JP2007137745A - Quick hardening material and high-penetrating grout - Google Patents

Quick hardening material and high-penetrating grout Download PDF

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JP2007137745A
JP2007137745A JP2005337069A JP2005337069A JP2007137745A JP 2007137745 A JP2007137745 A JP 2007137745A JP 2005337069 A JP2005337069 A JP 2005337069A JP 2005337069 A JP2005337069 A JP 2005337069A JP 2007137745 A JP2007137745 A JP 2007137745A
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liquid
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Masaaki Noguchi
雅朗 野口
Ryozo Yoshida
了三 吉田
Norio Takahashi
則雄 高橋
Makoto Fukuyama
誠 福山
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Taiheiyo Materials Corp
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    • 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
    • C04B28/06—Aluminous cements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lining And Supports For Tunnels (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a quick hardening material in which respective liquid components before mixing have a long hardening time, but strength is developed after the lapse of a definite period of time after mixing, good initial strength and long-term strength development are exerted, high penetration into the ground is exerted over the long period of time and further, the ground is stabilized after reaction, and also to provide a grout prepared by mixing a liquid component A including the quick hardening material and a liquid component B including a main hardening ingredient. <P>SOLUTION: The powdery quick hardening material is produced by blending 0.5-5 pts.wt. of sodium aluminate based on 100 pts.wt. of the mixture which is prepared by mixing calcium aluminate having the 12CaO-7Al<SB>2</SB>O<SB>3</SB>content rate of ≥50 wt.% and gypsum in a weight ratio of 3/7 to 7/3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、トンネルやダムなどの構造物周辺の不安定な地盤を強化安定させる地盤注入材に関する。   The present invention relates to a ground injection material that strengthens and stabilizes unstable ground around structures such as tunnels and dams.

トンネルやダムなどの構造物を付設する場合、周囲の地盤が不安定である場合には、地盤を強化した後に構造物の施工を行う。地盤の強化には、硬化成分を含む液体状のものを地盤中へ注入し強化安定を図る。   When a structure such as a tunnel or dam is attached, if the surrounding ground is unstable, the structure is constructed after the ground is strengthened. In order to strengthen the ground, a liquid material containing a hardened component is injected into the ground to stabilize it.

注入材として使用される材料は、有機系と無機系のもの材料があり、有機系では、アクリルアミド、尿素ホルマリン、ウレタン等があり、短時間で強度発現する。しかしながら有機系の材料は、有害な有機成分が微量溶出し、地下水へ汚染することが懸念されている。   Materials used as the injection material include organic and inorganic materials, and organic materials include acrylamide, urea formalin, urethane, and the like, and develop strength in a short time. However, organic materials are concerned that toxic organic components may elute in minute amounts and contaminate groundwater.

無機系の材料は、セメントを主成分とするスラリーと、急硬化材を成分とするスラリーを注入箇所まで圧送し、地盤に浸透注入させる。この注入材には、ある程度浸透した後に、硬化が始まることが求められている。この場合、各スラリーのみではほとんど硬化せず、もしくは数時間から数日硬化せず、両材料を混合することにより、すみやかにもしくは数分から数時間後にゲル化し、硬化が開始される材料が求められる。
急硬化材には、珪酸ナトリウム、カルシウムアルミネートが用いられている。急硬化材に珪酸ナトリウムを使用した場合には、初期強度発現性は高いが、長期強度発現性が悪く、ゲルタイムの調整が困難である。また、地盤が高いアルカリ性になることに加え、ナトリウムが溶出する為、長期の耐久性も悪い。
また、普通ポルトランドセメント等を使用したセメントスラリーと急硬化材を使用する注入材は、砂質土に注入する場合、セメント粒子が概して大きいため砂粒子間を通ることができず、また、急結成分と併用すると水和反応が著しく速くなって浸透中に硬化し易く、これが目詰まりして、地盤中への浸透性が著しく劣る。 As for the inorganic material, a slurry containing cement as a main component and a slurry containing a rapid hardening material as a component are pumped to an injection site and injected into the ground. This injecting material is required to begin curing after it has penetrated to some extent. In this case, there is a need for a material that is hardly cured by only each slurry, or that is not cured for several hours to several days, and that gels immediately after mixing for several hours to several hours by mixing both materials to start curing. .
Sodium silicate and calcium aluminate are used for the rapid curing material. When sodium silicate is used as the rapid-curing material, the initial strength development is high, but the long-term strength development is poor and it is difficult to adjust the gel time. In addition to high alkalinity of the ground, sodium elutes, so long-term durability is poor.
In addition, cement slurry using ordinary Portland cement, etc. and an injection material using a quick-hardening material, when injected into sandy soil, the cement particles are generally large and cannot pass between the sand particles. When it is used in combination with water, the hydration reaction is remarkably fast and is easily cured during infiltration. This clogs and remarkably deteriorates the permeability into the ground.

特許文献１には、カルシウムアルミネートを主成分とするセメント用の急結材が記載されている。主としてモルタルコンクリートの急結材であり、注入材に用するものではない。この急結材を水セメント比が大きい注入材として使用した場合には、急結性能が不十分である。
特許文献２には、カルシウムアルミネート、石膏およびスケール発生防止剤を含有する注入材が記載されている。この成分を含有するＡ液と、セメントを含むＢ液を混合し、地盤中へ注入することで急結させ、地盤を固化する。スケール発生防止剤としてミョウバン、アルミニウム塩や鉄塩が挙げられている。特許文献３には、カルシウムアルミネート、石膏、硫酸アルミニウムを含有する注入材が記載されており、特許文献２と同様である。これらの引用文献２及び３に記載されているアルミニウム塩や鉄塩等が存在すると、Ａ液単独の可使時間としては長くなるが、Ａ液のカルシウムアルミネートと石膏とが水和反応するため、時間経過につれゲルタイムが短くなり、強度が低下する等、長時間にわたって性能を保持できない。
特許第３２０５６７２号公報 特開２００１−１６４２４９号公報 特開２００１−１６４２４８号公報 Patent Document 1 describes a rapid setting material for cement mainly composed of calcium aluminate. It is mainly a quick-setting material for mortar concrete and is not used as an injection material. When this quick setting material is used as an injection material having a large water-cement ratio, the quick setting performance is insufficient.
Patent Document 2 describes an injection material containing calcium aluminate, gypsum, and a scale generation inhibitor. The liquid A containing this component and the liquid B containing cement are mixed and injected into the ground to quickly set them and solidify the ground. Alum, aluminum salt and iron salt are listed as scale generation inhibitors. Patent Document 3 describes an injection material containing calcium aluminate, gypsum, and aluminum sulfate, and is similar to Patent Document 2. If the aluminum salt, iron salt, etc. described in these cited references 2 and 3 are present, the pot life of liquid A alone will be long, but the calcium aluminate of liquid A and gypsum will hydrate. As the time elapses, the gel time is shortened and the strength is lowered, so that the performance cannot be maintained for a long time.
Japanese Patent No. 3205672 JP 2001-164249 A JP 2001-164248 A

本発明は、混合前の各成分液では硬化時間が遅く、それぞれを混合することにより一定時間経過後に強度発現を生じ、初期強度および長期強度発現性が良好であり、長時間にわたって地盤中へ高い浸透性を有し、反応後は地盤を安定させる急硬化材、および当該急硬化材を含む成分Ａ液と主硬化成分を含む成分Ｂ液を混合してなる注入材を提供することを目的とする。   In the present invention, each component liquid before mixing has a slow curing time, and by mixing each of them, strength development occurs after a lapse of a certain time, initial strength and long-term strength development are good, and it is high in the ground for a long time. An object of the present invention is to provide a rapid curing material that has permeability and stabilizes the ground after the reaction, and an injection material obtained by mixing the component A liquid containing the rapid curing material and the component B liquid containing the main curing component. To do.

この目的を達成するために、本発明者らは鋭意研究した結果、１２ＣａＯ・７Ａｌ2Ｏ3のを特定量含有するカルシウムアルミネートと石膏とを一定比で配合し、かつさらにアルミン酸ナトリウムを一定量混合した成分Ａ液と、スラグを含む主硬化材と分散剤と水からなる成分Ｂ液を注入箇所で混合し注入することで、浸透途中で硬化して目詰まりを起こし難く、高い浸透能力を有し、且つ初期から長期にわたって良好な強度発現を持つ注入材を見出した。また、製造後数１０分経過後でもゲル化時間が変化しないことも見出した。 In order to achieve this object, the present inventors have intensively studied. As a result, calcium aluminate containing a specific amount of 12CaO · 7Al 2 O 3 and gypsum are blended at a constant ratio, and sodium aluminate is further fixed. Mixing component A liquid mixed in quantity, and component B liquid consisting of main curing material containing slag, dispersing agent and water at the injection point, it hardens in the middle of penetration and does not cause clogging, and has high penetration ability And an injection material having a good strength expression from the beginning to the long term was found. It has also been found that the gelation time does not change even after several tens of minutes have elapsed after production.

即ち、本発明は、１２ＣａＯ・７Ａｌ2Ｏ3の含有率が５０重量％以上であるカルシウムアルミネートと石膏とを３／７〜７／３の重量比率で混合した混合物１００重量部に対し、アルミン酸ナトリウムを０．５〜５重量部混合した粉体からなることを特徴とする急硬化材を提供するものである。
また、本発明は、上記急硬化材と遅延剤と水からなる成分Ａ液と、少なくともスラグを含む主硬化材と分散剤と水からなる成分Ｂ液を混合してなることを特徴とする注入材を提供するものである。 That is, the present invention relates to 100 parts by weight of a mixture of calcium aluminate having a content of 12CaO · 7Al 2 O 3 of 50% by weight or more and gypsum mixed at a weight ratio of 3/7 to 7/3. The present invention provides a rapid-curing material comprising a powder in which 0.5 to 5 parts by weight of sodium acid is mixed.
Further, the present invention is an injection characterized by mixing the component A liquid consisting of the rapid curing material, the retarder and water, and the component B liquid consisting of at least a main curing material containing slag, a dispersant and water. The material is provided.

本発明によれば、急硬化材を含む成分Ａ液と、スラグ等の潜在水硬性物質を硬化成分とする主硬化材を含む成分Ｂ液が、それぞれ単独の状態では硬化反応は著しく遅く、また強度も低いが、両液を混合することにより急硬化成分による硬化材の硬化が適度な急速性を呈する反応となることに加え、注入材中の硬化成分が凝集し難いため、注入浸透中に目詰まりが起こり難く、地盤深部まで満遍なく浸透できかつ一定時間経過後早期に強度発現を得ることができる。   According to the present invention, the component A liquid containing the rapid curing material and the component B liquid containing the main curing material having a latent hydraulic substance such as slag as the curing component are each extremely slow in the curing reaction. Although the strength is low, by mixing both liquids, the curing of the cured material by the rapid curing component becomes a reaction that exhibits an appropriate rapidity, and since the cured component in the injected material is less likely to aggregate, Clogging is unlikely to occur, it can penetrate evenly into the ground, and strength can be obtained early after a certain period of time.

本発明の急硬化材は、カルシウムアルミネートと石膏とアルミン酸ナトリウムを混合した粉体からなる。さらに、当該急硬化材は、スラグ含有物を硬化成分とする注入材用であることが好ましい。
本発明の急硬化材に用いるカルシウムアルミネートは、化学成分としてのＣａＯとＡｌ2Ｏ3の含有モル比が１．５〜２、好ましくは１．６〜１．８の混合物又は組成物を、例えば約１３００℃以上の温度で焼成し、望ましくは徐冷することによって得ることができる。その主な鉱物組成としてはＣａＯ・Ａｌ2Ｏ3（以下、ＣＡ）、１２ＣａＯ・７Ａｌ2Ｏ3（以下、Ｃ１２Ａ７）、３ＣａＯ・Ａｌ2Ｏ3（以下、Ｃ３Ａ）等の１種又は２種以上を有し、特に１２ＣａＯ・７Ａｌ2Ｏ3の含有率が５０重量％以上含むものである。
ここでカルシウムアルミネートに含まれるＣａＯとＡｌ2Ｏ3の含有モル比が１．５〜２から外れると、結晶質として比較的安定なＣ１２Ａ７成分が形成され難くなる。また、冷却過程で急冷すると非晶質相が支配的に形成されるので好ましくない。 The rapid-curing material of the present invention consists of a powder obtained by mixing calcium aluminate, gypsum and sodium aluminate. Furthermore, it is preferable that the rapid-curing material is for an injection material containing a slag-containing material as a curing component.
The calcium aluminate used for the rapid-curing material of the present invention is a mixture or composition having a molar ratio of CaO and Al 2 O 3 as a chemical component of 1.5 to 2, preferably 1.6 to 1.8. For example, it can be obtained by firing at a temperature of about 1300 ° C. or higher, desirably by slow cooling. The main mineral composition is one or more of CaO.Al 2 O 3 (hereinafter CA), 12CaO.7Al 2 O 3 (hereinafter C12A7), 3CaO.Al 2 O 3 (hereinafter C3A), etc. In particular, the content of 12CaO · 7Al 2 O 3 is 50% by weight or more.
Here, if the molar ratio of CaO and Al 2 O 3 contained in the calcium aluminate deviates from 1.5 to 2, it becomes difficult to form a relatively stable C12A7 component as crystalline. In addition, rapid cooling during the cooling process is not preferable because an amorphous phase is predominantly formed.

該カルシウムアルミネートの鉱物組成としての各成分の含有割合は、成分Ａ液と成分Ｂ液混合後も高い浸透性を有する注入材を得るために、Ｃ１２Ａ７成分が５０重量％以上が好ましく、さらに６０重量％以上、特に７５重量％以上が好ましい。該カルシウムアルミネート中に、Ｃ１２Ａ７成分が５０重量％以上含まれると、１日程度の初期強度発現性に優れ、かつ長期にわたって強度発現する。
なお、他のＣＡ成分やＣ３Ａ成分等の含有率は特に限定されないが、該カルシウムアルミネート中に、ＣＡ成分の含有率が高くなると初期強度が悪くなり、Ｃ３Ａ成分の含有率が高くなると長期強度が悪くなる。また、非晶質の含有率が高くなると、非晶質は反応活性が高い為、水と混合した後の液の安定性が悪くなる。さらに、Ｃ３Ａ成分および非晶質の含有率が高くなると、成分Ａ液と成分Ｂ液を混合後直ちに反応が開始されるため、瞬結化したり、反応生成物による粘性の上昇および注入材の粒子径の増大し、浸透性が著しく低下する。また、カルシウムアルミネートを粉体のままで長期間放置すると空気中の水分と反応するため性能が劣化して保存期間が短くなる。 The content ratio of each component as the mineral composition of the calcium aluminate is preferably 50% by weight or more of the C12A7 component in order to obtain an injection material having high permeability even after mixing the component A liquid and the component B liquid. % By weight or more, particularly 75% by weight or more is preferable. When the C12A7 component is contained in the calcium aluminate in an amount of 50% by weight or more, the initial strength development of about one day is excellent and the strength is developed over a long period of time.
The content of other CA components, C3A components, etc. is not particularly limited, but in the calcium aluminate, the initial strength deteriorates when the CA content increases, and the long-term strength increases when the C3A content increases. Becomes worse. In addition, when the amorphous content increases, the amorphous has high reaction activity, so that the stability of the liquid after mixing with water becomes poor. Further, when the content ratio of the C3A component and the amorphous material becomes high, the reaction starts immediately after mixing the component A liquid and the component B liquid. The diameter increases and the permeability is significantly reduced. Further, if calcium aluminate is left in powder form for a long period of time, it reacts with moisture in the air, so that the performance deteriorates and the storage period is shortened.

本発明の急硬化材に用いる石膏は、特に限定されず、無水石こう、半水石こう、ニ水石こうから選ばれる１種又２種以上を用いることができる。
本発明の急硬化材に用いるカルシウムアルミネートと石膏の混合比率は３／７〜７／３が好ましく、４／６〜７／３がより好ましい。この範囲内であればエトリンガイトの生成に必要十分な量となり、注入材として反応後の強度特性も良好なものとなる。石膏とカルシウムアルミネートを含む成分Ａ液と水硬性成分を含む成分Ｂ液を混練すると急速に反応し、エトリンガイト等を生成し、早期のゲル化を実現させる。 The gypsum used for the rapid-curing material of the present invention is not particularly limited, and one or more kinds selected from anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum can be used.
The mixing ratio of calcium aluminate and gypsum used in the rapid-curing material of the present invention is preferably 3/7 to 7/3, and more preferably 4/6 to 7/3. If it is in this range, the amount necessary and sufficient for the production of ettringite is obtained, and the strength characteristics after reaction as an injection material are also good. When component A liquid containing gypsum and calcium aluminate and component B liquid containing hydraulic components are kneaded, they react rapidly to produce ettringite and the like, thereby realizing early gelation.

また、カルシウムアルミネートと石膏の混合物は、浸透性を良好なものとする為、粉体のブレーン比表面積が５０００〜１００００ｃｍ2／ｇの範囲内であることが好ましく、さらに６０００〜９０００ｃｍ2／ｇの範囲内であることが好ましい。５０００ｃｍ2／ｇを下回ると注入材粒子が地盤中への間隙を通過することができず、また１００００ｃｍ2／ｇを超えると反応活性が高くなるため、スラリーＡ液作製直後およびスラリーＡ液とＢ液混合後には直ちに反応が開始され、反応生成物による粘性の上昇および注入材の粒子径の増大のため、施工性及び浸透性が著しく低下する。 Mixtures of calcium aluminate and gypsum, for the permeability and favorable, it is preferable that the Blaine specific surface area of the powder is in the range of 5000~10000cm 2 / g, further 6000~9000cm 2 / g It is preferable to be within the range. If it is less than 5000 cm 2 / g, the injected particles cannot pass through the gap into the ground, and if it exceeds 10000 cm 2 / g, the reaction activity becomes high. The reaction starts immediately after the liquid mixing, and the workability and permeability are significantly reduced due to the increase in viscosity due to the reaction product and the increase in the particle size of the injection material.

本発明の急硬化材に用いるアルミン酸ナトリウムは、石膏とカルシウムアルミネートの反応を抑制することができる。石膏とカルシウムアルミネートと水の混合物は、このスラリー自身でエトリンガイトを生成するため、混合直後から反応を開始し、セメントとの反応有効成分が時間と共に減少していく。このスラリーにアルミン酸ナトリウムを混合すると、アルミニウムイオンとナトリウムイオンの作用によりこの反応を抑制することが出来る。このためセメントとの硬化反応有効成分が長時間にわたり残存する。   Sodium aluminate used in the rapid-curing material of the present invention can suppress the reaction between gypsum and calcium aluminate. Since the mixture of gypsum, calcium aluminate and water produces ettringite by this slurry itself, the reaction starts immediately after mixing, and the reaction active ingredient with cement decreases with time. When sodium aluminate is mixed with this slurry, this reaction can be suppressed by the action of aluminum ions and sodium ions. For this reason, the effective component of the curing reaction with the cement remains for a long time.

アルミン酸ナトリウムの添加量は、カルシウムアルミネートと石膏の混合物１００重量部に対して０．５〜５重量部添加するのが好ましく、０．７５〜３重量部がより好ましい。０．５重量部より少ないと、Ａ液単独の反応が急速に進むためセメントとの硬化成分が減少し、セメントスラリーと混合した注入材の強度特性が悪くなる。５重量部よりも多いと、硬化遅延となるため、短期の強度発現が悪くなる。   The amount of sodium aluminate added is preferably 0.5 to 5 parts by weight, more preferably 0.75 to 3 parts by weight, based on 100 parts by weight of the mixture of calcium aluminate and gypsum. If the amount is less than 0.5 parts by weight, the reaction of the liquid A alone proceeds rapidly, so that the hardening component with the cement is reduced, and the strength characteristics of the injection material mixed with the cement slurry are deteriorated. If the amount is more than 5 parts by weight, the curing is delayed, and the short-term strength development is deteriorated.

本発明における注入材は、上記急硬化材と遅延剤と水からなる成分Ａ液と、少なくともスラグを含んだ主硬化材と分散剤と水からなる成分Ｂ液を混合してなる。
それぞれ単独の状態では硬化反応は著しく遅く、また強度も低いが、両液を混合することにより一定時間経過後急硬化材が硬化材の硬化を急速に反応させ、早期に強度発現を得ることができる。
さらに、少なくとも一日強度で１Ｎ／ｍｍ2以上必要であり、２液混合後のゲルタイムは施工状況に応じた所望の時間を確保できれば良い。 The injection material in the present invention is formed by mixing the component A liquid composed of the rapid curing material, the retarder, and water, and the component B liquid composed of the main curing material containing at least slag, the dispersant, and water.
In each state, the curing reaction is extremely slow and the strength is low, but by mixing both liquids, the rapid curing material can rapidly react with the curing of the curing material after a certain period of time, and the strength can be expressed early. it can.
Furthermore, at least 1 N / mm 2 is necessary for the daily strength, and the gel time after mixing the two liquids only needs to ensure a desired time according to the construction situation.

本発明における注入材の特性として、２液混合後目的の注入範囲に浸透後地盤中へ留まり、そこで強度発現する必要がある。２液混合後に一定時間経過後急速に反応して可塑状態となり、このときの可塑状態になるまでの時間は２液の成分、注入する圧力や注入範囲等によって設定されるが、初期の設定した可塑状態までの時間が各液作製直後に２液混合した場合と時間経過して２液混合した場合でも変化しないことが好ましい。この時間の差が大きすぎるとすると地盤を改良する範囲が変り、安定して十分な補強ができず、また、砂地盤の間隙に注入されるため強度としてはこれら軟弱地盤を強化する必要がある。一方で、２液混合後、作業工程中に急速に反応しすぎて可塑すると注入作業が困難となるため、一定時間経過後急速に反応して可塑状態になることが好ましい。   As a characteristic of the injection material in the present invention, it is necessary to stay in the ground after penetration into the target injection range after mixing the two liquids and to develop strength there. After mixing for two liquids, it reacts rapidly after a certain period of time and becomes a plastic state. The time until the plastic state at this time is set is determined by the components of the two liquids, the pressure to be injected, the injection range, etc. It is preferable that the time until the plastic state does not change even when two liquids are mixed immediately after the preparation of each liquid and when two liquids are mixed after a lapse of time. If this time difference is too large, the ground improvement range will change, and stable and sufficient reinforcement will not be possible, and since it will be injected into the gap between the sand ground, it is necessary to strengthen these soft ground as strength . On the other hand, after mixing the two liquids, if it reacts too quickly during the working process and plasticizes, the injection operation becomes difficult.

本発明に用いる成分Ａ液は、上記急硬化材と遅延剤と水からなる。上記急硬化材１００重量部に対して水を１００〜１０００重量部添加するものが好ましい。添加する水が上記１００重量部を下回ると、スラリーの粘性が上昇し、施工性が著しく低下する。一方で１０００重量部超えると、水硬性成分に対する硬化促進の為の有効成分が少なくなる為、注入した注入材が未硬化のまま流冒したり、初期から長期にわたって強度発現が低迷することがある。   The component A liquid used for this invention consists of the said rapid hardening material, a retarder, and water. What adds 100-1000 weight part of water with respect to 100 weight part of said rapid hardening materials is preferable. If the water to be added is less than 100 parts by weight, the viscosity of the slurry is increased and the workability is significantly reduced. On the other hand, when the amount exceeds 1000 parts by weight, the effective component for accelerating the curing with respect to the hydraulic component is reduced, and thus the injected injection material may flow out without being cured, or the strength expression may be sluggish from the beginning to the long term.

本発明に用いる遅延剤は、種類について特に限定されないが、例えばモルタルやコンクリートで使用できるもので良く、遅延剤の種類としてクエン酸、グルコン酸、酒石酸等のカルボン酸やグルコース、マルトース、デキストリン等の多糖類、二糖類、単糖類等を１種または２種以上混合して使用することができる。遅延剤は、急硬化材のスラリーと水硬性成分のスラリーを混合した後の急速な反応を抑制し、また急硬化材のスラリーの安定性を高くすることができる。この急速な反応は液状から可塑状態とり、浸透中の注入材はそこで地盤中に留まる。
本発明に用いる遅延剤は、添加量の増加とともにゲルタイムは長くなるが、注入方法によって添加量を決定する。特に、遅延剤の添加量は、上記急硬化材１００重量部に対して０．０１〜５重量部添加し、より好ましくは０．０５〜３重量部添加する。０．０１重量部未満ではスラリーの安定性が悪くなり、時間経過と共にセメントに対する急硬化材の有効成分が減少し、水硬性成分のスラリー混合後の強度発現性は低いものとなる５重量部をこえると、初期強度が著しく低下する。 The retarder used in the present invention is not particularly limited in terms of type, but may be one that can be used in, for example, mortar and concrete. Examples of the retarder include carboxylic acids such as citric acid, gluconic acid, and tartaric acid, glucose, maltose, dextrin, and the like. Polysaccharides, disaccharides, monosaccharides and the like can be used alone or in combination. The retarder can suppress a rapid reaction after mixing the slurry of the rapid curing material and the slurry of the hydraulic component, and can increase the stability of the slurry of the rapid curing material. This rapid reaction takes a liquid to plastic state, and the infiltrated injectant then remains in the ground.
The retarder used in the present invention has a longer gel time as the addition amount increases, but the addition amount is determined by the injection method. Particularly, the retarder is added in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the rapid-curing material. If the amount is less than 0.01 parts by weight, the stability of the slurry is deteriorated, and the effective component of the rapid-curing material with respect to cement decreases with time, and 5 parts by weight becomes low in strength development after slurry mixing of the hydraulic component. Beyond that, the initial strength is significantly reduced.

本発明に用いる成分Ｂ液は、主硬化材と分散剤（減水剤）と水からなるものであることが好ましい。主硬化材には、少なくとも潜在水硬性物質であるスラグを含む主硬化成分を含み、さらに施工性や浸透性を高めるためにモルタルやコンクリート用の混和材・剤を添加してもよい。
一般的に、スラグ以外の主硬化成分としては、水と反応して硬化する水硬性物質を挙げることが出来る。主硬化成分は、Ｃ１２Ａ７を含有するカルシウムアルミネートと石膏がエトリンガイト等へ急速に反応するための刺激材であるとともに、それ自身が水和反応し強度発現する。水硬性物質として普通ポルトランドセメント、早強ポルトランドセメント等のポルトランドセメントを使用することができるが、スラグを含ませずにポルトランドセメント等のみを使用した場合、シルト質のような土粒子の小さい地盤中への注入は困難となる。また、これらポルトランドセメント等の粒子径を小さくすると地盤中に広い範囲で浸透させることができるが、セメントのみでは粒子同士が凝集しやすく、凝集によって浸透性を阻害する。また普通ポルトランドセメントやそれよりも水和活性の高い水硬性物質のみの使用では注入浸透中に凝結し易く、これが地盤浸透時に目詰まりを起こし、深部まで注入材が浸透し難くなることがある。よって、本発明では、微粒子でも凝集が起こりにくく、潜在水硬性物質であるスラグを含有する主硬化成分を使用する。 The component B liquid used in the present invention is preferably composed of a main curing material, a dispersant (water reducing agent) and water. The main curing material contains at least a main curing component including slag, which is a latent hydraulic substance, and an admixture / agent for mortar or concrete may be added to further improve workability and permeability.
In general, examples of the main curing component other than slag include a hydraulic substance that cures by reacting with water. The main curing component is a stimulant for rapidly reacting calcium aluminate and gypsum containing C12A7 to ettringite and the like, and itself hydrates and develops strength. Portland cement such as ordinary Portland cement and early-strength Portland cement can be used as the hydraulic material, but when only Portland cement is used without slag, it is in the ground with small silty-like soil particles. Injection into the can be difficult. In addition, when the particle diameter of these Portland cements and the like is reduced, they can be permeated in a wide range in the ground, but the particles are easily aggregated with cement alone, and the permeability is inhibited by aggregation. In addition, when only ordinary Portland cement or a hydraulic substance having a higher hydration activity is used, it is easy to condense during the infiltration, which may cause clogging during the infiltration of the ground and make it difficult for the injection material to penetrate deeply. Therefore, in the present invention, a main curing component containing slag, which is a latent hydraulic substance, is used because aggregation is unlikely to occur even with fine particles.

本発明のスラグを含む主硬化成分におけるスラグは、セメント１００重量部に対し、３５０〜９００重量部配合するのが好ましい。
本発明に用いるスラグの種類は特に限定されず、例えば高炉スラグ、下水溶融スラグ、都市ゴミ焼却灰溶融スラグ、転炉スラグ、脱リンスラグ等が挙げられ、これらのスラグ微粉末を用いることができる。
本発明に用いる主硬化成分のブレーン比表面積は、８０００〜１２０００ｃｍ2／ｇが好ましく、８０００ｃｍ2／ｇ未満では、浸透性が著しく低下する。また、１２０００ｃｍ2／ｇを超えるとスラリーの粘性が高くなるため、圧送性、浸透性が低下する。 The slag in the main curing component containing the slag of the present invention is preferably blended in an amount of 350 to 900 parts by weight with respect to 100 parts by weight of cement.
The kind of slag used in the present invention is not particularly limited, and examples thereof include blast furnace slag, sewage molten slag, municipal waste incineration ash molten slag, converter slag, dephosphorization slag, and the like, and these slag fine powders can be used.
Blaine specific surface area of the main curing component used in the present invention is preferably 8000~12000cm 2 / g, is less than 8000 cm 2 / g, permeability is significantly decreased. Moreover, since viscosity of a slurry will become high when it exceeds 12000 cm < 2 > / g, pumpability and permeability will fall.

本発明に用いる成分Ｂ液に含まれる水の量は、主硬化成分１００重量部に対して６０〜１０００重量部、さらに１００〜５００重量部が好ましい。添加する水が６０重量部未満では、粘性が高くなり浸透が困難となる。一方で１０００重量部を超えると、急硬化材と混合後の硬化強度が著しく悪くなる。   The amount of water contained in Component B liquid used in the present invention is preferably 60 to 1000 parts by weight, more preferably 100 to 500 parts by weight, based on 100 parts by weight of the main curing component. If the water to be added is less than 60 parts by weight, the viscosity becomes high and penetration becomes difficult. On the other hand, when it exceeds 1000 parts by weight, the curing strength after mixing with the rapid-curing material is remarkably deteriorated.

Ｂ液に含まれる分散剤（減水剤）は、特に限定されず、例えば、高性能減水剤、高性能ＡＥ減水剤、ＡＥ減水剤及び流動化剤を含む減水剤等が挙げられる。
分散剤は地盤への浸透性に支障をきたさないようにするため、セメント１００重量部に対し、０．０５〜５重量部、さらに０．５〜３重量部添加するのが好ましい。
また、主硬化材は、主硬化成分と共に、モルタルやコンクリートで使用可能な他の混和材・剤を適宜含むものであっても良い。このような混和材・剤として、例えばシリカフューム等のポゾラン等の潜在水硬性物質、石粉、樹脂エマルション、膨張材、起泡剤、発泡剤、防錆剤、顔料、繊維、撥水剤、防水材、消泡剤、硬化促進剤、粉塵低減剤、収縮低減剤、増粘剤、水中不分離性混和剤等が挙げられ、これらの１種又は２種以上を本発明による効果を阻害しない範囲で使用することができる。 The dispersing agent (water reducing agent) contained in B liquid is not specifically limited, For example, the water reducing agent containing a high performance water reducing agent, a high performance AE water reducing agent, an AE water reducing agent, and a fluidizing agent etc. are mentioned.
The dispersant is preferably added in an amount of 0.05 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of cement so as not to hinder the permeability to the ground.
Further, the main curing material may appropriately contain other admixtures / agents that can be used in mortar and concrete together with the main curing component. Examples of such admixtures / agents include latent hydraulic materials such as pozzolans such as silica fume, stone powder, resin emulsions, expansion materials, foaming agents, foaming agents, rust preventives, pigments, fibers, water repellents, and waterproofing materials. , Antifoaming agents, curing accelerators, dust reducing agents, shrinkage reducing agents, thickeners, water-inseparable admixtures, and the like. Can be used.

成分Ａ液と成分Ｂ液の混合比率は、所望のゲルタイムを確保し、且つ良好な施工性を得る上で、容積比で２５：７５〜７５：２５が好ましく、４０：６０〜６０：４０がより好ましい。   The mixing ratio of the component A liquid and the component B liquid is preferably 25:75 to 75:25, and preferably 40:60 to 60:40 in terms of volume ratio in order to secure a desired gel time and obtain good workability. More preferred.

成分Ａ液と成分Ｂ液の混合方法としては、特に限定されるものではなく、例えば、それぞれのミキサーに混練、調整した後に、成分Ａ液と成分Ｂ液を別々に圧送し、Ｙ字管で混合する方法や二重管を用い内管と外管に別々に圧送し二重管の先端部で合流させる方法等いずれの方法も使用できる。即ち、単管ロッド工法、単管ストレーナ工法、二重管単相ストレーナ工法、及び二重管複相ストレーナ工法等の現在使用されている注入工法に本発明の注入材が使用できる。これらの中では、単管ロッド工法や単相ストレーナ工法に比べ、均一な改良体を形成できる点で、二重管単相ストレーナ工法又は二重管複相ストレーナ工法を使用することが好ましい。   The mixing method of the component A liquid and the component B liquid is not particularly limited. For example, after kneading and adjusting each mixer, the component A liquid and the component B liquid are separately pumped, and a Y-shaped tube is used. Any method can be used, such as a mixing method or a method in which a double tube is used to separately pump the inner tube and the outer tube and merge at the tip of the double tube. That is, the injection material of the present invention can be used in the currently used injection methods such as the single tube rod method, the single tube strainer method, the double tube single phase strainer method, and the double tube double phase strainer method. Among these, it is preferable to use a double-pipe single-phase strainer method or a double-pipe multi-phase strainer method in that a uniform improved body can be formed as compared with a single-pipe rod method or a single-phase strainer method.

使用した材料である、主成分（カルシウムアルミネート及び石膏）と添加剤を含む急硬化材と遅延剤と水からなる成分Ａ液（Ａ液ともいう）および少なくともスラグを含む主硬化材と分散剤と水からなる成分Ｂ液（Ｂ液ともいう）を表１に示す。
なお、ゲルタイムを調整するため、遅延剤として、混和材を成分Ａ液に添加した。また、主硬化材は、セメント１００重量部に対してスラグを重量比で４００重量部混合したものをボールミルで粉砕し，所定の粒度となるように調整したものを使用した。 Component A liquid (also referred to as liquid A) consisting of a rapid curing material containing a main component (calcium aluminate and gypsum) and additives, a retarder, and water, and a main curing material and a dispersant containing at least slag. Table 1 shows component B liquid (also referred to as B liquid) composed of water and water.
In addition, in order to adjust gel time, the admixture was added to the component A liquid as a retarder. Moreover, the main hardening material used what grind | pulverized what mixed 400 weight part of slag by weight ratio with respect to 100 weight part of cement with a ball mill, and became a predetermined particle size.

カルシウムアルミネートは、ＣａＣＯ3とＡｌ2Ｏ3を混合粉砕して電気炉で１４００℃で焼成して、徐冷したものを用いた。この焼成徐冷物は、Ｘ線回折の結果、結晶質Ｃ１２Ａ７含有率が７５％、非晶質含有率が２５％であった。また、焼成徐冷物に添加する焼成非晶質（非晶質１００％）は、１４００℃から水で急冷したものを使用した。
なお、焼成徐冷物中のＣ１２Ａ７と非晶質の含有率は、Ｃ１２Ａ７含有量１００％の粉末と非晶質含有量１００％の粉末を一定の比率で混合してものを用いて検量線を作成して本実施例で用いたカルシウムアルミネート中の含有量を測定した。 As the calcium aluminate, CaCO 3 and Al 2 O 3 were mixed and pulverized, fired at 1400 ° C. in an electric furnace, and gradually cooled. As a result of X-ray diffraction, the sintered annealed product had a crystalline C12A7 content of 75% and an amorphous content of 25%. Further, the fired amorphous (100% amorphous) to be added to the fired slow-cooled product was used which was rapidly cooled from 1400 ° C. with water.
Note that the content of C12A7 and amorphous in the annealed slow-cooled product is a calibration curve obtained by mixing a powder with 100% C12A7 content and a powder with 100% amorphous content at a certain ratio. The content in the calcium aluminate prepared and used in this example was measured.

（実施例１）
急硬化材を含むＡ液及び主硬化材を含むＢ液を同量混合してなるスラリーについて測定した。測定は、Ａ液を作製直後にＢ液と混合したのもの（Ａ作製直後）と、作製したＡ液を３０分練り置きさせた後にＢ液と混合したもの（Ａ作製後３０分経過）について実施した。
各試料を作製後、ゲル化するまでの時間をゲルタイムとして測定し、さらに混合した液をモールドに充填し、所定期間湿空養生にて養生し、ＪＩＳ Ａ １２１６の「土の一軸圧縮試験方法」で材齢1日後の一軸圧縮強さを測定した。
急硬化材を含むＡ液の配合を表２に示し、主硬化材を含むＢ液の配合を表３に示す。主硬化材として、ブレーン比表面積が８１２０ｃｍ2／ｇの物を使用した。 Example 1
It measured about the slurry formed by mixing A liquid containing the rapid hardening material and B liquid containing the main hardening material. Measurements were made for the liquid A mixed with the liquid B immediately after production (immediately after the production of A) and the liquid A prepared after kneading for 30 minutes and then mixed with the liquid B (30 minutes after the production of A). Carried out.
After preparing each sample, the time until gelation is measured as gel time, and the mixed liquid is filled into a mold and cured by moisture curing for a predetermined period of time. JIS A 1216 “Uniaxial compression test method for soil” The uniaxial compressive strength after 1 day of age was measured.
Table 2 shows the composition of Liquid A containing the rapid curing material, and Table 3 shows the composition of Liquid B containing the main curing material. As the main curing material, a material having a Blaine specific surface area of 8120 cm 2 / g was used.

実施例１の結果を表４に示す。
本発明における注入材は、ゲルタイムが確保でき、材齢１日の一軸圧縮強さが１Ｎ／ｍｍ2以上認められるものを良好とした。Ａ液作製直後にＢ液を混合したものとＡ液作製後３０分経過後にＢ液を混合したものとの差が少ないものほどより良好である。 The results of Example 1 are shown in Table 4.
The injection material in the present invention is good in that the gel time can be secured and the uniaxial compressive strength of 1 day / day is 1 N / mm 2 or more. The smaller the difference between the mixture of the B liquid immediately after the preparation of the A liquid and the mixture of the B liquid 30 minutes after the preparation of the A liquid, the better.

Ｃ１２Ａ７含有率が約５０％以上のカルシウムアルミネートと石膏を混合したもの１００重量部に対してアルミン酸ナトリウムを０.５〜５重量部添加すると、混練直後から混練３０経過後までほぼ性能が変らない、もしくは劣化の割合が小さい。
しかしながら、カルシウムアルミネート中のＣ１２Ａ７含有率が５０％を下回ると、混練後３０分経過した時のゲルタイムが大幅に短くなる。また他の添加剤を使用すると、混練後時間経過すると性能が変化する。 When 0.5 to 5 parts by weight of sodium aluminate is added to 100 parts by weight of a mixture of calcium aluminate and gypsum having a C12A7 content of about 50% or more, the performance changes almost immediately after kneading and after 30 minutes of kneading. No or the rate of deterioration is small.
However, when the content of C12A7 in the calcium aluminate is less than 50%, the gel time when 30 minutes have elapsed after kneading is significantly shortened. When other additives are used, the performance changes after a lapse of time after kneading.

（実施例２）
表５および表６に示す配合で浸透性の試験を実施した。浸透性の試験は、直径５０ｍｍの下部に***のあいたビニール袋に珪砂（６号）を２０ｃｍ詰め、上部からＡ液Ｂ液を混合した注入材１００ｍＬを注ぎ込み、浸透状態を観察した。 (Example 2)
A permeability test was conducted with the formulations shown in Tables 5 and 6. In the penetration test, 20 cm of silica sand (No. 6) was packed in a plastic bag having a small hole at the bottom of a diameter of 50 mm, and 100 mL of an injection material mixed with liquid A and liquid B was poured from the top, and the state of penetration was observed.

実施例２の結果を表７に示す。Ｃ１２Ａ７含有率が５０％以上のカルシウムアルミネートの急硬化材（配合ｐ）とブレーン比表面積が６２５０〜１２０００ｃｍ2／ｇの主硬化材（配合Ｂ〜Ｅ）を混合した注入材で浸透性が見られ、ブレーン比表面積が８１２０〜１００００ｃｍ2／ｇでより高い浸透性が見られた。 The results of Example 2 are shown in Table 7. C12A7 content is 50% or more calcium aluminate rapid-curing material (compounding p) and bran specific surface area of 6250-12000 cm 2 / g main curing material (blending B-E) injection material mixed to see permeability And a higher permeability was observed at a Blaine specific surface area of 8120 to 10000 cm 2 / g.

Claims (4)

１２ＣａＯ・７Ａｌ2Ｏ3の含有率が５０重量％以上であるカルシウムアルミネートと石膏とを３／７〜７／３の重量比率で混合した混合物１００重量部に対し、アルミン酸ナトリウムを０．５〜５重量部混合した粉体からなることを特徴とする急硬化材。 Sodium aluminate is added to 100 parts by weight of a mixture of calcium aluminate and gypsum having a content of 12CaO · 7Al 2 O 3 of 50% by weight or more in a weight ratio of 3/7 to 7/3. A rapid-curing material comprising powder mixed with 5 parts by weight. スラグ含有物を主硬化材とする注入材用である請求項１記載の急硬化材。   The rapid-curing material according to claim 1, wherein the rapid-curing material is for an injection material containing a slag-containing material as a main curing material. 請求項１記載の急硬化材と遅延剤と水からなる成分Ａ液と、少なくともスラグを含む主硬化材と分散剤と水からなる成分Ｂ液を混合してなることを特徴とする注入材。   An injection material, comprising: the component A liquid comprising the rapid-curing material according to claim 1; a retarder and water; and the component B liquid comprising at least a main curing material containing slag, a dispersant and water. 主硬化材のブレーン比表面積が８０００ｃｍ2／ｇ以上であることを特徴とする請求項３記載の注入材。 4. The injection material according to claim 3, wherein the main curing material has a Blaine specific surface area of 8000 cm 2 / g or more.
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