JP2010024099A - Early strengthening agent for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an early strengthening agent for a hydraulic composition, which achieves an excellent result when used for improving the short-term strength. <P>SOLUTION: The early strengthening agent for the hydraulic composition includes a compound (a) obtained by reacting (A) one or more selected from dihydric alcohol and an alkylene oxide adduct of dihydric alcohol with (B) a sulfating agent. An additive composition for the hydraulic composition contains the compound (a). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an early strengthening agent for a hydraulic composition, an additive composition for a hydraulic composition, and a hydraulic composition.

  Concrete products are kneaded with materials such as cement, aggregate, water, and a dispersant (water reducing agent), placed in various molds, and commercialized through a curing (hardening) process. It is important from the viewpoint of productivity (improving the rotation rate of the formwork) that high strength is developed in the initial age. For this purpose, (1) using early strong cement as cement, (2) admixture Measures are taken such as reducing the amount of water in the cement composition using various polycarboxylic acid compounds, and (3) performing steam curing as a curing method. Today, there is a case where further shortening of the curing process is desired due to demands for higher productivity, for example, it may be necessary to develop a high strength (initial strength) in a curing time of 16 hours. Usually, in the curing process, complicated processes such as a heating work process such as steam are incorporated, but measures for improving the initial strength by changing the design of these processes are not practical methods. Therefore, a method for easily obtaining concrete with high initial strength without changing the process is eagerly desired in the market from the viewpoint of manufacturing cost and the like.

  In addition, the curing time is usually shortened by steam curing, but this leads to a rise in energy costs associated with the use of steam, and from the viewpoint of energy cost reduction (shortening of steam curing time and curing temperature). The above method is eagerly desired.

Patent Document 1 discloses a cement strength improver containing glycerin or a glycerin derivative and a specific polycarboxylic acid copolymer. Patent Document 2 discloses a cement admixture in which a polyether compound that is a dihydric alcohol and a sulfate thereof and a sulfonic acid group-containing copolymer are used in combination. Patent Document 3 discloses polysaccharide sulfate as a cement additive. Patent Documents 2 and 3 suggest that by sulfating the raw polyhydric alcohol, the setting time is shortened (hardens quickly), or the early strength (initial strength) within 16 hours at room temperature is improved. There is no.
JP 2006-282414 A Japanese Patent Laid-Open No. 9-194244 Japanese Patent Laid-Open No. 7-10624

  An object of the present invention is to provide an early strengthening agent for a hydraulic composition that improves initial strength, that is, improves early strength, and also achieves an improvement in initial strength while achieving surface aesthetics. It is providing the additive composition for hydraulic compositions from which the hardened | cured hydraulic composition excellent in (for example) concrete products is obtained.

  The present invention includes (A) one or more selected from (A) dihydric alcohols and alkylene oxide adducts of dihydric alcohols (hereinafter referred to as component (A)) and (B) a sulfating agent (hereinafter referred to as component (B)). Is a fast-acting agent for a hydraulic composition comprising the compound (a) obtained by reacting with the compound (hereinafter referred to as the compound (a)), wherein the compound (a) is 1 mol of the hydroxyl group of the component (A). It is related with the early strengthening agent for hydraulic compositions which is what reacted said (B) component of 0.1-0.9 mol per average.

  The present invention also relates to a hydraulic composition comprising (A) a sulfuric monoester of one or more compounds selected from dihydric alcohols and alkylene oxide adducts of dihydric alcohols (hereinafter referred to as compound (a ′)). It relates to early strength agents.

  Moreover, this invention relates to the additive composition for hydraulic compositions containing the said early strengthening agent of this invention, and a dispersing agent.

  The present invention also relates to a hydraulic composition containing the early strengthening agent of the present invention, a hydraulic powder, an aggregate, and water.

  The present invention also relates to a concrete product containing the early strengthening agent of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the early strength agent for hydraulic compositions which improve initial strength, ie, short-term early strength, and the additive composition for hydraulic compositions using the same are provided. When the early strengthening agent of the present invention is used, the early strength is improved, the working time can be shortened by shortening the curing time, and the productivity is improved. In addition, such effects can be easily obtained without special changes in equipment and processes.

<Compound (a)>
The compound (a) is a compound obtained by reacting the component (A) and the component (B), and is a component (early strong agent) that contributes to improving the early strength. The compound (a) is a sulfate of the component (A) and usually contains the sulfuric acid monoester of the component (A), that is, the compound (a ′). Such a compound (a ′) is a component (early strong agent) that contributes to improvement of early strength. Hereinafter, the compound (a) may include the compound (a ′).

  In addition, among the component (A), the carbon number of the dihydric alcohol is 2 or more, preferably 4 or more. The number of carbon atoms in the compound (A) is preferably 30 or less, more preferably 14 or less, and still more preferably 9 or less. As a more preferable form of the compound (A), the dihydric alcohol does not contain nitrogen and is obtained from a compound composed of three elements of carbon, hydrogen and oxygen. That is, 2-30 are preferable, as for carbon number of a bihydric alcohol among (A) component, 4-14 are more preferable, and 4-9 are still more preferable.

  Examples of the dihydric alcohol include polyvinyl alcohol (having 3 to 20 hydroxyl groups), polyglycidol (having 3 to 20 hydroxyl groups), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, 1, Examples include 2-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like. These can use 1 type (s) or 2 or more types. Among these, in the present invention, diethylene glycol and 1,2-butanediol are preferable as the dihydric alcohol from the viewpoint of short-term and early strength, and diethylene glycol is more preferable.

  As the component (A), an alkylene oxide (hereinafter referred to as AO) adduct of a dihydric alcohol can be used. AO is preferably at least one selected from ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO).

  In the present invention, the component (A) is preferably one or more selected from diethylene glycol and AO adducts of 1,2-butanediol from the viewpoint of short-term rapid strength.

  From the viewpoint of improving the initial strength of concrete, for example, after curing, in-air curing (20 ° C.), strength after 16 hours, that is, the compound (a) improves the short-term early strength (A). An average of 0.1 to 0.9 mol, preferably an average of 0.2 to 0.7 mol, more preferably an average of 0.4 to 0.6 mol of component (B) is reacted with 1 mol of hydroxyl group of the component (sulfuric acid). Compound) is used.

  The degree of sulfation can be used as an index indicating the degree of sulfation of component (A). This degree of sulfation indicates the degree of sulfation of the hydroxyl group of component (A), and is, for example, 2.0 at maximum for ethylene glycol. When two, one, and 0.5 hydroxyl groups on average among the two hydroxyl groups are sulfated, the sulfation degrees are 2.0, 1.0, and 0.5, respectively. The compound (a) has a sulfation degree of 0.5 to 1.5, more preferably 0.5 to 1.0. With the sulfate of component (A) having a sulfation degree of 2.0, the effect of the present invention cannot be obtained.

  In addition, compound (a) is composed of (A) component, compound (sulfuric monoester) in which one hydroxyl group of component (A) is sulfated, and compound (sulfuric acid in which two hydroxyl groups in component (A) are sulfated. Available as a mixture of diesters). In that case, it is preferable that the average sulfation degree of this mixture is 0.5-1.5. That is, the early strengthening agent for a hydraulic composition of the present invention is a sulfate ester mixture containing a sulfate monoester as the component (A), and contains a sulfate ester mixture having a sulfation degree of 0.5 to 1.5. You may do. The proportion of the component (A) in the mixture is preferably 0 to 20% by weight, the proportion of monosulfate is preferably 20 to 60% by weight, and the proportion of diester is preferably 20 to 40% by weight.

Compound (a) can be obtained by reacting component (A) with component (B). The manufacturing method can be performed according to a known method. Examples of the component (B) include sulfuric anhydride such as SO ₃ gas and liquid SO ₃ , sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, anhydrous sulfuric acid / Lewis base complex, and the like. Preferred are anhydrous sulfuric acid such as SO ₃ gas and liquid SO ₃ , and fuming sulfuric acid. Examples of the sulfation method include gas-liquid methods such as a method using sulfuric acid, a method using chlorosulfonic acid, a liquid phase method such as a method using anhydrous sulfuric acid, and a method using gaseous sulfuric anhydride diluted with an inert gas. A mixing method (preferably a method using a thin film sulfation reactor) can be mentioned. A gas-liquid mixing method is preferable from the viewpoint of suppressing the formation of by-products, and a method using gaseous sulfuric anhydride diluted with an inert gas is preferable from the viewpoint of low impurities and excellent economic efficiency.

  The early strengthening agent for a hydraulic composition of the present invention is preferably used so that the amount of the compound (a) added is 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder. That is, the early strengthening agent for a hydraulic composition of the present invention is more preferably used in a proportion of 0.01 to 5 parts by weight of the compound (a) with respect to 100 parts by weight of the hydraulic powder. Preferably it is 0.05-3 weight part, More preferably, it is 0.1-2 weight part.

  The early strengthening agent of the present invention promotes the formation and precipitation of calcium hydroxide derived from alite (C3S) as well as the production of monosulfate of aluminate (C3A) by promoting the dissolution of the gypsum component contained in the cement. It is presumed that That is, it is considered that by hydrating both C3A and C3S, which contribute to early strength, curing is accelerated and early strength is improved.

  Accordingly, a compound in which one or more oxygen atoms selected from a hydroxyl group, an ether group, a carboxyl group and an ester group in one molecule and a calcium ion can form a 2- to 4-dentate coordination structure is preferable.

  The compound (a) of the present invention can be used by mixing with a hydraulic powder or the like at the time of preparing a hydraulic composition in the same manner as a normal early strengthening agent. Alternatively, a hydraulic compound such as a clinker may be pulverized in the presence of the compound (a) to form a hydraulic powder, and a hydraulic composition may be prepared using this.

  The compound (a) of the present invention is usually a phosphate ester polymer, a polycarboxylic acid copolymer, a sulfonic acid copolymer, a naphthalene polymer, a melamine polymer, a phenol polymer, a lignin system. It is preferably used in combination with a component known as a dispersant (concrete admixture) such as a polymer. Suitable combination components are the later-described (C) component and (D) component, more preferably (C) component, or a combination of (C) component and (D) component.

<Additive composition for hydraulic composition>
In the present invention, there can be provided an additive composition for a hydraulic composition containing the early strengthening agent [compound (a)] for the hydraulic composition of the present invention and the dispersant. From the viewpoint of improving the early strength of the cured hydraulic composition, the dispersant is one or more kinds of co-polymers selected from a phosphoric acid ester-based polymer (component (C) described later) and a copolymer (component (D)). Polymers are preferred.

<(C) component>
From the viewpoint of improving the early strength of the cured hydraulic composition, the additive composition for a hydraulic composition of the present invention includes a monomer 1 represented by the following general formula (C1) and the following general formula (C2). ) And the monomer 3 represented by the following general formula (C3) at a pH of 7 or less to obtain a phosphate ester polymer (C) [hereinafter, ( C) ”). Component (C) is a known compound described in JP-A-2006-52381.

[Wherein, R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or —COO (AO) _n X, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, p is the number of 0 or 1, n is the average added mole number of AO, 3 to 200, and X represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

[Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to 12 carbon atoms, m4 is a number of 1 to 30, M is a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom) ). ]

[Wherein, R ⁶ and R ⁸ are each independently a hydrogen atom or a methyl group, R ⁷ and R ⁹ are each independently an alkylene group having 2 to 12 carbon atoms, m5 and m6 are each independently 1 to 30 , M represents a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom). ]

  Component (C) is a phosphate ester polymer obtained by copolymerizing monomer 1 and a mixed monomer including monomer 2 and monomer 3 at a pH of 7 or less.

[Monomer 1]
For monomer 1, R ³ in general formula (C1) is preferably a hydrogen atom, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group (hereinafter referred to as EO group). The EO group is preferably 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all AO are EO groups. X is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12, further 1 to 4, and further 1 or 2, and more preferably a methyl group. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable. Here, n in the general formula (C1) is 3 to 200, preferably 4 to 120, from the viewpoint of the dispersibility of the polymer in the hydraulic composition and the effect of imparting low viscosity. In addition, AO is different among n repeating units on average, and random addition, block addition, or a mixture thereof may be included. AO can contain a propyleneoxy group etc. besides EO group.

[Monomer 2]
Examples of the monomer 2 include phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid mono (2-hydroxyethyl) acrylic acid ester, polyalkylene glycol mono (meth) acrylate acid phosphoric acid ester, and the like. Of these, mono (2-hydroxyethyl) methacrylic acid phosphate is preferable from the viewpoint of ease of production and product quality stability.

[Monomer 3]
Examples of the monomer 3 include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product.

  Either monomer 2 or monomer 3 may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or the like of these compounds.

  From the viewpoint of dispersibility, m4 of monomer 2 and m5 and m6 of monomer 3 are each preferably 1 to 20, more preferably 1 to 10, and more preferably 1 to 5.

  As the monomer 2 and the monomer 3, a mixed monomer containing these can be used. That is, a commercially available product containing a monoester form and a diester form can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical), JAMP514, JAMP514P, JMP100 (all are Johoku Chemical), Light Ester P -1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich Reagent), etc. are available.

  The phosphate ester polymer as the component (C) of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. Moreover, it is preferable that Mw / Mn is 1.0-2.6. Here, Mn is the number average molecular weight. Mw is preferably 10,000 or more, more preferably 12,000 or more, still more preferably 13,000 or more, still more preferably 14,000 or more, and even more preferably 15 from the viewpoint of the expression of the dispersion effect and the viscosity reduction effect. 15,000 or less, preferably 150,000 or less, more preferably 130,000 or less, and still more preferably 120,000 from the viewpoints of high molecular weight by crosslinking, suppression of gelation, and performance in terms of dispersion effect and viscosity reduction effect. Or less, more preferably 110,000 or less, still more preferably 100,000 or less. Therefore, from the viewpoints of the both, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, More preferably, 14,000 to 110,000, still more preferably 15,000 to 100,000. A. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, the value of Mw / Mn represents the degree of dispersion of the molecular weight distribution, and the closer to 1, the closer the molecular weight distribution to monodispersion, and the farther from 1 (larger), the wider the molecular weight distribution.

  The phosphate ester polymer according to the present invention having the above Mw / Mn value is a polymer having a branched structure based on a diester structure, but has a great feature that the molecular weight distribution is very narrow. Such a phosphoric ester polymer of the present invention can be suitably produced by a production method described later.

  The Mw / Mn of the phosphate ester polymer according to the present invention as described above is 1.0 from the viewpoint of ensuring practical production ease, dispersibility, viscosity reduction effect, and versatility with respect to materials and temperature. From the viewpoint of achieving both dispersibility and viscosity reducing effect, it is 2.6 or less, preferably 2.4 or less, more preferably 2.2 or less, still more preferably 2.0 or less, and still more preferably. From the viewpoint of combining the above two points, it is preferably 1.0 to 2.4, more preferably 1.0 to 2.2, still more preferably 1.0 to 2.0, and still more. Preferably it is 1.0-1.8.

  Mw and Mn of the phosphate ester polymer according to the present invention are those measured by gel permeation chromatography (GPC) method described in JP-A-2006-52381. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer.

  The phosphate ester polymer satisfying Mw / Mn as described above has an appropriate branched structure by suppressing cross-linking by the monomer 3 which is a diester body, and has a structure in which adsorbing groups are densely present in the molecule. It is thought to form. Further, since the degree of dispersion Mw / Mn is controlled within a predetermined range, it approaches a system in which molecules of the same size are monodispersed, so that it is considered possible to increase the amount of adsorption on the adsorption target substance (for example, cement particles). Satisfying both of these conditions makes it possible to densely pack the substance to be adsorbed, such as cement particles, and is estimated to be effective in achieving both a dispersibility and a viscosity reducing effect.

  Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area having a molecular weight of 100,000 or more is 5% or less of the total area of the chart, so that dispersibility (required addition amount reduction) It is more preferable in terms of the viscosity reducing effect.

In addition, since the double bond derived from a monomer has disappeared by ¹ H-NMR under the following conditions, the phosphate ester polymer according to the present invention is derived from monomers 1, 2, and 3, respectively. It is estimated that it has a constitutional unit.
[ ¹ H-NMR conditions]
The polymer dissolved in water which was vacuum dried and dissolved in heavy methanol at a concentration of 3-4 wt.%, Measured by ¹ H-NMR. The residual rate of double bonds is measured by an integrated value of 5.5 to 6.2 ppm. In addition, the measurement of ¹ H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 s, and the measurement temperature is 25.0 ° C. Performed under conditions.

  That is, the phosphoric acid ester-based polymer having the Mw / Mn value as described above has, as its constituent units, constituent units derived from monomer 1, constituent units derived from monomer 2, and constituents derived from monomer 3. Includes units. These structural units are structural units derived from the respective monomers incorporated into the polymer by cleavage of the ethylenically unsaturated bonds of the monomers 1, 2 and 3 and addition polymerization. The ratio of these structural units in the polymer depends on the charging ratio, and when the monomers used for copolymerization are only monomers 1 to 3, the molar ratio of each structural unit is the monomer charging molar ratio. It is thought that it is almost the same.

<< Production Method of Phosphate Ester Polymer >>
(C) component can be manufactured by a well-known method. For example, a method described in JP 2006-52381 A can be mentioned.

  In this invention, (C) component can use 2 or more types, and also 3 or more types. The criterion for selecting a plurality of components (C) depends on the composition, constituent materials, performance, etc. of the hydraulic composition. For example, the ratio of the monomer 1 represented by the general formula (C1) is in the total amount of monomers. A combination containing 1 to 55 mol% of the copolymer (C1a) and a copolymer (C1b) in which the ratio of the monomer 1 is more than 55 mol% in the total amount of the monomers is desirable. Furthermore, in the case where a third copolymer is selected in addition to (C1a) and (C1b), that is, when three types of copolymers are used in total, (C1b) should be two types. Preferably, one of (C1b) (second copolymer) is a copolymer in which the proportion of monomer 1 is more than 55 mol% and not more than 65 mol% in the total amount of monomers, (C1b) The other (third copolymer) is preferably a copolymer in which the proportion of monomer 1 is more than 65 mol% in the total amount of monomers.

<(D) component>
The additive composition for a hydraulic composition of the present invention can contain a specific copolymer as the component (D) from the viewpoint of improving the early strength of the cured hydraulic composition. As the component (D), an admixture containing the component (D), for example, one that can be obtained as a dispersant for a hydraulic composition can be used.

  The component (D) is represented by the monomer (A) represented by the following general formula (D1-1), the monomer represented by the following general formula (D1-2), and the following general formula (D1-3). A copolymer containing a monomer (b) selected from the monomers as a constituent unit.

[Where,
R ¹³ , R ¹⁴ : hydrogen atom or —CH ₃
R ¹⁵ : hydrogen atom or —COO (AO) _n X
A ² : an alkylene group having 2 to 4 carbon atoms
X ¹ : a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
m ': number from 0 to 2
n ': Number from 2 to 300
p ': The number of 0 or 1 is shown. ]

[Where,
R ¹⁶ , R ¹⁷ , R ^18, which may be the same or different, are a hydrogen atom, —CH ₃ or (CH ₂ ) _r COOM ² , and (CH ₂ ) _r COOM ² is COOM ¹ or another (CH ₂ ) _r COOM ² and anhydride may be formed, in which case M ¹ and M ² of those groups are not present.
M ¹ and M ^{2 are each a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group, or a substituted alkylammonium group r: a number of 0 to 2. ]

[Where,
R ¹⁹ : hydrogen atom or —CH ₃
Z ^{1 represents a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group or a substituted alkyl ammonium group. ]

The n ′ alkylene glycols A ² O in the formula (D1-1) may be the same or different, and when they are different, random addition or block addition may be used.

  Considering the polymerization efficiency of the polyalkylene glycol, the number of added moles n ′ needs to be 300 or less, preferably 150 or less, and more preferably 130 or less. From the viewpoint of cement dispersibility, it is 2 to 300 mol.

Specific examples of the monomer (A) include (half) esterified products of polyalkylene glycols with one-terminal lower alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropylene glycol, (meth) acrylic acid and maleic acid. And ether compounds with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, ethylene oxide and propylene oxide adducts to (meth) allyl alcohol are preferably used, and in general formula (D1-1) R ¹⁵ is preferably a hydrogen atom, and p ′ = 1 and m ′ = 0 are preferable. The alkylene oxide (A ² O group in the formula (D1-1)) is preferably an oxyethylene group. More preferred are alkoxy, and still more preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid.

  As monomers represented by the formula (D1-2), unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid Monomers or salts thereof such as alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and the like can be mentioned, and (meth) acrylic acid or alkali metal salts thereof are preferable.

  Examples of the monomer represented by the formula (D1-3) include (meth) allylsulfonic acid or a salt thereof such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an amine salt.

  As the monomer (b), it is more preferable to use only the monomer represented by the formula (D1-2) from the viewpoint of controlling the molecular weight of the copolymer.

  The total amount of the monomer (A) and the monomer (B) in the monomer mixture constituting the component (D) is preferably 50% by weight or more, more preferably 80% by weight or more, and further preferably 100% by weight. Examples of the copolymerizable monomer other than the monomer (i) and the monomer (b) include acrylonitrile, (meth) acrylic acid alkyl ester, (meth) acrylamide, and styrene sulfonic acid.

  (D) component can be manufactured by a well-known method. For example, there is a solution polymerization method disclosed in JP-A No. 11-157877. In the presence of a polymerization initiator such as ammonium persulfate or hydrogen peroxide in water or a lower alcohol having 1 to 4 carbon atoms, if necessary, sodium sulfite or What is necessary is just to add mercaptoethanol etc. and to make it react at 50-100 degreeC for 0.5 to 10 hours.

  The component (D) preferably has a weight average molecular weight (gel permeation chromatography method / standard substance sodium polystyrene sulfonate equivalent / water system) in the range of 10,000 to 10,000, more preferably 10,000 to 80,000.

  In addition, when using the dispersing agent for hydraulic compositions containing (D) component, this dispersing agent becomes (D) component, Preferably it is 1-50 weight%, More preferably, it is 10-40 weight%, More preferably Contains 20-30% by weight. The component (D) is preferably 10 to 45% by weight, more preferably 10 to 40% by weight, more preferably 20 to 30% by weight in the hydraulic composition additive composition of the present invention. It is preferable to use the dispersant so that In general, the balance of the dispersant is water, an antifoaming agent, and other components.

  In the additive composition for a hydraulic composition of the present invention, the content of the compound (a) is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 30% by weight. is there. 5% by weight or more is preferable from the viewpoint of improvement of demolding strength, that is, improvement of early strength, and 95% by weight or less is preferable from the viewpoint of uniform stabilization of the product.

  In the additive composition for a hydraulic composition of the present invention, the amount of the compound (a) added is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder. That is, the additive composition for hydraulic composition of the present invention is preferably used in a proportion of 0.01 to 5 parts by weight of compound (a) with respect to 100 parts by weight of hydraulic powder. Preferably it is 0.05-3 weight part, More preferably, it is 0.1-2 weight part.

  In the additive composition for hydraulic compositions of the present invention, the content of the component (C) is preferably 5% by weight or more from the viewpoint of lowering the mortar viscosity, and 50% by weight from the viewpoint of uniform stabilization of the product. The following is preferred. That is, it is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and more preferably 20 to 35% by weight.

  In addition, the additive composition for hydraulic composition of the present invention has a ratio of component (C) of 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder from the viewpoint of fluidity of the concrete. It is preferably used, more preferably 0.1 to 5 parts by weight, more preferably 0.2 to 1 part by weight.

  Moreover, in the additive composition for hydraulic compositions of the present invention, the weight ratio of the total amount of the compound (a) to the total amount of the component (C) is (C) / (a) = 15 from the viewpoint of early strength. It is preferably / 85 to 96/4, more preferably 25/75 to 80/20, and even more preferably 50/50 to 80/20.

  Moreover, in the additive composition for hydraulic compositions of the present invention, from the viewpoint of easy handling of the product, the total content of the compound (a) and the component (C) is 10 to 100% by weight in the composition. It is preferably 10 to 60% by weight, more preferably 20 to 40% by weight.

  Moreover, the additive composition for hydraulic compositions of the present invention is 0.1 to 0.1 in total of the components (a) and (C) with respect to 100 parts by weight of the hydraulic powder from the viewpoint of early strength. It is preferably used at a ratio of 10 parts by weight, more preferably 0.2 to 5 parts by weight, and still more preferably 0.2 to 1 part by weight.

  Moreover, when the additive composition for hydraulic compositions of this invention contains (D) component, (D) component is 0 with respect to 100 weight part of hydraulic powder from a viewpoint of the fluidity | liquidity improvement of concrete. It is preferably used in a ratio of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 1 part by weight.

  Moreover, when the additive composition for hydraulic compositions of the present invention contains the component (D), the total content of the component (C) and the component (D) in the composition from the viewpoint of improving the fluidity of the concrete. The amount is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In that case, the weight ratio of the component (C) and the component (D) is preferably (D) / (C) = 1/100 to 80/100. In this weight ratio, the upper limit value occupied by the component (D) is preferably (D) / (C) = 65/100, more preferably 40/100, and even more preferably 25/100. On the other hand, the lower limit occupied by the component (D) is preferably (D) / (C) = 3/100, more preferably 10/100.

  The additive composition for a hydraulic composition of the present invention can be used for various inorganic hydraulic powders that exhibit curability by a hydration reaction, including various cements. The additive composition for hydraulic composition of the present invention may be in the form of powder or liquid. In the case of a liquid form, those using water as a solvent or a dispersion medium (such as an aqueous solution) are preferable from the viewpoint of workability and reduction of environmental load.

  Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214). As hydraulic powder other than cement, blast furnace slag, fly ash, silica fume and the like may be included, and non-hydraulic limestone fine powder and the like may be included. Silica fume cement or blast furnace cement mixed with cement may be used.

  The additive composition for hydraulic compositions of the present invention can also contain other additives. For example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfate (salt) ), Polyoxyalkylene alkyl (phenyl) ether phosphates (salts), protein materials, AE agents such as alkenyl succinic acid and α-olefin sulfonate; oxy such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid Delayers such as carboxylic acids, dextrins, monosaccharides, oligosaccharides, polysaccharides, etc .; foaming agents; thickeners; silica sand; AE water reducing agents; calcium chloride, calcium nitrite, calcium nitrate , Cal bromide Soluble calcium salts such as um, calcium iodide, chlorides such as iron chloride and magnesium chloride, sulfates, potassium hydroxide, sodium hydroxide, carbonates, thiosulfates, formic acid (salts), alkanolamines, etc. Strongening agent or accelerator; foaming agent; waterproofing agent such as resin acid (salt), fatty acid ester, oil, fat, silicone, paraffin, asphalt, wax; blast furnace slag; fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester Anti-foaming agents such as mineral oils, fats and oils, oxyalkylenes, alcohols and amides; antifoaming agents; fly ash; high-performance water reducing agents such as melamine sulfonic acid formalin condensates and aminosulfonic acids; silica fume Rust preventives such as nitrite, phosphate, zinc oxide; cellulose such as methylcellulose and hydroxyethylcellulose; Water-based systems such as natural products such as β-type, β-1,3-glucan, xanthan gum, synthetic systems such as polyacrylic acid amide, polyethylene glycol, ethylene oxide adduct of oleyl alcohol or a reaction product thereof with vinylcyclohexene diepoxide Polymer emulsions such as alkyl (meth) acrylates. These components may be blended in the dispersant for hydraulic composition.

  In addition, the additive composition for hydraulic composition of the present invention is used in the field of ready-mixed concrete, concrete vibration products, for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, It is useful in any field of various concrete such as repair, prepacked, torme, ground improvement, grout, and cold.

<Hydraulic composition>
The present invention provides a hydraulic composition containing the early strengthening agent for hydraulic composition or the additive composition for hydraulic composition of the present invention, a hydraulic powder, and water.

  The hydraulic composition of the present invention is paste, mortar, concrete or the like containing water and hydraulic powder (cement), but may contain 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).

  The hydraulic composition has a water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the slurry, usually abbreviated as W / P. Abbreviated as / C. ] Is preferably 65% by weight or less, more preferably 60% by weight or less, further 55% by weight or less, and even more preferably 50% by weight or less. Moreover, 20 weight% or more, Furthermore 30 weight% or more is preferable. Accordingly, the range of W / P is preferably 20 to 65% by weight, more preferably 20 to 60% by weight, further 30 to 55% by weight, and still more preferably 30 to 50% by weight.

  Moreover, the hydraulic composition of this invention can contain a dispersing agent further as needed. Examples of the dispersant include dispersants such as the components (C) and (D) or known dispersants. In the present invention, it is preferable to use the component (C) and the component (D) in combination.

  A preferable combination of the component (C) and the component (D) may be the same as the preferable aspect in the additive composition for hydraulic composition. Therefore, this invention provides the manufacturing method of the hydraulic composition which mix | blends the additive composition for hydraulic compositions of this invention, and water with hydraulic powder and an aggregate.

  The present invention also includes the early strengthening agent for hydraulic composition or the additive for hydraulic composition of the present invention, a hydraulic powder, water, and, if necessary, an aggregate and / or a dispersing agent. The contained hydraulic composition can be cured to produce a concrete product. The concrete product containing the early strengthening agent of the present invention can be produced without the need for energy such as steam heating, and is excellent for the environment because it improves productivity.

<Used ingredients>
(1) Compound (a)
As the compound (a), the compounds a-1 and a-2 obtained in the following Production Examples 1 and 2, respectively, were used.

Production Example 1 [Production of diethylene glycol sulfate (a-1) (degree of sulfation 1.0)]
Using a thin-film sulfation reactor (inner diameter: 14 mmφ, length: 4 m), diethylene glycol (DEG) was SO ₃ concentration of about 1% by volume (diluted with air), reaction molar ratio [SO ₃ /DEG]=1.0 Sulfation was carried out at a temperature of 34 to 64 ° C. (SO ₃ was 0.5 mol per mol of hydroxyl group of DEG). 553.2 g (acid value: 310.8 mg KOH / g) of the obtained sulfate was added to 1070.7 g in an 8.7 wt% aqueous sodium hydroxide solution, the pH of the aqueous solution was adjusted, and DEG sulfate (a-1 ) (Sulfation degree 1.0) was obtained. The aqueous solution had a pH of 12.1, a volatile content of 70.5% by weight, and sodium sulfate of 0.1% by weight or less. Absorption based on the sulfate ester bond was confirmed to be 1224 cm ⁻¹ in the infrared absorption spectrum analysis of the nonvolatile content.

Production Example 2 [Production of 1,2-butanediol EO average 1-mole adduct sulfate (a-2) (sulfation degree 1.0)]
(1) 1,2-butanediol EO average 1-mole adduct 223.5 g and 1.4 g of 1,2-butanediol and KOH were charged in an autoclave equipped with a 2-liter stirrer and stirred at about 600 rpm. After the inside of the system was replaced with nitrogen, the temperature was raised to 155 ° C. 109.1 g of ethylene oxide (hereinafter referred to as EO) at a pressure of 0.1 to 0.3 MPa (gauge pressure) and a temperature of 155 ° C. (corresponding to 1 mol of EO with respect to 1 mol of 1,2-butanediol). Introduced. After the introduction of a predetermined amount of EO, no pressure drop was observed (after completion of the reaction), the temperature was cooled to 80 ° C., and 334 g of 1,2-butanediol EO average 1 mol adduct was obtained.

(2) 1,2-butanediol EO average 1 mol adduct sulfate (a-2)
The 1,2-butanediol EO average 1-mole adduct obtained in (1) was diluted with air using a thin-film sulfation reactor (inner diameter: 14 mmφ, length: 4 m) with an SO ₃ concentration of about 1 vol%. ), Reaction molar ratio [SO ₃ / 1,2-butanediol EO average 1 mol adduct] = 1.0 (SO ₃ is 0.5 per mol of hydroxyl group of 1,2-butanediol EO average 1 mol adduct) Mol), and sulfated at a temperature of 35-60 ° C. 532.4 g of the obtained sulfate (acid value: 262 mgKOH / g) was added to 1864 g in a 5.3 wt% aqueous sodium hydroxide solution, the pH of the aqueous solution was adjusted, and 1 mol of 1,2-butanediol EO was added in an average of 1 mol. An aqueous solution of the product sulfate (a-2) (sulfation degree 1.0) was obtained. The aqueous solution had a pH of 8.5, a volatile content of 75.5% by weight, and sodium sulfate of 0.1% by weight or less. Absorption based on the binding of sulfate ester was confirmed at 1217 cm ⁻¹ in infrared absorption spectrum analysis of the nonvolatile content.

(2) Comparative compound As a comparative compound, the compound obtained in the following Comparative Production Example 1 was used.
Comparative production example 1 [production of DEG sulfate (sulfation degree 2.0)]
To 730.9 g of N, N-dimethylformamide (DMF), 80.1 g (1.00 mol) of liquid SO _{3 was} added dropwise at 0 ° C. over 1 hour with stirring. Further, 53.1 g (0.5 mol) of DEG was dropped over 30 minutes (1.0 mol of SO ₃ per mol of hydroxyl group of DEG). After completion of dropping, the temperature was raised to 10 ° C. and stirred for 1 hour. 200.0 g of ion-exchanged water was poured into the reaction mixture, and neutralized with 131 g (1.05 mol) of a 32 wt% aqueous sodium hydroxide solution. N, N-dimethylformamide (DMF) was distilled off using a rotary evaporator, and ion exchange water was further added to obtain 840.6 g of a reaction product. Unreacted DEG was extracted with a solvent (methanol / hexane = 2/1) to obtain an aqueous solution of DEG sulfate (sulfation degree 2.0). The aqueous solution had a pH of 11.0, a volatile content (105 ° C., 2 hours) of 80.1% by weight, and sodium sulfate of 1.2% by weight. Absorption based on the binding of sulfate ester was confirmed at 1217 cm ⁻¹ in infrared absorption spectrum analysis of the nonvolatile content.

(3) Component (C) As the component (C), copolymers C-1 and C-2 obtained in the following Production Examples C-1 and C-2 were used.

[Production Example C-1] (Production of Copolymer C-1)
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 395 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 261 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), Phosmer M [mixture of 2-hydroxyethyl methacrylate monophosphate and 2-hydroxyethyl methacrylate diphosphate, Uni Chemical Co., Ltd.] 67.3 g and a solution of 4.3 g of mercaptopropionic acid mixed in 141 g of water and a solution of 8.0 g of ammonium persulfate dissolved in 45 g of water over 1.5 hours each. It was dripped in the said reaction container. Thereafter, the mixture was aged for 1 hour, and a solution prepared by dissolving 1.8 g of ammonium persulfate in 10 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 the aging, the mixture was cooled to 40 ° C. or less and then neutralized with 66 g of a 30% sodium hydroxide solution to obtain a copolymer C-1 having a molecular weight of 37,000. Then, it adjusted to 20% of solid content using ion-exchange water.

[Production Example C-2] (Production of Copolymer C-2)
355 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 509 g of 60% by weight of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 120: aqueous solution of 97% ester purity), Phosmer M [mixture of 2-hydroxyethyl methacrylate monophosphate and 2-hydroxyethyl methacrylate diphosphate Unichemical Co., Ltd.] 35.6 g and a solution of 2.0 g of mercaptopropionic acid mixed and a solution of 2.9 g of ammonium persulfate dissolved in 45 g of water, It was dripped in the reaction vessel. Thereafter, aging was performed for 1 hour, and a solution obtained by dissolving 0.6 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 then neutralized with 35.0 g of a 30% sodium hydroxide solution to obtain a copolymer C-2 having a molecular weight of 48,000. Then, it adjusted to 20% of solid content using ion-exchange water.

(4) (D) Component As the (D) component, copolymers D-1 to D-5 obtained in the following Production Examples D-1 to D-5 were used.

[Production Example D-1] (Production of Copolymer D-1)
Into a glass reaction vessel (four-necked flask) equipped with a stirrer, 141 g of water was charged, and purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 60% by weight 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.) 25.9 g, and mercaptopropionic acid 1 Two solutions, a solution in which .96 g was mixed and dissolved, and a solution in which 3.82 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 1.53 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 then neutralized with 19.4 g of 48% sodium hydroxide solution to obtain a copolymer D-1 having a weight average molecular weight of 70000. Then, it adjusted to 20% of solid content using ion-exchange water.

[Production Example D-2] (Production of Copolymer D-2)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 333 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 300 g of ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), 69.7 g of methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.), and 6.3 g of mercaptopropionic acid A solution prepared by mixing and dissolving 200 g of water in 200 g of water and a solution prepared by dissolving 12.3 g of ammonium persulfate 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 4.9 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 then neutralized with 50.2 g of a 48% sodium hydroxide solution to obtain a copolymer D-2 having a weight average molecular weight of 43,000. Then, it adjusted to 20% of solid content using ion-exchange water.

[Production Example D-3] (Production of Copolymer D-3)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 145 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 230 g of 70% aqueous solution of ω-methoxypolyethylene glycol monoacrylate (average number of added moles of ethylene oxide 23: NK ester AM230G manufactured by Shin-Nakamura Chemical Co., Ltd.), acrylic acid (reagent: Wako Pure Chemical Industries, Ltd. purity: 99%) 32. 1 g of the mixed solution, a solution in which 1.44 g of mercaptopropionic acid was mixed and dissolved in 28.6 g of water, and a solution in which 1.34 g of ammonium persulfate was dissolved in 13.4 g of water each took 1.5 hours. Then, it was dropped into the reaction vessel. Further, a solution prepared by dissolving 0.67 g of ammonium persulfate in 6.7 g of water was dropped over 30 minutes, and then aged for 1 hour. 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 then neutralized with 53 g of 40% sodium hydroxide solution to obtain a copolymer D-3 having a weight average molecular weight of 43,000. Then, it adjusted to 20% of solid content using ion-exchange water.

[Production Example D-4] (Production of Copolymer D-4)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 225 g of water and 300 g of polyoxyethylene (average added mole number of ethylene oxide: 30) allyl ether, and purged with nitrogen while stirring, up to 80 ° C. in a nitrogen atmosphere. The temperature rose. A solution in which 47.4 g of maleic acid (reagent: Wako Pure Chemical Industries, Ltd. purity: 99%) and 3.7 g of mercaptopropionic acid are mixed and dissolved in 137 g of water, and a solution in which 7.1 g of ammonium persulfate is dissolved in 90 g of water The two were dropped into the reaction vessel over 2.5 hours. Thereafter, the mixture was aged for 2 hours, and a solution obtained by dissolving 2.8 g of ammonium persulfate in 45 g of water was added dropwise over 60 minutes, followed by aging for 2 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 26.6 g of 48% sodium hydroxide solution to obtain a copolymer D-4 having a weight average molecular weight of 31,000. Then, it adjusted to 20% of solid content using ion-exchange water.

[Production Example D-5] (Production of Copolymer D-5)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 406 g of a 65% aqueous solution of polyoxyethylene (average number of moles of ethylene oxide added 100) allyl ether, and the temperature was raised to 65 ° C. 20.1 g of a 2% aqueous hydrogen peroxide solution was added dropwise thereto. After dropping, 38.4 g of acrylic acid was dropped over 3.0 hours, and at the same time 1.26 g of 3-mercaptopropionic acid (Sigma Aldrich Japan Co., Ltd., reagent), 0.52 g of L-ascorbic acid, ion-exchanged water 33 A monomer solution in which 0.8 g was mixed and dissolved was dropped over 3.5 hours. After completion of the dropwise addition, the reaction was terminated by maintaining 65 ° C. for 1 hour. Then, it neutralized with 20% sodium hydroxide aqueous solution, and the copolymer D-5 with a weight average molecular weight 60000 was obtained. Then, it adjusted to 20% of solid content using ion-exchange water.

<Preparation and evaluation of mortar>
(1) Preparation of mortar Under the mixing conditions shown in Table 1, using a mortar mixer (all-purpose mixing stirrer manufactured by Dalton Co., Ltd. Model: 5DM-03-γ), cement (C) and fine aggregate (S) It is added and kneaded for 10 seconds, and contains an additive composition for hydraulic composition (used as an aqueous solution with a solid content of 25% by weight) so that the target slump is 21 ± 1 cm and the target air entrainment amount is 2 ± 1%. Kneading water (W) was added, and this kneading was performed for 60 seconds at a low speed rotation and further for 120 seconds at a high speed rotation. The addition amount (% by weight) of the compound (a), other components, and the dispersant (effective component concentration) with respect to the cement weight is as shown in Table 2, and added to the kneading water so that the addition amount shown in Table 2 is obtained. Used.

Cement (C): ordinary Portland cement (ordinary Portland cement of Taiheiyo Cement Co., Ltd./ordinary Portland cement of Sumitomo Osaka Cement Co., Ltd. = 1/1, weight ratio), density 3.16 g / cm ³
-Fine aggregate (S): produced in Jyoyo, mountain sand, FM = 2.67, density 2.56 g / cm ³
・ Water (W): Tap water

(2) Mortar evaluation The mortar was evaluated for demolding strength and slump flow according to the test methods shown below. The evaluation results are shown in Table 2.

(2-1) Evaluation of Demolding Strength Based on JIS A 1132, a cylindrical plastic mold (bottom diameter: 5 cm, height: 10 cm) is filled with mortar by a two-layer filling method, and the interior is 16 in a room at 20 ° C. A specimen subjected to curing in air (20 ° C.) for a time was prepared, and the compressive strength of the specimen was measured based on JIS A 1108. In addition, about the compressive strength of each example, the relative value with respect to the intensity | strength of Comparative Example 1-1 was written together in Table 2 as intensity ratio (%).

(2-2) Evaluation of slump flow The mortar prepared by the above method was immediately packed in two layers in the flow cone based on JIS R 5201, the flow cone was correctly removed upward, and the direction recognized as the maximum, The length in the direction perpendicular to this was measured. Note that the falling motion described in JIS R 5201 is not performed.

  In the table, the addition amount is an addition amount (parts by weight) based on the effective amount of each component relative to 100 parts by weight of cement. In addition, "reaction mole number of (B) component" in the diethylene glycol sulfate of Comparative Example 1-3 is the reaction mole number of (B) component per mole of hydroxyl group of (A) component.

Claims (7)

  (A) An early strengthening agent for a hydraulic composition comprising a compound (a) obtained by reacting at least one selected from dihydric alcohols and alkylene oxide adducts of dihydric alcohols with (B) a sulfating agent. An early strengthening agent for a hydraulic composition, wherein the compound (a) is obtained by reacting an average of 0.1 to 0.9 mol of the (B) per 1 mol of the hydroxyl group of the (A).   (A) An early strengthening agent for a hydraulic composition containing a sulfuric monoester of one or more compounds selected from dihydric alcohols and alkylene oxide adducts of dihydric alcohols.   The early strengthening agent for hydraulic composition according to claim 1 or 2, wherein (A) is at least one compound selected from diethylene glycol and an alkylene oxide adduct of 1,2-butanediol.   The additive composition for hydraulic compositions containing the early hardening agent for hydraulic compositions of any one of Claims 1-3, and a dispersing agent.   The hydraulic composition containing the early strengthening agent for hydraulic compositions of any one of Claims 1-3, hydraulic powder, an aggregate, and water.   Furthermore, the hydraulic composition of Claim 5 containing a dispersing agent.   The concrete product containing the early strengthening agent for hydraulic compositions of any one of Claims 1-3.