Calcium carbonate coated material and method for producing the same

Abstract

The present invention provides a calcium carbonate coated material and a simple method for producing the calcium carbonate coated material. [Solution] A method for producing a calcium carbonate coated body, comprising a base material containing at least one selected from organic and inorganic materials and calcium carbonate, and having a calcium carbonate coating layer on at least a part of the surface of the base material, wherein the method for producing a calcium carbonate coated body includes the step of mixing a calcium ion-containing solution containing polycarboxylic acid amine, a carbonate ion-containing substance, a pH adjusting agent containing a base, and the base material.

Description

Technical Field

[0001] The present disclosure relates to a calcium carbonate coating and a method for producing the same.

Background Art

[0002] Modification of solid surfaces such as particles and substrates with organic molecules, polymers, metal oxides, etc. is carried out for the purpose of improving wear resistance, imparting mechanical properties such as elasticity, suppressing deterioration, controlling wettability, controlling adsorption and desorption properties, improving dispersibility in matrices such as solutions, resins, polymers, etc.

[0003] For example, Patent Document 1 discloses a method of forming a silica coating film on the surface of titanium oxide particles or zinc oxide particles to suppress the reactivity of the particles.

[0004] Also, Patent Document 2 discloses a method of forming a carbon nanotube coating film on the surface of a polymer substrate to impart electrical properties, etc. to the substrate.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Here, calcium carbonate can be cited as an example of the substance to be coated on the solid surface. Calcium carbonate is used as an additive for various materials such as resins, rubbers, plastics, paints, printing inks, paper making, etc., and a number of knowledges for appropriately dispersing it into these matrices have been established. Therefore, it can be said that core-shell particles coated with calcium carbonate can be easily dispersed in the matrix described above. Furthermore, by coating the surface of the substrate used in electrodes for sensors and the like, it is expected that, for example, the selectivity of the substance being measured can be improved.

[0007] However, the technology for coating solid surfaces such as particles and substrates with calcium carbonate has not been sufficiently studied. The same applies to its manufacturing methods.

[0008] Therefore, the object of this disclosure is to provide a calcium carbonate coated material that can exhibit useful properties, and a simple method for producing said calcium carbonate coated material. [Means for solving the problem]

[0009] The disclosing parties have diligently considered how to resolve the above-mentioned issues. As a result, we have come to realize that the above issues can be resolved by disclosing the following. In other words, the following [1] to [2] are provided by this disclosure. [1] A matrix containing at least one selected from organic and inorganic materials and calcium carbonate, A calcium carbonate coated body having a calcium carbonate coating layer on at least a portion of the surface of the base material. [2] A matrix containing at least one selected from organic and inorganic materials and calcium carbonate, A method for producing a calcium carbonate coated body, wherein at least a portion of the surface of the base material is covered with a calcium carbonate coating layer, A method for producing a calcium carbonate coated material, comprising the step of contacting a calcium ion-containing solution containing polycarboxylate amine, a carbonate ion-containing substance, a pH adjusting agent containing a base, and the base material. [Effects of the Invention]

[0010] This disclosure provides a calcium carbonate coating that can exhibit useful properties, and a simple method for producing the calcium carbonate coating. [Brief explanation of the drawing]

[0011] [Figure 1] These are transmission electron microscope (TEM) images (a) and energy-dispersive X-ray spectroscopy (EDS) analysis (b, c) results of the calcium carbonate coated material obtained in Example 1. [Figure 2] These are transmission electron microscope (TEM) images (a) and energy-dispersive X-ray spectroscopy (EDS) analysis (b, c) results of the calcium carbonate coated material obtained in Example 2. [Figure 3] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 3 are shown. [Figure 4] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 4 are shown. [Figure 5] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 5 are shown. [Figure 6] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 6 are shown. [Figure 7] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 7 are shown. [Figure 8] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 8 are shown. [Figure 9] The images on the left (SEM) and right (EDS) of the calcium carbonate coated material obtained in Example 9 are shown. [Figure 10] The results of a scanning electron microscope (SEM) image (left) and an energy-dispersive X-ray spectroscopy (EDS) analysis (right) of the calcium carbonate coating obtained in Example 10. [Figure 11] The results of a scanning electron microscope (SEM) image (left) and an energy-dispersive X-ray spectroscopy (EDS) analysis (right) of the calcium carbonate coating obtained in Example 11. [Figure 12] The results of a scanning electron microscope (SEM) image (left) and an energy-dispersive X-ray spectroscopy (EDS) analysis (right) of the calcium carbonate coating obtained in Example 12. [Figure 13] The results of a scanning electron microscope (SEM) image (left) and an energy-dispersive X-ray spectroscopy (EDS) analysis (right) of the calcium carbonate coating obtained in Example 13. [Figure 14] The results of a scanning electron microscope (SEM) image (left) and an energy-dispersive X-ray spectroscopy (EDS) analysis (right) of the calcium carbonate coating obtained in Example 14.

Mode for Carrying Out the Invention

[0012] The upper and lower limit values of the numerical ranges described in this specification can be arbitrarily combined. For example, when the numerical ranges "A to B" and "C to D" are described, the numerical ranges "A to D" and "C to B" are also included in the scope of this disclosure. In addition, the numerical range "lower limit value to upper limit value" described in this specification means that it is not less than the lower limit value and not more than the upper limit value, unless otherwise specified.

[0013] Hereinafter, the details of the calcium carbonate coating of the present disclosure will be described.

[0014] <Calcium Carbonate Coating> The calcium carbonate coating of the present disclosure contains a base material containing at least one selected from organic substances and inorganic substances and calcium carbonate, and has a calcium carbonate coating layer on at least a part of the surface of the base material. As mentioned above, coating the surface of the base material with calcium carbonate is expected to facilitate dispersion into various matrices when the base material is in the form of particles. Furthermore, it is expected that coating the surface of a substrate used in electrodes for sensors with calcium carbonate can improve the selectivity of the substance being measured, or coating the surface of a metal material, such as an implant, with calcium carbonate can improve biocompatibility.

[0015] (Calcium carbonate coating layer) The calcium carbonate coated material of this disclosure has a calcium carbonate coating layer on at least a portion of the surface of the base material. The calcium carbonate coating layer may be formed on a part of the surface of the base material or on the entire surface. However, if it is formed on a part of the surface of the base material, for example, the coating rate based on the surface area of ​​the base material may be 10% or more, 25% or more, 50% or more, 75% or more, or 90% or more. The surface condition of the coating layer can be confirmed, for example, using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Furthermore, the formation of a calcium carbonate coating layer on the surface of the base material can be confirmed, for example, by measuring the calcium distribution on the surface of the base material using energy-dispersive X-ray spectroscopy (EDS) analysis.

[0016] The calcium carbonate forming the calcium carbonate coating layer may be amorphous or crystalline (calcite, vaterite, and aragonite). Furthermore, the calcium carbonate forming the calcium carbonate coating layer may be a composite containing substances other than calcium carbonate on its surface and / or internally. Specifically, the calcium carbonate forming the calcium carbonate coating layer may contain a polycarboxylic acid amine.

[0017] (base material) The base material of this disclosure comprises at least one selected from organic and inorganic materials. The base material may consist solely of organic materials, solely of inorganic materials, or a mixture of organic and inorganic materials. The base material may be of one type, or it may be a combination of two or more types. The shape of the base material is not particularly limited, but examples include spherical, ellipsoidal, polyhedral, plate-like, rod-like, tubular, fibrous, and combinations thereof. Furthermore, the base material may have a hollow structure with internal voids, such as a hollow sphere or a hollow plate. Furthermore, the surface of the base material may have irregularities as desired. Furthermore, the base material may be a porous body having multiple pores.

[0018] [Organic matter] The organic matter contained in the base material is not particularly limited, but resin is an example. Organic matter may be used individually, or in combination of two or more types. Examples of resins include epoxy resins, phenolic resins, polyimide resins, polyolefin resins such as polyethylene, polypropylene, and polybutene, vinyl resins, acrylic resins such as polyacrylate and polymethacrylate, polystyrene resins, diene resins, terpene resins, cellulose resins, polyamide resins, polyurethane resins, polyester resins, polycarbonate resins, fluororesins, and resins composed of two or more monomers such as acrylonitrile styrene resin.

[0019] Among these organic materials, it is preferable that they contain resins, preferably one or more selected from polyolefin resins and acrylic resins, and more preferably one or more selected from polypropylene and polyacrylate.

[0020] When using organic matter as the base material, the organic matter may be directly added to the reaction system in the form of lumps or powder, or it may be mixed with a dispersion medium such as water beforehand to disperse it, and then added to the reaction system in the form of an emulsion.

[0021] [Inorganic substances] The inorganic materials contained in the base material are not particularly limited, but examples include metallic materials, silicon materials, carbon materials, germanium materials, etc. These materials may each be composite materials, for example, those containing metallic elements and silicon, such as ceramics. Inorganic materials may be used individually, or in combination of two or more. Metallic materials include all elements, alloys, compounds, or intermetallic compounds of any metallic element. Specifically, examples include alloys of iron or stainless steel (SUS), alloys of aluminum or duralumin, titanium or its alloys, nickel or its alloys, alloys of copper or bronze, zinc or its alloys, gold or its alloys, zirconium or its alloys, lead or its alloys, silver or its alloys, and so on. Examples of compounds containing metal elements include oxides, nitrides, fluorides, and borides of the above-mentioned metal elements. In other words, metallic materials include metal oxides, metal nitrides, metal fluorides, metal borides, and the like. Examples of silicon materials include elemental silicon such as polycrystalline silicon, amorphous silicon, and single-crystal silicon, as well as silicon oxide (silica), silicon nitride, and glass. Specific examples of silica include hollow silica, fumed silica, and colloidal silica. Examples of carbon materials include fullerenes, graphite, diamond, carbon black, carbon nanotubes, activated carbon, and carbon fibers. Examples of germanium materials include elemental germanium such as crystalline germanium and amorphous germanium, and germanium dioxide.

[0022] Among these inorganic materials, it is preferable to include one or more selected from metallic materials, silicon materials, and carbon materials. Furthermore, the metal material preferably includes one or more selected from iron or stainless steel (SUS) alloys, aluminum or duralumin alloys, copper or bronze alloys, and gold or its alloys, and more preferably includes one or more selected from stainless steel (SUS), aluminum, copper, and gold. The silicon material preferably contains one or more selected from silicon oxide (silica) and glass, and more preferably contains one or more selected from hollow silica, colloidal silica, and glass. The carbon material preferably includes one or more selected from fullerene, graphite, diamond, carbon black, carbon nanotubes, activated carbon, and carbon fibers, and more preferably includes carbon fibers.

[0023] In other words, it is more preferable that the inorganic material includes one or more selected from the group consisting of stainless steel (SUS), aluminum, copper, gold, hollow silica, colloidal silica, glass, and carbon fiber.

[0024] <Method for producing calcium carbonate coated material> The method for producing a calcium carbonate coating according to this disclosure includes a step of contacting a calcium ion-containing solution containing a polycarboxylic acid amine with a carbonate ion-containing substance, a pH adjusting agent containing a base, and a base material containing at least one selected from organic and inorganic materials.

[0025] In the step of contacting the calcium ion-containing solution containing the polycarboxylate amine of this disclosure with a carbonate ion-containing substance, a pH adjusting agent containing a base, and a base material containing at least one selected from organic and inorganic materials, there are no particular restrictions on the order in which the components are brought into contact. For example, a mixture of a pH adjusting agent containing a base and a carbonate ion-containing substance may be prepared by mixing them beforehand, and then a calcium ion-containing solution containing polycarboxylate amine may be mixed with the mixture of the carbonate ion-containing substance and the pH adjusting agent (hereinafter also referred to as mixing step 1). Alternatively, a calcium ion-containing solution containing polycarboxylate amine may be mixed separately with a carbonate ion-containing substance and a pH adjusting agent containing a base (hereinafter also referred to as mixing step 2). In other words, the step of obtaining the calcium carbonate coating of this disclosure may include the step of mixing a carbonate ion-containing substance with a pH adjusting agent containing a base to prepare a mixture of the carbonate ion-containing substance and the pH adjusting agent containing a base. Furthermore, the order in which the base materials are added is arbitrary. The base materials may be brought into contact with a calcium ion-containing solution containing polycarboxylate amine beforehand, and then the solution, a carbonate ion-containing substance, and a pH adjuster containing a base may be mixed together. Alternatively, a mixture of a pH adjusting agent containing a base and a carbonate ion-containing substance may be prepared in advance by mixing the carbonate ion-containing substance and the pH adjusting agent containing a base, and this mixture may be brought into contact with the base material, and then mixed with a calcium ion-containing solution containing polycarboxylate amine. Alternatively, the base material may be brought into contact with either a carbonate ion-containing substance or a pH adjusting agent containing a base beforehand, the mixture may be mixed with the other substance, and then further mixed with a calcium ion-containing solution containing polycarboxylate amine; or the base material may be brought into contact with both a carbonate ion-containing substance and a calcium ion-containing solution containing polycarboxylate amine beforehand, and finally a pH adjusting agent containing a base may be mixed in. Furthermore, depending on the type of base material used, there may be a more favorable order for adding the aforementioned base materials. For example, if the base material is a material that aggregates at low pH, such as silica particles, it is preferable to bring the base material into contact with the carbonate ion-containing substance beforehand.

[0026] (A calcium ion-containing solution containing polycarboxylate amine) A calcium ion-containing solution containing polycarboxylate amine comprises a calcium ion source, polycarboxylate amine, and a solvent that dissolves both. Examples of calcium ion sources include calcium chloride (CaCl2), calcium nitrate (Ca(NO3)2), calcium acetate (Ca(CH3COO)2), and calcium hydroxide (Ca(OH)2), with calcium chloride (CaCl2) being the preferred choice. A single calcium ion source may be used, or two or more may be mixed together. Polycarboxylate amines are compounds having an amine skeleton (-N<) and two or more carboxyl groups. For example, a polycarboxylate amine represented by the following formula (1) can be used.

[0027] [ka]

[0028] In formula (1), A represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, or a carboxyl group, and L 1 ~L 3 Each of these independently represents a single bond or an alkylene group having 1 to 3 carbon atoms.

[0029] The alkyl group having 1 to 15 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, t-butyl, and cyclohexyl groups, and may also have substituents such as hydroxyl and carboxyl groups. Among these, linear alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred. Examples of aryl groups having 6 to 10 carbon atoms include phenyl groups, methylphenyl groups, and naphthyl groups, and may further have substituents such as hydroxyl groups, carboxyl groups, sulfonic acid groups, and amino groups. Among these, phenyl groups are preferred. The alkylene group having 1 to 3 carbon atoms may be linear or branched, and examples include methylene groups and ethylene groups, and may further have substituents such as hydroxyl groups and carboxyl groups. Among these, linear alkylene groups are preferred, and methylene groups and ethylene groups are more preferred.

[0030] The number of carboxyl groups in a polycarboxylate amine is not particularly limited as long as it is two or more, but it is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2. In other words, the polycarboxylate amine is even more preferably a dicarboxylate amine. Only one type of polycarboxylate amine may be used, or two or more types may be used in mixture form.

[0031] Examples of polycarboxylate amines represented by formula (1) include hydroxyethyliminodiacetic acid (sometimes abbreviated as HIDA), methyliminodiacetic acid (sometimes abbreviated as Me-IDA), benzyliminodiacetic acid (sometimes abbreviated as Benzyl-IDA), and iminodiacetic acid (sometimes abbreviated as IDA). These polycarboxylate amines have the following structures.

[0032] [ka]

[0033] In the mixing process, the amount of coating on the resulting calcium carbonate coating can be adjusted by changing the type of polycarboxylate amine. Specifically, for example, using benzyliminodiacetic acid (Benzyl-IDA) results in a greater amount of calcium carbonate coating compared to using hydroxyethyliminodiacetic acid (HIDA). Furthermore, by changing the amount of base material used, the amount of calcium carbonate coating obtained can be adjusted; the more base material used, the less calcium carbonate coating will be applied.

[0034] The solvent can be a source of calcium ions and a solvent that dissolves polycarboxylic acid amines. Water is usually used, but it may also contain water-soluble organic solvents such as alcohols, tetrahydrofuran, and oxazine.

[0035] The calcium ion source and polycarboxylate amine content in the calcium ion-containing solution are not particularly limited; the calcium ion-containing solution can be prepared by dissolving an equal molar equivalent of calcium ions and polycarboxylate amine in a solvent. For example, a solution with a calcium ion concentration of 50-100 mmol / L or a calcium content of 0.2-0.4% by mass can be prepared by adding an equal molar equivalent of calcium ions and polycarboxylate amine. It is expected that the coating amount of the resulting calcium carbonate coated material can be adjusted by adjusting the concentrations of the calcium ion source and polycarboxylate amine in the calcium ion-containing solution. Note that the mass percentage concentration of polycarboxylic acid in the solution varies depending on the molecular weight of the polycarboxylic acid amine.

[0036] (Substances containing carbonate ions) A carbonate ion-containing substance is a substance that contains carbonate ions, and its form may be gas, liquid, or solid. The carbonate ion-containing substance used in mixing step 1 is pre-mixed with a pH adjusting agent containing a base, and is used as a "mixture of carbonate ion-containing substance and pH adjusting agent containing a base" that also contains a pH adjusting agent containing a base in addition to carbonate ions. The carbonate ion-containing substance used in mixing step 2 does not contain a pH adjusting agent containing a base. Hereinafter, in this specification, when the term "carbonate ion-containing substance" is used, it refers to a carbonate ion-containing substance that does not contain a pH adjusting agent containing a base. A mixture of a carbonate ion-containing substance and a pH adjusting agent containing a base, such as the carbonate ion-containing substance used in mixing step 1, may be described as "base and carbonate ion-containing substance."

[0037] Examples of carbonate ion-containing substances (carbonate ion-containing substances that do not contain pH adjusting agents containing bases) include carbon dioxide (CO2 gas); a solution of carbon dioxide (CO2 gas) dissolved in a solvent; and a solution of a carbonate ion source such as sodium bicarbonate or sodium carbonate dissolved in a solvent. For example, when carbon dioxide is used as the carbonate ion-containing substance, the step of mixing the calcium ion-containing solution containing polycarboxylate amine with the carbonate ion-containing substance can be carried out by blowing carbon dioxide into the calcium ion-containing solution containing polycarboxylate amine. Among the carbonate ion-containing substances mentioned above, aqueous solutions of metal carbonates are preferred, and aqueous solutions of sodium carbonate are more preferred. Furthermore, any solvent capable of dissolving the carbonate ion source can be used without particular restrictions, but water is usually used. Furthermore, the carbonate ion-containing substance may be used alone or in a mixture of two or more types.

[0038] (pH adjuster) In mixing step 1, the carbonate ion-containing substance further contains a pH adjusting agent containing a base. When using carbon dioxide as the carbonate ion-containing substance, a solution can be prepared by dissolving carbon dioxide in a solvent such as water, and then adding a pH adjuster containing a base. Alternatively, carbon dioxide can be dissolved in a solution prepared by dissolving a pH adjuster containing a base in a solvent such as water. The bases included in the pH adjuster can be ammonia, methylamine, trimethylamine, tetramethylamine hydroxide, etc., either alone or in a mixture of two or more. Metal hydroxides such as sodium hydroxide and potassium hydroxide can also be used as pH adjusters. The amount of pH adjusting agent containing a base added is adjusted according to the concentration and type of base contained in the pH adjusting agent, so that the pH after mixing the calcium-containing solution containing polycarboxylate amine with the carbonate ion-containing substance containing the pH adjusting agent reaches a value at which calcium carbonate or a complex of calcium carbonate and dicarboxylate amine precipitates. It is expected that the amount of coating layer in the resulting calcium carbonate coated material can be adjusted by changing the type of base and using an appropriate amount of pH adjuster.

[0039] The concentration of the carbonate ion source in a carbonate ion-containing substance is not particularly limited; a solution containing the same molar equivalent of the carbonate ion source as the calcium ion source in a calcium ion-containing solution can be prepared. When a carbonate ion-containing substance contains a pH adjusting agent containing a base, in other words, when preparing a "base and carbonate ion-containing substance," add a pH adjusting agent containing 2 to 8 molar equivalents of base to the carbonate ion source. For example, for 100 g of a carbonate ion-containing solution with a concentration of 50 mmol / L to 100 mmol / L, add 3 to 6 mL of 25% by mass aqueous ammonia.

[0040] In mixing step 2 according to this disclosure, in addition to mixing the calcium ion-containing solution with the carbonate ion-containing substance, a pH adjusting agent containing a base is further mixed. At this time, the carbonate ion-containing substance does not contain the pH adjusting agent containing a base. Furthermore, as methods for adding a pH adjuster containing a base to a calcium ion-containing solution, the method of combining the pH adjuster containing a base with a carbonate ion-containing substance and then adding it to the calcium ion-containing solution is called "combined addition," while the method of adding the pH adjuster containing a base separately to the calcium ion-containing solution without combining them is called "separate addition." In other words, the method of adding the pH adjuster containing a base in mixing step 1 is "combined addition," and the method of adding the pH adjuster containing a base in mixing step 2 is "separate addition."

[0041] An example of the mixing process according to this disclosure when carbon dioxide is used as the carbonate ion-containing substance is described below, for both blending and separate addition. In the case of compounding (mixing step 1), as described above, either add the pH adjuster to a solution in which carbon dioxide is dissolved in a solvent such as water, or dissolve carbon dioxide in a solution in which the pH adjuster is dissolved in a solvent such as water. Then, mix the solution containing dissolved carbon dioxide and pH adjuster with the calcium ion-containing solution containing polycarboxylate amine.

[0042] In the case of separate addition (mixing step 2), the pH adjuster should be added to the calcium ion-containing solution containing polycarboxylate amine, and then carbon dioxide gas should be blown in. Furthermore, adding a pH adjuster to the carbonate ion-containing substance is expected to shorten the manufacturing time of the calcium carbonate coating; therefore, from the viewpoint of production efficiency, adding the pH adjuster is preferable. On the other hand, in the case of separate addition, for example, by gradually adding a pH adjusting agent containing a base after mixing a calcium ion-containing solution, a carbonate ion-containing substance, and the base material, it is possible to suppress homogeneous nucleation and proceed with the reaction under conditions where heterogeneous nucleation preferentially occurs. This is expected to result in a thicker and more uniform coating of the base material compared to the case of combined addition. Furthermore, in this case, it is possible to reduce the amount of pH adjusting agent containing a base added and keep the pH at the end of the reaction lower compared to combined addition, and since the pH of the reaction solution starts in the acidic or neutral range and gradually increases with the addition of the pH adjusting agent, the base material is coated, so it is assumed that even base materials with low resistance to bases can be coated.

[0043] When using a pH adjuster added separately, in addition to ammonia, if amines such as methylamine, trimethylamine, or tetramethylamine hydroxide are used, a pH adjuster containing 2 to 8 molar equivalents of base relative to the carbonate ion source used in mixing step 2 can be used. The specific amount used will vary depending on the type and concentration of the amine used. In addition, when added separately, metal hydroxides such as sodium hydroxide or potassium hydroxide can also be used as pH adjusters, and a pH adjuster containing 1 to 3 molar equivalents of base relative to the carbonate ion source used in mixing step 2 can be used.

[0044] The mixing of each component in mixing step 1 and mixing step 2 can be carried out under atmospheric pressure (0.1 MPa) and at room temperature (25°C). The mixing of each component can be carried out for 1 to 5 minutes using a stirring device as needed. In addition, when mixing a calcium ion-containing solution with a carbonate ion-containing substance and a base material, and then mixing in a pH adjuster, it is preferable to add the pH adjuster to the reaction system over 40 to 50 minutes, depending on the base concentration in the pH adjuster, from the viewpoint of maintaining uniformity within the system and preferentially promoting heterogeneous nucleation. If the base material is in particulate form, a calcium carbonate coated material can be obtained by stirring for a predetermined time, filtering it with filter paper or the like, washing it with alcohol, and then drying the solid matter on the filter paper. Furthermore, if filtration is not required, such as when the base material is a single large substrate, the base material can be recovered by stirring for a predetermined time, discarding the solution, washing it with alcohol, and then drying the base material to obtain a calcium carbonate coated material. According to the manufacturing method of this disclosure, calcium carbonate can be uniformly coated along the shape of the base material. Therefore, for example, if the base material is spherical particles, the calcium coating can also be made of spherical particles, and a coating that reflects the shape of the base material can be provided. Furthermore, by further heating the calcium carbonate coated material obtained by the manufacturing method described herein, it is expected that the calcium carbonate will crystallize while maintaining the coated state.

[0045] (base material) The preferred embodiment of the base material, which includes at least one selected from organic and inorganic materials, in the method for producing a calcium carbonate coating according to this disclosure is as described above. In other words, the organic material contained in the base material preferably includes resin, and the inorganic material contained in the base material preferably includes one or more selected from metal materials, silicon materials, and carbon materials.

[0046] [One aspect of the disclosure provided] One aspect of this disclosure provides the following [1] to [7]. [1] It contains a base material containing at least one selected from organic and inorganic materials, and calcium carbonate. A calcium carbonate coated body having a calcium carbonate coating layer on at least a portion of the surface of the base material. [2] The calcium carbonate coated body according to [1], wherein the organic material comprises a resin. [3] The calcium carbonate coating according to [1], wherein the inorganic material comprises at least one selected from a metallic material, a silicon material, and a carbon material. [4] It contains a base material containing at least one selected from organic and inorganic materials, and calcium carbonate. A method for producing a calcium carbonate coated body, wherein at least a portion of the surface of the base material is covered with a calcium carbonate coating layer, A method for producing a calcium carbonate coated material, comprising the step of contacting a calcium ion-containing solution containing polycarboxylate amine, a carbonate ion-containing substance, a pH adjusting agent containing a base, and the base material. [5] The method for producing a calcium carbonate coated body according to [4], wherein the organic material comprises a resin. [6] The method for producing a calcium carbonate coating according to [4], wherein the inorganic material comprises at least one selected from a metallic material, a silicon material, and a carbon material. [7] A method for producing a calcium carbonate coated product according to any one of [4] to [6], wherein the polycarboxylic acid amine is a dicarboxylic acid amine. [Examples]

[0047] The technology of this disclosure will now be specifically described by examples, but the technology of this disclosure is not limited in any way by these examples.

[0048] [Example 1] Calcium chloride aqueous solution (50 mmol / L) (Ca 2+To the source, 1 molar equivalent of hydroxyethyliminodiacetic acid (HIDA) (organic molecule) was dissolved in calcium ions to prepare solution A (solution A1). The same concentration and volume of sodium carbonate aqueous solution (CO3) as the prepared calcium chloride aqueous solution. 2- To the source, 8.0 molar equivalents of ammonia (NH3) (base) relative to carbonate ions and 50 μL of a suspension of colloidal silica particles as a matrix material ("MP-4540M", silica concentration 40 wt.%, pH 8-10, average silica particle diameter: 450 nm, manufactured by Nissan Chemical Corporation) were added to prepare solution B (solution B1). Solution A (Solution A1) was added to Solution B (Solution B1), stirred at room temperature for 5 minutes, filtered, and the product on the filter paper was washed with ethanol and then dried.

[0049] [Example 2] In preparing solution B (solution B1) of Example 1, instead of colloidal silica, 62 mg of hollow silica particles ("HS-200", D50: 2 μm, apparent specific gravity: 0.5~0.6, manufactured by AGC SI-TEC, Inc.) were used as the base material, as shown in Table 1. Otherwise, solution B was prepared in the same manner as in Example 1. Solution B of Example 2 will be referred to as solution B2. In Example 1, the same procedure was followed except that solution B (solution B2) was used instead of solution B (solution B1). Solution A was added to solution B, stirred at room temperature for 5 minutes, filtered, and the product on the filter paper was washed with ethanol and then dried.

[0050] [Examples 3-10] In preparing solution B (solution B1) of Example 1, instead of colloidal silica, the following substrates were used as the base material: glass substrate, polypropylene substrate, acrylic substrate, copper substrate, stainless steel (SUS) substrate, aluminum substrate, gold substrate (prepared by depositing gold on both sides of an aluminum substrate for 6 minutes on each side), and carbon fiber substrate ("TGP-H-090", water repellency 5%, manufactured by Toray Industries, Inc.). Otherwise, solution B was prepared in the same manner as in Example 1. The solutions B of Examples 3 to 10 are designated as solutions B3 to B10, respectively. In Example 1, the procedure was the same as before, except that Solution B (Solution B3 to B10) was used instead of Solution B (Solution B1). Solution A was added to Solution B, stirred at room temperature for 5 minutes, then allowed to stand for 10 minutes. Various substrates were then separated, washed with ethanol, and dried.

[0051] [Examples 11-14] In the preparation of Solution A (Solution A1) in Example 1, benzyliminodiacetic acid (Benzyl-IDA) was used as the organic molecule instead of hydroxyethyliminodiacetic acid (HIDA), as shown in Table 1. Otherwise, Solution A was prepared in the same manner as in Example 1. Solutions A in Examples 11 to 14 are designated as Solutions A11 to A14, respectively. Furthermore, in the preparation of solution B (solution B1) in Example 1, instead of colloidal silica, a stainless steel (SUS) substrate, an aluminum substrate, a gold substrate (prepared by depositing gold onto both sides of an aluminum substrate for 6 minutes each), and a carbon fiber substrate were used as the base material, as shown in Table 1. Otherwise, solution B was prepared in the same manner as in Example 1. The solutions B in Examples 11 to 14 are designated as solutions B11 to B14, respectively. In Example 1, the same procedure was followed except that Solution A (Solution A1) was replaced with Solution A (Solution A11 to Solution A14), and Solution B (Solution B11 to Solution B14) was replaced with Solution B (Solution B11 to Solution B14). Solution A was added to Solution B, stirred at room temperature for 5 minutes, then allowed to stand for 10 minutes. Various substrates were then separated, washed with ethanol, and dried.

[0052] [Examples 15-17] In the preparation of Solution B (Solution B2) in Example 2, Solution B was prepared in the same manner as in Example 2, except that the amount of hollow silica particles added as the base material was changed as shown in Table 2. The Solutions B in Examples 15-17 are referred to as Solutions B15-17. In Example 2, the procedure was the same as in Example 2, except that Solution B (Solution B15-17) was used instead of Solution B (Solution B2). Solution A was added to Solution B, stirred at room temperature for 5 minutes, filtered, and the product on the filter paper was washed with ethanol and then dried.

[0053] In each example, the mass of the base material before coating and the mass of the resulting calcium carbonate coating were measured, and the difference between these masses was defined as the amount of calcium carbonate coating. Furthermore, the amount of calcium carbonate coating per unit surface area was calculated by dividing the obtained amount of calcium carbonate coating by the surface area of ​​each base material. The results are shown in Tables 1 and 2.

[0054] The detailed test conditions for Examples 1 to 17 are shown in Tables 1 and 2. Tables 1 and 2 also show the components of Solution A and Solution B, as well as the reaction times. 2+ "Concentration" column and "CO3" 2- In the "Concentration" column, "mM" means "mmol / L".

[0055] <Rating> The products prepared in Examples 1 to 14 were evaluated for the formation of a calcium carbonate coating layer on the surface of various particles and substrates using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The specific evaluation methods and measurement conditions are as follows. The evaluation results are shown in Table 1.

[0056] 1. Transmission electron microscope (TEM) observation The products prepared in Examples 1 and 2 were observed using a transmission electron microscope ("JEM2100Plus", manufactured by JEOL Ltd.) (acceleration voltage 200kV). Furthermore, elemental analysis was performed using an energy-dispersive X-ray elemental analyzer ("EX230BU," manufactured by JEOL Ltd.) attached to the transmission electron microscope, and it was determined that a calcium carbonate coating layer had formed in the area where calcium was detected.

[0057] 2. Scanning electron microscope (SEM) observation The products prepared in Examples 3 to 14 were observed using a scanning electron microscope ("JCM-6000", manufactured by JEOL Ltd.) (acceleration voltage 15kV). Furthermore, elemental analysis was performed using an energy-dispersive X-ray elemental analyzer ("EX-37001," manufactured by JEOL Ltd.) attached to the scanning electron microscope, and it was determined that a calcium carbonate coating layer had formed in the areas where calcium was detected.

[0058] [Table 1]

[0059] [Table 2]

[0060] Furthermore, the results of analyzing the products of Examples 1 and 2 using a transmission electron microscope (TEM) ("JEM2100Plus," manufactured by JEOL Ltd.) and an energy-dispersive X-ray elemental analyzer ("EX230BU," manufactured by JEOL Ltd.) are shown in Figures 1 and 2. Furthermore, the results of analyzing the products of Examples 3 to 14 using a scanning electron microscope (SEM) ("JCM-6000", manufactured by JEOL Ltd.) and an energy-dispersive X-ray elemental analyzer ("EX-37001", manufactured by JEOL Ltd.) are shown in Figures 3 to 14. In Figures 1-14, the length indicated to the right of the white line at the bottom of each image refers to the length of the white line.

[0061] According to the analysis results obtained by energy-dispersive X-ray elemental analysis in Figures 1-14, the presence of calcium was confirmed on at least a portion of the surface of each particle in Examples 1 and 2, each substrate in Examples 3-14, and each particle in Examples 15-17. Therefore, it was confirmed that a calcium carbonate coating layer was formed on all of the base materials. Furthermore, the presence of calcium was confirmed uniformly throughout almost all of the examples. Furthermore, the results from Examples 7-10 and 11-14 showed that using benzyliminodiacetic acid (Benzyl-IDA) as the polycarboxylate amine resulted in a higher calcium carbonate coating per unit surface area compared to using hydroxyethyliminodiacetic acid (HIDA), indicating that the amount of calcium carbonate coating can be controlled by the type of polycarboxylate amine used. Furthermore, the results from Examples 2, 15-17 showed that the amount of calcium carbonate coating per unit surface area decreases as the amount of base material used increases, indicating that the amount of calcium carbonate coating can be controlled by the amount of base material used. [Industrial applicability]

[0062] According to this disclosure, calcium carbonate coated materials can be easily manufactured. These calcium carbonate coated materials are expected to exhibit improved properties, such as dispersibility in various matrices.

Claims

1. It contains a matrix material comprising at least one selected from organic and inorganic materials, and calcium carbonate. A calcium carbonate coated body having a calcium carbonate coating layer on at least a portion of the surface of the base material.

2. The calcium carbonate coated body according to claim 1, wherein the organic material includes a resin.

3. The calcium carbonate coating according to claim 1, wherein the inorganic material comprises at least one selected from a metallic material, a silicon material, and a carbon material.

4. It contains a matrix material comprising at least one selected from organic and inorganic materials, and calcium carbonate. A method for producing a calcium carbonate coated body, wherein at least a portion of the surface of the base material is covered with a calcium carbonate coating layer, A method for producing a calcium carbonate coated material, comprising the step of contacting a calcium ion-containing solution containing polycarboxylate amine, a carbonate ion-containing substance, a pH adjusting agent containing a base, and the base material.

5. The method for producing a calcium carbonate coated body according to claim 4, wherein the organic substance includes a resin.

6. The method for producing a calcium carbonate coating according to claim 4, wherein the inorganic material includes at least one selected from a metallic material, a silicon material, and a carbon material.

7. A method for producing a calcium carbonate coated body according to any one of claims 4 to 6, wherein the polycarboxylic acid amine is a dicarboxylic acid amine.

Images