JP3530977B2 - Composition for ground compaction - Google Patents
Composition for ground compactionInfo
- Publication number
- JP3530977B2 JP3530977B2 JP2000340947A JP2000340947A JP3530977B2 JP 3530977 B2 JP3530977 B2 JP 3530977B2 JP 2000340947 A JP2000340947 A JP 2000340947A JP 2000340947 A JP2000340947 A JP 2000340947A JP 3530977 B2 JP3530977 B2 JP 3530977B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- composition
- liquid
- ground
- consolidation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/30—Polyisocyanates; Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Biological Depolymerization Polymers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、軟弱な地山（地
盤、岩盤等も含む）を固結安定化するために用いられる
地山固結用組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for solidifying rock, which is used for solidifying and stabilizing soft ground (including ground, rock, etc.).
【０００２】[0002]
【従来の技術】従来より、軟弱な地盤を対象としたトン
ネル工事は、トンネル切羽の天盤の落下防止のため、ト
ンネル切羽先端の天盤前方部に孔を穿設し、この孔内に
二液硬化型のウレタン系薬液を注入して地盤に浸透させ
硬化させることにより、トンネル切羽先端前方部の地盤
を安定強化した後、トンネル切羽先端前方部の地盤を掘
削し、掘り進めてトンネル工事を行っている。2. Description of the Related Art Conventionally, in tunnel construction for soft ground, in order to prevent the roof of the tunnel face from falling, a hole is made in the front part of the top face of the tunnel face, and a hole is cut into this hole. By injecting a liquid-curable urethane-based chemical into the ground and hardening it, the ground in front of the tip of the tunnel face is stabilized and strengthened.After that, the ground in front of the face of the tunnel face is excavated and digged to perform tunnel construction. Is going.
【０００３】しかしながら、この場合の工事では、掘削
された地盤はポリウレタン発泡体を含むが、このポリウ
レタン発泡体は自然には分解されないため、掘削した地
盤をそのまま廃棄することは地球環境の劣化を引き起こ
すため許されない。したがって、地球環境の劣化を防ぐ
ためには、ポリウレタン発泡体を分解するための特別の
処理工程が必要となり、コスト及び時間を要するという
難点があった。そのため、生分解性に優れた地山固結用
組成物の開発が待望されていた。However, in the construction in this case, the excavated ground contains polyurethane foam, but since this polyurethane foam is not decomposed naturally, discarding the excavated ground as it is causes deterioration of the global environment. Because it is not allowed. Therefore, in order to prevent the deterioration of the global environment, a special treatment step for decomposing the polyurethane foam is required, and there is a drawback in that cost and time are required. Therefore, the development of a composition for solidifying rocks, which is excellent in biodegradability, has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、生分解性に
優れた地山固結用組成物を提供することをその課題とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for natural consolidation which is excellent in biodegradability.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、生分解性
に優れた地山固結用組成物を得るため、鋭意研究を重ね
た。その結果、ポリイソシアネートとともに、イソシア
ネート基に対して反応性を有する反応基をもつ天然有機
材料を併用すると、天然有機材料中の反応基が、ポリイ
ソシアネート中のイソシアネート基と反応して、ポリウ
レタンの分子骨格中に天然有機材料に由来する構造が組
み込まれ、これが土壌中の微生物によって自然に分解さ
れ、該ポリウレタンが優れた生分解性を示すことを見い
だし、本発明に到達した。即ち、本発明によれば、以下
に示す地山固結用組成物が提供される。（１）イソシアネート基に対して反応性を有する反応基
をもつ天然有機材料を液状の多官能性含活性水素化合物
に溶解した溶液からなるＡ成分と、ポリイソシアネート
からなるＢ成分とからなり、該Ａ成分及び該Ｂ成分はい
ずれも５〜５００ｃｐｓ（２０℃）の粘度を有する液体
であることを特徴とする地山固結用組成物。 （２）該Ａ成分の天然有機材料が、リグニン、糖蜜、澱
粉およびそれらの変性物からなる群から選ばれた少なく
とも一つの化合物である前記（１）記載の地山固結組成
物。 （３）Ａ成分とＢ成分の混合物が、粘度５〜５００ｃｐ
ｓ（２０℃）の液体である前記（１）又は（２）記載の
地山固結用組成物。 （４）Ａ成分とＢ成分の混合物からなる液体を４倍に発
泡させた発泡体の難燃性が酸素指数２２以上である前記
（１）〜（３）のいずれかに記載の地山固結用組成物。 （５）該地山固結用組成物を砂カラム法で試験したとき
の発泡倍率が１．５〜６．０倍である前記（１）〜
（４）のいずれかに記載の地山固結用組成物。 （６）上記砂カラム法で試験した後の、砂を含む試験体
の一軸圧縮強度が０．５〜２０ＭＰａである前記（５）
記載の地山固結用組成物。 The present inventors have found that biodegradability
Earnestly researched to obtain a composition for solidifying rock
It was As a result, together with the polyisocyanate,
Natural organic compounds with reactive groups that are reactive towards nate groups
When the materials are used together, the reactive groups in the natural organic material are
Reacts with the isocyanate groups in the cyanate,
Structures derived from natural organic materials are assembled in the molecular skeleton of lettan
Which is naturally degraded by microorganisms in the soil.
And found that the polyurethane exhibits excellent biodegradability.
However, the present invention has been reached. That is, according to the present invention,Less than
Shown inA ground consolidation composition is provided.(1) Reactive group having reactivity with isocyanate group
Liquid polyfunctional active hydrogen compounds containing natural organic materials
A component consisting of a solution dissolved in
And B component, and the A component and the B component are Yes.
Liquid with a viscosity of 5 to 500 cps (20 ° C)
The composition for solidifying rocks according to claim 1. (2) The natural organic material of the component A is lignin, molasses, starch
A few selected from the group consisting of flour and their modified products
The solid rock composition according to (1) above, which is one compound
object. (3) The mixture of the A component and the B component has a viscosity of 5 to 500 cp.
The liquid of s (20 ° C) described in (1) or (2) above.
Ground consolidation composition. (4) Four times as much liquid as the mixture of A and B components
The flame retardance of the foamed product is 22 or more oxygen index.
The ground consolidation composition according to any one of (1) to (3). (5) When the composition for solidifying rock is tested by a sand column method
(1) -wherein the expansion ratio is 1.5 to 6.0 times
The composition for solidifying rock according to any one of (4). (6) Sand-containing test body after being tested by the sand column method
(5) whose uniaxial compressive strength is 0.5 to 20 MPa
A composition for solidifying the ground as described.
【０００６】[0006]
【発明の実施の形態】本発明の地山固結用組成物は、イ
ソシアネート基に対して反応性を有する反応基をもつ天
然有機材料（Ａ成分）と、ポリイソシアネート（Ｂ成
分）とからなることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The ground consolidation composition of the present invention comprises a natural organic material (component A) having a reactive group having reactivity with an isocyanate group and a polyisocyanate (component B). It is characterized by
【０００７】本発明で用いる天然有機材料（Ａ成分）と
しては、イソシアネート基に対して反応性を有する反応
基（例えば、ヒドロキシル基やカルボキシル基等）をも
つものであれば特に限定はされず、各種のものを用いる
ことができる。このようなものには、リグニン、糖蜜、
単糖類、二糖類、糖類等の単糖類又は小糖類の他、澱
粉、セルロース、ヘミセルロース等の多糖類やそれらの
変性物等があげられる。これらは単独でもしくは２種以
上併せて用いられる。これらの中でも、生分解性に優れ
る点で、リグニン、糖蜜、澱粉又は澱粉変性物が好適に
用いられる。The natural organic material (component A) used in the present invention is not particularly limited as long as it has a reactive group having reactivity with an isocyanate group (eg, a hydroxyl group or a carboxyl group). Various types can be used. These include lignin, molasses,
In addition to monosaccharides and small sugars such as monosaccharides, disaccharides and sugars, polysaccharides such as starch, cellulose and hemicellulose and modified products thereof can be mentioned. These may be used alone or in combination of two or more. Among these, lignin, molasses, starch or modified starch is preferably used because of its excellent biodegradability.
【０００８】上記リグニンとしては、木材、わら等を木
質化した植物体の主成分として一般に用いられるもので
あれば特に限定はなく、例えば、クラフトリグニン、ソ
ルボルシスリグニン、リグノスルフォン等があげられ
る。上記糖蜜としては、サトウキビ、テンサイ等から得
られるものであれば特に限定はなく、未精製糖蜜、精製
糖蜜、氷精蜜や、精糖後に得られる廃糖蜜等があげられ
る。上記澱粉としては、グルコースが重合した多糖類
で、穀物、植物の根等に多く存在するものであれば特に
限定はなく、直鎖状のアミロースや分枝状のアミロペク
チン等があげられる。また、上記特定の天然有機材料
（Ａ成分）として、リグニン変性物、糖蜜変性物、澱粉
変性物等を用いることも可能である。The above-mentioned lignin is not particularly limited as long as it is generally used as a main component of a plant body obtained by converting wood, straw or the like into wood, and examples thereof include kraft lignin, sorborsis lignin and lignosulphone. The molasses is not particularly limited as long as it is obtained from sugar cane, sugar beet and the like, and examples include unrefined molasses, purified molasses, ice molasses, and molasses obtained after refined sugar. The above-mentioned starch is not particularly limited as long as it is a polysaccharide obtained by polymerizing glucose and is abundant in grains, roots of plants and the like, and examples thereof include linear amylose and branched amylopectin. It is also possible to use a lignin-modified product, molasses-modified product, starch-modified product or the like as the specific natural organic material (component A).
【０００９】本発明においては、前記天然有機材料は、
溶液として用いるのが好ましい。この場合、その材料を
溶解させるための薬剤としては、その材料を溶解するも
のであればどのようなものでも使用可能であるが、本発
明の場合、特に、ポリイソシアネートに対して反応性を
有する有機薬剤の使用が好ましい。このようなものとし
ては、分子中に少なくとも２つの活性水素を有する有機
薬剤、特にポリオールの使用が好ましい。このような多
官能性の活性水素含有化合物としては、エチレングリコ
ール、ポリエチレングリコール、プロピレングリコー
ル、ポリプロピレングリコール、トリメチロールエタ
ン、トリメチロールプロパン、へキシレングリコール、
ヒマシ油等のアルキレングリコールや、グリセリン、ソ
ルビトール、蔗糖、エチレンジアミン、ジエタノールア
ミン、トリエタノールアミン等が挙げられる。これらの
多官能性活性水素含有化合物は、単独でもしくは２種以
上併せて用いることができる。さらに、それらの化合物
に、エチレンオキサイドやプロピレンオキサイド等のア
ルキレンオキサイドを開環重合させたポリエーテルポリ
オール等を用いることもできる。これらのものは単独で
もしくは２種以上併せて用いられる。In the present invention, the natural organic material is
It is preferably used as a solution. In this case, as the agent for dissolving the material, any agent can be used as long as it dissolves the material, but in the case of the present invention, it is particularly reactive with polyisocyanate. The use of organic agents is preferred. As such, it is preferable to use an organic drug having at least two active hydrogens in the molecule, particularly a polyol. Such polyfunctional active hydrogen-containing compounds include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, hexylene glycol,
Examples include alkylene glycols such as castor oil, glycerin, sorbitol, sucrose, ethylenediamine, diethanolamine, and triethanolamine. These polyfunctional active hydrogen-containing compounds can be used alone or in combination of two or more. Furthermore, polyether polyols obtained by ring-opening polymerization of alkylene oxides such as ethylene oxide and propylene oxide can also be used for these compounds. These may be used alone or in combination of two or more.
【００１０】前記天然有機材料をポリオール等の多官能
性含活性水素化合物（有機薬剤）に溶解して用いる場
合、その材料と有機薬剤との混合重量比は、生分解性等
の観点から、材料／有機薬剤＝１０／９０〜９０／１０
の範囲に設定することが好ましく、特に好ましくは材料
／有機薬剤＝２０／８０〜８０／２０である。When the above-mentioned natural organic material is used by dissolving it in a polyfunctional active hydrogen compound (organic drug) such as polyol, the mixing weight ratio of the material and the organic drug is from the viewpoint of biodegradability and the like. / Organic drug = 10/90 to 90/10
It is preferable to set in the range of, and particularly preferably, material / organic drug = 20/80 to 80/20.
【００１１】なお、上記Ａ成分には、発泡開始時間を調
整する目的で、アミン触媒を配合することが好ましい。
上記アミン触媒としては、例えば、トリエチレンジアミ
ン、ビス−（ジメチルアミノエチル）エーテル、テトラ
メチルヘキサメチレンジアミン、テトラメチルプロパン
−１,３−ジアミン、ペンタメチルジエチレントリアミ
ン、テトラメチルプロパン１，３−ジアミン、ペンタメ
チルジエチレントリアミン、ビス（ジメチルアミノエチ
ル）エーテル、トリメチルアミノエチルピペラジン、１
−メチルイミダゾール、１−イソブチル−２−メチルイ
ミダゾ−ル等があげられる。また、鉛、スズ等の金属を
もったウレタン触媒ジブチルチンジラウレート等もあげ
られる。これら単独でもしくは２種以上併せて用いられ
る。It should be noted that an amine catalyst is preferably added to the component A for the purpose of adjusting the foaming start time.
Examples of the amine catalyst include triethylenediamine, bis- (dimethylaminoethyl) ether, tetramethylhexamethylenediamine, tetramethylpropane-1,3-diamine, pentamethyldiethylenetriamine, tetramethylpropane-1,3-diamine, penta Methyldiethylenetriamine, bis (dimethylaminoethyl) ether, trimethylaminoethylpiperazine, 1
-Methylimidazole, 1-isobutyl-2-methylimidazole and the like can be mentioned. Further, a urethane catalyst such as dibutyltin dilaurate having a metal such as lead or tin may be used. These may be used alone or in combination of two or more.
【００１２】上記アミン触媒の配合量は、その添加によ
る効果などの点から、上記天然有機材料と多官能性活性
水素含有化合物の合計１００重量部（以下「部」と略
す）に対して、０．１〜５部の範囲に設定することが好
ましく、特に好ましくは０．１〜２部である。From the standpoint of the effect of the addition of the amine catalyst, the amount of the amine catalyst is 0 based on 100 parts by weight of the total of the natural organic material and the polyfunctional active hydrogen-containing compound (hereinafter abbreviated as “part”). It is preferably set in the range of 1 to 5 parts, and particularly preferably 0.1 to 2 parts.
【００１３】さらに、上記Ａ成分には、整泡剤、難燃
剤、減粘剤等を配合しても差し支えない。上記整泡剤と
しては、例えば、ポリオキシアルキレン・ジメチルポリ
シロキサコポリマー、オルガノポリシロキサン、オキシ
エチル化高級アルコール等があげられ、これらは単独で
もしくは２種以上併せて用いられる。上記難燃剤として
は、例えば、トリスクロロプロピルホスフォート、トリ
ス・β−クロロプロピルホスフォート等があげられ、こ
れらは単独でもしくは２種以上併せて用いられる。上記
減粘剤としては、例えば、プロピレンカーボネート（Ｐ
Ｃ）、脂肪酸メチルエステル類等があげられる。Further, a foam stabilizer, a flame retardant, a viscosity reducing agent and the like may be added to the component A. Examples of the foam stabilizers include polyoxyalkylene / dimethylpolysiloxacopolymers, organopolysiloxanes, oxyethylated higher alcohols, etc. These may be used alone or in combination of two or more. Examples of the flame retardant include tris chloropropyl phosphate, tris .beta.-chloropropyl phosphate and the like, and these may be used alone or in combination of two or more kinds. Examples of the above-mentioned viscosity reducer include propylene carbonate (P
C), fatty acid methyl esters and the like.
【００１４】上記特定の天然有機材料（Ａ成分）を含む
溶液の粘度は、５〜５００ｃｐｓ／２０℃の範囲が好ま
しく、特に好ましくは３５〜２００ｃｐｓ／２０℃であ
る。溶液の粘度が５ｃｐｓ／２０℃未満であると、減粘
剤、低分子量分が多くなり、固結物がもろくなる。逆に
５００ｃｐｓ／２０℃を超えると、浸透性が劣る傾向が
見られるようになる。The viscosity of the solution containing the specific natural organic material (component A) is preferably in the range of 5 to 500 cps / 20 ° C., particularly preferably 35 to 200 cps / 20 ° C. When the viscosity of the solution is less than 5 cps / 20 ° C., the thickener and the low molecular weight component are increased, and the solidified product becomes brittle. On the contrary, if it exceeds 500 cps / 20 ° C., the penetrability tends to be poor.
【００１５】本発明で用いるポリイソシアネートとして
は、特に限定はなく、従来公知の各種のもので、芳香族
系ポリイソシアネートや、脂肪族系ポリイソシアネート
等を好ましく用いることができる。ポリイソシアネート
の具体例としては、例えば、ジフェニルメタン−４,
４’−ジイソシアネート（ＭＤＩ）、ポリメリックＭＤ
Ｉ（クルードＭＤＩ：Ｃ−ＭＤＩ）、トリレンジイソシ
アネート（ＴＤＩ）、ヘキサメチレンジイソシアネート
（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤ
Ｉ）、キシリレンジイソシアネート（ＸＤＩ）等および
それらの変性例があげられる。これらは単独でもしくは
２種以上併せて用いられる。なかでも、作業環境性や経
済性を考慮して、ＭＤＩ、Ｃ−ＭＤＩやこれらの変性体
が好適に用いられる。The polyisocyanate used in the present invention is not particularly limited, and various conventionally known polyisocyanates such as aromatic polyisocyanate and aliphatic polyisocyanate can be preferably used. Specific examples of the polyisocyanate include, for example, diphenylmethane-4,
4'-diisocyanate (MDI), polymeric MD
I (crude MDI: C-MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPD)
I), xylylene diisocyanate (XDI), and modified examples thereof. These may be used alone or in combination of two or more. Among them, MDI, C-MDI and modified products thereof are preferably used in consideration of work environment and economy.
【００１６】なお、上記Ｂ成分には、ポリイソシアネー
トとともに、粘度低化剤等を配合しても差し支えない。
この場合、上記ポリイソシアネートの含有量は、Ｂ成分
全体の５０重量％以上に設定することが好ましく、特に
好ましくは８０重量％以上である。The component B may be blended with a polyisocyanate and a viscosity reducing agent.
In this case, the content of the polyisocyanate is preferably set to 50% by weight or more, and particularly preferably 80% by weight or more based on the whole B component.
【００１７】上記ポリイソシアネートからなるＢ成分
（液体）の粘度は、混合性、地山への浸透性の点から、
５〜５００ｃｐｓ／２０℃の範囲が好ましく、特に好ま
しくは３５〜２００ｃｐｓ／２０℃である。Ｂ成分の粘
度が５ｃｐｓ／２０℃未満であると、固結物の強度が低
くなる。逆に、３００ｃｐｓ／２０℃を超えると、浸透
性に劣る傾向が見られるようになる。The viscosity of the component B (liquid) composed of the above polyisocyanate is, from the viewpoint of mixing properties and permeability into the ground,
The range of 5 to 500 cps / 20 ° C is preferable, and the range of 35 to 200 cps / 20 ° C is particularly preferable. If the viscosity of the component B is less than 5 cps / 20 ° C, the strength of the solidified product will be low. On the contrary, when it exceeds 300 cps / 20 ° C., the permeability tends to be poor.
【００１８】本発明の組成物を用いて地山を固結化する
には、先ず、Ａ成分を含むＡ液と、Ｂ成分を含むＢ液を
調製する。Ａ成分を含むＡ液は、Ａ成分とそれを溶解さ
せるグリコール類等の有機薬剤を含むものであるが、そ
の他、慣用の補助成分、例えば、発泡剤（水）、ウレタ
ン化触媒（アミン触媒）、整泡剤、減粘剤等を含有する
ことができる。これらの補助成分は、いずれも、通常の
ポリウレタンフォームの製造において使用されているも
のであり、本発明では、従来公知の各種のものを適宜選
定して用いることができる。一方、Ｂ成分を含むＢ液
は、通常、液状のＢ成分単独からなるが、必要に応じ、
減粘剤、非反応性有機溶媒等の慣用の補助成分を適量含
有することができる。次に、Ａ液とＢ液を混合し、この
混合液を、固結処理対象となる地山に対して注入あるい
は混合する。これによって、混合液中のＡ成分とＢ成分
とが反応し、生分解性の天然有機材料に由来する生分解
性構造が組み込まれたポリウレタンが生成する。そし
て、このポリウレタンは、地山を固結化する。前記Ａ液
とＢ液との混合重量比は、Ａ液１重量部当り、Ｂ液０．
５〜６、好ましくは１〜３重量部の割合である。Ａ成分
とＢ成分を含む混合液からなる組成物を調整する場合、
前記の方法の他、工事現場において、ポリオール等の有
機薬剤中に、Ａ成分、Ｂ成分及び補助成分を混合する方
法等も採用することができる。In order to consolidate the ground using the composition of the present invention, first, solution A containing component A and solution B containing component B are prepared. The solution A containing the component A contains the component A and an organic agent such as glycols that dissolves the component A, but other conventional auxiliary components such as a foaming agent (water), a urethane-forming catalyst (amine catalyst), and a conditioning agent. A foaming agent, a viscosity reducing agent, etc. can be contained. All of these auxiliary components are used in ordinary production of polyurethane foam, and various conventionally known components can be appropriately selected and used in the present invention. On the other hand, the B liquid containing the B component is usually composed of the liquid B component alone.
A conventional auxiliary component such as a viscosity reducing agent or a non-reactive organic solvent may be contained in an appropriate amount. Next, the liquid A and the liquid B are mixed, and this mixed liquid is injected or mixed into the ground to be consolidated. As a result, the A component and the B component in the mixed liquid react with each other to produce polyurethane having a biodegradable structure derived from a biodegradable natural organic material incorporated therein. And this polyurethane solidifies the ground. The mixing weight ratio of the liquid A and the liquid B was such that the amount of the liquid B was 0.
The proportion is 5 to 6, preferably 1 to 3 parts by weight. When preparing a composition comprising a mixed liquid containing the A component and the B component,
In addition to the above method, a method of mixing the component A, the component B, and the auxiliary component in an organic chemical such as polyol at the construction site can also be adopted.
【００１９】本発明の組成物は、砂カラム法（ジェオフ
ロンテ研究会、標準試験方法）で試験したときの発泡倍
率が１．５〜６．０倍の範囲のものが好ましく、特に好
ましくは２.０〜６．０倍である。発泡倍率が１．５倍
未満であると、地山改良が少なく、注入液の量が多くな
りコスト高になる。逆に発泡倍率が６．０倍を超える
と、地山の改良体強度が低くなる傾向を示す。The composition of the present invention preferably has an expansion ratio in the range of 1.5 to 6.0 times when tested by the sand column method (Geofronte Research Group, standard test method), particularly preferably 2. It is 0.0 to 6.0 times. If the expansion ratio is less than 1.5 times, the amount of ground improvement is small, the amount of the injection liquid is large, and the cost is high. On the contrary, when the expansion ratio exceeds 6.0 times, the strength of the improved body of natural ground tends to be low.
【００２０】また、本発明の組成物は、上記砂カラム法
で試験した後の、砂を含む試験体の一軸圧縮強度が０．
５〜２０ＭＰａの範囲のものが好ましく、特に好ましく
は１．０〜１０ＭＰａである。一軸圧縮強度が０．５Ｍ
Ｐａ未満であると、改良体強度が低く、掘削時にくずれ
る可能性があり、逆に２０ＭＰａを超えると、高強度す
ぎて掘削に時間、コストがかかるようになる。The composition of the present invention has a uniaxial compressive strength of 0. 0 after being tested by the sand column method.
It is preferably in the range of 5 to 20 MPa, particularly preferably 1.0 to 10 MPa. Uniaxial compressive strength is 0.5M
If it is less than Pa, the strength of the improved body is low and there is a possibility that it will collapse during excavation. On the contrary, if it exceeds 20 MPa, the strength will be too high and it will take time and cost to excavate.
【００２１】本発明の組成物は、軟弱な地山（地盤、岩
盤等も含む）を堅固な地山に改善するために用いること
が好ましく、これ以外にもロックボルトの定着剤、法面
のボルト定着剤等に使用することもできる。The composition of the present invention is preferably used for improving soft ground (including ground, bedrock, etc.) into a solid ground. It can also be used as a bolt fixing agent or the like.
【００２２】[0022]
【実施例】次に、本発明を実施例によりさらに詳細に説
明する。なお、以下の実施例に用いた材料は、以下の通
りである。EXAMPLES Next, the present invention will be described in more detail by way of examples. The materials used in the following examples are as follows.
【００２３】［ＫＬ−Ｐ３３］クラフトリグニン、水酸
基当量７.０ｍｅｑ／ｇをポリエチレングリコール（Ｐ
ＥＧ−２００、分子量２００）に溶解させてなる溶液
（クラフトリグニン濃度：３３重量％）[KL-P33] Kraft lignin, hydroxyl group equivalent of 7.0 meq / g is polyethylene glycol (P
EG-200, molecular weight 200) solution (craft lignin concentration: 33% by weight)
【００２４】［ＭＰ−３３］糖蜜（水酸基当量１１．５
ｍｅｑ／ｇ）をポリエチレングリコール（ＰＥＧ−２０
０、分子量２００）に溶解させてなる溶液（糖蜜濃度：
３３重量％）[MP-33] molasses (hydroxyl equivalent 11.5
meq / g) to polyethylene glycol (PEG-20)
0 (molecular weight: 200) dissolved in a solution (molasses concentration:
33% by weight)
【００２５】［ＳＬ−３３］ソルポリシスリグニン(水
酸基当量７．０ｍｅｑ／ｇ)をポリエチレングリコール
（ＰＥＧ−２００、分子量２００）に溶解させてなる溶
液)（ソルポリシスリグニン濃度３３重量％）[SL-33] Solpolycis lignin (hydroxyl equivalent 7.0 meq / g) dissolved in polyethylene glycol (PEG-200, molecular weight 200) (sol polycis lignin concentration 33% by weight)
【００２６】［ＬＳ−３３］
リグノスルホン酸（水酸基当量 ７．０ｍｅｑ／ｇ）を
ポリエチレングリコール（ＰＥＧ２００、分子量２０
０）に溶解させてなる溶液）（リグノスルホン酸濃度：
３３重量％）[LS-33] Lignosulfonic acid (hydroxyl equivalent 7.0 meq / g) was added to polyethylene glycol (PEG200, molecular weight 20).
0) solution) (concentration of lignosulfonic acid:
33% by weight)
【００２７】［ＬＳＭｅ］
リグソスルフォン酸（Ｃａ塩あるいはＮａ塩を水に５０
％溶解した水溶液。[LSMe] Lignosulphonic acid (Ca salt or Na salt in water
% Dissolved aqueous solution.
【００２８】［アミン触媒］
トリエチレンジアミンをジプロピレングリコールに溶解
した溶液（カオライザーＮｏ．３１）[Amine Catalyst] A solution prepared by dissolving triethylenediamine in dipropylene glycol (Kaolizer No. 31).
【００２９】［アミン触媒］
Ｎ，Ｎ，Ｎ′，Ｎ"，Ｎ"−ペンタメチルジエチレントリ
アミン（カオライザーＮｏ．３）[Amine Catalyst] N, N, N ′, N ″, N ″ -Pentamethyldiethylenetriamine (Kaolizer No. 3)
【００３０】［整泡剤］
シリコーン界面活性剤（日本ユニカー社製、Ｌ−５４２
１）[Foam stabilizer] Silicone surfactant (L-542 manufactured by Nippon Unicar Co., Ltd.)
1)
【００３１】［難燃剤］
トリス・β−クロロプロピルホスフェート（大八化学工
業社製、ＴＭＣＰＰ）[Flame Retardant] Tris .beta.-chloropropyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., TMCPP)
【００３２】［減粘剤］ ポリカーボネート（ＰＣ）[Thickening agent] Polycarbonate (PC)
【００３３】［ポリイソシアネート］
Ｃ−ＭＤＩ（ＢＡＳＦイノアック社製、ルプラネートＭ
Ｂ−５Ｓ）[Polyisocyanate] C-MDI (manufactured by BASF Inoac, Luplanate M)
B-5S)
【００３４】実施例１〜４、比較例１
下記の表１に示す各成分を同表に示す割合（重量部）で
配合してなるＡ液と、ポリイソシアネートからなるＢ液
をそれぞれ準備した。なお、実施例５については、Ｌｓ
Ｍｅ５０部を先に注入してから、ＭＰ−３３の５０部か
らなるＡ液を注入した。そして、このＡ液およびＢ液を
用いて、下記の基準に従い、各特性の評価を行った。こ
れらの結果を、後記の表１に併せて示した。Examples 1 to 4 and Comparative Example 1 Liquid A prepared by mixing the components shown in Table 1 below in the proportions (parts by weight) shown in the same table and liquid B formed of polyisocyanate were prepared. In addition, about Example 5, Ls
50 parts of Me was injected first, and then the solution A consisting of 50 parts of MP-33 was injected. Then, using the solutions A and B, the respective characteristics were evaluated according to the following criteria. The results are also shown in Table 1 below.
【００３５】[0035]
【表１】 [Table 1]
【００３６】［クリームタイム（ＣＴ）］ミキシング完
了後混合体が泡化を開始し、白濁状のクリーム状液体と
なる液体が膨張開始する寸前までの時間を測定した。[Cream time (CT)] After the mixing was completed, the mixture started foaming, and the time immediately before the start of expansion of the liquid, which became a cloudy creamy liquid, was measured.
【００３７】［ライズタイム（ＲＴ）］クリーム状液体
が膨張し泡状物質となりつつ成長し、膨張が完了するま
での時間を測定した。[Rise Time (RT)] The time until the creamy liquid swelled and grew into a foamy substance and the swelling was completed was measured.
【００３８】［発泡倍率］上記Ａ液とＢ液を５０ｇずつ
計量し、これらを１リットルのディスカップにとり、攪
拌装置（スリーワンモーター）を用いて、液温２０℃で
１０００ｒｐｍ×１０秒間攪拌し反応させた。そして、
反応終了後の発泡高さを測定し、発泡倍率を求めた。[Expansion ratio] 50 g each of the above-mentioned liquid A and liquid B were weighed, placed in a 1-liter discup, and stirred with a stirring device (three one motor) at a liquid temperature of 20 ° C. for 1000 rpm × 10 seconds to react. Let And
The foaming height after completion of the reaction was measured to determine the foaming ratio.
【００３９】［最大発熱温度］上記１リットルのディス
カップ中に温度センサーを入れ、記録計を用いて最大発
熱温度を測定した。[Maximum exothermic temperature] A temperature sensor was placed in the 1-liter discup and the maximum exothermic temperature was measured using a recorder.
【００４０】［難燃性］ＪＩＳ Ｋ ７２０１に準拠
し、難燃性の評価を行った。すなわち、Ａ液とＢ液とを
所定の混合比で、４倍に発泡させた発泡体の難燃性を酸
素指数で示した。[Flame retardancy] The flame retardancy was evaluated according to JIS K 7201. That is, the flame retardancy of a foam obtained by expanding the liquid A and the liquid B four times at a predetermined mixing ratio was shown by an oxygen index.
【００４１】［生分解性］所定の混合比で発泡させた樹
脂を、土壌抽出液と混合、振とうし、発泡体の重量の減
少率を測定する。６ヶ月で１０重量％以上減少した場合
を○、１０％未満を×とした。[Biodegradability] A resin foamed at a predetermined mixing ratio is mixed with a soil extract and shaken to measure the weight reduction rate of the foam. The case where the amount decreased by 10% by weight or more in 6 months was evaluated as ◯, and the case where less than 10% was evaluated as x.
【００４２】上記表１に示した結果から、すべての実施
例品は、比較例品に比べて生分解性に優れていることが
わかる。また、すべての実施例品は比較例品と略同等の
ウレタン物性を備えていることもわかる。From the results shown in Table 1 above, it can be seen that all the products of Examples are superior in biodegradability to the products of Comparative Examples. It can also be seen that all the example products have urethane properties that are substantially the same as the comparative example products.
【００４３】なお、実施例品と比較例品の粘度を比較し
たところ、実施例品は比較例品に比べて若干粘度が高く
なっているが、Ｂ液（ルプラネートＭＢ−５Ｓ）単独の
場合と略同等の粘度であり、実用上問題がないレベルで
あった。When the viscosities of the example product and the comparative example product were compared, it was found that the viscosity of the example product was slightly higher than that of the comparative example product, but it was compared with the case of liquid B (luplanate MB-5S) alone. The viscosity was almost the same, and there was no problem in practical use.
【００４４】次に、実施例品および比較例品を用いて、
砂カラム法（ジェオフロンテ研究会、ウレタン注入オフ
ァポーリング技術塗料内、標準試験方法）により、浸透
性試験及び一軸圧縮強度試験を行った。これらの結果
を、後記の表２に併せて示した。Next, using the products of Examples and Comparative Examples,
A permeability test and a uniaxial compressive strength test were conducted by a sand column method (Geofronte Research Group, urethane infusion polling technology paint, standard test method). The results are also shown in Table 2 below.
【００４５】［浸透性試験］予め離型処理を行ったアク
リル製パイプの内部に市販の４号珪砂２７０ｇを入れ
た。ついで、過剰の水を入れ振動させ余分な水を出し、
砂を締め固め砂の高さを１４〜１５ｃｍにした。つぎ
に、薬液（実施例品、比較例品）を所定量注型し、混合
撹拌させて、浸透距離、固結比、砂内発砲倍率を求め
た。[Permeability Test] 270 g of commercially available No. 4 silica sand was put into the inside of an acrylic pipe which had been previously subjected to a mold release treatment. Then, add excess water and vibrate to remove excess water.
The sand was compacted and the sand height was 14-15 cm. Next, a predetermined amount of the chemical solution (Example product, Comparative example product) was cast, mixed and stirred, and the permeation distance, the solidification ratio, and the sand expansion ratio were determined.
【００４６】［一軸圧縮強度試験］脱型した試験体を円
柱状（直径４０ｍｍ×高さ８０ｍｍ）に成形した後、密
度を測定した。また、ＪＩＳ Ｋ １２１６に準拠し、
一軸圧縮試験を行った。[Uniaxial Compressive Strength Test] The demolded test body was molded into a columnar shape (diameter 40 mm × height 80 mm), and the density was measured. Also, in accordance with JIS K 1216,
A uniaxial compression test was conducted.
【００４７】[0047]
【表２】 [Table 2]
【００４８】上記表２に示した結果から、すべての実施
例品は比較例品と略同等の浸透性及び強度を備えている
ことがわかる。したがって、全ての実施例品は、地山改
良用薬液として適しているといえる。From the results shown in Table 2 above, it can be seen that all the Example products have substantially the same permeability and strength as the Comparative Example products. Therefore, it can be said that all the example products are suitable as a chemical solution for improving ground.
【００４９】[0049]
【発明の効果】以上のように、本発明の地山固結用組成
物は、ポリイソシアネートとともに、イソシアネート基
に対して反応性を有する反応基をもつ天然有機材料を併
用するものである。そのため、天然有機材料中の反応基
がポリイソシアネート中のイソシアネート基と反応し
て、ポリウレタンの分子骨格注に天然有機材料に由来す
る構造が組み込まれ、これが土壌中の微生物によって自
然に分解され、ポリウレタンが優れた生分解性を示すよ
うになる。そして、上記Ａ液とＢ液の粘度を特定の範囲
に設定すると、浸透性が良好でどの地質にも注入するこ
とができる。また、上記Ａ液とＢ液とを混合し、４倍に
発泡させた発泡体の難燃性が特定の酸素指数の範囲内で
ある場合、ポリウレタンが特に優れた難燃性を示すよう
になる。さらに、地山固結用組成物を砂カラム法で試験
したときの発泡倍率が特定の範囲内である場合、地山改
良剤としてより優れた浸透性を示すようになる。また、
上記砂カラム法で試験した後の、砂を含む試験体の一軸
圧縮強度が特定の範囲内である場合、地山改良剤として
より優れた強度を示すようになる。INDUSTRIAL APPLICABILITY As described above, the ground consolidation composition of the present invention uses, together with polyisocyanate, a natural organic material having a reactive group having reactivity with an isocyanate group. Therefore, the reactive group in the natural organic material reacts with the isocyanate group in the polyisocyanate, and the structure derived from the natural organic material is incorporated into the molecular skeleton of polyurethane, which is naturally decomposed by microorganisms in the soil and Shows excellent biodegradability. When the viscosities of the liquid A and the liquid B are set within a specific range, the permeability is good and the liquid can be injected into any geology. Further, when the flame retardancy of the foam obtained by mixing the liquid A and the liquid B and expanding the mixture four times is within a specific oxygen index range, the polyurethane exhibits particularly excellent flame retardancy. . Furthermore, when the expansion ratio when the composition for solidifying rocks is tested by the sand column method is within a specific range, the composition shows more excellent permeability as a natural improving agent. Also,
When the uniaxial compressive strength of the sand-containing test body after the test by the sand column method is within a specific range, it shows more excellent strength as a ground improvement agent.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｋ 103:00 Ｃ０９Ｋ 103:00 (72)発明者 水野 昇 愛知県小牧市東三丁目１番地 東海ゴム 工業株式会社内 (72)発明者 伊香賀 修治 愛知県小牧市東三丁目１番地 東海ゴム 工業株式会社内 (72)発明者 畠山 兵衛 福井県丹生郡越廼村八ッ俣73−８ (72)発明者 廣瀬 重雄 千葉県松戸市下矢切205 (56)参考文献 特開 平10−212481（ＪＰ，Ａ) 特開 平11−124576（ＪＰ，Ａ) 特開 平５−320647（ＪＰ，Ａ) 特開 平８−231955（ＪＰ，Ａ) 特開 平11−80732（ＪＰ，Ａ) 特開 平９−132634（ＪＰ，Ａ) 特開 平８−225628（ＪＰ，Ａ) 特開 平６−80966（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09K 17/30 C09K 17/32 C08G 18/64 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C09K 103: 00 C09K 103: 00 (72) Inventor Noboru Mizuno Tokai Rubber Industrial Co., Ltd. 1st Higashi 3-chome 1 Komaki-shi, Aichi (72) Inventor Shuji Ikaga 1-chome, Higashi 3-chome, Komaki City, Aichi Prefecture Tokai Rubber Industrial Co., Ltd. 205 (56) Reference JP-A-10-212481 (JP, A) JP-A-11-124576 (JP, A) JP-A-5-320647 (JP, A) JP-A-8-231955 (JP, A) JP-A-11-80732 (JP, A) JP-A-9-132634 (JP, A) JP-A-8-225628 (JP, A) JP-A-6-80966 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C09K 17/30 C09K 17/32 C08G 18 / 64
Claims (6)
る反応基をもつ天然有機材料を液状の多官能性含活性水
素化合物に溶解した溶液からなるＡ成分と、ポリイソシ
アネートからなるＢ成分とからなり、該Ａ成分及び該Ｂ
成分はいずれも５〜５００ｃｐｓ（２０℃）の粘度を有
する液体であることを特徴とする地山固結用組成物。1. A natural organic material having a reactive group having reactivity with an isocyanate group, which is a liquid polyfunctional activated water.
A component A consisting of a solution prepared by dissolving containing compound, Ri Do and a B component consisting of a polyisocyanate, said component A and said B
All components have a viscosity of 5 to 500 cps (20 ° C)
Natural ground consolidating composition characterized liquid der Rukoto to.
糖蜜、澱粉およびそれらの変性物からなる群から選ばれ
た少なくとも一つの化合物である請求項１記載の地山固
結組成物。2. The natural organic material of component A is lignin,
The natural rock solidifying composition according to claim 1, which is at least one compound selected from the group consisting of molasses, starch, and modified products thereof.
００ｃｐｓ（２０℃）の液体である請求項１又は２記載
の地山固結用組成物。3. A mixture of the component A and the component B has a viscosity of 5-5.
The ground consolidating composition according to claim 1 or 2, which is a liquid of 00 cps (20 ° C).
４倍に発泡させた発泡体の難燃性が酸素指数２２以上で
ある請求項１〜３のいずれかに記載の地山固結用組成
物。4. The solidified consolidation according to any one of claims 1 to 3, wherein a foam obtained by foaming a liquid comprising a mixture of A component and B component four times has an oxygen index of 22 or more. Composition.
したときの発泡倍率が１．５〜６．０倍である請求項１
〜４のいずれかに記載の地山固結用組成物。5. The foaming ratio of the ground consolidation composition as tested by a sand column method is 1.5 to 6.0.
The composition for rock mass consolidation according to any one of to 4.
む試験体の一軸圧縮強度が０．５〜２０ＭＰａである請
求項５記載の地山固結用組成物。6. The ground consolidation composition according to claim 5, which has a uniaxial compressive strength of 0.5 to 20 MPa after being tested by the sand column method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000340947A JP3530977B2 (en) | 2000-11-08 | 2000-11-08 | Composition for ground compaction |
| DE2001153980 DE10153980A1 (en) | 2000-11-08 | 2001-11-06 | Biodegradable polyurethane composition for stabilizing soil, e.g. in tunnel building, contains natural organic material with isocyanate-reactive groups, e.g. lignin, and polyisocyanate component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000340947A JP3530977B2 (en) | 2000-11-08 | 2000-11-08 | Composition for ground compaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002146351A JP2002146351A (en) | 2002-05-22 |
| JP3530977B2 true JP3530977B2 (en) | 2004-05-24 |
Family
ID=18815774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000340947A Expired - Fee Related JP3530977B2 (en) | 2000-11-08 | 2000-11-08 | Composition for ground compaction |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3530977B2 (en) |
| DE (1) | DE10153980A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260366A (en) * | 2010-05-29 | 2011-11-30 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2450852A1 (en) * | 2001-06-15 | 2002-12-27 | National Institute Of Advanced Industrial Science And Technology | Lignin-containing polyurethane and process for producing the same |
| CN102649906B (en) * | 2011-02-23 | 2014-04-16 | 柯正侃 | Soil body stabilizing agent, and preparation method and application thereof |
| CA2874970A1 (en) * | 2012-06-01 | 2013-12-05 | Henri J.M. Grunbauer | A composition in the form of a dispersion comprising a lignin, a method for the manufacturing thereof and use thereof |
| CN109265297B (en) * | 2018-11-20 | 2021-08-20 | 宁夏宁苗生态园林(集团)股份有限公司 | Alkaline soil remediation material and preparation method thereof |
| CN110157439B (en) * | 2019-06-21 | 2021-06-15 | 湖南凯迪工程科技有限公司 | Wind erosion resistant modified polyurethane sand-fixation soil remediation agent and preparation method thereof |
| CN116063687B (en) * | 2021-11-01 | 2024-05-07 | 中国石油化工股份有限公司 | Hydrophobic quartz sand and preparation method and application thereof |
| CN114106844A (en) * | 2021-12-06 | 2022-03-01 | 江苏路邦道昇新材料科技有限公司 | Bio-based liquid soil curing agent with improved strength and preparation method thereof |
-
2000
- 2000-11-08 JP JP2000340947A patent/JP3530977B2/en not_active Expired - Fee Related
-
2001
- 2001-11-06 DE DE2001153980 patent/DE10153980A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260366A (en) * | 2010-05-29 | 2011-11-30 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
| CN102260366B (en) * | 2010-05-29 | 2014-04-02 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10153980A1 (en) | 2002-06-06 |
| JP2002146351A (en) | 2002-05-22 |
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