WO2020044708A1 - Curing agent for concrete composition and method for curing concrete composition - Google Patents

Curing agent for concrete composition and method for curing concrete composition Download PDF

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Publication number
WO2020044708A1
WO2020044708A1 PCT/JP2019/022450 JP2019022450W WO2020044708A1 WO 2020044708 A1 WO2020044708 A1 WO 2020044708A1 JP 2019022450 W JP2019022450 W JP 2019022450W WO 2020044708 A1 WO2020044708 A1 WO 2020044708A1
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Prior art keywords
concrete
concrete composition
curing agent
curing
agent
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PCT/JP2019/022450
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French (fr)
Japanese (ja)
Inventor
万穂 吉岡
一裕 相澤
泰一郎 森
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デンカ株式会社
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Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to CN201980056946.0A priority Critical patent/CN112638844A/en
Priority to JP2020540076A priority patent/JP7209001B2/en
Publication of WO2020044708A1 publication Critical patent/WO2020044708A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02—Selection of the hardening environment

Definitions

  • the present invention relates to a curing agent for a concrete composition and a method for curing a concrete composition.
  • Quick-hardened concrete may not satisfy sufficient strength at early age depending on the cement type.
  • the initial strength development is greatly affected by the outside temperature, when the temperature is low in winter or the like, the required strength development may not be satisfied.
  • Patent Documents 1 and 2 For the purpose of accelerating the setting and hardening of concrete, a method of adding a setting accelerator to concrete, for example, a method of adding aluminum sulfate (Patent Documents 1 and 2) has been proposed.
  • Patent Document 3 a method of coating a paraffin-based film curing agent after the concrete has hardened, that is, after finishing ironing, is known.
  • Patent Document 3 is a method for suppressing carbonation and salt damage of concrete, but does not increase the strength.
  • the present inventors have made various efforts to solve the above problems, and as a result, for example, by using a curing agent containing a specific component at a construction site, a cured product of a concrete composition having excellent initial strength development. was found to be able to be prepared, and the present invention was completed. That is, the present invention is as follows.
  • a curing agent for concrete compositions containing at least one selected from the group consisting of aluminum sulfate, sodium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, calcium aluminate, diethanolamine, and formic acid.
  • a method for curing a concrete composition comprising using the curing agent for a concrete composition according to any one of [1] to [3] for curing the concrete composition.
  • a curing agent for a concrete composition capable of improving the initial strength development when the concrete composition is cured.
  • the curing agent for concrete composition of the present invention (hereinafter, may be simply referred to as “curing agent”) comprises aluminum sulfate, sodium aluminate, calcium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, diethanolamine, and formic acid. At least one selected from the group.
  • Aluminum sulfate is a general term for compounds containing an Al 2 O 3 component and an SO 3 component, and is not particularly limited. It is represented by the general formula Al 2 (SO 4 ) 3 .nH 2 O, where n is in the range of 0 to 18, and aluminum sulfate of various crystallization waters is present. In the present invention, it is preferable to use octahydrate from the viewpoint of the development of the initial strength.
  • Sodium aluminate contains Na 2 O and Al 2 O 3 as chemical components and has a composition ratio of 0.1 in terms of a molar ratio of Na 2 O and Al 2 O 3 (Na 2 O / Al 2 O 3 ). Preferably, it is 7 to 1.5 sodium aluminate.
  • Calcium aluminate is a hydration active substance having a crystalline or vitrified structure containing CaO and Al 2 O 3 as contained chemical components, and has a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) is preferably a calcium aluminate compound having a molecular weight of 1.50 to 2.60. It is preferable that the amorphous content is 90% by mass or more, since a higher hydration reaction activity can be obtained. Specifically, 12CaO ⁇ 7Al 2 O 3, CaO ⁇ Al 2 O 3, calcium aluminate such as 3CaO ⁇ Al 2 O 3 and the like. Calcium aluminate quick-setting agents can also be used as long as they contain the calcium aluminate compound. Commercial products of calcium aluminate-based quick setting agents include NATMIC TYPE Z manufactured by Denka Corporation.
  • Lithium nitrate includes 0.5 hydrate (0.5 hydrate) and 3 hydrate (3 hydrate) in addition to anhydride (anhydrous salt), and is not particularly limited, but anhydrous is preferable. .
  • the sodium nitrate is represented by NaNO 3 , and is not particularly limited in the present invention.
  • Naturally produced chile saltpeter may be used after being pulverized.
  • (Calcium nitrate) As calcium nitrate, Ca (NO 3 ) 2 .nH 2 O is used, and there are dehydrated products obtained by dehydrating tetrahydrate in addition to tetrahydrate, but the present invention is not particularly limited thereto.
  • Diethanolamine represented by HN (CH 2 CH 2 OH) 2 and having a purity of 98% or more is preferably used.
  • Formic acid has various purities ranging from 76% to 98.6%, but is not particularly limited in the present invention.
  • aluminum sulfate, sodium aluminate, and calcium aluminate are preferable, and aluminum sulfate is more preferable, from the viewpoint of the initial amount of ettringite generated.
  • the curing agent of the present invention preferably further contains liquid paraffin.
  • the ratio is not particularly limited, but the mass ratio of liquid paraffin to the curing agent is preferably from 10:90 to 90:10, and more preferably from 30:70 to 70/30.
  • Paraffin is a general term for a mixture of non-volatile purified saturated hydrocarbons, and is a kind of hydrocarbon compound.
  • Alkanes having 20 or more carbon atoms alkane, alkane group, and the general formula is CnH 2n + 2 ) (Chain-type saturated hydrocarbon represented).
  • paraffin is not a homogeneous substance, but various things are mixed in "constituting carbon chains".
  • those containing many long carbon chains are solid and called “petroleum wax”.
  • those containing many short carbon chains are liquid at normal temperature and pressure, and are called “liquid paraffin".
  • a commercially available paraffin-based curing agent can be used. Specific examples thereof include “Master Cure” manufactured by BASF Pozzolith Co., Ltd. and “Concure” manufactured by Fosrock Co., Ltd.
  • Method of curing concrete composition In the method for curing a concrete composition of the present invention, the curing agent for a concrete composition of the present invention is used for curing the concrete composition.
  • the method of using the curing agent of the present invention is not particularly limited, but a method of casting a concrete composition and thereafter applying a curing agent for the concrete composition to the surface thereof before the concrete composition is cured; A method in which a curing agent for concrete composition is applied to a casting location, then a concrete composition is cast, and then, before the concrete composition is cured, a curing agent is applied to the surface of the concrete composition.
  • a method of casting a concrete composition and thereafter applying a curing agent for the concrete composition to the surface thereof before the concrete composition is cured A method in which a curing agent for concrete composition is applied to a casting location, then a concrete composition is cast, and then, before the concrete composition is cured, a curing agent is applied to the surface of the concrete composition.
  • the concrete is cast to before the start of the setting, it is desirable to use the concrete as soon as possible after the concrete is cast, from the viewpoint of the development of the initial strength. It is preferred to use the curing agent within hours, more preferably within 30 minutes.
  • the method of applying the curing agent of the present invention is not particularly limited as long as it can be applied uniformly, and can be applied by spraying, coating, spraying, spraying, etc., and coating is preferable.
  • the amount of the curing agent of the present invention is not particularly limited, it is generally preferable to use the curing agent in an amount of 50 g to 500 g, more preferably 100 g to 300 g, per m 2 of the concrete composition. When used in the range of 50 g to 500 g, sufficient initial strength can be easily obtained.
  • the object of the curing method of the present invention is not particularly limited to known mortar, concrete and the like, but it is preferable to use it as a concrete composition for ready-mixed shipping-type rapid hardened concrete.
  • the ready-mixed concrete shipped hardened concrete the initial strength of the ready-mixed ready-hardened concrete can be increased.
  • concrete ready-to-cook hard concrete refers to a ready-mixed concrete plant or a ready-mixed concrete plant to which a large amount of a sleeping agent is added, kneaded, and then abruptly hardened concrete (concrete for which hydration hardening has almost stopped) is agitated. It is transported by car and shipped to construction sites such as civil engineering construction sites and construction sites, and it is a concrete that can restore hydration hardening again by adding a hardening agent for ready-mixed concrete quick-hardening concrete at the site. .
  • a ready-mixed shipping quick-hardened concrete in which the curing agent of the present invention is preferably used will be described.
  • a ready-mixed plant it is necessary to prepare various base concretes in which a rapid hardening material and a sleep aid are added and mixed in advance, and it is necessary to add and mix a hardening agent to various base concretes after being transported to the site. If the hardener is mixed with various base concretes in advance at a ready-mixed plant rather than at the construction site, the pot life cannot be secured. Further, when both the hardened material and the hardening agent are added at the ready-mixed concrete factory, the pot life becomes extremely short, and the concrete must be discarded during transportation.
  • the pot life after the addition of the hardened material is extremely shortened to 10 minutes or less, and the work cannot be performed.
  • the pot life is shortened, the compressive strength becomes low, the wear resistance tends to deteriorate, and the drum volume of the agitator is reduced by 30%. Can be transported only to the extent.
  • the timing of adding the hardened material and the hardening agent is extremely important.
  • concretely by using a two-material type including the material A including cement, a hardened material, and a sleep-inducing agent, and the material B including a hardening agent for ready-mixed concrete shipping-type hardened concrete, Can be used as the ready-mixed concrete-hardened concrete composition of the present embodiment by separately transporting the materials A and B from the ready-mixed plant to the construction site and mixing them at the construction site.
  • a two-material type including the material A including cement, a hardened material, and a sleep-inducing agent, and the material B including a hardening agent for ready-mixed concrete shipping-type hardened concrete
  • the ready-mixed shipping quick-hardening concrete hardening agent (hereinafter, may be simply referred to as “hardening agent”) is a large amount of a sleeping agent described below. It means a material that rehydrates the hydration hardening of the added hardened concrete (the concrete whose hydration hardening is almost stopped), for example, at the construction site.
  • Specific examples thereof include one or more of calcium hydroxide, calcium carbonate, calcium aluminate compounds, calcium silicate compounds, colloidal silica, portland cement, calcium sulfoaluminate cement, blast furnace slag, and the like. It is possible.
  • the “fresh concrete shipping-type rapid hardened concrete” referred to in the present embodiment is as described above. From the relationship of the transport time, from the shipping to the completion of the work, at least the working time is required to be 120 minutes or more. When the transport distance is long, it is desired to secure a pot life of 180 minutes or more. The present embodiment is used specifically for such a use.
  • the "agitator truck” is a truck equipped with a mixing drum (container for mixing) on the loading platform that can transport ready-mixed concrete while stirring it, and there is no significant difference in its function. , With a maximum loading capacity of 2 to 26t class, which are used properly according to the application.
  • the hardener for ready-mixed concrete quick-hardening concrete contains any of the above-mentioned components as essential components, but in order to improve the temperature dependence, only calcium hydroxide, or calcium hydroxide and a calcium aluminate compound It is more preferable to use both.
  • the mixing ratio is not particularly limited, but may be from 1/99 to 99/1 in terms of the mass ratio of calcium hydroxide to calcium aluminate compound (calcium hydroxide / calcium aluminate compound). It is more preferably 2/98 to 98/2.
  • the mass ratio is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20.
  • the 300 ⁇ m sieve residue is preferably 5% or less, and the 100 ⁇ m sieve residue is preferably 10% or less.
  • the calcium aluminate-based compound is used for a hardening material described later, but the calcium aluminate-based compound used for the hardening agent has a CaO / Al 2 O 3 molar ratio of 0.5 to 2.4. Those in the range are preferred.
  • the CaO / Al 2 O 3 molar ratio is 0.5 or more, the effect of improving the temperature dependency can be sufficiently exhibited, and when the CaO / Al 2 O 3 molar ratio is 2.4 or less, a hardening agent is used in the slurry. In this case, rapid hardening can be suppressed.
  • a range of 0.5 to 1.2 is more preferable, and a range of 0.75 to 1.0 is more preferable.
  • those having a range of 1.2 to 2.4 are more preferable, and those having a range of 1.25 to 2.3 are still more preferable.
  • Calcium aluminate compounds are further roughly classified into amorphous calcium aluminate compounds and crystalline calcium aluminate compounds, and the use of amorphous calcium aluminate compounds is preferred from the viewpoint of long-term strength.
  • the total thereof is preferably 70% or more, more preferably 80% or more, from the viewpoint of efficiently exhibiting the respective effects or the combined effects.
  • a substance (other component) other than the above-described hardener can also enhance the dispersibility of the hardener or promote the effect of the hardener, and impair the effects of the present invention. If not, it can be contained in a range of 30% or less.
  • the hardening agent preferably further contains gypsum, more preferably a calcium aluminate-based compound and gypsum, in addition to any of the above-described components.
  • the gypsum to be used may be any of anhydrous gypsum, hemihydrate gypsum and dihydrate gypsum. Further, natural gypsum, chemical gypsum such as gypsum by-produced by phosphoric acid, gypsum excreted by gypsum, and gypsum by-produced by hydrofluoric acid, or gypsum obtained by heat-treating these may also be used.
  • anhydrous gypsum and / or hemihydrate gypsum are preferred from the viewpoint of strength development, but anhydrous gypsum is preferably selected from the viewpoint of cost, and type II anhydrous gypsum and / or natural anhydrous gypsum are preferred.
  • the particle size of gypsum is preferably from 3000 cm 2 / g or more in Blaine value, more preferably 4000 ⁇ 7000cm 2 / g. When it is 3,000 cm 2 / g or more, the initial strength can be sufficiently exhibited.
  • the amount of gypsum used is preferably 10 to 200 parts, more preferably 15 to 150 parts, and even more preferably 90 to 130 parts with respect to 100 parts of a hardening agent (preferably a calcium aluminate compound). Within these ranges, long-term strength development and durability can be improved.
  • the amount of the hardening agent for ready-mixed concrete quick-hardened concrete is not particularly limited, but is preferably 0.5 to 7 parts with respect to a total of 100 parts of cement and quick-hardening material described below. -5 parts is more preferred. When the amount is 0.5 to 7 parts, the strength can be sufficiently developed in a short-term age, and the pot life can be secured.
  • the hardening agent may be slurried and added to various types of base concrete. In this case, it is desirable from the viewpoint of strength development to apply a part of the mixing water from the concrete mixture to the slurry of the hardening agent and subtract the water from the base concrete.
  • the hardening agent may be added to various types of base concrete or the like in a state of being packaged in advance with a water-soluble film such as a polyvinyl alcohol (PVA) film.
  • a water-soluble film such as a polyvinyl alcohol (PVA) film.
  • various additives may be mixed together with the hardening agent as long as the effect is not impaired.
  • the base concrete refers to a concrete obtained by kneading at least cement, a rapid hardening material, a sleep aid, an aggregate, and kneading water.
  • the water-soluble film of the preferred embodiment is made of wood pulp, polysaccharide, poval, cellulose, polyvinyl alcohol, carboxymethylcellulose, starch or the like, and the content of wood pulp in the raw material is 75 to 95%. Is preferable, and 80 to 90% is more preferable.
  • Raw materials such as polysaccharides other than wood pulp, poval, cellulose, polyvinyl alcohol, carboxymethylcellulose, and starch are preferably 5 to 25%, more preferably 10 to 20%. If the raw materials such as polysaccharides, poval, cellulose, polyvinyl alcohol, carboxymethyl cellulose, and starch are less than the above ranges, the amount of adhesive raw materials necessary for heat sealing when producing water-soluble paper is insufficient, making the production difficult.
  • the water-soluble film of the preferred embodiment is not particularly limited as long as it is water-soluble, but 10 g of the water-soluble film is added to a beaker (capacity: 1000 ml) containing 500 ml of water at 20 ° C., and a stirrer (Ikeda Riko Co., Ltd.) Is preferably 30 seconds or less, and more preferably 20 seconds or less.
  • the dispersion time refers to the time when the aggregates have disappeared visually. Those having a dispersion time of more than 30 seconds may not be completely dispersed after kneading the concrete and may remain in the concrete.
  • the kneading time of the concrete using the embodiment in which the hardener is packaged by the water-soluble film of the preferred embodiment is substantially the same as that of the non-mixable concrete not using the embodiment,
  • the mixing time of the concrete may be long, and in the case of the same mixing time, even if the number of bags is the same as the water-soluble film of the preferred embodiment, the water-soluble film is in the concrete. May remain.
  • the hardening agent is slurried and added to various types of base concrete by pressure feeding
  • dextrin or a combination of dextrin and a cellulose derivative is more preferable.
  • Dextrin can enhance the stability of the ready-mixed concrete-hardened concrete composition to be described later by delaying the setting of cement.
  • Dextrin is also generally referred to as modified starch, and is usually obtained by hydrolyzing corn starch, potato, tapioca starch, wheat starch, sweet potato starch, rice starch and the like.
  • acid-roasted dextrin obtained by adding a dilute acid and decomposing is most common, and is obtained by an acid dipping method, maltodextrin obtained by enzymatic decomposition of starch, and British gum obtained by non-roasting
  • pre-gelatinized starch obtained by heating and dewatering starch added with water, or pre-gelatinizing by adding an alkali or concentrated salt solution, or dissolving these in water A powder obtained by drying the residue can be used.
  • those which have been chemically modified such as carboxylic acid esterification, carbonate esterification, and etherification can be used.
  • Dextrin is preferably 0.01 to 5 parts, more preferably 0.1 to 3 parts, based on 100 parts of the hardening agent.
  • the content is 0.01 to 5 parts, the strength can be sufficiently developed in a short-term age, and heat generation when the hardened material is slurried can be suppressed.
  • the cellulose derivative contributes to the prevention of bleeding when the hardened material is slurried, and is not particularly limited, but is generally referred to as a water-soluble polymer substance, and includes methyl cellulose (MC), Carboxymethyl cellulose (CMC) and the like.
  • MC methyl cellulose
  • CMC Carboxymethyl cellulose
  • the amount of the cellulose derivative to be used is preferably 5 to 80 parts, more preferably 10 to 50 parts, per 100 parts of dextrin. When the amount is 5 to 80 parts, it is possible to achieve both bleeding prevention and long distance pumpability.
  • cement in the present embodiment is not particularly limited, but includes, for example, various kinds of Portland cement, blast furnace slag, fly ash of normal, fast strength, moderate heat and low heat defined by Japanese Industrial Standards (JIS). And cement mixed with silica, filler cement mixed with limestone powder and blast furnace slowly cooled slag fine powder, and environmentally friendly cement (eco-cement) manufactured from municipal waste incineration ash or sewage sludge incineration ash. )).
  • JIS Japanese Industrial Standards
  • cement mixed with silica filler cement mixed with limestone powder and blast furnace slowly cooled slag fine powder
  • environmentally friendly cement eco-cement manufactured from municipal waste incineration ash or sewage sludge incineration ash.
  • gypsum dihydrate are also mixed (a part of this may change to hemihydrate gypsum).
  • the corresponding cement include, for example, Japanese cement, and early cement and ordinary cement.
  • PII52.5 and PII42.5 can be cited as examples of Chinese cement.
  • the rapidly hardened material of this embodiment is composed of a calcium aluminate compound and gypsum.
  • the calcium aluminate-based compound is a general term for compounds mainly composed of CaO and Al 2 O 3 , and is not particularly limited. Specific examples, CaO ⁇ Al 2 O 3, 12CaO ⁇ 7Al 2 O 3, 11CaO ⁇ 7Al 2 O 3 ⁇ CaF 2, 3CaO ⁇ Al 2 O 3, 3CaO ⁇ 3Al 2 O 3 ⁇ CaSO 4, further, CaO And an amorphous substance mainly composed of Al 2 O 3 (for example, CaO—Al 2 O 3 —SiO 2 -based compound). Among them, it is preferable to select an amorphous substance from the viewpoint of strength development.
  • general industrial raw materials include impurities such as SiO 2 , MgO, Fe 2 O 3 , TiO 2 , K 2 O, and Na 2 O. These impurities are non-calcium aluminate-based compounds. There is also a surface that promotes crystallization, and the total amount thereof may be in the range of 20% or less. Above all, the presence of SiO 2 is preferable, and it can be contained in the range of 1 to 18% for the purpose of obtaining amorphous calcium aluminate.
  • the hardened material includes a CaO—Al 2 O 3 —SiO 2 compound and gypsum, and the CaO—Al 2 O 3 —SiO 2 compound has an amorphous degree of 70% or more, and , SiO 2 is preferably in the range of 1 to 18% by mass. More preferably, the CaO—Al 2 O 3 —SiO 2 -based compound has an amorphous degree of 80% or more and SiO 2 in a range of 2 to 13% by mass.
  • the calcium aluminate compound is preferably adjusted to have a Blaine specific surface area of 3,000 to 9000 cm 2 / g, more preferably 4,000 to 8,000 cm 2 / g, by a pulverizing treatment.
  • a Blaine specific surface area of the calcium aluminate compound is 4000 to 9000 cm 2 / g, sufficient rapid hardening can be easily obtained, and strength at low temperatures can be easily obtained.
  • the rapid hardened material of the present embodiment is preferably adjusted to have a Blaine specific surface area of 3,000 to 9000 cm 2 / g, more preferably 4,000 to 8,000 cm 2 / g, by a pulverizing treatment.
  • a Blaine specific surface area of 3,000 to 9000 cm 2 / g, more preferably 4,000 to 8,000 cm 2 / g, by a pulverizing treatment.
  • the amount of the hardened material used is preferably from 10 to 35 parts, more preferably from 15 to 30 parts, even more preferably from 20 to 25 parts, out of 100 parts in total of the cement and the hardened material.
  • the content is 10 to 35 parts, good initial strength can be easily obtained, and the long-term strength does not easily decrease.
  • the sleeping agent used in the present embodiment has a function of causing the hard concrete to be shipped from the ready-mixed concrete to sleep (substantially stops hydration hardening). This is to avoid sudden hardening trouble.
  • the somnol include oxycarboxylic acid, or a salt thereof, or a combination thereof with an alkali metal carbonate, a saccharide, boric acid, and the like. It is preferable to use an oxycarboxylic acid and an alkali metal carbonate in combination from the aspect that the effect of making the rapidly hardened concrete sleep is large and that the strength development after adding a hardening agent is good. However, it is preferable to select an alkali metal carbonate other than lithium as the alkali metal carbonate. It is necessary to ensure a sufficient pot life of the base concrete, and to maintain a certain pot life even after the addition of a hardening agent, and to improve the strength development. Application is not preferred.
  • the sleeping agent preferably contains a mixture of oxycarboxylic acid, an alkali metal carbonate other than lithium and oxycarboxylic acid, and more preferably contains an alkali metal carbonate other than lithium and oxycarboxylic acid.
  • the mixing ratio of the alkali metal carbonate other than lithium to the oxycarboxylic acid is preferably alkali metal carbonate / oxycarboxylic acid, and is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. Is more preferred.
  • Examples of the hydroxycarboxylic acid or a salt thereof include citric acid, gluconic acid, tartaric acid, and malic acid, and examples of the salt include a sodium salt, a potassium salt, a calcium salt, and a magnesium salt. One or more of these may be used in combination.
  • the amount of the sleeping agent used is preferably 0.3 to 5 parts, more preferably 0.3 to 4.5 parts, based on 100 parts in total of cement and hardwood.
  • the amount is 0.3 to 5 parts, it becomes easy to secure sufficient operation time in addition to the transportation time to the site.
  • a hardening agent is added, hydration hardening is easily induced again.
  • the gypsum used in the present embodiment may be any of gypsum, anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. Further, natural gypsum, chemical gypsum such as gypsum by-produced by phosphoric acid, gypsum excreted by gypsum, and gypsum by-produced by hydrofluoric acid, or gypsum obtained by heat-treating these may also be used.
  • anhydrous gypsum and / or hemihydrate gypsum are preferred from the viewpoint of strength development, but anhydrous gypsum is preferably selected from the viewpoint of cost, and type II anhydrous gypsum and / or natural anhydrous gypsum are preferred.
  • the particle size of gypsum is preferably from 3000 cm 2 / g or more in Blaine value, more preferably 4000 ⁇ 7000cm 2 / g. When it is 3,000 cm 2 / g or more, the initial strength can be sufficiently exhibited.
  • the amount of gypsum used is preferably 10 to 200 parts, more preferably 15 to 150 parts, and even more preferably 20 to 130 parts with respect to 100 parts of the calcium aluminate compound. When the content is within these ranges, the strength can be exhibited satisfactorily.
  • an expanding material in addition to the above-described rapid hardening material, sleep agent, and hardening agent, an expanding material, a water reducing agent, an AE water reducing agent, a high-performance water reducing agent, a blast furnace slowly cooled slag fine powder, and a blast furnace slowly cooled slag fine powder.
  • a water reducing agent such as slag, limestone fine powder, fly ash, silica fume and other admixtures, defoamers, thickeners, rust inhibitors, antifreeze agents, shrinkage reducers, polymers, clay minerals such as bentonite, hydrotalcite, etc. It is possible to use one or more of the above anion exchangers and the like as long as the object of the present invention is not substantially inhibited.
  • the embodiment of the method for preparing ready-mixed concrete fast-hardened concrete includes, at least, a step of kneading cement, a quick-hardening material, and a sleep aid in a kneading container together with kneading water; Mixing the hardener at a construction site, for example.
  • the kneading water is shipped from, for example, a ready-mix plant or a ready-mix plant.
  • transport is often performed together with the kneading and mixing.
  • the kneading (and transporting) process which is shipped from a ready-mixed plant or ready-mixed plant, at least the volume of the base concrete containing cement, quick-hardening material, sleep agent, and kneading water is used for kneading (or carrying). It is preferably at least 40% (volume%) of the inner volume of the container, more preferably at least 50 vol%.
  • the kneading (or carrying) container refers to a container provided on a ready-mixed concrete carrier such as a drum of an agitator truck and capable of holding the ready-mixed concrete while stirring.
  • the type and amount of the hardener for ready-mixed shipping quick-hardening concrete are set so that the pot life after mixing the hardener for ready-mixed shipping quick-hardening concrete can be secured for 10 minutes or more, preferably 15 minutes or more. It is preferable to determine.
  • the ready-mixed shipping-type hardening agent for ready-mixed concrete according to the present embodiment is obtained by kneading ready-mixed concrete (ready mixed concrete), and then transporting the kneaded material to be shipped to a construction site, and is added after the driving operation. It is suitable for use as an admixture material.
  • the ready-mixed shipping quick-hardened concrete material according to the present embodiment is also suitable for use as an admixture added after the driving work, like the hardening agent. Then, the pot life can be, for example, 120 minutes or more, preferably 180 minutes or more.
  • Compressive strength (initial compressive strength) was measured 6 hours after application of the curing agent (8 hours after kneading). The results are shown in Table 1 below.
  • s / a is a fine aggregate ratio, and is a value expressing the absolute volume ratio of the fine aggregate amount to the total aggregate amount in the concrete in percentage.
  • Curing agent curing agent A Aluminum sulfate octahydrate
  • reagent first class curing agent C CaO / Al 2 O 3 molar ratio of calcium aluminate quick-setting admixture comprising calcium aluminate 2.20, commercially available, Denka Co.
  • Reagent 1st grade curing agent H Formic acid, Reagent 1st grade
  • Rapid hardened material Equivalent mixture of CaO—Al 2 O 3 —SiO 2 based amorphous substance and anhydrous gypsum.
  • the CaO—Al 2 O 3 —SiO 2 amorphous material has a CaO content of 43%, an Al 2 O 3 of 44%, a SiO 2 of 10%, and the others of 3%. Density 2.85 g / cm 3 , Blaine specific surface area 5000 cm 2 / g, degree of amorphousness 90%.
  • Example 2 The procedure was performed in the same manner as in Experimental Example 1 except that curing agent A was used and liquid paraffin was used in combination as shown in Table 2. Table 2 shows the results.
  • Liquid paraffin paraffin-based curing agent, Master Cure (registered trademark) 106 (manufactured by BASF Pozzolith Co., Ltd.)
  • Example 3 The procedure was performed in the same manner as in Experimental Example 1 except that aluminum sulfate having different numbers of water of crystallization was used as shown in Table 3. Table 3 shows the results.
  • Curing agent anhydrous aluminum sulfate, reagent grade 1 Curing agent: aluminum sulfate 18-hydrate, reagent grade 1
  • Example 4 The procedure was performed in the same manner as in Experimental Example 1 except that the curing agent A was used and the timing of applying the curing agent was changed as shown in Table 4. Table 4 shows the results.
  • the curing agent Lee was 200g applied per 1m 3 in advance striking ⁇ offices in striking ⁇ of concrete.
  • 1.5 parts of the sleeping agent 1 was added to 100 parts of the binder composed of the cement and the rapidly hardened material to prevent hydration and hardening for 24 hours or more (material A).
  • a hardening agent material B
  • material B a hardening agent
  • s / a is a fine aggregate ratio, and is a value expressing the absolute volume ratio of the fine aggregate amount to the total aggregate amount in the concrete in percentage.
  • Example 6 The same procedure as in Experimental Example 1 was carried out, except that the curing agent A was used and the application amount of the curing agent was changed as shown in Table 6. Table 6 shows the results.

Abstract

This curing agent for a concrete composition contains at least one selected from the group consisting of aluminum sulfate, sodium aluminate, calcium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, diethanolamine and formic acid.

Description

コンクリート組成物用養生剤、及びコンクリート組成物の養生方法Curing agent for concrete composition and method for curing concrete composition
　本発明は、コンクリート組成物用養生剤、及びコンクリート組成物の養生方法に関する。 The present invention relates to a curing agent for a concrete composition and a method for curing a concrete composition.
　世界的に見るとセメントの生産量は増加しており、急速にインフラ整備が進められている。特に、中国や東南アジアでの建設ラッシュは現在も続いている。インフラ整備の中でも、道路整備は重要な位置付けにある。道路は新設の際にも、また、補修の際にも、早期解放が望まれるため、使用する材料としても早期供用を可能とする材料が求められている。その一例として、急硬コンクリートが挙げられる。 セ メ ン ト Globally, cement production is increasing, and infrastructure development is progressing rapidly. In particular, construction rushes in China and Southeast Asia continue today. Road development is an important part of infrastructure development. Since a road is required to be released early when it is newly constructed or when it is repaired, a material that can be used quickly is required as a material to be used. One example is rapid hardened concrete.
　急硬コンクリートは、セメント種により初期材齢で十分な強度発現性を満たさない場合がある。また、初期の強度発現性は外気温に大きく左右されるため、冬期等の気温が低い場合は、必要な強度発現性を満たさない場合がある。 Quick-hardened concrete may not satisfy sufficient strength at early age depending on the cement type. In addition, since the initial strength development is greatly affected by the outside temperature, when the temperature is low in winter or the like, the required strength development may not be satisfied.
　今日、セメント種や外気温に関わらず、初期材齢で十分な強度発現性を有する急硬コンクリートの開発が強く望まれている。 Today, there is a strong demand for the development of rapid hardened concrete that has sufficient strength at the early age regardless of cement type and outside temperature.
　他方、コンクリートの凝結硬化を促進する目的で、凝結促進剤をコンクートに添加する方法、例えば、硫酸アルミニウムを添加する方法（特許文献１、特許文献２）が提案されている。 On the other hand, for the purpose of accelerating the setting and hardening of concrete, a method of adding a setting accelerator to concrete, for example, a method of adding aluminum sulfate (Patent Documents 1 and 2) has been proposed.
　また、コンクリートが硬化した後、すなわち、コテ仕上げを終えた後、しばらくしてからパラフィン系の塗膜養生剤を被覆する方法も知られている（特許文献３）。 Also, a method of coating a paraffin-based film curing agent after the concrete has hardened, that is, after finishing ironing, is known (Patent Document 3).
フランス特許２０３１９５０号French Patent No. 2031950 特開平０８－４８５５３号公報JP 08-48553 A 特開２００７－３０８３５３号公報JP 2007-308353 A
　しかし、特許文献１や２の方法だと、運搬中にコンクリートのコンシステンシーが低下し、打設時の作業性が著しく悪くなり、施工が上手くいかず、施工欠陥を招くおそれもあった。また、特許文献３の方法はコンクリートの中性化や塩害を抑制する方法であるが、強度を増進させるものではなかった。 However, according to the methods of Patent Documents 1 and 2, the concrete consistency was reduced during transportation, the workability at the time of casting was significantly deteriorated, the construction did not work well, and there was a risk of causing construction defects. The method disclosed in Patent Document 3 is a method for suppressing carbonation and salt damage of concrete, but does not increase the strength.
　以上から、本発明は、コンクリート組成物を硬化させる際に初期の強度発現性を向上させることが可能なコンクリート組成物用養生剤を提供することを目的とする。 From the above, it is an object of the present invention to provide a curing agent for a concrete composition capable of improving the initial strength development when the concrete composition is cured.
　本発明者らは、上記課題を解決すべく、種々努力を重ねた結果、例えば施工現場にて特定の成分を含む養生剤を用いることにより、初期の強度発現性に優れるコンクリート組成物の硬化物を調製できることを知見し、本発明を完成するに至った。すなわち、本発明は下記の通りである。 The present inventors have made various efforts to solve the above problems, and as a result, for example, by using a curing agent containing a specific component at a construction site, a cured product of a concrete composition having excellent initial strength development. Was found to be able to be prepared, and the present invention was completed. That is, the present invention is as follows.
[１]　硫酸アルミニウム、アルミン酸ナトリウム、硝酸リチウム、硝酸ナトリウム、硝酸カルシウム、カルシウムアルミネート、ジエタノールアミン、及びギ酸からなる群から選択される少なくとも１種を含むコンクリート組成物用養生剤。
[２]　さらに流動パラフィンを含有してなる[１]に記載のコンクリート組成物用養生剤。
[３]　前記硫酸アルミニウムが、硫酸アルミニウム８水塩である[１]又は[２]に記載のコンクリート組成物用養生剤。
[４]　コンクリート組成物の養生に、[１]～[３]のいずれかに記載のコンクリート組成物用養生剤を用いるコンクリート組成物の養生方法。
[５]　前記コンクリート組成物を打設し、その後、該コンクリート組成物が硬化する前に、その表面に前記コンクリート組成物用養生剤を塗布する[４]に記載のコンクリート組成物の養生方法。
[６]　前記コンクリート組成物用養生剤を打設箇所に塗布してから、前記コンクリート組成物を打設し、その後、該コンクリート組成物が硬化する前に、その表面に養生剤を塗布する[４]又は[５]に記載のコンクリート組成物の養生方法。
[７]　前記コンクリート組成物が生コン出荷型急硬コンクリートであることを特徴とする[４]～[６]のいずれかに記載のコンクリート組成物の養生方法。 [1] A curing agent for concrete compositions containing at least one selected from the group consisting of aluminum sulfate, sodium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, calcium aluminate, diethanolamine, and formic acid.
[2] The curing agent for concrete compositions according to [1], further comprising liquid paraffin.
[3] The curing agent according to [1] or [2], wherein the aluminum sulfate is aluminum sulfate octahydrate.
[4] A method for curing a concrete composition, comprising using the curing agent for a concrete composition according to any one of [1] to [3] for curing the concrete composition.
[5] The method for curing a concrete composition according to [4], wherein the concrete composition is cast, and thereafter, the curing agent for the concrete composition is applied to the surface of the concrete composition before the concrete composition hardens.
[6] After applying the curing agent for concrete composition to a casting site, the concrete composition is poured, and then, before the concrete composition is cured, a curing agent is applied to the surface thereof [ A method for curing the concrete composition according to [4] or [5].
[7] The method for curing a concrete composition according to any one of [4] to [6], wherein the concrete composition is a ready-mixed shipping quick-hardened concrete.
　本発明によれば、コンクリート組成物を硬化させる際に初期の強度発現性を向上させることが可能なコンクリート組成物用養生剤を提供することができる。 According to the present invention, it is possible to provide a curing agent for a concrete composition capable of improving the initial strength development when the concrete composition is cured.
　以下、本発明の実施形態を詳細に説明するが、本発明は当該実施形態に限定されるものではない。なお、本明細書における「部」や「％」は特に規定しない限り質量基準とする。また、本明細書におけるコンクリート組成物とは、モルタル、コンクリートを総称するものである。 Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments. In this specification, “parts” and “%” are based on mass unless otherwise specified. Moreover, the concrete composition in this specification is a general term for mortar and concrete.
［コンクリート組成物用養生剤］
　本発明のコンクリート組成物用養生剤（以下、単に「養生剤」ということがある）は、硫酸アルミニウム、アルミン酸ナトリウム、カルシウムアルミネート、硝酸リチウム、硝酸ナトリウム、硝酸カルシウム、ジエタノールアミン、及びギ酸からなる群から選択される少なくとも１種を含む。 [Cure agent for concrete composition]
The curing agent for concrete composition of the present invention (hereinafter, may be simply referred to as “curing agent”) comprises aluminum sulfate, sodium aluminate, calcium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, diethanolamine, and formic acid. At least one selected from the group.
　これらは、初期のエトリンガイト生成が卓越することで、コンクリート組成物を硬化させる際に初期の強度発現性を向上させることができる。 These are excellent in initial ettringite generation and can improve initial strength development when hardening the concrete composition.
（硫酸アルミニウム）
　硫酸アルミニウムとは、Ａｌ２Ｏ３成分とＳＯ３成分を含有する化合物を総称するものであり、特に限定されるものではない。一般式Ａｌ２（ＳＯ４）３・ｎＨ２Ｏで表され、式中のｎは０～１８の範囲にあり、様々な結晶水の硫酸アルミニウムが存在する。本発明では、初期強度の発現性の観点から、８水塩を使用することが好ましい。 (Aluminum sulfate)
Aluminum sulfate is a general term for compounds containing an Al 2 O 3 component and an SO 3 component, and is not particularly limited. It is represented by the general formula Al 2 (SO 4 ) 3 .nH 2 O, where n is in the range of 0 to 18, and aluminum sulfate of various crystallization waters is present. In the present invention, it is preferable to use octahydrate from the viewpoint of the development of the initial strength.
（アルミン酸ナトリウム）
　アルミン酸ナトリウムは、化学成分としてＮａ２ＯとＡｌ２Ｏ３を含有するもので、組成比がＮａ２ＯとＡｌ２Ｏ３の含有モル比（Ｎａ２Ｏ／Ａｌ２Ｏ３）で０．７～１．５のアルミン酸ナトリウムであることが好ましい。 (Sodium aluminate)
Sodium aluminate contains Na 2 O and Al 2 O 3 as chemical components and has a composition ratio of 0.1 in terms of a molar ratio of Na 2 O and Al 2 O 3 (Na 2 O / Al 2 O 3 ). Preferably, it is 7 to 1.5 sodium aluminate.
（カルシウムアルミネート）
　カルシウムアルミネートとは、含有化学成分としてＣａＯとＡｌ２Ｏ３を含む結晶質やガラス化が進んだ構造の水和活性物質であって、ＣａＯとＡｌ２Ｏ３の含有モル比（ＣａＯ／Ａｌ２Ｏ３）が１．５０～２．６０のカルシウムアルミネート化合物であることが好ましい。水和反応活性がより高いものが得られることから、非晶質含有割合が９０質量％以上であることが好ましい。
　具体的には、１２ＣａＯ・７Ａｌ２Ｏ３、ＣａＯ・Ａｌ２Ｏ３、３ＣａＯ・Ａｌ２Ｏ３等のカルシウムアルミネート等が挙げられる。また、カルシウムアルミネート系急結剤も、上記カルシウムアルミネート化合物を含んでいれば使用することができる。カルシウムアルミネート系急結剤の市販品としては、デンカ社製ナトミックタイプＺ等が挙げられる。 (Calcium aluminate)
Calcium aluminate is a hydration active substance having a crystalline or vitrified structure containing CaO and Al 2 O 3 as contained chemical components, and has a molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) is preferably a calcium aluminate compound having a molecular weight of 1.50 to 2.60. It is preferable that the amorphous content is 90% by mass or more, since a higher hydration reaction activity can be obtained.
Specifically, 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, calcium aluminate such as 3CaO · Al 2 O 3 and the like. Calcium aluminate quick-setting agents can also be used as long as they contain the calcium aluminate compound. Commercial products of calcium aluminate-based quick setting agents include NATMIC TYPE Z manufactured by Denka Corporation.
（硝酸リチウム）
　硝酸リチウムとしては、無水物（無水塩）の他、０．５水和物（０．５水塩）及び３水和物（３水塩）が存在し、特に限定されないが、無水物が好ましい。 (Lithium nitrate)
Lithium nitrate includes 0.5 hydrate (0.5 hydrate) and 3 hydrate (3 hydrate) in addition to anhydride (anhydrous salt), and is not particularly limited, but anhydrous is preferable. .
（硝酸ナトリウム）
　硝酸ナトリウムとしては、ＮａＮＯ３で表され、本発明では特に限定されるものではなく、天然に産出されるチリ硝石を粉砕して用いることも可能である。 (Sodium nitrate)
The sodium nitrate is represented by NaNO 3 , and is not particularly limited in the present invention. Naturally produced chile saltpeter may be used after being pulverized.
（硝酸カルシウム）
　硝酸カルシウムとしては、Ｃａ（ＮＯ３）２・ｎＨ２Ｏで表され、４水塩の他、４水塩を脱水した脱水製品が存在するが、本発明では特に限定されるものではない。 (Calcium nitrate)
As calcium nitrate, Ca (NO 3 ) 2 .nH 2 O is used, and there are dehydrated products obtained by dehydrating tetrahydrate in addition to tetrahydrate, but the present invention is not particularly limited thereto.
（ジエタノールアミン）
　ジエタノールアミンとしては、ＨＮ（ＣＨ２ＣＨ２ＯＨ）２で表され、純度９８％以上のものを用いるのが好ましい。 (Diethanolamine)
Diethanolamine represented by HN (CH 2 CH 2 OH) 2 and having a purity of 98% or more is preferably used.
（ギ酸）
　ギ酸としては、７６％～９８．６％までの様々な純度が存在するが、本発明では特に限定されるものではない。 (Formic acid)
Formic acid has various purities ranging from 76% to 98.6%, but is not particularly limited in the present invention.
　上記の各成分の中でも、初期のエトリンガイトの生成量の観点から、硫酸アルミニウム、アルミン酸ナトリウム、カルシウムアルミネートが好ましく、硫酸アルミニウムがより好ましい。 中 で も Among the above components, aluminum sulfate, sodium aluminate, and calcium aluminate are preferable, and aluminum sulfate is more preferable, from the viewpoint of the initial amount of ettringite generated.
　本発明の養生剤にさらに、流動パラフィンを含有することが好ましい。その割合は特に限定されるものでないが、流動パラフィンと養生剤との質量比は、１０：９０～９０：１０が好ましく３０：７０～７０／３０がより好ましい。 養 The curing agent of the present invention preferably further contains liquid paraffin. The ratio is not particularly limited, but the mass ratio of liquid paraffin to the curing agent is preferably from 10:90 to 90:10, and more preferably from 30:70 to 70/30.
　パラフィンとは、非揮発性の精製した飽和炭化水素の混合物の総称であり、炭化水素化合物の一種であり、炭素原子の数ｎが２０以上のアルカン（alkane、アルカン族、一般式がＣｎＨ２ｎ＋２とあらわされる鎖式飽和炭化水素）を総称するものである。通常、パラフィンは均一の物質ではなく「構成する炭素鎖」に、さまざまなものが混ざっている。パラフィンのなかで、炭素鎖が長いものを多く含むものは、固体状で、「石油ワックス」と呼ばれる。一方、炭素鎖に短いものが多く含まれるものは、常温常圧で液状であり、「流動パラフィン」(liquid paraffin)と呼ばれる。本発明では、流動パラフィンを用いることが好ましい。本発明では、市販されているパラフィン系養生剤を用いることができる。その具体例としては、例えば、ＢＡＳＦポゾリス（株）製「マスターキュア」や、フォスロック社製「コンキュアー」等を挙げることができる。 Paraffin is a general term for a mixture of non-volatile purified saturated hydrocarbons, and is a kind of hydrocarbon compound. Alkanes having 20 or more carbon atoms (alkane, alkane group, and the general formula is CnH 2n + 2 ) (Chain-type saturated hydrocarbon represented). Normally, paraffin is not a homogeneous substance, but various things are mixed in "constituting carbon chains". Among paraffins, those containing many long carbon chains are solid and called "petroleum wax". On the other hand, those containing many short carbon chains are liquid at normal temperature and pressure, and are called "liquid paraffin". In the present invention, it is preferable to use liquid paraffin. In the present invention, a commercially available paraffin-based curing agent can be used. Specific examples thereof include "Master Cure" manufactured by BASF Pozzolith Co., Ltd. and "Concure" manufactured by Fosrock Co., Ltd.
［コンクリート組成物の養生方法］
　本発明のコンクリート組成物の養生方法においては、コンクリート組成物の養生に、本発明のコンクリート組成物用養生剤を用いる。 [Method of curing concrete composition]
In the method for curing a concrete composition of the present invention, the curing agent for a concrete composition of the present invention is used for curing the concrete composition.
　本発明の養生剤を使用する方法としては、特に限定されないが、コンクリート組成物を打設し、その後、コンクリート組成物が硬化する前に、その表面にコンクリート組成物用養生剤を塗布する方法；コンクリート組成物用養生剤を打設箇所に塗布してから、コンクリート組成物を打設し、その後、該コンクリート組成物が硬化する前に、その表面に養生剤を塗布する方法；等が好ましく挙げられる。 The method of using the curing agent of the present invention is not particularly limited, but a method of casting a concrete composition and thereafter applying a curing agent for the concrete composition to the surface thereof before the concrete composition is cured; A method in which a curing agent for concrete composition is applied to a casting location, then a concrete composition is cast, and then, before the concrete composition is cured, a curing agent is applied to the surface of the concrete composition. Can be
　コンクリート打設後から凝結の始発前までのいずれのタイミングでも可能であるが、初期強度の発現性の観点から、コンクリート打設後はできるだけ早いタイミングで使用することが望ましく、コンクリート打設後、１時間以内に養生剤を使用することが好ましく、３０分以内がより好ましい。 Although it is possible at any timing from after the concrete is cast to before the start of the setting, it is desirable to use the concrete as soon as possible after the concrete is cast, from the viewpoint of the development of the initial strength. It is preferred to use the curing agent within hours, more preferably within 30 minutes.
　本発明の養生剤の施工方法は、均一に施工できるものであれば、特に限定されるものではなく、散布、塗布、吹付け、噴霧等で行うことが可能であり、塗布が好ましい。 施工 The method of applying the curing agent of the present invention is not particularly limited as long as it can be applied uniformly, and can be applied by spraying, coating, spraying, spraying, etc., and coating is preferable.
　本発明の養生剤の使用量は特に限定されるものではないが、通常、コンクリート組成物１ｍ２当たり、養生剤５０ｇ～５００ｇの範囲で使用することが好ましく、１００ｇ～３００ｇがより好ましい。５０ｇ～５００ｇの範囲で使用することで、十分な初期強度発現性が得られやすくなる。 Although the amount of the curing agent of the present invention is not particularly limited, it is generally preferable to use the curing agent in an amount of 50 g to 500 g, more preferably 100 g to 300 g, per m 2 of the concrete composition. When used in the range of 50 g to 500 g, sufficient initial strength can be easily obtained.
　本発明の養生方法の対象としては、公知のモルタル及びコンクリート等で特に限定されないが、コンクリート組成物として生コン出荷型急硬コンクリートに使用することが好ましい。
　生コン出荷型急硬コンクリートに使用することで、当該生コン出荷型急硬コンクリートの初期強度を増進させることができる。 The object of the curing method of the present invention is not particularly limited to known mortar, concrete and the like, but it is preferable to use it as a concrete composition for ready-mixed shipping-type rapid hardened concrete.
By using the ready-mixed concrete shipped hardened concrete, the initial strength of the ready-mixed ready-hardened concrete can be increased.
　ここで、「生コン出荷型急硬コンクリート」とは、生コン工場や生コンプラント等で眠剤を多量に添加し、眠らせた急硬コンクリート（水和硬化がほぼ停止したコンクリート）を混練した後、アジテータ車によって搬送されて、土木工事現場や建設現場等の施工現場に出荷され、現場で生コン出荷型急硬コンクリート用起硬剤を添加することで水和硬化を再び復活させることができるコンクリートである。 Here, “concrete ready-to-cook hard concrete” refers to a ready-mixed concrete plant or a ready-mixed concrete plant to which a large amount of a sleeping agent is added, kneaded, and then abruptly hardened concrete (concrete for which hydration hardening has almost stopped) is agitated. It is transported by car and shipped to construction sites such as civil engineering construction sites and construction sites, and it is a concrete that can restore hydration hardening again by adding a hardening agent for ready-mixed concrete quick-hardening concrete at the site. .
　以下では、本発明の養生剤が好ましく用いられる生コン出荷型急硬コンクリートについて説明する。
　まず生コンプラントでは、急硬材と眠剤を予め添加混合した各種のベースコンクリートを用意する必要があり、起硬剤は現場まで搬送後に各種のベースコンクリートに対して添加混合する必要がある。起硬剤を施工現場でなく生コンプラントで予め各種のベースコンクリートに対して混合すると、可使時間が確保できない。また、生コン工場で急硬材と起硬剤の双方を添加すると、可使時間が極端に短くなり、搬送途中でコンクリートの破棄を余儀なくされる。
　起硬剤を生コン工場で添加し、施工現場で急硬材を添加する場合には、急硬材を添加した後の可使時間が１０分以下と極端に短くなり、施工ができない。急硬材と起硬剤を施工現場で添加する場合には、可使時間が短縮され、圧縮強度も低い値となり、耐摩耗性も改悪傾向となることに加え、アジテータのドラム容積の３０％程度しか搬送できない。このように、急硬材と起硬剤の添加タイミングは極めて重要である。 Hereinafter, a ready-mixed shipping quick-hardened concrete in which the curing agent of the present invention is preferably used will be described.
First, in a ready-mixed plant, it is necessary to prepare various base concretes in which a rapid hardening material and a sleep aid are added and mixed in advance, and it is necessary to add and mix a hardening agent to various base concretes after being transported to the site. If the hardener is mixed with various base concretes in advance at a ready-mixed plant rather than at the construction site, the pot life cannot be secured. Further, when both the hardened material and the hardening agent are added at the ready-mixed concrete factory, the pot life becomes extremely short, and the concrete must be discarded during transportation.
When a hardening agent is added at a ready-mixed concrete plant and a hardened material is added at a construction site, the pot life after the addition of the hardened material is extremely shortened to 10 minutes or less, and the work cannot be performed. When a hardened material and a hardening agent are added at the construction site, the pot life is shortened, the compressive strength becomes low, the wear resistance tends to deteriorate, and the drum volume of the agitator is reduced by 30%. Can be transported only to the extent. Thus, the timing of adding the hardened material and the hardening agent is extremely important.
　そこで、本実施形態では、セメント、急硬材、及び眠剤を含むＡ材と、生コン出荷型急硬コンクリート用起硬剤を含むＢ材とからなる２材型とすることで、具体的には、生コンプラントから施工現場まで、Ａ材とＢ材を別々に搬送し、施工現場でこれらを混合することで、本実施形態の生コン出荷型急硬コンクリート組成物とすることができる。以下、本実施形態に係る各成分等を詳細に説明する。 Therefore, in the present embodiment, concretely, by using a two-material type including the material A including cement, a hardened material, and a sleep-inducing agent, and the material B including a hardening agent for ready-mixed concrete shipping-type hardened concrete, Can be used as the ready-mixed concrete-hardened concrete composition of the present embodiment by separately transporting the materials A and B from the ready-mixed plant to the construction site and mixing them at the construction site. Hereinafter, each component and the like according to the present embodiment will be described in detail.
（生コン出荷型急硬コンクリート用起硬剤）
　生コン出荷型急硬コンクリート用起硬剤に係る実施形態において、生コン出荷型急硬コンクリート用起硬剤（以下、単に「起硬剤」ということがある）とは、後述する眠剤を多量に添加し、眠らせた急硬コンクリート（水和硬化がほぼ停止したコンクリート）の水和硬化を例えば施工現場で再び呼び覚ます材料を意味する。その具体例としては、水酸化カルシウム、炭酸カルシウム、カルシウムアルミネート系化合物、カルシウムシリケート系化合物、コロイダルシリカ、ポルトランドセメント、カルシウムサルフォアルミネートセメント、高炉スラグなどの１種または２種以上を併用することが可能である。 (Hardener for quick-concrete shipping ready-mixed concrete)
In the embodiment relating to the ready-mixed shipping quick-hardening concrete hardening agent, the ready-mixed shipping quick-hardening concrete hardening agent (hereinafter, may be simply referred to as “hardening agent”) is a large amount of a sleeping agent described below. It means a material that rehydrates the hydration hardening of the added hardened concrete (the concrete whose hydration hardening is almost stopped), for example, at the construction site. Specific examples thereof include one or more of calcium hydroxide, calcium carbonate, calcium aluminate compounds, calcium silicate compounds, colloidal silica, portland cement, calcium sulfoaluminate cement, blast furnace slag, and the like. It is possible.
　ここで、本実施形態でいう「生コン出荷型急硬コンクリート」とは、既述のとおりであり、搬送時間の関係から、出荷から作業完了まで、最低でも可使時間は１２０分以上必要であり、搬送距離が長い場合には１８０分以上の可使時間を確保することが望まれる。本実施形態は、このような用途に特化して用いられるものである。
　なお、上記の「アジテータ車」とは、生コンを撹拌しながら輸送することができる、荷台部分にミキシング・ドラム（練り混ぜ用容器）を備えた貨物自動車であり、その機能に大きな差はないが、最大積載量２～２６ｔ級のものがあり、用途に応じて使い分けられている。 Here, the “fresh concrete shipping-type rapid hardened concrete” referred to in the present embodiment is as described above. From the relationship of the transport time, from the shipping to the completion of the work, at least the working time is required to be 120 minutes or more. When the transport distance is long, it is desired to secure a pot life of 180 minutes or more. The present embodiment is used specifically for such a use.
The "agitator truck" is a truck equipped with a mixing drum (container for mixing) on the loading platform that can transport ready-mixed concrete while stirring it, and there is no significant difference in its function. , With a maximum loading capacity of 2 to 26t class, which are used properly according to the application.
　ただし、生コン出荷型急硬コンクリート用起硬剤を添加した後も、作業時間を確保する必要があり、少なくとも１５分以上の可使時間が確保できる起硬剤の種類の選定と添加量の設定が必要である。その観点から、起硬剤として、アルミン酸ナトリウム、硫酸アルミニウム、ケイ酸ナトリウム等の急結剤の選定は避ける必要がある。これらの急結剤は、添加後直ちに急結性を示し、１０分以上の可使時間を確保することが困難となる。したがって、これら急結剤は生コン出荷型急硬コンクリート用起硬剤１００部に対して、３０部以下とすることが好ましく、まったく使用しないことがより好ましい。 However, it is necessary to secure the working time even after adding the hardener for ready-mixed concrete-type hardened concrete, and to select the type of hardener that can secure at least 15 minutes of usable time and set the amount of hardener. is necessary. From that viewpoint, it is necessary to avoid selecting a quick setting agent such as sodium aluminate, aluminum sulfate, and sodium silicate as a hardening agent. These quick-setting agents exhibit quick-setting properties immediately after addition, making it difficult to secure a pot life of 10 minutes or more. Therefore, these quick-setting agents are preferably used in an amount of not more than 30 parts, and more preferably not used at all, with respect to 100 parts of the hardening agent for ready-mixed concrete shipping-type hardened concrete.
　生コン出荷型急硬コンクリート用起硬剤は既述のいずれかの成分を必須成分とするが、温度依存性を改善するために、水酸化カルシウムだけ、又は、水酸化カルシウムとカルシウムアルミネート系化合物とを併用することがより好ましい。併用する場合のその配合割合は特に限定されないが、水酸化カルシウムとカルシウムアルミネート系化合物との質量比（水酸化カルシウム／カルシウムアルミネート系化合物）で、１／９９～９９／１であることが好ましく、２／９８～９８／２であることがより好ましい。質量比１／９９～９９／１であることで、温度依存性を小さくできることに加え、セメントの種類が変化した際にも安定した起硬剤の効果を発揮することができる。当該質量比は、さらに、１０／９０～９０／１０であることが好ましく、２０／８０～８０／２０であることがより好ましい。 The hardener for ready-mixed concrete quick-hardening concrete contains any of the above-mentioned components as essential components, but in order to improve the temperature dependence, only calcium hydroxide, or calcium hydroxide and a calcium aluminate compound It is more preferable to use both. When used in combination, the mixing ratio is not particularly limited, but may be from 1/99 to 99/1 in terms of the mass ratio of calcium hydroxide to calcium aluminate compound (calcium hydroxide / calcium aluminate compound). It is more preferably 2/98 to 98/2. When the mass ratio is 1/99 to 99/1, the temperature dependency can be reduced, and the effect of the hardening agent can be exhibited stably even when the type of cement changes. The mass ratio is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20.
　生コン出荷型急硬コンクリート用起硬剤は、例えば、３００μｍ篩い残分が５％以下であり、１００μｍ篩い残分が１０％以下であることが好ましい。 起 In the ready-mixed concrete-type hardening agent for hardened concrete, for example, the 300 μm sieve residue is preferably 5% or less, and the 100 μm sieve residue is preferably 10% or less.
　本発明においてカルシウムアルミネート系化合物は、後述する急硬材にも用いるが、起硬剤に適用するカルシウムアルミネート系化合物は、ＣａＯ／Ａｌ２Ｏ３モル比で０．５～２．４の範囲のものが好ましい。ＣａＯ／Ａｌ２Ｏ３モル比が０．５以上であることで、温度依存性の改善効果をより十分に発揮させることができ、２．４以下であることで、起硬剤をスラリーで用いる際に急硬を抑えることができる。
　なお、上記の好ましい範囲内でも、可使時間を長くする観点からは、０．５～１．２の範囲のものがより好ましく、０．７５～１．０の範囲のものがさらに好ましい。初期の強度発現の観点からは、１．２～２．４の範囲のものがより好ましく、１．２５～２．３の範囲のものがさらに好ましい。
　さらにカルシウムアルミネート系化合物は、非晶質カルシウムアルミネート系化合物と結晶質カルシウムアルミネート系化合物に大別されるが、長期強度の発現性から非晶質カルシウムアルミネート系化合物の使用が好ましい。 In the present invention, the calcium aluminate-based compound is used for a hardening material described later, but the calcium aluminate-based compound used for the hardening agent has a CaO / Al 2 O 3 molar ratio of 0.5 to 2.4. Those in the range are preferred. When the CaO / Al 2 O 3 molar ratio is 0.5 or more, the effect of improving the temperature dependency can be sufficiently exhibited, and when the CaO / Al 2 O 3 molar ratio is 2.4 or less, a hardening agent is used in the slurry. In this case, rapid hardening can be suppressed.
Even within the above preferred range, from the viewpoint of prolonging the pot life, a range of 0.5 to 1.2 is more preferable, and a range of 0.75 to 1.0 is more preferable. From the viewpoint of initial strength development, those having a range of 1.2 to 2.4 are more preferable, and those having a range of 1.25 to 2.3 are still more preferable.
Calcium aluminate compounds are further roughly classified into amorphous calcium aluminate compounds and crystalline calcium aluminate compounds, and the use of amorphous calcium aluminate compounds is preferred from the viewpoint of long-term strength.
　また、生コン出荷型急硬コンクリート用起硬剤における、水酸化カルシウム、炭酸カルシウム、カルシウムアルミネート系化合物、カルシウムシリケート系化合物、コロイダルシリカ、ポルトランドセメント、カルシウムサルフォアルミネートセメント、及び高炉スラグのそれぞれ、又は、併用する場合はそれらの合計は、それぞれの効果、又は、複合効果を効率よく発揮させる観点から、７０％以上であることが好ましく、８０％以上であることがより好ましい。 In addition, calcium hydroxide, calcium carbonate, calcium aluminate-based compounds, calcium silicate-based compounds, colloidal silica, portland cement, calcium sulfoaluminate cement, and blast furnace slag in the hardener for ready-mixed concrete hardened concrete Or, when they are used in combination, the total thereof is preferably 70% or more, more preferably 80% or more, from the viewpoint of efficiently exhibiting the respective effects or the combined effects.
　なお、上記例示した起硬剤以外の物質（その他の成分）の存在も、当該起硬剤の分散性を高めたり、起硬剤の効果を助長したりできるもので、本発明の効果を阻害しないものあれば、３０％以下の範囲で含有させることができる。 The presence of a substance (other component) other than the above-described hardener can also enhance the dispersibility of the hardener or promote the effect of the hardener, and impair the effects of the present invention. If not, it can be contained in a range of 30% or less.
　起硬剤においては、既述のいずれかの成分に、さらに、セッコウを含有することが好ましく、カルシウムアルミネート系化合物とセッコウとを含有してなることがより好ましい。使用するセッコウは、無水セッコウ、半水セッコウ、二水セッコウのいずれのセッコウも使用できる。さらに天然セッコウや、リン酸副生セッコウ、排脱セッコウ、及びフッ酸副生セッコウなどの化学セッコウ、または、これらを熱処理して得られるセッコウなども使用できる。これらの中では、強度発現性の点で、無水セッコウ及び／又は半水セッコウが好ましいが、コストの観点から無水セッコウを選定することが好ましく、ＩＩ型無水セッコウ及び／又は天然無水セッコウが好ましい。セッコウの粒度はブレーン値で３０００ｃｍ２／ｇ以上が好ましく、４０００～７０００ｃｍ２／ｇがより好ましい。３０００ｃｍ２／ｇ以上であることで初期強度発現性を良好に発揮させることができる。 The hardening agent preferably further contains gypsum, more preferably a calcium aluminate-based compound and gypsum, in addition to any of the above-described components. The gypsum to be used may be any of anhydrous gypsum, hemihydrate gypsum and dihydrate gypsum. Further, natural gypsum, chemical gypsum such as gypsum by-produced by phosphoric acid, gypsum excreted by gypsum, and gypsum by-produced by hydrofluoric acid, or gypsum obtained by heat-treating these may also be used. Among these, anhydrous gypsum and / or hemihydrate gypsum are preferred from the viewpoint of strength development, but anhydrous gypsum is preferably selected from the viewpoint of cost, and type II anhydrous gypsum and / or natural anhydrous gypsum are preferred. The particle size of gypsum is preferably from 3000 cm 2 / g or more in Blaine value, more preferably 4000 ~ 7000cm 2 / g. When it is 3,000 cm 2 / g or more, the initial strength can be sufficiently exhibited.
　セッコウの使用量は、起硬剤（好ましくはカルシウムアルミネート系化合物）１００部に対して１０～２００部が好ましく、１５～１５０部がより好ましく、９０～１３０部がさらに好ましい。これらの範囲であることで長期強度発現性と耐久性を良好にすることができる。 The amount of gypsum used is preferably 10 to 200 parts, more preferably 15 to 150 parts, and even more preferably 90 to 130 parts with respect to 100 parts of a hardening agent (preferably a calcium aluminate compound). Within these ranges, long-term strength development and durability can be improved.
　生コン出荷型急硬コンクリート用起硬剤の使用量は、特に限定されるものではないが、後述のセメントと急硬材との合計１００部に対して、０．５～７部が好ましく、１～５部がより好ましい。０．５～７部であることで、短時間材齢の強度発現性を十分なものとし、可使時間を確保することができる。なお、起硬剤はスラリー化して各種のベースコンクリートなどに添加してもよい。この場合、コンクリート配合から練り混ぜ水の一部を起硬剤のスラリーに充て、ベースコンクリートからその分の水を差し引いておくことが、強度発現性の観点から望ましい。また、起硬剤は予めポリビニルアルコール（ＰＶＡ）フィルムなどの水溶性フィルムによって包装された状態で各種のベースコンクリートなどに添加してもよい。この場合、起硬剤とともにその効果を阻害しない範囲で種々の添加物を混合してもよい。なお、本明細書において、ベースコンクリートとは、少なくとも、セメント、急硬材、眠剤、骨材、及び混練水を混練してなるコンクリートをいう。 The amount of the hardening agent for ready-mixed concrete quick-hardened concrete is not particularly limited, but is preferably 0.5 to 7 parts with respect to a total of 100 parts of cement and quick-hardening material described below. -5 parts is more preferred. When the amount is 0.5 to 7 parts, the strength can be sufficiently developed in a short-term age, and the pot life can be secured. The hardening agent may be slurried and added to various types of base concrete. In this case, it is desirable from the viewpoint of strength development to apply a part of the mixing water from the concrete mixture to the slurry of the hardening agent and subtract the water from the base concrete. Further, the hardening agent may be added to various types of base concrete or the like in a state of being packaged in advance with a water-soluble film such as a polyvinyl alcohol (PVA) film. In this case, various additives may be mixed together with the hardening agent as long as the effect is not impaired. In the present specification, the base concrete refers to a concrete obtained by kneading at least cement, a rapid hardening material, a sleep aid, an aggregate, and kneading water.
　ここで、好ましい態様の水溶性フィルムは、木材パルプ、多糖類、ポバール、セルロース、ポリビニルアルコール、カルボキシメチルセルロース、でんぷん等を原料としたものを用い、原料中の木材パルプの含有量は７５～９５％が好ましく、８０～９０％はより好ましい。木材パルプを除く多糖類、ポバール、セルロース、ポリビニルアルコール、カルボキシメチルセルロース、でんぷん等の原料は、５～２５％が好ましく、１０～２０％がより好ましい。
　上記範囲より多糖類、ポバール、セルロース、ポリビニルアルコール、カルボキシメチルセルロース、でんぷん等の原料が少ない場合、水溶紙を製造する際のヒートシールに必要な接着剤原料が不足し、製造が困難となり、上記範囲より多い場合、コンクリート中に空気を巻き込むので好ましくない。
　また、好ましい態様の水溶性フィルムは水溶性であれば特に限定されるものではないが、２０℃の水５００ｍｌが入ったビーカー(容量１０００ｍｌ)に水溶性フィルムを１０ｇ添加し、スターラー（池田理工社製）により８００ｒｐｍで撹拌した時の分散時間が、３０秒以下であることが好ましく、２０秒以下がより好ましい。分散時間は目視により凝集物がなくなった状態の時を言う。分散時間が３０秒を超えるものはコンクリート練混ぜ後に分散しきらず、コンクリート中に残存する場合がある。
　上記好ましい態様の水溶性フィルムによって起硬剤を包装した態様を用いたコンクリートの練混ぜ時間は、当該態様を用いない無混和のコンクリートと比較して同程度であるが、上記好ましい態様の水溶性フィルムでない水溶性フィルムを用いた場合、コンクリートの練混ぜ時間が長くなることがあり、同じ練混ぜ時間の場合、投入袋数が好ましい態様の水溶性フィルムと同じでも、水溶性フィルムがコンクリート中に残存する場合がある。 Here, the water-soluble film of the preferred embodiment is made of wood pulp, polysaccharide, poval, cellulose, polyvinyl alcohol, carboxymethylcellulose, starch or the like, and the content of wood pulp in the raw material is 75 to 95%. Is preferable, and 80 to 90% is more preferable. Raw materials such as polysaccharides other than wood pulp, poval, cellulose, polyvinyl alcohol, carboxymethylcellulose, and starch are preferably 5 to 25%, more preferably 10 to 20%.
If the raw materials such as polysaccharides, poval, cellulose, polyvinyl alcohol, carboxymethyl cellulose, and starch are less than the above ranges, the amount of adhesive raw materials necessary for heat sealing when producing water-soluble paper is insufficient, making the production difficult. If it is larger, air is entrained in the concrete, which is not preferable.
The water-soluble film of the preferred embodiment is not particularly limited as long as it is water-soluble, but 10 g of the water-soluble film is added to a beaker (capacity: 1000 ml) containing 500 ml of water at 20 ° C., and a stirrer (Ikeda Riko Co., Ltd.) Is preferably 30 seconds or less, and more preferably 20 seconds or less. The dispersion time refers to the time when the aggregates have disappeared visually. Those having a dispersion time of more than 30 seconds may not be completely dispersed after kneading the concrete and may remain in the concrete.
The kneading time of the concrete using the embodiment in which the hardener is packaged by the water-soluble film of the preferred embodiment is substantially the same as that of the non-mixable concrete not using the embodiment, When using a water-soluble film that is not a film, the mixing time of the concrete may be long, and in the case of the same mixing time, even if the number of bags is the same as the water-soluble film of the preferred embodiment, the water-soluble film is in the concrete. May remain.
　さらに、起硬剤をスラリー化して各種のベースコンクリートなどに圧送添加する場合においては、デキストリン及びセルロース誘導体からなる群から選ばれる少なくとも１種を含有してなることが好ましい。なかでも、デキストリン、あるいはデキストリンとセルロース誘導体との組み合わせがより好ましい。
　デキストリンは、セメントの凝結を遅らせることで後述の生コン出荷型急硬コンクリート組成物の安定性を高めることができる。デキストリンは、一般に化工澱粉とも呼ばれ、通常、トウモロコシ澱粉、馬鈴薯、タピオカ澱粉、小麦澱粉、甘薯澱粉、及び米澱粉等を加水分解して得られる。なかでも、希酸を加え、分解して得られる酸焙焼デキストリンが最も一般的であり、酸浸漬法で得られるもの、澱粉の酵素分解で得られるマルトデキストリン、無焙焼で得られるブリティッシュガム、あるいは、澱粉に水を加えたものを加熱したり、アルカリや濃厚な塩類の溶液を加えてアルファー化したりしたものを急速に脱水乾燥して得られるアルファー化澱粉、もしくは、これらを水に溶解させて残留分を乾燥させた粉末等が使用できる。この他、カルボン酸エステル化、炭酸エステル化、及びエーテル化等の化学変性をさせたものが使用できる。特に、デキストリンの２０℃における冷水可溶分が５～９０％のものが好ましく、１０～６５％がより好ましい。デキストリンの２０℃における冷水可溶分が小さくなると充分な凝結遅延効果が得られない場合があり、デキストリンの２０℃における冷水可溶分が大きくなると硬化不良を引き起こすおそれがある。 Further, in the case where the hardening agent is slurried and added to various types of base concrete by pressure feeding, it is preferable to contain at least one selected from the group consisting of dextrins and cellulose derivatives. Among them, dextrin or a combination of dextrin and a cellulose derivative is more preferable.
Dextrin can enhance the stability of the ready-mixed concrete-hardened concrete composition to be described later by delaying the setting of cement. Dextrin is also generally referred to as modified starch, and is usually obtained by hydrolyzing corn starch, potato, tapioca starch, wheat starch, sweet potato starch, rice starch and the like. Above all, acid-roasted dextrin obtained by adding a dilute acid and decomposing is most common, and is obtained by an acid dipping method, maltodextrin obtained by enzymatic decomposition of starch, and British gum obtained by non-roasting Alternatively, pre-gelatinized starch obtained by heating and dewatering starch added with water, or pre-gelatinizing by adding an alkali or concentrated salt solution, or dissolving these in water A powder obtained by drying the residue can be used. In addition, those which have been chemically modified such as carboxylic acid esterification, carbonate esterification, and etherification can be used. In particular, dextrin having a cold water soluble content at 20 ° C. of 5 to 90% is preferable, and 10 to 65% is more preferable. If the cold water soluble content of dextrin at 20 ° C. is small, a sufficient setting retardation effect may not be obtained, and if the cold water soluble content of dextrin at 20 ° C. is large, poor curing may be caused.
　デキストリンは、起硬剤１００部に対して、０．０１～５部が好ましく、０．１～３部がより好ましい。０．０１～５部であることで、短時間材齢の強度発現性を十分なものとし、起硬材をスラリー化したときの発熱を抑制することができる。 Dextrin is preferably 0.01 to 5 parts, more preferably 0.1 to 3 parts, based on 100 parts of the hardening agent. When the content is 0.01 to 5 parts, the strength can be sufficiently developed in a short-term age, and heat generation when the hardened material is slurried can be suppressed.
　セルロース誘導体は、起硬材をスラリー化したときのブリーディング防止に寄与するものであり、特に限定されるものではないが、一般に水溶性高分子物質と呼ばれているもので、メチルセルロース（ＭＣ）、カルボキシルメチルセルロース（ＣＭＣ）等が挙げられる。 The cellulose derivative contributes to the prevention of bleeding when the hardened material is slurried, and is not particularly limited, but is generally referred to as a water-soluble polymer substance, and includes methyl cellulose (MC), Carboxymethyl cellulose (CMC) and the like.
　セルロース誘導体の使用量は、デキストリン１００部に対して、５～８０部が好ましく、１０～５０部がより好ましい。５～８０部であることで、ブリーディング防止と長距離圧送性を両立することができる。 The amount of the cellulose derivative to be used is preferably 5 to 80 parts, more preferably 10 to 50 parts, per 100 parts of dextrin. When the amount is 5 to 80 parts, it is possible to achieve both bleeding prevention and long distance pumpability.
（セメント）
　本実施形態でいう「セメント」とは、特に限定されるものではないが、例えば、日本工業規格（ＪＩＳ）で定められる普通、早強、中庸熱、低熱の各種ポルトランドセメント、高炉スラグ、フライアッシュ、シリカを混合した各種の混合セメント、石灰石粉末や高炉徐冷スラグ微粉末などを混合したフィラーセメント、並びに、都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント（エコセメント）などのあらゆるセメントが挙げられる。また、海外のＥＮ１９７－２０００で定められたセメントや中国ＧＢ規格で定められるあらゆるセメントを挙げることができ、これらのうちの一種又は二種以上が使用可能である。 (cement)
The “cement” in the present embodiment is not particularly limited, but includes, for example, various kinds of Portland cement, blast furnace slag, fly ash of normal, fast strength, moderate heat and low heat defined by Japanese Industrial Standards (JIS). And cement mixed with silica, filler cement mixed with limestone powder and blast furnace slowly cooled slag fine powder, and environmentally friendly cement (eco-cement) manufactured from municipal waste incineration ash or sewage sludge incineration ash. )). In addition, cements specified in EN197-2000 abroad and all cements specified in Chinese GB standards can be cited, and one or more of these can be used.
　ポルトランドセメントの構成化合物は、エーライト（３ＣａＯ・ＳｉＯ２）、ビーライト（２ＣａＯ・ＳｉＯ２）、アルミネート（３ＣａＯ・Ａｌ２Ｏ３）、フェライト（４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３）と、さらに、二水セッコウが混合されている（この一部が半水セッコウに変化することもある）。本実施形態では、高炉スラグ、フライアッシュ、シリカ、石灰石微粉末などの混合材を含まないセメントを選定することが強度発現性の観点から望ましく、中でも、エーライト含有量が高く、粉末度の高い（粒度が細かい）セメントを選定することが好ましい。これに該当するセメントとしては、例えば、日本のセメントで例示すると、早強セメントや普通セメントを挙げることができる。また、中国のセメントで例示すると、ＰＩＩ５２．５やＰＩＩ４２．５を挙げることができる。 Configuration compound of Portland cement, alite (3CaO · SiO 2), belite (2CaO · SiO 2), aluminate (3CaO · Al 2 O 3) , ferrite (4CaO · Al 2 O 3 · Fe 2 O 3) And gypsum dihydrate are also mixed (a part of this may change to hemihydrate gypsum). In the present embodiment, it is desirable from the viewpoint of strength development to select a cement that does not contain a mixture such as blast furnace slag, fly ash, silica, limestone fine powder, etc., among which, the alite content is high and the fineness is high. It is preferable to select cement (fine particle size). Examples of the corresponding cement include, for example, Japanese cement, and early cement and ordinary cement. PII52.5 and PII42.5 can be cited as examples of Chinese cement.
（急硬材）
　本実施形態の急硬材は、カルシウムアルミネート系化合物とセッコウ類とからなる。ここで、カルシウムアルミネート系化合物とは、ＣａＯとＡｌ２Ｏ３を主体とする化合物を総称するものであり、特に限定されるものではない。その具体例としては、ＣａＯ・Ａｌ２Ｏ３、１２ＣａＯ・７Ａｌ２Ｏ３、１１ＣａＯ・７Ａｌ２Ｏ３・ＣａＦ２、３ＣａＯ・Ａｌ２Ｏ３、３ＣａＯ・３Ａｌ２Ｏ３・ＣａＳＯ４、更に、ＣａＯとＡｌ２Ｏ３を主体とする非晶質物質（例えば、ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系化合物）等が挙げられる。中でも、非晶質物質を選定することが強度発現性の観点から好ましい。 (Rapidly hardened material)
The rapidly hardened material of this embodiment is composed of a calcium aluminate compound and gypsum. Here, the calcium aluminate-based compound is a general term for compounds mainly composed of CaO and Al 2 O 3 , and is not particularly limited. Specific examples, CaO · Al 2 O 3, 12CaO · 7Al 2 O 3, 11CaO · 7Al 2 O 3 · CaF 2, 3CaO · Al 2 O 3, 3CaO · 3Al 2 O 3 · CaSO 4, further, CaO And an amorphous substance mainly composed of Al 2 O 3 (for example, CaO—Al 2 O 3 —SiO 2 -based compound). Among them, it is preferable to select an amorphous substance from the viewpoint of strength development.
　ここで、本明細書における非晶質度とは、以下のように定義する。対象物質を１０００℃で２時間焼きなました後、５℃／分の冷却速度で徐冷して結晶化させる。そして、結晶化させたものを粉末Ｘ線回折法により測定し、結晶鉱物のメインピークの面積Ｓ０を求める。次いで、焼きなまし前の物質の結晶のメインピーク面積Ｓから、以下の式により非晶質度Ｘを求める。
　Ｘ（％）＝１００×（１－Ｓ／Ｓ０） Here, the degree of amorphousness in the present specification is defined as follows. After the target substance is annealed at 1000 ° C. for 2 hours, it is gradually cooled at a cooling rate of 5 ° C./min for crystallization. Then, the crystallized product is measured by the powder X-ray diffraction method, and the area S 0 of the main peak of the crystalline mineral is determined. Next, the degree of amorphousness X is determined from the main peak area S of the crystal of the substance before annealing by the following equation.
X (%) = 100 × (1−S / S 0 )
　なお、一般の工業原料にはＳｉＯ２、ＭｇＯ、Ｆｅ２Ｏ３、ＴｉＯ２、Ｋ２Ｏ、Ｎａ２Ｏ等の不純物が含まれているが、これらの不純物は、カルシウムアルミネート系化合物の非晶質化を助長する面もあり、これらの総量が２０％以下の範囲で存在しても差し支えない。中でも、ＳｉＯ２の存在は好ましく、非晶質カルシウムアルミネートを得る目的で、１～１８％の範囲で含有させることもできる。 Incidentally, general industrial raw materials include impurities such as SiO 2 , MgO, Fe 2 O 3 , TiO 2 , K 2 O, and Na 2 O. These impurities are non-calcium aluminate-based compounds. There is also a surface that promotes crystallization, and the total amount thereof may be in the range of 20% or less. Above all, the presence of SiO 2 is preferable, and it can be contained in the range of 1 to 18% for the purpose of obtaining amorphous calcium aluminate.
　したがって、急硬材としては、ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系化合物とセッコウ類とを含み、このＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系化合物の非晶質度が７０％以上で、かつ、ＳｉＯ２が１～１８質量％の範囲であることが好ましい。より好ましくは、ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系化合物の非晶質度が８０％以上で、かつ、ＳｉＯ２が２～１３質量％の範囲である。 Therefore, the hardened material includes a CaO—Al 2 O 3 —SiO 2 compound and gypsum, and the CaO—Al 2 O 3 —SiO 2 compound has an amorphous degree of 70% or more, and , SiO 2 is preferably in the range of 1 to 18% by mass. More preferably, the CaO—Al 2 O 3 —SiO 2 -based compound has an amorphous degree of 80% or more and SiO 2 in a range of 2 to 13% by mass.
　カルシウムアルミネート系化合物は、粉砕処理により、ブレーン比表面積で３０００～９０００ｃｍ２／ｇに調整することが好ましく、４０００～８０００ｃｍ２／ｇに調整することがより好ましい。カルシウムアルミネート系化合物の粉末度（ブレーン比表面積）が、４０００～９０００ｃｍ２／ｇであることで十分な急硬性が得られやすくなり、低温での強度発現性も得られやすくなる。 The calcium aluminate compound is preferably adjusted to have a Blaine specific surface area of 3,000 to 9000 cm 2 / g, more preferably 4,000 to 8,000 cm 2 / g, by a pulverizing treatment. When the fineness (blaine specific surface area) of the calcium aluminate compound is 4000 to 9000 cm 2 / g, sufficient rapid hardening can be easily obtained, and strength at low temperatures can be easily obtained.
　また、本実施形態の急硬材は、粉砕処理により、ブレーン比表面積で３０００～９０００ｃｍ２／ｇに調整することが好ましく、４０００～８０００ｃｍ２／ｇに調整することがより好ましい。急硬材の粉末度が、３０００～９０００ｃｍ２／ｇであることで十分な超速硬性が得られやすくなり、低温での強度発現性も得られやすくなる。 Further, the rapid hardened material of the present embodiment is preferably adjusted to have a Blaine specific surface area of 3,000 to 9000 cm 2 / g, more preferably 4,000 to 8,000 cm 2 / g, by a pulverizing treatment. When the fineness of the rapidly hardened material is 3000 to 9000 cm 2 / g, sufficient super-rapid hardening is easily obtained, and strength at low temperatures is easily obtained.
　急硬材の使用量は、セメントと急硬材との合計１００部中、１０～３５部が好ましく、１５～３０部がより好ましく、２０～２５部がさらに好ましい。１０～３５部であることで、良好な初期強度発現性が得られやすくなり、長期強度の低下も起こりにくくなる。 The amount of the hardened material used is preferably from 10 to 35 parts, more preferably from 15 to 30 parts, even more preferably from 20 to 25 parts, out of 100 parts in total of the cement and the hardened material. When the content is 10 to 35 parts, good initial strength can be easily obtained, and the long-term strength does not easily decrease.
（眠剤）
　本実施形態で使用する眠剤は、生コンから出荷した急硬コンクリートを眠らせる（水和硬化をほぼ停止させる）働きを持つものであり、生コンプラントでの急硬トラブルや、アジテータ車で搬送する際の急硬トラブルを回避するものである。眠剤としては、例えば、オキシカルボン酸、又は、その塩、或いはこれらとアルカリ金属炭酸塩の併用、糖類、ホウ酸等が挙げられる。オキシカルボン酸とアルカリ金属炭酸塩を併用することが、急硬コンクリートを眠らせる効果が大きい面や、起硬剤を添加した後の強度発現性が良好な面から好ましい。ただし、アルカリ金属炭酸塩はリチウム以外のアルカリ金属炭酸塩を選定することが好ましい。ベースコンクリートの十分な可使時間を確保し、かつ、起硬剤を添加した後も一定の可使時間を確保し、さらに、強度発現性を良好にする必要があり、この観点から炭酸リチウムの適用は好ましくない。 (Sleep)
The sleeping agent used in the present embodiment has a function of causing the hard concrete to be shipped from the ready-mixed concrete to sleep (substantially stops hydration hardening). This is to avoid sudden hardening trouble. Examples of the somnol include oxycarboxylic acid, or a salt thereof, or a combination thereof with an alkali metal carbonate, a saccharide, boric acid, and the like. It is preferable to use an oxycarboxylic acid and an alkali metal carbonate in combination from the aspect that the effect of making the rapidly hardened concrete sleep is large and that the strength development after adding a hardening agent is good. However, it is preferable to select an alkali metal carbonate other than lithium as the alkali metal carbonate. It is necessary to ensure a sufficient pot life of the base concrete, and to maintain a certain pot life even after the addition of a hardening agent, and to improve the strength development. Application is not preferred.
　眠剤としては、オキシカルボン酸、リチウム以外のアルカリ金属炭酸塩及びオキシカルボン酸の混合物を含むことが好ましく、リチウム以外のアルカリ金属炭酸塩とオキシカルボン酸とを含むことがより好ましい。リチウム以外のアルカリ金属炭酸塩とオキシカルボン酸との混合比は、アルカリ金属炭酸塩／オキシカルボン酸で、１０／９０～９０／１０であることが好ましく、２０／８０～８０／２０であることがより好ましい。 The sleeping agent preferably contains a mixture of oxycarboxylic acid, an alkali metal carbonate other than lithium and oxycarboxylic acid, and more preferably contains an alkali metal carbonate other than lithium and oxycarboxylic acid. The mixing ratio of the alkali metal carbonate other than lithium to the oxycarboxylic acid is preferably alkali metal carbonate / oxycarboxylic acid, and is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. Is more preferred.
　オキシカルボン酸又はその塩としては、クエン酸、グルコン酸、酒石酸、リンゴ酸等が挙げられ、その塩としては、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等が挙げられる。これらの１種又は２種以上を併用してもよい。 (4) Examples of the hydroxycarboxylic acid or a salt thereof include citric acid, gluconic acid, tartaric acid, and malic acid, and examples of the salt include a sodium salt, a potassium salt, a calcium salt, and a magnesium salt. One or more of these may be used in combination.
　眠剤の使用量は、セメントと急硬材の合計１００部に対して、０．３～５部が好ましく、０．３～４．５部がより好ましい。０．３～５部であることで、現場までの搬送時間に加え、十分な作業時間の確保がしやすくなる。また、起硬剤を添加した際に水和硬化を再び呼び起こしやすくなる。 The amount of the sleeping agent used is preferably 0.3 to 5 parts, more preferably 0.3 to 4.5 parts, based on 100 parts in total of cement and hardwood. When the amount is 0.3 to 5 parts, it becomes easy to secure sufficient operation time in addition to the transportation time to the site. In addition, when a hardening agent is added, hydration hardening is easily induced again.
（セッコウ）
　本実施形態で使用するセッコウ類は、無水セッコウ、半水セッコウ、二水セッコウのいずれのセッコウも使用できる。さらに天然セッコウや、リン酸副生セッコウ、排脱セッコウ、及びフッ酸副生セッコウなどの化学セッコウ、または、これらを熱処理して得られるセッコウなども使用できる。これらの中では、強度発現性の点で、無水セッコウ及び／又は半水セッコウが好ましいが、コストの観点から無水セッコウを選定することが望ましく、ＩＩ型無水セッコウ及び／又は天然無水セッコウが好ましい。セッコウの粒度はブレーン値で３０００ｃｍ２／ｇ以上が好ましく、４０００～７０００ｃｍ２／ｇがより好ましい。３０００ｃｍ２／ｇ以上であることで初期強度発現性を良好に発揮させることができる。 (Gypsum)
The gypsum used in the present embodiment may be any of gypsum, anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. Further, natural gypsum, chemical gypsum such as gypsum by-produced by phosphoric acid, gypsum excreted by gypsum, and gypsum by-produced by hydrofluoric acid, or gypsum obtained by heat-treating these may also be used. Among them, anhydrous gypsum and / or hemihydrate gypsum are preferred from the viewpoint of strength development, but anhydrous gypsum is preferably selected from the viewpoint of cost, and type II anhydrous gypsum and / or natural anhydrous gypsum are preferred. The particle size of gypsum is preferably from 3000 cm 2 / g or more in Blaine value, more preferably 4000 ~ 7000cm 2 / g. When it is 3,000 cm 2 / g or more, the initial strength can be sufficiently exhibited.
　セッコウ類の使用量は、カルシウムアルミネート系化合物１００部に対して１０～２００部が好ましく、１５～１５０部がより好ましく、２０～１３０部がさらに好ましい。これらの範囲であることで強度発現性を良好に発揮させることができる。 The amount of gypsum used is preferably 10 to 200 parts, more preferably 15 to 150 parts, and even more preferably 20 to 130 parts with respect to 100 parts of the calcium aluminate compound. When the content is within these ranges, the strength can be exhibited satisfactorily.
　本実施形態では、既述の急硬材、眠剤、起硬剤の他に、膨張材、減水剤、ＡＥ減水剤、高性能減水剤、高炉徐冷スラグ微粉末や高炉徐冷スラグ微粉末などのスラグ、石灰石微粉末やフライアッシュ、シリカフューム等の混和材料、消泡剤、増粘剤、防錆剤、防凍剤、収縮低減剤、ポリマー、ベントナイトなどの粘土鉱物、並びに、ハイドロタルサイトなどのアニオン交換体等のうちの一種又は二種以上を、本発明の目的を実質的に阻害しない範囲で使用することが可能である。 In the present embodiment, in addition to the above-described rapid hardening material, sleep agent, and hardening agent, an expanding material, a water reducing agent, an AE water reducing agent, a high-performance water reducing agent, a blast furnace slowly cooled slag fine powder, and a blast furnace slowly cooled slag fine powder. Such as slag, limestone fine powder, fly ash, silica fume and other admixtures, defoamers, thickeners, rust inhibitors, antifreeze agents, shrinkage reducers, polymers, clay minerals such as bentonite, hydrotalcite, etc. It is possible to use one or more of the above anion exchangers and the like as long as the object of the present invention is not substantially inhibited.
　生コン出荷型急硬コンクリートの調製方法の実施形態は、少なくとも、セメント、急硬材、及び眠剤を混練水とともに練り混ぜ用容器内で練り混ぜる工程と、さらに、生コン出荷型急硬コンクリート用起硬剤を例えば施工現場で混合する工程と、を順次含む。
　なお、上記混練水は例えば、生コン工場や生コンプラント等から出荷される。また、練り混ぜ工程では、練り混ぜとともに運搬も行われる場合が多い。 The embodiment of the method for preparing ready-mixed concrete fast-hardened concrete includes, at least, a step of kneading cement, a quick-hardening material, and a sleep aid in a kneading container together with kneading water; Mixing the hardener at a construction site, for example.
The kneading water is shipped from, for example, a ready-mix plant or a ready-mix plant. In addition, in the kneading and mixing step, transport is often performed together with the kneading and mixing.
　生コン工場や生コンプラント等から出荷され、練り混ぜ（・運搬する）工程においては、少なくとも、セメント、急硬材、眠剤、及び混練水を含むベースコンクリートの容量を、練り混ぜ（・運搬）用容器の内容積の４０％（容量％）以上とすることが好ましく、５０容量％以上とすることがより好ましい。
　ここで、練り混ぜ（・運搬）用容器とは、例えば、アジテータ車のドラム等のような生コン運搬車に備え付けられ、生コンを撹拌しながら保持できる容器をいう。 In the kneading (and transporting) process, which is shipped from a ready-mixed plant or ready-mixed plant, at least the volume of the base concrete containing cement, quick-hardening material, sleep agent, and kneading water is used for kneading (or carrying). It is preferably at least 40% (volume%) of the inner volume of the container, more preferably at least 50 vol%.
Here, the kneading (or carrying) container refers to a container provided on a ready-mixed concrete carrier such as a drum of an agitator truck and capable of holding the ready-mixed concrete while stirring.
　そして、生コン出荷型急硬コンクリート用起硬剤を混合した後の可使時間が１０分以上、好ましくは１５分以上確保できるように生コン出荷型急硬コンクリート用起硬剤の種類と混合量を定めることが好ましい。 Then, the type and amount of the hardener for ready-mixed shipping quick-hardening concrete are set so that the pot life after mixing the hardener for ready-mixed shipping quick-hardening concrete can be secured for 10 minutes or more, preferably 15 minutes or more. It is preferable to determine.
　以上のように、本実施形態に係る生コン出荷型急硬コンクリート用起硬剤は、生コン（レディミクストコンクリート）を混練した後、この混練物が搬送されて施工現場に出荷され、打ち込み作業後に添加される混和材料としての使用に好適である。また、同様に、本実施形態に係る生コン出荷型急硬コンクリート材料も、起硬剤と同様に、打ち込み作業後に添加される混和材料としての使用に好適である。そして、可使時間を例えば、１２０分以上、好ましくは１８０分以上とすることができる。 As described above, the ready-mixed shipping-type hardening agent for ready-mixed concrete according to the present embodiment is obtained by kneading ready-mixed concrete (ready mixed concrete), and then transporting the kneaded material to be shipped to a construction site, and is added after the driving operation. It is suitable for use as an admixture material. Similarly, the ready-mixed shipping quick-hardened concrete material according to the present embodiment is also suitable for use as an admixture added after the driving work, like the hardening agent. Then, the pot life can be, for example, 120 minutes or more, preferably 180 minutes or more.
　以下、実験例に基づいて、本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on experimental examples, but the present invention is not limited thereto.
（実験例１）
　セメント３８０ｋｇ／ｍ３、急硬材Ａを１２０ｋｇ／ｍ３、水／結合材比３２％、ｓ／ａ＝４２％、空気量２．０±１．５容量％の急硬コンクリートを調製した。この際、セメントと急硬材からなる結合材１００部に対して、眠剤を１．５部添加し、２４時間以上、水和硬化しないようにした（Ａ材）。急硬コンクリートを調製して１２０分後に起硬剤（Ｂ材）を結合材１００部に対して３部添加した。このコンクリート打設直後に下記に示す様々な養生剤をコンクリート１ｍ３当たり２００ｇ塗布した。養生剤塗布後から６時間後（練り上がりから８時間後）の圧縮強度（初期圧縮強度）を測定した。結果を下記表１に併記する。
　なお、ｓ／ａは、細骨材率で、コンクリート中の全骨材量に対する細骨材量の絶対容積比を百分率で表した値である。 (Experimental example 1)
Rapid hardened concrete having 380 kg / m 3 of cement, 120 kg / m 3 of hardened material A, a water / binder ratio of 32%, s / a = 42%, and an air volume of 2.0 ± 1.5% by volume was prepared. At this time, 1.5 parts of a sleeping agent was added to 100 parts of a binder composed of cement and a hardened material to prevent hydration and hardening for 24 hours or more (material A). 120 minutes after preparing the hardened concrete, 3 parts of a hardening agent (material B) was added to 100 parts of the binder. Various curing agents shown below after the concrete設直and concrete 1 m 3 per 200g coating. Compressive strength (initial compressive strength) was measured 6 hours after application of the curing agent (8 hours after kneading). The results are shown in Table 1 below.
In addition, s / a is a fine aggregate ratio, and is a value expressing the absolute volume ratio of the fine aggregate amount to the total aggregate amount in the concrete in percentage.
＜使用材料＞
（１）養生剤
養生剤イ：硫酸アルミニウム８水塩、試薬１級
養生剤ロ：アルミン酸ナトリウム（Ｎａ２Ｏ／ＳｉＯ２モル比＝１．０）、試薬１級
養生剤ハ：ＣａＯ／Ａｌ２Ｏ３モル比が２．２０のカルシウムアルミネートを含むカルシウムアルミネート系急結剤、市販品、デンカ社製ナトミックタイプＺ
養生剤ニ：硝酸リチウム（無水塩）、試薬１級
養生剤ホ：硝酸ナトリウム、試薬１級
養生剤ヘ：硝酸カルシウム（４水塩）、試薬１級
養生剤ト：ジエタノールアミン（純度９８％）、試薬１級
養生剤チ：ギ酸、試薬１級 <Material used>
(1) Curing agent curing agent A: Aluminum sulfate octahydrate, reagent first class curing agent b: Sodium aluminate (Na 2 O / SiO 2 molar ratio = 1.0), reagent first class curing agent C: CaO / Al 2 O 3 molar ratio of calcium aluminate quick-setting admixture comprising calcium aluminate 2.20, commercially available, Denka Co. isocyanatomethyl Mick type Z
Curing agent d: Lithium nitrate (anhydrous salt), Reagent first grade curing agent E: Sodium nitrate, Reagent first grade curing agent: Calcium nitrate (tetrahydrate), Reagent first grade curing agent G: Diethanolamine (98% purity), Reagent 1st grade curing agent H: Formic acid, Reagent 1st grade
（２）起硬剤
水酸化カルシウム、市販品、３００μｍ残分１％未満、１００μｍ残分が５％ (2) Calcium hydroxide hardener, commercial product, 300 μm residue less than 1%, 100 μm residue 5%
（３）急硬材
急硬材Ａ：ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系非晶質物質と無水セッコウの等量混合物。ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系非晶質物質のＣａＯ含有量は４３％、Ａｌ２Ｏ３は４４％、ＳｉＯ２は１０％、その他は３％。密度２．８５ｇ／ｃｍ３、ブレーン比表面積５０００ｃｍ２／ｇ、非晶質度９０％。 (3) Rapid hardened material Rapid hardened material A: Equivalent mixture of CaO—Al 2 O 3 —SiO 2 based amorphous substance and anhydrous gypsum. The CaO—Al 2 O 3 —SiO 2 amorphous material has a CaO content of 43%, an Al 2 O 3 of 44%, a SiO 2 of 10%, and the others of 3%. Density 2.85 g / cm 3 , Blaine specific surface area 5000 cm 2 / g, degree of amorphousness 90%.
（４）眠剤
試薬１級の炭酸カリウム７５部と試薬１級のクエン酸２５部の混合物 (4) Mixture of 75 parts of first grade potassium carbonate and 25 parts of first grade citric acid
（５）その他
セメント：市販の普通ポルトランドセメント（デンカ社製　密度３．１５ｇ／ｃｍ３）
水：水道水
細骨材：天然川砂
粗骨材：砕石 (5) Other cement: Commercial ordinary Portland cement (density 3.15 g / cm 3 manufactured by Denka)
Water: tap water fine aggregate: natural river sand coarse aggregate: crushed stone
＜測定方法＞
・圧縮強度（初期圧縮強度）：ＪＩＳ　Ａ　１１０８に準じて測定した。 <Measurement method>
-Compressive strength (initial compressive strength): Measured according to JIS A 1108.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、各種養生剤を塗布することにより良好な圧縮強度が発現することが分かった。 よ り From Table 1, it was found that good compressive strength was exhibited by applying various curing agents.
（実験例２）
　養生剤イを使用し、表２に示すように流動パラフィンを併用したこと以外は、実験例１と同様に行った。結果を表２に示す。 (Experimental example 2)
The procedure was performed in the same manner as in Experimental Example 1 except that curing agent A was used and liquid paraffin was used in combination as shown in Table 2. Table 2 shows the results.
＜使用材料＞
　流動パラフィン：パラフィン系養生剤、マスターキュア（登録商標）１０６（ＢＡＳＦポゾリス（株）製） <Material used>
Liquid paraffin: paraffin-based curing agent, Master Cure (registered trademark) 106 (manufactured by BASF Pozzolith Co., Ltd.)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２より、養生剤／流動パラフィン＝１０：９０～９０：１０であると圧縮強度が高くなることが分かった。 よ り From Table 2, it was found that the compressive strength increased when the curing agent / liquid paraffin was 10:90 to 90:10.
（実験例３）
　表３に示すように結晶水の数の異なる硫酸アルミニウムを使用したこと以外は、実験例１と同様に行った。結果を表３に示す。 (Experimental example 3)
The procedure was performed in the same manner as in Experimental Example 1 except that aluminum sulfate having different numbers of water of crystallization was used as shown in Table 3. Table 3 shows the results.
＜使用材料＞
　養生剤リ：無水硫酸アルミニウム、試薬１級
　養生剤ヌ：硫酸アルミニウム１８水塩、試薬１級 <Material used>
Curing agent: anhydrous aluminum sulfate, reagent grade 1 Curing agent: aluminum sulfate 18-hydrate, reagent grade 1
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３より、硫酸アルミニウム８水塩であると圧縮強度が高くなることが分かった。 よ り From Table 3, it was found that compressive strength was increased when aluminum sulfate octahydrate was used.
（実験例４）
　養生剤イを使用し、表４に示すように養生剤を塗布するタイミングを変化させたこと以外は、実験例１と同様に行った。結果を表４に示す。 (Experimental example 4)
The procedure was performed in the same manner as in Experimental Example 1 except that the curing agent A was used and the timing of applying the curing agent was changed as shown in Table 4. Table 4 shows the results.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４より、養生剤を塗布するタイミングはコンクリートが硬化する前であると圧縮強度が高くなることが分かった。 よ り From Table 4, it was found that the compressive strength increased when the curing agent was applied before the concrete hardened.
（実験例５）
　コンクリートの打設前に予め打設箇所に養生剤イを１ｍ３当たり２００ｇ塗布した。セメント３８０ｋｇ／ｍ３、急硬材Ａを１２０ｋｇ／ｍ３、水／結合材比３２％、ｓ／ａ＝４２％、空気量２．０±１．５容量％の急硬コンクリートを調製した。この際、セメントと急硬材からなる結合材１００部に対して、眠剤１を１．５部添加し、２４時間以上、水和硬化しないようにした（Ａ材）。急硬コンクリート調製１２０分後に起硬剤（Ｂ材）を結合材１００部に対して３部添加し、養生剤を塗布した打設箇所に、このコンクリートを打設した。コンクリート打設直後に養生剤イをさらに１ｍ３当たり２００ｇ塗布した。養生剤塗布後から６時間後（練り上がりから８時間後）の圧縮強度を測定した。結果を下記表５に示す。
　なお、ｓ／ａは、細骨材率で、コンクリート中の全骨材量に対する細骨材量の絶対容積比を百分率で表した値である。 (Experimental example 5)
The curing agent Lee was 200g applied per 1m 3 in advance striking設箇offices in striking設前of concrete. Rapid hardened concrete having 380 kg / m 3 of cement, 120 kg / m 3 of hardened material A, a water / binder ratio of 32%, s / a = 42%, and an air volume of 2.0 ± 1.5% by volume was prepared. At this time, 1.5 parts of the sleeping agent 1 was added to 100 parts of the binder composed of the cement and the rapidly hardened material to prevent hydration and hardening for 24 hours or more (material A). 120 minutes after the preparation of the rapidly hardened concrete, 3 parts of a hardening agent (material B) was added to 100 parts of the binder, and the concrete was poured into the placement site where the curing agent was applied. Immediately after the concrete was cast, a further 200 g of the curing agent A was applied per 1 m 3 . Compressive strength was measured 6 hours after application of the curing agent (8 hours after kneading). The results are shown in Table 5 below.
In addition, s / a is a fine aggregate ratio, and is a value expressing the absolute volume ratio of the fine aggregate amount to the total aggregate amount in the concrete in percentage.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５より、養生剤を打設後のコンクリート表面に塗布するだけでなく、養生剤を打設前の打設箇所及び打設後のコンクリート表面に塗布すると圧縮強度が高くなることが分かった。 よ り From Table 5, it was found that not only the curing agent was applied to the concrete surface after the casting, but also the compressive strength was increased when the curing agent was applied to the placement site before the casting and to the concrete surface after the casting.
（実験例６）
　養生剤イを使用し、表６に示すように養生剤の塗布量を変化させたこと以外は、実験例１と同様に行った。結果を表６に示す。 (Experimental example 6)
The same procedure as in Experimental Example 1 was carried out, except that the curing agent A was used and the application amount of the curing agent was changed as shown in Table 6. Table 6 shows the results.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表６より、養生剤の塗布量は１ｍ２あたり５０～５００ｇであると圧縮強度が高くなることが分かった。 From Table 6, it was found that the compressive strength increased when the application amount of the curing agent was 50 to 500 g per 1 m 2 .
　本発明の養生剤を用いることにより、短時間で優れた強度発現性が得られるため、特に、土木建築分野で好適に用いられる。 た め By using the curing agent of the present invention, excellent strength developability can be obtained in a short time, so that it is suitably used particularly in the field of civil engineering and construction.

Claims (7)

  1. 　硫酸アルミニウム、アルミン酸ナトリウム、硝酸リチウム、硝酸ナトリウム、硝酸カルシウム、カルシウムアルミネート、ジエタノールアミン、及びギ酸からなる群から選択される少なくとも１種を含むコンクリート組成物用養生剤。 (4) A curing agent for a concrete composition containing at least one selected from the group consisting of aluminum sulfate, sodium aluminate, lithium nitrate, sodium nitrate, calcium nitrate, calcium aluminate, diethanolamine, and formic acid.
  2. 　さらに流動パラフィンを含有してなる請求項１に記載のコンクリート組成物用養生剤。 養 The curing agent for concrete composition according to claim 1, further comprising liquid paraffin.
  3. 　前記硫酸アルミニウムが、硫酸アルミニウム８水塩である請求項１又は２に記載のコンクリート組成物用養生剤。 (3) The curing agent for a concrete composition according to (1) or (2), wherein the aluminum sulfate is aluminum sulfate octahydrate.
  4. 　コンクリート組成物の養生に、請求項１～３のいずれか１項に記載のコンクリート組成物用養生剤を用いるコンクリート組成物の養生方法。 (4) A method for curing a concrete composition, comprising using the curing agent for a concrete composition according to any one of claims 1 to 3 for curing the concrete composition.
  5. 　前記コンクリート組成物を打設し、その後、該コンクリート組成物が硬化する前に、その表面に前記コンクリート組成物用養生剤を塗布する請求項４に記載のコンクリート組成物の養生方法。 The method for curing a concrete composition according to claim 4, wherein the concrete composition is cast, and thereafter, the curing agent for the concrete composition is applied to the surface of the concrete composition before the concrete composition hardens.
  6. 　前記コンクリート組成物用養生剤を打設箇所に塗布してから、前記コンクリート組成物を打設し、その後、該コンクリート組成物が硬化する前に、その表面に養生剤を塗布する請求項４又は５に記載のコンクリート組成物の養生方法。 The concrete composition is applied to the casting site, and then the concrete composition is applied. Thereafter, before the concrete composition is cured, the curing agent is applied to the surface of the concrete composition. A method for curing the concrete composition according to item 5.
  7. 　前記コンクリート組成物が生コン出荷型急硬コンクリートであることを特徴とする請求項４～６のいずれか１項に記載のコンクリート組成物の養生方法。
          The method for curing a concrete composition according to any one of claims 4 to 6, wherein the concrete composition is a ready-mixed shipping-type rapid hardened concrete.
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