JP2018087104A - Additive for hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for a hydraulic composition capable of obtaining a hydraulic composition using blast furnace slag cement excellent in the initial strength of a cured body.SOLUTION: There is provided an additive for a hydraulic composition comprising: thiosulfuric acid or its salt; thiocyanic acid or its salt; and α-hydroxyalkanesulfonic acid or its salt.SELECTED DRAWING: None

Description

  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 body of the hydraulic composition.

  Hydraulic powder, such as cement and blast furnace slag, has a property of reacting with water and hardening, and is called mortar by mixing with sand and concrete by mixing 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.

  Patent Document 1 discloses an early strengthening agent for a hydraulic composition comprising a specific compound (1) such as glycerin and at least one inorganic salt A selected from alkali metal sulfate and alkali metal thiosulfate. An early strengthening agent for a hydraulic composition in which the molar ratio of the compound (1) to the inorganic salt A is 5/95 to 45/55 in terms of the compound (1) / inorganic salt A is disclosed.

  Patent Document 2 contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene dispersant, and the molar ratio of glycerin and inorganic salt A is glycerin. / The additive composition for hydraulic compositions which is 5/95 to 55/45 in inorganic salt A is disclosed.

  Patent Document 3 contains glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, a hydraulic powder, an aggregate, and water, and the content of glycerin is 100 parts by mass of the hydraulic powder. 0.040 parts by mass or more and 0.280 parts by mass or less, and the content of hydroxymethanesulfonic acid or a salt thereof is 0.010 parts by mass or more and 0.420 parts by mass with respect to 100 parts by mass of the hydraulic powder. The following hydraulic compositions are disclosed.

  Patent Document 4 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.
Patent Document 5 discloses a hydraulic composition containing α-hydroxysulfonic acid or a salt thereof, a hydraulic powder and water, wherein the ratio of slag is 60% by mass or more in the hydraulic powder. Yes.

JP 2011-153068 A JP 2011-162400 A JP 2014-208574 A JP 61-117142 A JP 2006-56083 A

The hydraulic composition using blast furnace slag cement is desired to further improve the strength of the material from the 1st day to the 7th day from the viewpoint of improving the 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.

  The present invention is 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. Relating to additives.

  The present invention also includes 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.

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.

  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). .

  According to the present invention, it is an additive for a hydraulic composition using blast furnace slag cement, and has excellent 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.

<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 7-day strength. 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 7-day strength, alkali metal salts are preferred.

[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. From the viewpoint of shortening the time required for the hydraulic composition to reach the required strength, α-hydroxysulfonate is preferable. An alkali metal salt of α-hydroxysulfonic acid is more preferable, and a sodium salt of α-hydroxysulfonic acid is more preferable.

  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.

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

[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.

In the additive for the hydraulic composition of the present invention, a dispersant can be further mixed from the viewpoint of improving workability.
Dispersants such as phosphate ester polymers, polycarboxylic acid copolymers, sulfonic acid copolymers, naphthalene polymers, melamine polymers, phenol polymers, lignin polymers, etc. Is mentioned. The dispersant may be an admixture containing other components.
When the additive for a hydraulic composition of the present invention contains a dispersant, 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 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, and α-olefin sulfonate.

  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, amide It may also contain an anti-foaming agent and the like.

  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.

<Hydraulic composition>
The hydraulic composition of the present invention contains (A) component, (B) component, (C) component, blast furnace slag cement, and water. Specific examples and preferred embodiments of the component (A), the component (B) and the component (C) 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 dispersing agent, a polyol, and an alkanolamine. Specific examples and preferred embodiments of the dispersant, polyol and alkanolamine 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 defined in JIS R 5211 can be used. Blast furnace cement type B and C are preferable, and blast furnace cement type B is more preferable. According to JIS R 5211, three types of blast furnace cement, A type, B type, and C type, are defined according to 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 preferably 0.001% by mass or more, more preferably, thiosulfuric acid or a salt thereof as component (A) with respect to the blast furnace slag cement, from the viewpoint of 7-day strength and salt resistance. 0.01% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of workability, it is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and still more preferably 1.0% by mass. Contain less than mass%.

  The hydraulic composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% of thiocyanic acid or a salt thereof as component (B) from the viewpoint of 7-day strength with respect to the blast furnace slag cement. From the viewpoint of workability, it is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and further preferably 1.0% by mass or less. contains.

  In the hydraulic composition of the present invention, the (C) component α-hydroxyalkanesulfonic acid or a salt thereof is preferably 0.0001% by mass or more, more preferably, relative to the blast furnace slag cement, from the viewpoint of strength for 7 days. Is 0.001% by mass or more, more preferably 0.01% by mass or more, and from the viewpoint of workability, it is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and still more preferably 1.% by mass. The content is 0% by mass or less, more preferably 0.5% by mass or less.

  When the hydraulic composition of the present invention contains a dispersant, the dispersant is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of workability with respect to the blast furnace slag cement. 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 0.01% by mass or more, from the viewpoint of strength for 7 days with respect to the blast furnace slag cement. And from a viewpoint of workability, Preferably it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it contains 0.25 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 water / blast furnace slag cement mass ratio of 40 mass% to 60 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.

  The hydraulic composition of the present invention can be used as a material for concrete structures and concrete products. The concrete using the hydraulic composition obtained according to the present invention has an improved initial compressive strength such as 7 days after contact with water, so that, for example, a demolding time similar to that of concrete using cement can be obtained. In addition, long-term strength can be improved compared to ordinary Portland cement. In addition, even if hydraulic powders (fly ash, silica fume, limestone, etc.) with low initial age strength after water contact are blended and replaced within a range that does not impair the ratio of slag in the hydraulic powder, equivalent or higher The initial compressive strength, for example, the compressive strength after 7 days from water contact can be obtained.

  Examples of the hydraulic composition of the present invention include 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.

<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. Specific examples and preferred embodiments of the component (A), the component (B) and the component (C) 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 dispersing agent, a polyol, and an alkanolamine. Specific examples and preferred embodiments of the dispersant, polyol and alkanolamine are the same as those of the additive of the present invention.
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. Alternatively, a hydraulic composition is obtained by adding and mixing the salt, water, optionally a dispersant, optionally glycerin, optionally alkanolamine, and optionally aggregate. In this invention, it is preferable to mix the mixture containing (A) component, (B) component, (C) component, and water, and blast furnace slag cement. From the viewpoint of obtaining a hydraulic composition having stable physical properties, a mixture containing (A) component, (B) component, (C) component, water, optionally glycerin, and optionally alkanolamine, A mixture containing (A) component, (B) component, (C) component, water, optionally dispersing agent, optionally glycerin, optionally alkanolamine, and optionally AE agent. It is preferable to use it.

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, dispersant, glycerin, alkanolamine, bone When mixing the material and water, from the viewpoint of mixing them smoothly, (A) component, (B) component, (C) component, dispersant, glycerin, alkanolamine and water are mixed in advance, and blast furnace slag cement It is preferable to mix with the 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) component, (B) component, (C) component, dispersant, glycerin and alkanolamine are added to water.
The mixing is preferably performed for 30 seconds or longer, more preferably for 1 minute or longer, and preferably for 10 minutes or shorter, more preferably for 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

  About the process of manufacturing a hydraulic composition with the manufacturing method of the said this invention, it is as above-mentioned.

  In the step of filling and curing the hydraulic composition in the mold, the uncured hydraulic composition after preparation is filled in the mold and 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 product of the hydraulic composition of the present invention, additional energy such as steam heating may be added to accelerate the curing of 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 when heat curing such as steam is performed, 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 body 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 1 and Comparative Example 1>
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. α-Hydroxymethanesulfonic acid sodium is 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 also 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 1-1 to 1-7 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 1-8 to 1-12 and Examples 1-1 to 1-2 in Table 2, when the blast furnace cement B type is used, it is 7 days by adding all the additives of the present invention. It can be seen that the strength is improved.

<Example 2 and Comparative Example 2>
A cured mortar was produced in the same manner as in Example 1, 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. Agent A or Agent B was 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 3 and Comparative Example 3>
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 (Blast furnace cement B type) as Example 1 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 2 were used.

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

<Example 4 and Comparative Example 4>
A cured mortar was produced in the same manner as in Example 3, 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 5 and Comparative Example 5>
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 4000 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 2.65g / 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), Master Pozzolith No. manufactured by BASF Japan Ltd. 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 6 and Comparative Example 6>
A hardened concrete was produced in the same manner as in Example 5, 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 6-1 and Example 6-2, it can be seen that the compressive strength is improved by using the additive (I).

<Example 7 and Comparative Example 7>
A hardened concrete was produced in the same manner as in Example 5, 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 1 was used.
Additive: Additive (II) of Example 2 was used.
Admixture (1) and Admixture (2): The same as in Example 5 was used.
・ Admixture (3): AE water reducing agent (high function type), Mighty 1000S manufactured by Kao Corporation
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, when the addition amount of an additive and the curing temperature are the same conditions with the same concrete mixing | blending.

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).

Claims (20)

  An additive for a hydraulic composition using a blast furnace slag cement, comprising (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, and (C) α-hydroxyalkanesulfonic acid or a salt thereof.   The additive according to claim 1, wherein the blast furnace slag cement contains 5% by mass to 95% by mass of cement and 5% by mass to 70% by mass of blast furnace slag.   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.   The hydraulic composition according to claim 3, wherein the blast furnace slag cement contains 5% by mass to 95% by mass of cement and 5% by mass to 70% by mass of blast furnace slag.   The hydraulic composition of Claim 3 or 4 which contains 0.001 mass% or more and 3.0 mass% or less of (A) thiosulfuric acid or its salt with respect to a blast furnace slag cement.   The hydraulic composition of any one of Claims 3-5 which contains 0.001 mass% or more and 3.0 mass% or less of (B) thiocyanic acid or its salt with respect to a blast furnace slag cement.   The hydraulic composition according to any one of claims 3 to 6, comprising (C) α-hydroxyalkanesulfonic 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. object.   The hydraulic composition of any one of Claims 3-7 containing a dispersing agent.   The hydraulic composition of Claim 8 which contains a dispersing agent 0.0001 mass% or more and 5.0 mass% or less with respect to blast furnace slag cement.   The hydraulic composition of any one of Claims 3-9 containing a polyol.   The hydraulic composition of Claim 10 which contains a polyol 0.001 mass% or more and 1.0 mass% or less with respect to a blast furnace slag cement.   The hydraulic composition according to claim 10 or 11, wherein the polyol is glycerin.   The hydraulic composition according to any one of claims 3 to 12, comprising an alkanolamine.   The hydraulic composition of Claim 13 which contains 0.001 mass% or more and 1.0 mass% or less of alkanolamine with respect to a blast furnace slag cement.   The hydraulic composition according to claim 13 or 14, wherein the alkanolamine is methyldiethanolamine.   The hydraulic composition according to any one of claims 3 to 15, comprising an aggregate.   The hydraulic composition of any one of Claims 3-16 which contains a blast furnace slag cement and water so that mass ratio of water / blast furnace slag cement may be 40 to 60 mass%.   A method for producing a hydraulic composition according to any one of claims 3 to 17, wherein (A) thiosulfuric acid or a salt thereof, (B) thiocyanic acid or a salt thereof, (C) α-hydroxyalkanesulfonic acid. Or the manufacturing method of the hydraulic composition which mixes the salt, blast furnace slag cement, and water.   19. 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. A step of producing a hydraulic composition by the production method according to claim 18 or 19,
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.