JP6401986B2 - Hydraulic composition - Google Patents

Description

  The present invention relates to a hydraulic composition, an early strengthening agent for a hydraulic composition, and a method for producing a cured body of the hydraulic composition.

  Concrete may be required to exhibit a certain degree of strength within about one day after being kneaded with hydraulic powder such as cement and water. For example, a concrete secondary product is kneaded with materials such as cement, aggregate, water, and a dispersant, placed in various molds, and commercialized through a curing (hardening) process. Since the same formwork is used many times, it is important to develop a high strength in the initial age from the viewpoint of improving the productivity, that is, the rotation rate of the formwork. Therefore, (1) Use early-strength cement as cement, (2) Use various polycarboxylic acid compounds as admixtures to reduce the amount of water in the cement composition, (3) Steam curing as a curing method Measures such as performing are taken.

  Today, there is a case where further shortening of the curing process is desired due to a demand for higher productivity. For example, in order to shorten the time until demolding in the manufacture of concrete products, it is desired to develop high strength 24 hours after kneading with the hydraulic powder and water.

  In addition, although the curing time is shortened by heat curing such as steam curing, heat curing is not performed from the viewpoint of reducing energy costs associated with heat curing, that is, shortening the heating curing time and reducing the curing temperature. The method is anxious.

  Patent Document 1 discloses a composition and method for improving the grinding efficiency of cement, cement clinker, cement raw material, and other inorganic particles. Biomass-derived polyols, such as diols, triols or mixtures thereof, optionally in combination with conventional grinding aids, cement quality improvers and / or hexavalent chloro-containing water reducing agents, compared to glycerides obtained from fossil fuel sources It is described that the risk of sludge generation is reduced, and it is described that sodium dithionate can be used as a water reducing agent containing hexavalent chromium.

Special table 2008-542182 gazette

  The present invention relates to a hydraulic composition in which the strength of a cured product is improved for about 24 hours after preparation, a method for producing a cured product of a hydraulic composition from which such a cured product is obtained, and an early strengthening agent for a hydraulic composition. I will provide a. Hereinafter, the strength after 24 hours (including the compressive strength after 24 hours) is described as the strength for 24 hours.

  The present invention is represented by the following general formula (1) of 0.1 to 4.5 parts by mass with respect to 100 parts by mass of hydraulic powder, water, a dispersant, and 100 parts by mass of the hydraulic powder. The present invention relates to a hydraulic composition comprising a compound [hereinafter referred to as compound (1)].

[In the formula, n is an integer of 0 or more and 8 or less, and two Ms each independently represent a counter ion, which is a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion (1/2 ion). ]

  Moreover, this invention relates to the early strengthening agent for hydraulic compositions containing the said compound (1).

Moreover, this invention relates to the manufacturing method of the hardening body of the hydraulic composition including the following process 1-process 5.
(Step 1) A step of mixing water, a dispersant and the compound (1).
(Step 2) A step of kneading the mixture obtained in step 1, the hydraulic powder and the aggregate to obtain a hydraulic composition, wherein the compound (1) in the mixture is 100 masses of the hydraulic powder. The process of using the said mixture so that it may become 0.1 to 4.5 mass parts with respect to a part.
(Step 3) A step of filling the formwork with the hydraulic composition obtained in Step 2.
(Step 4) A step of curing the hydraulic composition filled in the mold obtained in Step 3 under a condition that the time for maintaining the hydraulic composition at 50 ° C. or higher is 1 hour or shorter.
(Step 5) A step of removing the cured body obtained in Step 4 from the mold.

  ADVANTAGE OF THE INVENTION According to this invention, the hydraulic composition which can improve intensity | strength for 24 hours, the manufacturing method of the hardening body of a hydraulic composition, and the early strengthening agent for hydraulic compositions are provided.

The mechanism for producing the effect of the present invention is unknown, but is estimated as follows.
The compound (1) used in the present invention promotes the hydration of C ₃ S (3CaO · SiO ₂ , alite), which is one of the minerals contained in the cement, when the cement and water are kneaded. It is estimated that the reaction rate is increased and the strength is improved early.
It is known that the hydration reaction promoting effect of C ₃ S has a high correlation with the ultimate molar conductivity of anions among the added salts. Further, it is known that an anion having a higher ultimate molar conductivity has a higher diffusion rate, and the elution reaction rate of C ₃ S is increased by a mutual diffusion action between the anion and the hydroxide ion. (Kondo Renichi et al .: Cement Technology Annual Report 29 pp.57-60 (1975))
It is presumed that the compound (1) has a higher ultimate molar conductivity than other disulfonic acids, thereby increasing the elution rate of C ₃ S.

<Hydraulic composition>
The hydraulic composition of the present invention contains hydraulic powder, water, a dispersant, and a predetermined amount of the compound (1).

  The hydraulic powder includes cement. Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, sulfate-resistant Portland cement, low heat Portland cement, white Portland cement, and eco-cement (for example, JIS R5214). Among these, from the viewpoint of improving the 24-hour strength of the obtained cured product, a cement selected from ordinary Portland cement and early-strength Portland cement is preferable, and ordinary Portland cement is more preferable.

  The cement may include blast furnace slag, fly ash, silica fume, and the like, and may include non-hydraulic limestone fine powder and the like. Silica fume cement or blast furnace cement mixed with cement may be used.

  The hydraulic composition of the present invention contains a dispersant from the viewpoint of improving fluidity. 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.

  As the dispersant, a polycarboxylic acid copolymer is preferable from the viewpoint of improving the strength of the obtained cured product for 24 hours. As the polycarboxylic acid copolymer, a copolymer of a monoester of polyalkylene glycol and (meth) acrylic acid and a carboxylic acid such as (meth) acrylic acid (compound described in JP-A-8-12397) Etc.), a copolymer of an unsaturated alcohol having a polyalkylene glycol and a carboxylic acid such as (meth) acrylic acid, a copolymer of an unsaturated alcohol having a polyalkylene glycol and a dicarboxylic acid such as maleic acid, etc. be able to. Here, (meth) acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

  The polycarboxylic acid copolymer of the dispersing agent includes a monomer (A1) represented by the following general formula (A1) and a monomer (A2) represented by the following general formula (A2). A copolymer obtained by polymerizing the polymer (hereinafter referred to as copolymer (A)) is preferred.

[Where,
R ¹ and R ² : each independently a hydrogen atom or a methyl group m1: an integer of 0 or more and 2 or less AO: an alkyleneoxy group having 2 or 3 carbon atoms n1: an average added mole number of AO, 4 or more and 300 or less X: A hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[Where,
R ³ , R ⁴ , R ⁵ : each independently a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ²
M ¹ and M ² : each independently represents a counter ion, hydrogen ion, alkali metal ion, alkaline earth metal ion (1/2 ion), organic ammonium ion, or ammonium ion,
m2: An integer of 0 or more and 2 or less. ]

  The copolymer (A) polymerizes a monomer containing the monomer (A1) represented by the general formula (A1) and the monomer (A2) represented by the general formula (A2). It is a copolymer obtained.

In general formula (A1), R ¹ and R ² are each a hydrogen atom or a methyl group. R ¹ is preferably a hydrogen atom. R ² is preferably a methyl group from the viewpoint of improving the strength for 24 hours. m1 is an integer of 0 or more and 2 or less, preferably 0, from the viewpoint of improving the strength for 24 hours.
AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms from the viewpoint of improving the strength for 24 hours, and an alkyleneoxy group having 2 carbon atoms is preferable.
n is an average added mole number of AO, and is a number of 4 or more and 300 or less. n is preferably 100 or more, more preferably 105 or more, and even more preferably 110 or more, from the viewpoint of suppressing the setting delay and improvement of the 24-hour strength, and from the viewpoint of ease of copolymerization and improvement of the 24-hour strength. From the viewpoint, 200 or less is preferable, and 150 or less is more preferable. n is preferably 4 or more, more preferably 8 or more, and preferably 50 or less, more preferably 30 or less, from the viewpoint of reducing the viscosity of the hydraulic composition and improving the strength for 24 hours.
X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and from the viewpoint of fluid retention of the hydraulic composition and the improvement of strength for 24 hours, a hydrogen atom or a methyl group is preferable, and a methyl group is more preferable. preferable.

  As the monomer (A1), (1) one-end alkyl-blocked polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, acrylic acid, methacrylic acid, And (2) ethylene oxide (hereinafter sometimes referred to as EO) and / or propylene oxide to a carboxylic acid selected from acrylic acid, methacrylic acid, and maleic acid Additives (hereinafter also referred to as PO) may be mentioned. The monomer (A1) is preferably an esterified product of methoxypolyethylene glycol and acrylic acid or methallylic acid, more preferably an esterified product of methoxypolyethylene glycol and methacrylic acid, from the viewpoint of improving the strength for 24 hours.

In General Formula (A2), R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ² . R ³ and R ⁵ are each preferably a hydrogen atom from the viewpoint of improving the strength for 24 hours. R ⁴ is preferably a methyl group from the viewpoint of improving the strength for 24 hours. M ¹ and M ² each represent a counter ion, which is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1/2 ion), an ammonium ion, or an organic ammonium ion, from the viewpoint of improving the strength for 24 hours. Sodium ions are preferred.

  As the monomer (A2), monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid, and their anhydrides or Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and mono, di, and trialkyl (2 to 8 carbon atoms) ammonium salts in which a hydroxyl group may be substituted. From the viewpoint of improving the strength for 24 hours, it is preferably a monomer selected from acrylic acid, methacrylic acid, maleic acid, and alkali metal salts thereof, and maleic anhydride, more preferably acrylic acid, methacrylic acid, And a monomer selected from these alkali metal salts. More preferred are monomers selected from methacrylic acid and alkali metal salts of methacrylic acid.

  In the copolymer (A), the molar ratio (A1) / (A2) of the monomer (A1) to the monomer (A2) is the improvement in the strength of the hydraulic composition and the improvement in strength for 24 hours. From the viewpoint, 5/95 or more is preferable, 8/92 or more is more preferable, 50/50 or less is preferable, 40/60 or less is more preferable, and 38/62 or less is still more preferable.

  Of all the constituent monomers of the copolymer (A), the total amount of the monomer (A1) and the monomer (A2) is preferably 90% by mass or more, and 95% by mass from the viewpoint of improving the strength for 24 hours. % Or more is more preferable, 98 mass% or more is further more preferable, 100 mass parts or less is preferable, substantial 100 mass% is still more preferable, and 100 mass% is still more preferable.

  The ratio of the mass of the monomer (A2) to the total mass of the monomer (A1) and the monomer (A2) is preferably 4% by mass or more, and preferably 5% by mass or more from the viewpoint of improving the strength for 24 hours. More preferably, 25% by mass or less is preferable, and 16% by mass or less is more preferable.

The weight average molecular weight of the copolymer (A) is preferably 20000 or more, more preferably 30000 or more, still more preferably 40000 or more, from the viewpoint of fluidity retention of the hydraulic composition and the improvement of the strength for 24 hours. 150,000 or less, more preferably 100,000 or less. In addition, the weight average molecular weight of a copolymer (A) is based on the gel permeation chromatography method (polyethylene glycol conversion), and specific conditions are as follows.
* Gel permeation chromatography conditions Apparatus: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PW _XL + G2500PW _XL (made by Tosoh Corporation)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: Polyethylene glycol equivalent (molecular weight 87500, 250,000, 145000, 46000, 24000)

  For example, the copolymer (A) is charged with water in a reaction vessel and heated, and the monomer (A1) and the monomer (A2) are mixed in a predetermined molar ratio ( It can be produced by reacting with A1) / (A2) and neutralizing after aging.

  The content of the dispersant is set to 0.1% with respect to the hydraulic powder, preferably 100 parts by mass of cement, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing the delay in curing and improving the strength for 24 hours. 005 parts by mass or more, further 0.05 parts by mass or more, further 0.01 parts by mass or more, and 2.5 parts by mass or less, 1.0 parts by mass or less, and further 0.5 parts by mass or less. preferable.

  In the compound (1), n in the general formula (1) is an integer of 0 or more and 8 or less, and n is preferably 1 or more, preferably 6 or less, more preferably 4 or less, from the viewpoint of 24 hour strength. 2 or less is more preferable.

Further, M in the general formula (1) of the compound (1) is a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion (1/2 ion). In general formula (1), from the viewpoint of improving the strength for 24 hours, one or both of M is preferably an alkali metal ion, or M is preferably an alkaline earth metal ion (1/2 atom). One of M is preferably an alkali metal ion and the other is a hydrogen ion, or both are alkali metal ions. Examples of the alkali metal ion include sodium ion and potassium ion, and sodium ion is preferable from the viewpoint of improving the strength for 24 hours. Examples of alkaline earth metal ions include calcium ions. When M is an alkaline earth metal ion (1/2 ion), a salt in which two SO ₃ ions are bonded to one alkaline earth metal ion is obtained.

Compound (1) includes ethanedisulfonic acid, propanedisulfonic acid, alkali metal salt of ethanedisulfonic acid, alkali metal salt of propanedisulfonic acid, alkaline earth metal salt of ethanedisulfonic acid, and alkaline earth metal of propanedisulfonic acid One or more compounds selected from salts are listed.
Examples of the compound (1) include one or more compounds selected from ethanedisulfonic acid, an alkali metal salt of ethanedisulfonic acid, and an alkaline earth metal salt of ethanedisulfonic acid. From the viewpoint of availability, ethane One or more compounds selected from alkali metal salts of disulfonic acid and alkaline earth metal salts of ethanedisulfonic acid are preferred. From the viewpoint of suppressing the alkali-aggregate reaction and improving the strength for 24 hours, an alkaline earth metal salt of ethanedisulfonic acid is preferred.
Examples of the compound (1) include disodium ethanedisulfonate, calcium ethanedisulfonate, disodium dithionate, potassium methanedisulfonate, disodium 1,3-propanedisulfonate, calcium 1,3-propanedisulfonate, 1,4 -One or more types of compounds chosen from disodium butane disulfonate are mentioned.
From the viewpoint of improving the strength for 24 hours, the compound (1) contains disodium ethanedisulfonate, calcium ethanedisulfonate, disodium dithionate, potassium methanedisulfonate, disodium 1,3-propanedisulfonate, 1,3- Calcium propanedisulfonate and disodium 1,4-butanedisulfonate are preferred, disodium ethanedisulfonate, calcium ethanedisulfonate, disodium dithionate, and potassium methanedisulfonate, disodium ethanedisulfonate, ethanedisulfonic acid Calcium and potassium methanedisulfonate are more preferable.

In the hydraulic composition of the present invention, the content of the compound (1) is 0.1 parts by mass or more and 0.2 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of improving the strength for 24 hours. Part or more, preferably 0.5 part by weight or more, more preferably 0.8 part by weight or more, still more preferably 1 part by weight or more, still more preferably 2 parts by weight or more, and even more preferably 3 parts by weight or more. Preferably, 3.5 parts by mass or more is even more preferable. In addition, the content of the compound (1) is 4.5 parts by mass or less, preferably 4.2 parts by mass or less, with respect to 100 parts by mass of the hydraulic powder, from the viewpoint of improving the strength for 24 hours. 0 parts by mass or less is more preferable.
Compound (1) may be a hydrate. In the present invention, when the compound (1) is a hydrate, the amount of the compound (1) is an amount converted to an anhydride.

  The hydraulic composition has a water / cement ratio [mass ratio of water to cement in slurry (mass of water / mass of cement × 100), usually W / C, from the viewpoint of improving the 24 hour strength of the obtained cured product. Abbreviated. ] Is 65% or less, more preferably 60% or less, and further preferably 55% or less. Further, from the viewpoint of improving workability such as ease of kneading of the hydraulic composition, improvement of filling into the mold at the time of casting, and improvement of 24-hour strength, 20% or more, and further 30% The above is preferable.

  The hydraulic composition of the present invention can further contain an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is 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).

Aggregates can be used in the usual ranges used for the preparation of concrete, mortar and the like. When the hydraulic composition is concrete, the amount of coarse aggregate used reduces the expression of the strength of the hydraulic composition and the amount of hydraulic powder such as cement, and improves the filling properties of the formwork and the like. From the viewpoint, the bulk volume is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, more preferably 100% or less, more preferably 90% or less, and still more preferably 80% or less.
Further, when the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m ³ or more, more preferably 600 kg / m ³ or more, and 700 kg from the viewpoint of improving the filling property to the formwork or the like. / M ³ or more is more preferable, 1000 kg / m ³ or less is preferable, and 900 kg / m ³ or less is more preferable.
Also, if the hydraulic composition is mortar, the amount of fine aggregate is preferably from 800 kg / ^{m 3} or more, more preferably 900 kg / ^{m 3} or more, more preferably 1000 kg / ^{m 3} or more, and, 2000 kg / m ³ or less is preferable, 1800 kg / m ³ or less is more preferable, and 1700 kg / m ³ or less is more preferable.

  The hydraulic composition of the present invention can further contain other components. For example, AE agent, retarder, foaming agent, thickener, foaming agent, waterproofing agent, fluidizing agent, antifoaming agent and the like can be mentioned.

  The hydraulic composition of the present invention may be concrete or mortar. The hydraulic composition of the present invention can be used for self-leveling, for refractories, for plaster, for lightweight or mass concrete, for AE, for repair, for prepacked, for tramy, for ground improvement, for grout, for cold, etc. It is also useful in the field. From the viewpoint of developing strength about 24 hours after the preparation of the hydraulic composition and enabling early demolding from the mold, it is preferably used for concrete products such as concrete vibration products and centrifugal molded products.

<Early strength agent for hydraulic composition>
The early strengthening agent for hydraulic composition of the present invention contains compound (1). A preferred embodiment of compound (1) is the same as the hydraulic composition of the present invention described above.

  The early strengthening agent for a hydraulic composition of the present invention is preferably 0.01% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass of the compound (1) from the viewpoint of improving the strength for 24 hours. % Or more, preferably 40% by mass or less, more preferably 30% by mass or less. Moreover, the early strengthening agent for hydraulic composition of the present invention may be composed of the compound (1).

  The early strengthening agent for a hydraulic composition of the present invention can be added and used at the time of preparing a hydraulic composition in which hydraulic powder such as cement and water are mixed. The early strengthening agent for hydraulic composition of the present invention is preferably mixed with water in advance when mixing the hydraulic powder and water from the viewpoint of improving the mixing property with the hydraulic powder. Moreover, the early strengthening agent for hydraulic compositions of the present invention can be mixed with water in advance and used as an aqueous solution from the viewpoint of workability such as addition of the early strengthening agent. That is, it is preferable to mix the mixture containing water and the early strengthening agent for hydraulic composition of the present invention with the hydraulic powder.

  In addition, the early strengthening agent for a hydraulic composition of the present invention is a hydraulic powder, preferably 0.1 parts by mass or more and 4 parts by mass with respect to 100 parts by mass of cement from the viewpoint of improving the strength of the obtained cured product for 24 hours. It is preferable to add so that it may become 5 mass parts or less. The added amount is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, still more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. Preferably, 3 parts by mass or more is more preferable, and 3.5 parts by mass or more is more preferable. Moreover, 4.2 mass parts or less are more preferable, and 4.0 mass parts or less are still more preferable. In addition, the early strengthening agent for hydraulic composition of the present invention is a compound in the early strengthening agent with respect to hydraulic powder, preferably 100 parts by weight of cement, from the viewpoint of improving the strength of the resulting cured body for 24 hours. (1) is preferably added so as to be 0.1 parts by mass or more and 4.5 parts by mass or less. The added amount is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, still more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. Preferably, 3 parts by mass or more is more preferable, and 3.5 parts by mass or more is more preferable. Moreover, 4.2 mass parts or less are more preferable, and 4.0 mass parts or less are still more preferable.

  Using the early strengthening agent for a hydraulic composition of the present invention, a cured product of the hydraulic composition can be obtained by air curing at room temperature (for example, 10 to 30 ° C.). In this invention, the intensity | strength of the hardening body 24 hours after can be improved even if it does not perform the curing under the heating of 40 degreeC or more, ie, what is called a heat curing.

According to the present invention, there is provided an additive composition for a hydraulic composition containing the early strengthening agent for a hydraulic composition of the present invention and a dispersant,
The dispersant is a phosphate ester polymer, a polycarboxylic acid copolymer, a sulfonic acid copolymer, a naphthalene polymer, a melamine polymer, a phenol polymer, from the viewpoint of improving the strength for 24 hours. One or more dispersants selected from lignin polymers are preferred, polycarboxylic acid copolymers are more preferred,
An additive composition for a hydraulic composition is provided. The preferable aspect of the early strengthening agent for a hydraulic composition in this additive composition for a hydraulic composition is the same as the early strengthening agent for a hydraulic composition of the present invention described above. Moreover, the preferable aspect of the dispersing agent in this additive composition for hydraulic compositions is the same as the hydraulic composition of the above-mentioned this invention.

Further, according to the present invention, there is provided an additive composition for hydraulic composition comprising compound (1) and a dispersant,
The dispersant is a phosphate ester polymer, a polycarboxylic acid copolymer, a sulfonic acid copolymer, a naphthalene polymer, a melamine polymer, a phenol polymer, from the viewpoint of improving the strength for 24 hours. One or more dispersants selected from lignin-based polymers are preferable, and an additive composition for a hydraulic composition, which is more preferably a polycarboxylic acid-based copolymer, is provided.
Preferred embodiments of the compound (1) and the dispersant in the additive composition for hydraulic composition are the same as those of the hydraulic composition of the present invention described above.

The additive composition for a hydraulic composition according to the present invention is preferably 0.01% by mass or more, more preferably 1% by mass or more, more preferably from the viewpoint of improving the strength of the compound (1) for 24 hours. It is contained in an amount of 40% by mass or less, more preferably 30% by mass or less.
In the additive composition for hydraulic composition of the present invention, the dispersant is preferably 0.01% by mass or more, more preferably 1% by mass or more, and preferably 50% by mass from the viewpoint of improving the strength for 24 hours. % Or less, more preferably 40% by mass or less.
In addition, the additive composition for hydraulic compositions of this invention can contain water as components other than a compound (1) and a dispersing agent. Moreover, the additive composition for hard compositions of the present invention may further contain other components. For example, AE agent, retarder, foaming agent, thickener, foaming agent, waterproofing agent, fluidizing agent, antifoaming agent and the like can be mentioned.

  The dispersant is 0.005 parts by mass with respect to hydraulic powder, preferably 100 parts by mass of cement, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing the delay in curing and improving the strength for 24 hours. Further, 0.05 parts by mass or more, 0.01 parts by mass or more, and 2.5 parts by mass or less, 1.0 parts by mass or less, and 0.5 parts by mass or less are further added. It is preferable. Moreover, in the additive composition for hydraulic compositions of the present invention, the mass ratio of the compound (1) and the dispersant (compound (1) / dispersant) is from the viewpoint of improving the strength of the obtained cured product for 24 hours. 1.0 or more is preferable, 1.3 or more is more preferable, 1.4 or more is further preferable, 15 or more is more preferable, 20 or more is more preferable, 25 or more is further more preferable, and 28 or more is still more preferable. . Moreover, 33 or less is preferable, 30 or less is more preferable, and 29 or less is still more preferable. In addition, the additive composition for hydraulic compositions of the present invention may be an additive for hydraulic compositions comprising the compound (1) and a dispersant. In this case, the mass ratio of the compound (1) / dispersant is preferably in the above range.

<Method for producing cured body>
The method for producing a cured product of the hydraulic composition according to the present invention includes a step of filling the hydraulic composition of the present invention into a mold, curing and curing, a step of demolding the cured hydraulic composition, and Have
More specifically, the manufacturing method of the hardening body of the hydraulic composition containing the following process 1-process 5 is mentioned.
(Step 1) A step of mixing water, a dispersant and the compound (1).
(Step 2) A step of kneading the mixture obtained in step 1, the hydraulic powder and the aggregate to obtain a hydraulic composition, wherein the compound (1) in the mixture is 100 masses of the hydraulic powder. The process of using the said mixture so that it may become 0.1 to 4.5 mass parts with respect to a part.
(Step 3) A step of filling the formwork with the hydraulic composition obtained in Step 2.
(Step 4) A step of curing the hydraulic composition filled in the mold obtained in Step 3 under a condition that the time for maintaining the hydraulic composition at 50 ° C. or higher is 1 hour or shorter.
(Step 5) A step of removing the cured body obtained in Step 4 from the mold.

  The compound (1), dispersant, and aggregate used in the method for producing a cured product of the present invention are the same as those mentioned for the hydraulic composition and the early strengthening agent for hydraulic composition of the present invention, respectively. The aspect is also the same. Moreover, it can replace and apply the content in a hydraulic composition to a compounding quantity.

  In step 1, water, a dispersant and compound (1) are mixed. The mixing ratio is adjusted according to the composition of the hydraulic composition finally obtained.

  In step 2, the mixture obtained in step 1, the hydraulic powder and the aggregate are kneaded to obtain a hydraulic composition. The mixture is used so that the compound (1) in the mixture is 0.1 to 4.5 parts by mass with respect to 100 parts by mass of the hydraulic powder, preferably cement. This amount is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, and even more preferably 1 part by mass or more, from the viewpoint of improving the strength for 24 hours. 2 parts by mass or more is more preferable, 3 parts by mass or more is more preferable, and 3.5 parts by mass or more is still more preferable. Moreover, 4.2 mass parts or less are more preferable, and 4.0 mass parts or less are still more preferable. The mixing ratio of the mixture, the hydraulic powder, and the aggregate is adjusted in consideration of the amount of the compound (1), the composition of the finally obtained hydraulic composition, and the like.

  The mixture obtained in step 1 and the hydraulic powder can be mixed using a mixer such as a mortar mixer or a forced biaxial mixer. From the viewpoint of improving the strength for 24 hours, the mixing is preferably performed for 1 minute or longer, more preferably 2 minutes or longer, and preferably 5 minutes or shorter, more preferably 3 minutes or shorter.

  In step 3, the hydraulic composition obtained in step 2 is filled into a mold. As a formwork, a formwork for a building, a formwork for a concrete product, and the like can be given. 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.

In step 4, the hydraulic composition filled in the mold obtained in step 3 is cured under the condition that the time maintained at 50 ° C. or higher is 1 hour or shorter. In the method for producing a cured body of the hydraulic composition of the present invention, when curing the hydraulic composition, additional energy such as steam heating is not required to accelerate curing, and heating curing such as steam curing is performed. Without this, it becomes possible to produce a cured body of a hydraulic composition such as a concrete product. In step 4, the time for maintaining the hydraulic composition at a curing temperature of 50 ° C. or higher as curing conditions is 1 hour or less, preferably 0.5 hours or less, more preferably 0 hours or more. Also, it may be 0 hours. The time from contact of water with cement in the preparation of a hydraulic composition when producing concrete products without steam curing until the time of demolding improves the viewpoint of obtaining the strength necessary for demolding and the production cycle. From a viewpoint, 4 hours or more and 48 hours or less are preferable. In this case, the temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and 40 ° C. or lower, more preferably 30 ° C. or lower. Heating and / or cooling in this temperature range can be appropriately performed.
In addition, when performing the curing by holding the hydraulic composition filled in the mold at 50 ° C. or higher, it is possible to perform heating curing such as autoclave curing and steam curing.

  The method for producing a cured body of the hydraulic composition of the present invention can improve the strength of a cured body after 24 hours without performing heat curing, and therefore can be suitably used for the production of concrete products. In the method for producing a cured product of the hydraulic composition of the present invention, such as the production of a concrete product, the hydraulic composition to which the additive for the hydraulic composition of the present invention is added is filled in a mold and cured and cured. And a step of removing the cured hydraulic composition from the mold. In the method for producing a cured body of the hydraulic composition of the present invention, since the curing of the hydraulic composition is accelerated, the time from preparation of the hydraulic composition to demolding can be shortened. The manufacturing method of the hardened | cured material of the hydraulic composition of this invention has the process 2 which prepares the said hydraulic composition by making water contact hydraulic hydraulic powder, such as cement. In the present invention, the time from the start of the preparation of the hydraulic composition to the demolding, that is, the time from the contact of water with the cement to the start of demolding, obtains the strength necessary for demolding. From a viewpoint and a viewpoint which improves a manufacturing cycle, 4 hours or more, 6 hours or more are preferable, and 48 hours or less, and also 30 hours or less are preferable.

  The method for producing a cured body of the hydraulic composition of the present invention can improve the productivity of a cured body of a hydraulic composition such as a concrete product without performing heat curing, and thus is excellent in terms of reducing the burden on the environment. Is. As a hardened body of a hydraulic composition using a formwork that is a concrete product, as a civil engineering product, there are various block products for revetment, box culvert products, segment products used for tunnel construction, pier girder products, etc. Examples of building products include curtain wall products, pillars, beams, building member products used for floor boards, and the like.

The mortar formulation is shown in Table 1, and the evaluation results are shown in Table 2. The compounds in the table are as follows.
[Compound (1)]
・ Ethane disulfonic acid disodium: manufactured by Kanto Chemical Co., Ltd. ・ Ethandisulfonic acid calcium: Tokyo Chemical Industry Co., Ltd. ethane disulfonic acid dihydrate was dissolved in ion-exchanged water to obtain 8.6 parts by mass of ethane disulfonic acid aqueous solution. It was. To the above aqueous solution, equimolar calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was added and stirred with a stirrer to obtain a 10 parts by weight aqueous solution of calcium ethanedisulfonate.
-Disodium dithionate dihydrate: manufactured by Kanto Chemical Co., Ltd. (Table 2 shows parts by mass based on the amount in terms of anhydride.)
-Dipotassium methane disulfonate: manufactured by Sigma-Aldrich Japan Co., Ltd.-Disodium 1,3-propanedisulfonate: manufactured by Tokyo Chemical Industry Co., Ltd.-Calcium 1,3-propanedisulfonate: produced in the same manner as calcium ethane disulfonate.
・ 1,4-Butanedisulfonic acid disodium: manufactured by Tokyo Chemical Industry Co., Ltd.

[Comparative compound]
・ 1,5-Naphthalenedisulfonic acid disodium: Wako Pure Chemical Industries, Ltd. ・ 2,6-Naphthalenedisulfonic acid disodium: Tokyo Kasei Kogyo Co., Ltd. ・ m-Benzenedisulfonic acid disodium: Wako Pure Chemical Industries, Ltd. -Sodium methyl sulfate: Wako Pure Chemical Industries, Ltd.-Ethyl sulfate: Tokyo Chemical Industry Co., Ltd.-Sodium ethanesulfonate: Tokyo Chemical Industry Co., Ltd.

[Dispersant]
Polycarboxylic acid dispersant: A copolymer produced by the following method was used.
(Method for producing copolymer)
Into a glass reaction vessel (four-necked flask) equipped with a stirrer, 114 g of water was charged, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 60 g of ω-methoxypolyethylene glycol monomethacrylate (average addition mole number of ethylene oxide 120: ester purity 100%) aqueous solution 300 g, methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.) 11.5 g, and mercaptopropionic acid 0 Two solutions, a solution in which .98 g was mixed and dissolved, and a solution in which 1.9 g of ammonium persulfate was dissolved in 45 g of water were dropped into the reaction vessel over 1.5 hours. Thereafter, aging was performed for 1 hour, and a solution obtained by dissolving 0.8 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of aging, the mixture was cooled to 40 ° C. or lower and neutralized with 9.6 g of a 48 wt% sodium hydroxide solution to obtain a copolymer having a weight average molecular weight of 53,000.

The mass ratio (W / C) of water and cement is 0.40 (50 parts by mass with respect to 100 parts by mass of cement). The fine aggregate is 175 parts by mass with respect to 100 parts by mass of cement. The components used are as follows.
・ W: Kneaded water (tap water containing cement dispersant and early strengthening agent)
C: Normal Portland cement (manufactured by Taiheiyo Cement Co., Ltd.), density 3.16 g / cm ³
S: Fine aggregate, from Joyo, mountain sand, FM = 2.67, density 2.56 g / cm ³

<Preparation and evaluation of mortar>
(1) Mortar preparation process The kneading water (W) which mixed the cement dispersing agent and the early strengthening agent of Table 2 with water was prepared. Since the amounts of the cement dispersant and the early strengthening agent in the kneading water are very small, the total amount of the cement dispersing agent, the early strengthening agent and the water was set to the amount of the kneading water (W) in Table 1. As a cement dispersant, 0.14 parts by mass of a polycarboxylic acid-based dispersant was added to 100 parts by mass of cement. In Table 2, compound (1) or a comparative compound was used as an early strengthening agent.

  Under the blending conditions shown in Table 1, cement (C) and fine aggregate (S) were added using a mortar mixer (universal mixing stirrer model: 5DM-03-γ) manufactured by Dalton Co., Ltd. The kneading water (W) containing the cement dispersant and the compound (1) or the comparative compound was added. At this time, an antifoaming agent was added so that the air entrainment amount was 2% or less. Then, mortar was prepared by main kneading for 60 seconds at a low speed rotation (63 rpm) of the mortar mixer and 120 seconds at a high speed rotation (128 rpm).

(2) Filling mold and curing process Based on JIS A 1132, three cylindrical molds (bottom diameter: 5 cm, height 10 cm) are filled with mortar by a two-layer packing method at 20 ° C. Curing was performed in the air (20 ° C.) and cured. The specimen cured 24 hours after the preparation of the mortar was removed from the mold to obtain a specimen. Three of these specimens were used for measurement of compressive strength after 24 hours.

(4) Evaluation of Curing Strength The 24-hour strength of the specimen was measured based on JIS A1108, and the average value of three specimens was obtained. The results are shown in Table 2.

  In Table 2, “parts by mass” is parts by mass with respect to 100 parts by mass of cement. In Table 2, the “ratio” of the strength for 24 hours is a ratio where the strength of Comparative Example 1 in which no early strengthening agent is added to cement is 100.

  From Table 2, it can be seen that a high strength improvement effect can be obtained by adding a specific amount of the compound (1) to the hydraulic composition.

Claims (4)

A hydraulic powder, water, a dispersant, and a compound represented by the following general formula (1) of 0.1 to 4.5 parts by mass with respect to 100 parts by mass of the hydraulic powder. A hydraulic composition comprising.

[Wherein, n is an integer of 0 or more and 8 or less, and M independently represents a counter ion and is a hydrogen ion, an alkali metal ion or an alkaline earth metal ion (1/2 ion). ] The early strengthening agent for hydraulic compositions containing the compound represented by following General formula (1).

[Wherein, n is an integer of 0 or more and 8 or less, and M independently represents a counter ion and is a hydrogen ion, an alkali metal ion or an alkaline earth metal ion (1/2 ion). ] The manufacturing method of the hardening body of the hydraulic composition containing the following process 1-process 5.
(Step 1) A step of mixing water, a dispersant and a compound represented by the following general formula (1).
(Step 2) A step of kneading the mixture obtained in step 1 with hydraulic powder and aggregate to obtain a hydraulic composition, wherein the compound represented by the general formula (1) in the mixture is The process of using the said mixture so that it may become 0.1 to 4.5 mass parts with respect to 100 mass parts of hydraulic powder.
(Step 3) A step of filling the formwork with the hydraulic composition obtained in Step 2.
(Step 4) A step of curing the hydraulic composition filled in the mold obtained in Step 3 under the condition that the time maintained at 50 ° C. or higher is 0 hour or longer and 1 hour or shorter.
(Step 5) A step of removing the cured body obtained in Step 4 from the mold.

[Wherein, n is an integer of 0 or more and 8 or less, and M independently represents a counter ion and is a hydrogen ion, an alkali metal ion or an alkaline earth metal ion (1/2 ion). ]   The manufacturing method of the hardening body of the hydraulic composition of Claim 3 which does not implement steam curing in the process 4.