Additive composition for extrusion molding hydraulic composition

Abstract

To provide an additive for an extrusion molding hydraulic composition which has good storage stability and improves workability during extrusion molding of the extrusion molding hydraulic composition that uses porous low quality fly ash having much unburnt carbon and to provide an extrusion molding hydraulic composition having excellent workability during extrusion molding even when porous low quality fly ash having much unburnt carbon is used.SOLUTION: There is provided an additive composition for an extrusion molding hydraulic composition, comprising the following components (A) and (B), wherein the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is 2.0 or more and 9.0 or less, the extrusion molding hydraulic composition comprising fly ash having a BET specific surface area of 0.5 m3 / g or more and less than 12.0 m3 / g and an ignition loss of 1% or more and 10% or less. Component (A): a naphthalenesulfonic acid-based dispersant. Component (B): an alkyl sulfonate ester or a salt thereof, the alkyl having 8 or more and 10 or less carbon atoms.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an additive composition for an extrusion-molded hydraulic composition, and an extrusion-molded hydraulic composition. [Background technology]

[0002] In recent years, in the field of extrusion molding hydraulic compositions for exterior wall materials, coal ash or fly ash generated from coal-fired power plants, etc., has been used as a raw material from the viewpoint of promoting the effective use of industrial by-products and protecting resources. High-quality fly ash is made of spherical fine particles, and therefore has various effects such as imparting fluidity to the kneaded material due to the bearing effect and making it easier to mold due to reduced resistance during extrusion molding. However, the quality of fly ash produced from coal-fired power plants has declined due to the active use of cheap coal in coal-fired power plants. Low-quality fly ash contains a lot of unburned carbon as an impurity, has a high ratio of non-spherical particles, and is porous. When low-quality fly ash is mixed into an extrusion-molded hydraulic composition, the unburned carbon as an impurity of the fly ash is easily adsorbed by the dispersant contained in the hydraulic composition, and the porous fly ash absorbs water, so the amount of water required for plasticization is reduced, which causes a problem of significantly decreasing the workability when extruding the hydraulic composition. In addition, even if the amount of dispersant contained in the hydraulic composition is increased, the workability does not improve, and there are cases where it has the opposite effect. Therefore, in the field of extrusion molding hydraulic compositions, from the viewpoint of maintaining productivity by securing a stable number of supply destinations, it is necessary to utilize low-quality fly ash.

[0003] Patent Document 1 discloses a bubble-containing hydraulic composition that contains hydraulic powder, (A) one or more copolymers selected from three specific types of copolymers, (B) one or more compounds selected from linear alkylsulfonic acids having a linear alkyl group with 8 to 10 carbon atoms, linear alkyl sulfates having a linear alkyl group with 8 to 10 carbon atoms, and salts thereof, and water, the bubble-containing hydraulic composition containing 0.01 to 1 part by mass of (A) per 100 parts by mass of the hydraulic powder and 0.01 to 1 part by mass of (B) per 100 parts by mass of the hydraulic powder. Patent Document 2 discloses an additive for extrusion molding of cement compositions, which contains a sulfate ester salt represented by chemical formula (1) and a sulfate ester salt represented by chemical formula (2), and discloses that the additive improves the extrudability of a cement composition containing low-quality fly ash and the surface condition of the extrusion molded product. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-60658 A [Patent Document 2] JP 2019-34880 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides an additive composition for an extrusion-molded hydraulic composition, which has good storage stability and improves the workability during extrusion molding of an extrusion-molded hydraulic composition using low-quality fly ash that has a large amount of unburned carbon and is porous, and an extrusion-molded hydraulic composition that has excellent workability during extrusion molding even when low-quality fly ash that has a large amount of unburned carbon and is porous is used. [Means for solving the problem]

[0006] The present invention relates to an additive composition comprising the following components (A) and (B), in which the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is 2.0 or more and 9.0 or less, and the composition has a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 The present invention relates to an additive composition for an extrusion-molded hydraulic composition, which contains fly ash having a viscosity of less than 100 μm / g and an ignition loss of 1% or more and 10% or less. (A) Component: Naphthalenesulfonic acid-based dispersant (B) Component: an alkyl sulfate ester or its salt having an alkyl group carbon number of 8 to 10.

[0007] The present invention also relates to a composition comprising the component (A), the component (B), cement, and a composition having a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 The present invention relates to an extrusion-molded hydraulic composition comprising fly ash having a viscosity of less than 1000 mg / g and an ignition loss of 1% to 10% and water, and a mass ratio (A) / (B) of the content of component (A) to the content of component (B) of 2.0 to 9.0. Effect of the Invention

[0008] According to the present invention, there are provided an additive composition for an extrusion-molded hydraulic composition which has good storage stability and improves the workability during extrusion molding of an extrusion-molded hydraulic composition using low-quality fly ash which has a large amount of unburned carbon and is porous, and an extrusion-molded hydraulic composition which has excellent workability during extrusion molding even when low-quality fly ash which has a large amount of unburned carbon and is porous is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The reason why the additive composition for extrusion-molded hydraulic compositions of the present invention improves the workability when extrusion-molding an extrusion-molded hydraulic composition using low-quality fly ash that is porous and contains a lot of unburned carbon is not entirely clear, but it is presumed to be as follows. When low-quality fly ash is blended into an extrusion-molded hydraulic composition with a general dispersant, the dispersant contained in the hydraulic composition is likely to adsorb unburned carbon, which is an impurity of the fly ash, and the porous fly ash absorbs water, so the amount of water required for plasticization is reduced, and the workability when extruding the hydraulic composition is significantly reduced. However, when the additive composition for extrusion-molded hydraulic compositions of the present invention is added to an extrusion-molded hydraulic composition containing low-quality fly ash, the naphthalene sulfonic acid-based dispersant of component (A) can impart fluidity to cement and low-quality fly ash, so it is presumed that the workability when extruding the hydraulic composition is improved. In addition, component (A) has the advantage of being more versatile in terms of materials and temperatures than general polycarboxylic acid-based compositions and is easy to handle. Furthermore, the additive composition for extrusion-molded hydraulic compositions of the present invention contains a specific sulfate ester or its salt as component (B), which makes it possible to improve the fluidity of extrusion-molded hydraulic compositions containing low-quality fly ash during kneading. This is presumably because component (B) allows fine air to be kneaded into the hydraulic composition, thereby further improving the workability during extrusion molding.

[0010] [Additive composition for extrusion-molded hydraulic composition] The additive composition for extrusion-molded hydraulic compositions of the present invention contains a naphthalenesulfonic acid-based dispersant as component (A). As the naphthalene sulfonic acid-based dispersant, preferably, naphthalene sulfonic acid formaldehyde condensate or its salt can be mentioned. Naphthalene sulfonic acid formaldehyde condensate or its salt is a condensate of naphthalene sulfonic acid and formaldehyde or its salt. Naphthalene sulfonic acid formaldehyde condensate may be co-condensed with aromatic compounds that can be co-condensed with naphthalene sulfonic acid as a monomer, such as, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalene carboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid and / or their derivatives, as long as the performance is not impaired.

[0011] The naphthalenesulfonic acid formaldehyde condensate or its salt may be, for example, a commercially available product such as Mighty 150, DEMOL N, DEMOL RN, DEMOL MS, DEMOL SN-B, DEMOL SS-L (all manufactured by Kao Corporation), Celluflow 120, Labelin FD-40, Labelin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.), etc.

[0012] From the viewpoint of imparting dispersibility to an extrusion-molded hydraulic composition, the naphthalenesulfonic acid formaldehyde condensate or its salt has a weight average molecular weight of preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, still more preferably 5,000 or more, and preferably 200,000 or less, more preferably 100,000 or less, still more preferably 80,000 or less, still more preferably 50,000 or less, still more preferably 30,000 or less. The naphthalenesulfonic acid formaldehyde condensate may be in an acid state or a neutralized product.

[0013] The molecular weight of the naphthalenesulfonic acid-formaldehyde condensate or its salt can be measured by gel permeation chromatography under the following conditions. [GPC conditions] Column: G4000SWXL+G2000SWXL (Tosoh) Eluent: 30mM CH3COONa / CH3CN=6 / 4 Flow rate: 0.7ml / min Detection: UV280nm Sample size: 0.2mg / ml Standard material: Nishio Kogyo Co., Ltd., polystyrene sulfonate sodium conversion (monodisperse polystyrene sulfonate sodium: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020

[0014] The method for producing the naphthalenesulfonic acid-formaldehyde condensate or its salt includes, for example, a method of obtaining a condensate by condensation reaction of naphthalenesulfonic acid and formaldehyde. The condensate may be neutralized. In addition, water-insoluble substances by-produced by neutralization may be removed. Specifically, in order to obtain naphthalenesulfonic acid, 1.2 to 1.4 moles of sulfuric acid are used per mole of naphthalene, and the mixture is reacted at 150 to 165°C for 2 to 5 hours to obtain a sulfonated product. Next, formalin is dropped at 85 to 105°C for 3 to 6 hours so that the amount of formaldehyde becomes 0.93 to 0.99 moles per mole of the sulfonated product, and the condensation reaction is carried out at 95 to 105°C after the dropwise addition. Furthermore, since the aqueous solution of the obtained condensate has a high acidity, from the viewpoint of suppressing metal corrosion of a storage tank or the like, water and a neutralizing agent are added to the obtained condensate, and a neutralization step can be carried out at 80 to 95°C. The neutralizing agent is preferably added in an amount of 1.0 to 1.1 times by mole relative to naphthalenesulfonic acid and unreacted sulfuric acid. In addition, water-insoluble matters resulting from neutralization can be removed, and a preferred method for this is separation by filtration. These steps provide an aqueous solution of a water-soluble salt of a naphthalenesulfonic acid-formaldehyde condensate. This aqueous solution can be used as an aqueous solution of a naphthalenesulfonic acid-based dispersant as is. If necessary, the aqueous solution can be dried and powdered to obtain a powdered salt of a naphthalenesulfonic acid-formaldehyde condensate, which can be used as a powdered naphthalenesulfonic acid-based dispersant. Drying and powdering can be performed by spray drying, drum drying, freeze drying, etc.

[0015] The additive composition for extrusion-molded hydraulic compositions of the present invention contains, as component (B), an alkyl sulfate ester or a salt thereof in which the alkyl group has 8 to 10 carbon atoms. From the viewpoint of stable supply, the number of carbon atoms in the alkyl group of component (B) is 8 or more and 10 or less, and preferably 10. The alkyl group of component (B) is linear or branched, and preferably linear. Examples of salts of component (B) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium.

[0016] The additive composition for extrusion-molded hydraulic compositions of the present invention contains the component (A) in an amount of preferably 10% by mass or more, more preferably 13% by mass or more, even more preferably 16% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 23% by mass or less, in terms of imparting dispersibility to the extrusion-molded hydraulic composition and the storage stability of the additive composition.

[0017] The additive composition for an extrusion-molded hydraulic composition of the present invention contains the (B) component in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, even more preferably 9% by mass or less, in terms of improving the workability when extruding the extrusion-molded hydraulic composition and the storage stability of the additive composition. In the present invention, the mass of the component (B) is specified based on the value converted into the sodium salt.

[0018] In the additive composition for an extrusion-molded hydraulic composition of the present invention, the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is 2.0 or more and 9.0 or less, preferably 8.0 or less, more preferably 7.0 or less, even more preferably 6.0 or less, and even more preferably 5.0 or less, from the viewpoints of improving the workability when extruding the extrusion-molded hydraulic composition and the storage stability of the additive composition.

[0019] The additive composition for an extrusion-molded hydraulic composition of the present invention may contain water. The additive composition for an extrusion-molded hydraulic composition of the present invention is preferably in the form of a liquid containing water. The additive composition for extrusion-molded hydraulic compositions of the present invention contains water in an amount of preferably 70% by mass or more, more preferably 73% by mass or more, and preferably 80% by mass or less, more preferably 78% by mass or less.

[0020] The additive composition for extrusion-molded hydraulic compositions of the present invention may further contain other components, such as air-enhancing agents, retarders, foaming agents, foaming agents, waterproofing agents, fluidizing agents, defoaming agents, weight-reducing agents, colorants, pigments, etc. (excluding components (A) and (B)).

[0021] The additive composition for extrusion molding hydraulic compositions of the present invention is made from low-quality fly ash that is porous and has a high unburned carbon content, i.e., a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 / g and an ignition loss of 1% or more and 10% or less, the workability during extrusion molding of the hydraulic composition can be improved.

[0022] [Extrusion molded hydraulic composition] The present invention comprises component (A), component (B), cement, and a composition having a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 The present invention provides an extrusion-molded hydraulic composition comprising fly ash having a viscosity of less than 1000 mg / g and an ignition loss of 1% to 10% and water, and a mass ratio (A) / (B) of the content of component (A) to the content of component (B) of 2.0 to 9.0. The components (A) and (B) are the same as those described in the additive composition for the extrusion-molded hydraulic composition of the present invention. The components (A) and (B) may be incorporated into the extrusion-molded hydraulic composition of the present invention by using the additive composition for the extrusion-molded hydraulic composition of the present invention. The extrusion-molded hydraulic composition of the present invention can be appropriately applied with the embodiments described in the additive composition for the extrusion-molded hydraulic composition of the present invention.

[0023] The extrusion-molded hydraulic composition of the present invention contains cement. The cement may be one or more selected from normal Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.). From the viewpoint of stable productivity, normal Portland cement is preferred.

[0024] The extrusion molding hydraulic composition of the present invention has a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 / g and contains fly ash with an ignition loss of 1% or more and 10% or less.

[0025] The BET specific surface area of ​​the fly ash was set to 0.5 m from the viewpoint of improving the workability during extrusion molding even when using fly ash with a large specific surface area. 3 / g or more, and 4m 3 / g or more, and 5m 3 / g or more, and 12.0m 3 / g. BET specific surface area is a gas adsorption method in which gas particles such as nitrogen (N2) are adsorbed onto solid particles, and the surface area is measured from the amount of adsorption. Specifically, the specific surface area is calculated by measuring the monomolecular adsorption amount VM using the BET equation (Brunauer, Emmet and Teller's equation) based on the relationship between pressure P and adsorption amount V, and can be measured using a fully automatic specific surface area measuring device (for example, the fully automatic specific surface area measuring device Macsorb, manufactured by Mountec Co., Ltd.).

[0026] The ignition loss of the fly ash may be 1% or more, further 3% or more, further 5% or more, and 10% or less, from the viewpoint of improving the workability during extrusion molding even when using fly ash with a large amount of unburned carbon. The ignition loss of fly ash is measured by weighing out about 0.4 mg of each fly ash onto a platinum pan and measuring it using a TG-DTA (e.g., Thermoplus EVO2, manufactured by Rigaku Corporation) in a N2 atmosphere at 200 mL / min under the following temperature conditions, and then calculating. [1]30℃→1,000℃(10.0℃ / min) [2]1,000℃→ 30℃(-30.0℃ / min)

[0027] The extrusion molding hydraulic composition of the present invention may contain, in addition to the above-mentioned cement and fly ash, powders having posolan action and / or latent hydraulic properties such as blast furnace slag and silica fume, non-hydraulic fine limestone powder, etc. These are included in the aggregate of component (E) described below. The extrusion molding hydraulic composition of the present invention may use blast furnace cement in which blast furnace slag, fly ash, silica fume or the like is mixed, fly ash cement, or silica fume cement.

[0028] The extrusion-molded hydraulic composition of the present invention contains, relative to 100 parts by mass of cement, preferably 0.2 parts by mass or more of component (A) from the viewpoint of imparting dispersibility to the extrusion-molded hydraulic composition and improving workability during extrusion molding, more preferably 0.35 parts by mass or more, and even more preferably 0.5 parts by mass or more, and from the viewpoint of suppressing setting delay, preferably 3.0 parts by mass or less, more preferably 2.4 parts by mass or less, even more preferably 1.8 parts by mass or less, still more preferably 1.2 parts by mass or less, and even more preferably 0.8 parts by mass or less.

[0029] The extrusion-molded hydraulic composition of the present invention contains, from the viewpoint of imparting dispersibility to the extrusion-molded hydraulic composition and improving workability during extrusion molding, preferably 0.05 parts by mass or more of component (B) per 100 parts by mass of cement, more preferably 0.09 parts by mass or more, even more preferably 0.15 parts by mass or more, and preferably 0.45 parts by mass or less, more preferably 0.36 parts by mass or less, even more preferably 0.30 parts by mass or less, and still more preferably 0.26 parts by mass or less.

[0030] In the extrusion-molded hydraulic composition of the present invention, the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is, from the viewpoint of improving workability during extrusion molding, 2.0 or more and 9.0 or less, preferably 8.0 or less, more preferably 7.0 or less, even more preferably 6.0 or less, and still more preferably 5.0 or less.

[0031] In the extrusion-molded hydraulic composition of the present invention, the mass percentage of the water content in the hydraulic composition to the total content of cement and fly ash (water / (cement+fly ash)) is preferably 77 mass% or more, more preferably 78 mass% or more, and preferably 84 mass% or less, more preferably 82 mass% or less, from the viewpoints of workability and moldability during extrusion molding. In addition, when the extrusion-molded hydraulic composition of the present invention contains, in addition to cement and fly ash, a powder having the physical property of hardening by a hydration reaction, and a powder selected from a powder having pozzolanic action, a powder having latent hydraulic properties, and stone powder (calcium carbonate powder), the amounts of these powders are not included in the amounts of cement and fly ash in the present invention.

[0032] The extrusion-molded hydraulic composition of the present invention contains, from the viewpoint of reducing production costs, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and preferably 150 parts by mass or less, more preferably 110 parts by mass or less, even more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less of fly ash per 100 parts by mass of cement.

[0033] The extrusion-molded hydraulic composition of the present invention may contain a cellulose-based thickener as component (C) from the viewpoint of adjusting the viscosity. The cellulose-based thickener of component (C) may be one or more selected from methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, etc., and from the standpoints of formability, availability, cost, etc., methyl cellulose is preferred.

[0034] The extrusion-molded hydraulic composition of the present invention contains, from the viewpoint of viscosity adjustment, preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, even more preferably 2.5 parts by mass or more of component (C) per 100 parts by mass of cement, and preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, even more preferably 3.5 parts by mass or less.

[0035] The extrusion-molded hydraulic composition of the present invention may contain a fibrous material as component (D) in order to impart excellent toughness. The fiber material of component (D) may be one or more selected from virgin pulp, waste paper pulp, mineral fiber, carbon fiber, glass fiber, etc., with waste paper pulp being preferred from the viewpoint of low cost.

[0036] The extrusion-molded hydraulic composition of the present invention contains, from the viewpoints of excellent toughness and stable productivity, preferably 12 parts by mass or more, more preferably 18 parts by mass or more, even more preferably 21 parts by mass or more of component (D) per 100 parts by mass of cement, and preferably 36 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 27 parts by mass or less.

[0037] The extrusion-molded hydraulic composition of the present invention may contain an aggregate as component (E). Examples of aggregates include mountain sand, mountain gravel, aggregate river sand, river gravel, sea sand, crushed sand, powdered stone, silica sand, silica powder, wollastonite, limestone, mica, lightweight aggregate, silica fume, blast furnace slag, pozzolana, and extenders. Examples of bulking materials include crushed inorganic boards, such as defective products during cement board production, crushed scraps generated during cement board construction, and recycled powders of crushed cement board waste generated during building demolition.

[0038] From the viewpoint of producing a lightweight extrusion molded product, the extrusion molding hydraulic composition of the present invention contains the component (E) in an amount of preferably 30 parts by mass or more, more preferably 60 parts by mass or more, and preferably 100 parts by mass or less, more preferably 80 parts by mass or less, per 100 parts by mass of cement. In the present invention, when the component (E) contains recycled powder obtained by crushing cement board waste or the like, the recycled powder contains cement but does not already have hydraulic properties, so the content of the component (E) is used.

[0039] The extrusion-molded hydraulic composition of the present invention may further contain other components, such as a weight-reducing agent, a colorant, a pigment, an air-enhancing agent, a retarder, a waterproofing agent, a fluidizing agent, and an antifoaming agent (excluding the components (A) to (E)). Examples of the lightweight material include hollow microspheres of resin (polyvinylidene chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resin, etc.), shirasu balloons, and perlite. The coloring agent includes iron black, carbon black, chromium oxide, and the like.

[0040] The extrusion molding hydraulic composition of the present invention comprises the component (A), the component (B), cement, and a composition having a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 The composition can be produced by mixing fly ash having a viscosity of less than 1 / g and an ignition loss of 1% to 10%, water, optionally component (C), optionally component (D), and optionally component (E). The components (A) and (B) may be mixed with the extrusion-molded hydraulic composition of the present invention using an additive composition for the extrusion-molded hydraulic composition of the present invention. The matters described in the additive composition for extrusion-molded hydraulic compositions and the extrusion-molded hydraulic compositions of the present invention can be appropriately applied to the manufacturing method of the extrusion-molded hydraulic composition of the present invention. For example, specific examples and preferred aspects of each component are the same as those of the additive composition for extrusion-molded hydraulic compositions and the extrusion-molded hydraulic composition of the present invention. In addition, the content and mass ratio of each component in the extrusion-molded hydraulic composition of the present invention can be applied to the manufacturing method of the extrusion-molded hydraulic composition of the present invention by replacing the content of each component with the mixed amount. The method for producing the extrusion-molded hydraulic composition of the present invention is not particularly limited, and examples thereof include the following methods. The present invention relates to components (A) and (B), cement, and a composition having a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 One example of such a method is to add fly ash having a viscosity of less than 1 / g and an ignition loss of 1% to 10%, water, optionally component (C), optionally component (D), and optionally component (E) to a kneading machine such as a kneader, an omni mixer, or an Eirich mixer, without any restrictions on the timing or order of addition, and knead them together. When the additive composition for extrusion-molded hydraulic compositions is in the form of a liquid containing water, the additive composition for extrusion-molded hydraulic compositions can be dissolved in the water constituting the extrusion-molded hydraulic composition, and then mixed with various raw materials. When the additive composition for extrusion-molded hydraulic compositions is in the form of a powder, the hydraulic substance and the additive for cement products can be dry-blended, and then mixed with various raw materials.

[0041] The extrusion-molded hydraulic composition obtained by the above method can be molded into a plate shape using an extrusion molding machine equipped with a mold having a predetermined product cross-section, and then a surface pattern can be transferred using a roll or press to produce an extrusion-molded product. The extrusion molded product is cut to a predetermined length using a cutter, and then hardened by steam curing (at 60-100°C for 4-36 hours) and / or autoclave curing (at 120-200°C for 5-15 hours) to form a cement product. The cement product of the present invention can be used mainly as an exterior wall material, but can also be applied to the production of building materials and accessories such as roofing materials, partition materials, and ceiling materials. EXAMPLES

[0042] The materials used in the examples and comparative examples are shown below. <Component (A)> MY150: Naphthalenesulfonic acid dispersant, Mytei 150, manufactured by Kao Corporation, specific gravity 1.20

[0043] <(B) component> B-1: Sodium alkyl sulfate with 10 carbon atoms in the alkyl group B-2: Sodium alkyl sulfate with 8 carbon atoms in the alkyl group

[0044] <Component (B') (comparison component of component (B))> B'-1: Sodium alkyl sulfate with 12 carbon atoms in the alkyl group B'-2: Polyoxyethylene alkyl sulfate sodium salt having an alkyl group carbon number of 11 and an average added mole number of oxyethylene groups of 2 B'-3: Alcohol with 10 carbon atoms B'-4: Alkyl glycoside with 10 carbon atoms in the alkyl group B'-5: Alkylamine with 10 carbon atoms in the alkyl group B'-6: fatty acid with 10 carbon atoms

[0045] <Cement> NC: Ordinary Portland cement, a 50 / 50 mix of Pacific Cement and Sumitomo Osaka Cement, specific gravity 3.16

[0046] <Fly ash (FA)> FA1: BET specific surface area is 3.9m 3 / g, fly ash with loss on ignition of 1.8% FA2: BET specific surface area is 5.3m 3 / g, fly ash with loss on ignition of 3.4%

[0047] The BET specific surface area of ​​each fly ash was measured by the BET method using a fully automatic specific surface area measuring device (fully automatic specific surface area measuring device Macsorb, manufactured by Mountec Co., Ltd.) with nitrogen gas as the adsorption gas.

[0048] The ignition loss of the fly ash was calculated by weighing approximately 0.4 mg of each fly ash onto a platinum pan and measuring it using a TG-DTA (Thermo plusEVO2, manufactured by Rigaku Corporation) under a N2 atmosphere at 200 mL / min under the following temperature conditions. [1]30℃ →1,000℃(10.0℃ / min) [2]1,000℃→ 30℃(-30.0℃ / min)

[0049] W: Tap water (Wakayama City tap water, specific gravity 1.00) <(C) component> MC: Methylcellulose, Metolose SHV-PF, manufactured by Shin-Etsu Chemical Co., Ltd. <(D) component> Pulp: Waste paper pulp, water content in waste paper pulp adjusted to 40% by mass <(E) component> · Expander: Defective inorganic boards and crushed scraps

[0050] [Preparation of additive composition for extrusion-molded hydraulic composition] The (A) or (A') component, the (B) or (B') component, and ion-exchanged water were mixed in the amounts shown in Tables 1 and 2 (the balance being ion-exchanged water) to prepare an additive composition for an extrusion-molded hydraulic composition.

[0051] [Evaluation of storage stability] 100 g of each of the obtained additive compositions for extrusion molding hydraulic compositions was placed in a 100 ml vial and left to stand at 20° C. for 3 days. The appearance of each additive composition after standing was checked and evaluated according to the following indices. The results are shown in Tables 1 and 2. ◯: Uniformly transparent. ×: Cloudy or separated into layers.

[0052] [Table 1]

[0053] [Table 2]

[0054] [Method for preparing extrusion-molded hydraulic composition] Cement (NC), fly ash (FA), component (C), component (D), and component (E) were added to a mortar mixer specified in JIS R 5201 so as to obtain the respective compositions shown in Table 3, and dry mixing was performed for 10 seconds (revolution: 62 rpm, rotation: 141 rpm). Thereafter, water (W) containing component (A) or (A'), component (B) or component (B') was added so as to obtain the contents shown in Tables 4 and 5, and the mixture was stirred for 240 seconds (revolution: 180 rpm, rotation: 410 rpm) to prepare the extrusion-molded hydraulic compositions shown in Tables 4 and 5. In Table 3, the water contained in component (D) was included in the water (W) content. In Tables 4 and 5, the content of the (A) or (A') component indicates the content (parts by mass) relative to 100 parts by mass of cement (NC) in the extrusion-molded hydraulic composition, and the content of the (B) or (B') component indicates the content (parts by mass) relative to 100 parts by mass of cement (NC) in the extrusion-molded hydraulic composition. In addition, (A) / (B) (mass ratio) in the tables indicates the mass ratio (A) / (B) of the content of the (A) component to the content of the (B) component in the extrusion-molded hydraulic composition.

[0055] [Table 3]

[0056] [Method of measuring needle penetration hardness] The needle penetration hardness of each extrusion-molded hydraulic composition prepared in Tables 4 and 5 immediately after preparation was measured using a viscosity hardness tester ("CRAY HARDNESS TESTER" manufactured by Nippon Insulators, Ltd.) The results are shown in Tables 4 and 5. It can be said that the lower the needle penetration hardness, the better the workability when molding into a plate using an extrusion molding machine.

[0057]

Table 4

[0058]

Table 5

Claims

1. An additive composition comprising the following components (A) and (B), wherein the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 2.0 or more and 9.0 or less, and wherein the BET specific surface area is 0.5 m ３ / g or more 12.0m ３ 1. An additive composition for an extrusion-molded hydraulic composition, comprising fly ash having a viscosity of less than 1000 saturates / g and a loss on ignition of 1% or more and 10% or less. Component (A): Naphthalenesulfonic acid-based dispersant Component (B): an alkyl sulfate ester or a salt thereof, the alkyl group of which has 8 to 10 carbon atoms.

2. The following components (A), (B), cement, and a BET specific surface area of ​​0.5 m ３ / g or more 12.0m ３ 1. An extrusion-molded hydraulic composition comprising: fly ash having a viscosity of less than 1000 kJ / g and a loss on ignition of 1% or more and 10% or less; and water; and a mass ratio (A) / (B) of the content of component (A) to the content of component (B) of 2.0 or more and 9.0 or less. Component (A): Naphthalenesulfonic acid-based dispersant Component (B): an alkyl sulfate ester or a salt thereof, the alkyl group of which has 8 to 10 carbon atoms.

3. 3. The extrusion-molded hydraulic composition according to claim 2, wherein the mass percentage of the water content to the total content of cement and fly ash in the extrusion-molded hydraulic composition (water / (cement + fly ash)) is 77 mass% or more and 84 mass% or less.

4. The extrusion-molded hydraulic composition according to claim 2 or 3, further comprising (C) a cellulose-based thickener (hereinafter referred to as component (C)).

5. 5. The extrusion-molded hydraulic composition according to claim 4, wherein component (C) is methyl cellulose.

6. The extrusion-molded hydraulic composition according to claim 2 or 3, further comprising (D) a fibrous material (hereinafter referred to as component (D)).

7. 7. The extrusion-molded hydraulic composition according to claim 6, wherein component (D) is wastepaper pulp.