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

Abstract

To provide a chemical liquid composition which has a preferable foaming ratio, and reduces a reaction temperature dependency for preventing foaming failure, an expanded body and a production method of the same.SOLUTION: There is provided a chemical liquid composition for injection into soil which is formed of: two kinds of liquid which 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 having a hydroxy group and a second tertiary amine having no hydroxy group. The polyol is polyol whose number average molecular weight is greater than 200. 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 chemical liquid composition for ground injection, a foam, and a method for producing the same. More specifically, it relates to a chemical liquid composition for ground injection using silicate and polyisocyanurate, a foam, and a method for producing the same.

Background Art

[0002] Conventionally, foamed urethane grout used as a grout material for ground improvement and filling cavities in structures is known. Since foamed urethane grout as a reaction product is an organic material obtained by substantially reacting a polyol and a polyisocyanate, blending a flame retardant is necessary to obtain high flame retardancy. In addition, foamed urethane grout has a problem that its raw material cost is high. On the other hand, a composite grout obtained as a composite reaction product of an inorganic material and an organic material, in which part of the polyol is replaced with water glass (an aqueous solution of silicate), an inorganic material, is known. Since the composite grout contains an inorganic material as an aggregate, it has excellent flame retardancy compared to grout made of only organic aggregates. In addition, the composite grout has an advantage that its raw material cost is low. Technologies related to such composite grouts are known in Patent Documents 1 and 2 below.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[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] While the expansion ratio of these grout materials can be controlled by catalyst selection, catalyst selection can also lead to temperature sensitivity. In particular, high reaction temperatures can cause unstable foaming, resulting in issues such as post-foaming shrinkage, the formation of cavities within the foam, or uneven foaming 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 a good expansion ratio.

[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 can have a good foaming ratio while reducing the dependence on reaction temperature and preventing 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, a polyol, and a catalyst. The aforementioned solution B contains polyisocyanate, The catalyst comprises two types of tertiary amines: a first tertiary amine having a hydroxyl group and a second tertiary amine not having a hydroxyl group. The aforementioned polyol is a polyol having a number-average molecular weight of more than 200, and is characterized as a chemical composition for ground injection. [2] The ground injection chemical composition according to [1] above, wherein the polyol is a polyether polyol. [3] The soil injection chemical composition according to [2] above, wherein the polyether polyol comprises a polyether polyol having a number average molecular weight greater than 200 and less than 500, and a polyether polyol having a number average molecular weight of 500 or more. [4] The soil injection chemical composition according to any one of [1] to [3] above, wherein the polyol is 8% by mass or less with respect to 100% by mass of the entire liquid A. [5] The first tertiary amine is a ground injection chemical composition according to any one of [1] to [4] above, wherein the main chain comprises a tertiary amino group and the hydroxyl group and does not have a ring structure. [6] The first tertiary amine is a ground injection chemical composition according to any one of [1] to [5] above, having an oxygen atom and / or a nitrogen atom in a main chain comprising a tertiary amino group and the hydroxyl group. [7] The first tertiary amine is a ground injection chemical composition according to any one of [1] to [6] above, having a dimethylamino group. [8] The second tertiary amine is a ground injection chemical composition according to any one of [1] to [7] above, which does not have a ring structure. [9] A foam obtained by mixing liquid A and liquid B, which constitute the ground injection chemical composition described in any of [1] to [8] above.

[10] A method for producing a foam, characterized by mixing liquid A and liquid B, which constitute the ground injection chemical composition described in any of [1] to [8] above, to form a foam. [Effects of the Invention]

[0009] According to the ground injection chemical composition of the present invention, it is possible to obtain a foam that has a good foaming ratio while reducing the dependence on reaction temperature and preventing foaming defects. According to the foam of the present invention, foaming defects are prevented. According to the foam manufacturing method of the present invention, it is possible to obtain a foam that has a good foaming ratio while preventing foaming defects. [Modes 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, a polyol, and a catalyst. Solution B contains polyisocyanate, The catalyst contains two types of tertiary amines: a primary tertiary amine having a hydroxyl group (hereinafter also referred to as "primary-tertiary amine") and a secondary tertiary amine not having a hydroxyl group (hereinafter also referred to as "secondary-tertiary amine"). The polyol is characterized by having a number-average molecular weight greater than 200.

[0012] [1]Liquid A Solution A contains "water-soluble silicate," "polyol," and "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. Among them, water-soluble sodium silicate usually has n>1, and for the water-soluble sodium silicate used in the present invention, n is preferably 2.0 to 4.0. Within this range, it has excellent storage stability and can suppress low-temperature coagulation. Also, usually, when preparing the liquid A, water-soluble silicate is incorporated as its aqueous solution (hereinafter also simply referred to as "silicate aqueous solution"). The silicate aqueous solution may be appropriately prepared and used, but since it is also commercially available as a silicate aqueous solution (sodium silicate aqueous solution), sodium silicate, water glass, etc., these commercial products can be utilized. Regarding sodium silicate, each sodium silicate such as No. 1, No. 2, No. 3, etc. defined in the JIS standard (JIS K1408) can be used. These may be used alone or in combination of two or more. Also, those conforming to this JIS standard, such as No. 4, No. 5, etc., 1.5, 2.5, etc. can be used. These may be used alone or in combination of two or more. The solid content of the silicate aqueous solution is not limited, but from the viewpoints of the stability and solidification characteristics of the liquid A, etc., 20 to 60% by mass is preferable, and 30 to 50% by mass is more preferable with respect to the whole silicate aqueous solution.

[0015] The amount of the water-soluble silicate contained in the liquid A is not limited, but when the total amount of the liquid A is 100% by mass, it is preferable that the total of the water-soluble silicate and water is 80% by mass or more, more preferably 85% by mass or more, still 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, still more preferably 99.6% by mass or less, and particularly preferably 99.4% by mass or less. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be 80 to 99.99% by mass, can be 85 to 99.8% by mass, can be 88 to 99.6% by mass, and can be 89 to 99.4% by mass. Note that the above water means the total amount of water contained in the liquid A. That is, the water at this time is the total of the amount of water contained in the aqueous solution when the water-soluble silicate is used as an aqueous solution (i.e., water glass), the amount of water contained in other additives, and the amount added as water.

[0016] (2) Polyol The polyol is an organic compound having two or more hydroxy groups. The type of the polyol is not limited, and the polyols that have been conventionally used as components of the chemical liquid composition for ground injection can be appropriately used. That is, examples of the polyol include aliphatic polyols, polyester polyols, polyether polyols, polycarbonate polyols, olefin polyols, acrylic polyols, siloxane polyols and the like. Among these, aliphatic polyols, polyester polyols, and polyether polyols are preferable, and polyether polyols are particularly preferable. These may be used alone or in combination of two or more.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] Furthermore, when using polyether polyols, their molecular weight is not limited, but it is preferable that the number average molecular weight is greater than 200. When a polyether polyol with a number average molecular weight greater than 200 is used, the foaming stability is higher compared to when a polyether polyol with a number average molecular weight of 200 or less is used, reducing the influence of foaming temperature and improving the stability of high-temperature foaming. In other words, the rate at which the foaming ratio changes with foaming temperature can be suppressed to a smaller extent, and shrinkage, voiding, and coarsening of the foam obtained at high foaming temperatures can be suppressed. 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.

[0022] In this composition, it is preferable to use two or more polyether polyols with different Mn values, where Mn > 200. This combination further improves the stability of high-temperature foaming and further stabilizes the foaming ratio. Specifically, it is possible to more effectively suppress shrinkage, void formation, and coarsening of the foam obtained at high foaming temperatures, and to suppress the relatively large or relatively small bias in the foaming ratio.

[0023] When using polyether polyols with different Mn values in combination, any number of different Mn polyether polyols may be used in combination. However, from the perspectives of cost and production, 2 to 3 types are preferred, and 2 types are particularly preferred. When using two types of polyether polyols with different Mn values in combination, the polyether polyol with a smaller Mn is used as the first polyether polyol, and its Mn is designated as "Mn1", and the polyether polyol with a larger Mn is used as the second polyether polyol, and its Mn is designated as "Mn2". In this case, 200 < Mn1 and 200 < Mn2.

[0024] And it is preferable that Mn1 and Mn2 differ by at least 100 or more (100 ≦ Mn2 - Mn1), and more preferably differ by 200 or more (200 ≦ Mn2 - Mn1). The difference in Mn (Mn2 - Mn1) is usually 2500 or less (Mn2 - Mn1 ≦ 2500), preferably 800 or less (Mn2 - Mn1 ≦ 800), and more preferably 500 or less (Mn2 - Mn1 ≦ 500). That is, for example, 100 ≦ Mn2 - Mn1 ≦ 2500 can be set, 200 ≦ Mn2 - Mn1 ≦ 800 can be set, and 200 ≦ Mn2 - Mn1 ≦ 500 can be set. That is, for example, 200 < Mn1 ≦ 500, 500 < Mn2 ≦ 5000, and 100 ≦ Mn2 - Mn1 can be set, and 300 ≦ Mn1 ≦ 500, 500 < Mn2 ≦ 2500, and 200 ≦ Mn2 - Mn1 can be set

[0025] 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, based on 100% by mass of the entire solution A.

[0026] (3) 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".

[0027] (3-1) Primary-tertiary amines Primary, secondary, and tertiary amines are tertiary amines that possess a hydroxyl group. 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 defects. Furthermore, because primary, secondary, and tertiary amines possess hydroxyl groups, their affinity for water-soluble silicates is improved compared to tertiary amines that do not possess 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 a good foaming ratio while reducing the temperature dependence of the reaction and preventing foaming defects.

[0028] Primary, secondary, and tertiary amines may have one tertiary amino group or two or more. They may also have one hydroxyl group or two or more. Therefore, examples of primary, secondary, and tertiary amines include (1) compounds having one tertiary amino group and one hydroxyl group; (2) compounds having multiple tertiary amino groups and one hydroxyl group; and (3) compounds having one tertiary amino group and multiple hydroxyl groups. These may be used individually or in combination of two or more.

[0029] The primary-tertiary amines having one tertiary amino group and one hydroxyl group as described above (1) include 2-(dimethylamino)ethanol (CAS RN: 108-01-0), 2-(ethylmethylamino)ethanol (CAS RN: 2893-43-8), 2-(diethylamino)ethanol (CAS RN: 100-37-8), 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), 3-(diethylamino)-1-propanol (CAS RN: 622-93-5), and 1-(diethylamino)-2-propanol (CAS 4-(dimethylamino)-1-butanol (CAS RN: 13330-96-6), 3-(dimethylamino)-1-butanol (CAS RN: 2893-65-4), 4-(diethylamino)-1-butanol (CAS RN: 2683-56-9), 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 2-[2-(diethylamino)ethoxy]ethanol (CAS RN: 140-82-9), 4-(dimethylamino)benzyl alcohol (CAS RN: 1703-46-4), 2-[4-(dimethylamino)phenyl]ethanol (CAS RN: 1703-46-4), 2-[4-(dimethylamino)phenyl]ethanol (CAS Examples include 1-methyl-4-piperidinemethanol (CAS RN: 20691-89-8), 1-methyl-3-piperidinemethanol (CAS RN: 7583-53-1), and 1-methyl-2-piperidinemethanol (CAS RN: 20845-34-5). These may be used individually or in combination of two or more. Among these, primary-tertiary amines having a tertiary amino group with a methyl group directly attached to a nitrogen atom (hereinafter also simply referred to as "methyl tertiary amino group") are preferred, and primary-tertiary amines having a tertiary amino group with two methyl groups directly attached to a nitrogen atom (hereinafter also simply referred to as "dimethyl tertiary amino group") are more preferred.

[0030] Examples of primary to tertiary amines comprising multiple tertiary amino groups and one hydroxyl group as described in (2) above include 1,3-bis(dimethylamino)-2-propanol (CAS RN: 5966-51-8), 1,3-bis(diethylamino)-2-propanol (CAS RN: 3492-47-5), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7), 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN: 90-72-2), 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. Among these, primary and tertiary amines having a methyl tertiary amino group are preferred as the tertiary amino group, and primary and tertiary amines having a dimethyl tertiary amino group are more preferred.

[0031] Examples of primary to tertiary amines comprising one tertiary amino group and multiple hydroxyl groups as described in (3) above include compounds comprising one methyl tertiary amino group and multiple hydroxyl groups, such as 3-(dimethylamino)-1,2-propanediol (CAS RN: 623-57-4), 3-(diethylamino)-1,2-propanediol (CAS RN: 621-56-7), N-methyldiethanolamine (CAS RN: 105-59-9), and N-ethyldiethanolamine (CAS RN: 139-87-7). These may be used individually or in combination of two or more.

[0032] Among those mentioned above, 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 2-[2-(diethylamino)ethoxy]ethanol (CAS RN: 140-82-9), and N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (CAS RN: 83016-70-0) are examples of primary, secondary, and tertiary amines having an oxygen atom in the main chain comprising a tertiary amino group and a hydroxyl group. Compared to primary, secondary, and tertiary amines that do not have an oxygen atom in the main chain, these are considered to have an even greater affinity for water-soluble silicates and to have a more accelerated reaction between water-soluble silicates and polyisocyanates, making them more preferable as primary, secondary, and tertiary amines. These may be used individually or in combination of two or more.

[0033] Furthermore, among those mentioned above, examples of primary, secondary, and tertiary amines having a nitrogen atom in the main chain comprising a tertiary amino group and a hydroxyl group include 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). Compared to primary, secondary, and tertiary amines that do not have a nitrogen atom in the main chain, these are considered to have an even greater affinity for water-soluble silicates and to have a more accelerated reaction between water-soluble silicates and polyisocyanates, making them more preferable as primary, secondary, and tertiary amines. These may be used individually or in combination of two or more.

[0034] Furthermore, among the above, as primary-tertiary amines in which the tertiary amino group is a dimethylamino group (dimethyl tertiary amino group), there are 2-(dimethylamino)ethanol (CAS RN: 108-01-0), 3-(dimethylamino)-1-propanol (CAS RN: 3179-63-3), 1-(dimethylamino)-2-propanol (CAS RN: 108-16-7), 4-(dimethylamino)-1-butanol (CAS RN: 13330-96-6), 3-(dimethylamino)-1-butanol (CAS RN: 2893-65-4), 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), and 4-(dimethylamino)benzyl alcohol (CAS 2-[4-(dimethylamino)phenyl]ethanol (CAS RN: 50438-75-0), 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), 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN: 90-72-2), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) ether (CAS RN: 83016-70-0), 3-(dimethylamino)-1,2-propanediol (CAS RN:623-57-4) is one example. Due to the presence of a dimethyl tertiary amino group, the tertiary amino group constitutes the terminal end of the compound. Furthermore, 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 in the initial stages of the reaction of primary, secondary, and tertiary amines.

[0035] Furthermore, among the above, examples of primary-tertiary amines having a dimethyl tertiary amino group and further having an oxygen atom and / or nitrogen atom in the main chain comprising a dimethyl tertiary amino group and a hydroxyl group include 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), and N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (CAS RN: 83016-70-0). These are particularly preferred from the viewpoint that they can have both the effect due to having a dimethyl tertiary amino group and the effect due to having an oxygen atom and / or nitrogen atom in the main chain comprising a tertiary amino group and a hydroxyl group.

[0036] (3-2) Secondary and tertiary amines Secondary and tertiary amines are tertiary amines that do not contain 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. On the other hand, since secondary and tertiary amines do not have hydroxyl groups, they are thought to be able to promote the reaction of polyisocyanates. 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 failures.

[0037] Secondary and tertiary amines may have one tertiary amino group or two or more. Therefore, examples of secondary and tertiary amines include: (1) a tertiary amine having one tertiary amino group; (2) a tertiary amine having two tertiary amino groups; (3) a tertiary amine having three tertiary amino groups; and (4) a tertiary amine having four or more tertiary amino groups. These may be used individually or in combination of two or more.

[0038] The above (1) secondary and tertiary amines having only one tertiary amino group include N,N-dimethylbutylamine (CAS RN: 927-62-8), N,N-diethylbutylamine (CAS RN: 4444-68-2), 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), and other N,N-dialkyl-alkylamines, as well as 2-(dimethylamino)ethylamine (CAS RN: 108-00-9), 2-(diethylamino)ethylamine (CAS (Dialkylamino)alkylamines such as 3-(dimethylamino)propylamine (CAS RN: 109-55-7), 3-(diethylamino)propylamine (CAS RN: 104-78-9), triethylenediamine (CAS RN: 280-57-9), (dimethylamino)acetonitrile (CAS RN: 926-64-7), N,N,N'-trimethylethylenediamine (CAS RN: 142-25-6), trimethylamine (CAS RN: 75-50-3), triethylamine (CAS RN: 121-44-8), N,N-dimethylcyclohexylamine (CAS RN: 98-94-2), N,N-diethylcyclohexylamine (CAS RN: 91-65-6), 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:5683-33-0), 4-(dimethylamino)pyridine (CAS RN:1122-58-3), 4-(dimethylamino)benzonitrile (CAS RN:1197-19-9), N,Examples include N-dimethylbenzylamine (CAS RN: 103-83-3). These may be used individually or in combination of two or more. Among these, secondary-tertiary amines having a tertiary amino group with a methyl group directly attached to a nitrogen atom (hereinafter also simply referred to as a "methyl tertiary amino group") are preferred, and secondary-tertiary amines having a tertiary amino group with two methyl groups directly attached to a nitrogen atom (hereinafter also simply referred to as a "dimethyl tertiary amino group") are more preferred.

[0039] Examples of secondary and tertiary amines having only two tertiary amino groups as described in (2) above include tetraalkylalkanediamines 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'-tetraethylethane-1,2-diamine (CAS RN: 150-77-6), 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), bis(2-(N,N-dimethylamino)ethyl) ether (CAS RN: 3033-62-3), and tert-butoxybis(dimethylamino)methane (CAS Examples include 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'-dimethylpiperazine (CAS RN: 106-58-1), N,N,N',N'-tetramethyl-1,8-naphthalenediamine (CAS RN: 20734-58-1), and 4-methylmorpholine (CAS RN: 109-02-4). These may be used individually or in combination of two or more. Among these, secondary-tertiary amines having a methyl tertiary amino group are preferred as the tertiary amino group, and secondary-tertiary amines having a dimethyl tertiary amino group are more preferred.

[0040] Examples of secondary and tertiary amines having only three tertiary amino groups as described in (3) above include 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), tris(dimethylamino)methane (CAS RN: 5762-56-1), and bis(4-dimethylaminophenyl)-4-dimethylamino-d6-phenylmethane (CAS RN: 1173023-92-1). These may be used individually or in combination of two or more. Among these, secondary and tertiary amines having a methyl tertiary amino group as the tertiary amino group are preferred, and secondary and tertiary amines having a dimethyl tertiary amino group are more preferred.

[0041] Examples of secondary and tertiary amines having four or more tertiary amino groups as described in (4) above include 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. Among these, secondary and tertiary amines having a methyl tertiary amino group as the tertiary amino group are preferred, and secondary and tertiary amines having a dimethyl tertiary amino group are more preferred.

[0042] Furthermore, among the above, it is preferable that the secondary-tertiary amine is a compound having multiple tertiary amino groups. Therefore, it is preferable that it is at least one of the above-mentioned (2) tertiary amine having only two tertiary amino groups, (3) tertiary amine having only three tertiary amino groups, or (4) tertiary amine having four or more tertiary amino groups. Furthermore, it is preferable that the secondary and tertiary amines in this composition have a dimethylamino group (i.e., a dimethyl tertiary amino group) as their tertiary amino group. Having a dimethylamino group means that the tertiary amino group forms the terminal end of the compound. And, 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 the secondary and tertiary amines in the initial stages of the reaction. Therefore, it is even more preferable that the secondary and tertiary amines in this composition have multiple tertiary amino groups, and that at least two of the tertiary amino groups are dimethylamino groups (i.e., dimethyl tertiary amino groups). In addition, it is preferable that the secondary and tertiary amines in this composition do not have a ring structure in the main chain connecting different tertiary amino groups.

[0043] As mentioned above, secondary and tertiary amines that have multiple dimethylamino groups and do not have a ring structure in the main chain connecting the dimethylamino groups include tetraalkylalkanediamines 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), and N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN: 111-18-2), as well as bis(2-(N,N-dimethylamino)ethyl) ether (CAS RN: 3033-62-3) and tert-butoxybis(dimethylamino)methane (CAS 5815-08-7), 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'',N''-Pentamethyldiethylenetriamine (CAS RN: 3030-47-5), Tris(dimethylamino)methane (CAS RN: 5762-56-1), Tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), Tetrakis(dimethylamino)ethylene (CAS RN: 996-70-3), 1,1,4,7,10,10-Hexamethyltriethylenetetramine (CAS RN: 3083-10-1)

[0044] Furthermore, the secondary and tertiary amines in this composition can preferably be compounds having oxygen and / or nitrogen atoms in the main chain connecting different tertiary amino groups. In other words, compounds having multiple dimethylamino groups, without a ring structure in the main chain connecting the dimethylamino groups, and having oxygen and / or nitrogen atoms in the main chain connecting the dimethylamino groups can be suitably used. Examples of such secondary and tertiary amines include bis(2-(N,N-dimethylamino)ethyl) ether (CAS RN: 3033-62-3), tert-butoxybis(dimethylamino)methane (CAS RN: 5815-08-7), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN: 6711-48-4), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), 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.

[0045] (3-3) 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 good foaming ratio can be achieved while reducing the reaction temperature dependence and preventing foaming defects.

[0046] 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.

[0047] (3-4) 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.

[0048] 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.

[0049] 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.

[0050] (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.

[0051] [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.

[0052] 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.

[0053] 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.

[0054] 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).

[0055] 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.

[0056] (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.

[0057] [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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] [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.

[0063] [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.

[0064] 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.

[0065] The foaming ratio of the foam obtained using this composition is not limited, but is preferably 25 times or less, more preferably 22 times or less, even more preferably 20 times or less, particularly preferably 18 times or less, and especially preferably 16 times or less, in the range of 10 to 30°C. On the other hand, this foaming ratio is more preferably 2 times or more, even more preferably 4 times or more, particularly preferably 4.5 times or more, and especially preferably 5 times or more. These upper and lower limits can be combined arbitrarily. That is, for example, it can be 2 to 22 times, 4 to 20 times, 4.5 to 18 times, and 5 to 16 times. Within these preferred ranges, sufficient strength can be obtained in the resulting foam while suppressing the effect of temperature in the foaming environment, and it is also economically efficient.

[0066] Furthermore, when measuring the foaming ratio of foams obtained at 10°C, 20°C, and 30°C using this composition, the ratio of the minimum foaming ratio to the maximum foaming ratio (foaming ratio ratio = minimum foaming ratio / maximum foaming ratio) at each temperature is not limited, but is preferably 0.38 or higher, more preferably 0.40 or higher, even more preferably 0.42 or higher, particularly preferably 0.44 or higher, and especially preferably 0.46 or higher. Ideally, the closer the foaming ratio ratio is to 1.0, the better. These upper and lower limits can be combined arbitrarily. That is, for example, it can be 0.38 to 1.0, 0.40 to 1.0, 0.42 to 1.0, 0.44 to 1.0, and 0.46 to 1.0. Within these preferred ranges, it is possible to obtain sufficient strength in the resulting foam while suppressing the influence of temperature in the foaming environment, and it is also economically efficient. [Examples]

[0067] 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.

[0068] [1] Preparation of composition Each of the components listed below was mixed in the combinations and formulations shown in Tables 1 to 3 to obtain soil injection chemical compositions having liquids A and B for Examples 1 to 21 and Comparative Examples 1 to 14.

[0069] (1) Water-soluble silicates (silicate aqueous solution) • Sodium silicate No. 2: Sodium silicate No. 2, manufactured by Fuji Chemical Co., Ltd., solid 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).

[0070] (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 • PB-700: Polyether polyol (polypropylene glycol), manufactured by NOF Corporation, product name "Uniol PB-700", initiator: butylene glycol, number average molecular weight: 700, 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 • DPG / TPG: A polyol mixture obtained by mixing dipropylene glycol (number average molecular weight 134, number of functional groups 2, Tokyo Chemical Industries, Ltd.) and tripropylene glycol (number average molecular weight 192, number of functional groups 2, Tokyo Chemical Industries, Ltd.) in a mass ratio of 3:7.

[0071] (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 dimethylamino 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 dimethylamino group. • Dimethylaminohexanol: 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), manufactured by Kao Corporation, product name "Kaorizer No. 25", contains OH group and dimethylamino group. • Diethylaminoethanol: 2-(diethylamino)ethanol (CAS RN: 100-37-8), manufactured by Tokyo Chemical Industry Co., Ltd., contains OH group, does not contain dimethylamino group.

[0072] (3-2) 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), dimethylamino 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), dimethylamino 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 (none), dimethylamino group (none) Triethylenediamine: 33% Triethylenediamine (CAS RN: 280-57-9) Dipropylene glycol solution, manufactured by Kao Corporation, product name "Kaorizer No. 31", OH group (none), dimethylamino group (none)

[0073] (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.

[0074] (5) Foam stabilizers • Foam stabilizer: Polyether-modified siloxane, manufactured by Momentive Performance Materials Japan LLC, product name "Niax Silicone L-6970")

[0075] (6) Viscosity reducers • Viscosity reducer: Propylene carbonate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0076] (7) Flame retardants • Flame retardant: Tris(chloropropyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] [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 injection chemical composition of Examples 1-18 and Comparative Examples 1-12 was measured at 25°C in accordance with JIS K7117-1. The results are shown in Tables 1-3.

[0081] (2) Foaming evaluation Using the chemical solutions for injecting each of the Examples 1 to 21 and Comparative Examples 1 to 14 obtained in [1] above, foams were prepared in the following manner, and the foaming ratio and the appearance of the foams were measured and evaluated.

[0082] (2-1) Preparation of foam (foaming in air) From each of the injectable chemical compositions for each section of the ground for injection in Examples 1-21 and Comparative Examples 1-14, 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 these liquids A and B to 10°C, both were placed in a 1 L cup and stirred at 400 rpm for 10 seconds (hand mixing), and then foamed in the air to obtain a foam. Furthermore, the foam was prepared in the same manner, except that the foam preparation temperature was changed from 10°C to 20°C. Furthermore, the foam was prepared in the same manner, except that the foam preparation temperature was changed from 10°C to 30°C.

[0083] (2-2) Measurement of expansion ratio In (2-1) above, the foaming ratios of the foams obtained at 10°C, 20°C, and 30°C were measured using the method described below and are shown in Tables 1 to 3 as "Foaming Ratio 10°C", "Foaming Ratio 20°C", and "Foaming Ratio 30°C". In addition, the ratio of the smallest foaming ratio to the largest foaming ratio among the foaming ratios at 10°C, 20°C, and 30°C (minimum foaming ratio / maximum foaming ratio) was calculated and is shown in Tables 1 to 3 as the "Foaming Ratio Ratio". Measurement of foaming ratio: The height of the liquid level in the cup after mixing liquids A and B was measured as H1. Next, the height of the foam at the top of the foam when foaming began and the foam formed in the cup reached its maximum height 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, the foaming ratio was calculated as H2 / H1 using the measured values ​​of H1 and H2. Note that each height was measured visually using a gauge.

[0084] (2-3) Visual evaluation of foam The appearance of the foams obtained in the 10°C environment, the 20°C environment, and the 30°C environment, as described in (2-1) above, was evaluated according to the following criteria and is shown in Tables 1 to 3. "○": 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.

[0085] (2-4) Preparation of foam (underwater foaming) 1000 ml of water was divided into a 2 L cup, and the water temperature in the cup was adjusted to 20°C. Meanwhile, from each of the ground injection chemical compositions of Example 1 and Examples 10-15, liquid A and liquid B were divided 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 these liquids A and B to 20°C, both were added to a single cup and stirred at 400 rpm for 10 seconds (hand mixing). Then, the mixture of liquids A and B was added to the cup containing the 20°C water and foamed in the water.

[0086] (2-5) Evaluation of water turbidity due to underwater foaming After waiting for the foaming process described in (2-4) above to complete, the state of the water used as the reaction environment was observed and evaluated according to the following criteria, as shown in Table 4. "○": Almost no water turbidity is observed. "△": Slight turbidity is observed in the water. "×": Water turbidity is observed.

[0087] (2-6) Evaluation of defoaming time by underwater foaming Furthermore, water (the water used as the reaction environment) one hour after the foaming process was completed was collected in a 500 ml transparent plastic container with a lid, and the foaming was observed after shaking for 10 seconds. The results were evaluated according to the following criteria and are shown in Table 4. "◎": The foam disappeared within 10 seconds. "○": The foam disappeared within 10 to 30 seconds. "△": The foam disappeared between 30 and 60 seconds. "×": Foam remains even after 60 seconds or more.

[0088] [Table 4]

[0089] [3] Effects of the example Tables 1 to 3 show that in Comparative Examples 1 to 4 and 9, where Solution A does not contain secondary or tertiary amines, foaming stability is insufficient, and shrinkage and coarsening are observed in the resulting foam. Furthermore, the foaming ratio is small and is affected by temperature. Similarly, in Comparative Examples 5 to 8 and 11, where Solution A does not contain primary or tertiary amines, foaming stability is insufficient, and shrinkage, voiding, or coarsening are observed in the resulting foam. Furthermore, the foaming ratio is small and is affected by temperature. In Comparative Example 10, where Solution A does not contain primary or tertiary amines, a stable foam is obtained, but the foaming ratio is small and is affected by temperature. Furthermore, in Comparative Example 12, where Solution A does not contain polyols, and in Comparative Examples 13 and 14, where polyols are present but Mn ≤ 200, the foaming ratio is small and is affected by temperature. In contrast, the compositions of Examples 1 to 21, in which Solution A contains a water-soluble silicate, a polyol with Mn > 200, a primary-tertiary amine, and a secondary-tertiary amine, exhibit a good foaming ratio while reducing the reaction temperature dependence and preventing foaming failure. [Industrial applicability]

[0090] 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 polyol, a catalyst, and water. The aforementioned solution B contains polyisocyanate, The catalyst comprises two types of tertiary amines: a first tertiary amine having a hydroxyl group and a second tertiary amine not having a hydroxyl group. The aforementioned polyol is a polyol having a number-average molecular weight of more than 200. The polyol includes polyOC polyol, The aforementioned polyether polyol includes a polyether polyol having a number average molecular weight greater than 200 and less than 500, and a polyether polyol having a number average molecular weight of 500 or more. When the total amount of the water-soluble silicate and water contained in solution A is 100 parts by mass, the polyol content is 15 parts by mass or less. The total amount of the first tertiary amine and the second tertiary amine contained in solution A is 5 parts by mass or less per 100 parts by mass of the polyisocyanate contained in solution B. A chemical composition for ground injection, characterized in that the mixing ratio of liquid A and liquid B is 2:1 to 1:3 by mass.

2. The soil injection chemical composition according to claim 1, wherein the polyol is present in an amount of 8% by mass or less relative to 100% by mass of the entire liquid A.

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 a tertiary amino group and the hydroxyl group.

4. The ground injection chemical composition according to any one of claims 1 to 3, wherein the first tertiary amine has an oxygen atom and / or a nitrogen atom in a main chain comprising a tertiary amino group and the hydroxyl group.

5. The first tertiary amine is a ground injection chemical composition according to any one of claims 1 to 4, wherein the first tertiary amine has a dimethylamino group.

6. The ground injection chemical composition according to any one of claims 1 to 5, wherein the second tertiary amine has no ring structure.

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.

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