved.
A leveling agent is a material effective mainly in controlling the wettability of the powder surface. As an effect, for example, the permeability of the modeling liquid to the powder is increased, the strength of the three-dimensionally shaped article can be increased, the speed can be increased, and the shape can be stably maintained.
The sintering aid is a material effective in increasing the sintering efficiency when sintering the obtained cured product (sintering precursor). As effects, for example, the strength of the cured product (sintered precursor) can be improved, the sintering temperature can be lowered, and the sintering time can be shortened.

The powder can be suitably used for the simple and efficient production of various three-dimensional objects and structures, and is particularly suitable for the three-dimensional object manufacturing kit of the present invention and the three-dimensional object production method of the present invention. be able to.
Only by applying the modeling liquid set of the present invention to powder, a cured product having a complicated three-dimensional shape can be produced simply and efficiently with high dimensional accuracy. The cured product thus obtained is a green body (sintered precursor) having sufficient hardness, and can be held by hand, put in and out of a mold, or subjected to an air blow treatment to remove excess powder. It does not lose its shape even when used, and is excellent in handleability and handleability. The cured product may be used as it is, or may be further subjected to a sintering treatment as a sintering precursor to form a molded product (a sintered body of a three-dimensional model).

(Manufacturing method of three-dimensional object)
The method for producing a three-dimensional object of the present invention includes a modeling liquid applying step and a hardened product forming step, preferably includes a degreasing step and a sintering step, and further includes other steps as necessary.

<Modeling liquid application process>
The modeling liquid application step is a step of applying the first modeling liquid and the second modeling liquid in the modeling liquid set of the present invention to the powder, and is carried out by the modeling liquid application means.
Before applying the first modeling liquid and the second modeling liquid to the powder, the powder is placed on a support (on the modeling stage) to form a powder layer.

-Formation of powder layer-
The method of forming a powder layer by arranging the powder on the support (on the modeling stage) is not particularly limited and can be appropriately selected depending on the purpose. is a method using a known counter rotating mechanism (flattening roller) or the like, which is used in the selective laser sintering method described in Japanese Patent No. 3607300; Preferable examples include a method of spreading to a layer, a method of pressing the surface of the powder with a pressing member to spread it into a thin layer, and a method of using a known powder layered modeling apparatus.

A counter-rotating mechanism, a brush or a blade, a pressing member, or the like may be used as the powder layer forming means to form a thin layer of powder on the support, for example, in the following manner.
That is, it is arranged in an outer frame (sometimes called a “modeling tank”, a “mold”, a “hollow cylinder”, a “cylindrical structure”, etc.) so that it can move up and down while sliding on the inner wall of the outer frame. The powder is placed on the support that has been formed using a counter rotating mechanism or the like. At this time, when a support capable of moving up and down in the outer frame is used, the support is arranged at a position slightly lower than the upper end opening of the outer frame, that is, by the thickness of the powder layer. It is positioned downward and the powder is placed on the support. As described above, the powder can be placed in a thin layer on the support.

In addition, in order to place the powder on the support in a thin layer, it is also possible to automatically and conveniently use a known three-dimensional object manufacturing apparatus. A three-dimensional object manufacturing apparatus generally includes a recoater (flattening roller) for laminating powder, a movable supply tank for supplying powder onto a support, and a thin layer of powder. and a movable modeling tank for stacking. In the powder additive manufacturing apparatus, the surface of the supply tank can always be slightly raised above the surface of the modeling tank by raising the supply tank, lowering the modeling tank, or both. A recoater can be used to dispose the powder in a thin layer, and by repeatedly moving the recoater, thin layers of the powder can be stacked.

The thickness of the powder layer is not particularly limited and can be appropriately selected depending on the intended purpose.
When the average thickness is 30 μm or more, the strength of the cured product (sintered precursor) of the powder (layer) formed by applying the first modeling liquid and the second modeling liquid to the powder is sufficient. If the particle size is 500 μm or less, the powder formed by applying the first modeling liquid and the second modeling liquid to the powder does not cause problems such as deformation during subsequent processing such as sintering or handling. (layer) improves the dimensional accuracy of the cured product.
The average thickness is not particularly limited and can be measured according to a known method.

The method of applying the first modeling liquid and the second modeling liquid to the powder (layer) is not particularly limited and can be appropriately selected according to the purpose. method, etc.
Among these, the dispenser method is excellent in the amount of droplets, but the application area is narrow. The quantification is poor, and powder scattering occurs due to the spray flow. Therefore, the inkjet method is particularly preferable in the present invention. The ink jet method is preferable in that it has the advantage that the droplets can be quantified better than the spray method, the application area can be widened compared to the dispenser method, and complicated three-dimensional shapes can be formed with high accuracy and efficiency.

In the case of the inkjet method, the modeling liquid application means has a nozzle capable of applying the modeling liquid to the powder layer by the inkjet method. As the nozzle, a nozzle (ejection head) of a known inkjet printer can be suitably used, and an inkjet printer can be suitably used as the modeling liquid application means. In addition, as an inkjet printer, for example, SG7100 manufactured by Ricoh Co., Ltd. is preferably used. Inkjet printers are preferable in that the amount of the modeling liquid that can be dropped from the head portion at one time is large and the application area is wide, so that the speed of application can be increased.
In the present invention, even when an inkjet printer capable of applying the first modeling liquid and the second modeling liquid with high accuracy and high efficiency is used, the first modeling liquid and the second modeling liquid are particles. Since it does not contain solids such as resins and high-viscosity materials such as resins, clogging does not occur in the nozzle or its head, corrosion does not occur, and it is applied to the powder layer ( When discharged), it can efficiently penetrate into the organic material in the powder, so it is excellent in the production efficiency of the three-dimensional model, and moreover, it does not add polymer components such as resin, so it is not expected to increase in volume. It is advantageous in that a cured product with good dimensional accuracy can be obtained easily and efficiently in a short period of time.

<Cured product forming step>
The cured product forming step is a step of curing the powder applied with the first modeling liquid and the second modeling liquid to form a cured product, and is carried out by the cured product forming means.
The term "cured product" means a structure in which the first modeling liquid and the second modeling liquid react and become non-fluid, thereby maintaining a certain three-dimensional shape.

As a method of curing the powder to which the first modeling liquid and the second modeling liquid are applied to form a cured product, for example, a method of curing at room temperature is preferable, specifically, at 25° C. for 24 hours. A method of letting go, etc.
In the method for producing a three-dimensional object of the present invention, curing is performed at room temperature, so that the monomers in the first and second modeling liquids evaporate and fix the non-modeling portions to which the modeling liquid is not applied. can be prevented. In addition, since it has sufficient reactivity even at room temperature, it is possible to prevent the modeling liquid from leaking out in the direction opposite to the stacking direction (Z direction) and lowering the dimensional accuracy in the Z direction.

In the method for producing a three-dimensional object of the present invention, a layered product is formed by sequentially repeating the forming liquid application step and the cured product forming step (hereinafter referred to as a "lamination step"). A “laminate” is a structure in which a plurality of layers of powder having regions to which the modeling liquid is applied are laminated.

In the lamination step, a thin layer, which is a powder layer having regions to which the first modeling liquid and the second modeling liquid are applied, is subjected to a modeling liquid applying step and a cured product forming step in the same manner as described above. , thereby forming regions in the newly deposited layer of powder where the first and second modeling liquids are applied. At this time, the region to which the first modeling liquid and the second modeling liquid generated in the thin layer of the uppermost layered powder are applied is the first modeling liquid in the thin layer of powder existing therebelow. It is continuous with the area to which the liquid and the second modeling liquid are applied. As a result, a region to which the first modeling liquid and the second modeling liquid having the thickness of two powder layers are applied is obtained.
The lamination pitch when laminating the next powder layer on the powder layer is preferably 50 μm or more and 150 μm or less.

<Degreasing process>
The method for producing a three-dimensional object of the present invention preferably includes a degreasing step of heating the green body to remove organic components to obtain a degreased body. A "degreased body" is a three-dimensional object obtained by degreasing an organic component such as a crosslinked resin from a green body. A cured product, a green body, and a degreased body, which are shaped objects before the sintering process described later, are collectively referred to as a "sintered precursor".
In the degreasing step, a degreasing means is used to heat the green body at a temperature higher than the thermal decomposition temperature of the organic component and lower than the melting point or solidus temperature of the material constituting the base material, thereby decomposing the organic component. Remove. Examples of degreasing means include a known sintering furnace and an electric furnace.

<Sintering process>
The sintering step is a step of subjecting the cured product to sintering treatment, and is carried out by a sintering means.
The sintering step is a step of sintering a three-dimensional object (green body) in which the cured products formed in the cured product forming step are laminated. By performing the sintering step, the green body can be densified and integrated into a metal or ceramic molding (sintered body of a three-dimensional model).
The sintering means includes, for example, a known sintering furnace, and may be the same means as the degreasing means described above. Also, the degreasing step and the sintering step may be performed continuously.

<Other processes>
The other steps are not particularly limited and can be appropriately selected depending on the intended purpose.

-Drying process-
The method for producing a three-dimensional object of the present invention preferably has a drying step of drying the green body to remove liquid components remaining in the green body.
The drying step may remove not only liquid components such as organic solvents contained in the green body, but also organic matter. As a drying means, for example, a known dryer, a constant temperature and humidity bath, or the like can be used.

- Surplus powder removal process -
It is preferable that the method for producing a three-dimensional object of the present invention includes a surplus powder removing step of removing surplus powder, which is powder adhering to the cured product, to obtain a green body. A "green body" is a three-dimensional object in which a certain three-dimensional shape is maintained due to the reaction of reactive monomers, resulting in a lack of fluidity, and surplus powder that does not constitute a cured product. It represents a three-dimensional object that has undergone a surplus powder removal step of removing, preferably to which surplus powder is not substantially adhered.
Examples of methods for removing excess powder include a method of removing excess powder from the cured product by air blowing, a method of removing excess powder from the cured product by immersing the cured product in a removing liquid, and the like.

- Post-treatment process -
The method for producing a three-dimensional object of the present invention preferably has a post-treatment step of post-treating the sintered body. The post-treatment process is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a surface protection treatment process and a coating process.

The surface protection treatment step is a step of forming a protective layer on a three-dimensional object (green body) in which the cured product formed in the cured product forming step is laminated. By carrying out this surface protection treatment step, the surface of the cured product can be endowed with such durability that the cured product can be used as it is. Specific examples of the protective layer include a water-resistant layer, a weather-resistant layer, a light-resistant layer, a heat-insulating layer, and a glossy layer. Examples of surface protection treatment means include known surface protection treatment devices such as spray devices and coating devices.

The coating step is a step of coating a three-dimensional molded object (green body) in which the cured products formed in the cured product forming step are laminated. By performing the coating process, the green body can be colored in a desired color. Examples of coating means include known coating devices such as coating devices using sprays, rollers, brushes, and the like.

Here, the flow of modeling in the method of manufacturing a three-dimensionally shaped article of the present invention will be described with reference to FIGS. 1A to 1E. 1A to 1E are schematic diagrams showing an example of the operation of the three-dimensional object manufacturing apparatus used in the three-dimensional object manufacturing method of the present invention.

First, the state in which the first powder layer 30 is formed on the modeling stage of the modeling tank will be described. When forming the next powder layer on the first powder layer 30, as shown in FIG. 1A, the supply stage 23 of the supply tank is raised and the modeling stage 24 of the modeling tank is lowered. At this time, the lowering distance of the modeling stage 24 is set so that the interval (stacking pitch) between the upper surface of the powder layer in the modeling tank 22 and the lower portion (lower tangential portion) of the flattening roller 12 becomes Δt1. Although the interval Δt1 is not particularly limited, it is preferably 50 μm or more and 150 μm or less.

In this embodiment, the flattening roller 12 is arranged so as to form a gap with respect to the upper end surfaces of the supply tank 21 and the modeling tank 22 . Therefore, when the powder 20 is transferred and supplied to the modeling tank 22 to be flattened, the upper surface of the powder layer is positioned higher than the upper end surfaces of the supply tank 21 and the modeling tank 22 . As a result, it is possible to reliably prevent the flattening roller 12 from coming into contact with the upper end surfaces of the supply tank 21 and the modeling tank 22 , thereby reducing damage to the flattening roller 12 . If the surface of the flattening roller 12 is damaged, streaks are generated on the surface of the powder layer 31 (see FIG. 1D) supplied to the modeling tank 22, and the flatness is likely to deteriorate.

Next, as shown in FIG. 1B, the powder 20 placed at a position higher than the upper end surface of the supply tank 21 is moved toward the modeling tank 22 while rotating the flattening roller 12 in the direction of the arrow. 20 is transported and supplied to the modeling tank 22 (powder supply). Further, as shown in FIG. 1C, the flattening roller 12 is moved parallel to the stage surface of the modeling stage 24 of the modeling tank 22, and the powder layer having a predetermined thickness Δt1 on the modeling tank 22 of the modeling stage 24 is formed. 31 is formed (planarization). At this time, the surplus powder 20 that has not been used to form the powder layer 31 drops into the surplus powder receiving tank 29 . After forming the powder layer 31, the flattening roller 12 is moved to the supply tank 21 side and returned (returned) to the initial position (origin position), as shown in FIG. 1D.

Here, the flattening roller 12 can move while maintaining a constant distance from the upper end surfaces of the modeling tank 22 and the supply tank 21 . By being able to move while being kept constant, the flattening roller 12 conveys the powder 20 onto the modeling tank 22, and a uniform thickness h (stacking pitch (corresponding to Δt1) can be formed. Hereinafter, the thickness h of the powder layer 31 and the lamination pitch Δt1 may be described without distinguishing between them, but unless otherwise specified, they have the same thickness and have the same meaning. Alternatively, the thickness h of the powder layer 31 may be obtained by actually measuring it. In this case, it is preferable to use the average value of a plurality of locations.

After that, as shown in FIG. 1E, droplets 10 of the modeling liquid are ejected from the head 52 of the liquid ejection unit, and a layer 30 to which the modeling liquid is applied having a desired shape is laminated on the next powder layer 31 ( molding). Next, the powder layer forming process and the modeling liquid application process described above are repeated to form a new layer 30 to which the modeling liquid is applied, and the layer is laminated. At this time, the new layer 30 to which the modeling liquid is applied and the underlying layer 30 to which the modeling liquid is applied are integrated. After that, the powder layer forming step and the modeling liquid application step are further repeated to complete the laminate.

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

(Preparation example of the first modeling liquid)
After the low-viscosity diluent monomers shown in Table 1 were mixed with a magnetic stirrer for 5 minutes, the high-viscosity bifunctional epoxy monomers shown in Table 1 were mixed with a magnetic stirrer for 30 minutes and sufficiently dissolved. The resulting solution was filtered through a disposable membrane filter (28CP020AS, manufactured by Advantech Co., Ltd.) to prepare first modeling liquids 1 to 3.

表１中の使用した材料の詳細については以下の通りである。
－２官能エポキシ化合物－
・ｊＥＲ８２８：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製、エポキシ当量１８４～１９４ｇ／ｅｑ）
・ＹＸ８０００：ビスフェノールＡ型水添エポキシ樹脂（三菱ケミカル株式会社製、エポキシ当量２０５ｇ／ｅｑ）
・２，２－ビス（４－グリシジルオキシフェニル）プロパン（東京化成工業株式会社製）

Details of the materials used in Table 1 are as follows.
-Bifunctional epoxy compound-
・ jER828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq)
YX8000: Bisphenol A type hydrogenated epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 205 g / eq)
・ 2,2-bis (4-glycidyloxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)

- Monomer for dilution -
・ ED-523L (manufactured by ADEKA Co., Ltd., molecular weight 216.28)

(Preparation example of the second modeling liquid)
After mixing the low-viscosity diluent monomers shown in Table 2 with a magnetic stirrer for 5 minutes, the high-viscosity trifunctional amine monomers shown in Table 2 and the catalyst were mixed with a magnetic stirrer for 30 minutes and sufficiently dissolved. The resulting solution was filtered through a disposable membrane filter (28CP020AS, manufactured by Advantech) to obtain second modeling liquids 1-6.

Next, pot life was measured as follows for each of the obtained second modeling liquids. Table 2 shows the results.

<Method for measuring pot life>
Each second molding liquid and an epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) having an epoxy equivalent of about 190 g/eq were blended to 100 g by equivalent mixing, and the time and temperature to reach the maximum exothermic temperature at 23 ° C. were determined. , a differential scanning calorimeter (DSC) (equipment name: DSC Q2000, manufactured by TA Instruments Co., Ltd.), and the pot life was calculated from the intersection of the tangent lines in the exothermic curve x 0.7 times.

表２中における各材料の詳細については以下の通りである。
－３官能アミンモノマー－
・ＦＸＨ８０９５（株式会社Ｔ＆Ｋ ＴＯＫＡ製）
・８１０６－Ａ（株式会社Ｔ＆Ｋ ＴＯＫＡ製）
・ＦＸＤ－８２１－Ｆ（脂肪族ポリアミン系硬化剤、株式会社Ｔ＆Ｋ ＴＯＫＡ製）
・ポリエーテルトリアミンＴ－４０３（三井化学ファイン株式会社製）

Details of each material in Table 2 are as follows.
-Trifunctional amine monomer-
・FXH8095 (manufactured by T&K TOKA Co., Ltd.)
・8106-A (manufactured by T&K TOKA Co., Ltd.)
・ FXD-821-F (aliphatic polyamine curing agent, manufactured by T&K TOKA Co., Ltd.)
・ Polyether triamine T-403 (manufactured by Mitsui Chemicals Fine Co., Ltd.)

-Bifunctional amine monomer-
・ Polyetherdiamine D-2000 (manufactured by Mitsui Chemicals Fine Co., Ltd.)

- Monomer for dilution -
・ 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight 142.24)
・Norbornene diamine (manufactured by Mitsui Chemicals Fine Co., Ltd., molecular weight 154.26)

-catalyst-
・Dimethylaminopropylamine (manufactured by Mitsui Chemicals Fine Co., Ltd.)

(Examples 1-6 and Comparative Examples 1-2)
<Shaping the green body>
Using AlSi ₃ Mg powder (manufactured by Toyo Aluminum Co., Ltd., Si30Mg-30BB, volume average particle size: 35 μm) as a powder, and the first and second modeling liquids shown in Table 3, green bodies were formed as follows. It was modeled as
(1) First, using the three-dimensional object manufacturing apparatus as shown in FIGS. 1A to 1E, the powder is transferred from the supply side powder storage tank to the modeling side powder storage tank, and the A thin layer of powder with a thickness of 84 μm was formed.
(2) Next, the first modeling liquid and the second modeling liquid were ejected from nozzles of a known inkjet ejection head onto the surface of the formed thin layer of powder. In addition, the ejection area of the first modeling liquid and the second modeling liquid was a rectangular shape of 40 mm×10 mm, and the total amount of ink per voxel was 36 pL at 300 dpi.
(3) Next, the steps (1) and (2) were repeated until a predetermined total average thickness of 3 mm was obtained, and thin layers of the powder were successively laminated to form a laminate. After that, after standing at 25° C. for 24 hours, excess powder was removed to obtain green bodies of Examples 1-6 and Comparative Examples 1-2.

Next, the green bodies of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated for bending strength and Z-direction dimensional accuracy as follows. Table 3 shows the results.

<Bending strength>
The bending strength of each obtained green body was measured as follows. For measuring the bending strength of the green body, a universal testing machine (autograph, model AG-I, manufactured by Shimadzu Corporation) was used, and a load cell for 1 kN and a three-point bending jig were used. In addition, the distance between the fulcrums is 24 mm, the stress when the load point is displaced at a rate of 1 mm / minute is plotted against the amount of strain, the stress at the breaking point is the maximum stress, the bending strength is obtained, and the following criteria are used. evaluated with The green body was used for measurement after removing surplus powder with a spatula. A level of B or higher is a practically usable level.
[Evaluation criteria]
A: Bending strength of 5 MPa or more B: Bending strength of 3 MPa or more and less than 5 MPa C: Bending strength of 1 MPa or more and less than 3 MPa D: Bending strength of less than 1 MPa

<Z direction dimensional accuracy>
For each green body obtained, the dimensional accuracy in the Z direction was measured as follows and evaluated based on the following evaluation criteria. A digital caliper manufactured by Shinwa Measurement Co., Ltd. was used to measure the Z-direction thickness of the green body, and the thickness was measured at three different measurement positions to determine the Z-direction average thickness. A dimensional error (Δd) in the Z direction (laminating direction) was calculated from the following formula. Note that B or higher is a level that can be actually used.
Δd (mm) = Z direction average thickness (mm) - 3 (mm)
[Evaluation criteria]
A: Dimensional error (Δd) is less than 0.3 mm B: Dimensional error (Δd) is 0.3 mm or more and less than 0.5 mm C: Dimensional error (Δd) is 0.5 mm or more

表３の結果から、実施例１および２によると、第２の造形液中の触媒の有無によってグリーン体の曲げ強度および第２の造形液の可使時間に変化は生じないことがわかった。
比較例１は、実施例２の３官能のアミン化合物を２官能のアミン化合物に変更したものであり、その結果、グリーン体の曲げ強度が低下した。
実施例３～４および比較例４は、第２の造形液の可使時間を変化させたものであり、第２の造形液の可使時間が長いほどＺ方向の寸法精度が悪くなることがわかった。
実施例５および６は、２官能のエポキシ化合物の構造を変化させたものであり、２官能のエポキシ化合物の構造はグリーン体のＺ方向の寸法精度と曲げ強度に影響はみられなかった。

From the results in Table 3, it was found that according to Examples 1 and 2, the presence or absence of the catalyst in the second modeling liquid did not change the flexural strength of the green body and the pot life of the second modeling liquid.
In Comparative Example 1, the trifunctional amine compound of Example 2 was changed to a bifunctional amine compound, and as a result, the bending strength of the green body was lowered.
In Examples 3 to 4 and Comparative Example 4, the pot life of the second modeling liquid was changed, and the longer the pot life of the second modeling liquid, the worse the dimensional accuracy in the Z direction. all right.
In Examples 5 and 6, the structure of the bifunctional epoxy compound was changed, and the structure of the bifunctional epoxy compound did not affect the Z-direction dimensional accuracy and bending strength of the green bodies.

Embodiments of the present invention are, for example, as follows.
<1> a first modeling liquid containing an epoxy compound;
a second modeling liquid containing an amine compound having 3 or more amine groups;
has
The modeling liquid set is characterized in that the usable time of the second modeling liquid is 30 minutes or less.
<2> The modeling liquid set according to <1>, wherein the first modeling liquid contains a diluent monomer having a molecular weight of 250 or less.
<3> The modeling liquid set according to <2>, wherein the content of the diluting monomer is 50% by mass or more and 90% by mass or less with respect to the total amount of the first modeling liquid.
<4> The modeling liquid set according to any one of <1> to <3>, wherein the second modeling liquid contains a diluting monomer having a molecular weight of 200 or less.
<5> The modeling liquid set according to <4>, wherein the content of the diluent monomer is 50% by mass or more and 90% by mass or less with respect to the total amount of the second modeling liquid.
<6> A modeling liquid application step of applying the first modeling liquid and the second modeling liquid in the modeling liquid set according to any one of <1> to <5> to the powder, respectively;
A cured product forming step of curing the powder to which the first modeling liquid and the second modeling liquid are applied to form a cured product;
A method for manufacturing a three-dimensional object, comprising:
<7> The method for producing a three-dimensional model according to <6>, wherein the powder applied with the first modeling liquid and the second modeling liquid is cured at room temperature.
<8> The method for producing a three-dimensional object according to any one of <6> to <7>, wherein the powder contains at least one of metal and ceramics.
<9> The method for producing a three-dimensional object according to any one of <6> to <8>, including a surplus powder removing step of removing the powder adhering to the cured product from the cured product.
<10> The method for manufacturing a three-dimensional object according to <9>, further comprising a sintering step of subjecting the cured product to a sintering process after the surplus powder removing step.
<11> Powder and
a first modeling liquid containing an epoxy compound;
a second modeling liquid containing an amine compound having 3 or more amine groups;
has
The three-dimensional modeling kit is characterized in that the usable time of the second modeling liquid is 30 minutes or less.

The modeling liquid set according to any one of <1> to <5>, the method for producing a three-dimensional object according to any one of <6> to <10>, and the three-dimensional modeling according to <11> According to the kit, various conventional problems can be solved and the object of the present invention can be achieved.

Japanese Patent Application Laid-Open No. 2019-59102

Claims (11)

a first modeling liquid containing an epoxy compound;
a second modeling liquid containing an amine compound having 3 or more amine groups;
has
A modeling liquid set, wherein the pot life of the second modeling liquid is 30 minutes or less. The modeling liquid set according to claim 1, wherein the first modeling liquid contains a diluent monomer having a molecular weight of 250 or less. The modeling liquid set according to claim 2, wherein the content of the diluent monomer is 50% by mass or more and 90% by mass or less with respect to the total amount of the first modeling liquid. The modeling liquid set according to any one of claims 1 to 3, wherein the second modeling liquid contains a diluent monomer having a molecular weight of 200 or less. The modeling liquid set according to claim 4, wherein the content of the diluent monomer is 50% by mass or more and 90% by mass or less with respect to the total amount of the second modeling liquid. a modeling liquid application step of applying the first modeling liquid and the second modeling liquid in the modeling liquid set according to any one of claims 1 to 5 to the powder;
A cured product forming step of curing the powder to which the first modeling liquid and the second modeling liquid are applied to form a cured product;
A method of manufacturing a three-dimensional object, comprising: 7. The method of manufacturing a three-dimensional object according to claim 6, wherein the powder to which the first modeling liquid and the second modeling liquid are applied is cured at room temperature. The method for manufacturing a three-dimensional molded article according to any one of claims 6 to 7, wherein the powder contains at least one of metal and ceramics. The method for manufacturing a three-dimensional object according to any one of claims 6 to 8, further comprising a surplus powder removing step of removing the powder adhering to the cured product from the cured product. 10. The method of manufacturing a three-dimensional molded object according to claim 9, comprising a sintering step of performing a sintering treatment on the cured product after the excess powder removing step. powder;
a first modeling liquid containing an epoxy compound;
a second modeling liquid containing an amine compound having 3 or more amine groups;
has
A three-dimensional modeling kit, wherein the usable time of the second modeling liquid is 30 minutes or less.

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