Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/08—Diatomaceous earth
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/10—Clay
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/14—Minerals of vulcanic origin
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/20—Mica; Vermiculite
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • G—PHYSICS
  • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
  • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
  • G21F1/00—Shielding characterised by the composition of the materials
  • G21F1/02—Selection of uniform shielding materials
  • G21F1/04—Concretes; Other hydraulic hardening materials

Definitions

• the present invention relates to a gypsum composition that is used for forming a hardened body by adding water and mixing minerals, gypsum of calcined water and a polycarboxylate-based water reducing agent to form a gypsum of calcined slurry, and the gypsum of calcined slurry is excellent.
• It is a low-viscosity material that exhibits excellent fluidity (moldability), and the slurry makes it possible to form a hardened body such as a gypsum-based building material with improved functionality such as fire resistance, strength, and sound insulation.
• Patent Document 1 proposes a dicarboxylic acid-based water reducing agent for gypsum as a water reducing agent for use in dental gypsum slurry.
• Patent Document 2 it is described that in recent years, in the gypsum/water slurry used for gypsum board, switching to a polycarboxylic acid-based water reducing agent that does not generate formaldehyde is being promoted. It is
• Patent Document 3 discloses that by adding colemanite to the gypsum-based molded body, it is possible to improve the neutron shielding performance in addition to improving the fire resistance performance.
• the addition of minerals to the gypsum composition can enhance the functionality of the gypsum-based building material formed. For this reason, it is desired to develop a gypsum composition capable of forming a building material with improved desired functions by adding various minerals.
• the present inventors found that when a mineral-containing calcined gypsum slurry is prepared, if a water-reducing agent is used to reduce the amount of mixed water, the desired water-reducing performance may not be obtained. Specifically, the present inventors found that when water is added to a gypsum composition containing minerals, calcined gypsum, and a polycarboxylate-based water reducing agent to form a calcined gypsum slurry, the viscosity increases and the calcined gypsum The inventors have found that there is a problem that the slurry becomes poor in fluidity and affects moldability, and that improvement is necessary.
• an object of the present invention is to provide a slurry produced by adding water to a gypsum composition containing minerals, gypsum of Paris, and a polycarboxylate-based water reducing agent discovered by the present inventors to obtain a gypsum of Paris slurry. It is to solve the technical problem that the viscosity of is increased by a simple means.
• a mineral to a calcined gypsum slurry for forming a hardened body such as a gypsum-based building material, the hardened body such as a building material formed using the slurry has fire resistance, Functionality such as strength and sound insulation is improved.
• a method for producing a gypsum composition characterized by:
• Preferred embodiments of the method for producing the gypsum composition of the present invention are as follows. [2] The gypsum composition according to [1] above, wherein in the pretreatment step, the liquid polyamide polyamine and/or the alkylene oxide adduct of polyamide polyamine is sprayed onto the mineral, and then the mineral is dried. manufacturing method.
• a gypsum composition for preparing a gypsum slurry of calcined gypsum which is a mixture with water, comprising minerals, gypsum of calcined water, and a polycarboxylate-based water reducing agent, wherein the minerals are , a polyamide polyamine and/or an alkylene oxide adduct of a polyamide polyamine, in terms of solid content, is added in an amount within the range of 0.1 to 10 wt% based on the mass of the gypsum of Paris.
• Preferred forms of the above gypsum composition of the present invention include the following.
• the present invention provides the following mineral raw materials for gypsum compositions.
• a mineral raw material for a gypsum composition characterized in that it is
• the present invention provides, as another embodiment, the following method for manufacturing a building material.
• [7] Using the gypsum composition according to any one of [3] to [5] above, mixing the gypsum composition and water to form a calcined gypsum slurry, and using the slurry to mold a hardened body.
• a method for producing a cured body characterized by:
• Preferred embodiments of the method for producing a building material of the present invention are as follows. [8] In the above [7], wherein the viscosity (25°C) of the slurry is 150 dPa s or less when the amount of water mixed is 15 to 60 wt% based on the mass of the gypsum composition. A method for producing the described cured body.
• the viscosity of the slurry increases.
• the problem can be solved by a very simple means of adding polyamide polyamine and/or an alkylene oxide adduct of polyamide polyamine (hereinafter also referred to as polyamide polyamine, etc.) in advance to the mineral to be used.
• the viscosity of the gypsum calcined slurry is It is desired to be 150 dPa ⁇ s or less, preferably about 20 to 100 dPa ⁇ s, more preferably about 20 to 50 dPa ⁇ s.
• the present inventors have investigated the reason why the viscosity increased when water was added to a gypsum composition containing colemanite, calcined gypsum, and a polycarboxylate-based water reducing agent to form a calcined gypsum slurry. Although it is not certain, it is speculated as follows. As described in the above-mentioned patent documents, polycarboxylate-based water reducing agents are used in gypsum compositions.
• the present inventors found that the reason why the viscosity of the slurry increased was that when minerals such as colemanite coexisted in the gypsum composition, when water was added and mixed to prepare a calcined gypsum slurry, polycarboxylic acid It was thought that the acid salt-based water reducing agent was adsorbed to the mineral before the gypsum, and as a result, the boric acid ester was generated and the viscosity of the slurry was increased.
• the present inventors constructed a gypsum composition to solve the technical problem that the viscosity of the slurry becomes high, which occurs in the calcined gypsum slurry composed of the gypsum composition having the above configuration.
• the present invention has been accomplished.
• the present inventors have found that the mineral used in obtaining the gypsum slurry, which is a mixture with water, and which contains a mineral, gypsum of calcined water, and a polycarboxylate-based water reducing agent, It was found that the viscosity of the plaster of Paris slurry can be reduced without causing the problem of increasing the viscosity of the calcined gypsum slurry by adding polyamide polyamine or the like to the mineral in advance in an amount within a specific range. rice field.
• the present inventors have found that the minerals used in obtaining a gypsum slurry containing minerals, gypsum of Paris, and a polycarboxylate-based water reducing agent include polyamide polyamine, etc. It has been found that the excellent effect of the present invention can be obtained by providing the composition in an amount within the range of 0.1 to 10 wt% in terms of solid content to the calcined gypsum.
• the minerals used as raw materials, such as polyamide polyamine should have a ratio of about 0.02 to 120 wt% on a mass basis to the minerals in terms of solid content. Within the range of, it has been found that it is preferably given in advance.
• each raw material constituting the gypsum composition of the present invention will be described.
• Minerals constituting the present invention are not particularly limited.
• minerals having a volume average particle diameter (MV) of about 10 ⁇ m to 3 mm, more preferably about 20 ⁇ m to 1 mm may be used, and minerals whose particle size is adjusted by pulverization or the like may also be used.
• MV volume average particle diameter
• the amount of minerals used varies depending on the type of mineral and the purpose of using the mineral, but according to the study of the present inventors, for example, each mineral should be used in an amount within the range shown below. is preferred.
• Examples of minerals constituting the present invention include bentonite, colemanite, diatomaceous shale, vermiculite, shirasu and natural gypsum. It can be appropriately selected and used from among those listed above, depending on the application and desired function.
• colemanite has been described as a representative example of the mineral, but the "mineral" constituting the present invention is not limited to colemanite, and minerals having various properties such as those described below can be used for purposes. It can be selected as appropriate.
• the useful effects of the present invention can be obtained when any mineral is used.
• Bentonite is a general term for clay mainly composed of montmorillonite, has high viscosity and adhesiveness, and is widely used as a functional material such as a moisturizing agent and a thickening agent. It is also widely used in fields such as building materials.
• the amount of bentonite used (compounded) is preferably such that the mass ratio of bentonite to gypsum of calcined slurry is 0.01 to 30 wt %, for example.
• Colemanite is a natural mineral containing boron, and is used as a herbicide, a secondary material for steel, and the like.
• the amount of colemanite to be used is preferably such that the mass ratio of colemanite to gypsum of Paris is 0.1 to 60% by weight in the case of gypsum of Paris slurry.
• Diatom shale is a porous natural mineral consisting of fossilized diatom shells, and is widely used as a material for humidity control building materials, health building materials, daily necessities, etc., because of its unique functions.
• the amount of diatomaceous shale to be used is preferably such that the mass ratio of gypsum of Paris to gypsum of Paris is 0.1 to 50% by weight in the case of a gypsum of Paris slurry.
• Vermiculite is a porous, very light mineral that is water-retentive and breathable, and is used as a soil conditioner and fire-resistant aggregate for building materials.
• the amount of vermiculite to be used is preferably such that the mass ratio of vermiculite to gypsum of calcined slurry is 0.01 to 30 wt %, for example.
• Shirasu is fine-grained pumice and volcanic ash distributed in thick strata throughout southern Kyushu.
• dihydrate gypsum When dihydrate gypsum is used as a bulking agent, it can be applied to the minerals constituting the present invention, and not only natural gypsum but also by-product gypsum and recycled gypsum can be applied.
• the amount of gypsum dihydrate used is preferably such that the mass ratio of gypsum to calcined gypsum is, for example, 0.1 to 50 wt % in the case of calcined gypsum slurry.
• gypsum dihydrate can also be used as a hardening accelerator added as necessary to the gypsum composition of the present invention.
• the gypsum dihydrate When used as a hardening accelerator, it can be applied to the minerals constituting the present invention, and the gypsum dihydrate in that case can be not only natural gypsum, but also by-product gypsum and recycled gypsum. In that case, the amount used is about 0.1 to 5% by weight with respect to the calcined gypsum, which is a small amount compared to the case where it is used as an extender.
• the technical feature of the present invention constitutes a gypsum composition used in preparing a gypsum slurry of calcined water, which is a mixture with water, and which contains minerals, gypsum of calcined water, and a polycarboxylate-based water reducing agent.
• the reason is that the minerals are pretreated with a specific compound in advance.
• liquid polyamide polyamine or the like is added in advance to the above-mentioned minerals constituting the present invention so that the ratio to the calcined gypsum is 0 on a mass basis in terms of solid content. .1 to 10 wt % is used.
• Polyamide polyamines and alkylene oxide adducts of polyamide polyamines used for pretreatment of minerals constituting the present invention are described, for example, in Japanese Patent No. 4844878 and Japanese Patent No. 6095644. It is used as a forming component when obtaining a gypsum dispersant (water reducing agent).
• a gypsum dispersant water reducing agent.
• Japanese Patent No. 6095644 (A) a polycarboxylic acid-based polymer, (B) a polyalkylene polyamine and a dibasic acid are reacted as essential components, and the weight average molecular weight is 500 to 4800.
• component (A):(B) 1:1 to 30:1 by mass.
• Gypsum dispersants water reducers
• the present inventors have found that when water is added to a gypsum composition containing minerals, gypsum of Paris, and a polycarboxylate-based water reducing agent to form a gypsum of Paris slurry, the viscosity of the slurry is 300 dPa. ⁇ We found a technical problem that it becomes hard when it becomes as high as s. To solve this problem, the present inventors referred to the above-described prior art, premixed polyamide polyamine with calcined gypsum constituting the gypsum composition, and prepared a carboxylate-based water reducing agent and polyamide polyamine.
• the object of the present invention is to obtain a low-viscosity calcined gypsum slurry that can stably impart sufficient fluidity. I could't.
• the present inventors conducted further studies on how to make the mineral-containing gypsum slurry of low viscosity with sufficient fluidity and stability by a simple means.
• the minerals that have been pretreated in advance to attach (provide) polyamide polyamine or the like in an amount within a specific range, as a material for the calcined gypsum slurry It was found that it is possible to obtain a low-viscosity calcined gypsum slurry to which sufficient fluidity is stably imparted.
• the treatment of minerals that characterizes the present invention is performed by adding liquid polyamide polyamine or the like to minerals in advance, in terms of solid content, with a ratio of calcined gypsum of 0.1 to 0.1 on a mass basis. It is carried out by imparting (adhering) such that it is within the range of 10 wt %. More preferably, a polyamide polyamine or the like is added to the mineral, and the ratio to the calcined gypsum is in the range of 0.2 to 5 wt% on the mass basis, further 0.5 to 1 wt% on the mass basis, in terms of solid content. is given (adhered) so as to be within the range of
• the amount of polyamide polyamine or the like to be added to the mineral is preferably such that the ratio to the mineral in terms of solid content is in the range of 0.02 to 120 wt% on the mass basis. . Furthermore, it is more preferable that the content is previously applied within the range of 0.2 to 20 wt%.
• the water reducing agent has the effect of facilitating kneading of the gypsum composition and water when water is added to the gypsum composition containing minerals and calcined gypsum and used as calcined gypsum slurry. It is a substance that reduces the amount of and improves the strength of the molded article after curing. It is said that adding a water-reducing agent lowers the viscosity of the slurry without increasing the amount of water to be mixed, thereby improving fluidity and improving kneadability and workability. In addition, the suppression of the increase in the amount of mixed water means that the drying energy can be reduced, and this point is strongly desired from the viewpoint of industrial applicability.
• the polycarboxylate-based water reducing agent is solid in the standard state, and is also effective in the present invention in this respect.
• a powdery polycarboxylate-based water-reducing agent it is preferable to use a powdery polycarboxylate-based water-reducing agent, since it requires fewer steps.
• polycarboxylate-based water reducing agents include the following, and any of the following can be used in the present invention. Specifically, a water-soluble salt of a copolymer of a chain olefin having 5 or 6 carbon atoms and an ethylenically unsaturated dicarboxylic acid anhydride, a copolymer of polyethylene glycol monoallyl ether and an unsaturated dicarboxylic acid , a copolymer of polyalkylene glycol mono(meth)acrylic acid ester and (meth)acrylic acid, a copolymer of (meth)acrylic acid amide having a sulfone group at the end, acrylic acid ester and (meth)acrylic acid , a monomer having a sulfone group such as vinylsulfonate, arylsulfonate or methacrylsulfonate, a copolymer of (meth)acrylic acid and other monomers, a monomer having an aromatic
• Example 2 As in Example 1, colemanite was pretreated in advance to adhere polyamide polyamine to the mineral used in this example.
• a gypsum composition of this example was obtained in the same manner as in Example 1 except for the following points, and a calcined gypsum slurry was prepared using the obtained gypsum composition.
• 1.5 g of a polycarboxylate-based water reducing agent was used. This amount is 0.3%/ ⁇ -St relative to the calcined gypsum.
• the amount of the adhered liquid polyamide polyamine used was 0.3%/ ⁇ -St with respect to the calcined gypsum, and the amount adhered to the colemanite after drying was 0.1%/ ⁇ -St in terms of solid content. was made to be The amount of liquid polyamide polyamine used was 0.7% (1.7 g) relative to colemanite.
• a hardening accelerator was added at 2.0%/ ⁇ -St (10.0 g) to the calcined gypsum.
• Example 4 In the same manner as in Example 2, colemanite was previously pretreated to adhere polyamide polyamine to the mineral used in this example.
• a gypsum composition of this example was obtained in the same manner as in Example 2 except for the following points, and a calcined gypsum slurry was prepared using the obtained gypsum composition.
• the amount of liquid polyamide polyamine attached to colemanite was 3.3%/ ⁇ -St relative to the calcined gypsum, and the amount attached to colemanite after drying was 1.0%/ ⁇ in terms of solid content. ⁇ St.
• the amount of liquid polyamide polyamine used is 6.6% (16.7 g) with respect to the mineral.
• Example 5 In the same manner as in Example 2, colemanite was previously pretreated to adhere polyamide polyamine to the mineral used in this example.
• a gypsum composition of this example was obtained in the same manner as in Example 2 except for the following points, and a calcined gypsum slurry was prepared using the obtained gypsum composition.
• the amount of liquid polyamide polyamine attached to colemanite is 33%/ ⁇ -St with respect to calcined gypsum, and the amount attached to colemanite after drying is 10%/ ⁇ -St in terms of solid content. I made it
• the amount of liquid polyamide polyamine used is 66% (167 g) of the mineral.
• a gypsum composition for comparison was prepared by mixing colemanite, calcined gypsum, a polycarboxylate-based water reducing agent, and a hardening accelerator.
• the polycarboxylate-based water reducing agent was 2.7%/ ⁇ -St (13.5 g) for the calcined gypsum
• the hardening accelerator was 0.2%/ ⁇ -St for the calcined gypsum. (1.0 g), respectively.
• Water was added to the obtained gypsum composition for comparison to prepare a calcined gypsum slurry in the same manner as in Examples, and the viscosity was measured and shown in Table 2.
• Example 2 As another powder sample, in the same manner as in Example 2, a polycarboxylate-based water reducing agent was added at 0.3% / ⁇ -St (1.5 g) to the calcined gypsum, and the hardening acceleration 1.0%/ ⁇ -St (5.0 g) was added to the calcined gypsum. Water was added to the obtained gypsum composition for comparison to prepare a calcined gypsum slurry in the same manner as in Examples, and the viscosity was measured and shown in Table 2.
• the viscosities of the calcined gypsum slurries obtained from the gypsum compositions of the examples were lower than the viscosities of the calcined gypsum slurries obtained from the gypsum compositions of the comparative examples, and all were 100 dPa ⁇ s or less. For this reason, it was confirmed that the gypsum slurries obtained in each example had better fluidity and were easier to mold than the comparative examples, and that gypsum slurries with moderate viscosities yielded good hardened bodies. bottom.
• the gypsum compositions of the examples can reduce the viscosity compared to the gypsum compositions of the comparative examples when the amount of the water reducing agent is the same, and are also effective in terms of raw material cost.

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• 2022
  • 2022-12-26 JP JP2023570997A patent/JPWO2023127776A1/ja active Pending
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