WO2018101140A1 - Additive for hydraulic-setting composition - Google Patents

Abstract

The present invention pertains to an additive for a hydraulic-setting composition, the additive containing thiosulfuric acid or a salt thereof, thiocyanic acid or a salt thereof, and an α-hydroxyalkanesulfonic acid or a salt thereof.

Description

Additives for hydraulic compositions

The present invention relates to an additive for a hydraulic composition using a blast furnace slag cement, a hydraulic composition, a method for producing a hydraulic composition, and a method for producing a cured product of the hydraulic composition.

Background Art Hydraulic powders such as cement and blast furnace slag are hardened by reacting with water, and are called mortar when mixed with sand and concrete when mixed with gravel. These materials have been used in various structures because they can be easily changed in form before curing. By adding a chemical agent to the concrete before curing, the strength of the cured body can be adjusted, workable time can be improved, workability can be improved, and the like.

Japanese Patent Application Laid-Open No. 2011-153068 discloses a rapid composition for a hydraulic composition comprising a specific compound (1) such as glycerin and one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates. An early strengthening agent for a hydraulic composition, which is a strong agent and the molar ratio of compound (1) to inorganic salt A is 5/95 to 45/55 of compound (1) / inorganic salt A, is disclosed.

Japanese Patent Application Laid-Open No. 2011-162400 contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene-based dispersant. An additive composition for hydraulic compositions having a molar ratio of glycerin / inorganic salt A of 5/95 to 55/45 is disclosed.

Japanese Patent Application Laid-Open No. 2014-208574 discloses glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, a hydraulic powder, an aggregate, and water, and the content of glycerin is a hydraulic powder. 0.040 parts by mass or more and 0.280 parts by mass or less with respect to 100 parts by mass of the body, and the content of hydroxymethanesulfonic acid or a salt thereof is 0.010 parts by mass or more with respect to 100 parts by mass of the hydraulic powder. A hydraulic composition that is 420 parts by weight or less is disclosed.

JP-A-61-117142 discloses a cement composition containing an aldehyde and bisulfite or an addition compound of the aldehyde and bisulfite and a water-soluble thiocyanate.

On the other hand, in the steel industry, a substance containing a mineral component separated from a metal to be metallurgically separated by melting is generated as a by-product during iron smelting from ore. This material is called slag. Conventionally, slag has been actively used mainly as a raw material and product in the building materials field. In particular, in the cement field, slag is used not only as a raw material but also as a product and a blended material in cement. ing.
JP-A-2016-56083 discloses α-hydroxysulfonic acid or a salt thereof, a hydraulic powder and water, and the hydraulic composition has a slag ratio of 60% by mass or more in the hydraulic powder. Is disclosed.

SUMMARY OF THE INVENTION A hydraulic composition using blast furnace slag cement is desired to further improve the initial strength, for example, the strength from 1 to 7 days of age, from the viewpoint of improving productivity. In addition, it is desired that the hydraulic composition further enhances the medium- to long-term strength from the viewpoint of quality improvement.
The present invention provides an additive for a hydraulic composition that is an additive for a hydraulic composition using blast furnace slag cement, and that provides a hydraulic composition having excellent initial strength of a cured product.
Further, the present invention is an additive for a hydraulic composition using a blast furnace slag cement, and has a suitable workability, and a hydraulic composition excellent in strength and durability of a cured product is obtained. Additives for hydraulic compositions are provided.

The present invention relates to a hydraulic composition using a blast furnace slag cement containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof. Relating to additives.

The present invention also provides a hydraulic composition comprising (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, a blast furnace slag cement, and water. Related to things.

The present invention also provides a method for producing the hydraulic composition of the present invention, wherein (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof. The present invention relates to a method for producing a hydraulic composition, in which salt, blast furnace slag cement, and water are mixed.

Hereinafter, (A) thiosulfuric acid or a salt thereof will be described as component (A), (B) thiocyanic acid or a salt thereof as component (B), and (C) α-hydroxyalkanesulfonic acid or a salt thereof as component (C). .

The additive for the hydraulic composition of the present invention comprises (A) component, (B) component, (C) component, and (D) lignin sulfonic acid and its derivative, lignin sulfonate and its derivative, and naphthalene sulfone. An additive for a hydraulic composition using a blast furnace slag cement containing an admixture selected from an acid salt formaldehyde condensate and a salt thereof.

Further, the hydraulic composition of the present invention comprises (A) component, (B) component, (C) component, (D) lignin sulfonic acid or derivative thereof, lignin sulfonate or derivative thereof, and naphthalene sulfonate formaldehyde. A hydraulic composition containing an admixture selected from a condensate or a salt thereof, a blast furnace slag cement, and water is included.

Moreover, the manufacturing method of the hydraulic composition of this invention is a manufacturing method of the said hydraulic composition of this invention containing (D), Comprising: (A) component, (B) component, (C) component, (D) A hydraulic composition comprising admixture selected from lignin sulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and a naphthalene sulfonate formaldehyde condensate or a salt thereof, a blast furnace slag cement, and water. Includes manufacturing methods.

Hereinafter, an admixture selected from (D) lignin sulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and a naphthalene sulfonate formaldehyde condensate or a salt thereof will be described as the component (D).

The present invention also provides:
A step of producing a hydraulic composition by the production method of the present invention;
Filling the mold with the obtained hydraulic composition and curing;
Removing the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition;
The present invention relates to a method for producing a cured product of a hydraulic composition.

According to the present invention, it is an additive for a hydraulic composition using a blast furnace slag cement, and is excellent in initial strength of the cured body, for example, strength after 7 days (hereinafter referred to as 7-day strength). Additives for hydraulic compositions from which the composition is obtained are provided.
Further, according to the present invention using the component (D), it is an additive for a hydraulic composition using a blast furnace slag cement, has an appropriate workability, and is excellent in strength and durability of a cured body. An additive for a hydraulic composition is provided from which a hydraulic composition is obtained.

BEST MODE FOR CARRYING OUT THE INVENTION <Additive for Hydraulic Composition>
[Component (A)]
Among the components (A), the salt of thiosulfuric acid is preferably an alkali metal salt such as sodium salt or potassium salt from the viewpoint of strength, for example, 7-day strength. Alkali metal salts are also preferable from the viewpoint of fluidity. Specific examples of the component (A) include sodium thiosulfate (Na ₂ S ₂ O ₃ ), potassium thiosulfate (K ₂ S ₂ O ₃ ), and lithium thiosulfate (Li ₂ S ₂ O ₃ ). .

[(B) component]
Among the components (B), examples of the thiocyanic acid salt include alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium salt. From the viewpoint of strength, for example, 7-day strength, alkali metal salts are preferred. Alkali metal salts are also preferable from the viewpoint of fluidity.

[Component (C)]
α-Hydroxyalkanesulfonic acid is a compound represented by the following formula.

Here, R ¹ and R ² are each independently a hydrocarbon group which may have a proton or a hydroxy group, for example, an alkyl group having 1 to 10 carbon atoms which may have a hydroxy group. is there.
Examples of the α-hydroxysulfonic acid include those having 1 or more carbon atoms, preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less. Specific examples include hydroxymethanesulfonic acid and 1,2-dihydroxypropane-2-sulfonic acid.
Examples of the salt of α-hydroxysulfonic acid include alkali metal salts such as sodium salt and potassium salt. The α-hydroxysulfonic acid salt is preferably an α-hydroxysulfonic acid salt, more preferably an alkali metal of α-hydroxysulfonic acid, from the viewpoint of shortening the time required for the hydraulic composition to reach the required strength. A salt, more preferably a sodium salt of α-hydroxysulfonic acid.

The α-hydroxysulfonic acid or a salt thereof is preferably one or more compounds selected from hydroxymethanesulfonic acid, 1,2-dihydroxypropane-2-sulfonic acid, and salts thereof.

Commercially available products can be used for α-hydroxysulfonic acid or a salt thereof.

[Component (D)]
The additive for the hydraulic composition of the present invention can contain the following component (D). The additive containing the component (D) is a preferred embodiment of the present invention.
Component (D): Admixture selected from lignin sulfonic acid and derivatives thereof, lignin sulfonate and derivatives thereof, and naphthalene sulfonate formaldehyde condensates and salts thereof. Component (D) is a dispersant in a hydraulic composition. It may have a function as a water reducing agent or AE agent.

(D) Component can use a commercial item. In the case of lignin sulfonic acid and salts thereof and derivatives thereof, for example, as a water reducing agent and an AE water reducing agent, Master Pozzolith No. 70, Master Polyhed 15S series, Floric's Floric S series, Floric R series, Grace Chemical's Darrex WRDA, Nihon Seika's Plus Cleat NC, Plus Cleat R, Yamaso Chemical's Yamaso 80P , Yamaso 90 series, Yamaso 98 series, Yamaso 02NL-P, Yamaso 02NLR-P, Yamaso 09NL-P, Yamaso NLR-P, Takemoto Yushi Co., Ltd. Tupole EX60 series, Tupole LS-A series, Rigace ligace UA Series, Rigace UR series, Rigace VF series and the like.

Specific examples of lignin sulfonic acid derivatives and lignin sulfonates or derivatives thereof are given below.
(I) Alkali metal salt, alkaline earth metal salt, ammonium salt, or amine salt of lignin sulfonic acid (II) Lignin derivative in which an amine compound or an amino group is introduced into lignin sulfonate (for example, JP-A-2016-108183 issue)
(III) Lignin derivatives reacted with lignin sulfonate and formaldehyde (for example, JP-A-2015-229764)
(IV) Modified lignin such as oxidized lignin and sulfonated lignin (for example, JP 2003-2714 A)
(V) Lignin sulfonic acid compound polyol complex (for example, JP-A-2007-105899)
(VI) Modified lignin sulfonates of the following 1) to 3) (for example, JP 2007-261119 A)
1) Modified lignin sulfonate by graft copolymerization of lignin sulfonic acid or its salt and an acrylic monomer having a functional group 2) Graft copolymer of lignin sulfonic acid or its salt and a vinyl monomer having a functional group Polymerized lignin sulfonate modified product 3) Lignin sulfonate modified product obtained by adding naphthalene sulfonate formaldehyde condensate to lignin sulfonic acid or its salt (VII) Lignin derivative with polyalkylene glycol compound introduced into lignin sulfonate (For example, JP-A-2015-193804)
(VIII) Reaction product of lignin sulfonic acid compound and water-soluble monomer (for example, JP 2011-240224)
Here, examples of the lignin sulfonic acid compound include compounds having a skeleton in which the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfone group.
Examples of the water-soluble monomer include at least one ionic functional group such as carboxyl group, hydroxyl group, sulfone group, nitroxyl group, carbonyl group, phosphoric acid group, amino group, and epoxy group, and other polar groups. The compound which has the above is mentioned.
(IX) Lignin sulfonic acid derivatives of the following 4) to 5) (for example, JP-A-2015-212216)
4) A lignin derivative obtained by reacting at least one water-soluble monomer with a functional group such as a phenolic hydroxyl group, an alcoholic hydroxyl group, or a thiol group contained in a lignin sulfonic acid compound. 5) Lignin sulfonic acid. A lignin derivative obtained by radical copolymerizing at least one water-soluble monomer with a radical initiator (usually on a functional group of the compound) Although not specifically limited, what is obtained by digesting wood by a sulfurous acid method is exemplified.
Among water-soluble monomers, water-soluble monomers that can react with phenolic hydroxyl groups and / or alcoholic hydroxyl groups contained in lignin sulfonic acid compounds include alkylene oxides such as ethylene oxide and propylene oxide. Can be mentioned.
Among water-soluble monomers, water-soluble monomers that can react with thiol groups contained in lignin sulfonic acid compounds include alkylene oxides such as ethylene oxide and propylene oxide, and alkylene imines such as ethylene imine and propylene imine. Is mentioned.
In addition, as water-soluble monomers used for radical copolymerization, monomers described in JP-A-2015-212216 [0071] to [0074], specifically acrylic acid, methacrylic acid, (meth) acrylic Examples include adducts having 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the acid, and alkylene oxide addition compounds obtained by adding 2 to 300 moles of alkylene oxide to allyl alcohol.

The naphthalene sulfonic acid formaldehyde condensate or a salt thereof is a condensate of naphthalene sulfonic acid and formaldehyde or a salt thereof. The naphthalene sulfonic acid formaldehyde condensate may be used as a monomer, for example, methyl naphthalene, ethyl naphthalene, butyl naphthalene, hydroxy naphthalene, naphthalene carboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, as long as the performance is not impaired. It may be co-condensed with an aromatic compound capable of co-condensing with naphthalenesulfonic acid, such as urea, sulfanilic acid and / or derivatives thereof.

Naphthalene sulfonic acid formaldehyde condensate or salt thereof may be, for example, Mighty 150, Demol N, Demol RN, Demol MS, Demol SN-B, Demol SS-L (all manufactured by Kao Corporation), Cellflow 120, Labelin FD-40 Commercial products such as Labelin FM-45 (both manufactured by Daiichi Kogyo Co., Ltd.) can be used.

The naphthalene sulfonic acid formaldehyde condensate or salt thereof has a weight average molecular weight of preferably 200,000 or less, from the viewpoint of centrifugal moldability and / or strength development of the cured product and improvement of fluidity of the hydraulic composition. Preferably it is 100,000 or less, More preferably, it is 80,000 or less, More preferably, it is 50,000 or less, More preferably, it is 30,000 or less. The naphthalene sulfonic acid formaldehyde condensate or salt thereof has a weight average molecular weight of preferably 1,000 or more from the viewpoint of centrifugal moldability and / or strength expression of the cured product and improvement of fluidity of the hydraulic composition. More preferably, it is 3,000 or more, More preferably, it is 4,000 or more, More preferably, it is 5,000 or more. The naphthalene sulfonic acid formaldehyde condensate may be in the acid state or neutralized.

The molecular weight of naphthalenesulfonic acid formaldehyde condensate or a salt thereof can be measured using gel permeation chromatography (GPC) under the following conditions.
[GPC conditions]
Column: G4000SWXL + G2000SWXL (Tosoh Corporation)
Eluent: 30 mM CH ₃ COONa / CH ₃ CN = 6/4
Flow rate: 0.7ml / min
Detection: UV280nm
Sample size: 0.2 mg / ml
Standard substance: manufactured by Nishio Kogyo Co., Ltd. Polystyrene sulfonate sodium equivalent (monodispersed sodium polystyrene sulfonate: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000)
Detector: Tosoh Corporation UV-8020

Examples of the method for producing a naphthalenesulfonic acid formaldehyde condensate or a salt thereof include a method of obtaining a condensate by a condensation reaction of naphthalenesulfonic acid and formaldehyde. You may neutralize the said condensate. Moreover, you may remove the water insoluble matter byproduced by neutralization. Specifically, in order to obtain naphthalenesulfonic acid, 1.2 to 1.4 mol of sulfuric acid is used with respect to 1 mol of naphthalene and reacted at 150 to 165 ° C. for 2 to 5 hours to obtain a sulfonated product. Next, formalin is added dropwise at 85 to 105 ° C. over 3 to 6 hours to form 0.93 to 0.99 mol of formaldehyde with respect to 1 mol of the sulfonated product, followed by condensation at 95 to 105 ° C. Perform the reaction. Further, since the aqueous solution of the resulting condensate has a high acidity, water and a neutralizing agent are added to the obtained condensate from the viewpoint of suppressing metal corrosion in storage tanks, and a neutralization step is performed at 80 to 95 ° C. be able to. The neutralizing agent is preferably added in an amount of 1.0 to 1.1 moles per each of naphthalenesulfonic acid and unreacted sulfuric acid. Moreover, the water-insoluble matter which arises by neutralization can be removed, and preferably the separation by filtration is mentioned as the method. By these steps, an aqueous solution of a naphthalenesulfonic acid formaldehyde condensate water-soluble salt is obtained. This aqueous solution can be used as it is as the aqueous solution of component (D). Further, if necessary, the aqueous solution can be dried and pulverized to obtain a powdery salt of naphthalenesulfonic acid formaldehyde condensate, which can be used as the powdery component (D).
Drying and powdering can be performed by spray drying, drum drying, freeze drying, or the like.

[Additive composition, etc.]
The additive for the hydraulic composition of the present invention comprises the component (A), preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 95% by mass or less, more preferably 70% by mass or less is contained.

The additive for the hydraulic composition of the present invention comprises the component (B), preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 95% by mass or less, more preferably 70% by mass or less is contained.

The additive for the hydraulic composition of the present invention comprises the component (C), preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and preferably 95% by mass or less, more preferably 70% by mass or less is contained.

The additive of the present invention may be an additive composition containing the component (A), the component (B) and the component (C).
The additive of the present invention preferably contains water.

When the additive for the hydraulic composition of the present invention contains the component (D), the additive preferably contains the component (D) in an amount of 0.001% by mass or more, more preferably 0.01% by mass or more. And preferably 95% by mass or less, more preferably 70% by mass or less.

The additive of the present invention may be an additive composition containing the component (A), the component (B), the component (C) and the component (D).
(D) It is preferable that the additive of this invention containing a component contains water.

In the additive for the hydraulic composition of the present invention, a dispersant other than the component (D) can be further mixed from the viewpoint of improving workability.
Examples of the dispersant include a dispersant such as a phosphate ester polymer, a polycarboxylic acid copolymer, a sulfonic acid copolymer, a melamine polymer, and a phenol polymer. The dispersant may be an admixture containing other components.
When the additive for the hydraulic composition of the present invention contains a dispersant other than the component (D), it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 95% by mass. % Or less, more preferably 70% by mass or less.

The additive for the hydraulic composition of the present invention can contain a polyol from the viewpoint of promoting the setting. Examples of the polyol include divalent to hexavalent polyols. Specific examples include glycerin, alkylene oxide adducts of glycerol such as ethylene oxide adducts of glycerin, ethylene glycol, propylene glycol, diethylene glycol, saccharides and the like. The polyol is preferably glycerin from the viewpoint of strength development.
When the additive for the hydraulic composition of the present invention contains a polyol, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 95% by mass or less, more preferably 70%. Contain less than mass%.

The additive for the hydraulic composition of the present invention can contain an alkanolamine. Examples of the alkanolamine include alkanolamines having 1 to 3 alkanol groups having 1 to 5 carbon atoms. Specific examples of the alkanolamine include triethanolamine, diethanolamine, diisopropanol monoethanolamine, triisopropanolamine, methyldiethanolamine, and ethyldiethanolamine. The alkanolamine is preferably methyldiethanolamine from the viewpoint of strength development.
When the additive for the hydraulic composition of the present invention contains an alkanolamine, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 95% by mass or less, more preferably 70% by mass or less is contained.

The additive for the hydraulic composition of the present invention can further contain other components in order to entrain a predetermined amount of air. For example, resin soap, saturated or unsaturated fatty acid, lauryl sulfate, alkylbenzene sulfonic acid or salt thereof, alkane sulfonate, polyoxyalkylene alkyl (or alkylphenyl) ether, polyoxyalkylene alkyl (or alkylphenyl) ether sulfate or salt thereof AE agents such as polyoxyalkylene alkyl (or alkylphenyl) ether phosphates or salts thereof, protein materials, alkenyl succinic acid, α-olefin sulfonate, and the like.

Further, the additive for the hydraulic composition of the present invention includes oxycarboxylic acid type retarders such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid, citric acid, dextrin, monosaccharide, oligosaccharide, polysaccharide, etc. Sugar retarders such as sugar retarders and sugar alcohol retarders; foaming agents; thickeners; silica sand; soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, calcium iodide, iron chloride Fasteners or accelerators such as chlorides such as magnesium chloride, carbonates, formic acid or salts thereof; foaming agents; waterproofing agents such as resin acids or salts thereof, fatty acid esters, oils and fats, silicones, paraffin, asphalt, waxes, etc. Fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester, mineral oil, fat, oxyalkylene, alcohol, amino It may also contain an anti-foaming agent such as a system.

Further, the additive for the hydraulic composition of the present invention includes rust preventives such as nitrite, phosphate and zinc oxide; celluloses such as methylcellulose and hydroxyethylcellulose; natural such as β-1,3-glucan and xanthan gum Water-soluble polymers such as synthetic systems such as physical systems, polyacrylic acid amides, polyethylene glycol, ethylene oxide adducts of oleyl alcohol or reaction products thereof with vinylcyclohexene diepoxide; polymer emulsions such as alkyl (meth) acrylates Can also be contained.

The additive of the present invention is for a hydraulic composition using blast furnace slag cement. The blast furnace slag cement preferably contains 5% by mass to 95% by mass of cement and 5% by mass to 70% by mass of blast furnace slag. The content of cement and blast furnace slag is also preferably in the range described below.

The present invention relates to a hydraulic property of a composition containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof using a blast furnace slag cement. Use as an additive for compositions is provided.
The present invention also uses a blast furnace slag cement as a composition containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof. A method for use as an additive for hydraulic compositions is provided.
The present invention also provides a hydraulic composition using a blast furnace slag cement in which (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof are mixed. Provided is a method for producing a product additive.
The present invention also provides (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, and (D) ligninsulfonic acid and a derivative thereof, ligninsulfone. The use of a composition comprising an acid salt and derivatives thereof, and an admixture selected from naphthalene sulfonate formaldehyde condensate and salts thereof as an additive for hydraulic compositions using blast furnace slag cement is provided.
The present invention also provides (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, and (D) ligninsulfonic acid and a derivative thereof, ligninsulfone. Provided is a method of using a composition containing an acid salt and a derivative thereof, and an admixture selected from naphthalene sulfonate formaldehyde condensate and a salt thereof as an additive for a hydraulic composition using a blast furnace slag cement.
The present invention also provides (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, and (D) ligninsulfonic acid and a derivative thereof, ligninsulfone. Provided is a method for producing an additive for a hydraulic composition using a blast furnace slag cement, in which an admixture selected from an acid salt and a derivative thereof, and a naphthalenesulfonate formaldehyde condensate and a salt thereof are mixed.
The matters described in the additives for hydraulic compositions of the present invention can be appropriately applied to these uses or methods. In the method for producing an additive for a hydraulic composition of the present invention, the content in the additive for a hydraulic composition of the present invention can be replaced with a mixed amount.

<Hydraulic composition>
The hydraulic composition of the present invention contains (A) component, (B) component, (C) component, blast furnace slag cement, and water. Moreover, the hydraulic composition of this invention contains (A) component, (B) component, (C) component, (D) component, blast furnace slag cement, and water. Specific examples and preferred embodiments of the component (A), the component (B), the component (C), and the component (D) are the same as those of the additive of the present invention.
Moreover, it is preferable that the hydraulic composition of this invention contains a polyol and an alkanolamine. The hydraulic composition of the present invention can contain a dispersant other than the component (D). Specific examples and preferred embodiments of the dispersant, polyol, and alkanolamine other than the component (D) are the same as those of the additive of the present invention.

The blast furnace slag cement contains cement and blast furnace slag. Blast furnace slag cement may use cement and blast furnace slag separately when mixing materials. Further, a stimulant such as gypsum may be added. The cement is preferably Portland cement.
The blast furnace slag cement is cement, preferably 5% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably. Contains 70% by mass or less.
As the blast furnace slag, slowly cooled slag and quenched slag are known. Quenched slag is also known as blast furnace granulated slag. In the present invention, quenching slag is preferred.
The blast furnace slag cement is preferably blast furnace slag, preferably 5 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, and preferably 95 mass% or less, more preferably 70 mass% or less, Preferably it is 60 mass% or less, More preferably, it contains less than 60 mass%.
An example of the blast furnace slag cement is a blast furnace slag cement having a blast furnace slag content of 5% by mass or more and less than 30% by mass. Moreover, as a blast furnace slag cement, the blast furnace slag cement whose content of a blast furnace slag is 30 mass% or more and less than 60 mass% is mentioned. Moreover, as a blast furnace slag cement, the blast furnace slag cement whose content of a blast furnace slag is 60 mass% or more and less than 70 mass% is mentioned.

As the blast furnace slag cement, blast furnace cement type A, blast furnace cement type B and blast furnace cement type C specified in JIS R 5211 can be used. The blast furnace slag cement is preferably blast furnace cement type B or C, and more preferably blast furnace cement type B. According to JIS R 5211, three types of blast furnace cement, A type, B type, and C type, are specified depending on the amount of blast furnace slag. Some are composed of Portland cement and blast furnace slag, others are composed of clinker, gypsum, small amounts of mixed components and blast furnace slag. When JIS R 5211 blast furnace cement is used in the present invention, the entire blast furnace cement is used as the amount of blast furnace slag cement.

The hydraulic composition of the present invention is obtained by adding thiosulfuric acid or a salt thereof as component (A) to blast furnace slag cement from the viewpoint of initial strength, for example, strength from 1 to 7 days of age, salt resistance, and fluidity. , Preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and from the viewpoint of workability, preferably 3.0% by mass or less, more preferably 2.0 mass% or less, More preferably, it contains 1.0 mass% or less.

The hydraulic composition of the present invention preferably contains thiocyanic acid or a salt thereof as component (B) with respect to blast furnace slag cement from the viewpoint of initial strength, for example, strength from 1 to 7 days of age and fluidity. 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and from the viewpoint of workability, preferably 3.0% by mass or less, more preferably 2.0%. It is contained by mass% or less, more preferably 1.0 mass% or less.

In the hydraulic composition of the present invention, (C) component α-hydroxyalkanesulfonic acid or a salt thereof is added to blast furnace slag cement in terms of initial strength, for example, strength from 1 to 7 days of age and fluidity. Therefore, preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and from the viewpoint of workability, preferably 3.0% by mass or less, more preferably Is contained in an amount of 2.0% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.5% by mass or less.

When the hydraulic composition of the present invention contains the component (D), from the viewpoint of workability, the hydraulic composition is lignin sulfonic acid or a derivative thereof (D) component, lignin from the blast furnace slag cement. An admixture selected from a sulfonate or a derivative thereof and a naphthalenesulfonate formaldehyde condensate or a salt thereof is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1%. From the viewpoint of the mass% or more and strength, it is preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 2 mass% or less.

When the hydraulic composition of the present invention contains a dispersant other than the component (D), the dispersant is preferably 0.001% by mass or more, more preferably from the viewpoint of workability with respect to the blast furnace slag cement. 0.01% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less.

When the hydraulic composition of the present invention contains a polyol, the polyol is preferably 0.001% by mass or more, more preferably 0, from the viewpoint of strength, for example, 7-day strength and fluidity, with respect to the blast furnace slag cement. From the viewpoint of workability, it is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.25% by mass or less. The amount of polyol may be 0% by weight.

When the hydraulic composition of the present invention contains an alkanolamine, the alkanolamine is preferably 0.001% by mass or more, more preferably 0.01% from the viewpoint of improving the strength for 7 days with respect to the blast furnace slag cement. % Or more, and from the viewpoint of workability, the content is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. The amount of alkanolamine may be 0% by weight.

The hydraulic composition of the present invention preferably contains blast furnace slag cement and water at a mass ratio of water / blast furnace slag cement of 40% by mass to 60% by mass. The mass ratio of water / blast furnace slag cement is more preferably 42% by mass or more, further preferably 45% by mass or more, and more preferably 58% by mass or less, and further preferably 55% by mass or less. Here, the mass ratio of water / blast furnace slag cement is the mass percentage (mass%) of blast furnace slag cement and water mixed for the preparation of the hydraulic composition, and the mass of water / mass of blast furnace slag cement × 100. Is calculated by

The hydraulic composition of the present invention can contain an aggregate. Aggregates include fine aggregates and coarse aggregates. Fine aggregates are preferably mountain sand, land sand, river sand and crushed sand, and coarse aggregates are preferably mountain gravel, land gravel, river gravel and crushed stone. . Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin). The content of the aggregate can be used in a range of mortar or concrete that is usually used.

The hydraulic composition of the present invention can also contain other optional components described in the additive of the present invention.

The hydraulic composition of the present invention has improved compressive strength during curing, especially initial strength, for example, strength after 7 days. In addition, the period (for example, after 7 days) used as the object of intensity | strength starts from the time when blast furnace slag cement and water first contacted at the time of preparation of a hydraulic composition.

In addition, the hydraulic composition of the present invention, in particular, the hydraulic composition of the present invention containing the component (D) has good physical properties related to workability such as fluidity, and has strength and durability upon curing. It will be improved. In general, the durability of the cured body is ensured by mixing appropriate air into the hydraulic composition, but the hydraulic composition of the present invention, particularly, the hydraulic composition of the present invention containing the component (D). As for the thing, it is easy to secure the amount of air, and the amount of AE agent added can be reduced. In addition, the hydraulic composition of the present invention, in particular the hydraulic composition of the present invention containing the component (D), has a compressive strength equal to or higher than that of the conventional one when the amount of air is the same. .

The hydraulic composition of the present invention can be used as a material for concrete structures and concrete products. Since the concrete using the hydraulic composition of the present invention has improved initial compressive strength such as 7 days after contact with water, for example, the same demolding time as that of concrete using ordinary cement can be obtained. In addition, the hydraulic composition of the present invention has advantages in that long-term strength can be improved and chemical resistance can be improved as compared with concrete using ordinary Portland cement or blast furnace slag cement. Furthermore, the hydraulic composition of the present invention is a hydraulic powder (fly ash, silica fume, limestone, etc.) having a low initial age strength after water contact within a range that does not impair the proportion of slag in the hydraulic powder. Even if it mix | blends and substitutes, it has the advantage of being able to obtain the initial compression strength of the same or more, for example, the compression strength after seven days from water contact, etc.

The hydraulic composition of the present invention includes mortar and concrete. In addition, the hydraulic composition of the present invention can be used for box culverts (walls), bridge substructures, tunnel linings, marine structures, PC structures, ground improvement, grout, cold, etc. It is also useful in the field.

The present invention relates to a hydraulic property of a composition containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, blast furnace slag cement, and water. Provided for use as a composition.
The present invention also provides a composition containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, a blast furnace slag cement, and water. A method for use as a hydraulic composition is provided.
The present invention also includes (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, (D) ligninsulfonic acid or a derivative thereof, ligninsulfonic acid. Provided is a use of a composition comprising a salt or derivative thereof, and an admixture selected from naphthalenesulfonate formaldehyde condensate or salt thereof, a blast furnace slag cement, and water as a hydraulic composition.
The present invention also includes (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, (D) ligninsulfonic acid or a derivative thereof, ligninsulfonic acid. Provided is a method of using, as a hydraulic composition, a composition containing a salt or a derivative thereof, an admixture selected from a naphthalenesulfonate formaldehyde condensate or a salt thereof, a blast furnace slag cement, and water.
The matters described in the additives for hydraulic compositions of the present invention can be appropriately applied to these uses or methods.

<Method for producing hydraulic composition>
The manufacturing method of the hydraulic composition of this invention mixes (A) component, (B) component, (C) component, blast furnace slag cement, and water. Moreover, the manufacturing method of the hydraulic composition of this invention mixes (A) component, (B) component, (C) component, (D) component, blast furnace slag cement, and water. Specific examples and preferred embodiments of the component (A), the component (B), the component (C), and the component (D) are the same as those of the additive of the present invention.
Moreover, in the manufacturing method of the hydraulic composition of this invention, it is preferable to mix a polyol and an alkanolamine. Moreover, in the manufacturing method of the hydraulic composition of this invention, dispersing agents other than (D) component can be mixed. Specific examples and preferred embodiments of the dispersant, polyol, and alkanolamine other than the component (D) are the same as those of the additive of the present invention.
In the method for producing a hydraulic composition of the present invention, the content in the hydraulic composition of the present invention can be replaced with a mixed amount.
The manufacturing method of the hydraulic composition of the present invention is suitable as the manufacturing method of the hydraulic composition of the present invention.

In the step of preparing the hydraulic composition, blast furnace slag cement is mixed with (A) component thiosulfuric acid or a salt thereof, (B) component thiocyanic acid or a salt thereof, and (C) component α-hydroxyalkanesulfonic acid. Or a salt thereof, an admixture selected from (D) component lignin sulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and a naphthalene sulfonate formaldehyde condensate or a salt thereof, if necessary, water, and optionally A hydraulic composition is obtained by adding and mixing a dispersant other than the component (D), optionally glycerin, optionally alkanolamine, and optionally aggregate. In the present invention, a mixture containing (A) component, (B) component, (C) component and water or (A) component, (B) component, (C) component, (D) component and water-containing mixture And blast furnace slag cement are preferably mixed. From the viewpoint of obtaining a hydraulic composition having stable physical properties, (A) component, (B) component, (C) component, (D) component, if necessary, water, optionally glycerin, optionally A mixture containing an alkanolamine, a component (A), a component (B), a component (C), a component (D), water, and optionally a dispersant other than the component (D); It is preferable to use a mixture containing optionally glycerin, optionally alkanolamine, and optionally AE agent.

Blast furnace slag cement, (A) component thiosulfuric acid or salt thereof, (B) component thiocyanic acid or salt thereof, (C) component α-hydroxyalkanesulfonic acid or salt thereof, (D) component lignin sulfonic acid or The admixture selected from the derivative, lignin sulfonate or derivative thereof, naphthalene sulfonate formaldehyde condensate or salt thereof, dispersant other than component (D), glycerin, alkanolamine, aggregate, and water are mixed. In this case, from the viewpoint of smoothly mixing them, (A) component, (B) component, (C) component, (D) component, dispersant other than (D), glycerin, alkanolamine and water are mixed in advance, It is preferable to mix with blast furnace slag cement and aggregate. Moreover, it is preferable to mix a blast furnace slag cement and an aggregate beforehand.
Mixing with blast furnace slag cement, aggregate, and water can be carried out using a mortar mixer, tilting type, horizontal biaxial type, pan type or the like. It is preferable to use a mixture in which a dispersant other than the components (A), (B), (C), (D), and (D), glycerin, and alkanolamine are added to water.
In addition, the above components and materials are preferably mixed for 30 seconds or longer, more preferably 1 minute or longer, and preferably 10 minutes or shorter, more preferably 5 minutes or shorter.

In the production method of the present invention, the amount of air in the obtained hydraulic composition tends to increase. In general, when the amount of air in the hydraulic composition increases, the strength of the cured body decreases, but the hydraulic composition of the present invention improves the strength of the cured body regardless of the amount of air. Therefore, for example, when the amount of air may be the same as the conventional level, a hardened body with high strength can be obtained while reducing the amount of AE agent or AE water reducing agent added.

<Method for producing a cured product of hydraulic composition>
The method for producing a cured product of the hydraulic composition of the present invention comprises:
A step of producing a hydraulic composition by the production method of the present invention;
Filling the mold with the obtained hydraulic composition and curing;
Removing the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition;
Have

The process for producing the hydraulic composition by the production method of the present invention is as described above.

In the step of filling and hardening the hydraulic composition into the mold, the uncured hydraulic composition after preparation is filled into the mold, cured, and cured. Examples of the formwork include a structure formwork and a concrete product formwork. Examples of the method of filling the mold include a method of directly feeding from a mixer, a method of pumping the hydraulic composition with a pump and introducing it into the mold. When filling the mold and after filling, vibration may be added from the viewpoint of improving fillability.

In the method for producing a cured body of the hydraulic composition of the present invention, additional energy such as steam heating may be added to accelerate curing when curing the hydraulic composition. In the present invention, the curing temperature of the hydraulic composition filled in the mold is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, preferably lower than 50 ° C., more preferably 40 ° C. or lower, and 30 ° C. or lower. Further preferred. As curing, air curing at room temperature can be performed.

Even in the case of heat curing such as steam, it is preferable that the heat curing time is short from the viewpoint of reducing energy. The heat curing time may be 0 hour. That is, it is not necessary to perform heat curing.

In the step of demolding the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition, the cured composition of the hydraulic composition is obtained by demolding from the mold. The obtained cured product can be used for the uses described in the hydraulic composition.

In the present invention, in the preparation of the hydraulic composition, the time from contact of water with the hydraulic powder to demolding is 4 hours from the viewpoint of obtaining strength necessary for demolding and improving the production cycle. It is preferably 14 days or less. In the method for producing a cured body of the hydraulic composition of the present invention, since the curing of the hydraulic composition is promoted, it is possible to shorten the time from preparation of the hydraulic composition to demolding.

Example <Example 1a and Comparative Example 1a>
A cured mortar was produced and evaluated for strength. The blending, preparation and evaluation of mortar are described below.

(1) Preparation of mortar Under the blending conditions shown in Table 1, cement (C) and fine aggregate (S) were put into a mortar mixer (universal mixing stirrer model: 5DM-03-γ manufactured by Dalton Co., Ltd.) Empty kneading was performed for 10 seconds, kneading water (W) was added, and the mixture was kneaded for 120 seconds at a low speed rotation (rotation speed: 63 rpm). Here, the kneading water was obtained by mixing water and a mixture containing each component shown in Table 2 (for convenience, indicated as an additive) and water.
In addition, the addition amount (mass%) with respect to the cement (C) of each component is as Table 2, and it added and used for kneading water so that it might become the addition amount shown in Table 2.
Sodium thiosulfate, the table _was expressed as Na ₂ S 2 _{O 3.} Sodium thiocyanate was indicated as NaSCN in the table. Sodium α-hydroxymethanesulfonate was represented as HMS in the table.

Cement (C): Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., density 3.16 g / cm ³ , indicated as OPC in the table) or blast furnace cement B type (manufactured by Taiheiyo Cement Co., Ltd., density 3.04 g) / Cm ³ , indicated as BB in the table.)
Fine aggregate (S): produced in Jyoyo, mountain sand, FM = 2.67, density 2.56 g / cm ³
Water (W): Kneaded water obtained by adding a mixture containing each component of Table 2 and water to tap water

(2) Evaluation of mortar cured body About the mortar obtained above, the strength of the mortar cured body after 1 day and after 7 days was evaluated according to the test method shown below. The results are shown in Table 2.
Based on JIS A 1132, plastic concrete specimen molding mold (trade name: Plastic Mold, Marui Co., Ltd., cylindrical mold, bottom diameter 5cm, height 10cm) is filled with mortar by two-layer packing method. Then, it was cured in the air (20 ° C.) in a room at 20 ° C. and cured to prepare a specimen. A specimen cured one day after the preparation of the mortar was removed from the mold and cured under water (20 ° C.) until seven days later.
The compressive strength was measured based on JIS A 1108. The number of days from the preparation of the mortar started from the time when the water first contacted the cement during the preparation of the mortar. The relative value with respect to the strength of the reference product is shown in Table 2 as the strength ratio (%). For the standard product, a comparative example in which no additive is used is shown as a standard for each cement type.

In Table 2, the addition amount is mass% of solid content with respect to cement (C).

From the results of Comparative Examples 1a-1 to 1a-10 in Table 2, it can be seen that when ordinary Portland cement is used, the strength is not improved for 7 days even when all the additives of the present invention are added.
From the results of Comparative Examples 1a-11 to 1a-17 and Examples 1a-1 to 1a-3 in Table 2, when all types of additives of the present invention were added, 7 days were It can be seen that the strength is improved.

<Example 2a and Comparative Example 2a>
A cured mortar was produced in the same manner as in Example 1a, and the strength was evaluated. However, the components added to the mortar were added to the kneading water (W) as additives (I), (II) or (III) having the composition shown in Table 3. Additives (I), (II) or (III) were used so that the amount added to cement (C) was as shown in Table 4. The results are shown in Table 4. In addition, the relative value of intensity | strength was shown on the basis of the comparative example which does not use an additive for every cement kind.

In Table 4, the addition amount is mass% of solid content with respect to cement (C).

<Example 3a and Comparative Example 3a>
Under the compounding conditions shown in Table 5, a cured product was produced in accordance with JIS R 5201, and the strength was measured for 7 days. The results are shown in Table 6. In addition, the same BB (type blast furnace cement B) as Example 1a was used for the cement. As the fine aggregate (S), standard sand for cement strength test (manufactured by Cement Association) was used. Further, the same additives (I) and (II) as in Example 2a were used.

In Table 6, the addition amount is mass% of solid content with respect to cement (C).

<Example 4a and Comparative Example 4a>
A cured mortar was produced in the same manner as in Example 3a, and the strength was evaluated.
However, the cement shown in Table 7 was used. BFS in Table 7 is blast furnace slag fine powder (with gypsum, manufactured by Esment Kanto Co., Ltd., Blaine specific surface area 4,000 cm ² / g).
The results are shown in Table 7. In addition, the relative value of intensity | strength was shown on the basis of the comparative example which does not use an additive for every cement kind.

In Table 7, the addition amount is mass% of solid content with respect to cement (C).

<Example 5a and Comparative Example 5a>
Concrete was manufactured under the blending conditions shown in Table 8.
The concrete blending components are shown below.
Cement (OPC): ordinary Portland cement (Pacific Cement Co., Ltd.), density 3.16 g / cm ³
・ Blast furnace slag (BFS): ground powder of blast furnace slag (with gypsum, manufactured by Esmento Kanto Co., Ltd.), Blaine specific surface area 4,000 cm ² / g
Fine aggregate (S1): Crushed sand, coarse particle rate = 2.97, density 2.63 g / cm ³
-Fine aggregate (S2): Crushed sand, coarse grain ratio = 1.67, density 2.60 g / cm ³
Coarse aggregate (G1): crushed stone, 20-10 mm, actual rate 62.0%, density 2.65 g / cm ³
Coarse aggregate (G2): crushed stone, 10-5 mm, actual rate 62.1%, density 2.65 g / cm ³
Additive (I): The same one as shown in Table 3 was used.
Admixture (1): AE water reducing agent (standard type) containing lignin sulfonic acid, manufactured by BASF Japan Ltd., Master Pozzolith No. 70
Admixture (2): AE agent, Master Air 202 manufactured by BASF Japan
Water (W): Kneaded water obtained by adding a mixture containing the admixtures in Table 9 and the additives in Table 9 to tap water

(1) Preparation of concrete Under the blending conditions shown in Table 8, hydraulic powder containing blast furnace slag (mixture of OPC and BFS), fine aggregate, and coarse aggregate are put into a concrete mixer, and empty kneading is performed for 15 seconds. After adding the kneading water (W) containing the admixture (1), the admixture (2) and the additive (I), kneading for 30 seconds, scraping off, and further kneading for 60 seconds to obtain concrete . Admixture (1) and Admixture (2) were added to the kneaded water so that the apparent addition amount to the hydraulic powder (P) (total of OPC and BFS) was as shown in Table 9. In addition, the additive (I) was added to the kneaded water so that the amount of solid content added to the hydraulic powder (P) (total of OPC and BFS) was as shown in Table 9. In addition, the room temperature at the time of concrete preparation was 20 degreeC.
Further, the amount of air in the uncured concrete was measured in accordance with JIS A 1128 “Test method by pressure of air amount in fresh concrete”. The results are shown in Table 9.

(2) Evaluation of hardened concrete body After curing and demolding the concrete under the condition of 20 degrees based on JIS A 1132 “How to make a specimen for concrete strength test”, the hardened body is left at room temperature (20 ° C.). In the preparation of the hydraulic composition, after 3 days and 7 days after the first contact between the water and the hydraulic powder, the cured product was obtained in accordance with JIS A 1108 “Method for testing compressive strength of concrete”. The compressive strength of was measured. The results are shown in Table 9 as 3-day intensity and 7-day intensity.

In Table 9, the mass% of the admixtures (1) and (2) is mass% based on the apparent amount added to the hydraulic powder (P) (total of OPC and BFS).
In Table 9, the addition amount of the additive (I) is the solid content addition amount (mass%) relative to the hydraulic powder (P) (total of OPC and BFS).

<Example 6a and Comparative Example 6a>
A hardened concrete was produced in the same manner as in Example 5a, and the strength was evaluated. However, the mixing conditions of concrete were as shown in Table 10. Moreover, the intensity | strength measured 3 day intensity | strength, 7 day intensity | strength, 28 day intensity | strength, and 91 day intensity | strength. The results are shown in Table 11. The specimen size was set to φ100 mm × 200 mm. In addition, the room temperature at the time of concrete preparation was 20 degreeC.

In Table 11, the mass% of the admixtures (1) and (2) is mass% based on the apparent amount added to the hydraulic powder (P) (total of OPC and BFS).
In Table 11, the addition amount of the additive (I) is the solid content addition amount (mass%) relative to the hydraulic powder (P) (total of OPC and BFS).

From Comparative Example 6a-1 and Example 6a-2, it can be seen that the compressive strength is improved by using the additive (I).

<Example 7a and Comparative Example 7a>
A hardened concrete was produced in the same manner as in Example 5a, and the strength was evaluated. However, the mixing conditions of concrete were as shown in Table 12. The cement, additives and admixtures are as follows. The amounts of additives and admixtures added were as shown in Table 13. The curing temperature was as shown in Table 13.
Cement: The same BB (type blast furnace cement B) as in Example 1a was used.
Additive: Additive (II) of Example 2a was used.
Admixture (1) and Admixture (2): The same as in Example 5a was used.
Admixture (3): AE water reducing agent (high function type), manufactured by Kao Corporation, Mighty 1000S (polycarboxylic acid type special surfactant and natural resin acid derivative)
Intensity was measured as 1-day intensity, 2-day intensity, 3-day intensity, 7-day intensity, 28-day intensity, and 91-day intensity. The results are shown in Table 13. In addition, the relative value of intensity | strength was shown on the basis of the comparative example which does not use an additive in the same concrete mixing | blending, the addition amount of an additive, and curing temperature in the same conditions.

In Table 13, the mass% of the admixture (1), the admixture (2), and the admixture (3) is mass% based on the apparent amount added to the cement (BB).
In Table 13, the addition amount of the additive (II) is the addition amount (% by mass) of the solid content with respect to the cement (BB).

<Example 1b, Comparative Example 1b, and Reference Example 1b>
Mortar and its hardened | cured material were manufactured, and the fluidity | liquidity of the mortar and the intensity | strength of the hardened | cured material were evaluated. The blending, preparation and evaluation of mortar are described below.

(1) Preparation of mortar Under the blending conditions shown in Table 14, each component was kneaded according to JIS R 5201 to obtain a mortar. As the mortar mixer, a universal mixing stirrer (model: 5DM-03-γ) manufactured by Dalton Co., Ltd. was used. Here, the kneading water was obtained by mixing a mixture containing each component (shown as an additive for convenience) and an admixture (d1) in Table 15 with water.
Sodium thiosulfate, the table _was expressed as Na ₂ S 2 _{O 3.} Sodium thiocyanate was indicated as NaSCN in the table. Sodium α-hydroxymethanesulfonate was represented as HMS in the table.

Cement (C): Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., density 3.16 g / cm ³ , expressed as OPC in the table) and blast furnace slag (containing blast furnace slag fine powder, gypsum, Sment Kanto Co., Ltd.) Blast furnace cement in which a Blaine specific surface area of 4,000 cm ² / g, expressed as BFS in the table) was mixed at a 50/50 mass ratio.
-Fine aggregate (S): Standard sand for cement strength test (manufactured by Cement Association)
Water (W): Kneading water obtained by adding a mixture containing an additive and the following admixture (d1) to tap water. Admixture (d1): AE water reducing agent (standard type) containing lignin sulfonic acid, BASF Japan Ltd., Master Pozzolith No. 70

(2) Evaluation of mortar fluidity The fluidity of mortar was measured according to JIS R5201. In addition, the drop motion described in JIS R 5201 is not performed.

(3) Evaluation of mortar cured body About the mortar obtained above, the strength after 3 days of the mortar cured body was evaluated according to the test method shown below. The results are shown in Table 16.
Based on JIS A 1132, plastic concrete specimen molding mold (trade name: Plastic Mold, Marui Co., Ltd., cylindrical mold, bottom diameter 5cm, height 10cm) is filled with mortar by two-layer packing method. Then, it was cured in the air (20 ° C.) in a room at 20 ° C. and cured to prepare a specimen. A specimen cured one day after the preparation of the mortar was removed from the mold, and was cured under water (20 ° C.) until three days later.
The compressive strength was measured based on JIS A 1108. The number of days from the preparation of the mortar started from the time when the water first contacted the cement during the preparation of the mortar. The relative value with respect to the strength of the reference product is also shown in Table 16 as the strength ratio (%).

In Table 16, the addition amount of the admixture (d1) is the apparent addition amount (mass%) with respect to the cement (C) (total of OPC and BFS). Moreover, in Table 16, the addition amount of additive (I) is the addition amount (mass%) of solid content with respect to cement (C) (total of OPC and BFS).

From the results of Comparative Example 1b-1, Reference Examples 1b-2 to 1b-5, and Comparative Example 1b-6 in Table 16, when the additive of the present invention is added and no admixture is added, blast furnace slag cement is used. It can be seen that the fluidity of the existing hydraulic composition is not improved, but the compressive strength is improved.
From the results of Comparative Example 1b-1, Reference Examples 1b-2 to 1b-5, Comparative Example 1b-6 and Examples 1b-1 to 1b-2 in Table 16, the additive of the present invention was added and the admixture was added. When it adds, it turns out that both the fluidity | liquidity and compressive strength of the hydraulic composition using a blast furnace slag cement improve.

<Example 2b, Comparative Example 2b, and Reference Example 2b>
Mortar was manufactured and fluidity was evaluated. The blending, preparation and evaluation of mortar are described below.

(1) Mortar formulation Table 17 shows the mortar formulation conditions.
The blending ingredients of the mortar and the mortar mixer are as follows.
Water (W): Kneaded water / cement obtained by adding additive (I), (II) or (III) and admixture (d1), (d2), or (d3) to tap water C): Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., density 3.16 g / cm ³ , indicated as OPC in the table) or blast furnace cement B type (manufactured by Taiheiyo Cement Co., Ltd., density 3.04 g / cm ³⁾ In the table, indicated as BB.)
Fine aggregate (S): produced in Jyoyo, mountain sand, FM = 2.67, density 2.56 g / cm ³
・ Mortar mixer: Universal mixing stirrer manufactured by Dalton Co., Ltd. Model: 5DM-03-γ

(2) Additives and admixtures The additives (I), (II) or (III) used were those in Table 15.
The same admixture (d1) as in Example 1b was used.
Admixtures (d2) and (d3) are as follows.
・ Admixture (d2): Polycarboxylic acid dispersant, Mighty 21HP, manufactured by Kao Corporation ・ Admixture (d3): Naphthalenesulfonic acid formaldehyde high condensate, high-performance water reducing agent, Mighty 150, manufactured by Kao Corporation

(3) Preparation of mortar Under the blending conditions shown in Table 17, cement (C) and fine aggregate (S) were put into a mortar mixer and kneaded for 10 seconds, and the components shown in Table 18 (additives and / or blends) Water (W) containing the agent was added, and kneaded for 120 seconds at a low speed rotation (rotation speed: 63 rpm). Here, the kneading water was obtained by mixing water and a mixture containing each component (additive and / or admixture) in Table 18 and water.
In addition, the addition amount (mass%) with respect to the cement (C) of each component is as Table 18, and it added and used for kneading water so that it might become the addition amount shown in Table 18.

(4) Evaluation of mortar fluidity The fluidity of mortar was measured according to JIS R5201. In addition, the drop motion described in JIS R 5201 is not performed.
In addition, the relative value of fluidity | liquidity was shown on the basis of the comparative example which does not use an additive for every test group.

In Table 18, the addition amounts of the admixtures (d1), (d2), and (d3) are apparent addition amounts (mass%) with respect to the cement (C) (OPC or BB). Moreover, in Table 18, the addition amount of additives (I), (II), and (III) is the mass% of solid content with respect to cement (C) (OPC or BB).

From the results of Table 18, the mortar formulation in which the cement is blast furnace cement and the admixture is lignin sulfonic acid sodium salt (admixture (d1)) or naphthalenesulfonic acid formaldehyde condensate salt (admixture (d3)), It turns out that fluidity | liquidity improves by adding the additive (I), (II) or (III) of this invention.

<Example 3b and Comparative Example 3b>
Concrete and its hardened body were manufactured, and the strength of the concrete slump and hardened body was evaluated. The blending, preparation and evaluation of concrete are described below.

(1) Concrete blending Table 19 shows the concrete blending conditions.
The components of the concrete are as follows.
・ Kneaded water (W): tap water and cement (OPC): Taiheiyo Cement Co., Ltd., ordinary Portland cement, density 3.16 g / cm ³
・ Blast furnace slag (BFS): manufactured by Esment Kanto Co., Ltd., blast furnace slag fine powder (with gypsum), Blaine specific surface area 4,000 cm ² / g
Fine aggregate (S1): Crushed sand, coarse particle rate = 2.97, density 2.63 g / cm ³
-Fine aggregate (S2): Crushed sand, coarse grain ratio = 1.67, density 2.60 g / cm ³
Coarse aggregate (G1): crushed stone, 20-10 mm, actual rate 62.0%, density 2.65 g / cm ³
Coarse aggregate (G2): crushed stone, 10-5 mm, actual rate 62.1%, density 2.65 g / cm ³
Additive (I): The same one as used in Example 1b was used.
Admixture (d1): The same one as used in Example 1b was used.
Admixture (d4): AE agent, manufactured by BASF Japan, Master Air 202

(2) Preparation of concrete Under the blending conditions shown in Table 19, hydraulic powder containing blast furnace slag (mixture of OPC and BFS), fine aggregate, and coarse aggregate are put into a concrete mixer, and kneaded for 15 seconds. After adding kneading water (W) containing at least one of additive (I), admixture (d1), and admixture (d4), kneading for 30 seconds, scraping, and kneading for 60 seconds, Got concrete. The admixture (d1) and the admixture (d4) were added to water so that the apparent addition amount to the hydraulic powder (P) (total of OPC and BFS) was as shown in Table 20. Additive (I) was added to water so that the amount of solid content added to hydraulic powder (P) (total of OPC and BFS) was as shown in Table 20.
The slump of uncured concrete was measured according to JIS A 1101 “Concrete slump test method”. The results are shown in Table 20.
Further, the amount of air in the uncured concrete was measured in accordance with JIS A 1128 “Test method by pressure of air amount in fresh concrete”. The results are shown in Table 20.

(3) Evaluation of hardened concrete body After curing and demolding the concrete under the condition of 20 degrees according to JIS A 1132 “How to make a specimen for concrete strength test”, the hardened body is left at room temperature (20 ° C.). 1 day, 3 days, and 7 days after the first contact between water and the hydraulic powder during the preparation of the hydraulic composition, based on JIS A 1108 “Compressive strength test method for concrete” The compressive strength of the cured product was measured. The results are shown in Table 20 as 1-day intensity, 3-day intensity, and 7-day intensity.

In Table 20, the addition amount of the admixture (d1) and the admixture (d4) is the apparent addition amount (mass%) relative to the hydraulic powder (P) (total of OPC and BFS). Moreover, in Table 20, the addition amount of the additive (I) is mass% of solid content with respect to the hydraulic powder (P) (total of OPC and BFS).

From the results of Table 20, it can be seen that when the additive of the present invention is added, the amount of air is increased and the fluidity is improved. In Example 3b-1, the amount of admixture (d4) added was reduced, but the amount of air increased compared to Comparative Example 3b-1, and the compression strength after 3 days and 7 days was improved. Yes.

<Example 4b and Comparative Example 4b>
Concrete and its hardened body were produced in the same manner as in Example 3b, and the slump and strength were evaluated. However, the mixing conditions of concrete were as shown in Table 21. Moreover, the intensity | strength measured 1 day intensity | strength and 3 day intensity | strength. The results are shown in Table 22.

In Table 22, the addition amount of the admixture (d1) and the admixture (d4) is the apparent addition amount (mass%) with respect to the hydraulic powder (P) (total of OPC and BFS). Moreover, in Table 22, the addition amount of the additive (I) is mass% of solid content with respect to the hydraulic powder (P) (total of OPC and BFS).

As a result of Table 22, in comparison with Comparative Example 4b-1 and Example 4b-3, the fluidity and 3-day strength are improved by adding the additive of the present invention even when the air amount is the same. I understand.

<Example 5b and Comparative Example 5b>
Concrete and its hardened body were produced in the same manner as in Example 3b, and the slump and strength were evaluated. The concrete flow was measured in accordance with JIS A 1150 “Concrete Slump Flow Test Method”. However, the mixing conditions of concrete were as shown in Table 23. The same BB (type blast furnace cement B) as in Example 2b was used as the cement. As the additive, the additive (II) of Example 2b was used in the amount shown in Table 24. Table 24 shows the setting time in accordance with JIS A 1123 “Concrete Bleeding Test Method”. In addition, the room temperature at the time of concrete preparation and the curing temperature were 10 degreeC. Moreover, the intensity | strength measured 12 hours intensity | strength, 18 hours intensity | strength, and 24 hours intensity | strength. The results are shown in Table 24.
Admixture (d5): AE water reducing agent (standard form), manufactured by Kao Corporation, Mighty 1000S (polycarboxylic acid type special surfactant and natural resin acid derivative)

In Table 24, the addition amounts of the admixture (d1) and the admixture (d5) are apparent addition amounts (mass%) with respect to the cement (BB). Moreover, in Table 24, the addition amount of additive (II) is the mass% of solid content with respect to cement (BB).

From the results of Table 24, it can be seen that when the additive of the present invention is added, the fluidity is improved, the setting time is shortened, and the short-term strength can be improved.

Claims (23)

1. An additive for a hydraulic composition using a blast furnace slag cement, containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof.
2. (D) The additive according to claim 1, comprising an admixture selected from lignin sulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and a naphthalene sulfonate formaldehyde condensate or a salt thereof.
3. The additive according to claim 1 or 2, wherein the blast furnace slag cement contains 5 to 95% by mass of cement and 5 to 70% by mass of blast furnace slag.
4. A hydraulic composition containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, a blast furnace slag cement, and water.
5. (D) The hydraulic composition of Claim 4 containing the admixture chosen from a lignin sulfonic acid or its derivative (s), a lignin sulfonate or its derivative (s), and a naphthalene sulfonate formaldehyde condensate or its salt.
6. The hydraulic composition of Claim 5 which contains 0.001 mass% or more and 5 mass% or less of (D) with respect to a blast furnace slag cement.
7. The hydraulic composition according to any one of claims 4 to 6, wherein the blast furnace slag cement contains 5 mass% to 95 mass% of cement and 5 mass% to 70 mass% of blast furnace slag.
8. The hydraulic composition according to any one of claims 4 to 7, comprising (A) thiosulfuric acid or a salt thereof in an amount of 0.001% by mass to 3.0% by mass with respect to the blast furnace slag cement.
9. The hydraulic composition according to any one of claims 4 to 8, comprising (B) thiocyanic acid or a salt thereof in an amount of 0.001% by mass to 3.0% by mass with respect to the blast furnace slag cement.
10. The hydraulic composition according to any one of claims 4 to 9, comprising (C) α-hydroxyalkanesulfonic acid or a salt thereof in an amount of 0.0001 mass% to 3.0 mass% with respect to the blast furnace slag cement. object.
11. The hydraulic composition according to any one of claims 4 to 10, comprising a polyol.
12. The hydraulic composition of Claim 11 which contains a polyol 0.001 mass% or more and 1.0 mass% or less with respect to a blast furnace slag cement.
13. The hydraulic composition according to claim 11 or 12, wherein the polyol is glycerin.
14. The hydraulic composition according to any one of claims 4 to 13, comprising an alkanolamine.
15. The hydraulic composition of Claim 14 which contains 0.001 mass% or more and 1.0 mass% or less of alkanolamine with respect to a blast furnace slag cement.
16. The hydraulic composition according to claim 14 or 15, wherein the alkanolamine is methyldiethanolamine.
17. The hydraulic composition according to any one of claims 4 to 16, comprising an aggregate.
18. The hydraulic composition according to any one of claims 4 to 17, comprising a blast furnace slag cement and water so that a mass ratio of water / blast furnace slag cement is 40% by mass or more and 60% by mass or less.
19. The method for producing a hydraulic composition according to any one of claims 4 to 18, comprising (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) an α-hydroxyalkanesulfonic acid. Or the manufacturing method of the hydraulic composition which mixes the salt, blast furnace slag cement, and water.
20. 20. A mixture containing (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof and water, and blast furnace slag cement are mixed. A method for producing a hydraulic composition.
21. A method for producing a hydraulic composition according to any one of claims 5 to 18, wherein (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) an admixture selected from α-hydroxyalkanesulfonic acid or a salt thereof, (D) ligninsulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and a naphthalenesulfonate formaldehyde condensate or a salt thereof, blast furnace slag A method for producing a hydraulic composition, comprising mixing cement and water.
22. (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid or a salt thereof, (D) lignin sulfonic acid or a derivative thereof, lignin sulfonate or a derivative thereof, and The method for producing a hydraulic composition according to claim 21, wherein an admixture selected from naphthalene sulfonate formaldehyde condensate or a salt thereof and a mixture containing water and blast furnace slag cement are mixed.
23. A step of producing a hydraulic composition by the production method according to any one of claims 19 to 22;
    Filling the mold with the obtained hydraulic composition and curing;
    Removing the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition;
    The manufacturing method of the hardening body of a hydraulic composition which has.