JP2002155279A - Method for hardening ground - Google Patents
Method for hardening groundInfo
- Publication number
- JP2002155279A JP2002155279A JP2000355262A JP2000355262A JP2002155279A JP 2002155279 A JP2002155279 A JP 2002155279A JP 2000355262 A JP2000355262 A JP 2000355262A JP 2000355262 A JP2000355262 A JP 2000355262A JP 2002155279 A JP2002155279 A JP 2002155279A
- Authority
- JP
- Japan
- Prior art keywords
- hardening
- ground
- aqueous solution
- solution
- corrosion inhibitor
- 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.)
- Granted
Links
Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は地盤硬化方法に関す
る。地盤の強化及び止水を図るため、地盤中へ硬化用薬
液を注入して該地盤を硬化させることが行なわれる。本
発明はかかる地盤硬化方法の改良に関する。The present invention relates to a method for hardening a ground. In order to strengthen the ground and stop water, a hardening chemical is injected into the ground to harden the ground. The present invention relates to an improvement of such a ground hardening method.
【０００２】[0002]
【従来の技術】従来、前記のような地盤硬化方法として
一般に、地盤中へ、硬化用薬液として、酸性シリカゾル
と、アルカリ性剤の水溶液とを注入する方法が行なわれ
ている（特公昭５４−１９０８８、特公平３−２４５１
５）。この場合の酸性シリカゾルは水ガラスの水溶液と
酸性剤の水溶液とを混合してｐＨ１〜２程度に調製した
水分散液であり、かかる酸性剤としては通常、硫酸又は
硫酸を主成分とするものが用いられている。またアルカ
リ性剤としては、水酸化ナトリウム、水酸化マグネシウ
ム、水酸化カルシウム等が用いられている。一方、前記
のような地盤硬化方法としては、地盤中へ、硬化用薬液
として、水ガラスの水溶液と、酸性剤の水溶液とを注入
する方法も行なわれている。この場合の酸性剤としても
通常、硫酸又は硫酸を主成分とするものが用いられてい
る。2. Description of the Related Art Conventionally, as a method for hardening the ground as described above, generally, a method of injecting an acidic silica sol and an aqueous solution of an alkaline agent as a hardening chemical solution into the ground has been carried out (Japanese Patent Publication No. 54-19088). , Tokuhei 3-2451
5). The acidic silica sol in this case is an aqueous dispersion prepared by mixing an aqueous solution of water glass and an aqueous solution of an acid agent to adjust the pH to about 1 to 2. As such an acid agent, sulfuric acid or one containing sulfuric acid as a main component is usually used. Used. Further, as the alkaline agent, sodium hydroxide, magnesium hydroxide, calcium hydroxide and the like are used. On the other hand, as a method of hardening the ground as described above, a method of injecting an aqueous solution of water glass and an aqueous solution of an acid agent into the ground as a hardening chemical liquid is also performed. In this case, sulfuric acid or a compound containing sulfuric acid as a main component is usually used as the acid agent.
【０００３】かかる従来の地盤硬化方法ではいずれも、
水ガラスのゲル化を利用して地盤を硬化させている。既
によく知られている通り、水ガラスのゲル化は、地盤中
へ注入する硬化用薬液の組成やゲル化時の温度等によっ
ても影響されるが、硬化用薬液のｐＨにより大きく影響
される。例えば、水ガラスの水溶液に硫酸の水溶液を徐
々に加え、そのｐＨを順次下げると、該水ガラスは概し
て、ｐＨ６．０〜９．０において数秒〜数十秒でゲル化
する所謂瞬結状態になり、またｐＨ４．５〜６．０未満
において数分〜数十分でゲル化する所謂中結状態にな
り、更にｐＨ３．０〜４．５未満において数時間〜数十
時間でゲル化する所謂長結状態になり、そしてｐＨ２未
満では安定な酸性シリカゾルになる。[0003] In any of the conventional ground hardening methods,
The ground is hardened using the gelation of water glass. As is well known, the gelation of water glass is affected by the composition of the curing chemical injected into the ground, the temperature at the time of gelation, and the like, but is greatly affected by the pH of the curing chemical. For example, when an aqueous solution of sulfuric acid is gradually added to an aqueous solution of water glass and the pH thereof is sequentially lowered, the water glass generally becomes a so-called flashing state in which gelation occurs at pH 6.0 to 9.0 in several seconds to several tens of seconds. In addition, it becomes a so-called sintering state in which gelation occurs at pH 4.5 to less than 6.0 for several minutes to several tens of minutes, and further so-called gelation occurs for several hours to tens of hours at pH less than 3.0 to 4.5. It becomes a long-lasting state, and becomes a stable acidic silica sol below pH2.
【０００４】したがって前記した従来の地盤硬化方法で
は概して、地盤中へ注入する硬化用薬液のｐＨを調整す
ることにより地盤の硬化時間を調節しているのである
が、注入作業の現場では、その前後の作業をも全体とし
て円滑に進めるため、前記のような瞬結を行なう場合は
少なく、多くの場合は前記のような中結又は長結を行な
っているのが実情である。具体的には、酸性シリカゾル
に対するアルカリ性剤の水溶液の使用割合により、又は
水ガラスの水溶液に対する酸性剤の水溶液の使用割合に
より、地盤中へ注入する硬化用薬液のｐＨを酸性領域に
おける所望値となるように調整しているのである。Therefore, in the above-described conventional ground hardening method, the hardening time of the ground is generally adjusted by adjusting the pH of the hardening chemical solution injected into the ground. In order to smoothly carry out the above operation as a whole, there are few cases where the instantaneous connection is performed as described above, and in many cases, the above-described intermediate connection or long connection is performed. Specifically, depending on the usage ratio of the aqueous solution of the alkaline agent with respect to the acidic silica sol, or the usage ratio of the aqueous solution of the acidic agent with respect to the aqueous solution of water glass, the pH of the curing chemical solution to be injected into the ground becomes a desired value in the acidic region. It is adjusted as follows.
【０００５】ところで、注入作業の現場では、酸性シリ
カゾルとアルカリ性剤の水溶液とを、又は水ガラスの水
溶液と酸性剤の水溶液とを、１）双方を注入直前に混合
しておいてから注入する方法（１ショット法）、２）双
方を途中混合しながら注入する方法（１．５ショット
法）、３）双方を注入直後に混合する方法（２ショット
法）のいずれかで、地盤中へ硬化用薬液を注入してい
る。そしてこれらの方法において一般に、１）の方法で
は１本の注入管を用い、また２）の方法では１本のＹ字
管を用い、更に３）の方法では２本の注入管又は１本の
２重注入管を用いている。かかる注入作業の現場では、
前記のような注入管の外に、タンク、ポンプ、配管等の
各種の機材が使用されているが、これらのなかには、酸
性シリカゾルや酸性剤の水溶液等、酸性液と直接に接触
する機材もある。従来の地盤硬化方法では、かかる機材
が酸による腐食を受け易く、とりわけそれが鉄で作製さ
れている場合には酸による腐食が激しく、その寿命が短
いという問題があり、その改善が強く要請されている。[0005] At the site of the injection operation, an acidic silica sol and an aqueous solution of an alkaline agent, or an aqueous solution of water glass and an aqueous solution of an acidic agent, 1) a method in which both are mixed immediately before injection and then injected. (1 shot method), 2) a method of injecting while mixing both in the middle (1.5 shot method), and 3) a method of mixing both immediately after injection (2 shot method) for curing into the ground The drug solution is being injected. Generally, in these methods, one injection pipe is used in the method 1), one Y-shaped pipe is used in the method 2), and two injection pipes or one injection pipe is used in the method 3). A double injection tube is used. At the site of such injection work,
In addition to the above-described injection pipe, various equipment such as a tank, a pump, and piping are used, and among these, there are equipment that directly contacts an acidic liquid, such as an aqueous solution of an acidic silica sol or an acidic agent. . In the conventional ground hardening method, there is a problem that such equipment is susceptible to corrosion by acid, particularly when it is made of iron, and is severely corroded by acid, and its life is short. ing.
【０００６】[0006]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、地盤中への硬化用薬液の注入作業に用いる
機材の酸による腐食を抑えてその寿命を長くした地盤硬
化方法を提供する処にある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for hardening a ground in which the equipment used for the operation of injecting a hardening chemical solution into the ground is prevented from being corroded by acid and has a longer life. In the place.
【０００７】[0007]
【課題を解決するための手段】前記の課題を解決する本
発明は、地盤中へ硬化用薬液を注入して該地盤を硬化さ
せる方法において、硬化用薬液と共に腐食抑制剤を用い
ることを特徴とする地盤硬化方法に係る。According to the present invention, there is provided a method of curing a ground by injecting a hardening chemical into the ground, wherein a corrosion inhibitor is used together with the hardening chemical. Pertaining to the ground hardening method.
【０００８】本発明に係る地盤硬化方法でも、地盤中へ
硬化用薬液を注入して該地盤を硬化させる。地盤中へ注
入する硬化用薬液の組成は、それを地盤中へ注入するこ
とにより該地盤を硬化させ得るものであれば、特に制限
されないが、硬化用薬液としては通常、酸性シリカゾル
とアルカリ性剤の水溶液とを用いるか、又は水ガラスの
水溶液と酸性剤の水溶液とを用いる。この場合の酸性シ
リカゾルは水ガラスの水溶液と酸性剤の水溶液とを混合
してｐＨ１〜２程度に調製した水分散液である。[0008] Also in the ground hardening method according to the present invention, a hardening solution is injected into the ground to harden the ground. The composition of the hardening chemical solution to be injected into the ground is not particularly limited as long as it can harden the ground by injecting it into the ground, but the hardening chemical solution is usually an acidic silica sol and an alkaline agent. An aqueous solution is used, or an aqueous solution of water glass and an aqueous solution of an acidic agent are used. The acidic silica sol in this case is an aqueous dispersion prepared by mixing an aqueous solution of water glass and an aqueous solution of an acidic agent to adjust the pH to about 1 to 2.
【０００９】前記した酸性シリカゾルの調製に用いる水
ガラス、また前記した硬化用薬液として用いる水ガラス
としては、通常はＪＩＳ３号の水ガラスを用いるが、Ｎ
ａ2Ｏ１モル当たりＳｉＯ2を３．６〜４．５モルの割合
で含有するＳｉＯ2高モル比の水ガラスを用いることも
できる。前記した酸性シリカゾルの調製に用いる酸性
剤、また前記した硬化用薬液として用いる酸性剤として
は、通常は塩酸、硫酸、これらと共に用いる場合のリン
酸等の無機酸を用い、なかでも硫酸を用いるが、かかる
無機酸を主成分とし、更に無機酸のアルミニウム塩類及
びリン酸塩類から選ばれる一つ又は二つ以上を含有する
ものが好ましい。無機酸のアルミニウム塩類、例えば硫
酸アルミニウム、塩化アルミニウム、ポリ塩化アルミニ
ウム等を用いると、そのような硬化用薬液を地盤中へ注
入したとき、強固で耐久性の強いアルミニウムシリケー
トを形成する。またリン酸塩類、例えばリン酸２水素ナ
トリウム、トリポリリン酸ナトリウム、テトラポリリン
酸ナトリウム等を用いると、そのような硬化用薬液を地
盤中へ注入するとき、該硬化用薬液のｐＨの振れを抑え
る優れた緩衝作用を示す。前記した硬化用薬液として用
いるアルカリ性剤としては通常、水酸化ナトリウム、水
酸化マグネシウム、水酸化カルシウム等を用いる。As the water glass used for preparing the above-mentioned acidic silica sol and the water glass used as the above-mentioned hardening solution, water glass of JIS No. 3 is usually used.
Water glass with a high molar ratio of SiO 2 containing 3.6 to 4.5 mol of SiO 2 per mol of a 2 O can also be used. As the acid agent used for preparing the above-mentioned acidic silica sol, and the acid agent used as the above-mentioned curing chemical solution, usually, hydrochloric acid, sulfuric acid, an inorganic acid such as phosphoric acid when used with these, and among them, sulfuric acid is used. It is preferable that the inorganic acid be a main component and further contain one or more selected from aluminum salts and phosphates of the inorganic acid. When an aluminum salt of an inorganic acid such as aluminum sulfate, aluminum chloride, or polyaluminum chloride is used, a strong and durable aluminum silicate is formed when such a curing chemical is injected into the ground. Further, when phosphates such as sodium dihydrogen phosphate, sodium tripolyphosphate, sodium tetrapolyphosphate and the like are used, when such a hardening chemical is injected into the ground, the pH of the hardening chemical can be suppressed from fluctuating. Exhibits a buffering action. Sodium hydroxide, magnesium hydroxide, calcium hydroxide and the like are usually used as the alkaline agent used as the above-mentioned curing chemical.
【００１０】本発明に係る地盤硬化方法において、地盤
中への硬化用薬液の注入は、前記した１ショット法、
１．５ショット法、２ショット法のいずれによってもよ
い。硬化用薬液として、酸性シリカゾルとアルカリ性剤
の水溶液とを、又は水ガラスの水溶液と酸性剤の水溶液
とを用いる場合、１）双方を注入直前に混合しておいて
から注入する方法（１ショット法）、２）双方を途中混
合しながら注入する方法（１．５ショット法）、３）双
方を注入直後に混合する方法（２ショット法）のいずれ
によってもよいのである。In the ground hardening method according to the present invention, the hardening solution is injected into the ground by the one-shot method described above.
Either the 1.5 shot method or the two shot method may be used. When an acidic silica sol and an aqueous solution of an alkaline agent or an aqueous solution of water glass and an aqueous solution of an acidic agent are used as the curing liquid, 1) a method in which both are mixed immediately before injection and then injected (one-shot method) ), 2) a method of injecting while mixing both (1.5 shot method), and 3) a method of mixing both immediately after injection (2 shot method).
【００１１】本発明に係る地盤硬化方法では、以上説明
した硬化用薬液と共に腐食抑制剤を用いる。前記したよ
うに、硬化用薬液を地盤中へ注入する注入作業の現場で
は、硬化用薬液を地盤中へ注入するための注入管の外
に、タンク、ポンプ、配管等、各種の機材を使用し、こ
れらのなかには、硬化用薬液として用いる酸性シリカゾ
ル、該酸性シリカゾルの調製に用いる酸性剤の水溶液、
硬化用薬液として用いる酸性剤の水溶液、硬化用薬液と
して用いる酸性シリカゾルとアルカリ性剤の水溶液との
混合液、硬化用薬液として用いる水ガラスの水溶液と酸
性剤の水溶液との混合液等、酸性液と直接に接触するも
のもある。かかる機材は酸による腐食を受け易く、とり
わけそれが鉄で作製されている場合には酸による腐食が
激しい。本発明に係る地盤硬化方法では、かかる酸によ
る機材の腐食を抑えるため、腐食抑制剤を用いる。結果
として、硬化用薬液の外に、腐食抑制剤をも、地盤中へ
注入するのである。腐食抑制剤の注入方法には各種があ
るが、その性質上、前記のような酸性液のいずれかに予
め加えておくのが好ましい。In the ground hardening method according to the present invention, a corrosion inhibitor is used together with the above-described hardening solution. As described above, at the site of an injection operation for injecting a curing chemical into the ground, in addition to an injection pipe for injecting the curing chemical into the ground, various equipment such as a tank, a pump, and a pipe are used. Among these, an acidic silica sol used as a curing chemical solution, an aqueous solution of an acidic agent used for preparing the acidic silica sol,
Aqueous solution of an acidic agent used as a curing chemical, a mixed solution of an acidic silica sol used as a curing liquid and an aqueous solution of an alkaline agent, a mixed liquid of an aqueous solution of water glass used as a curing liquid and an aqueous solution of an acidic agent, and the like. Some are in direct contact. Such equipment is susceptible to acid corrosion, especially if it is made of iron. In the ground hardening method according to the present invention, a corrosion inhibitor is used in order to suppress the corrosion of the equipment due to the acid. As a result, in addition to the curing chemical, a corrosion inhibitor is also injected into the ground. Although there are various methods for injecting the corrosion inhibitor, it is preferable to add it in advance to any of the above-mentioned acidic liquids due to its properties.
【００１２】本発明に係る地盤硬化方法では、一方で本
来の地盤硬化を図りつつ、同時に他方で酸による機材の
腐食抑制を図る。これに適う腐食抑制剤としては、ジエ
チル尿素、ジブチルチオ尿素、ベンゾチアゾール等の有
機硫黄化合物、１級アミン、２級アミン、３級アミン等
を有するアミン化合物、第４級アンモニウム化合物等も
挙げられるが、分子中に２個以上のアミノ基を有する重
量平均分子量３００〜１５００００のポリアミン系化合
物又はその塩が好ましい。かかるポリアミン系化合物に
はポリアリルアミン系化合物やポリジアリルアミン系化
合物等があり、またその塩には塩酸塩やアンモニウム塩
等があるが、なかでも下記の式１、式２、式３、式４、
式５又は式６で示される構成単位を繰り返し単位とする
ものから選ばれる一つ又は二つ以上が好ましい。これら
はいずれも、それ自体としては公知であり、市販品を利
用できる。In the ground hardening method according to the present invention, on the one hand, the original ground hardening is achieved, and on the other hand, the corrosion of the equipment by the acid is suppressed. Suitable corrosion inhibitors include organic sulfur compounds such as diethyl urea, dibutyl thiourea and benzothiazole, amine compounds having a primary amine, secondary amine, tertiary amine and the like, and quaternary ammonium compounds. A polyamine compound having a weight average molecular weight of 300 to 150,000 having two or more amino groups in the molecule or a salt thereof is preferable. Such polyamine-based compounds include polyallylamine-based compounds and polydiallylamine-based compounds, and their salts include hydrochlorides and ammonium salts. Among them, the following formulas 1, 2, 3, 4,
One or more selected from those having a structural unit represented by Formula 5 or 6 as a repeating unit is preferable. All of these are known per se, and commercially available products can be used.
【００１３】[0013]
【式１】 (Equation 1)
【式２】 (Equation 2)
【式３】 (Equation 3)
【式４】 (Equation 4)
【式５】 (Equation 5)
【式６】 (Equation 6)
【００１４】本発明は係る地盤硬化方法において、地盤
中へ注入する硬化用薬液に対する腐食抑制剤の使用量は
特に制限されないが、腐食抑制剤として前記したような
ポリアミン系化合物又はその塩を用いる場合、硬化用薬
液１Ｌ当たり、０．１〜５０ｇの割合となるようにする
のが好ましく、０．５〜５ｇの割合となるようにするの
がより好ましい。経済的に機材の酸による腐食を抑える
ためである。According to the present invention, in the method for hardening the ground, the amount of the corrosion inhibitor used for the hardening liquid injected into the ground is not particularly limited, but when the above-mentioned polyamine compound or salt thereof is used as the corrosion inhibitor. Preferably, the ratio is from 0.1 to 50 g, more preferably from 0.5 to 5 g, per liter of the curing chemical. This is to economically suppress the corrosion of the equipment due to acid.
【００１５】[0015]
【発明の実施の形態】本発明に係る地盤硬化方法の実施
形態としては、下記の１）〜１２）が挙げられる。 １）ＪＩＳ３号の水ガラス７０kg、７８％硫酸１４kg及
び残部として水を用い、ｐＨ１．８の酸性シリカゾル２
００Ｌを調製し、この酸性シリカゾルに腐食抑制剤とし
て前記の式２で示される構成単位を繰り返し単位とする
重量平均分子量約１０００のポリアミン系化合物の塩
（日東紡績社製の商品名ＰＡＡ−ＨＣＩ−０１）を４０
０ｇ溶解する（Ａ液）。別に、水酸化マグネシウム０．
８kg及び残部として水を用い、アルカリ性剤の水溶液２
００Ｌを調製する（Ｂ液）。Ａ液とＢ液とを等量割合で
前記の１．５ショット法により地盤中へ注入する地盤硬
化方法。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the ground hardening method according to the present invention include the following 1) to 12). 1) Acid silica sol having a pH of 1.8 using 70 kg of JIS No. 3 water glass, 14 kg of 78% sulfuric acid and the balance water.
And a salt of a polyamine compound having a weight average molecular weight of about 1000 having a structural unit represented by the above formula 2 as a repeating unit as a corrosion inhibitor (PAA-HCI- manufactured by Nitto Boseki Co., Ltd.) as a corrosion inhibitor. 01) to 40
Dissolve 0 g (Solution A). Separately, magnesium hydroxide 0.
8 kg and water as balance, aqueous solution of alkaline agent 2
Prepare 00L (Solution B). A ground hardening method in which the liquid A and the liquid B are injected into the ground at an equal ratio by the above-mentioned 1.5 shot method.
【００１６】２）ＪＩＳ３号の水ガラス９８kg及び残部
として水を用い、水ガラスの水溶液２００Ｌを調製する
（Ａ液）。別に、７８％硫酸１８kg及び残部として水を
用い、酸性剤の水溶液２００Ｌを調製し、この酸性剤の
水溶液に前記１）と同じ腐食抑制剤を４００ｇ溶解する
（Ｂ液）。Ａ液とＢ液とを等量割合で前記の１．５ショ
ット法により地盤中へ注入する地盤硬化方法。2) Using 98 kg of JIS No. 3 water glass and water as the balance, 200 L of an aqueous solution of water glass is prepared (Solution A). Separately, 200 L of an aqueous solution of an acid agent is prepared using 18 kg of 78% sulfuric acid and water as the balance, and 400 g of the same corrosion inhibitor as in 1) is dissolved in the aqueous solution of the acid agent (Solution B). A ground hardening method in which the liquid A and the liquid B are injected into the ground at an equal ratio by the above-mentioned 1.5 shot method.
【００１７】３）ＪＩＳ３号の水ガラス１４０kg及び残
部として水を用い、水ガラスの水溶液２００Ｌを調製す
る（Ａ液）。別に、７８％硫酸２２kg、アルミナ分含有
量１７％の硫酸アルミニウム４kg及び残部として水を用
い、酸性剤の水溶液２００Ｌを調製する（Ｂ液）。Ａ液
とＢ液とを混合し、その混合液に前記１）と同じ腐食抑
制剤を４００ｇ溶解したものを前記の１ショット法によ
り地盤中へ注入する地盤硬化方法。3) Using 140 kg of JIS No. 3 water glass and water as the balance, 200 L of an aqueous solution of water glass is prepared (Solution A). Separately, 200 L of an aqueous solution of an acidic agent is prepared using 22 kg of 78% sulfuric acid, 4 kg of aluminum sulfate having an alumina content of 17%, and water as the balance (Solution B). A soil hardening method in which a solution A and a solution B are mixed, and 400 g of the same corrosion inhibitor as in 1) is dissolved in the mixed solution and injected into the ground by the one-shot method.
【００１８】４）腐食抑制剤として前記の式３で示され
る構成単位を繰り返し単位とする重量平均分子量約５０
００のポリアミン系化合物の塩（日東紡績社製の商品名
ＰＡＳ−Ａ−１）を２kg用いたこの以外は前記の１）と
同様に行なう地盤硬化方法。 ５）前記の４）と同じ腐食抑制剤を２kg用いたこと以外
は前記の２）と同様に行なう地盤硬化方法。 ６）前記の４）と同じ腐食抑制剤を２kg用いたこと以外
は前記の３）と同様に行なう地盤硬化方法。4) As a corrosion inhibitor, a weight average molecular weight of about 50 having a constitutional unit represented by the above formula 3 as a repeating unit.
A soil hardening method carried out in the same manner as in the above 1) except that 2 kg of a polyamine compound salt (trade name PAS-A-1 manufactured by Nitto Boseki Co., Ltd.) is used. 5) A ground hardening method performed in the same manner as in 2) except that 2 kg of the same corrosion inhibitor as in 4) is used. 6) A soil hardening method performed in the same manner as in 3) except that 2 kg of the same corrosion inhibitor as in 4) is used.
【００１９】７）腐食抑制剤として前記の式４で示され
る構成単位を繰り返し単位とする重量平均分子量約５０
００のポリアミン系化合物の塩（日東紡績社製の商品名
ＰＡＳ−９２）を２００ｇ用いたこの以外は前記の１）
と同様に行なう地盤硬化方法。 ８）前記の７）と同じ腐食抑制剤を２００ｇ用いたこと
以外は前記の２）と同様に行なう地盤硬化方法。 ９）前記の７）と同じ腐食抑制剤を２００ｇ用いたこと
以外は前記の３）と同様に行なう地盤硬化方法。7) As a corrosion inhibitor, a weight average molecular weight of about 50 having a constitutional unit represented by the above formula 4 as a repeating unit.
1) except that 200 g of a polyamine compound salt (trade name: PAS-92, manufactured by Nitto Boseki Co., Ltd.) was used.
Ground hardening method performed in the same manner as 8) A soil hardening method performed in the same manner as in 2) except that 200 g of the same corrosion inhibitor as in 7) is used. 9) A soil hardening method performed in the same manner as in 3) except that 200 g of the same corrosion inhibitor as in 7) is used.
【００２０】１０）腐食抑制剤として前記の式５で示さ
れる構成単位を繰り返し単位とする重量平均分子量約３
２８のポリアミン系化合物（三菱ガス化学社製の商品名
ガスカミン３２８）を４００ｇ用いたこと以外は前記の
１）と同様に行なう地盤硬化方法。 １１）前記の１０）と同じ腐食抑制剤を４００ｇ用いた
こと以外は前記の２）と同様に行なう地盤硬化方法。 １２）前記の１０）と同じ腐食抑制剤を４００ｇ用いた
こと以外は前記の３）と同様に行なう地盤硬化方法。10) As a corrosion inhibitor, a weight average molecular weight of about 3 having a constitutional unit represented by the above formula 5 as a repeating unit.
28. A soil hardening method carried out in the same manner as in the above 1) except that 400 g of the polyamine compound (Gaskamin 328 manufactured by Mitsubishi Gas Chemical Co., Ltd.) of No. 28 was used. 11) A ground hardening method performed in the same manner as in 2) except that 400 g of the same corrosion inhibitor as in 10) is used. 12) A ground hardening method performed in the same manner as in 3) except that 400 g of the same corrosion inhibitor as in 10) is used.
【００２１】[0021]
【実施例】試験区分１（硬化試験） 実施例１ ＪＩＳ３号の水ガラス７０ｇ、７８％硫酸１４ｇ及び残
部として水を用い、ｐＨ１．８の酸性シリカゾル２００
mlを調製し、この酸性シリカゾルに腐食抑制剤として前
記の式２で示される構成単位を繰り返し単位とする重量
平均分子量約１０００のポリアミン系化合物の塩（日東
紡績社製の商品名ＰＡＡ−ＨＣＩ−０１）を０．４ｇ溶
解した（Ａ液）。別に、水酸化マグネシウム０．８ｇ及
び残部として水を用い、アルカリ性剤の水溶液２００ml
を調製した（Ｂ液）。そして、Ａ液とＢ液とを混合し
た。混合液のｐＨは３．４、ゲルタイムは２０時間であ
った。EXAMPLES Test Category 1 (Curing Test) Example 1 An acidic silica sol 200 having a pH of 1.8 using 70 g of JIS No. 3 water glass, 14 g of 78% sulfuric acid and the balance water.
ml of a salt of a polyamine compound having a weight average molecular weight of about 1000 as a corrosion inhibitor as a corrosion inhibitor (PAA-HCI- manufactured by Nitto Boseki Co., Ltd.) as a corrosion inhibitor. 01) was dissolved in 0.4 g (solution A). Separately, using 0.8 g of magnesium hydroxide and water as the balance, 200 ml of an aqueous solution of an alkaline agent
Was prepared (Solution B). Then, the solution A and the solution B were mixed. The pH of the mixture was 3.4 and the gel time was 20 hours.
【００２２】比較例１ 腐食抑制剤を用いないこと以外は実施例１と同様に行な
った。混合液のｐＨは３．４、ゲルタイムは２０時間で
あり、ゲルの状態は実施例１と同じであった。Comparative Example 1 The same procedure as in Example 1 was carried out except that no corrosion inhibitor was used. The pH of the mixture was 3.4, the gel time was 20 hours, and the state of the gel was the same as in Example 1.
【００２３】実施例２ ＪＩＳ３号の水ガラス９８ｇ及び残部として水を用い、
水ガラスの水溶液２００mlを調製した（Ａ液）。別に、
７８％硫酸１８ｇ及び残部として水を用い、酸性剤の水
溶液２００mlを調製し、この酸性剤の水溶液に実施例１
と同じ腐食抑制剤を０．４ｇ溶解した（Ｂ液）。そし
て、Ａ液とＢ液とを混合した。混合液のｐＨは３．０、
ゲルタイムは２８時間であった。Example 2 Using 98 g of JIS No. 3 water glass and water as the balance,
200 ml of an aqueous solution of water glass was prepared (Solution A). Separately,
Using 18 g of 78% sulfuric acid and water as the balance, 200 ml of an aqueous solution of an acid agent was prepared.
0.4 g of the same corrosion inhibitor as above was dissolved (Solution B). Then, the solution A and the solution B were mixed. The pH of the mixture is 3.0,
The gel time was 28 hours.
【００２４】比較例２ 腐食抑制剤を用いないこと以外は実施例２と同様に行な
った。混合液のｐＨは３．０、ゲルタイムは２８時間で
あり、ゲルの状態は実施例２と同じであった。Comparative Example 2 The same procedure as in Example 2 was carried out except that no corrosion inhibitor was used. The pH of the mixture was 3.0, the gel time was 28 hours, and the state of the gel was the same as in Example 2.
【００２５】実施例３ ＪＩＳ３号の水ガラス１４０ｇ及び残部として水を用
い、水ガラスの水溶液２００mlを調製した（Ａ液）。別
に、７８％硫酸２２ｇ、アルミナ分含有量１７％の硫酸
アルミニウム４ｇ及び残部として水を用い、酸性剤の水
溶液２００mlを調製した（Ｂ液）。Ａ液とＢ液とを混合
し、その混合液に実施例１と同じ腐食抑制剤を０．４ｇ
溶解した。そのｐＨは３．５、ゲルタイムは５時間であ
った。Example 3 200 ml of an aqueous solution of water glass was prepared using 140 g of JIS No. 3 water glass and water as the balance (Solution A). Separately, 200 g of an aqueous solution of an acidic agent was prepared using 22 g of 78% sulfuric acid, 4 g of aluminum sulfate having an alumina content of 17%, and water as the balance (Solution B). Liquid A and liquid B are mixed, and 0.4 g of the same corrosion inhibitor as in Example 1 is added to the mixed liquid.
Dissolved. The pH was 3.5 and the gel time was 5 hours.
【００２６】比較例３ 腐食抑制剤を用いないこと以外は実施例３と同様に行な
った。そのｐＨは３．５、ゲルタイムは５時間であり、
ゲルの状態は実施例３と同じであった。Comparative Example 3 The same procedure as in Example 3 was carried out except that no corrosion inhibitor was used. Its pH is 3.5, gel time is 5 hours,
The state of the gel was the same as in Example 3.
【００２７】実施例４〜６ 腐食抑制剤として前記の式３で示される構成単位を繰り
返し単位とする重量平均分子量約５０００のポリアミン
系化合物の塩（日東紡績社製の商品名ＰＡＳ−Ａ−１）
を２ｇ用いたこと以外は実施例１〜３と同様に行なっ
た。実施例１に対応する実施例４のｐＨは３．４、ゲル
タイムは２０時間、実施例２に対応する実施例５のｐＨ
は３．０、ゲルタイムは２８時間、更に実施例３に対応
する実施例６のｐＨは３．５、ゲルタイムは５時間であ
った。Examples 4 to 6 As a corrosion inhibitor, a salt of a polyamine compound having a weight average molecular weight of about 5,000 having a repeating unit represented by the above formula 3 (PAS-A-1 manufactured by Nitto Boseki Co., Ltd.) )
Was performed in the same manner as in Examples 1 to 3, except that 2 g of was used. The pH of Example 4 corresponding to Example 1 was 3.4, the gel time was 20 hours, and the pH of Example 5 corresponding to Example 2 was
Was 3.0, the gel time was 28 hours, and the pH of Example 6 corresponding to Example 3 was 3.5, and the gel time was 5 hours.
【００２８】比較例４〜６ 腐食抑制剤を用いないこと以外は実施例４〜６と同様に
行なった。実施例４に対応する比較例４のｐＨは３．
４、ゲルタイムは２０時間、実施例５に対応する比較例
５のｐＨは３．０、ゲルタイムは２８時間、実施例６に
対応する比較例６のｐＨは３．５、ゲルタイムは５時間
であり、各比較例のゲルの状態は対応する各実施例と同
じであった。Comparative Examples 4 to 6 The same procedures as in Examples 4 to 6 were carried out except that no corrosion inhibitor was used. The pH of Comparative Example 4 corresponding to Example 4 was 3.
4. The gel time is 20 hours, the pH of Comparative Example 5 corresponding to Example 5 is 3.0, the gel time is 28 hours, the pH of Comparative Example 6 corresponding to Example 6 is 3.5, and the gel time is 5 hours. The state of the gel of each comparative example was the same as that of each corresponding example.
【００２９】実施例７〜９ 腐食抑制剤として前記の式４で示される構成単位を繰り
返し単位とする重量平均分子量約５０００のポリアミン
系化合物の塩（日東紡績社製の商品名ＰＡＳ−９２）を
０．２ｇ用いたこと以外は実施例１〜３と同様に行なっ
た。実施例１に対応する実施例７のｐＨは３．４、ゲル
タイムは２０時間、実施例２に対応する実施例８のｐＨ
は３．０、ゲルタイムは２８時間、更に実施例３に対応
する実施例９のｐＨは３．５、ゲルタイムは５時間であ
った。Examples 7 to 9 As a corrosion inhibitor, a salt of a polyamine compound having a weight average molecular weight of about 5,000 (PAS-92, manufactured by Nitto Boseki Co., Ltd.) having a repeating unit represented by the above formula 4 was used. It carried out like Example 1-3 except having used 0.2 g. Example 7 corresponding to Example 1 had a pH of 3.4, gel time was 20 hours, and Example 8 corresponding to Example 2 had a pH of 20 hours.
Was 3.0, the gel time was 28 hours, and the pH of Example 9 corresponding to Example 3 was 3.5, and the gel time was 5 hours.
【００３０】比較例７〜９ 腐食抑制剤を用いないこと以外は実施例７〜９と同様に
行なった。実施例７に対応する比較例７のｐＨは３．
４、ゲルタイムは２０時間、実施例８に対応する比較例
８のｐＨは３．０、ゲルタイムは２８時間、実施例９に
対応する比較例９のｐＨは３．５、ゲルタイムは５時間
であり、各比較例のゲルの状態は対応する各実施例と同
じであった。Comparative Examples 7 to 9 The same procedures as in Examples 7 to 9 were carried out except that no corrosion inhibitor was used. The pH of Comparative Example 7 corresponding to Example 7 was 3.
4. The gel time is 20 hours, the pH of Comparative Example 8 corresponding to Example 8 is 3.0, the gel time is 28 hours, the pH of Comparative Example 9 corresponding to Example 9 is 3.5, and the gel time is 5 hours. The state of the gel of each comparative example was the same as that of each corresponding example.
【００３１】実施例１０〜１２ 腐食抑制剤として前記の式５で示される構成単位を繰り
返し単位とする重量平均分子量約３２８のポリアミン系
化合物（三菱ガス化学社製の商品名ガスカミン３２８）
を０．４ｇ用いたこと以外は実施例１〜３と同様に行な
った。実施例１に対応する実施例１０のｐＨは３．４、
ゲルタイムは２０時間、実施例２に対応する実施例１１
のｐＨは３．０、ゲルタイムは２８時間、更に実施例３
に対応する実施例１２のｐＨは３．５、ゲルタイムは５
時間であった。Examples 10 to 12 As a corrosion inhibitor, a polyamine compound having a weight average molecular weight of about 328 having a constitutional unit represented by the above formula 5 as a repeating unit (trade name: Gascamine 328, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
Was performed in the same manner as in Examples 1 to 3, except that 0.4 g of was used. The pH of Example 10 corresponding to Example 1 was 3.4,
Gel time is 20 hours, Example 11 corresponding to Example 2
Has a pH of 3.0 and a gel time of 28 hours.
The pH of Example 12 corresponding to 3.5 and the gel time were 5
It was time.
【００３２】比較例１０〜１２ 腐食抑制剤を用いないこと以外は実施例１０〜１２と同
様に行なった。実施例１０に対応する比較例１０のｐＨ
は３．４、ゲルタイムは２０時間、実施例１１に対応す
る比較例１１のｐＨは３．０、ゲルタイムは２８時間、
実施例１２に対応する比較例１２のｐＨは３．５、ゲル
タイムは５時間であり、各比較例のゲルの状態は対応す
る各実施例と同じであった。Comparative Examples 10 to 12 The same procedures as in Examples 10 to 12 were carried out except that no corrosion inhibitor was used. PH of Comparative Example 10 corresponding to Example 10
Is 3.4, the gel time is 20 hours, the pH of Comparative Example 11 corresponding to Example 11 is 3.0, the gel time is 28 hours,
The pH of Comparative Example 12 corresponding to Example 12 was 3.5 and the gel time was 5 hours, and the gel state of each Comparative Example was the same as that of each corresponding Example.
【００３３】試験区分２（腐食抑制試験その１） 試験区分１の実施例１、４、７及び１０については腐食
抑制剤を溶解した酸性シリカゾルを試験液とし、またこ
れらに対応する比較例１、４、７及び１０については腐
食抑制剤を溶解しない酸性シリカゾルを試験液とした。
これらの各比較例の試験液は同じである。試験区分１の
実施例２、５、８及び１１については腐食抑制剤を溶解
した酸性剤の水溶液を試験液とし、またこれらに対応す
る比較例２、５、８及び１１については腐食抑制剤を溶
解しない酸性剤の水溶液を試験液とした。これらの各比
較例の試験液は同じである。試験区分１の実施例３、
６、９及び１２については腐食抑制剤を溶解した混合液
を試験液とし、またこれらに対応する比較例３、６、９
及び１２については腐食抑制剤を溶解しない混合液を試
験液とした。これらの各比較例の試験液は同じである。Test Category 2 (Corrosion Inhibition Test No. 1) For Examples 1, 4, 7 and 10 of Test Category 1, acidic silica sol in which a corrosion inhibitor was dissolved was used as a test solution, and Comparative Examples 1 and 2 corresponding to these were used. For 4, 7, and 10, acidic silica sols that did not dissolve the corrosion inhibitor were used as test liquids.
The test liquid of each of these comparative examples is the same. For Examples 2, 5, 8 and 11 of Test Category 1, an aqueous solution of an acidic agent in which a corrosion inhibitor was dissolved was used as a test solution, and for Comparative Examples 2, 5, 8 and 11 corresponding to these, a corrosion inhibitor was used. An aqueous solution of an insoluble acid agent was used as a test solution. The test liquid of each of these comparative examples is the same. Example 3 of Test Category 1,
With respect to 6, 9 and 12, a mixed solution in which a corrosion inhibitor was dissolved was used as a test solution, and Comparative Examples 3, 6, 9 corresponding to these were used.
For Examples 12 and 13, a mixed solution in which the corrosion inhibitor was not dissolved was used as a test solution. The test liquid of each of these comparative examples is the same.
【００３４】各試験液に、縦５０mm×横３２mm×厚さ６
mmの平板状の鉄片を３０分間浸漬した後、引き上げた鉄
片を同じ各試験液に再び３０分間浸漬するという操作
を、通算７日間行ない、その重量減（％）を求めた。結
果を表１にまとめて示した。Each test solution is 50 mm long × 32 mm wide × thickness 6
An operation of immersing a flat iron piece having a thickness of 30 mm for 30 minutes and then immersing the lifted iron piece in the same test solution again for 30 minutes was performed for a total of 7 days, and the weight loss (%) was determined. The results are summarized in Table 1.
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１において、腐食抑制剤の使用量は試験
液１００ml当たりの腐食抑制剤の使用量（ｇ）である。In Table 1, the amount of the corrosion inhibitor used is the amount (g) of the corrosion inhibitor used per 100 ml of the test solution.
【００３７】試験区分３（腐食抑制試験その２） 試験区分１の実施例１において、腐食抑制剤の使用量を
変えた複数の酸性シリカゾルを調製し、これらを試験液
として、試験区分２と同様に、鉄片の重量減（％）を求
めた。また試験区分１の実施例２において、腐食抑制剤
の使用量を変えた複数の酸性剤の水溶液を調製し、これ
らを試験液として、試験区分２と同様に、鉄片の重量減
（％）を求めた。更に試験区分１の実施例３において、
腐食抑制剤の使用量を変えた複数の混合液を調製し、こ
れらを試験液として、試験区分２と同様に、鉄片の重量
減（％）を求めた。結果を図１に示した。Test Category 3 (Corrosion Inhibition Test 2) In Example 1 of Test Category 1, a plurality of acidic silica sols were prepared in which the amount of the corrosion inhibitor used was changed, and these were used as test solutions in the same manner as in Test Category 2. Next, the weight loss (%) of the iron piece was determined. Also, in Example 2 of Test Category 1, aqueous solutions of a plurality of acidic agents in which the amount of the corrosion inhibitor was changed were prepared, and these were used as test solutions to reduce the weight loss (%) of the iron pieces in the same manner as in Test Category 2. I asked. Further, in Example 3 of Test Category 1,
A plurality of mixed solutions in which the amount of the corrosion inhibitor used was changed were prepared, and these were used as test solutions to determine the weight loss (%) of the iron pieces in the same manner as in Test Category 2. The results are shown in FIG.
【００３８】図１は、横軸に試験液１００ml当たりの腐
食抑制剤の使用量（ｇ）を目盛り、縦軸に鉄片の重量減
（％）を目盛っていて、片対数で腐食抑制剤の使用量
（ｇ）に対する重量減（％）を示している。図中、１は
酸性シリカゾルにおける鉄片の重量減曲線、２は酸性剤
の水溶液における鉄片の重量減曲線、３は混合液におけ
る鉄片の重量減曲線を示しており、点１１は実施例１の
酸性シリカゾル、点１２は比較例１の酸性シリカゾル、
点２１は実施例２の酸性剤の水溶液、点２２は比較例２
の酸性剤の水溶液、点３１は実施例３の混合液、点３２
は比較例３の混合液に相当している。In FIG. 1, the horizontal axis indicates the amount (g) of the corrosion inhibitor used per 100 ml of the test solution, and the vertical axis indicates the weight loss (%) of the iron piece. The weight loss (%) with respect to the amount used (g) is shown. In the figure, 1 is a weight loss curve of iron pieces in an acidic silica sol, 2 is a weight loss curve of iron pieces in an aqueous solution of an acid agent, 3 is a weight loss curve of iron pieces in a mixed solution, and point 11 is the acidity loss of Example 1. Silica sol, point 12 is an acidic silica sol of Comparative Example 1,
Point 21 is an aqueous solution of the acidic agent of Example 2, and Point 22 is Comparative Example 2.
An aqueous solution of an acidic agent, point 31 is a mixed solution of Example 3, point 32
Corresponds to the mixture of Comparative Example 3.
【００３９】図示を省略するが、試験区分１の実施例４
〜６、７〜９及び１０〜１２で用いた他の腐食抑制剤に
ついても同様にその使用量を変えた腐食抑制試験を行な
ったところ、図１とほぼ同様の傾向を示した。Although not shown, the fourth embodiment of test section 1
Corrosion inhibition tests were carried out for the other corrosion inhibitors used in Nos. 6, 7, 9 and 10 to 12 in which the amounts used were similarly varied.
【００４０】[0040]
【発明の効果】既に明らかなように、以上説明した本発
明には、本来の地盤硬化とこれに用いる機材の腐食抑制
とを同時に図ることができるという効果がある。As is apparent from the above, the present invention described above has an effect that the original hardening of the ground and the suppression of corrosion of the equipment used for the same can be achieved at the same time.
【図１】本発明に係る地盤硬化方法において腐食抑制剤
の使用による腐食抑制効果を例示するグラフ。FIG. 1 is a graph illustrating the effect of inhibiting corrosion by using a corrosion inhibitor in the method of hardening the ground according to the present invention.
１・・酸性シリカゾルにおける鉄片の重量減曲線、２・
・酸性剤の水溶液における鉄片の重量減曲線、３・・混
合液における鉄片の重量減曲線1. Weight loss curve of iron pieces in acidic silica sol 2.
-Weight loss curve of iron pieces in aqueous solution of acidic agent, 3-Weight loss curve of iron pieces in mixed solution
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 105:00 Ｃ０９Ｋ 105:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09K 105: 00 C09K 105: 00
Claims (9)
硬化させる方法において、硬化用薬液と共に腐食抑制剤
を用いることを特徴とする地盤硬化方法。1. A method of hardening a ground by injecting a hardening chemical into the ground, comprising using a corrosion inhibitor together with the hardening chemical.
び酸性剤の水溶液を用いて調製した酸性シリカゾルと、
アルカリ性剤の水溶液とを用いる請求項１記載の地盤硬
化方法。2. An acidic silica sol prepared by using an aqueous solution of water glass and an aqueous solution of an acid agent as a curing chemical.
The method for hardening a ground according to claim 1, wherein an aqueous solution of an alkaline agent is used.
と、酸性剤の水溶液とを用いる請求項１記載の地盤硬化
方法。3. The soil hardening method according to claim 1, wherein an aqueous solution of water glass and an aqueous solution of an acid agent are used as the hardening liquid.
記載の地盤硬化方法。4. The method according to claim 2, wherein the acidic agent is an inorganic acid.
The ground hardening method described.
機酸のアルミニウム塩類及びリン酸塩類から選ばれる一
つ又は二つ以上を含有するものである請求項２又は３記
載の地盤硬化方法。5. The soil hardening according to claim 2, wherein the acid agent has an inorganic acid as a main component, and further contains one or more selected from aluminum salts and phosphates of the inorganic acid. Method.
酸性シリカゾル、該酸性シリカゾルの調製に用いる酸性
剤の水溶液、硬化用薬液として用いる酸性剤の水溶液、
硬化用薬液として用いる酸性シリカゾルとアルカリ性剤
の水溶液との混合液又は硬化用薬液として用いる水ガラ
スの水溶液と酸性剤の水溶液との混合液に予め加えてお
く請求項２〜５のいずれか一つの項記載の地盤硬化方
法。6. An acidic silica sol used as a curing chemical solution, an aqueous solution of an acid agent used for preparing the acidic silica sol, an aqueous solution of an acid agent used as a curing chemical solution,
6. A liquid mixture of an acidic silica sol and an aqueous solution of an alkaline agent used as a curing chemical solution or a mixed solution of an aqueous solution of water glass and an aqueous solution of an acid agent used as a curing chemical solution, which is added in advance to any one of claims 2 to 5. Ground hardening method described in the item.
ノ基を有する重量平均分子量３００〜１５００００のポ
リアミン系化合物又はその塩である請求項１〜６のいず
れか一つの項記載の地盤硬化方法。7. The ground according to any one of claims 1 to 6, wherein the corrosion inhibitor is a polyamine compound having a weight average molecular weight of 300 to 150,000 having two or more amino groups in the molecule or a salt thereof. Curing method.
の式１、式２、式３、式４、式５又は式６で示される構
成単位を繰り返し単位とするものから選ばれる一つ又は
二つ以上である請求項７記載の地盤硬化方法。 【式１】 【式２】 【式３】 【式４】 【式５】 【式６】 8. The polyamine-based compound or a salt thereof is one or two selected from compounds having a repeating unit represented by the following formula 1, formula 2, formula 3, formula 4, formula 5 or formula 6. The ground hardening method according to claim 7, wherein the number is at least one. (Equation 1) (Equation 2) (Equation 3) (Equation 4) (Equation 5) (Equation 6)
用薬液１Ｌ当たり、０．１〜５０ｇの割合となるように
用いる請求項７又は８記載の地盤硬化方法。9. The soil hardening method according to claim 7, wherein the polyamine-based compound or a salt thereof is used in an amount of 0.1 to 50 g per 1 L of the hardening solution.
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| JP2000355262A JP4507393B2 (en) | 2000-11-22 | 2000-11-22 | Ground hardening method |
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|---|---|---|---|
| JP2000355262A JP4507393B2 (en) | 2000-11-22 | 2000-11-22 | Ground hardening method |
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| JP2002155279A true JP2002155279A (en) | 2002-05-28 |
| JP4507393B2 JP4507393B2 (en) | 2010-07-21 |
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|---|---|---|---|
| JP2000355262A Expired - Lifetime JP4507393B2 (en) | 2000-11-22 | 2000-11-22 | Ground hardening method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009078198A (en) * | 2007-09-25 | 2009-04-16 | Kurita Water Ind Ltd | Heavy metal fixing agent and ash treatment method using it |
| JP2009078197A (en) * | 2007-09-25 | 2009-04-16 | Kurita Water Ind Ltd | Heavy metal fixing agent and ash treatment method using it |
| JP2009078196A (en) * | 2007-09-25 | 2009-04-16 | Kurita Water Ind Ltd | Heavy metal fixing agent and ash treatment method using it |
| WO2016163310A1 (en) * | 2015-04-06 | 2016-10-13 | 栗田工業株式会社 | Heavy metal fixing agent for use in treatment of ash, and ash treatment method using same |
| JP2018104850A (en) * | 2016-12-27 | 2018-07-05 | 日東紡績株式会社 | Dye fixing agent for cellulose fiber |
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| JP2018104850A (en) * | 2016-12-27 | 2018-07-05 | 日東紡績株式会社 | Dye fixing agent for cellulose fiber |
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|---|---|
| JP4507393B2 (en) | 2010-07-21 |
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