Chemical composition for ground injection, foam, and method for manufacturing the same.

Abstract

To provide a chemical liquid composition for injection into soil, having a reaction schedule which can be easily handled by a user, and capable of reducing a reaction temperature dependence for preventing foaming failure, an expanded material and a production method of the same.SOLUTION: There is provided a chemical liquid composition for injection into soil which is a chemical liquid composition for injection into soil formed of two kinds of chemical liquid which are A liquid and B liquid. The A liquid includes a water soluble silicate, and a catalyst. The B liquid includes polyisocyanate, and includes as catalyst, two kinds of amines which are a first tertiary amine and a second tertiary amine. The first tertiary amine comprises: a hydroxy group and a tertiary amino group having a methyl group directly coupled to a nitrogen group. The second tertiary amine comprises a tertiary amino group having a methyl group directly coupled to a nitrogen group and includes no hydroxy group. An expanded body of the invention is obtained by mixing the A liquid and 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 B liquid forming the chemical liquid composition for injection into soil.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemical injection composition for ground injection, a foam, and a method for producing the same. More specifically, the present invention relates to a chemical injection composition for ground injection, a foam, and a method for producing the same using silicate and polyisocyanurate. [Background technology]

[0002] Traditionally, polyurethane foam grout has been known as a grouting material used for ground improvement and filling voids in structures. However, since polyurethane foam grout, as a reaction product, is essentially an organic material obtained by reacting polyols and polyisocyanates, the addition of flame retardants is necessary to achieve high flame retardancy. Furthermore, polyurethane foam grout has the problem of high raw material costs. In contrast, composite grout is known, which is obtained as a composite reaction product of inorganic and organic materials, in which a portion of the polyol is replaced with an inorganic material, water glass (silicate aqueous solution). Because composite grout contains inorganic materials as aggregate, it has superior flame retardancy compared to grout made only of organic aggregate. Furthermore, composite grout has the advantage of lower raw material costs. Technologies related to such composite grout are known in the following Patent Documents 1 and 2. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-152154 [Patent Document 2] Japanese Patent Publication No. 2011-037946 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Patent Document 1 discloses an injection chemical composition for stabilizing rock, ground, and artificial structures (Patent Document 1 [Claim 1]) comprising (A) an aqueous alkali silicate solution, (B) an organic polyisocyanate composition, (C) an imidazole-based catalyst with a molecular weight of less than 120, and (D) an aliphatic tertiary amine-based catalyst with a molecular weight of less than 120, with the aim of enabling stable reinforcement or watertight sealing of rock, ground, and artificial structures with high solidification strength, stable reinforcement effect, durability, injection workability, and economic efficiency by forming a foamy inorganic-organic composite solidified body (Patent Document 1

[0007] ).

[0005] Patent Document 2 discloses a rock bolt anchoring material composition for installation in the surrounding ground after tunnel excavation, comprising a component (A) containing a silicate aqueous solution and a component (B) containing an isocyanate compound, wherein component (A) contains (A1) an aqueous sodium silicate solution and (A2) an amine polyol selected from the group consisting of trialkanolamine and alkyldialkanolamine, and component (B) contains (B1) an isocyanate compound and (B2) an ester compound consisting of an aliphatic alcohol having 8 to 12 carbon atoms and a polybasic acid, with the aim of providing a rock bolt anchoring material composition that suppresses the separation of silicate aqueous solution, has excellent compatibility between silicate aqueous solution and isocyanate component, suppresses the elution of organic compounds from the cured product, can suppress environmental pollution (especially water pollution), and further imparts high strength to the cured product and also has excellent long-term durability (Patent Document 2 [Claim 1]).

[0006] With these grout materials, the reaction schedule, including the foaming start time, foaming end time, and their time ratios, can be controlled by catalyst selection. However, catalyst selection can also lead to temperature sensitivity. In particular, foaming becomes unstable at high reaction temperatures, which can result in post-foaming shrinkage, the formation of cavities within the foam, or non-uniform foam cells. Such foaming defects affect the strength of the resulting composite grout and should be avoided. However, as mentioned above, it is not easy to reduce temperature dependence and prevent foaming defects while ensuring an easy-to-handle reaction schedule.

[0007] This invention has been made in view of the above circumstances, and aims to provide a soil injection chemical composition, a foam, and a method for producing the same that have an easy-to-handle reaction schedule and can reduce reaction temperature dependence to prevent foaming defects. [Means for solving the problem]

[0008] In other words, the present invention is as follows. [1] A chemical solution composition for ground injection consisting of two chemical solutions, A and B, The aforementioned solution A comprises a water-soluble silicate and a catalyst. The aforementioned solution B contains polyisocyanate, The catalyst comprises two types of tertiary amines: a first tertiary amine and a second tertiary amine. The first tertiary amine comprises a hydroxyl group and a tertiary amino group having a methyl group directly attached to a nitrogen atom, The aforementioned second tertiary amine is characterized by having a tertiary amino group having a methyl group directly attached to a nitrogen atom, and not having a hydroxyl group, in a ground injection chemical composition. [2] The first tertiary amine is the ground injection chemical composition according to [1], having an oxygen atom and / or a nitrogen atom in a main chain comprising the tertiary amino group and the hydroxyl group. [3] The first tertiary amine is the ground injection chemical liquid composition according to [1] or [2] above, which has no ring structure in the main chain having the tertiary amino group and the hydroxy group. [4] The ground injection chemical liquid composition according to any one of [1] to [3] above, wherein the tertiary amino group of the first tertiary amine has a dimethylamino group. [5] The ground injection chemical liquid composition according to any one of [1] to [4] above, wherein when the total of the first tertiary amine and the second tertiary amine is 100% by mass, the proportion of the first tertiary amine is 5% by mass or more. [6] The ground injection chemical liquid composition according to any one of [1] to [5] above, wherein the liquid A contains a polyol. [7] The ground injection chemical liquid composition according to [6] above, wherein the polyol is a polyether polyol having a number average molecular weight exceeding 200. [8] The ground injection chemical liquid composition according to [6] or [7] above, wherein the polyol is 8% by mass or less with respect to 100% by mass of the entire liquid A. [9] A foam characterized by being obtained by mixing the liquid A and the liquid B constituting the ground injection chemical liquid composition according to any one of [1] to [8] above.

[10] A method for producing a foam, characterized by forming a foam by mixing the liquid A and the liquid B constituting the ground injection chemical liquid composition according to any one of [1] to [8] above.

Advantages of the Invention

[0009] According to the ground injection chemical liquid composition of the present invention, it is possible to obtain a foam having an easy-to-handle reaction schedule, while reducing the reaction temperature dependence and preventing foaming failure. According to the foam of the present invention, foaming failure is prevented. According to the method for producing a foam of the present invention, it is possible to obtain a foam having an easy-to-handle reaction schedule while preventing foaming failure.

Embodiments for Carrying Out the Invention

[0010] 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 illustrative examples provided for explanatory purposes, and the present invention is not limited in any sense to them. The present invention can be modified in various ways depending on the purpose and use. Furthermore, all publications, patents, and patent applications cited herein are incorporated herein by reference as they are. Furthermore, in this specification, the notation "XX~YY" means "XX or greater and YY or less." In addition, in the compounds exemplified in this specification, while some compound names have multiple notations, the CAS registry number may be listed alongside them. However, since the CAS registry number differs depending on the isomer, etc., the listed compound name is merely an example, and there is no one-to-one correspondence between the compound name and the CAS registry number.

[0011] [1] Chemical composition for ground injection The ground injection chemical composition of the present invention (hereinafter also simply referred to as "this composition") is composed of two chemical solutions, Solution A and Solution B. Solution A contains a water-soluble silicate and a catalyst. Solution B contains polyisocyanate, The catalyst contains two types of tertiary amines: a first tertiary amine (hereinafter also referred to as "first-tertiary amine") and a second tertiary amine (hereinafter also referred to as "second-tertiary amine"). Primary-tertiary amines comprise a hydroxyl group and a tertiary amino group having a methyl group directly attached to a nitrogen atom. Secondary and tertiary amines are characterized by having a tertiary amino group having a methyl group directly attached to a nitrogen atom, and lacking a hydroxyl group.

[0012] [1]Liquid A Solution A contains a "water-soluble silicate" and a "catalyst".

[0013] (1) Water-soluble silicates Water-soluble silicates are silicate compounds that exhibit water solubility, and generally include those referred to as water glass. Metasilicates, orthosilicates, etc., can also be used if they exhibit water solubility. The types of cations constituting the water-soluble silicate are not limited, but examples include monovalent alkali metal ions (Li ions, Na ions, K ions, etc.) and ammonium ions. Specifically, examples of water-soluble silicates include sodium silicate, potassium silicate, lithium silicate, and ammonium silicate. These may be used individually or in combination of two or more. In this invention, sodium silicate (sodium silicate) is preferred among the above due to its low cost and easy availability.

[0014] Sodium silicate can generally be represented as Na2O·nSiO2, and in the case of water-soluble sodium silicate, n is usually > 1, and in the water-soluble sodium silicate used in this invention, n is preferably between 2.0 and 4.0. Within this range, excellent storage stability is achieved, and low-temperature coagulation can be suppressed. Furthermore, when preparing solution A, water-soluble silicates are usually added as an aqueous solution (hereinafter simply referred to as "silicate aqueous solution"). While silicate aqueous solutions may be prepared as appropriate, they are also commercially available as silicate aqueous solutions (sodium silicate aqueous solution), sodium silicate, water glass, etc., so these commercially available products can be used. Regarding sodium silicate, various types of sodium silicate specified in the JIS standard (JIS K1408), such as No. 1, No. 2, and No. 3, can be used. These may be used individually or in combination of two or more types. In addition, products formulated in accordance with this JIS standard, such as No. 4, No. 5, No. 1.5, No. 2.5, etc., can be used. These may be used individually or in combination of two or more types. The solid content of the silicate aqueous solution is not limited, but from the viewpoint of the stability and solidification characteristics of solution A, it is preferably 20 to 60% by mass, and more preferably 30 to 50% by mass, relative to the total silicate aqueous solution.

[0015] The amount of water-soluble silicate contained in solution A is not limited, but when the entire solution A is considered to be 100% by mass, the total of 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. 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 combined arbitrarily. That is, for example, it can be 80-99.99% by mass, 85-99.8% by mass, 88-99.6% by mass, and 89-99.4% by mass. Note that the water mentioned above refers to the total amount of water contained in solution A. That is, when water-soluble silicate is used as an aqueous solution (i.e., water glass), the water 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 added as water.

[0016] (2) Catalyst A catalyst is a component that contributes as a catalyst when a foam (foamed solidified body), which is a reaction product, is formed from the components contained in liquids A and B after they are mixed. In this composition, the catalyst contains two types of tertiary amines: "primary-tertiary amines" and "secondary-tertiary amines".

[0017] (2-1) Primary-tertiary amines Primary, secondary, and tertiary amines are compounds that possess a hydroxyl group and a tertiary amino group (hereinafter also simply referred to as a "methyl tertiary amino group") that has a methyl group directly attached to a nitrogen atom. While primary, secondary, and tertiary amines exhibit poor foaming stability when used alone, in this composition, their combined use with secondary and tertiary amines allows the catalyst as a whole to function effectively. Specifically, it is thought that the combined use of primary, secondary, and tertiary amines reduces the temperature dependence of the reaction and suppresses foaming failure. Although the reason is not entirely clear, in primary, secondary, and tertiary amines, the group directly bonded to the nitrogen atom is a methyl group, resulting in less steric hindrance to the tertiary amino group compared to hydrocarbon groups with a larger number of carbon atoms, such as ethyl groups. This is thought to improve the catalytic activity of primary, secondary, and tertiary amines in the initial stages of the reaction. Furthermore, because primary, secondary, and tertiary amines possess hydroxyl groups, their affinity for water-soluble silicates is improved compared to tertiary amines without hydroxyl groups, thus promoting the reaction between water-soluble silicates and polyisocyanates. In this way, the combined use of primary, secondary, and tertiary amines with secondary and tertiary amines allows the catalyst as a whole to maintain an easy-to-handle reaction schedule while reducing the temperature dependence and preventing foaming failure.

[0018] Primary to tertiary amines may have one tertiary amino group or two or more. They may also have one methyl tertiary amino group (a tertiary amino group having a methyl group directly attached to a nitrogen atom, i.e., a monomethyl tertiary amino group, a dimethyl tertiary amino group, etc.) or two or more. Examples include (1) a compound having one tertiary amino group, which is a methyl tertiary amino group; (2) a compound having two or more tertiary amino groups, where only one of the tertiary amino groups is a methyl tertiary amino group and the others are nonmethyl tertiary amino groups; (3) a compound having two or more tertiary amino groups, where two or more of the tertiary amino groups are methyl tertiary amino groups and one or more nonmethyl tertiary amino groups; and (4) a compound having two or more tertiary amino groups, where all of the tertiary amino groups are methyl tertiary amino groups. These may be used individually or in combination of two or more. Furthermore, primary, secondary, and tertiary amines may have only one hydroxyl group or two or more. Therefore, examples of primary, secondary, and tertiary amines include compounds having one methyl tertiary amino group and one hydroxyl group. Also, compounds having multiple methyl tertiary amino groups and one hydroxyl group are examples. Furthermore, compounds having one methyl tertiary amino group and multiple hydroxyl groups are examples. These may be used individually or in combination of two or more.

[0019] More specifically, examples include compounds having one methyl tertiary amino group and one hydroxyl group, such as 2-(dimethylamino)ethanol (CAS RN: 108-01-0), 2-(ethylmethylamino)ethanol (CAS RN: 2893-43-8), 3-(dimethylamino)-1-propanol (CAS RN: 3179-63-3), 1-(dimethylamino)-2-propanol (CAS RN: 108-16-7), 2-[ethyl(methyl)amino]-1-propanol (CAS RN: 1060817-16-4), 4-(dimethylamino)-1-butanol (CAS RN: 13330-96-6), 3-(dimethylamino)-1-butanol (CAS RN: 2893-65-4), and 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3). These may be used individually or in combination of two or more types. Other examples include compounds having multiple methyl tertiary amino groups and one hydroxyl group, such as 1,3-bis(dimethylamino)-2-propanol (CAS RN: 5966-51-8), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7), and 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN: 90-72-2). These may be used individually or in combination of two or more. Other examples include compounds having one methyl tertiary amino group and multiple hydroxyl groups, such as 3-(dimethylamino)-1,2-propanediol (CAS RN: 623-57-4) and N-methyldiethanolamine (CAS RN: 105-59-9). These may be used individually or in combination of two or more.

[0020] Other examples include compounds having an oxygen atom in the main chain, which includes a methyl tertiary amino group and a hydroxyl group, such as 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7) and N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) ether (CAS RN: 83016-70-0). These may be used individually or in combination of two or more.

[0021] Other examples include compounds having a nitrogen atom in the main chain, which includes a methyl tertiary amino group and a hydroxyl group, such as 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7), and N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) ether (CAS RN: 83016-70-0). These may be used individually or in combination of two or more.

[0022] Other examples include compounds having a ring structure in the main chain, comprising a methyl tertiary amino group and a hydroxyl group, such as 4-(dimethylamino)benzyl alcohol (CAS RN: 1703-46-4), 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN: 90-72-2), and 2-[4-(dimethylamino)phenyl]ethanol (CAS RN: 50438-75-0). These may be used individually or in combination of two or more.

[0023] Among the primary, secondary, and tertiary amines listed above, compounds having an oxygen atom and / or a nitrogen atom in a main chain comprising a tertiary amino group and a hydroxyl group are preferred, and compounds having an oxygen atom and / or a nitrogen atom in a main chain comprising a methyl tertiary amino group and a hydroxyl group are even more preferred. Specifically, tertiary amines such as 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) ether (CAS RN: 83016-70-0), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7) can be suitably used. These may be used individually or in combination of two or more. It is believed that tertiary amines having oxygen and / or nitrogen atoms in their main chain exhibit even greater affinity for water-soluble silicates compared to tertiary amines that do not have oxygen and nitrogen atoms in their main chain, thereby promoting the reaction between water-soluble silicates and polyisocyanates.

[0024] On the other hand, among the primary, secondary, and tertiary amines mentioned above, compounds that do not have a ring structure in the main chain and possess a tertiary amino group and a hydroxyl group are preferred, and compounds that do not have a ring structure in the main chain and possess a methyl tertiary amino group and a hydroxyl group are even more preferred. Compared to tertiary amines that do not have a ring structure in the main chain, the affinity for water-soluble silicates is further improved, and it is thought that the reaction between water-soluble silicates and polyisocyanates can be promoted.

[0025] Furthermore, among the primary, secondary, and tertiary amines mentioned above, compounds in which the methyl tertiary amino group is a dimethylamino group (dimethyl tertiary amino group) are preferred. In other words, tertiary amines having a dimethyl tertiary amino group are preferred. That is, by having a dimethyl tertiary amino group, the tertiary amino group can form the terminal end of the compound. In addition, because the hydrocarbon group constituting the tertiary amino group has a small number of carbon atoms, the steric hindrance of the terminal tertiary amino group can be reduced, which is thought to further improve the catalytic activity of primary, secondary, and tertiary amines in the initial stages of the reaction.

[0026] (2-2) Secondary and tertiary amines Secondary and tertiary amines are compounds that possess a tertiary amino group (methyl tertiary amino group) with a methyl group directly attached to a nitrogen atom, and that do not possess a hydroxyl group. When used alone, secondary and tertiary amines exhibit problems such as poor foaming stability and temperature dependence of the reaction. However, in this composition, their combined use with primary and tertiary amines allows the catalyst as a whole to function effectively. Specifically, it is thought that the secondary and tertiary amines, when used in combination, exert an effect that promotes the overall reaction. Although the reason is not entirely clear, in secondary and tertiary amines, the group directly bonded to the nitrogen atom is a methyl group, which reduces the steric hindrance of the tertiary amino group compared to hydrocarbon groups with a larger number of carbon atoms, such as ethyl groups. This is thought to improve the catalytic activity of the secondary and tertiary amines in the initial stages of the reaction. Furthermore, since secondary and tertiary amines do not have hydroxyl groups, it is thought that they can promote the overall reaction between the polyisocyanate and solution A. Thus, by using primary and tertiary amines in combination with secondary and tertiary amines, it is thought that the catalyst as a whole can ensure an easy-to-handle reaction schedule while reducing temperature dependence and preventing foaming failure.

[0027] A secondary or tertiary amine may have one tertiary amino group or two or more. It may also have one methyl tertiary amino group (a tertiary amino group having a methyl group directly attached to a nitrogen atom) or two or more. Specifically, examples include (1) a compound having only one tertiary amino group, wherein the tertiary amino group is a methyl tertiary amino group; (2) a compound having two or more tertiary amino groups, wherein only one of the tertiary amino groups is a methyl tertiary amino group and the others are non-methyl tertiary amino groups; (3) a compound having two or more tertiary amino groups, wherein two or more of the tertiary amino groups are methyl tertiary amino groups and one or more non-methyl tertiary amino groups; and (4) a compound having two or more tertiary amino groups, wherein all of the tertiary amino groups are methyl tertiary amino groups. These can be used individually or in combination of two or more. Furthermore, secondary and tertiary amines do not contain a hydroxyl group.

[0028] More specifically, N,N-dimethylalkylamines such as N,N-dimethylbutylamine (CAS RN: 927-62-8), N,N-dimethylhexylamine (CAS RN: 4385-04-0), N,N-dimethyloctylamine (CAS RN: 7378-99-6), N,N-dimethyldecylamine (CAS RN: 1120-24-7), N,N-dimethyldodecylamine (CAS RN: 112-18-5), N,N-dimethylhexadecylamine (CAS RN: 112-69-6), (dimethylamino)alkylamines such as 2-(dimethylamino)ethylamine (CAS RN: 108-00-9), 3-(dimethylamino)propylamine (CAS RN: 109-55-7), and (dimethylamino)acetonitrile (CAS 1,2-(dimethylamino)pyrrole (CAS RN: 1739-84-0), 1,2-dimethylimidazole (CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (CAS RN: 4271-96-9), 4-dimethylaminotoluene (CAS RN: 99-97-8), dimethylaniline (CAS RN: 121-69-7), 4-dimethylaminoaniline (CAS RN: 99-98-9), 2-(dimethylamino)pyridine (CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (CAS RN: 4271-96-9), 4-dimethylaminotoluene (CAS RN: 99-97-8), dimethylaniline (CAS RN: 121-69-7), 4-dimethylaminoaniline (CAS RN: 99-98-9), 2-(dimethylamino)pyridine (CAS Examples include compounds having only one tertiary amino group, where the tertiary amino group is a methyl tertiary amino group, such as 4-(dimethylamino)pyridine (CAS RN: 1122-58-3), 4-(dimethylamino)benzonitrile (CAS RN: 1197-19-9), N,N-dimethylbenzylamine (CAS RN: 103-83-3), and 4-methylmorpholine (CAS RN: 109-02-4). These compounds may be used individually or in combination of two or more.

[0029] Also, tetramethylalkanediamines such as N,N,N',N'-tetramethyldiaminomethane (CAS RN: 51-80-9), N,N,N',N'-tetramethylethylenediamine (CAS RN: 110-18-9), N,N,N',N'-tetramethyl-1,4-butanediamine (CAS RN: 111-51-3), N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN: 111-18-2), 4,4'-bis-(dimethylamino)benzophenone (CAS RN: 90-94-8), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN: 6711-48-4), and N,N,N',N'-tetramethyl-1,3-diaminobutane (CAS Examples include compounds having two tertiary amino groups, such as N,N'-dimethylpiperazine (CAS RN: 97-84-7), bis(2-(N,N-dimethylamino)ethyl) ether (CAS RN: 3033-62-3), tert-butoxybis(dimethylamino)methane (CAS RN: 5815-08-7), and N,N,N',N'-tetramethyl-1,8-naphthalenediamine (CAS RN: 20734-58-1). These may be used individually or in combination of two or more.

[0030] Other examples include compounds having three tertiary amino groups, such as N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), tris(dimethylamino)methane (CAS RN: 5762-56-1), bis(4-dimethylaminophenyl)-4-dimethylamino-d6-phenylmethane (CAS RN: 1173023-92-1), and 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8). These may be used individually or in combination of two or more.

[0031] Other examples include compounds having four tertiary amino groups, such as tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), tetrakis(dimethylamino)ethylene (CAS RN: 996-70-3), and 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS RN: 3083-10-1). These may be used individually or in combination of two or more.

[0032] Furthermore, among the secondary and tertiary amines exemplified above, 1,2-dimethylimidazole (CAS RN: 1739-84-0), 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (CAS RN: 4271-96-9), 4-methylmorpholine (CAS RN: 109-02-4), N,N'-dimethylpiperazine (CAS RN: 106-58-1), 4-dimethylaminotoluene (CAS RN: 99-97-8), dimethylaniline (CAS RN: 121-69-7), 4-dimethylaminoaniline (CAS RN: 99-98-9), 2-(dimethylamino)pyridine (CAS 4-(dimethylamino)pyridine (CAS RN: 1122-58-3), 4-(dimethylamino)benzonitrile (CAS RN: 1197-19-9), N,N,N',N'-tetramethyl-1,8-naphthalenediamine (CAS RN: 20734-58-1), bis(4-dimethylaminophenyl)-4-dimethylamino-d6-phenylmethane (CAS RN: 1173023-92-1), N,N-dimethylbenzylamine (CAS RN: 103-83-3), N,N-dimethylcyclohexylamine (CAS RN: 98-94-2), 4,4'-bis-(dimethylamino)benzophenone (CAS RN: 90-94-8), etc., are tertiary amines having a ring structure.

[0033] Furthermore, among the tertiary amines having the above ring structure, 1,2-dimethylimidazole (CAS RN: 1739-84-0), 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8), triethylenediamine (CAS RN: 280-57-9), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (CAS RN: 4271-96-9), 4-methylmorpholine (CAS RN: 109-02-4), N,N'-dimethylpiperazine (CAS RN: 106-58-1), 2-(dimethylamino)pyridine (CAS RN: 5683-33-0), 4-(dimethylamino)pyridine (CAS RN:1122-58-3) is a heterocyclic compound in which the nitrogen atoms constituting the tertiary amino group themselves form a ring skeleton.

[0034] Among the secondary and tertiary amines mentioned above, tertiary amines having at least two dimethyl tertiary amino groups (tertiary amino groups in which two of the substituents directly attached to the nitrogen atom are methyl groups) at their molecular ends, or tertiary amines having a heterocycle in which the nitrogen atom constituting the tertiary amino group itself forms a cyclic skeleton (i.e., tertiary amines in which the nitrogen atom constituting the tertiary amine forms a heterocyclic skeleton) are preferred. That is, the former (tertiary amines having at least two dimethyl tertiary amino groups at their molecular ends) include the aforementioned tetramethylalkanediamines, N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), 4,4'-bis-(dimethylamino)benzophenone (CAS RN: 90-94-8), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN: 6711-48-4), N,N,N',N'-tetramethyl-1,3-diaminobutane (CAS RN: 97-84-7), N,N,N',N'-tetramethyl-1,8-naphthalenediamine (CAS RN: 20734-58-1), and tris[2-(dimethylamino)ethyl]amine (CAS Examples include 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS RN:3083-10-1), tris(dimethylamino)methane (CAS RN:5762-56-1), and bis(4-dimethylaminophenyl)-4-dimethylamino-d6-phenylmethane (CAS RN:1173023-92-1). Among these, compounds with 3 to 10 carbon atoms in the main chain connecting the terminal dimethyl tertiary amino groups (dimethyl tertiary amino groups located at the molecular ends) are preferred. Specifically, N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN: 111-18-2), N,N,N',N'-tetramethyl-1,4-butanediamine (CAS RN: 111-51-3), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5) are preferred.

[0035] Furthermore, the latter (tertiary amines that possess a heterocycle in which the nitrogen atom constituting the tertiary amino group itself forms a ring skeleton) includes 1,2-dimethylimidazole (CAS RN: 1739-84-0), 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8), triethylenediamine (CAS RN: 280-57-9), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (CAS RN: 4271-96-9), 4-methylmorpholine (CAS RN: 109-02-4), N,N'-dimethylpiperazine (CAS RN: 106-58-1), 2-(dimethylamino)pyridine (CAS RN: 5683-33-0), and 4-(dimethylamino)pyridine (CAS Examples include RN:1122-58-3). These may be used individually or in combination of two or more.

[0036] (2-3) Amount of catalyst The amount of catalyst contained in solution A (total amount of primary-tertiary amines and secondary-tertiary amines) is not limited, but is preferably 0.05 parts by mass or more per 100 parts by mass of polyisocyanate contained in solution B, can be 0.1 parts by mass or more, can be 0.3 parts by mass or more, can be 0.5 parts by mass or more, and can be 0.7 parts by mass or more. On the other hand, this content is preferably 5 parts by mass or less, can be 4 parts by mass or less, can be 3 parts by mass or less, can be 2 parts by mass or less, and can be 1.6 parts by mass or less. These upper and lower limits can be arbitrarily combined. That is, for example, is preferably 0.05 to 5 parts by mass, can be 0.1 to 4 parts by mass, can be 0.3 to 3 parts by mass, can be 0.5 to 2 parts by mass, and can be 0.7 to 1.6 parts by mass. In the preferred range, a reaction schedule that is easy to handle can be achieved while reducing the reaction temperature dependence and preventing foaming defects.

[0037] Furthermore, while the ratio of primary-tertiary amines to secondary-tertiary amines is not limited, when the total of primary-tertiary amines and secondary-tertiary amines is set to 100% by mass, the proportion of primary-tertiary amines is preferably 5% by mass or more, can be 10% by mass or more, and can be 18% by mass or more. On the other hand, this proportion is preferably 95% by mass or less, can be 85% by mass or less, and can be 75% by mass or less. These upper and lower limits can be combined arbitrarily. That is, for example, it can be 5 to 95% by mass, 10 to 85% by mass, and 18 to 75% by mass.

[0038] (2-4) Other catalysts Furthermore, other catalysts other than the primary, tertiary, and secondary tertiary amines mentioned above may be added to Solution A. However, the amount of other catalysts is usually 30 parts by mass or less, when the total amount of primary, tertiary, and secondary tertiary amines is 100 parts by mass. Other catalysts include metal catalysts and quaternary ammonium salts. These may be used individually or in combination of two or more.

[0039] Examples of metal catalysts include organic acid metal salts and organometallic complexes. Examples of metal species that make up organic acid metal salts include sodium, potassium, calcium, iron, cobalt, nickel, zinc, zirconium, tin, lead, and bismuth. Examples of organic acids that make up organic acid metal salts include acetic acid, octic acid, neodecanoic acid, naphthenic acid, and rosinic acid. Specifically, examples include sodium acetate, potassium acetate, potassium octoate, bismuth octoate, lead octoate, iron octoate, tin octoate, calcium octoate, zinc octoate, zirconium octoate, bismuth neodecanoate, zinc neodecanoate, lead neodecanoate, cobalt neodecanoate, bismuth rosinate, and dibutyltin dilaurate. These may be used individually or in combination of two or more. Furthermore, examples of metal species that constitute organometallic complexes include iron, cobalt, nickel, zinc, zirconium, tin, lead, and bismuth. Examples of ligands that constitute organometallic complexes include acetylacetone, such as iron acetylacetone, nickel acetylacetone, zinc acetylacetone, zirconium acetylacetone, and tin acetylacetone. These can be used individually or in combination of two or more.

[0040] Examples of cationic species constituting quaternary ammonium salts include alkylammonium (tetramethylammonium, tetraethylammonium, etc.) and hydroxyalkylammonium salts (hydroxypropyltrimethylammonium, hydroxyethyltrimethylammonium, etc.). The anionic species constituting quaternary ammonium salts may be used individually or in combination of two or more. Examples of anionic species constituting quaternary ammonium salts include organic groups such as formic acid, acetate, 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, octic acid, and phosphate ester groups; and inorganic groups such as halogen groups, hydroxyl groups, bicarbonate groups, and carbonate groups. These may be used individually or in combination of two or more.

[0041] (3) Polyol Solution A may contain other components besides the water-soluble silicate and catalyst. Examples of other components include polyols. A polyol is an organic compound having two or more hydroxyl groups. The type of polyol is not limited; polyols conventionally used as components of soil injection chemical compositions can be used as appropriate. Specifically, examples of polyols include aliphatic polyols, polyester polyols, polyether polyols, polycarbonate polyols, olefin polyols, acrylic polyols, and siloxane polyols. Among these, aliphatic polyols, polyester polyols, and polyether polyols are preferred, with polyether polyols being particularly preferred. These may be used individually or in combination of two or more.

[0042] Examples of aliphatic polyols include compounds having two hydroxyl 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 hydroxyl groups, such as glycerin, trimethylolpropane, and trimethylolethane; and sugar alcohols such as xylitol and sorbitol. These may be used individually or in combination of two or more.

[0043] 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 individually or in combination of two or more components. 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 dodecanedionic 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 individually or in combination of two or more.

[0044] Examples of polyether polyols include (1) reaction products obtained by addition reaction with alkylene oxide using a compound having two or more active hydrogens as an initiator, (2) Mannich condensates obtained by reacting phenols, aldehydes, and secondary amines, and (3) Mannich-type polyether polyols obtained by adding alkylene oxide to the Mannich condensate. These may be used individually or in combination of two or more. Furthermore, examples of compounds having two or more active hydrogens in (1) above include polyhydric alcohols and amine compounds. These may be used individually or in combination of two or more. Among these, examples of polyhydric alcohols include ethylene glycol, propylene glycol, tetramethylene glycol, butylene glycol, pentamethylene glycol, hexamethylene glycol, butanediol, glycerin, trimethylolpropane, and pentaerythritol. These may be used individually or in combination of two or more. Examples of amine compounds include diamines such as ethylenediamine, toluenediamine, and tolylenediamine; and alkanolamines such as ethanolamine and diethanolamine. These may be used individually or in combination of two or more. In addition, examples of alkylene oxides include ethylene oxide and propylene oxide. These may be used individually or in combination of two or more.

[0045] In this composition, it is preferable to include a polyether polyol among the various polyols mentioned above. When a polyether polyol is used, the miscibility between the silicate aqueous solution and the isocyanate is better compared to when other polyols are used, and the chemical stability can be improved.

[0046] Furthermore, when using a polyether polyol, its molecular weight is not limited, but it is preferable that its number average molecular weight is greater than 200. When a polyether polyol with a number average molecular weight greater than 200 is used, foaming stability is higher and a good foam can be obtained compared to when a polyether polyol with a number average molecular weight of 200 or less is used. The number average molecular weight of the polyether polyol is more preferably 250 or more, even more preferably 300 or more, and particularly preferably 350 or more. On the other hand, the number average molecular weight of the polyether polyol is preferably 10000 or less, more preferably 7000 or less, even more preferably 5000 or less, and particularly preferably 2500 or less. These upper and lower limits can be arbitrarily combined. That is, for example, if the number average molecular weight of the polyether polyol is Mn, then Mn is 200 <Mn≦10000とすることができ、250<Mn≦7000とすることができ、300<Mn≦5000とすることができ、350<Mn≦2500とすることができる。 Furthermore, the number-average molecular weight of polyether polyols can be measured according to JIS K7252-2 or calculated from their hydroxyl value.

[0047] Furthermore, when polyol is included in solution A, its content is not limited, but it is preferable that the polyol content be 20 parts by mass or less when the total amount of water-soluble silicate and water in solution A is 100 parts by mass. When the polyol content is 20 parts by mass or less, foam generation in the flowing water can be suppressed and the defoaming time can be shortened compared to when the polyol content exceeds 20 parts by mass, and costs can be reduced. The polyol content is more preferably 15 parts by mass or less, even more preferably 13 parts by mass or less, and particularly preferably 12 parts by mass or less. On the other hand, the polyol content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 1.5 parts by mass or more. These upper and lower limits can be combined arbitrarily. That is, for example, the polyol content can be 0.1 to 20 parts by mass, 0.5 to 15 parts by mass, 1 to 13 parts by mass, or 1.5 to 12 parts by mass, when the water-soluble silicate contained in solution A is considered to be 100 parts by mass. Furthermore, in order to suppress the generation of foam in the flowing water and shorten the defoaming time, the polyol content is preferably 8% by mass or less, more preferably 7% by mass or less, and even more preferably 6% by mass or less, relative to 100% by mass of the entire solution A.

[0048] (4) Viscosity of solution A The viscosity of liquid A in this composition is not limited and may be the same as or different from that of liquid B. However, 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 workability is excellent in terms of appropriate injection pressure, and it becomes less likely to be diluted with water, allowing for cleaner wastewater. The viscosity of liquid A can be measured at 25°C using a type B viscometer in accordance with JIS K7117-1.

[0049] [2]B liquid (1) Polyisocyanate Solution B contains "polyisocyanate." Polyisocyanate is an organic compound having two or more isocyanate groups (NCO groups) in its molecule. As the polyisocyanate, monomers having two or more isocyanate groups (NCO groups) in their molecule may be used, or polymers (prepolymers, etc.) may be used. Furthermore, if a polymer is used, the compound (monomer) constituting the polymer may be only one type (mononuclear) or two or more types (multinuclear). Furthermore, a mixture of monomers and polymers may be used. Examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These may be used individually or in combination of two or more types.

[0050] 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], and tetramethylxyl Examples include reylene 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-cyclohexyl isocyanate], triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris(isocyanatephenyl)-thiophosphate, etc. These may be used individually or in combination of two or more.

[0051] 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, and dimer acid diisocyanate. These may be used individually 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], and bis(isocyanatomethyl)cyclohexane [cis-1,3-(diisocyanatetomethyl)cyclohexane, trans-1,3-(diisocyanatetomethyl)cyclohexane, 1,4-(diisocyanatetomethyl)cyclohexane]. These may be used individually or in combination of two or more. Furthermore, the above-mentioned monomer compounds may be modified forms of these monomers (isocyanurate modified forms, carbodiimide modified forms, etc.), their block products, their hydrogenated products, etc. Alternatively, an isocyanate group-containing prepolymer obtained by reacting an active hydrogen group-containing compound with the polyisocyanate by a known method may be used. Each of these may be used individually or in combination of two or more.

[0052] Among the polyisocyanates contained in solution B of this composition, aromatic polyisocyanates are preferred from the viewpoint of the strength of the resulting foam and the reaction rate, and more preferably diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), and even more preferably diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI).

[0053] The amount of polyisocyanate contained in solution B is not limited; for example, solution B can consist solely of polyisocyanate. In this case, if the total volume of solution B is 100% by mass, the amount of polyisocyanate will be 100% by mass. On the other hand, if other components (e.g., additives) other than polyisocyanate are added to solution B, if the total volume of solution B is 100% by mass, 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. 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 combined arbitrarily. That is, for example, it can be 85-99.99% by mass, 90-99.8% by mass, 91-99.6% by mass, and 82-99.4% by mass.

[0054] (2) Viscosity of solution B The viscosity of liquid B in this composition is not limited and may be the same as or different from that of liquid A. However, 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 workability is excellent in terms of appropriate injection pressure, and it becomes less likely to be diluted with water, allowing for cleaner wastewater. Furthermore, the viscosity of solution B can be measured at 25°C using a type B viscometer in accordance with JIS K7117-1.

[0055] [3] Other ingredients Other components may be added to liquids A and B of this composition as needed. Examples of other components include foaming agents, foam stabilizers, flame retardants, and viscosity modifiers (thickening agents, thickening agents, etc.). These may be used individually or in combination of two or more.

[0056] The blowing agent is a component that forms the foamed state of the resulting solidified body (foam). The type of blowing agent is not limited, but examples include inorganic blowing agents and organic blowing agents. These may be used individually or in combination of two or more. Examples of inorganic blowing agents include water and carbon dioxide. Of these, water functions as a blowing agent in the presence of polyisocyanate, so if water is used as a blowing agent in this composition, it can be added to solution A. Also, when water-soluble silicates are used as water glass (silicate aqueous solution), the water constituting the water glass can be made to function as a blowing agent. As for organic blowing agents, non-fluorocarbon and fluorocarbon blowing agents can be used. Non-fluorocarbon organic blowing agents are preferred, and halogenated alkenes such as hydrofluoroolefins and hydrochlorofluoroolefins are more preferred. When a blowing agent is used, if the total amount of polyisocyanate contained in this composition is 100 parts by mass, the amount of blowing agent can be 0.01 to 50 parts by mass, 0.1 to 25 parts by mass, or 0.5 to 10 parts by mass.

[0057] A foam stabilizer is a component that improves the uniformity of the foam cells that make up the resulting solidified body (foam). The type of foam stabilizer is not limited, but examples of foam stabilizers that can be used include silicone-based foam stabilizers (silicone, etc.), nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, etc. These may be used individually or in combination of two or more. When using a foam stabilizer, if the total polyisocyanate in this composition is 100 parts by mass, the amount of foam stabilizer can be 0.05 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass. Within this range, it is possible to obtain a suitable foam-stable effect while also enabling clean wastewater.

[0058] The viscosity modifier is a component that can adjust the viscosity of liquid A and / or liquid B that constitute this composition. The type of viscosity modifier is not limited, but examples of viscosity modifiers include viscosity reducers and viscosity enhancers, and viscosity reducers can be suitably used in this composition. Examples of viscosity reducers include alcohols, ethers, esters, petroleum hydrocarbons, etc. These may be used individually or in combination of two or more. Examples of alcohols include methanol, ethanol, propanol, isopropyl alcohol, and butanol. Examples of ethers include ethyl cellsolve and butyl cellsolve. Examples of esters include cyclic esters such as propylene carbonate; and esters (acyclic esters) such as methyl dicarboxylate and ethylene glycol monomethyl ether acetate. When a viscosity modifier is used, if the total polyisocyanate contained in this composition is 100 parts by mass, the viscosity modifier can be 0.1 to 15 parts by mass, 0.5 to 10 parts by mass, or 1 to 8 parts by mass.

[0059] Flame retardants are components that improve the flame retardancy of the resulting solidified body (foam). The type of flame retardant is not limited, but examples of flame retardants include phosphate esters (monophosphate esters, condensed phosphate esters, organophosphate monoesters, organophosphate diesters, organophosphate triesters, monophosphates, pyrophosphates, polyphosphates, organophosphinates, etc.), red phosphorus, boron-based flame retardants, bromine-based flame retardants, chlorine-based flame retardants (halogenated paraffins, etc.), metal stannate salts, antimony-containing flame retardants, metal hydroxides, hydrates of metal compounds, clay minerals, etc. These may be used individually or in combination of two or more. When using a flame retardant, if the total amount of polyisocyanate contained in this composition is 100 parts by mass, the amount of the flame retardant can be 0.1 to 100 parts by mass, 0.5 to 50 parts by mass, or 1 to 10 parts by mass.

[0060] [4] Uses of chemical compositions for ground injection The uses of this composition are not limited, but due to its properties, it is particularly suitable for use in the fields of construction and civil engineering (architecture and civil engineering). Specifically, this composition can be used as a chemical injection solution for ground injection in the fields of construction and civil engineering. For example, in the field of architecture, it can be used for flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, insulation materials for walls, insulation materials for ceilings, insulation materials for floors, 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, this composition can be injected into the ground, underground, soil, ground, bedrock, gaps between these and structures (architectural structures), and even gaps within structures, and the injection site can be filled and reinforced by foaming and hardening.

[0061] [2] Foam (foamed solidified body) and method for producing the same The foam of the present invention is characterized by being obtained by mixing liquid A and liquid B. The mixing of liquid A and liquid B can be performed during the formation of the foam. That is, mixing can be done before injection, during injection, or after injection at the point where the composition is intended to be injected, and two or more of these mixing methods may be combined. More specifically, it is desirable to combine liquid A and liquid B just before the discharge nozzle in the piping and mix them immediately before discharge. This makes it easier to control the mixing ratio within the desired range.

[0062] Furthermore, the mixing ratio of liquid A and liquid B is not limited and can be set to an appropriate range depending on the physical properties of the foam formed by the reaction of liquid A and liquid B. However, it is generally preferable that the ratio of liquid A to liquid B is 2:1 to 1:3 by mass, and more preferably 1.5:1 to 1:2.

[0063] The foaming ratio of the foam obtained by mixing liquid A and liquid B is not limited, but at 20°C, it is preferably 20 times or less, and more preferably 3 to 15 times. Within this range, sufficient strength can be obtained in the resulting foam, and it is also economically efficient. The method for measuring the foaming ratio will be described later in the examples.

[0064] The time at which foaming begins after mixing solution A and solution B is called the "foaming start time" (T S ) is defined as the time when the hardening reaction is completed, and the time when the hardening reaction is completed is called the "foaming completion time" (T E If this is the case, the foaming completion time at 20℃ (T E20 The foaming time (T) is preferably 15 seconds or more, more preferably 20 seconds or more, even more preferably 25 seconds or more, and particularly preferably 30 seconds or more. E20 The foaming end time (T) is preferably 300 seconds or less, more preferably 250 seconds or less, even more preferably 200 seconds or less, and particularly preferably 180 seconds or less. These upper and lower limits can be combined in any way. That is, for example, the foaming end time (T) E20 The foaming time (T) is preferably 15 to 300 seconds, more preferably 20 to 250 seconds, even more preferably 25 to 200 seconds, and particularly preferably 30 to 180 seconds. E20In a preferred range, it is possible to obtain an easy-to-handle reaction schedule while reducing the reaction temperature dependence and preventing foaming defects.

[0065] Also, the foaming end time (T E30 ) at 30 °C is preferably 15 seconds or more, more preferably 20 seconds or more, still more preferably 25 seconds or more, and particularly preferably 30 seconds or more. On the other hand, the foaming end time (T E30 ) is preferably 300 seconds or less, more preferably 250 seconds or less, still more preferably 200 seconds or less, and particularly preferably 180 seconds or less. These upper and lower limit values can be arbitrarily combined. That is, for example, the foaming end time (T E30 ) is preferably 15 to 300 seconds, more preferably 20 to 250 seconds, still more preferably 25 to 200 seconds, and particularly preferably 30 to 180 seconds. In a preferred range of the foaming end time (T E30 ), it is possible to obtain an easy-to-handle reaction schedule while reducing the reaction temperature dependence and preventing foaming defects.

[0066] The time when foaming starts due to the mixing of liquid A and liquid B is defined as the "foaming start time" (T S ), and the time when the curing reaction ends is defined as the "foaming end time" (T E ). Further, when the ratio of the "foaming start time" to the "foaming end time" (foaming start time / foaming end time) is defined as the time ratio (T C ), the time ratio (T C20 ) at 20 °C is preferably 0.70 or less, more preferably 0.69 or less, and still more preferably 0.68 or less. On the other hand, the time ratio (T C20 ) is preferably 0.30 or more, more preferably 0.35 or more, and still more preferably 0.38 or more. These upper and lower limit values can be arbitrarily combined. That is, for example, the time ratio (T<​​​​​ Time ratio at 30℃ (T C30 The time ratio (T) is preferably 0.70 or less, more preferably 0.69 or less, and even more preferably 0.68 or less. C30 The time ratio (T) is preferably 0.30 or higher, more preferably 0.35 or higher, and even more preferably 0.38 or higher. These upper and lower limits can be combined in any way. That is, for example, the time ratio (T) C30 The time ratio (T) is preferably 0.30 to 0.70, more preferably 0.35 to 0.69, and even more preferably 0.38 to 0.68. C30 Within the preferred range, it is possible to obtain an easy-to-handle reaction schedule while reducing the reaction temperature dependence and preventing foaming defects. [Examples]

[0068] The present invention will be described in more detail below with reference to examples, but these examples are merely illustrative examples for explanatory purposes, and the present invention is not limited in any sense to these examples.

[0069] [1] Preparation of composition Each of the components listed below was mixed in the combinations and formulations shown in Tables 1 and 2 to obtain soil injection chemical compositions having liquid A and liquid B for Examples 1 to 18 and Comparative Examples 1 to 10.

[0070] (1) Water-soluble silicates (silicate aqueous solution) • Sodium silicate No. 2: Sodium silicate No. 2, manufactured by Fuji Chemical Co., Ltd., solids content 40% • Sodium Silicate No. 1: Sodium silicate No. 1, manufactured by Fuji Chemical Co., Ltd., solid content 48% (adjust to 40% solid content by adding water before use)

[0071] (2) Polyol • PP400: Polyether polyol (polypropylene glycol), manufactured by Sanyo Chemical Industries, Ltd., product name "Sannix PP-400", number average molecular weight 400, number of functional groups 2 • PP1000: Polyether polyol (polypropylene glycol), manufactured by Sanyo Chemical Industries, Ltd., product name "Sannix PP-1000", number average molecular weight 1000, number of functional groups 2 TPG (Mn192): Tripropylene glycol, Tokyo Chemical Industry Co., Ltd., number average molecular weight 192, number of functional groups 2

[0072] (3) Catalyst (3-1) First tertiary amine • Dimethylaminoethoxyethanol: 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), manufactured by Kao Corporation, product name "Kaorizer No. 26", contains OH group and methyl group. Trimethylaminoethylethanolamine: 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), manufactured by Tosoh Corporation, product name "Toyocat RX-5", contains OH group and methyl group. • Dimethylaminohexanol: 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), manufactured by Kao Corporation, product name "Kaorizer No. 25", contains OH group and methyl group.

[0073] (3-2) Comparative catalyst for the first tertiary amine • Diethylaminoethoxyethanol: 2-[2-(diethylamino)ethoxy]ethanol (CAS RN: 140-82-9), manufactured by Tokyo Chemical Industry Co., Ltd., contains OH group, does not contain methyl group.

[0074] (3-3) Second tertiary amine Tetramethylhexamethylenediamine: N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN: 111-18-2), manufactured by Kao Corporation, product name "Kaorizer No. 1", OH group (absent), methyl group (present) Pentamethyldiethylenetriamine: N,N,N',N",N"-Pentamethyldiethylenetriamine (CAS RN: 3030-47-5), manufactured by Kao Corporation, product name "Kaorizer No. 3", OH group (absent), methyl group (present) • Dimethylimidazole: 70% 1,2-dimethylimidazole (CAS RN: 1739-84-0) ethylene glycol solution, manufactured by Kao Corporation, product name "Kaorizer No. 350", OH group (absent), methyl group (present) (3-4) Comparative catalyst for the second tertiary amine • Triethylenediamine: 33% Triethylenediamine (CAS RN: 280-57-9) Dipropylene glycol solution, manufactured by Kao Corporation, product name "Kaorizer No. 31", OH group (none), methyl group (none)

[0075] (4) Polyisocyanates • MDI (M100): Polymeric MDI, manufactured by Kinko Mitsui Chemicals, product name "Cosmonate M100" • MDI (M200): Polymeric MDI, manufactured by Kinko Mitsui Chemicals, product name "Cosmonate M200" • Prepolymer: Prepolymer MDI, proprietary synthesis product, reaction product obtained by adding 5 parts of the above "PP-1000" to 100 parts of the above "M100" and reacting at 70°C for 3 hours.

[0076] (5) Foam stabilizers • Foam stabilizer: Polyether-modified siloxane, manufactured by Momentive Performance Materials Japan LLC, product name "Niax Silicone L-6970")

[0077] (6) Viscosity reducers • Viscosity reducer: Propylene carbonate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0078] (7) Flame retardants • Flame retardant: Tris(chloropropyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[0079] [Table 1]

[0080] [Table 2]

[0081] [2] Measurement and evaluation (1) Viscosity measurement of liquid A and liquid B Using a Type B viscometer, the viscosity of liquids A and B constituting each ground-filling chemical composition for Examples 1-18 and Comparative Examples 1-10 was measured at 25°C in accordance with JIS K7117-1. The results are shown in Tables 1 and 2.

[0082] (2) Foaming evaluation Using the chemical compositions for injecting each of the Examples 1 to 18 and Comparative Examples 1 to 10 obtained in [1] above, foams were prepared in the following manner, and the foaming start time, foaming end time, time ratio, foaming ratio, and appearance of the foam were measured and evaluated.

[0083] (2-1) Measurement and calculation of foaming start time, foaming end time, and time ratio From each of the injectable chemical compositions for each section of the ground for injection in Examples 1-18 and Comparative Examples 1-10, liquid A and liquid B were separated so that the mass ratio of liquid A to liquid B was 1:1 and the total volume of liquid A and liquid B was 100 mL. After adjusting the temperature of liquid A and liquid B to 20°C, both were placed in a 1 L cup and stirred at 400 rpm for 10 seconds (hand mixing). The time from the completion of stirring to the start of foaming of the mixture of liquid A and liquid B was called the "start time" (foaming start time T). S20 Furthermore, the time when the hardening reaction in the cup was completed was defined as the "completion time" (foaming completion time T). E20 ) was defined as the "time ratio" (T) of these times (start time / end time). C20 These were calculated as follows. The "start time," "end time," and "time ratio" are shown in Tables 1 and 2. Furthermore, except for changing the foam production and evaluation temperature from 20°C to 30°C, the process was carried out similarly, but with the "start time" (foam start time T) being the same. S30 ), "End time" (Foaming end time TE30 ), “time ratio” (T C30 The following values ​​were measured and calculated, and are shown in Tables 1 and 2.

[0084] (2-2) Measurement of expansion ratio The "completion time" measured in (2-1) above (Foaming completion time T E20 The foaming ratio was measured. Specifically, the height of the liquid level in the cup after mixing liquids A and B was completed was measured as H1. Next, when foaming began and the height of the foam formed in the cup reached its maximum, the height of the foam top was measured as the maximum foaming height. Subsequently, the height of the foam at the end of the curing reaction was measured as H2. Then, using the measured values ​​of H1 and H2, the foaming ratio was calculated as H2 / H1. Note that each height was measured visually using a gauge.

[0085] (2-3) Visual evaluation of foam The appearance of the foam obtained in (2-1) above was evaluated according to the following criteria and is shown in Tables 1 and 2. "○": The foam cells are fine, indicating a good quality foam. "△": Shrinkage of 15% to 30% from the maximum foaming height was observed. "×": One or more of the following appearance defects were observed: shrinkage exceeding 30% from the maximum foam height, formation of a large cavity in the center, or rough foam cells. Furthermore, in cases where the above "×" was indicated, "(Shrinkage)" was written for examples where the above shrinkage was observed, "(Cavity)" for examples where the above void was observed, and "(Coarse)" for examples where the above foam cell was rough.

[0086] [3] Effects of the example Tables 1 and 2 show that in the compositions of Comparative Examples 1 to 3, although Solution A contains primary and tertiary amines, it does not contain secondary or tertiary amines, resulting foams show shrinkage or coarsening. Furthermore, in the composition of Comparative Example 4, which contains an amine compound with a hydroxyl group but no tertiary amino group with a methyl group directly attached to a nitrogen atom (an amine compound that is not a primary or tertiary amine), and does not contain secondary or tertiary amines, both the time ratio at 20°C and the time ratio at 30°C are large, exceeding 0.70. Moreover, in the compositions of Comparative Examples 5 to 7, which contain secondary and tertiary amines but do not contain primary or tertiary amines, the resulting foams show shrinkage, voiding, or coarsening, and there is a tendency for either the time ratio at 20°C or the time ratio at 30°C to exceed 0.70. Furthermore, in the composition of Comparative Example 8, which contains an amine compound (an amine compound that is not a secondary or tertiary amine) in solution A that does not have a hydroxyl group, a tertiary amino group having a methyl group directly attached to a nitrogen atom, or any other group, and does not contain any primary or tertiary amines, the resulting foam shows coarsening, and both the time ratio at 20°C and the time ratio at 30°C tend to be larger, exceeding 0.70. Moreover, in the composition of Comparative Example 9, which contains two primary or tertiary amines in solution A but does not contain any secondary or tertiary amines, and in the composition of Comparative Example 10, which contains two secondary or tertiary amines in solution A but does not contain any primary or tertiary amines, the resulting foam shows shrinkage or voiding. In contrast, in the compositions of Examples 1 to 18, where Solution A contains both primary-tertiary amines and secondary-tertiary amines, it is possible to prevent shrinkage, voiding, or coarsening of the resulting foam, and both the time ratio at 20°C and the time ratio at 30°C can be suppressed to a small value of less than 0.70. [Industrial applicability]

[0087] It is suitably used in the fields of architecture and civil engineering (architecture and civil engineering). For example, in the field of architecture, it can be used for wall-filling foam, ceiling-filling foam, floor-filling foam, wall insulation, ceiling insulation, floor insulation, filling internal gaps during the manufacture of structures, and reinforcing structures that have deteriorated over time. In the field of civil engineering, this composition can be injected into the ground, underground, soil, ground, bedrock, the gaps between these and structures (architectural structures), and even gaps within structures, and then foamed and hardened to fill and reinforce the injection points.

Claims

1. A soil injection chemical composition comprising two chemical solutions, Solution A and Solution B, The aforementioned solution A comprises a water-soluble silicate, a catalyst, and a polyol. The aforementioned solution B contains polyisocyanate, The polyol is present in an amount of 8% by mass or less relative to 100% by mass of the entire liquid A. The catalyst comprises two types of tertiary amines: a first tertiary amine and a second tertiary amine. The first tertiary amine comprises a hydroxyl group and a tertiary amino group having a methyl group directly attached to a nitrogen atom, The aforementioned second tertiary amine is characterized by having a tertiary amino group having a methyl group directly attached to a nitrogen atom, and not having a hydroxyl group, in a ground injection chemical composition.

2. The ground injection chemical composition according to claim 1, wherein the first tertiary amine has an oxygen atom and / or a nitrogen atom in a main chain comprising the tertiary amino group and the hydroxyl group.

3. The ground injection chemical composition according to claim 1 or 2, wherein the first tertiary amine does not have a ring structure in the main chain comprising the tertiary amino group and the hydroxyl group.

4. The soil injection chemical composition according to any one of claims 1 to 3, wherein the tertiary amino group of the first tertiary amine is a dimethylamino group.

5. The soil injection chemical composition according to any one of claims 1 to 4, wherein when the total of the first tertiary amine and the second tertiary amine is 100% by mass, the proportion of the first tertiary amine is 5% by mass or more.

6. The soil injection chemical composition according to any one of claims 1 to 5, wherein the polyol is a polyether polyol having a number average molecular weight of more than 200.

7. A foam characterized by being obtained by mixing liquid A and liquid B, which constitute the ground injection chemical composition according to any one of claims 1 to 6.

8. A method for producing a foam, characterized by mixing liquid A and liquid B, which constitute the ground injection chemical composition according to any one of claims 1 to 6, to form a foam.

Images