Chemical liquid composition for ground consolidation

Abstract

To provide urethane-based chemical liquid for natural ground consolidation, excellent in reaction activity and causing less environment pollution, and to provide an urethane-based chemical liquid composition for natural ground consolidation, capable of forming a consolidated body having high strength and excellent flexibility, and high plasticity and fire retardancy, and not initiating problems such as white turbidness and foaming when contacting water such as water leakage and sump water.SOLUTION: A chemical liquid composition for natural ground consolidation comprises A liquid containing an active hydrogen group-containing compound and a catalyst as essential components, and B liquid containing polyisocyanate as the essential component. The A liquid contains at least an active hydrogen group-containing organic compound having a cyclic structure as the active hydrogen group-containing compound, and at least a carboxylic acid metal salt as the catalyst. The B liquid contains at least an aliphatic polyisocyanate compound as the polyisocyanate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a chemical solution composition for ground consolidation. In particular, a urethane-based chemical solution for ground consolidation that combines an active hydrogen group-containing organic compound having a cyclic structure and an aliphatic polyisocyanate compound to provide a high-strength solid, has excellent reaction activity, and causes less environmental pollution.

Background Art

[0002] Conventionally, as one of the measures adopted in ground improvement applications for stabilizing unstable rock masses or ground and in cavity filling applications for filling cracks and voids in artificial structures, an inorganic or organic grout is injected to consolidate the ground and the like. For example, in Japanese Patent Laid-Open No. 4-283290, as one such grout, an injection chemical solution composition comprising an aqueous sodium silicate solution (A) and a polyisocyanate composition (B) comprising a polyisocyanate and a reactive diluent that does not react with the polyisocyanate but is hydrolyzed by the aqueous sodium silicate solution and reacts with the aqueous sodium silicate solution and / or the polyisocyanate is known. Further, in Japanese Patent Laid-Open No. 5-78667, a two-component type foamed urethane resin comprising a liquid A mainly composed of water and an alkali metal salt of silicic acid and a liquid B mainly composed of an isocyanate prepolymer is disclosed as a chemical solution for rock consolidation. Furthermore, in Japanese Patent Laid-Open No. 2016-175982, in a two-component type chemical solution for ground consolidation comprising a liquid A prepared by blending water glass and a polyol and further adding water, and a liquid B having a polyisocyanate as an essential component, the water content in the liquid A is regulated, and the water and the polyol are prepared so as to have a predetermined ratio, and a dispersant is further added. A configuration has been proposed.

[0003] And as the polyisocyanate which is the main component of liquid B in those consolidating chemical solutions, various organic isocyanate compounds having two or more isocyanate groups in the molecule and modified products (prepolymers) thereof can be used. However, from the viewpoints of reaction activity and strength of the resulting consolidated body, etc., practically, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), polymeric MDI, tolylene diisocyanate (TDI) are used. However, when a liquid B composed of an aliphatic polyisocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate as the polyisocyanate component is combined with the above-described liquid A to form a consolidating chemical solution, the reaction between the liquid A and the liquid B is slow. Therefore, when stopping a large amount of leakage water or spring water, a part of the injected chemical solution flows out together with the leakage water or spring water, causing problems such as white turbidity and foaming of water, and bringing adverse effects to the environment. In addition, the strength and flame retardancy of the consolidated body formed by the reaction between liquid A and liquid B are not sufficient, and therefore, it cannot sufficiently meet the purpose of strengthening the stability of the ground and filling cavities.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] Against the backdrop of the above circumstances, as a result of various studies by the present inventors on a consolidating chemical solution using an aliphatic polyisocyanate compound as the polyisocyanate, it has been found that, with respect to such an aliphatic polyisocyanate compound, by combining, as the active hydrogen group-containing compound, an active hydrogen group-containing organic compound having a cyclic structure, and further using, as the catalyst, at least a metal carboxylate, all of the problems that occur when using the above-described aliphatic polyisocyanate compound can be solved, and thus the present invention has been completed.

[0006] Accordingly, the problem to be solved by the present invention is to provide a urethane-based base consolidation chemical solution composition that is excellent in reaction activity and causes little environmental pollution. Another problem is to provide a urethane-based base consolidation chemical solution that can form a consolidated body having high strength, excellent flexibility, high toughness and high flame retardancy, and does not cause problems such as clouding and foaming when in contact with water such as water leakage and gushing water.

Means for Solving the Problems

[0007] Then, the present invention can be preferably implemented in various aspects listed below in order to solve the above-described problems. Further, each of the aspects described below can be adopted in any combination. It should be considered that the aspects or technical features of the present invention are not limited to those described below, and should be understood based on the inventive concept grasped from the description of the entire specification.

[0008] First, a first aspect of the present invention is a base consolidation chemical solution composition comprising a liquid A containing an active hydrogen group-containing compound and a catalyst as essential components, and a liquid B containing a polyisocyanate as an essential component, wherein the liquid A contains at least an active hydrogen group-containing organic compound having a cyclic structure as the active hydrogen group-containing compound, and contains at least a metal carboxylate as the catalyst, and the liquid B contains at least an aliphatic polyisocyanate compound as the polyisocyanate.

[0009] Moreover, in the second aspect of the present invention, the cyclic structure of the active hydrogen group-containing organic compound has an aromatic cyclic structure, an alicyclic structure, or a heterocyclic structure.

[0010] Furthermore, in the third aspect according to the present invention, a phenolic compound is used as the active hydrogen group-containing organic compound.

[0011] Still further, in the fourth aspect according to the present invention, a phenolic resin is used as the active hydrogen group-containing organic compound.

[0012] In addition, in the fifth aspect of the present invention, the proportion of the cyclic structure in the active hydrogen group-containing organic compound is configured to be 15% by mass or more.

[0013] And in the sixth aspect according to the present invention, the ratio (X / Y) of the total number of moles (X) of the active hydrogen groups in the liquid A and the number of moles (Y) of the isocyanate groups in the liquid B is configured to be 0.3 to 3.0.

[0014] Moreover, in the seventh aspect of the present invention, the aliphatic polyisocyanate compound is a prepolymer and is configured to have a residual monomer content of less than 5% by mass.

[0015] Furthermore, in the eighth aspect of the present invention, the prepolymer of the aliphatic polyisocyanate compound is any one of an adduct, biuret, allophanate, and isocyanurate derived from an aliphatic polyisocyanate compound selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, and bis(isocyanatomethyl)cyclohexane.

[0016] In addition, in the ninth aspect according to the present invention, the catalyst further contains a tertiary amine.

[0017] Furthermore, a tenth aspect of the present invention is configured such that a flame retardant is further contained in the liquid A and / or the liquid B.

[0018] And an eleventh aspect of the present invention is that the liquid A and the liquid B each have a viscosity of 6000 mPa·s or less at a temperature of 25°C.

Advantages of the Invention

[0019] And according to the configuration of the chemical liquid composition for ground consolidation according to such a present invention, various effects listed below can be achieved. (1) A urethane-based chemical liquid for ground consolidation with excellent reaction activity and less environmental pollution is provided. By using such a chemical liquid, a consolidated body with high strength, excellent flexibility, high toughness, and high flame retardancy can be advantageously formed. (2) Since the curing reaction starts immediately after injecting the chemical liquid into the ground, the outflow of the chemical liquid into the environment can be suppressed, and the turbidity and foaming of leakage water and gushing water can be advantageously reduced. (3) A metal carboxylate is used as a catalyst, and a tertiary amine catalyst is used in combination therewith. As a result, it is difficult to be affected by the reaction rate even in the presence of water, and the target consolidated body can be formed quickly. Therefore, its practicality can be advantageously enhanced. (4) As the polyisocyanate, which is an essential component of the liquid B, an aliphatic polyisocyanate compound, particularly a prepolymer of an aliphatic polyisocyanate compound, is used. Thus, a strong consolidated body can be advantageously formed, and the pollution of the working environment at the chemical liquid injection site can also be effectively suppressed or avoided.

Embodiments for Carrying Out the Invention

[0020] In short, the present invention relates to a two-component urethane-based chemical liquid composition composed of liquid A and liquid B. As the active hydrogen group-containing compound, which is an essential component of liquid A, it contains an active hydrogen group-containing organic compound having a cyclic structure, and as a catalyst, it contains at least a metal carboxylate. On the other hand, as the polyisocyanate, which is an essential component in liquid B, it contains an aliphatic polyisocyanate compound, particularly a prepolymer of an aliphatic polyisocyanate compound. By doing so, even an aliphatic polyisocyanate compound can effectively achieve excellent reaction activity, and a high-strength solid can be advantageously formed. Therefore, the present invention has a great feature in that it can advantageously achieve the intended purpose.

[0021] By the way, in liquid A, which is one of the two liquids constituting the chemical liquid composition according to the present invention, the active hydrogen group-containing organic compound having a cyclic structure, which is contained as one of the essential components, is an organic compound having a cyclic structure or a cyclic structure in the molecule and having an active hydrogen group such as a hydroxyl group or an amino group. Examples of the cyclic structure include aromatic ring structures, alicyclic ring structures, and heterocyclic ring structures. Among them, aromatic ring compounds, alicyclic ring compounds, and heterocyclic ring compounds are preferred, and aromatic ring compounds are more preferably used. In particular, it is desirable that the hydroxyl group or amino group is directly bonded to the aromatic ring structure. Among these, polyfunctional compounds having two or more functional groups are more desirable. In addition, the proportion of the cyclic structure in such an active hydrogen group-containing organic compound, in other words, the content ratio in one molecule, is generally preferably 15% by mass or more, more preferably 25% by mass or more, and still more preferably 35% or more. Furthermore, it is desirable that such an active hydrogen group-containing organic compound is a bifunctional or higher-functional compound. In addition, its molecular weight is preferably in the range of 50 to 10,000, more preferably 80 to 5,000, and still more preferably 100 to 3,000, whereby the object of the present invention can be more advantageously achieved.

[0022] The active hydrogen group-containing organic compound having such a cyclic structure is not particularly limited, and for example, it will be appropriately selected from various known compounds such as phenols, alcohols, amines, thiols, etc. having an aromatic cyclic, alicyclic or heterocyclic structure.

[0023] Specifically, low molecular weight phenolic compounds such as phenol, cresol, xylenol, hydroquinone, catechol, resorcinol, pyrogallol, phloroglucinol, alkylhydroquinone, dialkylhydroquinone, trialkylhydroquinone, tetraalkylhydroquinone, dihydroxynaphthalene, etc., and phenolic compounds consisting of high molecular weight phenolic compounds such as bisphenol A, bisphenol F, novolak type phenolic resin, resol type phenolic resin, benzylic ether type phenolic resin, etc., obtained by reacting phenolic compounds such as phenol and cresol with aldehydes or ketones; aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, phenethyl alcohol, hydroxybenzyl alcohol, hydroxyphenethyl alcohol, methoxyphenylmethanol, benzenedimethanol, benzenediethanol, 1,4-bis(α-hydroxyisopropyl)benzene, etc.; aromatic amines having primary and / or secondary amino groups, such as aniline, phenylenediamine, tolylenediamine, xylylenediamine, toluenediamine, methylenedianiline, diaminodiphenyl ether, trimethylphenylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-bis(sec-butylamino)diphenylmethane, aminobenzylamine, methylenebis(ethylmethylaniline), methylenebis(diethylaniline), etc.; alicyclic alcohols such as cyclohexanol, methylcyclohexanol, dimethylcyclohexanol, cyclohexanemethanol, cyclohexaneethanol, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, hydroxypropylcyclohexanol, dicyclohexanediol, butylcyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, inositol, etc.; alicyclic amines such as cyclohexanediamine, norbornenediamine, isophoronediamine, bis(aminomethyl)norbornane, bis(4-aminocyclohexyl)methane, diaminodicyclohexylmethane, bisaminomethylcyclohexane, etc.;Heterocyclic compounds such as dihydroxypyridine, sucrose, glucoside, melamine, sorbitan, sorbitan monolaurate; hydroxyl group-containing compounds having a cyclic structure, and polyols obtained by reacting primary or secondary amines with alkylene oxides. For example, phenolic compounds, phenolic resins, aromatic alcohols, cyclic saccharides, etc. can be used as initiators, and polyether polyols and the like which are reaction products obtained by reacting ethylene oxide or propylene oxide can be mentioned. ;

[0024] In the present invention, among the above-mentioned active hydrogen group-containing organic compounds, various phenolic compounds including low-molecular-weight and high-molecular-weight phenolic compounds, and among them, in particular, phenolic resins are advantageously employed because they have a high density of aromatic rings having a cyclic structure. As a result, the formed solidified body is difficult to burn and it is easy to obtain high strength. Furthermore, as such a phenolic resin, generally, those having a weight average molecular weight in the range of 200 to 10,000, 300 to 5,000, 400 to 3,000 are preferably used.

[0025] In addition, as another essential component in the liquid A constituting the present invention, a catalyst is further used. In the present invention, at least one of such catalysts is a metal carboxylate. By using such a metal carboxylate, in the reaction between the above-mentioned active hydrogen group-containing organic compound and the aliphatic polyisocyanate compound, it is possible to increase the reaction rate to a rate suitable for practical use. Here, the metal carboxylate which is an essential component as one of the catalysts in the present invention is a compound in which hydrogen in the carboxyl group of an organic carboxylic acid is replaced by a metal such as tin, lead, zinc, iron, copper, nickel, cobalt, manganese, zirconium, bismuth, etc. Specifically, tin carboxylate, lead carboxylate, zinc carboxylate, iron carboxylate, copper carboxylate, nickel carboxylate, cobalt carboxylate, manganese carboxylate, zirconium carboxylate, bismuth carboxylate, etc. can be mentioned.

[0026] Among these metal carboxylates, as tin carboxylates, more specifically, tin acetate, tin butyrate, tin octylate, tin naphthenate, tin oleate, tin laurate, stannous octoate, stannous dilaurate, stannous dipalmitate, stannous distearate, stannous dioleate, tin bis(neodecanoate), tin stearate, tin benzoate, etc. can be mentioned. As lead carboxylates, lead acetate, lead butyrate, lead octylate, lead naphthenate, lead oleate, lead octoate, lead neodecanoate, lead laurate, lead stearate, lead benzoate, etc. can be mentioned. Further, as zinc carboxylates, zinc acetate, zinc butyrate, zinc octylate, zinc naphthenate, zinc oleate, zinc octoate, zinc neodecanoate, zinc laurate, zinc stearate, zinc benzoate, etc. can be mentioned.

[0027] In addition, as iron carboxylates, iron acetate, iron butyrate, iron octylate, iron naphthenate, iron oleate, iron octoate, iron neodecanoate, iron laurate, iron stearate, iron benzoate, etc. can be mentioned, and as copper carboxylates, copper acetate, copper butyrate, copper octylate, copper naphthenate, copper oleate, copper octoate, copper neodecanoate, copper laurate, copper stearate, copper benzoate, etc. can be mentioned. Further, as nickel carboxylates, nickel acetate, nickel butyrate, nickel octylate, nickel naphthenate, nickel oleate, nickel octoate, nickel neodecanoate, nickel laurate, nickel stearate, nickel benzoate, etc. can be mentioned, and as cobalt carboxylates, cobalt acetate, cobalt butyrate, cobalt octylate, cobalt naphthenate, cobalt oleate, cobalt octoate, cobalt neodecanoate, cobalt laurate, cobalt stearate, cobalt benzoate, etc. can be mentioned.

[0028] Furthermore, examples of the manganese carboxylate include manganese acetate, manganese butyrate, manganese octylate, manganese naphthenate, manganese oleate, manganese octanoate, manganese neodecanoate, manganese laurate, manganese stearate, manganese benzoate, and the like. Examples of the zirconium carboxylate include zirconium acetate, zirconium butyrate, zirconium octylate, zirconium naphthenate, zirconium oleate, zirconium octanoate, zirconium neodecanoate, zirconium laurate, zirconium stearate, zirconium benzoate, and the like. Further, examples of the bismuth carboxylate include bismuth acetate, bismuth butyrate, bismuth octylate, bismuth naphthenate, bismuth oleate, bismuth octanoate, bismuth neodecanoate, bismuth laurate, bismuth stearate, bismuth benzoate, and the like.

[0029] In particular, in the present invention, among the above-mentioned numerous metal carboxylates, bismuth carboxylate has characteristics such as a high reaction rate and no toxicity, and thus is advantageously used.

[0030] In addition, the amount of the metal carboxylate used as one of such catalysts is generally selected in the range of about 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the active hydrogen group-containing compound in the liquid A in order to effectively exhibit its function as a catalyst. If the amount of the metal carboxylate used is too small, there will be problems such as an excessively slow reaction rate between the active hydrogen group-containing compound and the polyisocyanate. On the other hand, if the amount used is too large, problems such as an excessively fast reaction rate will be caused.

[0031] In addition, the liquid A according to the present invention may contain various other known catalysts, namely reaction catalysts such as tertiary amine catalysts and quaternary ammonium salts, together with the above-described metal carboxylates, as required. In the present invention, however, a tertiary amine catalyst is particularly advantageously used. By using such a tertiary amine catalyst in combination, even in the presence of water, the chemical liquid composition according to the present invention is less likely to be affected by its reaction rate. Therefore, at the site where the chemical liquid composition according to the present invention is injected, it exhibits the characteristic that the difference in reaction time between the case where substantially no water is present and the case where water is present becomes small.

[0032] Here, as the tertiary amine catalyst, in the case where foaming is intended by contact with water, there are a foaming catalyst having an action of promoting the reaction between polyisocyanate and water, a resinification catalyst having an action of promoting the reaction between polyisocyanate and polyol, and further an isocyanuration catalyst having an action of promoting the trimerization of polyisocyanate. All of them will be appropriately selected from known ones.

[0033] Specifically, examples of the foaming catalyst include N,N,N’,N”,N”-pentamethyldiethylenetriamine, N,N,N’-triethylaminoethylethanolamine, bis(dimethylaminoethyl) ether, N,N,N’-trimethylaminoethylpiperazine, N,N-dimethylaminoethoxyethanol, triethylamine, and the like. Examples of the resinification catalyst include N,N,N’,N’-tetramethylethylenediamine, N,N,N’,N’-tetramethylpropanediamine, N,N,N’,N’-tetramethylhexanediamine, triethylenediamine, 33% triethylenediamine·67% dipropylene glycol, N,N-dimethylaminohexanol, N,N-dimethylaminoethanol, N-methyl-N’-hydroxyethylpiperazine, N-methylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, and the like. Further, examples of the isocyanuration catalyst include 2,4,6-tris(dimethylaminomethyl)phenol, N,N’,N”-tris(dimethylaminopropyl)-hexahydro-s-triazine, and the like. These catalysts can be used alone or in combination of two or more without any problem. Further, among these, the foaming catalyst or the resinification catalyst is preferably used.

[0034] In addition, the amount of the tertiary amine catalyst contained in such liquid A is generally determined at a ratio of 0.5 to 10 parts by mass, preferably 0.8 to 5 parts by mass, per 100 parts by mass of the active hydrogen group-containing compound. This is because if the catalyst content is less than 0.5 part by mass, the contribution to the reaction decreases and it becomes difficult to sufficiently contribute to the improvement of the reaction rate in the presence of water. On the other hand, if it exceeds 10 parts by mass, problems such as the reaction becoming too fast and the control of the reaction rate becoming difficult will occur. Further, when such a tertiary amine catalyst is used together with the above-mentioned metal carboxylate catalyst, the ratio (mass ratio) of the metal carboxylate to the tertiary amine is generally about 5:1 to 1:5, preferably about 3:1 to 1:3.

[0035] In addition, examples of the quaternary ammonium salt include aliphatic ammonium compounds such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium, etc.; hydroxyammonium compounds such as (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, etc.; and alicyclic ammonium compounds such as 1-methyl-1-azanium-4-azabicyclo[2,2,2]octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium, etc. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azanium-4-azabicyclo[2,2,2]octanium, and 1,1-dimethyl-4-methylpiperidinium are preferably used because of their excellent catalytic activity and industrial availability.

[0036] Examples of the organic acid group or inorganic acid group constituting such a quaternary ammonium salt include organic acid groups such as formate group, acetate group, octylate group, oxalate group, malonate group, succinate group, glutarate group, adipate group, benzoate group, toluylate group, ethylbenzoate group, methyl carbonate group, phenol group, alkylbenzene sulfonate group, toluene sulfonate group, benzene sulfonate group, phosphate ester group, and inorganic acid groups such as halogen group, hydroxyl group, hydrogen carbonate group, carbonate group. Among these, formate group, acetate group, octylate group, methyl carbonate group, halogen group, hydroxyl group, hydrogen carbonate group, and carbonate group are preferred because they have excellent catalytic activity and are industrially available.

[0037] On the other hand, as the polyisocyanate which is an essential constituent of the B liquid, which is one of the two liquids constituting the chemical liquid composition for consolidating the base material targeted by the present invention, in the present invention, not only the aliphatic polyisocyanate compound itself is used, but also a prepolymer (aliphatic polyisocyanate prepolymer) derived from such an aliphatic polyisocyanate compound will be advantageously used.

[0038] Here, examples of the aliphatic polyisocyanate compound include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate (lysine diisocyanate), etc., and aliphatic polyisocyanates such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. In addition to these aliphatic polyisocyanates, alicyclic diisocyanates such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hydrogenated xylylene diisocyanate) or a mixture thereof, methylene bis(4,1-cyclohexanediyl) diisocyanate (hydrogenated MDI), norbornane diisocyanate, etc., and alicyclic triisocyanates such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2,2,1)heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2,2,1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2,2,1) Alicyclic polyisocyanates such as alicyclic triisocyanates including heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2,2,1)-heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane; Aromatic aliphatic polyisocyanates such as aromatic aliphatic diisocyanates including 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and aromatic aliphatic triisocyanates including 1,3,5-triisocyanatomethylbenzene can be mentioned.,

[0039] Moreover, the aliphatic polyisocyanate prepolymer is not particularly limited. For example, adducts, biuret compounds, allophanate compounds obtained by reacting the above-mentioned aliphatic polyisocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate with an active hydrogen group-containing compound, and isocyanurate compounds obtained by trimerizing such polyisocyanate compounds are preferably used. The isocyanurate compound may contain a dimer uretdione compound without any problem. Considering properties such as the strength and flame retardancy of the solidified product, the isocyanurate compound is more preferably used for such an aliphatic polyisocyanate prepolymer.,

[0040] Furthermore, since such an aliphatic polyisocyanate prepolymer is obtained by using an aliphatic polyisocyanate compound as described above and modifying it, the aliphatic polyisocyanate compound as a raw material remains as an unreacted monomer component in the prepolymer which is the modified product. However, in the present invention, such a residual monomer component is preferably 5% by mass or less, and in particular, the prepolymer of the aliphatic polyisocyanate compound is prepared so as to be 1% by mass or less. When the amount of such a residual monomer component increases, problems such as a decrease in physical properties such as the strength of the solidified body are caused, and in addition, monomer components volatilize during construction, deteriorating the working environment.

[0041] And the aliphatic polyisocyanate compound and its prepolymer as described above are generally contained in the B liquid at a ratio of 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass. When the content of such an aliphatic polyisocyanate compound or its prepolymer is less than 50% by mass, there is a problem that the strength of the solidified body decreases. Therefore, it is desirable that the ratio of the aliphatic polyisocyanate compound or its prepolymer in the B liquid is higher, and it is also possible to constitute the B liquid only with such an aliphatic polyisocyanate compound or its prepolymer. It is also possible to contain a known aromatic polyisocyanate in the B liquid within a range not exceeding 10% by mass.

[0042] Incidentally, additives similar to those in the prior art can be added to the above-described Solution A and Solution B that constitute the base consolidation chemical solution according to the present invention, depending on the purpose of use. For example, as additives for Solution A, a foaming agent, a foam stabilizer, a flame retardant, a viscosity reducer, etc. can be mentioned. These additives for Solution A are generally used appropriately at a ratio of about 0.1 to 50 parts by mass, preferably about 0.5 to 40 parts by mass, with respect to 100 parts by mass of the active hydrogen group-containing organic compound. Further, as additives for Solution B, a foam stabilizer, a flame retardant, a viscosity reducer, etc. can be mentioned. Among them, the foam stabilizer is used at a ratio of 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, with respect to 100 parts by mass of the polyisocyanate component, the viscosity reducer is used at a ratio of 0.5 to 60 parts by mass, preferably 1 to 40 parts by mass, with respect to 100 parts by mass of the polyisocyanate component, and the flame retardant is used at a ratio of 1 to 50 parts by mass, preferably 5 to 40 parts by mass, with respect to 100 parts by mass of the polyisocyanate component.

[0043] Among these additives, as the foaming agent, known ones such as water, hydrocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, etc. can be used. This foaming agent is not particularly limited, but water is preferably used. This water is also supplied from the base to which the chemical solution composition is applied, and since it reacts with the polyisocyanate in Solution B to generate carbon dioxide gas, it functions as a foaming agent.

[0044] In addition, the foam stabilizer is used to uniformly arrange the cell structure of the foam formed by the reaction of liquid A and liquid B. Examples of such foam stabilizers include silicone, nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymers, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, lauryl fatty acid ethylene oxide adducts, etc. Among these, silicone and nonionic surfactants are preferably used. These may be used alone or in combination of two or more. Among the foam stabilizers, silicone-based foam stabilizers are more preferable, and polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymers, etc. are preferable.

[0045] Furthermore, as the flame retardant, a liquid flame retardant or a powdery flame retardant can be used. And these flame retardants can be dispersed and contained in either liquid A or liquid B. Also, these flame retardants may be used alone or in combination of two or more. In particular, from the point of also functioning as a viscosity reducer for the foaming composition, it is advisable to use a liquid flame retardant. Furthermore, by using a liquid flame retardant and a powdery flame retardant in combination, further improvement in flame retardancy can be achieved.

[0046] Examples of the liquid flame retardant include phosphate esters and bromine-containing flame retardants. Since the environmental load is small, phosphate esters are preferably used. Note that examples of the phosphate ester can include monophosphate esters and condensed phosphate esters.

[0047] Examples of the monophosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl)phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methane phosphonate, diethyl phenylphosphonate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, tris(β-chloropropyl) phosphate, and the like.

[0048] Examples of the condensed phosphate esters include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200), hydroquinone poly(2,6-xylyl) phosphate, and condensates thereof. Examples of commercially available condensed phosphate esters other than those described above include resorcinol polyphenyl phosphate (trade name: CR-733S), bisphenol A polycresyl phosphate (trade name: CR-741), aromatic condensed phosphate ester (trade name: CR747), resorcinol polyphenyl phosphate (manufactured by ADEKA Corporation, trade name: Adeka Stab PFR), bisphenol A polycresyl phosphate (trade names: FP-600, FP-700), and the like.

[0049] In addition, examples of bromine-containing flame retardants include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), and tetrabromobisphenol A; brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A and copolymers of the above polycarbonate oligomers and bisphenol A; brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin and monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin; poly(brominated benzyl acrylate); brominated polyphenylene ether; condensates of brominated bisphenol A, cyanuric chloride, and brominated phenol; brominated polystyrenes such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene; halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene), etc. can be mentioned.

[0050] Moreover, examples of powdery flame retardants include red phosphorus, phosphate-containing flame retardants, stannate-containing flame retardants, boron-containing flame retardants, metal hydroxides, metal oxides, etc. Red phosphorus, boron-containing flame retardants, and metal hydroxides are preferably used in terms of ease of handling. Note that known red phosphorus can be used as the red phosphorus.

[0051] Among them, examples of the phosphate-containing flame retardants include phosphates such as monophosphate, pyrophosphate, and polyphosphate. Examples of the monophosphates include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as sodium monophosphate, sodium diphosphate, trisodium phosphate, sodium hypophosphite, sodium phosphite, and sodium metaphosphate; potassium salts such as potassium monophosphate, potassium diphosphate, tripotassium phosphate, potassium hypophosphite, potassium phosphite, and potassium metaphosphate; lithium salts such as lithium monophosphate, lithium diphosphate, trilithium phosphate, lithium hypophosphite, lithium phosphite, and lithium metaphosphate; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, and barium hypophosphite; magnesium salts such as magnesium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite, etc. Examples of the polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate, etc.

[0052] Examples of the tin salt-containing flame retardants include zinc stannate, barium stannate, sodium stannate, potassium stannate, cobalt stannate, magnesium stannate, etc.

[0053] Furthermore, examples of the boron-containing flame retardant include borax, boron oxide, boric acid, borate, etc. Specifically, examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide, etc. Examples of borate include alkali metal borates such as lithium borate, sodium borate, potassium borate, cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, barium borate; zirconium borate, zinc borate, aluminum borate, ammonium borate, etc.

[0054] Examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. In addition, examples of the metal oxide include zinc oxide, aluminum oxide, titanium oxide, etc.

[0055] In addition, the viscosity reducer is used as a solvent and is dissolved in Liquid A or Liquid B to reduce the viscosity of these liquids. As long as it has such a function, it is not particularly limited. For example, alcohols such as methanol and ethanol, ethers such as ethyl cellosolve and butyl cellosolve, cyclic esters such as propylene carbonate, esters such as dimethyl dicarboxylate and ethylene glycol monomethyl ether acetate, petroleum-based hydrocarbons, etc. can be mentioned. These may be used alone or in combination of two or more.

[0056] Incidentally, the liquid A and liquid B prepared according to the present invention are each adjusted so that the viscosity at a temperature of 25°C is 6000 mPa·s or less, preferably 10 to 5000 mPa·s, more preferably 20 to 3500 mPa·s. When this viscosity becomes higher than 6000 mPa·s, the liquid A and liquid B become viscous liquids, and not only does the fluidity during mixing deteriorate, but the fluidity during pumping also deteriorates, which may cause problems such as an increase in the injection pressure. In addition, when such a viscosity becomes lower than 20 mPa·s, it becomes easy to be diluted by water, and problems such as white turbidity of drainage are likely to be caused. Further, the liquid A and liquid B may be temperature-adjusted using a heater to reduce the viscosity during pump feeding, and it is also possible to heat them to 0 to 50°C according to the outside air temperature.

[0057] In addition, when using the chemical liquid composition for ground consolidation according to the present invention, which is composed of such a liquid A and liquid B, both liquids are mixed at the time of use and injected into the target ground, foundation, rock mass, etc. according to a known method, and are reaction-cured to form a high-strength solid. Therefore, the mixing ratio of the liquid A and liquid B depends on the total content (total number of moles: X) of the active hydrogen groups (OH groups, NH2 groups) in the liquid A introduced by the active hydrogen group-containing organic compound having a cyclic structure and the content (number of moles: Y) of the isocyanate groups (NCO groups) in the liquid B introduced by the polyisocyanate, and will be appropriately changed. Generally, in terms of the molar ratio, it is adopted within the range of X / Y = 0.3 to 3.0, preferably 0.3 to 2.8, more preferably 0.4 to 2.4. When such a molar ratio (X / Y) is less than 0.3, it becomes difficult to impart sufficient strength to the formed solid, and there is a risk that the ground cannot be sufficiently improved. On the other hand, when it exceeds 3.0, the reaction may not proceed sufficiently, and the strength and flexibility of the solid may be insufficient.

[0058] Thus, when mixing Liquid A and Liquid B according to the present invention, while considering the content of active hydrogen groups in Liquid A and the content of isocyanate groups in Liquid B, their mixing ratio (A:B) will be appropriately determined. Generally, on a mass basis, A:B = 2:1 to 1:3, preferably in the range of 1:1 to 1:2, and it will be adopted. Also, regarding the usage methods of Liquid A and Liquid B, as long as the two liquids can be surely mixed immediately before their use, there is no particular limitation, and various known injection methods will be appropriately adopted.

[0059] Furthermore, the reaction time (the time from mixing to curing) when Liquid A and Liquid B are mixed is preferably within 600 seconds, more preferably 20 to 360 seconds, when the chemical solution temperature is 25°C. If this reaction time is longer than 600 seconds, after injection into the ground, before solidifying, problems such as the chemical solution flowing out into the spring water, causing white turbidity and foaming of the water will occur. In addition, if the reaction time is too short, for example, shorter than 20 seconds, problems such as the reaction proceeding too far, blocking the injection pipe of the chemical solution, and it becoming difficult to sufficiently penetrate into the ground will be caused.

Examples

[0060] Some examples and comparative examples of the present invention are shown below to clarify the present invention more specifically. Needless to say, the present invention is not restricted by the description of such examples. Also, it should be understood that in addition to the following examples and beyond the above specific descriptions, various changes, modifications, improvements, etc. can be made based on the knowledge of those skilled in the art without departing from the gist of the present invention.

[0061] In addition, along with the properties (viscosity) of Liquid A and Liquid B obtained in the following Examples and Comparative Examples, the miscibility when Liquid A and Liquid B are mixed, the turbidity of water after reacting and foaming Liquid A and Liquid B in water, the reaction time when Liquid A and Liquid B are mixed and react to cure, the compressive strength and flexural strength of the reaction product, the foaming ratio in the presence / absence of water, and the oxygen index of the reaction product were measured or evaluated according to the following methods, respectively. Also, the “%”, “ratio”, and “parts” shown below are all based on mass.

[0062] (1) Measurement of Viscosity The viscosities of Liquid A and Liquid B obtained in the Examples and Comparative Examples were measured using a B-type viscometer in accordance with JIS-K-7117-1:1999.

[0063] (2) Evaluation of Miscibility Liquid A and Liquid B adjusted to a temperature of 25°C were placed in a 300 ml cup in a total of 100 parts at the mixing ratios specified for each Example and each Comparative Example. Immediately after that, they were mixed with a spatula for 20 seconds, and the state from the start of mixing to after mixing was observed. Then, if Liquid A and Liquid B were sufficiently mixed at the 20-second mark, it was evaluated as ○; if the mixing was slightly insufficient due to thickening or the like during mixing, it was evaluated as △; and if the mixing was not sufficient due to thickening or the like during mixing and there were irregularities in the solidified matter, it was evaluated as ×.

[0064] (3) Evaluation of Turbidity Liquid A and Liquid B adjusted to a temperature of 25°C were weighed so that the total amount was 100 ml at the mixing ratios employed in each Example and Comparative Example and then mixed. Immediately after that, the mixture of Liquid A and Liquid B was poured into 1 L of water at 25°C contained in a 2 L cup and allowed to stand until the reaction subsided. After the reaction ended, the state of the water was observed visually. If no turbidity was observed immediately after the reaction subsided, it was evaluated as ○; if no turbidity was observed within 1 hour after the reaction subsided, it was evaluated as △; and if turbidity was still observed more than 1 hour after the reaction subsided, it was evaluated as ×.

[0065] (4) Measurement of reaction time The liquid A and liquid B adjusted to a temperature of 25°C were mixed at the mixing ratio adopted in each example and comparative example to initiate the reaction. After that, gas was generated from the formed reaction product, and the time until the foaming height no longer changed, or the time until a skewer was inserted into the reaction product and no longer penetrated to the inside was measured, and the slower of the two was taken as the reaction time.

[0066] (5) Compressive strength test and flexural strength test The liquid A and liquid B adjusted to a temperature of 25°C were measured so that the total amount was 100 ml at the mixing ratio adopted in each example and comparative example, and then mixed. Next, immediately after such mixing, a predetermined amount of the mixture of liquid A and liquid B was poured into a bottomed cylindrical mold with an inner diameter of 50 mm and a height of 100 mm, covered, and cured for 2 hours or more. After that, the demolded reaction product was cured at a temperature of 25°C for 24 hours or more, and the compressive strength was measured in accordance with JIS-K-7220:2006.

[0067] Also, for the flexural strength, using the test piece composed of the reaction product obtained in the same manner as above, the measurement was carried out in accordance with JIS-K-7221:2006.

[0068] (6) Measurement of foaming ratio The liquid A and liquid B adjusted to a temperature of 25°C were each measured so that the total amount was 100 ml at the mixing ratio adopted in each example and comparative example, and they were placed in a 2 L cup, sufficiently mixed and stirred, and cured. Then, the foaming height of the reaction product after the curing reaction was measured to obtain the foaming ratio.

[0069] (7) Measurement of reaction time and foaming ratio in the presence of water To the liquid A in each example and comparative example, 0.5 part of a foam stabilizer: B8450 (manufactured by Evonik) and 2 parts of water were further added, and in the same manner as the measurement of the reaction time in (4) and the measurement of the foaming ratio in (6) above, the reaction time and foaming ratio in the presence of water were respectively determined.

[0070] (8) Evaluation of Oxygen Index (Flammability) To the A liquid adjusted to a temperature of 25°C in each of the examples and comparative examples, 0.5 part of a foam stabilizer: B8450 (manufactured by Evonik) and 2 parts of water were further added. Then, the B liquid adjusted to a temperature of 25°C was mixed at the ratio adopted in each of the examples and comparative examples. Immediately after that, it was poured into a mold of 250 mm × 100 mm × 50 mm in an amount that would foam three times, and after covering it, it was cured for 2 hours or more. Then, after demolding and curing at 25°C for 24 hours or more, test specimens were cut out from the obtained reaction products, and the oxygen index of each test specimen was measured in accordance with JIS-K-7201-2:2007. Note that the higher this oxygen index, the better the flammability indicates.

[0071] First, the following various raw materials were prepared as the constituent components of the A liquid or B liquid used in the following examples and comparative examples. Polyol: Phenolic resin (prepared according to the following synthesis method) : Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd., aromatic ring content: 69%) : PF300 [manufactured by Asahi Organic Materials Co., Ltd., phenolic resin-based polyol (EOPO adduct), aromatic ring content: 46%] : Cyclohexanedimethanol (manufactured by Sanyo Chemical Industries, Ltd., 1,4-cyclohexanedimethanol, alicyclic ring content: 57%) : Sorbitan monolaurate (manufactured by Fujifilm Wako Pure Chemical Corporation, sorbitan monolaurate, heterocyclic ring content: 20%) : PP-400 [manufactured by Sanyo Chemical Industries, Ltd., Sunnex PP-2000( Polyether polyol, molecular weight 400, functional group number 2, without cyclic structure) : 450ED [manufactured by AGC Inc., Excenol 450ED (polyether polyol, molecular weight 400, functional group number 4), without cyclic structure) Polyamine: Diethyltoluenediamine (manufactured by Albemarle, Ethacure 100, aromatic ring content: 41%) Catalyst: Bismuth catalyst (manufactured by Nippon Chemical Industry Co., Ltd., bismuth octylate, bismuth concentration: 25%) : Tin catalyst (manufactured by Nippon Chemical Industry Co., Ltd., dibutyltin dioctate) : Kao Catalyzer No. 26 (manufactured by Kao Corporation, tertiary amine catalyst) : Kao Catalyzer No. 390 (manufactured by Kao Corporation, tertiary amine catalyst) Viscosity reducer: PC (manufactured by Tokyo Chemical Industry Co., Ltd., propylene carbonate) : DOP (manufactured by Tokyo Chemical Industry Co., Ltd., dioctyl phthalate) Flame retardant: Phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd., tris(chloropropyl) phosphate) : Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., Nova Excel 140) : Phosphinate (manufactured by Clariant Chemicals, EXOLIT OP-935) : Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., aluminum hydroxide) Polyisocyanate : HDI nurate (manufactured by Mitsui Chemicals, Inc., Takenate D-170N, hexamethylene diisocyanate prepolymer, nurate type, NCO content: 21%) : HDI biuret (manufactured by Mitsui Chemicals, Inc., Takenate D-165N, hexamethylene diisocyanate prepolymer, biuret type, NCO content: 23.5%) : PDI nurate (manufactured by Mitsui Chemicals, Inc., Stabio D-476N, pentamethylene diamine prepolymer, mixed nurate type / allophanate type, NCO content: 23.5%) : XDI (manufactured by Mitsui Chemicals, Inc., Takenate 500, xylylene diisocyanate, NCO content: 47%) : MDI (manufactured by Kinglake Mitsui Chemicals Co., Ltd., Cosmonate M-200, polymeric MDI, NCO content: 31%)

[0072] -Synthesis of phenol resin- Into a three-necked reaction flask equipped with a reflux condenser, thermometer, and stirrer, 50 parts of phenol and 50 parts of orthocresol (phenol / orthocresol = 50 / 50) were charged together with 51.9 parts of 92% paraformaldehyde and 0.15 part of zinc naphthenate as a divalent metal salt. After reacting for 90 minutes at the reflux temperature, it was washed with 100 parts of water, the aqueous layer was removed, and then it was concentrated by heating to obtain a phenol resin (orthocresol-modified benzyl ether type phenol resin) with a water content of 1% or less. The synthesized phenol resin had a content of free phenols of 1% or less and formaldehyde of 0.1% or less. Also, the aromatic ring content was 65%.

[0073] (Examples 1 to 19) -Preparation of Solution A- The various raw materials prepared above, namely, active hydrogen group-containing organic compounds (polyols, polyamines), catalysts, viscosity reducers, and flame retardants, were uniformly mixed in the various combinations and blending ratios shown in Tables 1 to 2 below to prepare various Solution A blending compositions according to Examples 1 to 20, respectively. Then, the viscosities of the obtained Solution A blending compositions were measured, and the results are shown in Tables 1 to 2 below.

[0074] -Preparation of Solution B- Using the various polyisocyanates prepared above, Solution B blending compositions consisting of 100% thereof were prepared, respectively. Then, the viscosities of the obtained Solution B blending compositions were measured, and the results are shown in Tables 1 to 2 below.

[0075] -Reaction of Solution A and Solution B- The Solution A and Solution B obtained above were combined in the ratios shown in Tables 1 to 2, uniformly mixed at room temperature, and reacted. Then, various evaluation tests were performed according to the evaluation methods described above, and the results are shown in Tables 1 to 2 below.

[0076] (Comparative Example 1) In Example 2, tests were conducted in the same manner as in Example 2, except that no bismuth catalyst was added as a catalyst. The obtained results are shown in Table 2 below.

[0077] (Comparative Example 2) In Example 2, tests were conducted in the same manner as in Example 2, except that a polyether polyol (450ED) having no cyclic structure was used instead of the phenolic resin. The obtained results are shown in Table 2 below.

[0078] (Comparative Example 3) In Example 2, tests were conducted in the same manner as in Example 2, except that MDI, an aromatic polyisocyanate which is not an aliphatic polyisocyanate compound, was used instead of the HDI nurate used as the polyisocyanate component. The obtained results are shown in Table 2 below.

[0079] [Table 1]

[0080] [Table 2]

[0081] As is clear from the results of Tables 1 to 2, in the chemical liquid compositions comprising Liquid A and Liquid B according to the present invention in Examples 1 to 20, all of them have a reaction time of 600 seconds or less, are excellent in reaction activity, have good miscibility, can form a consolidated body excellent in high compressive strength and flexural strength, and moreover, showed good results in the turbidity test.

[0082] On the other hand, among the chemical liquid compositions composed of Liquid A and Liquid B prepared in Comparative Examples 1 to 3, in the chemical liquid composition according to Comparative Example 1, the curing reaction took a long time, the reaction activity was poor, and it was recognized that the compression strength and bending strength of the solidified body were inferior. Further, in the chemical liquid composition according to Comparative Example 2, it was inferior in the turbidity test. Furthermore, in the chemical liquid composition according to Comparative Example 3, the miscibility was poor, and it was recognized that the compression strength and bending strength of the obtained solidified body were inferior.

[0083] -Changes in reaction time and foaming ratio in the presence of water- Using the chemical liquid compositions prepared in Example 1, Examples 5 to 7, Example 11, Examples 16 to 17, and Comparative Examples 1 to 3, 0.5 part of a foam stabilizer: B8450 (manufactured by Evonik) and 2 parts of water were further added to each Liquid A, and reacted by mixing with Liquid B, and the reaction time and foaming ratio were examined, and the results are shown in Table 3 below. For reference, the results shown in Tables 1 to 2 obtained by reacting Liquid A and Liquid B in the absence of water are shown in Table 4 as the reaction time and foaming ratio in the absence of water.

[0084]

Table 3

[0085] As is clear from the results in Table 3 above, in the chemical liquid compositions according to the respective examples of the present invention, the change rate (times) of the reaction time in the presence of water with respect to the reaction time in the absence of water is small. Therefore, it shows that the reaction between Liquid A and Liquid B is hardly affected by water. On the other hand, in Comparative Example 2 and Comparative Example 3, the change rate of the reaction time in the presence of water is large. Therefore, it is clear that the reaction between Liquid A and Liquid B is greatly affected by water.

[0086] -Examination of flame retardancy by oxygen index- Using the liquid A and liquid B prepared in Examples 4 to 8, Examples 21 to 23, and Comparative Example 2, the oxygen index of the foam products (consolidated bodies) obtained by foaming and curing was measured respectively, and the results are shown in Table 4 below.

[0087] [Table 4]

[0088] As is clear from the results in Table 4, in the chemical liquid compositions according to Examples 4 to 8 and Examples 21 to 23, which consist of liquid A and liquid B according to the present invention, the oxygen index has a larger value compared to the foam consolidated body obtained from the chemical liquid composition according to Comparative Example 2. Thus, it was confirmed that a foam consolidated body with good flame retardancy is provided.

Claims

1. A chemical liquid composition for ground consolidation, comprising a liquid A containing an active hydrogen group-containing compound and a catalyst as essential components, and a liquid B containing a polyisocyanate as an essential component, wherein the liquid A contains at least an active hydrogen group-containing organic compound having a cyclic structure as the active hydrogen group-containing compound, and contains at least a metal carboxylate (excluding fatty acid alkali metal salts) as the catalyst, and the liquid B contains at least an aliphatic polyisocyanate compound as the polyisocyanate. A chemical liquid composition for ground consolidation characterized by this.

2. The chemical liquid composition for ground consolidation according to claim 1, wherein the cyclic structure of the active hydrogen group-containing organic compound is an aromatic cyclic structure, an alicyclic structure, or a heterocyclic structure.

3. The chemical liquid composition for ground consolidation according to claim 1 or claim 2, wherein the active hydrogen group-containing organic compound is a phenolic compound.

4. The chemical liquid composition for ground consolidation according to claim 1 or claim 2, wherein the active hydrogen group-containing organic compound is a phenolic resin.

5. The chemical liquid composition for ground consolidation according to any one of claims 1 to 4, wherein the proportion of the cyclic structure in the active hydrogen group-containing organic compound is 15% by mass or more.

6. A chemical liquid composition for ground consolidation, comprising a liquid A containing an active hydrogen group-containing compound and a catalyst as essential components, and a liquid B containing a polyisocyanate as an essential component, wherein the liquid A contains at least a phenolic resin as the active hydrogen group-containing compound, and contains at least a metal carboxylate as the catalyst, and the liquid B contains at least an aliphatic polyisocyanate compound as the polyisocyanate. A chemical liquid composition for ground consolidation characterized by this.

7. The chemical liquid composition for ground consolidation according to any one of claims 1 to 6, wherein the ratio (X / Y) of the total number of moles of active hydrogen groups (X) in the liquid A to the number of moles of isocyanate groups (Y) in the liquid B is 0.3 to 3.

0.

8. The chemical liquid composition for ground consolidation according to any one of claims 1 to 7, wherein the aliphatic polyisocyanate compound is a prepolymer and has a residual monomer content of less than 5% by mass.

9. The prepolymer of the aliphatic polyisocyanate compound is any one of an adduct, biuret, allophanate, and isocyanurate derived from an aliphatic polyisocyanate compound selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, and bis(isocyanatomethyl)cyclohexane. The chemical liquid composition for ground consolidation according to claim 8, characterized in that it is as described above.

10. The chemical liquid composition for ground consolidation according to any one of claims 1 to 9, characterized in that the liquid A further contains a tertiary amine as a catalyst.

11. The chemical liquid composition for ground consolidation according to any one of claims 1 to 10, characterized in that a flame retardant is further contained in the liquid A and / or the liquid B.

12. The chemical liquid composition for ground consolidation according to any one of claims 1 to 11, characterized in that the liquid A and the liquid B each have a viscosity of 6000 mPa·s or less at a temperature of 25°C.

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