JP4503346B2 - Foaming agent for bubble shield method - Google Patents
Foaming agent for bubble shield method Download PDFInfo
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- JP4503346B2 JP4503346B2 JP2004131306A JP2004131306A JP4503346B2 JP 4503346 B2 JP4503346 B2 JP 4503346B2 JP 2004131306 A JP2004131306 A JP 2004131306A JP 2004131306 A JP2004131306 A JP 2004131306A JP 4503346 B2 JP4503346 B2 JP 4503346B2
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- 239000004088 foaming agent Substances 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000006260 foam Substances 0.000 description 14
- 238000005187 foaming Methods 0.000 description 11
- -1 alkyl ether sulfate ester Chemical class 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002689 soil Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical class OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- JJYWDMDTOCKULH-UHFFFAOYSA-N 1-hexadecoxyhexadecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC JJYWDMDTOCKULH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- FXZUKHDLJABRQU-UHFFFAOYSA-N sulfuric acid;1-tetradecoxytetradecane Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCCCOCCCCCCCCCCCCCC FXZUKHDLJABRQU-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- XWOVRWIRPYMVKK-UHFFFAOYSA-N 1-octadecoxyoctadecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC XWOVRWIRPYMVKK-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Excavating Of Shafts Or Tunnels (AREA)
Description
本発明は、気泡シールド工法用起泡剤に関する。 The present invention relates to a foaming agent for a bubble shield method.
起泡剤を含む液体を発泡させて掘削土壁に吹き付け、掘削土と気泡とを混合攪拌させながら掘削する工法、即ちカッターヘッドの掘削抵抗低減と摩耗低減及び掘削土運搬処理の作業性を向上させる気泡シールド工法が提案されている（特許文献１、２）。 Blowing a liquid containing foaming agent and spraying it on the excavated soil wall, and excavating while mixing and agitating the excavated soil and bubbles, that is, reducing the excavation resistance and wear of the cutter head and improving the workability of excavated soil transport processing A bubble shield construction method has been proposed (Patent Documents 1 and 2).
こうした気泡シールド工法に用いられる起泡剤として、蛋白系起泡剤やラウリルエーテル硫酸エステル塩等のアルキルエーテル硫酸エステル塩系起泡剤が提案されている。また、切削時の土砂と混合される泡沫が安定で、土砂の流動性を低下させない起泡剤として、特許文献３には、アルキルエーテル硫酸エステル塩とアルコールとを特定の重量比で含有する気泡シールド用起泡剤が開示されている。
特許文献３の起泡剤は、泡沫安定性を改善できるが、有効分濃度が低い領域で使用すると泡沫安定性は低下する傾向を示すため、起泡剤使用量の低減には有利ではない。すなわち、起泡力に優れ、有効分濃度が低い水溶液で用いた場合でも、優れた泡沫安定性を付与できる気泡シールド工法用起泡剤が望まれている。 The foaming agent of Patent Document 3 can improve the foam stability, but when used in a region where the effective component concentration is low, the foam stability tends to be lowered, and thus is not advantageous for reducing the amount of foaming agent used. That is, there is a demand for a foaming agent for a bubble shield method that has excellent foaming power and can provide excellent foam stability even when used in an aqueous solution having a low effective component concentration.
本発明は、下記一般式（Ｉ）で表される化合物〔以下、化合物（Ｉ）という〕と、下記一般式（II）で表される化合物〔以下、化合物（II）という〕とを含有する気泡シールド工法用起泡剤に関する。
［Ｒ1−Ｏ−(ＡＯ)mＳＯ3］pＸ （Ｉ）
〔式中、Ｒ1は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数７〜１５の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種又は２種以上の混合物、ｍはＡＯの平均付加モル数であって０〜５０の数、Ｘは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基又は水酸基置換アルキルアンモニウム基である。ｐはＸの価数である。〕
Ｒ2−Ｏ−(ＡＯ)yＨ （II）
〔式中、Ｒ2は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数７〜１５の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種又は２種以上の混合物、ｙはＡＯの平均付加モル数であって１〜１５の数である。〕
The present invention comprises a compound represented by the following general formula (I) [hereinafter referred to as compound (I)] and a compound represented by the following general formula (II) [hereinafter referred to as compound (II)]. The present invention relates to a foaming agent for a bubble shield method.
[R 1 -O- (AO) m SO 3] p X (I)
[Wherein, R 1 is an alkyl group or alkenyl group having 8 to 20 carbon atoms, or a hydrocarbon group having 7 to 15 carbon atoms having one or more benzene rings, and AO is one of oxyalkylene groups having 2 to 4 carbon atoms. Or a mixture of two or more, m is the average added mole number of AO and is a number from 0 to 50, X is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a hydroxyl group-substituted alkylammonium group is there. p is the valence of X. ]
R 2 —O— (AO) y H (II)
[Wherein R 2 is an alkyl group or alkenyl group having 8 to 20 carbon atoms or a hydrocarbon group having 7 to 15 carbon atoms having one or more benzene rings, and AO is one of oxyalkylene groups having 2 to 4 carbon atoms. Or a mixture of two or more, y is the average number of moles added of AO and is a number from 1 to 15. ]
本発明によれば、起泡力に優れ、低濃度の水溶液で用いた場合でも泡沫安定性に優れた気泡シールド工法用起泡剤が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the foaming agent for bubble shield methods excellent in foaming power and excellent in foam stability even when used by low concentration aqueous solution is obtained.
化合物（Ｉ）はアルキル硫酸エステル塩又はアルキルエーテル硫酸エステル塩であり、一般式（Ｉ）中のＲ1は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上、好ましくは１つのベンゼン環を有する炭素数７〜１５、好ましくは１４〜１５の炭化水素基である。一般式（Ｉ）中のＲ1の炭素数は、アルキル基又はアルケニル基の場合、１０〜１８、更に１０〜１４が起泡力の点で好ましく、またＲ1はアルキル基が好ましい。また、一般式（Ｉ）中のＡＯは、オキシエチレン基（以下、ＥＯと表記する）を含むことが起泡力の点で好ましく、全ＡＯ中、ＥＯの比率は、８０〜１００モル％、更に９０〜１００モル％が好ましい。ＡＯとしては、ＥＯの単独、ＥＯとオキシプロピレン基の混合が挙げられ、ＥＯの単独が好ましい。また、一般式（Ｉ）中のｍは、ＡＯの平均付加モル数であって、１〜１０、更に１〜５が起泡力の点で好ましい。また、一般式（Ｉ）中のＸはアルカリ金属が好ましく、なかでもナトリウムが好ましい。一般式（Ｉ）中のｐはＸの価数、すなわち１又は２であり、１が好ましい。 Compound (I) is an alkyl sulfate ester salt or an alkyl ether sulfate ester salt, and R 1 in the general formula (I) is an alkyl group or alkenyl group having 8 to 20 carbon atoms, or one or more, preferably one benzene ring. It is a hydrocarbon group having 7 to 15 carbon atoms, preferably 14 to 15 carbon atoms. In the case of an alkyl group or alkenyl group, R 1 in the general formula (I) is preferably 10 to 18, more preferably 10 to 14 in terms of foaming power, and R 1 is preferably an alkyl group. Moreover, it is preferable from the point of foaming power that AO in general formula (I) contains an oxyethylene group (henceforth EO), The ratio of EO is 80-100 mol% in all AO, Furthermore, 90-100 mol% is preferable. Examples of AO include EO alone and a mixture of EO and oxypropylene groups, and EO alone is preferred. Moreover, m in general formula (I) is the average added mole number of AO, and 1-10, Furthermore, 1-5 are preferable at the point of foaming power. Further, X in the general formula (I) is preferably an alkali metal, and sodium is particularly preferable. P in the general formula (I) is the valence of X, that is, 1 or 2, and 1 is preferable.
化合物（Ｉ）の具体例としては、ドデシルエーテル硫酸エステル塩、ラウリルエーテル硫酸エステル塩、セチルエーテル硫酸エステル塩、ミリスチルエーテル硫酸エステル塩、オレイルエーテル硫酸エステル塩、ポリオキシアルキレンドデシルエーテル硫酸エステル塩、ポリオキシアルキレンラウリルエーテル硫酸エステル塩、ポリオキシアルキレンセチルエーテル硫酸エステル塩、ポリオキシアルキレンミリスチルエーテル硫酸エステル塩、ポリオキシアルキレンパルミチルエーテル硫酸エステル塩、ポリオキシアルキレンステアリルエーテル硫酸エステル塩、ポリオキシアルキレンオレイルエーテル硫酸エステル塩等が一例として挙げられ、これらの混合物も使用することができる。化合物（Ｉ）は、エマール０、エマール４０、エマール２Ｆ、エマール２０Ｃ、エマール２７Ｃ、エマール２７０Ｊ（いずれも花王（株）製）のような市販品を使用することもできる。 Specific examples of the compound (I) include dodecyl ether sulfate, lauryl ether sulfate, cetyl ether sulfate, myristyl ether sulfate, oleyl ether sulfate, polyoxyalkylene dodecyl ether sulfate, poly Oxyalkylene lauryl ether sulfate, polyoxyalkylene cetyl ether sulfate, polyoxyalkylene myristyl ether sulfate, polyoxyalkylene palmityl ether sulfate, polyoxyalkylene stearyl ether sulfate, polyoxyalkylene oleyl ether A sulfate ester salt etc. are mentioned as an example, These mixtures can also be used. As compound (I), commercially available products such as Emar 0, Emar 40, Emar 2F, Emar 20C, Emar 27C, Emar 270J (all manufactured by Kao Corporation) can also be used.
化合物（II）は、高級アルコールやアルキルフェノール等にアルキレンオキサイドを付加して得られる化合物である。一般式（II）中のＲ2は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上、好ましくは１つのベンゼン環を有する炭素数７〜１５、好ましくは１４〜１５の炭化水素基である。一般式（II）中のＲ2の炭素数は、アルキル基又はアルケニル基の場合、１０〜１８、更に１０〜１４が、起泡力、流動性（気泡を混入した掘削土の流動性、以下同様）の向上効果の点で好ましく、またＲ2はアルキル基が好ましい。また、一般式（II）中のＡＯは、ＥＯを含むことが起泡力の点で好ましく、全ＡＯ中、ＥＯの比率は、５０〜１００モル％、更に８０〜１００モル％が好ましい。ＡＯとしては、ＥＯの単独、ＥＯとオキシプロピレン基の混合が挙げられ、ＥＯの単独が好ましい。また、一般式（II）中のｙは、ＡＯの平均付加モル数であって、１〜９、更に１〜６、特に２〜４が起泡力、流動性の向上効果の点で好ましい。 Compound (II) is a compound obtained by adding alkylene oxide to higher alcohol, alkylphenol or the like. R 2 in the general formula (II) is an alkyl group or alkenyl group having 8 to 20 carbon atoms, or a hydrocarbon group having 1 or more, preferably one having a single benzene ring, and having 7 to 15 carbon atoms, preferably 14 to 15 carbon atoms. . The carbon number of R 2 in the general formula (II) is 10 to 18, more preferably 10 to 14 in the case of an alkyl group or an alkenyl group, and foaming power and fluidity (fluidity of excavated soil mixed with bubbles, below The same is preferable, and R 2 is preferably an alkyl group. Moreover, it is preferable from the point of foaming power that AO in general formula (II) contains EO, and the ratio of EO in all AO is 50-100 mol%, Furthermore, 80-100 mol% is preferable. Examples of AO include EO alone and a mixture of EO and oxypropylene groups, and EO alone is preferred. Moreover, y in general formula (II) is the average addition mole number of AO, and 1-9, Furthermore, 1-6, especially 2-4 are preferable at the point of the foaming force and the improvement effect of fluidity | liquidity.
化合物（II）の製造に使用できる高級アルコールとしては、オクチルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール等、ならびに合成アルコールが挙げられる。これらは単独でもしくは２種以上併せて用いられる。 Examples of the higher alcohol that can be used for the production of the compound (II) include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and synthetic alcohol. These may be used alone or in combination of two or more.
本発明の起泡剤は、化合物（Ｉ）と化合物（II）の重量比が、（Ｉ）／（II）＝９５／５〜５０／５０、更に９５／５〜６０／４０、特に９０／１０〜７０／３０であることが、低濃度水溶液を用いた場合の土砂との混合時の泡沫安定性の向上効果の点で好ましい。 In the foaming agent of the present invention, the weight ratio of the compound (I) to the compound (II) is (I) / (II) = 95 / 5-50 / 50, more preferably 95 / 5-60 / 40, particularly 90 / It is preferable that it is 10-70 / 30 from the point of the improvement effect of foam stability at the time of mixing with the earth and sand at the time of using a low concentration aqueous solution.
また、本発明の起泡剤中、取り扱い性の観点から、化合物（Ｉ）は１．５〜４０重量％、更に５〜４０重量％、特に１０〜３０重量％、化合物（II）は０．１〜２０重量％、更に１〜１０重量％含有されることが好ましい。また、本発明の起泡剤中の化合物（Ｉ）と化合物（II）の合計は１０〜５０重量％、更に２０〜４０重量％が好ましい。 In the foaming agent of the present invention, from the viewpoint of handleability, the compound (I) is 1.5 to 40% by weight, more preferably 5 to 40% by weight, particularly 10 to 30% by weight, and the compound (II) is 0.8. It is preferable to contain 1 to 20 weight%, and also 1 to 10 weight%. Further, the total of the compound (I) and the compound (II) in the foaming agent of the present invention is preferably 10 to 50% by weight, more preferably 20 to 40% by weight.
本発明の起泡剤では、化合物（Ｉ）、（II）の混合溶解性を高めるために、アルコール類を併用することができる。例えば、エチルアルコール等の炭素数７以下の一価アルコール、エチレングリコール等のグリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル等のアルキレングリコールエーテルが一例として挙げられる。また、用途によっては、炭素数１〜４のアルコールのアルキレンオキサイド付加物も溶剤等として使用できる。また、その他の界面活性剤、水溶性高分子、増粘剤等を併用することもできる。 In the foaming agent of the present invention, alcohols can be used in combination in order to increase the mixed solubility of the compounds (I) and (II). Examples thereof include monohydric alcohols having 7 or less carbon atoms such as ethyl alcohol, glycols such as ethylene glycol, and alkylene glycol ethers such as ethylene glycol monobutyl ether and ethylene glycol monoisobutyl ether. Depending on the application, an alkylene oxide adduct of an alcohol having 1 to 4 carbon atoms can also be used as a solvent. In addition, other surfactants, water-soluble polymers, thickeners, and the like can be used in combination.
本発明の起泡剤は、化合物（Ｉ）と化合物（II）とを合計で０．００１〜３重量％、更に０．０１〜１．０重量％、特に０．１〜０．５重量％含有する水溶液として用いられることが好ましい。このような起泡剤水溶液を泡沫化させる方法については限定するものではなく、また起泡剤溶液を直接掘削土に練り込んでもよく、添加する方法についても限定しない。 The foaming agent of the present invention comprises a total of 0.001 to 3% by weight, further 0.01 to 1.0% by weight, particularly 0.1 to 0.5% by weight of the compound (I) and the compound (II). It is preferably used as an aqueous solution containing. The method of foaming such a foaming agent aqueous solution is not limited, and the foaming agent solution may be directly kneaded into excavated soil, and the method of adding it is not limited.
土砂との混合時の泡沫安定性の点で、本発明の好ましい態様は、一般式（Ｉ）中のＲ1が炭素数１０〜１４の炭化水素基、特にアルキル基、且つｍが１〜４の数、ｐが１、Ｘがアルカリ金属である化合物（Ｉ）と、一般式（II）中のＲ2が炭素数１０〜１４の炭化水素基、特にアルキル基である化合物（II）の併用であり、更にこの場合、両者の重量比が（Ｉ）／（II）＝７０／３０〜９０／１０であるものが好ましい。 In terms of mixing during the foam stability with the sediment, a preferred embodiment of the present invention have the general formula (I) R 1 is a hydrocarbon group having 10 to 14 carbon atoms in the, in particular alkyl groups, and m is 1 to 4 A compound (I) wherein p is 1 and X is an alkali metal, and a compound (II) wherein R 2 in the general formula (II) is a hydrocarbon group having 10 to 14 carbon atoms, particularly an alkyl group In this case, it is preferable that the weight ratio of the two is (I) / (II) = 70/30 to 90/10.
本発明の気泡シールド工法用起泡剤により形成された泡沫は、安定性に優れており、且つ土砂の流動性を低下させることもないので、気泡シールド工法用におけるカッターヘッドの掘削抵抗の低減や摩耗の低減、並びに掘削土運搬処理の作業性の向上が可能となる。特に、本発明の起泡剤は、低濃度水溶液で用いた場合でも優れた泡沫安定性を得ることができるが、これは、本発明の化合物（II）の構造が起泡力の発現のみらなず、化合物（Ｉ）と相俟って泡沫安定性の向上にも寄与するためと推察される。 Since the foam formed by the foaming agent for the bubble shield method of the present invention is excellent in stability and does not reduce the fluidity of the earth and sand, the excavation resistance of the cutter head in the bubble shield method can be reduced. It is possible to reduce wear and improve workability of excavated soil transport processing. In particular, the foaming agent of the present invention can obtain excellent foam stability even when used in a low-concentration aqueous solution. This is because the structure of the compound (II) of the present invention is only manifesting foaming power. It is presumed that, in combination with Compound (I), it also contributes to the improvement of foam stability.
表３に示す化合物（Ｉ）と化合物（II）とを合計で０．３重量％（比較例３は０．５重量％）（いずれも固形分換算）含有する水溶液を調製し、表１の発泡条件で泡沫を調製し、表２の配合に対する流動性を以下の方法で測定した。化合物（Ｉ）、（II）の組み合わせ及び重量比は表３の通りとした。結果を表３に示す。 An aqueous solution containing a total of 0.3% by weight of compound (I) and compound (II) shown in Table 3 (0.5% by weight in Comparative Example 3) (both in terms of solid content) was prepared. Foam was prepared under the foaming conditions, and the fluidity for the formulations shown in Table 2 was measured by the following method. The combinations and weight ratios of compounds (I) and (II) were as shown in Table 3. The results are shown in Table 3.
＜流動性＞
表２の所定量の豊浦標準砂と水をモルタル混練容器に入れ、モルタルミキサーにて３０秒攪拌混合する。泡沫６００ｍｌ（泡密度＝０．１６）を加え６０秒間混練し、モルタルを調製する。上部内径５ｃｍ×下部内径１０ｃｍ×高さ１５ｃｍのコーンにモルタルを詰め、モルタル用突き棒で上部を１０回突き、上部をヘラでならす。コーンを引き上げ、その広がり（フロー値ｍｍ）を測定する。泡沫の安定性はこのフロー値が大きいほど良好であると判定される。
<Fluidity>
A predetermined amount of Toyoura standard sand and water shown in Table 2 are put into a mortar kneading container, and mixed with stirring by a mortar mixer for 30 seconds. Add 600 ml of foam (bubble density = 0.16) and knead for 60 seconds to prepare mortar. Mortar is packed into a cone having an inner diameter of 5 cm, a lower inner diameter of 10 cm, and a height of 15 cm, and the upper part is pushed 10 times with a mortar stick, and the upper part is leveled with a spatula. Pull up the cone and measure its spread (flow value mm). It is determined that the foam stability is better as the flow value is larger.
（注）表中、Ｃ1は炭素数１のアルキル基、Ｃ10は炭素数１０のアルキル基、Ｃ12は炭素数１２のアルキル基、Ｃ14は炭素数１４のアルキル基、Ｃ18は炭素数１８のアルキル基であり、比較品で用いた蛋白系起泡剤は、ロケットエアーフォーム（櫻護膜社製）である。 (Note) In the table, C 1 is an alkyl group having 1 carbon atom, C 10 is an alkyl group having 10 carbon atoms, C 12 is an alkyl group having 12 carbon atoms, C 14 is an alkyl group having 14 carbon atoms, and C 18 is carbon. The protein foaming agent which is an alkyl group of formula 18 and used as a comparative product is Rocket Air Foam (manufactured by Ryogo Membrane Co., Ltd.).
Claims (2)
［Ｒ1−Ｏ−(ＡＯ)mＳＯ3］pＸ （Ｉ）
〔式中、Ｒ1は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数７〜１５の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種又は２種以上の混合物、ｍはＡＯの平均付加モル数であって０〜５０の数、Ｘは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基又は水酸基置換アルキルアンモニウム基である。ｐはＸの価数である。〕
Ｒ2−Ｏ−(ＡＯ)yＨ （II）
〔式中、Ｒ2は炭素数８〜２０のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数７〜１５の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種又は２種以上の混合物、ｙはＡＯの平均付加モル数であって１〜１５の数である。〕 A foaming agent for a bubble shield method comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II).
[R 1 -O- (AO) m SO 3] p X (I)
[Wherein, R 1 is an alkyl group or alkenyl group having 8 to 20 carbon atoms, or a hydrocarbon group having 7 to 15 carbon atoms having one or more benzene rings, and AO is one of oxyalkylene groups having 2 to 4 carbon atoms. Or a mixture of two or more, m is the average added mole number of AO and is a number from 0 to 50, X is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a hydroxyl group-substituted alkylammonium group is there. p is the valence of X. ]
R 2 —O— (AO) y H (II)
[Wherein R 2 is an alkyl group or alkenyl group having 8 to 20 carbon atoms or a hydrocarbon group having 7 to 15 carbon atoms having one or more benzene rings, and AO is one of oxyalkylene groups having 2 to 4 carbon atoms. Or a mixture of two or more, y is the average number of moles added of AO and is a number from 1 to 15. ]
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| JP2003314191A (en) * | 2002-04-19 | 2003-11-06 | Kao Corp | Foaming agent for use in foam shielding method |
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| JPS62153382A (en) * | 1985-12-27 | 1987-07-08 | Terunaito:Kk | Foaming agent for suspension |
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| JP2003314191A (en) * | 2002-04-19 | 2003-11-06 | Kao Corp | Foaming agent for use in foam shielding method |
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