JP6870392B2 - Manufacturing method of three-dimensional model, composition for three-dimensional model, material set for three-dimensional model, and manufacturing equipment for three-dimensional model - Google Patents

Description

The present invention relates to a method for manufacturing a three-dimensional model, a composition for three-dimensional modeling, a material set for three-dimensional modeling, and an apparatus for manufacturing a three-dimensional model.

In recent years, there has been an increasing need for manufacturing three-dimensional objects having complicated shapes. The method of manufacturing a three-dimensional model using a conventional mold has many problems such as there is a limit to the production of a complicated and fine model, the mold is expensive, and it cannot be applied to low-lot production. It was.

On the other hand, laminated modeling (also referred to as additional modeling), which directly manufactures a three-dimensional model while laminating various materials using shape data, is attracting attention as an effective method that can solve these problems.
Examples of these methods include a powder sintering laminating method in which a layer of a powder material is irradiated with a laser beam and laminated while being sintered, and a photocurable resin liquid is irradiated with an ultraviolet laser and laminated while being photocured. Modeling method, heat-melting lamination method in which resin melted by heat is extruded from a nozzle and laminated, material jet method in which a photocurable resin liquid is sprayed from an inkjet head and laminated while photocuring, inkjet on a layer of powder material Many methods have been proposed, such as a binder jet method in which a binder resin liquid is discharged from a head and these are repeated to laminate a powder material.

Among these, the binder jet method using an inkjet head has the advantage of high molding speed, but it uses a powder material, and the powder material has a limit in particle size reduction due to manufacturing and safety reasons. , Precise modeling becomes difficult in principle. Therefore, there is a problem in dealing with higher density, higher strength, and higher precision modeling.

In recent years, a binder jet method using a slurry in which fine powder is dispersed in a liquid has been proposed instead of powder, and it has become possible to apply it to ceramic fine powder, which has been difficult until now. There is.

Since this three-dimensional laminated molding enables delicate processing having an internal structure, it is expected as a new manufacturing method. For example, Patent Documents 1 and 2 report that an amphipathic polymer is used.

However, the removability of removing the non-molded part from the modeled object is not sufficient even with the prior art, and high dimensional accuracy has not yet been achieved due to the modeled object being damaged when the non-modeled part is removed. ..

An object of the present invention is to provide a method for manufacturing a three-dimensional model capable of producing a three-dimensional model having a complicated three-dimensional shape with high strength and high accuracy even when a material having a high melting point and high hardness is used. And.

In order to solve the above problems, the method for producing a three-dimensional model of the present invention forms a three-dimensional model composition layer using a three-dimensional model composition containing a phase-changing substance, particles, and a solvent. A three-dimensional model is formed by repeating the layer forming step and the curing step of curing a predetermined region of the three-dimensional modeling composition layer a plurality of times, and after the modeling, the three-dimensional modeling composition other than the predetermined region is formed. It has a removing step of removing, and the removing step includes a heating step .

According to the present invention, it is possible to provide a method for manufacturing a three-dimensional model capable of producing a three-dimensional model having a complicated three-dimensional shape with high strength and high accuracy even when a material having a high melting point and high hardness is used. Can be done.

It is the schematic which shows an example of the manufacturing apparatus of the three-dimensional object of this invention. It is the schematic which shows another example of the manufacturing apparatus of the three-dimensional object of this invention.

Hereinafter, a method for manufacturing a three-dimensional model, a composition for three-dimensional modeling, a material set for three-dimensional modeling, and an apparatus for manufacturing a three-dimensional model according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

(Composition for 3D modeling)
The three-dimensional modeling composition of the present invention (sometimes also referred to as "first three-dimensional modeling liquid material" or the like) contains a phase-changing substance, particles, and a solvent, and if necessary, other components. Contains material. According to the three-dimensional modeling composition of the present embodiment, it is possible to produce a three-dimensional model having a complicated three-dimensional shape with high strength and high accuracy even when a material having a high melting point and high hardness is used. Further, even when a material having a high melting point and a high hardness is used, a three-dimensional model can be easily and efficiently manufactured.

In particular, when the three-dimensional modeling composition is a slurry containing particles and a solvent, it is preferable to perform layer drying after forming the three-dimensional modeling composition layer, so that not only the molded product but also the non-molded portion is covered. It becomes hard due to the aggregation of particles due to drying, it is difficult to remove the non-molded part from the modeled object, and the modeled object may be lost. On the other hand, in the present invention, since it contains a phase-changing substance, the non-molded portion can be easily removed. Further, since it is possible to prevent deterioration of the fluidity of the particles and improve the transportability, a slurry containing a solvent and particles is preferable as the composition for three-dimensional modeling.

<Phase changing substance>
A phase-changing substance is a solid under normal temperature and pressure (25 ° C., 1 atm), and the state of the substance melts from a solid state to a liquid state due to heat or pressure change, or sublimates directly from a solid state to a gaseous state. Alternatively, it refers to a substance that changes from a solid to a glass state.
Since the composition for three-dimensional modeling contains a phase-changing substance, it becomes possible to easily remove the uncured portion by heat or the like, and the removability is improved, so that the green body that has been seen in the removal step can be easily removed. By reducing chips and the like, it is possible to improve dimensional accuracy while maintaining the strength of the modeled object.

As the phase-changing substance, a substance that is solid at normal temperature and pressure (25 ° C. and 1 atm) and whose phase change occurs between 40 and 230 ° C. is preferably used. In particular, a substance that is solid at the time of laminated molding and causes a phase change in the removal step is preferably used. Further, the phase-changing substance preferably exists as a solid in the slurry.

The phase-changing substance can be appropriately selected depending on the intended purpose, and examples thereof include an amorphous resin, a resin such as a crystalline resin, a wax, a metal compound, and a non-metal compound. Of these, wax, amorphous resin, and crystalline resin are preferable, and wax is more preferable.

Examples of the resin include low melting point resins such as amorphous polyester, crystalline polyester, polyvinyl chloride, and styrene-acrylic resin.
Examples of waxes include petroleum waxes such as paraffin wax and microcrystallin wax, mineral waxes such as Montan wax, animal and vegetable waxes such as carnauba wax and rice wax, and synthetic waxes such as fatty acid ester wax, polyethylene wax and Fishertrobsch wax. Be done.

Examples of the metal compound include low melting point metals such as lead, solder and aluminum, or alloy materials thereof.
As the non-metal compound, for example, sulfur, iodine and the like are used.

In addition, for example, sublimating substances such as camphor and anthracene, and sublimating dye substances such as azo, anthraquinone, quinophthalone, styryl, oxazine, xanthene, methine, and azomethine can be mentioned.

The phase change temperature can be appropriately selected depending on the solvent and other materials, but since the handleability deteriorates when the phase change temperature is changed at a low temperature, the phase change temperature of the phase change substance is preferably 35 ° C. or higher, preferably 50 ° C. or higher. Is more preferable, 75 ° C. or higher is further preferable, and 82 ° C. or higher is particularly preferable. Further, since the removal operation becomes difficult when the temperature changes at a high temperature, the phase change temperature of the phase changing substance is preferably 300 ° C. or lower, more preferably 230 ° C. or lower, further preferably 185 ° C. or lower, further preferably 150 ° C. or lower. 100 ° C. or lower is particularly preferable.

The content of the phase-changing substance is not particularly limited and can be appropriately adjusted according to the intended purpose. For example, with respect to 100 parts by mass of the three-dimensional modeling composition, the lower limit is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, and 1 part by mass. The above is particularly preferable. The upper limit is preferably less than 10 parts by mass, more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less. If the content of the phase-changing substance is less than 0.1 parts by mass, the effect of improving the removability may not be obtained, and if it is 10 parts by mass or more, the hardness of the entire modeled object is lowered at the time of removal. , The accuracy may deteriorate.

Further, the content (mass%) of the phase-changing substance in the three-dimensional modeling composition is preferably equal to or less than the content (mass%) of the particles in the three-dimensional modeling composition. That is, the content (mass%) of the phase-changing substance and the particles in the three-dimensional modeling composition is
It is preferable to satisfy the content of the phase-changing substance ≤ the content of the particles.

<Particles>
The particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic particles such as ceramic particles and metal particles, and resin particles. Of these, inorganic particles are preferable. The particles preferably have biocompatibility.
When the three-dimensional modeling composition contains particles, the hardness of the obtained three-dimensional modeling object can be improved.

<< Ceramic particles >>
The ceramic particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include zirconia particles, alumina particles, silica particles, lithium disilicate particles and the like. These may be used alone or in combination of two or more. Among these, zirconia particles are preferable. When zirconia particles are used as the ceramic particles, yttria, ceria, or the like as a stabilizer may be contained.

The volume average particle diameter of the ceramic particles is preferably less than 5 μm, more preferably less than 1 μm in the three-dimensional modeling composition. When the volume average particle size is less than 5 μm, it is possible to prevent the density of the green sheet or the green body from becoming low, sinter well, and improve the mechanical strength.

The volume average particle diameter of the ceramic particles is not particularly limited, and a known particle size measuring device can be appropriately selected depending on the intended purpose. For example, it can be measured according to a known method using Multisizer III (manufactured by Coulter Counter), FPIA-3000 (manufactured by Sysmex), or the like. The green sheet or green body is a sheet or molded body obtained by injection molding a compound which is a kneaded product of a slurry and a binder.

Since the zirconia particles have an extremely high melting point, it is preferable that the zirconia particles have a small volume average particle size for curing. The ideal volume average particle size is on the order of several tens of nm, and when it is 1 μm or more, many particle gaps remain, which makes it difficult to cure. In normal laminated molding, it is necessary to transport the material containing zirconia particles from the supply tank to the printing tank, but if the size of the particles constituting the material is small, the intermolecular force works strongly and the fluidity becomes high. It tends to get worse significantly. Therefore, in order to improve the fluidity while maintaining the curability, it is preferable to make the slurry so that it can be handled while maintaining the volume average particle diameter on the order of several hundred nm or less.

The content of the stabilizer (yttria, ceria, etc.) in the zirconia particles is preferably 2% by mass or more and 6% by mass or less, and 3% by mass or more and 5% by mass or less, based on the total amount of the three-dimensional modeling composition. Is more preferable. When the content is 2% by mass or more and 6% by mass or less, the function as a stabilizer is sufficiently exhibited, and cracks are less likely to occur during firing.
The content of the stabilizer in the zirconia particles can be measured by, for example, ICP emission spectroscopy.

The monoclinic phase ratio of the zirconia particles is preferably 30% or less, more preferably 20% or less. When the monoclinic phase ratio is 30% or less, the tetragonal phase ratio is appropriate and the mechanical strength is good. The monoclinic phase ratio of the inorganic particles can be measured under predetermined conditions using, for example, an X-ray powder diffractometer.

The method for producing the ceramic particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a thermal decomposition method, a coprecipitation method and a hydrolysis method. Among these, the thermal decomposition method and the coprecipitation method are preferable for the zirconia particles.

As the thermal decomposition method, for example, zirconium oxychloride and an aqueous solution of yttrium chloride are mixed in a predetermined amount, and sodium chloride (or potassium chloride) is added in an amount of 0.1% by mass or more and 1% by mass or less based on the total amount of zirconium oxychloride. , The method of mixing and the like. This mixed solution is instantly dried by a spray drying method or the like to obtain a dry powder.

The instant drying is a method that can be dried within 10 seconds, and the drying temperature is preferably performed in heated air of 200 ° C. or higher. Next, the dry powder is thermally decomposed in air at a temperature of 800 ° C. or higher and 1,200 ° C. or lower to obtain an oxide calcined powder. The oxide calcined powder is pulverized by a wet pulverization method so that the pulverization diameter is 2 μm or less, and washed with water.

The method of washing with water is not particularly limited and may be appropriately selected depending on the intended purpose, but a continuous washing and filtering method using a membrane filter is preferable. By the water washing, the sodium (or potassium) concentration in the inorganic particles is sufficiently washed with water so that the amount converted into an oxide is in the range of 10 ppm or more and 100 ppm or less. Inorganic particles (zirconia powder) can be obtained by drying the slurry after washing with water.

Examples of the coprecipitation method include a method of mixing zirconium oxychloride and an aqueous solution of yttrium chloride. Here, in order to form a metal complex so as to keep the pH at which each hydrate from zirconium oxychloride and yttrium chloride precipitates constant, the molar ratio of sodium sulfate (or potassium sulfate) to zirconia is preferably 0. . Add 3 or more and 0.7 or less, and react at a temperature of 50 ° C or more and 100 ° C or less for several hours or more.

An alkaline aqueous solution such as sodium hydroxide or ammonia is added to this mixed solution with stirring to adjust the pH of the aqueous solution to 8 or more and 10 or less. The obtained co-precipitated hydrate fine particles are thoroughly washed with water, and it is confirmed that the sodium (or potassium) in terms of oxide is in the range of 10 ppm or more and 100 ppm or less.

The hydrate fine particles after washing with water are dehydrated and dried, and calcined in air at a temperature of 800 ° C. or higher and 1,200 ° C. or lower to obtain an oxide calcined powder. Inorganic particles (zirconia powder) can be obtained by wet pulverizing the obtained oxide calcined powder to 2 μm or less and drying it.

<< Metal particles >>
The metal particles can be appropriately selected depending on the intended purpose, and examples thereof include titanium particles, titanium alloy particles, cobalt / chromium alloy particles, and stainless alloy particles. These may be used alone or in combination of two or more. Among these, titanium particles and titanium alloy particles are preferable.

The volume average particle diameter of the metal particles is preferably less than 50 μm, more preferably less than 10 μm. When the volume average particle diameter is less than 50 μm, the particle gap can be reduced and the density of the green sheet or green body can be increased, so that the firing shrinkage at the time of sintering can be reduced and the dimensional accuracy can be improved. The volume average particle size of the metal particles is not particularly limited, and a known particle size measuring device can be appropriately selected depending on the intended purpose. For example, Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (Sysmex). It can be measured according to a known method using (manufactured by the company) or the like.

<< Resin particles >>
The resin particles can be appropriately selected depending on the intended purpose. For example, polyetherketone, polyetheretherketone, polyphenylene sulfide, polyetherimide, liquid crystal polymer, polyphenyl sulphon, polyether sulphon, polyphthalamide, poly. Sulfon, polyamide, polybutylene terephthalate, polycarbonate, polyoxymethylene, polyacetal, polyphenylene ether, ultrahigh molecular weight polyethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile, butadiene, styrene, acrylonitrile, styrene, polyvinyl Examples thereof include particles of alcohol, polymethylmethacrylic, polyethylene teflate, polyvinyl chloride, epoxy resin, melamine resin, polyurethane, phenol resin, unsaturated polyester, silicon resin, and urea resin. These may be used alone or in combination of two or more.
Among these, polyacetal, polyphenylene sulfide, and polyetheretherketone are preferable.

The volume average particle diameter of the resin particles is preferably less than 50 μm, more preferably less than 10 μm. When the volume average particle diameter is less than 50 μm, the particle gap can be reduced and the density of the green sheet or green body can be increased, so that the firing shrinkage at the time of sintering can be reduced and the dimensional accuracy can be improved. The volume average particle size of the resin particles is not particularly limited, and a known particle size measuring device can be appropriately selected depending on the intended purpose. For example, Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (Sysmex). It can be measured according to a known method using (manufactured by the company) or the like.

<< Particle content >>
The content of the particles is not particularly limited and can be appropriately adjusted according to the intended purpose. For example, with respect to 100 parts by mass of the three-dimensional modeling composition, the lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. When the content of the particles is particularly 20 parts by mass or more, the amount of the volatile solvent can be relatively small, and the density of the green sheet or the green body can be increased. In particular, when it is 70 parts by mass or less, the fluidity as a slurry can be improved, and the slurry can be satisfactorily transferred by a doctor blade or the like.

As described above, the content (% by mass) of the particles in the three-dimensional modeling composition is preferably equal to or higher than the content (mass%) of the phase-changing substance in the three-dimensional modeling composition.

(Material set for 3D modeling)
The three-dimensional modeling material set of the present invention (sometimes referred to as a "laminated modeling material set") has a three-dimensional modeling composition and a curing material. The curing material can be changed as appropriate, but is preferably used as a curing liquid, for example. Hereinafter, the curing liquid will be described as an example, but the present invention is not limited to this.

When the three-dimensional modeling composition is a slurry containing a solvent and particles, for example, in ceramics such as zirconia in which the particles require sintering, it is necessary to reduce the particle size in order to ensure curability. In this case as well, deterioration of the fluidity of zirconia can be prevented and transportability can be improved. Therefore, a slurry containing a solvent and particles is preferable as the composition for three-dimensional modeling. Further, by including a coloring material in the curing material and adding the curing material, it is possible to add a color gradation to the modeled object.

When the three-dimensional modeling material set of the present embodiment is used, it can be cured easily and efficiently by applying a curing material to the three-dimensional modeling composition layer formed by using the three-dimensional modeling composition. , A desired three-dimensional model can be produced with high accuracy.
Further, the material set for three-dimensional modeling of the present embodiment may contain a polymerizable monomer, and by irradiating with active energy rays to cure the material set, a desired three-dimensional model can be produced easily, efficiently and with high accuracy. be able to.

In particular, when the three-dimensional modeling composition contains the following organic compound A and the curing material contains the following organic compound B, the organic compound A is applied at the moment when the curing material is applied to the three-dimensional modeling composition layer. And the organic compound B react with each other and cure immediately, which is preferable because molding can be performed with high dimensional accuracy.

Further, when the inkjet method is used, it is possible to add a gradation at the time of modeling by including a coloring material on the curing material side, and further high value addition can be expected.

The material set for three-dimensional modeling in the present embodiment can be suitably used for simple and efficient production of various laminated models and structures, and the method for producing a three-dimensional model and the three-dimensional model described later will be described later. It can be particularly preferably used in a manufacturing apparatus.

<Composition for 3D modeling>
As the three-dimensional modeling composition used in the three-dimensional modeling material set of the present embodiment, the above-mentioned three-dimensional modeling composition of the present embodiment can be used. In addition to the above, the three-dimensional modeling composition of the present embodiment may contain the following organic compound A and a solvent, and may contain other components as necessary. In addition to this, a polymerizable monomer may be contained as a component that is cured by irradiating with active energy rays. When a polymerizable monomer is contained, the polymerizable monomer may be contained in at least one of the three-dimensional modeling composition and the curing material.

<< Organic Compound A >>
The organic compound A is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polyanion binder and a water-soluble resin. The water solubility of the water-soluble resin means that it dissolves in water in an amount of 10% by mass or more at room temperature (25 ° C.).

The organic compound A preferably has an acidic functional group that is reactive with a basic functional group. Examples of the acidic functional group include a carboxyl group and a hydroxyl group.

Examples of the organic compound A having an acidic functional group include modified polyvinyl alcohol and polyacrylic acid. These may be used alone or in combination of two or more. Among these, polyacrylic acid is preferable because it has high reactivity with basic functional groups.

The weight average molecular weight (Mw) of the polyacrylic acid is preferably 400,000 or more, more preferably 400,000 or more and 1,000,000 or less, and particularly preferably 600,000 or more and 800,000 or less. When the weight average molecular weight (Mw) is 400,000 or more, it is easy to construct a crosslinked structure with the organic compound B when the organic compound B (described later) in the curing liquid having a basic functional group is used. , The curing time of the three-dimensional model can be appropriately controlled.

On the other hand, when the weight average molecular weight (Mw) is 1,000,000 or less, the viscosity of the three-dimensional modeling composition (slurry) can be made appropriate, and the variation of particles in the obtained slurry can be suppressed. it can. For the weight average molecular weight (Mw), for example, the molecular weight distribution of the isolated polyacrylic acid can be obtained by a gel permeation chromatography (GPC) method, and the weight average molecular weight can be calculated based on this.

The content of the organic compound A is preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the particles. When the content is 5 parts by mass or more, a sufficient binding effect can be obtained, the dispersed state of the particles in the slurry becomes good, and the dispersion stability can be improved. On the other hand, when the content is 30 parts by mass or less, the viscosity of the slurry can be lowered, and the slurry can be satisfactorily transferred by a doctor blade or the like.

The content of the organic compound A is not particularly limited, and a known thermal analyzer can be appropriately selected depending on the intended purpose. For example, DSC-200 (manufactured by Seiko Instruments Inc.) is used. It can be measured according to the method.

<< Solvent >>
The solvent is not particularly limited as long as the organic compound A can be dissolved, and can be appropriately selected depending on the intended purpose. For example, water, methanol, ethanol, toluene (boiling point: 110.6 ° C.) and the like can be used. Examples include polar solvents. These may be used alone or in combination of two or more. Among these, an organic solvent having a low boiling point is preferable, and an organic solvent having a boiling point of 80 ° C. or less is more preferable, from the viewpoint of improving the productivity of the green sheet or the green body molding.

Examples of the organic solvent having a boiling point of 80 ° C. or lower include ethanol (boiling point: 78.37 ° C.), methanol (boiling point: 64.7 ° C.), ethyl acetate (boiling point: 77.1 ° C.), and acetone (boiling point: 77.1 ° C.). 56 ° C.), methylene chloride (boiling point: 39.6 ° C.) and the like.

<< Polymerizable Monomer >>
The composition for three-dimensional modeling of the present embodiment may contain a polymerizable monomer. When a polymerizable monomer is contained, it is preferable to contain a polymerization initiator, although it depends on the polymerizable monomer used.

Examples of the polymerizable monomer include compounds having one or more unsaturated carbon-carbon bonds, and examples thereof include monofunctional monomers and polyfunctional monomers. Further, examples of the polyfunctional monomer include a bifunctional monomer, a trifunctional monomer, and a trifunctional or higher functional monomer.

The monofunctional monomer is a compound having one unsaturated carbon-carbon bond, for example, acrylamide, N-substituted acrylamide derivative, N, N-di-substituted acrylamide derivative, N-substituted methacrylamide derivative, N, N-. Examples thereof include di-substituted methacrylamide derivatives and other monofunctional monomers. These may be used alone or in combination of two or more.

Examples of the N-substituted acrylamide derivative, N, N-di-substituted acrylamide derivative, N-substituted methacrylamide derivative, or N, N-di-substituted methacrylamide derivative include N, N-dimethylacrylamide (DMAA) and N-. Examples include isopropylacrylamide.

Examples of the other monofunctional monomer include 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), and acryloylmorpholine (ACMO). ), Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, Examples thereof include isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, and urethane (meth) acrylate. These may be used alone or in combination of two or more.

By polymerizing the monofunctional monomer, a water-soluble organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group and the like can be obtained.
The water-soluble organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group and the like is an advantageous constituent component for maintaining the strength of the vascular model.

The content of the monofunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the hydrogel precursor. More preferably 5% by mass or less. When the content is in the range of 1% by mass or more and 10% by mass or less, there is an advantage that the dispersion stability of the layered clay mineral in the hydrogel precursor is maintained and the stretchability of the blood vessel model is improved. The stretchability refers to a property that stretches when the blood vessel model is pulled and does not break.

Examples of the bifunctional monomer include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and neopentyl glycol hydroxypivalic acid. Esterdi (meth) acrylate (MANDA), neopentyl glycol hydroxypivalate di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4-butanediol di (meth) Acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalate neopentyl glycol ester di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxy-modified bisphenol A di (meth) Examples thereof include acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, and methylenebisacrylamide. These may be used alone or in combination of two or more.

Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), triallyl isocyanate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. , Eethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate and the like. These may be used alone or in combination of two or more.

Examples of the trifunctional or higher functional monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and penta (pentaerythritol tetra (meth) acrylate). Examples thereof include meta) acrylate ester and dipentaerythritol hexa (meth) acrylate (DPHA). These may be used alone or in combination of two or more.

<< Polymerization Initiator >>
The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy ray and initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. Is preferable. Further, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the three-dimensional modeling composition or the curing material in order to obtain a sufficient curing rate.

Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

Moreover, as the polymerization initiator, for example, a photopolymerization initiator can be mentioned. As the photopolymerization initiator, any substance that generates radicals by irradiation with light (particularly ultraviolet rays having a wavelength of 220 nm to 400 nm) can be used.
Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone, and Michler ketone. , Phenyl, 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.

Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<< Other ingredients >>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dispersants, plasticizers and sintering aids.
When the three-dimensional modeling composition contains the dispersant, it is preferable in that the dispersibility of the particles can be improved and sedimentation at rest can be suppressed, and the particles are formed when forming a green sheet or a green body. It becomes easy to exist continuously.
Further, it is preferable to include the plasticizer in that cracks are less likely to occur when the green sheet or the green body precursor made of the three-dimensional modeling composition is dried.
The inclusion of the sintering aid is preferable in that it enables sintering at a lower temperature when the obtained laminated model is subjected to a sintering treatment.

<Curing material (curing liquid)>
The curing material of the present embodiment (also referred to as "second three-dimensional modeling liquid material" or the like) may contain an organic compound B that is reactive with the organic compound A, and is further required. Other components such as an aqueous medium may be included depending on the environment. In addition to this, a polymerizable monomer may be contained as a component that is cured by irradiating with active energy rays. When a polymerizable monomer is contained, the polymerizable monomer may be contained in at least one of the three-dimensional modeling composition and the curing material.

As described above, the curing material can be appropriately changed, but it is preferably used as a curing liquid, for example. Hereinafter, the curing liquid will be described as an example, but the present invention is not limited to this.

<< Organic Compound B >>
The organic compound B is not particularly limited as long as it is an organic compound that exhibits reactivity with the organic compound A, and can be appropriately selected depending on the intended purpose. For example, a polycation ink composition, a water-soluble resin, and the like can be mentioned. The water solubility of the water-soluble resin means that it dissolves in water in an amount of 10% by mass or more at room temperature (25 ° C.).

The organic compound B preferably has a basic functional group that is reactive with an acidic functional group. Examples of the basic functional group include an amino group and the like.
Examples of the organic compound B having an amino group include polyethyleneimine and polyvinylpyrrolidone. These may be used alone or in combination of two or more. Among these, polyethyleneimine having a high cation density is preferable from the viewpoint of reactivity with an acidic functional group.

The weight average molecular weight (Mw) of the organic compound B is preferably 1,800 or more, more preferably 1,800 or more and 70,000 or less, and particularly preferably 3,000 or more and 20,000 or less. When the weight average molecular weight (Mw) is 1,800 or more, it is easy to construct a crosslinked structure with the organic compound A having an acidic functional group, and the curing time of the three-dimensional model can be appropriately controlled. On the other hand, when the weight average molecular weight (Mw) is 70,000 or less, the viscosity of the curing material can be appropriately controlled, and stable discharge can be realized. The weight average molecular weight (Mw) can be measured by, for example, a gel permeation chromatography (GPC) method.

The content of the organic compound B is preferably 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the curing material. When the content is 3 parts by mass or more, a crosslinked structure with the organic compound A in the three-dimensional modeling composition can be sufficiently constructed, and the strength of the obtained green sheet or green body can be improved. On the other hand, when the content is 20 parts by mass or less, the viscosity of the curing material can be lowered and the discharge stability can be improved.

The content of the organic compound B is not particularly limited, and a known thermal analyzer can be appropriately selected depending on the intended purpose. For example, DSC-200 (manufactured by Seiko Instruments Inc.) is used. It can be measured according to the method.

<< Aqueous medium >>
Examples of the aqueous medium include water, alcohols such as methanol and ethanol, ethers, ketones, and the like. These may be used alone or in combination of two or more. Of these, water is preferable. In the aqueous medium, the water may contain a small amount of a component other than water such as alcohol.
Examples of the water include ion-exchanged water, ultra-filtered water, reverse osmosis water, pure water such as distilled water, and ultrapure water.

<< Polymerizable Monomer and Polymerization Initiator >>
The curing material of the present embodiment may contain a polymerizable monomer. When a polymerizable monomer is contained, it is preferable to contain a polymerization initiator, although it depends on the polymerizable monomer used. As the polymerizable monomer, the polymerizable monomer in the three-dimensional modeling composition of the present embodiment described above can be used. Further, as the polymerization initiator, the polymerization initiator in the above-mentioned three-dimensional modeling composition of the present embodiment can be used.

<< Other ingredients >>
Examples of the other components include surfactants, preservatives, preservatives, stabilizers, pH adjusters, ultraviolet curable resins and the like. Further high curability can be imparted by irradiating the ultraviolet curable resin with ultraviolet rays.

The ultraviolet curable resin includes a cationically polymerized ultraviolet curable resin that is cured by a polymerization reaction using a cation as an active species and a radical polymerization type ultraviolet curable resin that is cured by a polymerization reaction using a radical as an active species. There is something. In the present embodiment, an ultraviolet curable resin belonging to any of these can be used.

Examples of the radical polymerization type ultraviolet curable resin include acrylic resins and unsaturated polyester resins. Examples of the acrylic resin include polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, and polyether acrylate resin.

Examples of the cationically polymerized ultraviolet curable resin include epoxy resins, oxetane resins, vinyl ether resins, and silicone resins. Examples of the silicone-based resin include acrylic silicone-based resin, polyester silicone resin, epoxy silicone resin, and mercapto silicone resin.

(Manufacturing method of three-dimensional model and equipment for manufacturing three-dimensional model)
In the method for producing a three-dimensional model (also referred to as "laminated model" or the like) of the present invention, a composition layer for three-dimensional modeling is formed by using a composition for three-dimensional modeling containing a phase-changing substance, particles, and a solvent. A three-dimensional model is formed by repeating the layer forming step of forming and the curing step of curing a predetermined region of the three-dimensional modeling composition layer a plurality of times. In addition, it has other steps such as a removal step and a layer drying step as needed.

The three-dimensional modeling product manufacturing apparatus of the present invention uses a three-dimensional modeling composition layer holding means for holding the three-dimensional modeling composition layer and a three-dimensional modeling composition on the three-dimensional modeling composition layer holding means. A layer forming means for forming the three-dimensional modeling composition layer, a curing means for curing a predetermined region of the three-dimensional modeling composition layer formed on the three-dimensional modeling composition layer holding means, and the predetermined region. It has a removing means for removing the three-dimensional modeling composition other than the above, and the three-dimensional modeling composition contains a phase-changing substance, particles, and a solvent. In addition, it has other steps such as removing means and layer drying means as needed.

As the three-dimensional modeling composition in the method for producing a three-dimensional model and the apparatus for producing a three-dimensional model of the present invention, the above-mentioned three-dimensional modeling composition can be preferably used.

The method for producing a three-dimensional object of the present invention can be suitably carried out by using the apparatus for producing a three-dimensional object used in the present invention. The layer forming step can be preferably carried out by the layer forming means, the layer curing step can be preferably carried out by the layer hardening means, and the other steps are more suitable by the other means. Can be carried out.
In addition, the method for manufacturing a three-dimensional model and the apparatus for manufacturing a three-dimensional model of the present invention can be used for manufacturing a dental prosthesis.

<Layer forming step, layer forming means, and composition layer holding means for three-dimensional modeling>
The layer forming step is a step of forming a three-dimensional modeling composition layer using the three-dimensional modeling composition of the present embodiment.
The layer forming means is a means for forming a three-dimensional modeling composition layer using the three-dimensional modeling composition of the present embodiment.
The three-dimensional modeling composition layer holding means is a means for holding the three-dimensional modeling composition layer.

-Composition layer holding means for three-dimensional modeling-
The three-dimensional modeling composition layer holding means (also referred to as a support or the like) is not particularly limited as long as the three-dimensional modeling composition can be placed, and can be appropriately selected depending on the intended purpose. For example, a table having a mounting surface of the three-dimensional modeling composition, a base plate in the apparatus described in FIG. 1 of JP-A-2000-328106, and the like can be mentioned. The surface of the support, that is, the mounting surface on which the three-dimensional modeling composition is placed, may be, for example, a smooth surface, a rough surface, or a flat surface. It may be a curved surface or a curved surface.

-Formation of composition layer for three-dimensional modeling-
The method for arranging the three-dimensional modeling composition on the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a method for arranging the three-dimensional modeling composition (slurry material) in a thin layer, a known counter rotation mechanism (counter roller) used in the selective laser sintering method described in Japanese Patent No. 3607300 is used. A method to be used, a method of spreading the slurry material into a thin layer using a member such as a brush, a roller, or a blade, a method of pressing the surface of the slurry material layer with a pressing member to spread the slurry material into a thin layer, and known powder additive manufacturing. A method using an apparatus and the like are preferably mentioned.

The slurry material can be placed on the support by using the counter rotation mechanism (counter roller), the brush or blade, the pressing member, or the like, for example, as follows. That is, for example, they are arranged in an outer frame (sometimes referred to as a "mold", a "hollow cylinder", a "cylindrical structure", etc.) so as to be able to move up and down while sliding on the inner wall of the outer frame. The slurry material is placed on the support using the counter rotation mechanism (counter roller), the brush, the roller or blade, the pressing member, and the like.

At this time, when a support that can move 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, the three-dimensional modeling. The slurry material is placed on the support so as to be positioned below by the thickness of the composition layer (slurry material layer). As described above, the slurry material can be placed on the support in a thin layer.

Further, in order to place the slurry material on the support in a thin layer, it can be automatically and easily performed by using the known powder additive manufacturing apparatus. In the powder additive manufacturing apparatus, generally, a recorder for laminating the slurry material, a movable supply tank for supplying the slurry material on the support, and the powder material are placed in a thin layer. It is equipped with a movable molding tank for laminating.

In the additive manufacturing device, the surface of the supply tank can always be slightly raised above the surface of the molding tank by raising the supply tank, lowering the molding tank, or both. .. Further, the powder material can be arranged in a thin layer from the supply tank side using the recorder, and the slurry material in the thin layer can be laminated by repeatedly moving the recorder. This powder additive manufacturing device may be replaced as it is for slurry lamination, or the recorder portion may be changed to a doctor blade for sheet molding.

<Curing process and curing means>
The curing step is a step of curing a predetermined region of the three-dimensional modeling composition layer.
The curing means is a means for curing a predetermined region of the three-dimensional modeling composition layer.

As one embodiment of the curing step, the three-dimensional modeling composition contains the above-mentioned organic compound A, and the curing material containing the above-mentioned organic compound B exhibiting reactivity with the organic compound A is used for the three-dimensional modeling. It can be carried out by a step of applying the composition layer to a predetermined area. Since the three-dimensional modeling composition contains the organic compound A, it can be cured by imparting a curing material containing the organic compound B.

As one embodiment of the curing means, the three-dimensional modeling composition contains the above-mentioned organic compound A, and the curing material containing the above-mentioned organic compound B exhibiting reactivity with the organic compound A is used for the three-dimensional modeling. This can be done by means of applying to a predetermined area of the composition layer for use. Since the three-dimensional modeling composition contains the organic compound A, it can be cured by imparting a curing material containing the organic compound B.

Further, another embodiment of the curing step includes a step of applying a curing material to a predetermined region of the three-dimensional modeling composition layer and an active energy ray irradiation step, and the three-dimensional modeling composition. At least one of the product and the curing material contains the above-mentioned polymerizable monomer. It can be cured by containing a polymerizable monomer and irradiating it with active energy rays.

Further, as another embodiment of the curing means, it has a means for applying a curing material to a predetermined region of the three-dimensional modeling composition layer and an active energy ray irradiation means, and the three-dimensional modeling composition. At least one of the product and the curing material contains the above-mentioned polymerizable monomer. It can be cured by containing a polymerizable monomer and irradiating it with active energy rays.

The active energy ray irradiation means may be laser irradiation, electron beam irradiation, or the like, in addition to ultraviolet irradiation.
The laser in the laser irradiation is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a CO ₂ laser, an Nd-YAG laser, a fiber laser, a semiconductor laser and the like can be mentioned. The conditions for the laser irradiation are not particularly limited and may be appropriately selected depending on the intended purpose. For example, when a small laser is used, the powder material cannot be melted, so it is preferable to mix an adhesive (for example, a polyester-based adhesive) to be used in combination and melt the adhesive by laser irradiation for modeling. .. In that case, it is preferable to use _{a CO 2 laser.} As the irradiation conditions, for example, a laser output of 15 W, a wavelength of 10.6 μm, and a beam diameter of about 0.4 mm are preferable.

The electron beam irradiation is performed by irradiating an electron beam with energy that melts the particles in the three-dimensional modeling composition, which can be appropriately selected depending on the intended purpose. When irradiating the electron beam, it is preferable that the three-dimensional modeling composition is handled in a vacuum environment. The conditions for the electron beam irradiation are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the output is 1,500 W, the beam diameter is 0.1 mm, and the degree of vacuum is ^{about 1.0 × 10-5} mbar. Is preferable.

Depending on the mode of curing, the curing is performed not only in the three-dimensional modeling composition layer placed on the three-dimensional modeling composition layer, but also in the three-dimensional modeling composition existing under the three-dimensional modeling composition layer, which is obtained by previously curing. It also occurs with the cured product of the material layer. In this case, a cured product (three-dimensional model) having a thickness equivalent to about two layers of the three-dimensional model composition placed on the three-dimensional model composition layer can be obtained.

The thickness of the three-dimensional modeling composition layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the average thickness per layer is preferably 3 μm or more and 200 μm or less, and 10 μm or more and 100 μm or less. More preferred. When the average thickness is 3 μm or more, the time until the three-dimensional model is obtained can be made appropriate, and problems such as shape loss during processing or handling such as sintering do not occur. On the other hand, when the average thickness is 200 μm or less, sufficient dimensional accuracy of the three-dimensional model can be obtained. The average thickness can be measured according to a known method.

The method of applying the curing material to a predetermined region of the three-dimensional modeling composition layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a liquid discharge means used in a dispenser method, a spray method, an inkjet method, and the like can be mentioned. In the present embodiment, a liquid ejection means (using a vibrating element such as a piezoelectric actuator) used in the inkjet method is used to eject droplets from a plurality of nozzles in that a complicated three-dimensional shape can be formed accurately and efficiently. ) Is preferable.

Further, after the application of the liquid material, irradiation with active energy rays may be carried out depending on the components. When at least one of the three-dimensional modeling composition and the curing material contains a polymerizable monomer, an active energy ray irradiation step is performed.

As the active energy rays, in addition to ultraviolet rays, those capable of imparting energy necessary for advancing the polymerization reaction of polymerizable components in the composition such as electron beams, α rays, β rays, γ rays, and X-rays. It suffices, and is not particularly limited. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

The active energy rays may be applied to the entire three-dimensional modeling composition layer, but at least a predetermined region to which the curing material is applied may be irradiated. Further, the irradiation of the active energy rays may be performed alternately with the application of the curing material, may be performed every time the three-dimensional modeling composition layer is laminated, or may be performed on a plurality of three-dimensional modeling composition layers. You may go all at once.

<Removal process and removal means>
The method for producing a three-dimensional model of the present embodiment may further include a removal step of removing the three-dimensional modeling composition other than the predetermined region after modeling.
The device for producing a three-dimensional model of the present embodiment may further have a removing means for removing the composition for three-dimensional modeling other than the predetermined region after modeling.

The removal step of the present embodiment softens, disintegrates, separates and removes the uncured three-dimensional modeling composition by melting or sublimating the phase-changing substance in the three-dimensional modeling composition, and removes the phase change. Any means that can melt and sublimate the sex substance can be used as appropriate. For example, it is preferable to have a heating step.

Examples of the removing means include a method of heating the modeled object using a hot plate, a high temperature bath, a heat gun, steam, etc., a method of immersing the modeled object in a liquid heated by a water bath, an oil bath, or the like. .. Further, the above-mentioned heating method can be appropriately used such that the melting point and the sublimation point are lowered by carrying out the heating method in an environment where the pressure is reduced to a pressure lower than the normal pressure. For example, it is preferable to have a heating means.

In the removing step, the removability can be evaluated at the same time as the uncured three-dimensional modeling composition is removed. For example, when the uncured material can be easily removed by blow heating with a heat gun, it can be said that the removability is very good. Further, even if the uncured material cannot be easily removed, the uncured material can be removed by scraping the uncured portion with a spatula or the like while heating with a hot plate, for example, and it can be said that the removability is good. .. When the removability is good, a highly accurate three-dimensional model can be obtained.

<Layer drying process and layer drying means>
The layer drying step is a step of drying the obtained slurry layer after the layer forming step and before the curing step, and is performed by the layer drying means. After the curing step, a layer drying step may be further performed.

In the layer drying step, for example, the water (solvent) contained in the three-dimensional modeling composition layer before curing is volatilized. In the layer drying step, the solvent may not be completely removed from the three-dimensional modeling composition layer, and the layer may be in a semi-dried state. Examples of the layer drying means include known dryers. The layer drying step may be natural drying.

The drying time in the layer drying step can be appropriately changed. If the drying time is lengthened, the liquid material applied in the liquid material applying step after the layer drying step is suppressed from seeping out in the lateral direction, and the molding accuracy is improved, but the adhesive force between the layers tends to be weakened. It is in. On the other hand, if the drying time is shortened, particles move between the layers and the adhesive force between the layers becomes stronger, but the liquid material imparted in the liquid material applying step after the layer drying step exudes in the lateral direction. Tends to occur and the molding accuracy tends to deteriorate. This may be appropriately selected depending on the material type to be used.

<Other processes and other means>
Examples of the other steps include a surface protection step and a painting step.
Examples of the other means include surface protection means, painting means, and the like.

-Surface protection process and surface protection means-
The surface protection step is a step of forming a protective layer on the three-dimensional model formed in the liquid material applying step or the sintering step. By performing the surface protection step, the surface of the three-dimensional model can be provided with durability such that the three-dimensional model can be used as it is, for example.
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 the surface protection means include known surface protection treatment devices such as a spray device and a coating device.

-Painting process and painting means-
The painting step is a step of painting the three-dimensional modeled object. By performing this painting step, the three-dimensional model can be colored in a desired color. Examples of the coating means include known coating devices, such as a coating device using a spray, a roller, a brush, or the like.

<Example of manufacturing method and manufacturing equipment for three-dimensional objects>
Here, FIG. 1 shows an example of a three-dimensional model manufacturing apparatus of the present invention. The three-dimensional model manufacturing apparatus shown in FIG. 1 has a modeling side slurry storage tank 1 and a supply side slurry storage tank 2, and each of these slurry storage tanks has a stage 3 that can be moved up and down. A layer made of a slurry material is formed on the stage.

Above the modeling side slurry storage tank 1, an inkjet head 5 for discharging the curing material 4 toward the three-dimensional modeling composition (slurry material) in the slurry storage tank is provided, and further, a supply side slurry storage tank 1 is provided. A leveling mechanism 6 (hereinafter referred to as a recorder) that supplies the slurry material from 2 to the modeling side slurry storage tank 1 and smoothes the surface of the three-dimensional modeling composition layer (slurry material layer) of the modeling side slurry storage tank 1. There is).

The curing material 4 is dropped from the inkjet head 5 onto the slurry material of the modeling side slurry storage tank 1. At this time, the position where the curing material 4 is dropped is determined by the two-dimensional image data (slice data) obtained by slicing the three-dimensional shape to be finally formed into a plurality of plane layers.

After the drawing for one layer is completed, the stage 3 of the supply side slurry storage tank 2 is raised, and the stage 3 of the modeling side slurry storage tank 1 is lowered. The difference slurry material is moved to the modeling side slurry storage tank 1 by the leveling mechanism 6.

In this way, a new slurry material layer is further formed on the previously drawn slurry material layer surface. The thickness of the slurry material layer layer at this time is about several tens of μm or more and 100 μm or less. Drawing based on the slice data of the second layer is further performed on the newly formed slurry material layer, and this series of processes is repeated to obtain a three-dimensional model, which is then heated and dried by a heating means (not shown). Is obtained.

FIG. 2 shows another example of the three-dimensional model manufacturing apparatus of the present invention. The method for producing the three-dimensional model of FIG. 2 is basically the same as that of FIG. 1, but the supply mechanism of the composition for three-dimensional modeling (slurry material) is different. That is, the supply-side slurry storage tank 2 is arranged above the modeling-side slurry storage tank 1. When the drawing of the first layer is completed, the stage 3 of the modeling side slurry storage tank 1 is lowered by a predetermined amount, and the predetermined amount of slurry material is dropped into the modeling side slurry storage tank 1 while the supply side slurry storage tank 2 is moving. A new composition layer for three-dimensional modeling (slurry material layer) is formed. After that, the leveling mechanism 6 compresses the slurry material layer to increase the bulk density and level the height of the slurry material layer uniformly.
According to the three-dimensional model manufacturing apparatus having the configuration shown in FIG. 2, the apparatus can be made more compact than the configuration of FIG. 1 in which two slurry storage tanks are arranged in a plane.

<Three-dimensional model (laminated model)>
The three-dimensional model (laminated model) is manufactured by the method for manufacturing a three-dimensional model and the apparatus for manufacturing a three-dimensional model of the present invention.
The three-dimensional model is preferably an artificial tooth because it can withstand the masticatory force in the oral cavity for a long period of time and has aesthetic properties.
The artificial tooth is an artificial tooth made to restore the function of a natural tooth lost due to caries, trauma, periodontal disease, etc., and includes dental prostheses such as a bridge and a crown. Is done.

According to the method for manufacturing a three-dimensional model and the apparatus for manufacturing a three-dimensional model of the present embodiment, a complex three-dimensional model can be easily, efficiently, and dimensionally accurate by using the composition for three-dimensional modeling of the present embodiment. Can be manufactured well. The three-dimensional model (cured product) thus obtained is not cytotoxic, has sufficient strength, has excellent dimensional accuracy, and can reproduce fine irregularities, curved surfaces, etc., so it has an excellent aesthetic appearance and is of high quality. Yes, it is suitably used for various purposes.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
In the following Examples and Comparative Examples, an example in which a laminated model is manufactured using three-dimensional modeling (laminated modeling) without using a mold is shown, but the present invention is not limited thereto.

(Example 1)
<Synthesis of particle 1>
An 18% by mass yttrium chloride aqueous solution was mixed with a 20% by mass zirconium oxychloride aqueous solution so that the converted molar ratio of yttria and zirconia (yttria: zirconia) was 2.8: 97.2. To this, 0.5% by mass of sodium chloride was added and dissolved with respect to the total amount of zirconium oxychloride.
Then, aluminum chloride was added to the obtained aqueous solution so as to be 0.4% by mass as alumina with respect to the total amount of zirconia and dissolved. This aqueous solution was spray-dried in air at a temperature of 200 ° C. to obtain a dry powder. The obtained dry powder was calcined in air at a temperature of 1,000 ° C. to synthesize a calcined powder. The monoclinic phase ratio of the obtained calcined powder was 8.2%. This calcined powder was pulverized with a wet attritor to obtain a 30% by mass slurry. Next, the obtained slurry was repeatedly diluted and filtered and concentrated with a membrane filter having an opening of 0.5 μm, and washed repeatedly until the electrical conductivity of the filtered water became 20 μS or less to synthesize [Particle 1]. .. The monoclinic phase ratio of the calcined powder was identified as follows.

<< Identification of crystal phase ratio of particle 1 (zirconia particle) >>
The crystal phase of zirconia as the synthesized [particle 1] was identified using an X-ray powder diffractometer (RINT1100 manufactured by Rigaku Electric Co., Ltd.) under the following conditions.

[Measurement condition]
・ Tube: Cu
・ Voltage: 40kV
・ Current: 40mA
・ Starting angle: 3 °
・ End angle: 80 °
・ Scan speed: 0.5 ° / min

The monoclinic phase ratio (%) of zirconia is the reflection peak of 111 planes and 111-1 planes of the monoclinic crystal phase, 111 planes of the tetragonal phase and 111 planes of the cubic crystal phase by powder X-ray diffraction measurement. It was calculated by the following formula (1) from the intensities Im (111), Im (11-1), It (111), and Ic (111).

[Equation (1)]
Monoclinic phase ratio (%) = [Im (111) + Im (11-1)] / [Im (111) + Im (11-1) + It (111) + Ic (111)]

<Preparation of composition 1 (slurry material) for three-dimensional modeling>
[Particle 1] 30 parts by mass, 5 parts by mass of polyacrylic acid (PAA, AS-58 manufactured by Nippon Catalyst Co., Ltd.) having a weight average molecular weight (Mw) of 800,000, 10 parts by mass of benzylbutyl phthalate as a plasticizer, Mix 1.5 parts by mass of a plasticizer (Marialim, AKM-0531 manufactured by Nichiyu Co., Ltd.), 3 parts by mass of paraffin wax (HNP-9 manufactured by Nippon Seiko Co., Ltd.) as a phase-changing substance, and 60 parts by mass of water. [Composition 1 for three-dimensional modeling] was obtained by dispersing the zirconia beads having a diameter of 3 mm in a bead mill for 3 hours.

The volume average particle diameter of the particles in the obtained [three-dimensional modeling composition 1] was measured as follows. The volume average particle diameter of the particles obtained by the measurement was 0.60 μm.

<< Volume average particle size of particles >>
The volume average particle diameter of the particles in [Composition 1 for three-dimensional modeling] was measured using an apparatus name: LA-920 (manufactured by HORIBA, Ltd.). When measuring LA-920, analysis was performed using an application dedicated to LA-920 (Ver.3.32) (manufactured by HORIBA, Ltd.). Specifically, the background was measured after adjusting the optical axis with chloroform. Then, circulation was started, and [three-dimensional modeling composition 1] was added dropwise. After confirming that the transmittance was stable, ultrasonic waves were irradiated under the following conditions. After irradiation, the volume average particle diameter was measured under the condition that the transmittance value was in the range of 70% or more and 95% or less. From the viewpoint of measurement reproducibility of the volume average particle diameter, the measurement was performed under the condition that the transmittance value of LA-920 was 70% or more and 95% or less. In addition, when the transmittance deviated from the above value after ultrasonic irradiation, the measurement was performed again. The dropping amount of [three-dimensional modeling composition 1] was adjusted in order to obtain the value of the transmittance. The measurement and analysis conditions were set as follows.

[Measurement and analysis conditions]
・ Number of data acquisitions: 15 times ・ Relative refractive index: 1.20
・ Circulation: 5
・ Ultrasonic intensity: 7

<Preparation of curing solution 1>
88 parts by mass of water, 12 parts by mass of polyethyleneimine (PEI, SP-200 manufactured by Nippon Catalyst Co., Ltd.) having a weight average molecular weight (Mw) of 10,000, and Tween 20 (manufactured by Tokyo Chemical Industry Co., Ltd.) as a surfactant 0. [Curing solution 1] was prepared by dispersing 5 parts by mass with a homomixer for 30 minutes.

<Making a three-dimensional model (laminated model) 1>
The obtained [three-dimensional modeling composition 1] and [curing liquid 1] are used to form a [three-dimensional modeling material set 1], and the shape printing pattern of the size (length 70 mm x width 12 mm) is used to obtain [three-dimensional modeling]. An object (laminated model) 1] was produced as described in (1) to (4) below.

(1) First, the [three-dimensional modeling composition 1] is transferred from the supply-side powder storage tank to the modeling-side powder storage tank using the three-dimensional modeling product manufacturing apparatus as shown in FIG. 1, and is placed on the support. A three-dimensional modeling composition layer having an average thickness of 100 μm was formed. After the layer was formed, it was dried at room temperature to volatilize the solvent in the three-dimensional modeling composition layer.

(2) Next, [curing liquid 1] is applied (discharged) from a nozzle to the surface of the formed composition layer for three-dimensional modeling using an inkjet printer (SG7100 manufactured by Ricoh Co., Ltd.), and the composition layer for three-dimensional modeling is applied (discharged). Was cured.

(3) Next, the operations of (1) and (2) above were repeated until a predetermined total average thickness of 3 mm was obtained, and the cured three-dimensional modeling composition layers were sequentially laminated to form a cured product. The obtained cured product was dried at room temperature to volatilize the solvent.

(4) Next, a removal step was performed on the molded cured product. As a removal step, the uncured product was melted and sublimated by blow heating with a heat gun, and the uncured product was separated from the surface of the cured product. If the uncured material could not be separated by blowing with a heat gun, the uncured part was scraped off with a spatula or the like while heating with a hot plate.
In this way, [three-dimensional modeled object (laminated modeled object) 1] was produced.

(Example 2)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, three-dimensional modeling is carried out in the same manner as in Example 1 except that the phase-changing substance is changed to Montan wax (Ricowax LP manufactured by Clariant Co., Ltd.). An object (laminated model) was produced.

(Example 3)
In Example 1 <Preparation of composition 1 (slurry material) for three-dimensional modeling>, the same as in Example 1 except that the phase-changing substance was changed to carnauba wax (carnauba wax No. 1 manufactured by Toyo Adre Co., Ltd.). A three-dimensional model (laminated model) was produced.

(Example 4)
In Example 1 <Preparation of composition 1 (slurry material) for three-dimensional modeling>, the same as in Example 1 except that the phase-changing substance was changed to Fisher Trobschwax (FT100 manufactured by Nippon Seiro Co., Ltd.). A three-dimensional model (laminated model) was produced.

(Example 5)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, the three-dimensional shape is the same as in Example 1 except that the phase-changing substance is changed to fatty acid ester wax (WEP5 manufactured by Nippon Seiko Co., Ltd.). A modeled object (laminated modeled object) was produced.

(Example 6)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, the three-dimensional model (three-dimensional model) is the same as in Example 1 except that the phase-changing substance is changed to the following [low molecular weight polyester 1]. Laminated model) was produced.

<Making low molecular weight polyester>
781 parts of bisphenol A propylene oxide 3 mol adduct, 218 parts of terephthalic acid, 48 parts of adipic acid, and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube under normal pressure. After reacting at 230 ° C. for 8 hours and further reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, 65 parts of trimellitic anhydride was placed in a reaction vessel and reacted at 180 ° C. and normal pressure for 4 hours. ] Was obtained.
[Low molecular weight polyester 1] had a number average molecular weight of 4,200, a weight average molecular weight of 8,200, and a Tg of 42 ° C.

(Example 7)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, the three-dimensional model (three-dimensional model) was obtained in the same manner as in Example 1 except that the phase-changing substance was changed to the following [Crystalline polyester 1]. Laminated model) was produced.

<Production of crystalline polyester 1>
1260 g of 1,6-hexaneol, 120 g of ethylene glycol, 1400 g of fumaric acid, 350 g of trimellitic anhydride, 3.5 g of tin octylate, and 1.5 g of hydroquinone were added to a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. In a 5-liter volume four-necked flask equipped with the above, the mixture was reacted at 160 ° C. for 5 hours, then heated to 200 ° C. for 1 hour, and further reacted at 8.3 kPa for 1 hour. Polyester 1] was obtained.
[Crystalline polyester 1] had a melting point of 85 ° C.

(Example 8)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, the three-dimensional model is the same as in Example 1 except that the phase-changing substance is changed to solder (lead-free solder manufactured by Hakuko Co., Ltd.). (Laminated model) was produced.

(Example 9)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, the phase-changing substance was 2-phenoxy-1-amino-4-hydroxyanthracene-9,10-dione (Disperse Red manufactured by Sakai Kogyo Co., Ltd.). A three-dimensional model (laminated model) was produced in the same manner as in Example 1 except that it was changed to 60).

(Example 10)
<Preparation of composition 10 (slurry material) for three-dimensional modeling>
[Particle 2] (Silica particles, Excelica SE-5V manufactured by Tokuyama Co., Ltd.) 30 parts by mass, polyethylene oxide (viscosity average molecular weight: 150,000 to 400,000): 5 parts by mass, and paraffin wax as a phase-changing substance (Japan) HNP-9) manufactured by Seikan Co., Ltd. and 56 parts by mass of water were mixed to obtain [Composition for three-dimensional modeling 10].

<< Volume average particle size of particles >>
When the volume average particle diameter of the particles in the [three-dimensional modeling composition 10] was measured in the same manner as in Example 1, the volume average particle diameter was 4.6 μm.

<Preparation of material 1 for curing>
The active energy ray-curable composition was mixed as follows to obtain [Curing Material 1].

-UV curable resin-
-Phenoxyethyl acrylate: 40.8% by mass
-Diethylene glycol diacrylate: 5% by mass

-Water-soluble monomer-
4-Hydroxybutyl acrylate: 50% by mass

-Polymerization initiator-
-Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 1% by mass
-2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: 2% by mass

-Optical brightener (sensitizer)-
-1,4-Bis- (benzoxazoyl-2-yl) naphthalene: 0.2% by mass

-Surfactant-
-Polyether-modified polydimethylsiloxane: 1% by mass

<Manufacturing of 3D model (laminated model) 10>
The obtained [three-dimensional modeling composition 10] and [curing material 1] were used to form a [three-dimensional modeling material set 10], and the shape printing pattern of the size (length 70 mm x width 12 mm) was used to obtain [three-dimensional modeling]. A modeled object (laminated modeled object) 10] was produced as described in (1) to (4) below.

(1) First, using the three-dimensional model manufacturing apparatus as shown in FIG. 1, the [three-dimensional modeling composition 10 (slurry material)] is transferred from the supply-side powder storage tank to the modeling-side powder storage tank. A three-dimensional modeling composition layer having an average thickness of 100 μm was formed on the support. After the layer was formed, it was dried at room temperature to volatilize the solvent in the three-dimensional modeling composition layer.

(2) Next, [curing material 1] was applied (discharged) from a nozzle to the surface of the formed three-dimensional modeling composition layer using an inkjet printer (SG7100 manufactured by Ricoh Co., Ltd.).

(3) Next, ultraviolet irradiation was performed using a SubZero-LED (365 nm) manufactured by Integration. The condition of ultraviolet irradiation was a light intensity of ^{350 mJ / cm 2.} In this way, ultraviolet irradiation was performed to cure the three-dimensional modeling composition layer.
The above operations (1) to (3) were repeated until a predetermined total average thickness of 3 mm was obtained, and the cured three-dimensional modeling composition layers were sequentially laminated to form a cured product. The obtained cured product was dried at room temperature to volatilize the solvent.

(4) Next, a removal step was performed on the molded cured product. As a removing step, the uncured portion was scraped off with a spatula or the like while heating with a hot plate.
In this way, [three-dimensional modeled object (laminated modeled object) 10] was produced.

(Example 11)
<Preparation of composition 11 (slurry material) for three-dimensional modeling>
[Particle 3] (Polymethylmethacrylic resin particles, MP-100 manufactured by Soken Kagaku Co., Ltd.) 10 parts by mass, polyethylene oxide (viscosity average molecular weight: 150,000 to 400,000) 5 parts by mass, and paraffin wax as a phase-changing substance (HNP-9 manufactured by Nippon Seikan Co., Ltd.) 3 parts by mass and 56 parts by mass of water were mixed to obtain [Composition for three-dimensional modeling 11]. Then, a three-dimensional model (laminated model) was produced in the same manner as in Example 1 except that the [three-dimensional modeling composition 1] was changed to the [three-dimensional modeling composition 11].

(Comparative Example 1)
In <Preparation of composition 1 (slurry material) for three-dimensional modeling> of Example 1, a three-dimensional model (laminated model) was produced in the same manner as in Example 1 except that a phase-changing substance was not used.

(Evaluation)
<Removability>
In the removal step, the removability was visually evaluated based on the following evaluation criteria as to whether or not the uncured material could be separated.

[Evaluation criteria]
◯: By blowing and heating with a heat gun, the uncured material is easily melted and sublimated and separated from the surface of the three-dimensional model.
Δ: By scraping the uncured portion with a spatula or the like while heating with a hot plate, it can be separated from the surface of the three-dimensional model.
X: Cannot be separated even when heated.

<Dimensional accuracy>
Next, the obtained three-dimensional model was visually observed, and the dimensional accuracy was evaluated based on the following evaluation criteria.

[Evaluation criteria]
◯: The surface of the obtained three-dimensional model is smooth and beautiful, and there is no warpage. Δ: The surface of the obtained three-dimensional model is slightly distorted and slightly warped. ×: Obtained The surface of the three-dimensional model is distorted and warped violently.

The compositions of Examples and Comparative Examples and the evaluation results are shown in Table 1 below.
In the table, the numerical value of "content in slurry" indicates mass%.
In the table, * 1 indicates the following.
Phenoxyethyl Acrylate Diethylene Glycol Diacrylate 4-HydroxyButyl Acrylate

1 Modeling side slurry storage tank 2 Supply side slurry storage tank 3 Stage 4 Curing material 5 Inkjet head 6 Leveling mechanism

Japanese Patent No. 5692430 Japanese Patent No. 5831610

Claims (11)

A layer forming step of forming a three-dimensional modeling composition layer using a three-dimensional modeling composition containing a phase-changing substance, particles, and a solvent.
A three-dimensional model is formed by repeating the curing step of curing a predetermined region of the composition layer for three-dimensional modeling a plurality of times.
Further, it has a removing step of removing the three-dimensional modeling composition other than the predetermined region after modeling.
A method for producing a three-dimensional model , wherein the removing step includes a heating step. The three-dimensional modeling composition contains organic compound A and contains.
The curing step to claim 1, characterized in that it comprises a step of applying a curable material containing the organic compound B reactive toward the organic compound A in a predetermined area of the stereolithography composition layer The method for manufacturing a three-dimensional model according to the description. The curing step is
A step of applying a curing material to a predetermined region of the three-dimensional modeling composition layer, and
Has an active energy ray irradiation process,
The method for producing a three-dimensional model according to claim 1 or 2 , wherein at least one of the three-dimensional modeling composition and the curing material contains a polymerizable monomer. A layer forming step of forming a three-dimensional modeling composition layer using a three-dimensional modeling composition containing a phase-changing substance, particles, and a solvent.
A method for manufacturing a three-dimensional model, which forms a three-dimensional model by repeating a curing step of curing a predetermined region of the composition layer for three-dimensional modeling a plurality of times.
The three-dimensional modeling composition contains organic compound A and contains.
The curing step, the curable material containing an organic compound B showing reactivity further comprising the step of imparting a predetermined area of the stereolithography composition layer steric shaped you wherein with respect to the organic compound A How to make things. A layer forming step of forming a three-dimensional modeling composition layer using a three-dimensional modeling composition containing a phase-changing substance, particles, and a solvent.
A method for manufacturing a three-dimensional model, which forms a three-dimensional model by repeating a curing step of curing a predetermined region of the composition layer for three-dimensional modeling a plurality of times.
The curing step is
A step of applying a curing material to a predetermined region of the three-dimensional modeling composition layer, and
Has an active energy ray irradiation process,
Method for producing a steric molded product you characterized in that it contains at least one polymerizable monomer of the stereolithography compositions and the curable material. Further, it has a removing step of removing the three-dimensional modeling composition other than the predetermined region after modeling.
The method for producing a three-dimensional model according to claim 4 or 5 , wherein the removing step includes a heating step. The method for producing a three-dimensional model according to any one of claims 1 to 6, further comprising a layer drying step of drying the composition layer for three-dimensional modeling after the layer forming step and before the curing step. The method for producing a three-dimensional model according to any one of claims 1 to 7 , wherein the phase-changing substance is a solid under normal temperature and pressure, and the phase change occurs between 40 and 230 ° C. .. The method for producing a three-dimensional model according to any one of claims 1 to 8 , wherein the content of the phase-changing substance in the composition for three-dimensional modeling is less than 10% by mass. The content (mass%) of the phase-changing substance and the particles in the three-dimensional modeling composition is
The method for producing a three-dimensional model according to any one of claims 1 to 9 , wherein the content of the phase-changing substance ≤ the content of particles is satisfied. A three-dimensional modeling composition layer holding means for holding a three-dimensional modeling composition layer,
A layer forming means for forming the three-dimensional modeling composition layer on the three-dimensional modeling composition layer holding means by using the three-dimensional modeling composition.
A curing means for curing a predetermined region of the three-dimensional modeling composition layer formed on the three-dimensional modeling composition layer holding means, and a curing means.
It has a removing means for removing the three-dimensional modeling composition other than the predetermined region.
The three-dimensional modeling composition contains a phase-changing substance, particles, and a solvent .
An apparatus for manufacturing a three-dimensional object, wherein the removing means includes a heating means.

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