Ground grouting liquid composition, foam and method for producing same

Abstract

To provide a chemical liquid composition for injection into soil capable of forming an expanded body stably, and acquiring the expanded body having sufficient strength, the expanded body and a production method of the same.SOLUTION: A chemical liquid composition for injection into soil is formed of two kinds of liquid that are A liquid and B liquid. The A liquid includes: a water soluble silicate; polyol; and a catalyst. The B liquid includes polyisocyanate, and includes, as catalysts, two kinds of tertiary amines which are a first tertiary amine and a second tertiary amine. The first tertiary amine is tetramethyl-hexamnethylene diamine, and the second tertiary amine is a tertiary amine whose molecular weight is 80-400. The polyol is polyether polyol whose number average molecular weight is greater than 200, and the content of the polyol is, with respect to the whole A liquid, 10 mass% or less. An expanded body is obtained by mixing the A liquid and the B liquid forming the chemical liquid composition for injection into soil. A production method of the expanded body forms the expanded body by mixing the A liquid and the B liquid forming the chemical liquid composition for injection into soil.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a ground grouting liquid composition, a foam, and a method for producing the same, and more particularly to a ground grouting liquid composition using a silicate and a polyisocyanurate, a foam, and a method for producing the same. [Background technology]

[0002] Conventionally, foamed urethane grout has been known as a grout material used for ground improvement, filling cavity spaces in structures, etc. Foamed urethane grout, a reaction product, is essentially an organic material obtained by reacting polyol with polyisocyanate, so it requires the addition of a flame retardant to achieve high flame retardancy. Another problem with foamed urethane grout is the high cost of its raw materials. In contrast to this, composite grout is known, which is obtained as a composite reaction product of inorganic and organic materials, in which part of the polyol is replaced with water glass (aqueous silicate solution), which is an inorganic material. Composite grout contains inorganic material in the aggregate, so it has superior fire retardancy compared to grout made only of organic aggregate. Composite grout also has the advantage of low raw material costs. Technology related to such composite grout is known from Patent Document 1 below. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-233926 Summary of the Invention [Problem to be solved by the invention]

[0004] The above-mentioned Patent Document 1 discloses a method for producing a urea-based foam (Patent Document 1 [Claim 1]) by mixing Liquid A, which is composed of at least water and a catalyst, with Liquid B, which contains a polyfunctional isocyanate and a silicone-based surfactant, with the aim of improving the uniformity of the foam, optimizing the expansion ratio, controlling the reaction, and improving penetration into wood / soil (Patent Document 1

[0003] ). However, it is not easy to stably form a foam and obtain a foam having sufficient strength from a composition containing a high content of water-soluble silicate.

[0005] The present invention has been made in consideration of the above-mentioned situation, and aims to provide a chemical composition for ground injection that can stably form a foam and obtain a foam having sufficient strength, a foam, and a method for producing the same. [Means for solving the problem]

[0006] That is, the present invention is as follows. [1] A chemical composition for ground grouting consisting of two chemical liquids, liquid A and liquid B, The solution A contains a water-soluble silicate, a polyol, and a catalyst, The liquid B contains a polyisocyanate, The catalyst includes two types of tertiary amines, namely, a first tertiary amine and a second tertiary amine, the first tertiary amine is tetramethylhexamethylenediamine; the second tertiary amine is a tertiary amine other than the first tertiary amine and has a molecular weight of 80 to 400; The liquid composition for ground grouting, wherein the polyol is a polyether polyol having a number average molecular weight of more than 200, and the content of the polyol in the liquid A is 10 mass % or less based on the total mass of the liquid A. [2] The chemical composition for ground grouting described in [1] above, wherein the second tertiary amine has a heterocycle in which the nitrogen atom constituting the tertiary amino group is a heteroatom. [3] The second tertiary amine is a tertiary amine having a heterocycle and a tertiary amine not having a ring structure. [1] or [2] The composition for ground injection described above. [4] A ground grouting liquid composition according to any one of [1] to [3] above, wherein the proportion of the first tertiary amine is more than 50% by mass when the total of the first tertiary amine and the second tertiary amine is 100% by mass. [5] A foam obtained by mixing the liquid A and the liquid B that constitute the liquid composition for ground grouting described in any one of [1] to [4] above. [6] A method for producing a foam, comprising mixing the liquid A and the liquid B that constitute the liquid composition for ground injection described in any one of [1] to [4] above to form a foam. [Effects of the Invention]

[0007] According to the liquid grouting composition for ground injection of the present invention, a foam can be stably formed and a foam having sufficient strength can be obtained. The foam of the present invention can provide sufficient strength. According to the foam production method of the present invention, foams having sufficient strength can be stably obtained. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described below based on specific embodiments. However, the present invention is not limited to these embodiments. These embodiments are merely examples shown for the convenience of explanation, and the present invention is not limited to these in any sense. The present invention can be modified in various ways depending on the purpose and application. Furthermore, all publications, patents, and patent applications cited in this specification are incorporated herein by reference in their entirety. In addition, in this specification, the expression "XX to YY" means "XX or more and YY or less." Furthermore, for the compounds exemplified in this specification, a CAS registry number may be written in addition to a part of the compound name, which may have multiple notations. However, since CAS registry numbers vary depending on isomers, etc., this is merely an example of the compound name written in addition, and does not mean that there is a one-to-one correspondence between the compound name and the CAS registry number.

[0009] [1] Ground grouting liquid composition The liquid chemical composition for ground grouting of the present invention (hereinafter also simply referred to as "the composition") is composed of two liquid chemicals, liquid A and liquid B, Solution A contains a water-soluble silicate, a polyol, and a catalyst, Liquid B contains polyisocyanate, The catalyst contains two types of tertiary amines, namely, a first tertiary amine (hereinafter also referred to as "primary-tertiary amine") and a second tertiary amine (hereinafter also referred to as "second-tertiary amine"), the first tertiary amine is tetramethylhexamethylenediamine; the second tertiary amine is a tertiary amine other than the first tertiary amine and has a molecular weight of 80 to 400; The polyol is a polyether polyol having a number average molecular weight of more than 200, and is contained in the entire solution A in an amount of 10% by mass or less.

[0010] [1]Liquid A Solution A contains a "water-soluble silicate," a "polyol," and a "catalyst."

[0011] (1) Water-soluble silicate The water-soluble silicate is a silicate compound that exhibits water solubility, and includes what is generally called water glass. Metasilicates, orthosilicates, etc. can also be used if they are water-soluble. The type of cation constituting the water-soluble silicate is not limited, but examples include monovalent alkali metal ions (Li ions, Na ions, K ions, etc.), ammonium ions, etc. That is, examples of water-soluble silicates include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, etc. These may be used alone or in combination of two or more. In the present invention, among the above, sodium silicate (sodium silicate) is preferred because it is inexpensive and easily available.

[0012] Sodium silicate can generally be expressed as Na2O·nSiO2, and among these, water-soluble sodium silicate usually has n > 1, and n in the water-soluble sodium silicate used in the present invention is preferably 2.0 to 4.0. Within this range, storage stability is excellent and low-temperature solidification can be suppressed. Furthermore, when preparing Solution A, the water-soluble silicate is usually blended as its aqueous solution (hereinafter simply referred to as "silicate aqueous solution"). The silicate aqueous solution may be prepared as appropriate and used, but since it is also commercially available as a silicate aqueous solution (sodium silicate aqueous solution), sodium silicate, water glass, etc., these commercially available products can be used. As for sodium silicate, sodium silicate No. 1, No. 2, No. 3, etc., as specified in the JIS standard (JIS K1408) can be used. These can be used alone or in combination of two or more types. Furthermore, those formulated in accordance with this JIS standard, such as No. 4, No. 5, No. 1.5, No. 2.5, etc., can be used. These can be used alone or in combination of two or more types. The solid content of the aqueous silicate solution is not limited, but from the viewpoint of the stability and solidification characteristics of Solution A, it is preferably 20 to 60 mass % and more preferably 30 to 50 mass % based on the total silicate solution.

[0013] The amount of water-soluble silicate contained in Solution A is not limited. When the total amount of Solution A is taken as 100% by mass, the total amount of the water-soluble silicate and water is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 88% by mass or more, and particularly preferably 89% by mass or more. Meanwhile, this content is typically 99.99% by mass or less, more preferably 99.8% by mass or less, even more preferably 99.6% by mass or less, and particularly preferably 99.4% by mass or less. These upper and lower limits can be arbitrarily combined. That is, for example, it can be 80 to 99.99% by mass, 85 to 99.8% by mass, 88 to 99.6% by mass, or 89 to 99.4% by mass. The water mentioned above refers to the total amount of water contained in Solution A. In other words, when the water-soluble silicate is used as an aqueous solution (i.e., water glass), the water content here refers to the sum of the amount of water contained in the aqueous solution, the amount of water contained in other additives, and the amount of water added as water.

[0014] (2) Polyol The polyol is a polyether polyol having a number average molecular weight (hereinafter simply referred to as "Mn") of more than 200. If the number average molecular weight of the polyol is 200 or less, the foaming stability deteriorates, resulting in non-uniform foaming and insufficient foam height and strength. In the present composition, by using a polyether polyol having an Mn > 200, it is possible to obtain a good foam with higher foaming stability than when other polyols are used.

[0015] The type of polyether polyol is not limited, but examples include (1) a reaction product obtained by an addition reaction of an alkylene oxide with a compound having two or more active hydrogen atoms as an initiator, (2) a Mannich condensation product obtained by reacting a phenol, an aldehyde, and a secondary amine, and (3) a Mannich polyether polyol obtained by adding an alkylene oxide to the Mannich condensation product, etc. These may be used alone or in combination of two or more. In addition, examples of the compound having two or more active hydrogens in the above (1) include polyhydric alcohols, amine compounds, and the like. Only one of these may be used, or two or more thereof may be used in combination. Among these, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, butylene glycol, pentamethylene glycol, hexamethylene glycol, butanediol, glycerin, trimethylolpropane, pentaerythritol, and the like. Only one of these may be used, or two or more thereof may be used in combination. Further, examples of the amine compound include diamines such as ethylenediamine, toluenediamine, and tolylenediamine; alkanolamines such as ethanolamine and diethanolamine, and the like. Only one of these may be used, or two or more thereof may be used in combination. Furthermore, examples of the above alkylene oxide include ethylene oxide and propylene oxide, and the like. Only one of these may be used, or two or more thereof may be used in combination.

[0016] The Mn of the polyether polyol only needs to exceed 200, but more preferably 250 or more, still more preferably 300 or more, and even more preferably 350 or more. On the other hand, the Mn of the polyether polyol is preferably 10,000 or less, more preferably 7,000 or less, still more preferably 5,000 or less, and particularly preferably 2,500 or less. These upper and lower limit values can be arbitrarily combined. That is, for example, the Mn of the polyether polyol can be set to 200 < Mn ≤ 10,000, 250 < Mn ≤ 7,000, 300 < Mn ≤ 5,000, or 350 < Mn ≤ 2,500. In addition, in this composition, two or more polyether polyols having different Mn values can be used in combination. In addition, the number average molecular weight of the polyether polyol can be measured according to JIS K7252-2 or calculated from the hydroxyl value.

[0017] Furthermore, when a polyether polyol is contained in Solution A, its content is not limited, but when the entire Solution A is taken as 100% by mass, the content of the polyether polyol is 10% by mass or less. When the content of the polyether polyol is 10% by mass or less, strength (including compressive strength and flexural strength) can be improved compared to when the content of the polyether polyol is more than 10% by mass. The content of the polyether polyol is more preferably 9% by mass or less, even more preferably 8% by mass or less, and particularly preferably 7.5% by mass or less. On the other hand, the content of the polyether polyol is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more. These upper and lower limits can be combined arbitrarily. That is, for example, the content of polyether polyol can be 0.1 to 10 mass%, 0.5 to 9 mass%, 1.0 to 8 mass%, or 1.5 to 7.5 mass%, when the entire A solution is taken as 100 mass%.

[0018] The composition may contain no other polyols than the polyether polyol, but may contain other polyols. When other polyols are contained, it is preferable to limit the amount of the other polyols to 20% by mass or less (more than 0 mass) when the total amount of polyols (the sum of the polyether polyol and the other polyols) is taken as 100% by mass.

[0019] The type of other polyol is not limited, and polyols other than polyether polyols that have been used as components of conventional ground grouting compositions can be used as appropriate. Examples of other polyols include aliphatic polyols, polyester polyols, polycarbonate polyols, olefin polyols, acrylic polyols, and siloxane polyols. These may be used alone or in combination of two or more.

[0020] Examples of aliphatic polyols include compounds having two hydroxy groups such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, dialkylpropanediol, tetramethylenediol, hexamethylenediol, nonanediol, and methyloctanediol; compounds having three or more hydroxy groups such as glycerin, trimethylolpropane, and trimethylolethane; and sugar alcohols such as xylitol and sorbitol. These may be used alone or in combination of two or more.

[0021] Examples of polyester polyols include condensation polymers of aliphatic polyols and polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reaction products of three components: aliphatic polyols, polycarboxylic acids, and cyclic esters. These may be used alone or in combination of two or more. Examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid. Examples of cyclic esters include propiolactone, valerolactone, and caprolactone. These may be used alone or in combination of two or more.

[0022] (3) Catalyst The catalyst is a component that contributes as a catalyst when, after mixing of liquid A and liquid B, the components contained in liquid A and liquid B form a foam (solid foam), which is a reaction product. This composition contains two types of tertiary amines as catalysts: a "primary-tertiary amine" and a "secondary-tertiary amine."

[0023] (3-1) Primary to Tertiary Amines The primary to tertiary amine is tetramethylhexamethylenediamine, i.e., N,N,N',N'-tetramethyl-1,6-hexanediamine (molecular weight 172.32, CAS RN: 111-18-2). By using tetramethylhexamethylenediamine as the primary to tertiary amine, the stability of the resulting foam can be improved.

[0024] (3-2) Secondary and tertiary amines The secondary and tertiary amines are tertiary amines excluding primary and tertiary amines, and are tertiary amines having a molecular weight of 80 to 400. The combined use of primary and tertiary amines and tertiary amines having a molecular weight of 80 to 400 can improve the strength of the resulting foam. The molecular weight of the secondary and tertiary amines may be 80 to 400, but can also be 85 to 300, or 90 to 200.

[0025] Furthermore, the secondary-tertiary amine may have only one tertiary amino group or two or more. Therefore, examples of the secondary-tertiary amine include (1) a compound having one tertiary amino group. Further examples include (2) a compound having two tertiary amino groups. Further examples include (3) a compound having three tertiary amino groups. Further examples include (4) a compound having four tertiary amino groups. These may be used alone or in combination of two or more.

[0026] Examples of the (1) secondary-tertiary amines having one tertiary amino group include 2-(dimethylamino)ethanol (molecular weight 89.14, CAS RN: 108-01-0), 2-(ethylmethylamino)ethanol (molecular weight 103.17, CAS RN: 2893-43-8), 2-(diethylamino)ethanol (molecular weight 117.19, CAS RN: 100-37-8), 3-(dimethylamino)-1-propanol (molecular weight 103.17, CAS RN: 3179-63-3), 1-(dimethylamino)-2-propanol (molecular weight 103.17, CAS RN: 108-16-7), 2-[ethyl(methyl)amino]-1-propanol (molecular weight 117.19, CAS RN: 1060817-16-4), 3-(diethylamino)-1-propanol (molecular weight 131.22, CAS RN: 622-93-5), 1-(diethylamino)-2-propanol (molecular weight 131.22, CAS RN: 4402-32-8), 4-(dimethylamino)-1-butanol (molecular weight 117.19, CAS RN: 13330-96-6), 3-(dimethylamino)-1-butanol (molecular weight 117.19, CAS RN: 2893-65-4), 4-(diethylamino)-1-butanol (molecular weight 145.24, CAS RN: 2683-56-9), 6-(dimethylamino)-1-hexanol (molecular weight 145.24, CAS RN: 1862-07-3), 2-[2-(dimethylamino)ethoxy]ethanol (molecular weight 133.19, CAS RN: 1704-62-7), 2-[2-(diethylamino)ethoxy]ethanol (molecular weight 161.25, CAS RN: 140-82-9), 4-(dimethylamino)benzyl alcohol (molecular weight 151.21, CAS RN: 1703-46-4), 2-[4-(dimethylamino)phenyl]ethanol (molecular weight 165.23, CAS RN: 50438-75-0), 1-methyl-4-piperidinemethanol (molecular weight 129.20, CAS RN: 20691-89-8), 1-methyl-3-piperidinemethanol (molecular weight 129.20, CAS RN:7583-53-1), 1-methyl-2-piperidinemethanol (molecular weight 129.20, CAS RN:20845-34-5), 3-(dimethylamino)-1,2-propanediol (molecular weight 119.16, CAS RN: 623-57-4), 3-(diethylamino)-1,2-propanediol (molecular weight 147.22, CAS RN: 621-56-7), N-methyldiethanolamine (molecular weight 119.16, CAS RN: 105-59-9), N-ethyldiethanolamine (molecular weight 133.19, CAS RN: 139-87-7), N,N-dimethylbutylamine (molecular weight 101.19, CAS RN: 927-62-8), N,N-diethylbutylamine (molecular weight 129.24, CAS RN: 4444-68-2), N,N-dimethylhexylamine (molecular weight 129.24, CAS RN: 4385-04-0), N,N-dimethyloctylamine (molecular weight 157.30, CAS N,N-Dialkyl-alkylamines such as N,N-dimethyldecylamine (molecular weight 185.36, CAS RN: 1120-24-7), N,N-dimethyldodecylamine (molecular weight 213.41, CAS RN: 112-18-5), and N,N-dimethylhexadecylamine (molecular weight 269.52, CAS RN: 112-69-6), 2-(dimethylamino)ethylamine (molecular weight 88.15, CAS RN: 108-00-9), 2-(diethylamino)ethylamine (molecular weight 116.21, CAS RN: 100-36-7), 3-(dimethylamino)propylamine (molecular weight 102.18, CAS RN: 109-55-7), and 3-(diethylamino)propylamine (molecular weight 130.24, CAS RN: 112-69-6). (Dialkylamino)alkylamines such as triethylenediamine (molecular weight 112.18, CAS RN: 280-57-9), (dimethylamino)acetonitrile (molecular weight 84.12, CAS RN: 926-64-7), N,N,N'-trimethylethylenediamine (molecular weight 102.18, CAS RN: 142-25-6), triethylamine (molecular weight 101.19, CAS RN: 121-44-8), N,N-dimethylcyclohexylamine (molecular weight 127.23, CAS RN: 98-94-2), N,N-diethylcyclohexylamine (molecular weight 155.29, CAS RN: 91-65-6), 1,2-dimethylimidazole (molecular weight 96.13, CAS RN:1739-84-0), 1-(dimethylamino)pyrrole (molecular weight 110.16, CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (molecular weight 112.17, CAS RN: 4271-96-9), 4-dimethylaminotoluene (molecular weight 135.21, CAS RN: 99-97-8), dimethylaniline (molecular weight 121.18, CAS RN: 121-69-7), 4-dimethylaminoaniline (molecular weight 136.20, CAS RN: 99-98-9), 2-(dimethylamino)pyridine (molecular weight 122.17, CAS RN: 5683-33-0), 4-(dimethylamino)pyridine (molecular weight 122.17, CAS RN: 1122-58-3), 4-(dimethylamino)benzonitrile (molecular weight 146.19, CAS Examples of suitable amines include N,N-dimethylbenzylamine (molecular weight 135.21, CAS RN: 103-83-3), and 4-methylmorpholine (molecular weight 101.15, CAS RN: 109-02-4). These may be used alone or in combination of two or more.

[0027] Examples of the (2) secondary-tertiary amines having two tertiary amino groups include 1,3-bis(dimethylamino)-2-propanol (molecular weight 146.23, CAS RN: 5966-51-8), 1,3-bis(diethylamino)-2-propanol (molecular weight 202.34, CAS RN: 3492-47-5), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (molecular weight 146.23, CAS RN: 2212-32-0), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (molecular weight 190.28, CAS RN: 83016-70-0), N,N,N',N'-tetramethyldiaminomethane (molecular weight 102.16, CAS RN: 51-80-9), N,N,N',N'-tetramethylethylenediamine (molecular weight 116.21, CAS RN: 110-18-9), N,N,N',N'-tetraethylethane-1,2-diamine (molecular weight 172.23, CAS RN: 150-77-6), N,N,N',N'-tetramethyl-1,4-butanediamine (molecular weight 144.26, CAS RN: 111-51-3), and other tetraalkylalkanediamines; bis(2-(N,N-dimethylamino)ethyl)ether (molecular weight 160.26, CAS RN: 3033-62-3), tert-butoxybis(dimethylamino)methane (molecular weight 174.28, CAS RN: 5815-08-7), 4,4'-bis-(dimethylamino)benzophenone (molecular weight 268.36, CAS RN:90-94-8), 3,3'-iminobis(N,N-dimethylpropylamine) (molecular weight 187.33, CAS RN:6711-48-4), N,N,N',N'-tetramethyl-1,3-diaminobutane (molecular weight 144.26, CAS RN:97-84-7), N,N'-dimethylpiperazine (molecular weight 114.19, CAS RN:106-58-1), N,N,N',N'-tetramethyl-1,8-naphthalenediamine (molecular weight 214.31, CAS RN:20734-58-1), etc. These may be used alone or in combination of two or more.

[0028] Examples of the (3) secondary-tertiary amines having three tertiary amino groups include 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (molecular weight 245.40, CAS RN: 67151-63-7), 2,4,6-tris(dimethylaminomethyl)phenol (molecular weight 265.40, CAS RN: 90-72-2), 1-(2-dimethylaminoethyl)-4-methylpiperazine (molecular weight 171.29, CAS RN: 104-19-8), N,N,N',N'',N''-pentamethyldiethylenetriamine (molecular weight 173.30, CAS RN: 3030-47-5), tris(dimethylamino)methane (molecular weight 145.25, CAS RN: 5762-56-1), bis(4-dimethylaminophenyl)-4-dimethylamino-d6-phenylmethane (molecular weight 379.57, CAS RN: 1173023-92-1)

[0029] Examples of the (4) secondary-tertiary amine having four tertiary amino groups include tris[2-(dimethylamino)ethyl]amine (molecular weight 230.40, CAS RN: 33527-91-2), tetrakis(dimethylamino)ethylene (molecular weight 200.33, CAS RN: 996-70-3), 1,1,4,7,10,10-hexamethyltriethylenetetramine (molecular weight 230.40, CAS RN: 3083-10-1), etc. These may be used alone or in combination of two or more.

[0030] Among these, the secondary-tertiary amine is preferably a compound having a heterocycle in which the nitrogen atom constituting the tertiary amino group is a heteroatom. That is, examples of the tertiary amine having a heterocycle in which the nitrogen atom constituting the tertiary amino group is a heteroatom include 1-methyl-4-piperidinemethanol (molecular weight 129.20, CAS RN: 20691-89-8), 1-methyl-3-piperidinemethanol (molecular weight 129.20, CAS RN: 7583-53-1), 1-methyl-2-piperidinemethanol (molecular weight 129.20, CAS RN: 20845-34-5), triethylenediamine (molecular weight 112.18, CAS RN: 280-57-9), 1,2-dimethylimidazole (molecular weight 96.13, CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (molecular weight 110.16, CAS Examples include 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (molecular weight 114.19, CAS RN: 4271-96-9), N,N'-dimethylpiperazine (molecular weight 112.17, CAS RN: 106-58-1), 1-(2-dimethylaminoethyl)-4-methylpiperazine (molecular weight 171.29, CAS RN: 104-19-8), and 4-methylmorpholine (molecular weight 101.15, CAS RN: 109-02-4).

[0031] Among the above-mentioned preferred compounds, compounds having no hydroxy group are more preferred. That is, examples of tertiary amines having a heterocycle in which a nitrogen atom constituting a tertiary amino group is a heteroatom but having no hydroxy group include triethylenediamine (molecular weight 112.18, CAS RN: 280-57-9), 1,2-dimethylimidazole (molecular weight 96.13, CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (molecular weight 110.16, CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (molecular weight 112.17, CAS RN: 4271-96-9), N,N'-dimethylpiperazine (molecular weight 114.19, CAS RN: 106-58-1), 1-(2-dimethylaminoethyl)-4-methylpiperazine (molecular weight 171.29, CAS 4-methylmorpholine (molecular weight 101.15, CAS RN: 109-02-4), etc. These may be used alone or in combination of two or more.

[0032] Furthermore, when a tertiary amine having a heterocycle in which the nitrogen atom constituting the tertiary amino group is a heteroatom is used as the secondary-tertiary amine, it is preferable to use a tertiary amine having no ring structure in combination with the tertiary amine. That is, it is preferable to use two different tertiary amines, a tertiary amine having a heterocycle and a tertiary amine having no ring structure in combination as the secondary-tertiary amine.

[0033] The tertiary amine not having a ring structure is preferably a compound further having a hydroxy group. Compared to tertiary amines not having a hydroxy group, secondary and tertiary amines having a hydroxy group have improved affinity for water-soluble silicates and can promote the reaction between the water-soluble silicates and polyisocyanates, which is thought to result in superior foam strength. Additionally, when the tertiary amine not having a ring structure has a hydroxy group, it is preferably a compound having a tertiary amino group and a hydroxy group and an oxygen atom and / or a nitrogen atom in the main chain. When an oxygen atom and / or a nitrogen atom is present in the main chain, the affinity for water-soluble silicates is further improved, which is thought to further promote the reaction between the water-soluble silicates and polyisocyanates. Tertiary amines that do not have a ring structure, have a hydroxy group, and have an oxygen atom and / or a nitrogen atom in the main chain connecting the tertiary amino group and the hydroxy group include 2-[2-(dimethylamino)ethoxy]ethanol (molecular weight 133.19, CAS RN: 1704-62-7), 2-[2-(diethylamino)ethoxy]ethanol (molecular weight 161.25, CAS RN: 140-82-9), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (molecular weight 146.23, CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (molecular weight 245.40, CAS RN: 67151-63-7), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (molecular weight 190.28, CAS RN:83016-70-0) and the like. These may be used alone or in combination of two or more.

[0034] Furthermore, the tertiary amine having no ring structure preferably has a tertiary amino group having a methyl group directly bonded to the nitrogen atom (hereinafter simply referred to as a "methyl tertiary amino group"), and more preferably has a tertiary amino group having two methyl groups directly bonded to the nitrogen atom (hereinafter simply referred to as a "dimethyl tertiary amino group"). When a dimethyl tertiary amino group is present, the tertiary amino group constitutes the terminal of the compound. Furthermore, since the number of carbon atoms in the hydrocarbon group constituting the tertiary amino group is small, the steric hindrance of the terminal tertiary amino group can be reduced, which is thought to further improve the catalytic activity of secondary and tertiary amines at the initial stage of the reaction. Therefore, examples of tertiary amines that do not have a ring structure, have hydroxy groups, have oxygen atoms and / or nitrogen atoms in the main chain connecting the tertiary amino groups, and have a dimethyl tertiary amino group include 2-[2-(dimethylamino)ethoxy]ethanol (molecular weight 133.19, CAS RN: 1704-62-7), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (molecular weight 146.23, CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (molecular weight 245.40, CAS RN: 67151-63-7), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (molecular weight 190.28, CAS RN: 83016-70-0), etc. These may be used alone or in combination of two or more.

[0035] (3-3) Amount of catalyst The amount of catalyst contained in Solution A (the total amount of primary-tertiary amine and secondary-tertiary amine) is not limited, but is preferably 0.05 parts by mass or more, and can be 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, or 0.4 parts by mass or more, per 100 parts by mass of polyisocyanate contained in Solution B. On the other hand, this content is preferably 7 parts by mass or less, and can be 5 parts by mass or less, 4.5 parts by mass or less, 3.5 parts by mass or less, or 2.5 parts by mass or less. These upper and lower limits can be arbitrarily combined. That is, for example, the amount is preferably 0.05 to 7 parts by mass, and can be 0.1 to 5 parts by mass, 0.2 to 4.5 parts by mass, 0.3 to 3.5 parts by mass, or 0.4 to 2.5 parts by mass. Within the preferred range, a good expansion ratio can be achieved while reducing reaction temperature dependency and preventing poor expansion.

[0036] The ratio of the primary-tertiary amine to the secondary-tertiary amine is not limited, but it is preferable that the primary-tertiary amine and the secondary-tertiary amine are present in equal amounts by mass, or that the primary-tertiary amine is present in a greater amount. Specifically, when the total of the primary-tertiary amine and the secondary-tertiary amine is taken as 100% by mass, the proportion of the primary-tertiary amine is preferably 50% by mass or more, and can be 51% by mass or more, or 52% by mass or more. On the other hand, this proportion is preferably 90% by mass or less, and can be 70% by mass or less, or can be 60% by mass or less. These upper and lower limits can be arbitrarily combined. That is, for example, it can be 50 to 90% by mass, 51 to 70% by mass, or 52 to 60% by mass.

[0037] (3-4) Other catalysts Solution A may contain catalysts other than the above-mentioned primary-tertiary amines and secondary-tertiary amines, but the amount of the other catalysts is usually 30 parts by mass or less when the total amount of the primary-tertiary amines and secondary-tertiary amines is 100 parts by mass. Examples of other catalysts include metal catalysts, quaternary ammonium salts, etc. These may be used alone or in combination of two or more.

[0038] Examples of the metal catalyst include organic acid metal salts and organometallic complexes. Examples of metal species constituting the organic acid metal salt include sodium, potassium, calcium, iron, cobalt, nickel, zinc, zirconium, tin, lead, and bismuth. Examples of organic acids constituting the organic acid metal salt include acetic acid, octylic acid, neodecanoic acid, naphthenic acid, and rosin acid. Specific examples include sodium acetate, potassium acetate, potassium octylate, bismuth octylate, lead octylate, iron octylate, tin octylate, calcium octylate, zinc octylate, zirconium octylate, bismuth neodecanoate, zinc neodecanoate, lead neodecanoate, cobalt neodecanoate, bismuth rosinate, and dibutyltin dilaurate. These may be used alone or in combination of two or more. Furthermore, examples of metal species constituting the organometallic complex include iron, cobalt, nickel, zinc, zirconium, tin, lead, and bismuth. Examples of ligands constituting the organometallic complex include acetylacetone. Examples include iron acetylacetone, nickel acetylacetone, zinc acetylacetone, zirconium acetylacetone, and tin acetylacetone. These may be used alone or in combination of two or more.

[0039] Examples of cationic species constituting quaternary ammonium salts include alkylammonium (tetramethylammonium, tetraethylammonium, etc.) and hydroxyalkylammonium salts (hydroxypropyltrimethylammonium, hydroxyethyltrimethylammonium, etc.). Examples of anionic species constituting quaternary ammonium salts include organic groups such as formate, acetate, 2-ethylhexanoate, 2,2-dimethylpropanoate, octylate, and phosphate; and inorganic groups such as halogen, hydroxy, hydrogencarbonate, and carbonate. These may be used alone or in combination of two or more.

[0040] (4) Viscosity of Liquid A The viscosity of Solution A in this composition is not limited and may be the same as or different from Solution B, but the viscosity at 25°C is preferably 400 mPa·s or less, more preferably 5 to 300 mPa·s, and even more preferably 10 to 200 mPa·s. Within this range, the composition is easy to work with in terms of appropriate injection pressure, and is less likely to be diluted with water, allowing for cleaner wastewater. The viscosity of Liquid A can be measured at 25°C using a B-type viscometer in accordance with JIS K7117-1.

[0041] [2]B liquid (1) Polyisocyanate Liquid B contains a "polyisocyanate." A polyisocyanate is an organic compound having two or more isocyanate groups (NCO groups) in the molecule. As the polyisocyanate, a monomer having two or more isocyanate groups (NCO groups) in the molecule may be used, or a polymer (such as a prepolymer) may be used. Furthermore, in the case of a polymer, the compound (monomer) constituting the polymer may be of only one type (mononuclear) or of two or more types (polynuclear). Furthermore, a mixture of a monomer and a polymer may be used. Examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These may be used alone or in combination of two or more types.

[0042] Aromatic polyisocyanates include diphenylmethane diisocyanate (2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate), tolylene diisocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), phenylene diisocyanate (1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate), xylylene diisocyanate (1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate), tetramethylxylene diisocyanate, Examples of the isocyanate include rylene diisocyanate (1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate), 3,3'-dimethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate (1,5-naphthalene diisocyanate, etc.), dianisidine diisocyanate, isopropylidenebis (4-cyclohexylisocyanate), triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris(isocyanatophenyl)-thiophosphate, etc. These may be used alone or in combination of two or more.

[0043] Examples of aliphatic polyisocyanates include hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), trimethylhexamethylene diisocyanate (2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate), lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, etc. These may be used alone or in combination of two or more. Examples of alicyclic polyisocyanates include 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate [methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate], bis(isocyanatomethyl)cyclohexane [cis-1,3-(diisocyanatomethyl)cyclohexane, trans-1,3-(diisocyanatomethyl)cyclohexane, 1,4-(diisocyanatomethyl)cyclohexane], etc. These may be used alone or in combination of two or more. The above-mentioned various monomers may be modified products thereof (isocyanurate modified products, carbodiimide modified products, etc.), blocked products thereof, hydrogenated products thereof, etc. Also, an isocyanate group-containing prepolymer obtained by reacting an active hydrogen group-containing compound with the above-mentioned polyisocyanate by a known method may be used. These may be used alone or in combination of two or more types.

[0044] Of the polyisocyanates contained in Liquid B of the present composition, among those mentioned above, aromatic polyisocyanates are preferred from the viewpoints of the strength of the resulting foam and the reaction rate, and diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate (IPDI) are more preferred, and diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI) is even more preferred.

[0045] The amount of polyisocyanate contained in Liquid B is not limited; for example, Liquid B can be composed solely of polyisocyanate. In this case, the amount of polyisocyanate is 100% by mass when the entire amount of Liquid B is taken as 100% by mass. On the other hand, when components other than polyisocyanate (e.g., additives) are added to Liquid B, the amount of polyisocyanate is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 91% by mass or more, and particularly preferably 92% by mass or more when the entire amount of Liquid B is taken as 100% by mass. On the other hand, this content is usually 99.99% by mass or less, more preferably 99.8% by mass or less, even more preferably 99.6% by mass or less, and particularly preferably 99.4% by mass or less. These upper and lower limits can be arbitrarily combined. That is, for example, it can be 85 to 99.99% by mass, 90 to 99.8% by mass, 91 to 99.6% by mass, or 82 to 99.4% by mass.

[0046] (2) Viscosity of Liquid B The viscosity of Solution B in this composition is not limited and may be the same as or different from Solution A, but the viscosity at 25°C is preferably 400 mPa s or less, more preferably 5 to 300 mPa s, and even more preferably 10 to 200 mPa s. Within this range, the composition is easy to work with in terms of appropriate injection pressure, and is less likely to be diluted with water, allowing for cleaner wastewater. The viscosity of Liquid B can be measured at 25° C. using a B-type viscometer in accordance with JIS K7117-1.

[0047] [3] Other ingredients Other components may be blended into the liquids A and B of the composition as needed. Examples of other components include blowing agents, foam stabilizers, flame retardants, viscosity modifiers (thickeners, thickeners, etc.). These may be used alone or in combination of two or more.

[0048] The blowing agent is a component that forms a foamed state in the resulting solid (foam). While the type of blowing agent is not limited, examples include inorganic blowing agents and organic blowing agents. These may be used alone or in combination. Examples of inorganic blowing agents include water and carbon dioxide. Water functions as a blowing agent when coexisting with polyisocyanate, so when water is used as a blowing agent in this composition, it can be blended into Liquid A. Furthermore, when a water-soluble silicate is used as water glass (silicate aqueous solution), the water that constitutes the water glass can function as a blowing agent. Non-fluorocarbon or fluorocarbon-based blowing agents can be used as organic blowing agents. Non-fluorocarbon organic blowing agents are preferred, with halogenated alkenes such as hydrofluoroolefins and hydrochlorofluoroolefins being more preferred. When a foaming agent is used, the amount of the foaming agent may be 0.01 to 50 parts by mass, 0.1 to 25 parts by mass, or 0.5 to 10 parts by mass, relative to 100 parts by mass of the entire polyisocyanate contained in the composition.

[0049] The foam stabilizer is a component that improves the uniformity of the foam cells that make up the resulting solid (foam). The type of foam stabilizer is not limited, but examples of foam stabilizers that can be used include silicone-based foam stabilizers (such as silicone), nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxanes, polysiloxane oxyalkylene copolymers, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, and lauryl fatty acid ethylene oxide adducts. These may be used alone or in combination of two or more. When a foam stabilizer is used, the amount of the foam stabilizer may be 0.05 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass, relative to 100 parts by mass of the total polyisocyanate contained in the composition. Within this range, an appropriate foam stabilizing effect can be obtained while enabling clean wastewater discharge.

[0050] The viscosity modifier is a component capable of adjusting the viscosity of the A and / or B liquids constituting the present composition. The type of viscosity modifier is not limited, but examples of the viscosity modifier include a viscosity reducer and a thickener, and a viscosity reducer can be suitably used in the present composition. Examples of viscosity reducers that can be used include alcohols, ethers, esters, and petroleum hydrocarbons. These may be used alone or in combination of two or more. Examples of alcohols include methanol, ethanol, propanol, isopropyl alcohol, butanol, etc. Examples of ethers include ethyl cellosolve, butyl cellosolve, etc. Examples of esters include cyclic esters such as propylene carbonate; esters (non-cyclic esters) such as dicarboxylic acid methyl ester and ethylene glycol monomethyl ether acetate; etc. When a viscosity modifier is used, the amount of the viscosity reducer may be 0.1 to 15 parts by mass, 0.5 to 10 parts by mass, or 1 to 8 parts by mass, relative to 100 parts by mass of the total polyisocyanate contained in the composition.

[0051] The flame retardant is a component that improves the flame retardancy of the resulting solidified body (foam). The type of flame retardant is not limited, but examples include phosphate esters (monophosphate esters, condensed phosphate esters, organic phosphate monoesters, organic phosphate diesters, organic phosphate triesters, monophosphates, pyrophosphates, polyphosphates, organic phosphinates, etc.), red phosphorus, boron-based flame retardants, bromine-based flame retardants, chlorine-based flame retardants (halogenated paraffins, etc.), metal stannates, antimony-containing flame retardants, metal hydroxides, hydrates of metal compounds, clay minerals, etc. These may be used alone or in combination of two or more. When a flame retardant is used, the amount of the flame retardant may be 0.1 to 100 parts by mass, 0.5 to 50 parts by mass, or 1 to 10 parts by mass, relative to 100 parts by mass of the entire polyisocyanate contained in the composition.

[0052] [4] Uses of ground grouting chemical compositions Although the use of the present composition is not limited, its properties make it particularly suitable for use in the fields of construction and civil engineering (architecture and civil engineering). That is, the present composition can be used as a liquid ground injection composition in the field of construction and civil engineering. For example, in the field of construction, the composition can be used for flame-retardant foams for walls, ceilings, and floors, wall insulation, ceiling insulation, floor insulation, on-site spraying during the manufacture of structures, filling internal gaps, and reinforcing structures that have deteriorated over time. In the field of civil engineering, the present composition can be injected into natural ground, underground, soil, ground, bedrock, gaps between these and structures (architectural structures), and even gaps within structures, and then foamed and cured to fill and reinforce the injection site.

[0053] [2] Foam (solidified foam) and its manufacturing method The foam of the present invention is characterized in that it is obtained by mixing liquid A and liquid B. The mixing of liquid A and liquid B can be carried out during the formation of a foam. That is, the composition may be mixed before, during, or after injection into the target location, or two or more of these methods may be combined. More specifically, it is desirable to mix liquid A and liquid B just before the discharge nozzle of the piping and then mix them immediately before discharge. This makes it easier to control the mixing ratio within the desired range.

[0054] Furthermore, the mixing ratio of liquid A to liquid B is not limited and can be set within an appropriate range depending on the physical properties of the foam produced by the reaction of liquid A and liquid B. Generally, however, it is preferable that the ratio of liquid A to liquid B is 2:1 to 1:3, and more preferably 1.5:1 to 1:2, on a mass basis.

[0055] The expansion ratio of the foam obtained using the present composition is not limited, but is preferably 20 times or less, and more preferably 3 to 15 times at 20° C. Within this range, the foam obtained can have sufficient strength and is also economical. The expansion ratio is measured as follows: when Liquid A and Liquid B are mixed in the cup, the height of the liquid surface in the cup is measured as H1, then when foaming starts and a foam is formed in the cup and the curing reaction is completed, the height of the foam is measured as H2, and the obtained values ​​of H1 and H2 are used to calculate the expansion ratio as H2 / H1. In this measurement, each height can be measured visually using a gauge.

[0056] In addition, the foam obtained using this composition has a compressive strength of 4.0 to 6.0 N / cm 2 Furthermore, it can be made 4.1 to 5.8 N / cm 2 It can be set to 4.2~5.5N / cm 2 It can be set to 4.3~5.3N / cm 2 It can be made into. Furthermore, the foam obtained using this composition has a bending strength of 3.9 to 6.0 N / cm 2 Furthermore, it can be made 4.0 to 5.8 N / cm 2It can be set to 4.1~5.5N / cm 2 It can be set to 4.1~5.3N / cm 2 It can be made into. The time when foaming begins upon mixing of liquid A and liquid B is defined as the "foaming start time," the time when foam height reaches its maximum is defined as the "foaming end time," and the difference between the foaming start time and the foaming end time is defined as the rise time. The rise time at 20°C is preferably 20 to 300 seconds. [Example]

[0057] The present invention will be described in more detail below with reference to examples. However, these examples are merely examples shown for the convenience of explanation, and the present invention is not limited to these examples in any sense.

[0058] [1] Preparation of the composition The following components were mixed in the combinations and proportions shown in Tables 1 and 2 below to obtain liquid grouting compositions for ground grouting containing Liquid A and Liquid B of Examples 1 to 13 and Comparative Examples 1 to 8.

[0059] (1) Water-soluble silicate (silicate aqueous solution) No. 2 sodium silicate: No. 2 sodium silicate, manufactured by Fuji Chemical Co., Ltd., solids content 40% No. 1 sodium silicate: No. 1 sodium silicate, manufactured by Fuji Chemical Co., Ltd., 48% solids (adjust to 40% solids with water before use)

[0060] (2) Polyol PP400: Polyether polyol, manufactured by Sanyo Chemical Industry Co., Ltd., product name "Sannix PP-400", number average molecular weight 400, number of functional groups 2 PP1000: Polyether polyol, manufactured by Sanyo Chemical Industry Co., Ltd., product name "Sannix PP-1000", number average molecular weight 1000, number of functional groups 2

[0061] (3) Catalyst (3-1) First tertiary amine Tetramethylhexamethylenediamine: N,N,N',N'-tetramethyl-1,6-hexanediamine (molecular weight 172.32, CAS RN: 111-18-2), manufactured by Kao Corporation, product name "Kao Raiser No. 1"

[0062] (3-2) Second tertiary amine Triethylenediamine: 33% triethylenediamine (molecular weight 112.18, CAS RN: 280-57-9) dipropylene glycol solution, manufactured by Kao Corporation, product name "Kao Raiser No. 31" Dimethylimidazole: 70% 1,2-dimethylimidazole (molecular weight 96.13, CAS RN: 1739-84-0) ethylene glycol solution, manufactured by Kao Corporation, product name "Kao Raiser No. 350" Trimethylaminoethylpiperazine: 1-(2-dimethylaminoethyl)-4-methylpiperazine (molecular weight 171.29, CAS RN: 104-19-8), manufactured by Kao Corporation, product name "Kao Raiser No. 8" Trimethylaminoethylethanolamine: 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (molecular weight 146.23, CAS RN: 2212-32-0), manufactured by Tosoh Corporation, product name "Toyocat RX-5" Tridodecylamine: Tridodecylamine (molecular weight 522.00, CAS RN: 102-87-4), Tokyo Chemical Industry Co., Ltd.

[0063] (4) Polyisocyanate MDI (M100): Polymeric MDI, manufactured by Kumho Mitsui Chemicals, product name "Cosmonate M100" MDI (M200): Polymeric MDI, manufactured by Kumho Mitsui Chemicals, product name "Cosmonate M200"

[0064] (5) Foam stabilizer Foam stabilizer: Polyether-modified siloxane, manufactured by Momentive Performance Materials Japan, LLC, product name "Niax Silicone L-6970"

[0065] (6) Viscosity reducer Viscosity reducer: Propylene carbonate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0066] (7) Flame retardants Flame retardant: Tris(chloropropyl)phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[0067] [Table 1]

[0068] [Table 2]

[0069] [2] Measurement and evaluation (1) Viscosity measurement of liquid A and liquid B The viscosities of Liquids A and B constituting the ground grouting liquid compositions of Examples 1 to 13 and Comparative Examples 1 to 8 were measured at 25°C using a Brookfield viscometer in accordance with JIS K7117-1. The results are shown in Tables 1 and 2.

[0070] (2) Evaluation of foam Foams were produced in the following manner using the liquid chemical compositions for ground grouting of Examples 1 to 13 and Comparative Examples 1 to 8 obtained in [1] above, and the obtained foams were evaluated in the following manner.

[0071] (2-1) Evaluation of compressive strength Liquid A and liquid B were separated from each of the ground grouting liquid compositions of Examples 1 to 13 and Comparative Examples 1 to 8 so that the mass ratio of liquid A to liquid B was 1:1. After adjusting the temperature of these liquids A and B to 20°C, they were poured into a bottomed cylindrical container with an inner diameter of 50 mm and a height of 100 mm so that the expansion ratio would be 3 times. After the container was covered with a lid, the container was cured for at least 2 hours. The mixture was then demolded and further cured at 20°C for at least 24 hours to obtain a foam for evaluation. The compressive strength of each foam for evaluation obtained was measured in accordance with JIS K7220, and the results are shown in Tables 1 and 2. In the compressive strength evaluation columns of Tables 1 and 2, "x" indicates that the foam obtained was too soft to be measured.

[0072] (2-2) Evaluation of bending strength Liquid A and liquid B were separated from each of the ground grouting liquid compositions of Examples 1 to 13 and Comparative Examples 1 to 8 so that the mass ratio of liquid A to liquid B was 1:1. Liquid A and liquid B were adjusted to a temperature of 20°C, then poured into a mold measuring 180 mm in length, 170 mm in width, and 20 mm in thickness so that the expansion ratio was 3 times. The mold was then closed and cured for at least 2 hours. The mixture was then demolded and further cured at 20°C for at least 24 hours to obtain a foam. From the resulting foam, a foam for evaluation measuring 150 mm in length, 25 mm in width, and 20 mm in thickness was cut out. The flexural strength of each foam obtained for evaluation was measured in accordance with JIS K7221, and the results are shown in Tables 1 and 2. In the flexural strength evaluation columns of Tables 1 and 2, "x" indicates that the foam obtained was too weak to be measured.

[0073] [3] Effects of the embodiment From Tables 1 and 2, it can be seen that the composition of Comparative Example 1, in which the solution A did not contain any secondary or tertiary amine, produced a foam, but the compressive strength and flexural strength were both 4.0 N / cm 2 It can be seen that the foam obtained is less than 4.0 N / cm. In addition, with the compositions of Comparative Examples 2 to 4 and 6, in which no primary, secondary, or tertiary amines were contained in Solution A, foams were obtained, but they were weak foams whose compressive strength and flexural strength were not measurable. Furthermore, with the composition of Comparative Example 5, in which no primary, secondary, or tertiary amines were contained in Solution A, foams were obtained, but their compressive strength and flexural strength were both 4.0 N / cm. 2 Furthermore, in the composition of Comparative Example 7, in which the amount of polyol contained in Solution A was in excess of 10% by mass, a foam was obtained, but the compressive strength and flexural strength were both 4.0 N / cm 2Furthermore, in the composition of Comparative Example 8, in which the molecular weight of the secondary-tertiary amine contained in Solution A exceeds 400, a foam is obtained, but the compressive strength and flexural strength are both 4.0 N / cm 2 It can be seen that the foam becomes less than 100%. In contrast, it can be seen that the compositions of Examples 1 to 13, in which Liquid A contains a water-soluble silicate, a predetermined amount of polyol, a primary to tertiary amine, and a secondary to tertiary amine, can stably form foams while providing foams with sufficient strength. [Industrial Applicability]

[0074] The composition is suitably used in the fields of construction and civil engineering (architecture and civil engineering), etc. Among these, for example, in the field of construction, it can be used as a wall filling foam, a ceiling filling foam, a floor filling foam, a wall insulating material, a ceiling insulating material, a floor insulating material, filling internal gaps during the manufacture of a structure, and reinforcing structures that have deteriorated over time. Furthermore, in the field of civil engineering, the composition can be injected into natural ground, underground, soil, ground, bedrock, gaps between these and structures (architectural structures), and even gaps within structures, and then foamed and cured, thereby filling and reinforcing the injected areas.

Claims

1. A chemical composition for ground injection consisting of two chemical liquids, namely, liquid A and liquid B, The solution A contains a water-soluble silicate, a polyol, and a catalyst, The liquid B contains a polyisocyanate, The catalyst includes two types of tertiary amines, namely, a first tertiary amine and a second tertiary amine; the first tertiary amine is tetramethylhexamethylenediamine; the second tertiary amine is a tertiary amine other than the first tertiary amine and has a molecular weight of 80 to 400; the polyol is a polyether polyol having a number average molecular weight of more than 200, and the content thereof is 10% by mass or less based on the total mass of the solution A; The second tertiary amine is a tertiary amine having a heterocycle in which the nitrogen atom constituting the tertiary amino group is a heteroatom, and a tertiary amine having no ring structure.

2. 2. The ground injection liquid composition according to claim 1, wherein the proportion of the first tertiary amine is more than 50% by mass when the total of the first tertiary amine and the second tertiary amine is 100% by mass.

3. A foam obtained by mixing the liquid A and the liquid B that constitute the liquid grouting composition according to claim 1 or 2.

4. A method for producing a foam, comprising mixing the liquid A and the liquid B that constitute the liquid grouting composition according to claim 1 or 2 to form a foam.

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