Cavity filler

Abstract

To provide a cavity filler with suppressed bleeding.SOLUTION: A cavity filler includes a thickener containing an amine oxide, a silicone-based antifoamer, a powder containing a hydraulic powder, and water, and has a water / powder mass ratio of 40 mass% or more and 200 mass% or less, a flow value at 20°C of 200 mm or more and 470 mm or less, and an air content of 7.5 volume% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cavity filler. The present invention also relates to a cavity filling method of pumping and filling the cavity filler into a cavity where water exists, and then solidifying it.

Background Art

[0002] When water pipes or gas pipes buried underground have completed their roles and become obsolete pipes after a certain number of years, some of them may be damaged and sediment may flow into the inside, causing problems such as the road surface subsiding. Therefore, in principle, the buried obsolete pipes are dug up and disposed of. However, when the obsolete pipe is buried, for example, under a road, the traffic of the road must be blocked once to dig it up, and the removal must be completed quickly within a short time. Therefore, a method has been developed in which, without removing the obsolete pipe, a filler or the like is poured in while the pipe is buried, and it is solidified in the obsolete pipe as it is. However, with this method, it is difficult to completely fill the inside of the obsolete pipe, and there is a fear that cavities may remain in part. In addition, stagnant water often exists in such obsolete pipes. When conventional fillers such as air milk and air mortar come into contact with stagnant water, cement particles scatter, and it is difficult to ensure quality or there are problems such as material separation (bleeding) due to the foaming of the air contained in the filler. Therefore, there is a demand for the development of a filler that does not separate from water even in the presence of stagnant water, suppresses bleeding, and has a small air volume.

[0003] As a composition for suppressing bleeding, a composition containing amine oxides, which are surfactants, has been disclosed. Patent Document 1 discloses a self-compacting concrete composition having a slump flow value of 50 cm or more in a concrete composition containing an alkylamine oxide having an alkyl group with 8 to 22 carbon atoms and a high-performance water reducing agent.

[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. In addition, if bleeding occurs after filling the abandoned pipe with the filler, the water will separate in the upper layer of the filled part, and the strength of the part where the water separates may be different from that of other parts. In addition, the same adverse effects occur even with a filler with a large air volume, and it also hinders uniform filling without unevenness to every corner in the abandoned pipe.

[0007] The present invention provides a cavity filler that can be placed even in the presence of stagnant water and in which bleeding is suppressed.

Means for Solving the Problems

[0008] The present invention relates to a cavity filler containing a thickener containing amine oxide, a silicone-based defoaming agent, a powder containing hydraulic powder, and water, having a mass ratio of water / powder of 40% by mass or more and 200% by mass or less, a flow value at 20°C of 200 mm or more and 470 mm or less, and an air volume of 7.5% by volume or less.

[0009] The present invention also relates to a method for filling a cavity, which comprises pumping and filling the cavity filler into a cavity where stagnant water exists, and then solidifying it.

Effects of the Invention

[0010] According to the present invention, there is provided a cavity filler that can be placed even in the presence of stagnant water and has suppressed bleeding. Further, there is provided a method for filling a waste pipe or the like with a hydraulic composition using the cavity filler of the present invention, in which bleeding is suppressed.

Modes for Carrying Out the Invention

[0011] The cavity filler of the present invention contains a thickener containing amine oxide, a silicone-based antifoaming agent, a powder containing hydraulic powder, and water, and has a mass ratio of water / powder of 40% by mass or more and 200% by mass or less, a flow value at 20°C of 200 mm or more and 470 mm or less, and an air content of 7.5% by volume or less.

[0012] The cavity filler of the present invention contains a thickener containing two or more kinds of amine oxides. As the amine oxide, it is preferable that two or more kinds having different X are selected from the amine oxides represented by the following general formula (1).

Chemical formula

[0013] Regarding compound (1), when X in general formula (1) is different, taking the case where there are two types of compound (1) as an example, for example, the following aspects can be mentioned. In the following aspects, among the two types of compound (1), at least one of the R 1a or R 1b is an alkenyl group. (i) One of R 1a or R 1b is an alkyl group, and the other R 1a or R 1b is an alkenyl group. (ii) The number of carbon atoms of one of R 1a or R 1b is different from the number of carbon atoms of the other R 1a or R 1b . (iii) One of X is R 1a , and the other X is R 1b -[CONH-CH 2 CH 2 CH 2 n . (iv) Both X are R 1b -[CONH-CH 2 CH 2 CH 2 n , and one n is different from the other n. (v) Combinations of (i) to (iv) above.

[0014] In general formula (1), X is a group represented by R 1a or R 1b -[CONH-CH 2 CH 2 CH 2 n . R 1a is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. ​​​R 1a When R is an alkenyl group, the number of carbon atoms is preferably 18 or more, and preferably 22 or less. R 1a When R is an alkyl group, the number of carbon atoms is preferably 16 or more, and preferably 22 or less. R 1b is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. R 1b When R is an alkenyl group, the number of carbon atoms is preferably 17 or more, and preferably 21 or less. R 1b When R is an alkyl group, the number of carbon atoms is preferably 15 or more, and preferably 21 or less. n is an integer of 1 or more and 3 or less. Preferably, n is 0 or 1. R 2 and R 3 are each independently preferably an alkyl group having 1 to 2 carbon atoms or a group represented by (C 2 H 4 O) p H. p is preferably a number of 0 or more and 3 or less.

[0015] The cavity filler of the present invention contains two or more, preferably five or less, more preferably two compounds (1) in which X in the general formula (1) is different. And among the two or more compounds (1) contained in the cavity filler of the present invention, at least one is a compound in which R 1a or R 1b in X in the general formula (1) is an alkenyl group having 14 to 22 carbon atoms, that is, R 1a in X in the general formula (1) is an alkenyl group having 14 to 22 carbon atoms or a compound containing an alkenyl group having 13 to 21 carbon atoms as R 1b in X in the general formula (1).

[0016] In the present invention, there are two compounds (1), and among the two compounds (1) including the above (i) to (v), one is such that X in the general formula (1) is R 1aand preferably a compound having an alkenyl group with 14 to 22 carbon atoms. That is, as the cavity filler of the present invention, a cavity filler containing two compounds represented by the general formula (1), wherein X in the general formula (1) is different for the two compounds, and among the two compounds, one has X in the general formula (1) being R 1a and R 1a is a compound having an alkenyl group, and examples of the cavity filler include those described above.

[0017] As the cavity filler of the present invention, X in the general formula (1) is R 1a or R 1b -[CONH-CH 2 CH 2 CH 2 n -represented groups (wherein R 1a is an alkenyl group having 14 to 22 carbon atoms, and R 1b is an alkenyl group having 13 to 21 carbon atoms), and a cavity filler containing a compound (1a) and a compound (1b) in which X in the general formula (1) is different from that of the compound (1a) is exemplified. Specifically, examples include a cavity filler containing a compound (1a) represented by the following general formula (1a) and a compound (1b) represented by the following general formula (1b).

[0018]

Chemical formula

[0019] [In the formula, n1 and n2 are each independently an integer of 0 or more and 3 or less. R 11a is an alkenyl group having 14 to 22 carbon atoms when n1 is 0, and an alkenyl group having 13 to 21 carbon atoms when n1 is 1 to 3. R 11b is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms when n2 is 0, and an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms when n2 is 1 to 3. However, when n1 and n2 are the same number, the alkenyl group of R 11b is R 11a ​is an alkenyl group different from 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 added, and the total of R 2 and R 3 is a number from 0 to 5. ]]

[0020] In general formula (1a), the number of carbon atoms of R 11a is preferably 17 or more, and preferably 22 or less. Also, in general formula (1a), n1 is preferably 0 or 1, more preferably 0.

[0021] In general formula (1b), when n2 is 0 and R 11b is an alkyl group, the number of carbon atoms of R 11b is preferably 16 or more, and preferably 22 or less. In general formula (1b), when n2 is 0 and R 11b is an alkenyl group, the number of carbon atoms of R 11b is preferably 18 or more, and preferably 22 or less. In general formula (1b), when n2 is 1 to 3 and R 11b is an alkyl group, the number of carbon atoms of R 11b is preferably 15 or more, and preferably 21 or less. In general formula (1b), when n2 is 1 to 3 and R 11b is an alkenyl group, the number of carbon atoms of R 11b is preferably 17 or more, and preferably 21 or less. In general formula (1b), R 11b is preferably an alkyl group. Also, in general formula (1b), n2 is preferably 0 or 1.

[0022] In general formula (1a) or (1b), R 2 and R 3 are each independently preferably an alkyl group having 1 or 2 carbon atoms or -(C 2 H 4 O) pA group represented by H, more preferably an alkyl group having 1 or 2 carbon atoms. In the general formula (1a) or (1b), p is preferably a number of 0 or more and 3 or less. When n1 and n2 are the same number, the alkenyl group of R 11b is an alkenyl group different from R 11a .

[0023] Examples of the compound (1) contained in the cavity filler of the present invention include a combination of a compound (11a) represented by the following general formula (11a) and a compound (1b) represented by the following general formula (1b).

[0024]

Chemical formula

[0025] 〔In the formula, n2 is an integer of 0 or more and 3 or less. R 11a is an alkenyl group having 14 or more and 22 or less carbon atoms. R 11b is an alkyl group having 14 or more and 22 or less carbon atoms or an alkenyl group having 14 or more and 22 or less carbon atoms when n2 is 0, and is an alkyl group having 13 or more and 21 or less carbon atoms or an alkenyl group having 13 or more and 21 or less carbon atoms when n2 is 1 to 3. However, when n2 is 0, the alkenyl group of R 11b is an alkenyl group different from R 11a . R 2 and R 3 are each independently an alkyl group having 1 or more and 4 or less carbon atoms or a group represented by -(C 2 H 4 O) p H. p is the average number of moles of addition, and the total of R 2 and R 3 is a number of 0 or more and 5 or less .〕

[0026] The compound (11a) represented by the general formula (11a) corresponds to the compound in which n1 is 0 in the general formula (1a). R 11a , R 2 and R 3The preferred embodiment is the same as general formula (1a). Also in this combination, the preferred embodiment of compound (1b) is the same as described above.

[0027] In the present invention, from the viewpoint of suppressing breeding, the mass ratio of compound (1b) / compound (1a) is preferably 5 / 95 or more, more preferably 25 / 75 or more, still more preferably 30 / 70 or more, even more preferably 40 / 60 or more, and preferably 95 / 5 or less, more preferably 90 / 10 or less, still more preferably 85 / 15 or less.

[0028] Also, from the viewpoint of suppressing breeding, the total content of compound (1) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more with respect to the water in the void filler. And from the viewpoints of economy and fluidity, it is preferably 5% by mass or less, more preferably 2.5% by mass or less, still more preferably 1.0% by mass or less. Here, the water in the void filler does not include the water of the thickener described later.

[0029] Also, when the void filler of the present invention contains the compound (1a) and the compound (1b), from the viewpoint of suppressing material separation in the presence of water with respect to the water in the void filler, the content of the compound (1a) is preferably 0.00095% by mass or more, more preferably 0.0075% by mass or more, still more preferably 0.035% by mass or more, even more preferably 0.06% by mass or more, and from the viewpoints of economy and thickening property, it is preferably 3.75% by mass or less, more preferably 3% by mass or less, still more preferably 2.8% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less. Here, the water in the void filler does not include the water of the thickener described later. Also, when the cavity filling material of the present invention contains the compound (1a) and the compound (1b), from the viewpoint of suppressing material separation in the presence of water with respect to the water in the cavity filling material, the content of the compound (1b) is preferably 0.00005% by mass or more, more preferably 0.0025% by mass or more, still more preferably 0.015% by mass or more, even more preferably 0.04% by mass or more, and from the viewpoints of economy and thickening property, it is preferably 19% by mass or less, more preferably 11.25% by mass or less, still more preferably 7% by mass or less, even more preferably 5.2% by mass or less, and even more preferably 3% by mass or less. Here, the water in the cavity filling material does not include the water of the thickener described later. It is preferable that the total content of the compound (1a) and the compound (1b) in the cavity filling material of the present invention is within a predetermined range, and the content of each of the compound (1a) and the compound (1b) is within a predetermined range.

[0030] From the viewpoint of suppressing bleeding and from the viewpoint of exhibiting a better rheology modifying effect in a wide temperature range, the thickener can contain an anionic aromatic compound. Examples of the anionic aromatic compound include one or more compounds selected from sulfonic acids having an aromatic ring, carboxylic acids having an aromatic ring, phosphonic acids having an aromatic ring, or salts thereof. The anionic aromatic compound is preferably an acid-type compound having a total carbon number of 6 or more and 12 or less. Specific examples of the anionic aromatic compound include salicylic acid, p-toluenesulfonic acid, sulfosalicylic acid, benzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid, methyl salicylic acid, styrenesulfonic acid, chlorobenzoic acid, and the like. These may form salts with metal ions such as alkali metals and alkaline earth metals or ammonium ions. Two or more anionic aromatic compounds may be used. The anionic aromatic compound is preferably one or more compounds selected from sulfonic acids having an aromatic ring, carboxylic acids having an aromatic ring, or salts thereof, and more preferably a sodium salt.

[0031] The mass ratio of the total content of compound (1) to the content of the anionic aromatic compound, i.e., compound (1) / anionic aromatic compound, is preferably 50 / 50 or more, more preferably 70 / 30 or more, still more preferably 80 / 20 or more, and preferably 99.9 / 0.1 or less, more preferably 95 / 5 or less, from the viewpoint of suppressing bleeding. Further, the content of the anionic aromatic compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 0.5% by mass or less, more preferably 0.25% by mass or less, based on the water in the cavity filler.

[0032] The thickener contains water as a component other than compound (1) which is the active ingredient as a thickener and the anionic aromatic compound. The water content may be the amount obtained by subtracting compound (1) and the anionic aromatic compound from the total mass part of the thickener.

[0033] From the viewpoint of suppressing bleeding, the content of the active ingredient of the thickener contained in the cavity filler of the present invention is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, based on the water in the cavity filler. And from the viewpoints of economy and fluidity, it is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less.

[0034] The cavity filler of the present invention contains a silicone-based defoaming agent. The silicone-based defoaming agent may be any of oil type, paste type, oil compound type, solution type, solid type, self-emulsifying type, and emulsion type. However, from the viewpoint of easy adjustment of the addition amount and reduction of the air amount, the self-emulsifying type and the emulsion type are preferred, and the emulsion type is more preferred.

[0035] The silicone-based defoaming agent contains water as a component other than the active ingredient as a silicone-based defoaming agent. The water content may be the amount obtained by subtracting the active ingredient.

[0036] From the perspective of suppressing bleeding, the content of the active ingredient of the silicone-based antifoaming agent is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, still more preferably 1.0% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, based on the active ingredient of the thickener.

[0037] The cavity filler of the present invention contains a powder containing hydraulic powder and water. The hydraulic powder is a powder that hardens by mixing with water. Examples thereof include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R5214, etc.). Among these, from the perspective of shortening the time until the required strength of the hydraulic composition is reached, cement selected from early-strength Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferable, and cement selected from early-strength Portland cement and ordinary Portland cement is more preferable.

[0038] In addition, the hydraulic powder may contain blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also contain non-hydraulic fine limestone powder, etc. As the hydraulic powder, blast furnace cement, fly ash cement, silica fume cement, etc., in which cement is mixed with blast furnace slag, fly ash, silica fume, etc., may be used. Also, clay such as bentonite may be contained within a range that does not impair the effects of the present invention. When clay is contained, the cavity filler of the present invention preferably contains a predetermined polyether compound described later.

[0039] The void filler of the present invention has a water / (powder containing hydraulic powder) ratio (W / P ratio) that, from the perspective of ensuring the fluidity of the void filler and suppressing bleeding, is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more. And, from the perspective of ensuring the hydraulicity of the void filler, it is preferably 200% by mass or less, more preferably 180% by mass or less, and still more preferably 160% by mass or less. Here, the W / P ratio is the mass percentage (% by mass) of the water and the powder containing the hydraulic powder in the void filler, and is calculated by [water / (powder containing hydraulic powder)]×100. The W / P ratio is calculated based on the amount of the hydraulic powder having physical properties that harden by a hydration reaction and the total amount of blast furnace slag, fly ash, silica fume, anhydrous gypsum, non-hydraulic limestone fine powder, etc. contained therein. When the hydraulic powder is only cement, the W / P ratio may be denoted as the W / C ratio in some cases. In addition, when the hydraulic powder contains, in addition to the powder having physical properties that harden by a hydration reaction such as cement, a powder having a pozzolanic action, a powder having latent hydraulicity, and a powder selected from stone powder (calcium carbonate powder), in the present invention, their amounts are also included in the amount of the powder containing the hydraulic powder. Also, when the powder having physical properties that harden by a hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the powder containing the hydraulic powder. This is the same for other parts by mass and the like related to the mass of the hydraulic powder.

[0040] The powder in the void filler of the present invention may contain an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand, or crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel, or crushed stone. Depending on the application, lightweight aggregate may be used. The term "aggregate" is based on "General Concrete Handbook" (issued by Gijutsu Syoin on June 10, 1998).

[0041] The cavity filler of the present invention can contain one or more compounds selected from polyethylene glycol having a weight average molecular weight of 500 or more, preferably 200,000 or less, polypropylene glycol having a weight average molecular weight of 500 or more, preferably 5,000 or less, a copolymer of ethylene oxide and propylene oxide having a weight average molecular weight of 500 or more, preferably 30,000 or less, and an ether compound having a hydrocarbon group, preferably a hydrocarbon group having 10 to 22 carbon atoms and a polyoxyalkylene group having an average added mole number of preferably 9 to 5,000 (hereinafter also referred to as a polyether compound). The polyether compound is a preferable component from the viewpoint of enabling the cavity filler to exhibit a good bleeding suppression effect even when the cavity filler contains an aggregate containing bentonite or a clay mineral, for example.

[0042] The weight average molecular weight of the polyether compound is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard. When the polyether compound is polyethylene glycol, water / ethanol can be used as a solvent.

[0043] The polyether compound is more preferable because one or more polymers selected from polyethylene glycol having a weight average molecular weight of 500 or more and 200,000 or less can suppress a decrease in performance due to contamination with foreign substances such as clay minerals.

[0044] When the cavity filler of the present invention contains the above-described polyether compound, the content thereof is preferably 0.15% by mass or more, more preferably 0.25% by mass or more, still more preferably 0.35% by mass or more, even more preferably 0.45% by mass or more, even more preferably 0.5% by mass or more, from the viewpoint of suppressing a decrease in performance due to contamination with foreign substances such as clay minerals with respect to water, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1.5% by mass or less, even more preferably 1% by mass or less, from the viewpoint of suppressing thickening of the cavity filler.

[0045] The fluidity of the cavity filling material of the present invention is such that the flow value at 20 °C evaluated according to the test method (flow test) of JIS R 5201 is preferably 200 mm or more, more preferably 250 mm or more, from the viewpoints of workability and pumpability, and preferably 470 mm or less, more preferably 450 mm or less, from the viewpoint of bleeding suppression. The flow value is obtained as the average value of the value in the maximum direction of the spread diameter and the value in the direction perpendicular thereto.

[0046] The cavity filling material of the present invention has an air content of 0% by volume or more, and in terms of reducing the volume of air in the cavity, it is 7.5% by volume or less, preferably 5% by volume or less, more preferably 3% by volume or less, and even more preferably 1.5% by volume or less.

[0047] The cavity filling material of the present invention can contain a dispersant. The dispersant is a preferable component from the viewpoints of exhibiting a good bleeding suppression effect and fluidity.

[0048] Examples of the dispersant include naphthalene-based polymers, polycarboxylic acid-based polymers, melamine-based polymers, phenol-based polymers, and lignin-based polymers.

[0049] More specifically, the dispersant includes one or more dispersants selected from (D1) naphthalene-based dispersants, (D2) polycarboxylic acid-based dispersants, (D3) dispersants composed of the following polycondensation products (hereinafter also referred to as PAE-based dispersants), (D4) lignin-based dispersants, and (D5) melamine-based dispersants. <Polycondensation product> A polycondensation product composed of the following component D31, component D33, and optionally component D32 [Component D31] An aromatic compound or heteroaromatic compound having 5 to 10 carbon atoms or heteroatoms, wherein the aromatic compound or heteroaromatic compound is bonded via an O atom or an N atom, and on average 1 to 300 oxyethylene and / or oxypropylene groups per molecule are included, and the aromatic compound or heteroaromatic compound [Component D32] (D32-1) Phenol, (D32-2) phenol ether, (D32-3) naphthol, (D32-4) naphthol ether, (D32-5) aniline, (D32-6) furfuryl alcohol, and at least one aromatic compound as an optional component selected from the group consisting of (D32-7) melamine or its derivative, urea or its derivative, and carboxamide, hydroxybenzoic acid, benzoic acid, isophthalic acid, oxynaphthoic acid [Component D33] An aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or a mixture thereof (wherein benzaldehyde may further have an acidic group represented by the formula COOM a , SO 3 M a , and PO 3 M a (wherein 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).)

[0050] From the viewpoint of the fluidity of the cavity filler, the dispersant is preferably at least one selected from (D1) naphthalene-based dispersants, (D2) polycarboxylic acid-based dispersants, and (D4) lignin-based dispersants, more preferably at least one selected from (D1) naphthalene-based dispersants and (D2) polycarboxylic acid-based dispersants, and even more preferably (D2) polycarboxylic acid-based dispersants. Hereinafter, the dispersant will be described.

[0051] (D1) Naphthalene-based dispersant As the naphthalene-based dispersant, preferably a naphthalene sulfonic acid formaldehyde condensate or a salt thereof can be mentioned. The 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 with an aromatic compound co-condensable with naphthalene sulfonic acid, such as, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalene carboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid and / or derivatives thereof, etc., as long as the performance is not impaired.

[0052] As the naphthalene sulfonic acid formaldehyde condensate or a salt thereof, commercially available products such as, for example, Mytei 150, Demol N, Demol RN, Demol MS, Demol SN-B, Demol SS-L (all manufactured by Kao Corporation), Selflow 120, Labelin FD-40, Labelin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.) can be used.

[0053] From the viewpoint of improving the fluidity of the cavity filler, the weight average molecular weight of the naphthalene sulfonic acid formaldehyde condensate or a salt thereof is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less. And, from the viewpoint of improving the fluidity of the cavity filler, the weight average molecular weight of the naphthalene sulfonic acid formaldehyde condensate or a salt thereof is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and even more preferably 5,000 or more. The naphthalene sulfonic acid formaldehyde condensate may be in the form of an acid or a neutralized product.

[0054] The molecular weight of the naphthalene sulfonic acid formaldehyde condensate or a salt thereof can be measured using gel permeation chromatography under the following conditions. [GPC Conditions] Column: G4000SWXL + G2000SWXL (Tosoh) Eluent: 30 mM CH 3 COONa / CH 3 CN = 6 / 4 Flow rate: 0.7 ml / min Detection: UV280 nm Sample size: 0.2 mg / ml Standard substance: Sodium polystyrene sulfonate equivalent manufactured by Nishi-aoi Kogyo Co., Ltd. (monodisperse sodium polystyrene sulfonate: molecular weights, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020

[0055] (D2) Polycarboxylic acid-based dispersant As the polycarboxylic acid-based dispersant, a copolymer of a monoester of a polyalkylene glycol and (meth)acrylic acid and a carboxylic acid such as (meth)acrylic acid (for example, the compounds described in JP-A-8-12397), a copolymer of an unsaturated alcohol having a polyalkylene glycol and a carboxylic acid such as (meth)acrylic acid, a copolymer of an unsaturated alcohol having a 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.

[0056] As the polycarboxylic acid-based dispersant, a copolymer containing the monomer (d21) represented by the following general formula (d21) as a constituent monomer is preferable from the viewpoint of initial fluidity. As the polycarboxylic acid-based dispersant, a copolymer containing the monomer (d21) represented by the following general formula (d21) and the monomer (d22) represented by the following general formula (d22) as constituent monomers is more preferable.

[0057]

Chemical formula

[0058] [In the formula, R 1d , R2d may be the same or different and represents a hydrogen atom or a methyl group. R 3d is a hydrogen atom or -COO(AO) n1 X 1d represents, where X 1d is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is a group selected from an ethyleneoxy group and a propyleneoxy group, n1 is the average number of moles of AO added and is a number from 1 to 300. q represents a number from 0 to 2. p represents a number of 0 or 1. ]]

[0059] [Chemical formula]

[0060] [In the formula, R 4d , R 5d and R 6d are the same or different and are a hydrogen atom, a methyl group or (CH 2 ) r COOM 2d represents, (CH 2 ) r COOM 2d is COOM 1d or another (CH 2 ) r COOM 2d may form an anhydride with, and in that case, M 1d , M 2d do not exist. M 1d , M 2d are the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group or an alkenyl group. r represents a number from 0 to 2. ]]

[0061] For the polycarboxylic acid-based dispersant, two or more dispersants with different average addition mole numbers of AO, ratios of monomers (d21) and monomers (d22), etc. can also be used.

[0062] Preferred PAE-based dispersants include a polycondensation product composed of the following component D31, component D32, and component D33, where the molar ratio of component D33:(component D31 + component D32) is from 1:0.01 to 1:10, and the molar ratio of component D31:component D32 is from 10:1 to 1:10. [Component D31] A compound in which 1 to 300 oxyethylene groups and / or oxypropylene groups are bonded per molecule on average via an O atom or an 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 a mixture thereof (where benzaldehyde may further have an acidic group represented by the formula COOMa, SO 3 Ma, or PO 3 Ma (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))

[0063] When the cavity filler of the present invention contains the above-mentioned dispersant, from the viewpoint of obtaining practically sufficient fluidity, the content of the dispersant is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more, based on the powder containing hydraulic powder, and from the viewpoint of not inhibiting the hydration reaction of the cavity filler, it is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less.

[0064] In the void filling material of the present invention, the mass ratio of the total content of compound (1) to the content of the dispersant, i.e., compound (1) / dispersant, is preferably 3 / 97 or more, more preferably 5 / 95 or more, still more preferably 10 / 90 or more, and preferably 97 / 3 or less, more preferably 95 / 5 or less, 90 / 10 or less, from the viewpoint of the bleeding suppression effect.

[0065] The void filling material can contain an AE agent, a retarder, a foaming agent, a thickener, a foaming agent, a waterproof agent, a fluidizing agent, etc. within a range that does not affect the effects of the present invention.

[0066] <Method for manufacturing void filling material> The void filling material of the present invention can be manufactured by mixing a thickener containing amine oxide, a silicone-based antifoaming agent, a powder containing hydraulic powder, and water.

[0067] In the method for manufacturing the void filling material of the present invention, for example, a slurry containing water and a powder containing hydraulic powder is prepared in advance, and a thickener containing two or more kinds of compound (1) is added and mixed to manufacture the void filling material. The mixing of each component can be carried out according to a known method for manufacturing a hydraulic composition.

[0068] <Void filling method> Next, a void filling method for filling the void filling material of the present invention into a void such as an abandoned pipe in the ground and solidifying it will be described.

[0069] The void filling material of the present invention is injected in an uncured paste-like or liquid state. The amounts and quantity ratios of the hydraulic powder, thickener, etc. of the void filling material to be injected are as described above. Although there is no limitation on the method of injecting the cavity filling material into the buried conduits or cavities underground, the method of pressurized injection using a pressure pump is preferred. For example, when targeting buried pipes with a diameter of 40mmΦ to 200mmΦ, if the flow value, which is an index of fluidity, is 200mm to 470mm, it can be poured into the buried pipe at a speed of 50L / h to 300L / h under the pressure of the pressure pump for filling, and the workability is good. Also, no cavity is created while being transferred inside the buried pipe, and the cavity filling material remains dense without collapsing overall while maintaining its density, and is surely filled stably in a dense state. On the other hand, if the fluidity is too large, when the cavity filling material is transferred inside the buried pipe, a kind of collapse may occur from the tip, which may reach the inside and make it difficult to achieve a dense filling. Furthermore, if the strength of the hydraulic powder in the cavity filling material after 28 days (material age of 28 days) is 1.0 N / mm 2 or more, it will have no impact on the road surface where the conduits or cavities are buried.

Industrial Applicability

[0070] The cavity filling material of the present invention is mainly applied to abandoned pipes such as conduits, gas pipes, and electrical pipes, but is not limited thereto, and can be widely applied to the disposal of buried pipes that meet the conditions if the conditions are met. It can also be used for backfilling of civil engineering structures, void filling, lightweight embankment, and landfill. In particular, it is suitable for applications where cavities with stagnant water are filled.

Examples

[0071] <Thickening Agent and Its Preparation> The following amine oxides were used for the preparation of the thickening agent. Compound (1a): Oleic acid amide propyl dimethylamine oxide (in the general formula (1a), R 11a : alkenyl group with 17 carbon atoms, n1: 1, R 2 : methyl group, R 3 : methyl group) Compound (1b): Oleyl dimethylamine oxide (in the general formula (1b), R 11b : alkenyl group with 18 carbon atoms (oleyl group), n2: 0, R2 : Methyl group, R 3 : (methyl group)

[0072] Compound (1a) and compound (1b) can each be produced, for example, by the method described in JP-A-2001-213859. In this example, compound (1a) and compound (1b) were each produced by oxidizing the corresponding alkenyldimethylamine or alkenylamidopropylamine.

[0073] Compound (1a) and compound (1b) were mixed so that the mass ratio was 85 / 15, and an amount corresponding to 30% by mass based on the total thickener was used. Also, as the aromatic anionic compound, sodium m-xylene sulfonate was used in an amount corresponding to 3% by mass based on the total thickener.

[0074] A predetermined amount of compound (1a), compound (1b), and the above aromatic anionic compound were mixed with water (the balance, 67% by mass) and used as a thickener. In Comparative Example 5, bentonite (manufactured by Tachibana Materials) was used instead of the above thickener.

[0075] As the silicone-based defoaming agent (hereinafter referred to as the defoaming agent), AF-146 (emulsion type, active ingredient 27% by mass, balance 73% by mass of water) manufactured by Asahi Dye Manufacturing Co., Ltd. was used. As the cement (C), blast furnace type B cement manufactured by Sumitomo Osaka Cement Co., Ltd. was used. As the fly ash (FA), Central Fly Ash manufactured by Techno Central was used.

[0076] <Hole filling material> (1) Preparation of hole filling material Using the above thickener, defoaming agent, cement (C), and fly ash (FA), various hole filling materials were prepared by the following method. The mixing ratio (kg / m 3 ) and mixing ratio (% by mass) shown in Table 1 were used to prepare the hole filling material by mixing in the following method.

[0077] As an example, the manufacturing method of the cavity filling material of Example 1 is shown. 2.15 kg of cement was mixed with 1.29 kg of water containing 0.21 g of a silicone-based antifoaming agent and kneaded for 30 seconds using a hand mixer. Then, 10.4 g of a thickener was added and kneaded for another 120 seconds.

[0078] For the cavity filling material of Comparative Example 4, 6.4 g of a foaming agent (manufactured by Kao Corporation: Emal D-3-D) was added to 640 g of water and foamed by stirring with a hand mixer for 60 seconds. Then, 900 g of cement was added and further stirred for 60 seconds to produce it.

[0079] For the cavity filling material of Comparative Example 5, 100 g of bentonite was added to 1.73 kg of water while stirring with a hand mixer. After adding the total amount and stirring for 60 seconds, 700 g of cement was added and kneaded for another 60 seconds to produce it.

[0080] Mixing ratio (kg / m 3 ) was calculated by conversion so that the total volume of (water + cement + fly ash) was 1.0 m 3 . For example, the volume of the cavity filling material of Example 1 is 647 L + (1075 / 3.04) L = 1000 L = 1.0 m 3 The volume of the cavity filling material of Example 7 is 685 L + (350 / 3.04) L + (450 / 2.25) L = 1000 L = 1.0 m 3 . Since the thickener and the antifoaming agent are in small amounts with respect to the total amount of water (W), cement (C), and fly ash (FA), they are ignored in the calculation of the mixing ratio of water (W), cement (C), and fly ash (FA).

[0081] (2) Measurement of fluidity (flow) The kneaded cavity filler was placed in a cylindrical container with a diameter of φ8 cm and a height of H8 cm, and its fluidity immediately after placement was evaluated according to the test method (flow test) of JHS A313. The flow value was determined as the average of the value in the maximum direction of the spread diameter and the value in the direction perpendicular to this.

[0082]

Table 1

[0083] <Evaluation of Cavity Filler> (1) Measurement of bleeding rate The kneaded filler was measured according to the polyethylene bag method described in JSCE-F532-2013.

[0084] (2) Strength measurement at 28 days of age The kneaded filler was poured into a cylindrical mold container with a diameter of φ50 mm and a height of H100 mm, and three cylindrical test specimens were prepared. Then, water curing was carried out at the stage where the strength was developed and demolding was possible. The uniaxial compressive strength was measured in accordance with JSCE-G 505―2010 at 28 days of age.

[0085] (3) Measurement of air content The test was carried out according to the unit volume mass (gravimetric method) described in JHS A313. Specifically, the kneaded cavity filler was added to a 400 mL container whose weight had been measured in advance, the total weight was measured, and the air content was calculated.

[0086] (4) Water resistance test method (measurement of pH of supernatant water) The pH of the supernatant water of the cavity filler in water was measured by the following method and used as an index of water resistance. 300 mL of water was added to a 500 mL container, and then the prepared cavity filler was poured in. After all of it was poured in, 200 mL of the supernatant water was sampled and the pH was measured at 20°C. It can be said that the higher the pH value, the lower the water resistance.

[0087]

Table 2

[0088] As shown in Examples 1 to 7, the cavity filling material obtained by mixing a predetermined amount of thickener and antifoaming agent exhibited appropriate fluidity and no bleeding was observed at all. On the other hand, in Comparative Example 1 without a thickener, the flow value was also as large as 500 mm × 500 mm or more, and significant bleeding was observed. Even in Comparative Example 2 with a flow value of 489 mm × 485 mm, although the amount of the thickener was relatively small regardless of the large water / powder mass ratio (W / P), bleeding was observed. In Comparative Example 3 where the amount of the antifoaming agent was as small as 0.1% by mass relative to the thickener, the amount of air in the cavity filling material was large, and the pH of the supernatant water was 12

Claims

1. A cavity filling material containing a thickener containing amine oxide, a silicone-based antifoaming agent, a powder containing hydraulic powder, and water, having a mass ratio of water / powder of 40% by mass or more and 200% by mass or less, a flow value at 20°C of 200 mm or more and 470 mm or less, and an air volume of 7.5% by volume or less.

2. The cavity filling material according to Claim 1, wherein the amine oxide is selected from two or more compounds represented by the following general formula (1). 【Chemical Formula 1】 [wherein, X is R １ａ or R １ｂ - [CONH-CH ２ CH ２ CH ２ ｎ - and is a group represented by, where R １ａ is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 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 1 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 added, and the total of R ２ and R ３ is a number of 0 or more and 5 or less.]​

3. The cavity filling material according to Claim 1 or 2, wherein the content of the active ingredient of the silicone-based antifoaming agent is 0.5% by mass or more and 15% by mass or less with respect to the content of the active ingredient of the thickener.

4. The cavity filling material according to any one of Claims 1 to 3, wherein the content of the active ingredient of the thickener is 0.03% by mass or more and 10% by mass or less with respect to water.

5. A cavity filling method of pumping and filling the cavity filling material according to any one of Claims 1 to 4 into a cavity where stagnant water exists and solidifying it.

6. The cavity filling method according to Claim 5, wherein the cavity is a cavity existing in a buried conduit or ground underground.

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