Ground consolidation agent and method for consolidating ground using the same

Abstract

The amount of nonionic surfactant detected under running water is small, and it has excellent performance as a ground consolidation agent. [Solution] The rock mass consolidation agent comprises component (A) containing polyol (a), amine compound (b) having a primary amino group and / or a secondary amino group, catalyst (c), and flame retardant (d), and component (B) containing aromatic polyisocyanate. Polyol (a) contains ether-based polyol (a1) having a functionality of 1.5 to 2.5 and a hydroxyl value of 400 to 1100 mgKOH / g, and polyester polyol (a2) having a hydroxyl value of 100 to 400 mgKOH / g. 90% by mass or more of the ether-based polyol contained in polyol (a) is ether-based polyol (a1). The total amount of ether-based polyol (a1) and polyester polyol (a2) in polyol (a) is 50% by mass or more.

Description

[Technical Field]

[0001] The present invention relates to a ground consolidation agent and a method for consolidating ground using the same. [Background technology]

[0002] Conventionally, inorganic or organic grouts have been injected to stabilize and strengthen unstable rock masses and ground. Urethane-based ground consolidators, which are primarily composed of polyol and isocyanate, are useful because they consolidate quickly and can solidify the ground to develop strength in a short period of time.

[0003] For example, Patent Document 1 discloses a chemical composition that is substantially free of water and that comprises a component (A) containing a polyol and an amine compound and a component (B) containing an isocyanate. In this chemical composition, a polyether polyol and a castor oil-based polyester polyol are used as the polyol, and an amine compound having a primary or secondary amino group is used as the amine compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5851481 Summary of the Invention [Problem to be solved by the invention]

[0005] A problem with urethane-based ground consolidants is that when they are injected into rock or ground under running water, nonionic surfactants are detected in the components that run off into the environment. Therefore, there is a demand for a ground consolidant that has good performance while reducing the amount of nonionic surfactant detected.

[0006] In view of the above, an embodiment of the present invention aims to provide a ground consolidation agent that detects a small amount of nonionic surfactant and has excellent performance as a ground consolidation agent, and a method for consolidating ground using the same. [Means for solving the problem]

[0007] The present invention includes the embodiments shown below. [1] Component (A) including polyol (a), amine compound (b) having a primary amino group and / or a secondary amino group, catalyst (c), and flame retardant (d); and (B) component containing an aromatic polyisocyanate, the polyol (a) comprises an ether-based polyol (a1) having a functionality of 1.5 to 2.5 and a hydroxyl value of 400 to 1100 mgKOH / g, and a polyester polyol (a2) having a hydroxyl value of 100 to 400 mgKOH / g; 90% by mass or more of the ether-based polyol contained in the polyol (a) is the ether-based polyol (a1), A rock mass consolidation agent, wherein the total amount of the ether-based polyol (a1) and the polyester polyol (a2) in the polyol (a) is 50 mass % or more.

[0008] [2] The rock mass consolidation agent according to [1], wherein the content of the ether-based polyol (a1) in the polyol (a) is 5 to 95 mass%, and the content of the polyester polyol (a2) in the polyol (a) is 5 to 95 mass%. [3] The rock mass consolidation agent according to [1] or [2], wherein the content of the amine compound (b) in the component (A) is 1 to 30 mass %. [4] The ground consolidation agent according to any one of [1] to [3], wherein the aromatic polyisocyanate comprises at least one selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and modified products thereof. [5] A method for consolidating ground, comprising the steps of drilling a plurality of holes at predetermined intervals in bedrock or ground, inserting hollow bolts into the holes, and injecting the ground consolidation agent according to any one of [1] to [4] into the bedrock or ground through the openings of the bolts to consolidate the bedrock or ground. [Effects of the Invention]

[0009] The ground consolidation agent according to the embodiment of the present invention detects a small amount of nonionic surfactant and has excellent performance as a ground consolidation agent. DETAILED DESCRIPTION OF THE INVENTION

[0010] The rock mass consolidation agent according to this embodiment comprises an (A) component containing a polyol (a), an amine compound (b), a catalyst (c), and a flame retardant (d), and a (B) component containing an aromatic polyisocyanate. The rock mass consolidation agent is typically a two-component curing type rock mass consolidation agent, with component (A) as component A and component (B) as component B. In addition to components (A) and (B), a third component may be included as an optional component.

[0011] [Component (A)] Component (A) is a component containing an active hydrogen compound. An active hydrogen compound is a compound (excluding water) that has one or more active hydrogen groups in its molecule. An active hydrogen group is a group containing a hydrogen atom that reacts with an isocyanate group, and examples thereof include a hydroxyl group, a primary amino group (-NH), and a secondary amino group (-NHR).

[0012] (Polyol (a)) Component (A) contains polyol (a) as an active hydrogen compound. Polyol (a) contains ether-based polyol (a1) having a functionality of 1.5 to 2.5 and a hydroxyl value of 400 to 1100 mgKOH / g and polyester polyol (a2) having a hydroxyl value of 100 to 400 mgKOH / g, and 90 mass % or more of the ether-based polyol contained in polyol (a) is ether-based polyol (a1).

[0013] Here, ether polyol refers to a polyol containing an ether bond (-O-) in the molecule, and is not limited to polyether polyols having multiple ether bonds, but also includes polyols having one ether bond. However, polyester polyols are not included in ether polyols even if they have an ether bond in the molecule. Here, polyester polyol refers to a polyol having multiple ester bonds (-COO-) in the molecule.

[0014] According to this embodiment, the ether-based polyol used in combination with the polyester polyol (a2) is essentially composed of the specific ether-based polyol (a1) alone, thereby making it possible to exhibit the performance of a ground consolidation agent, such as water-stopping properties and ground improvement properties, while reducing the amount of nonionic surfactants detected in the components that flow into the environment under flowing water.

[0015] Specifically, when the functionality of the ether-based polyol (a1) is 1.5 or more, the strength after hardening can be increased, thereby improving the performance of the ground consolidation agent. When the functionality of the ether-based polyol (a1) is 2.5 or less, the amount of detected nonionic surfactant can be reduced. Furthermore, when the hydroxyl value of the ether-based polyol (a1) is 400 mg KOH or more, the strength after hardening can be increased, improving the performance of the ground consolidation agent, and the amount of detected nonionic surfactant can be reduced.

[0016] The number of functional groups of the ether-based polyol (a1) is preferably 1.7 to 2.3, more preferably 1.8 to 2.2, more preferably 1.9 to 2.1, and even more preferably 2.0. Here, the number of functional groups refers to the number of hydroxyl groups per molecule of the polyol (weighted average value according to the molar ratio).

[0017] The hydroxyl value of the ether polyol (a1) is preferably 420 to 1100 mgKOH / g, more preferably 450 to 1000 mgKOH / g, and more preferably 500 to 900 mgKOH / g. In this specification, the hydroxyl value is measured in accordance with Method A of JIS K1557-1:2007.

[0018] The ether polyol (a1) may be an aliphatic ether polyol, an aromatic ether polyol, or a combination of both. The aliphatic ether polyol refers to an ether polyol that does not have an aromatic ring in the molecule. The aromatic ether polyol refers to an ether polyol that has an aromatic ring in the molecule.

[0019] Examples of aliphatic ether polyols include aliphatic polyether polyols obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide with aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol, and aliphatic active hydrogen compounds such as monoethanolamine, diethanolamine, and ethylenediamine, using a known method. Examples of aliphatic ether polyols include diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. These aliphatic ether polyols may be used alone or in combination.

[0020] Examples of aromatic ether polyols include aromatic polyether polyols obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide with aromatic active hydrogen compounds such as aniline, benzenediol, and bisphenol compounds using a known method. The aromatic ether polyols may also be used alone or in combination of two or more.

[0021] The polyol (a) may contain an ether-based polyol other than the ether-based polyol (a1), but even if it does contain one, the amount is preferably small. Specifically, in this embodiment, 90% by mass or more of the ether-based polyol contained in the polyol (a) is the ether-based polyol (a1). That is, the content of the ether-based polyol (a1) in 100% by mass of the ether-based polyol contained in the polyol (a) is 90% by mass or more, preferably 95% by mass or more, and more preferably 100% by mass. That is, the ether-based polyol may consist solely of the ether-based polyol (a1). This can reduce the amount of nonionic surfactant detected under running water.

[0022] The polyol (a) contains the ether-based polyol (a1) and a polyester polyol (a2) having a hydroxyl value of 100 to 400 mgKOH / g. By using a polyester polyol having a relatively low hydroxyl value in this manner, the amount of nonionic surfactant detected can be reduced and the performance of the ground consolidation agent can be improved.

[0023] Specifically, when the polyester polyol (a2) has a hydroxyl value of 100 mgKOH / g or more, strength after curing can be increased, and water-stopping properties and ground improvement properties can be improved. When the polyester polyol (a2) has a hydroxyl value of 400 mgKOH / g or less, embrittlement after curing can be suppressed, and ground improvement properties can be improved. The hydroxyl value of the polyester polyol (a2) is preferably 130 to 350 mgKOH / g or less, more preferably 150 to 300 mgKOH / g, and even more preferably 150 to 250 mgKOH / g. In one embodiment, the hydroxyl value of the polyester polyol may be 100 to 250 mgKOH / g, or 100 to 161 mgKOH / g.

[0024] The number of functional groups of the polyester polyol (a2) is not particularly limited, and is, for example, preferably from 1.5 to 4.0, more preferably from 1.8 to 3.0, and even more preferably from 1.9 to 3.0.

[0025] The polyester polyol (a2) may be, for example, one obtained by reacting a polyhydric alcohol such as a dihydric alcohol with a dibasic acid, and may be an aliphatic polyester polyol, an aromatic polyester polyol, or a combination of both. The aliphatic polyester polyol refers to a polyester polyol that does not have an aromatic ring in the molecule. The aromatic polyester polyol refers to a polyester polyol that has an aromatic ring in the molecule.

[0026] Examples of aliphatic polyester polyols include aliphatic polyols obtained by reacting aliphatic diols with aliphatic dibasic acids, and castor oil-based polyester polyols (i.e., castor oil-based aliphatic polyester polyols). These may be used alone or in combination. Examples of aliphatic diols constituting the aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Examples of aliphatic dibasic acids include adipic acid, succinic acid, sebacic acid, azelaic acid, maleic acid, and fumaric acid.

[0027] Castor oil-based aliphatic polyester polyols are polyols produced using castor oil, castor oil fatty acids, hydrogenated castor oils obtained by hydrogenating castor oil, and hydrogenated castor oil fatty acids obtained by hydrogenating castor oil fatty acids. Specific examples of castor oil-based aliphatic polyester polyols include castor oil, transesterification products of castor oil and other natural fats and oils, reaction products of castor oil and polyhydric alcohols, esterification products of castor oil fatty acids and polyhydric alcohols, hydrogenated castor oil, transesterification products of hydrogenated castor oil and other natural fats and oils, reaction products of hydrogenated castor oil and polyhydric alcohols, and esterification products of hydrogenated castor oil fatty acids and polyhydric alcohols. Any of these may be used alone or in combination of two or more.

[0028] Examples of aromatic polyester polyols include aromatic polyols obtained by reacting a diol with an aromatic dibasic acid, and castor oil-based aromatic polyester polyols. Either one of these may be used alone, or two or more may be used in combination. Examples of diols constituting the aromatic polyol include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Examples of aromatic dibasic acids include phthalic acid, terephthalic acid, and isophthalic acid. Castor oil-based aromatic polyester polyols are castor oil-modified polyols containing an aromatic skeleton.

[0029] The hydroxyl value of the polyester polyol (a2) is preferably 400 mgKOH / g or less, more preferably 100 to 350 mgKOH / g, when it is an aliphatic polyester polyol. That is, the polyester polyol (a2) preferably contains an aliphatic polyester polyol having a hydroxyl value of 100 to 400 mgKOH / g (more preferably 100 to 350 mgKOH / g). The hydroxyl value of the polyester polyol (a2) is preferably 250 mgKOH / g or less, more preferably 100 to 230 mgKOH / g, when it is an aromatic polyester polyol. That is, the polyester polyol (a2) preferably contains an aromatic polyester polyol having a hydroxyl value of 100 to 250 mgKOH / g (more preferably 100 to 230 mgKOH / g). Aromatic polyester polyols have a more rigid molecular structure than aliphatic polyester polyols, so by using one with a smaller hydroxyl value, it is easier to prevent the polyol from becoming brittle after curing, and the effect of improving ground improvement can be enhanced.

[0030] The polyol (a) may or may not contain a polyol other than the ether-based polyol (a1) and the polyester polyol (a2). Specifically, the total amount of the ether-based polyol (a1) and the polyester polyol (a2) in the polyol (a) is 50% by mass or more. That is, the total content of the ether-based polyol (a1) and the polyester polyol (a2) is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass, based on 100% by mass of the polyol (a).

[0031] The polyols other than the ether polyol (a1) and the polyester polyol (a2) are not particularly limited, and examples thereof include ether polyols other than (a1), polyester polyols other than (a2), and polyols containing neither an ether bond nor an ester bond. The polyols containing neither an ether bond nor an ester bond are not particularly limited, and examples thereof include alkanediols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, and nonanediol, and alkanetriols such as glycerin. These may be used alone or in combination of two or more.

[0032] The content of the ether polyol (a1) in the polyol (a) is not particularly limited and may be, for example, 5 to 95 mass%, 10 to 85 mass%, 15 to 80 mass%, or 20 to 75 mass%. The content of the polyester polyol (a2) in the polyol (a) is not particularly limited and may be, for example, 5 to 95 mass%, 10 to 85 mass%, 15 to 80 mass%, or 20 to 75 mass%. The content of the alkanediol and / or alkanetriol in the polyol (a) is not particularly limited and may be, for example, 0 to 50 mass%, 0 to 30 mass%, or 0 to 10 mass%, and in one embodiment, may be 5 mass% or more.

[0033] The content of ether-based polyol (a1) in component (A) (i.e., the content of (a1) relative to 100% by mass of component (A)) is preferably 1 to 60% by mass, more preferably 2 to 57% by mass, more preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass. The content of polyester polyol (a2) in component (A) is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, more preferably 10 to 55% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass.

[0034] In the polyol (a), the mass ratio (a2) / (a1) of the polyester polyol (a2) to the ether polyol (a1) is not particularly limited and may be, for example, 0.1 to 15, 0.1 to 4.0, 0.15 to 3.3, 0.2 to 3.0, 0.3 to 2.5, 0.4 to 2.0, or 0.5 to 1.6. When the mass ratio (a2) / (a1) is 0.1 or more, embrittlement after curing is suppressed, and ground improvement properties are easily improved. When the mass ratio (a2) / (a1) is 15 or less, strength after curing is increased, and ground improvement properties are easily improved.

[0035] (Amine compound (b)) Component (A) contains an amine compound (b) having a primary amino group and / or a secondary amino group as an active hydrogen compound. The amine compound (b) may have a primary amino group, a secondary amino group, or both a primary amino group and a secondary amino group. The amine compound (b) acts as a modifier, and the inclusion of the amine compound (b) can increase reactivity, improve water-stopping properties, and reduce the amount of nonionic surfactant detected. Note that even if the amine compound (b) has multiple hydroxyl groups in its molecule, it is not included in the polyol (a).

[0036] Examples of the amine compound (b) include aliphatic monoamines, alicyclic monoamines, aromatic monoamines, heterocyclic monoamines, aliphatic diamines, alicyclic diamines, aromatic diamines, aliphatic triamines, alicyclic triamines, aromatic triamines, and hydrazine.

[0037] Examples of aliphatic monoamines include alkyl monoamines such as monomethylamine, monoethylamine, monobutylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, methylethylamine, methylpropylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, and bis(2-ethylhexyl)amine; and alkanol monoamines such as monoethanolamine, diethanolamine, and diisopropanolamine.

[0038] Examples of alicyclic monoamines include cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, and dicyclohexylamine.

[0039] Examples of aromatic monoamines include N-methylbenzylamine, dibenzylamine, benzylamine, and p-methylbenzylamine.

[0040] Examples of heterocyclic monoamines include morpholine, pyrrolidine, piperidine, and pyrazole.

[0041] Examples of aliphatic diamines include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, neopentanediamine, polyetherdiamine, etc. Here, polyetherdiamines are compounds obtained by converting hydroxyl groups of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc., into primary amino groups, and are also called polyoxyalkylenediamines.

[0042] Examples of the alicyclic diamine include 4,4'-diaminocyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo[2,2,1]heptane, and diaminocyclohexane.

[0043] Examples of aromatic diamines include diaminodiphenylmethane, diaminodiphenyl ether, xylylenediamine, phenylenediamine, diethyltoluenediamine (e.g., 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene), and 4,4′-methylenebis[N-(1-methylpropyl)aniline].

[0044] Examples of aliphatic triamines include diethylenetriamine, polyethertriamine, etc. Here, polyethertriamine is a compound obtained by converting the hydroxyl groups of polyoxyalkylenetriols obtained by addition polymerization of propylene oxide and / or ethylene oxide to glycerin, trimethylolpropane, or the like, into primary amino groups, and is also called polyoxyalkylenetriamine.

[0045] Examples of alicyclic triamines include 1,3,5-tris(aminomethyl)cyclohexane, etc. Examples of aromatic triamines include 1,3,5-tris(aminomethyl)benzene, etc.

[0046] These amine compounds (b) may be used either alone or in combination of two or more.

[0047] In one embodiment, the amine compound (b) preferably contains a primary amine (b1) having a primary amino group, more preferably contains a primary diamine (b2), and even more preferably contains an aliphatic primary diamine and / or an aromatic primary diamine (b3). A secondary amine having a secondary amino group may be used in combination with the primary amine (b1).

[0048] The content of amine compound (b) in component (A) (i.e., the amount of (b) relative to 100% by mass of component (A)) is preferably 1 to 30% by mass, more preferably 1.5 to 25% by mass, more preferably 2.0 to 20% by mass, more preferably 2.5 to 15% by mass, and even more preferably 3.0 to 10% by mass. When the content of amine compound (b) is 1% by mass or more, the water-stopping properties can be improved and the effect of reducing the amount of nonionic surfactant detected can be enhanced. When the content of amine compound (b) is 30% by mass or less, the load on mixer bolts and the like during construction can be reduced.

[0049] In one embodiment, the content of the primary amine (b1) (preferably a primary diamine (b2), more preferably an aliphatic primary diamine and / or an aromatic primary diamine (b3)) in the component (A) is preferably 1.0 to 15 mass%, more preferably 2.0 to 10 mass%.

[0050] The amount of the amine compound (b) relative to 100 parts by mass of the polyol (a) is not particularly limited, and may be, for example, 5 to 55 parts by mass, 6 to 40 parts by mass, 7 to 20 parts by mass, or 8 to 15 parts by mass.

[0051] (Catalyst (c)) Component (A) contains a catalyst (c) to promote the reaction between polyol (a) and isocyanate. Examples of catalyst (c) include tertiary amine catalysts, fatty acid alkali metal salts, and quaternary ammonium salts. Among these, tertiary amine catalysts are preferred. In one embodiment, catalyst (c) may contain a tertiary amine catalyst, a fatty acid alkali metal salt, and / or a quaternary ammonium salt.

[0052] Examples of tertiary amine catalysts include triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, bis-(dimethylaminoethyl)ether, N,N',N''-tris(dialkylaminoalkyl)-s-hexahydrotriazine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, and N,N,N-tris(3-dimethylaminopropyl)amine, which can be used alone or in combination of two or more.

[0053] Examples of fatty acid alkali metal salts include alkali metal salts of acetic acid or octylic acid, which are trimerization catalysts. The carbon number of the fatty acid constituting the fatty acid alkali metal salt may be 1 to 10. Specific examples of fatty acid alkali metal salts include potassium acetate and potassium octylate, and either one or both may be used in combination.

[0054] As the quaternary ammonium salt, for example, commercially available trimerization catalysts can be used, such as Kaolizer No. 410 and Kaolizer No. 420 (manufactured by Kao Corporation), TOYOCAT-TR20, and TOYOCAT-TRX (manufactured by Tosoh Corporation).

[0055] The amount of catalyst (c) (preferably a tertiary amine catalyst) is not particularly limited, but is preferably 0.05 to 10 mass %, more preferably 0.1 to 8.0 mass %, more preferably 0.1 to 5.0 mass %, and even more preferably 0.1 to 3.0 mass %, relative to 100 mass % of component (A).

[0056] (Flame retardant (d)) A flame retardant (d) is blended with component (A). This imparts flame retardancy to the cured product. There are no particular limitations on the flame retardant (d), and either an additive-type or a reactive-type flame retardant may be used. Preferably, an additive-type flame retardant is used.

[0057] Specific examples of additive flame retardants include phosphate ester flame retardants such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, tris(chloropropyl) phosphate, and tris(tribromoneopentyl) phosphate, and halogen-containing flame retardants such as chlorinated paraffin, pentabromoethylbenzene, and decabromodiphenyl ether. These may be used alone or in combination of two or more.

[0058] Specific examples of reactive flame retardants include halogen-containing, phosphorus-containing compounds having a hydroxyl group or an amino group, such as dibromoneopentyl glycol, tetrabromobisphenol A, O,O-diethyl N,N-dihydroxyethylaminomethylphosphonate, and various phosphorus-containing polyols.

[0059] Among these, it is preferable to use a phosphate ester flame retardant as the flame retardant (d).

[0060] The amount of flame retardant (d) (preferably a phosphate ester-based flame retardant) is not particularly limited, and may be, for example, 5 to 50 mass %, 10 to 45 mass %, or 15 to 40 mass % relative to 100 mass % of component (A).

[0061] (Other ingredients) In addition to the components described above, known additives such as foaming agents, silicone-based foam stabilizers, diluents, pigments, inorganic fillers, crosslinking agents, and coupling agents may be added to component (A) as needed, provided that the object of the present embodiment is not impaired.

[0062] An example of a blowing agent is water. Water acts as a blowing agent by reacting with the isocyanate of component (B) to generate carbon dioxide gas. When added, the amount of water is not particularly limited, but may be 0.2 to 5.0 mass%, 0.3 to 3.0 mass%, or 0.5 to 2.0 mass% relative to 100 mass% of component (A). In one embodiment, component (A) is preferably substantially free of water. "Substantially free of water" means that the amount of water is 1.0 mass% or less, preferably 0.5 mass% or less, and more preferably 0.3 mass% or less, relative to 100 mass% of component (A).

[0063] An example of a silicone foam stabilizer is polyoxyalkylenedimethylpolysiloxane copolymer, which is commonly used in rigid urethane foam resins.

[0064] Examples of diluents include phthalates such as dibutyl phthalate, dioctyl phthalate, and diisononyl phthalate; adipates such as dibutyl adipate, dioctyl adipate, diisononyl adipate, and bis(2-(2-butoxyethoxy)ethyl)adipate; and trimellitates such as tri(2-ethylhexyl) trimellitate.

[0065] [(B) Component] The component (B) is a component containing an isocyanate that reacts with the active hydrogen compound of the component (A), and in this embodiment, contains an aromatic polyisocyanate (B1).

[0066] (Aromatic polyisocyanate (B1)) Examples of the aromatic polyisocyanate (B1) include diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and modified products thereof. These may be used alone or in combination of two or more. Examples of the modified products include isocyanurate modified products, allophanate modified products, biuret modified products, adduct modified products, carbodiimide modified products, and dimers.

[0067] Among these, the aromatic polyisocyanate (B1) is preferably an MDI-based polyisocyanate (B2), that is, the aromatic polyisocyanate (B1) preferably contains at least one MDI-based polyisocyanate (B2) selected from the group consisting of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), and modified products thereof.

[0068] Diphenylmethane diisocyanate may be any of 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI, or any mixture thereof. Polymethylene polyphenyl polyisocyanate (polymeric MDI) is a polynuclear condensation product of diphenylmethane diisocyanate, and may be a mixture of the polynuclear condensation product and diphenylmethane diisocyanate (monomeric MDI).

[0069] The aromatic polyisocyanate (B1) preferably contains the above-mentioned MDI-based polyisocyanate (B2) (more preferably polymethylene polyphenyl polyisocyanate) in an amount of 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, and may even be 100% by mass.

[0070] Component (B) may contain an isocyanate other than the aromatic polyisocyanate (B1), such as an aliphatic polyisocyanate and / or an alicyclic polyisocyanate. The isocyanate contained in component (B) preferably contains aromatic polyisocyanate (B1) as a main component, and more preferably contains 70% by mass or more, more preferably 90% by mass or more, or may even contain 100% by mass of aromatic polyisocyanate (B1) per 100% by mass of isocyanate.

[0071] (Other ingredients) Component (B) may consist solely of isocyanate. Other components, such as the conventionally known additives described in the section on component (A), may be added to component (B) as needed, provided that the purpose of this embodiment is not impaired.

[0072] [Mixing of component (A) and component (B)] Components (A) and (B) are mixed at the time of use to form a cured product. The mixing ratio of components (A) and (B) is not particularly limited, but the reaction equivalent ratio between the isocyanate groups (NCO) in component (B) and the active hydrogen groups of the active hydrogen compound in component (A), i.e., NCO / active hydrogen groups, is preferably in the range of 1 / 5 to 5 / 1, more preferably 1 / 2 to 3 / 1, and even more preferably 2 / 3 to 2 / 1, and may even be 1 / 1 to 5 / 3. By keeping the reaction equivalent ratio within the above range, a cured product with appropriate strength can be obtained in an appropriate curing time.

[0073] [Consolidation method of natural ground] The ground consolidation agent according to this embodiment is used, for example, to stabilize and strengthen rock masses with fractured zones or unstable soft ground during tunnel excavation, and can consolidate the ground by mixing component (A) and component (B) and injecting the mixture into the rock mass or ground.

[0074] The method for this injection and consolidation is not particularly limited, and any known method can be used. For example, it is preferable that the method includes the steps of drilling a plurality of holes at predetermined intervals in the rock mass or ground, inserting hollow bolts into the holes, and injecting the rock mass or ground consolidation agent through the openings of the bolts to consolidate the rock mass or ground.

[0075] To give one example, components (A) and (B) are placed in separate tanks using a pump that can control the injection amount, pressure, and mixing ratio of components (A) and (B). A perforated rock bolt or injection rod equipped with a pre-fixed static mixer and check valve is inserted into the tunnel face or roof, which is made of sandy soil that is difficult to penetrate. Components (A) and (B) from the tank are injected into this at an injection pressure of 0.05 to 5 MPa, and the uniformly mixed components (A) and (B) are allowed to penetrate and harden into the natural ground through the static mixer. This allows the natural ground to be consolidated and stabilized.

[0076] The ground consolidation agent composed of the above-mentioned components (A) and (B) has excellent hardening properties and can stop large amounts of water leakage and seepage. Therefore, the ground consolidation agent of this embodiment may be used for stabilizing and strengthening soil and for water sealing. Furthermore, the ground consolidation agent reduces the amount of nonionic surfactant detected under flowing water, thereby reducing the adverse effects on water quality. [Example]

[0077] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0078] <Raw materials used> [Component (A)] (Polyol (a)) (a1): Ether polyols and their comparative raw materials: Tripropylene glycol: Functionality 2.0, hydroxyl value 584 mg KOH / g Dipropylene glycol: Functionality 2.0, hydroxyl value 836 mg KOH / g PA-400: Aromatic polyether polyol, "Polyhardener PA-400" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., functionality 2.0, hydroxyl value 420 mg KOH / g Diethylene glycol: Functionality 2.0, hydroxyl value 1057 mg KOH / g G-480: Aliphatic polyether polyol, "DK Polyol G-480" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., functionality 3.0, hydroxyl value 480 mg KOH / g (comparison material) 420: Aliphatic polyether polyol, AGC Corporation's "Exenol 420", functionality 2.0, hydroxyl value 280 mg KOH / g (comparison material)

[0079] (a2): Polyester polyols and their comparative raw materials: RFK-556: "Maximol RFK-556" manufactured by Air Water Performance Chemicals Inc. Contains 95% by mass of aromatic polyester polyol (functionality 2.0, hydroxyl value 208 mg KOH / g) obtained from polycarboxylic acids and polyhydric alcohols, and 5% by mass of unreacted diethylene glycol. RDK-133: "Maximol RDK-133" manufactured by Air Water Performance Chemicals Inc. Contains 80% by mass of aromatic polyester polyol (functionality 2.0, hydroxyl value 130 mg KOH / g) obtained from polycarboxylic acids and polyhydric alcohols, and 20% by mass of unreacted diethylene glycol. RDK-142: "Maximol RDK-142" manufactured by Air Water Performance Chemicals Inc. Contains 70% by mass of aromatic polyester polyol (functionality 2.0, hydroxyl value 118 mg KOH / g) obtained from polycarboxylic acids and polyhydric alcohols, and 30% by mass of unreacted diethylene glycol. Castor oil: "Castor Oil D" manufactured by Ito Oil Mills, functional group number 2.7, hydroxyl value 161 mg KOH / g H-81: "URIC H-81" manufactured by Ito Oil Mills, castor oil-based aliphatic polyester polyol, functionality 3, hydroxyl value 340 mg KOH / g P-1010: Aliphatic polyester polyol, Kuraray Co., Ltd. "Kuraray Polyol P-1010", functionality 2.0, hydroxyl value 112 mg KOH / g P-2010: Aliphatic polyester polyol, Kuraray Co., Ltd. "Kuraray Polyol P-2010", functionality 2.0, hydroxyl value 56 mg KOH / g (comparison material)

[0080] Other polyols: Octanediol: 2-ethyl-1,3-hexanediol, "Octanediol" manufactured by KH Neochem Co., Ltd., functionality 2.0, hydroxyl value 768 mg KOH / g

[0081] (Amine compound (b)) Diethyltoluenediamine: "DETDA80" manufactured by Lonza Japan Co., Ltd., functional group number 2.0, amine value 630 mg KOH / g Polyether diamine: "Polyetheramine D-230" manufactured by Mitsui Fine Chemicals, Inc., functional group number 2.0, amine value 488 mg KOH / g Secondary diamine: 4,4'-methylenebis[N-(1-methylpropyl)aniline], "Ethacure 420" manufactured by Mitsui Chemicals Fine Co., Ltd., functional group number 2.0, amine value 361 mg KOH / g

[0082] (Catalyst (c)) Tertiary amine catalyst: N,N,N-tris(3-dimethylaminopropyl)amine, EVONIK "PolyCat 9" Trimerization catalyst 1: "DABCO K15" manufactured by Evonik Japan Co., Ltd., containing 75% by mass of potassium octoate and 25% by mass of diethylene glycol. Trimerization catalyst 2: Kao Corporation's "Kaolizer No. 420", quaternary ammonium salt

[0083] (Flame retardant) TMCPP: Tris(chloropropyl)phosphate, "TMCPP" manufactured by Daihachi Chemical Industry Co., Ltd. TCP: Tricresyl phosphate, "TCP" manufactured by Daihachi Chemical Industry Co., Ltd.

[0084] [Component (B)] (Isocyanate) · MR-200: Polymeric MDI, "Millionate MR-200" manufactured by Tosoh Corporation · MR-400: Polymeric MDI, "Millionate MR-400" manufactured by Tosoh Corporation · 376N: Isocyanurate-modified pentamethylene diisocyanate (PDI), "Stabio 376N" manufactured by Mitsui Chemicals, Inc.

[0085] [Preparation of Liquid A and Liquid B] A liquid composed of component (A) is designated as Liquid A, and a liquid composed of component (B) is designated as Liquid B. Liquid A and Liquid B were respectively prepared by appropriately mixing the raw materials according to the formulations (parts by mass) described in Tables 1 to 6 below.

[0086] The parts by weight of each component in the table represent the amount of each component as a raw material. Therefore, the parts by weight in the table for "RFK-556," "RDK-133," and "RDK-142" represent the amount of each product, i.e., the total amount of polyester polyol and diethylene glycol contained in the product. Meanwhile, the "mass ratio (a2) / (a1)" in the table represents the mass ratio of polyester polyol (a2) to ether polyol (a1) actually contained in Solution A. Therefore, in the examples and comparative examples using these products, the amount of polyester polyol (a2) is calculated by subtracting the amount of diethylene glycol from the amount of each product, and the amount of ether polyol (a1) is calculated by adding the amount of diethylene glycol subtracted from the amount of each product, resulting in the value of (a2) / (a1). For example, in Example 1, the amount of "RFK-556" is 29.0 parts by weight, of which 27.55 parts by weight represents the amount of polyester polyol (a2), and the remaining 1.45 parts by weight represents the amount of diethylene glycol. Therefore, the amount of ether-based polyol (a1) is 36.45 parts by mass, which is 35.0 parts by mass of tripropylene glycol plus 1.45 parts by mass, and therefore (a2) / (a1) is 27.55 / 36.45, which is rounded to one decimal place to 0.8. The same applies to the mass ratios in the table: "{(a1) + (a2)} / (a) × 100," "(a1) / (a) × 100," "(a2) / (a) × 100," "(a1) / (A) × 100," and "(a2) / (A) × 100," and these are calculated using the amounts of polyester polyol (a2) and ether-based polyol (a1) actually contained in Solution A.

[0087] The parts by mass in the table for "Trimerization catalyst 1" are also the amount of the product, and are the total amount of potassium octoate and diethylene glycol solvent contained in the product. Therefore, for each mass ratio in the table, the amount of ether polyol (a1) is the sum of the amount of diethylene glycol contained in trimerization catalyst 1.

[0088] The "equivalent ratio (NCO / active hydrogen group)" in the table is the reaction equivalent ratio between the isocyanate group (NCO) in component (B) and the active hydrogen group of the active hydrogen compound in component (A).

[0089] <Evaluation> [Curing time, foaming ratio] Liquids A and B were mixed by hand at a liquid temperature of 20°C, and the curing time (the time it takes for curing to progress and stringiness to begin) was measured when no blowing agent was added, and the curing time (the time from the start of mixing to the completion of foaming) was measured when a blowing agent was added. After the curing reaction was completed, the volume of the cured product was divided by the initial volume of the raw materials, Liquids A and B, to calculate the expansion ratio.

[0090] [Detected amount of nonionic surfactants] A 2L plastic cup was filled with 900g of 20°C water and stirred with a mixer to simulate running water. 60g of 20°C solution A and 60g of solution B were hand-mixed and the mixture was poured into the running water. After the mixture hardened, a sample was taken of the running water and the amount of nonionic surfactant detected was measured according to the Water Supply Act, Appendix 28, solid-phase extraction-spectrophotometric method. The detected amount was rated as "A" if it was less than 1 mg / L, "B" if it was 1 mg / L or more but less than 10 mg / L, and "C" if it was 10 mg / L or more.

[0091] [Waterproof] Crushed stone was packed into an acrylic cylinder (inner diameter / outer diameter = φ44mm / φ48mm, length = 300mm), and water was run through one side of the cylinder at 2L / min to recreate simulated natural ground. A hole was drilled in the middle of the cylinder, and 50mL of a mixture of liquids A and B was injected into the simulated natural ground through the hole using a syringe. After injection, the ability to stop water leakage and the length of the resin filling were checked. Cases where water could be stopped and the filling length was 100 mm or less were rated "A", cases where water could be stopped and the filling length was more than 100 mm but less than 200 mm were rated "B", and cases where water could not be stopped were rated "C".

[0092] [Ground improvement] Liquid A, liquid B, and No. 7 silica sand were mixed in a 50 / 50 / 30 (mass ratio) to create a sand gel (φ50mm x height 100mm), which simulated the natural ground being solidified with a chemical solution. The sand gel was compressed in accordance with JIS K 7220:2006 "Rigid foam plastics - Determination of compression". When compressed, the sand gel did not break and the compressive strength was 20N / mm 2 The above cases are classified as "A", and no breakage and 10N / mm 2 Super 20N / mm 2 If it is less than 10N / mm, it is marked "B"; if there is a break or 2 The following cases were rated as "C".

[0093] [Table 1]

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] [Table 5]

[0098] [Table 6]

[0099] The results are shown in Tables 1 to 6. Comparative Example 1 used an ether polyol with a functionality of 3.0, and a large amount of nonionic surfactant was detected. Comparative Example 2 used an ether polyol with a hydroxyl value smaller than the set value, and the water-stopping properties and ground improvement properties were poor, and a large amount of nonionic surfactant was detected. Comparative Example 3 used a polyester polyol with a hydroxyl value smaller than the set value, and the water-stopping properties and ground improvement properties were poor.

[0100] Comparative Example 4 is an example in which no ether polyol was blended, and was inferior in water-stopping properties and ground improvement properties. Comparative Example 5 is an example in which no polyester polyol was blended, and was inferior in ground improvement properties. Comparative Example 6 is an example in which an ether polyol with a low hydroxyl value was blended instead of polyester polyol (a2), and although the ground improvement properties were improved compared to Comparative Example 5, the amount of nonionic surfactant detected was increased.

[0101] In Comparative Examples 7 and 8, the amount of ether-based polyol (a1) in the ether-based polyol was small, and the amount of nonionic surfactant detected was large. Comparative Example 9, which does not contain the amine compound (b) as a modifier, was poor in water-stopping properties and the amount of nonionic surfactant detected was large. Comparative Example 10, which uses an aliphatic polyisocyanate instead of an aromatic polyisocyanate, was poor in water-stopping properties and ground improvement properties, and the amount of nonionic surfactant detected was large.

[0102] In contrast, Examples 1 to 27 according to this embodiment, which used an ether-based polyol (a1) and a polyester polyol (a2), showed low levels of nonionic surfactants, good water-stopping properties, and excellent rock mass improvement properties, demonstrating excellent performance as a rock mass consolidation agent. Examples 1 to 4 used ether-based polyols (a1) with different hydroxyl values, while Examples 5 to 9 used polyester polyols (a2) with different hydroxyl values ​​or different types (aromatic and aliphatic), and Examples 10 to 12 varied the amounts of (a1) and (a2). Example 13 varied the type of amine compound (b) used as a modifier, and Examples 14 to 16 varied the amount and type of amine compound (b). Example 17 varied the type of flame retardant (d), Example 18 added water as a blowing agent, and Example 19 varied the type of isocyanate. Examples 20 and 21 used other polyols in addition to the ether-based polyol (a1) and polyester polyol (a2). In Examples 22, 23, and 25 to 27, a fatty acid alkali metal salt or a quaternary ammonium salt was used in combination with a tertiary amine catalyst as catalyst (c).

[0103] The various numerical ranges described in this specification can be arbitrarily combined with their upper and lower limits, and all such combinations are considered to be preferred numerical ranges described in this specification. Furthermore, a numerical range described as "X to Y" means from X to Y.

[0104] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their omissions, substitutions, modifications, etc. are included within the scope and spirit of the invention, as well as within the scope of the invention described in the claims and their equivalents.

Claims

1. a component (A) including a polyol (a), an amine compound (b) having a primary amino group and / or a secondary amino group, a catalyst (c), and a flame retardant (d); and a component (B) containing an aromatic polyisocyanate, the polyol (a) comprises an ether-based polyol (a1) having a functionality of 1.5 to 2.5 and a hydroxyl value of 400 to 1100 mgKOH / g, and a polyester polyol (a2) having a hydroxyl value of 100 to 400 mgKOH / g; the ether-based polyol (a1) accounts for 90 mass% or more of the ether-based polyol contained in the polyol (a), the total amount of the ether-based polyol (a1) and the polyester polyol (a2) in the polyol (a) is 50% by mass or more; Ground consolidation agent.

2. The content of the ether-based polyol (a1) in the polyol (a) is 5 to 95% by mass, and the content of the polyester polyol (a2) in the polyol (a) is 5 to 95% by mass. The ground consolidation agent according to claim 1.

3. 2. The ground consolidation agent according to claim 1, wherein the content of the amine compound (b) in the component (A) is 1 to 30 mass%.

4. The rock consolidation agent according to claim 1, wherein the aromatic polyisocyanate comprises at least one selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and modified products thereof.

5. drilling a plurality of holes at predetermined intervals in the rock or ground; inserting a hollow bolt into the hole; and A step of injecting the ground consolidation agent according to any one of claims 1 to 4 into the rock mass or ground through the opening of the bolt to consolidate it. A method for consolidating ground, including:

Images