Extrusion molding hydraulic composition

Abstract

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 extrusion molding hydraulic composition which comprises the following component (A), cement, 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, and water. Component (A): a copolymer comprising a monomer (1a) represented by the general formula (1a) and a monomer (2a) represented by the general formula (2a) as constituent monomers, in which the ratio of monomer (2a) in the total constituent monomers is 15 mass% or more and 35 mass% or less and the weight average molecular weight is 40000 or more and 80000 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to 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 the use of a copolymer mixture (a) obtained by copolymerizing a specific monomer (A1), such as an ethylenically unsaturated carboxylic acid derivative having a polyoxyalkylene group, with a specific monomer (A2), such as (meth)acrylic acid, in which the molar ratio (A1) / (A2) is changed at least once during the reaction, together with a specific water-soluble polymer (b), such as a nonionic cellulose ether, as an admixture for extrusion molded bodies. Patent Document 2 discloses an additive for extrusion-molded cement products, which comprises an unsaturated carboxylic acid (salt) (a), an ester (b) of a polyether (b1) represented by general formula (1) and having an HLB of 18 to 20 and an unsaturated carboxylic acid (b2), and, if necessary, another monomer (c) as constituent units, and a water-soluble polymer [A] having a weight average molecular weight of 20,000 to 1,800,000. Patent Document 3 discloses a cement-based composition for extrusion molding, which is prepared by adding, to 100 parts by weight of a mixture consisting of a hydraulic substance, aggregate, and fiber, 0.1 to 1.5 parts by weight of an extrusion aid in an external proportion, 15 to 45 parts by weight of water in an external proportion, and 0.01 to 2.0 parts by weight of a copolymer having a composition consisting of 50 to 99% by weight of structural units (A) based on a polyoxyalkylene derivative represented by general formula (1), 1 to 50% by weight of structural units (B) based on a dicarboxylic acid or maleic anhydride represented by general formula (2), and 0 to 30% by weight of structural units (C) based on other copolymerizable monomers. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2003-002719 A [Patent Document 2] JP 2001-253743 A [Patent Document 3] International Publication No. 2005 / 123625 Summary of the Invention [Problem to be solved by the invention]

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

[0006] The present invention relates to a composition comprising the following component (A), 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 containing fly ash having a viscosity of less than 1000 mg / g and an ignition loss of 1% or more and 10% or less, and water. Component (A): A copolymer containing, as constituent monomers, a monomer (1a) represented by the following general formula (1a) and a monomer (2a) represented by the following general formula (2a), in which the proportion of the monomer (2a) in all constituent monomers is 15% by mass or more and 35% by mass or less, and the weight average molecular weight is 40,000 or more and 80,000 or less.

[0007] [ka]

[0008] [During the ceremony, R 1a , R 2a may be the same or different, and may be a hydrogen atom or a methyl group. R 3a : Hydrogen atom or -COO(AO) n1 R 4a R 4a : Hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of moles of AO added, a number between 20 and 130 q1: A number between 0 and 2 p1: 0 or 1 Indicates the following.

[0009] [ka]

[0010] [During the ceremony, R 5a , R 6a , R 7a may be the same or different, and may be a hydrogen atom, a methyl group or (CH2) r COOM 2 and (CH2) r COOM 2 COOM 1or other (CH2) r COOM 2 and an anhydride may be formed, in which case, M 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. r: A number between 0 and 2 Indicates the following. Effect of the Invention

[0011] According to the present invention, there is provided an extrusion molding hydraulic composition which is excellent in workability during extrusion molding, even when low-quality fly ash which is porous and contains a large amount of unburned carbon is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The reason why the extrusion-molded hydraulic composition of the present invention has excellent workability in extrusion molding even when it is mixed with low-quality fly ash that is porous and has a large amount of unburned carbon is not necessarily clear, but it is presumed to be as follows: When low-quality fly ash is mixed with an extrusion-molded hydraulic composition using 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, reducing the amount of water required for plasticization, which significantly reduces the workability when extruding the hydraulic composition. However, the extrusion-molded hydraulic composition of the present invention is presumed to have improved workability when extruding the hydraulic composition because the component (A) of the present invention is quickly adsorbed and dispersed in cement and fly ash, efficiently releasing the bound water contained in the hydraulic composition before it is absorbed by the pulp that is optionally mixed, thereby ensuring the amount of water required for plasticization.

[0013] [Extrusion molded hydraulic composition] The extrusion-molded hydraulic composition of the present invention contains, as component (A), a copolymer containing, as constituent monomers, a monomer (1a) represented by the following general formula (1a) and a monomer (2a) represented by the following general formula (2a), in which the proportion of the monomer (2a) in all constituent monomers is 15% by mass or more and 35% by mass or less and the weight average molecular weight is 40,000 or more and 80,000 or less.

[0014] [ka]

[0015] [During the ceremony, R 1a , R 2a may be the same or different, and may be a hydrogen atom or a methyl group. R 3a : Hydrogen atom or -COO(AO) n1 R 4a R 4a : Hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of moles of AO added, a number between 20 and 130 q1: A number between 0 and 2 p1: 0 or 1 Indicates the following.

[0016] [ka]

[0017] [During the ceremony, R 5a , R 6a , R 7a may be the same or different, and may be a hydrogen atom, a methyl group or (CH2) r COOM 2 and (CH2) r COOM 2 COOM 1 or other (CH2) r COOM 2and an anhydride may be formed, in which case, M 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. r: A number between 0 and 2 Indicates the following.

[0018] In general formula (1a), R 1a From the viewpoint of stable supply of the copolymer, is preferably a hydrogen atom. In general formula (1a), R 2a From the viewpoints of stable supply of the copolymer and safety, a methyl group is preferred. In general formula (1a), R 3a From the viewpoint of stable supply of the copolymer, is preferably a hydrogen atom. In general formula (1a), R 4a From the viewpoints of stable supply of the copolymer and safety, is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In general formula (1a), AO is preferably an ethyleneoxy group from the viewpoint of dispersibility. AO preferably contains an ethyleneoxy group. In general formula (1a), n1 is the average number of moles of AO added, and from the viewpoints of dispersibility and workability during extrusion molding, it is preferably 5 or more, more preferably 15 or more, and preferably 200 or less, more preferably 150 or less, even more preferably 100 or less, and still more preferably 60 or less. In the present invention, when the copolymer of component (A) contains one type of monomer (1a), n1 of this monomer (1a) is taken as the average number of moles of AO added. When the copolymer of component (A) contains two or more types of monomer (1a), the average number of moles of AO added is calculated from n1 of each monomer (1a) and the proportion (mol %) of each monomer (1a) in the total monomers (1a). In the general formula (1a), q1 is preferably 0 from the viewpoint of reactivity for obtaining a copolymer. In the general formula (1a), p1 is preferably 1 from the viewpoint of reactivity for obtaining a copolymer.

[0019] In the general formula (2a), from the viewpoint of reactivity to obtain a copolymer, R 5a is preferably a hydrogen atom. In the general formula (2a), from the viewpoint of the stability of the copolymer, R 6a is preferably a methyl group. In the general formula (2a), from the viewpoint of reactivity to obtain a copolymer, R 7a is preferably a hydrogen atom. (CH2) r COOM 2 About COOM 1 or other (CH2) r COOM 2 and an anhydride may be formed, in which case, M 1 , M 2 does not exist. M 1 and M. 2 may be the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. M 1 , M 2 The alkyl group, the hydroalkyl group, and the alkenyl group each preferably have 1 to 4 carbon atoms. M 1 and M. 2 may be the same or different and are preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, or an alkylammonium group, more preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), or an ammonium group, even more preferably a hydrogen atom, an alkali metal, or an alkaline earth metal (1 / 2 atom), and even more preferably a hydrogen atom or an alkali metal. (CH2) in general formula (2a) r COOM 2 In the formula, r is preferably 0.

[0020] The copolymer of component (A) may further contain a monomer (3a) represented by the following general formula (3a) as a constituent monomer.

[0021] [ka]

[0022] [In the formula, R 8a represents an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0023] The proportion of monomer (1a) in all constituent monomers of component (A), from the viewpoint of improving workability during extrusion molding by imparting practical adsorption properties and steric repulsion to the hydraulic powder, is preferably 65 mass% or more, more preferably 67 mass% or more, even more preferably 67.5 mass% or more, and preferably 85 mass% or less, more preferably 83 mass% or less, even more preferably 81 mass% or less, and even more preferably 75 mass% or less. The proportion of monomer (1a) in all constituent monomers of component (A) is preferably 9 mol% or more, more preferably 11 mol% or more, even more preferably 13 mol% or more, from the viewpoint of improving workability during extrusion molding by imparting practical adsorption properties and steric repulsion to the hydraulic powder, and is preferably 20 mol% or less, more preferably 18 mol% or less, even more preferably 17 mol% or less.

[0024] The proportion of monomer (2a) in all constituent monomers of component (A) is 15 mass% or more, preferably 18 mass% or more, more preferably 21 mass% or more, even more preferably 25 mass% or more, from the viewpoint of improving workability during extrusion molding due to practical adsorption to hydraulic powder, and is 35 mass% or less, preferably 34 mass% or less, more preferably 33 mass% or less. The proportion of monomer (2a) in all constituent monomers of component (A) is preferably 80 mol % or more, more preferably 82 mol % or more, even more preferably 83 mol % or more, from the viewpoint of improving workability during extrusion molding due to practical adsorption to hydraulic powder, and is preferably 91 mol % or less, more preferably 89 mol % or less, even more preferably 87 mol % or less.

[0025] From the viewpoint of ensuring efficient dispersibility of the extrusion-molded hydraulic composition, the total amount of the monomers (1a) and (2a) in the entire constituent monomers of the component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. This total amount may be 100% by mass. From the viewpoint of ensuring efficient dispersibility of the extrusion-molded hydraulic composition, the total amount of the monomers (1a) and (2a) in the entire constituent monomers of the component (A) is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. This total amount may be 100 mol%.

[0026] When the copolymer of component (A) contains monomer (3a), the proportion of monomer (3a) in all constituent monomers is, from the viewpoint of imparting long-term dispersibility in the extrusion-molded hydraulic composition, preferably 5 mass % or more, more preferably 10 mass % or more, even more preferably 15 mass % or more, and preferably 50 mass % or less, more preferably 45 mass % or less, even more preferably 40 mass % or less. When the copolymer of component (A) contains monomer (3a), the proportion of monomer (3a) in all constituent monomers is, from the viewpoint of imparting long-term dispersibility in the extrusion-molded hydraulic composition, preferably 10 mol % or more, more preferably 20 mol % or more, even more preferably 30 mol % or more, and preferably 80 mol % or less, more preferably 70 mol % or less, even more preferably 60 mol % or less.

[0027] The weight average molecular weight (Mw) of the (A) component is 40,000 or more, preferably 50,000 or more, more preferably 55,000 or more, and is 80,000 or less, preferably 70,000 or less, more preferably 65,000 or less, from the viewpoint of imparting dispersibility to the extrusion-molded hydraulic composition and improving workability during extrusion molding. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (A) component, is preferably 1.0 or more, more preferably 1.1 or more, even more preferably 1.2 or more, from the viewpoint of imparting dispersibility to the extrusion-molded hydraulic composition and improving workability during extrusion molding, and is preferably less than 4.0, more preferably 2.0 or less, even more preferably 1.8 or less.

[0028] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (A) were measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL+G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

[0029] 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.

[0030] 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.

[0031] 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 7m 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.).

[0032] 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 fly ash containing a large amount of unburned carbon is used. 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)

[0033] 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 (D) 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.

[0034] The extrusion-molded hydraulic composition of the present invention contains, relative to 100 parts by mass of cement, preferably 0.3 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 0.45 parts by mass or more, even more preferably 0.6 parts by mass or more, still more preferably 0.8 parts by mass or more, and even more preferably 1.0 part by mass or more, and from the viewpoint of suppressing setting retardation, preferably 3.0 parts by mass or less, more preferably 2.4 parts by mass or less, and even more preferably 1.8 parts by mass or less.

[0035] 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.

[0036] 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 of fly ash relative to 100 parts by mass of cement, 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.

[0037] The extrusion-molded hydraulic composition of the present invention may contain a cellulose-based thickener as component (B) from the viewpoint of adjusting the viscosity. The cellulose-based thickener of component (B) 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.

[0038] 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 (B) relative to 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.

[0039] The extrusion-molded hydraulic composition of the present invention may contain a fibrous material as component (C) in order to impart excellent toughness. The fiber material of component (C) 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.

[0040] 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 (C) 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.

[0041] The extrusion-molded hydraulic composition of the present invention may contain an aggregate as component (D). 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.

[0042] From the viewpoint of producing a lightweight extrusion molding, the extrusion molding hydraulic composition of the present invention contains component (D) 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 component (D) 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 component (D) is used.

[0043] 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 (D)). 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.

[0044] The extrusion molding hydraulic composition of the present invention comprises the component (A) of the present invention, 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, and optionally component (B), optionally component (C), and optionally component (D). The manufacturing method of the extrusion-molded hydraulic composition of the present invention can be appropriately applied to the matters described in 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 extrusion-molded hydraulic composition of the present invention. In addition, the content of each component in the extrusion-molded hydraulic composition of the present invention can be applied to the manufacturing method of the hydraulic composition of the present invention by replacing the content of each component with the mixing 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 component (A) of the present invention, cement, a BET specific surface area of ​​0.5 m 3 / g or more 12.0m 3 One example of such a method is to feed fly ash having a viscosity of less than 1 / g and an ignition loss of 1% to 10%, water, optionally component (B), optionally component (C), and optionally component (D) into a kneading machine such as a kneader, an omni mixer, or an Eirich mixer, without any restrictions on the timing or order of feeding, and knead them together.

[0045] 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

[0046] The materials used in the examples and comparative examples are shown below. <Component (A) or Component (A')> Table 1 shows the copolymers A-1 to A-7 as the component (A) and the copolymer (A'). As components (comparison components to component (A)), the compositions of copolymers A'-1 to A'-9 are shown.

[0047] [Table 1]

[0048] The monomers of each copolymer in Table 1 are as follows: TPEG(45): isoprenol (polyethylene glycol (45)) ether (the number in parentheses is the average number of moles of ethylene oxide added. The same applies below), monomer (1a) MEPEG(120): Methoxypolyethyleneglycol(120) monomethacrylate, monomer(1a) MEPEG (23): Methoxypolyethylene glycol (23) monomethacrylate, monomer (1a) MEPEG(9): Methoxypolyethyleneglycol(9) monomethacrylate, monomer(1a) TPEG(70): Isoprenol (polyethylene glycol (70)) ether, monomer (1a) Acrylic acid: sodium acrylate, monomer (2a) Methacrylic acid: sodium methacrylate, monomer (2a) In Table 1, the copolymer composition (type and mass%) of each copolymer indicates the type of monomer and the composition in mass ratio in parentheses. Also, the copolymer composition (type and molar%) of each copolymer indicates the type of monomer and the composition in molar ratio in parentheses. Also shown are the average number of moles of EO (ethylene oxide) added in the monomer (1a) in each copolymer, the weight average molecular weight (Mw) of each copolymer, and the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). With regard to the average number of moles of EO added in the monomer (1a), when the copolymer of component (A) contains one type of monomer (1a), n1 in the general formula (1a) of this monomer (1a) is taken as the average number of moles of EO added. When the copolymer contains two types of monomer (1a), the average number of moles of EO added is calculated from n1 in the general formula (1a) of each monomer (1a) and the proportion (mol %) of each monomer (1a) in the total monomers (1a). For example, A-2 contains two types of monomers (1a), MEPEG (120) (n1 is 120) and MEPEG (9) (n1 is 9), in a molar ratio of 3.6 / 5.9. Therefore, the average number of moles of EO added in monomer (1a) is 120×(3.6 / 9.5)+9×(5.9 / 9.5)=60.

[0049] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (A) or (A') were measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL+G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

[0050] <Cement> NC: Ordinary Portland cement, a 50 / 50 mix of Pacific Cement and Sumitomo Osaka Cement, specific gravity 3.16

[0051] <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 6.6m 3 / g, fly ash with loss on ignition of 4.9% FA3: BET specific surface area is 10.6m 3 / g, fly ash with loss on ignition of 7.6%

[0052] 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.

[0053] 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)

[0054] <Water> W: Tap water (Wakayama City tap water, specific gravity 1.00) <(B) component> MC: Methylcellulose, Metolose SHV-PF, manufactured by Shin-Etsu Chemical Co., Ltd. <(C) component> Pulp: Waste paper pulp, water content in waste paper pulp adjusted to 40% by mass <(D) component> · Expander: Defective inorganic boards and crushed scraps

[0055] [Method for preparing extrusion-molded hydraulic composition] Cement (NC), fly ash (FA), component (B), component (C), and component (D) were added to a mortar mixer specified in JIS R 5201 so as to obtain the respective compositions shown in Table 2, and dry mixing was performed for 10 seconds (revolution: 62 rpm, rotation: 141 rpm). Thereafter, water (W) containing component (A) or component (A') was added so as to obtain the contents shown in Tables 3 to 8, and the mixture was stirred for 240 seconds (revolution: 180 rpm, rotation: 410 rpm) to prepare the extrusion-molded hydraulic compositions shown in Tables 3 to 8. In Table 2, the water contained in component (C) was included in the water (W) content. In Tables 3 to 8, the content of the component (A) or the component (A') is shown as the content (parts by mass) relative to 100 parts by mass of cement (NC) in the extrusion-molded hydraulic composition.

[0056] [Table 2]

[0057] [Method of measuring needle penetration hardness] The needle penetration hardness of each of the prepared extrusion-molded hydraulic compositions shown in Tables 3 to 8 immediately after preparation was measured using a viscosity hardness tester ("CRAY HARDNESS TESTER" manufactured by Nippon Insulators Co., Ltd.). The results are shown in Tables 3 to 8. 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.

[0058] [Table 3]

[0059] [Table 4]

[0060] [Table 5]

[0061] [Table 6]

[0062]

Table 7

[0063]

Table 8

Claims

1. The following component (A), cement, 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 an ignition loss of 1% or more and 10% or less; and water. Component (A): A copolymer containing, as constituent monomers, a monomer (1a) represented by the following general formula (1a) and a monomer (2a) represented by the following general formula (2a), in which the proportion of the monomer (2a) in all constituent monomers is 15% by mass or more and 35% by mass or less, and the weight average molecular weight is 40,000 or more and 80,000 or less. 【Chemical 1】 [During the ceremony, R １ａ , R ２ａ : may be the same or different, and may be a hydrogen atom or a methyl group R ３ａ : a hydrogen atom or -COO(AO) ｎ１ R ４ａ R ４ａ : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of moles of AO added, which is 20 or more and 130 or less q1: a number between 0 and 2 p1: 0 or 1 indicates.] 【Chemistry 2】 [During the ceremony, R ５ａ , R ６ａ , R ７ａ may be the same or different, and may be a hydrogen atom, a methyl group, or (CH ２ ) ｒ COOM ２ and (CH ２ ) ｒ COOM ２ is COOM １ or other (CH ２ ) ｒ COOM ２ and an anhydride may be formed, in which case the M １ , M ２ does not exist. M １ , M ２ may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group r: a number between 0 and 2 indicates.]

2. 2. The extrusion-molded hydraulic composition according to claim 1, wherein the component (A) is a copolymer having a molecular weight distribution (Mw / Mn), which is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), of 1.0 or more and less than 4.

0.

3. 3. The extrusion-molded hydraulic composition according to claim 1, wherein the mass percentage of the water content in the extrusion-molded hydraulic composition to the total content of cement and fly ash (water / (cement + fly ash)) is 77 mass% or more and 84 mass% or less.

4. 3. The extrusion-molded hydraulic composition according to claim 1, further comprising (B) a cellulose-based thickener (hereinafter referred to as component (B)).

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

6. The extrusion-molded hydraulic composition according to claim 1 or 2, further comprising a fibrous material (C) (hereinafter referred to as component (C)).

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

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