JP3337716B2 - Injection material for flame-retardant rock consolidation - Google Patents
Injection material for flame-retardant rock consolidationInfo
- Publication number
- JP3337716B2 JP3337716B2 JP15732092A JP15732092A JP3337716B2 JP 3337716 B2 JP3337716 B2 JP 3337716B2 JP 15732092 A JP15732092 A JP 15732092A JP 15732092 A JP15732092 A JP 15732092A JP 3337716 B2 JP3337716 B2 JP 3337716B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- liquid
- sodium silicate
- flame
- isocyanate
- 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.)
- Expired - Fee Related
Links
Landscapes
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、軟弱な地盤に注入し
て、強固な地盤に改善する難燃性岩盤固結用注入材薬液
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injectable liquid chemical for hardening a non-combustible rock mass which is injected into a soft ground to improve the solid ground.
【０００２】[0002]
【従来の技術とその課題】従来、軟弱な地盤に注入して
これを強固にする薬液としては、水ガラス系や速硬性セ
メント系などの無機系と、アクリルアミド系やウレタン
系などの有機系等種々の注入材薬液が提案されている。
しかしながら、いずれも一長一短があり、地盤安定化処
理工事で要求する条件を全て満足する性能は得られてい
ないのが現状である。2. Description of the Related Art Conventionally, chemicals for injecting into soft ground to strengthen it include inorganic liquids such as water glass and quick-setting cement, and organic liquids such as acrylamide and urethane. Various injectable chemicals have been proposed.
However, each of them has advantages and disadvantages, and at present, performance that satisfies all the conditions required in the ground stabilization work has not been obtained.
【０００３】一般にトンネルのように密閉化された場所
での地盤安定化処理工事で最も恐ろしいものは坑内火災
である。[0003] In general, the most fearsome thing in ground stabilization work in a closed place such as a tunnel is an underground fire.
【０００４】無機系薬液は、不燃性又は難燃性であるた
め、このような火災時に燃焼するなどの問題は全く無い
が、注入工事に手間がかかり、かつ、注入後の固結時間
が長く強度の発生に時間がかかるので、現場の工事を長
期間停止しなければならない等の課題があり、それを改
良した２液型ウレタン系薬液が提案されている(特開昭6
3−8477号公報、特開平 4−73313号公報)。[0004] Since inorganic chemicals are nonflammable or nonflammable, there is no problem such as burning in the event of a fire, but the injection work is troublesome and the solidification time after injection is long. There is a problem that the construction of the site must be stopped for a long period of time because the generation of strength takes time, and a two-pack type urethane-based chemical solution which has improved such a problem has been proposed (Japanese Patent Application Laid-Open No.
3-8477, JP-A-4-73313).
【０００５】ウレタン系薬液は固結時間が短く、かつ、
注入工事も簡単で工事の進行にも余り障害にならない極
めて優れた岩盤固結用薬液として知られている。しかし
ながら、ウレタン系薬液は、多価アルコールとイソシア
ネートとが反応しポリウレタンフォームを形成する、主
成分が有機物のものであり、坑内火災が発生した場合、
その硬化物が燃焼して状況をますます悪化させる恐れが
あるという課題があった。[0005] Urethane chemicals have a short consolidation time,
It is known as an extremely excellent liquid chemical for rock consolidation, which is easy to inject and does not hinder the progress of the construction. However, urethane-based chemicals react with polyhydric alcohol and isocyanate to form a polyurethane foam. The main component is an organic substance, and when an underground fire occurs,
There is a problem that the cured product may burn to worsen the situation.
【０００６】また、ポリウレタンは高価な樹脂であり、
これを多量に地盤中に注入することは経済的にも実現性
を欠くものであった。[0006] Polyurethane is an expensive resin,
Injecting a large amount of this into the ground was not economically feasible.
【０００７】本発明者は、種々検討した結果、特定の成
分を使用することによって、前記の無機系薬液や有機系
薬液のもつ課題を解決できる知見を得て本発明を完成す
るに至った。As a result of various studies, the present inventors have found that the use of specific components can solve the above-mentioned problems of the inorganic and organic chemical solutions, and have completed the present invention.
【０００８】[0008]
【課題を解決するための手段】即ち、本発明は、ケイ酸
ナトリウム水溶液とウレタン反応触媒とを主成分とする
Ａ液と、イソシアネートを主成分とするＢ液とからな
り、該ウレタン反応触媒がテトラメチルヘキサメチレン
ジアミン、ジメチルノルマルオクチルアミン、ジメチル
ノルマルドデシルアミンを主成分とすることを特徴とす
る難燃性岩盤固結用注入材薬液である。That is, the present invention comprises a solution A having a sodium silicate aqueous solution and a urethane reaction catalyst as main components and a solution B having an isocyanate as a main component.
The urethane reaction catalyst is tetramethylhexamethylene
Diamine, dimethyl normal octylamine, dimethyl
Characterized by having normal dodecylamine as the main component
That is a flame retardant rock consolidating grout chemicals.
【０００９】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１０】本発明は、Ａ液として難燃性の無機系薬液
であるケイ酸ナトリウム水溶液とウレタン反応触媒と
を、Ｂ液としては、このケイ酸ナトリウム水溶液を、例
えば、２分以内のように速やかに固結するイソシアネー
トを用いて、ケイ酸ナトリウムを骨格とする強固な難燃
性硬化物を地盤中に形成し、軟弱地盤を安定化させるも
のである。特に、この反応によって地盤中に形成した硬
化物は、難燃性のケイ酸ナトリウムを骨格としているた
め、坑内火災に対しても問題はほとんどみられないもの
である。According to the present invention, the aqueous solution of sodium silicate and the urethane reaction catalyst, which are flame retardant inorganic chemicals, are used as the liquid A, and the aqueous sodium silicate solution is used as the liquid B, for example, within 2 minutes. with isocyanates to promptly solidify, sodium silicate solid fire retardant cured product as a skeleton formed in the ground, it is intended to stabilize the soft ground. In particular, since the cured product formed in the ground by this reaction has flame-retardant sodium silicate as a skeleton, there is almost no problem with underground fire.
【００１１】また、この反応はいわゆるイソシアネート
基によるウレタン反応であるため、その固結反応は極め
て迅速で、無機系薬液のみの場合のように、注入後の固
結時間が長く、強度の発生に時間がかかるものではな
く、工事の進行の障害にはならないものである。Further, since this reaction is a so-called urethane reaction due to an isocyanate group, the consolidation reaction is extremely rapid, and the consolidation time after injection is long as in the case of only an inorganic chemical solution, resulting in the generation of strength. It does not take much time and does not hinder the progress of construction.
【００１２】本発明に係るＡ液とは、ケイ酸ナトリウム
水溶液とウレタン反応触媒とを主成分とするものであ
る。The solution A according to the present invention contains an aqueous solution of sodium silicate and a urethane reaction catalyst as main components.
【００１３】ここで、ケイ酸ナトリウム水溶液は、一般
には水ガラスとして市販されておりJIS規格で１号〜４
号まで規定されている。Here, the sodium silicate aqueous solution is generally commercially available as water glass, and is JIS standard No. 1 to 4
No. is specified.
【００１４】本発明に使用されるケイ酸ナトリウム水溶
液は、硬化物の強度の面から、なるべく固形分濃度の高
いものが好ましいが、地盤中に注入した場合、粘度が小
さい程Ｂ液との混合性が良く、粘度が高いと岩盤への浸
透が阻害されて工事が困難となることから、本発明で
は、20℃の水溶液粘度が500cps以下が好ましく、300cps
以下がより好ましい。具体的には、粘度が150cps以下の
市販の水ガラスのJIS ２号やJIS ３号の使用が好まし
く、特にJIS ２号の水ガラスの使用がより好ましい。The aqueous sodium silicate solution used in the present invention preferably has a solid content as high as possible from the viewpoint of the strength of the cured product. In the present invention, the viscosity of the aqueous solution at 20 ° C. is preferably 500 cps or less, and the viscosity is preferably 300 cps.
The following is more preferred. Specifically, it is preferable to use JIS No. 2 or JIS No. 3 of a commercially available water glass having a viscosity of 150 cps or less, and particularly preferable to use JIS No. 2 water glass.
【００１５】本発明では、ケイ酸ナトリウム水溶液とイ
ソシアネートとを混合することにより、ケイ酸ナトリウ
ムとイソシアネート基との反応は直ちに開始されるが、
注入工事を順調に進行させるためにはウレタン反応触媒
をＡ液中に配合してその反応速度を促進させることが必
要である。In the present invention, the reaction between the sodium silicate and the isocyanate group is immediately started by mixing the aqueous solution of sodium silicate with the isocyanate.
In order for the injection work to proceed smoothly, it is necessary to mix a urethane reaction catalyst in the solution A to accelerate the reaction rate.
【００１６】一般に、イソシアネート基によりウレタン
を生成するウレタン反応触媒としては、トリエチレンジ
アミン等のアミン系触媒とジブチル錫ジラウレートのよ
うな有機金属系触媒など各種があるが、本発明のケイ酸
ナトリウム水溶液は、酸、アルカリ、及び金属等により
ゲルが析出しやすくなるため、ケイ酸ナトリウム水溶液
に難溶な、アミン系触媒を使用することが必要である。In general, there are various urethane reaction catalysts for producing urethane by an isocyanate group, such as amine catalysts such as triethylenediamine and organometallic catalysts such as dibutyltin dilaurate. It is necessary to use an amine-based catalyst which is hardly soluble in an aqueous solution of sodium silicate since a gel is easily precipitated by an acid, an alkali, a metal or the like.
【００１７】アミン系触媒としては、N,N,N',N'-テトラ
メチルヘキサメチレンジアミン、N,N-ジメチル-N- オク
チルアミン、及びN,N-ジメチル-N-ドデシルアミンが挙
げられる。[0017] As amine-based catalyst, N, N, N ', N'-tetramethyl hexamethylenediamine, N, N-dimethyl -N- octylamine, and N, N- dimethyl -N- dodecylamine ani
I can do it .
【００１８】ウレタン反応触媒の使用量は、その工事の
やり方や要求される硬化速度などによって決定されるも
のであるが、Ａ液100重量部に対して、0.5〜10重量部が
好ましく、１〜５重量部がより好ましい。0.5重量部未
満では、反応速度が遅く実用的でない。The amount of the urethane reaction catalyst to be used is determined by the manner of construction and the required curing rate, but is preferably 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the solution A. 5 parts by weight is more preferred. If the amount is less than 0.5 part by weight, the reaction rate is too low to be practical.
【００１９】本発明に係るＢ液とは、前記Ａ液と接触す
ると、Ａ液中のケイ酸ナトリウム水溶液を、例えば、２
分以内で速やかに固結するイソシアネートを主成分とす
るものである。The solution B according to the present invention, when contacted with the solution A, converts the aqueous solution of sodium silicate in the solution A into, for example, 2
Isocyanate to promptly consolidated within a minute as a main component.
【００２０】ここで、イソシアネートとしては、ジフェ
ニルメタン−４，４′−ジイソシアネート(ＭＤＩ)、ポ
リメチレン・ポリフェニル・ポリイソシアネート(ポリ
メリックＭＤＩ又はクルードＭＤＩ)、及びトリレンジ
イソシアネート(ＴＤＩ)等が好ましく、そのうちの一種
又は二種以上の使用が可能である。As the isocyanate, diphenylmethane-4,4'-diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI or crude MDI), tolylene diisocyanate (TDI) and the like are preferable. One or more types can be used.
【００２１】本発明で用いるイソシアネートのイソシア
ネート基含有量は、特に制限されるものではないが、通
常、イソシアネート基含有量が20〜50重量％程度である
イソシアネートの使用が好ましく、イソシアネート基含
有量30〜35重量％のポリメリックＭＤＩの使用がより好
ましい。Although the isocyanate group content of the isocyanate used in the present invention is not particularly limited, it is preferable to use an isocyanate having an isocyanate group content of about 20 to 50% by weight. More preferably, ~ 35% by weight of polymeric MDI is used.
【００２２】また、本発明では、例へば、ポリメリック
ＭＤＩと、ジエチレングリコール、ジプロピレングリコ
ール、又はポリブタジエン等との反応生成物でイソシア
ネート基含有量が３〜20重量％である、いわゆる、変性
イソシアネートを、ポリメリックＭＤＩ100重量部に対
して、１〜20重量部併用することは、硬化物の発泡倍率
や硬化物の実用強度などの物性を改良する面から有効で
ある。In the present invention, for example, a so-called modified isocyanate having a isocyanate group content of 3 to 20% by weight in a reaction product of polymeric MDI and diethylene glycol, dipropylene glycol or polybutadiene is used as a polymer. The combined use of 1 to 20 parts by weight with respect to 100 parts by weight of MDI is effective from the viewpoint of improving the physical properties such as the expansion ratio of the cured product and the practical strength of the cured product.
【００２３】Ａ液とＢ液の混合割合は、Ａ液100重量部
に対して、Ｂ液50〜200重量部が好ましい。Ａ液に対す
るＢ液の割合が少なくなると、難燃性物質であるケイ酸
ナトリウム水溶液の割合が多くなるので硬化物の難燃性
は増加するが、発泡性がほとんど無くなり岩盤への浸透
性は低下する。一方、Ａ液に対するＢ液の割合が多くな
ると、ケイ酸ナトリウム水溶液の割合が低下するので硬
化物の難燃性は低下するが、イソシアネート基と水との
反応で発生する炭酸ガスによる発泡倍率は1.5〜2.5倍と
なり岩盤への浸透性は向上する。Ａ液100重量部に対し
て、Ｂ液100重量部とすると、Ａ液とＢ液の２液混合後
の硬化時間が10〜60秒と極めて短時間で硬化を終了し、
必要強度を発現することが可能である。The mixing ratio of the A liquid and the B liquid is preferably 50 to 200 parts by weight of the B liquid to 100 parts by weight of the A liquid. When the ratio of the liquid B to the liquid A decreases, the ratio of the aqueous solution of sodium silicate, which is a flame retardant, increases, so that the flame retardancy of the cured product increases, but the foaming property is almost lost and the permeability into the rock decreases. I do. On the other hand, when the ratio of the solution B to the solution A increases, the flame retardancy of the cured product decreases because the ratio of the aqueous solution of sodium silicate decreases, but the expansion ratio due to the carbon dioxide gas generated by the reaction between the isocyanate group and water decreases. It becomes 1.5 to 2.5 times, and the permeability to rock is improved. Assuming that 100 parts by weight of liquid A and 100 parts by weight of liquid B, the curing time after mixing two liquids of liquid A and liquid B is 10 to 60 seconds, and the curing is completed in a very short time,
It is possible to develop the required strength.
【００２４】[0024]
【実施例】以下、本発明を実施例に基づいてさらに説明
する。The present invention will be further described below with reference to examples.
【００２５】実施例１ 表１に示すようにケイ酸ナトリウム水溶液とウレタン反
応触媒を用いてＡ液とし、Ａ液100重量部に対して、表
１に示すイソシアネート液(Ｂ液)を配合し、その固結時
間、発泡倍率、及び圧縮強度を測定し、難燃性の評価を
行った。結果を表１に併記する。Example 1 As shown in Table 1, a solution A was prepared using an aqueous solution of sodium silicate and a urethane reaction catalyst, and an isocyanate solution (solution B) shown in Table 1 was blended with 100 parts by weight of solution A. The consolidation time, expansion ratio, and compression strength were measured, and the flame retardancy was evaluated. The results are also shown in Table 1.
【００２６】＜試験方法＞ 固結時間：Ａ液とＢ液を混合してから、最大に発泡した
時点までの時間 発泡倍率：Ａ液とＢ液の合計の容積に対する最大発泡時
の容積 圧縮強度：縦２cm×横２cm×高さ２cmの型枠にＡ液とＢ
液の混合液を入れ、成形１日後の強度を測定した。 難燃性 ：JIS K 7201に基づき、３mm厚のシートを作成
して酸素指数を測定。 難燃性の評価は、酸素指数30以上を良好、30未満を不良
とした。<Test method> Consolidation time: time from mixing of liquid A and liquid B to the time of maximum foaming Expansion ratio: volume at maximum foaming with respect to the total volume of liquid A and liquid B Compressive strength : Liquid A and B on a mold 2cm long x 2cm wide x 2cm high
A mixed solution of the liquids was added, and the strength one day after molding was measured. Flame retardancy: Based on JIS K 7201, a 3 mm thick sheet was prepared and the oxygen index was measured. The flame retardancy was evaluated as good when the oxygen index was 30 or more, and poor when the oxygen index was less than 30.
【００２７】＜使用材料＞ ケイ酸ナトリウム水溶液ａ：日本化学工業(株)製水ガラ
ス、JIS ２号 ケイ酸ナトリウム水溶液ｂ：日本化学工業(株)製水ガラ
ス、JIS ３号 ウレタン反応触媒Ａ：テトラメチルヘキサメチレンジア
ミン ウレタン反応触媒Ｂ：N,N-ジメチル-ノルマルオクチル
アミン イソシアネートα：三井東圧(株)製ポリメリックＭＤＩ、イソシアネート基含有 量31重量％ 〃 β：ポリブタジエン系プレポリマー 〃 γ：エチレングリコール系プレポリマー<Materials> Aqueous solution of sodium silicate a: Water glass manufactured by Nippon Chemical Industry Co., Ltd., JIS No. 2 Aqueous solution of sodium silicate b: Water glass manufactured by Nippon Chemical Industry Co., Ltd., JIS No. 3 Urethane reaction catalyst A: Tetramethylhexamethylenediamine urethane reaction catalyst B: N, N-dimethyl-normal octylamine Isocyanate α: Polymeric MDI manufactured by Mitsui Toatsu Co., Ltd., isocyanate group content 31% by weight 〃 β: polybutadiene-based prepolymer γ γ: ethylene Glycol prepolymer
【００２８】[0028]
【表１】 [Table 1]
【００２９】実施例２ 実験No.1- 4の配合のＡ液とＢ液を用いて、３ｍのフォ
アパイリング施工を行った。ボルト１本当たり60kgのＡ
液とＢ液の混合物を注入圧力20kg/cm2で注入し、トンネ
ル断面当たり18本のボルトの打ち込み施工を行った。Ａ
液とＢ液の混合物は混合後30秒でゲル化した。ボルトの
打ち込み施工終了後３時間でトンネル掘削を実施した
が、注入前には落下した岩盤が、本発明の薬液の注入後
はまったく落下がなく、十分に注入目的が達せられた。
また、崩れやすかった地山が完全に自立し、湧水も完全
に止めることができた。Example 2 A fore piling of 3 m was performed using the solution A and the solution B having the composition of Experiment No. 1-4. 60kg A per bolt
The mixture of the liquid and the liquid B was injected at an injection pressure of 20 kg / cm 2 , and 18 bolts were driven per tunnel cross section. A
The mixture of the liquid and the liquid B gelled 30 seconds after mixing. Tunnel excavation was performed 3 hours after the completion of the bolting work. However, the rock which had fallen before the injection did not fall at all after the injection of the chemical solution of the present invention, and the injection purpose was sufficiently achieved.
In addition, the ground that was easy to collapse completely became independent, and the spring water was completely stopped.
【００３０】[0030]
【発明の効果】本発明の難燃性岩盤固結用注入材薬液を
使用することによって、ケイ酸ナトリウム水溶液とイソ
シアネートとの化学反応によって２分以内に固結は完了
するため土木工事のスピードアップが可能となる。ま
た、生成した硬化物は無機物であるケイ酸ナトリウムを
骨格としているために極めて難燃性で、たとえ、坑内火
災が発生しても燃焼に対する抵抗性がある。さらに、本
発明の反応は、イソシアネート基によるウレタンフォー
ムを生成するウレタン反応であるため、反応が極めて迅
速であり、無機系薬液のみの場合のように強度の発現に
時間がかかるものではなく、注入工事も簡単である。こ
のように、ウレタン系薬液の長所を残しながら難燃性硬
化物を得られ、薬液の半分以上がケイ酸ナトリウム水溶
液であるため、ウレタン系薬液に比較してその価格も大
巾に低く、経済的にも実現化が容易となる、等の効果を
奏する。By using the flame-retardant rock consolidating grout chemical the present invention, the speed-up of the civil works for complete solidification within 2 minutes by a chemical reaction between sodium silicate solution and an isocyanate Becomes possible. In addition, the resulting cured product is extremely flame-retardant since it has an inorganic sodium silicate as a skeleton. Even if an underground fire occurs, it has resistance to combustion. Furthermore, since the reaction of the present invention is a urethane reaction that generates urethane foam by an isocyanate group, the reaction is extremely rapid, and it does not take a long time to develop strength as in the case of only an inorganic chemical solution. The construction is easy. In this way, a flame-retardant cured product can be obtained while retaining the advantages of a urethane-based chemical, and more than half of the chemical is an aqueous solution of sodium silicate. specifically also realization is facilitated, the effect and the like.
フロントページの続き (72)発明者 岩崎 昌浩 新潟県西頸城郡青海町大字青海2209番地 電気化学工業株式会社 青海工場内 (56)参考文献 特開 昭55−160079（ＪＰ，Ａ) 特開 昭61−9482（ＪＰ，Ａ) 特開 昭50−86598（ＪＰ，Ａ) 特開 昭50−19885（ＪＰ，Ａ) 特開 平４−283290（ＪＰ，Ａ) 特開 平７−242873（ＪＰ，Ａ) 特開 平５−320644（ＪＰ，Ａ) 特開 平４−318096（ＪＰ，Ａ) 特開 平５−78667（ＪＰ，Ａ) 特開 平５−78668（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09K 17/00 - 17/52 E02D 3/12 Continuation of the front page (72) Inventor Masahiro Iwasaki 2209 Aomi, Aomi-cho, Nishikubiki-gun, Niigata Denki Kagaku Kogyo Co., Ltd. Aomi Plant (56) References JP-A-55-160079 (JP, A) JP-A-61- 9482 (JP, A) JP-A-50-86598 (JP, A) JP-A-50-19885 (JP, A) JP-A-4-283290 (JP, A) JP-A-7-242873 (JP, A) JP-A-5-320644 (JP, A) JP-A-4-318096 (JP, A) JP-A-5-78667 (JP, A) JP-A-5-78668 (JP, A) (58) (Int.Cl. 7 , DB name) C09K 17/00-17/52 E02D 3/12
Claims (1)
触媒とを主成分とするＡ液と、イソシアネートを主成分
とするＢ液とからなり、該ウレタン反応触媒がテトラメ
チルヘキサメチレンジアミン、N,N-ジメチルノルマルオ
クチルアミン、ジメチルノルマルドデシルアミンを主成
分とすることを特徴とする難燃性岩盤固結用注入材薬
液。1. A and A solution mainly composed of sodium silicate solution and a urethane reaction catalyst, Ri Do and a B solution mainly composed of isocyanate, the urethane reaction catalyst is tetramethylene
Tylhexamethylene diamine, N, N-dimethyl normalo
Mainly octylamine and dimethyl normal dodecylamine
A filler material for flame-retardant rock consolidation characterized by the following:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15732092A JP3337716B2 (en) | 1992-05-26 | 1992-05-26 | Injection material for flame-retardant rock consolidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15732092A JP3337716B2 (en) | 1992-05-26 | 1992-05-26 | Injection material for flame-retardant rock consolidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320645A JPH05320645A (en) | 1993-12-03 |
| JP3337716B2 true JP3337716B2 (en) | 2002-10-21 |
Family
ID=15647122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15732092A Expired - Fee Related JP3337716B2 (en) | 1992-05-26 | 1992-05-26 | Injection material for flame-retardant rock consolidation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3337716B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2896083B2 (en) * | 1993-11-30 | 1999-05-31 | 第一工業製薬株式会社 | Injectable chemical composition for ground stabilization and method of water stabilization using the same |
-
1992
- 1992-05-26 JP JP15732092A patent/JP3337716B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05320645A (en) | 1993-12-03 |
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