JP2019048429A - Manufacturing method for three-dimensional object and precursor composition used for the same - Google Patents

Abstract

To provide a method for manufacturing a three-dimensional ceramic object by a laminate molding method, capable of producing a composite with a dissimilar material such as a resin material, without requiring a high temperature sintering process.SOLUTION: A three-dimensional object is produced by repeating, by multiple times, a step of forming a precursor composition layer with a liquid precursor composition at least containing at least one of metalalkoxide, a hydrolysate of the metalalkoxide and a polycondensate of the hydrolysate, an acid catalyst to accelerate hydrolysis of the metalalkoxide and water, with a solid content concentration of a ceramic to be formed being 1 mass% or more, and drying the precursor composition layer to form a ceramic layer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a ceramic three-dimensional object by a lamination molding method, and a precursor composition used for the production method.

  In recent years, as a method for forming a three-dimensional object, attention has been focused on a layered manufacturing method in which a modeling material is laminated in accordance with cross-sectional data of a three-dimensional object model which is a forming object. Conventionally, a three-dimensional object using a resin material as a modeling material has been mainstream, but recently, reports on modeling of ceramics and metals have been made. For example, Patent Document 1 discloses a method of producing a ceramic three-dimensional object by forming a ceramic particle layer, irradiating a desired region with a laser, performing local heating, and bonding the region particles. ing.

JP, 2015-38237, A

Generally, when manufacturing a ceramic three-dimensional object, as disclosed in Patent Document 1, it is necessary to sinter ceramic particles at a high temperature. Therefore, it was not possible to produce a composite of different materials such as resin materials and ceramics at the same time that equipment for heat treatment was required.
An object of the present invention is to provide a method for producing a ceramic three-dimensional object by a lamination molding method, which does not require a sintering process at a high temperature and can produce a composite with a different material such as a resin material. .

The first aspect of the present invention is a method for producing a three-dimensional object by additive manufacturing,
Liquid precursor containing at least one of metal alkoxide, metal chloride, hydrolyzate of metal alkoxide and polycondensate of metal alkoxide, acidic catalyst for promoting hydrolysis of metal alkoxide, water Forming a precursor composition layer by using a precursor composition in which the ratio of the ceramic formed from the precursor composition to the precursor composition is 1% by mass or more; Forming a ceramic layer by drying the precursor composition layer;
Are repeated several times.
A second aspect of the present invention is a liquid precursor composition used for additive manufacturing, which comprises at least one of a metal alkoxide, a metal chloride, a hydrolyzate of the metal alkoxide and a polycondensate of the hydrolyzate. At least one acidic catalyst promoting hydrolysis of the metal alkoxide, water, and the ratio of the ceramic formed from the precursor composition to the precursor composition is 1% by mass or more. Do.

  According to the present invention, since a ceramic layer is formed using a sol-gel method, a ceramic three-dimensional object can be obtained without heat treatment at a high temperature. Therefore, it becomes possible to manufacture a complex with a material which can not withstand the sintering temperature of ceramics, such as a resin material, which does not require high temperature heat treatment equipment.

It is a cross section showing the process of one embodiment of the present invention. It is a cross-sectional schematic diagram which shows the process of embodiment which manufactures a composite body by this invention. FIG. 7 is a schematic cross sectional view schematically showing a process of Example 2.

  Hereinafter, the present invention will be described in detail by showing embodiments of the present invention. In the drawings, the same reference numerals are given to the portions showing the same members or the corresponding members. It is possible to apply the well-known technique or well-known technique of the said technical field to the structure and process which are not especially shown or described. Also, duplicate descriptions may be omitted.

  The present invention relates to a method for producing a three-dimensional object by additive manufacturing, and a precursor composition used in the method. The production method of the present invention is characterized in that the step of forming a precursor composition layer comprising the precursor composition of the present invention and drying the same to form a ceramic layer is repeated a plurality of times. In the precursor composition of the present invention, at least one of a metal alkoxide, a metal chloride, a hydrolyzate of the metal alkoxide and a polycondensate of the metal alkoxide, and an acid which promotes the hydrolysis of the metal alkoxide It is characterized in that it is a liquid containing a catalyst and water. First, in the present invention, the principle of obtaining a ceramic from a metal alkoxide will be described.

  When water is added to the metal alkoxide to hydrolyze the metal alkoxide, a sol (colloidal solution) containing a hydrolyzate and a polycondensate by a polycondensation reaction of the hydrolyzate is obtained, and the reaction is further promoted. When this is done, a gel which has lost fluidity is obtained. Then, when this gel is dried, the polycondensation reaction proceeds further, the water and the solvent contained in the gel are evaporated, and a ceramic made of metal oxide is obtained. Therefore, in the present invention, the ceramic can be formed without passing through the sintering process at high temperature. In addition, the method to form ceramics in such a process is generally called a sol-gel method.

  The hydrolysis reaction of metal alkoxide is promoted by the addition of an acidic catalyst or a basic catalyst, but the state and speed of the gel differ depending on which one is added.

  When an acid catalyst is added to carry out a hydrolysis reaction of a metal alkoxide, a hydrolysis reaction of the metal alkoxide occurs by electrophilic reaction by the acid catalyst. When the hydrolysis reaction starts, the polycondensation reaction also starts, and the polycondensation reaction proceeds sequentially, so the polycondensation reaction proceeds linearly. Therefore, when an acidic catalyst is used, it is easy to form a sol having a linear polycondensate, and when such a sol gels, the linear polycondensates are entangled with each other to form a three-dimensional network. Form a structure. Therefore, when the gel is dried, the polycondensate is finely linear and has a high degree of freedom, and as a result, it is considered that the stress is dispersed and the crack is suppressed.

  On the other hand, when a basic catalyst is added to carry out a hydrolysis reaction of a metal alkoxide, a hydrolysis reaction of the metal alkoxide occurs by a nucleophilic reaction with the basic catalyst. At this time, the basic catalyst directly attacks the central metal atom, but the reaction is suppressed by steric hindrance. However, when the reaction progresses stochastically, the steric hindrance of the OH group generated by the reaction is reduced. As a result, once the reaction proceeds, most of the reaction sites possessed by the metal atom are replaced by OH groups. Even in the case of a basic catalyst, when the hydrolysis reaction starts, the polycondensation reaction also starts, but since almost all of the reaction points possessed by the metal atoms are replaced by OH groups, they react in three dimensions in a network. The reaction proceeds. As a result, a gel having high three-dimensionality and high density is obtained, and when the gel is dried, the stress generated in the gel tends to cause cracking.

  Since metal alkoxides are obtained from metal chlorides, even if metal chlorides are used as starting materials instead of metal alkoxides, ceramics with reduced cracking can be produced by the sol-gel method. When an alcohol is used in combination to obtain a metal alkoxide from a metal chloride, hydrogen chloride is generated by the reaction of the metal chloride and the alcohol, so that such hydrogen chloride can be used as an acidic catalyst.

  Therefore, in the present invention, either a metal chloride or a metal alkoxide may be used as a starting material, or both may be used as a mixture. From the viewpoint of stability in the production process, metal alkoxides are preferred.

The precursor composition of the present invention has a composition containing at least a metal alkoxide, an acidic catalyst that promotes the hydrolysis of the metal alkoxide, and water, and promotes the hydrolysis of the metal chloride, water, and the metal alkoxide. The composition is prepared as either a composition containing at least an acidic catalyst, or a composition obtained by mixing these compositions. However, the formation of a metal alkoxide from a metal chloride, and the hydrolysis and polycondensation reaction of the metal alkoxide proceed with time immediately after the preparation of the precursor composition. Therefore, the precursor composition of the present invention is an acid which promotes hydrolysis of the metal alkoxide, at least one of metal alkoxide, metal chloride, hydrolyzate of the metal alkoxide and polycondensate of the hydrolyzate, and the metal alkoxide. It contains at least a catalyst and water.
Metal alkoxides include silicon alkoxides. Specific examples thereof include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and tetraisobutoxysilane. Further, an alkoxide of aluminum is also preferably used, and the same alkoxide as the above silicon can be mentioned.
Examples of the metal chloride include, but are not limited to, titanium tetrachloride, zirconium oxychloride and the like.
The metal alkoxide and the metal chloride may be a complexed metal compound containing two or more component metals.

  The acidic catalyst used in the present invention is not particularly limited as long as it is an acidic catalyst. Specifically, hydrochloric acid and acetic acid can be used. In addition, as described above, when metal chloride is used as the starting material, hydrogen chloride (hydrochloric acid) generated by the reaction of metal chloride and alcohol is also used as an acid catalyst by using alcohol in combination. The acid catalyst may be added separately.

  In the present invention, water needs to be contained for the hydrolysis of the metal alkoxide, and preferably pure water is used.

  An organic solvent may be added to the precursor composition of the present invention in order to increase the layer uniformity of the metal alkoxide. Specific examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol (IPA), ketones such as methyl ethyl ketone, acetone and acetylacetone, and hydrocarbons such as hexane and cyclohexane. These organic solvents evaporate at a suitable rate in the step of drying the precursor composition layer described later, and thus a homogeneous ceramic layer is easily obtained, which is preferable.

  When metal chloride is used as a starting material, an alcohol may be added to form a metal alkoxide. Specifically, it is selected according to the type of metal chloride, but in the case of titanium tetrachloride, for example, 2-propanol is used.

  The precursor composition of the present invention is preferably a sol containing a polycondensate formed by the hydrolysis and polycondensation reaction of a metal alkoxide. When the precursor composition is a sol, when the precursor composition layer is dried, the stress is easily dispersed by the polycondensate existing in advance, and the crack is less likely to occur.

  In the precursor composition of the present invention, when a metal chloride is used as a starting material, the formation of a metal alkoxide and the hydrolysis and polycondensation reaction of the metal alkoxide start immediately after preparation. When a metal alkoxide is used as the starting material, the hydrolysis and polycondensation reaction of the metal alkoxide starts. Therefore, the longer the time from preparation to use, the more hydrolyzate and polycondensate contained, and finally gelation. Therefore, the precursor composition is prepared from the preparation of the precursor composition in consideration of the rates of hydrolysis and polycondensation reaction and the concentration of the polycondensate contained in the precursor composition at the time of forming the precursor composition layer. It is desirable to adjust the time to layer formation.

  The precursor composition of the present invention may further contain inorganic particles. By containing the inorganic particles, the solid content of the precursor composition can be increased, and the thickness of the ceramic layer that can be formed at one time can be increased. Furthermore, by dispersing the inorganic particles in the precursor composition layer, the stress generated upon drying of the precursor composition can be dispersed, and the occurrence of cracking can be suppressed. In the case where such inorganic particles are not added, the lamination conditions may need to be precisely controlled depending on the type and concentration of the metal alkoxide and the thickness of the ceramic layer.

The inorganic particles are preferably metal oxides. Among them, silicon oxide is preferable, and in addition, oxide inorganic materials such as aluminum oxide, titanium oxide, and zirconium oxide can be used. Moreover, it is preferable that the metal element of the said metal oxide is the same as the metal element contained in the metal alkoxide which is a starting raw material, and a metal chloride. For example, when the metal contained in the metal alkoxide or metal chloride is silicon, silicon oxide can be suitably used as the inorganic particles. If the inorganic particles to be added and the ceramic formed from the metal chloride or metal alkoxide have the same composition, the polycondensate and the inorganic particles can be bound more firmly when the precursor composition layer is dried, It is preferable because a strong ceramic layer is formed.
The inorganic particles preferably have a porous structure on the surface. In this case, since the polycondensate is also bound to the inside of the porous surface of the inorganic particle when the precursor composition layer is dried, the adhesion area between the inorganic particle and the polycondensate is increased, and the porous and the porous inside and outside The binding strength is increased by the continuous solidification of the polycondensate.

When inorganic particles are added, in the case where the precursor composition is the above-described sol, the inorganic particles are larger than the polycondensate contained in the precursor composition, so that the polycondensate in the gaps of the inorganic particles Is preferable because it is easy to form a high-density ceramic layer.
Specifically, the volume average particle diameter of the inorganic particles is preferably in the range of 0.05 μm to 200 μm, and more preferably 1 μm to 80 μm. When the volume average particle diameter of the inorganic particles is 1 μm or more, the thickness of the layer of the ceramic layer that can be molded is large, and thus the modeling speed tends to be high. Moreover, the surface roughness of a ceramic layer can be restrained small as it is 200 micrometers or less.

  The volume average particle diameter of the inorganic particles can be measured using a laser diffraction / scattering particle size distribution analyzer “LA-950” (manufactured by HORIBA). For setting of measurement conditions and analysis of measurement data, attached special software is used. As a specific measurement method, first, a batch-type cell containing a measurement solvent is set in a laser diffraction / scattering type particle size distribution measuring apparatus “LA-950” (manufactured by HORIBA), adjustment of optical axis, adjustment of background Do. Here, it is necessary to select the solvent to be used that does not dissolve the inorganic particles to be measured. In addition, a dispersing agent may be appropriately added to the solvent as needed to improve the dispersion of the inorganic particles to be measured. Powder of inorganic particles to be measured is added to a batch cell until the transmittance of the tungsten lamp reaches 95% to 90%, the particle size distribution is measured, and the volume-based average particle diameter is calculated from the obtained measurement results. It can be calculated.

  The inorganic particles preferably have an average circularity of 0.94 or more, more preferably 0.96 or more, in the cross section of the imaginary surface. If the average circularity of the cross section of the virtual surface of the inorganic particles is 0.94 or more, it has a structure close to a sphere. Accordingly, the inorganic particles come into point contact with each other, the flowability is easily maintained, and the minute filling is easily performed in the precursor composition layer, so that it is easy to form the ceramic layer with few voids.

The circularity of the inorganic particles can be measured as follows, and the average circularity can be obtained by averaging the circularities obtained by measuring 10 or more arbitrary shaped particles.
Circularity = (peripheral length of circle having the same area as the projected area of the virtual surface of the particle) / (peripheral length of the projected image of the virtual surface of the particle)

  Here, the “projected area of the virtual surface of the particle” is the area of the projected image of the virtual surface of the binarized particle, and the “perimeter of the projected image of the virtual surface of the particle” is the virtual surface of the particle It is defined as the length of the outline obtained by connecting the edge points of the projected image. The degree of circularity is an index indicating the complexity of the shape of the inorganic particles, and indicates 1.00 when the inorganic particles are completely spherical, and the smaller the degree of circularity of the projected image of the virtual surface of the inorganic particles, the smaller the value of circularity It becomes. The degree of circularity of the inorganic particles may be measured by image processing of an observation image such as an electron microscope, a flow type particle image measuring apparatus (for example, “FPIA-3000 type” manufactured by Toa Medical Electronics Co., Ltd.), etc. it can.

  Moreover, the precursor composition of this invention may contain the coloring agent as needed.

  In the precursor composition of the present invention, the ratio of the ceramic to be formed to the precursor composition is preferably 1% by mass to 50% by mass, more preferably 25% by mass, in the composition not containing the inorganic particles. % Or less. When it exceeds 50% by mass, when the ceramic layer is formed in a large area, cracking is likely to occur and the size of the three-dimensional object may be limited.

  Moreover, 5 mass% or more is preferable, as for solid content concentration of the precursor composition of this invention, 30 mass% or more is more preferable, More preferably, it is 50 mass% or more. When the solid content concentration is less than 5% by mass, the thickness per one layer of the obtained ceramic layer may be reduced, which may cause a limitation on the shaping speed of the three-dimensional object.

  In the present invention, the precursor composition is applied to a desired region according to the slice data of the object to be shaped to form a precursor composition layer. The slice data of the object to be formed is obtained by slicing the object to be formed at predetermined intervals in the direction of formation, and is data including information such as the shape of the cross section of the structure and the arrangement of materials. The precursor composition layer according to the present invention is gelled in the drying process after the application of the precursor composition, and the polycondensation reaction proceeds as the drying progresses, and at the same time, the water and the organic solvent evaporate and the ceramic layer becomes can get. In addition, in order to promote the polycondensation reaction in a precursor composition, you may heat a precursor composition as needed.

  The precursor composition layer can be formed using a method of discharging a precursor composition to draw, etc., and any general method can be used, but the liquid amount and the arrangement position can be controlled. From the point of view, it is preferable to use an inkjet.

  The thickness of the precursor composition layer is preferably such that the thickness per one ceramic layer after drying is preferably 0.05 μm or more and 1 mm or less, more preferably 1 μm or more and 200 μm or less . The thickness per ceramic layer is preferably 0.05 μm or more in order to laminate the ceramic layers efficiently, and is preferably 1 mm or less in order to keep the surface roughness low.

  In the present invention, one precursor composition may be used, or two or more precursor compositions may be used in combination. When using two or more types, the thickness of the ceramic layer obtained by each precursor composition is suitably determined according to modeling accuracy.

In the present invention, the precursor composition layer is formed separately on a layer by layer basis, transferred onto a substrate, dried and laminated, from the first layer intermediate onto the substrate The second and subsequent layers may be formed directly on the previously formed ceramic layer. When transferring the precursor composition layer from a separate body, known transfer methods such as transfer using a difference in adhesion can be used. The drying step may be performed simultaneously with or after the lamination, or may be performed at a plurality of timings among them.
In the precursor composition layer, the polycondensation reaction in the precursor composition further proceeds by the drying step, and combines with the previously formed ceramic layer to be integrated.

The drying time of the precursor composition layer can be optionally changed according to the composition and concentration of the precursor composition, but if the drying time is too fast, the polycondensation reaction proceeds sufficiently in the precursor composition layer. Also, if it is too long, the production efficiency will be reduced. Therefore, it is preferable to set the drying time in which the polymerization reaction sufficiently proceeds in the range of 60 minutes or less per layer.
In the present invention, since the hydrolysis is promoted by the acidic catalyst, the drying step can be performed at room temperature, but when the polycondensation reaction is slow, the precursor composition layer is appropriately heated and dried. It does not matter.

  An example of the manufacturing process of the solid thing by the manufacturing method of this invention is typically shown in FIG. First, as shown in FIG. 1A, a precursor composition layer 11 composed of a precursor composition is formed and dried. In the precursor composition layer 11, a polycondensation reaction proceeds in the drying process, and after gelation, it becomes a ceramic layer 12 as shown in FIG. 1 (b). Next, a new precursor composition layer 11 is formed on the ceramic layer 12 (FIG. 1 (b)) and dried to form the ceramic layer 12. Then, the upper layer precursor composition layer 11 is integrated with the lower layer ceramic layer 12 in the drying process, and a laminated ceramic layer 13 is obtained (FIG. 1 (c)). By repeating the process of FIG.1 (c) and (d), the three-dimensional thing 14 with which the ceramic layer of multiple layers was united is obtained.

  In the present invention, in the case where the three-dimensional object is made of only ceramics, after a plurality of ceramic layers 12 are laminated to obtain the three-dimensional object 14, the three-dimensional object is further strengthened by heating and sintering at high temperature. You can get

Next, a method of producing a composite of resin and ceramic will be described.
In the present invention, since the ceramic layer can be formed at a low temperature, a composite with a resin material can be manufactured. Specifically, the step of forming the ceramic layer using the precursor composition described above in contact with the resin precursor layer or the resin layer is repeated, and when the resin precursor layer is used, the resin precursor is cured. To obtain a complex. As the resin precursor, a photocurable resin or a thermosetting resin is used, and as the resin, a thermoplastic resin is used. The resin precursor layer or the resin layer may be formed in a plurality of layers in parallel with the step of forming the ceramic layer, or the step of forming the ceramic layer on the resin precursor layer or resin layer previously formed may be repeated. good.

  An example of the manufacturing process of the composite_body | complex by the manufacturing method of this invention is typically shown in FIG. First, as shown in FIG. 2A, a resin precursor layer or a resin layer 21 is formed, and a precursor composition layer 11 made of the precursor composition is formed in contact with the resin layer 21. Then, the precursor composition layer 11 is dried to form a ceramic layer 12 (FIG. 2 (b)). Furthermore, the process of FIG. 2 (a) and (b) is repeated, and the composite body which consists of the solid thing 22 which consists of resin, and the solid thing 14 which consists of ceramics is obtained. In addition, what is necessary is just to comprise so that the other may be included by one side, when the bond strength of resin and ceramics is weak.

  Examples of the present invention and comparative examples are shown below, but the present invention is not limited thereto.

(Example 1, Comparative Example 1)
Hereinafter, precursor compositions 1 to 5 as Example 1 and a precursor composition 6 as Comparative Example 1 were prepared and evaluated.

Preparation of Precursor Composition 1
After mixing 4.7 g of ethyl silicate (special grade, manufactured by Kishida Chemical Co., Ltd.) and 1.0 g of ethanol (special grade, manufactured by Kishida Chemical Co., Ltd.), the solution A was stirred at room temperature for 4 hours. Separately, 1.2 g of a 0.01 mol / L aqueous hydrochloric acid solution (manufactured by Kishida Chemical Co., Ltd.) and 3.1 g of ethanol (special grade manufactured by Kishida Chemical Co., Ltd.) were mixed, and then stirred at room temperature for 4 hours to obtain a solution B. The solution B was added to the solution A, and the mixture was further stirred for 24 hours to obtain a precursor composition 1. The ratio of the silica to the precursor composition 1 is 13.6% by mass when all the silicon components contained in the precursor composition 1 become silica.

Preparation of Precursor Composition 2
A precursor composition 2 was obtained by adding 1.0 g of a silica powder (ADMATEX "FEF 75A", volume average particle diameter: 20 μm) to 1.0 g of the precursor composition 1 and mixing them.

Preparation of Precursor Composition 3
A precursor composition is prepared by adding 1.0 g of silica powder ("AG Gel S-Tech" MS gel EP-DM- 50-1000 A W ", volume average particle diameter: 50 μm) to 1.0 g of precursor composition 1 and mixing. I got the thing 3.

Preparation of Precursor Composition 4
After mixing 5.2 g of aluminum sec-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.2 g of IPA (special grade, manufactured by Kishida Chemical Co., Ltd.) and 1.4 g of ethyl acetoacetate (special grade, manufactured by Kishida Chemical Co., Ltd.) Stir for 4 hours to obtain solution C. Separately, 0.38 g of a 0.01 mol / L aqueous hydrochloric acid solution and 1.2 g of IPA (special grade, manufactured by Kishida Chemical Co., Ltd.) were mixed, and then stirred at room temperature for 4 hours to obtain a solution D. The solution D was added to the solution C, and the mixture was further stirred for 24 hours to obtain a precursor composition 4. The ratio of the alumina to the precursor composition 4 is 3.3% by mass when all the aluminum components contained in the precursor composition 4 become alumina.

<Preparation of Precursor Composition 5>
Precursor composition 5 was obtained by adding 1.0 g of an alumina powder (ADMATEX "AO-509", volume average particle diameter: 11 μm) to 1.0 g of precursor composition 4 and mixing.

Preparation of Precursor Composition 6
After mixing 4.7 g of ethyl silicate (special grade, manufactured by Kishida Chemical Co., Ltd.) and 1.0 g of ethanol (special grade, manufactured by Kishida Chemical Co., Ltd.), the mixture was stirred at normal temperature for 4 hours to obtain a solution E. Separately, 1.2 g of an aqueous solution of 0.01 mol / L ammonia and 3.1 g of ethanol (special grade, manufactured by Kishida Chemical Co., Ltd.) were mixed, and then stirred at room temperature for 4 hours to obtain a solution F. The solution F was added to the solution E, and stirred for additional 24 hours to obtain a precursor composition 6. The ratio of the silica to the precursor composition 6 when the silicon component contained in the precursor composition 6 is all silica is 13.6% by mass.

<Evaluation of lamination properties>
After each of the precursor compositions 1 to 6 was dropped, it was dried at 22 ° C. to form a ceramic layer. Next, the same precursor composition was dropped onto the ceramic layer previously formed, and layer stacking was repeated five times to produce a three-dimensional object.

  The three-dimensional objects produced from precursor compositions 1 to 5 maintained their shape even if they were handled by direct touch, but the three-dimensional objects produced from precursor composition 6 had cracks. The shape was broken while I touched it with my hand directly. Therefore, according to the present invention, it was found that a strong ceramic three-dimensional object can be obtained without heat treatment at a high temperature.

(Example 2, Comparative Example 2)
As Example 2, a composite of a ceramic and an ABS resin (acrylonitrile-butadiene-styrene copolymer) was produced. The manufacturing process is shown in FIG.

  An ABS resin layer 31a of 80 mm long × 10 mm wide × 0.53 mm thick was extruded into a mold of 80 mm long × 10 mm wide and 10 mm deep (FIG. 3 (a)). Subsequently, an ABS resin layer 31b having 11 grooves 32 having a width of 0.3 mm and a thickness of 0.35 mm in the longitudinal direction in the mold at intervals of 0.5 mm was extruded on the ABS resin layer 31a (see FIG. Fig. 3 (b). The precursor composition 2 prepared in Example 1 was applied to the grooves 32, dried at 20 ° C., and solidified to form a ceramic layer 41 having a thickness of 0.005 mm (FIG. 3 (c)).

  Thereafter, an ABS resin was extruded into the mold to fill the groove 32 in which the ceramic layer 41 was formed, and at the same time, an ABS resin layer 31c having a thickness of 0.18 mm was laminated on the ABS resin layer 31b (FIG. 3). (D)).

  Subsequently, in the same manner as the ABS resin layer 31b, an ABS resin layer 31d was produced in which ten grooves 32 having a width of 0.3 mm and a thickness of 0.35 mm were present at intervals of 0.5 mm in the longitudinal direction (FIG. 3 (e)) ). The precursor composition 2 prepared in Example 1 was applied to the groove 32, dried at 22 ° C., and solidified to form a ceramic layer 41 with a thickness of 0.005 mm (FIG. 3 (f)).

  Thereafter, an ABS resin layer 31c having a thickness of 0.18 mm was laminated in the mold. Subsequently, the step of forming the ABS resin layer 31b, the ceramic layer 41, and the ABS resin layer 31c, and the step of forming the ABS resin layer 31d, the ceramic layer 41, and the ABS resin layer 31c were repeated twice.

  Finally, an ABS resin layer 31e having a thickness of 0.29 mm was formed, and the laminate was taken out from the inside of the mold to obtain an 80 mm × 10 mm × 3.82 mm three-dimensional object (FIG. 3 (g)). The obtained three-dimensional object was confirmed to be a composite having the ceramic layer 41 inside the ABS resin layer, as shown in FIG. 3 (g).

  ABS resin layers 31a to 31e were laminated in the same manner as in Example 2 except that the ceramic layer 41 was not formed, to obtain an 80 mm × 10 mm × 3.82 mm three-dimensional object of Comparative Example 2.

<Evaluation of bending strength of three-dimensional object>
Using an autograph (Shimadzu Corporation "AG-20 kNIST"), the bending strength was measured by the method according to JIS K 7171. As a result, in comparison with the three-dimensional object of Comparative Example 2, the three-dimensional object of Example 2 was confirmed to have improved bending strength and flexural modulus, and the characteristic improvement of the resin molded product by simultaneous formation of ceramic could be confirmed.

  11: Precursor composition layer, 12, 41: ceramic layer, 14: three-dimensional object, 21: resin precursor or resin layer

Claims (17)

It is a method of manufacturing a three-dimensional object by the additive manufacturing method,
Liquid precursor containing at least one of metal alkoxide, metal chloride, hydrolyzate of metal alkoxide and polycondensate of metal alkoxide, acidic catalyst for promoting hydrolysis of metal alkoxide, water Forming a precursor composition layer with a body composition, wherein the ratio of the ceramic formed from the precursor composition to the precursor composition is 1% by mass or more;
Forming a ceramic layer by drying the precursor composition layer;
A method for producing a three-dimensional object, characterized in that   The method for producing a three-dimensional object according to claim 1, wherein the precursor composition contains an organic solvent.   The method for producing a three-dimensional object according to claim 2, wherein the organic solvent is any of an alcohol, a ketone and a hydrocarbon.   The method according to any one of claims 1 to 3, wherein the acidic catalyst is hydrochloric acid or acetic acid.   The thickness of the said ceramic layer is 0.05 micrometer or more and 1 mm or less, The manufacturing method of the three-dimensional object as described in any one of the Claims 1 thru | or 4 characterized by the above-mentioned.   The method for producing a three-dimensional object according to any one of claims 1 to 5, wherein the precursor composition contains at least inorganic particles.   The volume average particle diameter of the said inorganic particle is 0.05 micrometer or more and 200 micrometers or less, The manufacturing method of the three-dimensional object of Claim 6 characterized by the above-mentioned.   The method according to claim 6, wherein the inorganic particles have a porous structure on the surface.   The method for producing a three-dimensional object according to any one of claims 6 to 8, wherein the inorganic particle is a metal oxide.   10. The method for producing a three-dimensional object according to claim 9, wherein the metal oxide contains at least a metal element contained in the metal alkoxide or metal chloride.   The three-dimensional object according to any one of claims 1 to 10, wherein the precursor composition is a sol containing a polycondensation product formed by hydrolysis and polycondensation reaction of the metal alkoxide. Manufacturing method.   The precursor composition is a sol containing a polycondensate formed by hydrolysis and polycondensation reaction of the metal alkoxide, and the size of the inorganic particle is larger than that of the polycondensate. Item 11. A method for producing a three-dimensional object according to any one of items 6 to 10.   The solid content concentration of the said precursor composition is 50 mass% or less, The manufacturing method as described in any one of the Claims 1-12 characterized by the above-mentioned.   The method for producing a three-dimensional object according to any one of claims 1 to 13, wherein the precursor composition layer is formed by discharging the precursor composition by an inkjet.   The method for producing a three-dimensional object according to any one of claims 1 to 14, further comprising a step of heating and sintering after laminating a plurality of ceramic layers.   The method according to any one of claims 1 to 15, wherein a three-dimensional object composed of a resin and a ceramic is formed by repeating the step of forming the ceramic layer a plurality of times in contact with the resin precursor layer or the resin layer. The method for forming a three-dimensional object according to the above.   It is a liquid precursor composition used for additive manufacturing, which is at least one of a metal alkoxide, a metal chloride, a hydrolyzate of the metal alkoxide and a polycondensate of the hydrolyzate, and a water of the metal alkoxide. A precursor composition comprising at least an acidic catalyst that promotes decomposition, water, and a ratio of a ceramic formed from the precursor composition to the precursor composition is 1% by mass or more.

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