JPH1036840A - Soil stabilizer excellent in solution stability at low temperature and soil stabilization method - Google Patents

Soil stabilizer excellent in solution stability at low temperature and soil stabilization method

Info

Publication number
JPH1036840A
JPH1036840A JP21314196A JP21314196A JPH1036840A JP H1036840 A JPH1036840 A JP H1036840A JP 21314196 A JP21314196 A JP 21314196A JP 21314196 A JP21314196 A JP 21314196A JP H1036840 A JPH1036840 A JP H1036840A
Authority
JP
Japan
Prior art keywords
soil
acid
solution
soil stabilizer
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP21314196A
Other languages
Japanese (ja)
Inventor
Tadashi Kitamura
正 北村
Hideki Kuroki
英樹 黒木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Petrochemical Industries Ltd
Original Assignee
Mitsui Petrochemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Petrochemical Industries Ltd filed Critical Mitsui Petrochemical Industries Ltd
Priority to JP21314196A priority Critical patent/JPH1036840A/en
Publication of JPH1036840A publication Critical patent/JPH1036840A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24Compositions 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
    • C04B28/26Silicates of the alkali metals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10Accelerators; Activators
    • C04B2103/14Hardening accelerators
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732Uses not provided for elsewhere in C04B2111/00 for soil stabilisation

Landscapes

  • 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)
  • Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a soil stabilizer excellent in soln. stability at a low temp. which can solve problems of phenomena, such as precipitation derived from precipitation of a crystal, retardation of gelation, and clogging of a pouring pipe by mixing an aq. sodium silicate soln. having a predetermined compsn. as a main agent with a specified hardening agent. SOLUTION: This soil stabilizer excellent in soln. stability at a low temp. comprises: a main agent of an aq. soln. contg. sodium silicate having an SiO2 to Na2 O molar ratio of (2.45:1) to (4.5:1) in an amt. of 10 to 50wt.% in terms of the total amt. of SiO2 and Na2 O, or a mixed aq. soln. composed of sodium silicate having an SiO2 to Na2 O molar ratio of not more than (4.5:1) and a colloidal silica having an SiO2 to Na2 O molar ratio of (20:1) to (250:1), the SiO2 to Na2 O molar ratio in the mixed aq. soln. being (3:1) to (50:1), the total amt. of SiO2 and Na2 O in the mixed aq. soln. being 10 to 50wt.%; and a curing agent soln. comprising phosphoric acid in an amt. capable of neutralizing 1 to 50mol% of Na2 O in the main agent, glyoxal in an amt. capable of neutralizing 5 to 30mol% of Na2 O in the main agent, and an alkali metal salt of hexametaphosphoric acid in an amt. capable of neutralizing 2 to 20wt.% of Na2 O in the main agent, the volume ratio of the main agent to the curing agent being (1:0.9) to (0.9:1).

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、珪酸ソーダと燐酸
とグリオキザールとヘキサメタ燐酸アルカリ金属塩とを
含有する土質安定化剤とそれを用いた土質安定化工法に
関する。より詳しくは、珪酸ソーダ水溶液または珪酸ソ
ーダとコロイダルシリカ混合水溶液を主剤とし、人体に
対する安全性が高い燐酸とグリオキザール及び少量のヘ
キサメタ燐酸アルカリ金属塩とを含有する水溶液を硬化
剤とする土質安定化剤およびそれを用いた土質安定化工
法に関する。本発明の土質安定化剤は、冬場のゲルタイ
ムが15分〜45分間の任意に調整が可能で、かつ1液
土質安定化剤としたときの冬場の低温下での溶液安定性
に優れ、再現性あるゲル化挙動を示し、そのゲル体の圧
縮強度従来の水ガラス系のものに比し高く、省力化が図
れるという特徴を有し、経済的な低コスト型の土質安定
化剤である。
The present invention relates to a soil stabilizer containing sodium silicate, phosphoric acid, glyoxal and alkali metal hexametaphosphate, and a soil stabilization method using the same. More specifically, a soil stabilizer containing an aqueous solution of sodium silicate or an aqueous solution of a mixture of sodium silicate and colloidal silica as a main agent, and a hardener containing an aqueous solution containing phosphoric acid and glyoxal and a small amount of alkali metal hexametaphosphate, which is highly safe for the human body. And a soil stabilization method using the same. The soil stabilizing agent of the present invention can be arbitrarily adjusted to have a gel time in winter of 15 minutes to 45 minutes, and is excellent in solution stability at a low temperature in winter when used as a one-pack soil stabilizing agent. It is an economical low-cost soil stabilizer that has a characteristic gelling behavior, has a high compressive strength of the gel body, and has a feature of saving labor as compared with the conventional water glass type.

【0002】[0002]

【従来の技術】従来、トンネル工事、都市土木工事に於
ける軟弱地盤の安定化や止水を目的としたグラウト工法
に際しては、種々の土質安定化剤がその地盤の性状に応
じて使い分けされている。グラウト工法に於いて使用さ
れる土質安定化剤は、地盤注入薬液やグラウト薬剤とも
言われる。これまでに種々の土質安定化剤とその工法が
提案され実用化されているが、いずれに於いてもグラウ
ト剤に対する要求性能は、硬化後の強度、ゲルタイム調
整の容易さ、地盤への浸透性、環境への影響等様々であ
り、コストと機能の両面から種々選択使用されている。
現在最も多く用いられているのは珪酸ソーダ(水ガラ
ス)水溶液を主剤とする土質安定化剤である。
2. Description of the Related Art Conventionally, in a grouting method for stabilizing a soft ground or stopping water in tunnel works and urban civil works, various soil stabilizing agents are selectively used according to the properties of the ground. I have. The soil stabilizer used in the grouting method is also referred to as a ground injection chemical or a grout chemical. Until now, various soil stabilizers and their methods have been proposed and put to practical use, but in each case, the required performance for the grouting agent is the strength after hardening, the ease of gel time adjustment, and the permeability to the ground. They have various effects on the environment, and are selected and used in terms of both cost and function.
Currently, the most widely used soil stabilizer is a sodium silicate (water glass) aqueous solution as a main component.

【0003】水ガラス系土質安定化剤には懸濁型と溶液
型の2つがある。このうち、前者の懸濁型においては、
水ガラスの硬化剤成分として、セメント、石灰、スラグ
等の水に懸濁する物質が知られている。例えば特開平7
−166163号には、モル比が1.5〜2.8の範囲
にある水ガラスと微粒子スラグを有効成分とする土質安
定化剤が、また特開平1−133965号にはポルトラ
ンドセメントを有効成分とする土質安定化剤が提案され
ている。一般に懸濁型の土質安定化剤は総じてその1次
粒子径が比較的大きいため地盤への浸透性が不足するこ
とが知られており、主流となっていない。また後者の溶
液型では、水ガラスの硬化剤として硫酸、塩酸、燐酸等
の無機酸やその塩類、グリオキザール、エチレンカーボ
ネート等の強アルカリ中で有機酸を徐放する水溶性有機
単量体が公知である。特にグリオキザールは安全性が高
く、高強度の水ガラス系固結体を与えるとして近年では
水ガラスの有機系硬化剤成分の主流になっている。
[0003] There are two types of water glass soil stabilizers: suspension type and solution type. Among them, in the former suspension type,
Substances suspended in water, such as cement, lime and slag, are known as hardener components of water glass. For example, JP-A-7
JP-166163 discloses a soil stabilizer containing water glass and fine particle slag having a molar ratio in the range of 1.5 to 2.8 as an active ingredient, and JP-A-1-133965 discloses an active ingredient comprising Portland cement. Has been proposed. In general, it is known that suspended soil stabilizers generally have a relatively large primary particle diameter and thus lack sufficient permeability to the ground, and are not the mainstream. In the latter solution type, known as water glass hardeners are inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid and salts thereof, and water-soluble organic monomers that gradually release organic acids in strong alkalis such as glyoxal and ethylene carbonate. It is. In particular, glyoxal has recently become the mainstream organic hardener component of water glass, because it is highly safe and provides a high-strength water glass-based compact.

【0004】また最近では、水ガラスのアルカリ成分溶
出を嫌らって酸性水ガラスやコロイダルシリカを主成分
とする土質安定化剤の提案がなされている。例えば水性
コロイダルシリカ系土質安定化剤にあっては、硬化剤と
して消石灰やポルトランドセメントを使用する方法が特
開昭59−66482号に、硬化剤としてスルファミン
酸マグネシウム塩等のアルカリ土類金属塩とする方法が
特開昭63−168485号等に開示されている。また
硬化剤として塩化ナトリウムや硫酸水素ナトリウム等を
使用する方法が特開昭59−152985号に、グリオ
キザール等を使用する方法が特開平2−36156号に
それぞれ開示されており、それぞれ水ガラス系と同様
な、懸濁ないし溶液性の電解質を加えて硬化される方法
が提案されている。しかしこれまで提案された水性コロ
イダルシリカ系土質安定化剤では、ゲル強度が比較的低
いという問題を抱えている。
[0004] Recently, a soil stabilizer containing acidic water glass or colloidal silica as a main component has been proposed in order to avoid dissolution of alkali components from water glass. For example, in the case of aqueous colloidal silica-based soil stabilizers, a method of using slaked lime or Portland cement as a hardening agent is disclosed in JP-A-59-66482, and an alkali earth metal salt such as magnesium sulfamate is used as a hardening agent. A method for performing this is disclosed in JP-A-63-168485. Further, a method using sodium chloride or sodium hydrogen sulfate as a curing agent is disclosed in JP-A-59-152985, and a method using glyoxal or the like is disclosed in JP-A-2-36156. A similar method of curing by adding a suspended or solution electrolyte has been proposed. However, the aqueous colloidal silica-based soil stabilizer proposed so far has a problem that the gel strength is relatively low.

【0005】一方、近年では水ガラス系土質安定化剤の
ゲル化時間を20〜60分程度とする長結型(ゲルタイ
ムが長いタイプ)の土質安定化剤が特に重宝されてい
る。長結型の土質安定化剤の使用によって、薬液注入を
必要とする対象軟弱地盤に対し、より均一に地盤浸透固
結させることが可能で、従来の瞬結型土質安定化剤を用
いる方法よりも、より一層高度に地盤の高強度化が図れ
るとされている。
On the other hand, in recent years, long-lasting (long gel time type) soil stabilizers having a gelling time of about 20 to 60 minutes for water glass based soil stabilizers have been particularly useful. The use of a long-settled soil stabilizer makes it possible to more uniformly infiltrate and solidify the target soft ground that requires chemical injection, as compared to the conventional method using the instantaneously-set soil stabilizer. However, it is said that the strength of the ground can be further enhanced.

【0006】高強度化と長結型の両方の目的に最適とさ
れる土質安定化剤としては、例えば特開昭51−481
5号に開示される技術等によってアルカリ性水ガラス溶
液を主剤とし、硬化剤として燐酸とグリオキザールを併
用する技術が公知である。この技術によれば、前記効果
と共にさらに薬剤の温度変化によってゲルタイムが影響
されにくいとしている。また、特に水ガラスの硬化剤と
して、ゲル化促進剤として酢酸で代表される第3成分の
併用により、より一層効果的になると提案している。こ
の技術の最大の特徴は1ショット注入方式で対応できる
点にあり、グラウト注入装置が安価で経済性に富み省力
・省エネ型の工法と言える事から使用実績は高い。しか
しながら、この技術は以下のような問題がある。
As a soil stabilizer which is optimized for both high strength and long-lasting purposes, for example, Japanese Unexamined Patent Publication No. Sho 51-481
A technique using an alkaline water glass solution as a main component and a combination of phosphoric acid and glyoxal as a curing agent is known by the technique disclosed in No. 5 and the like. According to this technique, the gel time is less likely to be affected by the temperature change of the drug in addition to the above effects. In addition, it is proposed that the combination of a third component represented by acetic acid as a gelling accelerator particularly as a hardening agent for water glass further enhances the effect. The greatest feature of this technology is that it can be handled by a one-shot injection method. The grout injection device is inexpensive, economical, and can be said to be a labor-saving and energy-saving construction method. However, this technique has the following problems.

【0007】即ち、該技術に従って調製された土質安定
化剤を冬場1〜10℃の低温下で1液とし、1ショット
方式で地盤注入を実施する際、その薬液が連続または断
続的に攪拌混合された場合や微振動が連続または断続的
に加わった場合等には、しばしば比較的短時間の内に系
全体が白濁し所定時間内の固結挙動が観察されなくなる
と同時に、その進行と共に送液やグラウト管を介した地
盤注入が全く出来なくなる等の問題が頻繁に発生する。
その白濁の原因は本発明者が行なった解析結果では、該
薬液中に化学的に生成存在する燐酸塩の過飽和溶解にあ
り、その過飽和が崩れて燐酸塩水和結晶を析出する挙動
であり、この析出物質は分析の結果、燐酸第2ナトリウ
ム水和物結晶や燐酸第3ナトリウム水和物結晶であり、
珪酸ナトリウムや珪酸コロイドを該結晶に取込んだ複雑
な複塩結晶沈殿となっている事が判明した。
That is, when a soil stabilizer prepared according to this technique is used as one liquid at a low temperature of 1 to 10 ° C. in winter and the ground is injected in a one-shot manner, the chemical liquid is continuously or intermittently stirred and mixed. When the vibration is applied or when micro-vibration is applied continuously or intermittently, the entire system often becomes cloudy in a relatively short time, and the consolidation behavior within a predetermined time is not observed. Frequently, problems such as the inability to inject the ground through a liquid or grout pipe occur at all.
The cause of the white turbidity, according to the analysis results performed by the present inventor, is due to the supersaturated dissolution of the phosphate chemically generated and present in the chemical solution, and the behavior of the supersaturation being broken to precipitate phosphate hydrated crystals. As a result of the analysis, the precipitated substance is a sodium phosphate hydrate crystal or a sodium phosphate hydrate crystal,
It was found that complex double salt crystal precipitation was obtained in which sodium silicate and silicate colloid were incorporated into the crystal.

【0008】このように該技術に開示されたグラウト剤
は、冬場の注入現場作業下では種々の刺激を複雑に受け
る結果、初期の透明溶液が短時間の内に白濁・スラリー
溶液と変化し、浸透作業や送液ポンプ注入作業に著しく
支障を来す等の数々の現場トラブルを発生していた。よ
り具体的には、例えば、該技術の最も代表的な開示例で
ある3号水ガラスの35ccと75重量%の燐酸の1.
5ccと40重量%グリオキザールの3.5ccとを含
有し市水で総量を100ccとする1液型土質安定化剤
では、液温が5℃±3℃、線速度で秒速60m程度の刺
激を連続または断続で与えたり、または50〜2、00
0Hzの振動を連続または断続的に与えた条件下等で
は、調製後数分から数十分で難溶性燐酸塩の水和物結晶
が析出する現象が再現性良く観察される。析出量はその
刺激の程度によって異なるが、時間経過と共により肥大
化し、ついにはタンク低部にケーキ物を作る等して、現
場注入に供する事が出来ない状態へと変化する。
[0008] As described above, the grouting agent disclosed in this technique is subjected to various stimuli in the work of an injection site in winter, and as a result, the initial clear solution changes to a cloudy / slurry solution within a short time, Numerous on-site troubles occurred, such as significantly impairing the infiltration work and the liquid feed pump injection work. More specifically, for example, 35 cc of No. 3 water glass and 75 wt.
A one-pack type soil stabilizer containing 5 cc and 3.5 cc of 40 wt% glyoxal with a total volume of 100 cc in city water continuously stimulates at a liquid temperature of 5 ° C. ± 3 ° C. and a linear velocity of about 60 m / sec. Or given intermittently, or 50-2,000
Under conditions where vibration of 0 Hz is continuously or intermittently applied, a phenomenon in which hydrate crystals of a sparingly soluble phosphate precipitate in a few minutes to several minutes after preparation is observed with good reproducibility. The amount of precipitation varies depending on the degree of irritation, but it grows larger with the passage of time, and eventually changes to a state where it cannot be used for in-situ injection, for example, by making a cake in the lower part of the tank.

【0009】結晶の形態は刺激の種類と度合いにより種
々に変化するが、その形態の差に関係なく、系全体が懸
濁化するため、結果として、地盤浸透性不良や注入ノズ
ルを詰めるなどのトラブルを発生させることが確認され
た。またその系に少量の酢酸を含有させた土質安定化剤
においてもこの問題は解決出来ず、その系に多量に酢酸
を含有させるとゲル化時間が極端に短縮され、もはや長
結型土質安定化剤としては機能しなくなることも確認さ
れた。
The morphology of the crystal varies depending on the type and degree of the stimulus. Regardless of the difference in the morphology, the entire system is suspended, resulting in poor ground permeability or clogging of the injection nozzle. It was confirmed that it caused trouble. In addition, this problem cannot be solved even with a soil stabilizer containing a small amount of acetic acid in the system, and if the system contains a large amount of acetic acid, the gelation time is extremely shortened, and the long-lasting soil stabilization is no longer possible. It was also confirmed that it no longer functions as an agent.

【0010】特開昭51−4815号等によって開示さ
れている水ガラス/燐酸・グリオキザールからなる長結
型の1液型土質安定化剤は、調製時以外は全く振動も攪
拌も与えない静置状態下ではたしかにゲルタイムは液温
度の変動に際して比較的影響されにくい。しかし実際の
多くの地盤改良注入現場では、例えば、連続攪拌槽によ
る稼働、送液ポンプの稼働による振動、薬液の注入圧調
整用バイパスラインの作動による液循環等があり、それ
らの攪拌・振動因子が複雑に該組成物溶液に作用する
為、そのゲル化特性は静置状態下の結果と著しく異な
る。すなわち、低温下での取扱現場では、沈殿の発生、
ゲル化遅延、注入管や注入ノズルの閉鎖等の現象が見ら
れ、現場不適合の問題がある。すなわち、特開昭51−
4815号で示された開示技術等はグラウト剤分野では
夏場実績が高い技術であるが、冬場の現場作業安定性と
ゲル化挙動の不安定性という重要な問題をかかえてお
り、その解決手段が強く求められている。
The long-lasting, one-pack type soil stabilizer composed of water glass / phosphoric acid / glyoxal disclosed in Japanese Patent Application Laid-Open No. 51-4815 and the like is allowed to stand without any vibration or stirring except during preparation. Under these conditions, the gel time is certainly relatively unaffected by fluctuations in the liquid temperature. However, at many actual ground improvement injection sites, there are, for example, operation by a continuous stirring tank, vibration by operation of a liquid feed pump, and liquid circulation by operation of a bypass line for adjusting the injection pressure of a chemical solution. Act on the composition solution in a complex manner, so that its gelling properties are significantly different from the results under standing conditions. That is, at the handling site under low temperature,
Phenomena such as gelation delay, injection pipe and injection nozzle closure, and the like are observed, and there is a problem of site incompatibility. That is, JP-A-51-
The disclosed technology disclosed in No. 4815 is a technology with a high track record in the summer in the grouting agent field, but it has important problems of in-situ work stability in the winter and instability of the gelation behavior, and its solution is strong. It has been demanded.

【0011】[0011]

【発明が解決しようとする課題】本発明の目的は、水ガ
ラス/燐酸・グリオキザールからなる長結型の1液型土
質安定化剤の問題である、結晶の析出に伴う沈殿の発
生、ゲル化遅延、注入管や注入ノズルの閉鎖等の現象を
解決し、冬場でも現場の作業安定性が優れたグラウト剤
を提供することである。
SUMMARY OF THE INVENTION It is an object of the present invention to provide a long-lasting, one-pack type soil stabilizer comprising water glass / phosphoric acid / glyoxal, which is accompanied by precipitation of crystals and gelation. It is an object of the present invention to provide a grouting agent that solves such phenomena as delay, closure of an injection pipe and an injection nozzle, and has excellent work stability on site even in winter.

【0012】[0012]

【課題を解決するための手段】本発明者は上記課題を克
服するため鋭意検討した結果、珪酸ソーダ水溶液または
珪酸ソーダとコロイダルシリカの混合水溶液のいずれか
を主剤成分とし、これに硬化剤成分として燐酸とグリオ
キザールとヘキサメタ燐酸アルカリ金属塩とを含有させ
た1液型土質安定化剤とすることで前記課題を解決でき
る事を見出し本発明を完成した。
Means for Solving the Problems As a result of extensive studies to overcome the above problems, the present inventor has found that either a sodium silicate aqueous solution or a mixed aqueous solution of sodium silicate and colloidal silica is used as a main component and a curing agent component. The present inventors have found that the above-mentioned problems can be solved by using a one-pack type soil stabilizer containing phosphoric acid, glyoxal, and alkali metal hexametaphosphate to complete the present invention.

【0013】すなわち本発明は、主剤が下記(a)また
は(b)であり、(a)SiO2/Na2Oモル比が2.
45〜4.5の珪酸ソーダを、そのSiO2とNa2Oの
総量で10〜50重量%含有してなる水溶液、(b)S
iO2/Na2Oモル比が4.5を超えない珪酸ソーダ
と、SiO2/Na2Oモル比が20〜250のコロイダ
ルシリカとを含有し、その混合水溶液のSiO2/Na2
Oモル比が3〜50、SiO2とNa2Oの総量が10〜
50重量%である混合水溶液、硬化剤が、該硬化剤と主
剤とを下記の割合で混合したときに、主剤中のNa2
の1〜50モル%相当分を中和する事が出来る量の燐酸
(c)と、5〜30モル%相当分を中和する事が出来る
量のグリオキザール(d)と、2〜20重量%相当分を
中和する事が出来る量のヘキサメタ燐酸アルカリ金属塩
(e)とを含有させてなる水溶液であって、上記主剤と
硬化剤を容積比で(1:0.9)〜(0.9:1)の割
合で混合してなる低温下での溶液安定性に優れる土質安
定化剤である。
That is, in the present invention, the main agent is the following (a) or (b), and (a) the molar ratio of SiO 2 / Na 2 O is 2.
An aqueous solution containing 10 to 50% by weight of sodium silicate of 45 to 4.5 in total of SiO 2 and Na 2 O, (b) S
It contains sodium silicate having an iO 2 / Na 2 O molar ratio not exceeding 4.5 and colloidal silica having an SiO 2 / Na 2 O molar ratio of 20 to 250, and a mixed aqueous solution of SiO 2 / Na 2
O molar ratio is 3 to 50, and the total amount of SiO 2 and Na 2 O is 10 to
When a 50% by weight mixed aqueous solution and a curing agent are mixed with the curing agent and the base at the following ratio, Na 2 O in the base is mixed.
An amount of phosphoric acid (c) capable of neutralizing an amount equivalent to 1 to 50 mol% of glyoxal (d) of an amount capable of neutralizing an equivalent amount of 5 to 30 mol%; An aqueous solution containing an amount of alkali metal hexametaphosphate (e) capable of neutralizing a considerable amount, wherein the main agent and the curing agent are in a volume ratio of (1: 0.9) to (0. 9: 1) is a soil stabilizer excellent in solution stability at low temperature mixed at a ratio of 9: 1).

【0014】また本発明の土質安定化工法とは、軟弱地
盤中に予めセットされたグラウト注入管を介して、前記
本発明の土質安定化剤を、1ショット方式で注入し、浸
透・流動・固結させ、土質を強化安定させる方法であ
る。
Further, the soil stabilization method of the present invention means that the soil stabilizer of the present invention is injected in a one-shot manner through a grout injection pipe which is previously set in soft ground, and is subjected to infiltration, flow, It is a method of consolidating and strengthening and stabilizing the soil.

【0015】[0015]

【発明の実施の形態】本発明の主剤の一つである(a)
液における珪酸ソーダは、SiO2/Na2Oモル比が
2.45〜4.5であり、好ましくは2.45〜4.
0、より好ましくは3.0〜3.5である。またその珪
酸ソーダは、通常、JIS K 1408に規定されて
いる3号珪酸ソーダが好ましく挙げられ、その他、2号
珪酸ソーダや4号珪酸ソーダ等であっても、またそれら
の混合珪酸ソーダであっても、何等問題なく使用でき
る。
BEST MODE FOR CARRYING OUT THE INVENTION One of the main ingredients of the present invention (a)
The sodium silicate in the liquid has a SiO 2 / Na 2 O molar ratio of 2.45 to 4.5, preferably 2.45 to 4.5.
0, more preferably 3.0 to 3.5. As the sodium silicate, preferably, sodium silicate No. 3 specified in JIS K 1408 is preferably mentioned. In addition, sodium silicate No. 2, sodium silicate No. 4, and the like, and a mixed silicate thereof are also available. However, it can be used without any problems.

【0016】(a)液中の該珪酸ソーダの含有濃度はS
iO2とNa2Oの総量濃度であらわした場合、10〜5
0重量%であり、好ましくは15〜45重量%、特に好
ましくは18〜40重量%である。含有量が10重量%
未満では、固結した後の土質の強度が低くて安定強化が
図りにくく、含有量が50重量%を越えると、液自体の
粘度が高すぎて土質浸透性に欠ける傾向にある。
(A) The content of the sodium silicate in the solution is S
When expressed as the total concentration of iO 2 and Na 2 O, 10 to 5
0% by weight, preferably 15 to 45% by weight, particularly preferably 18 to 40% by weight. Content is 10% by weight
If the content is less than 50% by weight, the strength of the soil after consolidation is low and it is difficult to stabilize the soil. If the content exceeds 50% by weight, the viscosity of the liquid itself is too high and the soil tends to lack permeability.

【0017】(b)液における珪酸ソーダは、SiO2
/Na2Oモル比が4.5を超えないものであり、好ま
しくは3.0〜3.5である。通常、JIS K 14
08に規定されている3号珪酸ソーダが好ましく挙げら
れ、その他、1号珪酸ソーダ、2号珪酸ソーダや4号珪
酸ソーダ等であっても何等問題なく使用できる。
The sodium silicate in the solution (b) is SiO 2
/ Na 2 O molar ratio does not exceed 4.5, preferably from 3.0 to 3.5. Usually, JIS K14
Preferred is No. 3 sodium silicate specified in No. 08. In addition, No. 1 sodium silicate, No. 2 sodium silicate and No. 4 sodium silicate can be used without any problem.

【0018】(b)液におけるコロイダルシリカとは、
通称シリカゾルと呼ばれているもので、例えば前記した
珪酸ソーダ水溶液を原料にして、イオン交換法、酸中和
法、電気透析法、微細シリカ粉末の水分散法等で製造さ
れるものが代表的である。その分散粒子径としては3〜
100nmのものがよく、より実用的には3〜30nm
のものが良い。コロイダルシリカはSiO2/Na2Oモ
ル比が20〜250であり、好ましくは20〜130、
より好ましくは20〜80である。モル比が20未満で
は密度と分子量の大きい独立分散シロキサンゾル粒子が
得られにくく、250を越えると一次分散粒子径が10
0nmを超えるため、それ自体の液安定性に欠けると同
時に、得られる土質安定化剤組成物が懸濁溶液型に近似
した挙動を示す結果となり、軟弱土質への均一浸透性に
欠ける。
The colloidal silica in the liquid (b) is
What is commonly called silica sol, for example, the one produced by the above-mentioned sodium silicate aqueous solution as a raw material and produced by an ion exchange method, an acid neutralization method, an electrodialysis method, an aqueous dispersion method of fine silica powder, or the like is typical. It is. The dispersed particle size is 3 to
It is preferably 100 nm, more practically 3 to 30 nm.
Is good. Colloidal silica is a SiO 2 / Na 2 O molar ratio of 20 to 250, preferably 20 to 130,
More preferably, it is 20 to 80. When the molar ratio is less than 20, it is difficult to obtain independently dispersed siloxane sol particles having a large density and a high molecular weight.
Since it exceeds 0 nm, the resulting soil stabilizer composition lacks its own liquid stability, and at the same time, exhibits a behavior similar to a suspension solution type, and lacks uniform permeability to soft soil.

【0019】前記(b)液の珪酸ソーダとコロイダルシ
リカとを含有する混合水溶液のSiO2/Na2Oモル比
は3〜50であり、好ましくは3〜35、より好ましく
は3〜30である。また、有効成分であるSiO2とN
2Oの総量は混合水溶液中で10〜50重量%であ
り、好ましくは15〜45重量%、最も好ましくは18
〜40重量%がホモゲル強度が高くて経済的でありかつ
作業性が良い。両成分の総含有量が10重量%未満であ
る時は、固結した後の土質の強度が低く安定強化が図り
にくく、含有量が50重量%を越えると液自体の粘度が
高すぎて土質浸透性に欠けるかまたは溶液自体の安定性
が欠ける傾向にある。主剤を前記(b)とする事によ
り、固結後の土質強度を一層向上させる事やゲルタイム
を安定かつ任意に調整する事ができる。
The mixed aqueous solution containing sodium silicate and colloidal silica in the liquid (b) has a SiO 2 / Na 2 O molar ratio of 3 to 50, preferably 3 to 35, more preferably 3 to 30. . In addition, the active ingredients SiO 2 and N
The total amount of a 2 O is 10 to 50% by weight, preferably 15 to 45% by weight, most preferably 18% by weight in the mixed aqueous solution.
Up to 40% by weight has high homogel strength, is economical, and has good workability. If the total content of both components is less than 10% by weight, the strength of the soil after consolidation is low, and it is difficult to stably strengthen. If the content exceeds 50% by weight, the viscosity of the liquid itself is too high, and They tend to lack permeability or lack stability of the solution itself. By setting the main agent to (b), the soil strength after consolidation can be further improved and the gel time can be adjusted stably and arbitrarily.

【0020】また主剤液中には、事前に重炭酸アルカリ
有機化合物またはアルカリ性金属塩類を加えてその水溶
液pHを11以上とすることは好ましい。その理由は、
主剤液のpHを11未満とした場合、液は不安定とな
り、数十分以内にはゲル化して使用出来ない状態となる
からである。pHが11以上である場合は少なくとも調
製後数時間は溶液状態を確保できると共に、硬化剤液と
の混合時には気温によるゲルタイムの変動が低い土質安
定化剤となる。重炭酸アルカリ有機化合物としては炭酸
グアニジンや炭酸コリン等が挙げられる。アルカリ金属
塩類としては例えば炭酸水素ナトリウム、炭酸水素カリ
ウム、燐酸水素二カリウム、燐酸水素二ナトリウム、硫
酸水素ナトリウム、硫酸水素カリウム等が挙げられる。
It is preferable to add an alkali organic bicarbonate compound or an alkali metal salt in advance to the main solution to adjust the pH of the aqueous solution to 11 or more. The reason is,
If the pH of the main agent liquid is less than 11, the liquid becomes unstable and becomes gelled within several tens of minutes and becomes unusable. When the pH is 11 or more, a solution state can be ensured for at least several hours after preparation, and at the time of mixing with the curing agent liquid, the soil stabilizer has a low gel time variation due to air temperature. Examples of the alkali bicarbonate organic compound include guanidine carbonate and choline carbonate. Examples of the alkali metal salts include sodium hydrogen carbonate, potassium hydrogen carbonate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, sodium hydrogen sulfate, potassium hydrogen sulfate and the like.

【0021】次に、本発明の硬化剤液について以下に述
べる。本発明の硬化剤液とは、該硬化剤と主剤とを所定
の割合で混合したときに、主剤中のNa2Oの1〜50
モル%相当分を中和することが出来る量の燐酸(c)
と、5〜30モル%相当分を中和することが出来る量の
グリオキザール(d)と、2〜20重量%相当分を中和
することが出来る量のヘキサメタ燐酸アルカリ金属塩
(e)とを含有させてなる水溶液である。好ましくは、
主剤液中のNa2Oの5〜40モル%相当分を中和する
ことが出来る量の燐酸(c)と、10〜25モル%相当
分を中和することが出来る量のグリオキザール(d)
と、2〜10モル%相当分を中和することが出来る量の
ヘキサメタ燐酸アルカリ金属塩(e)とを含有させてな
る水溶液である。
Next, the curing agent liquid of the present invention will be described below. When the curing agent and the main agent are mixed at a predetermined ratio, the curing agent liquid of the present invention contains 1 to 50 of Na 2 O in the main agent.
An amount of phosphoric acid (c) capable of neutralizing the equivalent of mol%
And glyoxal (d) in an amount capable of neutralizing 5 to 30 mol% equivalent and alkali metal hexametaphosphate (e) in an amount capable of neutralizing 2 to 20 wt% equivalent. It is an aqueous solution that is contained. Preferably,
Phosphoric acid (c) in an amount capable of neutralizing 5 to 40 mol% of Na 2 O in the base solution and glyoxal (d) in an amount capable of neutralizing 10 to 25 mol% of Na 2 O
And an aqueous solution containing an amount of an alkali metal hexametaphosphate (e) capable of neutralizing an equivalent of 2 to 10 mol%.

【0022】前記(c)(d)(e)のそれぞれの使用
割合はゲルタイムが60分以下となる様に決定されるこ
とが肝要である。その意味では、アルカリ水ガラスのア
ルカリ成分をほぼ瞬間的に中和する物質として機能する
燐酸(c)及びヘキサメタ燐酸アルカリ金属塩(e)の
合計使用割合を、主剤液中のNa2Oの60モル%相当
分を中和する量を超えないで使用することが好ましく、
その結果、目的とする長結型の土質安定化剤とすること
が出来る。また一方、その合計使用割合が主剤液中のN
2Oの60モル%相当分を越えて中和すること出来る
量以上で使用した場合では瞬結型〜緩結型の土質安定化
剤を与える。
It is important that the respective proportions of (c), (d) and (e) are determined so that the gel time is 60 minutes or less. In that sense, the total use ratio of phosphoric acid (c) and alkali metal hexametaphosphate (e), which function as a substance that almost instantaneously neutralizes the alkali component of the alkali water glass, is adjusted to 60% of Na 2 O in the main solution. It is preferable to use the amount that does not exceed the amount that neutralizes the mole% equivalent,
As a result, it is possible to obtain a desired long-soil-type soil stabilizer. On the other hand, the total use ratio is N
In the case of using by possible amount or more to neutralize than 60 mol% equivalent of a 2 O gives the Madokayui type-slow-forming type soil stabilizer.

【0023】(c)の燐酸とは精製燐酸、粗燐酸等であ
り、特に限定はなく、前記のように主剤液のNa2Oの
1〜50モル%を中和出来る量を用いる。このモル%は
燐酸1モルが主剤液のNa2Oの1モルを消費するとみ
なして算出され、以下同様である。1モル%相当分を中
和する事が出来る量未満の使用では、一般に経済性に欠
け、またゲルタイムが不適当であり生成する珪酸ゲルの
1軸圧縮強度特性が低くなる傾向にある。また50モル
%相当分を中和する事が出来る量を越えて使用した場合
では、ゲルタイムが短すぎて均等かつ高範囲への浸透固
結が可能とならない傾向にあり、いわゆる長結型の1シ
ョット注入方式が採用困難となる。
The phosphoric acid of (c) is purified phosphoric acid, crude phosphoric acid, etc., and is not particularly limited, and an amount capable of neutralizing 1 to 50 mol% of Na 2 O of the main solution as described above is used. This mol% is calculated assuming that 1 mol of phosphoric acid consumes 1 mol of Na 2 O of the main solution, and so on. If the amount used is less than the amount that can be neutralized by 1 mol%, the economy is generally low, and the gel time is unsuitable, and the uniaxial compressive strength characteristics of the resulting silica gel tend to be low. If the amount used is greater than the amount capable of neutralizing the equivalent of 50 mol%, the gel time is too short, so that it tends to be impossible to evenly and permeate into a high range. It becomes difficult to adopt the shot injection method.

【0024】(c)の燐酸はその酸分の1〜50%相当
分を硫酸、硝酸、塩酸、ほう酸又はこれらの混合物で代
替してもよい。また同様に1〜50%相当分をフィチン
酸またはその酸性アルカリ金属塩で代替してもよい。こ
の場合、燐酸との合計で、主剤液のNa2Oの50モル
%を中和出来る量を越えないようにする。ここで酸分と
はアルカリを中和できる量の酸をいい、以下同様であ
る。
The phosphoric acid of (c) may be replaced with sulfuric acid, nitric acid, hydrochloric acid, boric acid or a mixture thereof in an amount corresponding to 1 to 50% of the acid content. Similarly, 1 to 50% equivalent may be replaced with phytic acid or its acidic alkali metal salt. In this case, the total amount of phosphoric acid and 50 mol% of Na 2 O in the main solution should not exceed an amount capable of neutralizing. Here, the acid content means an amount of acid capable of neutralizing the alkali, and the same applies hereinafter.

【0025】(d)のグリオキザールは、公知の製造方
法で得た物を適宜使用する事で良く、特に限定はない。
例えば、アセトアルデヒドの硝酸酸化法で得られたグリ
オキザール水溶液や、エチレングリコールから1分子を
脱水する方法等で得たグリオキザール水溶液等が代表的
な例として挙げられる。通常40重量%前後のグリオキ
ザール水溶液として市販されており、各種製造方法の違
いにより、精製グリオキザール水溶液であっても、また
蟻酸、酢酸、グリオキシル酸、蓚酸などの不純物をグリ
オキザール100に対して数重量%以内で含有している
非精製グリオキザール水溶液であっても本発明のグリオ
キザール成分として使用できる。
As the glyoxal (d), a product obtained by a known production method may be appropriately used, and there is no particular limitation.
For example, representative examples include an aqueous glyoxal solution obtained by a nitric acid oxidation method of acetaldehyde, an aqueous glyoxal solution obtained by a method of dehydrating one molecule from ethylene glycol, and the like. Usually, it is commercially available as an aqueous glyoxal solution of about 40% by weight, and depending on the difference in various production methods, even in a purified aqueous glyoxal solution, impurities such as formic acid, acetic acid, glyoxylic acid, and oxalic acid are several weight% relative to 100 glyoxal. Even an unpurified aqueous glyoxal solution contained within can be used as the glyoxal component of the present invention.

【0026】また精製グリオキザールの40重量%前後
の水溶液等は、しばしば長期溶液安定性確保の点から
0.01〜3重量%の極く少量の添加剤、例えば、グリ
セリン、エチレングリコール等の水溶性グルコール類、
また特公昭57−45729等で公知の窒素または窒素
とイオウとを環内に含む複素環式化合物等のグリオキザ
ール液安定化助剤を含んでいる場合があるが、このよう
なグリオキザール水溶液であっても問題なく使用でき、
特に制約はない。
Also, an aqueous solution of about 40% by weight of the purified glyoxal is often used in a very small amount of 0.01 to 3% by weight of an additive such as glycerin, ethylene glycol or the like in view of securing long-term solution stability. Glycols,
Further, a glyoxal solution stabilizing aid such as a heterocyclic compound containing nitrogen or nitrogen and sulfur in a ring known in Japanese Patent Publication No. 57-45729 may be contained. Can be used without any problem,
There are no particular restrictions.

【0027】グリオキザール自体は一般的にpH値が1
0以上の強アルカリ水溶液中で、カニツァロ反応(不均
化反応)によってグリコール酸に徐々に変質する事が知
られている。したがって本発明の(d)のグリオキザー
ルの使用割合は次のようにして算出する。即ち、1分子
のグリオキザールが完全にカニツァロ反応で100%グ
リコール酸に改質したと仮定し、それにより生成したグ
リコール酸の1分子がNa2Oの1/2分子と結合する
とし、この方法によって主剤液のNa2Oの5〜30モ
ル%相当を中和出来る量のグリオキザール(遊離グリー
コール酸換算)を算出する。5モル%相当分を中和する
事が出来る量未満の使用では、一般にゲルタイムが不適
当であり生成する珪酸ゲルの1軸圧縮強度特性が低くな
る傾向にある。また30モル%相当分を中和する事が出
来る量を越えてグリオキザールを使用した場合では、低
温作業性が欠如すると同時に、ゲルタイムが一般に短か
くなり過ぎて均等かつ高範囲への浸透固結が可能となら
ない傾向にある。またいわゆる長結型の1ショット注入
方式が採用困難となる。
Glyoxal itself generally has a pH value of 1
It is known that in a strongly alkaline aqueous solution of 0 or more, glycolic acid is gradually transformed by a Cannizzaro reaction (proportionation reaction). Therefore, the use ratio of glyoxal of (d) of the present invention is calculated as follows. In other words, it is assumed that one molecule of glyoxal is completely modified to 100% glycolic acid by the Cannizzaro reaction, and one molecule of glycolic acid generated by this is bound to a half molecule of Na 2 O. The amount of glyoxal (in terms of free glycolic acid) capable of neutralizing 5 to 30 mol% of Na 2 O in the main solution is calculated. If the amount is less than the amount that can neutralize the equivalent of 5 mol%, the gel time is generally inappropriate and the resulting silica gel tends to have low uniaxial compressive strength. In addition, when glyoxal is used in an amount exceeding the amount capable of neutralizing the equivalent of 30 mol%, the low-temperature workability is lacking, and at the same time, the gel time is generally too short, so that the permeation and consolidation in a uniform and high range is not achieved. It tends not to be possible. In addition, it becomes difficult to adopt a so-called long-type one-shot injection method.

【0028】また(d)のグリオキザールは、その遊離
グリコール酸換算の酸分であらわしたときの1〜100
相当量をグリコール酸2酢酸エステル、エチレンカーボ
ネート、プロピレンカーボネート、γ−ブチロラクトン
またはこれらの混合物で置き換えてもよい。この場合、
グリオキザールとの合計で主剤液のNa2Oの30モル
%を中和出来る量を越えないようにする。
The glyoxal of (d) is 1 to 100 when expressed in terms of its acid content in terms of free glycolic acid.
A significant amount may be replaced by glycolic acid diacetate, ethylene carbonate, propylene carbonate, γ-butyrolactone or mixtures thereof. in this case,
So as not to exceed the amount that can neutralize 30 mole% of Na 2 O of base material liquid, the total of glyoxal.

【0029】本発明の硬化剤液には前記燐酸(c)と、
グリオキザール(d)の他に主剤液中のNa2Oの2〜
20モル%相当分を中和する事が出来る量のヘキサメタ
燐酸アルカリ金属塩(e)を含有させる事が最も肝要で
ある。一般に、特開昭51−4815号等ですでに明ら
かになっている土質安定化剤、すなわち、3号水ガラス
(前記(a)の一種)と燐酸(c)とグリオキザール
(d)からなる1液型土質安定化剤は、冬場の1液化注
入現場に於いて白濁化とゲルタイム不安定化が重要な問
題となっていることはすでに述べてきたとおりである。
この課題を解決する上で、本発明の土質安定化剤では、
硬化剤液中の第3成分としてヘキサメタ燐酸アルカリ金
属塩(e)の使用は欠くことが出来ない。(e)による
前記の作用効果発現の理由はまだ十分明確になっていな
いが、その一つには水ガラスの酸性硬化剤成分として働
くこと、またそのひとつにスケール発生防止剤としての
働きが強いこと、金属防錆効果が強くキレート形成剤と
して働くこと、それ自体非晶質であり他の微細結晶に吸
着して成長を阻害する働き等が推定され、それらの相乗
効果と考えられる。
The curing agent liquid of the present invention contains the phosphoric acid (c),
In addition to the glyoxal (d), 2 to 2 of Na 2 O in the base solution
It is most important to contain an alkali metal hexametaphosphate (e) in an amount capable of neutralizing the equivalent of 20 mol%. In general, a soil stabilizer already disclosed in JP-A-51-4815 or the like, that is, a soil stabilizer composed of No. 3 water glass (a kind of the above (a)), phosphoric acid (c) and glyoxal (d) As described above, the liquid soil stabilizer has significant problems of cloudiness and instability of gel time at the site of one liquefaction injection in winter.
In solving this problem, in the soil stabilizer of the present invention,
The use of alkali metal hexametaphosphate (e) as the third component in the curing agent liquid is indispensable. Although the reason for the above-mentioned effect exerted by (e) has not been clarified yet, one of them has a strong function as an acidic hardener component of water glass, and one has a strong function as a scale generation inhibitor. It is presumed that the metal has a strong metal rust-preventing effect and acts as a chelating agent, and that it is amorphous itself and adsorbs to other fine crystals to inhibit growth, and the like, and is considered to be a synergistic effect thereof.

【0030】本発明記載のヘキサメタ燐酸アルカリ金属
塩(e)とは、平均重合度が6以上のものが好ましく、
より好ましくは重合度が6〜50、最も好ましくは6〜
35のものが良い。またヘキサメタ燐酸アルカリ金属塩
とは具体的にヘキサメタ燐酸ナトリウム、ヘキサメタ燐
酸カリウム等である。これらは無水物、含水化合物また
は水溶液であっても良く、その状態や形態には特に制約
はない。またヘキサメタ燐酸アルカリ金属塩以外の、例
えばヘキサメタ燐酸アルカリ土類金属塩等は溶解度が低
く、また前記液安定性の効果がほとんど期待されない。
The alkali metal hexametaphosphate (e) according to the present invention preferably has an average degree of polymerization of 6 or more,
More preferably, the degree of polymerization is from 6 to 50, most preferably from 6 to 50.
35 is good. The alkali metal hexametaphosphate specifically includes sodium hexametaphosphate and potassium hexametaphosphate. These may be an anhydride, a hydrated compound or an aqueous solution, and their state and form are not particularly limited. Further, other than the alkali metal salt of hexametaphosphate, for example, an alkaline earth metal salt of hexametaphosphate is low in solubility, and the effect of the liquid stability is hardly expected.

【0031】ヘキサメタ燐酸アルカリ金属塩(e)の量
は主剤液中のNa2Oの2〜20モル%相当分を中和す
る事が出来る量である。このモル%は(e)の1モルが
主剤中のNa2Oの1モルを消費するとみなして算出さ
れ、以下同様である。2モル%相当分を中和する事が出
来る量未満では、冬場薬液安定性が確保されず、20モ
ル%相当分を中和する事が出来る量を越えると、系の粘
度が上がりすぎて浸透注入効率を低下させる、価格的に
不利となる、低下懸案の浸透性不良やゲル化遅延を一層
促進する等の傾向にある。さらには、以下に述べるヘキ
サメタ燐酸アルカリ金属塩(e)をあらかじめグリオキ
ザール(c)溶液中に混和させておくという硬化剤の調
製方法において、(e)の量をこの範囲とすると、比較
的(c)と(e)を混和させ易い。(e)の使用割合は
この範囲内であれば経済的に優位に目的を達成できる。
また、ヘキサメタ燐酸アルカリ金属塩(e)の硬化剤中
へのおおよその配合量は特に制限するものではないが、
通常硬化剤液総量200リットル当り1〜30kg、好
ましくは5〜20kg、より好ましくは5〜15kgで
ある。
The amount of the alkali metal hexametaphosphate (e) is such that 2 to 20 mol% of Na 2 O in the base solution can be neutralized. This mol% is calculated assuming that 1 mol of (e) consumes 1 mol of Na 2 O in the main agent, and so on. If the amount is less than 2 mol%, the stability of the drug solution in winter is not secured. If the amount is more than 20 mol%, the viscosity of the system is too high to penetrate. There is a tendency to lower the injection efficiency, to be disadvantageous in terms of price, to further promote poor permeability and gelation delay that are pending, and the like. Further, in the method for preparing a curing agent in which the alkali metal hexametaphosphate (e) described below is previously mixed in a glyoxal (c) solution, when the amount of (e) is within this range, (c) ) And (e) are easily mixed. If the use ratio of (e) is within this range, the objective can be achieved economically.
Further, the approximate blending amount of the alkali metal hexametaphosphate (e) in the curing agent is not particularly limited,
Usually, the amount is 1 to 30 kg, preferably 5 to 20 kg, more preferably 5 to 15 kg per 200 liters of the total amount of the curing agent liquid.

【0032】本発明の硬化剤を調製するに当たっては、
硬化剤成分(c)(d)(e)をそれぞれ所定量別々に
計量し、同時に配合してもよいが、事前にグリオキザー
ル(c)とヘキサメタ燐酸アルカリ金属塩(e)を混和
させておき、現場でさらに燐酸(c)と配合して使用す
ると、計量作業の繁雑さを軽減出来、またグリオキザー
ル自体の溶液安定性が一層確保されるなどの効果が期待
されることから、好ましい調製方法である。その結果、
本発明の土質安定化剤は冬場の、例えば5℃±3℃の低
温下で1ショット注入液とするいわゆる1液組成物とし
て現場調製することが容易であり、該現場で取扱う際の
経時溶液安定性がきわめて優れるという特徴を持つ。
In preparing the curing agent of the present invention,
The curing agent components (c), (d), and (e) may be separately measured in predetermined amounts, and may be mixed at the same time. However, glyoxal (c) and alkali metal hexametaphosphate (e) are mixed in advance, It is a preferable preparation method when it is used in combination with phosphoric acid (c) on the spot because it is expected to have an effect of reducing the complexity of the weighing operation and further securing the solution stability of glyoxal itself. . as a result,
The soil stabilizing agent of the present invention can be easily prepared on site as a so-called one-part composition that is used as a one-shot injection solution in winter, for example, at a low temperature of 5 ° C. ± 3 ° C. It has the feature of being extremely stable.

【0033】本発明の硬化剤には、更に本発明の薬液安
定性をより一層図る目的など、必要に応じて、他に水酸
化マグネシウム錯化合物、水溶性第二鉄錯化合物、糖、
尿素またはその水溶性誘導体、蛋白質、水溶性セルロー
ス化合物等を適宜併用してよい。これらの中で好ましく
は糖、尿素またはその水溶性誘導体である。また毒性が
強いことを問題にしない場合等では水溶性銅錯化合物、
水溶性錫鉛錯化合物、水溶性カドミウム錯化合物等の水
溶性の遷移金属錯錯化合物を併用してもよい。またさら
に価格的に問題はあるものの、水溶性の銀錯化合物や水
溶性白金錯化合物類も同様に併用できる。糖としては、
単糖類、二糖類、三糖類、多糖類等が例示でき、その中
で好ましくは燐酸塩との包接化合物または錯化合物を形
成可能なものである。水溶性の尿素誘導体としては、モ
ノメチロール尿素、ジメチロール尿素、チオ尿素、モノ
メチロールチオ尿素、ジメチロールチオ尿素が例示で
き、燐酸塩との錯化合物を形成可能な化合物が好まし
い。これらの使用量は、通常薬液総量200リットル当
たり水溶性マグネシウム錯化合物や水溶性第二鉄錯化合
物では0.01〜3モル、糖類では0.01〜5kg、
尿素または水溶性誘導体では0.01〜10kgとなる
ような量である。
The curing agent of the present invention may further contain a magnesium hydroxide complex compound, a water-soluble ferric complex compound, a saccharide, and the like, if necessary, for the purpose of further improving the stability of the chemical solution of the present invention.
Urea or a water-soluble derivative thereof, a protein, a water-soluble cellulose compound or the like may be appropriately used in combination. Among them, sugar, urea or a water-soluble derivative thereof is preferable. In cases where the toxicity is not a problem, a water-soluble copper complex compound,
A water-soluble transition metal complex compound such as a water-soluble tin-lead complex compound and a water-soluble cadmium complex compound may be used in combination. Further, although there is a problem in terms of cost, a water-soluble silver complex compound or a water-soluble platinum complex compound can be used in the same manner. As sugar,
Monosaccharides, disaccharides, trisaccharides, polysaccharides and the like can be exemplified, and among them, those capable of forming an inclusion compound or a complex compound with a phosphate are preferable. Examples of the water-soluble urea derivative include monomethylol urea, dimethylol urea, thiourea, monomethylol thiourea, and dimethylol thiourea, and a compound capable of forming a complex compound with phosphate is preferable. These amounts are usually 0.01 to 3 moles for water-soluble magnesium complex compound and water-soluble ferric complex compound per 200 liter total chemical solution, 0.01 to 5 kg for sugars,
For urea or water-soluble derivatives, the amount is 0.01 to 10 kg.

【0034】その他に本発明の硬化剤には必要に応じて
水溶性有機脂肪酸を主剤液のNa2Oの0.01〜5モ
ル%相当量を中和できる範囲で使用してもよい。有機脂
肪酸としては、例えば蟻酸、酢酸、グリコール酸、グリ
オキシル酸、乳酸、リンゴ酸、イタコン酸、コハク酸等
が好ましい。有機脂肪酸を少量併用すると薬液のゲルタ
イムの温度依存性が極めて少なくなる等の効果がある。
In addition, if necessary, a water-soluble organic fatty acid may be used in the curing agent of the present invention within a range capable of neutralizing an equivalent of 0.01 to 5 mol% of Na 2 O in the base solution. As the organic fatty acid, for example, formic acid, acetic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, itaconic acid, succinic acid and the like are preferable. When a small amount of an organic fatty acid is used in combination, there is an effect that the temperature dependency of the gel time of the drug solution is extremely reduced.

【0035】本発明の土質安定化剤は、主剤液と硬化剤
液とを容積比で1:0.9〜0.9:1の範囲、好まし
くは1:1により近似させて混合する。その結果、冬場
の現場に即した液安定性が確保された、実用性のあるホ
モゲル強度を呈する経時安定性と一定したゲル化挙動と
を兼ね備えた組成物となる。
The soil stabilizer of the present invention is prepared by mixing the base liquid and the hardener liquid in a volume ratio of 1: 0.9 to 0.9: 1, preferably 1: 1. As a result, a composition is obtained that has a stable stability over time exhibiting practical homogel strength and a constant gelation behavior, while ensuring liquid stability suitable for the field in winter.

【0036】本発明の土質安定化剤を1液・1ショット
方式で取り扱う際は、主剤と硬化剤は地盤に注入を開始
する数分前、例えば3〜8分前に混合することが好まし
い。しかし、1.5ショット方式または2ショット方式
等で地盤に注入する地盤改良工法では2液を送液すると
同時に最終的に混合され注入されるのでこの限りではな
い。また本発明の土質安定化剤を調製する際に使用され
る水は、例えば、河川水、湖水、湧水、地下水、水道
水、海水、蒸留水、イオン交換水、氷水、雪水、雨水な
どであって良く、特に限定は無い。
When the soil stabilizer of the present invention is handled in a one-liquid / one-shot system, it is preferable that the main agent and the hardener are mixed several minutes before the start of injection into the ground, for example, 3 to 8 minutes. However, in the ground improvement method of injecting into the ground by the 1.5 shot method, the 2 shot method, or the like, the two liquids are simultaneously sent and finally mixed and injected. The water used for preparing the soil stabilizer of the present invention includes, for example, river water, lake water, spring water, groundwater, tap water, seawater, distilled water, ion-exchanged water, ice water, snow water, rainwater, and the like. And there is no particular limitation.

【0037】本発明の土質安定化剤を用いる土質安定化
方法は、ゲルタイムに応じて両者を混合し、1液1系統
式で地盤注入固結させるいわゆる1ショット方式、2液
1系統式で地盤注入固結させるいわゆる1.5ショット
方式、2液2系統式で地盤注入固結させるいわゆる2シ
ョット方式で行ないうる。特に本発明の土質安定化剤の
特徴を生かした経済的な方法としては、1ショット方式
が適当な例としてあげられる。本発明の土質安定化剤
は、現場の1ショット配合注入装置の稼働時のゲル化前
の溶液安定性と安定したゲル化特性が確保される他、極
めて顕著な止水性能、強固な実用性の高い地盤強度確保
がされる等の特徴も有する。
The soil stabilization method using the soil stabilizing agent of the present invention is a so-called one-shot method and a two-liquid one-system method in which the two are mixed according to the gel time, and the ground is solidified and solidified in a one-liquid system. A so-called two-shot method of injecting and consolidating the ground by a so-called 1.5 shot method and a two-liquid two-system method can be used. In particular, as an economical method utilizing the characteristics of the soil stabilizer of the present invention, a one-shot method is a suitable example. The soil stabilizing agent of the present invention not only ensures the solution stability before gelation and the stable gelling property during the operation of the one-shot compounding / injection device on site, but also has extremely remarkable water stopping performance and strong practicality. It also has features such as ensuring high ground strength.

【0038】本発明の作用について以下に考察するが、
仮に以下の推定が事実と異なっていたとしても本発明に
何等影響を及ぼすものではない。後述の比較例1で生成
した沈殿をロ紙でロ過分別した後、メタノール−水1:
1の混合液にて水洗浄して精製沈殿物を得た。この沈殿
物に関してはNa元素の含有量として15.3%、Si
元素含有量が5.2%、P元素含有量が7.22%、結
晶水として50〜52%と定量分析された。この結果と
赤外吸収スペクトルの測定結果より、第2燐酸ナトリウ
ム12水塩と第3燐酸ナトリウム12水塩及び少量の水
ガラスゲルを内包する複塩結晶構造体である可能性がき
わめて高いと考えられた。おおよそ第2燐酸ナトリウム
12水塩として55〜65%、第3燐酸ナトリウム12
水塩として15%前後、水ガラス珪酸水和物として5〜
15%の複塩沈殿と推定された。
The operation of the present invention will be discussed below.
Even if the following presumption is different from the fact, it has no effect on the present invention. After the precipitate formed in Comparative Example 1 to be described below was subjected to filtration through a paper filter, methanol-water 1:
The mixture was washed with water to obtain a purified precipitate. Regarding this precipitate, the content of Na element is 15.3%,
Quantitative analysis was performed with an element content of 5.2%, a P element content of 7.22%, and crystallization water of 50 to 52%. From this result and the measurement result of the infrared absorption spectrum, it is considered that the possibility of the double salt crystal structure containing sodium dibasic phosphate dodecahydrate, sodium tertiary phosphate dodecahydrate and a small amount of water glass gel is extremely high. Was. Approximately 55 to 65% as sodium diphosphate 12 hydrate, sodium tertiary phosphate 12
About 15% as water salt, 5 to 5 as water glass silicic acid hydrate
Estimated to be 15% double salt precipitate.

【0039】一方、燐酸の中和曲線は第1変曲点がpH
値で4〜6にあり、第2変曲点がpH値で9〜10に在
ることが知られている。その事と、後述の実施例2また
は比較例1のおのおのの土質安定化剤の溶液pH値は概
略10.8と言う事が出来、したがって各液中には燐酸
の使用量に応じた第2燐酸ナトリウム・12水塩ないし
少割合の第3燐酸ナトリウム・12水塩の生成が理論付
けされる。
On the other hand, the neutralization curve of phosphoric acid has a first inflection point at pH
It is known that the pH value is between 4 and 6, and the second inflection point is between 9 and 10 in terms of pH value. In addition, it can be said that the pH value of the solution of the soil stabilizer in each of Example 2 and Comparative Example 1 described later is approximately 10.8. The formation of sodium phosphate dodecahydrate or a small proportion of tertiary sodium phosphate dodecahydrate is theorized.

【0040】日本化学会発行編者、昭和59年6月25
日発行の化学便覧基礎編・改定3版のII−173に、第
2燐酸ナトリウム・12水和物の水100gに対する飽
和溶解度が記載されており、その値は0℃で1.58
g、10℃で3.48g、20℃で7.15gとされ
る。すなわち、該第2燐酸塩は0℃で0.04モル/L
が飽和濃度と算出でき、5℃では0.06モル/L、1
0℃では0.09モル/Lが飽和濃度であることが判
る。
The editor of the Chemical Society of Japan, June 25, 1984
II-173 of the 3rd Handbook of Chemical Handbook, Revised 3rd Edition, describes the saturated solubility of sodium diphosphate didecahydrate in 100 g of water, and the value is 1.58 at 0 ° C.
g at 10.degree. C. and 3.15 g at 20.degree. That is, the second phosphate is 0.04 mol / L at 0 ° C.
Can be calculated as the saturation concentration, and at 5 ° C., 0.06 mol / L, 1
At 0 ° C., 0.09 mol / L is found to be the saturation concentration.

【0041】ところで後述の実施例2、比較例1ではそ
の燐酸の使用量から、100%の確率で該第2燐酸塩水
和物が生成すると仮定するとおおよそ0.18モル/L
(5℃)の存在濃度と算出され、前記公知の値の3倍に
相当し、かなりの過飽和系である事が判る。また50%
の確率で該第2燐酸塩水和物が生成すると仮定するとお
およそ0.09モル/L(5℃)の存在濃度と算出さ
れ、前記公知の値の1.5倍に相当し、やはり過飽和系
が成立している事が判る。これらの計算結果と沈殿物の
成分の特定結果とを合せると、特開昭51−4815号
に開示された土質安定化処方に於ける冬場の液安定性の
問題がきわめて明瞭になる。
By the way, in Example 2 and Comparative Example 1 described later, it is assumed that the second phosphate hydrate is formed at a probability of 100% from the amount of the phosphoric acid used, which is approximately 0.18 mol / L.
(5 ° C.), which is equivalent to three times the known value, indicating that the system is considerably supersaturated. Also 50%
Assuming that the second phosphate hydrate is formed with the probability of, the calculated concentration is approximately 0.09 mol / L (5 ° C.), which corresponds to 1.5 times the known value. You can see that it holds. When these calculation results are combined with the results of specifying the components of the sediment, the problem of liquid stability in winter in the soil stabilization formulation disclosed in JP-A-51-4815 becomes very clear.

【0042】本発明の土質安定化剤は、この問題の原因
と考えられる燐酸ナトリウム塩複塩結晶の析出を何等か
の作用効果で抑制しており、結果として、低温下の該薬
液の過飽和状態をゲル化するまでの時間内安定化してい
ることが明らかである。その理由はヘキサメタ燐酸アル
カリ金属塩が硬化促進硬化と共に優れた過飽和安定剤と
して働いていると考えられ、それらの相乗効果と推察さ
れる。一方、後述の比較例1の土質安定化剤では過飽和
系が加えられた攪伴刺激で崩れ微細な結晶核の生成と共
に経時で肥大化し、ついには過飽和分の結晶を大量に系
中に析出させていると判断出来る。この様にしてみると
本発明の効果は明らかであり、特定された第3成分とそ
の特定された使用量によって本発明の目的が達成される
事が判る。
The soil stabilizer of the present invention suppresses the precipitation of sodium phosphate double salt crystals, which is considered to be the cause of this problem, by any effect, and as a result, the chemical solution in a supersaturated state at low temperature It is clear that was stabilized within the time until gelation. The reason is considered to be that the alkali metal hexametaphosphate works as an excellent supersaturation stabilizer together with the accelerated curing, which is presumed to be a synergistic effect thereof. On the other hand, in the soil stabilizer of Comparative Example 1 to be described later, the supersaturated system collapses due to the added stimulus to generate fine crystal nuclei and enlarges over time, and finally a large amount of supersaturated crystals precipitate in the system. Can be determined to be. The effect of the present invention is apparent from this, and it can be seen that the object of the present invention can be achieved by the specified third component and the specified use amount.

【0043】[0043]

【実施例】以下に本発明の実施例および比較例を示す
が、本発明はこれらによって限定されない。また、%、
部とは特記する以外はそれぞれ重量%、重量部を意味す
る。また、以下の記載・表中のLの記号は容積単位でリ
ットルの意味で使用する。また各例に於ける土質安定化
剤の評価は、次の方法で行なった。
EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. Also,%,
Parts mean parts by weight and parts by weight, respectively, unless otherwise specified. The symbol L in the following description and tables is used in units of volume in liters. The evaluation of the soil stabilizer in each example was performed by the following method.

【0044】[ゲルタイム測定方法]主剤液と硬化剤液
とを混合均一化した時間を基点とし、調製された混合液
の静置状態から90度傾斜させた時に流動性が失われて
流出しなくなるまでの時点までの経過時間で計測して表
示した。
[Measurement method of gel time] Based on the time when the main liquid and the hardener liquid are mixed and homogenized, when the prepared liquid mixture is inclined by 90 degrees from the stationary state, the fluidity is lost and the liquid does not flow out. The elapsed time up to the time was measured and displayed.

【0045】[低温作業・液安定性試験方法]内容量2
00mlの円筒形ビーカーを2ケ用意し、5℃に調整さ
れた恒温水槽中にセットし、その内の1ケに半径2.5
cmのタービン型またはスクリュー型攪拌棒をビーカー
内の液を連続攪拌できる位置にセットする。もうひとつ
のビーカーは静置するのみの条件で使用する。セット完
了後、予め3℃にそれぞれ調温した主剤と硬化剤の各液
をすばやく混合して後、その150mlづつを各ビーカ
ー中に注いで、一方は連続攪拌下に、もう一方は無刺激
下で放置した。
[Test method for low-temperature work / liquid stability] Content 2
Prepare two 00 ml cylindrical beakers, set them in a thermostatic water bath adjusted to 5 ° C., and place one of them in a 2.5 cm radius.
cm of a turbine-type or screw-type stirring rod is set at a position where the liquid in the beaker can be continuously stirred. The other beaker is used only for standing. After the setting is completed, each liquid of the base agent and the curing agent, each of which has been previously adjusted to 3 ° C., is quickly mixed, and then 150 ml of the mixture is poured into each beaker, one under continuous stirring and the other under non-irritating. Left.

【0046】攪拌は線速度で60m/秒速の剪断抵抗を
連続的に加える条件下を選定した。前記方法でゲル化す
るまでの時間と系の状態を観察し、低温作業性を判断し
た。攪拌下したビーカー内でゲル化せず、系内が著しく
白濁した場合を×の記号で表示し、極く少量の析出が見
られるものの静置ビーカー内液とほぼ同様なゲル化が観
察された場合を○の記号で、全く正常なゲル化挙動をそ
の2つのビーカー試験で得た場合を◎の記号で表示し
た。
For the stirring, conditions were selected in which a shear resistance of 60 m / sec at a linear speed was continuously applied. The time until gelation by the above method and the state of the system were observed, and the low-temperature workability was determined. The gel was not gelled in the stirred beaker, and the case where the inside of the system became extremely cloudy was indicated by a symbol x, and although a very small amount of precipitation was observed, almost the same gelation as the liquid in the standing beaker was observed. The case was indicated by the symbol ○, and the case where completely normal gelation behavior was obtained by the two beaker tests was indicated by the symbol ◎.

【0047】[地盤注入簡易試験]前記の低温作業液安
定性試験と同様にして調製した20〜25分経過後のゲ
ル化前の土質安定化剤液を採り、150メッシュのステ
ンレス製ロ布でその液をロ過する方法で、注入管先端部
の注入ノズル詰める問題が発生しないかの判定をおこな
った。ロ布に沈殿が残る場合はノズルを詰めやすいと判
定し、記号×と表示した。全くロ布に沈殿が認められな
い場合をノズルを詰めないとして記号○で表示した。
[Simplified Ground Injection Test] Take the soil stabilizer solution before gelation after elapse of 20 to 25 minutes prepared in the same manner as the low temperature working fluid stability test, and use a 150 mesh stainless steel cloth. It was determined whether or not the problem of clogging the injection nozzle at the tip of the injection pipe by the method of filtering the liquid occurred. When sediment remains on the cloth, it was judged that the nozzle was easy to be packed, and the symbol x was displayed. The case where no sediment was observed on the cloth was indicated by the symbol と し て as not filling the nozzle.

【0048】[圧縮強度]成分を均一に混合してなる土
質安定化剤をゲル化前に50mmφ×100mmHの型
枠に注ぎ込み、ゲル化させて、そのまま水分の気散を防
止して一定期間養生させて後、脱型し、アームスラー型
強度試験機を用いてホモゲルの一軸圧縮強度を測定し
た。
[Compressive strength] A soil stabilizer prepared by uniformly mixing the components is poured into a mold of 50 mmφ × 100 mmH before gelling, and gelling is performed. Thereafter, the mold was demolded, and the uniaxial compressive strength of the homogel was measured using an arm slur type strength tester.

【0049】調製例1 [実施例の主剤a−1液]JIS3号珪酸ソーダ原液
(SiO2分濃度29.8重量%、Na2O分濃度9.1
5重量%、SiO2/Na2Oモル比が3.16)の1L
と水道水1Lとを混合してSiO2/Na2Oモル比が
3.16、SiO2とNa2O分の総量が22.77%
(5.35%のNa2O含有量、17.42%のSiO2
含有量)の番号(a−1)の珪酸ソーダ水溶液2Lとし
た。
Preparation Example 1 [Main agent a-1 solution of the example] JIS No. 3 sodium silicate stock solution (SiO 2 concentration: 29.8% by weight, Na 2 O concentration: 9.1)
1 L of 5% by weight and a SiO 2 / Na 2 O molar ratio of 3.16)
And 1 L of tap water, the molar ratio of SiO 2 / Na 2 O is 3.16, and the total amount of SiO 2 and Na 2 O is 22.77%
(5.35% Na 2 O content, 17.42% SiO 2
2 L of an aqueous solution of sodium silicate having the content (a-1).

【0050】調製例2 [実施例の主剤a−2液]JIS3号珪酸ソーダ原液
(SiO2分濃度29.8重量%、Na2O分濃度9.1
5重量%、SiO2/Na2Oモル比が3.16)の1.
4Lと水道水0.6Lとを混合してSiO2/Na2Oモ
ル比が3.16、SiO2とNa2O分の総量が30.5
3%(7.02%のNa2O含有量)の番号(a−2)
の珪酸ソーダ水溶液2Lとした。
Preparation Example 2 [Main Agent a-2 Solution of Example] JIS No. 3 sodium silicate stock solution (SiO 2 concentration: 29.8% by weight, Na 2 O content: 9.1)
5% by weight, and the SiO 2 / Na 2 O molar ratio is 3.16).
4 L and 0.6 L of tap water were mixed to give a SiO 2 / Na 2 O molar ratio of 3.16 and a total amount of SiO 2 and Na 2 O of 30.5.
3% (7.02% Na 2 O content) number (a-2)
2 L of an aqueous sodium silicate solution.

【0051】調製例3 [実施例の主剤a−3液]市販2号珪酸ソーダ原液(S
iO2分濃度35.90重量%、Na2O分濃度14.0
5重量%、SiO2/Na2Oモル比が2.50)の1.
5Lと水道水0.5Lとを混合してSiO2/Na2Oモ
ル比が2.50、SiO2とNa2O分の総量が41.3
8%(11.64%のNa2O含有量、29.74%の
SiO2含有量)の番号(a−3)の珪酸ソーダ水溶液
2Lとした。
Preparation Example 3 [Main agent a-3 solution of Example] Commercially available No. 2 sodium silicate stock solution (S
iO 2 concentration 35.90% by weight, Na 2 O concentration 14.0
5% by weight, and the SiO 2 / Na 2 O molar ratio is 2.50).
5 L and 0.5 L of tap water are mixed to give a SiO 2 / Na 2 O molar ratio of 2.50 and a total amount of SiO 2 and Na 2 O of 41.3.
2 L of an aqueous sodium silicate solution having a number (a-3) of 8% (11.64% Na 2 O content, 29.74% SiO 2 content) was used.

【0052】調製例4 [実施例の主剤b−1液]JIS3号珪酸ソーダ原液
(SiO2分濃度29.8重量%、Na2O分濃度9.1
5重量%、SiO2/Na2Oモル比が3.16)の1L
と表1の番号(S−1)で示されたS−1コロイダルシ
リカ溶液(SiO2分濃度29.8重量%、Na2O分濃
度0.55重量%、SiO2/Na2Oモル比が52.
5、粒子径が12nm、比重1.23)の0.2Lと水
道水0.8Lとを混合して、該混合液中のSiO2/N
2Oモル比が4.33、SiO2とNa2O分の総量が
27.61%(5.32%のNa2O含有量)の番号
(b−1)の珪酸ソーダ水溶液2Lとした。
Preparation Example 4 [Main agent b-1 solution of Example] JIS No. 3 sodium silicate stock solution (SiO 2 concentration: 29.8% by weight, Na 2 O concentration: 9.1)
1 L of 5% by weight and a SiO 2 / Na 2 O molar ratio of 3.16)
And the S-1 colloidal silica solution indicated by the number (S-1) in Table 1 (SiO 2 concentration: 29.8% by weight, Na 2 O content: 0.55% by weight, SiO 2 / Na 2 O molar ratio) Is 52.
5, 0.2 L of a particle diameter of 12 nm and a specific gravity of 1.23) is mixed with 0.8 L of tap water, and SiO 2 / N in the mixed solution is mixed.
A 2 O aqueous sodium silicate solution having a molar ratio of a 2 O of 4.33 and a total amount of SiO 2 and Na 2 O of 27.61% (Na 2 O content of 5.32%) of number (b-1) was used. .

【0053】調製例5 [実施例の主剤b−2液]市販4号珪酸ソーダ原液(S
iO2分濃度24.55重量%、Na2O分濃度6.67
重量%、SiO2/Na2Oモル比が3.57)の1Lと
表1の番号(S−1)で示されたS−1コロイダルシリ
カ溶液(SiO2分濃度29.8重量%、Na2O分濃度
0.55重量%、SiO2/Na2Oモル比が52.5、
粒子径が12nm、比重1.23)の0.2Lと市水
0.8Lとを混合して、該混合液中のSiO2/Na2
モル比が11.5、SiO2とNa2O分の総量が20.
4%(3.7%のNa2O含有量)の番号(b−2)の
珪酸ソーダ水溶液2Lとした。
Preparation Example 5 [Main solution b-2 of Example] Commercially available sodium 4 silicate stock solution (S
iO 2 concentration 24.55% by weight, Na 2 O concentration 6.67
Wt., 1 L of SiO 2 / Na 2 O molar ratio of 3.57) and S-1 colloidal silica solution indicated by the number (S-1) in Table 1 (SiO 2 concentration: 29.8 wt%, Na 2 O concentration 0.55 wt%, SiO 2 / Na 2 O molar ratio of 52.5,
A mixture of 0.2 L having a particle diameter of 12 nm and a specific gravity of 1.23) and 0.8 L of city water was mixed with SiO 2 / Na 2 O in the mixture.
The molar ratio is 11.5, and the total amount of SiO 2 and Na 2 O is 20.
2 L of an aqueous sodium silicate solution having the number (b-2) of 4% (3.7% Na 2 O content) was used.

【0054】調製例6 [実施例の主剤a−4液]JIS3号珪酸ソーダ原液
(SiO2分濃度29.8重量%、Na2O分濃度9.1
5重量%、SiO2/Na2Oモル比が3.16)の1.
2Lと水道水0.8Lとを混合してSiO2/Na2Oモ
ル比が3.16、SiO2とNa2O分の総量が23.3
7%(5.49%のNa2O含有量)の番号(a−4)
の珪酸ソーダ水溶液2Lとした。表1に前記実施例の主
剤液(a−1)〜(a−4)、(b−1)〜(b−2)
の各組成を纏めて表示した。
Preparation Example 6 [Main agent a-4 in Example] JIS No. 3 sodium silicate stock solution (SiO 2 concentration: 29.8% by weight, Na 2 O concentration: 9.1)
5% by weight, and the SiO 2 / Na 2 O molar ratio is 3.16).
2 L and 0.8 L of tap water were mixed to give a SiO 2 / Na 2 O molar ratio of 3.16 and a total amount of SiO 2 and Na 2 O of 23.3.
7% (5.49% Na 2 O content) number (a-4)
2 L of an aqueous sodium silicate solution. Table 1 shows the base liquids (a-1) to (a-4) and (b-1) to (b-2) of the above examples.
Are collectively displayed.

【0055】比較調製例1 [比較例の主剤液a1]JIS3号珪酸ソーダ溶液(S
iO2分濃度29.8重量%、Na2O分濃度9.15重
量%、SiO2/Na2Oモル比が3.16)の0.2L
と水道水1.8Lとを混合してSiO2/Na2Oモル比
が3.16、SiO2とNa2O分の総量が5.27%
(1.24%のNa2O含有量、4.03%のSiO2
有量)の番号(a1)の珪酸ソーダ水溶液2Lとした。
Comparative Preparation Example 1 [Main agent liquid a1 of Comparative example] JIS No. 3 sodium silicate solution (S
0.2 L having an iO 2 concentration of 29.8% by weight, a Na 2 O concentration of 9.15% by weight, and a SiO 2 / Na 2 O molar ratio of 3.16)
And 1.8 L of tap water are mixed to give a SiO 2 / Na 2 O molar ratio of 3.16 and a total amount of SiO 2 and Na 2 O of 5.27%
It was sodium silicate aqueous solution 2L number (a1) of (1.24% of the content of Na 2 O, SiO 2 content of 4.03%).

【0056】比較調製例2 [比較例の主剤液b1]S−2コロイダルシリカ溶液
(SiO2分濃度49.9重量%、Na2O分濃度0.7
1重量%、SiO2/Na2Oモル比が70.3、粒子径
が15nm、比重1.34)そのものをあてた。表2に
前記比較例の主剤液(a1)、(b1)の各組成を纏め
て表示した。
Comparative Preparation Example 2 [Base solution b1 of Comparative example] S-2 colloidal silica solution (SiO 2 concentration: 49.9% by weight, Na 2 O concentration: 0.7)
1% by weight, a SiO 2 / Na 2 O molar ratio of 70.3, a particle diameter of 15 nm, and a specific gravity of 1.34) were applied. Table 2 shows the respective compositions of the main agent liquids (a1) and (b1) of the comparative example.

【0057】[0057]

【表1】 [Table 1]

【0058】[0058]

【表2】 [Table 2]

【0059】実施例1 主剤として表1記載の(a−1)溶液を選択しその10
0mlと、74%粗燐酸の3mlと34%グリオキザー
ルの3mlと更に重合度6のヘキサメタ燐酸ナトリウム
の1.5部および水道水の94部とから成る硬化剤液1
00mlとを、それぞれ3.5℃で混合均一化した。主
剤中のアルカリ分の中和理論算出%は、各硬化剤成分毎
に、燐酸分で35.5%、グリオキザールで11%、ヘ
キサメタ燐酸アルカリ金属塩で2.3%と算出される。
混合2分後の液温度は5℃を示した。
Example 1 A solution (a-1) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 74% crude phosphoric acid, 3 ml of 34% glyoxal, 1.5 parts of sodium hexametaphosphate having a polymerization degree of 6 and 94 parts of tap water 1
00 ml at 3.5 ° C. and homogenized. The theoretical calculation% of neutralization of alkali in the base agent is calculated as 35.5% for phosphoric acid, 11% for glyoxal, and 2.3% for alkali metal hexametaphosphate for each curing agent component.
The liquid temperature after mixing for 2 minutes was 5 ° C.

【0060】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが32〜
35分で正常ゲル化し、沈殿生成はいずれも全く観察さ
れなかった。従って低温作業・液安定性試験の判定結果
は◎であった。上記低温作業・液安定性試験と同様にし
て行なった、攪拌法/20分経過後の5℃液を用いて行
なった、簡易地盤注入試験の結果は○であり、低温現場
作業性が確保されている事が判明した。
As a result of the low-temperature work / liquid stability test, the drug measured by the stationary method and the continuous stirring method has a gel time of 32 to
It gelled normally in 35 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the low-temperature work / liquid stability test was ◎. The result of the simple ground injection test, which was performed in the same manner as the low-temperature work / liquid stability test described above and performed using the stirring method / 5 ° C. liquid after elapse of 20 minutes, was ○, and low-temperature on-site workability was secured. It turned out that.

【0061】なお、室温20℃のゲルタイムは静置法で
おおよそ24〜25分であった。またその固結したホモ
ゲルの1軸圧縮強度は5日室温養生品で0.35kgf/c
m2でゲル収縮率が7.9vol%と測定された。また本
土質安定化剤を豊浦標準砂に隙間充填率97%となる様
に砂と配合して固結させたサンドゲルの5日室温養生ゲ
ルの1軸圧縮強度は、3.89kgf/cm2と高強度を示し
た。
The gel time at room temperature of 20 ° C. was about 24 to 25 minutes by the static method. The uniaxial compressive strength of the consolidated homogel was 0.35 kgf / c for 5 days at room temperature.
Gel shrinkage was measured to 7.9Vol% in m 2. The uniaxial compressive strength of a 5-day room temperature cured gel of a sand gel obtained by blending the soil stabilizer with Toyoura standard sand and sand so as to have a gap filling rate of 97% is 3.89 kgf / cm 2 . It showed high strength.

【0062】実施例2 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、75%精製燐酸の3mlと34%グリオキザ
ールの5.25mlと更に重合度6のヘキサメタ燐酸ナ
トリウムの2部および水道水の91部とから成る硬化剤
液100mlとを、それぞれ3.5℃で混合均一化し
た。主剤中のアルカリ分の中和理論算出%は、各硬化剤
成分毎に、燐酸分で24.1%、グリオキザールで14
%、ヘキサメタ燐酸アルカリ金属塩で2.2%と算出さ
れる。混合2分後の液温度は5℃を示し、混合溶液の初
期pH値は10.77であった。
Example 2 A solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 75% purified phosphoric acid, 5.25 ml of 34% glyoxal, 2 parts of sodium hexametaphosphate having a degree of polymerization of 6 and 100 ml of a curing agent liquid consisting of 91 parts of tap water, each at 3.5 ° C. And homogenized. The theoretical calculation% of the neutralization of the alkali in the base agent is 24.1% for phosphoric acid and 14% for glyoxal for each curing agent component.
%, And 2.2% in terms of alkali metal hexametaphosphate. The liquid temperature after 2 minutes of mixing showed 5 ° C., and the initial pH value of the mixed solution was 10.77.

【0063】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが29〜
31分で正常ゲル化し、沈殿生成はいずれも全く観察さ
れなかった。従って該低温作業・液安定性試験の判定結
果は◎であった。上記低温作業・液安定性試験と同様に
して行なった本薬液は、攪拌法/18分経過後の5℃液
を用いて行なった簡易地盤注入試験の結果は○であり、
低温現場作業性が確保されている事が判明した。
As a result of the low-temperature work / liquid stability test, the drug measured by the stationary method and the continuous stirring method has a gel time of 29 to
It gelled normally in 31 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the low temperature work / liquid stability test was ◎. This drug solution, which was performed in the same manner as in the low-temperature work / liquid stability test, showed a result of a simple ground injection test performed using a stirring method / 5 ° C. liquid after 18 minutes, of ○,
It turned out that low-temperature workability was secured.

【0064】なお、実施例2の薬液の液温20℃のゲル
タイムは静置法でおおよそ29〜30分であった。また
そのホモゲルの1軸圧縮強度は5日室温養生品で1.4
3kgf/cm2でゲル収縮率が16.9vol%と測定され
た。また本土質安定化剤を豊浦標準砂に隙間充填率97
%となる様に砂と配合して固結させたサンドゲルの5日
室温養生ゲルの1軸圧縮強度は、7.51kgf/cm2と高
強度を示した。
The gel time of the liquid medicine of Example 2 at a liquid temperature of 20 ° C. was about 29 to 30 minutes by the static method. The homogel has a uniaxial compressive strength of 1.4 at room temperature after 5 days.
At 3 kgf / cm 2 , the gel shrinkage was determined to be 16.9 vol%. In addition, the soil filling agent was filled with a gap filling rate of 97 to Toyoura standard sand.
%, And the unconfined compressive strength of the 5-day room temperature cured gel of the sand gel mixed with sand and consolidated was as high as 7.51 kgf / cm 2 .

【0065】実施例3 実施例2に於いて使用した、34%グリオキザールの
5.25mlと更に重合度6のヘキサメタ燐酸ナトリウ
ムの2部を、事前に1週間前にブレンド保存して使用し
た以外は全く同様にして行なった結果、実施例2と同様
な作業適性及びゲル化性が観察された。
Example 3 Except that 5.25 ml of 34% glyoxal and 2 parts of sodium hexametaphosphate having a degree of polymerization of 6 used in Example 2 were previously blended and stored one week before use. As a result, the same workability and gelling property as in Example 2 were observed.

【0066】実施例4 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、75%精製燐酸の3mlと34%グリオキザ
ールの5.25mlと更に重合度33のヘキサメタ燐酸
ナトリウムの6部および水道水の88部とから成る硬化
剤液100mlとを、それぞれ3.5℃で混合均一化し
た。主剤中のアルカリ分の中和理論算出%は、各硬化剤
成分毎に、以下燐酸分で24.1%、グリオキザールで
14%、ヘキサメタ燐酸アルカリ金属塩で1.2%と算
出される。混合2分後の液温度は5℃を示した。
Example 4 A solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 75% purified phosphoric acid, 5.25 ml of 34% glyoxal, 6 parts of sodium hexametaphosphate having a degree of polymerization of 33, and 100 ml of a curing agent liquid consisting of 88 parts of tap water at 3.5 ° C. And homogenized. The theoretical calculation percentage of neutralization of alkali in the base agent is calculated as follows: 24.1% for phosphoric acid, 14% for glyoxal, and 1.2% for alkali metal hexametaphosphate for each curing agent component. The liquid temperature after mixing for 2 minutes was 5 ° C.

【0067】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが34〜
35分で正常ゲル化し、沈殿生成はいずれも全く観察さ
れなかった。従って本薬液を用いた現場低温下の液安定
性試験の判定結果は◎と判明した。また上記低温作業・
液安定性試験と同様にして行なった本薬液の攪拌法/1
8分経過後の5℃液を用いて行なった簡易地盤注入試験
の結果は○であり、低温現場作業性が確保されている事
が判明した。なお、本薬液の液温20℃のゲルタイムは
静置法でおおよそ32〜33分であった。またそのホモ
ゲルの1軸圧縮強度は5日室温養生品で1.38kgf/c
m2でゲル収縮率が16.2vol%と測定された。
As a result of the low-temperature work / liquid stability test, the drug measured by the stationary method and the continuous stirring method has a gel time of 34 to
It gelled normally in 35 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the liquid stability test under low temperature in situ using this drug solution was determined to be ◎. The above low temperature work
Stirring method of this drug solution performed in the same manner as the liquid stability test / 1
The result of the simple ground injection test performed using the 5 ° C. liquid after the lapse of 8 minutes was ○, indicating that low-temperature workability was secured. The gel time at a liquid temperature of 20 ° C. of the drug solution was approximately 32 to 33 minutes by the static method. The uniaxial compressive strength of the homogel was 1.38 kgf / c for 5 days at room temperature.
Gel shrinkage was measured to 16.2Vol% in m 2.

【0068】実施例5 主剤として表1記載の(a−4)溶液を選択しその10
0mlと、75%精製燐酸の1.5mlと40%グリオ
キザールの4mlと更に重合度6のヘキサメタ燐酸ナト
リウムの10部(20kg/硬化剤200L)および1
%海水が混合された水の93部とから成る硬化剤液10
0mlとを、それぞれ3.5℃で混合均一化した。主剤
中のアルカリ分の中和理論算出%は、各硬化剤成分毎
に、燐酸分で16.4%、グリオキザールで17.1
%、ヘキサメタ燐酸アルカリ金属塩で14.4と算出さ
れる。混合2分後の液温度は5℃を示した。
Example 5 A solution (a-4) shown in Table 1 was selected as the main ingredient,
0 ml, 1.5 ml of 75% purified phosphoric acid, 4 ml of 40% glyoxal, and 10 parts of sodium hexametaphosphate having a polymerization degree of 6 (20 kg / 200 L of curing agent) and 1 part
% Hard water containing 93 parts of water mixed with 0.1% seawater
And 0 ml each at 3.5 ° C. and homogenized. The theoretical calculation% of the neutralization of the alkali in the base agent was 16.4% for phosphoric acid and 17.1 for glyoxal for each curing agent component.
%, Calculated as 14.4 in terms of alkali metal hexametaphosphate. The liquid temperature after mixing for 2 minutes was 5 ° C.

【0069】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが13〜
16分で正常ゲル化し、沈殿生成は全くいずれも観察さ
れなかった。従って低温作業・液安定性試験の判定結果
は◎であった。また、上記低温作業・液安定性試験と同
様にして行なった攪拌法/10分経過後の5℃液を用い
て行なった簡易地盤注入試験の結果は○であり、低温現
場作業性が確保されている事が判明した。なお、室温2
0℃のゲルタイムは静置法でおおよそ20〜21分であ
り、そのホモゲルの1軸圧縮強度は5日室温養生品で
0.66kgf/cm2でゲル収縮率が9.7vol%と測定
された。
As a result of the low-temperature work / liquid stability test, the drug measured by the standing method and the continuous stirring method has a gel time of 13 to
It gelled normally in 16 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the low-temperature work / liquid stability test was ◎. In addition, the result of the agitation method / simple ground injection test performed using the 5 ° C. liquid after the elapse of 10 minutes, which was performed in the same manner as the low-temperature work / liquid stability test, was ○, and the low-temperature workability was secured. It turned out that. In addition, room temperature 2
The gel time at 0 ° C. was about 20 to 21 minutes by the static method, and the uniaxial compressive strength of the homogel was 0.66 kgf / cm 2 for the cured product at room temperature for 5 days, and the gel shrinkage was 9.7 vol%. .

【0070】実施例6 主剤として表1記載の(b−1)溶液を選択しその10
0mlと、75%精製燐酸の3mlと36%グリオキザ
ールの2.5mlと更に重合度6のヘキサメタ燐酸カリ
ウムの2部および水道水の94部とから成る硬化剤液1
00mlとを、それぞれ3.5℃で混合均一化した。主
剤中のアルカリ分の中和理論算出%は、各硬化剤成分毎
に、燐酸分で34.5%、グリオキザールで9.7%、
ヘキサメタ燐酸アルカリ金属塩で2.8%と算出され
る。混合2分後の液温度は5℃を示した。
Example 6 The solution (b-1) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 75% purified phosphoric acid, 2.5 ml of 36% glyoxal, 2 parts of potassium hexametaphosphate having a degree of polymerization of 6, and 94 parts of tap water 1
00 ml at 3.5 ° C. and homogenized. The theoretical calculation% of the neutralization of the alkali in the base agent was 34.5% for phosphoric acid, 9.7% for glyoxal,
It is calculated to be 2.8% with an alkali metal hexametaphosphate. The liquid temperature after mixing for 2 minutes was 5 ° C.

【0071】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した実施例6の薬剤は、ゲルタイム
が26〜28分で正常ゲル化し、沈殿生成はいずれも全
く観察されなかった。従って低温作業・液安定性試験の
判定結果は◎であった。上記低温作業・液安定性試験と
同様にして行なった攪拌法/20分経過後の5℃液を用
いて行なった簡易地盤注入試験の結果は○であり、低温
現場作業性が確保されている事が判明した。
As a result of the low-temperature working / liquid stability test, the drug of Example 6 measured by the stationary method and the continuous stirring method had a gel time of 26 to 28 minutes and became a normal gel, and no precipitation was observed at all. Was. Therefore, the judgment result of the low-temperature work / liquid stability test was ◎. The results of the stirring method performed in the same manner as the low-temperature work / liquid stability test / simple ground injection test performed using the 5 ° C. liquid after elapse of 20 minutes are ○, and low-temperature on-site workability is secured. The thing turned out.

【0072】実施例7 主剤として表1記載の(b−2)溶液を選択しその10
0mlと、75%精製燐酸の0.2mlと40%グリオ
キザールの1.7mlと更に重合度6のヘキサメタ燐酸
ナトリウムの3部および水道水の98部とから成る硬化
剤液100mlとを、それぞれ5℃で混合均一化した。
主剤中のアルカリ分の中和理論算出%は、各硬化剤成分
毎に、燐酸分で3.5%、グリオキザールで10.9
%、ヘキサメタ燐酸アルカリ金属塩で6.9%と算出さ
れる。
Example 7 A solution (b-2) shown in Table 1 was selected as the main ingredient,
0 ml, 0.2 ml of 75% purified phosphoric acid, 1.7 ml of 40% glyoxal, 3 parts of sodium hexametaphosphate with a degree of polymerization of 6 and 100 ml of a hardening agent solution containing 98 parts of tap water at 5 ° C. And homogenized.
The theoretical calculation% of the neutralization of the alkali component in the base agent was 3.5% for phosphoric acid and 10.9 for glyoxal for each curing agent component.
%, Calculated as 6.9% in terms of alkali metal hexametaphosphate.

【0073】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが11〜
12分で正常ゲル化し、沈殿生成はいずれも全く観察さ
れなかった。従って低温作業・液安定性試験の判定結果
は◎であった。上記低温作業・液安定性試験と同様にし
て行なった攪拌法/8分経過後の5℃液を用いて行なっ
た簡易地盤注入試験の結果は○であり、低温現場作業性
が確保されている事が判明した。
As a result of the low-temperature work / liquid stability test, this drug measured by the stationary method and the continuous stirring method has a gel time of 11 to 11.
It gelled normally in 12 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the low-temperature work / liquid stability test was ◎. The result of a simple ground injection test performed using a 5 ° C. liquid after a lapse of 8 minutes with the stirring method performed in the same manner as the low-temperature work / liquid stability test is “○”, and low-temperature on-site workability is secured. The thing turned out.

【0074】実施例8 主剤として表1記載の(a−3)溶液を選択しその10
0mlと、75%精製燐酸の2.23mlと34%グリ
オキザールの7.35mlと更に重合度33のヘキサメ
タ燐酸カリウムの15部および水道水の80部とから成
る硬化剤液100mlとを、それぞれ5℃で混合均一化
した。主剤中のアルカリ分の中和理論算出%は、各硬化
剤成分毎に、燐酸分で10%、グリオキザールで20.
8%、ヘキサメタ燐酸アルカリ金属塩で9%と算出され
る。
Example 8 A solution (a-3) shown in Table 1 was selected as the main ingredient,
0 ml, 2.23 ml of 75% purified phosphoric acid, 7.35 ml of 34% glyoxal, 15 parts of potassium hexametaphosphate having a degree of polymerization of 33 and 80 parts of tap water, and 100 ml of a curing agent liquid were added at 5 ° C. And homogenized. The theoretical calculation% of neutralization of alkali in the base agent is 10% for phosphoric acid and 20.g for glyoxal for each curing agent component.
It is calculated to be 8%, and 9% for alkali metal hexametaphosphate.

【0075】低温作業・液安定性試験の結果、静置法及
び連続攪拌法で測定した本薬剤は、ゲルタイムが21〜
22分で正常ゲル化し、沈殿生成はいずれも全く観察さ
れなかった。従って低温作業・液安定性試験の判定結果
は◎であった。上記低温作業・液安定性試験と同様にし
て行なった攪拌法/20分経過後の5℃液を用いて行な
った簡易地盤注入試験の結果は○であり、低温現場作業
性が確保されている事が判明した。
As a result of the low-temperature working / liquid stability test, the drug measured by the stationary method and the continuous stirring method has a gel time of 21 to 21.
It gelled normally in 22 minutes and no precipitate formation was observed at all. Therefore, the judgment result of the low-temperature work / liquid stability test was ◎. The results of the stirring method performed in the same manner as the low-temperature work / liquid stability test / simple ground injection test performed using the 5 ° C. liquid after elapse of 20 minutes are ○, and low-temperature on-site workability is secured. The thing turned out.

【0076】比較例1 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、74%粗燐酸の30mlと40%グリオキザ
ールの52.5mlと酢酸の1部(3.3モル/硬化剤
200L)および水道水の910mlとから成る硬化剤
液の100mlとを、それぞれ3.5℃で混合均一化し
た。その結果、主剤中のアルカリ分の中和理論算出%
は、各硬化剤成分毎に、燐酸分で25.1%、グリオキ
ザールで16.4%と算出される。混合2分後の液温度
は5℃を示し、溶液のpH値は10.79を示した。
Comparative Example 1 A solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml and 100 ml of a curing agent solution consisting of 30 ml of 74% crude phosphoric acid, 52.5 ml of 40% glyoxal, 1 part of acetic acid (3.3 mol / 200 l of curing agent) and 910 ml of tap water, respectively. The mixture was homogenized at 0.5 ° C. As a result, the theoretical calculation of neutralization of alkali in the base agent
Is calculated as 25.1% for phosphoric acid and 16.4% for glyoxal for each curing agent component. The liquid temperature after 2 minutes of mixing showed 5 ° C., and the pH value of the solution showed 10.79.

【0077】低温作業・液安定性試験の結果、静置法で
測定したゲルタイムは18〜19分で白濁せずに正常ゲ
ル化した。一方、連続攪拌法で測定した場合には7〜8
分後に、系中に微細結晶の析出が観察され始め、15〜
16分後には完全に系が白濁スラリー状となり、60分
後に於いてもゲル化は全く観察されなかった。従って本
薬液の低温作業・液安定性試験の判定結果は×であっ
た。
As a result of the low-temperature work / liquid stability test, the gel time measured by the stationary method was 18 to 19 minutes, and the gel was formed normally without clouding. On the other hand, when measured by the continuous stirring method, 7 to 8
Minutes later, precipitation of fine crystals began to be observed in the system.
After 16 minutes, the system completely became a cloudy slurry, and no gelation was observed even after 60 minutes. Therefore, the judgment result of the low temperature work / solution stability test of this drug solution was x.

【0078】比較例2 主剤として表1記載の(a1)溶液を選択しその100
mlと、74%粗燐酸の8.6mlと40%グリオキザ
ールの7mlと重合度6のヘキサメタ燐酸ナトリウムの
10部および水道水の978部とから成る硬化剤液の1
00mlとを、それぞれ3.5℃で混合均一化して得た
ホモゲルの1軸圧縮強度は0.1kgf/cm2以下と弱く脆
弱で土質安定化には適さない物であった。
Comparative Example 2 The solution (a1) shown in Table 1 was selected as the main ingredient,
1 ml of a hardener solution consisting of 8.6 ml of 74% crude phosphoric acid, 7 ml of 40% glyoxal, 10 parts of sodium hexametaphosphate having a degree of polymerization of 6 and 978 parts of tap water.
The homogel obtained by mixing and homogenizing 00 ml each at 3.5 ° C. had a uniaxial compressive strength of 0.1 kgf / cm 2 or less, which was weak and brittle, and was not suitable for soil stabilization.

【0079】比較例3 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、75%精製燐酸の3mlと40%グリオキザ
ールの5.25mlと更にピロ燐酸ナトリウムの3部お
よび水道水の91部とから成る硬化剤液100mlと
を、それぞれ3.5℃で混合均一化した。主剤中のアル
カリ分の中和理論算出%は、各硬化剤成分毎に、燐酸分
で25.1%、グリオキザールで16.4%と算出され
る。混合2分後の液温度は5℃を示し、混合溶液の初期
PH値は10.79であった。
Comparative Example 3 The solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 75% purified phosphoric acid, 5.25 ml of 40% glyoxal, 3 parts of sodium pyrophosphate, and 100 ml of a curing agent liquid consisting of 91 parts of tap water are mixed and homogenized at 3.5 ° C. respectively. did. The theoretical calculation percentage of neutralization of alkali in the base agent is calculated as 25.1% for phosphoric acid and 16.4% for glyoxal for each curing agent component. The liquid temperature after 2 minutes of mixing showed 5 ° C., and the initial PH value of the mixed solution was 10.79.

【0080】低温作業・液安定性試験の結果、連続攪拌
法で測定した本薬剤は、8分後に系中に微細結晶の析出
が観察され始め、15〜16分後には完全に系が白濁ス
ラリー状となり、60分後に於いてもゲル化は全く観察
されなかった。従って本薬液の低温作業・液安定性試験
の判定結果は×であった。20分経過後の薬液を用いた
簡易地盤注入試験の結果も×であった。
As a result of the low-temperature work / liquid stability test, this drug, which was measured by the continuous agitation method, showed that the precipitation of fine crystals began to be observed in the system after 8 minutes, and that the system was completely opaque after 15 to 16 minutes. No gelling was observed even after 60 minutes. Therefore, the judgment result of the low temperature work / solution stability test of this drug solution was x. The result of the simple ground injection test using the drug solution after the elapse of 20 minutes was also ×.

【0081】比較例4 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、75%精製燐酸の3mlと40%グリオキザ
ールの5.25mlと更にトリポル燐酸ナトリウムの3
部および水道水の91部とから成る硬化剤液100ml
とを、それぞれ3.5℃で混合均一化した。混合2分後
の液温度は5℃を示し、混合溶液の初期PH値は10.
79であった。低温作業・液安定性試験の結果、連続攪
拌法で測定した本薬剤は、8分後に系中に微細結晶の析
出が観察され始め、15〜16分後には完全に系が白濁
スラリー状となり、60分後に於いてもゲル化は全く観
察されなかった。従って本薬液の低温作業・液安定性試
験の判定結果は×であった。20分経過後の薬液を用い
た簡易地盤注入試験の結果も×であった。
Comparative Example 4 A solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml, 3 ml of 75% purified phosphoric acid, 5.25 ml of 40% glyoxal, and 3% of sodium tripolphosphate.
100 ml of hardener liquid consisting of 1 part of water and 91 parts of tap water
Were mixed and homogenized at 3.5 ° C. respectively. The liquid temperature after 2 minutes of mixing shows 5 ° C., and the initial PH value of the mixed solution is 10.
79. As a result of the low-temperature work / liquid stability test, this drug measured by the continuous stirring method started to precipitate fine crystals in the system after 8 minutes, and after 15 to 16 minutes the system completely became a cloudy slurry, No gelling was observed even after 60 minutes. Therefore, the judgment result of the low temperature work / solution stability test of this drug solution was x. The result of the simple ground injection test using the drug solution after the elapse of 20 minutes was also ×.

【0082】比較例5 主剤として表1記載の(b1)溶液を選択しその100
mlと、74%粗燐酸の0.86mlと40%グリオキ
ザールの0.7mlと重合度6のヘキサメタ燐酸カリウ
ムの2部および水道水の98部とから成る硬化剤液の1
00mlとを、それぞれ3.5℃で混合均一化して得た
ホモゲルの1軸圧縮強度は0.1kgf/cm2程度と強度の
弱いゲルしか生成しなかった。
Comparative Example 5 The solution (b1) shown in Table 1 was selected as the main ingredient, and 100
1 part of a hardener liquid consisting of 0.86 ml of 74% crude phosphoric acid, 0.7 ml of 40% glyoxal, 2 parts of potassium hexametaphosphate having a degree of polymerization of 6 and 98 parts of tap water.
The homogel obtained by mixing and homogenizing 00 ml at 3.5 ° C. respectively had a uniaxial compressive strength of about 0.1 kgf / cm 2, and produced only a gel having a low strength.

【0083】実施例9 主剤として表1記載の(a−2)溶液を選択しその10
0mlと、74%粗燐酸の30mlと34%グリオキザ
ールの26.25mlとエチレングリコールジアセテー
トの33.6部と重合度6のヘキサメタ燐酸ナトリウム
の15部および水道水の900部とから成る硬化剤液の
100mlとを、それぞれ5℃で混合均一化した。主剤
中のアルカリ分の中和理論算出%は、各硬化剤成分毎
に、燐酸分で25.1%、グリオキザール分で7.0
%、エチレングリコールジアセテート分で8.2%、ヘ
キサメタ燐酸アルカリ金属塩で4.9%と算出される。
混合直後の溶液のpH値は10.78を示した。低温作
業・液安定性試験の連続攪拌法で測定した結果は、沈殿
の生成が無く、ゲルタイムが22〜24分で正常ゲル化
をした。従って低温作業・液安定性試験の判定結果は◎
であった。
Example 9 A solution (a-2) shown in Table 1 was selected as the main ingredient,
0 ml, 30% of 74% crude phosphoric acid, 26.25 ml of 34% glyoxal, 33.6 parts of ethylene glycol diacetate, 15 parts of sodium hexametaphosphate having a polymerization degree of 6, and 900 parts of tap water Was mixed and homogenized at 5 ° C. The theoretical calculation% of neutralization of alkali in the base agent is 25.1% for phosphoric acid and 7.0 for glyoxal for each curing agent component.
%, 8.2% for ethylene glycol diacetate, and 4.9% for alkali metal hexametaphosphate.
The pH value of the solution immediately after mixing was 10.78. As a result of the measurement by the continuous stirring method in the low-temperature work / liquid stability test, no precipitation was generated, and the gel time was 22 to 24 minutes and the gelation was normal. Therefore, the judgment result of the low temperature work / liquid stability test is ◎
Met.

【0084】実施例10〜11 実施例9に於いて、エチレングリコールジアセテートに
替えて、同モル当量のγ−ブチロラクトン(実施例1
0)またはエチレンカーボネート(実施例11)とした
以外は全く同様にして得た土質安定化薬剤は低温作業・
液安定性試験の判定結果はそれぞれ◎であった。
Examples 10 to 11 In Example 9, the same molar equivalent of γ-butyrolactone (Example 1) was used in place of ethylene glycol diacetate.
0) or ethylene carbonate (Example 11), except that the soil stabilizing agent obtained in exactly the same manner
The results of the liquid stability tests were ◎.

【0085】実施例12 実施例9に於いて、使用した燐酸の20モル%分だけを
その相当モル量の硫酸に代替して無機酸成分を併用使用
した以外は全く同様にして得た土質安定化薬剤の低温作
業・液安定性試験の判定結果は◎であった。
Example 12 Soil stability was obtained in exactly the same manner as in Example 9 except that only 20 mol% of the phosphoric acid used was replaced by a corresponding molar amount of sulfuric acid and an inorganic acid component was used in combination. The judgment result of the low-temperature working / liquid stability test of the chemical agent was ◎.

【0086】実施例13 実施例1に記載の主剤と硬化剤の各液200リットルを
1m3容量のタンクに注ぎ液温を5℃とした。ただし注
入開始20分前に主剤液に対し硬化剤液を全量添加配合
した。主剤液と硬化剤液との混合は添加後、スクリュウ
ー型電動攪拌機で毎分30回転で連続とした。その土質
安定化剤を混合2分後から、定量送液ポンプを介して、
いわゆる1ショット方式にて、先端部に0.5mm直径
のノズル孔を50ケ有した長さ1mの直径2インチ単管
からなる注入管から5℃雰囲気の空気中に定量吐出させ
た。吐出量は18L/分とした。以上の試験の結果、実
施例1の土質安定化剤はスムーズかつ安定した現場注入
作業が可能である事が確認された。
Example 13 200 liters of each of the main agent and the curing agent described in Example 1 was poured into a 1 m 3 volume tank, and the temperature of the solution was set at 5 ° C. However, 20 minutes before the start of the injection, the entire amount of the curing agent liquid was added to and mixed with the main agent liquid. After the addition, the main agent liquid and the curing agent liquid were continuously mixed at 30 revolutions per minute by a screw type electric stirrer. Two minutes after mixing the soil stabilizer, via a fixed-rate liquid sending pump,
By a so-called one-shot method, a fixed amount of liquid was discharged into an air at 5 ° C. from an injection pipe consisting of a single 2-inch diameter pipe having a length of 1 m and having 50 nozzle holes having a diameter of 0.5 mm at the tip. The discharge rate was 18 L / min. As a result of the above test, it was confirmed that the soil stabilizer of Example 1 was capable of performing a smooth and stable on-site injection operation.

【0087】[0087]

【発明の効果】実施例1〜9から、本発明の土質安定剤
はその主要な解決すべき課題、すなわち、低温下での種
々の刺激が加わった状態で取扱われる際の液挙動安定性
を確保できることが明きらかである。本発明の土質安定
剤が20〜40分程度の長結型土質安定化剤の分類に入
り、その薬液を用いた注入方式として経済的に最適なも
のが1ショットである事も実施例13で明らかである。
また本発明の土質安定化薬剤は最終的に高強度な固結体
を形成するとともに離漿の発生度合いも比較的低いレベ
ルにある。本発明の土質安定化剤は夏冬に関係なく現場
で安定して使用可能であり、各種の液刺激に対して過飽
和安定性が長時間確保された新規な組成物である。
As can be seen from Examples 1 to 9, the soil stabilizer of the present invention has a major problem to be solved, namely, the stability of liquid behavior when handled under various stimuli at low temperatures. It is clear that it can be secured. In Example 13, the soil stabilizer of the present invention falls into the category of long-lasting soil stabilizers of about 20 to 40 minutes, and one shot is economically optimal as an injection method using the chemical solution. it is obvious.
Further, the soil stabilizing agent of the present invention finally forms a high-strength compact and has a relatively low level of syneresis. INDUSTRIAL APPLICABILITY The soil stabilizer of the present invention is a novel composition which can be used stably in the field regardless of summer and winter, and which has long-term supersaturation stability against various liquid stimuli.

【0088】一方、比較例1、3および5では、冬場の
液刺激安定性に問題があり、燐酸−グリオキザールを基
本硬化系とし更に酢酸を併用使用しても本発明の課題を
解決出来ない事が判明した。特に比較例3と比較例4は
ピロリン酸アルカリ金属塩またはトリポリ燐酸アルカリ
金属塩を第3成分とした場合であるが、いずれも本発明
の課題を解決するには為の手段として不適当であった。
また本発明の土質安定剤は、軟弱地盤の強化安定化、地
下水の止水機能に有効な土質安定化剤である。
On the other hand, in Comparative Examples 1, 3 and 5, there is a problem in the stability of the liquid stimulus in winter, and even if phosphoric acid-glyoxal is used as a basic curing system and acetic acid is used in combination, the problem of the present invention cannot be solved. There was found. In particular, Comparative Examples 3 and 4 are cases in which an alkali metal salt of pyrophosphate or an alkali metal salt of tripolyphosphate is used as the third component, but both are unsuitable as means for solving the problems of the present invention. Was.
Further, the soil stabilizer of the present invention is an effective soil stabilizer for strengthening and stabilizing soft ground and for stopping water in groundwater.

Claims (10)

【特許請求の範囲】[Claims] 【請求項1】 主剤が下記(a)または(b)であり、
(a)SiO2/Na2Oモル比が2.45〜4.5の珪
酸ソーダを、そのSiO2とNa2Oの総量で10〜50
重量%含有してなる水溶液、(b)SiO2/Na2Oモ
ル比が4.5を超えない珪酸ソーダと、SiO2/Na2
Oモル比が20〜250のコロイダルシリカとを含有
し、その混合水溶液のSiO2/Na2Oモル比が3〜5
0、SiO2とNa2Oの総量が10〜50重量%である
混合水溶液、 硬化剤が、該硬化剤と主剤とを下記の割合で混合したと
きに、主剤中のNa2Oの1〜50モル%相当分を中和
する事が出来る量の燐酸と、5〜30モル%相当分を中
和する事が出来る量のグリオキザールと、2〜20重量
%相当分を中和する事が出来る量のヘキサメタ燐酸アル
カリ金属塩とを含有させてなる水溶液であって、上記主
剤と硬化剤を容積比で(1:0.9)〜(0.9:1)
の割合で混合してなる低温下での溶液安定性に優れる土
質安定化剤。
1. The main agent is the following (a) or (b):
(A) Sodium silicate having a SiO 2 / Na 2 O molar ratio of 2.45 to 4.5 is converted to 10 to 50 in total amount of SiO 2 and Na 2 O.
(B) sodium silicate having a molar ratio of SiO 2 / Na 2 O not exceeding 4.5, and an aqueous solution containing SiO 2 / Na 2
And a colloidal silica having an O molar ratio of 20 to 250, and a mixed aqueous solution having a SiO 2 / Na 2 O molar ratio of 3 to 5
0, SiO 2 and Na 2 O mixed aqueous solution the total amount of from 10 to 50% by weight of curing agent, the curing agent and the main agent when mixed in the following proportions, Na 2 O. 1 to the in base resin Phosphoric acid in an amount capable of neutralizing 50 mol% equivalent, glyoxal in an amount capable of neutralizing 5-30 mol% equivalent, and 2-20 wt% equivalent neutralization An aqueous solution containing an amount of an alkali metal hexametaphosphate in an amount of (1: 0.9) to (0.9: 1) by volume ratio of the main agent and the curing agent.
Soil stabilizer excellent in solution stability under low temperature, which is mixed in the ratio of
【請求項2】 (a)または(b)の珪酸ソーダのSi
2/Na2Oモル比が3.0〜3.5であることを特徴
とする請求項1記載の土質安定化剤。
2. The sodium silicate of (a) or (b)
The soil stabilizer according to claim 1, wherein the molar ratio of O 2 / Na 2 O is 3.0 to 3.5.
【請求項3】 ヘキサメタ燐酸アルカリ金属塩の重合度
が6〜50であることを特徴とする請求項1または2記
載の土質安定化剤。
3. The soil stabilizer according to claim 1, wherein the degree of polymerization of the alkali metal hexametaphosphate is from 6 to 50.
【請求項4】 ヘキサメタ燐酸アルカリ金属塩がヘキサ
メタ燐酸ナトリウムであることを特徴とする請求項1〜
3のいずれか1項記載の土質安定化剤。
4. The method according to claim 1, wherein the alkali metal hexametaphosphate is sodium hexametaphosphate.
The soil stabilizer according to any one of claims 3 to 4.
【請求項5】 硬化剤が、ヘキサメタ燐酸ナトリウムと
グリオキザールとを配合した後に燐酸を配合して得られ
たものであることを特徴とする請求項4記載の土質安定
化剤。
5. The soil stabilizer according to claim 4, wherein the curing agent is obtained by blending sodium hexametaphosphate and glyoxal and then phosphoric acid.
【請求項6】 請求項1〜5のいずれか1項記載の土質
安定化剤における燐酸の酸分の1〜50%相当量を硫
酸、塩酸、硝酸およびほう酸から選ばれた1種または2
種以上で置き換えることを特徴とする土質安定化剤。
6. The soil stabilizer according to claim 1, wherein 1 to 50% of the acid content of phosphoric acid is selected from sulfuric acid, hydrochloric acid, nitric acid and boric acid.
A soil stabilizer characterized by being replaced with a seed or more.
【請求項7】 請求項1〜5のいずれか1項記載の土質
安定化剤における燐酸の酸分の1〜50%相当量をフィ
チン酸またはその酸性アルカリ金属塩で置き換えること
を特徴とする土質安定化剤。
7. A soil according to claim 1, wherein 1 to 50% of the acid content of phosphoric acid in the soil stabilizer according to any one of claims 1 to 5 is replaced with phytic acid or an acidic alkali metal salt thereof. Stabilizer.
【請求項8】 請求項1〜5のいずれか1項記載の土質
安定化剤におけるグリオキザールの遊離グリコール酸換
算の酸分の1〜100%相当量をグリコール酸2酢酸エ
ステル、エチレンカーボネート、プロピレンカーボネー
トおよびγ−ブチロラクトンから選ばれた1種または2
種以上で置き換えることを特徴とする土質安定化剤。
8. Glyoxal in the soil stabilizer according to any one of claims 1 to 5, wherein 1 to 100% of an acid content in terms of free glycolic acid is equivalent to glycolic acid diacetate, ethylene carbonate, propylene carbonate. And one or two selected from γ-butyrolactone
A soil stabilizer characterized by being replaced with a seed or more.
【請求項9】 地盤注入開始の数分前に主剤と硬化剤と
を混合均一化させて1液として得られたものである請求
項1〜8のいずれか1項記載の土質安定化剤。
9. The soil stabilizer according to any one of claims 1 to 8, which is obtained by mixing and homogenizing the main agent and the hardening agent several minutes before the start of the ground injection to obtain one liquid.
【請求項10】 請求項1〜9記載のいずれか1項記載
の土質安定化剤を地盤中に1ショット方式で注入し、浸
透・流動・固結させて、土質を強化安定させることを特
徴とする土質安定化工法。
10. The soil stabilizing agent according to any one of claims 1 to 9 is injected into the ground in a one-shot manner, and is permeated, flowed, and consolidated to strengthen and stabilize the soil. Soil stabilization method.
JP21314196A 1996-07-24 1996-07-24 Soil stabilizer excellent in solution stability at low temperature and soil stabilization method Pending JPH1036840A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21314196A JPH1036840A (en) 1996-07-24 1996-07-24 Soil stabilizer excellent in solution stability at low temperature and soil stabilization method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21314196A JPH1036840A (en) 1996-07-24 1996-07-24 Soil stabilizer excellent in solution stability at low temperature and soil stabilization method

Publications (1)

Publication Number Publication Date
JPH1036840A true JPH1036840A (en) 1998-02-10

Family

ID=16634262

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21314196A Pending JPH1036840A (en) 1996-07-24 1996-07-24 Soil stabilizer excellent in solution stability at low temperature and soil stabilization method

Country Status (1)

Country Link
JP (1) JPH1036840A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013189539A (en) * 2012-03-13 2013-09-26 Fuji Kagaku Kk Solidifying material for ground grouting and method for manufacturing the same
JP2016153499A (en) * 2016-03-28 2016-08-25 富士化学株式会社 Method for manufacturing solidifying material for grouting
EP4060122A1 (en) * 2021-03-18 2022-09-21 BAUER Spezialtiefbau GmbH Installation and method for producing an injection silicate gel solution for injecting into a base

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013189539A (en) * 2012-03-13 2013-09-26 Fuji Kagaku Kk Solidifying material for ground grouting and method for manufacturing the same
JP2016153499A (en) * 2016-03-28 2016-08-25 富士化学株式会社 Method for manufacturing solidifying material for grouting
EP4060122A1 (en) * 2021-03-18 2022-09-21 BAUER Spezialtiefbau GmbH Installation and method for producing an injection silicate gel solution for injecting into a base
WO2022194704A1 (en) 2021-03-18 2022-09-22 Bauer Spezialtiefbau Gmbh System and process for production of an injection silicate gel solution for injection into a soil

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