WO2021157371A1 - Rapid hardening agent for spray - Google Patents

Rapid hardening agent for spray Download PDF

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Publication number
WO2021157371A1
WO2021157371A1 PCT/JP2021/001998 JP2021001998W WO2021157371A1 WO 2021157371 A1 WO2021157371 A1 WO 2021157371A1 JP 2021001998 W JP2021001998 W JP 2021001998W WO 2021157371 A1 WO2021157371 A1 WO 2021157371A1
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WO
WIPO (PCT)
Prior art keywords
alkaline earth
mass
earth metal
aluminum sulfate
quick
Prior art date
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PCT/JP2021/001998
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French (fr)
Japanese (ja)
Inventor
博貴 水野
貴光 室川
岩崎　昌浩
三島　俊一
Original Assignee
デンカ株式会社
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Publication of WO2021157371A1 publication Critical patent/WO2021157371A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/68—Aluminium compounds containing sulfur
    • C01F7/74—Sulfates
    • 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
    • C04B22/06—Oxides, Hydroxides
    • 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
    • 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
    • C04B22/10—Acids or salts thereof containing carbon in the anion
    • 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
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides

Definitions

  • the present invention relates to a quick-setting agent for spraying.
  • Patent Document 1 a quick-setting concrete spraying method in which a quick-setting agent is mixed with concrete has been used.
  • sprayed concrete is usually prepared at a cement, aggregate, and water metering and mixing plant installed at the excavation site, transported by an agitator truck, pumped by a concrete pump, and a confluence pipe installed in the middle.
  • This is a construction method in which the concrete is mixed with a quick-setting agent pumped from the other side and sprayed onto the ground surface as quick-setting spray concrete until it reaches a predetermined thickness.
  • Quick-setting agents include a mixture of calcium aluminate, alkali metal aluminate, alkali metal carbonate, etc.; a mixture of baked myoban, alkali metal aluminate, alkali metal carbonate, etc.; calcium.
  • a mixture of aluminate and 3CaO ⁇ SiO 2 ; a mixture of slaked lime, an alkali metal aluminate, and an alkali metal carbonate; and the like are known (Patent Documents 2 to 5).
  • These quick-setting agents have a function of promoting the coagulation of cement, and all of them are mixed with cement concrete and sprayed on the ground surface.
  • the method of adding the quick-setting admixture was usually a method of increasing the amount of dust due to powder mixing by air transportation. Therefore, the working environment may deteriorate, and it is necessary to wear protective goggles, a dustproof mask, etc. at the time of spraying, and a construction method with a smaller amount of dust has been required.
  • a construction method with a small amount of dust generated a method has been proposed in which a quick-setting admixture is slurried, added and mixed with cement concrete, and then a solution of alkali metal aluminate is separately pumped, mixed, and sprayed. (Patent Document 6). Since this method uses a highly alkaline liquid, it is difficult to handle, and protective glasses, gloves, etc. are required at the time of spraying, which causes a problem that workability is lowered.
  • Patent Document 7 proposes a quick-setting agent using a combination of amorphous calcium aluminate and crystalline calcium aluminate. Patent Document 7 clearly states that a better effect can be obtained by further using sodium aluminate at a low temperature. However, in recent years, it is preferable not to use strong alkaline raw materials such as alkali metal aluminate and alkali metal hydroxide as much as possible in the quick-setting agent from the viewpoint of blindness and chemical damage due to strong alkalinity, but in terms of high temperature and cost. At present, there are still many issues in such areas.
  • strong alkaline materials have strong reactivity with cement and show high initial strength development, but their strength promotion in long-term strength is low, and it is difficult to apply them to places where long-term strength development is required.
  • the present invention has high rapid binding and high initial strength development equal to or higher than that of a rapid binder containing the above materials even in high temperature conditions without using materials such as alkali metal aluminate and alkali metal hydroxide. It is an object of the present invention to provide a quick-setting agent for spraying, which can be applied to a place where long-term strength development is required.
  • the present invention is as follows.
  • a quick-setting agent for spraying that does not substantially contain alkali metal aluminate and alkali metal hydroxide but contains calcium aluminate and aluminum sulfate, and the content of the aluminum sulfate is high. It is 5 to 105 parts by mass with respect to 100 parts by mass of the calcium aluminate, and the content of the alkaline earth metal in the aluminum sulfate is 0.007 to 4% by mass in terms of alkaline earth metal oxide.
  • Fast-setting agent for attachment [2] The quick-setting agent for spraying according to [1], wherein the aluminum sulfate contains 0.005 to 2% by mass of CaO and 0.002 to 2% by mass of MgO.
  • the quick-setting agent for spraying according to [4] which contains the alkali metal carbonate and has a content of the alkali metal carbonate of 1 to 30% by mass.
  • the present invention even in a high temperature condition without using materials such as alkali metal aluminate and alkali metal hydroxide, high quick-setting property and high initial strength equal to or higher than those of a quick-setting agent containing the above-mentioned materials. It is possible to provide a quick-setting agent for spraying, which can be applied to a place where expressiveness is obtained and long-term strength development is required. In addition, higher safety is ensured in handling as compared with a quick-setting admixture containing at least one of an alkali metal aluminate and an alkali metal hydroxide.
  • the quick-setting agent for spraying does not substantially contain alkali metal aluminate and alkali metal hydroxide, but contains calcium aluminate and aluminum sulfate. Since it does not contain alkali metal aluminate and alkali metal hydroxide substantially, it is easy to handle, and protective glasses and gloves are not required at the time of spraying, which does not reduce workability and ensures high safety. can do.
  • examples of the alkali metal aluminate include sodium aluminate and potassium aluminate
  • examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
  • substantially not contained means a content below the lower limit of detection by XRF measurement, and specifically, is 0 ppm.
  • the content of aluminum sulfate is 5 to 105 parts by mass with respect to 100 parts by mass of calcium aluminate, and the content of alkaline earth metal in the aluminum sulfate is 0.
  • the content is 007 to 4% by mass, high rapid binding and high initial strength development can be obtained even in a high temperature state without substantially containing alkali metal aluminate and alkali metal hydroxide. If aluminum sulfate contains hydrated water, the amount of aluminum sulfate is calculated as the amount containing this.
  • parts and% are shown on a mass basis unless otherwise specified.
  • Calcium aluminate is a mixture of a raw material containing calcia and a raw material containing alumina, which is subjected to heat treatment such as firing in a kiln or melting in an electric furnace, and then rapidly or slowly cooled to obtain crystals and crystals.
  • heat treatment such as firing in a kiln or melting in an electric furnace, and then rapidly or slowly cooled to obtain crystals and crystals.
  • Or is a general term for substances that are non-crystalline and have CaO and Al 2 O 3 as the main components and have hydration activity. Part of CaO and Al 2 O 3 is alkali metal oxide and alkaline earth metal oxidation.
  • the particle size of the calcium aluminate, Blaine specific surface area (based on JIS R 5201 (Physical testing methods for cement).
  • the Blaine value is preferably at least 3,000 cm 2 / g in, 5,000 cm 2 / g or more More preferred. When it is 3,000 cm 2 / g or more, it is possible to enhance the quick-setting property and the initial strength development of the sprayed material in which the quick-setting agent and cement concrete are mixed.
  • the CaO / Al 2 O 3 molar ratio in calcium aluminate is preferably in the range of 2.0 to 2.6, more preferably in the range of 2.2 to 2.4, in terms of quick-setting property and initial strength development. ..
  • the aluminum sulfate according to the present embodiment contains an alkaline earth metal, and the content thereof (the total amount when there are a plurality of types of alkaline earth metals) is 0.007 to 4 in terms of alkaline earth metal oxide. It is by mass%, preferably 0.01 to 2% by mass. In particular, the content of magnesium and calcium in aluminum sulfate is 0.007 to 4% by mass, preferably 0.01 to 2% by mass, in terms of oxide.
  • the above-mentioned aluminum sulfate can be obtained by mixing, for example, sulfuric acid containing an alkaline earth metal compound such as an alkaline earth metal oxide as an impurity with aluminum hydroxide.
  • the aluminum sulfate "aluminum sulfate" according to the present embodiment contains alkaline earth metals, but X-ray diffraction (XRD) does not show peaks indicating their presence, which is substantially the same. It can be regarded as aluminum sulfate.
  • the aluminum sulfate according to the present embodiment is amorphous, which can be confirmed as a broad peak by X-ray diffraction.
  • alkaline earth metals alkaline earth metal oxides
  • CaO and MgO cannot be identified by X-ray fluorescence, but the results of fluorescent X-ray analysis (XRF) show that they are CaO and MgO. Alkaline earth metal (alkaline earth metal oxide) is confirmed.
  • Aluminum sulfate contributes to the adhesion to the wall surface and the strength development at the very early stage as a spraying material, and in particular, the one containing an alkaline earth metal can impart sufficient adhesion even in a normal temperature to low temperature environment. It is also possible to prevent a significant decrease in long-term strength in a high temperature environment. If the content of the alkaline earth metal in aluminum sulfate is less than 0.007% by mass in terms of oxide, it is difficult to develop long-term strength in a high temperature environment, and the initial strength development may be significantly reduced, which is not preferable. ..
  • the above-mentioned action can be exhibited by using aluminum sulfate containing a predetermined amount of alkaline earth metal-containing substance, and in addition to aluminum sulfate containing no alkaline earth metal-containing substance, for example, a commercially available reagent. Even if alkaline earth metal oxides such as calcium oxide and magnesium oxide are added and mixed later, the above effects cannot be sufficiently obtained.
  • the "low temperature” in the above "low temperature environment” means 5 ° C. or lower
  • the "high temperature” in the "high temperature environment” means 25 ° C. or higher.
  • the alkaline earth metal means at least any one of beryllium, magnesium, calcium, strontium, and barium.
  • These alkaline earth metals, together with aluminum sulfate, are simple substances of alkaline earth metals, or alkaline earth metal-containing substances such as alkaline earth metal compounds, alkaline earth metal-containing solid solutions, and alkaline earth metal-containing amorphous substances.
  • Exists as. Specific coexistence states include, for example, alkaline earth metals, alkaline earth metal oxides (BeO, MgO, CaO, SrO, BaO, etc.), alkaline earth metal hydroxides, alkaline earth metal carbonates, and alkalis. Examples thereof include a solid solution in aluminum sulfate as an earth metal oxide. Preferably, it does not contain alkaline earth metal sulphate.
  • the content of aluminum sulfate is 5 to 105 parts, preferably 10 to 90 parts, and more preferably 20 to 80 parts with respect to 100 parts of calcium aluminate. If the content of aluminum sulfate is outside the range of 5 to 105 parts, the cohesiveness will decrease.
  • the CaO content in aluminum sulfate is preferably 0.005 to 2%, and the MgO content is preferably 0.002 to 2%.
  • the CaO content is more preferably 0.01 to 1.5%, and the MgO content is more preferably 0.008 to 1.5%.
  • the CaO content and MgO content contained in aluminum sulfate are, for example, mixed without removing CaO and / or MgO contained in sulfuric acid when mixing high-purity aluminum hydroxide and sulfuric acid, or The content can be adjusted by intentionally adding it.
  • the CaO content is 0.005% or more, long-term strength is more likely to be obtained in a high temperature condition, and when it is 2% or less, a decrease in coagulation properties is likely to be suppressed. Further, when the MgO content is 0.002% or more, long-term strength is more likely to be obtained in a high temperature condition, and when it is 2% or less, abnormal expansion is likely to be suppressed in a high temperature condition.
  • anhydrous salts to 14 to 18 hydroxides can be used, but 14 hydroxides or more may not be pulverized, and 12 hydroxides or less is preferable. In addition, anhydrous salts may have reduced coagulation properties, so tetrahydrate or more is preferable. More preferably, 4 to 12 hydroxides, that is, aluminum sulfate is the hydrate, and the number of hydrated waters thereof is more preferably 4 to 12. The number of hydrated water may be, for example, dehydrated to a desired number of hydrated water by heating aluminum sulfate of 18 hydroxides or the like.
  • Aluminum sulfate can be used in any form as a powder such as flakes, coarse powder, and powder, but from the viewpoint of extremely initial strength development, powder is preferable, and the particle size is 1 to 10 ⁇ m or less. It is preferable to adjust at 40%. When the particle size is 10 ⁇ m or less and 1% or more, the very initial strength development is easily obtained, and when the particle size is 40% or less, the long-term strength is more easily obtained. In order to make the particle size of 10 ⁇ m or less 1 to 40%, a sieve or the like may be used.
  • the spraying quick-setting admixture according to the present embodiment preferably further contains an alkaline earth metal hydroxide.
  • an alkaline earth metal hydroxide By containing an alkaline earth metal hydroxide, the long-term strength can be further improved.
  • Alkaline earth metal hydroxides refer to, for example, hydroxides such as beryllium, magnesium, calcium, strontium, and barium, such as calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydroxide, and radium hydroxide. It is possible to use one or more of them. Of these, calcium hydroxide and magnesium hydroxide are preferably used from an industrial point of view such as price and ease of handling, and carbide slag and the like produced as a by-product when acetylene is generated from calcium carbide can also be mentioned as calcium hydroxide. ..
  • the particle size of the alkaline earth metal hydroxide is preferably 250 ⁇ m residual 30% or less, and more preferably 250 ⁇ m residual 10% or less.
  • the content of the alkaline earth metal hydroxide is preferably 2 to 120 parts, more preferably 5 to 105 parts, further preferably 5 to 100 parts, and particularly preferably 10 to 50 parts, when calcium aluminate is 100 parts. Part is preferable. In particular, when the number of parts is 5 or more, the cohesiveness is less likely to decrease, and when the amount is 100 or less, the long-term strength can be improved.
  • the spraying quick-setting admixture according to the present embodiment may contain a material expected from a normal quick-setting admixture.
  • a substance selected from the group consisting of alkali metal carbonate, alkaline earth metal carbonate, and alkaline earth metal sulfate can be mentioned, and the group consisting of alkaline earth metal carbonate and alkaline earth metal sulfate can be mentioned. It is preferable that it is at least one selected from. At least one selected from the group consisting of alkaline earth metal carbonates and alkaline earth metal sulfates is preferable in that it contributes to the enhancement of long-term strength, and is preferably 3 to 50% in the spray binder. It is preferably present, and more preferably 5 to 40%.
  • the alkaline earth metal carbonate and the alkaline earth metal sulfate include calcium carbonate and calcium sulfate.
  • an alkali metal carbonate in order to obtain a predetermined strength particularly with a 3-hour strength or a 1-day strength, it is preferable to use an alkali metal carbonate, and the amount thereof is preferably 1 to 30% in the quick-setting admixture for spraying. More preferably, it is 5 to 20%. If it is 1% or more, the desired strength can be easily obtained at the age of 3 hours or 1 day, and if it is 30% or less, the long-term strength can be easily obtained.
  • the alkali metal carbonate include sodium carbonate and potassium carbonate.
  • the form of the quick-setting admixture for spraying according to the present embodiment when blended in cement concrete may be, for example, powder, liquid, suspension, slurry, or the like.
  • the cement of concrete is not particularly limited, and various Portland cements of ordinary, early-strength, ultra-fast-strength, moderate heat, and low heat, and blast furnace slag, fly ash, and fine limestone powder are added to these Portland cements.
  • Examples include mixed filler cement, environment-friendly cement (eco-cement) produced from municipal waste incineration ash and sewage sludge incineration ash as raw materials, and these can also be used in fine powder.
  • the ratio of the mixture to the cement in the mixed cement is not particularly limited, and a mixture of these admixtures in a range larger than that assumed by JIS can be used.
  • the cement concrete of the present embodiment contains cement and an aggregate, and the aggregate preferably has a low water absorption rate and a high aggregate strength.
  • the aggregate is not particularly limited as long as it can be sprayed, but river sand, mountain sand, sea sand, lime sand, silica sand and the like can be used as the fine aggregate, and river gravel as the coarse aggregate. , Mountain gravel, lime gravel, etc. can be used, and crushed sand and crushed stone can also be used.
  • the spraying method using the quick-setting admixture of the present invention various spraying methods according to the required physical properties, economic efficiency, workability, etc. are possible.
  • the spraying method using the quick-setting agent of the present invention either a dry spraying method or a wet spraying method can be used.
  • Example 1 The measurement method and materials used for each physical property are as follows. (Proctor penetration test and compressive strength) Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of a quick-setting agent (quick-setting agent for spraying) having the content ratio shown in Table 1, and then perform a proctor penetration test. The starting time (starting) and ending time (ending) of coagulation were measured, and the compressive strength (JIS R 5201, the same applies hereinafter) was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent. .. Each quick-setting admixture having a content ratio shown in Table 1 was prepared by mixing the respective materials (the same applies to other experimental examples).
  • Example 2 Similar to Experimental Example 1, a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand was prepared at a test temperature of 30 ° C., 10 parts of the quick-setting agent having the content ratio shown in Table 2 was added, and then a proctor penetration test was performed. The start and end times of coagulation were measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent.
  • the aluminum sulfate used contains an alkaline earth metal in an amount of 0.006% to 4.5% in terms of metal oxide, and the abbreviations are shown below.
  • the comparative example containing 0.005% of alkaline earth metal in terms of alkaline earth metal oxide has a later start and end time of the proctor than the example. ..
  • the compressive strength is also reduced.
  • both the proctor and the compressive strength are lower than those in the example.
  • the aluminum sulfate in the quick-setting admixture contains 0.007 to 4% of alkaline earth metal in terms of alkaline earth metal oxide.
  • Example 3 Similar to Experimental Examples 1 and 2, a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand was prepared at a test temperature of 30 ° C., and 10 parts of the quick-setting agent having the content ratio shown in Table 3 was added, and then the Procter penetration test was performed. The time of onset and end of coagulation was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent.
  • the content of calcium hydroxide in the quick-setting admixture is preferably 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of calcium aluminate.
  • Example 4 Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture.
  • the aluminum sulfate used was as shown below.
  • the amount of alkaline earth metal oxide contained in aluminum sulfate is CaO: 0.005% by mass to 2% by mass and MgO: 0.002% by mass to 2% by mass.
  • Example 5 Similar to Experimental Example 1, 100 parts of calcium aluminate, 50 parts of alkaline earth metal hydroxide, 50 parts of aluminum sulfate (AS-a), and the types and amounts shown in Table 5 are alkaline earth metal carbonate and alkaline soil.
  • a quick-setting agent composed of metalloid sulfate was prepared. Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the above-mentioned quick-setting admixture, and then measure the start and end times of condensation by a Procter penetration test. The compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the binder.
  • the alkaline earth metal carbonates and alkaline earth metal sulfates used were as shown below.
  • Alkaline earth metal carbonate A Magnesium carbonate industrial product, brain value 2800 cm 2 / g Alkaline earth metal carbonate a: Calcium carbonate industrial product, brain value 3000 cm 2 / g Alkaline earth metal sulfate ⁇ : Magnesium sulfate industrial product, brain value 3500 cm 2 / g Alkaline earth metal sulfate ⁇ : Calcium sulfate industrial product, brain value 4500 cm 2 / g
  • Alkali metal carbonate A Sodium carbonate industrial product, sodium carbonate content 98%, brain value 1000 cm 2 / g Alkali metal carbonate a: Potassium carbonate industrial product, potassium carbonate content 97%, brain value 1500 cm 2 / g Alkali metal carbonate C: Lithium carbonate industrial product, lithium carbonate content 98%, brain value 800 cm 2 / g
  • Example 7 Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the quick-setting agent having the content ratio shown in Table 7, and then perform a proctor penetration test to determine the start and end of condensation. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture.
  • the aluminum sulfate used was as shown below.
  • Example 8 Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the quick-setting agent having the content ratio shown in Table 8, and then perform a proctor penetration test to determine the start and end of condensation. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture.
  • the aluminum sulfate used was as shown below.
  • Particle size 10 ⁇ m or less 20%, 14 hydroxide AS-ts; CaO: 0.9% by mass, MgO: 0.7% by mass, alkaline earth Alkaline earth of 1.6% in terms of metal oxide
  • the spraying quick-setting admixture of the present invention can be suitably used for cement concrete sprayed on exposed ground surfaces such as tunnels and slopes of roads, railways, and headraces.

Abstract

This rapid hardening agent for a spray contains a calcium aluminate and an aluminum sulfate, and does not contain an alkali metal aluminate and an alkali metal hydroxide, wherein the content of the aluminum sulfate is 5-105 parts by mass with respect to 100 parts by mass of the calcium aluminate, and the content of an alkaline earth metal in the aluminum sulfate is 0.007-4 mass% in terms of an alkaline earth metal oxide.

Description

吹付け用急結剤Rapid binder for spraying
　本発明は、吹付け用急結剤に関する。 The present invention relates to a quick-setting agent for spraying.
　従来、トンネル掘削等で露出した地山の崩落を防止するために急結剤をコンクリートに配合した急結コンクリートの吹付工法が行われている（特許文献１）。この工法は、通常、掘削工事現場に設置した、セメント、骨材、及び水の計量混合プラントで吹付コンクリートを調製し、アジテータ車で運搬し、コンクリートポンプで圧送し、途中に設けた合流管で、他方から圧送した急結剤と混合し、急結性吹付コンクリートとして地山面に所定の厚みになるまで吹付ける工法である。 Conventionally, in order to prevent the collapse of the ground exposed by tunnel excavation or the like, a quick-setting concrete spraying method in which a quick-setting agent is mixed with concrete has been used (Patent Document 1). In this method, sprayed concrete is usually prepared at a cement, aggregate, and water metering and mixing plant installed at the excavation site, transported by an agitator truck, pumped by a concrete pump, and a confluence pipe installed in the middle. This is a construction method in which the concrete is mixed with a quick-setting agent pumped from the other side and sprayed onto the ground surface as quick-setting spray concrete until it reaches a predetermined thickness.
　従来使用されている急結剤としては、カルシウムアルミネート、アルカリ金属アルミン酸塩、及びアルカリ金属炭酸塩等との混合物；焼ミョウバン、アルカリ金属アルミン酸塩、及びアルカリ金属炭酸塩等の混合物；カルシウムアルミネートと３ＣａＯ・ＳｉＯ２との混合物；消石灰、アルカリ金属アルミン酸塩、及びアルカリ金属炭酸塩の混合物；等が知られている（特許文献２～５）。
　これらの急結剤は、セメントの凝結を促進させる働きがあり、いずれもセメントコンクリートと混合して地山面に吹付けられる。 Conventionally used quick-setting agents include a mixture of calcium aluminate, alkali metal aluminate, alkali metal carbonate, etc.; a mixture of baked myoban, alkali metal aluminate, alkali metal carbonate, etc.; calcium. A mixture of aluminate and 3CaO · SiO 2 ; a mixture of slaked lime, an alkali metal aluminate, and an alkali metal carbonate; and the like are known (Patent Documents 2 to 5).
These quick-setting agents have a function of promoting the coagulation of cement, and all of them are mixed with cement concrete and sprayed on the ground surface.
　急結剤の添加方法は、通常、空気輸送による粉体混合のために、粉塵量が多くなる方法であった。そのため、作業環境が悪化する場合があり、吹付け時には保護眼鏡や防塵マスクなどを着用して作業する必要があり、粉塵量のより少ない工法が求められていた。粉塵発生量が少ない工法として、急結剤をスラリー化してセメントコンクリートに添加混合した後、さらに、アルカリ金属アルミン酸塩の溶液を別途圧送し、混合し、吹付け施工する方法が提案されている（特許文献６）。この方法は、高アルカリの液体を使用するため、取り扱いにくく、吹付け時には保護眼鏡や手袋等が必要となり、作業性が低下するという課題があった。 The method of adding the quick-setting admixture was usually a method of increasing the amount of dust due to powder mixing by air transportation. Therefore, the working environment may deteriorate, and it is necessary to wear protective goggles, a dustproof mask, etc. at the time of spraying, and a construction method with a smaller amount of dust has been required. As a construction method with a small amount of dust generated, a method has been proposed in which a quick-setting admixture is slurried, added and mixed with cement concrete, and then a solution of alkali metal aluminate is separately pumped, mixed, and sprayed. (Patent Document 6). Since this method uses a highly alkaline liquid, it is difficult to handle, and protective glasses, gloves, etc. are required at the time of spraying, which causes a problem that workability is lowered.
　そこで、特許文献７では非晶質カルシウムアルミネートと結晶質カルシウムアルミネートの組み合わせによる急結剤が提案されている。特許文献７においては、低温において更にアルミン酸ナトリウムを併用することで、更に良い効果が得られることが明記されている。しかし近年、急結剤においては、強アルカリ性による失明や薬傷の観点から、アルカリ金属アルミン酸塩やアルカリ金属水酸化物といった強アルカリの原料をできるだけ用いないことが好ましいが、高温状況、コスト面等においてはまだまだ課題は多いのが現状である。 Therefore, Patent Document 7 proposes a quick-setting agent using a combination of amorphous calcium aluminate and crystalline calcium aluminate. Patent Document 7 clearly states that a better effect can be obtained by further using sodium aluminate at a low temperature. However, in recent years, it is preferable not to use strong alkaline raw materials such as alkali metal aluminate and alkali metal hydroxide as much as possible in the quick-setting agent from the viewpoint of blindness and chemical damage due to strong alkalinity, but in terms of high temperature and cost. At present, there are still many issues in such areas.
特公昭６０－４１４９号公報Special Publication No. 60-4149 特開昭６４－０５１３５１号公報Japanese Unexamined Patent Publication No. 64-051351 特公昭５６－２７４５７号公報Special Publication No. 56-27457 特開昭６１－０２６５３８号公報Japanese Unexamined Patent Publication No. 61-026538 特開昭６３－２１００５０号公報Japanese Unexamined Patent Publication No. 63-21050 特開平０５－１３９８０４号公報Japanese Unexamined Patent Publication No. 05-139804 特許第５０２６９２８号Patent No. 5026928
　一般的に強アルカリ性材料はセメントとの反応性が強く、高い初期強度発現性を示すが、長期強度における強度促進が低く、長期的な強度発現性が求められる箇所への適用が難しい。 In general, strong alkaline materials have strong reactivity with cement and show high initial strength development, but their strength promotion in long-term strength is low, and it is difficult to apply them to places where long-term strength development is required.
　本発明は、アルカリ金属アルミン酸塩及びアルカリ金属水酸化物といった材料を使用しなくても、高温状況においても、上記材料を含む急結剤と同等以上の高い急結性や高い初期強度発現性が得られ、長期的な強度発現性を求められる箇所への適用が可能な吹付け用急結剤を提供することを目的とする。 The present invention has high rapid binding and high initial strength development equal to or higher than that of a rapid binder containing the above materials even in high temperature conditions without using materials such as alkali metal aluminate and alkali metal hydroxide. It is an object of the present invention to provide a quick-setting agent for spraying, which can be applied to a place where long-term strength development is required.
　本発明者らは、上記課題を解決すべく種々検討を行った結果、下記本発明に想到し、当該課題を解決できることを見出した。すなわち本発明は下記のとおりである。 As a result of various studies to solve the above problems, the present inventors have come up with the following invention and found that the problem can be solved. That is, the present invention is as follows.
［１］　アルカリ金属アルミン酸塩及びアルカリ金属水酸化物を実質的に含有せず、カルシウムアルミネートと硫酸アルミニウムとを含有する吹付け用急結剤であって、前記硫酸アルミニウムの含有量が、前記カルシウムアルミネート１００質量部に対して５～１０５質量部であり、前記硫酸アルミニウム中のアルカリ土類金属の含有量が、アルカリ土類金属酸化物換算で０．００７～４質量％である吹付け用急結剤。
［２］　前記硫酸アルミニウムに含まれるＣａＯ含有量が０．００５～２質量％、ＭｇＯ含有量が０．００２～２質量％である［１］に記載の吹付け用急結剤。
［３］　さらに、アルカリ土類金属水酸化物を、前記カルシウムアルミネート１００質量部に対して５～１０５質量部含有する［１］又は［２］に記載の吹付け用急結剤。
［４］　さらに、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩からなる群から選択される少なくとも１種を含む［１］～［３］のいずれかに記載の吹付け用急結剤。
［５］　前記アルカリ金属炭酸塩を含有し、該アルカリ金属炭酸塩の含有量が１～３０質量％である［４］に記載の吹付け用急結剤。
［６］　前記硫酸アルミニウムにおける粒径１０μｍ以下の硫酸アルミニウムの割合が１～４０質量％である［１］～［５］のいずれかに記載の吹付け用急結剤。
［７］　前記硫酸アルミニウムが水和物であり、その水和水の数が４～１２である［１］～［６］のいずれかに記載の吹付け用急結剤。 [1] A quick-setting agent for spraying that does not substantially contain alkali metal aluminate and alkali metal hydroxide but contains calcium aluminate and aluminum sulfate, and the content of the aluminum sulfate is high. It is 5 to 105 parts by mass with respect to 100 parts by mass of the calcium aluminate, and the content of the alkaline earth metal in the aluminum sulfate is 0.007 to 4% by mass in terms of alkaline earth metal oxide. Fast-setting agent for attachment.
[2] The quick-setting agent for spraying according to [1], wherein the aluminum sulfate contains 0.005 to 2% by mass of CaO and 0.002 to 2% by mass of MgO.
[3] The quick-setting agent for spraying according to [1] or [2], which further contains 5 to 105 parts by mass of an alkaline earth metal hydroxide with respect to 100 parts by mass of the calcium aluminate.
[4] The blow according to any one of [1] to [3], further comprising at least one selected from the group consisting of alkali metal carbonates, alkaline earth metal carbonates, and alkaline earth metal sulfates. Quick binder for attachment.
[5] The quick-setting agent for spraying according to [4], which contains the alkali metal carbonate and has a content of the alkali metal carbonate of 1 to 30% by mass.
[6] The quick-setting agent for spraying according to any one of [1] to [5], wherein the proportion of aluminum sulfate having a particle size of 10 μm or less in the aluminum sulfate is 1 to 40% by mass.
[7] The quick-setting agent for spraying according to any one of [1] to [6], wherein the aluminum sulfate is a hydrate and the number of hydrated waters thereof is 4 to 12.
　本発明によれば、アルカリ金属アルミン酸塩及びアルカリ金属水酸化物といった材料を使用しなくても、高温状況においても、上記材料を含む急結剤と同等以上の高い急結性や高い初期強度発現性が得られ、長期的な強度発現性を求められる箇所への適用が可能な吹付け用急結剤を提供することができる。
　また、アルカリ金属アルミン酸塩及びアルカリ金属水酸化物の少なくともいずれかを含む急結剤に比べて、取扱いにおいても高い安全性が確保される。 According to the present invention, even in a high temperature condition without using materials such as alkali metal aluminate and alkali metal hydroxide, high quick-setting property and high initial strength equal to or higher than those of a quick-setting agent containing the above-mentioned materials. It is possible to provide a quick-setting agent for spraying, which can be applied to a place where expressiveness is obtained and long-term strength development is required.
In addition, higher safety is ensured in handling as compared with a quick-setting admixture containing at least one of an alkali metal aluminate and an alkali metal hydroxide.
　以下、本発明の実施形態に係る吹付け用急結剤は、アルカリ金属アルミン酸塩及びアルカリ金属水酸化物を実質的に含有せず、カルシウムアルミネートと硫酸アルミニウムとを含有する。アルカリ金属アルミン酸塩及びアルカリ金属水酸化物を実質的に含有しないため、取り扱い性が良好で、吹付け時に保護眼鏡や手袋等が不要となり作業性を低下させることがなく、高い安全性を確保することができる。
　ここで、アルカリ金属アルミン酸塩としては、アルミン酸ナトリウム、アルミン酸カリウムが挙げられ、アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウムが挙げられる。また、「実質的に含有せず」とは、ＸＲＦ測定による検出下限未満の含有量を指し、具体的には０ｐｐｍである。 Hereinafter, the quick-setting agent for spraying according to the embodiment of the present invention does not substantially contain alkali metal aluminate and alkali metal hydroxide, but contains calcium aluminate and aluminum sulfate. Since it does not contain alkali metal aluminate and alkali metal hydroxide substantially, it is easy to handle, and protective glasses and gloves are not required at the time of spraying, which does not reduce workability and ensures high safety. can do.
Here, examples of the alkali metal aluminate include sodium aluminate and potassium aluminate, and examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Further, "substantially not contained" means a content below the lower limit of detection by XRF measurement, and specifically, is 0 ppm.
　一方で、硫酸アルミニウムの含有量を、カルシウムアルミネート１００質量部に対して５～１０５質量部とし、当該硫酸アルミニウム中のアルカリ土類金属の含有量を、アルカリ土類金属酸化物換算で０．００７～４質量％とすることで、アルカリ金属アルミン酸塩及びアルカリ金属水酸化物を実質的に含有せずに、高温状況においても高い急結性や高い初期強度発現性が得られる。
　なお、硫酸アルミニウム量は硫酸アルミニウムが水和水を含む場合は、これを含む量として計算する。
　以下、本実施形態について詳細に説明する。なお、本明細書において、部や％は特に規定しない限り質量基準で示す。 On the other hand, the content of aluminum sulfate is 5 to 105 parts by mass with respect to 100 parts by mass of calcium aluminate, and the content of alkaline earth metal in the aluminum sulfate is 0. By setting the content to 007 to 4% by mass, high rapid binding and high initial strength development can be obtained even in a high temperature state without substantially containing alkali metal aluminate and alkali metal hydroxide.
If aluminum sulfate contains hydrated water, the amount of aluminum sulfate is calculated as the amount containing this.
Hereinafter, the present embodiment will be described in detail. In this specification, parts and% are shown on a mass basis unless otherwise specified.
（カルシウムアルミネート）
　カルシウムアルミネートとは、カルシアを含む原料と、アルミナを含む原料等を混合して、キルンでの焼成や電気炉での溶融等の熱処理をし、急冷または、徐冷して得られる、結晶および／または非結晶質でＣａＯとＡｌ２Ｏ３とを主たる成分とし、水和活性を有する物質の総称であり、ＣａＯやＡｌ２Ｏ３の一部が、アルカリ金属酸化物、アルカリ土類金属酸化物、酸化ケイ素、酸化チタン、酸化鉄、アルカリ金属ハロゲン化物、アルカリ土類金属ハロゲン化物、アルカリ金属硫酸塩、及びアルカリ土類金属硫酸塩等と置換した化合物、あるいは、ＣａＯとＡｌ２Ｏ３とを主成分とするものに、これらが少量固溶、または、単独でコンタミとして、存在する物質である。 (Calcium aluminumate)
Calcium aluminate is a mixture of a raw material containing calcia and a raw material containing alumina, which is subjected to heat treatment such as firing in a kiln or melting in an electric furnace, and then rapidly or slowly cooled to obtain crystals and crystals. / Or is a general term for substances that are non-crystalline and have CaO and Al 2 O 3 as the main components and have hydration activity. Part of CaO and Al 2 O 3 is alkali metal oxide and alkaline earth metal oxidation. Compounds replaced with substances, silicon oxide, titanium oxide, iron oxide, alkali metal halides, alkaline earth metal halides, alkali metal sulfates, alkaline earth metal sulfates, etc., or CaO and Al 2 O 3 These are substances that are present as a solid solution in a small amount or as a contamination alone in a substance containing the above as a main component.
　カルシウムアルミネートの粒度は、ブレーン比表面積（ＪＩＳ　Ｒ　５２０１（セメントの物理試験方法）に準拠。以下、ブレーン値ともいう）で３，０００ｃｍ２／ｇ以上が好ましく、５，０００ｃｍ２／ｇ以上がより好ましい。３，０００ｃｍ２／ｇ以上であることで、急結剤とセメントコンクリートとを混合した吹付け材料の急結性や初期強度発現性を高めることができる。 The particle size of the calcium aluminate, Blaine specific surface area (based on JIS R 5201 (Physical testing methods for cement). Hereinafter also referred to as the Blaine value) is preferably at least 3,000 cm 2 / g in, 5,000 cm 2 / g or more More preferred. When it is 3,000 cm 2 / g or more, it is possible to enhance the quick-setting property and the initial strength development of the sprayed material in which the quick-setting agent and cement concrete are mixed.
　カルシウムアルミネートにおけるＣａＯ／Ａｌ２Ｏ３モル比は、急結性や初期強度発現性の面で、２．０～２．６の範囲が好ましく、２．２～２．４の範囲がより好ましい。 The CaO / Al 2 O 3 molar ratio in calcium aluminate is preferably in the range of 2.0 to 2.6, more preferably in the range of 2.2 to 2.4, in terms of quick-setting property and initial strength development. ..
（硫酸アルミニウム）
　本実施形態に係る硫酸アルミニウムは、アルカリ土類金属を含有し、その含有量（アルカリ土類金属が複数種ある場合はその合計量）が、アルカリ土類金属酸化物換算で０．００７～４質量％であり、好ましくは０．０１～２質量％である。特に、硫酸アルミニウム中のマグネシウム及びカルシウムの含有量が、酸化物換算で０．００７～４質量％であり、好ましくは０．０１～２質量％である。
　上記のような硫酸アルミニウムは、例えば、アルカリ土類金属酸化物のようなアルカリ土類金属化合物を不純物として含む硫酸と水酸化アルミニウムとを混合して得ることができる。
　なお、本実施形態に係る硫酸アルミニウム「硫酸アルミニウム」は、上記のとおり、アルカリ土類金属を含有するが、Ｘ線回折（ＸＲＤ）ではそれらの存在を示すピークが認められないもので、実質的に硫酸アルミニウムとみなすことができるものである。本実施形態に係る硫酸アルミニウムは非晶質であり、これはＸ線回折でブロードなピークとして確認できる。一方で、例えばＣａＯ及びＭｇＯのようなアルカリ土類金属（アルカリ土類金属酸化物）をＸ線回折で同定することはできないが、蛍光Ｘ線分析（ＸＲＦ）の結果においてはＣａＯ及びＭｇＯのようなアルカリ土類金属（アルカリ土類金属酸化物）が確認される。 (Aluminum sulfate)
The aluminum sulfate according to the present embodiment contains an alkaline earth metal, and the content thereof (the total amount when there are a plurality of types of alkaline earth metals) is 0.007 to 4 in terms of alkaline earth metal oxide. It is by mass%, preferably 0.01 to 2% by mass. In particular, the content of magnesium and calcium in aluminum sulfate is 0.007 to 4% by mass, preferably 0.01 to 2% by mass, in terms of oxide.
The above-mentioned aluminum sulfate can be obtained by mixing, for example, sulfuric acid containing an alkaline earth metal compound such as an alkaline earth metal oxide as an impurity with aluminum hydroxide.
As described above, the aluminum sulfate "aluminum sulfate" according to the present embodiment contains alkaline earth metals, but X-ray diffraction (XRD) does not show peaks indicating their presence, which is substantially the same. It can be regarded as aluminum sulfate. The aluminum sulfate according to the present embodiment is amorphous, which can be confirmed as a broad peak by X-ray diffraction. On the other hand, alkaline earth metals (alkaline earth metal oxides) such as CaO and MgO cannot be identified by X-ray fluorescence, but the results of fluorescent X-ray analysis (XRF) show that they are CaO and MgO. Alkaline earth metal (alkaline earth metal oxide) is confirmed.
　硫酸アルミニウムは、吹付け材料として、壁面への付着や極初期の強度発現性に寄与し、特にアルカリ土類金属を含有したものは、常温から低温環境下でも十分な付着性を付与できると共に、高温環境下での長期強度の顕著な低下を防止することも可能になる。硫酸アルミニウム中のアルカリ土類金属の含有量が酸化物換算で０．００７質量％未満では高温環境下で長期強度を発現し難く、また初期強度発現性の低下が大きくなることがあるので好ましくない。また、アルカリ土類金属の含有量が酸化物換算で４質量％を超える場合は、初期強度が低下し、温度環境にかかわらず凝結性状が発現し難くなることがあるので好ましくない。特に、所定量のアルカリ土類金属含有物質を含有する硫酸アルミニウムを使用することによって既述の作用が発現できるのであって、アルカリ土類金属含有物質を含有しない硫酸アルミニウムに加えて、例えば市販試薬の酸化カルシウムや酸化マグネシウム等のアルカリ土類金属酸化物を後から添加混合しても上記のような効果は十分得られない。
　なお、上記の「低温環境下」における「低温」とは、５℃以下を指し、「高温環境下」における「高温」とは、２５℃以上を指す。 Aluminum sulfate contributes to the adhesion to the wall surface and the strength development at the very early stage as a spraying material, and in particular, the one containing an alkaline earth metal can impart sufficient adhesion even in a normal temperature to low temperature environment. It is also possible to prevent a significant decrease in long-term strength in a high temperature environment. If the content of the alkaline earth metal in aluminum sulfate is less than 0.007% by mass in terms of oxide, it is difficult to develop long-term strength in a high temperature environment, and the initial strength development may be significantly reduced, which is not preferable. .. Further, when the content of the alkaline earth metal exceeds 4% by mass in terms of oxide, the initial strength is lowered and the coagulation property may be difficult to develop regardless of the temperature environment, which is not preferable. In particular, the above-mentioned action can be exhibited by using aluminum sulfate containing a predetermined amount of alkaline earth metal-containing substance, and in addition to aluminum sulfate containing no alkaline earth metal-containing substance, for example, a commercially available reagent. Even if alkaline earth metal oxides such as calcium oxide and magnesium oxide are added and mixed later, the above effects cannot be sufficiently obtained.
The "low temperature" in the above "low temperature environment" means 5 ° C. or lower, and the "high temperature" in the "high temperature environment" means 25 ° C. or higher.
　ここで、アルカリ土類金属とは、少なくともベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムの何れかをいう。
　これらのアルカリ土類金属は、硫酸アルミニウムとともに、アルカリ土類金属単体、あるいは、アルカリ土類金属化合物、アルカリ土類金属含有固溶体、アルカリ土類金属含有非晶質体等のアルカリ土類金属含有物質として存在する。具体的な共存状態としては、例えば、アルカリ土類金属、アルカリ土類金属酸化物（ＢｅＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯなど）、アルカリ土類金属水酸化物、アルカリ土類金属炭酸塩、アルカリ土類金属酸化物としての硫酸アルミニウム中への固溶体などが挙げられる。好ましくは、アルカリ土類金属硫酸塩は含まない。 Here, the alkaline earth metal means at least any one of beryllium, magnesium, calcium, strontium, and barium.
These alkaline earth metals, together with aluminum sulfate, are simple substances of alkaline earth metals, or alkaline earth metal-containing substances such as alkaline earth metal compounds, alkaline earth metal-containing solid solutions, and alkaline earth metal-containing amorphous substances. Exists as. Specific coexistence states include, for example, alkaline earth metals, alkaline earth metal oxides (BeO, MgO, CaO, SrO, BaO, etc.), alkaline earth metal hydroxides, alkaline earth metal carbonates, and alkalis. Examples thereof include a solid solution in aluminum sulfate as an earth metal oxide. Preferably, it does not contain alkaline earth metal sulphate.
　硫酸アルミニウムの含有量は、カルシウムアルミネート１００部に対して５～１０５部であり、１０～９０部であることが好ましく、２０～８０部であることがより好ましい。硫酸アルミニウムの含有量が５～１０５部の範囲外では、凝結性が低下してしまう。 The content of aluminum sulfate is 5 to 105 parts, preferably 10 to 90 parts, and more preferably 20 to 80 parts with respect to 100 parts of calcium aluminate. If the content of aluminum sulfate is outside the range of 5 to 105 parts, the cohesiveness will decrease.
　硫酸アルミニウムに含まれるＣａＯ含有量は０．００５～２％であることが好ましく、ＭｇＯ含有量０．００２～２％であることが好ましい。ＣａＯ含有量は、０．０１～１．５％がより好ましく、ＭｇＯ含有量は、０．００８～１．５％がより好ましい。
　硫酸アルミニウムに含まれるＣａＯ含有量及びＭｇＯ含有量は、例えば、高純度の水酸化アルミニウムと、硫酸とを混合する際に硫酸に含まれるＣａＯ及び／又はＭｇＯを除去せずに混合するか、あるいは意図的に加えることによって含有量の調整を行うことができる。 The CaO content in aluminum sulfate is preferably 0.005 to 2%, and the MgO content is preferably 0.002 to 2%. The CaO content is more preferably 0.01 to 1.5%, and the MgO content is more preferably 0.008 to 1.5%.
The CaO content and MgO content contained in aluminum sulfate are, for example, mixed without removing CaO and / or MgO contained in sulfuric acid when mixing high-purity aluminum hydroxide and sulfuric acid, or The content can be adjusted by intentionally adding it.
　ＣａＯ含有量が０．００５％以上であると、高温状況で長期強度がより得られやすくなり、２％以下であると、凝結性状の低下が抑えられやすくなる。また、ＭｇＯ含有量が０．００２％以上であると、高温状況で長期強度がより得られやすくなり、２％以下であると、高温状況で異常膨張が抑制されやすくなる。 When the CaO content is 0.005% or more, long-term strength is more likely to be obtained in a high temperature condition, and when it is 2% or less, a decrease in coagulation properties is likely to be suppressed. Further, when the MgO content is 0.002% or more, long-term strength is more likely to be obtained in a high temperature condition, and when it is 2% or less, abnormal expansion is likely to be suppressed in a high temperature condition.
　硫酸アルミニウムは、無水塩から１４～１８水塩までが使用可能であるが、１４水塩以上では、粉砕できない場合があり、１２水塩以下が好ましい。また、無水塩は凝結性状が低下する場合があるため、４水塩以上が好ましい。より好ましくは４～１２水塩、すなわち、硫酸アルミニウムが水和物であり、その水和水の数が４～１２であることがより好ましい。
　水和水の数は、例えば、１８水塩の硫酸アルミニウムを加熱等して所望の水和水の数になるように脱水すればよい。 As aluminum sulfate, anhydrous salts to 14 to 18 hydroxides can be used, but 14 hydroxides or more may not be pulverized, and 12 hydroxides or less is preferable. In addition, anhydrous salts may have reduced coagulation properties, so tetrahydrate or more is preferable. More preferably, 4 to 12 hydroxides, that is, aluminum sulfate is the hydrate, and the number of hydrated waters thereof is more preferably 4 to 12.
The number of hydrated water may be, for example, dehydrated to a desired number of hydrated water by heating aluminum sulfate of 18 hydroxides or the like.
　硫酸アルミニウムはフレーク状、粗粉末、粉末状など粉体として、いずれの形態も使用可能であるが、極初期強度発現性の観点から、粉末状が好ましく、更に粒径として、１０μｍ以下が１～４０％で調整することが好ましい。粒径１０μｍ以下が１％以上であると、極初期強度発現性が得られやすくなり、４０％以下であると、長期強度がより得られやすくなる。粒径１０μｍ以下を１～４０％とするには、篩等を利用すればよい。 Aluminum sulfate can be used in any form as a powder such as flakes, coarse powder, and powder, but from the viewpoint of extremely initial strength development, powder is preferable, and the particle size is 1 to 10 μm or less. It is preferable to adjust at 40%. When the particle size is 10 μm or less and 1% or more, the very initial strength development is easily obtained, and when the particle size is 40% or less, the long-term strength is more easily obtained. In order to make the particle size of 10 μm or less 1 to 40%, a sieve or the like may be used.
（アルカリ土類金属水酸化物）
　本実施形態に係る吹付け用急結剤は、さらに、アルカリ土類金属水酸化物を含有することが好ましい。アルカリ土類金属水酸化物を含有することで、長期強度をより向上させることができる。 (Alkaline earth metal hydroxide)
The spraying quick-setting admixture according to the present embodiment preferably further contains an alkaline earth metal hydroxide. By containing an alkaline earth metal hydroxide, the long-term strength can be further improved.
　アルカリ土類金属水酸化物は、例えば、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなどの水酸化物を指し、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、水酸化マグネシウム、および水酸化ラジウム等のうちの一種又は二種以上を使用することが可能である。これらのうち、価格や取り扱いやすさなどの工業的見地から水酸化カルシウム、水酸化マグネシウムの使用が好ましく、カルシウムカーバイドからアセチレンを発生させる際に副生するカーバイド滓等も水酸化カルシウムとして、挙げられる。アルカリ土類金属水酸化物の粒度は、２５０μｍ残分３０％以下が好ましく、２５０μｍ残分１０％以下がより好ましい。 Alkaline earth metal hydroxides refer to, for example, hydroxides such as beryllium, magnesium, calcium, strontium, and barium, such as calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydroxide, and radium hydroxide. It is possible to use one or more of them. Of these, calcium hydroxide and magnesium hydroxide are preferably used from an industrial point of view such as price and ease of handling, and carbide slag and the like produced as a by-product when acetylene is generated from calcium carbide can also be mentioned as calcium hydroxide. .. The particle size of the alkaline earth metal hydroxide is preferably 250 μm residual 30% or less, and more preferably 250 μm residual 10% or less.
　アルカリ土類金属水酸化物の含有量は、カルシウムアルミネートを１００部としたとき、２～１２０部が好ましく、５～１０５部がより好ましく、５～１００部がさらに好ましく、なかでも１０～５０部が好ましい。特に、５部以上であることで凝結性状が低下しにくくなり、１００部以下であることで長期強度が良好することができる。 The content of the alkaline earth metal hydroxide is preferably 2 to 120 parts, more preferably 5 to 105 parts, further preferably 5 to 100 parts, and particularly preferably 10 to 50 parts, when calcium aluminate is 100 parts. Part is preferable. In particular, when the number of parts is 5 or more, the cohesiveness is less likely to decrease, and when the amount is 100 or less, the long-term strength can be improved.
（その他の成分）
　本実施形態に係る吹付け用急結剤には、必要に応じて、通常の急結剤で想定される材料を配合してもよい。例えば、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩からなる群より選ばれた物質が挙げられ、アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩からなる群から選択される少なくとも１種であることが好ましい。アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩からなる群から選択される少なくとも１種は、長期強度の増進に寄与する点で好ましく、吹付け用急結剤中、３～５０％であることが好ましく、５～４０％であることがより好ましい。アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩としては、炭酸カルシウム、及び硫酸カルシウムなどが挙げられる。 (Other ingredients)
If necessary, the spraying quick-setting admixture according to the present embodiment may contain a material expected from a normal quick-setting admixture. For example, a substance selected from the group consisting of alkali metal carbonate, alkaline earth metal carbonate, and alkaline earth metal sulfate can be mentioned, and the group consisting of alkaline earth metal carbonate and alkaline earth metal sulfate can be mentioned. It is preferable that it is at least one selected from. At least one selected from the group consisting of alkaline earth metal carbonates and alkaline earth metal sulfates is preferable in that it contributes to the enhancement of long-term strength, and is preferably 3 to 50% in the spray binder. It is preferably present, and more preferably 5 to 40%. Examples of the alkaline earth metal carbonate and the alkaline earth metal sulfate include calcium carbonate and calcium sulfate.
　また、特に３時間強度や１日強度などで所定の強度を得るためには、アルカリ金属炭酸塩の使用が好ましく、その量は吹付け用急結剤中、１～３０％であることが好ましく、５～２０％であることがより好ましい。１％以上であると、材齢３時間強度や１日強度で所望の強度が得られやすくなり、３０％以下であると、長期強度が得られやすくなる。アルカリ金属炭酸塩としては、炭酸ナトリウム、炭酸カリウムなどが挙げられる。 Further, in order to obtain a predetermined strength particularly with a 3-hour strength or a 1-day strength, it is preferable to use an alkali metal carbonate, and the amount thereof is preferably 1 to 30% in the quick-setting admixture for spraying. More preferably, it is 5 to 20%. If it is 1% or more, the desired strength can be easily obtained at the age of 3 hours or 1 day, and if it is 30% or less, the long-term strength can be easily obtained. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate.
　以上のような本実施形態に係る吹付け用急結剤は例えば、セメントコンクリートのセメント１００部に対して５～３０部配合させることが好ましい。５部以上であることで、吹付けに求められる付着性状、凝結性状、強度発現性が得られやすくなる。また、３０部以下であると、長期強度低下を抑制することができる。セメントコンクリートに配合する際の本実施形態に係る吹付け用急結剤の形態は、例えば、粉体、液体、懸濁液状、スラリー状など形態は問わない。 It is preferable to mix 5 to 30 parts of the quick-setting agent for spraying according to the present embodiment as described above with respect to 100 parts of cement of cement concrete, for example. When the number of parts is 5 or more, it becomes easy to obtain the adhesive property, the cohesive property, and the strength development required for spraying. Further, when the amount is 30 parts or less, a long-term decrease in strength can be suppressed. The form of the quick-setting admixture for spraying according to the present embodiment when blended in cement concrete may be, for example, powder, liquid, suspension, slurry, or the like.
　セメントコンクリートのセメントとしては、特に限定されるものではなく、普通、早強、超早強、中庸熱、及び低熱の各種ポルトランドセメントや、これらポルトランドセメントに高炉スラグ、フライアッシュ、及び石灰石微粉末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）等が挙げられ、これらを微粉末化して使用することも可能である。混合セメントにおける混合物とセメントの割合は特に限定されるものではなく、これら混和材をＪＩＳで想定する以上に混合したものも使用可能である。 Cement The cement of concrete is not particularly limited, and various Portland cements of ordinary, early-strength, ultra-fast-strength, moderate heat, and low heat, and blast furnace slag, fly ash, and fine limestone powder are added to these Portland cements. Examples include mixed filler cement, environment-friendly cement (eco-cement) produced from municipal waste incineration ash and sewage sludge incineration ash as raw materials, and these can also be used in fine powder. The ratio of the mixture to the cement in the mixed cement is not particularly limited, and a mixture of these admixtures in a range larger than that assumed by JIS can be used.
　本実施形態のセメントコンクリートは、セメントと骨材とを含有するものであり、骨材は吸水率が低くて、骨材強度が高いものが好ましい。骨材は、吹付けできれば特に限定されるものではないが、細骨材としては、川砂、山砂、海砂、石灰砂、及び珪砂等が使用可能であり、粗骨材としては、川砂利、山砂利、及び石灰砂利等が使用可能であり、砕砂、砕石の使用も可能である。 The cement concrete of the present embodiment contains cement and an aggregate, and the aggregate preferably has a low water absorption rate and a high aggregate strength. The aggregate is not particularly limited as long as it can be sprayed, but river sand, mountain sand, sea sand, lime sand, silica sand and the like can be used as the fine aggregate, and river gravel as the coarse aggregate. , Mountain gravel, lime gravel, etc. can be used, and crushed sand and crushed stone can also be used.
　また、本発明の急結剤を用いた吹付け工法としては、要求される物性、経済性、及び施工性等に応じた種々の吹付け工法が可能である。本発明の急結剤を用いた吹付け工法としては、乾式吹付け工法及び湿式吹付け工法のいずれの工法も可能である。 Further, as the spraying method using the quick-setting admixture of the present invention, various spraying methods according to the required physical properties, economic efficiency, workability, etc. are possible. As the spraying method using the quick-setting agent of the present invention, either a dry spraying method or a wet spraying method can be used.
［実験例１］
　各物性の測定方法及び使用材料は以下のとおりである。
（プロクター貫入試験及び圧縮強度）
　試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表１に示す含有割合の急結剤（吹付け用急結剤）を１０部加えてからプロクター貫入試験により、凝結の始発時間（始発）と終結時間（終結）を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度（ＪＩＳ　Ｒ　５２０１、以下同様）を測定した。
　なお、表１に示す含有割合の各急結剤は、それぞれの材料を混合することで調製した（他の実験例についても同様）。 [Experimental Example 1]
The measurement method and materials used for each physical property are as follows.
(Proctor penetration test and compressive strength)
Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of a quick-setting agent (quick-setting agent for spraying) having the content ratio shown in Table 1, and then perform a proctor penetration test. The starting time (starting) and ending time (ending) of coagulation were measured, and the compressive strength (JIS R 5201, the same applies hereinafter) was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent. ..
Each quick-setting admixture having a content ratio shown in Table 1 was prepared by mixing the respective materials (the same applies to other experimental examples).
（使用材料）
セメント：普通ポルトランドセメント、デンカ社製
砂：川砂、密度２．６４ｇ／ｃｍ３、粗粒率（Ｆ．Ｍ）２．８３
水：上水道水
カルシウムアルミネート：ＣａＯ／Ａｌ２Ｏ３モル比：２．２４、ブレーン比表面積：５９００ｃｍ２／ｇ、ＣａＯ源：生石灰（ＣａＯ：９５％）、Ａｌ２Ｏ３源：天然ボーキサイト（Ａｌ２Ｏ３：８５％）、製造方法：電気炉で溶融し、急冷したものを粉砕したガラス粉末、ガラス化率：９０％、ＣａＯとＡｌ２Ｏ３の合計が９６％
アルカリ土類金属水酸化物ａ：水酸化カルシウム（工業品）、水酸化カルシウム含有９８％、ブレーン比表面積１０，５００ｃｍ２／ｇ、
ＡＳ－ア：　ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩 (Material used)
Cement: Ordinary Portland cement, Denka sand: River sand, density 2.64 g / cm 3 , coarse grain ratio (FM) 2.83
Water: Tap water Calcium oxide: CaO / Al 2 O 3 molar ratio: 2.24, Brain ratio Surface area: 5900 cm 2 / g, CaO source: Quicklime (CaO: 95%), Al 2 O 3 source: Natural bokisite ( Al 2 O 3 : 85%), Manufacturing method: Glass powder melted in an electric furnace and crushed by quenching, vitrification rate: 90%, total of CaO and Al 2 O 3 96%
Alkaline earth metal hydroxide a: Calcium hydroxide (industrial product), calcium hydroxide content 98%, brain specific surface area 10,500 cm 2 / g,
AS-A: Aluminum sulfate containing 0.9% by mass of CaO and 0.7% by mass of MgO and 1.6% of alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, 8.5 water salt
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　表１の試験結果より、急結剤中の硫酸アルミニウム配合量を４質量部とすると、凝結の始発時間、終結時間ともにその凝結性が著しく低下し、圧縮強度も実施例と比較して低いことがわかる。また、硫酸アルミニウム配合量を１１０質量部とした場合も実施例と比較して凝結時間、圧縮強度が低いことがわかる。以上の結果より急結剤中の硫酸アルミニウムの含有量は５～１０５質量部で、特に５～１００質量部とすることが好ましい。 From the test results in Table 1, when the amount of aluminum sulfate blended in the quick-setting admixture is 4 parts by mass, the coagulation property is remarkably reduced in both the start time and the end time of coagulation, and the compressive strength is also lower than that in the examples. I understand. Further, it can be seen that the setting time and the compressive strength are lower than those in the examples even when the amount of aluminum sulfate compounded is 110 parts by mass. From the above results, the content of aluminum sulfate in the quick-setting admixture is 5 to 105 parts by mass, and particularly preferably 5 to 100 parts by mass.
［実験例２］
　実験例１と同様に試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表２に示す含有割合の急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。
　なお、使用した硫酸アルミニウムはアルカリ土類金属を、金属酸化物換算で０．００６％～４．５％含有するものとし、以下にその略号を示す。 [Experimental Example 2]
Similar to Experimental Example 1, a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand was prepared at a test temperature of 30 ° C., 10 parts of the quick-setting agent having the content ratio shown in Table 2 was added, and then a proctor penetration test was performed. The start and end times of coagulation were measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent.
The aluminum sulfate used contains an alkaline earth metal in an amount of 0.006% to 4.5% in terms of metal oxide, and the abbreviations are shown below.
ＡＳ－イ；ＣａＯ：０．００３質量％、ＭｇＯ：０．００２質量％を含み、アルカリ土類金属酸化物換算で０．００５％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－ウ；ＣａＯ：０．００５質量％、ＭｇＯ：０．００２質量％を含み、アルカリ土類金属酸化物換算で０．００７％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－エ；ＣａＯ：０．００６質量％、ＭｇＯ：０．００４質量％を含み、アルカリ土類金属酸化物換算で０．０１０％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－オ；ＣａＯ：０．８質量％、ＭｇＯ：０．５質量％を含み、アルカリ土類金属酸化物換算で１．３％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－カ；ＣａＯ：１質量％、ＭｇＯ：１質量％を含み、アルカリ土類金属酸化物換算で２．０％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－キ；ＣａＯ：１．３質量％、ＭｇＯ：１．１質量％を含み、アルカリ土類金属酸化物換算で２．４％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－ク；ＣａＯ：１．６質量％、ＭｇＯ：１．８質量％を含み、アルカリ土類金属酸化物換算で３．４％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－ケ；ＣａＯ：２．１質量％、ＭｇＯ：２．３質量％を含み、アルカリ土類金属酸化物換算で４．４％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩 AS-a; Aluminum sulfate containing 0.003% by mass of CaO and 0.002% by mass of MgO and 0.005% of alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, 8.5 hydroxide AS-c; CaO: 0.005% by mass, MgO: 0.002% by mass, and contains 0.007% alkaline earth metal in terms of alkaline earth metal oxide. Aluminum sulfate, particle size 10 μm or less: 20%, 8.5 hydroxide AS-d; CaO: 0.006% by mass, MgO: 0.004% by mass, 0.010% in terms of alkaline earth metal oxide Alkaline earth metal containing aluminum sulfate, particle size 10 μm or less: 20%, 8.5 hydroxide AS-o; CaO: 0.8% by mass, MgO: 0.5% by mass, alkaline earth metal Aluminum sulfate containing 1.3% alkaline earth metal in terms of oxide, particle size 10 μm or less: 20%, 8.5 hydroxide AS-ca; CaO: 1% by mass, MgO: 1% by mass, Aluminum sulfate containing 2.0% alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, 8.5 hydroxide AS-ki; CaO: 1.3% by mass, MgO: Aluminum sulfate containing 1.1% by mass and 2.4% of alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, 8.5 hydroxide AS-ku; CaO: Aluminum sulfate containing 1.6% by mass, MgO: 1.8% by mass, and 3.4% of alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, 8.5 Water salt AS-ke; CaO: 2.1% by mass, MgO: 2.3% by mass, aluminum sulfate containing 4.4% alkaline earth metal in terms of alkaline earth metal oxide, particle diameter 10 μm Below: 20%, 8.5 hydroxides
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　表２の試験結果より、アルカリ土類金属酸化物換算で０．００５％のアルカリ土類金属を含有する比較例は実施例と比較してプロクターの始発及び終結時間が遅くなっていることが分かる。また圧縮強度も低下している。アルカリ土類金属酸化物換算で４．４％のアルカリ土類金属を含有する比較例も同様にプロクター、圧縮強度ともに実施例と比較して低下している。以上の結果より、急結剤中の硫酸アルミニウムはアルカリ土類金属酸化物換算でアルカリ土類金属を０．００７～４％含有しているものが好ましい。 From the test results in Table 2, it can be seen that the comparative example containing 0.005% of alkaline earth metal in terms of alkaline earth metal oxide has a later start and end time of the proctor than the example. .. The compressive strength is also reduced. Similarly, in the comparative example containing 4.4% of the alkaline earth metal in terms of alkaline earth metal oxide, both the proctor and the compressive strength are lower than those in the example. From the above results, it is preferable that the aluminum sulfate in the quick-setting admixture contains 0.007 to 4% of alkaline earth metal in terms of alkaline earth metal oxide.
［実験例３］
　実験例１、２と同様に試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表３に示す含有割合の急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。 [Experimental Example 3]
Similar to Experimental Examples 1 and 2, a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand was prepared at a test temperature of 30 ° C., and 10 parts of the quick-setting agent having the content ratio shown in Table 3 was added, and then the Procter penetration test was performed. The time of onset and end of coagulation was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting agent.
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
　以上の結果より急結剤中の水酸化カルシウムの含有量は、カルシウムアルミネート１００質量部に対して５質量部～１００質量部とすることが好ましい。 From the above results, the content of calcium hydroxide in the quick-setting admixture is preferably 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of calcium aluminate.
［実験例４］
　試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表４に示す配合割合の急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。なお、使用した硫酸アルミニウムは以下に示すものを使用した。 [Experimental Example 4]
Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture. The aluminum sulfate used was as shown below.
ＡＳ－コ；ＣａＯ：０．００４質量％、ＭｇＯ：０．５質量％を含み、アルカリ土類金属酸化物換算で０．５０４％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－サ；ＣａＯ：３質量％、ＭｇＯ：０．５質量％を含み、アルカリ土類金属酸化物換算で３．５％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－シ；ＣａＯ：０．５質量％、ＭｇＯ：０．００１質量％を含み、アルカリ土類金属酸化物換算で０．５０１％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩
ＡＳ－ス；ＣａＯ：０．５質量％、ＭｇＯ：２質量％を含み、アルカリ土類金属酸化物換算で２．５％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、８．５水塩 AS-co; CaO: 0.004% by mass, MgO: 0.5% by mass, aluminum sulfate containing 0.504% alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: Aluminum sulfate containing 20%, 8.5 hydroxide AS-sa; CaO: 3% by mass, MgO: 0.5% by mass, and containing 3.5% alkaline earth metal in terms of alkaline earth metal oxide. , Particle size 10 μm or less: 20%, 8.5 hydroxide AS-si; CaO: 0.5% by mass, MgO: 0.001% by mass, 0.501% alkali in terms of alkaline earth metal oxide Aluminum sulfate containing earth metal, particle size 10 μm or less: 20%, 8.5 hydroxide AS-s; CaO: 0.5% by mass, MgO: 2% by mass, in terms of alkaline earth metal oxide Aluminum sulfate containing 2.5% alkaline earth metal, particle size 10 μm or less: 20%, 8.5 hydroxide
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
  
　表４より、硫酸アルミニウムに含まれるアルカリ土類金属酸化物量が、ＣａＯ：０．００５質量％～２質量％、ＭｇＯ：０．００２質量％～２質量％であることが好ましいといえる。 From Table 4, it can be said that it is preferable that the amount of alkaline earth metal oxide contained in aluminum sulfate is CaO: 0.005% by mass to 2% by mass and MgO: 0.002% by mass to 2% by mass.
［実験例５］
　実験例１と同様のカルシウムアルミネート１００部、アルカリ土類金属水酸化物ａ５０部、硫酸アルミニウム（ＡＳ－ア）５０部、更に表５に示す種類と量のアルカリ土類金属炭酸塩とアルカリ土類金属硫酸塩からなる急結剤を作製した。試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、上記急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。なお、使用したアルカリ土類金属炭酸塩とアルカリ土類金属硫酸塩は以下に示すものを使用した。 [Experimental Example 5]
Similar to Experimental Example 1, 100 parts of calcium aluminate, 50 parts of alkaline earth metal hydroxide, 50 parts of aluminum sulfate (AS-a), and the types and amounts shown in Table 5 are alkaline earth metal carbonate and alkaline soil. A quick-setting agent composed of metalloid sulfate was prepared. Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the above-mentioned quick-setting admixture, and then measure the start and end times of condensation by a Procter penetration test. The compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the binder. The alkaline earth metal carbonates and alkaline earth metal sulfates used were as shown below.
アルカリ土類金属炭酸塩ア：炭酸マグネシウム工業品、ブレーン値２８００ｃｍ２／ｇ
アルカリ土類金属炭酸塩イ：炭酸カルシウム工業品、ブレーン値３０００ｃｍ２／ｇ
アルカリ土類金属硫酸塩α：硫酸マグネシウム工業品、ブレーン値３５００ｃｍ２／ｇ
アルカリ土類金属硫酸塩β：硫酸カルシウム工業品、ブレーン値４５００ｃｍ２／ｇ Alkaline earth metal carbonate A: Magnesium carbonate industrial product, brain value 2800 cm 2 / g
Alkaline earth metal carbonate a: Calcium carbonate industrial product, brain value 3000 cm 2 / g
Alkaline earth metal sulfate α: Magnesium sulfate industrial product, brain value 3500 cm 2 / g
Alkaline earth metal sulfate β: Calcium sulfate industrial product, brain value 4500 cm 2 / g
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
［実験例６］
　実験例５と同様のカルシウムアルミネート１００部、アルカリ土類金属水酸化物ａ５０部、硫酸アルミニウム（ＡＳ－ア）５０部、アルカリ土類金属炭酸塩イ１０部、アルカリ土類金属硫酸塩β１０部、更に表６に示す種類と量のアルカリ金属炭酸塩からなる急結剤を作製した。試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、上記急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。なお、使用したアルカリ金属炭酸塩は以下に示すものを使用した。 [Experimental Example 6]
Similar to Experimental Example 5, 100 parts of calcium aluminate, 50 parts of alkaline earth metal hydroxide, 50 parts of aluminum sulfate (AS-a), 10 parts of alkaline earth metal carbonate, 10 parts of alkaline earth metal sulfate β Further, a quick-setting agent composed of the types and amounts of alkali metal carbonates shown in Table 6 was prepared. Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the above-mentioned quick-setting admixture, and then measure the start and end times of condensation by a Procter penetration test. The compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the binder. The alkali metal carbonates used were as shown below.
アルカリ金属炭酸塩ア：炭酸ナトリウム工業品、炭酸ナトリウム含有量９８％、ブレーン値１０００ｃｍ２／ｇ
アルカリ金属炭酸塩イ：炭酸カリウム工業品、炭酸カリウム含有量９７％、ブレーン値１５００ｃｍ２／ｇ
アルカリ金属炭酸塩ウ：炭酸リチウム工業品、炭酸リチウム含有量９８％、ブレーン値８００ｃｍ２／ｇ Alkali metal carbonate A: Sodium carbonate industrial product, sodium carbonate content 98%, brain value 1000 cm 2 / g
Alkali metal carbonate a: Potassium carbonate industrial product, potassium carbonate content 97%, brain value 1500 cm 2 / g
Alkali metal carbonate C: Lithium carbonate industrial product, lithium carbonate content 98%, brain value 800 cm 2 / g
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000006
  
［実験例７］
　試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表７に示す含有割合の急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。なお、使用した硫酸アルミニウムは以下に示すものを使用した。 [Experimental Example 7]
Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the quick-setting agent having the content ratio shown in Table 7, and then perform a proctor penetration test to determine the start and end of condensation. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture. The aluminum sulfate used was as shown below.
ＡＳ－シ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：０．５％、８．５水塩
ＡＳ－ス；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：１．０％、８．５水塩
ＡＳ－セ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：４０％、８．５水塩
ＡＳ－ソ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：４１％、８．５水塩 AS-si; aluminum sulfate containing 0.9% by mass of CaO and 0.7% by mass of MgO and 1.6% of alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 0.5%, 8.5 hydroxide AS-s; CaO: 0.9% by mass, MgO: 0.7% by mass, 1.6% alkaline earth metal in terms of alkaline earth metal oxide Contains aluminum sulfate, particle size 10 μm or less: 1.0%, 8.5 hydroxide AS-se; CaO: 0.9% by mass, MgO: 0.7% by mass, in terms of alkaline earth metal oxide Aluminum sulfate containing 1.6% alkaline earth metal, particle size 10 μm or less: 40%, 8.5 hydroxide AS-so; CaO: 0.9% by mass, MgO: 0.7% by mass, Aluminum sulfate containing 1.6% alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 41%, 8.5 hydroxide
Figure JPOXMLDOC01-appb-T000007
  
Figure JPOXMLDOC01-appb-T000007
  
［実験例８］
　試験温度３０℃でセメント１００部、水４０部、砂３００部からなるモルタルを調製し、表８に示す含有割合の急結剤を１０部加えてからプロクター貫入試験により、凝結の始発と終結の時間を測定し、急結剤を加えてから材齢１０分、３時間、２８日の圧縮強度を測定した。なお、使用した硫酸アルミニウムは以下に示すものを使用した。 [Experimental Example 8]
Prepare a mortar consisting of 100 parts of cement, 40 parts of water, and 300 parts of sand at a test temperature of 30 ° C., add 10 parts of the quick-setting agent having the content ratio shown in Table 8, and then perform a proctor penetration test to determine the start and end of condensation. The time was measured, and the compressive strength was measured at 10 minutes, 3 hours, and 28 days after the addition of the quick-setting admixture. The aluminum sulfate used was as shown below.
ＡＳ－タ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、１８水塩
ＡＳ－チ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、１４水塩
ＡＳ－ツ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、１２水塩
ＡＳ－テ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、１０．５水塩
ＡＳ－ト；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、４．０水塩
ＡＳ－ナ；ＣａＯ：０．９質量％、ＭｇＯ：０．７質量％を含み、アルカリ土類金属酸化物換算で１．６％のアルカリ土類金属を含有する硫酸アルミニウム、粒子径１０μｍ以下：２０％、無水塩 AS-ta; Aluminum sulfate containing CaO: 0.9% by mass, MgO: 0.7% by mass, and 1.6% alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: Aluminum sulfate containing 20%, 18 hydroxide AS-chi; CaO: 0.9% by mass, MgO: 0.7% by mass, and 1.6% alkaline earth metal in terms of alkaline earth metal oxide. , Particle size 10 μm or less: 20%, 14 hydroxide AS-ts; CaO: 0.9% by mass, MgO: 0.7% by mass, alkaline earth Alkaline earth of 1.6% in terms of metal oxide Aluminum sulfate containing metal, particle size 10 μm or less: 20%, 12 hydroxide AS-te; CaO: 0.9% by mass, MgO: 0.7% by mass, converted to alkaline earth metal oxide 1. Aluminum sulfate containing 6% alkaline earth metal, particle size 10 μm or less: 20%, 10.5 hydroxide AS-to; CaO: 0.9% by mass, MgO: 0.7% by mass, alkaline soil Aluminum sulfate containing 1.6% alkaline earth metal in terms of metal oxides, particle size 10 μm or less: 20%, 4.0 hydroxide AS-na; CaO: 0.9% by mass, MgO: 0. Aluminum sulfate containing 7% by mass and 1.6% alkaline earth metal in terms of alkaline earth metal oxide, particle size 10 μm or less: 20%, anhydrous salt
Figure JPOXMLDOC01-appb-T000008
  
Figure JPOXMLDOC01-appb-T000008
  
　本発明の吹付け用急結剤は、例えば、道路、鉄道、及び導水路等のトンネルや法面等において露出した地山面へ吹付けるセメントコンクリートに対して好適に使用できる。
 
 
 

  The spraying quick-setting admixture of the present invention can be suitably used for cement concrete sprayed on exposed ground surfaces such as tunnels and slopes of roads, railways, and headraces.

Claims (7)

  1. 　アルカリ金属アルミン酸塩及びアルカリ金属水酸化物を実質的に含有せず、カルシウムアルミネートと硫酸アルミニウムとを含有する吹付け用急結剤であって、
    　前記硫酸アルミニウムの含有量が、前記カルシウムアルミネート１００質量部に対して５～１０５質量部であり、
    　前記硫酸アルミニウム中のアルカリ土類金属の含有量が、アルカリ土類金属酸化物換算で０．００７～４質量％である吹付け用急結剤。     It is a quick-setting agent for spraying that does not substantially contain alkali metal aluminate and alkali metal hydroxide, but contains calcium aluminate and aluminum sulfate.
    The content of the aluminum sulfate is 5 to 105 parts by mass with respect to 100 parts by mass of the calcium aluminate.
    A quick-setting agent for spraying in which the content of alkaline earth metal in the aluminum sulfate is 0.007 to 4% by mass in terms of alkaline earth metal oxide.
  2. 　前記硫酸アルミニウムに含まれるＣａＯ含有量が０．００５～２質量％、ＭｇＯ含有量が０．００２～２質量％である請求項１に記載の吹付け用急結剤。 The quick-setting agent for spraying according to claim 1, wherein the aluminum sulfate contains 0.005 to 2% by mass of CaO and 0.002 to 2% by mass of MgO.
  3. 　さらに、アルカリ土類金属水酸化物を、前記カルシウムアルミネート１００質量部に対して５～１０５質量部含有する請求項１又は２に記載の吹付け用急結剤。 The quick-setting agent for spraying according to claim 1 or 2, further containing 5 to 105 parts by mass of alkaline earth metal hydroxide with respect to 100 parts by mass of the calcium aluminate.
  4. 　さらに、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、及びアルカリ土類金属硫酸塩からなる群から選択される少なくとも１種を含む請求項１～３のいずれか１項に記載の吹付け用急結剤。 The spray emergency according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of alkali metal carbonates, alkaline earth metal carbonates, and alkaline earth metal sulfates. Condensing agent.
  5. 　前記アルカリ金属炭酸塩を含有し、該アルカリ金属炭酸塩の含有量が１～３０質量％である請求項４に記載の吹付け用急結剤。 The quick-setting agent for spraying according to claim 4, which contains the alkali metal carbonate and has a content of the alkali metal carbonate of 1 to 30% by mass.
  6. 　前記硫酸アルミニウムにおける粒径１０μｍ以下の硫酸アルミニウムの割合が１～４０質量％である請求項１～５のいずれか１項に記載の吹付け用急結剤。 The quick-setting agent for spraying according to any one of claims 1 to 5, wherein the proportion of aluminum sulfate having a particle size of 10 μm or less in the aluminum sulfate is 1 to 40% by mass.
  7. 　前記硫酸アルミニウムが水和物であり、その水和水の数が４～１２である請求項１～６のいずれか１項に記載の吹付け用急結剤。

          The quick-setting agent for spraying according to any one of claims 1 to 6, wherein the aluminum sulfate is a hydrate and the number of hydrated waters thereof is 4 to 12.
PCT/JP2021/001998 2020-02-04 2021-01-21 Rapid hardening agent for spray WO2021157371A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023182477A1 (en) * 2022-03-25 2023-09-28 デンカ株式会社 Powder accelerating agent, slurry accelerating agent, spraying material, and spraying method

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Publication number Priority date Publication date Assignee Title
JPS53131998A (en) * 1977-04-25 1978-11-17 Akita Seiren Kk Method of removing mercury from sulfuric acid
JPS5939756A (en) * 1982-08-24 1984-03-05 堺化学工業株式会社 Manufacture of hardenable composition from waste sulfuric acid
JPH11199286A (en) * 1998-01-13 1999-07-27 Denki Kagaku Kogyo Kk Accelerator, spraying material and spraying using the same
JP5026928B2 (en) * 2007-11-06 2012-09-19 太平洋マテリアル株式会社 Quick set and spray material
JP6586417B2 (en) * 2014-05-30 2019-10-02 太平洋マテリアル株式会社 Quick setting admixture

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53131998A (en) * 1977-04-25 1978-11-17 Akita Seiren Kk Method of removing mercury from sulfuric acid
JPS5939756A (en) * 1982-08-24 1984-03-05 堺化学工業株式会社 Manufacture of hardenable composition from waste sulfuric acid
JPH11199286A (en) * 1998-01-13 1999-07-27 Denki Kagaku Kogyo Kk Accelerator, spraying material and spraying using the same
JP5026928B2 (en) * 2007-11-06 2012-09-19 太平洋マテリアル株式会社 Quick set and spray material
JP6586417B2 (en) * 2014-05-30 2019-10-02 太平洋マテリアル株式会社 Quick setting admixture

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023182477A1 (en) * 2022-03-25 2023-09-28 デンカ株式会社 Powder accelerating agent, slurry accelerating agent, spraying material, and spraying method

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