Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/307—Handling of material to be used in additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing

Definitions

• This disclosure relates to a modeling liquid, a modeling material set, and a method for manufacturing a modeled object.
• a method called powder bonding lamination method which is a kind of layered manufacturing method, is known (see, for example, Patent Document 1).
• a water-based fluid is supplied from an inkjet head to a granular material containing cast sand and plaster containing mineral gypsum that binds the cast sand to each other to form a layer having a cross-sectional shape of a three-dimensional product. It is formed and each layer is combined to produce a model.
• the thermal method and the piezo method are known as the inkjet method.
• the thermal inkjet head is generally used in the powder fixing laminating method because it easily ejects a liquid containing a large amount of water.
• the piezo type inkjet head which has superior durability, instead of the thermal type inkjet head, which has a short service life.
• the method of applying the pressure for discharging the liquid is different from that of the thermal type inkjet head, and a separate composition design for performing high-speed and stable discharge is required.
• the present disclosure is used for modeling a powder material that can be cured with water, and a modeling liquid having both ejection properties from a piezo inkjet head and curability, a modeling material set including the modeling liquid, and the modeling.
• the present invention relates to providing a method for manufacturing a modeled object using a liquid for use.
• a modeling liquid used for modeling a powder material that can be cured with water contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationship of the following formulas 1 and 2, a piezo type inkjet. For modeling liquid.
• a modeling liquid used for modeling a powder material that can be cured with water contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationship of the following formulas 3 and 4, a piezo type inkjet.
• Equation 4 y1 ⁇ 2241.0 ⁇ (x1) ⁇ 0.626 ⁇ 3>
• the modeling liquid contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• the viscosity at 20 ° C. is 2.0 mPa ⁇ s to 20 mPa ⁇ s.
• a modeling liquid for piezo inkjet. ⁇ 4> The modeling liquid according to ⁇ 3>, which has a viscosity at 20 ° C. of 4 mPa ⁇ s to 20 mPa ⁇ s.
• the viscosity modifier contains, in addition to the component A, a component B, which is a water-soluble polymer having a number average molecular weight of 60 to 900.
• the content of the component A is 23.0% by mass or less with respect to the total amount of the modeling liquid.
• the content of the component B is 1.0% by mass to 10% by mass with respect to the total amount of the modeling liquid.
• the total content of the component A and the component B is 24% by mass or less with respect to the total amount of the modeling liquid.
• ⁇ 6> The modeling liquid according to ⁇ 5>, wherein the water-soluble polymer of the component B has an ethylene glycol unit.
• ⁇ 7> The modeling liquid according to any one of ⁇ 1> to ⁇ 6>, wherein the water-soluble polymer of the component A has an ethylene glycol unit.
• the powder material can be molded by the powder fixing lamination method.
• the powder material comprises an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains
• the powdery precursor contains a curable component and a cure-promoting component.
• the aggregate contains 75% by mass to 97% by mass of at least one selected from the group consisting of ZrO 2 and Al 2 O 3 and 2% by mass to 25% by mass of SiO 2 as chemical components.
• Artificial casting sand the modeling liquid according to ⁇ 11>.
• the modeling liquid according to any one of ⁇ 1> to ⁇ 12>, and A powder material that can be cured with water and Equipped with The powder material comprises an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains
• the powdery precursor contains a curable component and a cure-promoting component. Material set for modeling.
• the aggregate contains 75% by mass to 97% by mass of at least one selected from the group consisting of ZrO 2 and Al 2 O 3 and 2% by mass to 25% by mass of SiO 2 as chemical components.
• Artificial casting sand the modeling material set according to ⁇ 13>.
• the modeling liquid according to any one of ⁇ 1> to ⁇ 12> is dropped onto a water-curable powder material by a piezo-type inkjet method to cure the powder material.
• the powder material comprises an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains
• the powdery precursor contains a curable component and a cure-promoting component. Manufacturing method of the modeled object.
• a modeling liquid used for modeling a powder material that can be cured with water and having both dischargeability and curability from a piezo inkjet head, a modeling material set including the modeling liquid, and a modeling material set.
• a method for manufacturing a modeled object using the modeling liquid is provided.
• each component may contain a plurality of applicable substances.
• the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
• the description referring to the first to fourth embodiments is a description of each corresponding embodiment, and the description not mentioned in any of the first to fourth embodiments is the first. It is applicable to any of the first to fourth embodiments.
• the modeling liquid according to the first to fourth embodiments may be comprehensively referred to as the modeling liquid of the present disclosure, or simply the modeling liquid.
• the modeling liquid is It is a modeling liquid for piezo inkjet. Used for modeling water-curable powder materials, The modeling liquid contains water and a viscosity modifier. The water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationships of the following formulas 1 and 2. [Equation 1] y1 ⁇ 4654.9 ⁇ (x1) ⁇ 0.622
• Equation 2 y1 ⁇ 2241.0 ⁇ (x1) ⁇ 0.69
• the modeling liquid is It is a modeling liquid for piezo inkjet. Used for modeling water-curable powder materials, The modeling liquid contains water and a viscosity modifier. The water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationships of the following formulas 3 and 4. [Equation 3] y1 ⁇ 4654.9 ⁇ (x1) ⁇ 0.622
• the modeling liquid is It is a modeling liquid for piezo inkjet. Used for modeling water-curable powder materials, The modeling liquid contains water and a viscosity modifier. The water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• the viscosity at 20 ° C. is 2.0 mPa ⁇ s to 20 mPa ⁇ s.
• the modeling liquid is It is a modeling liquid for piezo inkjet. Used for modeling water-curable powder materials, The modeling liquid contains water and a viscosity modifier. The water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000. The viscosity at 20 ° C. is 4 mPa ⁇ s to 20 mPa ⁇ s.
• the modeling liquid according to the first to fourth embodiments is excellent in ejection property from the piezo type inkjet head. It was also found that the curability of the model obtained by using the modeling liquid of the first to fourth embodiments was well maintained.
• the viscosity of the modeling liquid at 20 ° C. is preferably 2.0 mPa ⁇ s to 20 mPa ⁇ s, more preferably 4 mPa ⁇ s to 20 mPa ⁇ s, and further preferably 5 mPa ⁇ s to 15 mPa ⁇ s. It is preferably 6 mPa ⁇ s to 12 mPa ⁇ s, and is particularly preferable. It has been found that when the viscosity is in the above range, the ejection property from the piezo type inkjet head is excellent.
• the viscosity of the liquid for modeling at 20 ° C. is preferably 2.0 mPa ⁇ s or more, and 2.3 mPa ⁇ s or more. Is more preferable, 2.5 mPa ⁇ s or more is further preferable, and 3.0 mPa ⁇ s to 9.0 mPa ⁇ s is particularly preferable. Further, the viscosity of the modeling liquid at 20 ° C.
• mPa ⁇ s or less is preferably 20 mPa ⁇ s or less, more preferably 15 mPa ⁇ s or less, further preferably 12 mPa ⁇ s or less, and 10 mPa ⁇ s or less. Is particularly preferable, 9.0 mPa ⁇ s or less is particularly preferable, 7.0 mPa ⁇ s or less is extremely preferable, and 6.5 mPa ⁇ s or less is most preferable. It has been found that when the viscosity is within the above range, the ejection property from the piezo-type inkjet head capable of ejecting a relatively low-viscosity liquid for modeling is excellent, and the curing property of the modeled object is excellent.
• the viscosity of the modeling liquid according to the third embodiment at 20 ° C. is 2.0 mPa ⁇ s to 20 mPa ⁇ s, and the preferable viscosity range is as described above.
• the viscosity of the modeling liquid according to the fourth embodiment at 20 ° C. is 4 mPa ⁇ s to 20 mPa ⁇ s, and the preferable viscosity range is as described above.
• the viscosity of the modeling liquid can be measured with a rotary leometer (for example, manufactured by Antonio-Paar, MCR) at a shear rate of 500 / s. Specifically, it can be measured by the method described in Examples.
• the modeling liquid can form a powder material by a powder fixing lamination method.
• a powder fixing lamination method each component of the modeling liquid will be described.
• the viscosity adjusting agent contains the component A, and may optionally contain the component B described later, other additives, and the like.
• the viscosity modifier may be used alone or in combination of two or more.
• the "water-soluble polymer” refers to a polymer having a solubility of 1 g / 100 g or more in water at 25 ° C.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• the type of the water-soluble polymer is not particularly limited, and may be any of a nonionic polymer, an anionic polymer, and a cationic polymer. From the viewpoint of expanding the choice of other additive components and the stability during long-term storage, the water-soluble polymer is preferably a nonionic polymer.
• water-soluble polymer examples include various water-soluble polymers such as carboxyvinyl polymer, acrylic acid-based polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, cellulose derivative, water-soluble polyurethane, polyallylamine, and copolymers thereof.
• the component A may be used alone or in combination of two or more.
• the water-soluble polymer of component A may be a water-soluble polymer having ethylene glycol units.
• component A may be polyethylene glycol.
• the water-soluble polymer of the component A may be a water-soluble polymer having a vinylpyrrolidone unit.
• component A may be polyvinylpyrrolidone.
• Component A may be liquid or solid at 25 ° C., and is typically solid.
• the number average molecular weight of the component A is preferably small from the viewpoint of intermittent ejection property, while it is preferably large from the viewpoint of improving the water content of the modeling liquid.
• the number average molecular weight of component A is 5,000 to 85,000.
• the number average molecular weight of component A is preferably 5,000 to 60,000, more preferably 8,000 to 60,000, and more preferably 10,000 to 60,000. More preferably, it is particularly preferably 10,000 to 50,000, and extremely preferably 10,000 to 40,000.
• the number average molecular weight of component A is preferably 5,000 to 50,000, more preferably 5,000 to 40,000, and more preferably 5,000 to 30,000.
• the number average molecular weight of the component A is in the above range, the ejection property from the piezo type inkjet head tends to be improved.
• the number average molecular weight of the polymer is a nominal value or a number average molecular weight measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the number average molecular weight measured by GPC is also referred to as an actually measured value.
• the polymer is a polymer having ethylene glycol units such as polyethylene glycol, the measured value is adopted when the nominal value and the measured value are different.
• the polymer is other than a polymer having ethylene glycol units (for example, a polymer having vinylpyrrolidone units such as polyvinylpyrrolidone), the nominal value is adopted, and if the nominal value is unknown, the measured value is adopted.
• the GPC conditions for measuring the number average molecular weight are as follows. In the case of a polymer having high solubility in tetrahydrofuran (THF), for example, a water-soluble polymer having ethylene glycol units, THF is used as a mobile phase, and a polystyrene (nominal value) -equivalent number average molecular weight is obtained.
• THF tetrahydrofuran
• N, N-dimethylformamide (DMF) is used as a mobile phase, and a polystyrene (nominal value) -equivalent number average molecular weight is obtained.
• a solvent containing water as a main component such as a phosphate buffer solution is used as a mobile phase, and a number average molecular weight in terms of polyethylene glycol (nominal value) is obtained.
• the inventors focused on the relationship between the number average molecular weight and the content of the water-soluble polymer, and conducted a diligent study. As a result, if the number average molecular weight and the content of the water-soluble polymer in the modeling liquid satisfy the above formulas 1 and 2, even if the water content is 76% by mass or more, the modeling liquid It has been found that the viscosity can be adjusted to a viscosity suitable for ejection from a piezo type inkjet head, and the curability of the modeled object can be maintained well.
• the inventors focused on the relationship between the number average molecular weight and the content of the water-soluble polymer, and conducted a diligent study. As a result, if the number average molecular weight and the content of the water-soluble polymer in the modeling liquid satisfy the above formulas 3 and 4, even if the water content is 76% by mass or more, the modeling liquid It has been found that the viscosity can be adjusted to a viscosity suitable for ejection from a piezo type inkjet head, and the curability of the modeled object can be maintained well.
• the content of component A with respect to the total amount of the modeling liquid is 24% by mass or less, preferably 20% by mass or less, and preferably 18% by mass or less from the viewpoint of curability. It is more preferably 16% by mass or less, and particularly preferably 14% by mass or less. Further, from the viewpoint of viscosity adjustment, the content of the component A may be 1% by mass or more, 2% by mass or more, or 3% by mass or more. From this point of view, the content of component A with respect to the total amount of the modeling liquid may be 1% by mass to 24% by mass, 1% by mass to 20% by mass, or 2% by mass to 18% by mass.
• the content or content of component A is the total content or total content of the water-soluble polymer having a number average molecular weight of 5,000 to 85,000 in the modeling liquid. Means rate.
• the viscosity modifier may contain a component B, which is a water-soluble polymer having a number average molecular weight of 60 to 900.
• the content of the component A is 23.0% by mass or less with respect to the total amount of the modeling liquid
• the content of the component B is 1.0% by mass to 10% by mass with respect to the total amount of the modeling liquid. It may be mass% and the total content of the component A and the component B may be 24% by mass or less with respect to the total amount of the modeling liquid.
• the discharge and stop of the modeling liquid are repeated.
• the liquid for modeling is discharged using the piezo type inkjet head, if the discharge is temporarily stopped, the liquid for modeling remaining in the discharge port may be locally thickened, resulting in nozzle clogging.
• the inventors can satisfactorily adjust the intermittent ejection property by blending a component B having a molecular weight lower than that of the component A in addition to the component A and further adjusting the contents of the two types of components to the above ratios. I found that.
• the type of the water-soluble polymer as the component B is not particularly limited, and may be any of a nonionic polymer, an anionic polymer, and a cationic polymer. From the viewpoint of expanding the choice of other additive components and the stability during long-term storage, the viscosity modifier is preferably a nonionic polymer.
• water-soluble polymer examples include various water-soluble polymers such as carboxyvinyl polymer, acrylic acid-based polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and cellulose derivative.
• component B one type may be used alone or two or more types may be used in combination.
• the water-soluble polymer of component B may be a water-soluble polymer having ethylene glycol units.
• component B may be polyethylene glycol.
• Component B may be liquid or solid at 25 ° C., and is typically a liquid.
• the number average molecular weight of the component B is 60 to 900, preferably 70 to 800, more preferably 80 to 700, 90 to 500, or 100 to 300. .. When the number average molecular weight of the component B is in the above range, the intermittent ejection property tends to be adjusted better.
• the total content of the component A and the component B is 24% by mass or less with respect to the total amount of the modeling liquid.
• the content of the component A is 23.0% by mass or less with respect to the total amount of the modeling liquid
• the content of the component B is 1 with respect to the total amount of the modeling liquid. It is preferably 0.0% by mass to 10% by mass.
• the content or content is the total content of the water-soluble polymer having a number average molecular weight of 5,000 to 85,000 in the modeling liquid. It means the amount or the total content.
• the content or content of component B refers to the total content or total content of a water-soluble polymer having a number average molecular weight of 60 to 900 in a modeling liquid. means.
• the content of component A with respect to the total amount of the modeling liquid is preferably 23.0% by mass or less, preferably 22.5% by mass, from the viewpoint of curability and intermittent ejection property. % Or less, more preferably 18.5% by mass or less, particularly preferably 16.5% by mass or less, and extremely preferably 14.5% by mass or less.
• the content of the component A may be 1.0% by mass or more, 2.0% by mass or more, or 3.0% by mass or more. From this point of view, the content of the component A with respect to the total amount of the modeling liquid may be 1.0% by mass to 23.0% by mass, or 1.0% by mass to 22.5% by mass. It may be 1.0% by mass to 18.5% by mass, 2.0% by mass to 16.5% by mass, or 3.0% by mass to 14.5% by mass. ..
• the content of the component B with respect to the total amount of the modeling liquid is preferably 1.0% by mass or more, preferably 1.5% by mass or more, from the viewpoint of intermittent ejection property. It may be present, may be 2.0% by mass or more, and may be 3.0% by mass or more. Further, from the viewpoint of viscosity adjustment by the component A, the content of the component B is preferably 10% by mass or less, may be 9.5% by mass or less, or may be 8.0% by mass or less. It may be 6.0% by mass or less. From this point of view, the content of component B with respect to the total amount of the modeling liquid is preferably 1.0% by mass to 10% by mass, and may be 1.5% by mass to 10.0% by mass. It may be 5.5% by mass to 9.5% by mass, 2.0% by mass to 8.0% by mass, or 3.0% by mass to 6.0% by mass.
• the modeling liquid of the present disclosure contains water.
• the content of water in the modeling liquid is large from the viewpoint of curability of the modeled body.
• the content of water in the modeling liquid is 76% by mass or more, preferably 80% by mass or more, more preferably 83% by mass or more, and 85% by mass, based on the total amount of the modeling liquid.
• the above is more preferable, 87% by mass or more is particularly preferable, 89% by mass or more is extremely preferable, and 90% by mass or more may be used.
• the content of water with respect to the total amount of the modeling liquid is determined according to the content of the viscosity modifier and other optional components, and may be 99% by mass or less, 97% by mass or less, 95. It may be mass% or less.
• the modeling liquid may further contain a surfactant.
• the surfactant functions as a surface energy regulator.
• the surfactant examples include acetylene glycol-based surfactants, silicon-based surfactants, fluorine-based surfactants, polyoxyalkylene alkyl ethers and the like.
• an acetylene glycol-based surfactant is preferable from the viewpoint of ensuring the water content because the surface energy can be adjusted with a small amount of addition.
• the total amount of the component A, the surfactant, and any component B and other additives is 24% by mass or less in order to secure the water content.
• the content of the surfactant is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and 0. It is more preferably 05% by mass or more.
• the content of the surfactant is preferably 2.0% by mass or less, preferably 1.5% by mass or less, based on the total amount of the modeling liquid. It is more preferably 1.0% by mass or less, and even more preferably 1.0% by mass or less.
• the content of the surfactant is preferably 0.01% by mass to 2.0% by mass, more preferably 0.03% by mass to 1.5% by mass, and more preferably 0.05. It is more preferably mass% to 1.0% by mass.
• the surface energy value of the modeling liquid can be quantified by measuring the surface tension. Specifically, it can be measured using a dynamic surface tensiometer (for example, BP-D5 manufactured by Kyowa Surface Chemistry Co., Ltd.).
• the surface tension of the modeling liquid at 25 ° C. is preferably 20 mN / m to 50 mN / m, more preferably 25 mN / m to 40 mN / m, and further preferably 30 mN / m to 35 mN / m. preferable.
• the modeling liquid may contain additives other than the above-mentioned components such as preservatives, pH adjusters, colorants, and defoamers.
• the content of the additive is selected within the range in which the curability of a practically shaped product can be obtained.
• the content of component A, any component B, any surfactant, and additives other than these components is the content of the modeling liquid in order to secure the water content. It is 24% by mass or less with respect to the total amount.
• the modeling liquid does not contain volatile components other than water, or even if it is contained, the content is 10% by mass or less, more preferably 5 with respect to the total amount of the modeling liquid. It is preferably suppressed to mass% or less, more preferably 3 mass% or less.
• the volatile component refers to a component whose weight is reduced by 5% or more when thermogravimetric measurement is performed at 200 ° C. for 1 hour, and examples thereof include a solvent.
• the modeling liquid is for piezo inkjet and is used for modeling a powder material that can be cured with water. Any inkjet head can be used.
• Any inkjet head can be used.
• the modeling may be performed by a powder fixing lamination method including dropping a modeling liquid onto the powder material to cure the powder material.
• the powder fixation laminating method after laminating the cured powder material, the work of taking out the modeled object from the uncured powder material is performed.
• the liquid for modeling of the present disclosure is considered to be useful from the viewpoint of ensuring the strength of the modeled object and suppressing defects such as chipping.
• the modeling liquid of the present disclosure is used for a powder material that can be cured with water.
• the powder material is not particularly limited as long as it is a powder material containing a component that can be cured with water.
• the water-curable component include Portoland cement, alumina cement, quick-hardening cement, phosphoric acid cement, water glass, phosphoric acid compound, metal alkoxide material, sulfate, polyaluminum chloride and the like.
• the component that can be cured with water one type may be used alone or two or more types may be used in combination.
• the powder material comprises an aggregate and a powdery precursor that binds the aggregate to each other, the aggregate comprises casting sand, and the powdery precursor is a curable component. And a curing promoting component.
• the casting sand used as an aggregate may be natural casting sand or artificial casting sand such as ceramics.
• foundry sand for example, as a chemical component, at least one selected from the group consisting of ZrO 2 and Al 2 O 3 is contained in an amount of 75% by mass to 97% by mass, and SiO 2 is contained in an amount of 2% by mass to 25% by mass. Can be mentioned.
• FINE-Bz manufactured by AGC Ceramics Co., Ltd.
• Lunamos manufactured by Kao Quaker Co., Ltd.
• AR SAND manufactured by Gunei Chemical Industry Co., Ltd.
• Naigai Cera Beads manufactured by Itochu Ceratech Co., Ltd.
• Zircon sand chromate sand
• Espard manufactured by Yamakawa Sangyo Co., Ltd.
• spherical silica spherically processed silica sand, etc.
• At least one selected from the group consisting of ZrO 2 and Al 2 O 3 as chemical components is 75% by mass to 97% by mass, and SiO 2 is 2% by mass from the viewpoint of high refractory and high thermal conductivity.
• FINE-Bz which is a refractory particle containing up to 25% by mass, is preferable.
• the powdery precursor functions as a binder for binding aggregates to each other.
• the curable component in the powdery precursor include the above-mentioned Portoland cement, alumina cement, quick-hardening cement, phosphoric acid cement, water glass, phosphoric acid compound, metal alkoxide material, sulfate, polyaluminum chloride and the like.
• the curing accelerating component is not particularly limited as long as it has a function of accelerating the curing of the curable component, and a lithium salt or quicklime is preferable.
• the lithium salt examples include lithium carbonate, lithium hydrogen carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium oxalate and the like, and lithium carbonate is preferable from the viewpoint of availability and stability.
• the powdery precursor may optionally contain silica fume, magnesia ultrafine powder, heat-resistant resin and the like as functional components.
• the powder material may contain an adjusting agent that prevents water from seeping into the vicinity of the position where water is added when water is added to the powder material.
• an adjusting agent that prevents water from seeping into the vicinity of the position where water is added when water is added to the powder material.
• examples of such a modifier include sodium silicate, polyvinyl alcohol, carboxymethyl cellulose, dextrin and the like.
• each component in the powder material may be used alone or in combination of two or more. Details of the powder material of this embodiment are as described in International Publication No. 2018/212310.
• a modeling material set comprising the above-mentioned modeling liquid of the present disclosure and a water-curable powder material is provided.
• the modeling liquid of the present disclosure and a water-curable powder material are provided as a set in separate containers. Details of the modeling liquid and powder material are as described above.
• a method for producing a modeled product which comprises dropping the above-mentioned modeling liquid of the present disclosure onto a water-curable powder material by a piezo-type inkjet method to cure the powder material. Will be done. Details of the modeling liquid and powder material are as described above.
• Examples 5 to 7, 12 to 17, 19 to 23, 25, and 26 are examples, and Examples 1 to 4, 8 to 11, 18, and 24 are comparative examples.
• -Polyvinylpyrrolidone B Pittscol K-90 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• -Polyvinylpyrrolidone C Pittscol K-30L manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• glycerin, dipropylene glycol, and polyethylene glycols A and B are liquids
• polyethylene glycols C to G and polyvinylpyrrolidone A and B are solids.
• Polyvinylpyrrolidone C is an aqueous solution containing 30% by mass of solid polyvinylpyrrolidone.
• the blending amounts of the viscosity modifiers of Examples 25 and 26 in Table 2 are described in an amount corresponding to the solid polyvinylpyrrolidone contained in polyvinylpyrrolidone C.
• Surfactant 1 Orfin E1010 manufactured by Nissin Chemical Industry Co., Ltd.
• -Surfactant 2 Orfin E1004 manufactured by Nissin Chemical Industry Co., Ltd.
• Surfactant 3 Evonik, Surfinol 420
• the number average molecular weight (Mn) of the viscosity modifier was measured as follows. The sample was dissolved in tetrahydrofuran (THF) and the number average molecular weight in terms of polystyrene (nominal value) was measured using a gel permeation chromatography (GPC) device. Since polyethylene glycol has a different measured value from the nominal value, the measured value was adopted. Theoretical values were adopted for glycerin and dipropylene glycol. In addition, the nominal value was adopted for polyvinylpyrrolidone.
• THF tetrahydrofuran
• GPC gel permeation chromatography
• test solution was introduced and discharged from the piezo type head nozzle.
• the state of ejection from the nozzle was confirmed on the image, and those with no ejection abnormality such as bending were considered to be capable of ejection.
• "dischargeable” is represented by A and “dischargeable” is represented by C.
• "-" indicates that the evaluation has not been carried out.
• Tables 5 and 6 satisfy the formulas related to the number average molecular weight and content of the viscosity modifier, the comprehensive evaluation of the ejection property and the bending strength of the model, and the first and second embodiments in each example. Whether or not it is shown together.
• Tables 5 and 6 in the example in which a plurality of viscosity modifiers are used, the number average molecular weight and the content rate of the components comparatively examined as the component A are listed. Further, in the evaluation of 5,000 ⁇ x1 ⁇ 85,000 and whether or not each equation is satisfied, “y” indicates that the condition is satisfied, and “n” indicates that the condition is not satisfied.
• Example 1 and 2 using polyvinylpyrrolidone having a number average molecular weight of 360,000 and Example 8 using polyethylene glycol G having a number average molecular weight of 89,000 the ejection property was inferior. Further, even in Examples 9 to 11 in which the content of polyethylene glycol G was reduced by adding liquid low molecular weight polyethylene glycol in addition to polyethylene glycol G, intermittent discharge was stopped 1 second, 3 seconds, and 10 seconds later. Discharge resumption was not improved. In Examples 8 to 11, the ejection was not passed after 1 second, 3 seconds, and 10 seconds after the intermittent ejection stop, but the addition of liquid low-molecular-weight polyethylene glycol made the droplets fly. Since the improvement was observed, it was considered that the ejection property was improved by the addition of the liquid low molecular weight polyethylene glycol.
• Examples 5 to 8 when the viscosity is about 10 mPa ⁇ s and the molecular weight of polyethylene glycol is increased in the order of polyethylene glycol D, E, F, G, a suitable viscosity is obtained by adding a smaller amount of polyethylene glycol. And can increase the water content. Further, in Examples 6 to 9, it was confirmed that the water content was 90% by mass or more, and the modeled body exhibited high curability. On the other hand, in Examples 8 and 9 using polyethylene glycol G, although high curability was obtained, it was "failed" in the intermittent discharge test after 1 second, 3 seconds, and 10 seconds after stopping, and was practically used. The above was considered difficult to use.
• Example 12 the intermittent discharge property after 12 seconds was improved by adding the liquid polyethylene glycol A to the polyethylene glycol E. Further, in Examples 13 to 15, the intermittent ejection property was improved by reducing the molecular weight of the solid polyethylene glycol as compared with Example 12.
• Example 17 it was confirmed that the surface tension was relatively high, but there was no problem in ejection property and curability.
• Examples 1 to 17 it was found from the plot of the water content and the strength that good bending strength can be guaranteed when the water content is 76% by mass or more with respect to the total amount of the modeling liquid. Further, it was confirmed that when the water content is 90% by mass or more with respect to the total amount of the liquid for modeling, the modeled body can guarantee the better bending strength of the evaluation S. Further, by plotting the number average molecular weight (x1) of the water-soluble polymer and the content (y1 (%)) of the water-soluble polymer with respect to the total amount of the liquid for modeling, x1 and y1 are represented by the following formulas 3 and 4.
• Example 18 in order to achieve good curability, polyvinylpyrrolidone A having a relatively large molecular weight was used to increase the water content to 98% by mass, but the viscosity was low, and ejection abnormalities such as bending occurred in the ejection test, resulting in stability. Can not be discharged.
• Example 19 to 22 an appropriate viscosity can be obtained by increasing the amount of polyvinylpyrrolidone A added as compared with Example 18, stable ejection is possible, and the intermittent ejection test 3 seconds after stopping is passed. rice field.
• Example 23 stable ejection was possible, and it was at a level that could be practically used even in the intermittent ejection property test. Further, it was confirmed that the water content was 87% by mass or more, and the modeled body could secure the good bending strength of Evaluation A.
• Example 24 in which the amount of polyvinylpyrrolidone A added was increased, the evaluation of the bending strength was B, but stable ejection was not possible in the ejection test.
• Example 25 and 26 a liquid was prepared by adding polyvinylpyrrolidone C, which is an aqueous solution containing 30% by mass of polyvinylpyrrolidone having a number average molecular weight of 10,000. In Examples 25 and 26, an appropriate viscosity could be obtained, and stable ejection was possible. In Example 25, the intermittent discharge test after 5 seconds of stop was passed, and in Example 26, the intermittent discharge test after 3 seconds of stop was passed. In Examples 25 and 26, it was confirmed that the water content was 90% by mass or more, and the modeled body could secure a better evaluation S bending strength.
• Tables 5 and 6 show the number average molecular weight, the content of the viscosity modifier, and the values in [Equation 1] to [Equation 4] for each example. The following relationships can be found from Tables 5 and 6.
• the molecular weight (x1) of the water-soluble polymer is 5,000 to 85,000. It can be seen that x1 and y1 may be adjusted so as to satisfy the relations of the following equations 1 and 2.
• the disclosure also includes the following aspects: ⁇ 1> A modeling liquid used for modeling a powder material that can be cured with water.
• the modeling liquid contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationship of the following formulas 3 and 4, a piezo type inkjet.
• the modeling liquid contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• x1 and y1 satisfy the relationship of the following formulas 3 and
• a modeling liquid used for modeling a powder material that can be cured with water contains water and a viscosity modifier.
• the water content is 76% by mass or more with respect to the total amount of the modeling liquid.
• the viscosity modifier contains component A, which is a water-soluble polymer having a number average molecular weight of 5,000 to 85,000.
• the viscosity at 20 ° C. is 4 mPa ⁇ s to 20 mPa ⁇ s.
• a modeling liquid for piezo inkjet is 4 mPa ⁇ s to 20 mPa ⁇ s.
• the viscosity modifier contains, in addition to the component A, a component B, which is a water-soluble polymer having a number average molecular weight of 60 to 900.
• the content of the component A is 22.5% by mass or less with respect to the total amount of the modeling liquid.
• the content of the component B is 1.5% by mass to 10% by mass with respect to the total amount of the modeling liquid.
• the total content of the component A and the component B is 24% by mass or less with respect to the total amount of the modeling liquid.
• ⁇ 4> The modeling liquid according to ⁇ 3>, wherein the water-soluble polymer of the component B has an ethylene glycol unit.
• ⁇ 5> The modeling liquid according to any one of ⁇ 1> to ⁇ 4>, wherein the water-soluble polymer of the component A has an ethylene glycol unit.
• ⁇ 6> The modeling liquid according to any one of ⁇ 1> to ⁇ 5>, wherein the water content is 85% by mass or more with respect to the total amount of the modeling liquid.
• ⁇ 7> The modeling liquid according to any one of ⁇ 1> to ⁇ 6>, which has a viscosity at 20 ° C. of 5 mPa ⁇ s to 12 mPa ⁇ s.
• ⁇ 8> The modeling liquid according to any one of ⁇ 1> to ⁇ 7>, further containing a surfactant.
• the powder material contains an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains
• the powdery precursor contains a curable component and a cure-promoting component.
• ⁇ 11> The modeling liquid according to any one of ⁇ 1> to ⁇ 9>, and A powder material that can be cured with water and A set of materials for modeling.
• the powder material contains an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains The powdery precursor contains a curable component and a cure-promoting component.
• the modeling material set according to ⁇ 11>. ⁇ 13> The modeling liquid according to any one of ⁇ 1> to ⁇ 9> is dropped onto a water-curable powder material by a piezo-type inkjet method to cure the powder material. Including, manufacturing method of the modeled object. ⁇ 14>
• the powder material contains an aggregate and a powdery precursor that binds the aggregate to each other.
• the aggregate contains casting sand and contains The powdery precursor contains a curable component and a cure-promoting component.

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• 2021
  • 2021-12-13 JP JP2022569995A patent/JPWO2022131227A1/ja active Pending
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