JP2011162400A - Additive composition for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive composition for a hydraulic composition which is free from the deterioration of the flowability of the hydraulic composition and improving short age strength or initial strength without curing after kneading. <P>SOLUTION: The additive composition for hydraulic composition contains glycerol, one or more kinds of inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates and a naphthalene-based dispersant, in which the molar ratio (glycerol)/(inorganic salt A) of glycerol to the inorganic salt A is (5/95) to (55/45). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Concrete products are kneaded with materials such as cement, aggregate, water, and a dispersant, placed in various molds, and commercialized through a curing (hardening) process. It is important to develop high strength in the initial age from the viewpoint of improving the productivity, that is, the rotation rate of the formwork. For that 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, and for example, it may be necessary to develop high strength in a curing time of 16 hours in the manufacture of concrete products. . Usually, in the curing process, a complicated process such as a heating work process such as steam is incorporated, but it is difficult to improve the initial strength by changing these processes. Therefore, a method for easily obtaining a concrete product with high initial strength without changing the process is desired in the market from the viewpoint of manufacturing cost and the like.

  Usually, the curing time of steam curing is shortened, but steam curing leads to a rise in energy costs associated with the use of steam, and steam curing is performed from the viewpoint of reducing energy costs and considering the global environment. There is no longing for a way.

  Patent Document 1 discloses a hardening accelerator such as calcium nitrate and calcium nitrite as a hardening-promoting admixture that shortens the hardening time of a hydraulic cement composition at low temperatures without inducing or promoting corrosion of a steel reinforcement. Admixtures consisting of C2 to C6 glycol components present in an amount effective to increase the cure promoting properties of the components and cure accelerator components are described. Patent Document 2 discloses a method of using untreated glycerin containing 1 to 10% by weight of an alkali metal inorganic salt as a cement additive in order to improve the compressive strength of cement.

JP-A-6-199555 Special table 2008-519752 gazette

  An object of the present invention is to prepare a hydraulic composition such as a concrete product in about 8 hours after preparation without preparing the hydraulic composition without curing the hydraulic composition without reducing the fluidity of the hydraulic composition. It is to provide an additive composition for a hydraulic composition that improves the strength of a cured product, that is, improves short-term early strength, and is excellent in surface aesthetics while achieving such improvement in initial strength. It is providing the additive composition for hydraulic compositions from which a concrete product etc. can be obtained.

  The present invention contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene dispersant, and the molar ratio of glycerin and inorganic salt A is glycerin / inorganic. It is related with the additive composition for hydraulic compositions which is 5 / 95-55 / 45 in salt A.

  The present invention also includes glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, naphthalene dispersants, hydraulic powders, aggregates, and water. It is related and it is related with the hydraulic composition whose molar ratio of glycerol and inorganic salt A is 5 / 95-55 / 45 by glycerol / inorganic salt A.

  The present invention also provides a hydraulic powder, aggregate, water, glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene dispersant. Adding glycerin and inorganic salt A so that the molar ratio of glycerin / inorganic salt A is 5/95 to 55/45, preparing a hydraulic composition, and forming the obtained hydraulic composition into a formwork And a step of removing the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition, starting the preparation of the hydraulic composition and then removing the mold It is related with the manufacturing method of the hardening body of the hydraulic composition whose time until it is 4 to 10 hours.

According to the present invention, the strength is improved in a short time after the preparation of the hydraulic composition without reducing the fluidity of the hydraulic composition, for example, about 8 hours after preparing the concrete, preferably 7 N / mm ^2. As described above, an additive composition for a hydraulic composition that provides a strength of 8 N / mm ² or more, that is, improves short-term early strength, is provided. When the additive composition of the present invention is used, the short-term strength is improved, the working time can be shortened by shortening the curing time, and the productivity of the concrete product is improved. In addition, such effects can be obtained without any special changes in equipment and processes at the concrete product manufacturing site.

<Additive composition for hydraulic composition>
The additive composition for a hydraulic composition of the present invention contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene-based dispersant. The molar ratio of the inorganic salt A is 5/95 to 55/45 in terms of glycerin / inorganic salt A, and preferably 10/90 to 50/50, more preferably 20/50, from the viewpoint of improving short-term strength of the hydraulic composition. It is 80-50 / 50, More preferably, it is 25 / 75-40 / 60. When two or more inorganic salts A are used, the molar ratio is calculated by setting the total number of moles of each inorganic salt as the number of moles of the inorganic salt A. By using glycerin and inorganic salt A in a molar ratio within this range, for example, improving the short-term strength, for example, the strength of the cured hydraulic composition in about 8 hours after preparing concrete without including a steam curing step Can do.

The inorganic salt A is preferably an alkali metal sulfate from the viewpoint of improving the short-term early strength of the hydraulic composition. The inorganic salt A may take the form of a hydrate. For the weight and the like when using the inorganic salt A in the form of a hydrate, a value converted to an anhydride is used. Examples of the alkali metal constituting the salt include sodium, potassium, and lithium, and sodium and lithium are preferable from the viewpoint of improving the short-term strength of the hydraulic composition. As the inorganic salt A, sodium sulfate (Na ₂ SO ₄ ), potassium sulfate (K ₂ SO ₄ ), lithium sulfate (Li ₂ SO ₄ ), sodium thiosulfate (Na ₂ S ₂ O ₃ ), potassium thiosulfate (K ₂ S ₂ O ₃ ) and lithium thiosulfate (Li ₂ S ₂ O ₃ ). Among these, sulfates are preferable, and inorganic salts selected from sodium sulfate and lithium sulfate are more preferable.

  Although the mechanism of manifestation of the effect of the present invention is unknown, it is considered that strength is expressed early by the synergistic action of glycerin and inorganic salt A. Moreover, when glycerin and inorganic salt A express intensity | strength, it is thought that these do not inhibit the fluidity | liquidity provision effect by a naphthalene type dispersing agent. Specifically, in the initial curing of the hydraulic composition, generation of ettringite of aluminate (C3A) by promoting dissolution of gypsum components contained in the composition, and generation of calcium hydroxide derived from alite (C3S) It is considered that glycerin mainly acts on the formation of ettringite and inorganic salt A acts on the formation and precipitation of calcium hydroxide. Reflecting this, it was observed that the ratio of ettringite formation and calcium hydroxide formation, which gives a cured product with high initial strength, was governed by the optimum ratio of glycerin / inorganic salt A. Since naphthalene-based dispersants have sulfonic acid groups, they adsorb on the surface of the hydraulic powder, repel between the hydraulic powder particles by the three-dimensional action of the rigid structure of the naphthalene group, and flow of the hydraulic composition It is thought to impart sex. Even if ettringite formation, calcium hydroxide formation and precipitation are promoted on hydraulic powder, sulfonic acid groups have strong adsorption power, so they can also be adsorbed on ettringite and calcium hydroxide, and the rigid structure of naphthalene groups Has a low affinity for water and a high adsorption rate to the hydraulic powder particles, so that it is considered that the effect of imparting fluidity does not decrease.

  Examples of the naphthalene dispersant include a polymer compound having a naphthalene sulfonic acid skeleton, such as naphthalene sulfonic acid formaldehyde condensate. The weight average molecular weight of the naphthalene dispersant is preferably 200000 or less, more preferably 100000 or less, still more preferably 80000 or less, and even more preferably 50000 or less. Further, the weight average molecular weight is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, and more preferably 5000 or more. Therefore, 1000-200000 are preferable, 3000-100000 are more preferable, 4000-80000 are still more preferable, 5000-50000 are still more preferable. As the naphthalene dispersant, a 5 wt% aqueous solution having a pH of 3 to 12 at 20 ° C. can be used. Naphthalene-based dispersants can be used in liquid and powder form. A commercial item can be used as a naphthalene type dispersing agent, for example, Kao Co., Ltd. Mighty 150 is mentioned.

  Examples of the method for producing a naphthalenesulfonic acid formaldehyde condensate include a method of obtaining a condensate by a condensation reaction of naphthalenesulfonic acid and formaldehyde. You may neutralize the said condensate. Moreover, you may remove the water insoluble matter byproduced by neutralization. For example, in order to obtain naphthalenesulfonic acid, 1.2 to 1.4 mol of sulfuric acid is used with respect to 1 mol of naphthalene and reacted at 150 to 165 ° C. for 2 to 5 hours to obtain a sulfonated product. Next, formalin is added dropwise at 85 to 95 ° C. over 3 to 6 hours to form 0.95 to 0.99 mol as formaldehyde with respect to 1 mol of the sulfonated product, and condensed at 95 to 105 ° C. after the addition. Perform the reaction. If necessary, water and a neutralizing agent are added to the condensate, and a neutralization step is performed at 80 to 95 ° C. The neutralizing agent is preferably added in an amount of 1.0 to 1.1 moles per each of naphthalenesulfonic acid and unreacted sulfuric acid. Further, water-insoluble matter generated by neutralization may be removed, preferably separated by filtration. By these steps, an aqueous solution of a naphthalenesulfonic acid formaldehyde condensate water-soluble salt is obtained. This aqueous solution can be used as it is as a naphthalene dispersant. Further, if necessary, the aqueous solution can be dried and pulverized to obtain a powdery naphthalenesulfonic acid formaldehyde condensate water-soluble salt, which may be used as a powdery naphthalene dispersant. Drying and powdering can be performed by spray drying, drum drying, freeze drying, or the like. Although the naphthalenesulfonic acid formaldehyde condensate can be obtained by the above method, the desired product can be obtained by other conditions / methods.

  In the additive composition for hydraulic composition of the present invention, the total content of glycerin and inorganic salt A is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, and still more preferably 10 to 30%. 5% by weight or more is preferable from the viewpoint of improvement in weight% and demolding strength, that is, improvement in short-term early strength, and 95% by weight or less is preferable from the viewpoint of uniform stabilization of products. The content of glycerin is preferably 0.5 to 45% by weight, more preferably 1 to 25% by weight, and even more preferably 2 to 15% by weight. The content of the inorganic salt A is preferably 4.5 to 50% by weight, more preferably 4 to 25% by weight, and still more preferably 8 to 15% by weight. In the additive composition for a hydraulic composition of the present invention, the content of the naphthalene-based dispersant is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, and still more preferably 20 to 40% by weight. %.

  In the additive composition for hydraulic composition of the present invention, the weight ratio of the total content of glycerin and inorganic salt A to the naphthalene dispersant is a naphthalene dispersant from the viewpoint of short-term early strength. / [Total content of glycerin and inorganic salt A] = 5/95 to 96/4, more preferably 5/95 to 65/35, still more preferably 5/95 to 50/50, Even more preferably, it is 10/90 to 40/60, and even more preferably 20/80 to 40/60.

  The additive composition for a hydraulic composition of the present invention can contain a dispersant other than a naphthalene-based dispersant. As dispersants other than naphthalene dispersants, phosphate ester polymers, polycarboxylic acid copolymers, sulfonic acid copolymers, melamine polymers, phenol polymers, lignin polymers, etc. should be used. Can do. The dispersant may be an admixture containing other components. The content of the dispersant other than the naphthalene-based dispersant is preferably 40% by weight or less, more preferably 20% by weight or less, still more preferably 5%, based on the naphthalene-based dispersant from the viewpoint of lowering the fluidity of the hydraulic composition. % By weight or less.

  Moreover, in the additive composition for hydraulic compositions of the present invention, the total content of glycerin, inorganic salt A and naphthalene-based dispersant is 10 to 100% by weight in the composition from the viewpoint of easy handling of the product. It is preferably 10 to 60% by weight, more preferably 20 to 40% by weight.

  In the additive composition for hydraulic composition of the present invention, the total content of glycerin and inorganic salt A is 0.01 to 5 with respect to 100 parts by weight of the hydraulic powder from the viewpoint of improving short-term and early strength. It is preferably used in a proportion of parts by weight, more preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight.

  From the viewpoint of improving the fluidity of the hydraulic composition, the additive composition for hydraulic composition of the present invention has a naphthalene-based dispersant of 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder. It is preferably used in a proportion, more preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight.

  Further, the additive composition for hydraulic composition of the present invention is based on 100 parts by weight of the hydraulic powder from the viewpoint of improving short-term strength of the hydraulic composition and improving fluidity of the hydraulic composition. The total amount of glycerin, inorganic salt A and naphthalene-based dispersant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, more preferably 0.2 to 3 parts by weight. Part.

  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.

  In the additive composition for hydraulic composition of the present invention, the concentration in the case of an aqueous solution is 5 to 50% by weight in total of glycerin, inorganic salt A and naphthalene dispersant from the viewpoint of solubility of inorganic salt A. 10 to 50% by weight is more preferable.

  Moreover, the additive composition for hydraulic compositions of this invention can be used by mixing with hydraulic powder etc. at the time of preparation of a hydraulic composition. Moreover, it is set as the hydraulic powder containing the additive composition for hydraulic compositions of this invention, and a hydraulic composition may be prepared using this.

  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; foaming agents; resin acids (salts), fatty acid esters, fats and oils , Silicone, paraffin, a Anti-foaming agents such as water-proofing agents such as fats and waxes; blast furnace slag; fluidizing agents; dimethylpolysiloxanes, polyalkylene glycol fatty acid esters, mineral oils, oils and fats, oxyalkylenes, alcohols and amides; Agents; fly ash; silica fume; rust preventives such as nitrite, phosphate, zinc oxide; celluloses such as methylcellulose and hydroxyethylcellulose; natural products such as β-1,3-glucan and xanthan gum; polyacrylic amides Water-soluble polymers such as synthetic systems such as polyethylene glycol, ethylene oxide adducts of oleyl alcohol or reaction products thereof with vinylcyclohexene diepoxide, and 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 contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, naphthalene dispersants, hydraulic powders, aggregates, and water. A hydraulic composition having a glycerin / inorganic salt A molar ratio of 5/95 to 55/45 in terms of glycerin / inorganic salt A is provided. The hydraulic composition of the present invention may be a hydraulic composition containing the additive composition for hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water.

  The hydraulic composition of the present invention is mortar, concrete or the like containing water and hydraulic powder (cement). 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 (%) 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% or less, further 55% or less, and even more preferably 50% or less. Further, it is preferably 10% or more, more preferably 30% or more. Accordingly, the W / P range is preferably 20 to 65%, more preferably 20 to 60%, further 30 to 55%, and still more preferably 30 to 50%.

  The hydraulic composition of the present invention is a step of adding glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene dispersant to the hydraulic powder. And it can manufacture through the process of adding glycerol and inorganic salt A so that the molar ratio of glycerol / inorganic salt A may be set to 5 / 95-55 / 45. In that case, the total amount of glycerin and inorganic salt A is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder from the viewpoint of improving the short-term rapid strength of the hydraulic composition. 2-5 weight part is more preferable, and 0.2-3 weight part is still more preferable. Further, the hydraulic composition of the present invention includes a hydraulic powder, glycerin, in which an additive prepared by mixing glycerin or inorganic salt A in advance with a hydraulic powder is mixed in addition to the additive composition for hydraulic composition. Or selected from hydraulic powder, glycerin, inorganic salt A and naphthalene dispersant which are components constituting the hydraulic composition of the present invention, such as an admixture in which inorganic salt A and naphthalene dispersant are mixed It can also be produced using a blended product in which two or more components are mixed in advance. From the viewpoint that a large amount of glycerin and / or inorganic salt A according to the present invention can be blended, it is preferable to use a hydraulic powder in which glycerin and / or inorganic salt A is mixed in advance with the hydraulic powder.

  The hydraulic composition of the present invention can also contain other additives. As other additives, the other additives mentioned in the additive composition for hydraulic composition can be used.

  In the present invention, a hydraulic composition containing glycerin, an inorganic salt A, a naphthalene-based dispersant, a hydraulic powder, water, and, if necessary, an aggregate and / or a dispersant is cured. A cured product of a hydraulic composition such as a concrete product can be produced. Especially, it is suitable for manufacture of the concrete product which fills a formwork with a hydraulic composition at the point which can shorten mold release time by expression of early strength. A specific production method includes hydraulic powder, aggregate, water, glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and naphthalene dispersants. And adding the glycerin and the inorganic salt A so that the molar ratio of glycerin / inorganic salt A is 5/95 to 55/45, and preparing the hydraulic composition, and the obtained hydraulic composition A mold is filled and cured, and the cured hydraulic composition is demolded from the mold to obtain a cured body of the hydraulic composition, and the preparation of the hydraulic composition is started. The manufacturing method of the hardening body of the hydraulic composition whose time until demolding is 4 to 10 hours is mentioned. The hydraulic composition containing glycerin, the inorganic salt A according to the present invention and the naphthalene-based dispersant is accelerated in curing, so that it is possible to shorten the time from preparation of the hydraulic composition to demolding. It is. In the present invention, the time from the start of the preparation of the hydraulic composition to the demolding, that is, the time from when the water is brought into contact with the hydraulic powder to when the mold is first removed from the cured body, is demolded. From 4 to 24 hours is preferable from the viewpoint of obtaining the strength necessary for the mold and from the viewpoint of improving the production cycle, 4 to 10 hours is more preferable from the viewpoint of short-term and early strength by the additive composition of the present invention, and 6 to 10 hours. Is more preferable.

In addition, the hydraulic composition containing glycerin, the inorganic salt A according to the present invention, and a naphthalene-based dispersant does not require energy such as steam heating in order to promote curing, and does not require steam curing, such as a concrete product. It is also possible to produce a cured body of the hydraulic composition. The time from contact of water to the hydraulic powder in the preparation of the hydraulic composition when producing concrete products without steam curing, and the time from demolding to the required strength for demolding and the production cycle 4 to 24 hours are preferable, 4 to 16 hours are more preferable, 4 to 10 hours are more preferable, 6 to 10 hours are further preferable, and 7 to 9 hours are still more preferable. The strength of the concrete product at the time of demolding (JIS A 1108) is preferably 7 N / mm ² or more, and more preferably 8 N / mm ² or more, from the viewpoint of not causing damage during demolding.

  The method for producing a cured body of a hydraulic composition of the present invention can improve the productivity of a cured body of a hydraulic composition such as a concrete product, and also reduces the energy such as steam curing and is effective for the global environment. It is excellent. Examples of the hardened body of the hydraulic composition using formwork include civil engineering products such as various block products for revetment, box culvert products, segment products used for tunnel construction, bridge pier girder products, etc. Products for construction include curtain wall products, pillars, beams, building member products used for floor boards, and the like.

<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) Add and knead for 10 seconds, add the kneading water (W) containing the additive composition for hydraulic composition so that the mortar flow is the target flow value described later, and the target air entrainment amount 2 ± 1%, The main kneading was performed for 60 seconds at a low speed and for 120 seconds at a high speed. The addition amounts (parts by weight) of 100 parts by weight of alcohol (glycerin, etc.), inorganic salt, and dispersant are as shown in Tables 2-5, and alcohols (glycerin, etc.) so as to have the addition amounts shown in Tables 2-5. ), An inorganic salt, a dispersant, and water were mixed to prepare an additive composition for a hydraulic composition of an aqueous solution of 25% by weight of alcohol, inorganic salt, and dispersant in total.

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 Tables 2-5.

(2-1) Evaluation of strength of cured body Based on JIS A 1132, a mortar was filled in a cylindrical plastic mold (bottom diameter: 5 cm, height: 10 cm) by a two-layer packing method, Curing was performed indoors in the atmosphere to produce a cured body. After 8 hours or 24 hours from the preparation of the mortar, the cured product was removed from the mold, and the compression strength of the cured product was measured based on JIS A 1108.

  As for the compressive strength, relative values with the standard product as 100 are also shown in Tables 2-5. The reference product is a system in which glycerin and inorganic salt A are not added but only a dispersant is added. The added amount of the dispersant was determined so that the flow value measured by the following flow test in the reference product was within the range of the target flow value. For the dispersants (1) to (4) that can lower the concrete viscosity, the target flow value is 210 ± 30 mm, and for the dispersants (5) and (6) that increase the concrete viscosity, the target flow value is 260. ± 20 mm.

  In Tables 2 to 5, those having the same number as the branch number of the test example number indicate the evaluation results at the same time, but alcohol (glycerin or other alcohol) or inorganic under the same conditions due to the difference in the evaluation time. Even when the salt A and the dispersant were used, there was a slight difference in the measured strength values. Without considering this, simply showing the relative value of the strength relative to the reference product in each table, it is difficult to judge superiority or inferiority when compared with the relative value in other tables, so it is easy to compare between each table It is appropriate to indicate the relative intensity calculated by correcting the measured intensity value. Therefore, the relative intensity is obtained within the evaluation result of the simultaneous period with the case where only the dispersant (1) is used in the evaluation of the same period being 100, and then the criteria are defined in Test Example 1-7 in Table 2, which is the same as this. Regarding the measured values of the strengths of Test Examples 2-5, 3-3, and 4-2 in Tables 3 to 5 using glycerin, inorganic salt A, and dispersant (1) under the conditions, the relative strengths of the same values ( 381) is obtained, and the coefficient obtained by multiplying each coefficient by the coefficient is used as the corrected relative intensity. Therefore, in each table, Test Example 1-7 and Test Examples 2-5, 3-3, and 4-2 have the same relative strength value.

(2-2) Fluidity evaluation The mortar prepared by the above method was subjected to a flow test based on JIS R 5201, except that the falling motion was not performed. The relative value (relative mortar flow) with respect to the measured value of the reference product is also shown in Tables 2-5. Since flow expression differs depending on the structure of the dispersant, the relative mortar flow is based on the case where only each dispersant is used for each dispersant.

* Test examples 1-4 to 1-9 are the products of the present invention, and the others are comparative products.

  Table 2 shows the evaluation results when glycerin, sodium sulfate, and a naphthalene dispersant are used and the molar ratio of glycerin and sodium sulfate is changed with a constant addition amount. The product of the present invention can maintain a mortar flow and has a greater strength ratio after 8 hours than when glycerin or sodium sulfate is used alone, and glycerin and sodium sulfate are combined in a specific molar ratio with the naphthalene dispersant. It turns out that the effect by doing is remarkable.

* Test examples 2-4 and 2-5 are the products of the present invention, and the others are comparative products.

  Table 3 shows the evaluation results when various dispersants are used for glycerin and inorganic salt A. Dispersant (1), which is a naphthalene-based dispersant, is used in a system in which glycerin and inorganic salt A are used in combination at a specific molar ratio (Test Examples 2-4 and 2-5), thereby reducing the mortar flow. It can be seen that the strength ratio after 8 hours is large and the effect of improving short-term strength is high.

* Test Examples 3-3, 3-5, and 3-7 are the products of the present invention, and the others are comparative products.

  Table 4 shows the evaluation results when glycerin and various inorganic salts are combined.

* Test Example 4-2 is the product of the present invention, and the others are comparative products.

  Table 5 shows the evaluation results when various alcohols and sodium sulfate are combined.

In Tables 2 to 5, the addition amount is the addition amount (parts by weight) to mortar based on the effective content (solid content) of each component with respect to 100 parts by weight of cement. The components used are as follows.
Dispersant (1): Naphthalenesulfonic acid formalin condensate (Kao Corporation Mighty 150)
Dispersant (2): methoxypolyethylene glycol monomethacrylate (23 mol) / 2-hydroxyethyl methacrylate phosphate ester (mixture of mono and di) [45/55 mol ratio] copolymer (weight average molecular weight 35000) And manufactured according to the examples of JP-A-2006-52381.
Dispersant (3): Methoxypolyethylene glycol monomethacrylate (23 mol) / methacrylic acid copolymer (Nippon Shokubai Aqualock FC900)
Dispersant (4): polyoxyethylene allyl ether (30 mol) / maleic acid copolymer (NOF Co., Ltd. Marialim-AKM-60F)
Dispersant (5): polyoxyethylene alkylene ether / acrylic acid copolymer (Nippon Shokubai Aqualock HW-60)
Dispersant (6): Methoxypolyethylene glycol monomethacrylate (120 mol) / methacrylic acid copolymer (Kao Corporation Mighty 21ES)

Moreover, the molecular weight of each compound was as follows.
・ Na ₂ SO ₄ : 142.04
· K ₂ SO _4: 174.27
・ Li ₂ SO ₄ : 109.95
· CaSO _4: 136.14
・ Na ₂ CO ₃ : 105.989
NaNO ₃ : 84.99
・ Glycerin: 92
Diethylene glycol: 106.12
・ Ethylene glycol: 62.07
Triethanolamine: 149.19

Claims (5)

  It contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, and a naphthalene dispersant, and the molar ratio of glycerin to inorganic salt A is 5 for glycerin / inorganic salt A. The additive composition for hydraulic compositions, which is / 95 to 55/45.   Contains glycerin, one or more inorganic salts A selected from alkali metal sulfates and alkali metal thiosulfates, naphthalene-based dispersants, hydraulic powders, aggregates, and water, glycerin and inorganic The hydraulic composition whose molar ratio of salt A is 5 / 95-55 / 45 by glycerol / inorganic salt A.   The hydraulic composition according to claim 2, wherein the total amount of glycerin and inorganic salt A is 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydraulic powder.   In the hydraulic powder, aggregate, water, glycerin, one or more inorganic salt A selected from alkali metal sulfate and alkali metal thiosulfate, and naphthalene-based dispersant are mixed with glycerin and inorganic salt A. Is added so that the molar ratio of glycerin / inorganic salt A is 5/95 to 55/45, and a step of preparing a hydraulic composition and a step of filling the obtained hydraulic composition into a mold and curing it And a step of demolding the cured hydraulic composition from the mold to obtain a cured product of the hydraulic composition, and the time from the start of the preparation of the hydraulic composition to the demolding is 4 The manufacturing method of the hardening body of the hydraulic composition which is 10 hours.   The manufacturing method of the hardening body of the hydraulic composition of Claim 4 which does not contain steam curing.