JP3741520B2 - Organic polymer grout agent and ground improvement method using it, sewer pipe groundwater stop method, hazardous substance sealing method - Google Patents

Description

のように解離していて良く、負電荷を持った安定なミセル及び／又は微小コロイドを成していて良い。
【００４５】
また、Ｘとして−Ｏ^-・Ｎａ⁺基及び／又は−Ｏ^-・Ｋ⁺基を持つ前記（イ）は、一般にアルカリ性領域下で比較的安定な性質を示す。
すなわち、ｐＨ値で９〜１３のアルカリ性領域下で調製された（イ）は、その水溶液中で活性シラノール基が、下記式（Ｂ）［化９］及び／又は式（Ｃ）［化１０］で示されるような解離平衡にあるものとして良く、正電荷を持った安定なミセル及び／又は微小コロイドを成していて良い。
【化９】

【化１０】

また、例えば１分子中に−Ｓｉ−Ｏ^-・Ｎａ⁺と−Ｓｉ−Ｏ^-・Ｋ⁺のように、両方の活性シラノール基を持つものであっても好ましく包含される。
【００４６】
前記一般式（１）の官能基構造からも明らかなように、活性シラノール基含有プレポリマー（イ）は、条件によっては、単独で３０分以内の比較的短時間内に急増粘したりゲル化して架橋構造を形成する等の基本的性質を持つ。
特に主剤液中の活性シラノール基含有プレポリマー（イ）含有濃度が必要以上に高かったりするとその挙動が顕著に表われる傾向がしばしば見られる。したがって本発明の主剤液では活性シラノール基含有プレポリマー（イ）の含有濃度を１〜７５重量％の範囲とすることが肝要なこととして挙げられる。より好ましくは１〜６０重量％の範囲、更に好ましくは５〜５０重量％の範囲とすることが良い。
【００４７】
その活性シラノール基含有プレポリマー（イ）の水希釈溶液は、特に制約されるものではないが、例えば一般式（１）中のＸが−ＯＨ基主体である場合は酸性領域で取扱うことが肝要なことであり、また一方、例えば一般式（１）中のＸが−ＯＨ基とその他の基、例えば−Ｏ^-・Ｎａ⁺基、−Ｏ^-・Ｋ⁺基または−Ｏ^-・Ｌｉ⁺基等の１種とが主体であったりする場合にはアルカリ性領域で取扱うことが、液ライフを確保する意味で好ましいこととして挙げられる。
【００４８】
ところで、本発明記載の前記した活性シラノール基含有プレポリマー（イ）を得る為には、その前駆体樹脂として下記一般式（３）［化１１］
【化１１】
−Ｓｉ（Ｒ⁴）_m−（Ｚ）_3-m （３）
（但し、Ｒ⁴は塩素原子、水素原子、メチル基、エチル基またはプロピル基から選ばれた１種、Ｚは炭素数が１〜５の整数で表されるアルコキシル基、オキシム基またはアセトキシル基から選ばれた１種、ｍは０〜１をそれぞれ表す。）
で表される活性シリル基末端を１分子中に少なくとも平均０．７ケ以上導入され、かつその活性シリル基導入部分を除く主鎖の有機高分子鎖長部の重量平均分子量が４００〜５０，０００の範囲にある活性シリル基末端含有ポリマー（以下の記載では単にプレポリマーと呼び活性シラノール基含有プレポリマーと区別して用いる。）が好ましい前駆体樹脂例として挙げられる。
そして、そのプレポリマーをアルカリ金属水酸化物の存在下に水で加水分解し、必要に応じて単分子有機縮合成分を形外へ除去する等の製造方法によって、容易に本発明の主剤液として必須な活性シラノール基含有プレポリマー（イ）を容易に得ることが出来る。
【００４９】
上記したアルカリ金属水酸化物としては、具体的例として、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等が挙げられ、その１種または２種以上を併用して用いても良い。好ましくは水酸化ナトリウム及び／または水酸化カリウムである。一般的に前記アルカリ金属水酸化物の使用割合は、特に制約されるものではないが、一般式（３）のＺで表される基の１モル当量に対して０．１〜２モル当量に相当する量を用いることが好ましい。より好ましくは０．３〜１．２モル当量相当分である。より最も好ましくは０．５〜１モル当量相当分を用いると良い。
【００５０】
また更に、必要に応じて行なう単分子有機縮合成分を形外へ除去する手段としては、特に制約はなく、例えば減圧処理、空気バブリング処理、限外ロ過精製処理などを適宜選択して用いれば良い。その時の温度条件等については制約はないが、室温〜１００℃未満、好ましくは２０℃〜８０℃で行なうことが好ましい。
【００５１】
従って、本発明の主剤液の構成成分としては、結果的に、前記活性シラノール基含有プレポリマー（イ）と水（ロ）以外にプレポリマーに由来する単分子有機縮合成分、過剰なアルカリ金属水酸化物などを適宜含有していて何等問題ない。むしろアルカリ金属水酸化物の存在は大いに好ましい。
【００５２】
その際、プレポリマーの加水分解反応処理に於いて、本発明の活性シラノール基含有プレポリマー（イ）が直ちにゲル化したりまたは著しい増粘がないようにプレポリマーの加水分解条件をあらかじめ適切に求めておく等の、事前の製造条件の検討をおこなって好ましい条件を求める工夫が必要であることは言うまでもない。
すなわち、プレポリマーを本発明の活性シラノール基含有プレポリマーの前駆体樹脂として用いる際には、一般的に、例えば比較的高濃度のアルカリ性水溶液中に、最終的に８０重量％以下の活性シラノール基含有プレポリマー濃度となるようにプレポリマーを少しずつ添加し、すばやく加水分解反応を完結させる方法で製造出来る。必要に応じて脱縮合成分処理を行なうことも良い方法である。
【００５３】
従って、本発明の主剤液を事前に調整する際に用いることが出来る前記の前駆体樹脂の使用量は、アルカリ性の水溶液中に高くともおおよそ８０重量％以内、好ましくは６５重量％以内、更に好ましくは５５重量％以下とすることが肝要なこととして挙げられる。
【００５４】
本発明の主剤液を構成している成分としてはすでに説明しているように、活性シラノール基含有プレポリマー（イ）と水（ロ）とから成っている。
一方、前記した一般式（３）の活性シリル基含有プレポリマー等も、その基本的な性質として加水分解反応や本発明の硬化剤液と共存させることで架橋体を形成する性質を持つ。従って、本発明の主剤をあえて活性シラノール基含有プレポリマー（イ）を含有する水溶液とする理由は、プレポリマー主体の主剤液ではその硬化反応には加水分解反応が必須であると同時に単分子有機縮合成分の遊離が伴うという課題があるが、本発明の主剤液組成物ではその課題が解消されると言うことが利点としてまず挙げられる。すなわち、本発明の主剤液組成物ではより安定したゲル化挙動とその固結強度特性が確保出来ることが、本発明の有機高分子系グラウト剤の特徴点の一つとして加えることが出来る。
【００５５】
また一般にプレポリマー自体が疎水性の強い物質である場合、水と混合すると２層分離する為に水媒体からなる有機高分子グラウト剤組成物の形成が全く困難であるという課題があった。それに対し、本発明の主剤液組成物では、そうした疎水性の強い基本的に水と非相溶な性質を示す（２層分離する性質）プレポリマーを前駆体樹脂として用いて誘導された活性シラノール基含有プレポリマー（イ）は、親水性や自己乳化性に富むものとなり、結果として全く２相分離することのない良好な水混和性の性質を発揮するのである。またその架橋ゲルは水にほとんど不溶な強固な固結体を形成する。
【００５６】
すなわち、そうした水と非相溶な性質を示す（２層分離する性質）プレポリマーを前駆体樹脂として用いて誘導された本発明の活性シラノール基含有プレポリマー（イ）含有水溶液を本発明の主剤液として用いると、そのホモゲル固結体は疎水性／親水性バランス比（ｓｐ値とも言う）が高く設定できる結果、ホモゲルの耐水性や非水膨潤性が著しく向上する。また例えばそれを用いて行なった地盤改良固結体（サンドゲル）に於いても長期耐水耐久性や非透水性が従来にない高性能を発揮する特徴を持つという結果を生んだのである。
【００５７】
従って、本発明の有機高分子グラウト剤の主要な特徴の一つに加えられるべき性質としては、前記したこと、即ち、本発明の水系の有機高分子グラウト剤の固結体の疎水性／親水性バランス比を極限まで向上させることが可能になるということが挙げられる。
【００５８】
また前記した前駆体樹脂以外の前駆体樹脂を用いて本発明の主剤液を調整または製造することも本発明に好ましく包含される。その前記した以外の前駆体樹脂の例としては、例えば１分子中０．７ケ以上のジクロロシラン基及び／またはトリクロロシラン基を含有してなり、その官能基を除いた主鎖の重量平均分子量が４００〜５０，０００の範囲にある樹脂であって、かつそれから誘導される活性シラノール基含有プレポリマー（イ）は、水との混合状態で、２層分離することのない油滴状やコロイド状または完全に水と混和して透明になる性質を有するものであれば好ましく含まれる。
【００５９】
活性シラノール基含有プレポリマー（イ）は、活性シラノール基末端を１分子中に好ましくは０．７ケ以上有していることを必須な要件としたが、その理由は０．７ケ未満の場合には、充分なゲル強度、特に圧縮強度に欠け、良好な有機グラウト剤組成物とならない傾向にあるからである。好ましくは平均２〜６ケである。特に好ましくは平均２〜３ケである。
【００６０】
活性シラノール基含有プレポリマー（イ）の活性シラノール基を除く主鎖の有機高分子鎖長部の重量平均分子量は４００〜５０，０００であることを必須要件としたが、その理由は、４００未満では、有機高分子グラウト剤の靱性または弾性が劣り、５０，０００を越えると、剛性不足及び薬剤粘度が高すぎて一定範囲への地盤浸透固結性を十分確保できない傾向にあるからである。特に該主鎖の有機高分子鎖長部の重量平均分子量が１，０００〜２０，０００であると活性シラノール基含有プレポリマー（イ）を比較的低粘度体の組成物とすることが出来、好ましい。
【００６１】
活性シラノール基含有プレポリマー（イ）の活性シラノール基を除く主鎖の有機高分子鎖長部のガラス転移温度は特に制約されるものではないが、１００℃以下とすることが良い。より好ましくは２０℃以下、最も好ましくは−１００℃〜１０℃が良い。
【００６２】
活性シラノール基含有プレポリマー（イ）としては、具体的には、例えばポリアルキレンオキサイドより誘導されたポリエーテルポリオールを主骨格とするいわゆるポリエーテル系高分子連鎖長を有し前記一般式（１）で示された末端シラノール基変性のポリエーテル系プレポリマー、ポリエーテルエステル高分子連鎖長を有し前記一般式（１）で示された末端シラノール基変性のポリエーテルエステル系プレポリマー、ポリエステル高分子連鎖長を有し前記一般式（１）で示された末端シラノール基変性のポリエステル系プレポリマー、脂肪族ポリカーボネート高分子連鎖長を有し前記一般式（１）で示された末端シラノール基変性のポリカーボネート系プレポリマー、（メタ）アクリル酸アルキルエステル類の重合によって誘導される液状アクリルゴム高分子連鎖長を有し前記一般式（１）で示された末端シラノール基変性のアクリル系プレポリマー、等が挙げられる。
ここで、これらのプレポリマー種の中では経済性の点でポリエーテル系プレポリマーが好ましい。
【００６３】
本発明の主剤液のｐＨ値は特に制約はないが、好ましくは１０〜１４のアルカリ領域、より好ましくは１１〜１４の範囲とすることが良い。
一般的な事実として、そのｐＨ値によっては主剤液自体の保存安定性が異なることをここで指摘しておきたい。
ｐＨ値を１０〜１４の強アルカリ性領域で調製された本発明の主剤液では、アルカリ水ガラス溶液と同等な良好な液保存性（液ライフ）を確保できる性質を持つ。
【００６４】
前記した活性シラノール基含有プレポリマー（イ）含有水溶液である本発明の主剤液は、化学的な視点で見ると、その基本的な性質（活性）は、例えば分子内に−Ｓｉ−ＯＨや−Ｓｉ−Ｏ^-・Ｎａ⁺を主体に持つとされるアルカリ水ガラス水溶液等に対応するｐＨ領域においては同様な基本的性質（活性）を持つと言うことが、本発明の有機高分子グラウト剤のもうひとつの特徴として加えることが出来る。
【００６５】
活性シラノール基含有プレポリマー（イ）は、前駆体樹脂である前記したプレポリマーを適宜加水分解処理することで得られることから、好ましいプレポリマーとは、即ち、活性シリル基末端を１分子中に好ましくは０．７ケ以上有していること、好ましくは平均２〜６ケ有していること、特に好ましくは平均２〜３ケ有しているものが好ましいと言える。
また好ましいプレポリマーの主鎖の有機高分子鎖長部の重量平均分子量で見ると、その主鎖の有機高分子鎖長部の重量平均分子量は４００〜５０，０００の範囲と言うことになる。特に主鎖の有機高分子鎖長部の重量平均分子量が１，０００〜２０，０００であるプレポリマーを本発明の活性シラノール基含有プレポリマー（イ）の前駆体樹脂として使用することはおおいに好ましい。
【００６６】
また前記したプレポリマー自体を得る一般的な方法の例としては、例えば特開昭５０−１５６５９９号公報に代表されるポリエーテル骨格を持つシリル変性組成物の製造方法、または特開昭５３−１３９６９５号公報に代表されるポリエステル骨格を持つシリル変性組成物の製造方法等が具体的に適用できる。
【００６７】
より最も好ましい活性シラノール基含有プレポリマー（イ）には、総和重量平均ヒドロキシル価が１０ｍｇＫＯＨ／ｇ〜４５０ｍｇＫＯＨ／ｇの範囲である水溶性のポリエーテルモノオール及び／またはポリエーテルポリオールと、下記一般式（２）［化１２］
【化１２】
ＯＣＮ−Ｒ²−Ｓｉ（Ｒ³）_m−（Ｙ）_3-m （２）
（但し、式中のＲ²は炭素数３以上のアルキレン基を、Ｒ³はメチル基、エチル基またはプロピル基から選ばれた１種、Ｙは炭素数が１〜５の整数で表されるアルコキシル基、オキシム基またはアセトキシル基から選ばれた１種、ｍは０〜１をそれぞれ表す。）
で表されるイソシアナートシランとを、ＮＣＯ／ＯＨ当量比で０．７〜１．５の範囲で反応させて得られたものを、更にアルカリ金属水酸化物含有水溶液の存在下で加水分解して得られたものが挙げられる。
【００６８】
その理由としては、活性シラノール基含有プレポリマー（イ）の製造に必要な原料が市場で容易に入手できること、１段反応でプレポリマーが製造可能であること、毒性が低く保存安定性に優れる活性シラノール基含有プレポリマー（イ）が誘導できること、分子連鎖中にウレタン結合が存在することによりその固結ゲルは土や砂粒子との密着性向上がおおいに期待出来ることなどの点が挙げられる。また前記一般式（２）のＹは好ましくは炭素数が１〜５の整数で表されるアルコキシル基とすることがより好ましい。
【００６９】
また更に、ポリエーテルポリオールの総和重量平均ヒドロキシル価が２０ｍｇＫＯＨ／ｇ〜３５０ｍｇＫＯＨ／ｇの範囲であり、かつそのポリエーテル鎖長部がエチレンオキサイド（以下単にＥＯと言う）の１５〜１００重量％とプロピレンオキサイド（以下単にＰＯと言う）またはブチレンオキサイド（以下単にＢＯと言う）の８５〜０重量％から構成されてなるジオールまたはトリオールであり、ＮＣＯ／ＯＨ当量比で０．９５〜１．０５の範囲であるものとすることを特徴とする前記の活性シラノール基含有プレポリマー（イ）はより更に好ましい例である。
前記ジオールまたはトリオールは、より好ましくはＥＯの３０〜９０重量％とＰＯ及び／またはＢＯの７０〜１０重量％、より最も好ましくはＥＯの５０〜８５重量％とＰＯ及び／またはＢＯの５０〜１５重量％から構成されてなるものとすることが良い。
以下においては、ポリオールとイソシアナートシランとを反応して得られたものを更に加水分解する方法で調整された活性シラノール基含有プレポリマー（イ）を特に「活性Ｓポリマー」と呼ぶこととする。
【００７０】
前記したポリオール類は常温で液体または固体であってよく、好ましくは常温で液体のものが良い。常温で液体であるとは、単独で常温で液体であることはもちろん、２種以上のポリオールを併用した場合において、その１種以上が固体であっても混合物が常温で液体であれば含むものとする。就中、常温で固体のポリオール成分を全ポリオール中に２５重量％以内で併用使用し、かつ常温で液体を保つものは好ましく使用出来る。
さらには、必須成分である水（ロ）と良く混和することで、最終的に誘導される活性シラノール基含有プレポリマー（イ）が、室温で液体またはミクロな懸濁液状態（乳化状態とも言う）を安定に保つことができるポリオール類を選定使用することもできる。
しかし、前記ポリオールが、その主鎖の高分子鎖長部のガラス転移温度または融点のいずれかがが基本的に１００℃以上でかつ高結晶性の性質を持つ場合には、誘導された最終反応生成物も室温で塊状固体の性質を保持したままであり、たとえ必須成分である水（ロ）と混合されても、常温で液体を保つことが困難であるので除外されて良い。
【００７１】
なお、前記した総和重量平均ヒドロキシル価とは、それぞれ分子量が異なる同種または異種のポリオール成分を単独及び／または併用使用した場合の、全ポリオール成分の平均ヒドロキシル価を表す。
【００７２】
また活性Ｓポリマーを誘導する為に便利なポリオール原料としては、その総和重量平均ヒドロキシル価が１０ｍｇＫＯＨ／ｇ〜４５０ｍｇＫＯＨ／ｇの範囲とすることが好ましいとした。この範囲であれば、活性Ｓポリマーを用いて調整された本発明の有機高分子グラウト剤を用いた固結体の弾性と１軸圧縮強度等の剛性とがバランス良く確保されるからである。またそのヒドロキシル価が１０ｍｇＫＯＨ／ｇ未満のポリオールの使用では、誘導される活性Ｓポリマーが高粘度組成物となりやすく、保存性に欠け、かつまた最終的に得られる本発明の有機高分子グラウト剤の架橋密度が不十分でホモゲル強度が低くなる傾向にあり、好ましくない。また一方、そのヒドロキシル価が４５０ｍｇＫＯＨ／ｇを超えるポリオールの使用では、誘導された活性Ｓポリマーの製造単価が高くなる傾向にあり、また最終的な有機高分子グラウト剤が硬くて脆いものとなりやすい傾向にある。
【００７３】
活性Ｓポリマーを得る目的で使用されるポリオール原料としては公知のものを使用して良く、より具体的には例えば以下の（ａ）〜（ｆ）が好ましい例として挙げられる。
（ａ）ポリエーテルポリオール
（ｂ）テレケリックなアクリルポリオール
（ｃ）ポリカーボネートポリオール
（ｄ）非晶性ポリエステルポリオール
（ｅ）非晶性ポリエーテルポリエステルポリオール
（ｆ）ロジンポリオール及び／またはその水素付加物
【００７４】
（ａ）ポリエーテルポリオールとしては公知のものであって良く、製造方法等に特に制約はないが、例えばトリメチロールプロパン、グリセリン、ネオペンチルグリコール、ショ糖、トリエタノールアミン、エチレンジアミン等の安価な活性水素化合物に対し、ＥＯ、ＰＯ、ＢＯ、テトラヒドロフランなどで代表されるアルキレンオキサイド類等の原料物質をアニオン重合やカチオン重合などの方法で作用させて得たものが好ましい例として挙げられる。１分子中にヒドロキシル基が２ケ有るジオールや１分子中にヒドロキシル基が３ケ有るトリオールなどが特に好ましく使用できる。
【００７５】
前記したアルキレンオキサイド類の内、ＥＯとＰＯを両者のモル比で（１００：０）〜（１５：８５）の範囲の付加重合比率で作用させて得た、末端第１級及び／または末端第２級の−ＯＨ基を有する２〜６官能性の該ポリオールが、活性Ｓポリマー含有水溶液としたときの溶液安定性に富むと同時に、水と良く相溶及び／またはミクロ分散安定化出来ることが認められることから好ましいポリオールの例である。また（ａ）は、液体クロマト測定法で求めたポリスチレン換算値で表される重量平均分子量またはヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲、好ましくは１，０００〜２０，０００の範囲とすることが肝要なこととしてあげられる。
【００７６】
（ｂ）テレケリックなアクリルポリオールとは、分子末端に選択的にヒドロキシル基が導入された室温で液体のアクリルポリオールを意味する。その合成・製造方法の例は特開平４−１３２７０６号公報や特開平５−２６２８０８号公報等によってすでに明らかにされており、公知の方法で得てよく、特に制約はない。一般的な（ｂ）は、１分子中にヒドロキシル基が平均２ケ導入されてなるものが挙げられる。また（ｂ）は、液体クロマト測定法で求めたポリスチレン換算値で表される重量平均分子量またはヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲、好ましくは１，０００〜２０，０００の範囲とすることが肝要なこととしてあげられる。
【００７７】
（ｃ）ポリカーボネートポリオールとは、ラクトン環を含有する化合物を主たる出発物質として、公知の開環触媒の存在下で開環重合反応させて得られるものであり、液体クロマト測定法で求めたポリスチレン換算値で表される重量平均分子量またはヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲、好ましくは１，０００〜２０，０００の範囲のものが好ましく使用できる。その製造方法などには特に制約はなく、例えば市場で容易に入手できるものとして、ポリエチレンカーボネートジオール、ポリプロピレンカーボネートジオール、ポリブチレンカーボネートジオール等がある。
【００７８】
（ｄ）非晶性ポリエステルポリオールとは、室温で半固体または液体として取扱え、かつ液体クロマト測定法で求めたポリスチレン換算値で表される重量平均分子量またはヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲、好ましくは１，０００〜２０，０００の範囲のいわゆる末端ヒドロキシ基含有ポリエステルのことである。またその（ｄ）としては、１分子中にヒドロキシル基として２〜４ケ程度有した、いわゆる公知の軟質ポリエステルが好ましい例として挙げられる。特に制約されるものではないが、（ｄ）の具体例には、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ポリプロピレングリコール、プロピレンカーボネートジオール、エチレンカーボネートジオール、トリメチロールプロパン、シリコンポリオール、アクリルポリオール、水添オレフィンポリオール等の少なくとも１種と、公知の有機二塩基酸類とをエステル化反応させて得られたものが挙げられ、融点または針入法で測定したＴｇが１００℃未満のものであれば使用できる。
【００７９】
（ｅ）非晶性ポリエーテルポリエステルポリオールとは、室温で半固体または液体で、かつ液体クロマト測定法で求めたポリスチレン換算値で表される重量平均分子量またはヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲、好ましくは１，０００〜２０，０００の範囲のいわゆる軟質のポリエーテルポリエステルである。また（ｅ）としては、１分子中に末端官能基としてヒドロキシル基を少なくとも１．２ケ以上、好ましくは２〜４ケの範囲で有し、かつポリエーテル鎖が重合度で１０以上５０以下の繰返し単位を持つ軟質ポリエーテルポリエステルとすることが好ましい例である。特に制約されるものではないが、例えば、分子量５００〜１０００程度のポリエーテルポリオールと、公知の有機二塩基酸類とをエステル化反応させて得られたものが挙げられ、融点または針入法で測定したＴｇが１００℃未満のものが代表的である。
【００８０】
（ｆ）ロジンポリオール及び／またはその水素付加物とは、より具体的には天然ロジンやその水素付加物のグリシドール付加物であるロジンジオール誘導体や、更にそのロジンジオール誘導体に対し更にＥＯ／ＰＯを適宜付加して高分子量化したものなどが好ましい例として挙げられ、ヒドロシキル価から算出される重量平均分子量で４００〜５０，０００の範囲の公知のものを適宜選定使用して良い。
【００８１】
なお、前記した（ｃ）、（ｄ）または（ｅ）の１種とイソシアナートシランとから誘導された活性Ｓポリマー等は、そのポリマーの化学的な性質として、ポリオール鎖自体の加水分解安定性がやや欠ける傾向がある。したがって該骨格を有する活性Ｓポリマーを含有してなる本発明の主剤液では、ｐＨや環境温度による該要因に対する影響等の結果をよく調べて適切な配合条件の決定が成されなければならない。
【００８２】
これら（ａ）〜（ｆ）の中で、活性Ｓポリマーに関しては、（ａ）ポリエーテルポリオールから誘導されたものが最も好ましい。そしてその（ａ）ポリエーテルポリオールの総和ヒドロキシル価の値が２０〜３５０ｍｇＫＯＨ／ｇの範囲とすることがより好ましいことであり、更に好ましくは２５〜３００ｍｇＫＯＨ／ｇの範囲とすることである。またその（ａ）ポリエーテルポリオールでは、特に好ましくはポリエーテル系のジオール及び／またはトリオールを挙げることが出来る。
【００８３】
前記した（ａ）〜（ｆ）の少なくとも１種のポリオール、更に好ましくは（ａ）と一般式（２）で表されたイソシアナートシランとからは、本発明の主剤液の必須成分である活性シラノール基含有プレポリマー（イ）のひとつである活性Ｓポリマーが非常に安価に調整できる特徴（利点）がある。
【００８４】
またここで前記一般式（２）で表されるイソシアナートシランとは、特に制約されるものではないが、具体的には例えばγ−イソシアナートプロピルトリエトキシシラン、γ−イソシアナートプロピルトリメトキシシラン、γ−イソシアナートプロピルジエトキシメチルシラン、γ−イソシアナートプロピルジメトキシメチルシラン等が知られ、それらから選ばれた１種または２種以上を選定して使用することで良い。
【００８５】
また活性Ｓポリマーでは、好ましくは、前記した（ａ）のポリオールと前記のイソシアナートシランとを、ＮＣＯ／ＯＨ当量比で０．７〜１．５の範囲、好ましくは０．９〜１．２の範囲、特に好ましくは０．９５〜１．０５の範囲、最も特に好ましくは１に限りなく近づけた当量比で、必要に応じて公知のウレタン化触媒の極く少量の存在下に作用させて得られるものである。ＮＣＯ／ＯＨ当量比が０．７未満の場合には、誘導された活性Ｓプレポリマー中に未反応の遊離ポリオールが残存する為に十分なホモゲル強度の発現を見ない傾向にあり、またＮＣＯ／ＯＨ当量比で１．５を超える場合には特に顕著な弊害はないが、価格的に不利であるからである。ある程度のイソシアナートシランの残存は活性Ｓポリマーの粘度低下に寄与し、最終的な固結体分子に化学的に組込まれることからＮＣＯ／ＯＨ当量比が１以上となることは一向に差し支えない。
前記範囲で調整された活性Ｓポリマーの前駆体樹脂は、その大部分が１分子中少なくとも最低平均０．７ケ以上、より望ましくは平均２ケ〜６ケ程度、ジアルコキシシラン基及び／または同トリアルコキシシラン基が主鎖高分子の分子末端（１次反応段階で）に導入される。部分的に極く少量ヒドロキシル基が残っていても何等差し支えない。そして最終的に水で加水分解させて目的の活性Ｓポリマーとする。
【００８６】
最終的な有機高分子系グラウト剤の速硬化適性の付与及び反応時間の短縮を図るなどの目的で前記したポリオール類とイソシアナートシランの反応に際しては公知のウレタン化反応触媒存在下で行なって良い。
【００８７】
前記のウレタン化反応触媒としては、特に制約されるものではないが、例えばジブチルチンジラウレートやジブチルチンオキサイド等で代表される有機錫化合物、またオルトチタン酸アルキルエステルで代表される有機チタン化合物、その他ナフテン酸コバルト、ナフテン酸亜鉛、ナフテン酸鉛等のナフテン酸遷移金属化合物類、同オクテン酸遷移金属化合物類、アセチルアセトン遷移金属錯体類などがある。グラウト薬剤業界で、その存在量を規制または敬遠されているものに該当するとされる有機錫系ウレタン化促進触媒を添加使用する場合などでは可能な限り極く微量とすることが肝要なこととして挙げられる。
【００８８】
地盤注入用グラウト剤分野に於いては設定されたゲル化時間で固結する性質とその固結ゲルが一定範囲の強度を発揮することが重要であるから、本発明の主剤液には基本的に以下の硬化剤液を必須とする。
【００８９】
すなわち本発明の有機高分子グラウト剤では、任意なゲル化調整とその固結体強度や強靱性等の確保から活性シラノール基含有プレポリマー（イ）を含有する水溶液である主剤液の全量に対し、下記の硬化剤液を混合する。
上記した主剤液と硬化剤液の混合比率は、主剤液中のアルカリ性の成分と後述する硬化剤液中の酸性成分の比率で自ずから決定されるものである。その比率は、現場での実際の作業性等の観点から勘案すれば、具体的には、主剤液１００容量部に対し、下記の硬化剤液の１〜３００容量部とを混合するものである。また、より好ましくは主剤液１００容量部に対し、下記の硬化剤液の２０〜１００容量部とを混和する方法が混和配合量ミスを可能な限り軽減できることからより好ましい。最も好ましくは主剤液の１００容量部に対し下記の硬化剤液の１００容量部を混和する方法で得られた本発明の有機高分子グラウト剤が最も好ましい。また更に本発明の有機高分子グラウト剤組成物では、前記した主剤液と下記の硬化剤液との２液混合液において、特に制約されるものではないが、活性シラノール基含有プレポリマー（イ）の該グラウト剤中の濃度としては、１〜７０重量％の範囲、より好ましくは５〜３７．５重量％の範囲とすることが良い。
【００９０】
その硬化剤液とは、主剤液の全量と混合された時その主剤液中に含まれる（ＮａＯＨ＋ＫＯＨ＋ＬｉＯＨ）換算で表される全アルカリ分の３０〜２００モル％に相当する量の、無機酸（ハ）、無機酸のアルカリ金属塩（ニ）、水溶性有機酸（ホ）、アルカリ水中で徐放性の酸を放出する有機単量体（ヘ）から選ばれた１種または２種以上からなる硬化剤を含有してなる水溶液である。
より好ましい硬化剤液としては、主剤液の全量と混合された時その主剤液中に含まれる（ＮａＯＨ＋ＫＯＨ＋ＬｉＯＨ）換算で表される全アルカリ分の５０〜１２０モル％に相当する量の、無機酸（ハ）、無機酸のアルカリ金属塩（ニ）、水溶性有機酸（ホ）、アルカリ水中で徐放性の酸を放出する有機単量体（ヘ）から選ばれた１種または２種以上からなる硬化剤を含有してなる水溶液が挙げられる。
【００９１】
最も好ましくは、主剤液の全量と混合された時その主剤液中に含まれる（ＮａＯＨ＋ＫＯＨ＋ＬｉＯＨ）換算で表される全アルカリ分の７５〜１００モル％に相当する量の、無機酸（ハ）の１種または２種以上からなる硬化剤を含有してなる水溶液が挙げられる。
【００９２】
前記無機酸（ハ）としては、すでに公知の強酸性無機単量体物質が挙げられ、特に制約はない。具体的な例としては例えば塩酸、炭酸、硝酸、硫酸、燐酸、ホウ酸等を例示できる。
また無機酸のアルカリ金属塩（ニ）としては、すでに公知の無機酸のナトリウム塩、同カリウム塩、同リチウム塩等が挙げられ、特に制約はない。具体的な例としては例えば塩化ナトリウム、塩化カリウム、塩化リチウム、炭酸ナトリウム、炭酸水素ナトリウム（別名：重炭酸ナトリウム）、炭酸カリウム、炭酸水素カリウム（別名：重炭酸カリウム）、炭酸リチウム、炭酸水素リチウム（別名：重炭酸リチウム）、硝酸ナトリウム、硝酸カリウム、硝酸リチウム、硫酸ナトリウム、硫酸水素ナトリウム（別名：重硫酸ナトリウム）、硫酸カリウム、硫酸水素カリウム（別名：重硫酸カリウム）、硫酸リチウム、硫酸水素リチウム（別名：重硫酸リチウム）、燐酸ナトリウム、燐酸水素ナトリウム、燐酸カリウム、燐酸水素カリウム、燐酸リチウム、燐酸水素リチウム、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸リチウムなどが挙げられる。
これらの中で、好ましくは硫酸水素ナトリウム、硫酸水素カリウム、燐酸水素ナトリウム、燐酸水素カリウム、重炭酸ナトリウムまたは重炭酸カリウムのいずれか１種または２種以上から成る混合物を挙げることが出来る。
【００９３】
また水溶性有機酸（ホ）としては、アルカリ水ガラスの硬化剤として使用できるすでに公知の有機酸をそのまま使用出来、特に制約はない。好ましくは水への溶解度が高い公知のアルカリ水ガラスの有機酸系硬化剤を選定使用することが良い。例えば蟻酸、無水酢酸、酢酸、プロピオン酸で代表されるモノカルボン酸類、グリコール酸、リンゴ酸、乳酸で代表されるオキシカルボン酸類、グリオキシル酸で代表されるアルデヒドカルボン酸類、コハク酸、マレイン酸等で代表されるジカルボン酸類、フィチン酸やその酸性塩類で代表される天然から産出誘導された水溶性の天然物有機酸などが挙げられる。
【００９４】
またアルカリ水中で徐放性の酸を放出する有機単量体（ヘ）には、アルカリ水ガラスを硬化できる公知の有機単量体物質がそのまま使用でき、特に制約はない。代表的なアルカリ水ガラスの有機単量体硬化剤物質には例えば水溶性アルデヒド類、水溶性環状ラクトン類、水溶性アルキレンカーボネート類、水溶性アルキルエステル類がある。
【００９５】
水溶性アルデヒド類のより具体的な例としては、グリオキザールがある。また水溶性環状ラクトン類のより具体的な例としては、γ−ブチロラクトンが挙げられる。また水溶性アルキレンカーボネート類としては例えばエチレンカーボネート、プロピオンカーボネートがある。また更に、水溶性アルキルエステル類としては、例えばエチレングリコールジアセテート、グリセリンジアセテート、グリセリントリアセテート等があり、それらの１種または２種以上を使用して良い。
【００９６】
前記した（ハ）、（ニ）、（ホ）、（へ）から選ばれた１種または２種以上からなる硬化剤の使用に際し、特に本発明の有機高分子グラウト剤のゲルタイムを２０分以上〜２４時間未満の中長結〜長結タイプ（又は長結タイプ）としたい際に好ましい該硬化剤の組み合せは、特に制約されるものではないが、例えば（ハ）と（ヘ）の併用、（ニ）と（ヘ）との併用、（ホ）と（ヘ）の併用等の例をあげることができる。
【００９７】
また本発明の有機高分子グラウト剤組成物では、前記した硬化剤以外に必要に応じて以下の硬化助剤成分を併用して良い。
その硬化助剤成分としては、アルカリ土類金属塩類（ト）や水硬性無機微粒子（チ）等が好ましい例として挙げられる。
アルカリ土類金属塩類（ト）としては、具体的には例えば、酸化カルシウム（生石灰）、水酸化カルシウム（消石灰）、塩化カルシウム、酸化マグネシウム、水酸化マグネシウム、塩化マグネシウム、硫酸マグネシウム、水酸化アルミニウム、塩化アルミニウムなどが挙げられる。
また、水硬性無機微粒子（チ）としては、具体的には例えば、セメント、水砕スラグ、無水石膏または半水石膏または２水石膏またはそれらの石膏混合物、フライアッシュ、海水またはニガリなどが挙げられる。
これら（ト）や（チ）から選ばれた１種または２種以上が好ましく使用できる。
【００９８】
特に（ト）や（チ）が、ブレーン値で３，０００〜５０，０００ｃｍ²／ｇの範囲、好ましくは８，０００〜４５，０００ｃｍ²／ｇの範囲、最も好ましくは１０，０００〜４０，０００ｃｍ²／ｇの範囲にあるものは特に好ましい。
【００９９】
また本発明の有機高分子グラウト剤では、そのゲル化時間を任意に調整しかつその固結体の弾性を保持しつつ一層高強度化する目的で、以下に示すシラノール化縮合触媒を、必要に応じて、主剤液ないし硬化剤液のいずれか一方または両方に添加併用使用してよい。そのシラノール化縮合触媒には、例えば、アルキルチタン酸塩；有機珪素チタン酸塩；オクチル酸錫、ジブチル錫ラウレートや同マレート及び同フマレート等のジブチル錫カルボン酸塩；ジブチルアミン−２−エチルヘキソエート等のアミン塩等が挙げられる。シラノール化縮合触媒の併用使用に際しては、事前に十分なゲル化挙動試験等を実施してその添加配合量を決定することが肝要なことであり、活性シラノール基含有プレポリマー（イ）の１００重量部に対し、０．００１〜２０重量部とすることが好ましい。
【０１００】
本発明の有機高分子グラウト剤の２液混合後のゲル化時間が２０分以内と短い場合、１ショット方式での取扱はなるべくさけることが望ましい。場合によっては、該グラウト剤が注入管内で固結すること等により、注入管をダメにする恐れが在るからである。一方、ゲル化時間が２０分以上と長い場合には本発明の有機高分子グラウト剤の２液を混合させて１液化して取扱って良く、すなわち、１ショット方式での取扱がされて良い。
即ち、基本的には１．５ショットや２ショット方式のいずれかで取扱う方が、作業性のトラブルが回避出来るのでより好ましい。
【０１０１】
本発明の有機高分子グラウト剤の該主剤液または硬化剤液または２液混合組成物中には、作業性の改善、浸透速度調製、密着性改良、事前のｐＨ調整などを特に意識して、下記した添加助剤成分を０．０１〜１０重量％以内、好ましくは０．１〜３重量％以内でいずれかの液組成物に対して使用しても何等差し支えない。
例えば、ヒンダードアミン類で代表される光安定剤；ヒンダードフェノール系酸化防止剤；グリシジルシラン類、アミノシラン類、メルカプトシラン類、ビニルシラン類、クロロシラン類で代表されるシランカップリング剤；超微粒子アルミナ、超微粒子の粘土粉等に代表される無機物チクソ化付与剤；亜リン酸エステル類で代表される過酸化物補足剤；炭カル、タルク等で代表される無機充填剤；界面活性剤；砂糖、ブドウ糖、アスコルビン酸などの金属錯体形成剤等を適宜添加可能である。
【０１０２】
本発明の有機高分子グラウト剤に必須な水（ロ）成分には特に限定はない。人工海水、海水、河川の水、地下水、水道水、雨水、蒸留水、イオン交換水など注入工事現場附近で調達できる水であれば好ましく使用できる。
【０１０３】
以下においては、前記した本発明の有機高分子グラウト剤を用いた地盤改良方法（地盤改良工法とも言う）について説明する。
その地盤改良方法の１つとしては、不安定地盤に対し、グラウト注入管を介して、本発明の有機高分子グラウト剤を２液混合する形で加圧注入し、固結させて該地盤を強化または止水し、或いは透水性を極限まで低下させる方法である。 またその地盤改良方法のもう１つとしては、不安定地盤に対し、グラウト注入管を介して、２種以上の異なるゲルタイムを有する本発明の有機高分子グラウト剤の２種以上、即ち複数使用して、複相注入し、固結させて該地盤を強化または止水し、或いは透水性を極限まで低下させる方法である。
【０１０４】
前記した地盤改良方法では、注入に際して本発明の２液からなる有機高分子グラウト剤として示された硬化剤液のみを先行注入させた後、本発明の有機高分子グラウト剤の主剤液を、又は２液混合させて後注入することも良い方法である。また前記複相注入とは、例えば２種以上のゲルタイムを有する本発明の有機高分子グラウト剤を用意した後、まずゲルタイムが数秒から数分の比較的早い固結時間を持つ該組成物を選定して先行注入固結させた後、ゲルタイムがそれよりも更に遅い本発明の有機高分子グラウト剤を後注入する等の具体的方法例が好ましく挙げられる。また別の複相注入の例では、公知の瞬結または中結型である無機硬化剤−水ガラス主剤型、有機硬化剤−水ガラス主剤型、水ガラス−セメント懸濁型、水ガラス−スラグ懸濁型などから選ばれた１種の公知グラウト剤を先行注入固結させた後、本発明の有機高分子グラウト剤を後注入する、いわゆる異なった性質からなるグラウト剤を複層注入・固結させる方法も好ましく包含される。
また注入に際してはパッカー方式やスリーブ方式や高圧噴射方式など公知の方法を用いてもよく特に制約はない。
【０１０５】
以下では、本発明の有機高分子グラウト剤を用いた下水道管の地下水止水方法（地下水止水工法とも言う）について説明する。
その下水道管の地下水止水方法とは、地下埋設下水道管の地下水漏水箇所に対し、小口径のダブルパッカーとテレビカメラとを有する円筒形の自送式パーカー注入器を介して、本発明の有機高分子グラウト剤をその漏水部に加圧注入し固結させて止水する工法である。
また該工法では、地下水の大量の流入または下水の大量流出等が観察される際に用いられる好ましい有機高分子グラウト剤としては、注入に際してはできるだけ数秒〜数十秒と短いゲル化時間を有するものを選定使用することでその目的が達成できる。またその際には、例えば地表面から注入管を差込んで配置し、水流出入り流路（即ち、下水管からの流出箇所地盤周辺を該グラウト剤等で一体固結させて漏水が流出する流路）を抑制した後に、前記した方法で止水を完結させるなどの方法を包含するものである。
【０１０６】
以下においては、本発明の有機高分子グラウト剤を用いて行なう有害物質封止方法について説明する。
近年の主要な社会問題の１つとして、屋外に放置または貯蔵されている有害な重金属イオン等の有害物質を多く含む鉱砕や同産業廃棄物などがのざらしで放置され、その結果人が住む環境が著しく汚染され、動植物等に甚大な被害をもたらす危険性が数多く指摘されているのが実態であり、従って、このような環境汚染による被害を防止することという課題を緊急に解決することが強く求められている。
したがって本発明の有害物質封止方法では、その重金属イオン等を含む有害物質が、降雨等の浸透水によって該有害物質が外部へ漏出するのを防止する、或いは極限まで抑制する有害物質封止方法であって、本発明の有機高分子グラウト剤と該有害物質と一体化させて固結させ、その結果、該有害物質の外部への漏出を防止することを特徴とする有害物質封止方法である。
【０１０７】
本発明の有機高分子グラウト剤と有害物質とを一体化させる具体的な方法としては、公知の機械混合・含浸法、注入浸透固結法、振りまき含浸固結法、積層固結法などの混合または含浸固結手段を任意に選択してよく、特に制約はない。中でも好ましくは、処理費用面から本発明の有機高分子グラウト剤を上から振りまくかまたは流動含浸固結させる等の方法によって封止する工法がより好ましい工法である。最終的に該有害物質を含む鉱砕や産業廃棄物等の表層部位の透水係数が低くとも１０^-4 オーダー、好ましくは１０^-5 からそれ以上の極限値まで低下抑制できるように、本発明の有機高分子グラウト剤の使用量を決定することが肝要なこととして挙げられる。
【０１０８】
なお、本発明の有機高分子グラウト剤のゲルタイム調整は任意であってよく、好ましくはその目的から、数秒〜数時間の範囲とすることがよい。地下水の有無、土質の種類、土砂堆積構造、注入箇所周辺の状態に応じて任意なゲルタイムとすることで良く、特に制約はない。また前記したように、２種類以上のゲルタイムを持つ本発明の有機高分子グラウト剤を用意し、複相注入方式で目的を達成しても良く、また１ショット方式、１．５ショット方式、２ショット方式などを適宜採用してよい。
【０１０９】
ところで本発明の有機高分子グラウト剤組成物を、不安定地盤の改良用途、トンネル用コンクリートパネル裏面とその裏面に接する岩盤との一体化の用途、地下室コンクリート壁とその裏面に接する土壌との一体化の用途、地下または地中下のコンクリート製構造物の強化安定と恒久的な止水を兼ねて該構造物の裏面に裏込め充填する用途としても、好ましく使用できる。
【０１１０】
【実施例】
以下に本発明の実施例及び比較例を示すが、特に断らない限り記載の部または％はそれぞれ重量部、重量％を意味すると共に、記載の実施例によって本発明が特に限定されるものではない。
また以下の例中や表中の各記号の説明はそれぞれ以下のとおりである。
また各例中記載のグラウト剤組成物の各種性能試験方法については以下のようにしておこなった。
【０１１１】
難燃試験
有機高分子系グラウト剤単独の硬化体（厚さ２ｍｍ×幅５ｍｍ×長さ１００ｍｍの板状）の端面を４５゜の角度でガスバーナーの酸化小炎の直上位置にかざし２〜３秒間着炎させた後、直ちに該小炎から遠ざけて、３秒以内に延焼炎が消える場合を難燃性が高いとして◎の記号で表示。２０秒以内で消える場合は難燃性ありとして○の記号で表示。３０秒以内で消える場合は難燃性にやや欠けるとして△の記号で表示。３０秒を超えて燃え続けている場合には可燃性という意味で×の記号で表示した。
【０１１２】
ゲル化時間（ゲルタイム）測定
一定温度下で、硬化剤成分を添加または２液混合した時点からその組成物自体の溶液流動性がなくなるまでの時間で表し、その時間が１分未満のものを［瞬結］と表示、１分以上〜５分未満を［中結］と表示、５分以上〜３０分未満を［中長結］と表示、３０分以上のものを［長結］と表示した。
【０１１３】
１軸圧縮試験
ＪＩＳ−Ａ−１２１６に準じた方法であり、丸東製作所のＳＧ−２０３３Ｂ型電動式１軸圧縮試験機を用いて、圧縮速度１．５ｍｍ／分でおこなった。
【０１１４】
ホモゲル強度とその歪率測定
グラウト剤組成物単独の固結体の物性であり、直径５０ｍｍ，１００ｍｍ高さの円柱状のホモゲル硬化体を得た後、前記した１軸圧縮強度を求めその値をホモゲル強度とする。また、その１軸圧縮強度測定時の破壊に至るまでの変形量をもとの高さで割って１００を掛けた値を歪率として（％）で表示。
【０１１５】
サンドゲル強度
グラウト剤組成物の３８．５〜４０．５ｖｏｌ％と豊浦標準砂の５９．５〜６１．５ｖｏｌ％を均一混合させ、気泡が入らないようにしてモールド成形容器に詰めて固結させた後、養生し、脱型して直径５０ｍｍ，１００ｍｍ高さの円柱状のサンドゲル硬化体を得る。そのサンドゲルの１軸圧縮強度の値でサンドゲル強度とする。
【０１１６】
浸透適性試験
上部と下部にそれぞれ開口穴のある１０ｃｍ直径の透明アクリル製充填搭を用意し、充填高さが１ｍとなるように豊浦標準砂を水存在下に細密充填させた。充填搭上部の開口部より、注入圧力１．５Ｋｇ／ｃｍ2で各実施例ならびに比較例の各グラウト剤組成物をそれぞれ注入させた時、市水のみによる注入浸透速度（２００〜２１０ｍｌ／ｍｉｎ）を１００とした際の各グラウト剤組成物の水に対する注入浸透速度比が７０％以上でかつ粒子間浸透固結が可能な場合を◎の記号で表示した。また水に対する注入浸透速度比が５０％以上〜７０％未満でかつ粒子間浸透固結が可能な場合を○の記号、水に対する注入浸透速度比が１５％以上〜５０％未満でかつ粒子間浸透固結が可能な場合を△の記号、また同１５％未満の場合を×の記号でそれぞれ表示した。
【０１１７】
耐久性試験
前記方法で得た円柱状のホモゲル体またはサンドゲル硬化体のいずれかを１０リットルが１昼夜で１回置換するように設定された流水置換式水槽に一定期間浸漬させ、その時の１軸圧縮強度保持率（％）と外観変化を観察した結果を耐水耐久性試験結果（以下では耐久性試験１と表示）として表示した。一方ＪＩＳに規定されている人工海水溶液を調製し、その人工海水に一定期間浸漬させた後の外観変化と１軸圧縮強度保持率（％）で海水浸漬耐久性試験結果（以下では耐久性試験２と表示）とした。
【０１１８】
以下においては、まず後述する実施例及び比較例で用いる主剤液および比較主剤液について説明する。
【０１１９】
主剤液１
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ポリエーテルポリオールとして、ヒドロキシル価から算出された重量平均分子量が３，３００のポリエーテル系トリオール［エチレンオキサイド（ＥＯ）とプロピレンオキサイド（ＰＯ）のランダム付加モル比率が７５：２５である］の５００部（０．４５４モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリエトキシシランの１１４部（０．４６モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．０１部とを仕込、窒素気流中、８０℃で２時間反応させた後冷却し、ほぼ定量的に分子量が３，３００であるポリエーテル主鎖に加水分解活性シリル基末端を平均３ケ持つプレポリマー１を得た。プレポリマー１は単独では常温で液体を示し、その溶液粘度はＢ型粘度計による室温測定結果で９８０ｃｐｓであった。
【０１２０】
更に５０℃に加温された１Ｎ−水酸化ナトリウム水溶液の６９０部に前記プレポリマー１の３１０部を少しずつ投入し、投入終了後にはエアレーションして約３０部の遊離エタノールを除去した。その結果無色透明の溶液が得られ、固形分換算で３０．９７重量％濃度となるように調整した。その結果活性シラノール基含有プレポリマーを含有するアルカリ性水溶液が得られ、これを主剤液１とした。該主剤液１のｐＨ値は室温で１３．５を示し、おおよそ３〜４ｃｐｓの低粘度液体であった。また、該主剤液１は室温下３ケ月保存後においても安定であることが認められた。
【０１２１】
主剤液２
また別に５０℃に加温された１Ｎ−水酸化ナトリウム水溶液の５３４部と蒸留水６６部とからなるアルカリ性水溶液に前記プレポリマー１の４００部を少しずつ投入し、投入終了後にはエアレーションして約３８部の遊離エタノールを除去した。その結果無色透明の溶液が得られ、固形分換算で３９．８重量％濃度の活性シラノール基含有プレポリマーの水溶液を得、これを主剤液２とした。該主剤液２のｐＨ値は室温で１３．６を示し、おおよそ３．９ｃｐｓの低粘度液体であった。また該主剤液２の３ケ月保存後も何等変化がなく主剤液自体の保存安定性は良好であった。
【０１２２】
主剤液３
また別に５０℃に加温された１Ｎ−水酸化ナトリウム水溶液の１３８部とイオン交換水の５５２部とからなるアルカリ性水溶液に前記プレポリマー１の３１０部を少しずつ投入し、投入終了後にはエアレーションして約３０部の遊離エタノールを除去した。その結果無色透明の溶液が得られ、固形分換算で２９．２重量％濃度の活性シラノール基含有プレポリマー水溶液を得、これを主剤液３とした。該主剤液３のｐＨ値は室温で１３．４を示し、おおよそ２ｃｐｓの低粘度液体であった。また該主剤液３の５日間保存安定性は良好であったが、１０日以上の保存では増粘や部分ゲルの析出が見られた。
【０１２３】
主剤液４
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ポリエーテルポリオールとして、ヒドロキシル価から算出された重量平均分子量が３，３００ の水に難溶性のポリエーテル系トリオール［グリセリンに対しエチレンオキサイド（ＥＯ）とプロピレンオキサイド（ＰＯ）をランダム付加モル比率が５０：５０の割合で付加誘導されたトリオール］の５００部（０．４５４モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリエトキシシランの１１４部（０．４６モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．０１部とを仕込、窒素気流中、８０℃で２時間反応させた後冷却し、ほぼ定量的に分子量が３，３００であるポリエーテル主鎖に加水分解活性シリル基末端を平均３ケ持つプレポリマー６を得た。プレポリマー６は単独では常温で液体を示し、その溶液粘度はＢ型粘度計による室温測定結果で９８０ｃｐｓであった。
一方３Ｎ−水酸化カリウム水溶液の５０部と蒸留水の１５０部と前記プレポリマー６の１００部を少しずつ投入し、投入終了後には、８０℃で１時間攪拌した後、同温度・減圧下でエアレーションして脱エタノール化し、さらに希釈水で調整して活性シラノール基含有プレポリマーを固形分換算で３０重量％を含む乳白色の安定なエマルション溶液が得られ、これを主剤液４とした。該主剤液４のｐＨ値は室温で１３．９を示し、おおよそ３．１ｃｐｓの低粘度液体であった。この主剤液４は２４時間経過後の観察で、無色透明な水溶液に変化したものの液のゲル化はなく、安定な活性シラノール基含有プレポリマーを含有するアルカリ性水溶液であった。
【０１２４】
主剤液５
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ヒドロキシル価から算出された重量平均分子量が２０，０００の高純度なポリエチレングリコールの５００部（０．０５モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリエトキシシランの１３．５部（０．０５４モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．０１部とを仕込、窒素気流中、８０℃で５時間反応させた後冷却し、ほぼ定量的に１分子中に平均２ケの活性シリル基末端を持ち、主鎖が重量平均分子量２０，０００のポリエチレングリコール骨格であるプレポリマー２を得た。そのプレポリマー２は水溶性で常温で固体であり、融点約６０℃の水に非常に良く相溶するものであった。
次に別の４ツ口フラスコに６０℃に加温された０．１Ｎ−水酸化ナトリウム水溶液の１９５部と水道水５０５部とからなるアルカリ性水溶液を仕込、その液に前記プレポリマー２の３０４部を投入した。６０℃加温のまま窒素エアレーションして約４部の遊離エタノールを除去し、固形分を３０重量％に調整した。その結果無色透明の溶液が得られ、活性シラノール基含有プレポリマー含有水溶液である主剤液５を調整した。該主剤液５のｐＨ値は室温で１３．０を示し、おおよそ１．５ｃｐｓの低粘度液体であった。また１〜２カ月放置後でも何等ゲル化や増粘が認められず、安定性に富む主剤液５であった。
【０１２５】
主剤液６
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ヒドロキシル価が５６ｍｇＫＯＨ／ｇのポリエチレングリコール（分子量２，０００）の５００部（０．５モル／活性ＯＨ当量）と重量平均分子量が２，０５０の片末端ｎ−ブチルエーテル化されたポリアルキレングリコールモノブチルエーテルである水溶性モノオールの２００部（０．０９８モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリエトキシシランの１４９部（０．６モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．０１部とを仕込、窒素気流中、８０℃で２時間反応させた後冷却し、ほぼ定量的に平均１．７ケの活性シリル基末端を持つプレポリマー３を得た。
プレポリマー３は、その主鎖の高分子鎖長部の分子量が約２，０００のポリエーテル骨格からなり、水溶性でかつ常温で半固体の性質を示した。
次に別の４ツ口フラスコに２０℃の０．５Ｎ−水酸化カリウム水溶液の１００部と水道水４００部とからなるアルカリ水溶液を仕込、その液に前記プレポリマー３の５５５部を投入した。５０℃加温後、窒素エアレーションして約５５部の遊離エタノールを除去し、活性シラノール基含有プレポリマー含有濃度を固形分換算で５０．１重量％に調整した。その結果無色透明の溶液が得られ、活性シラノール基含有プレポリマー含有水溶液である主剤液６を調整した。該主剤液６のｐＨ値は室温で１３．４を示し、おおよそ５．７ｃｐｓの低粘度液体であった。なお、主剤液６の室温での液ライフは長くとも５日であった。
【０１２６】
比較主剤液１
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ヒドロキシル価が５４．８ｍｇＫＯＨ／ｇ、ＥＯ／ＰＯブロック付加比が１９／８１の１級ヒドロキシル基を持つポリエーテルグリコール系トリオールの５００部（０．４８８モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリメトキシシランの１０２部（０．４８８モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．０１部とを仕込、窒素気流中、８０℃で２時間反応させた後冷却し、ほぼ定量的に平均３ケの活性シリル基末端を持つプレポリマー４を得た。プレポリマー４はその主鎖の高分子鎖長部の分子量が約２，０００の疎水性のポリエーテル骨格からなり、常温で液体であるが、水にほとんど不溶であった。
このプレポリマー４を用いて１０重量％のイオン交換水による水希釈溶液とした比較主剤液１は、すぐ２層分離し上層が該プレポリマー４をなし、２４時間以内にそのままで熱硬化性で水不溶の架橋ゲル層を形成した。結果としてプレポリマー４は水に不溶性である為このままでは水希釈溶液の調整は出来なかった。
【０１２７】
主剤液７
１リットルビーカー容器を用意し、その中に０．６Ｎ−水酸化カリウム溶液６００部と、あらかじめ人口的に調整した海水５％分を混和した水道水の１５０部とを仕込、その系を攪拌下に、比較主剤液１で用いたプレポリマー４の２５０部を投入して２時間反応させた。その結果、薄い乳白色半透明溶液が得られ、数日間の放置試験で全く変化のない安定した半懸濁の活性シラノール基含有プレポリマー含有水溶液である主剤液７を得た。なお、仕込プレポリマー４換算で表される濃度が２５％の活性シラノール基含有プレポリマー含有のアルカリ性水溶液であった。比較主剤液１では安定な水希釈液が調整されなかったのに比べ、本主剤液７ではきわめて安定な水系の主剤液が調整された。溶液粘度は０．６ｃｐｓと低粘度系であった。
【０１２８】
主剤液８
１リットルビーカー容器を用意し、その中に１Ｎ−水酸化ナトリウム溶液２００部と、水道水の５００部とを仕込、その系を攪拌下に、比較主剤液１で用いたプレポリマー４の３００部を投入して２時間反応させた。その結果、濃い乳白色溶液が得られ、数日間の放置試験で全く変化のない安定な懸濁溶液である活性シラノール基含有プレポリマー含有水溶液である主剤液８を得た。なお、仕込プレポリマー４換算で表される濃度が３０％の活性シラノール基含有プレポリマー含有水溶液であり、そのｐＨ値が１３．５で０．７ｃｐｓの低粘度溶液であった。比較主剤液１では安定な水希釈液が調整されなかったのに比べ、主剤液８ではきわめて安定な水系の主剤液が調整された。溶液粘度は０．７ｃｐｓと低粘度系であった。
【０１２９】
比較主剤液２
環流冷却器付きの１リットル容量の４ツ口反応フラスコを用意し、ヒドロキシル価が６９ｍｇＫＯＨ／ｇであるロジンジオール（平均分子量１，６２６）の５００部（０．６１５モル／活性ＯＨ当量）とγ−イソシアナートプロピルトリメトキシシランの１２９．６部（０．６２モル／活性ＮＣＯ当量）及び触媒としてジブチルチンオキサイドの０．００５部とを仕込、窒素気流中、８０℃で５時間反応させた後冷却し、ほぼ定量的に平均２．０ケの活性シリル基末端と主鎖の高分子鎖長部の分子量が１，６２６のロジン骨格からなり、疎水性でかつ常温で液状のプレポリマー５を得た。
このプレポリマー５を用いて１０重量％のイオン交換水による水希釈溶液とした比較主剤液２では、混合後すぐ２層分離し上層が該プレポリマー５をなし、２４時間以内にそのままで熱硬化性で水不溶の架橋ゲル層を形成した。結果としてプレポリマー５は水に不溶性である為このままでは水希釈溶液の調整は出来なかった。
【０１３０】
主剤液９
１リットルビーカー容器を用意し、その中に０．５Ｎ−水酸化ナトリウム溶液６００部と水道水の１５０部とを仕込、その系を攪拌下に、比較主剤液２で用いたプレポリマー５の２５０部を投入して２時間反応させた。その結果、薄い乳白色半透明溶液が得られ、数日間の放置試験で全く変化のない安定した半懸濁の活性シラノール基含有プレポリマー含有水溶液である主剤液９を得た。なお、仕込プレポリマー５換算で表される濃度が２５％の活性シラノール基含有プレポリマー含有の、溶液ｐＨ値が１３．５を示す強アルカリ性水溶液であった。比較主剤液２では安定な水希釈液が調整されなかったのに比べ、主剤液９ではきわめて安定な水系の主剤液が調整され、溶液粘度は０．８ｃｐｓ程度と、低粘度液体であった。
【０１３１】
以下に実施例及び比較例を記載する。
【０１３２】
実施例１から実施例７
調整後３時間未満にある主剤液１〜主剤液７と必要に応じて水道水で希釈されてなる表１記載の配合組成とした各主剤液と更に表１記載の配合組成とした各硬化剤液との２液を用いて、表１記載の配合比率で主剤液と硬化剤液を混和させて実施例１〜実施例７の各有機高分子グラウト剤組成物を調整し、グラウト剤番号Ｄ１（実施例１記載の有機高分子グラウト剤）〜Ｄ７（実施例７記載の有機高分子グラウト剤）をそれぞれ得た。各グラウト剤の溶液物性と硬化体物性を同時に表１に記載した。
【０１３３】
なお、表１記載の各硬化剤液組成については、硬化剤をメスシリンダー内に規定重量採取し、水に溶解して希釈し、表１記載の配合容量となるように調製したものであることを表す。これにより調製された硬化剤液、Ｄ１の硬化剤液では、１５℃の時の液比重として、およそ１．０５１である。同様にＤ２、Ｄ３、Ｄ５の各硬化剤液では、１５℃でおよそ１．００５の液比重であり、またＤ４の硬化剤液ではおよそ１．１３８の液比重であり、さらにＤ６、Ｄ７の硬化剤液では、それぞれ１．０３０、１．２２５の液比重である。また、これらは表１の「合計又は配合量」欄中に、調製した各硬化剤液の液比重として表示した。
なお、表１中記載の粗燐酸とはＰ₂Ｏ₅換算で５０重量％（液比重がおよそ１．６３）の三井東圧化学（株）製品を、精製燐酸とは７５重量％純度の試薬品を使用し、その液比重は室温で１．５９〜１．６０であった。
またグリオキザールは純度４０％（液比重がおよそ１．３２／１５℃）の三井東圧化学（株）製品を、またγ−ブチロラクトン（液比重が１．１２／１５℃）、エチレンカーボネート（真比重が１．３）、プロピレンカーボネート（液比重が１．２１）、エチレングリコールジアセテート（液比重が１．１１）らはそれぞれ試薬品を使用した。
【０１３４】
その結果、表１から明らかなように、１分子中に数個の活性シラノール基を含有しかつ主鎖の分子量が３，０００〜２０，０００の範囲のいずれかにあるポリエーテル型の活性シラノール基含有プレポリマーを含有する主剤液では、その主剤液１００容量部に対し、硬化剤液の１０〜１００容量部の配合例に於いて、瞬結から中長結の幅広い範囲のゲル化挙動を持ち、かつ高い１軸圧縮強度特性ならびに高弾性特性とを合せ持つ固結体が生成することが明確となった。また本実施例１〜実施例７の有機高分子グラウト剤はそのすべてが水及び海水浸漬耐久性に富むこと、難燃性に優れること、標準砂に対する浸透注入作業性に優れる等の特性もまた同時に判明した。
また実施例１〜実施例３の各サンドゲル耐久性試験１のサンドゲル浸漬開始から２４時間後におこなった浸漬水中の低級アルコール分に関するガスクロマト分離分析結果においては、その存在は検出されなかった。
【０１３５】
【表１】

【０１３６】
実施例８から実施例１４
調整後３時間以内の主剤液１と主剤液２と主剤液５と主剤液８及び主剤液９とを適宜配合してなる表２記載の配合組成とした主剤液と表２記載の配合組成とした硬化剤液との２液を用いて、表２記載の配合比率で主剤液と硬化剤液を混和させて実施例８〜実施例１４の各有機高分子グラウト剤組成物を調整し、グラウト剤番号Ｅ１（実施例８記載の有機高分子グラウト剤）〜Ｅ７（実施例１４記載の有機高分子グラウト剤）をそれぞれ得た。各グラウト剤の溶液物性と硬化体物性を同時に表２に記載した。
なお、表２記載の各硬化剤液組成については、硬化剤をメスシリンダー内に規定重量採取し、水に溶解して希釈し、表２記載の配合容量となるように調製したものであることを表す。また、表１の「合計又は配合量」欄中に、調製した各硬化剤液の液比重を併せて表示した。
なお、表２中記載の有機酸である酢酸、グリコール酸、乳酸は試薬品を使用した。また重炭酸ナトリウム、重炭酸カリウムは旭硝子工業（株）社製品を、重硫酸ナトリウムは試薬１級品を、また酸性硫酸マグネシウム塩は馬居化成（株）社製品を用いた。
【０１３７】
その結果、表２から明らかなように、１分子中に数個の活性シラノール基を含有しかつ主鎖の分子量が３，０００〜２０，０００の範囲のいずれかにある、未変性では疎水性の強いポリエーテル型または同様の性質を持つロジンポリオール型の活性シラノール基含有プレポリマーを含有する主剤液では、その主剤液１００容量部に対し、無機酸のアルカリ塩、水溶性有機酸、アルカリ水中で徐放性の酸を放出する有機単量体等の硬化剤成分を少量含有する硬化剤液の１０〜４００容量部の配合例に於いて、瞬結から長結の幅広い範囲のゲル化挙動を持ち、かつ高い１軸圧縮強度特性ならびに高弾性特性とを合せ持つ固結ゲルが生成することが明確である。また本実施例８〜実施例１４の有機高分子グラウト剤はそのすべてが水及び海水浸漬耐久性に富むこと、難燃性に優れること、標準砂に対する浸透注入作業性に優れる等の特性もまた同時に判明した。
【０１３８】
【表２】

【０１３９】
実施例１５
上記表１の実施例２（グラウト剤番号Ｄ２）に記載したものと同様の組成物からなる主剤液、硬化剤液のそれぞれ２０リットルづつを用意し、その２液を混合容量比が１：１となるようにして、あらかじめ６号珪砂を圧密充填したモデル地盤の１ｍ深層部位に設置された注入単管より該グラウト液を、１．５ショット方式で、２００ｍｌ／分の割合で、かつゲージ圧１．５ｋｇ／ｃｍ²で吐出させた。吐出圧が５ｋｇ／ｃｍ²まで上昇した時点で吐出を停止し、その後そのまま３日放置して養生したのち、未固結土壌を水で洗い流す方式で、生成したサンドゲル固結体の外観観察を行った結果、半径約７０〜８０ｃｍ大の楕円状固結体の生成が確認された。その固結体の中心部附近より採取したサンドゲルの１軸圧縮強度特性は１５．２ｋｇｆ／ｃｍ²と高強度値を示した。
また採取されたサンドゲル固結体３点の透水係数の平均は７×１０^-6 と判明し、高止水性に富む地盤に改良できることを十分に示唆するものであった。
【０１４０】
実施例１６
３ｍｍから５ｍｍ大の珪石を主成分とする礫質モデル地盤を、基盤の上に１．５ｍ高さに盛った後、その上部に５号珪砂をさらに１．５ｍ高さに盛ったモデル地盤を用意した。
一方、上記表２の実施例１０（グラウト剤番号Ｅ３）に記載したものと同様のグラウト剤組成物（瞬結型）の主剤液、硬化剤液をそれぞれ各２０リットルづつと、表２の実施例８（グラウト剤番号Ｅ１）に記載したものと同様のグラウト剤組成物（中長結型）の主剤液、硬化剤液を事前に混合してなる１ショット薬液１００リットルとを用意した。
まず最初に礫層の中心に注入管の注入先端部が位置するように２重管からなる注入管を下ろして固定し、前記瞬結型のグラウト剤を２ショット方式にて全量１次注入後、注入管を引き上げて５号珪砂層まで移動させて後、前記中長結型のグラウト剤を１ショット方式で加圧注入して浸透固結させた結果、数日後に行った注入後の改良地盤の標準貫入試験値（Ｎ値）は最低値でも２５以上と十分締め固められており、高強度でかつ液状化しにくい安定な改良地盤となっていた。
【０１４１】
ここで、「標準貫入試験及びその試験値」とは、「土の硬軟・締まり程度を知る指標となるＮ値を求めるための試験であり、ボーリング孔を利用し、ロッドの先端に直径５．１ｍｍ、長さ８１ｃｍの標準貫入試験用サンプラーを、重さ６３．５Ｋｇのハンマー（落垂ハンマー）を７５ｃｍ高さから自由落下させ、サンプラーを３０ｃｍ貫入させるのに要する打撃回数（Ｎ値）を測定する方法」をいう。 一般的にＮ値が１０未満の土は、軟弱地盤と言われ、Ｎ値が１〜８の砂地盤は液状化の危険性を持つことが知られている。
【０１４２】
実施例１７
上記表１の実施例２（グラウト剤番号Ｄ２）に記載したものと同様の組成物からなる主剤液Ａ、硬化剤液Ｂのそれぞれ２０リットルづつを用意した。一方管口径５０ｃｍのコンクリート製フューム管を２本水平にして接続し、その２本の相互継手部分は約１ｍｍ程度の隙間を持たせ未シール状態とし、両サイドの開口部を閉鎖しない状態でその周辺１ｍ高さに木枠で囲み地中に埋設された下水道管モデルを構築した。その際、接続フューム管上部、すなわち木枠で囲まれた部分を豊浦標準砂を水潤状態で積層して締め固め、１ｍ高さに盛って前記モデルを作成した。
【０１４３】
また下記の下水道管の地下水止水注入試験中においては、該継手欠陥部より、毎分１〜２リットル程度の流水状態下になるようにして、以下の試験をおこなった。
該埋設下水道管モデルの中央部に、ダブルパッカーと注入機能が一体化してなり、かつテレビカメラが接続されてなる円筒形の自送式パッカー注入器（円形筒型で直径３０ｃｍ）を挿入して、テレビカメラを見ながらそのパッカー注入器の中心がフューム管接続部の中心位置となるように移動して、直ちにパッカー部へ加圧水を送液してパッカーをふくらませた。その後で該注入器を介して、該注入器出口で衝突混合する形式、いわゆる２ショット方式で、前記の主剤液Ａと硬化剤液Ｂを容積比率１：１で同時に供給し、約２．５ｋｇ／ｃｍ²の加圧下で全量を１：１容量比で混合注入させた。
【０１４４】
注入作業中はパッカー外周部からの漏液は全く観察されなかった。注入後１５分放置後に、パッカーの水を抜いて、該注入器を管内部より排出させた結果、２本の下水管内部継手部に実施例１８で示されたホモゲル固結体がドーナツ状に管内部に張付いて構築されていた。また更に管外周部の未硬化砂を注意深く取除いた所、２本の下水管内部継手部隙間から浸透してその周辺砂を一体的に浸透固結させて硬化した状態が観察された。また、その周辺の硬化範囲は、概ね幅５０ｃｍ、厚さ平均３０ｃｍの範囲を浸透固結させていた。
そしてテスト前に発生していた漏水流入は全くない状態であることが観察された。
最終的に試験７日後に実施例１７で形成された固結サンドゲルコア（５０ｍｍφ×１００ｍｍＨ）を数本採取し、実施例１７と同様な方法で行ったサンドゲルの１軸圧縮強度を測定した結果、１３〜１６ｋｇｆ／ｃｍ²と安定した高い強度値が得られた。またその際の圧縮破壊歪率は５〜６％であった。
【０１４５】
本結果より、豊浦標準砂への浸透注入固結性能は良好であることが改めて判明するとともに、前記実施例２の結果と合せると、下水道管の地下水止水性能が十分にあり、かつ長期耐久性を合わせ持つ改良が可能であることが判明した。
【０１４６】
比較実施例１
日本工業規格−３号珪酸ナトリウム（ＪＩＳ−３号水ガラス）溶液の６リットルを水道水４リットルで希釈した主剤液Ｐと、市販のポルトランドセメント粉の５ｋｇを水でといて懸濁型溶液の５リットルとした硬化剤液Ｑを用意し、容量比でＰ：Ｑ＝２：１となるようにした注入固結用グラウト薬剤液を用意し、実施例１７と同様にして下水道管の地下水止水試験を実施した。その結果、２本の下水管内部継手部隙間から浸透してその周辺砂を一体的に浸透固結させて硬化した状態が観察されたが、そのホモゲルは極くわずかの振動による衝撃でクラックや亀裂が入る非常に脆いものでしかなかった。
また別個に直径５０ｍｍφ、高さ１００ｍｍの成型モールド容器中で調製したホモゲル固結体は、水のブリージング現象が多く見られ、結果として体積収縮が激しいことが観察され、下水道管との接着性に欠けると共に恒久的な止水性能に著しく欠けることが判明した。また上記ホモゲル固結体及び別個に調製したサンドゲル固結体の１ケ月後の耐久性試験１の結果ではそれぞれ元の圧縮強度に較べて、著しい強度の低下が観察され、低下率の最大値は５３％にも達していた。これらの結果からも比較実施例１の注入固結用グラウト薬剤は耐久性に欠けるものであった。
【０１４７】
比較実施例２
市販のポルトランドセメント粉の５ｋｇと沈降防止付与剤として平均粒子径が７μｍのベントナイト粉の０．０３ｋｇとを水道水でといて懸濁溶液の１０リットルとした注入固結用グラウト薬剤液を用意し、実施例１７と同様にして下水道管の地下水止水試験を実施した。その結果、注入後１時間経過後であってもまだ注入液組成物は漏水を止めることという点では満足な状態にすることが出来ず、未硬化状態であった。従って、実用十分な強度発現までの養生期間は短くても１〜２日を要することが判明し、従って注入作業性や作業効率に著しく欠ける注入固結用グラウト薬剤であった。
【０１４８】
実施例１８
調整後３時間以内の主剤液８の８０容量％と水道水２０容量％とからなる主剤液Ａの２０リットルと、三井東圧化学（株）社製品・７５重量％粗燐酸の１リットルを含む硬化剤液Ｂの１０リットルをそれぞれ用意し、Ａ：Ｂの容量比２：１の比率で１．５ショット方式で混和吐出させた有機高分子グラウト剤組成物１００部と、主にプラスチック類のゴミ焼却に伴って生成集塵された集塵灰３００部とを機械的に懸濁化させた結果、５分後にはゲルを形成した。その固結体を３日間室温で密閉養生したものは水に濡れない性質を示し、疎水性が強く弾性に富むゲルであった。該ゲルの透水係数は３×１０^-6 と高い非透水性の性質を示した。以上の結果、有害金属を含む廃棄物を封止する組成物として有用であることが判明した。
【０１４９】
実施例１９
表１の実施例番号３（グラウト剤番号Ｄ３）の硬化剤液中で使用したエチレングリコールジアセテートの全量をグリセリンジアセテートに替えた以外は同様にして行った有機高分子グラウト剤組成物は中結性のゲルタイムを与え、標準砂に対する浸透作業性が◎、ホモゲル強度が１．５ｋｇｆ／ｃｍ²、一軸圧縮強度の歪値が４２％、サンドゲル強度で１５．５ｋｇｆ／ｃｍ²とほぼグラウト剤番号Ｄ３と同等な性能の物性値を示した。
【０１５０】
実施例２０
表１の実施例番号３（グラウト剤番号Ｄ３）の硬化剤液中で使用したエチレングリコールジアセテートの全量をグリセリントリアセテートに替えた以外は同様にして行った有機高分子グラウト剤組成物は中結性のゲルタイムを与え、標準砂に対する浸透作業性が◎、ホモゲル強度が１．７ｋｇｆ／ｃｍ²、一軸圧縮強度の歪値が４０％、サンドゲル強度で１６．２ｋｇｆ／ｃｍ²とほぼグラウト剤番号Ｄ３と同等な性能の物性値を示した。
【０１５１】
実施例２１
表２の実施例番号１２（グラウト剤番号Ｅ５）の硬化剤液中で使用した重硫酸ナトリウムに替えてその全量を燐酸水素ナトリウムと燐酸水素カリウムの重量比１：１混合物とした以外はまったく同様にして行った有機高分子グラウト剤組成物は中結性のゲルタイムを与え、標準砂に対する浸透作業性が◎、ホモゲル強度が１．７ｋｇｆ／ｃｍ²、一軸圧縮強度の歪値が４４％、サンドゲル強度で１４．７ｋｇｆ／ｃｍ²とほぼグラウト剤番号Ｅ５と同等な性能の物性値を示した。
【０１５２】
【発明の効果】
比較主剤液１〜２および主剤液７〜９の記載から明らかなように、本来疎水性の強い、そのままでは水にほとんど溶解せずに２層分離してしまう性質であるシリル末端高分子プレポリマーであっても、主剤液７または主剤液８の例のように高アルカリ性水溶液で処理すると、水と２層分離することのない安定な本発明の有機高分子グラウト剤の構成に必須な活性シラノール基含有プレポリマー含有水溶液（主剤液）が、容易に得られることが明らかである。
さらにその結果として、本発明の有機高分子グラウト剤の固結体は、本来持っていた強い疎水性の性質を固結後に回復する。したがって該固結体自体は地下水や湿潤水による影響をきわめて受けづらく、事実、実施例１〜実施例１５等や実施例１９〜実施例２１等のゲル特性結果により明らかである。
【０１５３】
比較実施例１と比較実施例２では、明らかに水ガラス−セメントまたはセメント系の注入固結用グラウト薬剤では耐久性と作業適性に長けた薬剤とはいえないことが明確である。
一方、実施例１〜実施例１７で明らかなように、本発明の注入固結用の有機高分子グラウト剤は、恒久的な地盤改良用として好ましい有機高分子グラウト剤組成物として、また更には好ましい下水道管の地下水止水用の薬液組成物としても大いに適していることが明確である。
より具体的には、実施例１〜実施例１５に示された組成物の固結体では、その機械的物性が弾性に富みかつ長期恒久性に富んでおり、グラウト剤市場の要請に十分答えることが出来る有機高分子グラウト剤である。
【０１５４】
特に実施例１７で明らかにしたように、本発明の注入固結用の有機高分子グラウト剤を用いた下水道管の地下水止水方法は、省力化適性や注入作業適性、地盤への浸透固結適性などに格段にすぐれ、かつ長期間に渡りその地下水止水性を確保できる特徴を有することが明確である。そして地盤変動や振動に対しても追従可能であると容易に想像できるものである。
また、更に実施例１８で明らかにしたように、本発明記載の注入固結用の有機高分子グラウト剤を用いた有害物質封止方法は、該有害物質を簡便かつ確実に封止する方法として優れていることが明白である。
すなわち、本発明の有機高分子グラウト剤組成物は「発明が解決しようとする課題」で挙げた５つの課題を合せて満足させることが出来る、きわめて実用上意味のある特性をもっていることは明らかである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel organic polymer grout agent composition. In addition, using the organic polymer grout agent composition, a ground improvement method of injecting under pressure into a soft disintegrating ground or a leaked ground, solidifying and stabilizing the ground, a groundwater shutoff method for an aged sewer pipe, The present invention relates to a method for sealing harmful substances.
Specifically, it can be handled by either one-shot injection method or two-shot injection method, and it generates organic polymer gel with high strength and elasticity, so it is stable for a long time without any separation. A liquid improvement type organic polymer grout agent composition is provided, and a ground improvement method which is performed by pressurizing and solidifying a chemical containing the grout agent composition, and groundwater stoppage of an aged sewer pipe The present invention relates to a method and other harmful substance sealing methods.
[0002]
Here, the ground improvement method is the construction foundation excavation site, subway excavation site, excavation site for sewage laying, ground improvement work for the purpose of avoiding the danger that ground damage is expected due to liquefaction A ground injection grout agent (hereinafter simply referred to as a grouting agent) is injected into a fragile or leaky ground (hereinafter simply referred to as an unstable ground) at the site, etc., and injected, infiltrated or spray-mixed under pressure to solidify the ground integrally. This is a method for reducing the water permeability of unstable ground to the limit and improving it to a ground with strong durability.
[0003]
In addition, the groundwater water shutoff method for aging sewer pipes is intended for aging sewer pipes that can be stopped using known self-feeding packer injectors that do not have a large diameter. This refers to a method of stopping water for a long period of time at a groundwater leakage point or a sewage leakage point that is seen at a defect or a defect.
In addition, the hazardous substance sealing method is from industrial waste or mining containing a large amount of the metal compound harmful to the human body represented by copper, lead, cadmium, tin, zinc, arsenic, hexavalent chromium, etc. Method of improving non-permeability to the limit so that contaminated water containing a high concentration of the harmful element does not leak out of the system due to infiltration into water and its dissolution and outflow during rainfall, and a secondary disaster does not occur Say.
[0004]
The 1-shot method is a method in which the main agent and the curing agent are mixed in advance, and the mixed solution is injected as a single solution through a single tube or the like. The 1.5-shot method is a method in which the main agent and the curing agent are mixed. A method of injecting the mixed liquid by collision mixing near the inlet of the injection pipe. Further, the two-shot method is a method in which the main agent and the curing agent are separately supplied via an injection pipe composed of multiple pipes such as a double pipe and a triple pipe, and are collided and mixed at the tip of the injection pipe and discharged. Say.
[0005]
[Prior art]
Conventionally, various grouting agents have been selected and used in accordance with the target ground for tunnel construction and urban civil engineering work for ground improvement methods aimed at reinforcing and stabilizing unstable ground.
In particular, the most frequently used grouting agent is a water glass grouting agent. On the other hand, although the use ratio is still small, various organic polymer grout agent compositions have been proposed since the latter half of the 1960s. For example, acrylamide grout agents, urea grout agents, urethane grout agents and the like are known.
[0006]
Acrylic amide grout agent causes groundwater contamination by the monomer and has an adverse effect on the human body. Therefore, its use is currently severely restricted and it cannot be used substantially.
Urea grout agent is a grout agent mainly composed of urea resin derived from urea and formalin, but there are many problems such as generation of free formalin and short liquid life. There is a problem, and it is almost no longer used now.
[0007]
In the urethane grout agent, for example, an organic polymer grout agent mainly composed of a urethane prepolymer having an isocyanate group at a terminal derived from a water-soluble monool and a diisocyanate compound in JP-A-47-36616. There is disclosure relating to the composition. Further, for example, JP-A-50-152507 discloses a ground improvement method using a mixed liquid of an isocyanate prepolymer and water as a ground improvement liquid, and in recent years, JP-A-3-293424, There are many disclosure examples regarding a rock mass consolidation method using a urethane grout agent in No. 4-102615.
[0008]
Furthermore, examples of disclosure relating to a urethane two-component soil layer curing agent composition can be found in, for example, JP-A-4-185694 and JP-A-4-185695. Japanese Patent Application Laid-Open No. 5-78665 has a disclosure example relating to a rock-solidifying agent using a urethane grout agent composition characterized by foam curing. Further, for example, Japanese Patent Laid-Open No. 4-283290 discloses an injectable liquid composition for stabilization of soil using a sodium silicate aqueous solution (water glass solution) and a polyisocyanate composition, and a stable reinforced waterstop method using the same. There is. Moreover, in the disclosure example regarding the urethane grout agent composition having excellent permeability and durability, there is a disclosure represented by JP-A-6-207174.
That is, in recent years, urethane grouting agents are attracting attention as organic polymer grouting agents in terms of their durability and high water-stopping properties, and are highly evaluated as rock mass consolidation stabilizers. This composition is the only representative example that is still used as an organic polymer grout agent.
[0009]
However, since the known urethane grout agents described above deal with a large amount of highly toxic isocyanate compounds and derivatives thereof, there is a strong concern about the risk of chemical injury and the risk of ignition fire.
[0010]
In addition, some organic polymer precursors exhibiting a property of gelation and crosslinking upon contact with moisture have been known so far. Typical examples of the precursor include those having an isocyanate group and those having a hydrolyzable silyl group introduced at the terminal. In the grout agent field, only those having the former isocyanate group are known. Not. The latter is, for example, disclosed in Japanese Patent Publication No. 61-18582, but most of them are limited to the adhesive field, the paint field, and the architectural sealant field. For example, there are no disclosure examples regarding compositions suitable for the ground improvement agent field or ground injection consolidation agent field (grouting agent field) and the ground improvement method thereof.
[0011]
By the way, the damage of the Great Hanshin Earthquake that occurred in January 1995 was due to the fact that a great deal of damage occurred on structures built on soft ground and its underground part. It can be said that it has raised major issues in securing safety against earthquakes and building permanent civil engineering foundations. In particular, there is a strong demand for ensuring the safety of various public important structures that have already been built on the ground where liquefaction is expected in major urban areas. There is a strong demand for the early provision of new grout agents with excellent long-term durability and reliability to the market. In the same way, permanent ground improvement and securing of strengthening and stability are essential for the needs such as construction of new large structures on or in soft ground such as landfills and sandy ground. Is the same.
[0012]
Recently, the underground space is being actively used even in the municipalities of soft ground, and the ground is being strengthened and stabilized for medium to long term (between 3 months and several years) during underground civil engineering work. It is essential, and medium- and long-term advance ground stabilization work is strongly demanded, and a grout agent is required for that purpose.
Also, as one of the major social problems in recent years, if a large amount of harmful heavy metal ions that are left or stored outdoors are left untouched, the industrial waste, etc. There is a concern that the environment in which people live is extremely polluted and can cause serious damage to animals and plants. Therefore, there is a demand for a method for urgently solving the problem of preventing damage due to environmental pollution, and a method for sealing the harmful substance is being sought.
In light of this social situation, a new organic polymer grout agent rich in osmotic injection solidification, durability (permanent) and high water-stopping properties (non-water-permeable), with which safety is sufficiently secured, has been introduced at an early stage. It can be said that providing is very significant.
[0013]
[Problems to be solved by the invention]
As described above, the object of the present invention is to strongly demand a composition relating to an organic polymer grout agent rich in safety that can be expected to have long-term durability, and provides a novel composition that meets the demand. There is to do.
More specifically, an object of the present invention is to provide a novel organic polymer solution type grout agent capable of simultaneously solving the following five main problems.
[0014]
As one of them, it has high permeation-injection caking properties, and has a long-lasting and durable function that can stabilize the caking strength for a long time.
The second is that it is basically composed of a two-component type of main agent and curing agent, and the gel time can be easily adjusted from instantaneous setting (gelation for several seconds) to long setting (gelation for several hours).
The third is that it can be easily handled by any one of the one-shot method and the two-shot method, injection management can be easily performed, and safety at the injection work site is ensured.
The fourth is that the consolidated gel is highly elastic and has excellent acid resistance and alkali resistance with almost no separation over time.
As the fifth, the water permeability of the injected solid body is extremely small and the water-stopping effect is high.
[0015]
[Means for solving the problems]
As a result of diligent research, the present inventor, as a means for solving the above-mentioned problem, by making a thermosetting prepolymer-containing composition comprising a specified component into a grout agent composition, the above-mentioned problem
It has been found that (object) can be solved, and the present invention has been completed.
[0016]
That is, the organic polymer grout agent of the present invention is
The main agent liquid is represented by the following general formula (1) [Chemical Formula 3]
[Chemical 3]
-Si (R ¹ ) _n -(X) _3-n (1)
(However, R ¹ Is one selected from a hydrogen atom, a chlorine atom, a methyl group, an ethyl group or a propyl group, X is an —OH group, —O ^- ・ Na ⁺ Group, -O ^- ・ K ⁺ Group or -O ^- ・ Li ⁺ 1 type selected from the group, n represents 0 to 1 respectively. )
In the molecule, at least 0.7 units of the active silanol group terminal represented by the formula is introduced into the molecule, and the weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group is in the range of 400 to 50,000. 1 to 75% by weight of one or more active silanol group-containing prepolymers, and when the curing agent liquid is mixed with the total amount of the main agent liquid, Releases a sustained-release acid in an inorganic acid, an alkali metal salt of an inorganic acid, a water-soluble organic acid or an alkaline water in an amount corresponding to 30 to 200 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH). It is a liquid or aqueous solution containing one or more selected from any one of organic monomers, and an organic polymer grout agent obtained by mixing these two liquids.
[0017]
In addition, the ground improvement method of the present invention means that the organic polymer grouting agent of the present invention is applied in any one of a 1-shot system to a 2-shot system via a grout injection pipe in the case of strengthening stabilization / water stoppage of unstable ground. It is a ground improvement method characterized in that the ground is strengthened or water-stopped or water-stopped is increased to the limit by injecting and solidifying under pressure.
[0018]
The particularly preferable ground improvement method includes an organic polymer having different gel times according to the present invention in any one of a 1-shot system and a 2-shot system through a grout injection pipe in the case of strengthening stabilization and water stoppage of unstable ground. There is a ground improvement method characterized by strengthening or water-stopping the ground or increasing water-stopping to the maximum by injecting and solidifying multiple phases using two or more kinds of grouting agents.
[0019]
Further, the groundwater shutoff method for sewer pipes of the present invention is the method of leaking the organic polymer grout agent of the present invention through the small-diameter self-feeding packer injector with respect to the underground water leak location of underground sewer pipes. This is a sewer pipe groundwater shutoff method characterized by pressurizing and consolidating the periphery to stop water.
[0020]
In addition, the hazardous substance sealing method of the present invention means that the harmful substances are leaked to the outside by osmotic water such as rainfall from mining and industrial waste containing harmful substances such as heavy metal ions that are left or stored outdoors. In order to suppress this to the limit, the organic polymer grout agent of the present invention is used and solidified with the harmful substance to prevent leakage of the harmful substance to the outside by water such as rain. It is a hazardous substance sealing method.
[0021]
In the organic polymer grout agent of the present invention described above, the following embodiments are more preferable. That is, the main agent liquid is adjusted beforehand to an alkali having a pH value of 10 to 14 in particular, and the inorganic acid is composed of one or two kinds selected from sulfuric acid, phosphoric acid or carbonic acid. The alkali metal salt of the inorganic acid is sodium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium bicarbonate or potassium bicarbonate, or a mixture thereof; An embodiment in which the organic monomer releasing acid is one or more selected from glyoxal, γ-butyrolactone, ethylene carbonate, propion carbonate, ethylene glycol diacetate, glycerol diacetate or glycerol triacetate Is preferred.
[0022]
Furthermore, the active silanol group-containing prepolymer-containing concentration in the main agent liquid is 5 to 50% by weight, and 20 to 100 parts by volume of the curing agent liquid is mixed with 100 parts by volume of the main agent liquid. It is highly desirable to do. The main chain organic polymer chain excluding the active silanol group is a polyether composed of 15 to 100% by weight of ethylene oxide and 85 to 0% by weight of propylene oxide or butylene oxide. This is a much more preferred embodiment.
[0023]
In addition, R in the above general formula (1) ¹ Is a methyl group or an ethyl group, X in the general formula (1) is an —OH group, —O ^- ・ Na ⁺ Group or -O ^- ・ K ⁺ The organic polymer chain length of the main chain that is composed of any one of the groups, and that the active silanol group-containing prepolymer contains an average of 2 to 6 active silanol group ends in one molecule and excludes the active silanol group One of the most preferred embodiments is that the weight average molecular weight of the part is in the range of 1,000 to 20,000.
[0024]
The active silanol group-containing prepolymer comprises a polyether monool and / or polyether polyol having a total weight average hydroxyl number in the range of 10 mgKOH / g to 450 mgKOH / g, and the following general formula (2) [Chemical Formula 4]
[Formula 4]
OCN-R ² -Si (R ^Three ) _m -(Y) _3-m (2)
(However, R in the formula ² Represents an alkylene group having 3 or more carbon atoms, R ^Three Is one selected from methyl, ethyl or propyl, Y is one selected from alkoxyl, oxime or acetoxyl represented by an integer having 1 to 5 carbon atoms, m is 0 to 1 Respectively. )
An active silyl group-containing prepolymer obtained by reacting an isocyanate silane represented by the formula (1) with an NCO / OH equivalent ratio in the range of 0.7 to 1.5, an alkali metal hydroxide-containing aqueous solution or an inorganic acid. It is an even more preferred embodiment that it is prepared by hydrolysis in the presence of any of the aqueous solutions.
[0025]
The isocyanate silane is one selected from γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldiethoxymethylsilane or γ-isocyanatopropyldimethoxymethylsilane. And the polyether polyol has a total weight average hydroxyl number in the range of 20 mg KOH / g to 350 mg KOH / g, and the polyether chain length is 15 to 100% by weight of ethylene oxide and 85 of propylene oxide or butylene oxide. It is a diol and / or triol composed of ˜0% by weight, and the NCO / OH equivalent ratio is in the range of 0.95 to 1.05. .
That is, the present invention provides the following (1) to (16).
[0026]
(1) The main agent solution is represented by the following general formula (1)
[Chemical formula 5]
-Si (R ¹ ) _n -(X) _3-n (1)
(However, R ¹ Is one selected from a hydrogen atom, a chlorine atom, a methyl group, an ethyl group or a propyl group, X is an —OH group, —O ^- ・ Na ⁺ Group, -O ^- ・ K ⁺ Group or -O ^- ・ Li ⁺ 1 type selected from the group, n represents 0 to 1 respectively. )
The active silanol group end represented by the formula is introduced in an average of at least 0.7 units, and the weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group is in the range of 400 to 50,000. An aqueous alkaline solution containing 1 to 75% by weight of one or more active silanol group-containing prepolymers,
When the curing agent solution is mixed with the total amount of the main agent solution, an inorganic acid or an inorganic acid in an amount corresponding to 30 to 200 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH) contained in the main agent solution. A liquid or an aqueous solution containing one or more selected from an alkali metal salt, a water-soluble organic acid, or an organic monomer that releases a sustained-release acid in alkaline water,
An organic polymer grout agent obtained by mixing two liquids of the main agent liquid and the curing agent liquid.
[0027]
(2) The organic polymer grout agent according to (1), wherein the main agent solution is adjusted to be alkaline with a pH value of the single solution of 10 to 14.
[0028]
(3) The organic polymer grout agent according to (1) or (2), wherein the inorganic acid is one or two selected from sulfuric acid, phosphoric acid or carbonic acid.
[0029]
(4) The alkali metal salt of an inorganic acid is any one of sodium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, or a mixture thereof (1) )-(3) The organic polymer grout agent in any one of.
[0030]
(5) The organic monomer that releases a sustained-release acid in alkaline water is one selected from glyoxal, γ-butyrolactone, ethylene carbonate, propion carbonate, ethylene glycol diacetate, glycerol diacetate, or glycerol triacetate, or The organic polymer grout agent according to any one of (1) to (4), wherein the organic polymer grout agent is at least two kinds.
[0031]
(6) The content of the active silanol group-containing prepolymer is 5 to 50% by weight, and 100 parts by volume of the main agent liquid is mixed with 20 to 100 parts by volume of the curing agent liquid (1 The organic polymer grout agent according to any one of) to (5).
[0032]
(7) The main chain organic polymer chain excluding the active silanol group is a polyether composed of 15 to 100% by weight of ethylene oxide and 85 to 0% by weight of propylene oxide or butylene oxide. The organic polymer grout agent according to any one of (1) to (6).
[0033]
(8) R in the general formula (1) ¹ Is either a methyl group or an ethyl group, X is an —OH group, —O ^- ・ Na ⁺ Group or -O ^- ・ K ⁺ The organic polymer grout agent according to any one of (1) to (7), which is any one of groups.
[0034]
(9) The active silanol group-containing prepolymer contains an average of 2 to 6 active silanol group ends in one molecule, and the weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group is The organic polymer grout agent according to any one of (1) to (8), wherein the organic polymer grout agent is in a range of 1,000 to 20,000.
[0035]
(10) A polyether monool and / or a polyether polyol in which the active silanol group-containing prepolymer has a total weight average hydroxyl number ranging from 10 mgKOH / g to 450 mgKOH / g, and the following general formula (2) [Chemical Formula 6]
[Chemical 6]
OCN-R ² -Si (R ^Three ) _m -(Y) _3-m (2)
(However, R in the formula ² Represents an alkylene group having 3 or more carbon atoms, R ^Three Is one selected from methyl, ethyl or propyl, Y is one selected from alkoxyl, oxime or acetoxyl represented by an integer having 1 to 5 carbon atoms, m is 0 to 1 Respectively. )
An active silyl group-containing prepolymer obtained by reacting an isocyanate silane represented by the formula (1) with an NCO / OH equivalent ratio in the range of 0.7 to 1.5, and the presence of an aqueous solution containing an alkali metal hydroxide. The organic polymer grout agent according to any one of (1) to (9), which is obtained by hydrolysis under pressure.
[0036]
(11) One type of isocyanate silane selected from γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldiethoxymethylsilane, or γ-isocyanatopropyldimethoxymethylsilane (10) The organic polymer grout agent according to (10).
[0037]
(12) The polyether polyol has a total weight average hydroxyl value in the range of 20 mg KOH / g to 350 mg KOH / g, and the polyether chain length is 15 to 100% by weight of ethylene oxide and 85 of propylene oxide or butylene oxide. The organic polymer grout according to (10), characterized in that it is a diol and / or triol composed of ˜0% by weight and has an NCO / OH equivalent ratio in the range of 0.95 to 1.05. Agent.
[0038]
(13) Any one of (1) to (12) using the 1-shot method, 1.5-shot method or 2-shot method via the grout injection pipe in the case of strengthening stability and water stoppage of unstable ground A ground improvement method comprising reinforcing and stopping the ground by pressurizing and solidifying the organic polymer grout agent described in 1 above.
[0039]
(14) In the case of strengthening stability and water stoppage of unstable ground, either 1 shot method, 1.5 shot method or ~ 2 shot method via grout injection pipe, (1) to (12) Two or more of the organic polymer grout agents selected from the organic polymer grout agents described in any one of the above and having different gel times are used for multiphase injection and solidification to strengthen or stop the ground. The ground improvement method characterized by doing.
[0040]
(15) With respect to the underground leakage point of the underground buried sewer pipe, the organic polymer grout agent according to any one of (1) to (12) is supplied to the leakage part and its through a small-diameter self-feeding packer injector. A sewer pipe groundwater shutoff method characterized by pressurizing and consolidating the surroundings to stop the water.
[0041]
(16) A hazardous substance sealing method for preventing leakage of harmful substances to the outside due to water or the like from crushed or industrial waste containing harmful substances such as heavy metal ions left or stored outdoors. The organic polymer grout agent according to any one of (1) to (12) is used, and the harmful substance is prevented from leaking to the outside by being consolidated with the harmful substance. Hazardous substance sealing method.
[0042]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The organic polymer grout agent of the present invention can be summarized as an active silanol group-containing prepolymer (a) and water (b) as the main component, an inorganic acid (c) as a curing agent component, an alkali metal salt of an inorganic acid ( D) A composition comprising, as an essential component, one or more selected from a water-soluble organic acid (e) or an organic monomer (f) that releases a sustained-release acid in alkaline water.
[0043]
The active silanol group-containing prepolymer (I) has the following general formula (1)
[Chemical 7]
-Si (R ¹ ) _n -(X) _3-n (1)
(However, R ¹ Is one selected from a hydrogen atom, a chlorine atom, a methyl group, an ethyl group or a propyl group, X is an —OH group, —O ^- ・ Na ⁺ Group, -O ^- ・ K ⁺ Group or -O ^- ・ Li ⁺ 1 type selected from the group, n represents 0 to 1 respectively. )
The weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group-introduced portion is 400 to 50, at least an average of 0.7 or more of the active silanol group terminals represented by It is a composition composed of one or two or more in the range of 000, and there are no particular restrictions on its production method.
[0044]
In the general formula (1) in the active silanol group-containing prepolymer (a), R ¹ Is preferably either a methyl group or an ethyl group, and preferred X is -OH group, -O ^- ・ Na ⁺ Group or -O ^- ・ K ⁺ At least one selected from the group. Particularly preferred X is -OH group or -O. ^- ・ Na ⁺ It is a group.
Here, in more detail, the active silanol group-containing prepolymer (a) having an —OH group as X is generally relatively stable in an acidic region.
That is, the active silanol group-containing prepolymer (a) prepared under acidic conditions has an active silanol group represented by the following formula (A) [Chemical Formula 8] in the aqueous solution.
[Chemical 8]

And may form stable micelles and / or microcolloids having a negative charge.
[0045]
X is -O ^- ・ Na ⁺ Group and / or -O ^- ・ K ⁺ The (a) having a group generally exhibits a relatively stable property in an alkaline region.
That is, (i) prepared in an alkaline region having a pH value of 9 to 13 has an active silanol group in the aqueous solution having the following formula (B) [Chemical Formula 9] and / or Formula (C) [Chemical Formula 10]. It may be in a dissociation equilibrium as shown by the following, and may form a stable micelle and / or microcolloid having a positive charge.
[Chemical 9]

[Chemical Formula 10]

For example, -Si-O in one molecule ^- ・ Na ⁺ And -Si-O ^- ・ K ⁺ As described above, those having both active silanol groups are also preferably included.
[0046]
As is clear from the functional group structure of the general formula (1), the active silanol group-containing prepolymer (a) may suddenly thicken or gel within a relatively short time of 30 minutes depending on conditions. It has basic properties such as forming a crosslinked structure.
In particular, when the concentration of the active silanol group-containing prepolymer (I) in the main agent solution is higher than necessary, the tendency of the behavior to appear remarkably is often observed. Therefore, in the main agent liquid of the present invention, it is essential that the concentration of the active silanol group-containing prepolymer (I) is in the range of 1 to 75% by weight. More preferably, it is good to set it as the range of 1 to 60 weight%, More preferably, it is 5 to 50 weight%.
[0047]
The water-diluted solution of the active silanol group-containing prepolymer (I) is not particularly limited. For example, when X in the general formula (1) is mainly an —OH group, it is important to handle it in the acidic region. On the other hand, for example, X in the general formula (1) is an -OH group and another group, for example, -O. ^- ・ Na ⁺ Group, -O ^- ・ K ⁺ Group or -O ^- ・ Li ⁺ When one type such as a group is the main component, handling in the alkaline region is preferable in terms of securing the liquid life.
[0048]
By the way, in order to obtain the active silanol group-containing prepolymer (A) described in the present invention, the precursor resin is represented by the following general formula (3)
Embedded image
-Si (R ^Four ) _m -(Z) _3-m (3)
(However, R ^Four Is one selected from a chlorine atom, a hydrogen atom, a methyl group, an ethyl group or a propyl group, Z is one selected from an alkoxyl group, an oxime group or an acetoxyl group represented by an integer having 1 to 5 carbon atoms , M represents 0 to 1, respectively. )
The weight average molecular weight of the organic polymer chain length part of the main chain excluding the active silyl group-introduced portion is 400 to 50, at least an average of 0.7 or more active silyl group terminals represented by An active silyl group-containing polymer in the range of 000 (in the following description, simply referred to as a prepolymer and used separately from an active silanol group-containing prepolymer) is a preferred precursor resin.
Then, the prepolymer is easily hydrolyzed with water in the presence of an alkali metal hydroxide, and easily removed as a main liquid of the present invention by a production method such as removing a monomolecular organic condensation component out of the shape as necessary. The essential active silanol group-containing prepolymer (I) can be easily obtained.
[0049]
Specific examples of the alkali metal hydroxide described above include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and one or more of them may be used in combination. Sodium hydroxide and / or potassium hydroxide are preferred. Generally, the use ratio of the alkali metal hydroxide is not particularly limited, but is 0.1 to 2 molar equivalents relative to 1 molar equivalent of the group represented by Z in the general formula (3). It is preferred to use a corresponding amount. More preferably, it is 0.3 to 1.2 molar equivalent. More preferably, 0.5 to 1 molar equivalent is used.
[0050]
Furthermore, there are no particular restrictions on the means for removing the monomolecular organic condensation component out of the form as necessary. For example, a decompression process, an air bubbling process, an ultrafiltration process, or the like may be appropriately selected and used. good. Although there is no restriction | limiting about the temperature conditions at that time, It is preferable to carry out at room temperature-less than 100 degreeC, Preferably it is 20 to 80 degreeC.
[0051]
Therefore, as a constituent component of the main agent liquid of the present invention, as a result, in addition to the active silanol group-containing prepolymer (A) and water (B), a monomolecular organic condensation component derived from the prepolymer, excess alkali metal water There is no problem if oxides are appropriately contained. Rather, the presence of alkali metal hydroxide is highly preferred.
[0052]
At this time, in the prepolymer hydrolysis reaction treatment, the prepolymer hydrolysis conditions are appropriately determined in advance so that the active silanol group-containing prepolymer (I) of the present invention is not immediately gelled or significantly thickened. Needless to say, it is necessary to devise a precondition by examining manufacturing conditions in advance.
That is, when the prepolymer is used as a precursor resin of the active silanol group-containing prepolymer of the present invention, generally, for example, in a relatively high concentration alkaline aqueous solution, finally, 80 wt% or less of the active silanol group is finally obtained. The prepolymer can be added little by little so that the concentration of the prepolymer is contained, and the hydrolysis reaction can be completed quickly. It is also a good method to perform the decondensation component treatment as necessary.
[0053]
Therefore, the amount of the precursor resin that can be used in preparing the main agent liquid of the present invention in advance is at most about 80% by weight, preferably 65% by weight, more preferably in the alkaline aqueous solution. It is important to set the amount to 55% by weight or less.
[0054]
As already explained, the component constituting the main agent liquid of the present invention comprises an active silanol group-containing prepolymer (I) and water (B).
On the other hand, the active silyl group-containing prepolymer of the general formula (3) has the property of forming a cross-linked product by coexisting with the hydrolysis reaction or the curing agent solution of the present invention as its basic property. Accordingly, the reason why the main agent of the present invention is intentionally made into an aqueous solution containing the active silanol group-containing prepolymer (A) is that the prepolymer-based main agent solution requires a hydrolysis reaction for its curing reaction and at the same time is a monomolecular organic. Although there is a problem that the condensation component is liberated, it is first mentioned as an advantage that the problem is solved in the main agent liquid composition of the present invention. That is, it can be added as one of the features of the organic polymer grout agent of the present invention that a more stable gelation behavior and its consolidation strength characteristic can be secured in the main agent liquid composition of the present invention.
[0055]
In general, when the prepolymer itself is a strongly hydrophobic substance, there is a problem that formation of an organic polymer grout agent composition comprising an aqueous medium is quite difficult because two layers are separated when mixed with water. On the other hand, in the main agent liquid composition of the present invention, active silanol derived using a prepolymer as a precursor resin having such a strong hydrophobic property that is basically incompatible with water (a property of separating two layers). The group-containing prepolymer (a) is rich in hydrophilicity and self-emulsifying property, and as a result, exhibits a good water-miscible property without any two-phase separation. Moreover, the crosslinked gel forms a strong solid body almost insoluble in water.
[0056]
That is, the active silanol group-containing prepolymer (I) -containing aqueous solution of the present invention, which is derived by using a prepolymer exhibiting properties incompatible with water (the property of separating two layers) as a precursor resin, is the main component of the present invention. When used as a liquid, the homogel consolidated body can be set to have a high hydrophobic / hydrophilic balance ratio (also referred to as sp value), so that the water resistance and non-water swelling property of the homogel are remarkably improved. In addition, for example, the ground improvement solidified body (sand gel) made using it has the result that long-term water resistance and non-permeability have the characteristics of exhibiting unprecedented high performance.
[0057]
Therefore, the property to be added to one of the main characteristics of the organic polymer grout agent of the present invention is as described above, that is, the hydrophobic / hydrophilicity of the solidified body of the aqueous organic polymer grout agent of the present invention. It is possible to improve the sex balance ratio to the limit.
[0058]
In addition, the present invention preferably includes adjusting or producing the main agent liquid of the present invention using a precursor resin other than the above-described precursor resins. Examples of precursor resins other than those described above include, for example, 0.7 or more dichlorosilane groups and / or trichlorosilane groups in one molecule, and the weight average molecular weight of the main chain excluding the functional groups. Is a resin in the range of 400 to 50,000, and the active silanol group-containing prepolymer (i) derived therefrom is in the form of oil droplets or colloids that are not separated into two layers when mixed with water. It is preferably included if it has a property of becoming transparent when mixed in water or completely.
[0059]
The active silanol group-containing prepolymer (I) has an essential requirement that the active silanol group end preferably has 0.7 or more in one molecule, but the reason is less than 0.7 This is because sufficient gel strength, particularly compressive strength, is lacking and the organic grout agent composition tends not to be obtained. The average is preferably 2-6. Particularly preferred is an average of 2-3.
[0060]
The weight average molecular weight of the organic polymer chain length part of the main chain excluding the active silanol group of the active silanol group-containing prepolymer (I) is essential to be 400 to 50,000, but the reason is less than 400 Then, the toughness or elasticity of the organic polymer grout agent is inferior, and if it exceeds 50,000, the rigidity is insufficient and the viscosity of the drug is too high, and there is a tendency that it is not possible to sufficiently secure the ground penetration consolidation property within a certain range. In particular, when the weight average molecular weight of the main chain organic polymer chain is 1,000 to 20,000, the active silanol group-containing prepolymer (I) can be made into a composition having a relatively low viscosity, preferable.
[0061]
The glass transition temperature of the organic polymer chain length portion of the main chain excluding the active silanol group of the active silanol group-containing prepolymer (I) is not particularly limited, but is preferably 100 ° C. or lower. More preferably, it is 20 ° C. or less, and most preferably −100 ° C. to 10 ° C.
[0062]
Specific examples of the active silanol group-containing prepolymer (A) include a so-called polyether polymer chain length having a polyether polyol derived from a polyalkylene oxide as a main skeleton, for example, the general formula (1) A terminal silanol group-modified polyether prepolymer represented by the formula (1), a terminal ester silanol group-modified polyether ester prepolymer represented by the general formula (1), and a polyester polymer The terminal silanol group-modified polyester prepolymer represented by the general formula (1) having a chain length, and the terminal silanol group-modified polyester represented by the general formula (1) having an aliphatic polycarbonate polymer chain length. Liquid derived from polymerization of polycarbonate-based prepolymers and alkyl (meth) acrylates Formula (1) with the indicated end silanol group-modified acrylic prepolymer having an acrylic rubber polymer chain length, and the like.
Here, among these prepolymer species, a polyether-based prepolymer is preferable in terms of economy.
[0063]
Although there is no restriction | limiting in particular in the pH value of the main ingredient liquid of this invention, Preferably it is 10-14 alkali range, More preferably, it is good to set it as the range of 11-14.
As a general fact, it should be pointed out here that the storage stability of the main solution itself varies depending on the pH value.
The main agent liquid of the present invention prepared in a strongly alkaline region having a pH value of 10 to 14 has a property that can ensure good liquid storage stability (liquid life) equivalent to an alkaline water glass solution.
[0064]
From the chemical point of view, the basic solution of the present invention, which is the aqueous solution containing the active silanol group-containing prepolymer (I), has a basic property (activity) such as -Si-OH or-in the molecule. Si-O ^- ・ Na ⁺ It is added as another feature of the organic polymer grout agent of the present invention that it has the same basic property (activity) in the pH range corresponding to the alkaline water glass aqueous solution etc. I can do it.
[0065]
Since the active silanol group-containing prepolymer (A) is obtained by appropriately hydrolyzing the above-mentioned prepolymer which is a precursor resin, the preferred prepolymer is that the active silyl group end is in one molecule. It is preferable to have 0.7 or more, preferably 2 to 6 on average, particularly preferably 2 to 3 on average.
In terms of the weight average molecular weight of the organic polymer chain length of the main chain of the prepolymer, the weight average molecular weight of the organic polymer chain length of the main chain is in the range of 400 to 50,000. It is particularly preferable to use a prepolymer having a weight average molecular weight of 1,000 to 20,000 in the main chain organic polymer chain length as the precursor resin of the active silanol group-containing prepolymer (I) of the present invention. .
[0066]
Examples of a general method for obtaining the prepolymer itself include, for example, a method for producing a silyl-modified composition having a polyether skeleton represented by JP-A-50-156599, or JP-A-53-139695. A method for producing a silyl-modified composition having a polyester skeleton represented by the publication No. can be specifically applied.
[0067]
The most preferred active silanol group-containing prepolymer (a) includes a water-soluble polyether monool and / or polyether polyol having a total weight average hydroxyl number ranging from 10 mgKOH / g to 450 mgKOH / g, and the following general formula: (2) [Chemical 12]
Embedded image
OCN-R ² -Si (R ^Three ) _m -(Y) _3-m (2)
(However, R in the formula ² Represents an alkylene group having 3 or more carbon atoms, R ^Three Is one selected from methyl, ethyl or propyl, Y is one selected from alkoxyl, oxime or acetoxyl represented by an integer having 1 to 5 carbon atoms, m is 0 to 1 Respectively. )
The product obtained by reacting the isocyanate silane represented by the formula (1) with an NCO / OH equivalent ratio in the range of 0.7 to 1.5 is further hydrolyzed in the presence of an aqueous solution containing an alkali metal hydroxide. What was obtained in this way is mentioned.
[0068]
The reason for this is that raw materials necessary for the production of the active silanol group-containing prepolymer (a) can be easily obtained in the market, the prepolymer can be produced by a one-step reaction, and the activity is low in toxicity and excellent in storage stability. For example, the silanol group-containing prepolymer (a) can be derived, and the presence of urethane bonds in the molecular chain can greatly increase the adhesion of the consolidated gel to soil and sand particles. Y in the general formula (2) is preferably an alkoxyl group represented by an integer having 1 to 5 carbon atoms.
[0069]
Furthermore, the total weight average hydroxyl value of the polyether polyol is in the range of 20 mg KOH / g to 350 mg KOH / g, and the polyether chain length is 15 to 100% by weight of ethylene oxide (hereinafter simply referred to as EO) and propylene. Diol or triol composed of 85 to 0% by weight of oxide (hereinafter simply referred to as PO) or butylene oxide (hereinafter simply referred to as BO), and having an NCO / OH equivalent ratio in the range of 0.95 to 1.05 The active silanol group-containing prepolymer (A), which is characterized in that it is a more preferable example.
The diol or triol is more preferably 30 to 90% by weight of EO and 70 to 10% by weight of PO and / or BO, and most preferably 50 to 85% by weight of EO and 50 to 15 of PO and / or BO. It is preferable to be composed of% by weight.
Hereinafter, the active silanol group-containing prepolymer (i) prepared by a method of further hydrolyzing a product obtained by reacting a polyol with isocyanate silane will be referred to as an “active S polymer”.
[0070]
The aforementioned polyols may be liquid or solid at normal temperature, and preferably liquid at normal temperature. “Liquid at normal temperature” means that it is liquid at normal temperature alone, and when two or more polyols are used in combination, even if one or more of them are solid, the mixture is included if it is liquid at normal temperature. . In particular, it is preferable to use a polyol component that is solid at room temperature within 25% by weight in all polyols and that keeps liquid at room temperature.
Furthermore, the active silanol group-containing prepolymer (A) finally derived by mixing well with the essential component water (B) is in a liquid or micro suspension state (also called an emulsified state) at room temperature. Can be selected and used.
However, if either the glass transition temperature or the melting point of the polymer chain length of the main chain is basically 100 ° C. or higher and has a high crystallinity, the polyol has an induced final reaction. The product also retains the properties of a bulk solid at room temperature, and even if mixed with water (b), which is an essential component, it may be difficult to keep the liquid at room temperature, so it may be excluded.
[0071]
The above-mentioned total weight average hydroxyl value represents the average hydroxyl value of all polyol components when the same or different polyol components having different molecular weights are used alone and / or in combination.
[0072]
In addition, as a convenient polyol raw material for deriving the active S polymer, the total weight average hydroxyl value is preferably in the range of 10 mgKOH / g to 450 mgKOH / g. This is because, within this range, the elasticity of the solidified body using the organic polymer grout agent of the present invention prepared using the active S polymer and the rigidity such as uniaxial compressive strength are secured in a well-balanced manner. In addition, when a polyol having a hydroxyl value of less than 10 mg KOH / g is used, the derived active S polymer tends to be a high-viscosity composition, lacks storage stability, and is finally obtained as an organic polymer grout agent of the present invention. It is not preferable because the crosslinking density is insufficient and the homogel strength tends to be low. On the other hand, the use of a polyol having a hydroxyl value exceeding 450 mgKOH / g tends to increase the unit cost of the derived active S polymer, and the final organic polymer grout tends to be hard and brittle. It is in.
[0073]
As the polyol raw material used for the purpose of obtaining the active S polymer, known materials may be used, and more specifically, for example, the following (a) to (f) are preferable.
(A) Polyether polyol
(B) Telechelic acrylic polyol
(C) Polycarbonate polyol
(D) Amorphous polyester polyol
(E) Amorphous polyether polyester polyol
(F) Rosin polyol and / or hydrogen adduct thereof
[0074]
(A) The polyether polyol may be a known one, and the production method is not particularly limited. For example, inexpensive activities such as trimethylolpropane, glycerin, neopentyl glycol, sucrose, triethanolamine, and ethylenediamine Preferable examples include those obtained by causing a raw material such as alkylene oxides represented by EO, PO, BO, tetrahydrofuran and the like to act on a hydrogen compound by a method such as anionic polymerization or cationic polymerization. A diol having 2 hydroxyl groups in one molecule or a triol having 3 hydroxyl groups in one molecule can be particularly preferably used.
[0075]
Among the above-described alkylene oxides, terminal primary and / or terminal end groups obtained by allowing EO and PO to act at an addition polymerization ratio in the range of (100: 0) to (15:85) in the molar ratio of both. The 2- to 6-functional polyol having a secondary -OH group has high solution stability when it is made into an aqueous solution containing an active S polymer, and at the same time, can be well compatible with water and / or microdispersed and stabilized. Since it is recognized, it is an example of a preferable polyol. Further, (a) is a weight average molecular weight calculated from a polystyrene conversion value obtained by a liquid chromatographic measurement method or a weight average molecular weight calculated from a hydroxyl value, in the range of 400 to 50,000, preferably 1,000 to 20, It is important that the range is 000.
[0076]
(B) The telechelic acrylic polyol means an acrylic polyol which is liquid at room temperature in which a hydroxyl group is selectively introduced at the molecular end. Examples of the synthesis / manufacturing method have already been clarified by JP-A-4-132706, JP-A-5-262808, etc., and may be obtained by a known method, and there is no particular limitation. General (b) includes those having an average of two hydroxyl groups introduced in one molecule. Further, (b) is a weight average molecular weight or a weight average molecular weight calculated from a polystyrene value calculated by a liquid chromatographic measurement method, and is in the range of 400 to 50,000, preferably 1,000 to 20, It is important that the range is 000.
[0077]
(C) Polycarbonate polyol is obtained by subjecting a compound containing a lactone ring as a main starting material to ring-opening polymerization reaction in the presence of a known ring-opening catalyst, and converted to polystyrene obtained by liquid chromatography measurement The weight average molecular weight represented by the value or the weight average molecular weight calculated from the hydroxyl value is in the range of 400 to 50,000, preferably in the range of 1,000 to 20,000. There are no particular restrictions on the production method, and examples of those that can be easily obtained in the market include polyethylene carbonate diol, polypropylene carbonate diol, and polybutylene carbonate diol.
[0078]
(D) Amorphous polyester polyol is a weight average molecular weight calculated from a weight average molecular weight or a hydroxy value, which is handled as a semi-solid or liquid at room temperature, and is expressed in terms of polystyrene determined by a liquid chromatographic measurement method. It is a so-called terminal hydroxy group-containing polyester in the range of 400 to 50,000, preferably in the range of 1,000 to 20,000. As the (d), a so-called known soft polyester having about 2 to 4 hydroxyl groups in one molecule can be mentioned as a preferred example. Although not particularly limited, specific examples of (d) include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propylene carbonate diol. , Ethylene carbonate diol, trimethylolpropane, silicon polyol, acrylic polyol, hydrogenated olefin polyol and the like, and those obtained by esterification reaction with known organic dibasic acids, melting point or needle If Tg measured by the insertion method is less than 100 ° C., it can be used.
[0079]
(E) Amorphous polyether polyester polyol is a weight average molecular weight calculated from a weight average molecular weight or a hydroxy value, which is a semi-solid or liquid at room temperature, and is expressed in terms of polystyrene determined by a liquid chromatographic measurement method. So-called soft polyether polyesters in the range of 400 to 50,000, preferably in the range of 1,000 to 20,000. As (e), at least 1.2 or more, preferably 2 to 4 hydroxyl groups as terminal functional groups in one molecule, and the polyether chain has a polymerization degree of 10 or more and 50 or less. A preferred example is a soft polyether polyester having repeating units. Although not particularly limited, for example, those obtained by esterifying a polyether polyol having a molecular weight of about 500 to 1000 and known organic dibasic acids can be mentioned, and measured by melting point or penetration method A Tg of less than 100 ° C. is typical.
[0080]
(F) The rosin polyol and / or its hydrogen adduct is more specifically a rosin diol derivative that is a glycidol adduct of natural rosin or its hydrogen adduct, and further EO / PO for the rosin diol derivative. Suitable examples include those having a high molecular weight by appropriate addition, and known ones having a weight average molecular weight in the range of 400 to 50,000 calculated from the hydroxy value may be appropriately selected and used.
[0081]
The active S polymer derived from one of the above-mentioned (c), (d) or (e) and an isocyanate silane has, as a chemical property of the polymer, a hydrolysis stability of the polyol chain itself. There is a tendency to lack a little. Therefore, in the main agent liquid of the present invention containing the active S polymer having the skeleton, the appropriate blending conditions must be determined by carefully examining the results such as the influence of the pH and environmental temperature on the factors.
[0082]
Among these (a) to (f), the active S polymer is most preferably derived from (a) a polyether polyol. And it is more preferable to set it as the range of the total hydroxyl value of the (a) polyether polyol of 20-350 mgKOH / g, More preferably, it shall be the range of 25-300 mgKOH / g. In the (a) polyether polyol, particularly preferred are polyether-based diols and / or triols.
[0083]
From the above-described at least one polyol (a) to (f), more preferably (a) and the isocyanate silane represented by the general formula (2), an activity which is an essential component of the main liquid of the present invention The active S polymer, which is one of the silanol group-containing prepolymers (a), has a feature (advantage) that can be adjusted very inexpensively.
[0084]
In addition, the isocyanate silane represented by the general formula (2) is not particularly limited, but specifically, for example, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane. , Γ-isocyanatopropyldiethoxymethylsilane, γ-isocyanatopropyldimethoxymethylsilane, and the like are known, and one or more selected from them may be selected and used.
[0085]
In the active S polymer, the polyol (a) described above and the isocyanate silane are preferably in the range of 0.7 to 1.5, preferably 0.9 to 1.2, in terms of an NCO / OH equivalent ratio. , Particularly preferably in the range of 0.95 to 1.05, most particularly preferably in an equivalent ratio as close as possible to 1 in the presence of a very small amount of a known urethanization catalyst. It is obtained. When the NCO / OH equivalent ratio is less than 0.7, there is a tendency not to show sufficient expression of homogel strength because unreacted free polyol remains in the derived active S prepolymer. This is because, when the OH equivalent ratio exceeds 1.5, there is no remarkable problem, but it is disadvantageous in price. A certain amount of isocyanate silane remaining contributes to a decrease in the viscosity of the active S polymer and is chemically incorporated into the final solidified molecule, so that the NCO / OH equivalent ratio may be 1 or more.
Most of the precursor resins of the active S polymer adjusted in the above range are at least an average of 0.7 or more, more preferably about 2 to 6 on average per molecule, more preferably a dialkoxysilane group and / or the same. A trialkoxysilane group is introduced at the molecular end (in the primary reaction stage) of the main chain polymer. There is no problem even if only a small amount of hydroxyl groups remain partially. Finally, it is hydrolyzed with water to obtain the desired active S polymer.
[0086]
The reaction of the above polyols and isocyanate silane may be performed in the presence of a known urethanization catalyst for the purpose of imparting rapid curing suitability of the final organic polymer grout agent and shortening the reaction time. .
[0087]
The urethanization reaction catalyst is not particularly limited. For example, an organic tin compound typified by dibutyltin dilaurate or dibutyltin oxide, an organic titanium compound typified by orthotitanate alkyl ester, and the like. Examples include naphthenic acid transition metal compounds such as cobalt naphthenate, zinc naphthenate, and lead naphthenate, octenoic acid transition metal compounds, and acetylacetone transition metal complexes. In the grout pharmaceutical industry, it is important to make the amount as small as possible when adding or using an organotin-based urethanization-promoting catalyst, which is considered to fall under the category of regulated or avoided. It is done.
[0088]
In the field of grout for ground injection, it is important to solidify within a set gelation time and it is important that the solidified gel exhibits a certain range of strength. The following curing solution is essential.
[0089]
That is, in the organic polymer grout agent of the present invention, it is based on the total amount of the main agent liquid, which is an aqueous solution containing the active silanol group-containing prepolymer (I), from the viewpoint of arbitrary gelation adjustment and securing the solidified strength and toughness. The following curing agent liquid is mixed.
The mixing ratio of the main agent liquid and the curing agent liquid described above is naturally determined by the ratio of the alkaline component in the main agent liquid and the acidic component in the curing agent liquid described later. The ratio is, specifically, from the viewpoint of actual workability on site, etc., specifically, 1 to 300 parts by volume of the following curing agent liquid is mixed with 100 parts by volume of the main agent liquid. . More preferably, the method of mixing 20 to 100 parts by volume of the following curing agent liquid with respect to 100 parts by volume of the main agent liquid is more preferable because mistakes in mixing amount can be reduced as much as possible. Most preferably, the organic polymer grout agent of the present invention obtained by mixing 100 volume parts of the following curing agent liquid with 100 volume parts of the main agent liquid is most preferable. Furthermore, in the organic polymer grout agent composition of the present invention, the two-component liquid mixture of the main agent liquid and the curing agent liquid described below is not particularly limited, but the active silanol group-containing prepolymer (I) The concentration in the grouting agent is preferably in the range of 1 to 70% by weight, more preferably in the range of 5 to 37.5% by weight.
[0090]
The curing agent liquid is an inorganic acid (ha) corresponding to 30 to 200 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH) contained in the main agent liquid when mixed with the total amount of the main agent liquid. ), An alkali metal salt of an inorganic acid (d), a water-soluble organic acid (e), or an organic monomer (f) that releases a sustained-release acid in alkaline water. An aqueous solution containing a curing agent.
As a more preferable curing agent liquid, an inorganic acid (in an amount corresponding to 50 to 120 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH) contained in the main agent liquid when mixed with the whole amount of the main agent liquid) C) From one or more selected from alkali metal salts of inorganic acids (d), water-soluble organic acids (e), organic monomers (f) that release sustained-release acids in alkaline water An aqueous solution containing a curing agent is mentioned.
[0091]
Most preferably, when mixed with the total amount of the main agent solution, 1 of the inorganic acid (c) in an amount corresponding to 75 to 100 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH) contained in the main agent solution. An aqueous solution containing a curing agent composed of seeds or two or more species is mentioned.
[0092]
Examples of the inorganic acid (c) include known strong acidic inorganic monomer substances, and are not particularly limited. Specific examples include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, phosphoric acid, boric acid and the like.
Examples of the alkali metal salt (d) of an inorganic acid include already known sodium salts, potassium salts and lithium salts of inorganic acids, and there is no particular limitation. Specific examples include sodium chloride, potassium chloride, lithium chloride, sodium carbonate, sodium bicarbonate (also known as sodium bicarbonate), potassium carbonate, potassium bicarbonate (also known as potassium bicarbonate), lithium carbonate, and lithium bicarbonate. (Also known as lithium bicarbonate), sodium nitrate, potassium nitrate, lithium nitrate, sodium sulfate, sodium hydrogen sulfate (also known as sodium bisulfate), potassium sulfate, potassium hydrogen sulfate (also known as potassium bisulfate), lithium sulfate, lithium hydrogen sulfate (Alternative name: lithium bisulfate), sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, lithium phosphate, lithium hydrogen phosphate, sodium borate, potassium borate, lithium borate and the like.
Among these, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium bicarbonate, or a mixture composed of two or more kinds of potassium bicarbonate can be mentioned.
[0093]
As the water-soluble organic acid (e), any known organic acid that can be used as a curing agent for alkaline water glass can be used as it is, and there is no particular limitation. It is preferable to select and use a known alkaline acid glass organic acid curing agent having a high solubility in water. For example, monocarboxylic acids represented by formic acid, acetic anhydride, acetic acid, propionic acid, oxycarboxylic acids represented by glycolic acid, malic acid, lactic acid, aldehyde carboxylic acids represented by glyoxylic acid, succinic acid, maleic acid, etc. Examples include dicarboxylic acids represented by water, water-soluble natural organic acids derived from nature represented by phytic acid and acid salts thereof, and the like.
[0094]
As the organic monomer (f) that releases a sustained-release acid in alkaline water, a known organic monomer substance capable of curing alkaline water glass can be used as it is, and there is no particular limitation. Typical alkaline water glass organic monomer curing agent materials include, for example, water-soluble aldehydes, water-soluble cyclic lactones, water-soluble alkylene carbonates, and water-soluble alkyl esters.
[0095]
A more specific example of the water-soluble aldehyde is glyoxal. A more specific example of the water-soluble cyclic lactone is γ-butyrolactone. Examples of water-soluble alkylene carbonates include ethylene carbonate and propion carbonate. Furthermore, examples of water-soluble alkyl esters include ethylene glycol diacetate, glycerin diacetate, and glycerin triacetate, and one or more of them may be used.
[0096]
When using a curing agent composed of one or more selected from (c), (d), (e), and (f), the gel time of the organic polymer grout agent of the present invention is 20 minutes or more. The combination of the curing agents preferred when it is desired to have a medium-long setting to a long-setting type (or long-setting type) for less than 24 hours is not particularly limited, but for example, a combination of (c) and (f), Examples include the combined use of (d) and (f) and the combined use of (e) and (f).
[0097]
Moreover, in the organic polymer grout agent composition of the present invention, the following curing aid components may be used in combination with the above-described curing agent as necessary.
Preferred examples of the curing aid component include alkaline earth metal salts (g) and hydraulic inorganic fine particles (h).
Specific examples of alkaline earth metal salts (g) include calcium oxide (quick lime), calcium hydroxide (slaked lime), calcium chloride, magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium sulfate, aluminum hydroxide, Examples include aluminum chloride.
Specific examples of the hydraulic inorganic fine particles (h) include cement, granulated slag, anhydrous gypsum or hemihydrate gypsum or dihydrate gypsum or a gypsum mixture thereof, fly ash, seawater, or bittern. .
One or more selected from (g) and (h) can be preferably used.
[0098]
Especially (G) and (H) are 3,000 to 50,000 cm in brain value ² / G, preferably 8,000 to 45,000 cm ² / G, most preferably 10,000 to 40,000 cm ² Those in the range of / g are particularly preferred.
[0099]
Further, in the organic polymer grout agent of the present invention, the silanolation condensation catalyst shown below is necessary for the purpose of arbitrarily adjusting the gelation time and further increasing the strength while maintaining the elasticity of the solidified body. Depending on the case, it may be added and used in either one or both of the main agent liquid and the curing agent liquid. The silanolation condensation catalyst includes, for example, alkyl titanates; organosilicon titanates; dibutyltin carboxylates such as tin octylate, dibutyltin laurate, malate and fumarate; dibutylamine-2-ethylhexo And amine salts such as ate. When using the silanol-condensation condensation catalyst in combination, it is important to determine the amount of addition by conducting a sufficient gelation behavior test or the like in advance. 100 weight of active silanol group-containing prepolymer (I) It is preferable to set it as 0.001-20 weight part with respect to a part.
[0100]
When the gelation time after mixing two liquids of the organic polymer grout agent of the present invention is as short as 20 minutes or less, it is desirable to avoid handling by a one-shot method as much as possible. This is because, depending on the case, the injection tube may be damaged due to the grouting agent being consolidated in the injection tube. On the other hand, when the gelation time is as long as 20 minutes or longer, two liquids of the organic polymer grout agent of the present invention may be mixed to form one liquid, that is, a one-shot system may be handled.
That is, it is basically more preferable to handle with either the 1.5 shot or the 2-shot method because troubles in workability can be avoided.
[0101]
In the main component liquid or curing agent liquid or two-component mixed composition of the organic polymer grout agent of the present invention, with particular attention to improvement in workability, adjustment of penetration rate, improvement in adhesion, prior pH adjustment, etc. The following additive aid components may be used for any one of the liquid compositions within 0.01 to 10% by weight, preferably within 0.1 to 3% by weight.
For example, light stabilizers represented by hindered amines; hindered phenolic antioxidants; silane coupling agents represented by glycidylsilanes, aminosilanes, mercaptosilanes, vinylsilanes, and chlorosilanes; ultrafine alumina, ultrafine Inorganic thixotropy imparting agents represented by fine clay powders, peroxide supplements represented by phosphites, inorganic fillers represented by charcoal, talc, etc., surfactants, sugar, glucose Further, a metal complex forming agent such as ascorbic acid can be appropriately added.
[0102]
There is no particular limitation on the water (b) component essential for the organic polymer grout agent of the present invention. Artificial seawater, seawater, river water, groundwater, tap water, rainwater, distilled water, ion-exchanged water and the like can be preferably used as long as they can be procured in the vicinity of the injection work site.
[0103]
Below, the ground improvement method (it is also called a ground improvement construction method) using the above-mentioned organic polymer grout agent of this invention is demonstrated.
As one of the ground improvement methods, an unstable ground is pressurized and injected through a grout injection tube in the form of mixing two liquids of the organic polymer grout agent of the present invention, and the ground is solidified by solidification. It is a method of strengthening or stopping water, or reducing water permeability to the limit. Another method for improving the ground is to use two or more organic polymer grouting agents of the present invention having two or more different gel times through a grouting pipe on the unstable ground, that is, a plurality of them. In this method, multiple phases are injected and solidified to strengthen or stop the ground, or to reduce the water permeability to the limit.
[0104]
In the ground improvement method described above, after injecting only the curing agent liquid shown as the organic polymer grout agent consisting of the two liquids of the present invention at the time of injection, the main agent liquid of the organic polymer grout agent of the present invention, or It is also a good method to mix the two liquids and inject them later. The multi-phase injection refers to, for example, after preparing the organic polymer grout agent of the present invention having two or more kinds of gel times, and first selecting the composition having a relatively fast setting time of several seconds to several minutes. A specific example of the method is preferable, for example, in which after the pre-injection solidification, the organic polymer grout agent of the present invention having a slower gel time is post-injected. In another example of multi-phase injection, a known instantaneous or intermediate-type inorganic curing agent-water glass main component type, organic curing agent-water glass main component type, water glass-cement suspension type, water glass-slag One type of known grout agent selected from a suspension type or the like is pre-injected and consolidated, followed by post-injection of the organic polymer grout agent of the present invention. A method of ligating is also preferably included.
In the injection, a known method such as a packer method, a sleeve method, or a high pressure injection method may be used without any particular limitation.
[0105]
Below, the groundwater water-stopping method of a sewer pipe using the organic polymer grout agent of this invention (it is also called a groundwater water-stopping construction method) is demonstrated.
The sewer pipe underground water shutoff method is the organic water supply method of the present invention through a cylindrical self-feeding Parker injector having a small-diameter double packer and a TV camera for the underground water leakage location of the underground sewer pipe. This is a construction method in which a polymer grout agent is injected under pressure into the water leakage portion and solidified to stop water.
Moreover, in this construction method, a preferable organic polymer grout agent used when a large amount of groundwater inflow or a large amount of sewage outflow is observed has a gelation time as short as possible from several seconds to several tens of seconds. The purpose can be achieved by selecting and using. In this case, for example, an injection pipe is inserted from the ground surface, and a water outflow flow path (that is, the outflow location ground from the sewer pipe is integrally solidified with the grout agent etc. so that the water leaks out. The method includes, for example, completing the water stop by the above-described method after the (path) is suppressed.
[0106]
Below, the harmful substance sealing method performed using the organic polymer grout agent of this invention is demonstrated.
As one of the major social problems in recent years, mines and industrial wastes containing a lot of harmful heavy metal ions and other harmful substances that are left or stored outdoors are left unattended, resulting in In fact, it has been pointed out that there are many dangers that the living environment is extremely polluted and can cause enormous damage to animals and plants. Therefore, urgently solve the problem of preventing damage caused by such environmental pollution. Is strongly demanded.
Therefore, in the hazardous substance sealing method of the present invention, the harmful substance containing the heavy metal ions or the like is prevented from leaking out to the outside by permeated water such as rain, or the harmful substance sealing method for suppressing to the limit In the method for sealing hazardous substances, the organic polymer grout agent of the present invention and the harmful substances are integrated and consolidated, and as a result, leakage of the harmful substances to the outside is prevented. is there.
[0107]
Specific methods for integrating the organic polymer grout agent and harmful substances of the present invention include known mechanical mixing / impregnation methods, injection permeation consolidation methods, sprinkling impregnation consolidation methods, lamination consolidation methods, and the like. Alternatively, the impregnation and consolidation means may be arbitrarily selected and there is no particular limitation. Among them, a method of sealing the organic polymer grout agent of the present invention by a method such as sprinkling from above or by fluid impregnation and solidification is more preferable from the viewpoint of processing cost. Ultimately, the permeability coefficient of the surface layer portion of the crushed or industrial waste containing the harmful substance is at least 10 ^-Four Order, preferably 10 ^-Five Therefore, it is important to determine the amount of the organic polymer grout agent of the present invention so that the decrease can be suppressed to the limit value beyond that.
[0108]
In addition, the gel time adjustment of the organic polymer grout agent of the present invention may be arbitrary, and preferably in the range of several seconds to several hours for that purpose. Any gel time may be set according to the presence / absence of groundwater, the kind of soil, the sediment accumulation structure, and the state around the injection site, and there is no particular limitation. Further, as described above, the organic polymer grout agent of the present invention having two or more kinds of gel times may be prepared, and the object may be achieved by a multi-phase injection method. You may employ | adopt a shot system etc. suitably.
[0109]
By the way, the organic polymer grout composition of the present invention is used for improving unstable ground, for integrating the back of a concrete panel for tunnel and the rock contacting the back, integration of the basement concrete wall and the soil contacting the back. It can also be preferably used as an application for backfilling the back surface of the structure in order to achieve both the strengthening stability of the concrete structure under the ground or the underground and permanent water stoppage.
[0110]
【Example】
Examples and Comparative Examples of the present invention are shown below, but unless otherwise specified, the described parts or% mean parts by weight and% by weight, respectively, and the present invention is not particularly limited by the described examples. .
In addition, the explanation of each symbol in the following examples and tables is as follows.
Moreover, about the various performance test methods of the grout agent composition as described in each example, it carried out as follows.
[0111]
Flame retardant test
Hold the end face of the organic polymer grout agent alone (thickness 2mm x width 5mm x length 100mm) at an angle of 45 ° directly above the gas burner oxidation flame for 2-3 seconds. Immediately away from the small flame, let the flame spread out within 3 seconds. If it disappears within 20 seconds, it is displayed as a circle with flame retardancy. If it disappears within 30 seconds, it is indicated by a symbol △ because it is somewhat lacking in flame retardancy. When it continued to burn for more than 30 seconds, it was indicated by a symbol x for flammability.
[0112]
Gelation time (gel time) measurement
Expressed as the time from when the hardener component is added or mixed with two liquids at a constant temperature until the solution fluidity of the composition itself disappears, and when the time is less than 1 minute, [instantaneous] is displayed. More than 5 minutes to less than 5 minutes was displayed as [Natural], 5 minutes or more to less than 30 minutes was displayed as [Medium and long], and those longer than 30 minutes were displayed as [Long].
[0113]
Uniaxial compression test
This was a method according to JIS-A-1216, and was performed at a compression speed of 1.5 mm / min using a SG-2033B type electric single-axis compression tester manufactured by Maruto Corporation.
[0114]
Homogel strength and strain rate measurement
After obtaining a columnar homogel hardened body having a diameter of 50 mm and a height of 100 mm, the uniaxial compressive strength is obtained and the value is defined as the homogel strength. In addition, the value obtained by dividing the amount of deformation until fracture at the time of measuring the uniaxial compressive strength by the original height and multiplying by 100 is displayed as a distortion rate (%).
[0115]
Sand gel strength
After 38.5 to 40.5 vol% of the grout agent composition and 59.5 to 61.5 vol% of Toyoura standard sand are uniformly mixed, packed in a molding container so as not to contain air bubbles, and solidified. Curing and demolding to obtain a cylindrical sand gel cured body having a diameter of 50 mm and a height of 100 mm. The sand gel strength is determined by the value of the uniaxial compressive strength of the sand gel.
[0116]
Penetration suitability test
A 10 cm diameter transparent acrylic filling tower with an opening hole in each of the upper part and the lower part was prepared, and Toyoura standard sand was finely filled in the presence of water so that the filling height was 1 m. When the grout composition of each Example and Comparative Example was injected from the opening at the top of the filling tower at an injection pressure of 1.5 kg / cm 2, the injection penetration rate (200 to 210 ml / min) with only city water was When the injection penetration rate ratio of each grout composition with respect to water is 70% or more when it is set to 100 and interparticle penetration solidification is possible, it is indicated by a symbol “◎”. Further, when the injection penetration rate ratio with respect to water is 50% or more and less than 70% and interparticle penetration consolidation is possible, the symbol “◯” indicates that the injection penetration rate ratio with respect to water is 15% or more and less than 50% and interparticle penetration. A case where consolidation is possible is indicated by a symbol Δ, and a case where it is less than 15% is indicated by a symbol X.
[0117]
Durability test
Either a cylindrical homogel body or a sand gel cured body obtained by the above method is immersed in a flowing water replacement water tank set so that 10 liters are replaced once a day and night, and the uniaxial compressive strength at that time is maintained. The result of observing the rate (%) and the appearance change was displayed as a water durability test result (hereinafter referred to as durability test 1). On the other hand, a seawater immersion durability test result (hereinafter referred to as a durability test) with the appearance change and uniaxial compressive strength retention rate (%) after preparing an artificial seawater solution prescribed in JIS and immersing in artificial seawater for a certain period of time. 2).
[0118]
In the following, first, the main agent solution and the comparative main agent solution used in Examples and Comparative Examples described later are described.
[0119]
Main liquid 1
A 1-liter four-necked reaction flask with a reflux condenser is prepared, and a polyether triol [ethylene oxide (EO) and propylene oxide having a weight average molecular weight of 3,300 calculated from the hydroxyl value as a polyether polyol. The random addition molar ratio of (PO) is 75:25] (0.454 mol / active OH equivalent) and 114 parts of γ-isocyanatopropyltriethoxysilane (0.46 mol / active NCO equivalent) And 0.01 part of dibutyltin oxide as a catalyst, reacted in a nitrogen stream at 80 ° C. for 2 hours, cooled, and hydrolyzed into a polyether main chain having a molecular weight of 3,300 almost quantitatively. A prepolymer 1 having an average of 3 silyl group terminals was obtained. Prepolymer 1 alone showed a liquid at room temperature, and its solution viscosity was 980 cps as measured at room temperature with a B-type viscometer.
[0120]
Further, 310 parts of the prepolymer 1 were added little by little to 690 parts of a 1N aqueous sodium hydroxide solution heated to 50 ° C., and after completion of the addition, about 30 parts of free ethanol was removed. As a result, a colorless and transparent solution was obtained and adjusted to a concentration of 30.97% by weight in terms of solid content. As a result, an alkaline aqueous solution containing an active silanol group-containing prepolymer was obtained. The pH value of the main agent liquid 1 was 13.5 at room temperature, and it was a low viscosity liquid of about 3 to 4 cps. Further, it was confirmed that the main agent solution 1 was stable even after storage at room temperature for 3 months.
[0121]
Main liquid 2
Separately, 400 parts of the prepolymer 1 was added little by little to an alkaline aqueous solution consisting of 534 parts of a 1N sodium hydroxide aqueous solution and 66 parts of distilled water heated to 50 ° C. 38 parts of free ethanol was removed. As a result, a colorless and transparent solution was obtained, and an aqueous solution of an active silanol group-containing prepolymer having a concentration of 39.8% by weight in terms of solid content was obtained. The pH value of the main agent liquid 2 was 13.6 at room temperature, and it was a low-viscosity liquid of approximately 3.9 cps. Moreover, there was no change even after the main agent solution 2 was stored for 3 months, and the storage stability of the main agent solution itself was good.
[0122]
Main liquid 3
Separately, 310 parts of the prepolymer 1 was added little by little to an alkaline aqueous solution consisting of 138 parts of 1N sodium hydroxide aqueous solution and 552 parts of ion-exchanged water heated to 50 ° C., and aeration was performed after completion of the addition. About 30 parts of free ethanol was removed. As a result, a colorless and transparent solution was obtained, and an active silanol group-containing prepolymer aqueous solution having a concentration of 29.2% by weight in terms of solid content was obtained. The pH value of the main agent liquid 3 was 13.4 at room temperature, and it was a low viscosity liquid of approximately 2 cps. Further, the storage stability of the main agent solution 3 was good for 5 days, but thickening and partial gel precipitation were observed after storage for 10 days or more.
[0123]
Main liquid 4
A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, and as a polyether polyol, a polyether triol hardly soluble in water having a weight average molecular weight calculated from a hydroxyl value of 3,300 [for glycerin] 500 parts (0.454 moles / active OH equivalent) of triol derived from addition of ethylene oxide (EO) and propylene oxide (PO) at a ratio of random addition of 50:50 and γ-isocyanatopropyltriethoxy 114 parts of silane (0.46 mol / active NCO equivalent) and 0.01 part of dibutyltin oxide as a catalyst were charged, reacted in a nitrogen stream at 80 ° C. for 2 hours, cooled, and almost quantitatively molecular weight A prepolymer 6 having an average of 3 hydrolyzable silyl group ends on a polyether main chain having a 3,300 polyether It was. Prepolymer 6 alone showed a liquid at room temperature, and its solution viscosity was 980 cps as measured at room temperature with a B-type viscometer.
On the other hand, 50 parts of 3N-potassium hydroxide aqueous solution, 150 parts of distilled water and 100 parts of the prepolymer 6 were added little by little. After completion of the addition, the mixture was stirred at 80 ° C. for 1 hour, and then at the same temperature and reduced pressure. Aeration and deethanolification, and further adjustment with dilution water gave a milky white stable emulsion solution containing 30% by weight of the active silanol group-containing prepolymer in terms of solid content. The pH value of the main agent liquid 4 was 13.9 at room temperature, and it was a low viscosity liquid of approximately 3.1 cps. This main agent liquid 4 was an alkaline aqueous solution containing a stable active silanol group-containing prepolymer, although it was changed to a colorless and transparent aqueous solution when observed after 24 hours, and the solution did not gel.
[0124]
Main liquid 5
A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, and 500 parts (0.05 mol / active OH equivalent) of high-purity polyethylene glycol having a weight average molecular weight of 20,000 calculated from the hydroxyl number. And 13.5 parts of γ-isocyanatopropyltriethoxysilane (0.054 mol / active NCO equivalent) and 0.01 part of dibutyltin oxide as a catalyst were reacted in a nitrogen stream at 80 ° C. for 5 hours. After cooling, a prepolymer 2 having an average of 2 active silyl group ends in one molecule and a main chain of a polyethylene glycol skeleton having a weight average molecular weight of 20,000 was obtained. The prepolymer 2 was water-soluble and solid at room temperature, and was very compatible with water having a melting point of about 60 ° C.
Next, an alkaline aqueous solution comprising 195 parts of a 0.1N sodium hydroxide aqueous solution heated to 60 ° C. and 505 parts of tap water was charged into another four-necked flask, and 304 parts of the prepolymer 2 were added to the liquid. Was introduced. While heating at 60 ° C., nitrogen aeration was performed to remove about 4 parts of free ethanol, and the solid content was adjusted to 30% by weight. As a result, a colorless and transparent solution was obtained, and a base solution 5 which was an aqueous solution containing an active silanol group-containing prepolymer was prepared. The pH value of the main agent liquid 5 was 13.0 at room temperature, and it was a low viscosity liquid of about 1.5 cps. Further, no gelation or thickening was observed even after standing for 1 to 2 months, and the main liquid 5 was rich in stability.
[0125]
Main liquid 6
A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared. 500 parts (0.5 mol / active OH equivalent) of polyethylene glycol (molecular weight 2,000) having a hydroxyl number of 56 mgKOH / g and a weight average molecular weight 200 parts of water-soluble monool (0.098 mol / active OH equivalent) which is 2,050 one-terminal n-butyl etherified polyalkylene glycol monobutyl ether and 149 parts of γ-isocyanatopropyltriethoxysilane ( 0.6 mol / active NCO equivalent) and 0.01 part of dibutyltin oxide as a catalyst, reacted in a nitrogen stream at 80 ° C. for 2 hours, and then cooled. A prepolymer 3 having an active silyl group end was obtained.
Prepolymer 3 was composed of a polyether skeleton having a molecular weight of about 2,000 in the main chain, and was water-soluble and semi-solid at room temperature.
Next, an alkaline aqueous solution consisting of 100 parts of a 0.5N potassium hydroxide aqueous solution at 20 ° C. and 400 parts of tap water was charged into another four-necked flask, and 555 parts of the prepolymer 3 was charged into the liquid. After heating at 50 ° C., nitrogen aeration was performed to remove about 55 parts of free ethanol, and the active silanol group-containing prepolymer-containing concentration was adjusted to 50.1% by weight in terms of solid content. As a result, a colorless and transparent solution was obtained, and a base liquid 6 that was an aqueous solution containing an active silanol group-containing prepolymer was prepared. The pH value of the main agent liquid 6 was 13.4 at room temperature, and it was a low viscosity liquid of approximately 5.7 cps. The liquid life at room temperature of the main agent liquid 6 was at most 5 days.
[0126]
Comparative base solution 1
A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared. A polyether glycol triol having a primary hydroxyl group having a hydroxyl number of 54.8 mgKOH / g and an EO / PO block addition ratio of 19/81 was prepared. 500 parts (0.488 mole / active OH equivalent), 102 parts of γ-isocyanatopropyltrimethoxysilane (0.488 mole / active NCO equivalent) and 0.01 part of dibutyltin oxide as catalyst were charged with nitrogen. After reacting at 80 ° C. for 2 hours in an air stream, the mixture was cooled to obtain a prepolymer 4 having an average of 3 active silyl group ends on an average basis. Prepolymer 4 is composed of a hydrophobic polyether skeleton having a molecular weight of about 2,000 in the main chain, and is liquid at room temperature, but almost insoluble in water.
The comparative main agent liquid 1 made into a water-diluted solution with 10% by weight of ion-exchanged water using this prepolymer 4 was immediately separated into two layers, and the upper layer formed the prepolymer 4 and remained in a thermosetting state within 24 hours. A water-insoluble crosslinked gel layer was formed. As a result, since the prepolymer 4 is insoluble in water, the water-diluted solution cannot be prepared as it is.
[0127]
Main liquid 7
A 1 liter beaker container is prepared, and 600 parts of a 0.6N potassium hydroxide solution and 150 parts of tap water mixed with 5% of artificially adjusted seawater are charged therein, and the system is stirred. Into this, 250 parts of the prepolymer 4 used in the comparative main agent liquid 1 was added and reacted for 2 hours. As a result, a thin milky white translucent solution was obtained, and a main agent liquid 7 was obtained which was a stable semi-suspended active silanol group-containing prepolymer-containing aqueous solution having no change in standing tests for several days. In addition, it was an alkaline aqueous solution containing an active silanol group-containing prepolymer having a concentration expressed in terms of charged prepolymer 4 of 25%. Compared with the comparative main agent liquid 1 in which no stable water dilution was prepared, in this main agent liquid 7, a very stable aqueous main agent liquid was prepared. The solution viscosity was 0.6 cps and a low viscosity system.
[0128]
Main liquid 8
A 1 liter beaker container is prepared, 200 parts of 1N sodium hydroxide solution and 500 parts of tap water are charged therein, and 300 parts of prepolymer 4 used in the comparative main agent liquid 1 while stirring the system. Was allowed to react for 2 hours. As a result, a deep milky white solution was obtained, and a main agent liquid 8 which was an aqueous solution containing an active silanol group-containing prepolymer, which was a stable suspension solution having no change in a standing test for several days, was obtained. In addition, it was the active silanol group containing prepolymer containing aqueous solution whose density | concentration represented by preparation prepolymer 4 conversion is 30%, and it was a low-viscosity solution whose pH value is 13.5 and 0.7 cps. Compared with the comparative main agent liquid 1 in which no stable water dilution was prepared, in the main agent liquid 8, an extremely stable aqueous main agent liquid was prepared. The solution viscosity was 0.7 cps and a low viscosity system.
[0129]
Comparison main liquid 2
A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, and 500 parts (0.615 mol / active OH equivalent) of rosindiol (average molecular weight 1,626) having a hydroxyl number of 69 mgKOH / g and γ -After charging 129.6 parts of isocyanate propyltrimethoxysilane (0.62 mol / active NCO equivalent) and 0.005 parts of dibutyltin oxide as a catalyst, the mixture was reacted at 80 ° C for 5 hours in a nitrogen stream. After cooling, prepolymer 5 consisting of a rosin skeleton having an average of 2.0 active silyl group ends and a main chain polymer chain molecular weight of 1,626 in an average quantity is hydrophobic and liquid at room temperature. Obtained.
In the comparative main agent liquid 2 made into a water-diluted solution with 10% by weight of ion-exchanged water using this prepolymer 5, the two layers were separated immediately after mixing, and the upper layer formed the prepolymer 5 and was heat-cured as it was within 24 hours. A water-insoluble crosslinked gel layer was formed. As a result, since prepolymer 5 is insoluble in water, it was not possible to prepare a dilute water solution.
[0130]
Main liquid 9
A 1 liter beaker container was prepared, and 600 parts of a 0.5N sodium hydroxide solution and 150 parts of tap water were charged therein, and 250 parts of prepolymer 5 used in the comparative main agent liquid 2 was stirred under the system. Part was added and reacted for 2 hours. As a result, a thin milky white translucent solution was obtained, and a main agent liquid 9 was obtained which was a stable semi-suspended active silanol group-containing prepolymer-containing aqueous solution having no change in a standing test for several days. In addition, it was a strong alkaline aqueous solution with a solution pH value of 13.5 containing an active silanol group-containing prepolymer having a concentration expressed in terms of charged prepolymer 5 of 25%. Compared with the comparative main agent liquid 2 in which a stable diluted water solution was not prepared, in the main agent liquid 9, a very stable aqueous main agent liquid was prepared, and the solution viscosity was about 0.8 cps, which was a low viscosity liquid.
[0131]
Examples and comparative examples are described below.
[0132]
Example 1 to Example 7
Main agent liquid 1 to main agent liquid 7 in less than 3 hours after adjustment, and each main agent liquid having the composition shown in Table 1 diluted with tap water as necessary, and further each curing agent having the composition shown in Table 1. Each of the organic polymer grout agent compositions of Examples 1 to 7 was prepared by mixing the main agent liquid and the curing agent liquid at the blending ratios shown in Table 1 using the two liquids, and the grout agent number D1. (Organic polymer grout agent described in Example 1) to D7 (Organic polymer grout agent described in Example 7) were obtained. Table 1 shows the solution properties and the cured product properties of each grout agent.
[0133]
In addition, about each hardening | curing agent liquid composition of Table 1, prescribed weight is extract | collected in hardening | curing agent in a graduated cylinder, it melt | dissolves and dilutes in water, and it prepares so that it may become the compounding capacity of Table 1. Represents. In the curing agent liquid thus prepared, the curing agent liquid of D1, the liquid specific gravity at 15 ° C. is about 1.051. Similarly, the D2, D3, and D5 curing agent liquids have a liquid specific gravity of approximately 1.005 at 15 ° C., and the D4 curing agent liquid has a liquid specific gravity of approximately 1.138, and further, D6 and D7 are cured. The liquid chemicals have liquid specific gravity of 1.030 and 1.225, respectively. Moreover, these were displayed as liquid specific gravity of each prepared hardening | curing agent liquid in the "total or compounding quantity" column of Table 1.
The crude phosphoric acid described in Table 1 is P ₂ O _Five Using a Mitsui Toatsu Chemical Co., Ltd. product of 50% by weight (liquid specific gravity is approximately 1.63), a reagent product with a purity of 75% by weight is used for purified phosphoric acid, and the liquid specific gravity is 1.59 to 1.60.
Glyoxal is a Mitsui Toatsu Chemical Co., Ltd. product with a purity of 40% (liquid specific gravity is approximately 1.32 / 15 ° C), γ-butyrolactone (liquid specific gravity is 1.12 / 15 ° C), ethylene carbonate (true specific gravity). 1.3), propylene carbonate (liquid specific gravity is 1.21), ethylene glycol diacetate (liquid specific gravity is 1.11) and the like, respectively.
[0134]
As a result, as is apparent from Table 1, a polyether type active silanol having several active silanol groups in one molecule and having a main chain molecular weight in the range of 3,000 to 20,000. In the main agent liquid containing the group-containing prepolymer, the gelation behavior in a wide range from instantaneous setting to medium-long setting is obtained in 10 to 100 parts by volume of the curing agent liquid with respect to 100 parts by volume of the main agent liquid. It has been clarified that a solid body having a high uniaxial compressive strength characteristic and a high elastic characteristic is produced. Moreover, the organic polymer grout agents of Examples 1 to 7 are all excellent in water and seawater immersion durability, excellent in flame retardancy, and excellent infiltration and injection workability with respect to standard sand. At the same time turned out.
Moreover, the presence was not detected in the gas chromatographic separation analysis result regarding the lower alcohol content in the immersion water performed 24 hours after the start of the sand gel immersion in each of the sand gel durability tests 1 of Examples 1 to 3.
[0135]
[Table 1]

[0136]
Example 8 to Example 14
The main agent liquid and the mixing composition described in Table 2 which are the mixing compositions shown in Table 2 obtained by appropriately mixing the main agent liquid 1, the main agent liquid 2, the main agent liquid 5, the main agent liquid 8, and the main agent liquid 9 within 3 hours after adjustment. The organic polymer grout agent compositions of Examples 8 to 14 were prepared by mixing the main agent liquid and the curing agent liquid at the blending ratios shown in Table 2 using the two liquids with the cured curing agent liquid, and grouted. Agent numbers E1 (organic polymer grout agent described in Example 8) to E7 (organic polymer grout agent described in Example 14) were obtained. Table 2 shows the solution physical properties and cured product physical properties of each grout agent.
In addition, about each hardening | curing agent liquid composition of Table 2, a hardening | curing agent is extract | collected to a specified weight in a graduated cylinder, it melt | dissolves and dilutes in water, and it is prepared so that it may become the mixing capacity of Table 2. Represents. Further, in the “total or blending amount” column of Table 1, the liquid specific gravity of each prepared curing agent liquid is also displayed.
Reagent products were used for acetic acid, glycolic acid, and lactic acid, which are the organic acids listed in Table 2. Sodium bicarbonate and potassium bicarbonate were manufactured by Asahi Glass Industry Co., Ltd., sodium bisulfate was a reagent grade 1 product, and acidic magnesium sulfate was manufactured by Umai Kasei Co., Ltd.
[0137]
As a result, as is apparent from Table 2, it contains several active silanol groups in one molecule and the molecular weight of the main chain is in the range of 3,000 to 20,000. In the main agent liquid containing an active silanol group-containing prepolymer of strong polyether type or rosin polyol type having the same properties, 100 parts by volume of the main agent liquid, alkali salt of inorganic acid, water-soluble organic acid, alkaline water In a blending example of 10 to 400 parts by volume of a curing agent liquid containing a small amount of a curing agent component such as an organic monomer that releases a slow-release acid, gelation behavior in a wide range from instantaneous setting to long setting It is clear that a solidified gel having a high uniaxial compressive strength characteristic and a high elastic characteristic is produced. In addition, the organic polymer grout agents of Examples 8 to 14 are all excellent in water and seawater immersion durability, excellent in flame retardancy, and excellent infiltration and injection workability with respect to standard sand. At the same time turned out.
[0138]
[Table 2]

[0139]
Example 15
20 liters each of a main agent solution and a curing agent solution comprising the same composition as those described in Example 2 (grouting agent number D2) in Table 1 above were prepared, and the mixing ratio of the two solutions was 1: 1. In this way, the grout liquid is injected in a 1.5 shot system at a rate of 200 ml / min and a gauge pressure from a single injection pipe installed in a 1 m deep part of the model ground previously compacted with No. 6 silica sand. 1.5kg / cm ² Was discharged. Discharge pressure is 5kg / cm ² Discharge was stopped at the time of rising to the point, and after leaving it to stand for 3 days as it was, the appearance of the formed sand gel consolidated body was observed by washing the unconsolidated soil with water. Formation of an 80 cm large oval solid body was confirmed. The uniaxial compressive strength characteristics of sand gel collected from the vicinity of the center of the consolidated body is 15.2 kgf / cm. ² And showed a high intensity value.
Moreover, the average of the hydraulic conductivity of three collected sand gel consolidated bodies was 7 × 10. ^-6 It was proved that it sufficiently suggested that the ground can be improved to have a high water-stopping property.
[0140]
Example 16
After a gravelly model ground consisting mainly of 3 to 5 mm of silica stone is raised to a height of 1.5 m on the base, a model ground with a No. 5 silica sand being further raised to a height of 1.5 m on the top. Prepared.
On the other hand, when 20 liters each of the main agent solution and the curing agent solution of the grout agent composition (instantaneous type) similar to those described in Example 10 (grouting agent number E3) in Table 2 are used, A 100-liter one-shot chemical solution prepared by mixing in advance a main agent solution and a curing agent solution of a grouting agent composition (medium-long type) similar to those described in Example 8 (grouting agent number E1) was prepared.
First, the injection pipe consisting of a double pipe is lowered and fixed so that the injection tip of the injection pipe is located at the center of the gravel layer, and after the primary injection of the instantaneous grouting agent by the two-shot method. After the injection pipe was lifted and moved to the No. 5 silica sand layer, the above-mentioned medium-long grouting agent was injected under pressure by a one-shot method and permeated and consolidated. The standard penetration test value (N value) of the ground was sufficiently compacted to a minimum value of 25 or more, and it was a stable improved ground that was high in strength and difficult to liquefy.
[0141]
Here, the “standard penetration test and its test value” are “tests for obtaining an N value as an index for knowing the degree of hardness / tightness of the soil, using a boring hole and a diameter of 5. 1mm, 81cm long standard penetration test sampler, 63.5kg weight hammer (drop hammer) is dropped from 75cm height, and the number of hits (N value) required to penetrate the sampler 30cm is measured. How to do ". In general, soil having an N value of less than 10 is said to be soft ground, and sand ground having an N value of 1 to 8 is known to have a risk of liquefaction.
[0142]
Example 17
20 liters of each of the main agent liquid A and the curing agent liquid B made of the same composition as those described in Example 2 (grouting agent number D2) in Table 1 were prepared. On the other hand, two concrete fume pipes with a pipe diameter of 50 cm are connected horizontally, and the two joint parts are not sealed with a gap of about 1 mm, and the openings on both sides are not closed. A sewer pipe model was constructed in a 1m high area surrounded by a wooden frame and buried in the ground. At that time, the upper part of the connection fume pipe, that is, the part surrounded by the wooden frame was laminated with Toyoura standard sand in a wet state, and compacted to a height of 1 m to create the model.
[0143]
In addition, during the groundwater still water injection test of the following sewer pipes, the following tests were conducted from the joint defect part so as to be in a flowing water state of about 1 to 2 liters per minute.
At the center of the buried sewer pipe model, insert a cylindrical self-feeding packer injector (circular cylinder type, 30 cm in diameter) with a double packer and injection function integrated and connected to a TV camera. While looking at the TV camera, the packer injector moved so that the center of the packer injector was at the center of the fume tube connection, and immediately the pressurized water was fed to the packer to inflate the packer. Thereafter, the main agent liquid A and the hardener liquid B are simultaneously supplied at a volume ratio of 1: 1 in the so-called two-shot method through the injector at the outlet of the injector, and about 2.5 kg. / Cm ² The whole amount was mixed and injected at a 1: 1 volume ratio under the pressure of.
[0144]
No leakage from the outer periphery of the packer was observed during the injection operation. After 15 minutes from the injection, the packer was drained and the injector was discharged from the inside of the pipe. As a result, the homogel consolidated body shown in Example 18 was formed in a donut shape in the two joints of the sewer pipes. It was built by sticking inside the tube. Further, when the uncured sand on the outer periphery of the pipe was carefully removed, it was observed that the sand had penetrated from the gap between the two joints of the sewage pipe and the surrounding sand was integrally infiltrated and consolidated. Moreover, the hardening range of the periphery was osmosis | solidifying and solidifying the range of width 50cm and thickness average 30cm in general.
It was observed that there was no leakage inflow that occurred before the test.
Finally, after several days of testing, several consolidated sand gel cores (50 mmφ × 100 mmH) formed in Example 17 were collected, and the uniaxial compressive strength of the sand gel performed in the same manner as in Example 17 was measured. ~ 16kgf / cm ² A stable high strength value was obtained. Further, the compressive fracture strain at that time was 5 to 6%.
[0145]
From these results, it was proved again that the infiltration-injection consolidation performance into Toyoura standard sand was good, and when combined with the result of Example 2, the sewer pipe had sufficient groundwater waterproof performance and long-term durability. It has been found that an improvement with a combination of properties is possible.
[0146]
Comparative Example 1
Japanese Industrial Standard-3 No. 3 sodium silicate (JIS-3 water glass) solution diluted 6 liters of tap water with 4 liters of tap water and 5 kg of commercially available Portland cement powder with water. Prepare 5 liters of hardener liquid Q, prepare a grout chemical liquid for injection consolidation so that the volume ratio is P: Q = 2: 1, and stop the sewer pipe underground water in the same way as in Example 17. A water test was performed. As a result, it was observed that the sand penetrated through the gap between the two joints of the sewage pipe and the surrounding sand was integrally infiltrated and consolidated, and the homogel was hardened. It was only very brittle with cracks.
In addition, the homogel consolidated body prepared separately in a molded mold container having a diameter of 50 mmφ and a height of 100 mm has a lot of water breathing phenomenon, and as a result, it is observed that the volume shrinkage is severe, and the adhesiveness to the sewer pipe is increased. It was found that the permanent water-stopping performance was remarkably lacking. In addition, in the results of durability test 1 after one month of the homogel consolidated body and the separately prepared sand gel consolidated body, a significant decrease in strength was observed compared to the original compressive strength, and the maximum value of the decrease rate was It reached 53%. Also from these results, the grout agent for infusion consolidation of Comparative Example 1 lacked durability.
[0147]
Comparative Example 2
Prepare a grout chemical solution for infusion solidification by taking 5 kg of commercially available Portland cement powder and 0.03 kg of bentonite powder with an average particle size of 7 μm as an anti-settling agent in tap water to make 10 liters of suspension solution. In the same manner as in Example 17, a groundwater stoppage test of the sewer pipe was performed. As a result, even after 1 hour had passed since the injection, the injected liquid composition was not yet satisfactory in terms of stopping water leakage and was in an uncured state. Therefore, it has been found that the curing period until the development of sufficient strength for practical use takes 1 to 2 days at the shortest. Therefore, the grouting agent for infusion consolidation lacks remarkably infusion workability and work efficiency.
[0148]
Example 18
Contains 20 liters of main agent solution A consisting of 80% by volume of main agent solution 8 and 20% by volume of tap water within 3 hours after adjustment, and 1 liter of Mitsui Toatsu Chemical Co., Ltd. product, 75% by weight crude phosphoric acid. 10 liters of each of the curing agent liquid B was prepared, and 100 parts of an organic polymer grout agent composition mixed and discharged by a 1.5 shot system at a volume ratio of 2: 1 of A: B, and mainly plastics As a result of mechanically suspending 300 parts of the collected ash generated and collected along with the incineration of the garbage, a gel was formed after 5 minutes. The solidified body was hermetically sealed at room temperature for 3 days and exhibited a property that it did not wet with water, and was a highly hydrophobic and elastic gel. The water permeability of the gel is 3 × 10 ^-6 And showed high water-impermeable properties. As a result, it has been found that the composition is useful as a composition for sealing waste containing toxic metals.
[0149]
Example 19
The organic polymer grout agent composition was the same except that the total amount of ethylene glycol diacetate used in the curing agent solution of Example No. 3 (grouting agent No. D3) in Table 1 was changed to glycerin diacetate. Gives the gel time of cohesiveness, ◎ workability of penetration into standard sand, homogel strength 1.5kgf / cm ² The strain value of the uniaxial compressive strength is 42%, and the sand gel strength is 15.5 kgf / cm. ² The physical property values of the performance almost equivalent to the grout agent number D3 were exhibited.
[0150]
Example 20
An organic polymer grout agent composition was prepared in the same manner except that the total amount of ethylene glycol diacetate used in the curing agent solution of Example No. 3 (grouting agent No. D3) in Table 1 was changed to glycerin triacetate. Gel time, osmosis workability against standard sand is ◎, homogel strength is 1.7kgf / cm ² The strain value of the uniaxial compressive strength is 40%, and the sand gel strength is 16.2 kgf / cm. ² The physical property values of the performance almost equivalent to the grout agent number D3 were exhibited.
[0151]
Example 21
Except for the sodium bisulfate used in the curing agent solution of Example No. 12 (grouting agent No. E5) in Table 2, the total amount was changed to a 1: 1 mixture by weight of sodium hydrogen phosphate and potassium hydrogen phosphate. The organic polymer grouting agent composition produced in this manner gives a neutral gel time, has a penetrating workability with respect to standard sand, and has a homogel strength of 1.7 kgf / cm. ² The strain value of uniaxial compressive strength is 44%, and the sand gel strength is 14.7 kgf / cm. ² The property values of the performance almost equivalent to the grout agent number E5 were exhibited.
[0152]
【The invention's effect】
As is clear from the descriptions of the comparative main agent liquids 1 and 2 and the main agent liquids 7 to 9, the silyl-terminated polymer prepolymer is inherently highly hydrophobic and has the property of being separated into two layers without dissolving in water as it is. However, when treated with a highly alkaline aqueous solution as in the examples of the main agent liquid 7 or the main agent liquid 8, the active silanol essential for the constitution of the stable organic polymer grout agent of the present invention that does not separate into two layers from water. It is clear that a group-containing prepolymer-containing aqueous solution (main agent solution) can be easily obtained.
Furthermore, as a result, the organic polymer grout agent solidified body of the present invention recovers the inherently strong hydrophobic property after consolidation. Therefore, the solidified body itself is hardly affected by ground water or wet water. In fact, it is clear from the gel characteristic results of Examples 1 to 15 and Examples 19 to 21.
[0153]
In Comparative Example 1 and Comparative Example 2, it is clear that water glass-cement or cement-based cement for injection and consolidation is not a drug with excellent durability and workability.
On the other hand, as is apparent from Examples 1 to 17, the organic polymer grout agent for injection consolidation of the present invention is a preferable organic polymer grout agent composition for permanent ground improvement, or even more. It is clear that it is also highly suitable as a chemical solution composition for stopping water in a preferable sewer pipe.
More specifically, in the consolidated body of the composition shown in Examples 1 to 15, the mechanical properties are rich in elasticity and long-term durability, and fully responds to the demand of the grout agent market. It is an organic polymer grout agent that can be used.
[0154]
In particular, as clarified in Example 17, the method for stopping groundwater in sewer pipes using the organic polymer grout agent for infusion consolidation of the present invention is suitable for labor saving, infusion work, and infiltration consolidation into the ground. It is clear that it has outstanding characteristics such as excellent suitability, and can maintain its water resistance for a long period of time. And it can be easily imagined that it can follow ground fluctuations and vibrations.
Furthermore, as further clarified in Example 18, the hazardous substance sealing method using the organic polymer grout agent for injection consolidation described in the present invention is a method for easily and reliably sealing the harmful substance. It is clear that it is excellent.
That is, it is clear that the organic polymer grout agent composition of the present invention has very practically meaningful characteristics that can satisfy the five problems listed in “Problems to be Solved by the Invention”. is there.

Claims (16)

The main agent liquid is represented by the following general formula (1)

(Wherein R ¹ is ^one selected from a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, or a propyl group, X is an —OH group, —O ⁻ .Na ⁺ group, —O ⁻ .K ⁺ group or — O ^- · Li ⁺ 1 kind selected from radical, n represents each 0-1).
The active silanol group end represented by the formula is introduced in an average of at least 0.7 units, and the weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group is in the range of 400 to 50,000. An aqueous alkaline solution containing 1 to 75% by weight of one or more active silanol group-containing prepolymers,
When the curing agent solution is mixed with the total amount of the main agent solution, an inorganic acid or an inorganic acid in an amount corresponding to 30 to 200 mol% of the total alkali content expressed in terms of (NaOH + KOH + LiOH) contained in the main agent solution. A liquid or an aqueous solution containing one or more selected from an alkali metal salt, a water-soluble organic acid, or an organic monomer that releases a sustained-release acid in alkaline water,
An organic polymer grout agent obtained by mixing two liquids of the main agent liquid and the curing agent liquid. 2. The organic polymer grout agent according to claim 1, wherein the main agent solution is adjusted to be alkaline with a pH value of the single solution of 10 to 14. The organic polymer grouting agent according to claim 1 or 2, wherein the inorganic acid is one or two selected from sulfuric acid, phosphoric acid or carbonic acid. The alkali metal salt of an inorganic acid is any one of sodium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, or a mixture thereof. The organic polymer grout agent according to any one of the above. The organic monomer that releases a sustained-release acid in alkaline water is one or more selected from glyoxal, γ-butyrolactone, ethylene carbonate, propion carbonate, ethylene glycol diacetate, glycerol diacetate or glycerol triacetate The organic polymer grout agent according to any one of claims 1 to 4, wherein 6. The content of the active silanol group-containing prepolymer is mixed with 20 to 100 parts by volume of the curing agent liquid to 100 parts by volume of the main agent liquid having a concentration of 5 to 50% by weight. The organic polymer grout agent according to any one of the above. The main chain organic polymer chain excluding the active silanol group is a polyether composed of 15 to 100% by weight of ethylene oxide and 85 to 0% by weight of propylene oxide or butylene oxide. The organic polymer grout agent according to any one of claims 1 to 6. R ¹ in the general formula (1) is either a methyl group or an ethyl group, X is -OH group, -O ^- and wherein a is either · K ⁺ group ^- · Na ⁺ group or -O The organic polymer grout agent according to any one of claims 1 to 7. The active silanol group-containing prepolymer contains an average of 2 to 6 active silanol group ends in one molecule, and the weight average molecular weight of the organic polymer chain length of the main chain excluding the active silanol group is 1,000. The organic polymer grout agent according to claim 1, wherein the organic polymer grout agent is in a range of ˜20,000. The active silanol group-containing prepolymer comprises a polyether monool and / or a polyether polyol having a total weight average hydroxyl number in the range of 10 mgKOH / g to 450 mgKOH / g, and the following general formula (2):

(In the formula, R ² represents an alkylene group having 3 or more carbon atoms, R ³ represents one selected from a methyl group, an ethyl group, or a propyl group, and Y represents an integer having 1 to 5 carbon atoms. 1 type selected from an alkoxyl group, an oxime group or an acetoxyl group, m represents 0 to 1 respectively.)
An active silyl group-containing prepolymer obtained by reacting an isocyanate silane represented by the formula (1) with an NCO / OH equivalent ratio in the range of 0.7 to 1.5, and the presence of an aqueous solution containing an alkali metal hydroxide. The organic polymer grout agent according to any one of claims 1 to 9, which is obtained by hydrolysis under pressure. The isocyanate silane is one selected from γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldiethoxymethylsilane or γ-isocyanatopropyldimethoxymethylsilane. The organic polymer grout agent according to claim 10, wherein The polyether polyol has a total weight average hydroxyl value in the range of 20 mg KOH / g to 350 mg KOH / g, and the polyether chain length is 15 to 100 wt% of ethylene oxide and 85 to 0 wt of propylene oxide or butylene oxide. The organic polymer grouting agent according to claim 10, wherein the organic polymer grouting agent is a diol and / or triol composed of%, and has an NCO / OH equivalent ratio in the range of 0.95 to 1.05. In the case of the reinforced stabilization / water stoppage work of unstable ground, the organic high according to any one of claims 1 to 12 is used by a one-shot method, a 1.5-shot method or a two-shot method through a grout injection pipe. A ground improvement method characterized by pressurizing and solidifying a molecular grouting agent to strengthen or stop the ground. In the case of reinforced stabilization / water stoppage work of unstable ground, any one of a 1 shot system, a 1.5 shot system, or a ~ 2 shot system through a grout injection pipe, according to any one of claims 1 to 12 It is characterized in that the ground is strengthened or water-stopped by selecting from among organic polymer grout agents and injecting and solidifying by using two or more kinds of organic polymer grout agents having different gel times. How to improve the ground. Pressure injection of the organic polymer grout agent according to any one of claims 1 to 12 through a small-diameter self-feeding packer injector to an underground water leakage point of an underground sewer pipe A sewer pipe groundwater shutoff method characterized in that it is solidified and stopped. A hazardous substance sealing method for preventing leakage of harmful substances to the outside due to water or the like from mining or industrial waste containing hazardous substances such as heavy metal ions left or stored outdoors. Use of the organic polymer grout agent according to any one of 1 to 12 to prevent the harmful substance from leaking to the outside by integrally solidifying with the harmful substance. Stop method.