JP5759766B2 - Method for producing cured body of hydraulic composition - Google Patents

Description

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

  Concrete secondary products are kneaded with materials such as cement, aggregate, water, and a dispersant, placed in various molds, and commercialized through a curing (hardening) process. Since the same formwork is used many times, it is important to develop a high strength in the initial age from the viewpoint of improving the productivity, that is, the rotation rate of the formwork. Therefore, (1) Use early-strength cement as cement, (2) Use various polycarboxylic acid compounds as admixtures to reduce the amount of water in the cement composition, (3) Steam curing as a curing method Measures such as performing are taken.

  Patent Document 1 describes a quick-hardening cement composition in which a quick-hardening cement contains a polyol and oxycarboxylic acid or a salt thereof. Patent Document 2 describes a strength improver for cement containing glycerin or a glycerin derivative and a polycarboxylic acid copolymer in a specific ratio.

  Today, there are cases where further shortening of the curing process is desired due to demands for higher productivity. For example, in the production of concrete products, it is necessary to develop high strength in curing time of 8 hours or 24 hours. There is a case. Usually, in the curing process, a complicated process such as a heating work process such as steam is incorporated. Therefore, a shortened process and a simplified method are desired, and it is desired in the market to omit the curing by steam.

  In addition, the steam curing time is usually shortened. However, since steam curing requires energy costs associated with steam use, a method that does not perform steam curing is also desired from the viewpoint of energy reduction. .

JP-A-64-83544 JP 2006-282414 A

  The object of the present invention is to describe the strength of a hardened concrete composition of concrete or mortar after preparation of the hydraulic composition, about 8 hours and 24 hours after preparation (hereinafter referred to as 8 hour strength and 24 hour strength, respectively). ) Is expressed.

The present invention is a method for producing a cured product of a hydraulic composition obtained by mixing glycerin, cement, and water, using a substance containing sulfate ions as a raw material of the hydraulic composition, and
A step of obtaining a hydraulic composition having a sulfate ion / glycerin molar ratio of 5.0 to 20 in terms of sulfate ion / glycerin and a sulfate ion content of 3.0 to 15 parts by weight per 100 parts by weight of cement. 1 and Step 2 for curing and curing the hydraulic composition obtained in Step 1
The manufacturing method of the hardening body of a hydraulic composition containing this.

Further, the present invention is a hydraulic composition containing sulfate ions obtained by mixing glycerin, cement, and water,
The content of sulfate ions in the hydraulic composition is 3.0 to 15 parts by weight with respect to 100 parts by weight of cement,
The molar ratio of sulfate ion to glycerin in the hydraulic composition is 5.0 to 20 in terms of sulfate ion / glycerin.
It relates to a hydraulic composition.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hardening body of the hydraulic composition which can express intensity | strength for 8 hours and intensity | strength for 24 hours is provided.

The mechanism that exhibits the effects of the present invention is estimated as follows.
The hydraulic composition according to the present invention is obtained by mixing glycerin, cement, and water, and a substance containing sulfate ions is used as a raw material of the hydraulic composition. Such a hydraulic composition contains sulfate ions (including cement-derived).

Cement usually contains the following components:
C ₃ S: 3CaO · SiO ₂ alite C ₂ S: 2CaO · SiO ₂ belite C ₃ A: 3CaO · Al ₂ O ₃ calcium aluminate C ₄ AF: 4CaO · Al ₂ O ₃ · Fe ₂ O ₃ calcium alumino Ferrite CaSO ₄ : Calcium sulfate Gypsum (In this industry, it is often expressed in terms of sulfur trioxide.)
CaCO ₃ : Calcium carbonate CaO: Calcium oxide MgO: Magnesium oxide

The rate of C ₃ A hydration reaction is faster than hydration reactions such as C ₃ S and C ₂ S, and is related to the 8-hour intensity and 24-hour intensity.

In a normal cement hydration reaction, C ₃ A and calcium sulfate in the hydraulic composition undergo a hydration reaction to produce ettringite. As this reaction proceeds and the calcium sulfate in the hydraulic composition is consumed, ettringite further reacts slowly (within 30-50 hours) with unreacted C ₃ A to produce monosulfate. As a result of the formation of monosulfate, the strength of the cured product is developed.

Glycerol chelates calcium ions of C ₃ A or calcium sulfate, accelerates the dissociation of calcium ions, and promotes the reaction between C ₃ A and calcium sulfate to produce ettringite. However, since glycerin also promotes the reaction between C ₃ A and water to form a C—A—H phase, even if the amount of glycerin is excessive, the amount of monosulfate finally formed in the hydraulic composition is reduced, It is considered that the 8-hour strength and the 24-hour strength are difficult to express.

Sulfate ions react with calcium ions other than C ₃ A in the cement to form calcium sulfate. The greater the amount of sulfate ions in the hydraulic composition, the more monosulfate that will eventually form in the hydraulic composition, but the ettringite to monosulfate will remain while calcium sulfate is present in the hydraulic composition. It is considered that the reaction that produces sucrose does not proceed, and the strength for 24 hours becomes difficult to develop.

  Therefore, it is presumed that the balance of both glycerin and sulfate ions can improve the strength for 8 hours and the strength for 24 hours.

  In the present invention, a hydraulic composition is prepared using glycerin, cement, and water. Hereinafter, these components will be described.

<Cement>
Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214).

  In order to prevent rapid setting and to secure, for example, work time for filling a mold, all of the above-mentioned cements usually contain sulfate ions (calcium sulfate).

  The sulfate ion content in the cement is generally expressed as the amount of sulfur trioxide. For example, it can be seen from the disclosure information of major domestic cement manufacturers that Japan's ordinary Portland cement contains about 2% by weight of sulfur trioxide relative to the cement. For example, Taiheiyo Cement Co., Ltd. website states that 2.10% by weight of sulfur trioxide is contained (Internet <URL: http://www.taiheiyo-cement.co.jp/service_product /cement/pdf/ncement_v2.pdf>[Search January 26, 2011]). The website of Sumitomo Osaka Cement Co., Ltd. states that 1.95% by weight of sulfur trioxide is contained (Internet <URL: http://www.soc.co.jp/cement/shohin/ index.html> [searched on January 26, 2011]). The website of Ube Mitsubishi Cement Co., Ltd. states that it contains 2.16% by weight of sulfur trioxide (Internet <URL: http://www.umcc.co.jp/html_set/products/ main_seihin_fs_seihin_new.html /> [Search January 26, 2011]).

  Therefore, in the present invention, cement (cement containing sulfate ions) can be used as the substance containing sulfate ions, which is a raw material of the hydraulic composition.

In addition, the content of C ₃ A in the cement is preferably 5 to 9% by weight in the cement, and 7 to 9% by weight from the viewpoint of suppressing rapid setting in the hydraulic composition and improving the strength for 8 hours. More preferred.

The measuring method of C ₃ A in cement is based on X-ray analysis (Rietveld method). The obtained measured value is converted per hydraulic composition.

  The hydraulic composition according to the present invention may include blast furnace slag, fly ash, silica fume, etc. as hydraulic powder other than cement, and non-hydraulic limestone fine powder, etc. Good. Silica fume cement or blast furnace cement mixed with cement may be used.

<Sulfate>
In the present invention, in addition to the sulfate ions contained in the cement, from the viewpoint of improving the strength for 8 hours and 24 hours, in Step 1, the sulfate is further mixed to further increase the amount of sulfate ions, and further the sulfate ions and glycerin. The molar ratio can be adjusted. Therefore, in this invention, a sulfate can be used as a substance containing the sulfate ion which is a raw material of a hydraulic composition.

The sulfate may be a compound capable of generating sulfate ions in the hydraulic composition, and examples of the sulfate include inorganic sulfates such as ions selected from alkaline earth metal ions, alkali metal ions, and ammonium ions. And inorganic salts composed of sulfate ions. Specific examples include alkaline earth metal sulfates and alkali metal sulfates, preferably alkaline earth metal sulfates, dihydrate gypsum (CaSO ₄ .2H ₂ O), and anhydrous gypsum (CaSO ₄ ). And calcium sulfate contained as a main component. In the present invention, as the sulfate, gypsum, for example, gypsum selected from dihydrate gypsum and anhydrous gypsum can be used.

  The amount of sulfate added is in the range where the sulfate ion content in the hydraulic composition is 3.0 to 15 parts by weight with respect to 100 parts by weight of cement in consideration of the amount of sulfate ions brought in from cement or the like. It can be selected as appropriate. The amount of sulfate added is preferably 0.1 to 12 parts by weight with respect to 100 parts by weight of cement, from the viewpoint of improving the strength for 8 hours and 24 hours in terms of sulfate ions, and 0.1 to 7 parts by weight. Part by weight is more preferred, 0.1 to 3 parts by weight is still more preferred, and 0.3 to 0.7 parts by weight is even more preferred. The amount of cement here is the amount of cement used as a raw material.

<Content of sulfate ion in hydraulic composition>
The content of sulfate ions in the hydraulic composition is 3.0 to 15 parts by weight with respect to 100 parts by weight of cement from the viewpoint of improving the strength for 8 hours and the economy, and 3.0 to 10 parts. Part by weight is more preferred, 3.0 to 6.0 parts by weight is still more preferred, 3.0 to 5.0 parts by weight is even more preferred, and 3.0 to 3.5 parts by weight is even more preferred. The amount of cement here is the amount of cement used as a raw material.

  In the present invention, the amount of sulfate ion in the hydraulic composition is the sum of the compounds present in the hydraulic composition as ionic bonds and those present as free sulfate ions in the aqueous phase of the hydraulic composition. It may be. Sulfate ions are usually brought into the hydraulic composition by cement and non-cement agents (or materials). Therefore, the sulfate ion content of the hydraulic composition includes, for example, the amount of calcium sulfate in the cement measured and the amount of sulfate ion calculated from this amount, and the sulfate ion of the agent (or material) other than cement. It can be obtained as a total value with the amount calculated. A specific method for measuring the content of calcium sulfate in the cement is shown in the Examples.

<Glycerin>
The hydraulic composition according to the present invention contains glycerin from the viewpoint of improving the strength for 8 hours and the strength for 24 hours.

  As glycerin, commercially available refined glycerin, for example, glycerin obtained by transesterification of oil derived from palm can be used. In addition, rough brine obtained by hydrolysis of beef tallow and vegetable oil, purified brine obtained by removing impurities from coarse brine, and the like can be used. From the viewpoint of improving the strength for 8 hours, rough brine and purified glycerin are preferable, and purified glycerin is more preferable.

<Content of glycerin in hydraulic composition>
The content of glycerin in the hydraulic composition is preferably 0.15 to 1.3 parts by weight with respect to 100 parts by weight of cement from the viewpoint of improving the strength for 8 hours and the strength for 24 hours. 0 parts by weight is more preferable, 0.25 to 0.80 parts by weight is still more preferable, and 0.30 to 0.60 parts by weight is still more preferable. Glycerin is usually not contained in cement or aggregate, and is brought about by the addition of an agent (or material) other than cement or aggregate. Therefore, the content of glycerin in the hydraulic composition can be determined from the amount of glycerin used for the preparation of the hydraulic composition. In the present invention, from the viewpoint of improving the strength for 8 hours and 24 hours, in Step 1, 0.15 to 1.3 parts by weight of glycerin, more preferably 100 parts by weight of cement (cement used as a raw material). It is preferable to mix 0.20 to 1.0 part by weight, more preferably 0.25 to 0.80 part by weight, and still more preferably 0.30 to 0.60 part by weight.

<Content of C ₃ A in hydraulic composition>
C ₃ A is usually provided by the addition of cement and agents (or materials) other than cement. Therefore, the content of C ₃ A hydraulic composition in the present invention the C ₃ A derived from C ₃ A content and C ₃ agent other than cement containing A was added in the cement from (or timber) It can be determined from the content. Examples of the agent (or material) other than the cement containing C ₃ A include calcium aluminate.

The content of C ₃ A in the hydraulic composition is preferably 1.0 to 2.5% by weight in the hydraulic composition from the viewpoint of suppressing rapid setting of the hydraulic composition and improving the strength for 8 hours. .

<Water content in hydraulic composition>
In the case of concrete, the content of water in the hydraulic composition is preferably 5% by weight or more from the viewpoint of improving the filling property when filling concrete into a mold. Further, from the viewpoint of suppressing breathing water, reducing surface defects, and improving the strength for 8 hours and 24 hours, the water content in the hydraulic composition is preferably 8% by weight or less, and 7.5% by weight. % Or less is more preferable, and 7% by weight or less is still more preferable. Therefore, when these viewpoints are combined, in the case of concrete, the water content in the hydraulic composition is preferably 5 to 8% by weight, more preferably 5 to 7.5% by weight, and 5 to 7% by weight. Further preferred.

  On the other hand, in the case of mortar, the content of water in the hydraulic composition is preferably 5% by weight or more, more preferably 7% by weight or more, more preferably 9% by weight from the viewpoint of improving the filling property when filling the mold. % Or more is more preferable. Further, from the viewpoint of suppressing breathing water, reducing surface defects, and improving 8 hour strength and 24 hour strength, 25 wt% or less is preferable, 18 wt% or less is more preferable, and 15 wt% or less is more preferable, It is still more preferably 13% by weight or less. Therefore, taking these viewpoints together, in the case of mortar, the water content in the hydraulic composition is preferably 5 to 25% by weight, more preferably 7 to 18% by weight, and more preferably 7 to 15% by weight of the hydraulic composition. % Is more preferable, and 9 to 13% by weight is still more preferable.

  In the present invention, from the viewpoint of improving the strength for 8 hours and the strength for 24 hours, the weight ratio of water to cement (water / cement × 100) is preferably 20 to 60, and more preferably 30 to 50. In step 1, it is preferable to mix water and cement at such a weight ratio.

<Mole ratio of sulfate ion / glycerin>
In the present invention, from the viewpoint of improving the strength for 8 hours and the strength for 24 hours, the molar ratio of sulfate ion to glycerin in the hydraulic composition is 5.0 to 20 in terms of sulfate ion / glycerin, and the strength for 8 hours is improved. From the viewpoint, the molar ratio of sulfate ion to glycerin (sulfate ion / glycerin) is preferably 5.0 to 12, more preferably 6.0 to 11, still more preferably 7.0 to 10, and 8.0 to 9.5. Is even more preferable.

<Other ingredients>
The hydraulic composition according to the present invention may further contain an aggregate from the viewpoint of reducing the amount of hydraulic powder such as cement used and reducing the material cost. 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. In the case of concrete, the amount of coarse aggregate used is from the viewpoint of increasing the strength of the hydraulic composition and reducing the amount of hydraulic powder used such as cement, and improving the filling properties of the formwork and the like. The volume is preferably 50 to 100%, more preferably 55 to 90%, and still more preferably 60 to 80%. In addition, the amount of fine aggregate used is preferably 500 to 1000 kg / m ³ , more preferably 600 to 900 kg / m ³ , and still more preferably 700 to 900 kg / m, from the viewpoint of improving the filling properties of the mold and the like. ³ . In the case of mortar, the amount of fine aggregate used is preferably 800 to 2000 kg / m ³ , more preferably 900 to 1800 kg / m ³ , and still more preferably 1000 to 1600 kg / m ³ . 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).

  In the present invention, the hydraulic composition can contain a dispersant as necessary from the viewpoint of increasing fluidity. Dispersants such as phosphate ester polymers, polycarboxylic acid copolymers, sulfonic acid copolymers, naphthalene polymers, melamine polymers, phenol polymers, lignin polymers, etc. Is known. The dispersant may be an admixture containing other components.

  When the hydraulic composition is used for a concrete secondary product, a naphthalene polymer and a polycarboxylic acid copolymer are preferable, and 0.1 to 3.0 parts by weight are used as a solid content with respect to 100 parts by weight of cement. Preferably, 0.1 to 1.0 part by weight is more preferable.

  The hydraulic composition of the present invention can further contain other components. For example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, alkylbenzene sulfonic acid or its salt, alkane sulfonate, polyoxyalkylene alkyl (or alkylphenyl) ether, polyoxyalkylene alkyl (or alkylphenyl) ether AE agent such as sulfate ester or salt thereof, polyoxyalkylene alkyl (or alkylphenyl) ether phosphate ester or salt thereof, protein material, alkenyl succinic acid, α-olefin sulfonate; gluconic acid, glucoheptonic acid, aravic acid, malic acid Retardants such as oxycarboxylic acid such as citric acid, dextrin, monosaccharide, oligosaccharide, polysaccharide, etc., sugar alcohol, etc .; foaming agent; thickener; quartz sand; calcium chloride, nitrous acid Soluble calcium salts such as lucium, calcium nitrate, calcium bromide and calcium iodide, chlorides such as iron chloride and magnesium chloride, and early strengthening agents or accelerators such as potassium hydroxide, carbonate, formic acid or salts thereof; foaming Agents; waterproofing agents such as resin acids or salts thereof, fatty acid esters, oils and fats, silicones, paraffin, asphalt, waxes; blast furnace slag; fluidizing agents; dimethylpolysiloxanes, polyalkylene glycol fatty acid esters, mineral oils, Antifoaming agents such as oxyalkylene-based, alcohol-based, and amide-based; antifoaming agents; rust-preventing agents such as nitrite, phosphate and zinc oxide; cellulose-based such as methylcellulose and hydroxyethylcellulose; β-1,3-glucan, Natural products such as xanthan gum, polyacrylic acid amide, polyethylene glycol, oleyl alcohol Water-soluble polymer synthesis system or the like of the reaction products of ethylene oxide adduct or this and vinylcyclohexene diepoxide; (meth) include polymeric emulsion alkyl acrylate.

  In the present invention, a specific hydraulic composition is cured to produce a cured body. In the present invention, for example, strength is developed in about 8 hours and about 24 hours. Therefore, the cured product is suitable for a concrete secondary product that uses the same mold many times and requires the mold to rotate. is there. Further, the hydraulic composition prepared in the present invention has fluidity in about 30 minutes immediately after the preparation, and can be suitably used for, for example, concrete whose fluidity is lowered after 30 minutes.

  The method for producing a cured body of a hydraulic composition according to the present invention includes mixing a raw material containing glycerin, cement, and water, and using a substance containing sulfate ions as a raw material of the hydraulic composition, Step 1 for preparing a hydraulic composition having a molar ratio of / glycerin of 5.0 to 20 and a sulfate ion content of 3.0 to 15 parts by weight with respect to 100 parts by weight of cement. And curing and curing the hydraulic composition.

  In step 1, at least glycerin, cement, water is used as a raw material for the hydraulic composition, and at least one of the raw materials for the hydraulic composition is a substance containing sulfate ions, and calcium sulfate in the cement is used as necessary. The amount of sulfate ions is determined from the content of calcium sulfate. In step 1, sulfate can be further mixed as a raw material for the hydraulic composition from the viewpoint of improving the strength for 8 hours and the strength for 24 hours. The components used in step 1 may be mixed in any form, but when sulfate is used, glycerin and sulfate can be mixed in advance and then mixed with other components such as cement and water. . Further, glycerin and sulfate can be separately mixed with other components such as cement and water. As an aspect of Step 1, confirm the amount of sulfate ions in all materials (cement, glycerin, water and components blended as necessary) used for preparing the hydraulic composition (for example, measure the amount of sulfate ions in the material) And a molar ratio with glycerin is 5.0 to 20 in terms of sulfate ion / glycerin, and the sulfate ion content is 3.0 to 15 with respect to 100 parts by weight of cement. There is a method of determining a blending composition (blending amount) to be a part by weight, and mixing cement, glycerin, water and components blended as necessary to obtain a hydraulic composition. From the viewpoint of improving the strength for 8 hours, the molar ratio of sulfate ion to glycerin is preferably 5.0 to 12, more preferably 6.0 to 11, still more preferably 7.0 to 10, and 8.0 to 9. 5 is even more preferable. Further, from the viewpoint of improving the strength for 8 hours and the strength for 24 hours, the content of sulfate ions is preferably 3.0 to 10 parts by weight with respect to 100 parts by weight of cement. 6.0 weight part is further more preferable, 3.0-5.0 weight part is still more preferable, 3.0-3.5 weight part is still more preferable.

  In step 2, the hydraulic composition is filled into a mold, cured and cured. Moreover, after the process 2, it can have the process of demolding the hardened hydraulic composition from a formwork. In the present invention, since the hardening of the hydraulic composition is accelerated, it is possible to shorten the time from preparation of the hydraulic composition to demolding. In the present invention, the time from the start of preparation of the hydraulic composition to demolding, that is, the time from contact of water with a hydraulic powder such as cement to demolding is necessary for demolding. From the viewpoint of obtaining sufficient strength and improving the production cycle, 4 to 24 hours are preferable, 4 to 10 hours are more preferable, and 6 to 10 hours are still more preferable.

  In addition, as the curing in step 2, autoclave curing, steam curing, room temperature curing, and the like can be performed. In the present invention, the hydraulic composition does not require energy such as steam heating to accelerate curing during curing, and a cured body of a hydraulic composition such as a concrete product can be produced without steam curing. It becomes possible. For example, in the method for producing a cured product of the hydraulic composition of the present invention, in step 2, the time for which the hydraulic composition is maintained at a curing temperature of 50 ° C. or higher is 1 hour or less, and further 0.5 hours or less. Can do. The time from contact of water to hydraulic powder such as cement in the preparation of a hydraulic composition when producing concrete products without steam curing is the viewpoint to obtain the strength necessary for demolding. From the viewpoint of improving the production cycle, the curing time is preferably 4 to 24 hours, more preferably 4 to 16 hours, more preferably 4 to 10 hours, still more preferably 6 to 10 hours, and even more preferably 7 to 9 hours. preferable. In this case, the curing temperature is preferably 0 to 40 ° C, more preferably 10 to 40 ° C.

  The method for producing a cured body of the hydraulic composition of the present invention improves the productivity of a cured body of a hydraulic composition such as a concrete product such as a concrete secondary product, and is therefore excellent in terms of reducing environmental impact. Is. As a hardened body of hydraulic composition using formwork, which is a concrete secondary product, for civil engineering products, various block products for revetment, box culvert products, segment products used for tunnel construction, pier girder products, etc. Examples of building products include building wall products, pillars, beams, and building member products used for floor boards.

<Example 1 and Comparative Example 1>
A concrete test using cement (C1) as a cement type was performed (Tables 1 and 2).

<Example 2 and Comparative Example 2>
A concrete test using cement (C2) as a cement type was performed (Tables 1 and 3).

<Example 3 and Comparative Example 3>
A mortar test using cement (C3) as a cement type was performed (Tables 4 and 5).

<Example 4 and Comparative Example 4>
A mortar test using cement (C4) as a cement type was performed (Tables 4 and 6).

<Example 5>
Cement (C1) was used as a cement type, and concrete tests using various glycerins were performed (Tables 1 and 7).

(1) Preparation of specimen (1-1) Preparation of concrete and specimen (step 1)
Cement, fine aggregate, coarse aggregate, glycerin and dihydrate gypsum (CaSO ₄ (2H ₂ O)) are added to the mixture under the mixing conditions shown in Tables 1 to 3 and Table 7, and kneaded. 10 seconds, so that the target slump is 21 ± 1 cm and the target air entrainment amount is 2 ± 1%, kneading water containing an AE agent and an antifoaming agent, and 1 part by weight of a dispersant (100% by solid content). .4 parts by weight) was added and kneaded for 90 seconds (rotation speed: 45 rpm) to obtain concrete. Tables 2, 3 and 7 show the molar ratios of sulfate ion and glycerin calculated from the amount of glycerin and dihydrate gypsum added and the amount of calcium sulfate in the cement.

(Process 2)
In accordance with JIS A 1132, a cylindrical plastic mold (bottom diameter: 10 cm, height 20 cm) is filled with concrete by a two-layer filling method, and air-cured at 20 ° C. to obtain a specimen. It was.

The concrete components and concrete mixer are as follows.
・ Glycerin: Purified glycerin (manufactured by Kao Corporation, glycerin obtained by transesterification of oil derived from palm)
・ Dihydrate gypsum: Dihydrate gypsum (Wako Pure Chemical Industries, Ltd., Wako First Grade)
・ AE agent: AE02 (manufactured by Kao Corporation)
Antifoaming agent: Antifoaming agent No. 21 (manufactured by Kao Corporation)
Dispersant: Mighty 150 (manufactured by Kao Corporation, naphthalene polymer, solid content 40% by weight)
・ Kneading water (W): tap water containing AE agent and antifoaming agent ・ Cement (C1): Normal Portland cement (manufactured by Sumitomo Osaka Cement Co., Ltd.), density 3.16 g / cm ³ , equivalent to calcium sulfate in cement The amount _and the content of C ₃ A are shown in Table 2.
Cement (C2): Normal Portland cement (manufactured by Sumitomo Osaka Cement Co., Ltd.), density 3.16 g / cm ³ , equivalent amount of calcium sulfate in cement, and content _of C ₃ A are shown in Table 3.
Fine aggregate (S1): crushed sand (Ansan crushed sand from Kawauchi village, Ishikawa Prefecture), density 2.55 g / cm ³
・ Fine aggregate (S2): Land sand (Ishikawa Prefecture's difficult production beach-based land sand), density 2.55 g / cm ³
Coarse aggregate (G1): crushed stone (crushed stone 1505 from Kawauchi village, Ishikawa Prefecture), density 2.55 g / cm ³
・ Concrete mixer: IHI forced biaxial mixer, 35 liters

The glycerin used in Example 5 is as follows.
・ Rough brine (beef tallow): glycerin aqueous solution obtained by hydrolysis of beef tallow (solid content 12.4% by weight)
・ Rough brine (plant): glycerin aqueous solution obtained by hydrolysis of vegetable oil (solids 16.6% by weight)
・ Rough brine (animal and plant mixture): Coarse brine (beef tallow) and coarse brine (plant) (solid content 12.6% by weight)
・ Rough brine (evaporated product): Evaporated water from coarse brine (animal and vegetable mixture) and concentrated (solid content 50.2% by weight)
-Purified brine: Crude brine (evaporated product) treated with charcoal and ion exchange to remove trace impurities (solid content 99.1% by weight)

(1-2) Preparation of mortar and specimen (step 1)
Under the blending conditions shown in Tables 4 to 6, using a mortar mixer, cement, fine aggregate and glycerin are added and kneaded for 10 seconds, and an antifoaming agent is included so that the air entrainment amount is 2% or less. 0.48 parts by weight of a dispersant in terms of solid content was added to 100 parts by weight of the kneading water and cement, and this was kneaded for 1 minute at a rotation speed of 63 rpm and for 2 minutes at a rotation speed of 128 rpm to obtain a mortar. Tables 5 and 6 show the molar ratio of sulfate ion to glycerin calculated from the amount of glycerin added and the amount of calcium sulfate in the cement.

(Process 2)
In accordance with JIS A 1132, a cylindrical plastic mold (bottom diameter: 10 cm, height: 20 cm) is filled with mortar by a two-layer filling method, and air-cured at 20 ° C. to obtain a specimen. It was.

The blending ingredients of the mortar and the mortar mixer are as follows.
・ Glycerin: Purified glycerin (manufactured by Kao Corporation)
Antifoaming agent: Antifoaming agent No. 21 (manufactured by Kao Corporation)
・ Dispersant: Mighty 150 (manufactured by Kao Corporation, naphthalene polymer)
・ Kneading water (W): tap water containing antifoaming agent ・ Cement (C3): Portland cement (CEM I42,5, manufactured by Heidelberger), density 3.15 g / cm ³ , equivalent amount of calcium sulfate in cement, C ₃ The content of A is shown in Table 5.
Cement (C4): Portland cement (manufactured by Siam Cement), density 3.15 g / cm ³ , equivalent amount of calcium sulfate in the cement, and content of C ₃ A are shown in Table 6.
・ Fine aggregate (S1): Mountain sand from Joyo, density 2.55g / cm ³
-Mortar mixer: manufactured by Dalton, universal mixing stirrer, model: 5DM-03-γ

(2) Quantification of components in cement (2-1) Quantification of calcium sulfate in cement Quantification of calcium sulfate (CaSO ₄ ) in cement uses a powder X-ray device, RINT-2500 (manufactured by Rigaku Corporation). Done using. Measurement conditions were a target CuKα, a tube current of 40 mA, a tube voltage of 200 kV, a scanning range of 5 to 70 deg. 2θ, and a scanning condition of step scanning, a step width of 0.02 °, and a counting time of 2 seconds.

0.3 g of standard substance “corundum (Al ₂ O ₃ ): AKP-100 (manufactured by Sumitomo Chemical Co., Ltd.)” was added to 2.7 g of cement, and quantified with Rietveld analysis software based on the peak area. . The Rietveld analysis software used PDXL Ver.1.6 manufactured by Rigaku Corporation, and the mineral to be analyzed was gypsum (dihydrate, semi-water, anhydrous). The amount of sulfate ion in the cement was calculated from the amount of calcium sulfate obtained.

(2-2) Determination of C ₃ A in quantitative cement C ₃ A in the cement, except that analyzed minerals C ₃ A, was carried out in the same manner as determination of calcium sulfate.

(3) Sulfate ion content in concrete or mortar Since the sulfate ion content in concrete or mortar is only dihydrate gypsum added with cement as the compound that gives sulfate ion, sulfuric acid obtained from analysis of cement It calculated | required from the sum of the quantity of calcium, and the quantity of the added dihydrate gypsum.

(4) Glycerin content in concrete or mortar The glycerin content in concrete or mortar was calculated from the amount of glycerin used in the preparation of the hydraulic composition.

(5) Concrete or mortar evaluation The demolding strength of the concrete or mortar was evaluated according to the following test method. The evaluation results are shown in Tables 2, 3 and 5-7.

(5-1) Evaluation of specimen strength The specimen cured 8 hours after the preparation of concrete or mortar was removed from the mold, and the compressive strength was measured based on JIS A 1108 to obtain the strength for 8 hours. In addition, after 8 hours until demolding was performed in the same manner as the measurement of 8 hours strength, and after demolding, it was stored in air at 20 ° C. for up to 24 hours, and then the compressive strength was measured based on JIS A 1108 The strength was 24 hours. The compressive strength is shown in Tables 2, 3 and 5 to 7 as the strength ratio (%) relative to the strength of the reference product. In Tables 2, 3, and 7, the comparative product indicated as the reference is a system in which glycerin and dihydrate gypsum are not added, but only the AE agent, the antifoaming agent and the dispersant are added (Comparative Example 1-1, comparison) Example 2-1) Moreover, in Tables 5 and 6, it is the system which added only an antifoamer and a dispersing agent, without adding glycerin (Comparative Example 4-1, Comparative Example 5-1). The content and molar ratio of sulfate ions are values calculated by setting the molecular weight of sulfate ions (SO ₄ ²⁻ ) to 96. Moreover, the addition amount of glycerol of Table 2, 3 and 5-7 is conversion of solid content.

  The concrete or mortar composition of the examples is a composition used for a secondary product, and can be demolded in about 8 hours without steam curing, and from the viewpoint of obtaining a cured body with high strength for 24 hours, 8 hours. The subsequent relative strength is preferably 145% or more, more preferably 170% or more, and still more preferably 250% or more. And the strength after 24 hours is preferably 110% or more.

  A hydraulic composition having a sulfate ion content of 3.0 to 15 parts by weight and a sulfate ion / glycerin molar ratio of 5.0 to 20 as in the present invention. When used, the relative strength after 8 hours of the cured body exceeds 145%, the relative strength after 24 hours exceeds 110%, and strength is obtained after 8 hours and 24 hours. When the content of sulfate ion in the hard composition or the molar ratio of sulfate ion / glycerin is outside the range of the present invention, the relative value after 8 hours and 24 hours of the cured product from the product of the present invention (Example) It can be seen that the strength is inferior.

  From Tables 5 and 6, when cement containing 5.8% by weight and 4.0% by weight of sulfate ion in the cement was used, the amount of glycerin added even without adding sulfate as a sulfate ion source. When the ratio of sulfate ion / glycerin is adjusted within the range of the present invention, the relative strength after 8 hours and after 24 hours is improved.

  Moreover, as shown in Table 7, even when the type of glycerin was changed, a relative strength of 180% or more after 8 hours and 140% or more after 24 hours was obtained regardless of the type of glycerin. Therefore, it can be seen that any glycerin can be used.

  When the hydraulic composition of the present invention is cured, the strength for 8 hours and the strength for 24 hours can be improved without curing by applying heat.

Claims (9)

A method for producing a cured product of a hydraulic composition obtained by mixing glycerin, cement, and water, using a substance containing sulfate ions as a raw material of the hydraulic composition, and
A step of obtaining a hydraulic composition having a sulfate ion / glycerin molar ratio of 5.0 to 20 in terms of sulfate ion / glycerin and a sulfate ion content of 3.0 to 15 parts by weight per 100 parts by weight of cement. 1 and Step 2 for curing and curing the hydraulic composition obtained in Step 1
The manufacturing method of the hardening body of a hydraulic composition containing this.   The manufacturing method of the hardening body of Claim 1 which further mixes a sulfate in the process 1.   In the process 1, the manufacturing method of the hardening body of Claim 1 or 2 which mixes 0.15-1.3 weight part of glycerol with respect to 100 weight part of cement. The cement contains calcium aluminate (hereinafter referred to as C ₃ A), and the content of C ₃ A in the hydraulic composition is 1.0 to 2.5% by weight. The manufacturing method of the hardening body of description.   The manufacturing method of the hardening body in any one of Claims 1-4 whose time for which a hydraulic composition is hold | maintained at the curing temperature of 50 degreeC or more in process 2 is 1 hour or less. A hydraulic composition containing sulfate ions, obtained by mixing glycerin, cement, and water,
The content of sulfate ions in the hydraulic composition is 3.0 to 15 parts by weight with respect to 100 parts by weight of cement,
The molar ratio of sulfate ion to glycerin in the hydraulic composition is 5.0 to 20 in terms of sulfate ion / glycerin.
Hydraulic composition.   Furthermore, the hydraulic composition of Claim 6 formed by adding a sulfate.   The hydraulic composition according to claim 6 or 7, wherein the content of glycerin in the hydraulic composition is 0.15 to 1.3 parts by weight with respect to 100 parts by weight of cement. Cement comprises C ₃ A, hydraulic composition according to any one of claims 6-8 content of C ₃ A hydraulic composition is 1.0 to 2.5 wt%.