hydraulic components

Abstract

The present invention provides a hydraulic composition that contains a large amount of air, yet exhibits resistance to material separation, and also exhibits non-separation in water. [Solution] (A) Component: One or more anionic surfactants selected from sulfates or sulfonates having an alkyl group with 8 to 16 carbon atoms, and (B) Components: Amine oxide represented by the following general formula (1), (C) Components: Powder containing hydraulic powder, and contains water, [Volume of air contained / Volume of hydraulic composition] × 100 (volume %) The present invention provides a hydraulic composition in which the air content in the hydraulic composition represented by is 10% by volume or more and 50% by volume or less.

Description

[Technical Field]

[0001] The present invention relates to a hydraulic composition and a method for producing the same. The present invention also relates to a cavity filling method, in which the hydraulic composition is pumped into a cavity containing water and allowed to solidify. [Background technology]

[0002] Water and gas pipes buried underground, after a certain period of time, become obsolete. When parts of these pipes break, soil and sediment can flow inside, causing problems such as road subsidence. Therefore, the principle is to excavate and remove these obsolete pipes. However, if these obsolete pipes are buried beneath a road, for example, it is necessary to temporarily close the road to excavate them and complete the removal quickly within a short timeframe. Therefore, a method has been developed in which, instead of removing the decommissioned pipes, a filling material is poured into them while they remain buried, and the material is allowed to solidify inside the pipes. However, this method makes it difficult to completely fill the inside of abandoned pipes, and there is a concern that some voids will remain. In addition, stagnant water is often present in such abandoned pipes. Air milk and air mortar, which have been conventionally used as fillers, are filled with air from a cost reduction perspective, but when they come into contact with stagnant water, cement particles scatter, making it difficult to ensure quality, and material separation (bleeding) occurs when the air contained in the filler bursts, making it extremely difficult to evenly fill every corner of abandoned pipes. Therefore, there is a need to develop a filler that does not separate from water even in the presence of stagnant water, suppresses bleeding, and has a high air content from a cost reduction perspective.

[0003] A composition containing amine oxides, which are surfactants, is disclosed as a composition that suppresses bleeding. Patent Document 1 discloses a self-compacting concrete composition containing an alkylamine oxide having an alkyl group with 8 to 22 carbon atoms and a high-performance water reducing agent, wherein the slump flow value of the concrete is 50 cm or more.

[0004] Patent Document 2 discloses a hydraulic composition for ground injection containing water, hydraulic powder, and two or more amine oxides including at least one amine oxide having an alkenyl group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] As described above, the filler used for filling the abandoned pipe is required to suppress bleeding. Bleeding refers to the phenomenon in which the water used during the kneading of the hydraulic composition separates and floats. If bleeding occurs in a short time, it is necessary to knead the filler in small portions, which increases the man-hours and prolongs the construction period. Further, if bleeding occurs after filling the filler into the abandoned pipe, the water separates in the upper layer that has been filled, and there is a risk that the strength of the part where the water has separated is different from other parts. Further, the same adverse effects occur even with a filler having a large air volume, and it hinders uniform filling without unevenness to every corner in the abandoned pipe.

[0007] The present invention provides a hydraulic composition that exhibits water separation resistance while containing a large amount of air and also exhibits water non-separability in water.

Means for Solving the Problems

[0008] The present invention is (A) component: one or more anionic surfactants selected from sulfates or sulfonates having an alkyl group with 8 to 16 carbon atoms (B) component: an amine oxide represented by the following general formula (1) (C) component: a powder containing hydraulic powder and contains water [Volume of contained air / Volume of hydraulic composition] × 100 (volume %) relates to a hydraulic composition in which the air content represented by is 10 volume % or more and 50 volume % or less.

Chemical formula

[0009] The present invention provides a hydraulic composition that contains a large amount of air, has resistance to material separation, and exhibits non-separation in water. Furthermore, the invention provides a method for filling discarded pipes and the like using the hydraulic composition of the present invention, which exhibits non-separation in water. [Modes for carrying out the invention]

[0010] <(A) Component: Anionic surfactant selected from sulfates or sulfonates having an alkyl group with 8 to 16 carbon atoms> The hydraulic composition of the present invention contains a sulfate or sulfonate having an alkyl group with 8 to 16 carbon atoms as an anionic surfactant. Specifically, examples include (alkyl group with 8 to 16 carbon atoms) sulfate, polyoxyethylene (alkyl group with 8 to 16 carbon atoms) ether sulfate, dialkyl sulfosuccinic acid having a total of 8 to 16 carbon atoms in the alkyl group, (alkyl group with 8 to 16 carbon atoms) sulfate, polyoxyethylene polyoxypropylene (alkyl group with 8 to 16 carbon atoms) ether sulfate, (alkyl group with 8 to 16 carbon atoms) benzenesulfonic acid, (alkyl group with 8 to 16 carbon atoms) diphenyl ether disulfonic acid, and alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, ammonium salts, triethanolamine salts, etc. From the viewpoint of good non-separation in water, (alkyl) sulfuric acid (having 8 to 16 carbon atoms), polyoxyethylene (alkyl) ether sulfuric acid (having 8 to 16 carbon atoms), dialkyl sulfosuccinic acid (where the sum of the carbon atoms of the alkyl group is 8 to 16), and their sodium or ammonium salts, or triethanolamine salts are preferred. Among these, (alkyl) sulfuric acid (having 8 to 16 carbon atoms), polyoxyethylene (alkyl) ether sulfuric acid (having 8 to 16 carbon atoms), and their sodium or ammonium salts, or triethanolamine salts are more preferred.

[0011] Furthermore, the content of component (A) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the water in the hydraulic composition, from the viewpoint of foaming properties, and preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and even more preferably 0.3% by mass or less, from the viewpoint of economy and fluidity.

[0012] <(B) Component: Amine oxide> The hydraulic composition of the present invention comprises, as component (B), an amine oxide represented by the following general formula (1) [ka] [In the formula, X is R1a or R 1b -[CONH-CH2CH2CH2] n - is a group represented by R 1a R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. 1b R is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer between 0 and 3. 2 and R 3 Each of these is independently an alkyl group having 1 to 4 carbon atoms or -(C2H4O) p It is a group represented by H. p is the average number of moles added, and R 2 and R 3 The sum of these numbers is between 0 and 5 (exclusive). It contains.

[0013] Furthermore, the content of the amine oxide of general formula (1) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the water in the hydraulic composition, from the viewpoint of good non-separation in water, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less, from the viewpoint of economy and fluidity.

[0014] The hydraulic composition of the present invention [(A) Component Content (Mass)] / [(B) Component Content (Mass)] The content of component (A) relative to the content of component (B), as shown in the formula, is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of exhibiting non-separation in water, and also preferably 50% by mass or less, and more preferably 45% by mass or less.

[0015] The hydraulic composition of the present invention comprises a powder containing the hydraulic powder of component (C), and water. The hydraulic composition of the present invention [(B) Component content (mass)] / [Water content (mass)] × 100 (mass%) The ratio of the content of component (B) to the water content, as expressed by , is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, from the viewpoint of good non-separation in water, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, from the same viewpoint.

[0016] The hydraulic powder contained in component (C) is a powder that hardens when mixed with water, and examples include ordinary Portland cement, blast furnace cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R5214). Among these, from the viewpoint of shortening the time it takes for the hydraulic composition to reach the required strength, cement selected from blast furnace cement, rapid-hardening Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and cement selected from blast furnace cement and ordinary Portland cement is more preferred.

[0017] Furthermore, the hydraulic powder may contain blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also contain non-hydraulic limestone fine powder, etc. Fly ash cement and silica fume cement, which are mixtures of fly ash, silica fume, etc., may be used as the hydraulic powder. In addition, clay such as bentonite may be included to the extent that it does not impair the effects of the present invention. If clay is included, it is preferable that the hydraulic composition of the present invention contains a predetermined polyether compound described later.

[0018] The hydraulic composition of the present invention is ([Mass of water] / [Mass of component (C)]) × 100 (mass%) The ratio of water content to the content of powder containing hydraulic powder, as expressed by , is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and even more preferably 55% by mass or more, from the viewpoint of ensuring the fluidity of the hydraulic composition and ensuring sufficient strength development, and preferably 150% by mass or less, more preferably 125% by mass or less, and even more preferably 100% by mass or less, from the viewpoint of ensuring the hydraulic properties of the hydraulic composition. The above ratio is sometimes referred to as the W / P ratio.

[0019] The W / P ratio is calculated based on the amount of hydraulic powder that hardens through hydration and the total amount of blast furnace slag, fly ash, silica fume, anhydrous gypsum, non-hydraulic limestone fine powder, etc. contained within it. If the hydraulic powder consists only of cement, the W / P ratio may be expressed as the W / C ratio. Furthermore, if the hydraulic powder includes powders selected from those having properties that harden through hydration reactions such as cement, powders having pozzolanic properties, powders having latent hydraulic properties, and stone powder (calcium carbonate powder), then in this invention, the amounts of these powders are also included in the amount of powder containing hydraulic powder. In addition, if the powder having properties that harden through hydration reactions contains a high-strength admixture, then the amount of the high-strength admixture is also included in the amount of powder containing hydraulic powder. This also applies to other parts of mass related to the mass of hydraulic powder.

[0020] Examples of powders other than the hydraulic powder of component (C) in the hydraulic composition of the present invention include aggregates. Examples of aggregates include fine aggregates and coarse aggregates. Fine aggregates are preferably mountain sand, land sand, river sand, and crushed sand, while coarse aggregates are preferably mountain gravel, land gravel, river gravel, and crushed stone. Depending on the application, lightweight aggregates may also be used. The term aggregate is defined in accordance with "Concrete General Survey" (published June 10, 1998, by Gijutsu Shoin).

[0021] The hydraulic composition of the present invention may contain one or more compounds selected from polyethylene glycol with a weight-average molecular weight of 500 or more, preferably 200,000 or less; polypropylene glycol with a weight-average molecular weight of 500 or more, preferably 5,000 or less; copolymers of ethylene oxide and propylene oxide with a weight-average molecular weight of 500 or more, preferably 30,000 or less; and ether compounds having hydrocarbon groups, preferably hydrocarbon groups with 10 to 22 carbon atoms and polyoxyalkylene groups with an average number of added moles of 9 to 5,000 (hereinafter also referred to as polyether compounds). Polyether compounds are preferred components from the viewpoint of exhibiting good water non-separation and foaming properties even when the hydraulic composition contains aggregates containing, for example, bentonite or clay minerals.

[0022] The weight-average molecular weight of the polyether compound was measured by gel permeation chromatography (GPC) using polystyrene as the standard. When the polyether compound is polyethylene glycol, water / ethanol can be used as the solvent.

[0023] Polyether compounds are more preferably one or more polymers selected from polyethylene glycol with a weight-average molecular weight of 500 to 200,000, because they can suppress performance degradation due to the inclusion of foreign substances such as clay minerals.

[0024] When the hydraulic composition of the present invention contains the polyether compound described above, the content thereof is preferably 0.15% by mass or more, more preferably 0.25% by mass or more, even more preferably 0.35% by mass or more, even more preferably 0.45% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of suppressing performance degradation due to the inclusion of foreign substances such as clay minerals relative to water, and from the viewpoint of suppressing viscosity increase of the hydraulic composition, it is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and even more preferably 1% by mass or less.

[0025] The hydraulic composition of the present invention may contain a dispersant. The dispersant is a preferred component from the viewpoint of exhibiting good non-separation and fluidity in water.

[0026] Examples of dispersants include naphthalene polymers, polycarboxylic acid polymers, melamine polymers, phenol polymers, and lignin polymers.

[0027] More specifically, the dispersants include one or more dispersants selected from (D1) naphthalene-based dispersants, (D2) polycarboxylic acid-based dispersants, (D3) dispersants consisting of the following polycondensation products (hereinafter also referred to as PAE-based dispersants), (D4) lignin-based dispersants, and (D5) melamine-based dispersants. <Polycondensation products> A polycondensation product consisting of the following components D31, D33, and optionally D32. [Component D31] Aromatic compounds or heteroaromatic compounds having 5 to 10 carbon atoms or heteroatoms, wherein the aromatic compound or heteroaromatic compound contains an average of 1 to 300 oxyethylene and / or oxypropylene groups per molecule, bonded to the aromatic compound or heteroaromatic compound via an O atom or N atom. [Component D32] (D32-1) Phenol, (D32-2) Phenol ether, (D32-3) Naphthol, (D32-4) Naphthol ether, (D32-5) Aniline, (D32-6) Furfuryl alcohol, and (D32-7) Aminoplast-forming agents selected from the group consisting of melamine or its derivatives, urea or its derivatives, and carboxamide, and at least one aromatic compound as an optional component selected from the group consisting of hydroxybenzoic acid, benzoic acid, isophthalic acid, and oxynaphthoic acid. [Component D33] Aldehydes selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or mixtures thereof (where benzaldehyde is further defined as COOM a SO3M a , and PO3M aIt may have an acidic group represented by the formula (where M is H, an alkali metal or alkaline earth metal, ammonium, or an organic amine group, and a may be 1 / 2, 1, or 2).

[0028] From the viewpoint of the fluidity of the hydraulic composition, the dispersant is preferably one or more selected from (D1) naphthalene-based dispersants, (D2) polycarboxylic acid-based dispersants, and (D4) lignin-based dispersants, more preferably one or more selected from (D1) naphthalene-based dispersants and (D2) polycarboxylic acid-based dispersants, and even more preferably (D2) polycarboxylic acid-based dispersants. The dispersants will be described below.

[0029] (D1) Naphthalene-based dispersant Preferably, naphthalene-based dispersants include naphthalene sulfonic acid formaldehyde condensate or a salt thereof. Naphthalene sulfonic acid formaldehyde condensate or a salt thereof is a condensate of naphthalene sulfonic acid and formaldehyde or a salt thereof. The naphthalene sulfonic acid formaldehyde condensate may be co-condensed as a monomer with an aromatic compound that can co-condense with naphthalene sulfonic acid, such as methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalenecarboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid and / or derivatives thereof, as long as the performance is not impaired.

[0030] For the naphthalene sulfonic acid formaldehyde condensate or its salt, commercially available products such as Mighty 150, Demoll N, Demoll RN, Demoll MS, Demoll SN-B, Demoll SS-L (all manufactured by Kao Corporation), Selfflow 120, Labellin FD-40, Labellin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.) can be used.

[0031] From the viewpoint of improving the fluidity of the hydraulic composition, the naphthalene sulfonic acid formaldehyde condensate or its salt preferably has a weight-average molecular weight of 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less. Furthermore, from the viewpoint of improving the fluidity of the hydraulic composition, the naphthalene sulfonic acid formaldehyde condensate or its salt preferably has a weight-average molecular weight of 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000 or more. The naphthalene sulfonic acid formaldehyde condensate may be in an acidic state or a neutralized product.

[0032] The molecular weight of naphthalene sulfonic acid formaldehyde condensate or its salt can be measured using gel permeation chromatography under the following conditions. [GPC conditions] Column: G4000SWXL + G2000SWXL (Tosoh) Eluent: 30mM CH3COONa / CH3CN=6 / 4 Flow rate: 0.7ml / min Detection: UV280nm Sample size: 0.2 mg / ml Standard material: Sodium polystyrene sulfonate equivalent manufactured by Nishio Kogyo Co., Ltd. (monodisperse sodium polystyrene sulfonate: molecular weight 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020

[0033] (D2) Polycarboxylic acid-based dispersant As polycarboxylic acid-based dispersants, copolymers of a monoester of polyalkylene glycol and (meth)acrylic acid with a carboxylic acid such as (meth)acrylic acid (for example, compounds described in Japanese Patent Publication No. 8-12397), copolymers of an unsaturated alcohol having polyalkylene glycol and a carboxylic acid such as (meth)acrylic acid, copolymers of an unsaturated alcohol having polyalkylene glycol and a dicarboxylic acid such as maleic acid, etc. can be used. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

[0034] As a polycarboxylic acid-based dispersant, copolymers containing the constituent units shown in the following general formula (d21) are preferred from the viewpoint of initial fluidity. As a polycarboxylic acid-based dispersant, a copolymer containing the constituent units shown in the following general formula (d21) and the constituent units shown in the following general formula (d22) is more preferred.

[0035] [ka] [In the formula, R 1d , R 2d These may be the same or different, and represent a hydrogen atom or a methyl group. 3d is a hydrogen atom or -COO(AO) n1 X 1d This shows that X 1d is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; AO is a group selected from ethyleneoxy and propyleneoxy groups; n1 is the average number of moles of AO added, a number between 1 and 300; q is a number between 0 and 2; p is a number between 0 and 1.

[0036] [ka] [In the formula, R 4d , R 5d and R 6d These are the same or different hydrogen atoms, methyl groups, or (CH2) r COOM2d (CH2) r COOM 2d COOM 1d or other (CH2) r COOM 2d They may also form anhydrous compounds, in which case the M of those groups 1d M 2d It does not exist. M 1d M 2d r represents a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or alkenyl group, either identical or distinct. r represents a number between 0 and 2.

[0037] Polycarboxylic acid-based dispersants can also be used by using two or more dispersants with different average moles of AO added, and different proportions of constituent units (d21) and (d22).

[0038] A preferred PAE-based dispersant is a dispersant comprising a polycondensation product consisting of the following components D31, D32, and D33, wherein the molar ratio of component D33:(component D31+component D32) is 1:0.01 to 1:10, and the molar ratio of component D31:component D32 is 10:1 to 1:10. [Component D31] Compounds to which an average of 1 to 300 oxyethylene groups and / or oxypropylene groups are bonded via an O atom or N atom to an aromatic compound selected from the group consisting of phenol, cresol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, and bisphenol A. [Component D32] At least one aromatic compound selected from the group consisting of phenoxyacetic acid, phenoxyethanol, phenoxyethanol phosphate, phenoxydiglycol, and phenoxy(poly)ethylene glycol phosphate, hydroxybenzoic acid, benzoic acid, isophthalic acid, and oxynaphthoic acid. [Component D33] An aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or mixtures thereof (wherein benzaldehyde may further have an acidic group represented by the formula COOMa, SO3Ma, or PO3Ma (where M is H, an alkali metal or alkaline earth metal, ammonium, or an organic amine group, and a may be 1 / 2, 1, or 2)).

[0039] When the hydraulic composition of the present invention contains the above-mentioned dispersant, the content of the dispersant is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more, relative to the powder containing the hydraulic powder, from the viewpoint of obtaining sufficient practical fluidity, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less, from the viewpoint of not inhibiting the hydration reaction of the hydraulic composition.

[0040] The hydraulic composition of the present invention has a mass ratio of [mass of amine oxide (1)] / [mass of dispersant], which is the total content of amine oxide of general formula (1) to the content of the dispersant, preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 30 or less, more preferably 20 or less, and 10 or less, from the viewpoint of the bleeding suppression effect.

[0041] The hydraulic composition may contain AE agents, retarders, foaming agents, foaming agents, waterproofing agents, fluidizing agents, etc., to the extent that it does not affect the effects of the present invention.

[0042] The hydraulic composition of the present invention [Volume of air contained / Volume of hydraulic composition] × 100 (volume %) The air content in the hydraulic composition represented by is 10% by volume or more, more preferably 15% by volume or more, from the viewpoint of ensuring the fluidity of the hydraulic composition and not impairing its strength development, and from the same viewpoint, 50% by volume or less, more preferably 40% by volume or less.

[0043] The specific gravity of the hydraulic composition of the present invention is preferably 1.0 or higher in order to prevent it from floating in water.

[0044] The pH of the supernatant water of the hydraulic composition of the present invention at 25°C is preferably 9 or higher, and the higher the pH value, the lower the water resistance tends to be. From the viewpoint of water resistance, it is preferably 12 or lower, more preferably 11 or lower.

[0045] The water non-separation property of the hydraulic composition of the present invention can be measured by the turbidity of the supernatant water. In other words, if the turbidity of the supernatant water exceeds 1000 NTU, the water non-separation property is considered low.

[0046] <Method for producing a hydraulic composition> The method for producing the hydraulic composition of the present invention is not particularly limited, but it can be produced by a method that includes at least the steps of foaming water containing either component (A) or component (B) to obtain bubbles (step 1), and mixing the bubbles obtained in step 1 with component (C) to obtain a slurry (step 2). Three preferred methods of production are exemplified below. Since the hydraulic composition of the present invention contains water and water-insoluble component (C), it is in the form of a slurry.

[0047] Manufacturing method 1 (i) Add ingredient (A) to the water. (ii) Then, foam is produced using a hand mixer or bubble generator to obtain bubbles (step 1 above). (iii) Once sufficient foaming has occurred, add component (C) to the bubbles obtained in (ii) (step 2 above). (iv) Add component (B) to the slurry obtained in (iii).

[0048] Manufacturing method 2 (i) Add component (B) to the water. (ii) Then, foam is produced using a hand mixer or bubble generator to obtain bubbles (step 1 above). (iii) Once sufficient foaming has occurred, add component (C) to the bubbles obtained in (ii) (step 2 above). (iv) Add component (A) to the slurry obtained in (iii).

[0049] Manufacturing method 3 (i) Add component (A) and component (B) to water. (ii) Then, foam is generated using a hand mixer or bubble generator to obtain bubbles (step 1 above). (iii) Once sufficient foaming has occurred, component (C) is added to the foam obtained in (ii) to obtain a slurry (step 2 above).

[0050] Furthermore, component (C) may be added in a slurry form by mixing it with water beforehand. When using component (C) in a slurry form by mixing it with water beforehand, component (C) may be mixed with a slurry containing component (C) and water instead of mixing it as a powder. Also, steps 1 and 2 may be performed in reverse order, and the following embodiments can be exemplified, for example.

[0051] Manufacturing method 4 (i) Add component (C) to water to obtain a slurry (corresponding to step 2 above). (ii) Add component (A) to the slurry obtained in (i), and then foam it using a hand mixer or bubble generator (corresponding to step 1 above). (iii) Once sufficient foaming has occurred, component (B) is added to the foam obtained in (ii) to obtain a slurry.

[0052] Manufacturing method 5 (i) Add component (C) to water to obtain a slurry (corresponding to step 2 above). (ii) Add component (B) to the slurry obtained in (i), and then foam it using a hand mixer or bubble generator (corresponding to step 1 above). (iii) Once sufficient foaming has occurred, component (A) is added to the foam obtained in (ii) to obtain a slurry (step 2 above).

[0053] Manufacturing method 6 (i) Add component (C) to water to obtain a slurry (corresponding to step 2 above). (ii) Add component (A) and component (B) to the slurry obtained in (i), and then foam it using a hand mixer or bubble generator to obtain a slurry (corresponding to step 1 above).

[0054] The polyether compound, dispersant, and other optional components can be added at any step of the above manufacturing method.

[0055] <Cavity filling method> Next, a cavity-filling method will be described, in which the hydraulic composition of the present invention is filled into cavities such as abandoned pipes underground and allowed to solidify.

[0056] The hydraulic composition of the present invention is injected in an uncured paste or liquid state. The amount and ratio of hydraulic powder, thickener, etc. of the hydraulic composition to be injected are as described above. There are no limitations on the method of injecting the hydraulic composition into underground pipes and cavities, but a method of injection under pressure using a pressure pump is preferred. For example, when targeting buried pipes with a diameter of 40 mmΦ to 200 mmΦ, if the flow value, which is an indicator of fluidity, is 200 mm to 470 mm, the composition can be poured into the buried pipe at a rate of 50 L / h to 300 L / h under the pressure of a pressure pump, resulting in good workability. Furthermore, it does not create cavities while being transported inside the buried pipe, and the cavity filler material maintains its density without losing its shape, ensuring a dense and stable filling. On the other hand, if the fluidity is too high, the hydraulic composition may lose its shape from the tip when transported inside the buried pipe, and this may extend to the interior, making dense filling difficult. Furthermore, the strength of the hydraulic powder in the hydraulic composition after 28 days (age 28 days) was 1.0 N / mm². 2 If the above conditions are met, there will be no impact whatsoever on the road surface where the pipes or cavities are buried.

[0057] The present invention provides a composition containing (A) an anionic surfactant comprising a sulfate or sulfonate having an alkyl group with 8 to 16 carbon atoms, and (B) an amine oxide represented by the following general formula (1), which can be used as a thickener. The compounds that can be used for (A) and (B) are those exemplified in the hydraulic composition. [ka] [In the formula, X is R 1a or R 1b -[CONH-CH2CH2CH2] n - is a group represented by R 1a R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 4 to 22 carbon atoms. 1b R is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer between 0 and 3. 2 and R 3 Each of these is independently an alkyl group having 1 to 4 carbon atoms or -(CH2CH2O) p The group is represented by H, and p is the average number of moles of oxyethylene groups (CH2CH2O) added. 2 and R 3 The sum of these numbers is between 0 and 5 (exclusive).

[0058] A thickening agent containing component (A) and component (B) [(A) Component Content (Mass)] / [(B) Component Content (Mass)] The ratio of the content of component (A) to the content of component (B), as shown above, is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of exhibiting non-separation in water, similar to the hydraulic composition, and also preferably 50% by mass or less, and more preferably 45% by mass or less, from the same viewpoint.

[0059] The thickening agent of the present invention contains water as an active ingredient other than components (A) and (B), which are the effective components of the thickening agent. The amount of water may be the amount obtained by subtracting components (A) and (B) from the total mass of the thickening agent. [Industrial applicability]

[0060] The hydraulic composition and thickener of the present invention are mainly applied to decommissioned pipes such as conduits, gas pipes, and electrical conduits, but are not limited to these and can be widely applied to the disposal of underground pipes if the conditions are met. They can also be used for backfilling of civil engineering structures, void filling, lightweight embankments, and landfill. They are particularly suitable for filling cavities where stagnant water exists. [Examples]

[0061] <(A) Ingredient: Anionic surfactant> The following compounds were used as the anionic surfactant for component (A). The number in parentheses after "polyoxyethylene" indicates the average number of moles of ethyleneoxy groups added. (A1): Sodium polyoxyethylene (1.5) alkyl (C8-C16) ether sulfate (manufactured by Kao Corporation) (A2): Sodium polyoxyethylene (3.0) lauryl ether sulfate (manufactured by Kao Corporation) (A3): Sodium lauryl sulfate (manufactured by Kao Corporation) (A4): Sodium dialkyl sulfosuccinate (manufactured by Kao Corporation) in which the sum of the number of carbon atoms in the alkyl group is between 8 and 16. (A5): Alkyl (C10-C16) ammonium sulfate (manufactured by Kao Corporation)

[0062] <(B) Component: Amine oxide> The following compounds were used as the amine oxide for component (B). (B1): (Oleylamidopropyl)dimethylamine oxide (manufactured by Kao Corporation) (B2): Oleyldimethylamine oxide (manufactured by Kao Corporation) (B3): Lauryldimethylamine oxide (manufactured by Kao Corporation)

[0063] Compound (B1) and compound (B2) can each be produced, for example, by the method described in Japanese Patent Application Publication No. 2001-213859. In this example, compound (B1) and compound (B2) were produced by oxidizing (oleylamidopropyl)dimethylamine or oleyldimethylamine.

[0064] <Hydraulic powder> As the hydraulic powder, blast furnace type B cement was used.

[0065] <Method for producing test mortar> The test mortar was manufactured using the following procedure. (i) A predetermined amount of anionic surfactant of component (A) was added to water. (ii) Then, whip with a hand mixer until it is full of bubbles. (iii) The hydraulic powder was added when sufficient foaming had occurred. (iv) Add a predetermined amount of amine oxide of component (B) to the obtained slurry, [Water content (mass)] / [Hydraulic powder content (mass)] x 100 (mass%) A test mortar was obtained in which the ratio of water content to hydraulic powder content was 84% ​​by mass, as shown by [formula]. Furthermore, the obtained test mortar was placed in a cylinder container measuring φ8cm × H8cm, and its fluidity immediately afterward was evaluated according to the JHS A313 test method (flow test). The flow value was calculated as the average of the value in the direction of the maximum expanded diameter and the value in the direction perpendicular to it. The flow values ​​of the mortars in both the example and comparative example were between 280mm and 450mm, indicating sufficient fluidity to fill voids.

[0066] Using various components (A) and (B), hydraulic compositions, which are test mortars, were prepared as shown in Table 1. [Table 1]

[0067] <Measuring air volume> The air content of each hydraulic composition in Table 1 was tested according to the unit volume mass (gravimetric method) described in JHS A313. Specifically, each hydraulic composition was added to a 400 mL container whose weight had been measured in advance, and the total weight after filling the container was measured. On the other hand, the theoretical specific gravity of the hydraulic composition with 0% air content was calculated from the specific gravity and amount of materials used in the formulation. Furthermore, the air content (%) was calculated using the formula [100 - {(total weight - container weight) / (400 × theoretical specific gravity with 0% air content)}.

[0068] <Water Non-Separation Test: Turbidity Measurement> Add 300g of water to a 500mL beaker, gently add 100g of the prepared slurry to the water, and immediately after adding, collect the supernatant water and measure it with a turbidimeter (Thermo Scientific). TM Eutech TM Turbidity was measured using a TN-100 Turbidmeter.

[0069] <Water Non-Separation Test: pH Measurement of Supernatant Water> The pH of the supernatant water of the hydraulic composition in water was measured using the following method to determine its water resistance. 300 mL of water was added to a 500 mL container, and then 100 g of the prepared packing material was poured in. After all the packing material had been added, 200 mL of the supernatant water was collected and its pH was measured at 20°C. A higher pH value indicates lower water resistance.

[0070] Table 2 shows the various measurement values ​​for each hydraulic composition in Table 1. [Table 2]

[0071] The hydraulic compositions of Examples 1 to 12, which represent preferred embodiments, showed good values ​​for specific gravity, turbidity, and pH. On the other hand, Comparative Example 1, which does not contain either component (A) or component (B), Comparative Example 2, which does not contain component (B), Comparative Example 3, which does not contain component (A), and Comparative Example 4, in which the long-chain alkyl group of the amine oxide of component (B) has 12 carbon atoms (B3), showed low water non-separation properties, resulting in turbidity exceeding 1000 NTU.

[0072] Next, test mortar was manufactured using the following three procedures. Manufacturing method 1 (i) Water (497.17 g) was charged with 0.40 g of (A1) polyoxyethylene (1.5) alkyl (C8-C16) ether sodium sulfate, which constitutes 25% of component (A) (addition rate 0.02% by mass). (ii) Then, whip with a hand mixer until it is sufficiently foamy. (iii) Once sufficient foaming had occurred, the hydraulic powder (600g) was added. (iv) 5.0 g of 30% (oleylamidopropyl)dimethylamine oxide (addition rate 0.3% by mass) was added to the obtained slurry to obtain a test mortar. This manufacturing method follows the same procedure as the manufacturing methods for Examples 1-16 and Comparative Examples 1-4, except for the amount of each component used.

[0073] Manufacturing method 2 (i) 5.0 g of 30% (oleylamidopropyl)dimethylamine oxide (addition rate 0.3% by mass) was added to water (497.17 g). (ii) Then, whip with a hand mixer until it is sufficiently foamy. (iii) Once sufficient foaming had occurred, the hydraulic powder (600g) was added. (iv) 0.40 g (addition rate 0.02% by mass) of (A1) polyoxyethylene (1.5) alkyl (C8-C16) ether sodium sulfate, which makes up 25% of (A), was added to the obtained slurry to obtain a test mortar.

[0074] Manufacturing method 3 (i) Water (497.17 g) was charged with 0.40 g of (A1) 25% (A1) sodium polyoxyethylene (1.5) alkyl (C8-C16) ether sulfate as component (A) (addition rate 0.02% by mass) and 5.0 g of (oleylamidopropyl) dimethylamine oxide as component (B) (addition rate 0.3% by mass). (ii) Then, whip with a hand mixer until it is sufficiently foamy. (iii) Once the mixture was sufficiently foamed, 600g of hydraulic powder was added to obtain a test mortar. Furthermore, all of the test mortars are [Water content (mass)] / [Hydraulic powder content (mass)] x 100 (mass%) The ratio of water content to hydraulic powder content, as shown by [formula], is 84% ​​by mass. Furthermore, all test mortars had a flow value of 300 mm to 400 mm, indicating sufficient fluidity for filling voids.

[0075] Flow tests and underwater non-separation tests were conducted using hydraulic compositions, which are test mortars manufactured using the three methods described above. The results are shown in Table 3. [Table 3]

[0076] The results in Table 3 show that by using components (A) and (B) in preferred embodiments, compositions exhibiting good flow, specific gravity, turbidity, and pH can be obtained in any manufacturing method.

Claims

1. (A) Components: One or more anionic surfactants selected from sulfates or sulfonates having an alkyl group with 8 to 16 carbon atoms, and (B) Component: Amine oxide represented by the following general formula (1), (C) Components: Powder containing hydraulic powder, and contains water, [Volume of air contained / Volume of hydraulic composition] × 100 (volume %) A hydraulic composition having an air content of 10% by volume or more and 50% by volume or less. 【Chemistry 1】 〔In the formula, X is a group represented by R １ａ or R １ｂ - [CONH-CH ２ CH ２ CH ２ , ｎ where R １ａ is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 4 to 22 carbon atoms, and R １ｂ is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer of 0 or more and 3 or less. R ２ and R ３ are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by - (C ２ H ４ O) ｐ H. p is the average number of moles of ethyleneoxy group (C ２ H ４ O) added, and the sum of R ２ and R ３ is a number of 0 or more and 5 or less.〕

2. In general formula (1), X is R １ａ or R １ｂ - [CONH-CH ２ CH ２ CH ２ ] ｎ It is a group represented by -, where R １ａ R is an alkyl group having 16 to 22 carbon atoms or an alkenyl group having 16 to 22 carbon atoms. １ｂ The hydraulic composition according to claim 1, wherein is an alkyl group having 16 to 21 carbon atoms or an alkenyl group having 16 to 21 carbon atoms.

3. [Content (mass) of component (A)] / [Content (mass) of component (B)] × 100 (mass%) The hydraulic composition according to claim 1, wherein the ratio of the content of component (A) to the content of component (B), represented by , is 1% by mass or more and 50% by mass or less.

4. [(B) Component content (mass)] / [Water content (mass)] × 100 (mass%) The hydraulic composition according to claim 1, wherein the ratio of the content of component (B) to the water content, as represented by , is 0.01% by mass or more and 1.0% by mass or less.

5. [Water content (mass)] / [Content of component (C) (mass)] × 100 (mass%) The hydraulic composition according to claim 1, wherein the ratio of the water content to the content of component (C), represented by (C), is 40% by mass or more and 150% by mass or less.

6. The hydraulic composition according to claim 1, wherein component (A) is one or more selected from polyoxyethylene alkyl ether sulfate, alkyl sulfate, and dialkyl sulfosuccinate.

7. A hydraulic composition according to any one of claims 1 to 6, used as a void filler.

8. at least, (A) Components: An anionic surfactant consisting of a sulfate or sulfonate having an alkyl group with 8 to 16 carbon atoms, (B) Component: Amine oxide represented by the following general formula (1), 【Chemistry 2】 [In the formula, X is R １ａ or R １ｂ - [CONH-CH ２ CH ２ CH ２ ] ｎ It is a group represented by -, where R １ａ R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 4 to 22 carbon atoms. １ｂ R is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer between 1 and 3. ２ and R ３ Each of these is independently an alkyl group having 1 to 4 carbon atoms or -(CH ２ CH ２ O) ｐ It is a group represented by H, and p is an oxyethylene group (CH ２ CH ２ This is the average number of moles added to O). ２ and R ３ The sum of these numbers is between 0 and 5 (inclusive). A method for producing a hydraulic composition according to any one of claims 1 to 6, comprising the steps of foaming water containing either of the above to obtain bubbles, and mixing the bubbles with a hydraulic powder.

9. A cavity filling method comprising pumping the hydraulic composition described in any one of claims 1 to 6 into a cavity containing stagnant water and allowing it to solidify.

10. (A) Components: An anionic surfactant consisting of a sulfate or sulfonate having an alkyl group with 8 to 16 carbon atoms, (B) Component: Contains an amine oxide represented by the following general formula (1), [Content (mass) of component (A)] / [Content (mass) of component (B)] × 100 (mass%) A thickening agent composition in which the ratio of the content of component (A) to the content of component (B), as represented by , is 1% by mass or more and 50% by mass or less. 【Transformation 3】 [In the formula, X is R １ａ or R １ｂ - [CONH-CH ２ CH ２ CH ２ ] ｎ It is a group represented by -, where R １ａ R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 4 to 22 carbon atoms. １ｂ R is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer between 1 and 3. ２ and R ３ Each of these is independently an alkyl group having 1 to 4 carbon atoms or -(CH ２ CH ２ O) ｐ It is a group represented by H, and p is an oxyethylene group (CH ２ CH ２ This is the average number of moles added to O). ２ and R ３ The sum of these numbers is between 0 and 5 (inclusive).

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