JP5189283B2 - Ground injection agent and ground injection method using the same - Google Patents

Ground injection agent and ground injection method using the same Download PDF

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JP5189283B2
JP5189283B2 JP2006331821A JP2006331821A JP5189283B2 JP 5189283 B2 JP5189283 B2 JP 5189283B2 JP 2006331821 A JP2006331821 A JP 2006331821A JP 2006331821 A JP2006331821 A JP 2006331821A JP 5189283 B2 JP5189283 B2 JP 5189283B2
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water
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ground injection
alkali metal
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JP2008144016A (en
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貴光 室川
康宏 中島
俊一 三島
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0641—Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
    • C04B40/065—Two or more component mortars
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Description

本発明は、各種土木工事における地盤改良工事や止水工事で用いられる地盤注入剤及びそれを用いた地盤注入工法に関する。   The present invention relates to a ground injecting agent used in ground improvement work and water stop work in various civil engineering works and a ground pouring method using the same.

トンネル土木や都市土木等で、地山や地盤の安定化を図るために、薬液型の地盤注入剤が用いられてきた。この地盤注入剤には、セメント系粒子を含有する懸濁型と、セメント系粒子を含有しない溶液型が知られている。   In order to stabilize natural ground and ground in tunnel civil engineering and urban civil engineering, chemical-type ground injection agents have been used. As this ground injection agent, a suspension type containing cementitious particles and a solution type not containing cementitious particles are known.

懸濁型は、強度発現性が優れるといったメリットを有する反面、薬液の浸透性が低いので粒子間隔の小さい緻密な砂質層に適さなかった。懸濁型の中でもセメント系注入剤はゲルタイムが長いため止水工事に適さなかった。   The suspension type has the merit that the strength development is excellent, but the penetrability of the chemical solution is low, so that it is not suitable for a dense sandy layer having a small particle interval. Among the suspension types, cement-based injectants were not suitable for waterstop work because of their long gel times.

一方、溶液型は、薬液の浸透性が高いので粒子間隔の小さい緻密な砂質層や止水工事に適している。
溶液型注入剤は、水に溶解する化合物を用いる注入剤であり、有機溶液、酸、及びアルカリ溶液を単体又は複合して使用するものである（特許文献１〜６参照）。
特開昭５２−１１３５０５号公報 特公昭５７−０４７２２６号公報 特開昭５２−０８７８０７号公報 特開昭５１−０８２９１３号公報 特開昭５２−１２０５０７号公報 特開昭５７−１９５７８６号公報 On the other hand, the solution type is suitable for a dense sandy layer having a small particle interval and water-stopping work because it has high chemical permeability.
The solution-type injection is an injection that uses a compound that dissolves in water, and uses an organic solution, an acid, and an alkaline solution alone or in combination (see Patent Documents 1 to 6).
JP 52-11505 A Japanese Examined Patent Publication No. 57-047226 JP 52-087807 A Japanese Patent Laid-Open No. 51-082913 JP-A-52-120507 JP-A-57-195786

上記のような溶液型注入剤に用いられる無機塩としては、例えば炭酸塩、塩化物、硫酸塩、ホウ酸塩、及びリン酸塩が知られている。有機溶液としては、エステル類−酢酸モノエーテルグリコール、プロピレンカーボネート、アルデヒド類−ホルムアルデヒド、ギ酸メチル、及びグリオキザール等が挙げられる。酸としては硫酸が挙げられる。   As inorganic salts used in the above-described solution-type injections, for example, carbonates, chlorides, sulfates, borates, and phosphates are known. Examples of the organic solution include esters-acetic acid monoether glycol, propylene carbonate, aldehydes-formaldehyde, methyl formate, and glyoxal. Examples of the acid include sulfuric acid.

また、注入後、直に注入物がゲル化して地盤を安定化させるものが求められているが、「（１）ケイ酸ソーダ、（２）グリオキサール、（３）水溶性のアルミニウム塩、および（４）水溶性の有機酸、水溶性の無機酸および水溶性の酸性無機塩のうちの少なくとも一種、が添加された水性混合液」を用いた地盤注入剤の発明（特許文献７）に挙げられるように、主剤と反応剤を混合してからゲル化するまでに数分を要するようなものであった。
特開昭６２−１９９６８４号公報 In addition, there is a demand for a product that gels immediately after injection and stabilizes the ground. However, “(1) sodium silicate, (2) glyoxal, (3) water-soluble aluminum salt, and ( 4) Invention of ground injecting agent using a water-soluble organic acid, an aqueous mixed solution to which at least one of a water-soluble inorganic acid and a water-soluble acidic inorganic salt is added ”(Patent Document 7) As described above, it took several minutes from the mixing of the main agent and the reactant to gelation.
JP-A 62-199684

さらに、特許文献８〜１０には、水ガラスと酸性材を有効成分として含有するゲルタイムの調整可能な地盤注入剤の発明が開示され、酸として、酢酸、クエン酸、グルコン酸等の有機酸を用いることが記載されている（特許文献８の段落［００４３］、段落［００９４］の表２、特許文献９の段落［００４８］、段落［０１０３］、特許文献１０の段落［００５２］、段落［０１１７］の表２）が、ゲルタイムを調整するために、有機酸塩（カルボン酸塩）を用いることは示されていない。
特開２００４−１９６９１５号公報 特開２００４−１９６９２２号公報 特開２００５−７５８９９号公報 Further, Patent Documents 8 to 10 disclose an invention of a ground injection capable of adjusting gel time containing water glass and an acidic material as active ingredients, and an organic acid such as acetic acid, citric acid or gluconic acid is used as the acid. (Patent Document 8, Paragraph [0043], Paragraph [0094] Table 2, Paragraph [0048], Paragraph [0048], Paragraph [0103], Patent Document 10, Paragraph [0052], Paragraph [ [0117] Table 2) does not show the use of organic acid salts (carboxylates) to adjust the gel time.
JP 2004-196915 A JP 2004-196922 A JP-A-2005-75899

また、特許文献１１には、「アルカリ金属珪酸塩を含有する水溶液のＡ剤と、アルカリ金属アルミン酸塩と有機酸を含有する水溶液のＢ剤とからなる地盤注入剤。」（請求項１）の発明において、クエン酸ソーダを用いることが示されているが、このクエン酸ソーダは、クエン酸、グルコン酸、リンゴ酸、酒石酸等の有機酸と同等のものとして示されている（段落［００１４］、［００２１］、［００２７］、［００２８］）だけであり、特にゲルタイムを調整するために用いるものではなく、また、「アルカリ金属アルミン酸塩」という特定の反応剤を必須とするものであるから、アルカリ金属珪酸塩と、「アルカリ金属アルミン酸塩」以外の無機塩を用いた場合のゲルタイムを調整するために、クエン酸ソーダを用いることを示唆するものではない。
特開２００５−１４６１６１号公報 Further, Patent Document 11 discloses a “ground injection agent comprising an aqueous solution A containing an alkali metal silicate and an aqueous solution B containing an alkali metal aluminate and an organic acid” (Claim 1). In this invention, it is shown that sodium citrate is used, and this sodium citrate is shown as being equivalent to organic acids such as citric acid, gluconic acid, malic acid, tartaric acid (paragraph [0014]. ], [0021], [0027], [0028]), and is not particularly used for adjusting the gel time, and also requires a specific reagent called “alkali metal aluminate”. Therefore, it is suggested to use sodium citrate to adjust the gel time when using inorganic salts other than alkali metal silicate and "alkali metal aluminate". Not.
JP 2005-146161 A

特許文献１２にも、「アルカリ金属珪酸塩を含有する水溶液のＡ剤と、アルカリ金属アルミン酸塩、アルカリ金属炭酸塩、及び有機酸を含有する水溶液のＢ剤とからなる地盤注入剤。」（請求項１）の発明において、クエン酸ソーダを用いることが示されているが、このクエン酸ソーダは、クエン酸、グルコン酸、リンゴ酸、酒石酸等の有機酸と同等のものとして示されている（段落［００１５］、［００２２］、［００２８］、［００２９］）だけであり、特にゲルタイムを調整するために用いるものではなく、また、「アルカリ金属アルミン酸塩、アルカリ金属炭酸塩」という特定の反応剤を必須とするものであるから、アルカリ金属珪酸塩と、「アルカリ金属アルミン酸塩、アルカリ金属炭酸塩」以外の無機塩を用いた場合のゲルタイムを調整するために、クエン酸ソーダを用いることを示唆するものではない。
特開２００５−１４６１６３号公報 Patent Document 12 also discloses a “ground injection agent composed of an aqueous solution A containing an alkali metal silicate and an aqueous solution B containing an alkali metal aluminate, an alkali metal carbonate, and an organic acid.” In the invention of claim 1), it is shown that sodium citrate is used, but this sodium citrate is shown to be equivalent to organic acids such as citric acid, gluconic acid, malic acid, tartaric acid and the like. (Paragraphs [0015], [0022], [0028], [0029]), not specifically used to adjust the gel time, and also specified as “alkali metal aluminate, alkali metal carbonate” In this case, the gel tie when using an alkali metal silicate and an inorganic salt other than “alkali metal aluminate, alkali metal carbonate” is essential. To adjust, not intended to suggest that the use of sodium citrate.
JP 2005-146163 A

さらに、これらの技術では、ゲルタイムを調製するのに、反応剤の種類を変えたり、主剤と反応剤の混合割合を変える必要があった。施工現場では、２連式の注入ポンプで主剤と反応剤を別々に圧送して使用することが多いが、２連式のポンプではその構造上、主剤と反応剤は等容積での圧送となり、例えば反応剤の種類は１種類で、その濃度を変えることでゲルタイムが調整できるようなものが利便性が高く、求められていた。   Further, in these techniques, it is necessary to change the kind of the reactant or the mixing ratio of the main agent and the reactant in order to prepare the gel time. At the construction site, the main agent and the reactant are often separately pumped and used with a double injection pump. However, due to the structure of the dual pump, the main agent and the reactant are pumped in equal volumes. For example, there is one kind of reactant, and it is highly convenient that the gel time can be adjusted by changing its concentration.

本発明は、ゲルタイムの調整が容易で、硬化後の溶液の流出が少ない地盤注入剤及びそれを用いた地盤注入工法を提供することを課題とする。   It is an object of the present invention to provide a ground injecting agent in which gel time can be easily adjusted and the outflow of a solution after curing is small, and a ground injecting method using the same.

本発明者は種々検討を重ねた結果、特定の反応剤を使用することにより、水ガラス系溶液型注入剤の中でもゲルタイムの調整が容易で、硬化後の溶液の流出が少ない注入剤が得られるという知見を得て本発明を完成するに至った。   As a result of repeated studies by the present inventors, by using a specific reactant, it is easy to adjust the gel time among water glass-based solution-type injections, and an injection with less outflow of the solution after curing can be obtained. As a result, the present invention has been completed.

本発明は、上記課題を解決するために、以下の手段を採用する。
（１）アルカリ金属珪酸塩、水溶性チタン塩、並びに、クエン酸ナトリウム及び／又はクエン酸カリウムを（以下、「カルボン酸塩」という。）を用いたことを特徴とする地盤注入剤である。
（２）アルカリ金属珪酸塩を含有するアルカリ性水溶液のＡ剤、及び水溶性チタン塩とカルボン酸塩を含有する酸性水溶液のＢ剤を用いた前記（１）の地盤注入剤である。
（３）前記の水溶性チタン塩１００部に対して、前記カルボン酸塩を５０〜２００部含有する前記（１）又は（２）の地盤注入剤である。
（４）前記水溶性チタン塩が、硫酸チタンであることを特徴とする前記（１）〜（３）のいずれか一項の地盤注入剤である。
（５）前記Ｂ剤の固形分濃度が５〜５０％の溶液であることを特徴とする前記（２）〜（４）のいずれか一項の地盤注入剤である。
（６）前記（２）〜（５）のいずれか一項のＡ剤とＢ剤とを別々に圧送し、注入口付近で合流混合することを特徴とする地盤注入工法である。
なお、本発明における部や％は、特に規定のない限り質量基準である。 The present invention employs the following means in order to solve the above problems.
(1) A ground injection agent characterized by using alkali metal silicate, water-soluble titanium salt, and sodium citrate and / or potassium citrate (hereinafter referred to as “carboxylate”).
(2) The ground injection agent according to (1) above, which uses an agent A of an alkaline aqueous solution containing an alkali metal silicate and an agent B of an acidic aqueous solution containing a water-soluble titanium salt and a carboxylate.
( 3 ) The ground injection agent according to (1) or (2) above, containing 50 to 200 parts of the carboxylate with respect to 100 parts of the water-soluble titanium salt.
( 4 ) The ground injection agent according to any one of (1) to ( 3 ), wherein the water-soluble titanium salt is titanium sulfate.
( 5 ) The ground injection agent according to any one of (2) to ( 4 ), wherein the B agent is a solution having a solid content concentration of 5 to 50%.
( 6 ) A ground injection method characterized in that the A agent and the B agent according to any one of (2) to ( 5 ) are separately pumped and merged and mixed in the vicinity of the injection port.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.

本発明の地盤注入剤及びそれを用いた地盤注入工法を採用することによって、ゲルタイムの調整が容易で、硬化後の溶液の流出が少なくなるといった効果を奏する。   By adopting the ground injecting agent and the ground injecting method using the same of the present invention, the gel time can be easily adjusted, and the effect of reducing the outflow of the solution after curing is achieved.

以下、本発明をさらに詳しく説明する。
（アルカリ金属珪酸塩）
アルカリ金属珪酸塩は、珪酸ナトリウムや珪酸カリウム等の水溶液である。アルカリ金属珪酸塩のＳｉＯ２／Ｒ２Ｏモル比（Ｒはアルカリ金属）は２〜５程度が好ましく、これらの混合液も使用可能である。これらの中でも安価に入手可能な珪酸ソーダ水溶液（水ガラス）を使用することが好ましい。水ガラスの中でもＪＩＳ３号珪酸ソーダがより好ましい。 Hereinafter, the present invention will be described in more detail.
(Alkali metal silicate)
The alkali metal silicate is an aqueous solution such as sodium silicate or potassium silicate. The alkali metal silicate has a SiO 2 / R 2 O molar ratio (R is an alkali metal) of preferably about 2 to 5, and a mixture thereof can also be used. Among these, it is preferable to use a sodium silicate aqueous solution (water glass) that can be obtained at low cost. Among water glasses, JIS No. 3 sodium silicate is more preferable.

アルカリ金属珪酸塩溶液の固形分濃度は、水溶液１００部中、５〜４０部が好ましく、１０〜３０部がより好ましい。固形分濃度が低いと固まらない場合があり、固形分濃度が高いと粘度が高くなり、反応剤との混合性や注入作業時の圧送性が悪くなる場合がある。   The solid content concentration of the alkali metal silicate solution is preferably 5 to 40 parts, more preferably 10 to 30 parts, in 100 parts of the aqueous solution. If the solid content concentration is low, it may not solidify, and if the solid content concentration is high, the viscosity increases, and the mixing property with the reactant and the pumpability during the injection operation may deteriorate.

（水溶性チタン塩）
本発明で使用する水溶性チタン塩とは、水に溶解してチタンを供給し中性から酸性を示す物質である。水溶性チタン塩の例としては、例えば硫酸チタンや、塩化チタン、ヘキサフルオロチタン酸アンモニウム等が挙げられ、これらの一種又は二種以上が使用可能である。これらの中ではアルカリ金属珪酸塩との反応性や反応後の安定性、コスト面から硫酸チタンが好ましい。 (Water-soluble titanium salt)
The water-soluble titanium salt used in the present invention is a substance which is neutral to acidic by being dissolved in water and supplying titanium. Examples of the water-soluble titanium salt include titanium sulfate, titanium chloride, ammonium hexafluorotitanate, and the like, and one or more of these can be used. Among these, titanium sulfate is preferable from the viewpoint of reactivity with alkali metal silicate, stability after reaction, and cost.

（カルボン酸塩）
本発明では、クエン酸ナトリウム及び／又はクエン酸カリウムをカルボン酸塩として使用する。 (Carboxylate)
In the present invention, sodium citrate and / or potassium citrate is used as the carboxylate.

カルボン酸塩としては、一般に、
（１）ぎ酸塩、酢酸塩、及びプロピオン酸塩等のモノカルボン酸塩、
（２）シュウ酸塩、マロン酸塩、コハク酸塩、グルタル酸塩、アジピン酸塩、ピメリン酸塩、マレイン酸塩、フマル酸塩、及びフタル酸塩等のジカルボン酸塩、
（３）トリメリト酸塩及びトリカルバリリル酸塩等のトリカルボン酸塩、
（４）ヒドロキシ酪酸塩、乳酸塩、サリチル酸塩、及びグルコン酸塩等のオキシモノカルボン酸塩、
（５）リンゴ酸塩及び酒石酸塩等のオキシジカルボン酸、
（６）クエン酸塩等のオキシトリカルボン酸塩等が挙げられる。
本発明では、クエン酸塩等のオキシトリカルボン酸塩、なかでも、クエン酸ナトリウム及び／又はクエン酸カリウムをカルボン酸として使用する。カルボン酸塩は無水物であっても水和物であってよい。 As carboxylates, in general,
(1) monocarboxylates such as formate, acetate, and propionate;
(2) Dicarboxylates such as oxalate, malonate, succinate, glutarate, adipate, pimelate, maleate, fumarate, and phthalate,
(3) Tricarboxylates such as trimellitic acid salts and tricarbaryl acrylates,
(4) oxymonocarboxylates such as hydroxybutyrate, lactate, salicylate, and gluconate,
(5) oxydicarboxylic acids such as malate and tartrate,
(6) Oxytricarboxylate such as citrate and the like.
In the present invention, oxytricarboxylates such as citrate, among which sodium citrate and / or potassium citrate are used as carboxylic acid. The carboxylate may be an anhydride or a hydrate.

カルボン酸塩と水溶性チタン塩との混合比率は、水溶性チタン塩（結晶水を含む場合、結晶水は水として換算）１００部に対してカルボン酸塩５０〜２００部が好ましく、８０〜１５０部がより好ましい。上記範囲であれば、硬化後の溶液の流出が少なく、良好な硬化状態と適度な粘度が得られる。   The mixing ratio of the carboxylate and the water-soluble titanium salt is preferably 50 to 200 parts of the carboxylate with respect to 100 parts of the water-soluble titanium salt (when water of crystallization is converted as water), 80 to 150 parts. Part is more preferred. If it is the said range, there will be little outflow of the solution after hardening, and a favorable hardening state and moderate viscosity will be obtained.

本発明においては、各成分を一度に混合してもよく、また、アルカリ金属珪酸塩をＡ剤とし、水溶性チタン塩とカルボン酸塩の混合溶液をＢ剤とし、Ａ剤とＢ剤を混合して用いてもよい。   In the present invention, each component may be mixed at one time. Also, alkali metal silicate is used as agent A, a mixed solution of water-soluble titanium salt and carboxylate is used as agent B, and agent A and agent B are mixed. May be used.

Ａ剤とＢ剤を混合する場合、Ｂ剤の固形分濃度は、５〜５０％が好ましく、７〜２５％がより好ましい。また、Ａ剤とＢ剤の合計の固形分濃度は、３〜５０％が好ましく、５〜２５％がより好ましい。上記範囲であれば、硬化後の溶液の流出が少なく、良好な硬化状態と適度な粘度が得られる。   When mixing A agent and B agent, 5-50% is preferable and, as for the solid content concentration of B agent, 7-25% is more preferable. Moreover, 3-50% is preferable and, as for the total solid content density | concentration of A agent and B agent, 5-25% is more preferable. If it is the said range, there will be little outflow of the solution after hardening, and a favorable hardening state and moderate viscosity will be obtained.

本発明の地盤注入剤の混合方法及び注入方法は、例えば、Ａ剤とＢ剤を別々に調製した後、それらを別々に圧送し、地盤注入前又は地盤注入後に両者を混合して反応させる方法が挙げられる。Ａ剤とＢ剤の混合比率は容積比で２０：８０〜８０：２０とすることが好ましい。   The mixing method and the injecting method of the ground injecting agent of the present invention are, for example, a method in which the agent A and the agent B are prepared separately, then they are separately pumped, and both are mixed and reacted before or after injecting the ground. Is mentioned. The mixing ratio of agent A and agent B is preferably 20:80 to 80:20 in volume ratio.

Ａ剤とＢ剤を別々に調製する場合、Ｂ剤については所定量の水溶性チタン塩とカルボン酸塩と水を混合して溶解させて調製する。溶解時に加熱して溶解させることが溶解時間を短くする観点から好ましい。固形分濃度で３０〜５０％の水溶液とし、使用現場にて所定のゲルタイムを得るように数倍〜１０倍程度に希釈して使用する方法が好ましい。   When preparing the A agent and the B agent separately, the B agent is prepared by mixing and dissolving a predetermined amount of water-soluble titanium salt, carboxylate and water. From the viewpoint of shortening the dissolution time, it is preferable to dissolve by heating at the time of dissolution. A method of using an aqueous solution having a solid concentration of 30 to 50% and diluting to several to 10 times so as to obtain a predetermined gel time at the use site is preferable.

地盤注入剤の使用方法は、例えば２連式の注入ポンプでＡ剤及びＢ剤を別々に圧送して使用する方法が挙げられる。２連式のポンプではＡ剤及びＢ剤は等容積で別々に圧送を行って注入口付近で合流混合した後に地盤に注入する。   The method of using the ground injecting agent includes, for example, a method in which the agent A and the agent B are separately pumped and used by a double infusion pump. In the dual-type pump, the A agent and the B agent are separately pumped in equal volumes, mixed and mixed in the vicinity of the inlet, and then injected into the ground.

ＪＩＳ３号珪酸ナトリウムを水で希釈して固形分濃度２０％のｐＨ１３の水溶液を調整し、これをＡ剤とした。一方、水溶性チタン塩として硫酸チタン、カルボン酸塩としてクエン酸Ｎａを使用し、４価の硫酸チタン１００部に対してクエン酸ナトリウムを１００部混合し、６０℃まで加熱して固形分濃度５０％、ｐＨ２のＢ剤原液を調製した。Ｂ剤は表１−１に示す希釈率でＢ剤原液を希釈して使用した。   JIS No. 3 sodium silicate was diluted with water to prepare an aqueous solution of pH 13 having a solid concentration of 20%, and this was designated as agent A. On the other hand, titanium sulfate is used as a water-soluble titanium salt, and sodium citrate is used as a carboxylate salt. 100 parts of sodium citrate is mixed with 100 parts of tetravalent titanium sulfate and heated to 60 ° C. to obtain a solid concentration of 50 %, PH 2 B stock solution was prepared. The B agent was used by diluting the B agent stock solution at the dilution rate shown in Table 1-1.

Ａ剤と各希釈率のＢ剤を、２０℃、相対湿度８０％の室内で５０：５０の容積比率で混合し、ゲルタイム、ゲル状態、分離水を評価した。また、比較のため、１Ａ族元素を含有しないクエン酸を用いてＢ剤を調製し、同様に試験した。結果を表１−２に併記する。   A agent and B agent of each dilution rate were mixed at a volume ratio of 50:50 in a room at 20 ° C. and a relative humidity of 80%, and gel time, gel state, and separated water were evaluated. For comparison, an agent B was prepared using citric acid containing no Group 1A element, and tested in the same manner. The results are also shown in Table 1-2.

＜使用材料＞
３号珪酸ナトリウム：ＪＩＳ珪酸３号品、Ｎａ２Ｏ＝９．４％、ＳｉＯ２＝２８．４％、ＳｉＯ２／Ａｌ２Ｏ３モル比＝３．１２
水溶性チタン塩 ：Ｔｉ（ＳＯ４）２、市販品、
カルボン酸塩 ：無水クエン酸ナトリウム、無水クエン酸カリウム、市販品
比較用カルボン酸 ：無水クエン酸、市販品
水 ：水道水 <Materials used>
No. 3 sodium silicate: JIS silicic acid No. 3 product, Na 2 O = 9.4%, SiO 2 = 28.4%, SiO 2 / Al 2 O 3 molar ratio = 3.12
Water-soluble titanium salt: Ti (SO 4 ) 2 , commercially available product,
Carboxylic acid salt: anhydrous sodium citrate, anhydrous potassium citrate, carboxylic acid for comparison with commercial product: anhydrous citric acid, commercial product water: tap water

＜評価方法＞
ゲルタイム：Ａ剤１００ｍｌとＢ剤１００ｍｌを混合後、著しく増粘して流動しなくなるまでの時点の時間を測定した。 <Evaluation method>
Gel time: After mixing 100 ml of agent A and 100 ml of agent B, the time at the point of time when it thickened significantly and stopped flowing was measured.

分離水量：ゲルタイムから１時間経過した時点での分離水をデカンテーションで採取して秤量した。
◎：分離水量が全重量中の分離水量が３％の未満
○：分離水量が３％以上で７％未満
△：分離水量が７％以上 Separation water amount: Separation water was collected by decantation after 1 hour from the gel time and weighed.
◎: The amount of separated water is less than 3% of the total weight ○: The amount of separated water is 3% or more and less than 7% △: The amount of separated water is 7% or more

ゲル状態：Ａ剤とＢ剤が均一に混合されているか否か、目視で調べた。
○：均一なゲル体が得られた
△：Ａ剤とＢ剤の混合が十分でなく、ゲル状態が不均一である Gel state: It was visually examined whether the agent A and the agent B were uniformly mixed.
○: A uniform gel was obtained. Δ: Mixing of agent A and agent B was insufficient, and the gel state was non-uniform.

Figure 0005189283
Figure 0005189283

Figure 0005189283
Figure 0005189283

表１−２に示すように、クエン酸を使用した場合には、溶解度が低いために完全に溶解した溶液が得られず、希釈率を変えた場合でもゲルタイムはほとんど変わらない（実験No.1-1〜1-4）。これに対して、クエン酸ナトリウムやクエン酸カリウムを使用した場合には、完全に溶解した溶液が得られ、希釈率によってゲルタイムを調整することが可能となる（実験No.1-5〜1-10）。したがって、クエン酸等のカルボン酸ではなく、クエン酸ナトリウム、クエン酸カリウム等の１Ａ族元素を含むカルボン酸塩を用いることにより、効果を奏することが分かる。
また、クエン酸ナトリウムやクエン酸カリウムを用いた場合、固形分濃度が５〜５０％で、分離水量が少なく、硬化状態が良好で、ゲルタイムの適当な注入剤が得られ、固形分濃度が高く、ゲルタイムが短い場合でも、クエン酸ナトリウムやクエン酸カリウムを用いることにより、クエン酸を用いた場合と比較して、分離水量を少なくすることができる（実験No.1-5〜1-9）。 As shown in Table 1-2, when citric acid was used, a completely dissolved solution was not obtained due to low solubility, and the gel time was hardly changed even when the dilution rate was changed (Experiment No. 1). -1 to 1-4). In contrast, when sodium citrate or potassium citrate is used, a completely dissolved solution is obtained, and the gel time can be adjusted by the dilution rate (Experiment No. 1-5 to 1- 1). Ten). Therefore, it turns out that there exists an effect by using carboxylate containing 1A group elements, such as sodium citrate and potassium citrate, instead of carboxylic acids, such as a citric acid.
In addition, when sodium citrate or potassium citrate is used, the solid content concentration is 5 to 50%, the amount of separated water is small, the cured state is good, and an appropriate injection time of gel time is obtained, and the solid content concentration is high. Even when the gel time is short, the amount of separated water can be reduced by using sodium citrate or potassium citrate compared to the case of using citric acid (Experiment No. 1-5 to 1-9) .

水溶性チタン塩として硫酸チタン、カルボン酸塩としてクエン酸ナトリウムを使用し、硫酸チタン５部に対して表２に示すクエン酸ナトリウムを使用してＢ剤を調整したこと以外は実施例１と同様に試験した。結果を表２に併記する。   Example 1 except that titanium sulfate was used as the water-soluble titanium salt, sodium citrate was used as the carboxylate salt, and B agent was prepared using sodium citrate shown in Table 2 for 5 parts of titanium sulfate. Tested. The results are also shown in Table 2.

Figure 0005189283
Figure 0005189283

表２に示すように、水溶性チタン塩（硫酸チタン）１００部に対してカルボン酸塩を５０〜２００部含有することにより、分離水量が少なく、硬化状態が良好であり、ゲルタイムの適当な注入剤が得られ、また、カルボン酸塩の含有量が少なく、ゲルタイムが短い場合でも、カルボン酸塩を用いることにより、カルボン酸を用いた場合と比較して、分離水量を少なくすることができる（実験No.2-2、1-7、2-3）。   As shown in Table 2, by containing 50 to 200 parts of carboxylate with respect to 100 parts of water-soluble titanium salt (titanium sulfate), the amount of separated water is small, the cured state is good, and the gel time is appropriately injected. Even when the content of carboxylate is low and the gel time is short, the amount of separated water can be reduced by using carboxylate compared to the case of using carboxylic acid ( Experiment No.2-2, 1-7, 2-3).

水溶性チタン塩として硫酸チタン、カルボン酸塩としてクエン酸ナトリウムを使用し、硫酸チタン１００部に対してクエン酸ナトリウムを１００部使用し、固形分濃度５０％、ｐＨ２のＢ剤を調製して５倍希釈液のＢ剤を調整し、表３に示す比率のＡ剤とＢ剤を使用して、ゲルタイムとゲル状態を測定したこと以外は、実施例１と同様に試験した。結果を表３に併記する。   Titanium sulfate is used as the water-soluble titanium salt, sodium citrate is used as the carboxylate, 100 parts of sodium citrate is used for 100 parts of titanium sulfate, and a B agent having a solid content of 50% and a pH of 2 is prepared. The test was conducted in the same manner as in Example 1 except that the B agent in the double dilution was adjusted and the gel time and gel state were measured using the A agent and B agent in the ratios shown in Table 3. The results are also shown in Table 3.

Figure 0005189283
Figure 0005189283

表３に示すように、Ａ剤とＢ剤の混合比率を容積比で２０：８０〜８０：２０の範囲で変えることにより、ゲルタイムを調整することができ、良好な硬化状態を得ることができる（実験No.3-2、1-7、3-3）。   As shown in Table 3, the gel time can be adjusted and a good cured state can be obtained by changing the mixing ratio of the A agent and the B agent in a volume ratio of 20:80 to 80:20. (Experiment No.3-2, 1-7, 3-3).

本発明の地盤注入剤及びそれを用いた地盤注入工法は、例えば、トンネル土木や都市土木等で地山や地盤の安定化を図るために使用され、より安全でかつより性能の良い注入剤として利用可能である。   The ground injection agent and the ground injection method using the same according to the present invention are used, for example, to stabilize ground and ground in tunnel civil engineering and urban civil engineering, etc., and as a safer and better performance injection. Is available.

Claims (6)

アルカリ金属珪酸塩、水溶性チタン塩、並びに、クエン酸ナトリウム及び／又はクエン酸カリウムを用いたことを特徴とする地盤注入剤。 A ground injection agent characterized by using an alkali metal silicate, a water-soluble titanium salt, and sodium citrate and / or potassium citrate . アルカリ金属珪酸塩を含有するアルカリ性水溶液のＡ剤、及び水溶性チタン塩とクエン酸ナトリウム及び／又はクエン酸カリウムを含有する酸性水溶液のＢ剤を用いた請求項１に記載の地盤注入剤。 The ground injection agent according to claim 1, wherein the agent A of an alkaline aqueous solution containing an alkali metal silicate and the agent B of an acidic aqueous solution containing a water-soluble titanium salt and sodium citrate and / or potassium citrate are used. 前記水溶性チタン塩１００部に対して、前記クエン酸ナトリウム及び／又はクエン酸カリウムを５０〜２００部含有する請求項１又は２に記載の地盤注入剤。 The ground injection agent according to claim 1 or 2 , comprising 50 to 200 parts of the sodium citrate and / or potassium citrate with respect to 100 parts of the water-soluble titanium salt. 前記水溶性チタン塩が、硫酸チタンであることを特徴とする請求項１〜３のいずれか一項に記載の地盤注入剤。 The ground injection agent according to any one of claims 1 to 3 , wherein the water-soluble titanium salt is titanium sulfate. 前記Ｂ剤の固形分濃度が５〜５０％の溶液であることを特徴とする請求項２〜４のいずれか一項に記載の地盤注入剤。 The ground injection agent according to any one of claims 2 to 4 , wherein the B agent is a solution having a solid content concentration of 5 to 50%. 請求項２〜５のいずれか一項に記載のＡ剤とＢ剤とを別々に圧送し、注入口付近で合流混合することを特徴とする地盤注入工法。 Ground grouting method, characterized in that billing pumping separately the A agent and the B agent according to any one of claims 2-5, merge mixing near the inlet.
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