JP7454406B2 - Hydraulic composition for additive manufacturing and its manufacturing method, laminate and its manufacturing method, and two-component hydraulic material - Google Patents

Description

The present invention relates to a hydraulic composition for additive manufacturing, a method for producing the same, a laminate and a method for producing the same, and a two-component hydraulic material.

The additive manufacturing method is a method of repeatedly performing two-dimensional processing of materials such as resin, metal, ceramic, etc. based on three-dimensional data of the target object, and layering and modeling. Among them, the material extrusion method is a method in which the modeling material is selectively extruded directly through an opening such as a nozzle and piled up, and in recent years, research has been conducted on extrusion-based additive manufacturing technology using cement or clay mineral slurry. is also being actively carried out.

When performing additive manufacturing using the material extrusion method, the performance required of the material for additive manufacturing includes, for example, ease of feeding the material (hereinafter referred to as liquid feeding ability), and the ability to One example of this is that the material does not deform under its own weight (hereinafter referred to as lamination). In general, there is a trade-off relationship between the liquid transportability and lamination property of a material; for example, a material with high fluidity and good liquid transportability is likely to be unable to maintain its laminated shape and collapse.

In order to resolve the trade-off relationship between liquid delivery and lamination properties, in terms of material design, it is common to aim for high thixotropy, where the viscosity is dependent on time and shear rate. If it is a highly thixotropic material, the viscosity will be lowered by the shear stress applied from the pump or flow path during liquid delivery, resulting in high liquid delivery performance, and the viscosity will recover after discharge, giving it laminability. . For example, Patent Documents 1 and 2 disclose a modeling cement composition based on the concept of a highly thixotropic material and an additive manufacturing method using the same.

Japanese Patent Application Publication No. 2017-185645 Japanese Patent Application Publication No. 2018-140906

However, looking at FIG. 6 of Patent Document 1, mortar sag has occurred in the modeled product, and it is difficult to say that the model has been accurately modeled to the desired shape. On the other hand, according to Table 8 and FIG. 3 of Patent Document 2, although the material described in Patent Document 2 is recognized to have high lamination properties, precise material design is required to ensure pot life. Note that the pot life is set in consideration of the kneading time and the time required for pumping.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hydraulic composition for layered manufacturing that has excellent liquid delivery properties and lamination properties, and a method for producing the same. Another object of the present invention is to provide a laminate made of a cured product of the hydraulic composition, a method for producing the same, and a two-component hydraulic material for preparing the hydraulic composition.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, it was found that mixing a cement-containing liquid and an alkaline solution containing an ionic emulsion-type thickener achieves both liquid transportability and lamination. The present inventors have discovered that the present invention is effective in producing hydraulic compositions that can be used in various ways, and have completed the present invention.

The method for producing a hydraulic composition for additive manufacturing according to the present invention includes a step of mixing a cement-containing liquid containing cement, water, and an inorganic acid, and an alkaline solution containing an ionic emulsion type thickener. The hydraulic composition for additive manufacturing according to the present invention is formed by mixing a cement-containing liquid containing cement, water, and an inorganic acid, and an alkaline solution containing an ionic emulsion type thickener. The two-component hydraulic material according to the present invention includes a cement-containing liquid containing cement, water, and an inorganic acid, and an alkaline solution containing an ionic emulsion-type thickener, which are separated. When using a two-component hydraulic material for additive manufacturing, it is preferable to mix the cement-containing liquid and the alkaline solution immediately before use.

By mixing the above-mentioned cement-containing liquid and the above-mentioned alkaline solution, a hydraulic composition for additive manufacturing in which a hydration reaction of cement proceeds can be obtained. According to the tests conducted by the present inventors, among various thickeners, it is useful to employ an ionic emulsion type thickener to achieve excellent liquid delivery properties, and the ionic emulsion type thickener It is useful to mix this into an alkaline solution in order to achieve both liquid delivery and lamination properties. Specifically, according to the present invention, pressure loss can be sufficiently reduced even when a cement-containing liquid and an alkaline solution are transferred to a location where a three-dimensional object is to be formed using a tube or pipe. In addition, by mixing these liquids immediately before the lamination process for manufacturing three-dimensional objects, the design can be sufficiently improved by the action of the ionic emulsion type thickener contained in the alkaline solution and the progress of the hydration reaction of cement. It is possible to create three-dimensional sculptures of streets.

The viscosity of the alkaline solution is 2.0×10 ² to 2.0×10 ⁴ mPa・under the conditions of 20°C and a shear rate of 10 s ⁻¹ from the viewpoint of achieving a higher level of both liquid delivery and lamination properties. It is preferable that it is s. The viscosity of the cement-containing liquid should be 1.0 × 10 ² to 1.2 × 10 ⁵ mPa・s at a temperature of 20°C and a shear rate of 10 s ^-1 from the viewpoint of even better liquid transferability. is preferred.

The cement-containing liquid may further contain aggregate. A hydraulic composition that is a mixture of a cement-containing liquid containing aggregate and the above alkaline solution is, for example, a hydraulic mortar. The mortar flow of the cement-containing liquid containing aggregate is preferably 105 mm or more at 0 stroke flow, from the viewpoint of achieving both higher liquid transferability and laminability. Note that the hydraulic composition that is a mixture of a cement-containing liquid that does not contain aggregate and the above alkaline solution is, for example, a hydraulic paste.

The method for producing a laminate according to the present invention includes (A) a step of mixing a cement-containing liquid containing cement, water and an inorganic acid, and an alkaline solution containing an ionic emulsion type thickener to obtain a hydraulic composition; and (B) shaping a laminate of the hydraulic composition. The laminate according to the present invention is made of a cured product of a hydraulic composition for layered manufacturing.

According to the present invention, there is provided a hydraulic composition for layered manufacturing that has excellent liquid delivery properties and lamination properties, and a method for producing the same. Further, according to the present invention, there are provided a laminate made of a cured product of the above-mentioned hydraulic composition, a method for producing the same, and a two-component hydraulic material for preparing the above-mentioned hydraulic composition.

Embodiments of the present invention will be described below. The present invention is not limited to the following embodiments.

<Two-component hydraulic material>
The two-component hydraulic material according to the present embodiment includes a cement-containing liquid and an alkaline solution, which are used by mixing them, and both liquids are mixed before use (for example, during storage or transportation). It is in a separated state. Both liquids may be contained in separate containers, or may be contained in a single container in a state where they are isolated from each other. This two-component hydraulic material is for additive manufacturing, and it is preferable to mix the cement-containing liquid and the alkaline solution immediately before use. The cement-containing liquid and the alkaline solution will be explained below.

(Cement-containing liquid)
The cement-containing liquid contains cement, water, an inorganic acid, and aggregate mixed as necessary. The cement-containing liquid becomes a hydraulic cement slurry (hydraulic composition for additive manufacturing) by being mixed with an alkaline solution. Note that when the cement-containing liquid does not contain aggregate, the cement slurry prepared by mixing an alkaline solution is a hydraulic paste. On the other hand, if the cement-containing liquid contains aggregate, the cement slurry prepared by mixing the alkaline solution is a hydraulic mortar.

The cement is not particularly limited, but may be, for example, ordinary Portland cement, early strength Portland cement, ultra early strength Portland cement, moderate heat Portland cement, low heat Portland cement, blast furnace cement, fly ash cement, silica fume cement, alumina cement, etc. . One type of cement can be used alone or two or more types can be used in combination.

It is preferable to use alumina cement as at least a part of the cement. Although the alumina cement is not particularly limited, it is preferable to use one having a relatively high alumina content. For example, alumina cement with a high alumina content or alumina cement with a medium content of alumina can be used. The high alumina content alumina cement has an alumina content of 60% by mass or more of the total mass of the alumina cement, and the alumina content in alumina cement has an alumina content of 45% by mass to 60% by mass.

Although water is not particularly limited, for example, tap water, distilled water, deionized water, etc. can be used. The content of water is preferably 20 to 100 parts by mass, more preferably 25 to 90 parts by mass, and still more preferably 30 to 80 parts by mass, based on 100 parts by mass of cement.

Preferably, the inorganic acid includes metaphosphoric acid, phosphorous acid, phosphoric acid, or phosphonic acid. Inorganic acids including metaphosphoric acid, phosphorous acid, phosphoric acid, or phosphonic acid include, for example, diphosphorus pentoxide, diphosphoric acid, triphosphoric acid, aminotrimethylenephosphonic acid, 2-aminoethylphosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, tetramethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, phosphonobutanetricarboxylic acid, N-(phosphonomethyl)imino It may be diacetic acid, 2-carboxyethylphosphonic acid, 2-hydroxyphosphonocarboxylic acid, and the like. Inorganic acids can be used alone or in combination of two or more. The content of the inorganic acid is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, and particularly preferably 0. .3 to 10 parts by mass.

The aggregate is, for example, sand. As the sand, sands such as silica sand, river sand, sea sand, mountain sand, and crushed sand can be used. The particle size of the sand is preferably less than 2000 μm, more preferably less than 1180 μm, from the viewpoint of ease of extrusion of hydraulic mortar. The particle size of sand can be measured using several sieves with different opening sizes as defined in JIS Z 8801-2006. When the cement-containing liquid contains sand, the content of sand in the cement-containing liquid is, for example, 30 to 80% by mass, preferably 40 to 70% by mass, more preferably 40 to 70% by mass, based on the total mass of cement and sand. It is 50 to 70% by mass.

When the cement-containing liquid contains aggregate, the mortar flow is preferably 105 mm or more at 0 stroke flow, more preferably 107 mm or more, in order to ensure fluidity. The mortar flow of the hydraulic mortar is preferably 103 mm or less, more preferably 102 mm or less at 0 stroke flow.

In addition to cement, water, inorganic acid, and sand, the cement-containing liquid contains thickeners, slag, coal ash, ink, pigments, dispersants, setting regulators, expanding agents, shrinkage reducers, gypsum, antifoaming agents, It may also contain short fibers and the like.

Preferred thickeners include xanthan gum, diutan gum, starch ether, guar gum, polyacrylamide, carrageenan gum, agar, and clay mineral bentonite. Thickeners can be used alone or in combination of two or more. Furthermore, the above-mentioned thickeners may be used in combination with cellulose-based, protein-based, latex-based, or water-soluble polymer-based thickeners.

The viscosity of the cement-containing liquid is, for example, 1.0×10 ² to 1.2×10 ⁵ mPa at a temperature of 20° C. and a shear rate of 10 s ⁻¹ from the viewpoint of achieving good fluidity during liquid feeding. - It is preferable that it is s. The viscosity of the cement-containing liquid measured at a temperature of 20° C. and a shear rate of 0.1 s ⁻¹ may be, for example, 1.0×10 ³ to 5.0×10 ⁶ mPa·s. The viscosity of the cement-containing liquid can be adjusted, for example, by adjusting the water-cement ratio and the amount of thickener added.

(alkaline solution)
The alkaline solution contains an alkaline source and an ionic emulsion type thickener. There is no particular limitation as long as the pH of the alkaline solution is greater than 7 and less than or equal to 14, but it is preferably a solution with a pH of greater than or equal to 9 and less than or equal to 14. Examples of the alkaline solution include solutions containing sodium hydroxide, amines, alkanolamines, sodium orthosilicate, lithium hydroxide, aminomethylpropanol, calcium hydroxide, potassium hydroxide, sodium aluminate, and the like.

Ionic emulsion type thickeners are ionic (anionic or cationic) and emulsion type thickeners. Ionic thickeners include acrylic acid metal salt polymers, methacrylic acid metal salt polymers, quaternary ammonium salt polymers, acrylamide polymers, acrylic acid quaternary ammonium salt polymers, methacrylic acid quaternary ammonium salt polymers, Examples include carboxylic acid polymers. An emulsion is a state in which these polymers are emulsified, and is solubilized by adding it to an alkaline solution at the time of use.

The viscosity of the alkaline solution is not particularly limited, and for example, the viscosity of the alkaline solution measured at a temperature of 20° C. and a shear rate of 10 s ⁻¹ is, for example, 2.0×10 ² to 2.0×10 ⁴ mPa・s, the lower limit may be 2.5×10 ² mPa・s or 3.0×10 ² mPa・s, and the upper limit is 1.80×10 ⁴ mPa・s or 1.90×10 ⁴ It may be mPa·s.

<Hydraulic paste for additive manufacturing>
A hydraulic paste for additive manufacturing is prepared by mixing an aggregate-free cement-containing liquid and an alkaline solution containing an ionic emulsion-type thickener. When a cement-containing liquid is mixed with an ionic emulsion-type thickener, the viscosity increases rapidly and a hydraulic paste with excellent lamination properties is obtained. The viscosity of the hydraulic paste measured at a temperature of 20° C. and 10 s ⁻¹ is, for example, 1.0×10 ⁵ to 1.0×10 ⁶ mPa·s. The viscosity of the hydraulic paste measured at a temperature of 20° C. and 0.1 s ⁻¹ is, for example, 5.0×10 ⁶ to 6.0×10 ⁷ mPa·s.

The pot life of a hydraulic paste for additive manufacturing that is a mixture of a cement-containing liquid and an alkaline solution is determined by the water-cement ratio of the cement-containing liquid and alkaline solution, the amount of solute in the alkaline solution, the type of thickener, the type of solute, the amount of gypsum, It can be adjusted by changing the concentration of inorganic acid, the amount of coagulation regulator, etc. The pot life is, for example, 10 seconds to 300 minutes, the lower limit may be 20 seconds or 30 seconds, and the upper limit may be 250 minutes or 200 minutes.

<Hydraulic mortar for additive manufacturing>
Hydraulic mortar can be produced by mixing the cement-containing liquid containing aggregate with an alkaline solution containing a thickener. The aggregate used in hydraulic mortar is preferably sand.

<Laminated body>
The method for manufacturing a laminate according to the present embodiment includes (A) mixing the cement-containing liquid and the alkaline solution to obtain a hydraulic composition (hydraulic paste or hydraulic mortar); (B) The method includes a step of shaping a laminate of the hydraulic composition, for example, by a method such as extrusion. The laminate according to this embodiment is made of a cured product of a hydraulic composition, and is, for example, a three-dimensional structure.

The hydraulic composition may contain a coloring component in addition to the cement-containing liquid and the alkaline solution. Coloring components include paints, pigments, and the like. The coloring component may be added at any step before obtaining the hydraulic composition; for example, it may be contained in the cement-containing liquid or the alkaline solution, or it may be directly added to a mixer for both liquids. In addition, from the viewpoint of preparing a sufficiently uniformly colored cement slurry in a mixer, it is preferable that a coloring component is included in advance in the cement-containing liquid, which is used in a larger amount than an alkaline solution.

Hereinafter, the present invention will be explained in more detail based on specific examples, but the present invention is not limited to the following examples in any way, and can be carried out with appropriate modifications within the scope of the gist. It is possible to do so.

<Method of measuring shear viscosity>
The shear viscosity of the material and sample was measured as follows. That is, a coaxial double cylindrical jig CC27 and a vane-shaped measuring jig ST14-4V-35 were attached to a rheometer ReolabQC manufactured by Anton Paar. Measurements were performed for 180 seconds at a temperature of 20° C. and a shear rate of 0.1 s ⁻¹ and 10 s ⁻¹ , respectively. In addition, for the measurement, a sample was used after 3 minutes had passed after kneading. In the table, "M-" indicates that the viscosity was lower than the torque detection limit of the device due to low viscosity.

<Fluidity and stackability evaluation>
After 3 minutes of kneading, the sample was placed in a cylindrical cup, tilted at 135°, and held for 10 seconds.
(Liquidity evaluation criteria)
○: Flowed at an angle of 135°.
×: No flow occurred when tilted at 135°.
(Evaluation criteria for stackability)
○: It did not flow when it was tilted at 135°.
×: Flowed at an angle of 135°.

<Flow test>
A flow test was conducted in accordance with "JIS R 5201: Physical testing method for cement." In addition, the sample was used after 3 minutes of kneading and mixing, and the flow value was measured as the flow value MF ₀ (flow at 0 stroke) immediately after the flow cone was removed and the flow value MF ₁₅ after 15 strokes. did. Note that the diameter of the bottom surface of the flow cone was φ100 mm.

<Materials used>
The following materials were prepared.
・Hydraulic binder: alumina cement with high alumina content (Al ₂ O ₃ : 68.7%) and hemihydrate gypsum (alumina cement: hemihydrate gypsum = 70:30)
・Inorganic acid: phosphoric acid (concentration: 85wt%)
・Cement-containing liquid A0: 51.2 parts by mass of water and 1.6 parts by mass of the above inorganic acid are blended with 100 parts by mass of the above hydraulic binder (MF ₀ : 203 mm)
・Alkaline solution B0: NaOH aqueous solution (concentration: 3 mol/L)
- Thickener C: Acrylic acid polymer/anionic/emulsion (viscosity of a product with a solid content of 35% measured at a temperature of 20°C and a shear rate of 10 s ^-1 , 2.69 x 10 ² mPa s)
・Thickener D: Methacrylate quaternary ammonium salt polymer/cationic/emulsion (viscosity of product with solid content of 35% measured at a temperature of 20°C and a shear rate of 10 s ^-1 , 5.20 x 10 ¹ mPa s )
・Thickener E: Quaternary ammonium salt-based polymer/cationic/emulsion (viscosity of a product with a solid content of 40% measured at a temperature of 20°C and a shear rate of 10 s ^-1 , 1.03 x 10 ³ mPa・s )
・Thickener F: Acrylamide polymer/nonionic/emulsion (viscosity of a product with a solid content of 35% measured at a temperature of 20°C and a shear rate of 10s ^-1 : 6.68×10 ² mPa・s)
・Thickener G: Diutan gum/Anionic/Powder ・Thickener H: Cellulose/Nonionic/Powder ・Sand: Kashima No. 6 silica sand (manufactured by Takano Shoji Co., Ltd.)

Table 1 shows the shear viscosity and evaluation results of each material. Note that since the thickeners G and H were powders, it was not possible to measure the shear viscosity and evaluate the fluidity and lamination properties.

(Preparation of cement-containing liquid A1)
Cement-containing liquid A0 (100 parts by mass) and thickener C (0.71 parts by mass) were placed in a plastic container and mixed for 20 seconds at a rotation speed of 1200 rpm using a three-one motor (stirring blade: disk turbine type). . Thereby, cement-containing liquid A1 (paste) was obtained. Table 2 shows the shear viscosity and evaluation results of cement-containing liquid A1. The flow value MF ₀ of the cement-containing liquid A1 was 102 mm, and MF ₁₅ was 121 mm. From the fluidity evaluation and flow value, it was found that the cement-containing liquid A1, in which the thickener C was added to the cement-containing liquid A0, had insufficient fluidity.

(Preparation of cement-containing liquids A2 to A6)
Cement-containing liquids A2 to A6 were prepared in the same manner as cement-containing liquid A1, except that thickeners D to H were used instead of thickener C. Table 2 shows the shear viscosity and evaluation results of cement-containing liquids A1 to A6. It was found that fluidity could not be ensured in cement-containing liquids to which a thickener was added (excluding cement-containing liquid A4).

(Preparation of cement-containing liquid A7)
Cement-containing liquid A0 (100 parts by mass) and sand (same mass as the hydraulic binder contained in cement-containing liquid A0) are placed in a plastic container, and a three-one motor (stirring blade: disk turbine type) is used to increase the number of rotations. The mixture was mixed at 1200 rpm for 1 minute. As a result, cement-containing liquid A7 (mortar, water/binder = 0.51, sand/binder = 1.0) was obtained. Table 3 shows the shear viscosity and evaluation results of cement-containing liquid A7. The flow value MF ₀ of cement-containing liquid A7 was 163 mm, and MF ₁₅ was 186 mm. The flow value showed that the fluidity was high.

(Preparation of cement-containing liquid A8)
Cement-containing liquid A8 was prepared in the same manner as cement-containing liquid A7, except that the amount of sand was increased by 1.5 times. That is, the water/binder ratio of cement-containing liquid A8 was set to 0.51, and the sand/binder ratio was set to 1.5. Table 3 shows the evaluation results for cement-containing liquid A8. The fluidity evaluation of cement-containing liquid A8 was ○. The flow value MF ₀ of cement-containing liquid A8 was 115 mm, and MF ₁₅ was 150 mm.

(Preparation of cement-containing liquid A9)
Cement-containing liquid A8 was prepared in the same manner as cement-containing liquid A7, except that the amounts of water and sand were changed. That is, the water/binder ratio of cement-containing liquid A9 was set to 0.6, and the sand/binder ratio was set to 2.0. Table 3 shows the evaluation results for cement-containing liquid A9. The fluidity evaluation of cement-containing liquid A9 was ○. The flow value MF ₀ of cement-containing liquid A9 was 107 mm.

(Preparation of cement-containing liquid A10)
0.71 parts by mass of thickener C was added to cement-containing liquid A7 (100 parts by mass) and mixed for 20 seconds at a rotation speed of 1200 rpm using a three-one motor (stirring blade: disk turbine type). As a result, cement-containing liquid A10 (water/binder = 0.51, sand/binder = 1.0) was obtained. Table 3 shows the shear viscosity and evaluation results of cement-containing liquid A10. The flow value MF ₀ of cement-containing liquid A10 was 100 mm, and MF ₁₅ was 112 mm. The fluidity evaluation of cement-containing liquid A10 was ×. It was found that fluidity could not be ensured when a thickener was added to the cement-containing liquid.

(Preparation of alkaline solution B1)
After putting alkaline solution B0 (100 parts by mass) and thickener C (11.6 parts by mass) into a 100 mL glass screw tube, the tube was covered with a lid and mixed by hand. In order to stabilize the sample, it was left undisturbed for 24 hours. Table 4 shows the shear viscosity and evaluation results of alkaline solution B1.

(Preparation of alkaline solutions B2 to B4)
Alkaline solutions B2 to B4 were prepared in the same manner as alkaline solution B1, except that thickeners D to F were used instead of thickener C, respectively. Table 4 shows the shear viscosity and evaluation results of alkaline solutions B2 to B4.

(Alkaline solution B5)
Alkaline solution B0 (100 parts by mass) was placed in a plastic container, and while stirring at a rotation speed of 1200 rpm using a three-one motor (stirring blade: disk turbine type), thickener G (11.6 parts by mass) was added to the lumps. I added it to make sure it doesn't happen. After adding the entire amount of thickener G, the mixture was further kneaded for 1 minute at a rotational speed of 1200 rpm. In order to stabilize the sample, it was covered with a lid to prevent water from evaporating and left to stand for 24 hours. Table 4 shows the shear viscosity and evaluation results of alkaline solution B5.

(Alkaline solution B6)
Alkaline solution B6 was prepared in the same manner as alkaline solution B5, except that thickener H was used instead of thickener G. Table 4 shows the shear viscosity and evaluation results of alkaline solution B6.

[Example 1]
Add alkaline solution B1 (6.83 parts by mass) to a plastic container containing cement-containing liquid A0 (100 parts by mass), and use a three-one motor (stirring blades: disk turbine type) to stir the mixture at a rotation speed of 1200 rpm for 20 minutes. Mixed for a second. Thereby, hydraulic paste P1 was obtained. Table 5 shows the shear viscosity and evaluation results of hydraulic paste P1. The flow value MF ₀ of the hydraulic paste P1 was 100 mm, and the MF ₁₅ was 126 mm.

To summarize the above, the fluidity of the cement-containing liquid A0 and the alkaline solution B1 is ○, and the lamination property of the hydraulic paste P1 that is a mixture of these is ○, and the flow value MF ₀ is 100 mm. It is possible to achieve both liquid delivery performance and lamination performance in the modeling process.

[Example 2]
A hydraulic paste P2 was obtained in the same manner as in Example 1, except that alkaline solution B2 was used instead of alkaline solution B1. Table 5 shows the shear viscosity and evaluation results of hydraulic paste P2. The hydraulic paste P2 is also capable of achieving both liquid delivery performance and lamination performance in the additive manufacturing process.

[Example 3]
A hydraulic paste P3 was obtained in the same manner as in Example 1 except that alkaline solution B3 was used instead of alkaline solution B1. Table 5 shows the shear viscosity and evaluation results of hydraulic paste P3. The hydraulic paste P3 is also capable of achieving both liquid delivery performance and lamination performance in the additive manufacturing process.

[Comparative example 1]
Add alkaline solution B0 (6.11 parts by mass) to a plastic container containing cement-containing liquid A0 (100 parts by mass), and use a three-one motor (stirring blades: disk turbine type) to stir the mixture at a rotation speed of 1200 rpm for 20 minutes. Mixed for a second. Thereby, hydraulic paste P4 was obtained. Table 5 shows the shear viscosity and evaluation results of hydraulic paste P4. The fluidity of both the cement-containing liquid A0 and the alkaline solution B0 is ○, but the lamination property of the hydraulic paste after mixing is poor, so it is difficult to achieve both liquid feedability and lamination property.

[Comparative example 2]
Hydraulic paste P5 was obtained in the same manner as in Comparative Example 1 except that cement-containing liquid A4 was used instead of cement-containing liquid A0. Table 5 shows the shear viscosity and evaluation results of hydraulic paste P5. Both the cement-containing liquid A4 and the alkaline solution B0 have a fluidity of ○, but the laminability of the hydraulic paste after mixing is poor, so it is difficult to achieve both liquid feedability and lamination.

[Example 4]
Add alkaline solution B1 (4.16 parts by mass) to a plastic container containing cement-containing liquid A7 (100 parts by mass), and use a three-one motor (stirring blades: disk turbine type) to stir the mixture at a rotation speed of 1200 rpm for 20 minutes. Mixed for a second. Thereby, hydraulic mortar M1 was obtained. Table 6 shows the shear viscosity and evaluation results of hydraulic mortar M1. From the results shown in Table 6, the hydraulic mortar M1 is capable of achieving both liquid delivery performance and lamination performance in the additive manufacturing process.

[Example 5]
Hydraulic mortar M2 was obtained in the same manner as in Example 4, except that cement-containing liquid A8 was used instead of cement-containing liquid A7. Table 6 shows the evaluation results of hydraulic mortar M2. Hydraulic mortar M2 is also capable of achieving both liquid delivery performance and lamination performance in the additive manufacturing process.

[Example 6]
Hydraulic mortar M3 was obtained in the same manner as in Example 4, except that cement-containing liquid A9 was used instead of cement-containing liquid A7. Table 6 shows the evaluation results of hydraulic mortar M3. Hydraulic mortar M3 is also capable of achieving both liquid delivery performance and lamination performance in the additive manufacturing process.

Claims (11)

A method for producing a hydraulic composition for additive manufacturing, comprising a step of mixing a cement-containing liquid containing alumina cement, water and phosphoric acid, and an alkaline solution containing an ionic emulsion type thickener. The method for producing a hydraulic composition for additive manufacturing according to claim 1, wherein the cement-containing liquid further contains aggregate. A hydraulic composition for additive manufacturing, which is made by mixing a cement-containing liquid containing alumina cement, water and phosphoric acid, and an alkaline solution containing an ionic emulsion type thickener. The hydraulic composition for additive manufacturing according to claim 3, wherein the cement-containing liquid further contains aggregate. A laminate comprising a cured product of the hydraulic composition for layered manufacturing according to claim 3 or 4. (A) mixing a cement-containing liquid containing alumina cement, water and phosphoric acid, and an alkaline solution containing an ionic emulsion type thickener to obtain a hydraulic composition for additive manufacturing ;
(B) a step of modeling a laminate of the hydraulic composition for additive manufacturing ;
A method for manufacturing a laminate, including: The method for manufacturing a laminate according to claim 6, wherein the cement-containing liquid further contains aggregate. a cement-containing liquid containing alumina cement, water and phosphoric acid;
an alkaline solution containing an ionic emulsion type thickener;
A two-component hydraulic material for additive manufacturing in which these are separated,
A two-component hydraulic material for additive manufacturing , wherein the alkaline solution has a viscosity of 2.0×10 ² to 2.0×10 ⁴ mPa·s at 20° C. and a shear rate of 10 s ⁻¹ . a cement-containing liquid containing alumina cement, water and phosphoric acid;
an alkaline solution containing an ionic emulsion type thickener;
A two-component hydraulic material for additive manufacturing in which these are separated,
A two-component hydraulic material for additive manufacturing , wherein the cement-containing liquid has a viscosity of 1.0×10 ² to 1.2×10 ⁵ mPa·s at a temperature of 20° C. and a shear rate of 10 s ⁻¹ . a cement-containing liquid containing alumina cement, water and phosphoric acid;
an alkaline solution containing an ionic emulsion type thickener;
A two-component hydraulic material for additive manufacturing in which these are separated,
the cement-containing liquid further includes aggregate;
A two-component hydraulic material for additive manufacturing , wherein the mortar flow of the cement-containing liquid is 105 mm or more at zero stroke flow. a cement-containing liquid containing alumina cement, water and phosphoric acid;
an alkaline solution containing an ionic emulsion type thickener;
A two-component hydraulic material in which these are separated,
A two-component hydraulic material for additive manufacturing.