Manufacturing method of iron and steel slag hydrated solidified body

Abstract

To solve a problem in which: unlike normal concrete, a steel slag hydrated matrix is difficult to control the work life during application, hydration adjustment and strength development.SOLUTION: A method for producing a steel slag hydrated matrix at least includes blending a first raw material group with a second raw material group and curing the blend, to acquire a hydrated matrix. The first raw material group at least contains (A) cement, and (B) steel slag aggregate that at least contains silicon oxide and calcium oxide, with a content of silicon oxide of 10.0 wt.% or more, a content of calcium oxide of 35.0 wt.% or more, and a content of particles with a size of 5 mm or more of 40.0 wt.% or more. The second raw material group contains (C) water, (D1) a retarder and (D2) at least one or more selected from a polycarboxylic acid copolymer, a glycol ether copolymer and salts thereof, with (D1): (D2)=10.0: 90.0-80.0: 20.0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a hydrated iron and steel slag body. [Background technology]

[0002] Steelmaking slag has been used for purposes such as temporary roadbed material and backfill material, but has now been effectively utilized as a steel slag hydrate, which is made up of ground granulated blast furnace slag, steelmaking slag, and water (Non-Patent Document 1). Non-Patent Document 2 has been officially recognized, and the number of application cases is increasing. Initially, steel slag hydrate had the problem of expansion due to f-CaO or f-MgO, but this problem has been avoided by specifying the powdering rate and MgO content. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Takano, Yoshihiro et al., Development Process, Characteristics and Application Examples of Steel Slag Hydrated Solids, Nippon Steel & Sumitomo Metal Technical Report No. 399, 2014, p42-50 [Non-Patent Document 2] Steel Slag Hydrated Solidification Technology Manual, Coastal Technology Research Center, 2008 Summary of the Invention [Problem to be solved by the invention]

[0004] However, to be used as an alternative material to concrete, there are difficulties in controlling the pot life of fresh slag, adjusting the setting time, and adjusting the time when strength is developed. There is no technology that can adjust these factors that must be adjusted to the same level as concrete. The object of the present invention is to provide a manufacturing method for a steel slag hydrated body that can replace conventional hydraulic compositions such as cement. In other words, the object of the present invention is to solve the problems of steel slag hydrated bodies, which, unlike ordinary concrete, are difficult to control the pot life for construction, hydration adjustment, and strength development. [Means for solving the problem]

[0005] The present invention provides the following: [1] (A) component: cement, and (B) component: A first raw material group containing at least a steel slag aggregate, which contains at least silicon oxide and calcium oxide, and has a silicon oxide content of 10.0% by weight or more, a calcium oxide content of 35.0% by weight or more, and a content of particles having a particle diameter of 5 mm or more of 40.0% by weight or more; (C) Component: water, (D1) component: retarder, and Component (D2): one or more selected from polycarboxylic acid copolymers, glycol ether copolymers, and salts thereof Contains at least A method for producing a hydrated iron and steel slag product, comprising at least adding the hydrated iron and steel slag product to a second raw material group having a weight ratio of components (D1):(D2) of 10.0:90.0-8.00:20.0, and hardening the raw material to obtain a hydrated product. [2] (B) component has a density of 1.75 to 3.30 g / cm 3 The manufacturing method according to [1], wherein the iron and steel slag aggregate has a water absorption rate of 0.5 to 16.0%, a basicity of 1.0 or more, and a pH of 8 to 13 when immersed in an equal amount of water for 24 hours. [3] The component (D1) is A polysaccharide composed of at least one sugar selected from the group consisting of glucose, galactose, mannose, rhamnose, arabinose, and xylose; Sodium gluconate, and Dextrin with a dextrose equivalent of 10 or more The manufacturing method according to [1], comprising at least one selected from the group consisting of: [4] The component (D2) is The following general formula (1): [ka] (In the formula, R 1 , R 2 and R 3each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; m represents a number from 0 to 2. 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. 1 is the average number of moles of oxyalkylene groups added, and is a number from 1 to 200; X is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; A structural unit derived from an unsaturated monocarboxylic acid monomer (II), The copolymer comprises a structural unit derived from the monomers (I) and (II) and another monomer (III) copolymerizable therewith, The weight ratio of each monomer during copolymerization is 50≦(I)≦97, 1≦(II)≦50, 0≦(III)≦50, or a salt thereof (D2-1), The polycarboxylic acid copolymer or its salt (D2-1) is The weight average molecular weight measured by gel permeation chromatography is 7,000 to 15,000, Weight average molecular weight Mw of polymer peak on gel permeation chromatogram (AH) and Mw (AL) The difference is 8,000 to 12,000 (Mw (AH) >Mw (AL) ) and When the peak area on the high molecular weight side of the gel permeation chromatogram is AH and the peak area on the low molecular weight side is AL, AH / (AH+AL)×100 is 70% to 80%. The method for producing the same according to any one of [1] to [3]. [5] The component (D2) is The following general formula (IV): R 4 -O-(A 2 O)-R 5 (2) (In general formula (IV), R 4 represents an alkenyl group having 2 to 5 carbon atoms. 2O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n1 represents the average number of moles of the oxyalkylene group added and is a number from 1 to 200. R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The method for producing a semiconductor device according to any one of [1] to [4] above. [6] The method for producing a composition according to any one of [1] to [5], further comprising adding fly ash as component (E). [7] The method according to any one of [1] to [6], wherein the component (B) contains at least ground slag. Effect of the Invention

[0006] According to the present invention, it is possible to produce a hydrated iron and steel slag product having performance equal to or greater than that of conventional hydraulic compositions such as cement, and to solve the problems associated with the hydrated iron and steel slag product, such as the difficulty in controlling the pot life, hydration adjustment, and strength development. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is an example of a chromatogram of a polycarboxylic acid copolymer or a salt thereof (A), and is a diagram for explaining the weight average molecular weight and area ratio of the polymer peak. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] [Components of hydrated iron and steel slag] The iron and steel slag hydrated material of the present invention is preferably produced using the following components (A) to (D), and may further include component (E). Components other than (A) to (E) may also be used as necessary.

[0009] <Component (A): Cement> Examples of cement include Portland cement (e.g., ordinary, early strength, super early strength, moderate heat, sulfate resistant, and low alkali form of each), mixed cement (e.g., blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, super rapid hardening cement (e.g., 1-clinker rapid hardening cement, 2-clinker rapid hardening cement, magnesium phosphate cement), cement for grouting, oil well cement, low heat cement (e.g., low heat type blast furnace cement, fly ash mixed low heat type blast furnace cement, high belite content cement), ultra high strength cement, cement-based solidification material, ecocement (e.g., cement manufactured using one or more of urban waste incineration ash and sewage sludge incineration ash as raw materials). Among these, Portland cement and mixed cement are preferred. As Portland cement, ordinary Portland cement is preferred. As mixed cement, blast furnace cement is preferred.

[0010] The component (A) may be one type of cement alone or a combination of two or more types.

[0011] <(B) Component: Steel slag aggregate> The steel slag aggregate is an aggregate made from steel slag. Steel slag is a by-product of steelmaking and is derived from limestone, which is a secondary raw material. Examples of steel slag include, but are not limited to, blast furnace slag (e.g., granulated slag, slowly cooled slag), steelmaking slag (converter furnace slag, electric furnace slag), ingot slag, AOD (Argon Oxygen Decarburization) slag (stainless steel slag).

[0012] -Inorganic components- Iron and steel slag aggregate usually contains inorganic components. Examples of inorganic components include magnesium oxide (MgO) and aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), sulfur oxide (SO 2 , S.O. 3 , S.O. 4 ), calcium oxide (CaO), manganese oxide (MnO, MnO2 , Mn 2 O 3 , Mn 3 O 4 ), iron oxide (Fe 2 O 3 , FeO, Fe 3 O 4 ), phosphorus oxide (P 2 O 5 The component (B) preferably contains at least one of silicon oxide and calcium oxide, and more preferably contains both.

[0013] The composition of the inorganic components in the (B) component is not particularly limited, but an example is as follows. The content of silicon oxide is usually 10.0 wt% or more, preferably 11.0 wt% or more, more preferably 12.0 wt% or more. The upper limit is usually 40.0 wt% or less, preferably 35.0 wt% or less, more preferably 30.0 wt% or less, but is not particularly limited. The content of calcium oxide is usually 35.0 wt% or more, preferably 36.0 wt% or more, more preferably 37.0 wt% or more. The upper limit is usually 80.0 wt% or less, preferably 75.0 wt% or less, more preferably 70.0 wt% or less, but is not particularly limited.

[0014] The content of magnesium oxide is usually 0.5% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more. The upper limit is usually 25.0% by weight or less, preferably 23.0% by weight or less, more preferably 20.0% by weight or less, but is not particularly limited. The content of aluminum oxide is usually 0.5% by weight or more, preferably 1.5% by weight or more, more preferably 2.0% by weight or more. The upper limit is usually 30.0% by weight or less, preferably 25.0% by weight or less, more preferably 20.0% by weight or less, but is not particularly limited. The content of sulfur oxide is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more. The upper limit is usually 10.0% by weight or less, preferably 9.0% by weight or less, more preferably 8.0% by weight or less, but is not particularly limited. The content of manganese oxide (MnO) is usually 0.5% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more. The upper limit is usually 10.0% by weight or less, preferably 9.0% by weight or less, and more preferably 8.0% by weight or less, but is not particularly limited. 2 O 3 ) is usually 0.5% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more. The upper limit is usually 40.0% by weight or less, preferably 35.0% by weight or less, more preferably 30.0% by weight or less, but is not particularly limited.

[0015] The composition of the inorganic components can be confirmed by fluorescent X-ray analysis (quantitative analysis) of the steel slag aggregate used as component (B), and was confirmed by this method in the examples described later.

[0016] -Particle size- The iron and steel slag aggregate usually contains iron and steel slag particles. Although there is no particular restriction on the lower limit of the particle size, it is preferable that the (B) component contains particles having a particle size of 5 mm or more. The content of particles having a particle size of 5 mm or more relative to the total amount of the (B) component is usually 40.0% by weight or more, preferably 45.0% by weight or more, and more preferably 50.0% by weight or more. The upper limit is usually 80.0% by weight or less, preferably 75.0% by weight or less, and more preferably 70.0% by weight or less. The content of particles having a particle size of 5 mm or more may be measured according to JIS A 1102:2009.

[0017] The content of particles having a particle size of 5 mm or more in the (B) component can be adjusted, for example, by using a combination of at least one type of steel slag aggregate (B1) having a particle size of 5 mm or more and at least one type of steel slag aggregate (B2) having particles having a particle size of 5 mm or less as the (B) component, and adjusting the amount of each. The steel slag aggregate (B1) (particle size of 5 mm or more) has a coarse particle ratio (FM, particle size) of usually more than 5.0, preferably 5.1 or more, more preferably 5.2 or more. The upper limit is 10.0 or less, preferably 9.0 or less, more preferably 8.0 or less. The steel slag aggregate (B2) (particle size less than 5 mm, excluding fine slag powder) has a coarse particle ratio of usually 1.0 or more, preferably 1.3 or more, more preferably 1.5 or more. The upper limit is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less. The coarse particle ratio may be measured in accordance with JIS A 1102. The particle size of the iron and steel slag aggregate may be adjusted according to a conventional method (for example, by adjusting the granulation conditions).

[0018] - Finely ground slag - The component (B) preferably contains ground granulated slag. In this specification, ground granulated slag means ground granulated blast furnace slag. Ground granulated blast furnace slag can be produced by pulverizing granulated blast furnace slag, and preferably satisfies the standard specified in JIS A 6206:2013. The average particle size of the ground granulated blast furnace slag is preferably 850 μm or less.

[0019] -Density, water absorption rate- The density of steel slag aggregate (surface dry) is usually 1.75 g / cm3 or more, preferably 1.80 or more, and more preferably 1.90 or more. The upper limit is usually 3.30 g / cm 3 Less than 3.20 g / cm 3 Less than or equal to 3.15 g / cm 3 The water absorption of the steel slag aggregate is usually 0.5% or more, preferably 2.0% or more, and more preferably 4.0% or more. The upper limit is usually 16.0%, preferably 15.5% or less, and more preferably 15.0% or less. The density (surface dry density) and water absorption of the slag aggregate (other than ground slag powder) can be measured in accordance with JIS A 1110, and this method was used to confirm the results in the examples described later. The density of the ground slag powder can be measured in accordance with JIS R 5201:2005, and this method was used to confirm the results in the examples described later.

[0020] -Basicity- The basicity of the iron and steel slag aggregate is usually 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more. The upper limit is usually 4.5 or less.

[0021] -pH of soaking water- The pH of the water when the steel slag aggregate is immersed in an equal amount of water for 24 hours is usually 8 or more, preferably 10 or more, and more preferably 11 or more. The upper limit is usually 13 or less.

[0022] Component (B) may be one type of iron and steel slag aggregate alone or a combination of two or more types. When component (B) is a combination of two or more types of iron and steel slag aggregate, it is preferable that at least one of the iron and steel slag aggregates satisfies at least one parameter selected from the above-mentioned density, water absorption, basicity, and pH, and it is more preferable that the iron and steel slag aggregate satisfies all of the parameters.

[0023] <(C) Component: Water> Examples of water include, but are not limited to, tap water, water other than tap water (e.g., river water, lake water, well water, groundwater, industrial water), recovered water (e.g., supernatant water, sludge water), and purified water (e.g., distilled water, ion-exchanged water).

[0024] <(D1) Component: Retarder> Examples of the retarder include sugars (e.g., monosaccharides such as glucose, galactose, mannose, rhamnose, arabinose, xylose, fructose, ribose, saccharose, and cellobiose, and disaccharides, trisaccharides, oligosaccharides, and polysaccharides (e.g., dextrin) composed of at least two of these), oxycarboxylic acid compounds (e.g., oxycarboxylic acids having 4 to 10 carbon atoms such as gluconic acid, glucoheptonic acid, arabinic acid, malic acid, and citric acid, and salts thereof (e.g., sodium, potassium, calcium, magnesium, alumina, and the like). Examples of the retarder include inorganic salts or organic salts such as ammonium and triethanolamine, and preferably polysaccharides composed of at least one sugar selected from the group consisting of glucose, galactose, mannose, rhamnose, arabinose, and xylose, gluconic acid, gluconate, and dextrin, and more preferably gluconate. The gluconate is preferably sodium gluconate. The dextrin is preferably dextrin having a dextrose equivalent of 10 or more. The component (D1) may be one type of retarder or a combination of two or more types.

[0025] <Component (D2): polycarboxylic acid copolymer, glycol ether copolymer, or salt thereof> Examples of the polycarboxylic acid copolymer or a salt thereof include a polycarboxylic acid copolymer or a salt thereof (D2-0) containing structural units derived from the following monomers (I) to (III), and a polyalkylene glycol monoallyl ether (D2-2) containing structural units derived from the following monomer (IV). (Copolymer or its salt (D2-0)) (D2-0) is represented by the following general formula (1): [ka] A structural unit derived from a monomer (I) represented by the formula: A structural unit derived from an unsaturated monocarboxylic acid monomer (II), A structural unit derived from an unsaturated monocarboxylic acid monomer (b) including a structural unit derived from another monomer (III) copolymerizable with the monomers (I) to (II), Examples of the salt include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts, and among these, calcium salts, magnesium salts, sodium salts, and mixed calcium-sodium salts are preferred.

[0026] -Weight ratio of monomers (I) to (III) during copolymerization- The polymerization ratio of each monomer during copolymerization is as follows. The weight ratio of monomer (I) is usually 50≦(I)≦97, preferably 60≦(I)≦97, and more preferably 65≦(I)≦97. The weight ratio of monomer (II) is usually 1≦(II)≦50, preferably 5≦(II)≦50, and more preferably 5≦(II)≦40. The weight ratio of monomer (III) is usually 0≦(III)≦50, preferably 0≦(III)≦40, more preferably 0≦(III)≦30, even more preferably 0≦(III)≦10, even more preferably 0≦(III)≦1, and particularly preferably 0≦(III)≦0.5. During copolymerization, a part of the monomer usually remains in the reaction system without being copolymerized, so it is difficult to specify the ratio of each constitutional unit in the polycarboxylic acid copolymer. Each of the monomers (I) to (III) may be one type or a combination of two or more types. When a plurality of each monomer is used, the above weight ratio is the weight ratio of the total amount thereof.

[0027] -Monomer (I): Monomer represented by general formula (1)- The monomer (I) is represented by the above general formula (1). 1 , R 2 and R 3 Each of A in the general formula (1) independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 1O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit), and an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are preferred. The term "the same or different" refers to A in the general formula (1). 1 When multiple Os are included (n 1 If A is 2 or more, 1 This means that the O may be the same oxyalkylene group or different (two or more) oxyalkylene groups. 1 In the case where a plurality of O's are included, there may be mentioned a mixture of two or more oxyalkylene groups selected from the group consisting of oxyethylene group (ethylene glycol unit), oxypropylene group (propylene glycol unit) and oxybutylene group (butylene glycol unit), and it is preferable that there is a mixture of oxyethylene group (ethylene glycol unit) and oxypropylene group (propylene glycol unit), or that there is a mixture of oxyethylene group (ethylene glycol unit) and oxybutylene group (butylene glycol unit), and it is more preferable that there is a mixture of oxyethylene group (ethylene glycol unit) and oxypropylene group (propylene glycol unit). In the embodiment where different oxyalkylene groups are mixed, the addition of two or more oxyalkylene groups may be block-like addition or random addition.

[0028] n in general formula (1) 1 is the average number of moles of oxyalkylene groups added. The lower limit is 1 or more, preferably 5 or more, and more preferably 10 or more. The upper limit is 200 or less, for example, 100 or less, less than 100, 90 or less, 80 or less, 70 or less, 60 or less, or 50 or less. Therefore, n 1represents a number from 1 to 200, preferably from 5 to 200, more preferably from 5 to 100, even more preferably from 10 to less than 100, and even more preferably from 10 to 50.

[0029] The monomer (I) may be a single monomer represented by the general formula (1), or may be a combination of two or more monomers. The combination of two or more monomers may be two monomers (Ia) and (Ib) having different average numbers of moles of oxyalkylene groups added (wherein each of the monomers has an average number of moles of oxyalkylene groups added of n). 1a , n 1b In this case, n 1a <n 1b It is preferable that the monomer (Ia) and the monomer (Ib) each contain an average number of moles of oxyalkylene groups added, n 1 Only the difference is R 1 , R 2 , R 3 , m, and X may be the same monomer, and n 1 In addition, R 1 , R 2 , R 3 At least one of n, m, and X may be a different monomer. 1a is, for example, 15 or less, 14 or less, or 13 or less. 1a is preferably 1 to 15, more preferably 1 to 14, even more preferably 1 to 13, and even more preferably 1 to 9. 1b is n 1a It may be any number larger than 14, for example, 14 or more, 15 or more, 16 or more, 17 or more, or 18 or more. It is preferably 10 to 200, 14 to 200, 15 to 200, 16 to 200, 17 to 200, or 18 to 200, more preferably 10 or more and less than 100, 14 or more and less than 100, 15 or more and less than 100, 16 or more and less than 100, 17 or more and less than 100, or 18 or more and less than 100, and even more preferably 10 or more and 50 or less, 14 or more and 50 or less, 15 or more and 50 or less, 16 or more and 50 or less, 17 or more and 50 or less, or 18 or more and 50 or less.

[0030] When the monomer (I) is a combination of monomers (Ia) and (Ib), the weight ratio (total being 100% by weight) of each is preferably (Ia) / (Ib) is (0.1 to 99.9) / (99.9 to 0.1), more preferably (1.0 to 99.0) / (99.0 to 1.0), even more preferably (10.0 to 90.0) / (90.0 to 10.0), and particularly preferably (25.0 to 75.0) / (75.0 to 25.0).

[0031] X in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Since a group having a relatively small number of carbon atoms can enhance the cement dispersibility of the hydraulic composition dispersant, X is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and further preferably a hydrogen atom or a methyl group.

[0032] Examples of the monomer (I) include esters of unsaturated monocarboxylic acids such as (meth)acrylates (hereinafter, "(meth)acrylate" means "acrylate or methacrylate") with (poly)alkylene glycols such as (poly)ethylene glycol, (poly)ethylene (poly)propylene glycol, (poly)ethylene (poly)butylene glycol, methoxy(poly)ethylene glycol, methoxy(poly)ethylene (poly)propylene glycol, and methoxy(poly)ethylene (poly)butylene glycol. Examples of the monomer (I) include (poly)alkylene glycol (meth)acrylates such as (poly)ethylene glycol (meth)acrylate, (poly)ethylene (poly)propylene glycol (meth)acrylate, (poly)ethylene (poly)butylene glycol (meth)acrylate, methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)ethylene (poly)propylene glycol (meth)acrylate, and methoxy(poly)ethylene (poly)butylene glycol (meth)acrylate. As the monomer (I), these may be used alone or in combination of two or more thereof, but it is preferable to use a (poly)alkylene glycol (meth)acrylate, and more preferably to use at least one of (poly)ethylene glycol (meth)acrylate (e.g., hydroxyethyl acrylate), (poly)propylene glycol (meth)acrylate (e.g., hydroxypropyl acrylate) and methoxy(poly)ethylene glycol (meth)acrylate. The average number of moles of (poly)alkylene glycol added is preferably 1 to 50. When the monomer (Ia) is a (poly)alkylene glycol, the number of moles of (poly)alkylene glycol added as the monomer (Ia) is preferably 1 to 9. When the monomer (Ib) is a (poly)alkylene glycol, the number of moles of (poly)alkylene glycol added as the monomer (Ib) is preferably 10 to 200, more preferably 10 to 100.When the monomer (Ia) is a methoxy (poly) alkylene glycol (meth) acrylate, the number of moles of the methoxy (poly) alkylene glycol (meth) acrylate added as the monomer (Ia) is preferably 1 to 13, 1 to 14, 1 to 15, 1 to 16, or 1 to 17. When the monomer (Ib) is a methoxy (poly) alkylene glycol (meth) acrylate, the number of moles of the methoxy (poly) alkylene glycol (meth) acrylate added as the monomer (Ib) is preferably 14 to 200, 15 to 200, 16 to 200, 17 to 200, or 18 to 200, and more preferably 14 to 100, 15 to 100, 16 to 100, 17 to 100, or 18 to 100.

[0033] -Monomer (II): Unsaturated monocarboxylic acid monomer- Examples of the unsaturated monocarboxylic acid monomer include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (for example, monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts). The monomer (II) may be one or more of these. When two or more are used, it is preferable that the monomer (II) contains one or more selected from the group consisting of acrylic acid, methacrylic acid, and any salts thereof, and it is preferable that the monomer (II) is one or more selected from such a group.

[0034] When acrylic acid and methacrylic acid are used in combination, the ratio thereof (total being 100% by weight) is usually acrylic acid / methacrylic acid (0.1% to 99.9%) / (99.9% to 0.1%), and preferably (1.0% to 99.0%) / (99.0% to 1.0%).

[0035] The monocarboxylic acid is preferably a mixture containing a monomer and a dimer. In the case of acrylic acid, it is preferably a mixture of an acrylic acid monomer and a dimer. The ratio of the two (total of 100% by weight) is preferably acrylic acid monomer / acrylic acid dimer=(90.0% by weight to 100% by weight) / (0% by weight to 10.0% by weight).

[0036] -Monomer (III): A monomer copolymerizable with one or more monomers selected from the group consisting of monomers (I) and (II)- Monomer (III) is distinguished from monomer (I) and monomer (II), and examples thereof include one or a combination of two or more selected from the following:

[0037] General formula (III-1): [ka] Diallyl bisphenols represented by the formula: for example, 3- and 3'-allyl substituted 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone;

[0038] General formula (III-2): [ka] monoallyl bisphenols represented by the following formula (I): for example, 3-allyl substituted bisphenols of 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone;

[0039] General formula (III-3): [ka] Allylphenol represented by the formula:

[0040] Half esters and diesters of unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, with alcohols having 1 to 30 carbon atoms; Half amides and diamides of the above unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms; half esters and diesters of alkyl (poly)alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines, and the above unsaturated dicarboxylic acids; half esters and diesters of the above unsaturated dicarboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of 2 to 500 of such glycols; half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of 2 to 500 of such glycols;

[0041] (poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate; Polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate; (Poly)alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; unsaturated sulfonic acids such as vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidomethyl sulfonic acid, (meth)acrylamidoethyl sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl (meth)acrylamide; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; Alkanediol mono(meth)acrylates such as 1,4-butanediol mono(meth)acrylate, 1,5-pentanediol mono(meth)acrylate, and 1,6-hexanediol mono(meth)acrylate; Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene;

[0042] Unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol (meth)acrylamide, and N,N-dimethyl (meth)acrylamide; Unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile; Unsaturated esters such as vinyl acetate and vinyl propionate; Unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine; Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; Allyls such as (meth)allyl alcohol and glycidyl (meth)allyl ether; Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono(meth)allyl ether, polyethylene glycol mono(meth)allyl ether, and the like; and Siloxane derivatives such as polydimethylsiloxane propylaminomaleamic acid, polydimethylsiloxane aminopropylene aminomaleamic acid, polydimethylsiloxane bis-(propylaminomaleamic acid), polydimethylsiloxane bis-(dipropyleneaminomaleamic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane bis-(1-propyl-3-acrylate), and polydimethylsiloxane bis-(1-propyl-3-methacrylate).

[0043] The monomer (III) may be used alone or in combination of two or more.

[0044] The monomer (III) preferably contains 3- and 3'-allyl-substituted 4,4'-dihydroxydiphenylsulfone and / or (poly)alkylene glycol di(meth)acrylate. The (poly)alkylene glycol di(meth)acrylate is preferably (poly)ethylene glycol di(meth)acrylate. The number of moles of oxyalkylene groups added in the (poly)alkylene glycol di(meth)acrylate is, for example, 1 to 200, 5 to 200, or 5 to 100, preferably 10 or more and less than 100, and more preferably 10 or more and 50 or less.

[0045] The polycarboxylic acid copolymer or its salt (D2-0) may have a structural unit derived from a monomer other than the monomers (I) to (III) (such as the monomer (V) described below) as necessary.

[0046] -Weight average molecular weight- Weight average molecular weight Mw of polycarboxylic acid copolymer or its salt (D2-0) (A)is preferably 7,000 or more, more preferably 8,000 or more. The upper limit of the weight average molecular weight is preferably 15,000 or less. Therefore, it is preferably 7,000 to 15,000, more preferably 8,000 to 15,000. By being in this range, component (A) can be applied to a wide range of concrete mixes from normal strength concrete to ultra-high strength concrete, high dispersibility can be obtained in the ultra-high strength range, dispersibility does not plateau, and the limit addition rate can be reduced.

[0047] The weight average molecular weight is measured by gel permeation chromatography (GPC). The GPC measurement may be performed under the following conditions using a known method in which the weight average molecular weight is converted into polyethylene glycol. Measuring device: Tosoh Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 0.05M sodium nitrate / acetonitrile 8 / 2 (v / v) Eluent flow rate; 1.00ml / min Column temperature: 50°C Measurement sample concentration: 0.5% by weight Standard material: Polyethylene glycol (Tosoh, GL Science) Detector: Differential refractometer (Tosoh) Calibration curve; Polyethylene glycol standard

[0048] The molecular weight distribution (Mw / Mn) of the polycarboxylic acid copolymer or its salt is not particularly limited, but the Mw / Mn of the polycarboxylic acid copolymer or its salt (D2-0) is preferably 1.2 or more, more preferably 1.25 or more. The upper limit is preferably 2.0 or less, more preferably 1.70 or less. Therefore, the molecular weight distribution is preferably 1.25 to 1.70.

[0049] (Polycarboxylic acid copolymer or its salt (D2-1)) The polycarboxylic acid copolymer or its salt (D2-0) contains the above-mentioned structural units, and the weight ratio of each monomer at the time of copolymerization, the weight average molecular weight Mw (A), the weight average molecular weight Mw of the polymer peak on the gel permeation chromatogram (AH) and Mw (AL) and the peak area ratio calculated by AH / (AH+AL)×100 satisfy the above-mentioned ranges.

[0050] -Difference in weight average molecular weight of polymer peak- Weight average molecular weight Mw of the polymer peak on the gel permeation chromatogram of polycarboxylic acid copolymer or its salt (AH) and Mw (AL) The difference between the Mw and Mw is preferably 8,000 to 12,000. This allows the dispersion to be well maintained and the concrete viscosity to be kept low. (AH) Mw is usually 11,000 to 16,000, more preferably 12,000 to 16,000 or 11,000 to 15,000, and further preferably 12,000 to 14,000. (AL) is usually 3,000 to 6,000, and preferably 3,500 to 5,000.

[0051] The two polymer peaks can be confirmed by obtaining a GPC chromatogram of the polycarboxylic acid copolymer or its salt after GPC measurement and creating a baseline. The GPC chromatogram can be plotted with peak intensity (mV) on the vertical axis and retention time on the horizontal axis. The baseline is usually taken from the start time of elution of the polymer peak to the end time of elution. If the end time of elution is not clearly visible, the baseline can be created and then separated at the midpoint between the peak and the valley of the peak, and this point can be taken as the end time of elution of the polymer peak.

[0052] As shown in FIG. 1, two polymer peaks are usually confirmed. When three or more polymer peaks are present in the polycarboxylic acid copolymer or its salt, peaks expected to be derived from the polycarboxylic acid copolymer or its salt (usually the two largest polymer peaks) are selected. In the example of FIG. 1, the two polymer peaks are adjacent to each other, but when three or more polymer peaks are present, the two selected peaks do not necessarily have to be adjacent to each other. The weight average molecular weight on the high molecular weight side, calculated as polyethylene glycol, is defined as Mw (AH) , the weight average molecular weight on the low molecular weight side is Mw (AL) That is, Mw (AH) >Mw (AL) This is in a relationship.

[0053] -Peak area ratio- When the peak area on the high molecular weight side of a gel permeation chromatogram of a polycarboxylic acid copolymer or a salt thereof is AH and the peak area on the low molecular weight side is AL, AH / (AH+AL)×100 (area ratio of AH) is preferably 70% to 80%.

[0054] The peak area on the high molecular weight side is the area enclosed by the ridgeline of the polymer peak on the high molecular weight side described in the section on the weight average molecular weight of the polymer peak, the line drawn vertically from the lowest intensity points (so-called valleys) on both sides of the ridgeline to the baseline, and the baseline. The peak area on the low molecular weight side is the area enclosed by the ridgeline of the polymer peak on the low molecular weight side described in (ii), the line drawn vertically from the lowest intensity points (so-called valleys) on both sides of the ridgeline to the baseline, and the baseline. If the area ratio of AH is 70% to 80%, the effect on dispersibility is suppressed, dispersibility can be improved, and concrete viscosity can be kept low.

[0055] (Polyalkylene glycol monoallyl ether (D2-2)) (D2-2) is represented by the following general formula (IV): R 4 -O-(A 2 O)-R 5 (2) Examples of the salt are the same as those given in (D2-1).

[0056] R in general formula (IV) 4 R represents an alkenyl group having 2 to 5 carbon atoms. The number of carbon atoms in the alkenyl group is preferably 3 to 5. 4 Examples of R include an allyl group, a methallyl group, and a residue of 3-methyl-3-buten-1-ol. 4 is not limited to these groups.

[0057] A in general formula (IV) 2 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include an oxyethylene group (ethylene glycol), an oxypropylene group (propylene glycol), and an oxybutylene group (butylene glycol). Among these, the oxyalkylene group is preferably an oxyethylene group (ethylene glycol) or an oxypropylene group (propylene glycol).

[0058] The above-mentioned "may be the same or different" means that A 2 If multiple Os are included (n1 is 2 or more), multiple A 2 This means that O may be the same oxyalkylene group or different (two or more types) oxyalkylene groups.

[0059] In general formula (IV), A 2In the case where a plurality of O's are contained, there may be mentioned an embodiment in which two or more oxyalkylene groups selected from the group consisting of an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit) are mixed. Among these, preferred is an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed, or an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxybutylene group (butylene glycol unit) are mixed, and more preferred is an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed.

[0060] In the case where oxyethylene groups and oxypropylene groups are mixed, the ratio of the average number of moles of oxyethylene groups to the average number of moles of oxypropylene groups ((average number of moles of oxyethylene groups added) / (average number of moles of oxypropylene groups added)) is preferably (50.0 to 99.9)% / (0.1 to 50.0)%.

[0061] In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more types of oxyalkylene groups may be in a block form or a random form.

[0062] In the general formula (IV), n1 is the average number of moles of oxyalkylene groups added, and is a number from 1 to 200. n1 is preferably 1 to 70, more preferably 5 to 70, and even more preferably 8 to 70.

[0063] R in general formula (IV) 5 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. If the number of carbon atoms is large, the dispersing ability of the dispersant for hydraulic compositions may not be fully exhibited. 5 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and further preferably a hydrogen atom or a methyl group.

[0064] The polyalkylene glycol monoallyl ether represented by the general formula (IV) can be produced, for example, by adding 1 to 200 moles of an alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, or 3-methyl-3-buten-1-ol.

[0065] The lower limit of the weight average molecular weight of the polyalkylene glycol monoallyl ether (D2-2) is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 14,000 or more. This allows the dispersibility of (D2-2) to be fully exhibited. On the other hand, the upper limit is preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 40,000 or less. This can suppress the aggregation action of cement particles and improve workability.

[0066] The lower limit of the molecular weight distribution (Mw / Mn) of the polyalkylene glycol monoallyl ether (D2-2) is preferably 1.20 or more, more preferably 1.25 or more, while the upper limit is preferably 3.00 or less, more preferably 2.90 or less.

[0067] -Methods of producing polycarboxylic acid copolymers, glycol ether polymers, and their salts- Each compound can be produced by polymerizing the monomer from which the constituent unit is derived. The polymerization method is not limited, but examples thereof include polymerization methods such as polymerization in a solvent and bulk polymerization.

[0068] Examples of the solvent used in the polymerization in a solvent include water, lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as cyclohexane, n-hexane, etc., esters such as ethyl acetate, etc., ketones such as acetone, methyl ethyl ketone, etc. From the viewpoint of the solubility of the raw material monomers and the resulting polymer, it is preferable to use one or more selected from the group consisting of water and lower alcohols, and among them, it is more preferable to use water.

[0069] When polymerization is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel. Alternatively, a solvent may be charged into a reaction vessel, and a mixture of the monomers and the solvent and a polymerization initiator solution may be continuously added into the reaction vessel, or a part or all of the monomers may be charged into a reaction vessel, and the polymerization initiator may be continuously added dropwise.

[0070] When polymerization is carried out in a solvent, it is preferable that the monomers are mixed in advance in a vessel different from the reaction vessel and placed upstream of the vessel in which the reaction is carried out, and then continuously added dropwise to the reaction vessel.

[0071] After the polymerization reaction is completed, the polycarboxylic acid copolymer, glycol ether polymer, and their salts may be contained in the hydraulic composition as is, including the reaction solvent, or may be further treated. Examples of such treatments include removing the reaction solvent, adjusting the concentration by concentration or dilution, purification, and pH adjustment. After the reaction is completed, it is preferable to adjust the concentration and / or pH in a vessel installed downstream of the reaction vessel. There is no particular limitation on the method of concentration adjustment, but it may be performed, for example, by concentration or dilution by adding water. The pH adjustment will be described later.

[0072] When polymerization is performed in a water solvent, examples of the polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble organic peroxides such as t-butyl hydroperoxide. In this case, accelerators such as sodium hydrogen sulfite and Mohr's salt can be used in combination. In addition, when polymerization is performed in a solvent such as a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester, or a ketone, for example, peroxides such as benzoyl peroxide and lauryl peroxide; hydroperoxides such as cumene peroxide; and azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator. In this case, accelerators such as amine compounds can be used in combination. Furthermore, when polymerization is performed in a water-lower alcohol mixed solvent, the above-mentioned polymerization initiators or combinations of polymerization initiators and accelerators can be appropriately selected and used. The polymerization temperature varies depending on the polymerization conditions such as the solvent used and the type of polymerization initiator, but is usually performed in the range of 50 to 120°C.

[0073] In the polymerization, a chain transfer agent may be used to adjust the molecular weight as necessary. Examples of the chain transfer agent used include known thiol compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid (β-mercaptopropionic acid), thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), and lower oxides and salts thereof; and the like. In addition, a polymerization inhibitor such as 4-methoxyphenol or phenothiazine may be used. The chain transfer agent and the polymerization inhibitor may each be used alone or in combination of two or more.

[0074] In addition to the monomers (I), (II) and (III) used as necessary, or in addition to the monomer (IV), a monomer (V) having higher chain transferability may be used. This allows the molecular weight of each polymer to be adjusted. As the monomer (V), for example, a (meth)allylsulfonic acid (salt)-based monomer may be mentioned. The weight ratio of the monomer (V) during polymerization is usually 20% by weight or less, and preferably 10% by weight or less. The above weight ratio is the weight ratio when the weight ratio of the monomer (I) + the weight ratio of the monomer (II) + the weight ratio of the monomer (III) = 100% by weight, or the weight ratio of the monomer (IV) = 100% by weight.

[0075] In the case of polymerization in an aqueous solvent, the pH during polymerization may become strongly acidic due to the influence of monomers having unsaturated bonds, but this may be adjusted to an appropriate pH. If pH adjustment is required during polymerization, the pH can be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, or (alkyl)benzenesulfonic acid. Among these acidic substances, it is preferable to use phosphoric acid because of its pH buffering effect. However, in order to eliminate the instability of the ester bond of the ester monomer, it is preferable to carry out the polymerization at a pH of 2 to 7. In addition, there is no particular limitation on the alkaline substance that can be used to adjust the pH, but NaOH, Ca(OH) 2 The alkaline substances are generally used. The pH adjustment may be performed on the monomer before polymerization, or on the polymer solution after polymerization. In addition, a part of the alkaline substance may be added before polymerization, polymerization may be performed, and then the pH of the polymer may be further adjusted.

[0076] The (D2) component may be one selected from polycarboxylic acid copolymers, glycol ether polymers, and salts thereof, or a combination of two or more of them. It is preferable to include at least the above (D2-1) or (D2-2), and more preferably to include at least a combination of (D2-1) and (D2-2), or to include at least a combination of (D2-1), (D2-2) and (D2-0). The proportion of (D2-1) in the (D2) component is usually 10% by weight or more, preferably 20% by weight or more, and more preferably 25% by weight or more. The upper limit is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 55% by weight or less. The proportion of (D2-2) in the (D2) component is usually 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more. The upper limit is usually 70% by weight or less, preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 50% by weight or less. (D2-1) / (D2-2) (weight ratio) is usually 0.7 or more, preferably 0.8 or more, and more preferably 0.85 or more. The upper limit is usually 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. The proportion (weight ratio) of (D2-1)+(D2-2) in the (D2) component is usually 40% by weight or more, preferably 50% by weight or more, and more preferably 55% or more. There is no particular upper limit, and it may be 100% by weight.

[0077] <(E) Component: Fly ash> The density of the fly ash is usually 1.7 or more, preferably 1.8 or more, and more preferably 2.0 or more. The upper limit of the ignition loss of the fly ash is usually 20.0 or less, preferably 8.0 or less, and more preferably 3.0 or less. The density and ignition loss can be measured in accordance with JIS A 6201, and were confirmed by this method in the examples described later.

[0078] The BET specific surface area of ​​fly ash is usually 1000 cm 2 / g or more, preferably 1500cm 2 / g or more, more preferably 2500cm 2 / g or more. The upper limit is 120000 cm 2 / g or less, preferably 5000cm 2 / g or less, more preferably 3500cm 2 The BET specific surface area can be measured by gas adsorption (nitrogen), and was confirmed by this method in the examples described later.

[0079] Component (E) may be one type of fly ash alone or a combination of two or more types. When component (B) is a combination of two or more types of fly ash, it is sufficient that at least one of the fly ash satisfies at least one parameter selected from the above-mentioned density, ignition loss, and BET specific surface area, and it is preferable that all of the parameters are satisfied.

[0080] <Optional raw materials> If necessary, any component other than the components (A) to (E) may be used. For example, fine powder (e.g., cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, slaked lime), aggregate (sand, gravel, crushed stone, recycled aggregate, silica stone, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromium, magnesia, and other refractory aggregate), other cement admixtures (e.g., water-soluble polymers, polymer emulsions, air entraining agents, cement wetting agents, expansion agents, waterproofing agents, retarders, thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, defoamers, AE agents, setting retarders, rust inhibitors, cement dispersants, surfactants, water reducing agents, high-performance water reducing agents, AE water reducing agents, high-performance AE water reducing agents, fluidizing agents, pumping aids, low thixotropy aids, and other known additives for concrete). The optional components may be one type or a combination of two or more types.

[0081] <Amount of each ingredient used (raw material blend amount)> The amount of each component used is not particularly limited, but the following is a rough guide: -Amount of component (A) used- Regarding component (A), the unit amount of cement is usually 50 kg / m 3 More than 100kg / m 3 More preferably, 150 kg / m 3 More preferably, 200 kg / m3 Above that. The upper limit is usually 900kg / m 3 Less than 800 kg / m 3 Less than or equal to 700 kg / m 3 The following is the result.

[0082] -(B) Amount of component used- The unit weight of steel slag aggregate is usually 400kg / m 3 More than 700kg / m 3 More preferably, 900kg / m 3 Above that. The upper limit is usually 2500kg / m 3 Less than 2300 kg / m 3 Less than or equal to 2100 kg / m 3 The unit weight of steel slag aggregate, which is a particle with a diameter of 5 mm or more, is usually 300 kg / m 3 More than 350kg / m 3 More preferably, 400 kg / m 3 Above that. The upper limit is usually 1500kg / m 3 Less than 1400 kg / m 3 Less than or equal to 1300 kg / m 3 The unit amount of steel slag aggregate, which is particles with a particle size of less than 5 mm (excluding finely divided slag powder), is usually 300 kg / m 3 More than 350kg / m 3 More preferably, 400 kg / m 3 Above that. The upper limit is usually 1200kg / m 3 Less than or equal to 1100 kg / m 3 Less than or equal to 1000 kg / m 3 The unit amount of ground slag is usually 50 kg / m 3 More than 100kg / m 3 More preferably, 120 kg / m 3 Above that. The upper limit is usually 500 kg / m 3 Less than 400 kg / m 3 Less than or equal to 300 kg / m 3 The following is the result.

[0083] -(C) Amount of component used- The unit amount of water is usually 120 kg / m 3 More than 150kg / m 3 More preferably, 170 kg / m 3 The upper limit is usually 300 kg / m 3 Less than or equal to 250 kg / m 3 Less than or equal to 200 kg / m 3 The following is the result.

[0084] The W / B (water-binder ratio) is usually 30% or more, preferably 35% or more, more preferably 40% or more. The upper limit is usually 90% or less, preferably 85% or less, more preferably 80% or less.

[0085] -Amount of components (D1) and (D2) used- The total amount of the (D1) and (D2) components used is usually 0.5% or more, preferably 0.7 or more, and more preferably 0.8 or more, based on the mass of the cement (however, when ground granulated slag is optionally included, the total mass of the cement and ground granulated slag). The upper limit is usually 5.0% or less, preferably 3.0% or less, and more preferably 2.0% or less. The strength index is calculated using the latter formula (1).

[0086] The ratio (weight ratio) of the amounts of the components (D1) and (D2) used is preferably (D1):(D2)=10.0:90.0 to 80.0:20.0, more preferably 12.0:87.0 to 75.0:25.0, and even more preferably 15.0:85.0 to 70.0:30.0.

[0087] -(E) Amount of Component Used- When component (E) is used, the unit amount of fly ash is usually 70 kg / m 3 More than 80kg / m 3 More preferably, 90kg / m 3 Above that. The upper limit is usually 400 kg / m 3 Less than 150 kg / m 3 Less than or equal to 110 kg / m 3The following is the result.

[0088] -s / a- The s / a (fine aggregate ratio) is usually 15% or more, preferably 20% or more, and more preferably 25% or more. The upper limit is usually 75% or less, preferably 70% or less, and more preferably 65% ​​or less. The fine aggregate ratio is the weight ratio of fine aggregate to the total aggregate. Here, aggregate and fine aggregate include aggregate and fine aggregate (including component (F)) other than the steel slag aggregate, which is component (B).

[0089] -Amount of AE agent used- The amount of the AE agent used is usually 0.01% or more, preferably 0.02% or more, more preferably 0.03% or more, based on the mass of cement (however, when ground granulated slag is included as necessary, the total mass of cement and ground granulated slag). The upper limit is usually 1.0% or less, preferably 0.5% or less, more preferably 0.1% or less.

[0090] - Defoamer usage amount - The amount of the antifoaming agent used is usually 0.005% or more, preferably 0.010% or more, more preferably 0.020% or more based on the mass of the cement (however, when ground granulated slag is optionally included, the total mass of the cement and ground granulated slag). The upper limit is usually 0.10% or less, preferably 0.08% or less, more preferably 0.05% or less.

[0091] <Characteristics of raw material composition> -Strength index- The strength index is usually 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more. The upper limit is 5.0 or less, preferably 4.5 or less, and more preferably 4.0 or less. The strength index is calculated by the following mathematical formula (1). Strength index=(BP+CH+2NP+0.35FA) / W ···(1) In formula (1), BP is the blending amount of ground slag powder (kg / m 3 ), CH is the amount of slaked lime mixed (kg / m 3 ), and NP is the mix ratio of ordinary Portland cement (kg / m 3) and FA is the fly ash content (kg / m 3 ), W is the unit water content (kg / m 3 ) respectively.

[0092] [Manufacturing method of iron and steel slag hydrated solidification material] The method for producing the iron and steel slag hydrated solidification material is not particularly limited as long as it is produced by mixing the above-mentioned components, but preferably includes a method including adding a second raw material group containing at least the components (C), (D1) and (D2) to a first raw material group containing at least the components (A) and (B) and hardening. When the component (E) is mixed, it is preferable to use it as the first raw material group. The first raw material group may be mixed in advance before adding the second raw material group. The second raw material group may be mixed before being added to the first raw material group, or each may be added separately to the first raw material group, the former being preferable. On the other hand, the first raw material group and the second raw material group may be added to the system sequentially or all at once without separating them. When using optional components, the aggregate and fine powder may be added at an appropriate time, and are not particularly limited. The mixing means may be a conventional method such as stirring. Hardening may be performed by heating the composition containing the first raw material group and the second raw material group as necessary. The heating temperature is usually 50 to 90° C., and preferably 60 to 70° C. The heating time is usually 1.5 to 5.0 hours, and preferably 2.5 to 4.0 hours. EXAMPLES

[0093] <Production Example 1> 3930 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device, the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, an aqueous monomer solution containing 605 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 13), 155 parts of methacrylic acid, 9 parts of β-mercaptopropionic acid and 300 parts of water, and a mixture of 9 parts of sodium persulfate and 191 parts of water were continuously dropped into the reaction vessel held at 100 ° C. for 2 hours each. After reacting for 1 hour while keeping the temperature at 100 ° C., the aqueous solution pH was adjusted to 6 using 48 wt % NaOH to obtain an aqueous solution of copolymer (D2-a) (Table 1).

[0094] <Production Example 2> 3500 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device, and the reaction vessel was heated to 100°C under stirring. Then, a monomer aqueous solution containing 140 parts of methacrylic acid, 333 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 23), and 600 parts of water, and a mixture of 12 parts of ammonium persulfate and 288 parts of water were continuously dropped into the reaction vessel held at 100°C for 2 hours each. After reacting for 1 hour while keeping the temperature at 100°C, the aqueous solution was adjusted to pH 6 using 48% by weight of NaOH to obtain an aqueous solution of copolymer (D2-b) (Table 1).

[0095] <Production Example 3> 3000 parts of water were charged into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device, and the reaction vessel was heated to 100°C under stirring. Then, a monomer aqueous solution containing 160 parts of methacrylic acid, 400 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 22), 2 parts of a compound in which the 3- and 3-positions of 4,4'-dihydroxydiphenylsulfone were allyl-substituted, and 450 parts of water, and a mixture of 13 parts of ammonium persulfate and 287 parts of water were continuously dropped into the reaction vessel held at 100°C for 2 hours each. Furthermore, the mixture was reacted for 1 hour while keeping the temperature at 100°C, and then the pH of the aqueous solution was adjusted to 6 using 48% by weight of NaOH to obtain an aqueous solution of copolymer (D2-c) (Table 1).

[0096] <Production Example 4> In a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube, and a dropping device, 383 parts of water, 384 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53), and 1 part of hydrogen peroxide were charged, and the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, a monomer aqueous solution containing 40.3 parts of acrylic acid, 5 parts of 2-hydroxyethyl acrylate, and 161 parts of water, and a mixed solution containing 3 parts of L-ascorbic acid, 2 parts of 3-mercaptopropionic acid, and 47 parts of water were continuously dropped into the reaction vessel held at 40°C for 2 hours each. After the dropping was completed, the mixture was reacted for another hour while maintaining the temperature, to obtain an aqueous solution of a polymer. The pH of this liquid was adjusted to 4 with a 30% NaOH aqueous solution. The copolymer in the liquid was polymer (D2-d) (weight average molecular weight: 36,000, Mw / Mn: 2.42) (Table 1).

[0097] [Table 1]

[0098] Example 1 A steel slag hydrated solid was produced according to Mixture A (Table 3-1). That is, cement and steel slag aggregate (chemical composition of slag aggregate: Table 3-2) were mixed, and then premixed water and Agent 1 (Table 2) adjusted to a solids concentration of 28% by weight were added and stirred to produce a steel slag hydrated solid.

[0099] Example 2 The same procedure as in Example 1 was carried out, except that Mixture B (Table 3-1) was used instead of Mixture A, and fly ash (FA) was added at the stage of adding cement.

[0100] Example 3 The same procedure as in Example 1 was repeated, except that Recipe C (Table 3-1) was used instead of Recipe A, Recipe 2 (Table 2) adjusted to a solids concentration of 13% by weight was used instead of Recipe 1, and blast furnace slag powder was added at the cement addition stage.

[0101] Example 4 The same procedure as in Example 2 was repeated, except that Recipe D (Table 3-1) was used instead of Recipe A, Recipe 3 (Table 2) adjusted to a solids concentration of 17% by weight was used instead of Recipe 1, and blast furnace slag powder was added at the cement addition stage.

[0102] Example 5 The same procedure as in Example 1 was carried out, except that Formulation E (Table 3) was used instead of Formulation A, and Formulation 4 (Table 2) adjusted to a solids concentration of 19% by weight was used instead of Formulation 1.

[0103] [Table 2]

[0104] [Notes to Table 2] D1: C-PARN (sodium gluconate), manufactured by Fuso Chemical Co., Ltd.

[0105] [Table 3-1]

[0106] [Table 3-2]

[0107] (Footnotes to Table 3) ·W / B: Water binder ratio Strength index: the value calculated using the above formula (1) ·s / a: fine aggregate ratio W: Unit water volume *1: Blast-furnace cement, density 3.04g / cm 3 (BB, used at Kimitsu Works and Wakayama Works) *2: Ordinary Portland cement, density 3.15g / cm 3 (OPC, used by Hirohata Steel Works) *3: Slag aggregate, surface dry density 2.85g / cm 3 , water absorption rate 8.50%, FM3.32 (KS, used at Kimitsu Steel Works) *4: Cast slag, surface dry density 2.72g / cm 3 , water absorption rate 10.23%, FM3.32 (HS, used at Hirohata Steel Works) *5: Cast slag, surface dry density 2.45g / cm 3 , water absorption rate 14.92%, FM2.84 (WS, used at Wakayama Steel Works) *6: Slag aggregate, surface dry density 3.09g / cm 3 , water absorption rate 5.48%, FM5.28 (KG, used at Kimitsu Steel Works) *7: Cast slag, surface dry density 3.13g / cm 3 , water absorption rate 3.55%, FM6.20 (HG, used at Hirohata Steel Works) *8: Cast slag, surface dry density 2.77g / cm 3 , water absorption rate 6.41%, FM7.06 (WG, used by Wakayama Steel Works) *9: Slowly cooled slag, surface dry density 2.81g / cm 3 , water absorption rate 2.57%, FM2.41 (WJS, used by Wakayama Steel Works) *10:AOD, surface dry density 2.54g / cm 3 , water absorption rate 7.90%, FM1.58 (used at Wakayama Steel Works) *11: Blast furnace slag powder, product name Esment (registered trademark) (no gypsum added), manufactured by Nippon Steel & Sumitomo Metal Cement Co., Ltd., density 2.91 g / cm 3 (BFS, used by Hirohata Steel Works) *12: Fly ash, density 2.20g / cm 3 , ignition loss 8.7%, BET specific surface area 11.37m 2 / g (FA, used at Kimitsu Steel Works) *13: Fly ash, density 2.20g / cm 3 , ignition loss 10.8%, BET specific surface area 11.45m 2 / g (FA, used by Hirohata Steel Works) *14: Tsukuba City tap water, density 1.00g / cm 3 Mix design by

[0108] The iron and steel slag hydrated bodies prepared in each of the Examples and Comparative Examples were subjected to the following tests.

[0109] [Test conditions in Examples 1 to 5] 1. Fresh property test (20℃, 30℃: Table 4, 5) (1) Slump (SL): Measured in accordance with JIS A 1101. (2) Slump flow (SLF): Measured in accordance with JIS A 1150. (3) Air volume: Measured in accordance with JIS A 1128. (4) Unit volume weight (unit volume mass): The air meter mass after air volume measurement. (5) Temperature (CT): Measured using a digital thermometer. (6) V-funnel flow time: Measured in accordance with JSCE-F512.

[0110] 2. Compressive strength test (Table 6) The test was conducted in accordance with JIS A 1108 (at material ages of 1 day, 7 days, 28 days, and 91 days).

[0111] 3. Length change test (Table 7) The test was conducted in accordance with JIS A 1129 (to some extent).

[0112] 4. Freeze-thaw test (Table 8) The test was conducted in accordance with JIS A 1148 (to some extent).

[0113] [Table 4]

[0114] (Footnotes to Table 4) *1: Drop height: 293mm

[0115] [Table 5]

[0116] (Footnotes to Table 5) *: Drop height 182mm (Notes to Tables 4 and 5)

[0117] [Table 6]

[0118] [Table 7]

[0119] [Table 8]

[0120] Example 6 The same procedure as in Example 1 was carried out, except that Mixture F (Table 10) was used instead of Mixture A, and Chemical 6 (Table 9) was used instead of Chemical 1. The chemical composition of each slag aggregate is shown in Table 11.

[0121] Comparative Example 1 The same procedure as in Example 6 was repeated, except that Drug 5 (Table 9) was used instead of Drug 6.

[0122] Example 7 The procedure was the same as in Example 6, except that Recipe G (Table 10) was used instead of Recipe A.

[0123] Example 8 The same procedure as in Example 7 was repeated, except that Drug 7 (Table 9) was used instead of Drug 6. Comparative Example 2 The same procedure as in Example 7 was repeated, except that Drug 5 (Table 9) was used instead of Drug 6.

[0124] [Table 9]

[0125] [Table 10]

[0126] (Footnotes to Table 10) W / C: Water-cement ratio Water: Tsukuba City tap water Cement: High-early-strength Portland cement (mixture F), blast-furnace cement (mixture G), surface dry density 3.14 g / cm 3 S: (NSS Sand), surface dry density 2.93g / cm 3 , absolute dry density 2.80g / cm 3 , water absorption rate 3.62%, coarse particle rate 2.88 G1-Ts: Slag aggregate (Nisshin Steel, Shunan Steel Works), granulated material made using NS powder, 5mm over, surface dry density 2.33g / cm 3 , absolute dry density 2.00g / cm 3 , water absorption rate 14.24%, coarse particle rate 7.50 G2-tsu: Slag aggregate (Nisshin Steel, Shunan Steel Works), granulated material made using NS powder, 5mm over, surface dry density 2.29g / cm 3 , absolute dry density 1.92g / cm 3 , water absorption rate 16.19% Others are the same as the footnotes in the previous table.

[0127] [Table 11]

[0128] The iron and steel slag hydrated bodies prepared in each of the Examples and Comparative Examples were subjected to the following tests.

[0129] [Test conditions in Examples 6 to 8 and Comparative Examples 1 and 2] 1. Fresh property test (Table 12) (1) Slump (SL): Measured in accordance with JIS A 1101. (2) Slump flow (SLF): Measured in accordance with JIS A 1150. (3) Air volume: Measured in accordance with JIS A 1128. (4) Concrete temperature (CT): Measured in accordance with JIS A 1156.

[0130] 2. Compressive strength test (Table 13) The test was conducted in accordance with JIS A 1132 and 1108 (at material ages of 3 days, 7 days, 28 days, and 91 days).

[0131] 3. Length change test (Table 14) The test was carried out in accordance with JIS A 1129.

[0132] 4. Accelerated neutralization test (Table 15) The test was carried out in accordance with JIS A 1153.

[0133] [Table 12]

[0134] (Notes to Table 12) Same as footnote in previous table

[0135] [Table 13]

[0136] [Table 14]

[0137] [Table 15]

[0138] The results of the examples show that the present invention makes it possible to appropriately control the working life, hydration adjustment, and strength development of the obtained hydrated solidified body by using materials with specified physical and chemical properties.

Claims

1. (A) component: cement, and (B) component: a first raw material group containing at least a steel slag aggregate, the first raw material group containing at least silicon oxide and calcium oxide, the silicon oxide content being 10.0% by weight or more, the calcium oxide content being 35.0% by weight or more, and the content of particles having a particle diameter of 5 mm or more being 40.0% by weight or more, (C) Component: water, Component (D1): retarder, and Component (D2): one or more selected from polycarboxylic acid copolymers, glycol ether copolymers, and salts thereof Contains at least The method includes at least adding a second raw material group having a weight ratio of the components (D1) and (D2) of (D1):(D2)=28.00:72.00 to 80.0:20.0, and hardening the second raw material group to obtain a hydrated solidified body, The component (D2) is The following general formula (1): 【Chemistry 1】 (wherein R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; m represents a number from 0 to 2; A 1 O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms; n 1 is the average number of moles added of the oxyalkylene group and represents a number from 1 to 200; and X represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), A structural unit derived from an unsaturated monocarboxylic acid monomer (II), The copolymer includes a structural unit derived from the monomers (I) to (II) and another monomer (III) copolymerizable therewith, The copolymer contains a polycarboxylic acid copolymer or a salt thereof (D2-1), in which the weight ratios of the respective monomers during copolymerization are 50≦(I)≦97, 1≦(II)≦50, and 0≦(III)≦50, The polycarboxylic acid copolymer or its salt (D2-1) is The weight average molecular weight as measured by gel permeation chromatography is 7,000 to 15,000; The difference between the weight average molecular weights Mw(AH) and Mw(AL) of the polymer peaks on a gel permeation chromatogram is 8,000 to 12,000 (provided that Mw(AH)>Mw(AL)); When the peak area on the high molecular weight side on the gel permeation chromatogram is AH and the peak area on the low molecular weight side is AL, AH / (AH+AL)×100 is 70% to 80%. A method for manufacturing hydrated iron and steel slag bodies.

2. The component (B) has a density of 1.75 to 3.30 g / cm 3 The manufacturing method according to claim 1, wherein the iron and steel slag aggregate has a water absorption rate of 0.5 to 16.0%, a basicity of 1.0 or more, and a pH of the water when immersed in an equal amount of water for 24 hours is 8 to 13.

3. The component (D1) is A polysaccharide composed of at least one sugar selected from the group consisting of glucose, galactose, mannose, rhamnose, arabinose, and xylose; Sodium gluconate, and Dextrin with a dextrose equivalent of 10 or more The method according to claim 1 or 2, comprising at least one selected from the group consisting of:

4. The component (D2) is The following general formula (IV): R 4 -O-(A 2 O)-R 5 ・・・(2) (In general formula (IV), R 4 represents an alkenyl group having 2 to 5 carbon atoms. 2 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n1 represents the average number of moles of the oxyalkylene group added and is a number from 1 to 200. 5 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The method according to any one of claims 1 to 3.

5. A manufacturing method described in any one of claims 1 to 4, wherein the first group of raw materials further contains (E) component: fly ash.

6. The method according to any one of claims 1 to 5, wherein component (B) further comprises ground slag.

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