JP2018089909A - Method of manufacturing three dimensional objects and manufacturing device of three dimensional objects - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing three dimensional objects that can simply and efficiently manufacture three dimensional objects with high density of sintered body, high strength and high esthetics.SOLUTION: This is a method of manufacturing three dimensional objects repeating itself which consists of the layer formation process that forms the first material layer for three dimensional forming by using the first three dimensional forming material, applying process of the second liquid material for three dimensional forming that applies the second liquid material for three dimensional forming on the first field of said first material layer for three dimensional forming which composes the surface of the formed three dimensional objects, and applying process of the third liquid material for three dimensional forming that applies the third liquid material for three dimensional forming on the second field that composes the inside of said three dimensional objects besides said first field.SELECTED DRAWING: Figure 2

Description

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

  The manufacture of dental prosthesis using a rapid prototype modeling apparatus does not require a mold, and has features such as the ability to obtain a prosthesis having a precise structure, and thus has been studied not only in the dental field but also in various fields.

  As a method for modeling the rapid prototype, a method of adding an adhesive to a powder layer or a thin layer of a material similar thereto, a method of modeling a three-dimensional shape by irradiating a liquid layer with a curable light beam, and the like are known. ing.

  For example, it has been proposed to obtain teeth having a configuration closer to natural teeth by a manufacturing method using a modeling apparatus such as a 3D inkjet printer in which colored resin is laminated and cured on a base material (see, for example, Patent Document 1). ).

  It is an object of the present invention to provide a method for producing a three-dimensional structure that can easily and efficiently produce a three-dimensional structure that has a high density and a high strength of a sintered body, and that is more aesthetic. To do.

  The manufacturing method of the three-dimensional modeled object of the present invention as a means for solving the above-mentioned object is modeled with the layer forming step of forming the first three-dimensional modeled material layer using the first three-dimensional modeled material. A second 3D modeling liquid material application step for applying a second 3D modeling liquid material to the first area of the first 3D modeling material layer constituting the surface layer of the 3D model, and the first area A third three-dimensional modeling liquid material application step of applying the third three-dimensional modeling liquid material to the second region constituting the inside of the three-dimensional modeling object other than is repeated a plurality of times.

  ADVANTAGE OF THE INVENTION According to this invention, the density of a sintered compact is high and it is high intensity | strength, The manufacturing method of the three-dimensional molded item which can manufacture a three-dimensional molded item with higher aesthetics simply and efficiently can be provided. .

FIG. 1 is a schematic diagram illustrating an example of a three-dimensional structure. FIG. 2 is a schematic diagram illustrating an example of a manufacturing apparatus for a three-dimensional structure. FIG. 3 is a schematic diagram illustrating another example of a manufacturing apparatus for a three-dimensional structure. FIG. 4 is a photograph showing a state in which the two layers of the three-dimensional structure after sintering are in close contact with each other. FIG. 5 is a photograph showing a state in which voids are generated between two layers of the three-dimensional structure after sintering.

(Manufacturing method of three-dimensional modeled object and manufacturing apparatus of three-dimensional modeled object)
The manufacturing method of the three-dimensional modeled object of the present invention includes the layer forming step of forming the first three-dimensional modeled material layer using the first three-dimensional modeled material, and the first layer constituting the surface layer of the modeled three-dimensional modeled object. The second three-dimensional modeling liquid material application step for applying the second three-dimensional modeling liquid material to the first region of the one three-dimensional modeling material layer, and the inside of the three-dimensional modeled object other than the first region It is preferable to repeat the third three-dimensional modeling liquid material application step for applying the third three-dimensional modeling liquid material to the second region to be performed a plurality of times, and include a removal step, and further perform other steps as necessary. Including.
The manufacturing method of the three-dimensional modeled object of the present invention is based on the knowledge that there is a problem that gradation can hardly be added to an artificial tooth in a manufacturing method using a modeling apparatus such as a conventional 3D inkjet printer. is there.

  Conventionally, since dental prostheses are compared in detail with adjacent teeth, a very high aesthetic requirement is required that a structure close to natural teeth is desired, but the structure and color of the teeth are In addition to various changes due to factors such as race, gender, age, etc., it is very difficult to make a prosthesis with the same structure as natural teeth by conventional methods, and technology such as dentists and dental technicians The fact was that it was supported only by and experience.

  Further, in the conventional method for producing a dental prosthesis, gradation can hardly be added to an artificial tooth. However, if an inkjet method is used, a color material can be contained in a three-dimensional modeling liquid. Coloration is possible, and further high added value can be expected.

  FIG. 1 is a schematic diagram illustrating an example of a tooth configuration. The tooth surface 10 has a structure in which an almost transparent enamel layer covers part or all of the teeth, and the interior 20 includes a dentin layer and a gum. The dentin layer and gingiva are colored, and the color varies greatly depending on race, gender, living environment, age, physical condition and the like. The internal color is slightly reflected on the tooth tip (tooth edge) of the enamel layer, but in the case of Zr ceramics by cutting such as conventional CAD / CAM, it exhibits a very distinct white color, so However, since the color of the adjacent teeth floated clearly, the aesthetics were significantly impaired.

  Therefore, through a build-up process that modified the colored glass on the surface as an additional work by a dental technician or the like, the color closer to natural teeth was reproduced, but the variation was large and the original tooth configuration Since the position of the colored portion is different, it has been pointed out that there is a sense of incongruity with adjacent teeth, and a dental prosthesis having the same configuration as that of a natural tooth is required.

  The manufacturing apparatus of the three-dimensional structure according to the present invention includes a three-dimensional material layer holding unit for holding the first three-dimensional material layer, and a first three-dimensional material using the first three-dimensional material. A second three-dimensional object that provides a second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer that constitutes the surface layer of the three-dimensional modeled object to be modeled and the layer forming means that forms the layer A liquid material applying unit for modeling, a third liquid material applying unit for three-dimensional modeling that applies the third liquid material for three-dimensional modeling to the second region constituting the inside of the three-dimensional modeled object other than the first region, It is preferable to have removal means, and further have other means as necessary.

  As a manufacturing method of the said three-dimensional molded item, it is preferable to manufacture a dental prosthesis.

<Layer forming step and layer forming means>
The layer forming step is a step of forming the first three-dimensional modeling material layer using the first three-dimensional modeling material, and further includes other processing as necessary.
The layer forming means is means for forming the first three-dimensional modeling material layer using the first three-dimensional modeling material, and further includes other members as necessary.
The layer forming step can be preferably performed by the layer forming means.

-First 3D modeling material-
As said 1st three-dimensional modeling material, it is preferable that it is a slurry containing an inorganic particle, the organic compound A, and a solvent, and also it is preferable that it is a liquid state containing the other component as needed.

  The first three-dimensional modeling material may be a powder, but when using inorganic particles that are powders reduced in size to ensure the accuracy of the three-dimensional model, the fluidity is significantly deteriorated, Since it may become impossible to convey, it is preferably in the form of a slurry dispersed in a solvent.

--Inorganic particles--
There is no restriction | limiting in particular as said inorganic particle, According to the objective, it can select suitably, For example, a ceramic particle, a metal particle, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to have biocompatibility.

---- Ceramic particles ---
There is no restriction | limiting in particular as said ceramic particle, According to the objective, it can select suitably, For example, oxide particles, such as a zirconia particle, an alumina particle, a silica particle, a lithium disilicate particle, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, zirconia particles are preferable.

  As the ceramic particles, when zirconia particles are used, yttria, ceria and the like may be contained as a stabilizer.

  The volume average particle size of the ceramic particles is preferably less than 5 μm, and more preferably less than 1 μm. 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 being lowered, to perform good sintering, and to improve the mechanical strength. The volume average particle size of the ceramic particles is not particularly limited, and a known particle size measuring device can be appropriately selected according to the purpose. For example, Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (Sysmex) It can measure according to a well-known method. The green sheet or green body is a sheet or molded body obtained by injection molding a compound that is a kneaded mixture of slurry and binder.

  Since the zirconia particles have an extremely high melting point, they tend not to be sintered unless the volume average particle size is reduced. The ideal volume average particle size is on the order of several tens of nanometers. When the average particle size is 1 μm or more, a large number of particle gaps remain, which may make sintering difficult. In normal additive manufacturing, it is necessary to transport a material containing zirconia particles from a supply tank to a printing tank, but if the size of the particles constituting the material is small, the interparticle force works strongly and the fluidity is high. There is a tendency to get worse. Therefore, in order to improve the fluidity while maintaining the sinterability, it is preferable that the volume average particle size is maintained in the order of several hundreds of nm or less and can be slurried and handled.

  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 preferably 3% by mass or more and 5% by mass or less with respect to the total amount of the first three-dimensional material. The mass% or less 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, for example, by ICP emission spectroscopy.

  The monoclinic phase ratio of the zirconia particles is preferably 30% or less, and more preferably 20% or less. When the monoclinic phase rate is 30% or less, the tetragonal phase rate 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.

As the method for producing the ceramic particles, known methods can be used and can be appropriately selected according to the purpose. Examples thereof include a thermal decomposition method, a coprecipitation method, and a hydrolysis method. Among these, for zirconia particles, a thermal decomposition method, a coprecipitation method, and the like are preferable.
As the pyrolysis method, for example, a predetermined amount of zirconium oxychloride and an aqueous yttrium chloride solution are mixed, 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. And a method of mixing. This mixture is subjected to instantaneous drying such as spray drying to obtain a dry powder.

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

  There is no restriction | limiting in particular as the method of the said water washing, Although it can select suitably according to the objective, The continuous washing filtration method which uses a membrane filter is preferable.

  By the water washing, the water is sufficiently washed so that the sodium (or potassium) concentration in the inorganic particles is in the range of 10 ppm or more and 100 ppm or less as an amount converted to oxide. By drying the slurry after washing with water, inorganic particles (zirconia powder) can be obtained.

  Examples of the coprecipitation method include a method of mixing zirconium oxychloride and an aqueous yttrium chloride solution. Here, in order to form a metal complex so that the pH at which each hydrate from zirconium oxychloride and yttrium chloride precipitates is made constant, the molar ratio of sodium sulfate (or potassium sulfate) to zirconia is Preferably, it is added so as to be 0.3 or more and 0.7 or less, and is reacted 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, and the pH of the aqueous solution is adjusted to 8 or more and 10 or less. The obtained coprecipitated hydrate particles are thoroughly washed with water, and it is confirmed that sodium (or potassium) when converted to an oxide is in the range of 10 ppm to 100 ppm. The hydrate particles after washing with water are dehydrated and dried, and calcined in air at a temperature of 800 ° C. or more and 1,200 ° C. or less to obtain an oxide calcined powder. The obtained oxide calcined powder is wet-pulverized to 2 μm or less and dried to obtain inorganic particles (zirconia powder).

---- Metal particles ---
There is no restriction | limiting in particular as said metal particle, According to the objective, it can select suitably, For example, a titanium particle, a titanium alloy particle, a cobalt / chromium alloy particle, a stainless alloy particle etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, titanium particles and titanium alloy particles are preferable.

  The volume average particle size of the metal particles is preferably less than 50 μm, and more preferably less than 10 μm. When the volume average particle size is less than 50 μm, the gap between particles can be reduced, and the density of the green sheet or green body can be increased, so that the shrinkage during firing 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 according to the purpose. For example, Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (Sysmex). It can measure according to a well-known method.

  As content of the said inorganic particle, 20 mass parts or more and 70 mass parts or less are preferable with respect to 100 mass parts of said 1st three-dimensional modeling materials. When the content is 20 parts by mass or more, the amount of the solvent to be volatilized can be relatively reduced, the density of the green sheet or the green body can be increased, and when the content is 70 parts by mass or less, fluidity as a slurry. It is possible to improve the performance, and the slurry fluid can be transported well by a doctor blade or the like.

--Organic compound A--
There is no restriction | limiting in particular as the said organic compound A, According to the objective, it can select suitably, For example, water-soluble resin etc. are mentioned.

The organic compound A preferably has an acidic functional group 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 individually by 1 type and may use 2 or more types together. Among these, polyacrylic acid is preferred because of its 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, a crosslinking reaction with the organic compound B in the second three-dimensional modeling liquid material or the third three-dimensional modeling liquid material having a basic functional group. Is easy, and the curing time of the three-dimensional structure is appropriate. On the other hand, if the weight average molecular weight (Mw) is 1,000,000 or less, the viscosity of the slurry liquid (slurry liquid) is appropriate, and the dispersion of inorganic particles in the resulting slurry tends not to occur more. is there. The weight average molecular weight (Mw) can be calculated based on the molecular weight distribution of the isolated polyacrylic acid obtained by, for example, a gel permeation chromatography (GPC) method.

  As content of the said organic compound A, 5 to 30 mass parts is preferable with respect to 100 mass parts of said inorganic particles. When the content is 5 parts by mass or more, a binding effect can be sufficiently obtained, the dispersed state of the inorganic particles in the slurry can be improved, 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 transported favorably by a doctor blade or the like. There is no restriction | limiting in particular in content of the said organic compound A, According to the objective, a well-known thermal analyzer can be selected suitably, For example, it is well-known using DSC-200 (made by Seiko Instruments Inc.) etc. It can be measured according to the method.

--Solvent--
The solvent is not particularly limited as long as it can dissolve the organic compound A, and can be appropriately selected according to the purpose. Examples thereof include water, methanol, ethanol, toluene (boiling point: 110.6 ° C.) and the like. Examples include polar solvents. These may be used individually by 1 type and may use 2 or more types together. Among these, an organic solvent having a low boiling point is preferable and an organic solvent having a boiling point of 80 ° C. or lower is more preferable from the viewpoint of improving the productivity of the green sheet or green body modeling.

  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.), acetone (boiling point: 56 ° C.), methylene chloride (boiling point: 39.6 ° C.) and the like.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a dispersing agent, a plasticizer, a sintering aid, etc. are mentioned. When the first three-dimensional modeling material contains the dispersant, it is preferable in terms of improving the dispersibility of the inorganic particles and suppressing sedimentation at rest, and when molding a green sheet or a green body. Inorganic particles easily exist continuously. Moreover, when the said plasticizer is included, when the green sheet or green body precursor which consists of said 1st three-dimensional modeling material dries, it is preferable at the point which a crack does not enter easily. When the sintering aid is included, it is preferable in that sintering can be performed at a lower temperature when the obtained layered product is subjected to a sintering process.

  The first three-dimensional modeling material layer is preferably laminated on a support (three-dimensional modeling material layer holding means).

-Support-
The support (three-dimensional modeling material layer holding means) is not particularly limited as long as it can hold the first three-dimensional modeling material, and can be appropriately selected according to the purpose. Examples include a base having a mounting surface for a modeling material, a base plate in the apparatus shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2000-328106, and the like. The surface of the support, that is, the placement surface on which the first three-dimensional modeling material is placed may be, for example, a smooth surface, a rough surface, or a flat surface. It may be a curved surface.

[Formation of first three-dimensional material layer]
There is no restriction | limiting in particular as a method of arrange | positioning said 1st three-dimensional modeling material on the said support body, Although it can select suitably according to the objective, For example, a 1st three-dimensional modeling material is made into a thin layer. As a method of arrangement, a method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in Japanese Patent No. 3607300, the first three-dimensional modeling material is a brush or roller. , A method of expanding a thin layer using a member such as a blade, a method of pressing the surface of the first three-dimensional modeling material layer using a pressing member to expand it into a thin layer, a method of using a known powder additive manufacturing apparatus, etc. Are preferable.

  To place the first three-dimensional modeling material on the support using the counter rotation mechanism (counter roller), the brush or blade, the pressing member, or the like, for example, the following is performed. be able to. That is, for example, it is disposed in an outer frame (sometimes referred to as “mold”, “hollow cylinder”, “tubular structure”, etc.) so as to be movable up and down while sliding on the inner wall of the outer frame. The first three-dimensional modeling material is placed on the support using the counter rotation mechanism (counter roller), the brush, a roller or a blade, the pressing member, and the like. At this time, when using the support that can move up and down in the outer frame, the support is arranged at a position slightly lower than the upper end opening of the outer frame. The first three-dimensional modeling material is placed on the support body by being positioned below the thickness of the three-dimensional modeling material layer. As described above, the first three-dimensional modeling material can be placed in a thin layer on the support.

  There is no restriction | limiting in particular as thickness of said 1st three-dimensional modeling material layer, Although it can select suitably according to the objective, For example, 3 micrometers-200 micrometers are preferable at the average thickness per layer, 10 micrometers-100 micrometers The following is more preferable. When the average thickness is 3 μm or more, the time until a three-dimensionally shaped product is obtained is appropriate, and problems such as loss of shape do not occur during processing such as sintering or handling. On the other hand, when the average thickness is 200 μm or less, the dimensional accuracy of the three-dimensional structure is sufficiently obtained. The average thickness can be measured according to a known method.

<Second 3D modeling liquid material application step and second 3D modeling liquid material application means>
In the second three-dimensional modeling liquid material application step, the second three-dimensional modeling liquid material is applied to the first region of the first three-dimensional modeling material layer that constitutes the surface layer of the three-dimensional modeling object to be modeled. It is a process and further includes other processes as necessary.
The second three-dimensional modeling liquid material application unit applies the second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer that constitutes the surface layer of the three-dimensional modeling object to be modeled. It is a means and has another member further as needed.
The second three-dimensional modeling liquid material application step can be suitably performed by the second three-dimensional modeling liquid material application unit.

-Second liquid material for 3D modeling-
The second three-dimensional modeling liquid material is not particularly limited as long as the predetermined region of the first three-dimensional modeling material can be cured, and can be appropriately selected according to the purpose. In the first three-dimensional modeling material, It is preferable to include an organic compound B, an aqueous solvent, and an alcohol compound that are reactive with the organic compound A contained, and if necessary, a pH adjuster, a viscosity adjuster, a surfactant, an inorganic pigment, etc. Contains other ingredients. Moreover, an active energy ray hardening-type composition can also be used.

--Organic compound B--
The organic compound B is not particularly limited as long as it is a material reactive with the organic compound A, and can be appropriately selected according to the purpose. The organic compound B is preferably a water-soluble resin.

The organic compound B preferably has a basic functional group reactive with the acidic functional group contained in the organic compound A.
Examples of the basic functional group include an amino group.

  Examples of the organic compound B having an amino group include polyethyleneimine and polyvinylpyrrolidone. These may be used individually by 1 type and may use 2 or more types together. Among these, polyethyleneimine having a high cation density is preferable from the viewpoint of reactivity with acidic functional groups.

  The weight average molecular weight (Mw) of the polyethyleneimine 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 in the first three-dimensional modeling material having an acidic functional group. The curing time is appropriate. On the other hand, when the weight average molecular weight (Mw) is 70,000 or less, the viscosity of the liquid for three-dimensional modeling can be made more appropriate, and stable ejection can be realized. The weight average molecular weight (Mw) can be measured by, for example, a gel permeation chromatography (GPC) method.

  As content of the said organic compound B, 3 mass parts or more and 20 mass parts or less are preferable with respect to 100 mass parts of said 2nd three-dimensional modeling liquid materials. When the content is 3 parts by mass or more, a crosslinked structure with the organic compound A in the first three-dimensional modeling material can be sufficiently constructed, and the strength of the resulting 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 second liquid material for three-dimensional modeling can be lowered, and the discharge stability can be improved. There is no restriction | limiting in particular in content of the said organic compound B, According to the objective, a well-known thermal analyzer can be selected suitably, For example, it is well-known using DSC-200 (made by Seiko Instruments Inc.) etc. It can be measured according to the method.

--Aqueous solvent--
Examples of the aqueous solvent include water, alcohols such as methanol and ethanol, ethers and ketones. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable. In the aqueous medium, the water may contain some amount of components other than water such as the alcohol.

--- Alcohol compound--
There is no restriction | limiting in particular as said alcohol compound, According to the objective, it can select suitably, For example, a diol compound, a glycol ether compound, etc. are mentioned.
As the diol compound, the lower limit value is preferably 8 or more carbon atoms, and the upper limit value is preferably 11 or less carbon atoms.

The effects of the alcohol compound are the following two points.
One is to increase the penetration speed of the second three-dimensional modeling liquid material with respect to the first three-dimensional modeling material layer, shorten the modeling time, and prevent unnecessary diffusion into the modeling tank. The modeling accuracy can be improved.
The other is that when the outer peripheral portion of the tooth is modeled with the second three-dimensional modeling liquid material, the one containing the alcohol compound causes the observation light to be scattered into the bulk, Transparency can be further improved.

  Examples of the diol compound having 8 to 11 carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the glycol ether compound include polyhydric alcohol alkyl ether compounds and polyhydric alcohol aryl ether compounds. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyhydric alcohol alkyl ether compound include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. It is done.
Examples of the polyhydric alcohol aryl ether compound include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  As content of the said alcohol compound, 0.1 mass part or more is preferable as a lower limit with respect to 100 mass parts of 2nd three-dimensional modeling liquid materials, 0.5 mass part or more is more preferable, and as an upper limit Is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

-Other ingredients-
Examples of the other components include coloring materials such as pigments, preservatives, stabilizers, pH adjusters, and viscosity adjusters.

  The method for applying the second three-dimensional modeling liquid material to the first three-dimensional modeling material layer is not particularly limited and can be appropriately selected depending on the purpose. For example, a dispenser method, a spray method And liquid ejecting means used in the ink jet method. In the present invention, a liquid ejecting means used in the ink jet system (which ejects droplets from a plurality of nozzles using a vibration element such as a piezoelectric actuator) can form a complicated three-dimensional shape with high accuracy and efficiency. Is preferred.

  Curing occurs when the liquid for three-dimensional modeling is applied to the first three-dimensional modeling material placed on the thin layer in the step using an inkjet head. In the present invention, at least two or more types of the three-dimensional modeling liquid material are prepared at this time, and first, after the second three-dimensional modeling liquid is discharged and cured on the outer peripheral portion (surface portion) of the three-dimensional modeling object, The third three-dimensional modeling liquid material including a coloring material is discharged and cured. As a result, an artificial tooth having a two-layer structure close to a natural tooth with an arbitrary color inside can be formed by prototyping in a state where the surface layer portion maintains transparency and has no color mixture.

<Third stereoscopic modeling liquid material application step and third stereoscopic modeling liquid material application means>
The third three-dimensional modeling liquid material application step is a step of applying a third three-dimensional modeling liquid material to the second region constituting the inside of the three-dimensional model other than the first region, and further required. Other processing is included accordingly.
The third three-dimensional modeling liquid material applying means is a means for applying a third three-dimensional modeling liquid material to the second region constituting the inside of the three-dimensional modeled object other than the first region, and further required. There are other members accordingly.
The third three-dimensional modeling liquid material application step can be suitably performed by the third three-dimensional modeling liquid material application unit.

  The third 3D modeling liquid material application step is preferably performed after the second 3D modeling liquid material application step.

-Third liquid material for 3D modeling-
The third three-dimensional modeling liquid material is not particularly limited as long as the predetermined region of the first three-dimensional modeling material can be cured, and can be appropriately selected according to the purpose. The second three-dimensional modeling liquid material In the same manner as above, it is preferable to include an organic compound B that is reactive to the organic compound A and an aqueous solvent, and further, an inorganic pigment is dispersed as a coloring material according to a modeling site, and a surface tension is prepared with a surfactant. It is preferable to use those, and further contains other components such as a pH adjusting agent, a viscosity adjusting agent, and an antifungal agent, if necessary. Moreover, an active energy ray hardening-type composition can also be used.

As said organic compound B, the thing similar to the organic compound B in said 2nd three-dimensional modeling liquid material can be used.
As said aqueous solvent, the thing similar to the aqueous solvent in said 2nd three-dimensional modeling liquid material can be used.

---- Color material ---
As the coloring material, an inorganic pigment that can develop color after sintering in the process is suitably used, and in particular, a material called a ceramic pigment is more preferably used. In many cases, the color material is used alone, but two or more color materials can be appropriately mixed and used. However, in view of practical safety of the dental prosthesis, those that do not contain elements that are particularly harmful to the human body (for example, Cd, Se, Pb, etc.) are preferable.
As the coloring material, titanium dioxide can be suitably used.

--- Surfactant ---
Examples of the surfactant include a cationic surfactant and a nonionic surfactant. These may be used individually by 1 type and may use 2 or more types together. The surfactant does not react with the organic compound B, and is a specification for promoting the solidification reaction when contacting with the organic compound A. Among these, nonionic surfactants are preferable.

  In order to discharge the three-dimensional modeling liquid to a correct position with a normal inkjet head, the surface tension of the third three-dimensional modeling liquid material is preferably 30 mN / m or less, and the cationic or nonionic surfactant is used. This is achieved by appropriately adjusting the content.

  Although it varies depending on the type of the surfactant, the content of the cationic surfactant or nonionic surfactant is 0.1% by mass or more with respect to the total amount of the third three-dimensional liquid material. Achieved.

  As the surfactant, a high-molecular-weight nonionic surfactant (hereinafter sometimes referred to as “dispersing agent polymer”) is used for the three-dimensional modeling liquid to which the inorganic pigment is added in addition to the above action. Specifically, the nonionic surfactant is preferably a dispersant polymer having a volume average molecular weight of 3,000 or more and less than 12,000, and particularly preferably has a volume average molecular weight of 3,000 or more and 10,000 or less. It is preferable. As a reason for this, when a dispersant polymer that satisfies the above conditions is used, it is considered that the inorganic pigment molecules form a weak aggregated state (soft cake state) in which the distances between the inorganic pigment molecules are maintained due to the steric hindrance of the dispersant polymer. It is done.

  As a method for applying the third three-dimensional modeling liquid material to the first three-dimensional modeling material layer, the second three-dimensional modeling liquid material may be applied to the first three-dimensional modeling material layer. The same method can be used.

<Removal process>
The removal step is a step of removing an uncured portion of the first three-dimensional structure material by immersing the three-dimensional structure in a fourth three-dimensional structure liquid material after forming the three-dimensional structure. Other processes are included depending on
The removing means is a means for removing an uncured portion of the first three-dimensional structure material by immersing the three-dimensional structure in a fourth three-dimensional structure liquid material after forming the three-dimensional structure, and further necessary Depending on the, other members are included.
The removing step can be preferably performed by the removing unit.

There is no restriction | limiting in particular as said immersion, According to the objective, immersion time, immersion temperature, etc. can be selected suitably.
The immersion time is preferably 5 seconds or more and 60 minutes or less.
The immersion temperature is preferably 0 ° C. or higher and 100 ° C. or lower under normal pressure.

-Fourth liquid material for 3D modeling-
As the fourth liquid material for three-dimensional modeling, a material that acts on an uncured portion of the three-dimensional object, removes the excess first three-dimensional material, and efficiently takes out the three-dimensional object is used.

The fourth liquid material for three-dimensional modeling preferably contains an aqueous solvent.
Examples of the aqueous solvent include water, alcohols such as methanol and ethanol, ethers and ketones. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable. In addition, in order to accelerate | stimulate the removability of the said molded object uncured site | part, you may contain components other than water, such as surfactant, in the said aqueous medium.

  In the present invention, the contents of the second, third, and fourth three-dimensional modeling liquid materials are typically exemplified. However, according to the case where a plurality of colors are used or other functions are added, the fifth In the case of using the above three-dimensional modeling liquid material or a material that reacts with the first three-dimensional modeling material, a solid material such as resin powder can be used.

<Other steps and other means>
Examples of the other processes include an active energy ray irradiation process, a layer drying process, a sintering process, a surface protection process, and a coating process.
Examples of the other means include active energy ray irradiation means, layer drying means, sintering means, surface protection means, and coating means.
The other steps can be preferably performed by other means.

<< Layer drying step and layer drying means >>
In the layer drying step, after the layer forming step, the obtained first three-dimensional modeling material layer is obtained before the second three-dimensional modeling liquid material application step and the third three-dimensional modeling liquid material application step. This is a step of drying, and is performed by layer drying means. Of course, you may dry naturally. In the layer drying step, moisture (solvent) contained in the first three-dimensional modeling material layer can be volatilized. In addition, as the said layer drying process, it is preferable to make it a semi-dry state, without removing all the solvents from the 1st three-dimensional modeling material layer. Examples of the layer drying means include a known dryer.

  The drying time in the layer drying step can be changed as appropriate. If the drying time is lengthened, the lateral exudation of each three-dimensional modeling liquid material applied in each three-dimensional modeling liquid material application step after the layer drying step is suppressed, and the modeling accuracy is improved. There is a tendency that the adhesive strength between the layers is weakened. On the other hand, if the drying time is shortened, particle movement between layers occurs, and the adhesion between the layers becomes stronger, but each three-dimensional modeling liquid applied in each three-dimensional modeling liquid material application step after the layer drying step The material oozes out in the lateral direction, and the molding accuracy tends to deteriorate. What is necessary is just to select this suitably with the material kind to be used.

<< Sintering process and sintering means >>
The sintering step is a step of sintering a three-dimensional structure (laminated structure) formed by sequentially repeating the layer forming step and each of the three-dimensional modeling liquid material application steps, and is performed by a sintering means. By performing the sintering step, the cured product can be formed into an integrated molded body (sintered body).

Examples of the sintering means include a known sintering furnace.
In addition to the method of sintering after obtaining the cured product as described above, there is a method of sintering at the stage of laminating the first three-dimensional modeling material. In the method of sintering in the step of laminating the first three-dimensional modeling material, the first three-dimensional modeling material layer is subjected to either laser irradiation or electron beam irradiation, and the first three-dimensional modeling material layer Is a method of sintering.

<< surface protection process and surface protection means >>
The surface protection step is a step of forming a protective layer on the three-dimensional object formed in the three-dimensional modeling liquid material application step or the sintering step. By performing the surface protection step, the surface of the three-dimensional object can be provided with durability or the like that allows the three-dimensional object to 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 spray devices and coating devices.

<< Painting process and painting means >>
The painting step is a step of painting the three-dimensional structure. By performing this coating process, the three-dimensional model can be colored in a desired color. As the coating means, a known coating apparatus, for example, a known coating apparatus such as a spray, a roller, a curtain, a brush, or a dipping can be suitably used.

The surface layer of the three-dimensional structure corresponds to the enamel layer in natural teeth, but as is apparent from FIG. 1, the shape is not plate-like but varies depending on the part, and the influence of various constituent factors. receive.
Basically, factors such as the refractive index, thickness, and light diffusivity inside and outside the surface layer are considered to form transparency, and in particular, the surface layer part hardly acts in light diffusivity, but the inside is almost omnidirectional. Diffuse reflection over the entire area.
Therefore, in the natural tooth, the transmittance is often higher in the surface layer than in the natural tooth.
The transmittance of the surface layer of the three-dimensional structure is preferably higher than the transmittance inside the three-dimensional structure.
The transmittance can be measured, for example, using a dental colorimeter crystal eye (manufactured by Olympus Corporation).

  Here, FIG. 2 is a schematic diagram illustrating an example of a manufacturing apparatus for a three-dimensional structure. 2 has a modeling-side three-dimensional modeling material storage tank 1 and a supply-side three-dimensional modeling material storage tank 2, and these three-dimensional modeling material storage tanks are movable stages up and down, respectively. 3 and a layer made of the first three-dimensional modeling material is formed on the stage.

  On the modeling side three-dimensional modeling material storage tank 1, the three-dimensional modeling liquid material (second three-dimensional modeling liquid material, or the third modeling material is directed toward the first three-dimensional modeling material in the three-dimensional modeling material storage tank. A liquid material for three-dimensional modeling) 4 and an inkjet head 5 for discharging the liquid, and the first three-dimensional modeling material is supplied from the supply-side three-dimensional modeling material storage tank 2 to the modeling-side three-dimensional modeling material storage tank 1; A leveling mechanism 6 (hereinafter sometimes referred to as a recoater) that levels the surface of the first three-dimensional modeling material layer of the side three-dimensional modeling material storage tank 1 is provided.

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

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

  In this way, a new first three-dimensional modeling material layer is formed on the first three-dimensional modeling material layer surface drawn in advance. At this time, the thickness of the first one-dimensional modeling material layer is about several tens μm to 100 μm. On the newly formed first three-dimensional modeling material layer, drawing based on the slice data of the second layer is further performed, this series of processes is repeated to obtain a three-dimensional modeled object, and heat drying by a heating means (not shown) By doing so, a three-dimensional model is obtained.

  FIG. 3 is a schematic diagram illustrating another example of a manufacturing apparatus for a three-dimensional structure. The manufacturing method of the three-dimensional structure used in the three-dimensional structure manufacturing apparatus in FIG. 3 is the same as that in FIG. 2 in principle, but the first three-dimensional material supply mechanism is different. That is, the supply-side three-dimensional modeling material storage tank 2 is arranged above the modeling-side three-dimensional modeling material storage tank 1. When the drawing of the first layer is finished, the stage 3 of the modeling-side three-dimensional modeling material storage tank 1 is lowered by a predetermined amount, and the supply-side three-dimensional modeling material storage tank 2 is moved to model a predetermined amount of the first three-dimensional modeling material. It is dropped into the side three-dimensional modeling material storage tank 1 to form a new first three-dimensional modeling material layer. Thereafter, the leveling mechanism 6 compresses the first three-dimensional modeling material layer to increase the bulk density and uniformly level the height of the first three-dimensional modeling material layer.

  According to the three-dimensional structure manufacturing apparatus having the configuration shown in FIG. 3, the apparatus can be made more compact than the configuration of FIG. 2 in which two three-dimensional material storage tanks are arranged in a plane.

(3D objects)
The said three-dimensional molded item (laminated molded item) is manufactured by the manufacturing method of the three-dimensional molded item of this 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 aesthetics.

The artificial tooth is an artificial tooth made to recover its function in place of a natural tooth lost due to caries, trauma, periodontal disease, etc., and includes dental prostheses such as bridges and crowns It is.
According to the manufacturing method of the three-dimensional modeled object of the present invention and the manufacturing apparatus of the three-dimensional modeled object of the present invention, the modeled object having a complicated three-dimensional shape can be easily and efficiently produced without loss of shape before sintering or the like. It can be manufactured with high dimensional accuracy. The three-dimensional model (cured product) obtained in this way has no cytotoxicity, has sufficient strength, has excellent dimensional accuracy, and can reproduce fine irregularities and curved surfaces, so it has excellent aesthetic appearance and high quality. Yes, it is suitable for various uses.

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

<Preparation of the first three-dimensional material>
Zirconia particles (trade name: TZ-3Y-E, Tosoh Corporation) 30.0 parts by mass, polyacrylic acid having a weight average molecular weight (Mw) of 800,000 (PAA, manufactured by Nippon Shokubai Co., Ltd., AS-58) 5.0 parts by mass, 10.0 parts by mass of benzylbutyl phthalate as a plasticizer, 1.5 parts by mass of a ceramic dispersant (polymer polycarboxylic acid, Mariarim, manufactured by NOF Corporation, AKM-053), and ethanol 60.0 parts by mass (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed, and a bead mill dispersion was performed with zirconia beads having a diameter of 3 mm for 3 hours to obtain a slurry-like first three-dimensional modeling material. The composition is shown in Table 1 below.
The volume average particle diameter of the zirconia particles in the obtained first three-dimensional modeling material was measured as follows.
-Volume average particle diameter of zirconia particles-
The volume average particle diameter of the zirconia particles in the first three-dimensional modeling material 1 was measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (Horiba, Ltd.). Measurement and analysis conditions were set as follows.
[Measurement and analysis conditions]
・ Data acquisition frequency: 15 times ・ Relative refractive index: 1.20
・ Circulation: 5
・ Ultrasonic intensity: 7
The volume average particle diameter of the zirconia particles in the first three-dimensional modeling material obtained by the above method was 0.2 μm.

(Preparation example of stock solution of liquid material for 3D modeling)
<Preparation of stock solution of liquid material for three-dimensional modeling>
88.0 parts by mass of water, 12.0 parts by mass of polyethyleneimine (PEI, Nippon Shokubai Co., Ltd., SP-200) having a weight average molecular weight (Mw) of 10,000, and Tween 20 (Tokyo Kasei) as a surfactant 0.5 parts by mass) (manufactured by Kogyo Co., Ltd.) was dispersed for 30 minutes using a homomixer to prepare a stock solution of a three-dimensional modeling liquid material. The composition is shown in Table 2 below.

(Preparation example 1 of second liquid material for three-dimensional modeling)
<Preparation of the second liquid material 1 for three-dimensional modeling>
Magnet stirrer obtained by adding 5.0 parts by mass of 2-ethyl-1,3-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an alcohol compound to 95.0 parts by mass of the liquid material stock solution 1 for three-dimensional modeling Was stirred for 20 minutes to obtain a second liquid material 1 for three-dimensional modeling.

(Second preparation example of liquid material for three-dimensional modeling 2)
<Preparation of the second three-dimensional modeling liquid material 2>
In Preparation Example 1 of the second three-dimensional modeling liquid material, 2-ethyl-1,3-hexanediol (Tokyo Kasei Kogyo Co., Ltd.) is used as the alcohol compound with respect to 99.5 parts by mass of the stock solution 1 of the three-dimensional modeling liquid material. Except for adding 0.5 parts by mass), a second three-dimensional modeling liquid material 2 was obtained in the same manner as in Preparation Example 1 of the second three-dimensional modeling liquid material.

(Preparation example 3 of the second liquid material for three-dimensional modeling)
<Preparation of the second three-dimensional modeling liquid material 3>
In Preparation Example 1 of the second three-dimensional modeling liquid material, ethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.15 as an alcohol compound with respect to 99.85 parts by mass of the three-dimensional modeling liquid material stock solution 1 A second liquid material for three-dimensional modeling 3 was obtained in the same manner as in Preparation Example 1 of the second liquid material for three-dimensional modeling, except that a mass part was added.

(Preparation example 4 of the second liquid material for three-dimensional modeling)
<Preparation of the second liquid material 4 for three-dimensional modeling>
With respect to 91.5 parts by mass of the stock solution 1 of the three-dimensional modeling liquid material, 5.0 parts by mass of 2-ethyl-1,3-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an alcohol compound and oxidation as a white pigment What added 3.0 mass parts of titanium pigments (trade name: GTR-100, manufactured by Sakai Chemical Industry Co., Ltd.) and 0.5 parts by mass of dispersant polymer (trade name: Aron A305L, manufactured by Toagosei Co., Ltd.) The bead mill was dispersed for 3 hours using zirconia beads having a diameter of 3 mm to obtain a second liquid material 4 for three-dimensional modeling.

(Example 5 of preparation of second liquid material for three-dimensional modeling)
<Preparation of the second liquid material 5 for three-dimensional modeling>
In Preparation Example 4 of the second three-dimensional modeling liquid material, 2-ethyl-1,3-hexanediol (Tokyo Kasei Kogyo Co., Ltd.) is used as the alcohol compound with respect to 84.5 parts by mass of the stock solution 1 of the three-dimensional modeling liquid material. 2D solid modeling except that 12.0 parts by mass was added to a mechanical stirrer (Primics Co., Ltd., Planetary Mixer HIVIS DISPER MIX Model 3D-2) in a multi-step process for a total of 65 minutes. A second liquid material 5 for three-dimensional modeling was obtained in the same manner as in Preparation Example 4 for liquid material for use.

  The compositions of the obtained second three-dimensional modeling liquid materials 1 to 5 are shown in Table 3 below.

(Preparation Example 1 of a third liquid material for three-dimensional modeling)
<Preparation of the third liquid material 1 for three-dimensional modeling>
Zr-V pigment 1 (trade name: Z-300, manufactured by Nikko Pigment Industries Co., Ltd.) 5.0 parts by mass as an inorganic pigment with respect to 94.5 parts by mass of the stock solution of the three-dimensional modeling liquid material, and Disperse polymer with 0.5 parts by mass of Aron A305L (manufactured by Toagosei Co., Ltd.) as a dispersant polymer was dispersed in a bead mill for 3 hours using zirconia beads with a diameter of 3 mm for third solid modeling A liquid material 1 was obtained.

(Preparation example 2 of third liquid material for three-dimensional modeling)
<Preparation of the third three-dimensional modeling liquid material 2>
In the third preparation example 1 of the three-dimensional modeling liquid material, except that the Zr-V pigment 1 is changed to a Zr-V pigment 2 (trade name: Z-500, manufactured by Nikko Pigment Industries Co., Ltd.) In the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 2 was obtained.

(Preparation example 3 of the third liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 3>
In the preparation example 1 of the third liquid material for three-dimensional modeling, except that the Zr-V pigment 1 is changed to a Zr-Si-Pr pigment (trade name: P-40, manufactured by Nikko Pigment Industries Co., Ltd.) In the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 3 was obtained.

(Preparation example 4 of third liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 4>
The third example except that the Zr-V pigment 1 was changed to a Sn-V pigment (trade name: M-600, manufactured by Nikko Pigment Industries Co., Ltd.) in Preparation Example 1 of the third liquid material for three-dimensional modeling. In the same manner as in Preparation Example 1 of the three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 4 was obtained.

(Third example of preparation of liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 5>
In Preparation Example 1 of the third liquid material for three-dimensional modeling, the Zr-V pigment 1 was changed to a Fe-Cr-Zn-Al pigment 1 (trade name: M-13, manufactured by Nikko Pigment Industries Co., Ltd.). Except for the above, in the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 5 was obtained.

(Third preparation example of liquid material for three-dimensional modeling 6)
<Preparation of the third liquid material 6 for three-dimensional modeling>
In Preparation Example 1 of the third three-dimensional modeling liquid material, the Zr-V pigment 1 was changed to an Fe-Cr-Zn-Al pigment 2 (trade name: M-309, manufactured by Nikko Pigment Industries Co., Ltd.). Otherwise, a third liquid material for three-dimensional modeling 6 was obtained in the same manner as in Preparation Example 1 of the third liquid material for three-dimensional modeling.

(Example 7 of preparation of third liquid material for three-dimensional modeling)
<Preparation of the third three-dimensional modeling liquid material 7>
In Preparation Example 1 of the third liquid material for three-dimensional modeling, except that the Zr-V pigment 1 is changed to a Sn-Ca-Si-Cr pigment (trade name: SP-72, manufactured by Nikko Pigment Industries Co., Ltd.) Obtained the 3rd three-dimensional modeling liquid material 7 in the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material.

(Example 8 of preparation of third three-dimensional modeling liquid material)
<Preparation of the third three-dimensional modeling liquid material 8>
Except for changing the Zr-V pigment 1 to Sn-Cr pigment (trade name: M-797, manufactured by Nikko Pigment Industries Co., Ltd.) In the same manner as in Preparation Example 1 of the three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 8 was obtained.

(Third preparation example 9 of liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 9>
Except that the Zr-V pigment 1 was changed to a Co-Si pigment (trade name: No. 10, manufactured by Nissho Pigment Industries Co., Ltd.) in Preparation Example 1 of the third three-dimensional modeling liquid material, the third In the same manner as in Preparation Example 1 of the three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 9 was obtained.

(Third example of preparation of liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 10>
In Preparation Example 1 of the third liquid material for three-dimensional modeling, the Zr-V pigment 1 is changed to a Cr-Al pigment (trade name: M-55, manufactured by Nikko Pigment Industries Co., Ltd.) A trade name: Aron A305L is trade name: Aron A6114 (Toagosei Co., Ltd., weight average molecular weight (Mw: 10,000)) In the same manner as 1, a third three-dimensional modeling liquid material 10 was obtained.

(Third example of preparation of liquid material for three-dimensional modeling 11)
<Preparation of the third three-dimensional modeling liquid material 11>
In Preparation Example 1 of the third liquid material for three-dimensional modeling, the Zr-V pigment 1 is changed to a Fe-Cr pigment (trade name: M-252, manufactured by Nissho Pigment Industries Co., Ltd.) A trade name: Aron A305L, trade name: Aron A210 (Toagosei Co., Ltd., weight average molecular weight (Mw): 3,000) Except for changing to 0.5 parts by mass, preparation of the third liquid material for three-dimensional modeling In the same manner as in Example 1, a third three-dimensional modeling liquid material 11 was obtained.

(Third example of preparation of liquid material for three-dimensional modeling 12)
<Preparation of third three-dimensional modeling liquid material 12>
Except that the Zr-V pigment 1 was changed to a Sn-Sb pigment (trade name: B-83, manufactured by Nikko Pigment Industries Co., Ltd.) in Preparation Example 1 of the third three-dimensional modeling liquid material, the third In the same manner as in Preparation Example 1 of the three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 12 was obtained.

(Example 13 of preparation of liquid material for third three-dimensional modeling)
<Preparation of third solid modeling liquid material 13>
In the preparation example 1 of the third three-dimensional modeling liquid material, except that the Zr-V pigment 1 is changed to an Fe-Cr-Zn-Mn pigment (trade name: M-2, manufactured by Nikko Pigment Industries Co., Ltd.) Obtained the 3rd three-dimensional modeling liquid material 13 like preparation example 1 of the 3rd three-dimensional modeling liquid material.

(Example 14 of preparing third liquid material for three-dimensional modeling)
<Preparation of third three-dimensional modeling liquid material 14>
In the preparation example 1 of the third liquid material for three-dimensional modeling, except that the Zr-V pigment 1 is changed to a Zr-Si-Fe pigment (trade name: M-663, manufactured by Nikko Pigment Industries, Ltd.) In the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material, a third three-dimensional modeling liquid material 14 was obtained.

(Example 15 of preparation of third solid modeling liquid material 15)
<Preparation of third solid modeling liquid material 15>
Except for changing the Zr-V pigment 1 to a Cr-Fe-Co-Ni pigment (trade name: M-800, manufactured by Nikko Pigment Industries Co., Ltd.) Obtained the 3rd three-dimensional modeling liquid material 15 like the preparation example 1 of the 3rd three-dimensional modeling liquid material.

(Third three-dimensional modeling liquid material preparation example 16)
<Preparation of third three-dimensional modeling liquid material 16>
In preparation example 1 of the third liquid material for three-dimensional modeling, the product name: Aron A305L, which is a dispersant polymer, is further polymerized to Aron A6114 (Toagosei Co., Ltd., weight average molecular weight (Mw) 10,000) and weight. Except having changed to the dispersing agent polymer A which raised the average molecular weight to 12,000, it carried out similarly to the preparation example 1 of the 3rd three-dimensional modeling liquid material, and obtained the 3rd three-dimensional modeling liquid material 16.

(Example 17 of preparing third liquid material for three-dimensional modeling)
<Preparation of the third three-dimensional modeling liquid material 17>
In preparation example 1 of the third liquid material for three-dimensional modeling, the content of trade name: Aron A305L (manufactured by Toagosei Co., Ltd.) as the dispersant polymer is 0.4 parts by mass, and the surface tension is 29.3 mN / m is 30. A third three-dimensional modeling liquid material 17 was obtained in the same manner as in Preparation Example 1 of the third three-dimensional modeling liquid material except that it was changed to 2 mN / m.

(Third example of preparation of three-dimensional modeling liquid material 18)
<Preparation of the third three-dimensional modeling liquid material 18>
In preparation example 1 of the third liquid material for three-dimensional modeling, the content of trade name: Aron A305L (manufactured by Toagosei Co., Ltd.) is adjusted as the dispersant polymer, and the surface tension of 29.3 mN / m is adjusted to 32.4 mN / m. Except having changed into 3rd, it was carried out similarly to the preparation example 1 of the 3rd three-dimensional modeling liquid material, and obtained the preparation example 18 of the 3rd three-dimensional modeling liquid material.

  The compositions of the obtained third three-dimensional modeling liquid materials 1 to 18 are shown in Tables 4 to 6 below.

Example 1
The first three-dimensional modeling material 1, the second three-dimensional modeling liquid material 1, and the third three-dimensional modeling liquid material 1 were combined to obtain a three-dimensional modeling material set 1.
Using the three-dimensional modeling material set 1, a three-dimensional modeled object was produced according to the following procedures (1) to (4).

(1) First, the first three-dimensional modeling material 1 is transferred from the supply-side powder storage tank to the modeling-side powder storage tank using the three-dimensional model manufacturing apparatus as shown in FIG. A thin layer (first three-dimensional modeling material layer) made of the first three-dimensional modeling material having an average thickness of 100 μm was formed.

(2) Next, the second three-dimensional modeling liquid material 1 is applied to the surface of the formed first three-dimensional modeling material layer from a nozzle using an inkjet printer (device name: SG7100, manufactured by Ricoh Co., Ltd.). Application (discharge) was performed, and a part of the first three-dimensional modeling material layer of the part (first region) that finally constituted the surface of the three-dimensional model was cured.
After drying at room temperature for several minutes and partially evaporating the solvent of the second three-dimensional modeling liquid material 1, the third three-dimensional modeling liquid material 1 is discharged from another nozzle of the inkjet printer. And the said 1st three-dimensional modeling material layer of the part (2nd area | region) which comprises the inside of the said three-dimensional molded item other than said 1st area | region was hardened.

(3) Next, the operations of (1) and (2) are repeated, and the thin layers made of the cured first three-dimensional modeling material are sequentially stacked until the total average thickness of 5 mm is reached. As a result, a desired cured product was obtained. The obtained hardened | cured material was dried at normal temperature standing, the solvent was volatilized, and the three-dimensional molded item was manufactured. By removing the uncured first three-dimensional modeling material part by immersing the obtained three-dimensional modeled object in water, which is the fourth three-dimensional modeled liquid material, the modeled product is out of shape. The three-dimensional model was excellent in strength and dimensional accuracy.

(4) The three-dimensional model was sintered at 1,500 ° C. in an air environment in a sintering furnace. The sintered body of the three-dimensional structure was a completely integrated structure, and no damage or the like occurred even when it was hit against a hard floor.

(Examples 2-20 and Comparative Examples 1-2)
In Example 1, except that it was changed to a three-dimensional modeling material set composed of the first three-dimensional modeling material, the second three-dimensional modeling liquid material, and the third three-dimensional modeling liquid material shown in Table 7 below. 1 was obtained in the same manner as in 1.

  Using the resulting three-dimensional model, “bending strength after sintering”, “density after sintering”, “mechanical strength”, and “esthetics (color reproducibility, tooth end) Partial transparency, interlayer adhesion and color mixing) ". The results are shown in Table 7 below.

(Bending strength)
Next, with respect to the sintered body of the three-dimensional structure obtained after sintering, a desktop precision universal testing machine (device name: AUTOGRAPH-AGS-J, manufactured by Shimadzu Corporation) is used based on ISO-6871. Then, the “bending strength after sintering” was measured.

(density)
About the obtained sintered body of the three-dimensional structure after sintering, linseed oil is used as an immersion solvent by the Archimedes method using a density measuring device (device name: BM-22 type, manufactured by A & D Co., Ltd.). It measured using.

(Mechanical strength)
Moreover, from the measurement result of the bending strength after the sintering, the mechanical strength of the three-dimensional structure was evaluated based on the following evaluation criteria.
-Evaluation criteria-
○: Bending strength after sintering is 840 MPa or more Δ: Bending strength after sintering is 700 MPa or more and less than 840 MPa ×: Bending strength after sintering is less than 700 MPa

(Color reproducibility)
Three samples produced under the same conditions were visually observed for the color reproducibility of the modeled object, and “color reproducibility” was evaluated based on the following evaluation criteria.
-Evaluation criteria-
○: There is no large color tone difference between samples, and there is no color unevenness. Δ: There is a slight color tone difference between samples, but there is no large color unevenness. ×: There is a color tone difference between samples, and the same sample. There was color irregularity among them

(End transparency)
Using the dental microscope (device name: Crystal Eye, manufactured by Olympus Co., Ltd.), the transmittance of the end of the molded object was measured. Was evaluated.
-Evaluation criteria-
○: End part transmittance is 80% or more Δ: End part transmittance is 60% or more and less than 80% ×: End part transmittance is less than 60%

(Interlayer adhesion)
The three-dimensional model after the sintering is polished with a diamond cutter, and the contact state between the two layers of the first region and the second region after destruction is observed by a simple scanning electron microscope (device name: VE-7800, Keyence Corporation). Manufactured) and evaluated “interlayer adhesion” based on the following evaluation criteria. FIG. 4 shows a state where the two layers are almost in close contact with each other, and FIG. 5 shows a state where a gap is generated between the two layers. The solid line portion in FIGS. 4 and 5 is a boundary line between two layers. In addition, it turns out that the space | gap has generate | occur | produced above the continuous line in FIG.
-Evaluation criteria-
○: The two layers are formed in close contact. Δ: There is a gap in part between the two layers. X: There is a gap or there is no boundary between the two layers.

(Mixed color)
The shaped object after sintering is polished with a diamond cutter, visually checked for color mixing between the two layers of the first region and the second region after destruction, and "color mixing" is evaluated based on the following evaluation criteria. did.
-Evaluation criteria-
○: No mixed color is observed. Δ: One of the internal colors is mixed on the surface. ×: Mixed color is generated or there is no boundary between two layers.

As an aspect of this invention, it is as follows, for example.
<1> A layer forming step of forming a first three-dimensional modeling material layer using the first three-dimensional modeling material;
A second three-dimensional modeling liquid material application step of applying a second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer constituting the surface layer of the three-dimensional modeled object to be modeled;
A third three-dimensional modeling liquid material application step of applying a third three-dimensional modeling liquid material to the second region constituting the interior of the three-dimensional model other than the first region;
Is a method for producing a three-dimensional modeled object characterized by repeating a plurality of times.
<2> At least one of the second three-dimensional modeling liquid material and the third three-dimensional modeling liquid material exhibits reactivity with respect to the first three-dimensional modeling material. It is a manufacturing method of the three-dimensional molded item as described in <1>.
<3> The solid according to any one of <1> to <2>, wherein the third solid modeling liquid material application step is performed after the second solid modeling liquid material application step. It is a manufacturing method of a molded article.
<4> The method for producing a three-dimensional structure according to any one of <1> to <3>, wherein the first three-dimensional material includes inorganic particles.
<5> The method for producing a three-dimensional structure according to <4>, wherein the inorganic particles are at least one of metal particles and ceramic particles.
<6> The method for producing a three-dimensional structure according to <5>, wherein the ceramic particles are zirconia particles.
<7> The method for producing a three-dimensional structure according to any one of <1> to <6>, wherein the first three-dimensional material is a slurry containing a solvent.
<8> The method further includes a removing step of removing the uncured portion of the first three-dimensional structure material by immersing the three-dimensional structure in a fourth three-dimensional structure liquid material after forming the three-dimensional structure. The method for producing a three-dimensional structure according to any one of <1> to <7>.
<9> The method for producing a three-dimensional structure according to <8>, wherein the fourth liquid material for three-dimensional modeling is water.
<10> The method for producing a three-dimensional structure according to any one of <1> to <9>, wherein the second liquid material for three-dimensional structure includes an alcohol compound.
<11> The method for producing a three-dimensional structure according to <10>, wherein the alcohol compound is at least one of a diol compound having 8 or more carbon atoms and a glycol ether compound.
<12> The method for producing a three-dimensional structure according to any one of <1> to <11>, wherein the surface tension of the third liquid material for three-dimensional structure is 30 mN / m or less. .
<13> The three-dimensional structure according to any one of <1> to <12>, wherein the transmittance of the surface layer of the three-dimensional structure is higher than the transmittance inside the three-dimensional structure. Is the method.
<14> A method for producing a three-dimensional structure according to any one of <1> to <13>, wherein a dental prosthesis is produced.
<15> The method for producing a three-dimensional structure according to any one of <1> to <14>, wherein the first three-dimensional material further includes an organic compound A.
<16> The method for producing a three-dimensional structure according to <15>, wherein the organic compound A is polyacrylic acid.
<17> The liquid material for second three-dimensional modeling further includes an organic compound B that is reactive with respect to the organic compound A contained in the first three-dimensional modeling material. It is a manufacturing method of the three-dimensional molded item in any one of <15> to <16>.
<18> The method for producing a three-dimensional structure according to <17>, wherein the organic compound B is polyethyleneimine.
<19> The method for producing a three-dimensional structure according to <18>, wherein the polyethyleneimine has a weight average molecular weight of 1,800 or more.
<20> The method for producing a three-dimensional structure according to any one of <1> to <19>, wherein the third liquid material for three-dimensional structure further includes an inorganic pigment.
<21> Three-dimensional modeling material layer holding means for holding the first three-dimensional modeling material layer;
Layer forming means for forming a first three-dimensional material layer using the first three-dimensional material;
A second three-dimensional modeling liquid material applying means for applying a second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer constituting the surface layer of the three-dimensional modeled object to be modeled;
And a third three-dimensional modeling liquid material applying means for applying a third three-dimensional modeling liquid material to the second region constituting the inside of the three-dimensional modeled object other than the first region. It is a manufacturing apparatus of a molded article.

  The manufacturing method of the three-dimensional structure according to any one of <1> to <20> and the manufacturing apparatus of the three-dimensional structure according to <21> solve the above-mentioned problems in the related art, and have the following objects: The challenge is to achieve.

JP 2003-507120 A

Claims (13)

A layer forming step of forming a first three-dimensional modeling material layer using the first three-dimensional modeling material;
A second three-dimensional modeling liquid material application step of applying a second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer constituting the surface layer of the three-dimensional modeled object to be modeled;
A third three-dimensional modeling liquid material application step of applying a third three-dimensional modeling liquid material to the second region constituting the interior of the three-dimensional model other than the first region;
A method for producing a three-dimensional modeled object characterized by repeating a plurality of times.   At least one of said 2nd three-dimensional modeling liquid material and said third three-dimensional modeling liquid material shows reactivity with respect to said 1st three-dimensional modeling material. The manufacturing method of the three-dimensional molded item of description.   3. The method for producing a three-dimensional structure according to claim 1, wherein after the second three-dimensional modeling liquid material application step, the third three-dimensional modeling liquid material application step is performed.   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the first three-dimensional structure material includes inorganic particles.   The method for producing a three-dimensional structure according to claim 4, wherein the inorganic particles are at least one of metal particles and ceramic particles.   The method for producing a three-dimensional structure according to any one of claims 1 to 5, wherein the first three-dimensional material is a slurry containing a solvent.   The method further comprises a removing step of removing an uncured portion of the first three-dimensional structure material by immersing the three-dimensional structure in a fourth three-dimensional structure liquid material after forming the three-dimensional structure. Item 7. A method for producing a three-dimensional structure according to any one of Items 1 to 6.   The method for producing a three-dimensional structure according to any one of claims 1 to 7, wherein the second liquid material for three-dimensional structure contains an alcohol compound.   The method for producing a three-dimensional structure according to claim 8, wherein the alcohol compound is at least one of a diol compound having 8 or more carbon atoms and a glycol ether compound.   The method for producing a three-dimensional structure according to any one of claims 1 to 9, wherein the surface tension of the third liquid material for three-dimensional structure is 30 mN / m or less.   The method for manufacturing a three-dimensional structure according to any one of claims 1 to 10, wherein the transmittance of the surface layer of the three-dimensional structure is higher than the transmittance inside the three-dimensional structure.   The method for producing a three-dimensional structure according to any one of claims 1 to 11, wherein a dental prosthesis is produced. 3D modeling material layer holding means for holding the first 3D modeling material layer;
Layer forming means for forming a first three-dimensional material layer using the first three-dimensional material;
A second three-dimensional modeling liquid material applying means for applying a second three-dimensional modeling liquid material to the first region of the first three-dimensional modeling material layer constituting the surface layer of the three-dimensional modeled object to be modeled;
And a third three-dimensional modeling liquid material applying means for applying a third three-dimensional modeling liquid material to the second region constituting the inside of the three-dimensional modeled object other than the first region. Manufacturing equipment for shaped objects.